USOO6232417 B1 (12) United States Patent (10) Patent No.: US 6,232,417 B1 Rhodes et al. (45) Date of Patent: May 15, 2001

(54) PHOTORESIST COMPOSITIONS FOREIGN PATENT DOCUMENTS COMPRISING POLYCYCLIC POLYMERS WITH ACID LABILE PENDANT GROUPS O789278 8/1997 (EP). 0836119 4/1998 (EP). 5297591 11/1993 (JP). (75) Inventors: Larry F Rhodes, Silverlake; Andrew 9230595 9/1997 (JP). Bell, Lakewood; Saikumar Jayaraman, Cuyahoga Falls, OTHER PUBLICATIONS John-Henry Lipian, Broadview Heights; Brian L. Goodall, Akron; J. V. Crivello et al., Chemically Amplified Electron-Beam Photoresists, Chem. Mater, 1996, 8,376-381. it. Shick, Strongsville, all of Louis A. Cappino et al., Novel Carboxylic Acid and Car boxamide Protective Groups Based on the Exceptional Sta (73) Assignee: The B. F. Goodrich Company, bilization of the Cyclopropylmethyl Cation, J. Org. Chem. 1995, 60, 7718. T719. Brecksville,reCKSVIIIe, OH (US)(US Patents wr’sAbstracts of Japan, vol. 018, No. 096 (P-1694), Feb. (*) Notice: Subject to any disclaimer, the term of this 16, 1994. patent is extended or adjusted under 35 Robert G. Gastinger et al., IL-Arene Complexes of Nickel U.S.C. 154(b) by 0 days. (II). Synthesis (from Metal Atoms) of (T-Arene)bis(pen tafluorophenyl)nickel(II). Properties, C-Arene Lability, and (21) Appl. No.: 08/928,573 Chemistry, J. Am. Chem. Soc., 1980, 102, 4959–4966. y - - - 9 (22) Filed: Sep. 12, 1997 Primary Examiner Donald R. Wilson e - as ASSistant Examiner-Caixia Lu (51) Int. Cl." ...... C08F 4/80 (74) Attorney, Agent, or Firm Thoburn T. Dunlap (52) U.S. Cl...... 526/171; 526/283; 526/308;526/309 (57) ABSTRACT (58) Field of Search ...... 526/283, 171, The present invention relates to a radiation Sensitive photo 526/308, 309 resist composition comprising a photoacid initiator and a polycyclic polymer comprising repeating units that contain (56) References Cited pendant acid labile groups. Upon exposure to an imaging radiation Source the photoacid initiator generates an acid U.S. PATENT DOCUMENTS which cleaves the pendant acid labile groups effecting a 4,491,628 1/1985 Ito et al. . polarity change in the polymer. The polymer is rendered 5,155,188 10/1992 Goodall et al.. Soluble in an aqueous base in the areas exposed to the 5,372,912 12/1994 Allen et al.. imaging Source. The polymer repeating units are polymer 5,399,647 3/1995 Nozaki. ized from polycyclic monomers in the presence of Single or 5,468.819 11/1995 Goodall et al.. multicomponent catalyst Systems containing a Group VIII 5,585,219 12/1996 Kaimoto et al.. 5,585,222 12/1996 Kaimoto et al.. metal 5,705,503 1/1998 Goodall et al. . 5,843,624 12/1998 Houlihan et al.. 13 Claims, 3 Drawing Sheets U.S. Patent May 15, 2001 Sheet 1 of 3 US 6,232,417 B1

Figure 1

U.S. Patent May 15, 2001 Sheet 2 of 3 US 6,232,417 B1

Figure 2

U.S. Patent May 15, 2001 Sheet 3 of 3 US 6,232,417 B1

Figure 3

US 6,232,417 B1 1 2 PHOTORESIST COMPOSITIONS ceSSes Suffer because of the undesirable environmental and COMPRISING POLYCYCLIC POLYMERS Safety ramifications. WITH ACID LABILE PENDANT GROUPS Various “dry” processes have been developed to over come the drawbacks of the wet chemical process. Such dry BACKGROUND OF THE INVENTION processes generally involve passing a gas through a chamber 1. Technical Field and ionizing the gas by applying a potential acroSS two The present invention is related to polycyclic polymers electrodes in the presence of the gas. The plasma containing and methods for their use as photoresists in the manufacture the ionic Species generated by the potential is used to etch a of integrated circuits. More Specifically, the invention is Substrate placed in the chamber. The ionic Species generated directed to photoresist compositions comprising a polycy in the plasma are directed to the exposed Substrate where clic polymer and a cationic photoinitiator. The polycyclic they interact with the Surface material forming volatile polymer contains recurring acid labile groups that are pen products that are removed from the Surface. Typical dant from the polymer backbone. The acid labile groups can examples of dry etching are plasma etching, Sputter etching be selectively cleaved to form recurring polar groups along and reactive ion etching. the backbone of the polymer. The polymers are transparent 15 Reactive ion etching provides well defined vertical Side to Short wave lengths of imaging radiation and exhibit wall profiles in the substrate as well as substrate to substrate resistance to reactive ion etching. etching uniformity. Because of these advantages, the reac 2. Background tive ion etching technique has become the Standard in IC Integrated circuits (ICs) are paramount in the manufac manufacture. ture of an array of electronic devices. They are fabricated Two types of photoresists are used in the industry, nega from the Sequential formation of alternating and intercon tive and positive photoresists. Negative resists, upon expo necting bands of conductive, Semiconductive and noncon Sure to imaging radiation, polymerize, crosslink, or change ductive layers on an appropriate Substrate (e.g., Silicon Solubility characteristics Such that the exposed regions are wafer) that are Selectively patterned to form circuits and 25 insoluble to the developer. UneXposed areas remain Soluble interconnections to produce Specific electrical functions. and are washed away. Positive resists function in the oppo The patterning of ICS is carried out according to various Site way, becoming Soluble in the developer Solution after lithography techniques known in the art. Photolithography exposure to imaging radiation. employing ultraViolet (UV) light and increasingly deep UV One type of positive photoresist material is based upon light or other radiation is a fundamental and important phenol-formaldehyde novolac polymers. A particular technology utilized in the production of IC devices. A example is the commercially utilized Shipley AZ1350 mate photosensitive polymer film (photoresist) is applied over the rial which comprises an m-creSol formaldehyde novolak wafer Surface and dried. A photomask containing the desired polymer composition and a diazoketone (2-diazo-1-napthol patterning information is then placed in close proximity to 5-Sulphonic acid ester). When exposed to imaging radiation, the photoresist film. The photoresist is irradiated through the 35 the diaZOketone is converted to a carboxylic acid, which in overlying photomask by one of Several types of imaging turn converts the phenolic polymer to one that is readily radiation including UV light, e-beam electrons, X-rays, or Soluble in weak acqueous base developing agent. ion beam. Upon eXposure to radiation, the photoresist under U.S. Pat. No. 4,491,628 to Ito et al. discloses positive and goes a chemical change with concomitant changes in Solu negative photoresist compositions with acid generating pho bility. After irradiation, the wafer is Soaked in a Solution that 40 toinitiators and polymers with acid labile pendant groups. develops (i.e., Selectively removes either the exposed or Because each acid generated causes deprotection of multiple unexposed regions) the patterned images in the photosensi acid labile groups this approach is known as chemical tive polymer film. Depending on the type of polymer used, amplification which Serves to increase the quantum yield of or the polarity of the developing Solvent, either the exposed the overall photochemical process. The disclosed polymers or noneXposed areas of film are removed in the developing 45 include Vinylic polymerS Such as poly Styrenes, process to expose the underlying Substrate, after which the polyvinylbenzoates, and polyacrylates that are Substituted patterned exposed or unwanted Substrate material is with recurrent pendant groups that undergo acidolysis to removed or changed by an etching process leaving the produce products that differ in Solubility than their precur desired pattern in a functional layer of the wafer. Etching is Sors. The preferred acid labile pendant groups include accomplished by plasma etching, Sputter etching, and reac 50 t-butyl esters of carboxylic acids and t-butyl carbonates of tive ion etching (RIE). The remaining photoresist material phenols. The photoresist can be made positive or negative functions as a protective barrier against the etching process. depending on the nature of the developing Solution Removal of the remaining photoresist material gives the employed. patterned circuit. Trends in the electronics industry continually require ICS In the manufacture of patterned IC devices, the processes 55 that are faster and consume less power. To meet this speci of etching different layers on the wafer are among the most fication the IC must be made Smaller. Conducting pathways crucial Steps involved. One method is to immerse the (i.e., lines) must be made thinner and placed closer together. Substrate and patterned resist in a chemical bath which The Significant reduction in the size of the transistors and the attacks the exposed Substrate Surfaces while leaving the lines produced yields a concomitant increase in the effi resist itself intact. This “wet' chemical process suffers from 60 ciency of the IC, e.g., greater Storage and processing of the difficulty of achieving well defined edges on the etched information on a computer chip. To achieve thinner line Surfaces. This is due to chemical undercutting of the resist widths, higher photoimaging resolution is necessary. Higher material and the formation of an isotropic image. In other resolutions are possible with Shorter wave lengths of the words, conventional chemical processes do not provide the exposure Source employed to irradiate the photoresist mate Selectivity of direction (anisotropy) considered necessary to 65 rial. However, the prior art photoresists Such as the phenol achieve optimum dimensional Specifications consistent with formaldehyde novolac polymers and the Substituted Styrenic current processing requirements. In addition, the wet pro polymers contain aromatic groups that inherently become US 6,232,417 B1 3 4 increasingly absorptive as the wave length of light falls Accordingly, there is a need for a photoresist composition below about 300 nm, (ACS Symposium Series 537, Poly which is compatible with the general chemical amplification mers for Microelectronics, Resists and Dielectrics, 203rd Scheme and provides transparency to short wave length National Meeting of the American Chemical Society, Apr. imaging radiation while being Sufficiently resistant to a 5-10, 1992, p.2–24, Polymers for Electronic and Photonic reactive ion etching processing environment. Applications, Edited by C. P. Wong, Academic Press, p. 67–118). Shorter wave length sources are typically less SUMMARY OF THE INVENTION bright than traditional Sources which necessitate a chemical amplification approach using photoacids. The opacity of It is a general object of the invention to provide a these aromatic polymers to short wave length light is a photoresist composition comprising a polycyclic polymer drawback in that the photoacids below the polymer Surface backbone having pendant acid labile groups and a photo are not uniformly exposed to the light Source and, initiator. consequently, the polymer is not developable. To overcome It is another object of the invention to provide polycyclic the transparency deficiencies of these polymers, the aro polymers that have recurrent pendant acid labile groups that matic content of photoresist polymers must be reduced. If 15 can be cleaved to form polar groups. deep UV transparency is desired (i.e., for 248 nm and It is still another object of the invention to provide particularly 193 nm wave length exposure), the polymer polymer compositions that are transparent to short wave should contain a minimum of aromatic character. length imaging radiation. U.S. Pat. No. 5,372,912 concerns a photoresist composi It is a further object of the invention to provide polymer tion containing an acrylate based copolymer, a phenolic type compositions that are resistant to dry etching processes. binder, and a photoSensitive acid generator. The acrylate It is a still further object of the invention to provide based copolymer is polymerized from acrylic acid, alkyl polymer compositions that are transparent to short wave acrylate or methacrylate, and a monomer having an acid length imaging radiation and are resistant to dry etching labile pendant group. While this composition is sufficiently proceSSeS. transparent to UV radiation at a wave length of about 240 25 It is yet another object of the invention to provide poly nm, the use of aromatic type binders limits the use of Shorter cyclic monomers that contain acid labile pendant groups that wave length radiation Sources. AS is common in the polymer can be polymerized to form polymers amenable to aqueous art, the enhancement of one property is usually accom base development. plished at the expense of another. When employing acrylate These and other objects of the invention are accomplished based polymers, the gain in transparency to shorter wave by polymerizing a reaction mixture comprising an acid length UV is achieved at the expense of Sacrificing the labile group functionalized polycycloolefinic monomer, a resists resistance to the reactive ion etch process. Solvent, a Single or multicomponent catalyst System each In many instances, the improvement in transparency to containing a Group VIII metal ion Source. In the multicom Short wave length imaging radiation results in the erosion of 35 ponent catalyst systems of the invention the Group VIII ion the resist material during the Subsequent dry etching pro Source is utilized in combination with one or both of an ceSS. Because photoresist materials are generally organic in organometal cocatalyst and a third component. The Single nature and Substrates utilized in the manufacture of ICS are and multicomponent catalyst Systems can be utilized with an typically inorganic, the photoresist material has an inher optional chain transfer agent (CTA) Selected from a com ently higher etch rate than the Substrate material when 40 pound having a terminal olefinic double bond between employing the RIE technique. This necessitates the need for adjacent carbon atoms, wherein at least one of Said adjacent the photoresist material to be much thicker than the under carbon atoms has two hydrogen atoms attached thereto. The lying Substrate. Otherwise, the photoresist material will CTA is Selected from unsaturated compounds that are typi erode away before the underlying Substrate could be fully cally cationically non-polymerizable and, therefore, exclude etched. It follows that lower etch rate resist materials can be Styrenes, vinyl ethers, and conjugated dienes. employed in thinner layers over the Substrate to be etched. 45 Thinner layers of resist material allow for higher resolution The polymers obtained are useful in photoresist compo which, ultimately, allows for narrower conductive lines and Sitions that include a radiation-Sensitive acid generator. Smaller transistors. BRIEF DESCRIPTION OF THE DRAWINGS J. V. Crivello et al. (Chemically Amplified Electron-Beam Photoresists, Chem. Mater, 1996, 8, 376-381) describe a 50 FIG. 1 is a ball and stick molecular representation of the polymer blend comprising 20 weight % of a free radically catalyst (PPhCHC(O)Ph)Ni(CF). polymerized homopolymer of a norbornene monomer bear FIG. 2 is an ORTEP drawing of the catalyst (THF).Ni ing acid labile groups and 80 weight % of a homopolymer (CFs). of 4-hydroxy-O-methylstyrene containing acid labile groups FIG. 3 is a ball and stick molecular representation of the for use in electron-beam photoresists. AS discussed Supra, 55 catalyst (1,2-dimethoxyethane) Ni(2,4,6-tris the increased absorbity (especially in high concentrations) of (trifluoromethyl)phenyl). aromatic groups renders these compositions opaque and unusable for short wave length imaging radiation below 200 DETAILED DESCRIPTION . 60 The present invention relates to a radiation-Sensitive resist The disclosed compositions are Suitable only for electron composition comprising an acid-generating initiator and a beam photoresists and can not be utilized for deep UV polycyclic polymer containing recurring acid labile pendant imaging (particularly not for 193 nm resists). groupS along the polymer backbone. The polymer contain Crivello et al. investigated blend compositions because ing the initiator is coated as a thin film on a Substrate, baked they observed the Oxygen plasma etch rate to be unaccept 65 under controlled conditions, exposed to radiation in a pat ably high for free radically polymerized homopolymers of terned configuration, and optionally post baked under con norbornene monomers bearing acid labile groups. trolled conditions to further promote the deprotection. In the US 6,232,417 B1 S 6 portions of the film that have been exposed to radiation, the diethers, and n is an integer of 0 or 1. When n is 0 it should recurrent acid labile pendant groups on the polymer back be apparent that A and A represent a Single covalent bond. bone are cleaved to form polar recurring groups. The By divalent is meant that a free Valence at each terminal end exposed areas So treated are Selectively removed with an of the radical are attached to two distinct groups. The alkaline developer. Alternatively, the unexposed regions of divalent hydrocarbon radicals can be represented by the the polymer remain nonpolar and can be selectively formula -(CH2)- where d represents the number of removed by treatment with a suitable nonpolar solvent for a carbon atoms in the alkylene chain and is an integer from 1 negative tone development. Image reversal can easily be to 10. The divalent hydrocarbon radicals are preferably Selected from linear and branched (C to Co) alkylene Such achieved by proper choice of developer owing to the dif as methylene, ethylene, propylene, butylene, pentylene, ference in the Solubility characteristics of the exposed and heXylene, heptylene, octylene, nonylene, and decylene. unexposed portions of the polymer. When branched alkylene radicals are contemplated, it is to The polymers of the present invention comprise polycy be understood that a hydrogen atom in the linear alkylene clic repeating units, a portion of which are Substituted with chain is replaced with a linear or branched (C to Cs) alkyl acid labile groups. The instant polymers are prepared by grOup. polymerizing the polycyclic monomers of this invention. By 15 The divalent cyclic hydrocarbon radicals include substi the term “polycyclic' (norbornene-type or norbornene tuted and unsubstituted (C. to Cs) cycloaliphatic moieties functional) is meant that the monomer contains at least one represented by the formula: norbornene moiety as shown below: R9 () –6. The Simplest polycyclic monomer of the invention is the 25 bicyclic monomer, bicyclo2.2.1]hept-2-ene, commonly wherein a is an integer from 2 to 7 and R7 when present referred to as norbornene. In one embodiment of the represents linear and branched (C to Co) alkyl groups. invention, the acid labile functionality is introduced into the Preferred divalent cycloalkylene radicals include cyclopen polymer chain by polymerizing a reaction medium compris tylene and cyclohexylene moieties represented by the fol ing one or more acid labile Substituted polycyclic monomers lowing Structures: set forth under Formula I below in optional combination with one or more polycyclic monomerS Set forth under Formulae II, III, IV, and V below in the presence of the R9 A. Group VIII metal catalyst system. h (7) In another embodiment of the invention one or more of 35 the acid labile substituted polycyclic monomers of Formula I are copolymerized with one or more of the polycyclic wherein R is defined above. As illustrated here and through monomers set forth under Formula II. out this Specification, it is to be understood that the bond Monomers 40 lines projecting from the cyclic Structures and/or formulae represent the divalent nature of the moiety and indicate the The acid labile polycyclic monomers useful in the prac points at which the carbocyclic atoms are bonded to the tice of the present invention are Selected from a monomer adjacent molecular moieties defined in the respective for represented by the formula below: mulae. AS is conventional in the art, the diagonal bond line 45 projecting from the center of the cyclic structure indicates that the bond is optionally connected to any one of the carbocyclic atoms in the ring. It is also to be understood that the carbocyclic atom to which the bond line is connected will accommodate one leSS hydrogen atom to Satisfy the 50 Valence requirement of carbon. Preferred divalent cyclic ethers and diethers are repre i. Sented by the Structures: R1. R2 3 R4 55 wherein R to R' independently represent a substituent selected from the group -(A),C(O)OR*, -(A), C(O) Carlo OR, -(A), OR, -(A), OC(O)R, -(A)-C(O)R, -(A), OC(O)OR, -(A), OCHC(O)OR*, -(A), C (O)O-A-OCHC(O)OR*, -(A)-OC(O)-A-C(O) 60 The divalent oxygen containing radicals include (C. to OR*, -(A), C(R)-CH(R)(C(O)OR**), and -(A)-C Co) alkylene ethers and polyethers. By (C. to Co) alkylene (R)-CH(CO)OR**) Subject to the proviso that at least one ether is meant that the total number of carbon atoms in the of R to R' is selected from the acid labile group -(A),C divalent ether moiety must at least be 2 and can not exceed (O)OR*. A and A' independently represent a divalent bridg 10. The divalent alkylene ethers are represented by the ing or Spacer radical Selected from divalent hydrocarbon 65 formula -alkylene-O-alkylene- wherein each of the alkylene radicals, divalent cyclic hydrocarbon radicals, divalent oxy groups that are bonded to the oxygen atom can be the same gen containing radicals, and divalent cyclic ethers and cyclic or different and are Selected from methylene, ethylene, US 6,232,417 B1 7 propylene, butylene, pentylene, heXylene, heptylene, octylene, and nonylene. The Simplest divalent alkylene ether of the series is the radical -CH-O-CH-. Preferred polyether moieties include divalent radicals of the formula: Y Y -CH, and C(CH3)2 - (-CH3(CH2).O) - wherein X is an integer from 0 to 5 and y is an integer from 1O Polycyclic monomers of the above formula with a sub 2 to 50 with the proviso that the terminal oxygen atom on the stituent selected from the group -(CH),C(R)-CH(R)(C(O) polyether spacer moiety can not be directly linked to a OR**) or -(CH),C(R)-CH(CO)OR**) can be repre terminal oxygen atom on an adjacent group to form a sented as follows: peroxide linkage. In other words, peroxide linkages (i.e., 15 -O-O-) are not contemplated when polyether spacers R are linked to any of the terminal oxygen containing Sub stituent groups set forth under R' to R' above. In the above formulae R represents hydrogen, linear and i. siz8.R R branched (C to Co) alkyl, and m is an integer from 0 to 5. R* represents moieties (i.e., blocking or protecting groups) COR** that are cleavable by photoacid initiators Selected from -C(CH), -Si(CH), -CH(R)OCHCH, -CH(R) i. or.R R OC(CH), or the following cyclic groups: 25 wherein m and -A- are defined above. C H3C/ V-CH In the above formulae m is preferably 0 or 1, more preferably m is 0. When m is 0 the preferred structures are RP represented below: RP RP Ia

o Ya 35

RP wherein R' to R' are previously defined. 40 It should be apparent to those skilled in the art that any photoacid cleavable moiety is Suitable in the practice of the invention So long as the polymerization reaction is not substantially inhibited by same. The preferred acid labile group is a protected organic ester 45 group in which the protecting or blocking group undergoes D a cleavage reaction in the presence of an acid. Tertiary butyl esters of carboxylic acids are especially preferred. The monomers described under Formula I, when poly wherein R represents hydrogen or a linear or branched (C merized into the polymer backbone, provide recurring pen to Cs) alkyl group. The alkyl Substituents include methyl, 50 dant acid Sensitive groups that are Subsequently cleaved to ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, t-pentyl confer polarity or Solubility to the polymer. and neopentyl. In the above Structures, the Single bond line The optional Second monomer is represented by the projecting from the cyclic groups indicates the carbon atom structure set forth under Formula II below: ring position where the protecting group is bonded to the 55 respective Substituent. Examples of acid labile groups II include 1-methyl-1-cyclohexyl, isobornyl, 2-methyl-2- isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranoyl, 3-oxocyclohexanonyl, mevalonic lactonyl, 1-ethoxyethyl, 1-t-butoxy ethyl, dicyclopropylm 60 ethyl (Dcpm), and dimethylcyclopropylmethyl (Dmcp) p groups. The alkyl Substituents on the protecting groups Set 5 8 forth above are selected from linear and branched (C to Cs) R R6 7 R alkyl groups. R** independently represents R and R* as 65 defined above. The Dcpm and Dmcp groups are respectively wherein R to Rindependently represent a neutral or polar represented by the following Structures: substituent selected from the group: -(A), C(O)OR", US 6,232,417 B1 9 10 -(A), OR", -(A), OC(O)R", -(A), OC(O)OR", will accommodate one leSS hydrogen atom to Satisfy the -(A), C(O)R", -(A), OC(O)C(O)OR", -(A), O Valence requirement of carbon. A-C(O)OR", -(A), OC(O)-A-C(O)OR", -(A)- Preferred divalent cyclic ethers and diethers are repre C(O)O-A'-C(O) OR", -(A)-C(O)-A'-OR", Sented by the Structures: -(A), C(O)O-A-OC(O)OR", -(A), C(O)O-A- O-A'-C(O)OR", -(A), C(O)O-A'-OC(O)C(O) OR", -(A), C(R")CH(R")(C(O)OR"), and -(A)-C (R")CH(CO)OR"), or the Succinic and carboxyimide moieties: r)X r)\ r)o\

The divalent oxygen containing radicals include (C. to Co) alkylene ethers and polyethers. By (C. to Co) alkylene ether is meant that the total number of carbon atoms in the wherein R is hydrogen, linear and branched (C, to Co) 15 alkyl, or (C. to Cs) aryl. divalent ether moiety must at least be 2 and can not exceed The moieties A and A independently represent a divalent 10. The divalent alkylene ethers are represented by the bridging or Spacer radical Selected from divalent hydrocar formula -alkylene-O-alkylene- wherein each of the alkylene bon radicals, divalent cyclic hydrocarbon radicals, divalent groups that are bonded to the oxygen atom can be the same oxygen containing radicals, and divalent cyclic ethers and or different and are Selected from methylene, ethylene, cyclic diethers, and n is an integer 0 or 1. When n is 0 it propylene, butylene, pentylene, heXylene, heptylene, should be apparent that A and A'represent a single covalent octylene, and nonylene. The Simplest divalent alkylene ether bond. By divalent is meant that a free Valence at each of the series is the radical -CH-O-CH-. Preferred terminal end of the radical are attached to two distinct polyether moieties include divalent radicals of the formula: groups. The divalent hydrocarbon radicals can be repre Sented by the formula -(CH2)- where d represents the 25 number of carbon atoms in the alkylene chain and is an integer from 1 to 10. The divalent hydrocarbon radicals are preferably Selected from linear and branched (C to Co) wherein X is an integer from 0 to 5 and y is an integer from alkylene Such as methylene, ethylene, propylene, butylene, 2 to 50 with the proviso that the terminal oxygen atom on the pentylene, hexylene, heptylene, octylene, nonylene, and polyether spacer moiety can not be directly linked to a decylene. When branched alkylene radicals are terminal oxygen atom on an adjacent group to form a contemplated, it is to be understood that a hydrogen atom in peroxide linkage. In other words, peroxide linkages (i.e., the linear alkylene chain is replaced with a linear or -O-O-) are not contemplated when polyether spacers branched (C to Cs) alkyl group. are linked to any of the terminal oxygen containing Sub The divalent cyclic hydrocarbon radicals include substi 35 stituent groups set forth under R to R above. tuted and unsubstituted (C. to Cs) cycloaliphatic moieties R to R' can also independently represent hydrogen, represented by the formula: linear and branched (C to Co) alkyl, So long as at least one of the remaining R to R substituents is selected from one R9 of the neutral or polar groups represented above. In the 40 formula above p is an integer from 0 to 5 (preferably 0 or 1, –6. more preferably 0). R" independently represents hydrogen, linear and branched (C to Co) alkyl, linear and branched (C. to Co) alkoxyalkylene, polyethers, monocyclic and polycyclic (C. to Co) cycloaliphatic moieties, cyclic ethers, wherein a is an integer from 2 to 7 and R' when present 45 cyclic ketones, and cyclic esters (lactones). By (C. to Co) represents linear and branched (C to Co) alkyl groups. alkoxyalkylene is meant that a terminal alkyl group is linked Preferred divalent cycloalkylene radicals include cyclopen through an ether oxygen atom to an alkylene moiety. The tylene and cyclohexylene moieties represented by the fol radical is a hydrocarbon based ether moiety that can be lowing Structures: generically represented as -alkylene-O-alkyl wherein the 50 alkylene and alkyl groups independently contain 1 to 10 carbon atoms each of which can be linear or branched. The fR9 / /yA polyether radical can be represented by the formula: 55 wherein R is defined above. As illustrated here and through wherein X is an integer from 0 to 5, y is an integer from 2 out this Specification, it is to be understood that the bond to 50 and R" represents hydrogen or linear and branched (C, lines projecting from the cyclic Structures and/or formulae to Co) alkyl. Preferred polyether radicals include poly represent the divalent nature of the moiety and indicate the 60 (ethylene oxide) and poly(propylene oxide). Examples of points at which the carbocyclic atoms are bonded to the monocyclic cycloaliphatic monocyclic moieties include adjacent molecular moieties defined in the respective for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the mulae. AS is conventional in the art, the diagonal bond line like. Examples of cycloaliphatic polycyclic moieties projecting from the center of the cyclic structure indicates include, no rb or nyl, a damanty 1, that the bond is optionally connected to any one of the 65 tetrahydrodicyclopentadienyl(tricyclo[5.2.1.0°ldecanyl), carbocyclic atoms in the ring. It is also to be understood that and the like. Examples of cyclic ethers include tetrahydro the carbocyclic atom to which the bond line is connected furanyl and tetrahydropyranyl moieties. An example of a US 6,232,417 B1 11 12 cyclic ketone is a 3-oxocyclohexanonyl moiety. An example represent hydrogen, linear and branched (C to Co) alkyl, So of a cyclic ester or lactone is a mevalonic lactonyl moiety. long as at least one of the remaining R to R' substituents Insofar as the Substituents described for R" in Formula II is Selected from one of the acids or acid Salts Set forth above. overlap with the acid labile or protecting groups described The monomers containing carboxylic acid functionality under R* in Formula I, it should be understood that R" in contribute to the hydrophilicity of the polymer consequently Formula II can not represent an ester moiety containing an aiding in the developability of the polymer in aqueous base acid labile group. For example, when R" is a norbornyl, adamantyl, tetrahydrodicyclopentadienyl(tricyclo5.2.1.0°. Systems at high rates. 6de canyl), tetrahydrofuranyl tetrahydropy ranyl, The optional monomers under Formula IV are represented 3-oxocyclohexanonyl or a mevalonic lactonyl moiety, it can by the structure below: not be directly attached to the oxygen atom in a ester moiety (-C(O)O). When any of R to R represent a succinic or IV carboxyimide moiety and A is present (i.e., n is 1) A can only represent a linear or branched (C1 to C10) alkylene group. Preferred neutral or polar substituents include the alkyl esters of carboxylic acids, the Spaced oxalate containing 15 moieties (e.g., -(A), OC(O)-A-C(O)OR"), and the oxalate containing moieties (e.g., -(A), OC(O)C(O) OR") wherein the formulae are as defined above. The ester, R13 R16 Spaced oxalate, and oxalate containing functionalities impart R14 R15 exceptional hydrophilicity, promote good wetting of the developer and improve film mechanical properties without wherein R' to R' independently represent linear or the concomitant problems associated with excessive car branched (C to C) alkyl and r is an integer from 0 to 5 boxylic acid functionalities. (preferably 0 or 1, more preferably 0). Any of R' to R' can R and R can be taken together with the ring carbon represent hydrogen So long as at least one of the remaining atoms to which they are attached to form an anhydride or 25 R" to R' substituents is selected from an alkyl group set dicarboxyimide group as shown in the Structures below: defined above. Of the above alkyl substituents, decyl is especially preferred. IIa The polymerization of alkyl substituted monomers into the polymer backbone is a method to control the Tg of the polymer as disclosed in U.S. Pat. No. 5,468.819 to Goodall et al. An economical route for the preparation of the functional or hydrocarbyl substituted polycyclic monomers of the 35 invention relies on the Diels-Alder reaction in which cyclo pentadiene (CPD) or substituted CPD is reacted with a Suitably Substituted dienophile at elevated temperatures to form a Substituted polycyclic adduct generally shown by the NR37 following reaction Scheme: 40 O R R'' R R" wherein R is hydrogen, (C. to Co) alkyl, or (C. to Cs) + CRC| 1 -- R'' aryl and V is an integer from 0 to 5. The optional third monomer component is represented by 45 R R R''' the structure under Formula III below: Other polycyclic adducts can be prepared by the thermal III pyrolysis of dicyclopentadiene (DCPD) in the presence of a 50 suitable dienophile. The reaction proceeds by the initial pyrolysis of DCPD to CPD followed by the Diels-Alder addition of CPD and the dienophile to give the adducts as shown below:

55 i R12 R R' R R10 R11 R" E Her wherein R to R' independently represent a carboxylic or OCH-OOCR" R' R'' Sulfonic acid Substituent or salts thereof selected from the 60 formulae -(CH),C(O)OH, -(CH), SOH, -(CH2)C (O)OX",-(CH), SOX" where n X represents tetraalky wherein R' to R" independently represents the substituents lammonium cations and the alkyl Substituents bonded to the defined under R to R' in Formulae I, II, III, and IV above. nitrogen atom are independently Selected from linear and For example the 2-norbornene-5-carboxylic acid (bicyclo branched (C to Co) alkyl, and q is an integer from 0 to 5 65 2.2.1]hept-5-ene-2-carboxylylic acid) can be prepared by (preferably 0 or 1, more preferably 0) and n is an integer the Diels-Alder reaction of cyclopentadiene with acrylic from 0 to 10 (preferably 0). R” to R' can independently acid in accordance with the following reaction Scheme: US 6,232,417 B1 13

Va. R7 R18

O O O COOH COOH. O-R19

1O The corresponding t-butyl ester of the carboxylic acid can Vb be prepared by reacting the carboxylic acid functionality R17 with isobutylene in the presence of triflic acid at reduced R18 O temperatures (i.e., -30 to -20° C) as shown in the reaction O Scheme below: 15 O R19

CFSOH H-r Vc + isobutylene -30°C R17 COOH R18 O O

25 O R19

wherein R'', R', and R' independently represent hydro COOC(CH3)3. gen and linear and branched (C to Cs) alkyl. The ortho esters of the present invention can be Synthesized in accor dance with the so-called Pinner synthesis (A. Pinner, Chem. Another more preferred route to the t-butyl ester of the Ber, 16, 1643 (1883), and via the procedure set forth by S. norbornene carboxylic acid involves the Diels-Alder reac M. McElvain and J. T. Venerable, J Am. Chem. Soc., 72, tion of cyclopentadiene with t-butyl acrylate. 35 1661 (1950); S. M. McElvain and C. L. Aldridge, J Am. Another Synthesis route to the acid and ester Substituted Chem. Soc.,75, 3987 (1953). A typical synthesis is set forth monomers of the present invention is through an ortho ester in the reaction Scheme below: Substituted polycyclic monomer with Subsequent hydrolysis to a carboxylic functionality or partial hydrolysis to an ester functionality. The carboxylic functionality can be esterified 40 to the desired ester. The ortho ester Substituted monomers of / + HCI / +CH3OH the invention are represented by Formula V below: CN CFNH 45 Cl

/ He+ 2CH3OH / 50 -NHCI sitect COCH(OCH3)3 OCH

55 An alternative Synthesis route wherein an alkyl acrylate is treated with a trialkyloxonium tetrafluoroborate salt fol wherein R'', R', and R' independently represent a linear lowed by an alkali metal (sodium alcoholate) to yield the or branched (C. to C) alkyl group or any R'7, R', and R' trialkoxymethyl ortho ester (H. Meerwein, P. Borner, O. can be taken together along with the Oxygen atoms to which Fuchs, H. J. Sasse, H. Schrodt, and J. Spille, Chem. Ber, 89, they are attached to form a substituted or unsubstituted 5 to 60 2060 (1956). 10 membered cyclic or bicyclic ring containing 3 to 8 carbon AS discussed above the otho ester can undergo a hydroly atoms (excluding Substituent groups), S is an integer from 0 sis reaction in the presence of dilute acid catalysts Such as to 5 (preferably 0), and t is an integer from 1 to 5 (preferably hydrobromic, hydroiodic, and acetic acid to yield the car 1). Representative structures whereins is 0, t is 1, and R'', boxylic acid. The carboxylic acid can in turn be esterified in R', and R' are taken with the oxygen atoms to which they 65 the presence of an aliphatic alcohol and an acid catalyst to are attached to form a cyclic or bicyclic ring are set forth yield the respective ester. It should be recognized that in the below: case of polycyclic monomers that are di- or multi-Substituted US 6,232,417 B1 15 16 with ortho ester groups that the ortho ester moieties can be It should be noted that the foregoing monomers contain partially hydrolyzed to yield the acid and a conventional ing the precursor functionalities can be converted to the ester on the same monomer as illustrated below: desired functional groups before they are polymerized or the monomers can be first polymerized and then the respective polymers containing the precursor functional Substituents C(OCH3)3 COOH can then be post reacted to give the desired functionality. It is contemplated within the scope of this invention that the monomers described under Formulae I to V wherein m, C(OCH3)3 C(O)OCH p. q, r, and S is 0 the methylene bridge unit can be replaced by oxygen to give 7-OXO-norbornene derivatives. C(OCH3)3 partial hydrolysis COOH It is also contemplated that for applications at 248 nm Ho wave length and above R to R' and R' in Formulae II, III, / C(OCH3)3 / C(O)CCH and IV can be aromatic Such as phenyl. C(OCH3)3 C(O)OCH Polymers 15 One or more of the acid labile substituted polycyclic C(OCH3)3 COOH monomerS described under Formula I are copolymerized alone or in combination with one or more of the polycyclic monomerS described under Formula II, in optional combi nation with one or more of the polycyclic monomers Another and more preferred route to difunctional poly cyclic monomers is through the hydrolysis and partial described under Formulae III, IV, and V. It is also contem hydrolysis of nadic anhydride(endo-5-norbornene-2,3- plated that the polycyclic monomers of Formulae I to V can dicarboxylic anhydride). Nadic anhydride can be fully be copolymerized with carbon monoxide to afford alternat hydrolyzed to the dicarboxylic acid or partially hydrolyzed ing copolymers of the polycyclic and carbon monoxide. to the an acid and ester functionality or diester functionality 25 Copolymers of norbornene having pendant carboxylic acid as shown below: groupS and carbon monoxide have been described in U.S. Pat. No. 4,960,857 the disclosure of which is hereby incor porated by reference. The monomers of Formulae I to V and C(O)OH carbon monoxide can be copolymerized in the presence of a palladium containing catalyst System as described in Chem. Rev. 1996, 96,663–681. It should be readily understood by O C(O)OH those skilled in the art that the alternating copolymers of u11. C(O)OR7 polycyclic/carbon monoxide can exist in either the keto or O 1 2 - Spiroketal isomeric form. Accordingly, the present invention 3 35 contemplates copolymers containing random repeating units C(O)OR7 derived (polymerized) from a monomer or monomers rep O 17 resented by Formulae I and II in optional combination with C(O)OR any monomer(s) represented by Formulae II to V. In nadic anhydride addition, the present invention contemplates alternating 40 copolymers containing repeating units derived C(O)OH (polymerized) from carbon monoxide and a monomer(s) represented by Formulae I to V. wherein R7 independently represents linear and branched Pendant carboxylic acid functionality is important from (C. to C.) alkyl. Preferably R'' is methyl, ethyl, or t-butyl. the Standpoint of imparting hydrophilic character, adhesion In a preferred Synthesis the nadic anhydride Starting material 45 characteristics and clean dissolution (development) proper is the eXO-isomer. The eXO-isomer is easily prepared by ties to the polymer backbone. In Some photoresist heating the endo-isomer at 190° C. followed by recrystalli applications, however, polymers bearing excessive carboxy zation from an appropriate Solvent (toluene). To obtain the lic acid functionalities are undesirable. Such polymers do diacid under reaction Scheme 1, nadic anhydride is simply not perform well in industry standard developers (0.26N hydrolyzed in boiling water to obtain almost a quantitative 50 tetramethylammonium hydroxide, TMAH). Swelling of the yield of the diacid product. The mixed carboxylic acid-alkyl polymer in unexposed regions, uncontrolled thinning during ester functionality shown in Scheme 3 is obtained by heating application, and Swelling of the polymer during exposed nadic anhydride under reflux for 3 to 4 hours in the presence dissolution are inherent disadvantages associated with these of the appropriate aliphatic alcohol (R''OH). Alternatively, highly acidic polymers. Accordingly, in Situations where the same product can be prepared by first reacting the nadic anhydride Starting material with an aliphatic alcohol and 55 excessive carboxylic acid functionality is undesirable but trialkyl amine followed by treatment with dilute HC1. The where hydrophilicity and good wetting characteristics are diester product substituted with identical alkyl (R') groups essential, copolymers polymerized from the monomers of can be prepared from the diacid by reacting the diacid with Formula I in necessary combination with the monomers of a trialkyloxonium tetrafluoroborate, e.g., R''OIBF), in Formula II are preferred. Especially preferred are the mono methylene chloride at ambient temperature, in the presence 60 mers of Formula II that contain alkyl ester, alkyl carbonate of diisopropylethylamine. To obtain esters with differing R' Spaced alkyl oxalate, and alkyl oxalate Substituents Such as alkyl groups the mixed acid-ester product obtained in -(A), C(O)OR" -, -(A), OC(O)OR", -(A), OC Scheme 3 is employed as the Starting material. In this (O)-A'-C(O)OR" and -(A)-OC(O)C(O) OR", embodiment the acid group is esterified as Set forth in respectively, wherein A, A, n, and R" are as defined above. reaction Scheme 2. However, a trialkyloxonium tetrafluo 65 The polymers of the present invention are the key ingre roborate having a differing alkyl group than the alkyl group dient of the composition. The polymer will generally com already present in the ester functionality is employed. prise about 5 to 100 mole % of the monomer (repeating unit) US 6,232,417 B1 17 18 that contains the acid labile group component. Preferably the polymerization (ROMP) preferably with subsequent hydro polymer contains about 20 to 90 mole % of the monomer genation. The cyclic polymers of the present invention are that contains the acid labile group. More preferably the represented by the following Structures: polymer contains about 30 to 70 mole % of the monomeric unit that contains the acid labile functionality. The remainder of polymer composition is made up of repeating units polymerized from the optional monomerS Set forth above under Formulae III to V. The choice and the amount of Specific monomers employed in the polymer can be varied according to the properties desired. For example, by varying the amount of carboxylic acid functionality in the polymer i. backbone, the solubility of the polymer to various develop ing Solvents can be adjusted as desired. Monomers contain ing the ester functionality can be varied to enhance the mechanical properties of the polymer and radiation Sensi 15 wherein R' to R" independently represents R' to R' as tivity of the System. Finally, the glass transition temperature defined in Formulae I to V above, m is an integer from 0 to properties of the polymer can be adjusted by incorporating 5 and a represents the number of repeating units in the cyclic repeating units that contain long chain alkyl groups polymer backbone. Such as decyl. The ROMP polymers of the present invention are poly merized in the presence of a metathesis ring-opening poly There are Several routes to polymerize cyclic olefin mono merization catalyst in an appropriate Solvent. Methods of merS Such as norbornene and higher cyclic (polycyclic) polymerizing via ROMP and the Subsequent hydrogenation monomers containing the norbornene moiety. These include: of the ring-opened polymerS So obtained are disclosed in (1) ring-opening metathesis polymerization (ROMP); (2) U.S. Pat. Nos. 5,053,471 and 5,202,388 which are incorpo ROMP followed by hydrogenation; and (3) addition poly rated herein by reference. merization. Each of the foregoing routes produces polymers 25 In one ROMP embodiment the polycyclic monomers of with Specific structures as shown in the diagram 1 below: the invention can be polymerized in the presence of a Single

Diagram 1

s

RN(1) 1,Homopolymerization Addition (3) e genation

A ROMP polymer has a different structure than that of an component ruthenium or osmium metal carbene complex addition polymer. A ROMP polymer contains a repeat unit catalyst such as those disclosed in WO 95-US9655. The with one less cyclic unit than did the Starting monomer. The monomer to catalyst ratio employed should range from repeat units are linked together in an unsaturated backbone 60 about 100:1 to about 2,000:1, with a preferred ratio of about as shown above. Because of this unsaturation the polymer 500:1. The reaction can be conducted in halohydrocarbon preferably should Subsequently be hydrogenated to confer Solvent Such as dichloroethane, dichloromethane, chlo oxidative stability to the backbone. Addition polymers on robenzene and the like or in a hydrocarbon Solvent Such as the other hand have no C=C unsaturation in the polymer toluene. The amount of Solvent employed in the reaction backbone despite being formed from the same monomer. 65 medium should be sufficient to achieve a Solids content of The monomers of this invention can be polymerized by about 5 to about 40 weight percent, with 6 to 25 weight addition polymerization and by ring-opening metathesis percent Solids to Solvent being preferred. The reaction can be US 6,232,417 B1 19 20 conducted at a temperature ranging from about 0° C. to L is a neutral ligand that is weakly coordinated to the about 60° C., with about 20° C. to 50° C. being preferred. Group VIII metal cation complex. In other words, the ligand A preferred metal carb ene catalyst is bis is relatively inert and is readily displaced from the metal (tricyclohexylphosphine)benzylidene ruthenium. Surpris cation complex by the inserting monomer in the growing ingly and advantageously, it has been found that this catalyst polymer chain. Suitable U-bond containing ligands include can be utilized as the initial ROMP reaction catalyst and as (C. to C) monoolefinic (e.g., 2,3-dimethyl-2-butene), an efficient hydrogenation catalyst to afford an essentially dioolefinic (C. to C2) (e.g., norbornadiene) and (Cs to Co) saturated ROMP polymer. No additional hydrogenation aromatic moieties. Preferably ligand L is a chelating biden catalyst need be employed. Following the initial ROMP tate cyclo(Cs to C) diolefin, for example cyclooctadiene reaction, all that is needed to effect the hydrogenation of the 1O (COD) or dibenzo COD, or an aromatic compound such as polymer backbone is to maintain hydrogen preSSure over the benzene, toluene, or mesitylene. reaction medium at a temperature above about 100° C. but Group VIII metal M is selected from Group VIII metals lower than about 220 C., preferably between about 150 to of the Periodic Table of the Elements. Preferably M is about 200 C. 15 Selected from the group consisting of nickel, palladium, The addition polymers of the present invention can be cobalt, platinum, iron, and ruthenium. The most preferred prepared via Standard free radical Solution polymerization metals are nickel and palladium. methods that are well-known by those skilled in the art. The Ligand X is selected from (i) a moiety that provides a monomers of Formulae I to V can be homopolymerized or Single metal-carbon O-bond (no JC bonds) to the metal in the copolymerized in the presence of maleic anhydride. Free cation complex or (ii) a moiety that provides a single metal radical polymerization techniques are set forth in the Ency carbon O-bond and 1 to 3 U-bonds to the metal in the cation clopedia of polymer Science, John Wiley & Sons, 13, 708 complex. Under embodiment (i) the moiety is bound to the (1988). Group VIII metal by a single metal-carbon O-bond and no Alternatively, and preferably, the monomers of this inven 25 JU-bonds. Representative ligands defined under this embodi tion are polymerized in the presence of a Single or multi ment include (C. to Co) alkyl moieties Selected from component catalyst System comprising a Group VIII metal methyl, ethyl, linear and branched moieties Such as propyl, ion Source (preferably palladium or nickel). Surprisingly, it butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and has been found that the addition-polymerS So produced decyl and (C, to Cs) aralkyl Such as benzyl. Under embodi possess excellent transparency to deep UV light (193 nm) ment (ii) generally defined above, the cation has a hydro and exhibit excellent resistance to reactive ion etching. carbyl group directly bound to the metal by a single metal The preferred polymers of this invention are polymerized carbon O-bond, and also by at least one, but no more than from reaction mixtures comprising at least one polycyclic three U-bonds. By hydrocarbyl is meant a group that is monomer Selected from Formulae I and II, a Solvent, a capable of stabilizing the Group VIII metal cation complex catalyst System containing a Group VIII metal ion Source, 35 by providing a carbon-metal O-bond and one to three olefinic and an optional chain transfer agent. The catalyst System can JU-bonds that may be conjugated or non-conjugated. Repre be a preformed single component Group VIII metal based Sentative hydrocarbyl groups are (C. to Co) alkenyl which catalyst or a multicomponent Group VIII metal catalyst. may be non-cyclic, monocyclic, or polycyclic and can be Substituted with linear and branched (C to Co) alkoxy, (C Single Component Systems 40 to Cs) aryloxy or halo groups (e.g., Cl and F). Preferably X is a single allyl ligand, or, a canonical form In one embodiment, the Single component catalyst System thereof, which provides a O-bond and a U-bond; or a of this invention comprises a Group VIII metal cation compound providing at least one olefinic U-bond to the complex and a weakly coordinating counteranion as repre 45 metal, and a O-bond to the metal from a distal carbon atom, sented by the following formula: Spaced apart from either olefinic carbon atom by at least two carbon-carbon Single bonds (embodiment iii). LyMX, CAa It should be readily apparent to those skilled in the art that when ligand L or X is absent (i.e., y or Z is Zero), the metal cation complex counteranion 50 cation complex will be weakly ligated by the Solvent in which the reaction was carried out. Representative Solvents wherein L represents a ligand containing 1, 2, or 3 JU-bonds, include but are not limited to halogenated hydrocarbons M represents a Group VIII transition metal; X represents a Such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane and aromatic Solvents Such as benzene, ligand containing 1 O-bond and between 0 to 3 U-bonds, y 55 is 0, 1, or 2 and Z is 0 or 1 and wherein y and Z cannot both toluene, mesitylene, chlorobenzene, and nitrobenzene, and be 0 at the same time, and when y is 0, a is 2 and when y the like. A more detailed discussion on appropriate Solvents is 1, a is 1; and CA is a weakly coordinating counteranion. will follow. The phrase “weakly coordinating counteranion” refers to Selected embodiments of the Group VIII metal cation an anion which is only weakly coordinated to the cation, 60 complexes of the Single component catalyst Systems of this thereby remaining sufficiently labile to be displaced by a invention are shown below. neutral Lewis base. More specifically the phrase refers to an Structure VII illustrates embodiment (i) wherein ligand X anion which when functioning as a Stabilizing anion in the is a methyl group that is bound to the metal via a single catalyst System of this invention does not transfer an anionic metal-carbon O-bond, and ligand L is COD that is weakly Substituent or fragment thereof to the cation, thereby form 65 coordinated to the palladium metal via two olefinic U-bonds. ing a neutral product. The counteranion is non-Oxidative, In the structure below M preferably represents palladium or non-reducing, non-nucleophilic, and relatively inert. nickel. US 6,232,417 B1 21 22

XI

5 N/Y CA N M-CH | CA >/ Y& XII Structures VIII, IX, and X illustrate various examples of embodiment (ii) wherein X is an allyl group that is bound to the metal (palladium is shown for illustrative purposes only) via a single metal-carbon O-bond and at least one but no more than three U-bonds. 15 2x CA In Structure VIII, L is not present but an aromatic group N/ N. providing three U-bonds is weakly coordinated to the pal ladium metal; X is an allyl group providing a single metal The above-described Group VIII cation complexes are carbon O-bond and an olefinic U-bond to the palladium. asSociated with a weakly coordinating or non-coordinating In Structure IX, L is COD and X is an allyl group counteranion, CA, which is relatively inert, a poor nucleo providing a metal-carbon O-bond and an olefinic U-bond to phile and provides the cation complex with essential Solu the palladium. bility in the reaction Solvent. The key to proper anion design Structure X illustrates an embodiment wherein ligand X is requires that it be labile, and Stable and inert toward reac tions with the cationic Group VIII metal complex in the final an unsaturated hydrocarbon group that provides a metal 25 catalyst Species and that it renders the Single component carbon O-bond, a conjugated U-bond and two additional catalyst soluble in the solvents of this invention. The anions JU-bonds to the palladium; L is absent. which are stable toward reactions with water or Bronsted acids, and which do not have acidic protons located on the VIII exterior of the anion (i.e., anionic complexes which do not react with strong acids or bases) possess the Stability nec essary to qualify as a Stable anion for the catalyst System. The properties of the anion which are important for maxi CA mum lability include overall size, and shape (i.e., large radius of curvature), and nucleophilicity. 35 In general, a Suitable anion may be any stable anion which allows the catalyst to be dissolved in a Solvent of choice, and has the following attributes: (1) the anion should form stable Salts with the aforementioned Lewis acid, Bronsted acids, reducible Lewis Acids, protonated Lewis bases, thallium and 40 Silver cations; (2) the negative charge on the anion should be IX delocalized over the framework of the anion or be localized within the core of the anion; (3) the anion should be a N relatively poor nucleophile, and (4) the anion should not be a powerful reducing or oxidizing agent. CA Anions that meet the foregoing criteria can be Selected 45 from the group consisting of a tetrafluoride of Ga, Al, or B; N a hexafluoride of P, Sb, or AS, perfluoro-acetates, propi onates and butyrates, hydrated perchlorate, toluene Sulfonates, and trifluoromethyl Sulfonate, and Substituted tetraphenyl borate wherein the phenyl ring is Substituted 50 with fluorine or trifluoromethyl moieties. Selected examples of counteranions include BF, PF, AlFOSCF, SbF, X SbFSOF, ASF, trifluoroacetate (CFCO), pentafluo ropropio nate (CFSCO), heptafluorobuty rate (CFCFCFCO), perchiorate (CIO.HO), p-toluene JX 4, 55 Sulfonate (p-CHCHSO) and tetraphenylborates repre Pd CA sented by the formula:

Substituents R', R, R will be described in detail below. 60 Structures XI and XII illustrate examples of embodiment (iii) wherein L is COD and X is a ligand that provides at least one olefinic U-bond to the Group VIII metal and a O-bond to wherein R" independently represents hydrogen, fluorine and the metal from a distal carbon atom, Spaced apart from either 65 trifluoromethyl and n is 1 to 5. olefinic carbon atom by at least two carbon-carbon Single A preferred Single component catalyst of the foregoing bonds. embodiment are represented by the formula: US 6,232,417 B1 23 24 -continued XIII R20 - M CA R22 wherein R is hydrogen, linear or branched (C, to Cs) alkyl Such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and pentyl, R' is methylcarbonyl, and R is linear or The catalyst comprises a L-allyl Group VIII metal com branched (C to Co) alkyl. Counteranion CA is defined as plex with a weakly coordinating counteranion. The allyl above. group of the metal cation complex is provided by a com 15 pound containing allylic functionality which functionality is Additional examples of t-allyl metal complexes are found bound to the M by a single carbon-metal O-bond and an in R. G. Guy and B. L. Shaw, Advances in Inorganic olefinic U-bond. The Group VIII metal M is preferably Chemistry and Radiochemistry, Vol. 4, Academic Press Inc., Selected from nickel and palladium with palladium being the New York, 1962; J. Birmingham, E. de Boer, M. L. H. most preferred metal. Surprisingly, it has been found that Green, R. B. King, R. Köster, P. L. I. Nagy, G. N. Schrauzer, these single component catalysts wherein M is palladium Advances in Organometallic Chemistry, Vol. 2, Academic and the cation complex is devoid of ligands other than the Press Inc., New York, 1964; W. T. Dent, R. Long and A. J. allyl functionality (i.e., L=0), exhibit excellent activity for Wilkinson, J. Chem. Soc., (1964) 1585; and H. C. Volger, the polymerization of functional polycyclic monomerS Such 25 Rec. Trav. Chim. Pay Bas, 88 (1969) 225; which are all as the Silyl containing monomers of this invention. AS hereby incorporated by reference. discussed above, it will be understood that the catalysts are Solvated by the reaction diluent which diluent can be con The Single component catalyst of the foregoing embodi sidered very weak ligands to the Group VIII metal in the ment can be prepared by combining a ligated Group VIII cation complex. metal halide component with a Salt that provides the coun teranion for the Subsequently formed metal cation complex. Substituents R', R', and R’ on the allyl group set forth The ligated Group VIII metal halide component, counter above in Structures VIII, IX and XIII are each independently anion providing Salt, and optional U-bond containing hydrogen, branched or unbranched (C to Cs) alkyl Such as 35 component, e.g., COD, are combined in a Solvent capable of methyl, ethyl, n-propyl, isopropyl, and t-butyl, (C. to C.) Solvating the formed Single component catalyst. The Solvent aryl, Such as phenyl and naphthyl, (C7 to Co) aralkyl Such utilized is preferably the Same Solvent chosen for the reac as benzyl, -COOR', -(CH), OR, CI and (Cs to C.) tion medium. The catalyst can be preformed in Solvent or cycloaliphatic, wherein R' is (C, to Cs) alkyl, Such as can be formed in Situ in the reaction medium. methyl, ethyl, n-propyl, isopropyl, n-butyl and i-butyl, and 40 n is 1 to 5. Suitable counteranion providing Salts are any Salts Optionally, any two of R, R', and R’ may be linked capable of providing the counteranions discussed above. For together to form a cyclic- or multi-cyclic ring Structure. The example, Salts of Sodium, lithium, potassium, Silver, cyclic ring Structure can be carbocyclic or heterocyclic. 45 thallium, and ammonia, wherein the anion is Selected from Preferably any two of R', R', and R' taken together with the counteranions (CA) defined previously. Illustrative the carbon atoms to which they are attached form rings of 5 counteranion providing Salts include TIPF, AgPF, AgSbF, to 20 atoms. Representative heteroatoms include nitrogen, LiBF, NHPF, KASF, AgCFCO, AgBFAgCFCO, Sulfur and carbonyl. Illustrative of the cyclic groups with AgClOHO, AgASF, AgCFCFCFCO, AgCFCO, allylic functionality are the following Structures: 50 (CHo). NB(C6F5), and S. R23 R23 S. 2- N. 55 \,, X, l X, R25 60 The specific catalyst: allyl-Pd-CODPF, is preformed by forming a ligated palladium halide component, i.e., N bis(allyl Pd bromide), which is then subjected to scission 65 with a halide abstracting agent in the form of a counteranion R24 O 2-n providing salt, i.e., TIPF in the presence of COD. The reaction Sequence is written as follows: US 6,232,417 B1 25 26 atoms, representative ethers include methyltertbutylether, Palladium (II) Chloride diethylether, furan, tetrahydrofuran, representative thioet hers include thiophene, tetrahydrothiophene, cyclic diethers Such as dioxane, ketones represented by the formula R-C (O)-R wherein R is as defined above and the R groups N p? BrYPd connected to the carbonyl moiety can be taken together to N / form a Substituted or unsubstituted cyclic ketone containing Br 5 to 8 carbon atoms, Substituents include linear or branched COD (C. to Co) alkyl and (Cs to C) aryl, representative ketones TIPF include acetone, methylethylketone and methylphenylke tone; amines of the formula N(R), wherein R indepen dently represents linear or branched (C to Co) alkyl, (C7 to Co)aralkyl Such as benzyl, (C. to C) aryl and cycloaliphatic groups containing 5 to 8 carbon atoms, the (r. 15 alkyl, aryland cycloaliphatic Substituents optionally contain halogen atoms Selected from chlorine, bromine, fluorine and iodine, representative amines include triethylamine, tripro When partitioned, only one COD ligand remains, which is pylamine and tributylamine, pyridine, linear and branched bonded by two U-bonds to the palladium. The allyl func tionality is bonded by one metal-carbon O-bond and one (C. to Co) alkyl group Substituted pyridines; phosphines of U-bond to the palladium. the formula P(R) wherein R is as defined above including For the preparation of the preferred L-allyl Group VIII alkylphosphines, arylphosphines and alkarylphosphines metal/counteranion Single component catalysts represented with trialkyl, triperfluoroalkyl, and triarylphosphines being in Structure XIII above, i.e., when M is palladium, allylpal preferred; alkylphosphine oxides, arylphosphine oxides, and ladium chloride is combined with the desired counteranion 25 alkarylphosphine oxides of the formula (R)-PO wherein R' providing Salt, preferably Silver Salts of the counteranion, in is as defined above, preferred are the trialkyl an appropriate Solvent. The chloride ligand comes off the triperfluoroalkyl, and triarylphosphine oxides; allyl palladium complex as a precipitate of Silver chloride alkylphosphites, arylphosphites and alkarylphosphites of the (AgCl) which can be filtered out of the solution. The formula P(OR), wherein R is as defined above, preferred allylpalladium cation complex/counteranion Single compo are the trialkyl, triperfluoroalkyl and triarylphosphites, nent catalyst remains in Solution. The palladium metal is esters of the formula RC(O)OR wherein R is defined above devoid of any ligands apart from the allylic functionality. and wherein the R substituents bonded to the carbonyl and An alternative Single component catalyst that is useful in oxygen atom can be taken together there with to form an the present invention is represented by the formula below: unsubstituted or Substituted lactone ring containing 3 to 8 35 carbon atoms, representative esters include ethyl acetate, PdLR27CNICA, representative lactones include B-propiolactone and wherein R7 independently represents linear and branched Y-butyrolactone. R represents a substituted or unsubstituted (C. to Co) alkyl and CA is a counteranion defined as allyl ligand set forth below: above. Preformed Single component catalyst System useful in 40 making polymers utilized in this invention is represented by the formula:

E.M.(Q), (R), 45 M is a Group VIII transition metal preferably selected from nickel, palladium, platinum, iron, rhodium and cobalt. Q is an electron withdrawing ligand preferably Selected from linear and branched (C to Co) perhaloalkyl, (C7 to C.) perhaloalkaryl and perhaloaryl, n is an integer of 0, 1, 2 or 50 wherein R', R', and R’ are as previously defined. 3; f is 1, 2, or 3 with the proviso that when M is rhodium f A representative preformed catalyst that contains no must be 3; and g is an integer of 0 or 1, when f is 1 R must ligands other than the electron withdrawing group ligand is be present. The perhaloalkyl ligands are preferably Selected bis(2,4,6-tris(trifluoromethylphenyl)) nickel. from trifluoromethyl, and perfluoroethyl. The perhaloaryl Representative preformed catalysts containing monoden ligands are preferably Selected from, pentafluorophenyl, 55 pentachlorophenyl, and pentabromophenyl groups. The per tate ligands are (toluene)bis(perfluorophenyl) nickel, halo alkaryl ligand is preferably 2,4,6-tris (mesitylene)bis(perfluorophenyl) nickel, (benzene)bis (trifluoromethylphenyl). E is selected from a monodentate or (perfluorophenyl) nickel, bis(tetrahydroftiran)bis bidentate ligand. (perfluorophenyl) nickel, (dimethoxyethane)bis(2,4,6-tris Examples of monodentate ligands include L-arenes Such 60 (trifluoromethylphenyl)) nickel, bis(dioxane)bis as benzene, toluene, and mesitylene; ethers, polyetherS Such (perfluorophenyl) nickel, (methallyl) nickel as glime, diglyme, triglyme, tetraglyme and thioetherS rep (pentafluorophenyl)(triphenylphosphine), and (methallyl) resented by the formulae R-O-R and R-S-R' nickel(pentafluorophenyl)(tricyclohexylphosphine), and the wherein R can be the same or different and represents a compound Ni(CF)Cl]- linear and branched (C, to Co) alkyl group, the R groups 65 Examples of bidentate ligands include hemilabile chelat that are connected to the heteroatom can be taken together ing ligands containing phosphorus, OXygen, nitrogen and to represent heterocyclic ring containing 4 to 8 carbon sulfur represented by the formula US 6,232,417 B1 27 28 from about 20,000:1 to about 100:1, more preferably from -Y about 2000:1 to about 100:1, and most preferably from about K 500:1 to about 100:1. The reaction can be run in the organic NZ solvents, specified hereinabove. Preferred solvents include the previously described aliphatic hydrocarbons Such as hexane, alicyclic hydrocarbons Such as cyclohexane and wherein Y and Z independently represent phosphorus, aromatic hydrocarbons Such as benzene, toluene and mesi oxygen, carbonyl, nitrogen and Sulfur and K is an unsub tylene as well as polar organic hydrocarbons which are Stituted and Substituted hydrocarbon backbone moiety con taining from 2 to 25 carbon atoms or a divalent alkylene described below. The foregoing Solvents can be used alone ether moiety wherein the alkylene radicals independently or in mixtures of two or more. Polar organic Solvents include contain 1 to 10 carbon atoms. The phosphorus, OXygen, the ethers, esters and ketones described as ligands in the Sulfur, nitrogen atoms and the carbonyl carbon can option description of the catalyst formula Set forth immediately ally be substituted with linear and branched(C. to Co) alkyl above. Suitable polar organic Solvents include ethyl acetate, and (Cs to C.) aryl groups. The hydrocarbon backbone methyltertbutylether, diethylether, tetrahydrofuran, dioxane, moiety can be Substituted with pendant linear and branched 15 acetone, methylethylketone, methylphenylketone, alkyl groups containing 1 to 10 carbon atoms, alicyclic B-propiolactone and Y-butyrolactone. The reaction tempera groups of 5 to 15 carbon atoms, aryl groups of containing 6 ture employed can range from about 0°C. to about 70° C., to 20 carbon atoms, and amines. The pendant Substituents on preferably from about 10 C. to about 50 C., and more the hydrocarbon backbone can optionally be substituted with preferably from about 20° C. to about 40° C. The preferred linear and branched (C to Co) alkyl, phenyl groups, concentration of monomer in reaction Solvent or diluent halides, and amino groups. Catalysts of the invention con ranges from about 5 weight percent monomer in Solvent to taining the above described bidentate ligands can be repre about to about 50 weight percent. sented by the formula When employing the preformed catalyst Systems of the formula E.M.(Q)(R), it has been found that effective 25 reduction of molecular weight of the polymer product can be attained by in increasing the catalyst concentration in the monomer along with decreasing the concentration of mono mer in reaction solvent. We have found a relative effect between catalyst concentration and monomer concentration wherein K, Y, Z, M, and Q are as defined above. Illustrative in the reaction medium. When operating within the preferred of the catalysts containing bidentate chelating ligands where monomer to catalyst ratioS and monomer to reaction Solvent Y and Z are phosphorus, oxygen or carbonyl are represented ranges an increase in catalyst loading with a concomitant by the formulae decrease in monomer to Solvent concentration a reduction in the molecular weight of the polymer product is observed. We P(R) P(R) P(R) 35 have also observed that by conducting the polymerization reaction in the presence of a dual component Solvent System yo f Yo f 1. Yo f while maintaining a relatively high catalyst to monomer and Rh s/ =. (RS/ monomer to Solvent concentration provides an effective reduction in molecular weight of the polymer product. By 40 dual component Solvent System is meant that a non-polar P(R) P(R) hydrocarbon diluent Such as cyclohexane is used in combi N Ya nation with a polar organic Solvent Such as ethyl acetate. to M(Q), Suitable non-polar Solvents include any Solvent that is a O s diluent, i.e., miscible with the polar organic Solvent. The 45 polar organic Solvents are preferably organic esters that are l suitable solvents for the catalyst component. The ratio of P(Rh) P(R) non-polar hydrocarbon Solvent to polar organic Solvent can range from 75:25 w/w to 25:75 w/w with 50:50 w/w being so f Yo f f / preferred. The dual component Solvent System method of eO 50 molecular weight reduction is advantageous from the Stand point of allowing for higher concentrations of monomer to Rh R be employed in the reaction medium. R The preformed Single component catalysts of the above formula can be Synthesized via Several routes. In one Syn 55 thesis route a Group VIII metal ion Source, e.g., nickel trifluoroacetate, is reacted with a reagent (e.g., bis C Yo/ f (pentafluorophenyl) Zinc, or a Grignard reagent Such as O pentafluorophenyl magnesium bromide) that is capable of transferring the appropriate electron withdrawing ligand to l 60 the Group VIII metal. The reaction is conducted in an appropriate solvent such as diethylether or THF. The solvent wherein R' independently represents hydrogen, linear and System can provide the Source of the remaining ligand(s). branched(C to Co) alkyl and (C to C) aryl and Ri For example, if THF is employed as the solvent, the catalyst represents linear and branched(C to Co) alkyl and (Cs to product of the synthesis is (THF).Ni(CFs). The synthesis C.) aryl. 65 can be conducted in a temperature range of from about The ratio of monomer to catalyst in the reaction medium -100° C. to about 100° C. Typically the reaction can be can range from about 50,000:1 to about 50:1, preferably conducted at room temperature but elevated temperatures US 6,232,417 B1 29 30 can be employed to increase the rate of reaction. In another VIII metal containing moiety should contain groups or synthesis route the THF ligand on the catalyst can be ligands that can be easily displaced by the electron with Substituted by a mono- orbidentate ligand Such as toluene or drawing ligand provided by the arylation or alkylation agent. triphenyl phosphine simply by reacting the (THF).Ni Preferably, the Group VIII metal compound is soluble or can (CFS) catalyst with toluene or triphenylphosphine. Repre be made to be Soluble (by the attachment of appropriate Sentative reaction Schemes are Set forth below. ligands) in the reaction medium. Examples of reagents containing the Group VIII metal include anionic ligands Selected from the halides Such as chloride, bromide, iodide or fluoride ions, pseudohalides Such as cyanide, cyanate, thiocyanate, hydride; carbanions Such as branched and r luene unbranched (C to Co) alkylanions, phenyl anions, cyclo pentadienylide anions, t-allyl groupings, enolates of (Toluene)Ni(CFs)2 + 2 THF 3-dicarbonyl compounds Such as acetylacetonate (4-pentanedionate), 2.2,6,6-tetramethyl-3,5-heptanedionate, In an alternate Synthesis route a reagent containing the 15 and halogenated acetylacetonoates Such as 1,1,1,5,5,5- Group VIII metal compound containing the desired the hexafluoro-2,4-pentanedionate, 1,1,1-trifluoro-2,4- mono- or bidentate ligand can be reacted with a reagent pentanedionate, anions of acidic oxides of carbon Such as containing the electron withdrawing group ligand. For carboxylates and halogenated carboxylates (e.g., acetates, example, bis(triphenylphosphine) nickel dibromide can be 2-ethylhexanoate, neodecanoate, trifluoroacetate, etc.) and reacted in a Suitable Solvent with the Grignard reagent, oxides of nitrogen (e.g., nitrates, nitrites, etc.) of bismuth pentafluorophenyl magnesium bromide, to give the catalyst (e.g., bismuthate, etc.), of aluminum (e.g., aluminates, etc.), ((CH3)P)Ni(CFs). The reaction Scheme is represented of Silicon (e.g., Silicate, etc.), of phosphorous (e.g., below. phosphates, phosphites, phosphines, etc.) of Sulfur (e.g., Sulfates Such as triflate, p-toluene Sulfonate, Sulfites, etc.); 25 ylides; amides, imides, oxides; phosphides; Sulfides; (C. to In another method for preparing the preformed catalyst, a C.) aryloxides, (C. to Co) alkoxides, hydroxide, hydroxy neutral (Zero oxidation State) Group VIII metal reagent, e.g., (C. to Co) alkyl, catechols, oxalate; chelating alkoxides and Ni(COD), in combination with an appropriate ligand aryloxides. reagent (e.g., THF) is reacted in a Solvent with an electron Examples of Group VIII transition metal compounds withdrawing group ligand reagent capable of undergoing suitable as the Group VIII metal ion source include: palla dium ethylhexanoate, trans-Pd Cl(PPh3), palladium (II) oxidative addition to the Group VIII metal. Pentafluoroben bis(trifluoroacetate), palladium (II) bis(acetylacetonate), Zoyl chloride can be employed as an electron withdrawing palladium (II) 2-ethylhexanoate, Pd(acetate)(PPh3), palla ligand reagent. The reaction Scheme is set forth below. dium (II) bromide, palladium (II) chloride, palladium (II) 35 iodide, monoacetonitriletris(triphenylphosphine) palladium Ni(COD) + CFSC(O)Cl. F (II) tetrafluoroborate, tetrakis(acetonitrile) palladium (II) tetrafluoroborate, dichlorobis(acetonitrile) palladium (II), dichlorobis(triphenylphosphine)palladium (II), dichlorobis (benzonitrile) palladium (II), palladium acetylacetonate, pal 40 ladium bis(acetonitrile) dichloride, palladium bis (THF).Ni(CFS) + (THF).NiCl2 (dimethylsulfoxide) dichloride, nickel acetylacetonates, nickel carboxylates, nickel dimethylglyoxime, nickel ethylhexanoate, NiCl2(PPh3), NiCl2(PPhCH), In another Synthesis route the catalyst can be prepared via (P(cyclohexyl)-)H Ni(Ph-P(CH)CO), (PPh) (CH)Ni the metal vapor and activated metal Synthesis procedure 45 (Ph. PCH=C(O)Ph), bis(2,2,6,6-tetramethyl-3,5- described by R. G. Gastinger, B. B. Anderson, K. J. heptanedionate) nickel (II), nickel (II) hexafluoroacetylac Klabunde, J. Am. Chem. Soc. 1980, 102, 4959–4966 and R. etonate tetrahydrate, nickel (II) trifluoroacetylacetonate D. Rieke, W.J. Wolf, N. Kujundzic, A. V. Kavaliunas, J. Am. dihydrate, nickel (II) acetylacetonate tetrahydrate, Chem. Soc. 1977, 99,4159–4160, respectively. The electron nickelocene, nickel (II) acetate, nickel bromide, nickel withdrawing ligand reagent undergoes oxidative addition to 50 chloride, dichlorohexyl nickel acetate, nickel lactate, nickel the activated Zero valent Group VIII metal to form the tetrafluoroborate, bis(allyl) nickel, bis(cyclopentadienyl) preformed catalyst. nickel, cobalt neodecanoate, cobalt (II) acetate, cobalt(II) It is to be understood that the catalysts described under the acetylacetonate, cobalt (III) acetylacetonate, cobalt (II) formula E.M.(Q),(R?), above can be prepared in Situ by benzoate, cobalt chloride, cobalt bromide, dichlorohexyl reacting a Group VIII metal containing (M) reagent with the 55 cobalt acetates, cobalt (II) Stearate, cobalt (II) desired electron withdrawing ligand (Q) reagent and the tetrafluoroborate, iron naphthenate, iron (II) chloride, iron mono- and bidentate ligand (E) reagent in the presence of the (III) chloride, iron (II) bromide, iron (III) bromide, iron (II) monomer Solution in the reaction medium. Alternatively, acetate, iron (III) acetylacetonate, ferrocene, rhodium these catalysts are prepared in Situ by arylating or alkylating chloride, rhodium tris(triphenylphosphine) trichloride. the Group VIII metal in the optional presence of activating 60 The arylating or alkylating agent or cocatalyst contains agents. The Group VIII metal containing reagents can be perhalophenyl and 2,4,6-tris(trifluoromethylphenyl) moi Selected from a compound containing nickel, palladium, eties. Preferred cocatalysts or arylation and alkylation agents platinum cobalt, iron, and rhodium, with nickel and palla include bis(pentahalophenyl)Zinc-dimethoxyethane (e.g., dium being most preferred. There are no restrictions on the (CX5)Zn.dme) where X represents a halogen Substituent, Group VIII metal compound So long as the compound 65 preferably fluorine, bromine and chlorine, and dime is provides a source of Group VIII metal ions that are capable dimethoxyethane, tris(perfluorophenyl)boron (e.g., of being arylated or alkylated. In other words, the Group B(C6F5) ), tris(perfluorophenyl)boron hydrate (e.g., US 6,232,417 B1 31 32 B(CF).3H2O) tris(2,4,6-trifluoromethyl) phenyl lithium, radical is an alkylene group represented by the formula bis(2,4,6-trifluoromethyl) phenyl zinc, bis(2,4,6- -(CH2)- where d represents the number of carbon trifluoromethyl) phenyl magnesium, and b is atoms in the alkylene chain and is an integer from 1 to 10. (trifluoromethyl)cadmium.dme (e.g., Cd(CF).dme). The divalent radicals are preferably selected from linear and Activating agents include trialkyl aluminum compounds branched (C to Co) alkylene Such as methylene, ethylene, Such as triethylaluminum, dialkylmagnesium compounds propylene, butylene, pentylene, heXylene, heptylene, Such as dibutylmagnesium, dialkylzinc Such as diethylzinc. octylene, nonylene, and decylene. When branched alkylene We have found that for most of the catalyst systems these radicals are contemplated, it is to be understood that a activators increase the rate of initiation of the polymeriza hydrogen atom in the linear alkylene chain is replaced with tion reaction. When aluminum alkyls are employed as a linear or branched (C to C) alkyl group. When n is 0 it activators, it is preferable that an oxygen containing com should be apparent that the Spacer radical is not present and pound is employed therewith. Suitable oxygen containing B represents a covalent bond. In other words the Silyl group, compounds can be selected from tetraethoxysilane, —SiRRR, is attached directly to the cyclic ring. Sub dimethyldiethoxysilane, diethylether, propanol or mono stituents R', R, and R independently represent halogen mers of the invention that contain oxygen Substituents. Selected from the group consisting of chlorine, fluorine, When aluminum alkyls are employed as the activator there 15 bromine and iodine, linear or branched (C to Co) alkyl, is no need to add an oxygen containing compound So long linear or branched (C to Co) alkoxy, Substituted or unsub as the cyclic monomer(s) to be polymerized bears an oxygen Stituted (Cs to Co) aryloxy, linear or branched (C to Co) containing Substituent Such as an carboxylic acid, ester, alkyl carbonyloxy, and (C to Co) alkyl peroxy. Preferably, carbonyl, ether, or alcohol containing Substituent. When at least one of R", R, or R is selected from a linear or utilizing non-polar hydrocarbon Solvents, e.g., hexane, branched (C to Co) alkoxy group or a halogen group. More cyclohexane, toluene, etc., as the reaction diluent, relatively preferably, each of R, R, and R are the same and are Small amounts of the oxygen containing compounds are Selected from methoxy, ethoxy, propoxy, butoxy, pentoxy, employed (about 10 moles of oxygen containing compound and chlorine groups. Still more preferably, n is 0, and R', per mole of Group VIII metal). When halohydrocarbon R and Rare ethoxy, e.g., at least one of R to R is a diluents, e.g., dichloromethane, dichloroethane, etc., are 25 triethoxysilyl substituent. used in the polymerization, higher levels of oxygen con In another embodiement, the arylated and alkylated cata taining compound (up to about 1000 moles of oxygen lysts of the formula E.M(Q)(R) are useful to homo- and containing compound per mole of Group VIII metal) are copolymerize one or more monomers of the monomer employed in the reaction medium. formula We have found that the Group IVB metals, preferably, titanium, Zirconium and hafnium; the lanthanide Series metals, preferably, Samarium and europium; the Group VB metals, preferably, Vanadium; and the Group VA metals, preferably, Silicon, germanium, tin and lead can be arylated in Situ to form active catalysts for cyclic olefin polymerZa 35 tion. These metals include ligands Such as halide groups, acetate groups and acetoacetonate groups that are easily displaced by the aryl groups provided by the arylating or alkylating agent described above. 40 In addition to being effective catalysts for the addition wherein R', R', R', and R' independently represent polymerization of monomerS Suitable for photoresist poly hydrogen, linear and branched (C to Co) alkyl, hydrocar mer applications, the above described catalysts are Suitable byl Substituted and unsubstituted (Cs to C2) cycloalkyl, (C7 for polymerizing many types of Substituted and unsubsti to Cs) aralkyl, (C. to Co) alkynyl, linear and branched (C- tuted cyclic olefin monomer classes. Preformed or in Situ 45 to Co) alkenyl, vinyl; any of R' and R' or R' and R' can prepared catalysts of the formula E.M(Q),(R) are useful be taken together to form a (C. to Co) alkylidenyl group, for polymerizing any combination of monomers of Formu R" and R' can be taken together with the two ring carbon lae I, II, III, IV and V defined above. Further to the cyclic atoms to which they are attached can represent Saturated and olefin monomers of decribed under Formulae I to V, we have unsaturated cyclic groups containing 4 to 12 carbon atoms or found that these catalysts are useful for polymerizing cyclic 50 an aromatic ring containing 6 to 17 carbon atoms, or an olefin monomers of Formulae VI and VII set forth below: anhydride or dicarboxyimide group; -(B), SiRRR wherein B is a divalent bridging or spacer radical Selected VI from linear and branched (C to Co) alkylene, n is an integer of 0 or 1, R", R, and Rindependently represent halogen, 55 linear or branched (C to Co) alkyl, linear or branched (C to Co) alkoxy, Substituted or unsubstituted (Cs to Co) aryloxy, linear or branched (C to Co) alkyl carbonyloxy, and (C to Co) alkyl peroxy; -(A)-C(O)CR", -(A)- OR", -(A), OC(O)R", -(A), OC(O)OR", -(A)-C R30 R33 60 (O)R", -(A), OCHC(O)OR*, -(A), C(O)O-A- R31 R32 OCHC(O)OR*, -(A), OC(O)C(O)OR", -(A), O A-C(O)OR", -(A), OC(O)-A-C(O)OR", -(A)- wherein R, R, R', and R independently represent C(O)O-A'-C(O) OR", -(A)-C(O)-A'-OR", hydrogen, linear or branched (C to Co) alkyl, (C. to C.) -(A), C(O)O-A-OC(O)OR", -(A), C(O)O-A- aryl and at least one of R to R representing the group 65 O-A'-C(O)OR", -(A), C(O)O-A'-OC(O)C(O) —(B), SiRRR wherein B is a divalent bridging or OR", -(A), C(R")-CH(R")(C(O)OR"), and -(A)-C Spacer radical and n is an integer of 0 or 1. The divalent (R")CH(CO)OR"), -(A), R" US 6,232,417 B1 33 34 active Group VIII metal ions. Preferably, the Group VIII metal compound is Soluble or can be made to be Soluble in the reaction medium. The Group VIII metal compound comprises ionic and/or neutral ligand(s) bound to the Group VIII metal. The ionic wherein R is hydrogen, linear and branched (C, to Co) and neutral ligands can be Selected from a variety of alkyl, or (C. to Cs) aryl, wherein n is 0 or 1, m is an integer monodentate, bidentate, or multidentate moieties and com from 0 to 5, -A- and -A- independently represent a binations thereof. divalent radical Selected from the group consisting of linear Representative of the ionic ligands that can be bonded to and branched (C to Co) alkylene, (C. to Co) alkylene the metal to form the Group VIII compound are anionic ethers, polyethers, or a cyclic group of the formula: ligands Selected from the halides Such as chloride, bromide, iodide or fluoride ions, pseudohalides Such as cyanide, cyanate, thiocyanate, hydride; carbanions Such as branched -CH (CH2), and unbranched (C to Co) alkylanions, phenyl anions; 15 cyclopentadienylide anions; L-allyl groupings, enolates of NX 3-dicarbonyl compounds Such as acetylacetonate (4-pentanedionate), 2.2,6,6-tetramethyl-3,5-heptanedionate, and halogenated acetylacetonoates Such as 1,1,1,5,5,5- wherein a is an integer from 2 to 7, R" represents hydrogen hexafluoro-2,4-pentanedionate, 1,1,1-trifluoro-2,4, or linear and branched (C to Co) alkyl, -C(CH), -Si pentanedionate, anions of acidic oxides of carbon Such as (CH), -CH(R)OCHCH, -CH(R)OC(CH), carboxylates and halogenated carboxylates (e.g., acetates, 2-ethylhexanoate, neodecanoate, trifluoroacetate, etc.) and oxides of nitrogen (e.g., nitrates, nitrites, etc.) of bismuth (e.g., bismuthate, etc.), of aluminum (e.g., aluminates, etc.), 25 of Silicon (e.g., Silicate, etc.), of phosphorous (e.g., phosphates, phosphites, phosphines, etc.) of Sulfur (e.g., RP RP RP Sulfates Such as triflate, p-toluene Sulfonate, Sulfites, etc.); ylides; amides, imides, oxides; phosphides; Sulfides; (C. to C.) aryloxides, (C. to Co) alkoxides, hydroxide, hydroxy (C. to Co) alkyl, catechols, oxalate; chelating alkoxides and aryloxides. Palladium compounds can also contain complex anions such as PF, AIFOSCF, SbF and compounds represented by the formulae: RP C(CH3)3 35 wherein R" and X independently represent a halogen atom O Selected from Cl, F, I, and Br, or a Substituted or unsubsti tuted hydrocarbyl group. Representative of hydrocarbyl are r D s OH (C. to Cs) alkyl Such as methyl, ethyl, propyl, butyl, pentyl, O 40 hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, C(CH3)3 tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonodecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, and isomeric forms thereof; (C. to Cs) alkenyl wherein R represents hydrogen or a linear or branched (C Such as Vinyl, allyl, crotyl, butenyl, pentenyl, hexenyl, to Cs) alkyl group; linear and branched (C to Co) octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, alkoxyalkylene, polyethers, monocyclic and polycyclic (C 45 tetradecenyl pentadecenyl, hexadecenyl, heptadecenyl, to Co) cycloaliphatic moieties, cyclic ethers, cyclic octadecenyl, nonadecenyl, pentacosenyl, and isomeric diethers, cyclic ketones, and cyclic esters (lactones), when forms thereof. (C. to Cs) aryl Such as phenyl, tolyl, xylyl, any of R" to R' represent a succinic or carboxyimide naphthyl, and the like; (C7 to Cs) aralkyl Such as benzyl, moiety and n is 1A can only represent a linear or branched phenethyl, phenpropyl, phenbutyl, phenhexyl, napthoctyl, (C. to Co) alkylene group. 50 and the like; (C. to Cs) cycloalkyl Such as cyclopropyl, Accordingly, homopolymers and copolymers comprising cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, repeating units polymerized from one or more of the mono cyclooctyl, 2-norbomyl, 2-norbomenyl, and the like. In mers of Formulae I to VI can be easily prepared. addition to the above definitions X represents the radical: Multicomponent Systems 55 The multicomponent catalyst System embodiment of the present invention comprises a Group VIII metal ion Source, in combination with one or both of an organometal cocata lyst and a third component. The cocatalyst is Selected from organoaluminum compounds, dialkylaluminum hydrides, 60 dialkyl Zinc compounds, dialkyl magnesium compounds, CF CF and alkyllithium compounds. The Group VIII metal ion source is preferably selected The term “substituted hydrocarbyl” means the hydrocar from a compound containing nickel, palladium, cobalt, iron, byl group as previously defined wherein one or more hydro and ruthenium with nickel and palladium being most pre 65 gen atoms have been replaced with a halogen atom Such as ferred. There are no restrictions on the Group VIII metal Cl, F, Br, and I (e.g., as in the perfluorophenyl radical); compound So long as it provides a Source of catalytically hydroxyl, amino; alkyl, nitro, mercapto, and the like. US 6,232,417 B1 35 36 The Group VIII metal compounds can also contain cat derivatives thereof; organic etherS Such as dimethyl ether of ions Such as, for example, organo anmonium, diethylene glycol, dioxane, tetrahrydrofuran, furan diallyl organoarSonium, organophosphonium, and pyridinium com ether, diethyl ether, cyclic etherS Such as diethylene glycol pounds represented by the formulae: cyclic oligomers, organic Sulfides Such as thioethers (diethyl Sulfide); arsines; Stibines; phosphines Such as triarylphos phines (e.g., triphenylphosphine), trialkylphosphines (e.g., (R0) trimethyl, triethyl, tripropyl, tripentacosyl, and halogenated 2A derivatives thereof), bis(diphenylphosphino)ethane, bis (diphenylphosphino)propane, bis(dimethylphosphino) A'(R28) C propane, bis(diphenylphosphino)butane, (S)-(–)2,2'-bis N (diphenylphosphino)-1,1'-binaphthyl, (R)-(+)-2,2'-bis R29 (diphenylphosphino)-1,1'-binaphthyl, and bis(2- diphenylphosphinoethyl)phenylphosphine; phosphine wherein A represents nitrogen, arsenic, and phosphorous and oxides, phosphorus halides, phosphites represented by the formula: the R radical can be independently selected from 15 hydrogen, branched or unbranched (C to Co) alkyl, P(OR), branched or unbranched (C. to Co) alkenyl, and (Cs to C.) cycloalkyl, e.g., cyclopentyl, cyclohexyl, cycloheptyl, wherein R independently represents a hydrocarbyl or Substituted hydrocarbyl as previously defined; phosphorus cyclooctyl, and the like. R” and R are independently Oxyhalides; phosphonates, phosphonites, phosphinites, Selected from hydrogen, branched and unbranched (C to ketones; Sulfoxides Such as (C. to Co) alkylsulfoxides; (C Cso) alkyl, linear and branched (C. to Co) alkenyl and (Cs to Co) arylsulfoxides, (C7 to Co) alkarylsulfoxides, and the to Ce) cycloalkyl groups as defined above; and n is 1 to 5, like. It should be recognized that the foregoing neutral preferably n is 1, 2, or 3, most preferably n is 1. The R' ligands can be utilized as optional third components as will radicals preferably are attached to positions 3, 4, and 5 on be described hereinbelow. the pyridine ring. 25 It should be noted that increasing the Sum of the carbon Examples of Group VIII transition metal compounds atoms contained in the R radicals confers better solubility suitable as the Group VIII metal ion source include: palla of the transition metal compound in organic media Such as dium ethylhexanoate, trans-Pd Cl(PPh), palladium (II) organic Solvents and polycyclic the monomer. Preferably, bis(trifluoroacetate), palladium (II) bis(acetylacetonate), the R radicals are selected from (C. to Cs) alkyl groups palladium (II) 2-ethylhexanoate, Pd(acetate)(PPh3), palla wherein the sum of carbon atoms for all R radicals is 15 dium (II) bromide, palladium (II) chloride, palladium (II) to 72, preferably 25 to 48, more preferably 21 to 42. The R' iodide, palladium (II) oxide, monoacetonitriletris radical is preferably selected from linear and branched (C (triphenylphosphine) palladium (II) tetrafluoroborate, to Cso) alkyl, more preferably (Co to Cao) alkyl. R' is tetrakis(acetonitrile) palladium (II) tetrafluoroborate, preferably Selected from linear and branched (C to Co) dichlorobis(acetonitrile) palladium (II), dichlorobis alkyl, more preferably (C. to Co) alkyl. 35 (triphenylphosphine) palladium (II), dichlorobis Specific examples of organoammonium cations include (benzonitrile) palladium (II), palladium acetylacetonate, pal tridodecylammonium, methyltricaprylammonium, tris ladium bis(acetonitrile) dichloride, palladium bis (tridecyl)ammonium and trioctylammonium. Specific (dimethylsulfoxide) dichloride, nickel acetylacetonates, examples of organoarSonium and organophosphonium cat nickel carboxylates, nickel dimethylglyoxime, nickel ions include tridodecylarSonium and phosphonium, methyl 40 ethylhexanoate, NiCl2(PPh3), NiCl2(PPhCH), tricaprylarsonium and phosphonium, tris(tridecyl)arSonium (P(cyclohexyl)-)H Ni(Ph-P(CH)CO), (PPh) (CH)Ni and phosphonium, and trioctylarSonium and phosphonium. (Ph. PCH=C(O)Ph), bis(2,2,6,6-tetramethyl-3,5- Specific pyridinium cations include eicosyl-4-(1- heptanedionate) nickel (II), nickel (II) hexafluoroacetylac butylpentyl)pyridinium, docosyl-4-(13-pentacosyl) etonate tetrahrydrate, nickel (II) trifluoroacetylacetonate pyridinium, and eicosyl-4-(1-butylpentyl)pyridinium. 45 dihydrate, nickel (II) acetylacetonate tetrahry drate, Suitable neutral ligands which can be bonded to the nickelocene, nickel (II) acetate, nickel bromide, nickel palladium transition metal are the olefins, the acetylenes, chloride, dichlorohexyl nickel acetate, nickel lactate, nickel carbon monoxide, nitric oxide, nitrogen compounds Such as oxide, nickel tetrafluoroborate, bis(allyl) nickel, bis ammonia, alkylisocyanide, alkylisocyanate, alkylisothiocy (cyclopentadienyl)nickel, cobalt neodecanoate, cobalt (II) anate; pyridines and pyridine derivatives (e.g., 1,10 50 acetate, cobalt (II) acetylacetonate, cobalt (III) phenanthroline, 2,2'-dipyridyl), 1,4-dialkyl-1,3- acetylacetonate, cobalt(II) benzoate, cobalt chloride, cobalt diazabutadienes, 1,4-diaryl-1,3-diazabutadienes and amines bromide, dichlorohexylcobalt acetates, cobalt(II) Stearate, Such as represented by the formulae: cobalt (II) tetrafluoroborate, iron napthenate, iron (II) chloride, iron (III) chloride, iron (II) bromide, iron (III) 55 bromide, iron (II) acetate, iron (III) acetylacetonate, N(R) ferrocene, ruthenium tris(triphenylphosphine) dichloride, N(R) (CH2) ruthenium tris(triphenylphosphine) hydrido chloride, ruthe nium trichloride, ruthenium tetrakis(acetonitrile) dichloride, N(R), (CH) , NRI ruthenium tetrakis(dimethylsulfoxide) dichloride, rhodium 60 chloride, rhodium tris(triphenylphosphine) trichloride. N(R)2 (CH2) The organoaluminum component of the multicomponent N(R31) catalyst System of the present invention is represented by the formula: wherein R is independently hydrocarbyl or substituted 65 AIR's Q. hydrocarbyl as previously defined and n is 2 to 10. Ureas; wherein R* independently represents linear and branched nitriles Such as acetonitrile, benzonitrile and halogenated (C. to Co) alkyl, (Cs to C2) aryl, (C7 to Co) aralkyl, (C-

US 6,232,417 B1 39 40 cally afford norbornene units which are exclusively 2.3 In the course of developing these catalyst and polymer enchained and showing Some degree of tacticity. The poly systems we have observed that the palladium-carbon bond mers catalyzed by the type 2 catalyst Systems and the Single which links the palladium catalysts to the growing polymer component catalyst Systems of the formula E.Ni(CFs). chain is particularly Stable. This is a major benefit in described above contain a perfluorophenyl group at at least polymerizing polycyclic monomers bearing acid labile one of the two terminal ends of the polymer chain. In other groups, esters and carboxylic acid functionalities Since the words, a perfluorophenyl moiety can be located at one or palladium catalysts are extremely tolerant to Such function both terminal ends of the polymer. In either case the per fluorophenyl group is covalently bonded to and pendant alities. However, this stability also makes it very difficult to from a terminal polycyclic repeating unit of the polymer remove the palladium catalyst residues from the resulting backbone. 1O polymer. During the development of these new Reactions utilizing the Single and multicomponent cata compositions, we discovered that the palladium-carbon lysts of the present invention are carried out in an organic bond can be conveniently cleaved (resulting in precipitation solvent which does not adversely interfere with the catalyst of palladium metal which can be removed by filtration or System and is a Solvent for the monomer. Examples of centrifugation) using carbon monoxide, preferably in the organic Solvents are aliphatic (non-polar) hydrocarbons Such 15 presence of a protic Solvent Such as an alcohol, moisture, or as pentane, hexane, heptane, octane and decane, alicyclic a carboxylic acid. hydrocarbons Such as cyclopentane and cyclohexane, aro The polymers obtained by the process of the present matic hydrocarbons Such as benzene, chlorobenzene, invention are produced in a molecular weight (M) range o-dichlorobenzene, toluene, and Xylenes; halogenated from about 1,000 to about 1,000,000, preferably from about (polar) hydrocarbons Such as methylene chloride, 2,000 to about 700,000, and more preferably from about chloroform, carbon tetrachloride, ethyl chloride, 1,1- 5,000 to about 500,000 and most preferably from about dichloroethane, 1,2-dichloroethane, 1,2-dichloroethylene, 10,000 to about 50,000. 1-chloropropane, 2-chloropropane, 1-chlorobutane, Molecular weight can be controlled by changing the 2-chlorobutane, 1-chloro-2-methylpropane, and catalyst to monomer ratio, i.e., by changing the initiator to 1-chloropentane. 25 monomer ratio. Lower molecular weight polymers and oli The choice of reaction Solvent is made on the basis of a gomers may also be formed in the range from about 500 to number of factors including the choice of catalyst and about 500,000 by carrying out the polymerization in the whether it is desired to run the polymerization as a slurry or presence of a chain transfer agent. Macromonomers or Solution process. For most of the catalysts described in this oligomers comprising from 4 to 50 repeating units can be invention, the preferred Solvents are chlorinated hydrocar prepared in the presence of a CTA (Chain Transfer Agent) bons Such as methylene chloride and 1,2-dichloroethane and Selected from a compound having a terminal olefinic double aromatic hydrocarbons Such as chlorobenzene and bond between adjacent carbon atoms, wherein at least one of nitrobenzene, with simple hydrocarbons being less preferred the adjacent carbon atoms has two hydrogen atoms attached due to the resulting lower conversion of the functional thereto. The CTA is exclusive of styrenes (non-styrenes), NB-type monomer(s). Surprisingly we have discovered that 35 vinyl ethers (non-vinyl ether) and conjugated dienes. By certain of the catalyst Systems, most notably the multicom non-styrenic, non-vinyl ether is meant that compounds hav ponent catalysts based on Group VIII metal compounds and ing the following Structures are excluded from the chain alkylaluminum halides, Specifically, monoalkylaluminum transfer agents of this invention: dihalides, (e.g., ethylaluminum dichloride), and the type 2 40 catalysts referred to above also give excellent results (and CHFC(R or H), CHFCH high monomer conversion) when run in simple hydrocar bons Such as heptane, cyclohexane, and toluene. A. OR The molar ratio of total monomer to Group VIII metal for the Single and multicomponent catalysts can run from 20:1 wherein A is an aromatic Substituent and R is hydrocarbyl. to 100,000:1, preferably 50:1 to 20,000:1, and most prefer 45 The preferred CTA compounds of this invention are ably 100:1 to 10,000:1. represented by the following formula: In the multicomponent catalyst Systems, the cocatalyst metal (e.g., aluminum, zinc, magnesium, and lithium) to / Group VIII metal molar ratio ranges from less than or equal 50 to 100:1, preferably less than or equal to 30:1, and most CHFC preferably less than or equal to 20:1. Rit The third component is employed in a molar ratio to Group VIII metal ranging from 0.25:1 to 20:1. When acids wherein R, and Rn independently represent hydrogen, are employed as third components, the acid to Group VIII 55 branched or unbranched (C to Co) alkyl, branched or metal range is less than or equal to 4:1, preferably less than unbranched (C. to Co) alkenyl, and halogen. or equal to 2:1. Of the above chain transfer agents the C-olefins having 2 The temperature at which the polymerization reactions of to 10 carbon atoms are preferred, e.g., ethylene, propylene, the present invention are carried out typically ranges from 4-methyl-1-pentene, 1-hexene, 1-decene, 1,7-octadiene, and -100° C. to 120° C., preferably -60° C. to 90° C., and most 60 1,6-octadiene, or isobutylene. Other CTA's include allyl preferably -10° C. to 80° C. halides Such as allyl chlorides, allyl bromides, etc., allyl The optimum temperature for the present invention is trifluoro-acetates, B-pineres, C-pineres. dependent on a number of variables, primarily the choice of While the optimum conditions for any given result should catalyst and the choice of reaction diluent. Thus, for any be experimentally determined by a skilled artisan taking into given polymerization the optimum temperature will be 65 the account all of the above factors there are a number of experimentally determined taking these variables into general guidelines which can be conveniently utilized where acCOunt. appropriate. We have learned that, in general, C-olefins (e.g., US 6,232,417 B1 41 42 ethylene, propylene, 1-hexene, 1-decene, 4-methyl-1- by reference. The invention is not limited to a specific class pentene) are the most effective chain transfer agents with of Sensitizer or photoacid initiator. 1,1-disubstituted olefins (e.g., isobutylene) being less effi The present invention also relates to a process for gener cient. In other words, all other things being equal, the ating a positive tone resist image on a Substrate comprising concentration of isobutylene required to achieve a given the steps of: (a) coating a Substrate with a film comprising molecular weight will be much higher than if ethylene were the positive tone resist composition of the present invention; chosen. Styrenic olefins, conjugated dienes, and vinyl ethers (b) imagewise exposing the film to radiation; and (c) devel are not effective as chain transfer agents due to their pro oping the image. pensity to polymerize with the catalysts described herein. The first step involves coating the substrate with a film The CTA can be employed in an amount ranging from comprising the positive tone resist composition dissolved in about 0.10 mole % to over 50 mole % relative to the moles a Suitable Solvent. Suitable Substrates are comprised of of total NB-type monomer. Preferably, the CTA is employed Silicon, ceramics, polymer or the like. Suitable Solvents in the range of 0.10 to 10 mole %, and more preferably from include propylene glycol methyl ether acetate (PGMEA) 0.1 to 5.0 mole %. As discussed above, depending on cyclohexanone, butyrolactate, ethyl lactate, and the like. The catalyst type and Sensitivities, CTA efficiencies and desired 15 film can be coated on the Substrate using art known tech end group, the concentration of CTA can be in excess of 50 niques Such as Spin or spray coating, or doctor blading. mole % (based on total NB-functional monomer present), Preferably, before the film has been exposed to radiation, the e.g., 60 to 80 mole %. Higher concentrations of CTA (e.g., film is heated to an elevated temperature of about 90° C. to greater than 100 mole %) may be necessary to achieve the 150 C. for a short period of time of about 1 min. In the low molecular weight embodiments of this invention Such as Second step of the process, the film is imagewise exposed to in oligomer and macromonomer applications. It is important radiation Suitably electron beam or electromagnetic prefer and Surprising to note that even Such high concentrations the ably electromagnetic radiation Such as ultraViolet or X-ray, CTA's (with the exception of isobutylene) do not copoly preferably ultraViolet radiation Suitably at a wave length of merize into the polymer backbone but rather insert as about 193 to 514 nm preferably about 193 nm to 248 nm. terminal end-groups on each polymer chain. Besides chain 25 Suitable radiation Sources include mercury, mercury/Xenon, transfer, the process of the present invention affords a way and Xenon lamps, X-ray or e-beam. The radiation is absorbed by which a terminal C-olefinic end group can be placed at by the radiation-Sensitive acid generator to produce free acid the end of a polymer chain. in the exposed area. The free acid catalyzes the cleavage of Polymers of the present invention that are prepared in the the acid labile pendant group of the copolymer which presence of the instant CTA's have molecular weights (M) converts the copolymer from dissolution inhibitor to disso ranging from about 1,000 to about 500,000, preferably from lution enhancer thereby increasing the Solubility of the about 2,000 to about 300,000, and most preferably from exposed resist composition in an aqueous base. Surprisingly, about 5,000 to about 200,000. the exposed resist composition is readily Soluble in aqueous The photoresist compositions of the present invention base. This Solubility is Surprising and unexpected in light of comprise the disclosed polycyclic compositions, a Solvent, 35 the complex nature of the cycloaliphatic backbone and the and an photosensitive acid generator (photoinitiator). high molecular weight of the norbornene monomer units Optionally, a dissolution inhibitor can be added in an amount bearing the carboxylic acid functionality. Preferably, after of up to about 20 weight % of the composition. A suitable the film has been exposed to radiation, the film is again dissolution inhibitor is t-butyl cholate (J. V. Crivello et al., heated to an elevated temperature of about 90° C. to 150 C. Chemically Amplified Electron-Beam Photoresists, Chem. 40 for a short period of time of about 1 minute. Mater, 1996, 8,376-381). The third step involves development of the positive tone Upon exposure to radiation, the radiation Sensitive acid image with a suitable solvent. Suitable solvents include generator generates a Strong acid. Suitable photoinitiators aqueous base preferably an aqueous base without metal ions include triflates (e.g., triphenylsulfonium triflate), pyrogallol Such as tetramethyl ammonium hydroxide or choline. The (e.g., trimeSylate of pyrogallol), onium salts. Such as triar 45 composition of the present invention provides positive ylsulfonium and diary liodium hexafluoroantimonates, images with high contrast and Straight walls. Uniquely, the hexafluoroarsenates, trifluoromethaneSulfonates, esters of dissolution property of the composition of the present inven hydroxyimides, C.C.'-bis-Sulfonyl-diazomethanes, Sulfonate tion can be varied by Simply varying the composition of the esters of nitro-substituted benzyl alcohols and copolymer. napthoguinone-4-diazides. Other Suitable photoacid initia 50 The present invention also relates to an integrated circuit tors are disclosed in Reichmanis et al., Chem. Mater. 3,395, assembly Such as an integrated circuit chip, multichip (1991). Compositions containing triarylsulfonium or diaryli module, or circuit board made by the process of the present odonium Salts are preferred because of their Sensitivity to invention. The integrated circuit assembly comprises a cir deep UV light (193 to 300 nm) and give very high resolution cuit formed on a Substrate by the steps of: (a) coating a images. Most preferred are the unsubstituted and Symmetri 55 Substrate with a film comprising the positive tone resist cally or unsymmetrically Substituted diaryliodium or triar composition of the present invention; (b) imagewise expos ylsulfonium Salts. The photoacid initiator component com ing the film to radiation; (c) developing the image to expose prises about 1 to 100 w/w % to polymer. The preferred the Substrate; and (d) forming the circuit in the developed concentration range is 5 to 50 w/w %. film on the Substrate by art known techniques. The photoresist compositions of the present invention 60 After the Substrate has been exposed, circuit patterns can optionally contain a Sensitizer capable of Sensitizing the be formed in the exposed areas by coating the Substrate with photoacid initiator to longer wave lengths ranging from mid a conductive material Such as conductive metals by art UV to visible light. Depending on the intended application, known techniqueS Such as evaporation, Sputtering, plating, Such Sensitizers include polycyclic aromatics Such as pyrene chemical vapor deposition, or laser induced deposition. The and perlene. The Sensitization of photoacid initiators is 65 Surface of the film can be milled to remove any exceSS well-known and is described in U.S. Pat. Nos. 4,250,053; conductive material. Dielectric materials may also be depos 4,371,605; and 4,491,628 which are all incorporated herein ited by Similar means during the process of making circuits. US 6,232,417 B1 43 44 Inorganic ions Such as boron, phosphorous, or arsenic can be S. Esho, and Y. Ohnishi, J. Electrochem. Soc. 130(1), 143 implanted in the Substrate in the proceSS for making p or n (1983)) that higher C/H ratios decreases the etch rate of doped circuit transistors. Other means for forming circuits polymeric materials. Based on this assumption, the etch rate are well known to those skilled in the art. of polymer 5 should be between the aromatic based systems The following examples are detailed descriptions of meth and the acrylate Systems. It is Surprising that the addition ods of preparation and use of certain compositions of the cyclic olefin exhibits etch resistance Superior to even the present invention. The detailed preparations fall within the aromatic Systems. Scope of, and Serve to exemplify, the more generally described methods of preparation set forth above. The Catalyst A examples are presented for illustrative purposes only, and Synthesis of (PhC(O)CH2PPh2)Ni(CF). are not intended as a restriction on the Scope of the inven (PhC(O)CHPPh.)Ni(Ph) (0.150 g, 0.171 mol) was tion. weighed into a 100 ml Kjeldahl flask in the dry box. Also in AS discussed above, photoresists are used to create and replicate a pattern from a photomask to a Substrate. The the dry box, 0.194 g of B(CF).3H2O (0.342 mol) was efficacy of this transfer is determined by the wave length of weighed into a separate flask. After each Solid was dissolved the imaging radiation, the Sensitivity of the photoresist and 15 Separately in a minimum of toluene (about 15 ml each), the the ability of the photoresist to withstand the etch conditions solution of B(CFs).3H2O was added to the solution/slurry which pattern the Substrate in the exposed regions. Photo of the nickel dimer (it was not completely soluble in resists are most often used in a consumable fashion, where toluene). The mixture changed from a cloudy orange to a the photoresist is etched in the non-exposed regions (for a translucent red-brown color upon addition of the boron positive tone photoresist) and the Substrate is etched in the reagent. The Solution was stirred for approximately one exposed regions. Because the photoresist is organic and the hour, after which time the toluene was removed in vacuo. Substrate is typically inorganic, the photoresist has an inher The yellowish-brown solid was redissolved in a small ently higher etch rate in the reactive ion etch (RIE) process, amount of toluene and cooled to -20° C. A yellow solid which necessitates that the photoresist needs to be thicker formed which was filtered and dried in vacuo. Yield 0.108 than the Substrate material. The lower the etch rate of the 25 g(45% yield). H NMR (CDC1): 7.90 (d. 2H), 7.67 (t,3H), photoresist matter, the thinner the photoresist layer has to be. 7.48 (m, 4H), 7.20 (m, 6H), 4.19 (d, J-5 Hz, 2H). P{H} Consequently, higher resolution can be obtained. Therefore, NMR (CD): 26.8 (s). 'F NMR (CD): -115.8 (m, 2F), the lower the RIE rate of the photoresist, the more attractive -119.0 (m, 2F), -159.8 (t, 1F), -160.9 (t, 1F), -162.9 it is from a process point of view. The etch rate is primarily (apparent t of d, 2F), -163.7 (apparent t, 2F). FD-MS: m/e determined by the polymer backbone, as shown below for 696 Mexhibits expected isotope pattern for nickel, exact the chlorine plasma etch process which is a RIE technique mass 696.021080, calculated 696.021083. CI-MS: m/e 529 typically employed in Semiconductor processing. M*-CFs exhibits expected isotope pattern for nickel, AS used in the examples and throughout the specification exact mass 529.029065, calculated mass 529.029067. the ratio of monomer to catalyst is based on a mole to mole Catalyst A basis. 35 Alternative synthesis of (PhC(O)CH2PPh2)Ni(CF). PhC(O)CHPPha was prepared as described in Inorg. Chem. 1986, 25, 3765. (-toluene)Ni(CF) (0.10 g, 0.21 mmol) was dissolved in 10 ml of toluene. To this solution Normalized PPhCHC(O)Ph (0.063 g, 0.21 mmol) in 10 ml of toluene No. Polymer RIE Rate (um/min) 40 was added dropwise. The color of the solution turned 1. Novolac resist 1.O yellow-brown after 10 min., and a yellow powder began to 2 polyhydroxystyrene resist O.98 3 248 nm (Deep UV) 1.14 precipitate from Solution. After Stirring at room temperature (acrylate terpolymer/novolac blend, for 1 hour, the Solvent was removed in vacuo resulting in a U.S. Pat. No. 5,372,912) yellow solid. This was dissolved in 10 ml of CHCl, filtered 4 193 nm (polyacrylate terpolymer, 1.96 45 and stored at -20° C. Bright yellow crystals were obtained Allen et al., Proceedings SPIE, 2438(1), 474 (1995)) in quantitative yield after 2 days. The X-ray crystal Structure 5 homopolynorbornene O.83 of (PhC(O)CHPPh)Ni(CF) is shown in FIG. 1. Catalyst B PolymerS 1 and 2 are primarily aromatic, whereas poly 50 Synthesis of cis-Ni(THF) (CFS) mer 3 was copolymerized with a Small amount of acrylate Pentafluorophenylbromide (12.9 g) was added slowly (1 which increased its etch rate. Polymer 4 is completely based ml every 20 min.) via an addition funnel to a flask containing on acrylates to allow transparency at 193 nm (aromatic rings of magnesium turnings in 50 ml of THF equipped with a stir render the material opaque in this region, hence there are no bar and a condenser. During the addition of the bromide, the viable resist candidates at 193 nm based on the traditional 55 THF solution turned dark and began to reflux. After about 2 novolacs or p-hydroxystyrene). The etch rate almost hours, the resulting brown Solution was added to a flask doubled for this polymer. Polymer 5 had an etch rate even containing NiBr (5.03 g) in 25 ml of THF. The resulting lower than the standard photoresist materials (1 & 2) in mixture was then refluxed for 2 hours to give a red Solution. addition to providing transparency at 193 nm. Therefore, the The Solution was allowed to cool and 35 ml of 1,4-dioxane backbone of polymer 5 (an addition cyclic olefin) prepared 60 was added. The Solution became orange and insoluble by a nickel multicomponent catalyst of this invention is an material appeared. The mixture was stored at 5 C. over improvement over all previous attempts in the literature to night. The next day, the Solution was allowed to warm to provide a resist which functions at 193 nm with RIE room temperature and then filtered to remove insoluble characteristics comparable to commercial materials exposed material. The insoluble material was washed with 1.4- at longer wave lengths. In fact, the addition cyclic olefin 65 dioxane to give a grey material. The red-orange filtrate was polymer may offer advantages in terms of etch resistance at placed stored at -20° C. overnight. The next day 3.0 g (23% longer wave lengths as well. It is in the literature (H. Gokan, yield) of orange crystalline cis-Ni(THF) (CF) were col US 6,232,417 B1 45 46 lected. The X-ray crystal structure of cis-Ni(THF) (CF) is solid was filtered and washed with toluene (2x20 ml). The shown in FIG. 2. Solutions were combined and dried overnight in vacuo. The Catalyst B resulting light brown solid was extracted with 50 ml of Alternative Synthesis of cis-Ni(THF) (CF) toluene and filtered. The insoluble grey solid was washed To a cold (-78° C) slurry of Ni(COD) (10.0 g) in a with 5 ml of toluene and the Solutions were combined. Slow mixture of THF (30 ml) and diethylether (40 ml) was added evaporation of the dark brown Solution to ca. 5 ml gave a a solution of CFC(O)C1 (8.4 g) in 25 ml of diethylether crystalline material. The remaining Solvent was evaporated dropwise. No color change was evident after addition. The and the crystals were washed with heptane and filtered and mixture was warmed to 0°C. for 1 hour. During this time the dried in vacuo to give 4.59 g (54%) of brick red crystals. color of the Solution changed to orange and an orange Catalyst A precipitate formed. After warming to room temperature all Synthesis of (PhC(O)CH2PPh2)Ni(CF). of the yellow nickel Starting material was consumed to yield (PhC(O)CHPPh.)Ni(Ph) (0.150 g, 0.171 mol) was an orange Solution and Solid. The Slurry was concentrated in weighed into a 100 ml Kjeldahl flask in the dry box. Also in vacuo (to ca. 20 ml) and cyclohexane was added (120 ml) to 15 the dry box, 0.194 g of B(CF).3H2O (0.342 mol) was precipitate out any remaining Soluble material. The Solvents weighed into a separate flask. After each Solid was dissolved were decanted and washed with cyclohexane (2x25ml). The Separately in a minimum of toluene (about 15 ml each), the Solid was dried in vacuo. solution of B(CFs).3H2O was added to the solution/slurry The orange solid was extracted twice with 50 ml of of the nickel dimer (it was not completely soluble in toluene. During the extractions, the initial light orange toluene). The mixture changed from a cloudy orange to a Solution became red-orange. The extractions were combined translucent red-brown color upon addition of the boron and cooled to -20° C. to yield orange crystals. The mother reagent. The Solution was stirred for approximately 1 hour, liquor was Stripped of Solvent and extracted once again with after which time the toluene was removed in vacuo. The toluene (2x50 ml), combined and cooled to -20° C. After a yellowish-brown solid was redissolved in a small amount of few days, this Solution yielded a Second batch of orange 25 toluene and cooled to -20° C. A yellow solid formed which crystals. The combined yields were 13%. The crystals was filtered and dried in vacuo. Yield 0.108 g (45% yield). decomposed at 183 C. and were pure by NMR spectros H NMR (CDC1): 7.90 (d. 2H), 7.67 (t,3H), 7.48 (m, 4H), copy. 7.20 (m, 6H), 4.19 (d, J-5 Hz, 2H). P{H} NMR Catalyst C (CD): 26.8 (s). 'F NMR (CD): -115.8 (m, 2F), -119.0 Synthesis of (Toluene)Ni(CF). (m, 2F), -159.8 (t, 1F), -160.9 (t, 1F), -162.9 (apparent t of This procedure followed a previously published method d, 2F), -163.7 (apparent t, 2F). FD-MS: m/e 696 M" found in Organometallics 1985, 4,571. Magnesium turnings exhibits expected isotope pattern for nickel, exact mass (0.945 g) was weighed in a three neck 250 ml flask equipped 696.021080, calculated 696.021083. CI-MS: m/e 529 with gas inlet, stir bar, and addition funnel (a reflux con MCFs exhibits expected isotope pattern for nickel, exact denser is also recommended). After purging with argon, 10 35 mass 529.029065, calculated mass 529.029067. ml of dry diethylether was added. With stirring, bromopen Catalyst A tafluorobenzene (1 ml) was added dropwise at room tem Alternative Synthesis of (PhC(O)CHPPh2)Ni(CFs). perature. Ten minutes after the addition of PhC(O)CH2PPh2 was prepared as described in Inorg bromopentafluorobenzene, a light brown color appeared in Chem. 1986, 25,3765. (m-toluene)Ni(CF) (0.10g, 0.21 the ethereal Solution. At this point, a Solution of bromopen 40 mmol) was dissolved in 10 ml of toluene. To this solution tafluorobenzene (3.38 ml) in 15 ml of ether was added PPhCHC(O)Ph (0.063 g, 0.21 mmol) in 10 ml of toluene dropwise at a rate which maintained reflux of the ether. The was added dropwise. The color of the solution turned brown color became very dark. The mixture was stirred for yellow-brown after 10 min., and a yellow powder began to 1 hour at room temperature. precipitate from Solution. After Stirring at room temperature In the dry box, anhydrous nickel bromide (3.83 g) was 45 for 1 hour, the Solvent was removed in vacuo resulting in a weighed into a 200 ml Kjeldahl flask equipped with a stir yellow solid. This was dissolved in 10 ml of CHCl, filtered bar. Only finely divided nickel bromide powder was used. and stored at -20° C. Bright yellow crystals were obtained Also in the dry box silver trifluoroacetate (7.78 g) was in quantitative yield after 2 days. The X-ray crystal Structure weighed into a Solid addition tube which was Subsequently of (PhC(O)CHPPh)Ni(CF) is shown in FIG. 1. attached to the Kjeldahl. About 75 ml of diethylether was 50 added to the nickel bromide to give an orange slurry. To this Catalyst B Slurry was added the Solid Silver Salt which gave a slightly Synthesis of cis-Ni(THF) (CFS) exothermic reaction and a green Solution of the Soluble Pentafluorophenylbromide (12.9 g) was added slowly (1 nickel Salt. The reaction mixture was allowed to continue to ml every 20 min.) via an addition funnel to a flask containing stir for three hours. The orange color of the insolubles 55 magnesium turnings in 50 ml of THF equipped with a stir changed to a dull yellow-orange as Silver bromide replaced bar and a condenser. During the addition of the bromide, the the nickel bromide. The mixture was filtered to yield a green THF solution turned dark and began to reflux. After about 2 Solution that was used in the Step below. hours, the resulting brown Solution was added to a flask The Grignard solution was cooled to 0° C. and the nickel containing NiBr (5.03 g) in 25 ml of THF. The resulting trifluoroacetate solution was added dropwise over 30 min. 60 mixture was then refluxed for 2 hours to give a red Solution. The solution was stirred for one hour at 0° C. and then The Solution was allowed to cool and 35 ml of 1,4-dioxane allowed to warm to room temperature. Then 40 ml of toluene was added. The Solution became orange and insoluble was added to the solution. The resulting dark brown solution material appeared. The mixture was stored at 5 C. over was evaporated to dryneSS. To the resulting dark brown Solid night. The next day, the Solution was allowed to warm to was added 100 ml of toluene and the brown Solution with a 65 room temperature and then filtered to remove insoluble grey Solid was stirred overnight. The Slurry was concen material. The insoluble material was washed with 1.4- trated to about 25 ml with heating to 45-50 C. The grey dioxane to give a grey material. The red-orange filtrate was US 6,232,417 B1 47 48 placed stored at -20° C. overnight. The next day 3.0 g (23% was added 100 ml of toluene and the brown Solution with a yield) of orange crystalline cis-Ni(THF) (CF) were col grey Solid was stirred overnight. The Slurry was concen lected. The X-ray crystal structure of cis-Ni(THF) (CF) is trated to about 25 ml with heating to 45-50 C. The grey shown in FIG. 2. solid was filtered and washed with toluene (2x20 ml). The Catalyst B Solutions were combined and the Solvent was removed Alternative Synthesis of cis-Ni(THF) (CF) overnight in vacuo. The resulting light brown Solid was To a cold (-78° C) slurry of Ni(COD) (10.0 g) in a extracted with 50 ml of toluene and filtered. The insoluble mixture of THF (30 ml) and diethylether (40 ml) was added grey solid was washed with 5 ml of toluene and the solutions a solution of CFC(O)C1 (8.4 g) in 25 ml of diethylether were combined. Slow evaporation of the dark brown solu dropwise. No color change was evident after addition. The tion to ca. 5 ml gave a crystalline material. The remaining mixture was warmed to 0°C. for 1 hour. During this time the Solvent was evaporated and the crystals were washed with color of the Solution changed to orange and an orange heptane and filtered and dried in vacuo to give 4.59 g (54%) precipitate formed. After warming to room temperature all of brick red crystals. of the yellow nickel Starting material was consumed to yield Catalyst D an orange Solution and Solid. The Slurry was concentrated in 15 Synthesis of (PhNC(O)CH2PPh2)Ni(CF). vacuo (to ca. 20 ml) and cyclohexane was added (120 ml) to PhNC(O)CHPPha was prepared as described in J. precipitate out any remaining Soluble material. The Solvents Chem. Res. (S), 1993, 380. (m-toluene)Ni(CF) (0.10 g, were decanted and washed with cyclohexane (2x25ml). The 0.21 mmol) was dissolved in 5 ml of toluene. To this solution Solid was dried in vacuo. PhNC(O)CH2PPh2 (0.081 g, 0.21 mmol) in 5 ml of toluene The orange solid was extracted twice with 50 ml of was added dropwise. The color of the solution turned light toluene. During the extractions, the initial light orange yellow-brown. After Stirring at room temperature for 1 hour, Solution became red-orange. The extractions were combined the Solvent was removed in vacuo resulting in a light yellow and cooled to -20° C. to yield orange crystals. The mother powder. liquor was Stripped of Solvent and extracted once again with 25 Catalyst E toluene (2x50 ml), combined and cooled to -20° C. After a Synthesis of (PhC(O)CHCH2PPh2)Ni(CF). few days, this Solution yielded a Second batch of orange (PhC(O)CH2CH2PPh2) was prepared as described in J. crystals. The combined yields were 13%. The crystals Pract. Chem. 1972, 315. (m-toluene)Ni(CF) (0.50 g, 1.0 decomposed at 183 C. and were pure by NMR spectros mmol) was dissolved in 20 ml of toluene. To this solution copy. PPhCHC(O)Ph (0.33 g, 1.0 mmol) in 10 ml of toluene was Catalyst C added dropwise. The color of the solution turned yellow Synthesis of (Toluene)Ni(CFS) after 10 m. After 1 hour, the Solvent was removed in vacuo This procedure followed a previously published method to yield a Solid. found in Organometallics 1985, 4,571. Magnesium turnings Catalyst F (0.945 g) was weighed in a three neck 250 ml flask equipped 35 with gas inlet, stir bar, and addition funnel (a reflux con Ni(COD) (0.60 g) was dissolved in 30 ml of THF. A denser is also recommended). After purging with argon, 10 solution of pentafluorobenzoyl chloride (0.315 ml in 3 ml of ml of dry diethylether was added. With stirring, bromopen THF) was added to the above solution. An immediate color tafluorobenzene (1 ml) was added dropwise at room tem change from yellow to orange occurred. The Solution was perature. Ten minutes after the addition of 40 stirred for 30 min. at room temperature after which the bromopentafluorobenzene, a light brown color appeared in volume of the Solution was reduced in vacuo to about 3 ml. the ethereal Solution. At this point, a Solution of bromopen To this Solution was added cyclohexane to precipitate a pink tafluorobenzene (3.38 ml) in 15 ml of ether was added solid. The solvent was decanted and the product was dried dropwise at a rate which maintained reflux of the ether. The in vacuo for 1 hour. Yield 0.80 g. brown color became very dark. The mixture was stirred for 45 Catalyst G 1 hour at room temperature. Ni(COD) (3.0 g) was dissolved in 100 ml of toluene. To In the dry box, anhydrous nickel bromide (3.83 g) was this Solution was added a Solution of pentafluorobenzoic weighed into a 200 ml Kjeldahl flask equipped with a stir acid (2.33 g in 30 ml of toluene) was added to the above bar. Only finely divided nickel bromide powder was used. Solution. An immediate color change from yellow to red/ Also in the dry box silver trifluoroacetate (7.78 g) was 50 brown occurred. The Solution was stirred for 1 hour at room weighed into a Solid addition tube which was Subsequently temperature after which time the toluene was removed in attached to the Kjeldahl. About 75 ml of diethylether was vacuo. The resulting brown solid was dissolved in hot added to the nickel bromide to give an orange slurry. To this cyclohexane and allowed to cool resulting in a brown Slurry was added the Solid Silver Salt which gave a slightly powder. The Solvent was decanted and the powder was dried exothermic reaction and a green Solution of the Soluble 55 nickel Salt. The reaction mixture was allowed to continue to in vacuo. Yield 2.8 g. stir for three hours. The orange color of the insolubles Catalyst H changed to a dull yellow-orange as Silver bromide replaced Ni(THF) (CFS) (0.126 g) was dissolved in about 10 ml the nickel bromide. The mixture was filtered to yield a green of toluene. To this solution was added 0.050 ml of beta solution of nickel trifluoroacetate (II) that was used in the 60 pinene in 2 ml of toluene. The orange color of the Starting step below. material changed immediately to blue. The Solution was The Grignard solution was cooled to 0° C. and the green stirred for two hours at room temperature after which time nickel trifluoroacetate solution was added dropwise over 30 the Solvent was removed in vacuo to give a blue, grey Solid. min. The solution was stirred for one hour at 0° C. and then allowed to warm to room temperature. Then 40 ml of toluene 65 Catalyst I was added to the solution. The resulting dark brown solution Ni(COD) (0.130 g) was dissolved in 10 ml of THF and was evaporated to dryneSS. To the resulting dark brown Solid cooled to -78 C. To this solution was added a solution of US 6,232,417 B1 49 SO 2,4,6-trifluorobenzoyl chloride (0.092 g) in 4 ml of THF. The red brown solution turned a deeper, brighter red almost The Solution was allowed to warm to room temperature after immediately after addition of the Et NCl. The solution was which time the Solution darkened to a dark orange color. The stirred for a four hours and then filtered. The Solution was Solution was concentrated to about 2 ml in vacuo and then layered with toluene (10 ml). The dark red crystals of cyclohexane was added (35 ml) to precipitate out a brown 5 (EtN)-Ni(CF),Cl) were collected by filtration. Yield= Solid. The solvent was decanted and the Solid was dried in 0.255 g, 83%). The compound was characterized analyzed WCUO. by H and F NMR. Catalyst J Catalyst M Synthesis of Ni(PPh3)2(CFs). Alternative Synthesis of (EtN)Ni(CFs)Cl]- To a small Schlenk flask, in the dry box, was added At 0° C., Zn(CF)-(dime) (1.0 g) dissolved in dichlo (toluene)Ni(CFs). (0.33 g) and PPH (0.36 g) followed by romethane was added to a sample of light blue, (EtN) toluene (20 ml). The solution was stirred for 20 minutes. The NiCl, (0.942 g) stirring in dichloromethane (15 ml). The Solvent was then removed in vacuo to yield the complex. light blue Suspension Slowly reacted to yield an orange red 15 murky Solution. The product was Stripped to dryneSS and Catalyst K then redissolved in tetrahydrofuran (THF), filtered to Synthesis of Tris(orthotolylphosphine)Ni(CF). remove the ZnCl2, and reprecipitated with pentane. The To a Small Schlenk flask, in an inert atmosphere box, was (EtN)-Ni(CFs)Cl] product was collected by filtration added tris(orthotolyl)phosphine (0.52 g, 1.7 mmol) and and washed with pentane to yield an orange red Solid. (toluene)Ni(CFs). (0.417 g., 0.85 mmol) followed by tolu Recrystallization of this product to a achieve red crystals can ene (15 ml) which resulted in the formation of a blood red be achieved from either dichloromethane/toluene or THF/ solution. The solvent was removed to afford the phosphine adduct as a red Solid. pentane mixtures. Yield=1.07 g (97%). Catalyst L Catalyst N Synthesis of (1,2-Dimethoxyethane)Ni(2,4,6-tris(trifluoro 25 Synthesis of (m-CH3C(CH))Ni(PPh)(CF) methyl)phenyl)- (m-CHC(CH))Ni(PPh3)C was prepared by adding of Preparation of lithium(2,4,6-tris(trifluoromethyl)phenyl). one equivalent of triphenylphosphine (0.78 g in toluene (10 To a clean, dry Kjeldahl flask was added 2,4,6-tris ml) to (m1-CHC(CH))NiCl (0.5 g) dissolved in toluene (trifluoromethyl)benzene (1.65 ml, 8.86 mmol) dissolved in (20 ml). After 16 hours of reaction at room temperature an a mixture of diethylether (20 ml) and hexane (20 ml). To this orange brown powder (0.85 g, 83%) was filtered from the Solution, cooled to 15 C. under argon, was added reaction. Recrystallization from toluene and pentane at -30 n-butyllithium (3.54 ml of a 2.5 molar solution in hexanes, C. yielded orange crystals. The product was characterized by 8.86 mmol). The solution turned yellow immediately. The "H and 'P NMR spectroscopies. Solution was allowed to warm to ambient temperature and A quantity of Zn(CFS)-(dime) (0.030 g) was dissolved in then allowed to stir at this temperature for an additional 60 35 diethyl ether (10 ml) and cooled to -78°C. This reagent was minutes. added dropwise into a diethyl ether solution of (m-CHC Preparation of (1,2-dimethoxyethane)Ni(2,4,6-tris (CH))Ni(PPh)C1 (0.05 g) held at -78° C. After about 10 (trifluoromethyl)phenyl). The above solution was trans minutes the Solution colored changed from its original ferred (under argon) to a Second Kjeldahl flask containing orange to yellow. After 18 hours at room temperature, the (1,2-dimethoxyethane)NiCl2 (0.973 g, 4.43 mmol) in a 40 Solvent was removed leaving a crystalline red-yellow Solid. mixture of diethylether (20 ml) and hexane (20 ml). The The product was recrystallized from toluene and pentane to mixture turned red-brown in color within 10 minutes and give (m-CHC(CH))Ni(PPh3)(CFs). The product was was allowed to stir at ambient temperature for 48 hours. The characterized as being pure by H and 'P NMR spec Solvent was then removed and the Solid residue was troscopies. extracted with toluene (50 ml) and filtered through Celite. 45 The toluene was removed to afford a slightly oily brown Catalyst O residue which was washed with hexane (3 aliquots of 20 ml) Synthesis of (m-CHC(CH))Ni(PCy)(CFs) to afford the product, a new compound, (1,2- (m-CHC(CH))Ni(PCy)C1 was prepared by adding of dimethoxyethane)Ni(2,4,6-tris(trifluoromethyl)phenyl), as one equivalent of tricyclohexylphosphine (PCy) (1.0 g in a purple microcrystalline Solid. The new compound was 50 diethyl ether) to (m-CHC(CH))NiCl) (0.532 g) dis characterized fully using NMR and MS techniques. Char solved in diethyl ether (15 ml). After 48 hours of reaction at acteristic of the new compound is a singlet in the 'F NMR room temperature an dark yellow Solution was obtained. The at -62.6 ppm in deuterobenzene and in the mass spectrum solids were filtered from the reaction and the yellow solution the molecular ion (with essentially no fragmentation) at 710. evaporated to yield a dark yellow powder (1.1 g, 87%). 55 Recrystallization from diethyl ether/pentane at -30° C. The X-ray crystal Structure of this compound is shown in yielded yellow-orange crystals. The product was character FIG. 3. ized by H and 'P NMR spectroscopies. Catalyst M A quantity of Zn(CFS)-(dime) (0.028 g) was dissolved in Synthesis of (EtN)Ni(CFS)Cl]- diethyl ether (15 ml) and cooled to -78°C. This reagent was The procedure employed was similar to that demonstrated 60 added dropwise into a diethyl ether solution of (m-CHC by K. Klabunde et al., Inorganic Chemistry, 1989, Volume (CH))Ni(PCy)C1 (0.05 g) held at -78° C. After about 15 28, pages 2414-2419. Tetraethylammonium chloride minutes the Solution colored changed from its original dark (Et NCI) was recrystallized from isopropanol/toluene (1:2) orange to yellow. After 18 hours at room temperature, the and dried by under vacuum prior to use. At room Solvent was removed leaving a crystalline yellow Solid. The temperature, a dichloromethane solution of EtNC1 (0.085 g, 65 product was recrystallized from toluene and pentane to give 0.516 mmol) was added to (m-toluene)Ni(CFs). (0.25 g, (m-CHC(CH))Ni(PCy)(CFs). The product was charac 0.516 mmol) dissolved quickly in dichloromethane (5 ml). terized as being pure by H and 'P NMR spectroscopies. US 6,232,417 B1 S1 52 Catalyst P Catalyst Component U Synthesis of Ni(2,4,6-tris(trifluoromethyl)phenyl) Synthesis of Ni(PhC(O)CHPPh)(Ph), Preparation of lithium(2,4,6-tris(trifluoromethyl)phenyl). This compound was synthesized by reacting Ni(PhC(O) To a clean, dry Kjeldahl flask was added 2,4,6-tris CHPPh2)(Ph)(PPh) (0.76 g) with Rh(acetylacetonate) (trifluoromethyl)benzene (5.0 g, 17.72 mmol) dissolved in (CH) (0.14 g) in a minimum amount of toluene (about 25 diethylether (20 ml) and hexane (20 ml). To this solution, ml). After Stirring the mixture for 4 hours, the precipitated cooled to 15 C. under argon, was added n-butyllithium solid was filtered and dried overnight in vacuo to yield 0.48 (3.54 ml of a 2.5 molar solution in hexanes, 8.86 mmol). The g of a yellow-brown solid. solution turned yellow immediately. The solution was allowed to warm to ambient temperature and then allowed to Catalyst Component V Stir at this temperature for an additional 60 minutes. (bpy)Ni(NBD). Dipyridyl (1.09 g) and bis(1,5- Preparation of Ni(2,4,6-tris(trifluoromethyl)phenyl). The cyclooctadiene) nickel (1.93 g) were dissolved in diethyl above Solution was transferred (under argon) to a second ether. The dipyridyl solution was added to the nickel solu Kjeldahl flask containing anhydrous NiCl (1.16 g, 9.0 tion with stirring. Immediately a violet color developed. The mmol) in a mixture of diethylether (20 ml) and hexane (20 15 Solution was allowed to react for approximately 5 hours. The ml). The mixture was allowed to Stir at ambient temperature solution was cooled to -78 C. and a diethyl ether solution for 96 hours. The solvent was then removed and the Solid of norbornadiene (2.88 ml) was added slowly. The mixture residue was extracted with toluene (50 ml) and filtered was allowed to warm to room temperature. No color change through Celite. The toluene was removed to afford a slightly was noted after 1.5 hours. An additional 2.88 ml of norbor oily brown residue which was then extracted again with nadiene in diethyl ether was added. The mixture was hexane (3 aliquots of 20 ml) to afford the product Ni(2,4, allowed to Stir at room temperature overnight after which 6-tris(trifluoromethyl)phenyl) as a brown solid. The com time a dark green precipitate resulted which was isolated by pound was characterized fully using NMR techniques. filtration, washed with cold ether and heptane, and dried in Catalyst Component Q 25 vacuo to a yield black solid. Yield 2.35 g (84%). Synthesis of Ni(PhC(O)CHPPh)(Ph)(PPh.) This preparation followed a published report in J. Polym. Catalyst Component W Sci. 1987, 25, 1989. A toluene slurry (150 ml) of PPha (5.00 Bis(2,2,6,6-tetramethyl-3,5-heptanedionato)nickel(II), or g, 19.1 mmol) and the ylid PhC(O)CHPPha (7.30 g, 19.1 Ni(dpm). This preparation follows a published procedure in mmol) was added to a chilled (0°C) toluene slurry (80 ml) Inorg. Chem. 1973, 12, 2983. A solution of 2.2,6,6- of Ni(COD) (5.30 g, 19.1 mmol). Upon completion of the tetramethyl-3,5-heptanedione (5.00 g) in 13.5 mL of ethanol addition, the mixture became a red-brown slurry. The mix was prepared. A solution of 3.93 g of nickel(II) nitrate ture was allowed to warm to room temperature and stirred hexahydrate in 35 ml of a 50% ethanol/water mixture was for 21 hours. The mixture was then heated to 50° C. for 2 added to the above solution. With stirring, a solution (50% hours. The mixture was cooled to room temperature and 35 ethanol/water) of 1.08 g of NaOH was added with imme allowed to stir for an additional 16 hours. The mixture was diate precipitation of a green Solid. The mixture was diluted filtered to give a red-brown filtrate which upon removal of with 200 mL of a 50% ethanol/water mixture, filtered, and Solvent in vacuo gave a brown residue. The residue was washed with more ethanol/water mixture. The resulting dissolved in toluene (50 ml) from which a tan precipitate green solid was air dried overnight in oven at 110° C. to a formed upon addition of 50 mL of hexane. The mixture was 40 constant weight. The green Solid changed to a purple color. Stored in the freezer overnight to give a gold-tan Solid which The solid was then recrystallized from 1,2-dichloroethane, was filtered, washed with hexane, and dried. Yield 10.5 g. filtered and dried. Yield 1.91 g of a purple solid. (79%). Catalyst Component X Catalyst Component R 45 Synthesis of (Toluene)Ni(SiCl3). Synthesis of Ni(OC(O)(CH)PPh)(H)(PCy) (Toluene)Ni(SiCl) was prepared following the method Ni(COD) (2.00 g, 7.27 mmol) was dissolved in 100 mL of Klabunde et al., Organometallics, 1985, 3,571. of toluene and cooled to -30°C. To this solution was added a toluene solution (50 ml) of 2-(diphenylphosphino)benzoic Catalyst Component Y acid (2.22g, 7.27 mmol). The mixture was stirred at -30°C. 50 Synthesis of (CH)(CH3)-N-NiCl for 30 min. and then warmed to -10° C. and stirred for 1 (CH)(C2H5)-N-NiCl, was prepared by reacting hour. To this mixture was added triphenylphosphine (2.03 g, NiCl2.6HO with 2 equivalents of tridodecylmethylammo 7.27 mmol) in 50 ml of toluene. The mixture was stirred at nium chloride in absolute ethanol and removing the Solvent. room temperature for one hour. The Solvent was removed in A light blue oil was obtained in 100% yield. vacuo to give a light yellow-brown solid. Yield of crude 55 product was 2.87 g (61%). Catalyst Component Z. Synthesis of (EtN)NiCl Catalyst Component S (EtN)NiCl, was prepared by reacting NiCl2(dime) Synthesis of Ni(PhC(O)CHPPh2)(Ph)(pyridine) with 2 equivalents of tetraethylammonium chloride in anhy This compound was Synthesized using a procedure pub 60 drous dimethoxyethane and removing the Solvent. A light lished previously in J. Polym. Sci. 1987, 25, 1989. blue powder was obtained in 100% yield. Catalyst Component T Arylating Agent B(C6F5).3H2O Synthesis of Ni(PhC(O)CHPPh)(Ph)(CH=PPh.) The Synthesis of reported here is based on a prior publi This compound was Synthesized using a procedure pub 65 cation (see U.S. Pat. No. 5,296,433, 1994). A 3.15 wt % lished previously in Angew. Chem., Int. Ed. Engl. 1985, 24, solution of B(C6F5) in Isopar(BE (50 ml, 2.22 mmol) was 599. placed in a 200 ml Kjeldahl flask equipped with a magnetic US 6,232,417 B1 S3 S4 stir bar. Approximately 50 ml of cyclohexane was added to polymer was 1.5 g (75%). The presence of the ester-bearing this Solution followed by 3 equiv of deoxygenated, dem monomer in the polymer was verified by infra-red analysis ineralized water (0.120 ml, 6.67 mmol), which resulted in which showed strong bands at 1728 cm (C=O stretch), precipitation of a white, microcrystalline Solid. The Slurry 1251 cm (C-O-C stretch) and 1369 and 1392 cm was stirred for 30 m, the Solvent was decanted, and the (characteristic of t-butyl groups) and the absence of uncon resulting solid was dried in vacuo. Yield, 0.826 g (66%). 'F verted monomer (proton NMR). The polymer was found to NMR (CD): -134.7 (apparent d, 2F), -1547 (apparent t, have a molecular weight (Mw) of 22,500. Thermogravimet 1F), -162.6 (apparent t, 2F). FI-MS: m/z 512M"), evi ric analysis (TGA) under nitrogen (heating rate 10 C. per dently loSS of water occurred in mass spectrometer. IR minute) showed the polymer to be thermally stable to about (Nujol):3666 m, 3597 m, 3499 m, 2950sh, 2920s, 1647 m, 210 C. and then to exhibit approximately 28% weight loss 1602 m, 1520s, 1468 s, 1379 m, 1288 m, 1111 m, 1098 m, by 260° C. (indicating clean loss of the t-butyl groups as 969 s, 859 w, 797 w, 771 w, 676 w, 614 w. isobutene to afford the homopolymer of 5-norbornene carboxylic acid) and then degradation of the polymer (90% Arylating Agent Zn(CFs). DME total weight loss) at around 400° C. This Synthesis method is a modification of the procedures 15 EXAMPLE 2 outlined by D. Naumann and H. Lange, Journal of Fluorine To a 50 ml glass vial equipped with a Teflon(R) coated stir Chemistry, Volume 26, 1984, pages 435-444. bar was added norbornene (0.8 g., 8.6 mmol), 1,2- Iodopentafluorobenzene, CFSI, (5.88 g, 20 mmoles) and dichloroethane (8 ml) and the t-butylester of 5-norbornene dimethoxyethane (0.9012 g, 10 mmoles) were mixed carboxylic acid (carbo-t-butoxynorbornene) (0.2g, 1 mmol, together in a glass vial and cooled to -30°C. To this solution exoendo 44/56). To this stirred solution at ambient tem was added a quantity of diethylzinc (1.235 g, 10 mmoles) perature was added nickel ethylhexanoate (3 umol), trisper that had also been cooled to -30°C. The reaction mixed was fluorophenylboron (23 umol) and triethylaluminum (27 Slowly warmed to room temperature. The reaction vessel almol). There ensued an immediate reaction with white was Scraped with the tip of a glass pipette and crystallization polymer precipitating from Solution within less than 10 immediately occurred. The white powder was washed 3 25 Seconds. The reaction was allowed to run for 60 minutes times with pentane to remove the ethyl iodide reaction before the reactor contents were dissolved in cyclohexane product and the Zn(CFs) (dime) dried to a white microc and poured into an excess of methanol. The polymer was rystaline powder. Yield=72%. The Zn(CFS)-(dime) sample washed with exceSS methanol and dried overnight in a was analyzed by Hand 'F NMR spectroscopies and found vacuum oven at 80° C. The yield of copolymer was 0.9 g, to be pure. The thermal stability of Zn(CFS)-(dime) was (90%). The molecular weight of the copolymer was deter determined by performing a differential Scanning calorimet mined using GPC methods and found to be 535,000 (Mw) ric measurement at a temperature ramping rate of 20 with a polydispersity of 4.7. C./min. This method provided a sharp melting point at 108 C. and indicated no decomposition below 300° C. EXAMPLE 3 35 To a 50 ml glass vial equipped with a Teflon(R) coated stir Arylating Agent Zn(2,4,6-tris(trifluoromethyl) bar was added the t-butylester of 5-norbornene-carboxylic phenyl) acid (carbo-t-butoxynorbornene) (2.2 g, 11.3 mmol, exo, Zn(2,4,6-tris(trifluoromethyl)phenyl) was prepared by a endo 44/56). To this stirred monomer at ambient temperature variation of the orginal literature Synthesis given by F. was added a catalyst Solution prepared by adding 40 m-allylpalladium chloride dimer (29 mg, 74 umol) in Edelmann et al., Organometallics, Volume 11, 1992, pages dichloroethane (6 ml) to silver tetrafluoroborate (61 mg,311 192-5. ZnCl was added to a freshly prepared sample of umol) in dichloroethane (6 ml) for 30 minutes and then 2,4,6-tris(trifluoromethyl)phenyllithium in diethyl ether. filtering through a micropore filter (to remove the precipi After refluxing for 6 hours the solvent was removed and the tated silver chloride). The reaction was allowed to run for 36 Solids extracted with toluene. After removal of the lithium 45 chloride the solvent is removed to yield an off-white solid. hours at which time the mixture had gelled to form a clear In our hands, the vacuum distillation of the crude was yellow gel. Upon adding the gel to exceSS methanol the deemed unnecessary and the white crystalline product was polymer precipitated as a white powder. The polymer was washed with excess methanol and dried. The yield of recrystallized from pentane at -35° C. Yield=53%. The polymer was 1.4 g (64%). The presence of the ester-bearing product of Zn(2,4,6-tris(trifluoromethyl)phenyl) was char 50 monomer in the polymer was verified by infra-red analysis acterized by H and 'F NMR spectroscopies. which showed strong bands at 1728 cm (C=O stretch), EXAMPLE 1. 1251 cm (C-O-C stretch) and 1369 and 1392 cm (characteristic of t-butyl groups) and the absence of uncon To a 50 ml glass vial equipped with a Teflon(R) coated stir verted monomer or carboxylic acid functionality (proton bar was added the t-butylester of 5-norbornene-carboxylic 55 NMR and IR). The polymer was found to have a molecular acid (carbo-t-butoxynorbornene) (2.0 g, 10.3 mmol, exo, weight (Mw) of 54,100. Thermogravimetric analysis (TGA) endo 44/56). To this stirred monomer at ambient temperature under nitrogen (heating rate 10 C. per minute) showed the was added a catalyst Solution prepared by adding polymer to be thermally stable to about 210 C. and then to m-allylpalladium chloride dimer (38 mg, 103 umol) in exhibit approximately 29% weight loss by 250 C. chlorobenzene (5 ml) to silver hexafluoroantimonate (99 60 (indicating clean loss of the t-butyl groups as isobutene to mg, 290 umol) in chlorobenzene (5 ml) for 30 minutes and afford the homopolymer of 5-norbornene-carboxylic acid) then filtering through a micropore filter (to remove the and then degradation of the polymer (80% total weight loss) precipitated Silver chloride). The reaction was allowed to run at around 400° C. for 36 hours at which time the mixture had gelled to form a clear yellow gel. Upon adding the gel to exceSS methanol the 65 EXAMPLE 4 polymer precipitated as a white powder. The polymer was To a 100 ml glass vial equipped with a Teflon(R) coated stir washed with excess methanol and dried. The yield of bar was added norbornene (1.16 g, 12.3 mmol), 1,2- US 6,232,417 B1 SS S6 dichloroethane (50 ml) and the t-butylester of 5-norbornene dichloroethane (50 ml) and the t-butylester of 5-norbornene carboxylic acid (carbo-t-butoxynorbornene) (0.6 g., 3.1 carboxylic acid (carbo-t-butoxynorbornene) (2 g, 10.3 mmol, exoendo 44/56). To this stirred solution at ambient mmol, exo,endo mixture). To this stirred Solution at ambient temperature was added palladium bis(2,2,6,6-tetramethyl-3, temperature was added a catalyst Solution prepared by 5-pentanedionate) (31 umol) and tris(perfluorophenyl)boron 5 reacting m-allylpalladium chloride dimer (10 mg, 27.3 (279 umol). The reaction was allowed to run for 16 hours umol) with silver hexafluoroantimonate (19.6 mg, 57 umol) before the reactor contents were poured into an excess of in 1,2-dichloroethane (3 ml) for 30 minutes and then filtering methanol. The polymer was washed with exceSS methanol through a micropore filter. The reaction was allowed to run and dried overnight in a vacuum oven at 80°C. The yield of for 20 hours before the reactor contents were poured into an copolymer was 0.54 g (31%). excess of methanol. The polymer was washed with exceSS methanol and dried. The yield of copolymer was 4.15g. The EXAMPLE 5 molecular weight of the copolymer was determined using To a 50 ml glass vial equipped with a Teflon(R) coated stir GPC methods and found to be 618,000 (Mw) with a poly bar was added the t-butylester of 5-norbornene-carboxylic dispersity of 7.1. acid (carbo-t-butoxynorbornene) (4.4 g, 22.7 mmol, exo, 15 endo 44/56). To this stirred monomer at ambient temperature EXAMPLE 8 was added a catalyst Solution prepared by adding To a 100 ml glass vial equipped with a Teflon(R) coated stir m-allylpalladium chloride dimer (41.5 mg, 113 umol) in bar was added norbornene (3.75 g, 39.8 mmol), 1,2- dichloroethane (7 ml) to silver tetrafluoroborate (42 mg, 215 dichloroethane (50 ml) and the t-butylester of 5-norbornene umol) in dichloroethane (7 ml) for 30 minutes and then carboxylic acid (carbo-t-butoxynorbornene) (2 g, 10.3 filtering through a micropore filter (to remove the precipi mmol, exo,endo mixture). To this stirred Solution at ambient tated silver chloride). The reaction mixture was then warmed temperature was added palladium ethylhexanoate (12 umol, in an oil bath to 75 C. After 90 minutes it was observed that tris(perfluorophenyl)boron (108 umol) and triethylalumi the mixture had Solidified to a grey polymeric mass. The num (120 umol). The reaction was allowed to run for 72 mass was dissolved in acetone to afford a dark colored 25 hours before the reactor contents were poured into an exceSS Solution. Gaseous carbon monoxide was bubbled through of methanol. The polymer was washed with excess methanol the Solution for 30 minutes resulting in copious amounts of and dried, redissolved in chlorobenzene and reprecipitated a finely divided black precipitate (metallic palladium and with an excess of methanol, filtered, and washed with possibly other catalyst residues). The precipitate was methanol before finally drying in a vacuum Oven overnight removed via centrifugation, and this process was repeated at 80°C. The yield of copolymer was 1.66 g. The molecular two more times. Finally the resulting colorleSS Solution was weight of the copolymer was determined using GPC meth filtered through a 0.45 micron microdisc and the polymer ods and found to be 194,000 (Mw) with a polydispersity of was precipitated by adding the acetone Solution to an excess 2.3. The presence of the ester-bearing monomer in the of hexane. The white polymer was separated using a cen copolymer was verified by infra-red analysis which showed trifuge and then dried overnight to afford the copolymer as 35 bands at 1730 cm (C=O stretch) and 1154 cm a white powder (2.21 g, 50%). Thermogravimetric analysis (C-O-C stretch) and the absence of unconverted mono (TGA) under nitrogen (heating rate 10° C. per minute) mer (proton NMR). showed the polymer to be thermally stable to about 210 C. and then to exhibit approximately 28% weight loss by 260 EXAMPLE 9 40 C. (indicating clean loss of the t-butyl groups as isobutene To a 100 ml glass vial equipped with a Teflon(R) coated stir to afford the homopolymer of 5-norbornene-carboxylic acid) bar was added 1,2-dichloroethane (25 ml) and the and then degradation of the polymer (90% total weight loss) t-butylester of 5-norbornene-carboxylic acid (carbo-t- at around 400 C. The molecular weight was observed to be butoxynorbornene) (10g, 51.5 mmol, exoendo mixture). To Mn=3,300 g/mole and Mw-6,900 g/mole (GPC in THF, this stirred Solution at ambient temperature was added a polystyrene Standards). 45 catalyst Solution prepared by reacting m-allylpalladium chloride dimer (82 mg, 223 umol) with silver hexafluoro EXAMPLE 6 antimonate (200 mg, 581 umol) in 1,2-dichloroethane (10 To a 50 ml glass vial equipped with a Teflon(R) coated stir ml) for 30 minutes and then filtering through a micropore bar was added the pure exo isomer of the t-butylester of 50 filter. The reaction was allowed to run for 48 hours before 5-norbornene-carboxylic acid (carbo-t-butoxynorbornene) the reactor contents were poured into an excess of methanol. (0.6 g). To this stirred monomer at ambient temperature was The polymer was washed with exceSS methanol and dried. added a catalyst Solution prepared by adding m-allyl-pal The yield of homopolymer was 4.5 g. ladium chloride dimer (30 mg) in dichloroethane (10 ml) to EXAMPLE 10 silver hexafluoroantimonate (50 mg) in dichloroethane (20 55 ml) for 30 minutes and then filtering through a micropore To a 100 ml glass vial equipped with a Teflon(R) coated stir filter (to remove the precipitated silver chloride). The reac bar was added 1,2-dichloroethane (50 ml), the t-butylester of tion was allowed to run for 15 hours at which time the 5-norbornene-carboxylic acid (carbo-t-butoxynorbornene) mixture was added to exceSS methanol causing the polymer (5g, 25.8 mmol, exoendo mixture), norbornene (0.82g, 8.7 to precipitate as a white powder. The polymer was washed 60 mmol) and 5-triethoxysilylnorbornene (0.47 g, 1.8 mmol). with excess methanol and dried. The yield of polymer was To this Stirred Solution at ambient temperature was added a 0.5 g (85%). The polymer was found to have a molecular catalyst Solution prepared by reacting m-allylpalladium weight (Mw) of 46,900, and a polydispersity of 2.4. chloride dimer (47.2 mg, 128 umol) with silver tetrafluo EXAMPLE 7 roborate (138 mg, 700 umol) in 1,2-dichloroethane (10 ml) 65 for 30 minutes and then filtering through a micropore filter. To a 100 ml glass vial equipped with a Teflon(E) coated stir The reaction was allowed to run for 48 hours before the bar was added norbornene (4.01 g, 42.6 mmol), 1,2- reactor contents were poured into an excess of methanol. US 6,232,417 B1 57 58 The polymer was washed with exceSS methanol and dried. EXAMPLE 13 The yield of terpolymer was 5.3 g. The molecular weight of the copolymer was determined using GPC methods and To a 25 ml glass vial equipped with a Teflon(R) coated stir found to be 39,900 (Mw) with a polydispersity of 3.2. bar was added 2 g (7.94 mmole) of pure of bicyclo[2.2. hept-5-ene-eXO,-2-t-butyl, exo-3-methyl ester of dicarboxy EXAMPLE 11 lic acid followed by 15 ml of freshly distilled methylene chloride and 10 ml of methanol, and the Solution was To a 50 ml glass vial equipped with a Teflon(R) coated stir degassed under argon atmosphere. A 10 ml glass Vial bar was added 7.25 g (37.5 mmole) of the t-butylester of equipped with a Teflon(E) coated Stir bar was charged with norbornene, 1.9 g (12.5 mmole) of methylester of 0.00588 g (0.0158 mmol) of m-allylpalladium chloride norbornene, 50 ml of freshly distilled dichloroethane and the dimer in a monomer to catalyst ratio of 500/1 and 2 ml of Solution was degassed under argon atmosphere. A 10 ml methylene chloride. Into another 10 ml glass vial was glass vial equipped with a Teflon(E) coated Stir bar was charged with 0.0108 g (0.0312 mmol) of silver hexafluoro charged with 0.0365 g (0.1 mmol) of m-allylpalladium antimonate and 2 ml of methylene chloride. The catalyst chloride dimer (to ultimately give a monomer to catalyst 15 Solution was prepared by mixing the m-allylpalladium ratio of 500/1) and 2 ml of dichloroethane. Into another 10 chloride dimer Solution with silver hexafluoroantimonate ml glass vial was charged with 0.0344 g (0.1 mmol) of silver Solution inside the dry box. Immediate precipitation of the hexafluoroantimonate and 2 ml of dichloroethane. The cata silver chloride Salt was observed, which was filtered, to lyst Solution was prepared by mixing the allylpalladium obtain a clear yellow solution. The active yellow catalyst chloride dimer Solution with silver hexafluoroantimonate Solution was added to the monomer Solution via a Syringe at Solution inside the dry box. Immediate precipitation of the 50° C. and the reaction mixture was allowed to stir for 16 silver chloride Salt was observed, which was filtered, to hours at room temperature. No appreciable increase in obtain a clear yellow solution. The active yellow catalyst Viscosity was observed and the Solution was filtered through Solution was added to the monomer Solution via a Syringe and the reaction mixture was allowed to stir for 20 hours at a 0.5u filter, concentrated using a rotovap. The thick Solution 60° C. No appreciable increase in viscosity was observed, 25 was dissolved in methanol and precipitate into methanol/ but Solids had precipitated in the Solution, the Solution was water mixture to obtain a white solid yield (65%). The cooled, concentrated in a rotovap, and precipitated into molecular weight was observed to be Mn=10,250 g/mole hexane to obtain a white polymer. Yield=2.3 g, 26%. The and Mw-19,700 g/mole (GPC in the THF, polystyrene polymer was dried in vacuum at room temperature and standards). H NMR indicates the presence of both methyl analyzed using GPC for molecular weight. GPC was and t-butyl ester of norbornene. obtained in THF using polystyrene standards. The molecular weight was observed to be Mn=1950 g/mole and Mw =3150 EXAMPLE 1.4 g/mole. H NMR indicated the presence of both methyl and To a 25 ml glass vial equipped with a Teflon(R) coated stir t-butyl ester of norbornene and also a Small amount of the 35 bar was added 3.06 g (12.8 mmole) of pure of bicyclo2.2.1 t-butyl hydrolyzed product, the acid. hept-5-ene-eXO,eXO-2,3-dicarboxylic acid diethyl ester, 2.5g EXAMPLE 12 (12.8 mmole) of t-butylester of norbornene, followed by 15 ml of freshly distilled methylene chloride and 10 ml of To a 50 ml glass vial equipped with a Teflon(R) coated stir methanol, and the Solution was degassed under argon atmo bar was added 2.42 g (12.5 mmole) of t-butylester of 40 Sphere. A 10 ml glass Vial equipped with a Teflon(E) coated norbornene, 5.7 g (37.5 mmole) of methylester of stir bar was charged with 0.0188 g (0.052 mmol) of allylpal norbornene, 50 ml of freshly distilled dichloroethane, and ladium chloride dimer (to give a monomer to catalyst ratio the Solution was degassed under argon atmosphere. A 10 ml of 500/1) and 2 ml of methylene chloride. Into another 10 ml glass vial equipped with a Teflon(E) coated Stir bar was glass vial was charged with 0.0357 g (0.104 mmol) of silver charged with 0.0365 g (0.1 mmol) of allylpalladium chloride 45 hexafluoroantimonate and 2 ml of methylene chloride. The dimer in a monomer to catalyst ratio of 500/1 and 2 ml of catalyst Solution was prepared by mixing the allylpalladium dichloroethane. Into another 10 ml glass vial was charged chloride dimer Solution with silver hexafluoroantimonate with 0.0344 g (0.1 mmol) of silver hexafluoro antimonate Solution inside the dry box. Immediate precipitation of the and 2 ml of dichloroethane. The catalyst solution was silver chloride Salt was observed, which was filtered, to prepared by mixing the allylpalladium chloride dimer Solu 50 obtain a clear yellow solution. The active yellow catalyst tion with silver hexafluoroantimonate solution inside the dry Solution was added to the monomer Solution via a Syringe at box. Immediate precipitation of the Silver chloride Salt was 50° C. and the reaction mixture was allowed to stir for 16 observed, which was filtered, to obtain a clear yellow hours at room temperature. No appreciable increase in Solution. The active yellow catalyst Solution was added to Viscosity was observed and the Solution was filtered through the monomer Solution via a Syringe and the reaction mixture 55 a 0.5u filter, concentrated using a rotovap. The resulting was allowed to stir for 20 hours at 60° C. No appreciable Viscous Solution was dissolved in methanol and precipitated increase in Viscosity was observed, but Solids had precipitate into methanol/water mixture to obtain a white solid yield in the Solution, the Solution was cooled, concentrated in a (23%). The molecular weight was observed to be Mn=15, rotovap, and precipitated into hexane to obtain a white 700 g/mole and Mw =32,100 g/mole (GPC in THF, polysty polymer. Yield=2.05 g, 25%. The polymer was dried in 60 rene standards). "H NMR indicates the presence of both Vacuum at room temperature and analyzed using GPC for methyl and t-butyl ester of norbornene. Thermogravimetric molecular weight. GPC was obtained in THF using Poly analysis (TGA) under nitrogen (heating rate 10 C./min.) Styrene Standards. The molecular weight was observed to be showed the polymer to be thermally stable to about 155 C. Mn=1440 g/mole and Mw-2000 g/mole. H NMR indicated and then to exhibit approximately 20 wt.% loss by 290 C. the presence of both methyl and t-butyl ester of norbornene 65 (indicating clean loss of the t-butyl groups as isobutylene to and also a Small amount of the t-butyl hydrolyzed product, afford the homopolymer of 5-norbornene-carboxylic acid) the acid. and then degradation of the polymer at around 450° C. US 6,232,417 B1 59 60 EXAMPLE 1.5 of pure exo t-butyl half ester of norbornene dicarboxylic Synthesis of Bicyclo[2.2. hept-5-ene-exo, exo-2,3- acid and 6.05 g (0.0408 mole) of trimethyloxonium tet dicarboxylic Acid Diethyl Ester rafluoroborate. The flask was stoppered, and to this 100 ml The exo, eXo diethyl ester of norbornene was Synthesized of dichloromethane was added via a cannula under argon from exo-5-norbornene-2,3-dicarboxylic acid. The exo iso atmosphere. The rubber Stopper was replaced with a con mer was prepared by thermal conversion of the endo-5- denser under argon atmosphere and the other neck was fitted norbornene-2,3-dicarboxylic anhydride at 190° C. followed with an additional funnel. To the additional funnel was by recrystallization from toluene Several times to obtain pure exo-5-norbornene-2,3-dicarboxylic anhydride. Part of the added 7.3 ml of ethyldiisopropyl amine and it was allowed exo-anhydride was hydrolyzed in boiling water and the to drip into the reaction vessel slowly. Small exotherm was Solution was cooled to obtain pure diacid in almost quanti observed and the solution was observed to reflux lightly. tative yield. The diacid was converted to the diethyl ester After the complete addition of the amine, the Solution was using triethyloxonium Salts as shown below: allowed to stand at room temperature for 15 hours. Work-up A 250 ml, three necked, round bottomed flask with a is initiated by extracting the reaction mixture with three 50 magnetic Stirring bar was charged with 16.0 g (0.0824 mole) ml portion of HCl solution, followed by three 50 ml extrac of pure exo norbornene dicarboxylic acid and 35 g (0.1846 15 tions with sodium bicarbonate and finally washed two times mole) of triethyloxonium tetrafluoroborate. The flask was with water. The organic Solution was dried over magnesium stoppered, and to this 300 ml of dichloromethane was added Sulfate, treated with carbon black, filtered, concentrated on via a cannula under argon atmosphere. The rubber Stopper a rotary evaporator. A colorleSS liquid was obtained which was replaced with a condenser under argon atmosphere and started to crystallize. The Solid was washed with cold the other neck was fitted with an additional funnel. To the pentane and the pentane Solution was concentrated in a additional funnel was added 35 ml of ethyldiisopropylamine rotovap to obtain a colorless liquid which on cooling crys and it was allowed to drip into the reaction vessel Slowly. A tallized. Yield 5.1 g. Small exotherm was observed and the Solution was allowed "H NMR (CDC1): d=1.45 (9H; s, t-butyl), d=1.47 (1H), to reflux lightly. After the complete addition of the amine, d=2.15 (1H), d=2.54 (2H; m, CHCOO), d=3.07 (2H; the Solution was allowed to Stand at room temperature for 15 25 s,bridge head), d=3.65 (3H; S, CH), d=6.19 (2H; S, C=C). hours. Work-up is initiated by extracting the reaction mix ture with three 50 ml portions of HCl solution, followed by EXAMPLE 1.8 three 50 ml extractions with sodium bicarbonate and finally To a 50 ml glass vial equipped with a Teflon(R) coated stir washed two times with water. The organic Solution was dried bar was added 5-norbornene-carboxylic acid (2.0 g, 14.5 over magnesium Sulfate, treated with carbon black, filtered, mmol, exo,endo mixture) and dichloroethane (20 ml). To concentrated on a rotary evaporator. Purification of the this stirred mixture at ambient temperature was added a residue by distillation at 110° C. provides 15 g (75%) of pure catalyst Solution prepared by adding m-allylpalladium chlo exo-diethyl ester of norbornene as a colorless, Viscous, fruity ride dimer (6 mg, 16 umol) in dichloroethane (5 ml) to silver Smelling liquid. hexafluoroantimonate (50 mg, 146 umol) in dichloroethane "H NMR (CDC1): d=1.22 (3H; t, CH), d=1.47 (1H), 35 (5 ml) for 30 minutes and then filtering through a micropore d=2.15 (1H), d=2.58 (2H; s, CHCOO), d=3.07 (2H; s,bridge filter (to remove the precipitated silver chloride). The reac head), d=4.10 (2H; m, CH), d=6.19 (2H; s, C=C), FI-MS tion was allowed to run for 18 hours at which time the (DIP)=M"(238). mixture had gelled to form a clear yellow gel. Upon adding EXAMPLE 16 the gel to exceSS hexane the polymer precipitated as a white Synthesis of Bicyclo2.2.1]hept-5-ene-exo-2-t-butyl ester, 40 powder. The polymer was washed with exceSS hexane and exo-3-carboxylic Acid dried. The yield of polymer was 1.2 g (60%). The polymer To a 50 ml Single necked round bottom flask equipped was found to have a molecular weight (M) of 22,000 and with a Teflon(R) coated stir bar was added 1.5 g (9.15 mmole) a polydispersity of 2.3. of pure exo-Nadicanhydride, 10 ml of freshly distilled Upon adding a portion of this polymer (0.5 g) to an 0.1 N methylenechloride, 20 mL oft-butanol (0.209 moles). To the 45 stirred aqueous solution of KOH (10 ml) the polymer solution was added 7.5 g (0.061 moles) of dimethylamino immediately dissolved to give a non-viscous, colorleSS Solu pyridine and the solution was refluxed at 75 C. for 8 hours. tion. This demonstrates the base developability of these Initially the anhydride was not soluble, but over the period materials since none of the homopolymers of the t-butylester of time the Solids had dissolved and the Solution had turned 50 of 5-norbornenecarboxylic acid showed any tendency to brown. The reaction was cooled, concentrated in a rotovap dissolve under the Same conditions. to remove methylene chloride and the thick Solution was added slowly into acidified water (HCl). The solid that EXAMPLE 1.9 precipitated out was filtered, washed with water and further The Pinner synthesis of ortho esters is a two-step synthe dissolved in ether treated with MgSO, followed by carbon 55 Sis: black and the Solution was filtered over Celite. The ether was Step 1. removed over a rotovap to obtain a white solid (yield 8.5 g. Synthesis of Imidic Ester Hydrochloride 60%). The reaction was carried out in a 1 L two-neck round "H NMR (CDC1): d=1.47 (9H; s, t-butyl), d=1.60 (1H), bottom flask equipped with a Stirrer, an oil bubbler, and a d=2.15 (1H), d=2.58 (2H; m, CHCOO), d=3.07 (2H; 60 tube with anhydrous calcium chloride. The following s,bridge head).d=6.19 (2H; s, C=C), d=10.31 (1H; broad, reagents were placed in the flask: 100 g (0.84 mol) nor COOH). bornene carbonitrile (NB-CN), 37 ml (0.91 mol) anhydrous EXAMPLE 1.7 methanol, and 200 mL anhydrous diethyl ether. The flask Synthesis of Bicyclo2.2.1]hept-5-ene-exo-2-t-butyl,exo-3- was placed into the ice-water bath and 61 g (1.67 mol) dry methyl Ester of Dicarboxylic Acid 65 hydrogen chloride was bubbled through the mixture with A 100 ml, three necked, round bottomed flask with a Stirring during 1.5 hours. The flask was placed overnight in magnetic stirring bar was charged with 9.7 g (0.0408 mole) a refrigerator at 0°C. In the morning, the mixture solidified US 6,232,417 B1 61 62 into a “cake”. It was broken into pieces and additional 200 (3.98 g., 0.0205 mol) and 50 ml of toluene. A solution of the ml of diethyl ether were added. The flask was kept in nickel catalyst toluene complex of bisperfluorophenyl refrigerator for another 10 days with occasional Stirring. At nickel, (toluene)Ni(CFS) was prepared in the dry box by the end of this period, precipitated imidic ester hydrochlo dissolving 0.0991 g (0.2049 mmol) of (toluene)Ni(CF) in ride was filtered by Suction and washed 5 times with ~300 15 ml of toluene. The active catalyst solution was added to mL diethyl ether. Ca. 20 g of unreacted NB-CN were the monomer Solution via a Syringe at ambient temperature. recovered from filtrate. The reaction was allowed to stir for 6 hours at room Yield of imidic ester hydrochloride-76% (120 g, 0.64 temperature. The solution was diluted with toluene and the mol). Structure of the product was confirmed by H NMR polymer was precipitated in exceSS methanol. The precipi SpectroScopy. tated polymer was filtered, washed with acetone and dried Step 2 overnight under vacuum. The isolated yield of polymer was Synthesis of Ortho Ester 4.16 g (52%). The polymer was characterized using GPC for In a 0.5 L flask, 56.7 g (0.30 mol) imidic ester molecular weight. Mn=22,000 and Mw =58,000. The NMR hydrochloride, 37 ml (0.91 mol) anhydrous methanol, and analysis of the copolymer indicated presence of 50 mole % 250 ml anhydrous petroleum ether were placed. The reaction 15 of the t-butyl groups. IR analysis of the copolymer indicated mixer was kept at room temperature for 5 days with occa the absence of acid groups. Sional Stirring. Precipitated ammonium chloride was filtered off and washed with petroleum ether three times. Filtrate and EXAMPLE 23 washes were combined, petroleum ether was distilled off, To a 50 ml glass vial equipped with a Teflon(R) coated stir and product was fractionally distilled in vacuum. A fraction bar was added bicyclo2.2.1]hept-5-ene-2-methylbutylcar with the boiling point 68-69 C./3 mm Hg was collected. bonate (17.15g, 0.0764 mol) and t-butylester of norbornene Yield–50% (30 g, 0.15 mol). According to H NMR (14.85g., 0.0764 mol) and 72 ml of toluene. A solution of the spectrum, the product is 97+% 5-norbornene-2- nickel catalyst toluene complex of bisperfluorophenyl trimethoxymethane (ortho ester). nickel, (toluene)Ni(CFS) was prepared in the dry box by 25 EXAMPLE 2.0 dissolving 0.3699 g (0.7644 mmol) of (toluene)Ni(CFs). in 15 ml of toluene. The active catalyst Solution was added To a solution of 2.16 g (10.9 mmol) CHC(OCH) to the monomer Solution via a Syringe at ambient tempera (norbornene trimethylorthoester) in 16 ml 1,2- ture. The reaction was allowed to stir for 6 hours at room dichloroethane, was added a Solution of the reaction product temperature. The solution was diluted with toluene and the of mixing 1 mole of allylpalladium chloride dimer with 2 polymer was precipitated in exceSS methanol. The precipi moles of Silver hexafluoroantimonate in dichloroethane and tated polymer was filtered, washed with acetone, and dried filtering off the resulting Silver chloride precipitate. The overnight under vacuum. The isolated yield of polymer was amount of catalyst added corresponded to 0.08 mmol of 17.53 (54%). The polymer was characterized using GPC for palladium dissolved in 2 ml dichloroethane. The stirred molecular weight. Mn 22,000 and Mw-58,000. The NMR reaction mixture was placed in an oil-bath at 70° C. and 35 analysis of the copolymer indicated presence of 54 mole % allowed to react for 20 hours. of the t-butyl groups. IR analysis of the copolymer indicated At the end of the reaction, 2 ml methanol was added, the absence of acid groups. Solvents removed on a rotary evaporator, and polymer dried EXAMPLE 24 to a constant weight in vacuum. 40 Yield–1.28 g (60%). To a 50 ml glass vial equipped with a Teflon(R) coated stir bar was added t-butyl ester of norbornene (29.92 g, 0.154 EXAMPLE 21 mol), followed by dried maleic anhydride (15.10 g, 0.154 To a 50 ml glass vial equipped with a Teflon(R) coated stir mol) and 90 ml of chlorobenzene. This mixture was bar was added bicyclo2.2.hept-5-ene-2-methyl acetate 45 degassed three times to remove any trace oxygen. The (18.44 g., 0.1109 mol) and t-butylester of norbornene (21.55 reaction mixture was then heated to 80 C. A degassed g, 0.1109 mol) and 75 ml of toluene. A solution of the ickel benzoyl peroxide solution consisting of 0.9948 g (0.04 mol) catalyst toluene complex of bisperfluorophenyl nickel, benzoyl peroxide free radical initiator in 10 ml of chloroben (toluene)Ni(CF) was prepared in the dry box by dissolv Zene was added to the reaction mixture with a dry Syringe. ing 0.5367 g (1.109 mmol) of (toluene)Ni(CF) in 15 ml 50 The reaction was left to stir for 19 hours. After the reaction, of toluene. The active catalyst Solution was added to the the polymer Solution was poured directly into hexane to monomer Solution via a Syringe at ambient temperature. The precipitate the polymer. A white precipitate was obtained. reaction was allowed to Stir for 6 hours at room temperature. The precipitated polymer was then Stripped out of any The solution was diluted with toluene and the polymer was unreacted maleic anhydride that may have been present. The precipitated in exceSS methanol. The precipitated polymer 55 polymer was then dried overnight in a vacuum oven at room was filtered, washed with acetone, and dried overnight under temperature. The weight of dry polymer obtained was 20.62 vacuum. The isolated yield of polymer was 24.9 g (63%). g, giving a 45.8% yield. The polymer was characterized The polymer was characterized using GPC for molecular using GPC for molecular weight. Mn=4,200 and Mw =8,800. weight. Mn=21,000 and Mw =52,000. The NMR analysis of The NMR analysis of the copolymer indicated presence of the copolymer indicated presence of 51 mole % of the 60 the t-butyl groups. IR analysis of the copolymer indicated t-butyl groups. IR analysis of the copolymer indicated the the presence of both t-butyl and maleic anhydride groups. absence of acid groups. EXAMPLE 25 EXAMPLE 22 To a 50 ml glass vial equipped with a Teflon(R) coated stir To a 50 ml glass vial equipped with a Teflon(R) coated stir 65 bar was added bicyclo2.2.1]hept-5-ene-2-methyl acetate bar was added bicyclo2.2.1]hept-5-ene-2-methyl ethylcar (13.3 g, 0.0799 mol), t-butyl ester of norbornene (15.70 g, bonate (4.03 g, 0.0205 mol) and t-butylester of norbornene 0.0808 mol), followed by dried maleic anhydride (15.85g, US 6,232,417 B1 63 64 0.162 mol) and 90 ml of chlorobenzene. This mixture was The copolymer was redissolved in toluene and passed degassed three times to remove any trace oxygen. The through a column of Silica gel with a resulting noticeable reaction mixture was then heated to 80° C. A degassed color (Ru) removal. The polymer was again precipitated in benzoyl peroxide solution consisting of 1.0438 g (0.041 exceSS MeOH rendering a pure white copolymer. mol) benzoyl peroxide free radical initiator in 10 ml of 5 chlorobenzene was added to the reaction mixture with a dry EXAMPLE 29 syringe. The reaction was left to stir for 19 hours. After the 50:50 Copolymer of t-BuNBEster/EtTDEster reaction, the polymer Solution was poured directly into To a 100 ml glass vial equipped with a magnetic Stirring hexane to precipitate the polymer. A white precipitate was bar and under a nitrogen atmosphere was added toluene (80 obtained. The precipitated polymer was then Stripped out of ml), t-butyl ester of norbornene carboxylic acid (3.9 g, 20 any unreacted maleic anhydride that may have been present. mmol) and ethyl ester of tetracyclododecene carboxylic acid The polymer was then dried overnight in a vacuum oven at (4.64 g, 20 mmol). To this stirred solution was added, at room temperature. The weight of dry polymer obtained was ambient temperature, a Solution of b is 21.89 g, giving a 48.7% yield. The polymer was character (tricyclohexylphosphine)benzylideneruthenium dichloride ized using GPC for molecular weight. Mn=3,000 and 15 (68 mg, 0.083 mmol) in 5 ml of toluene. After 2 hours ethyl Mw=6600. The NMR analysis of the copolymer indicated vinyl ether (0.030 ml, 0.31 mmol) was added and stirred 2 presence of the acetate and t-butyl groups. IR analysis of the hours. copolymer indicated presence of acetate, t-butyl and maleic The orange-amber Solution was passed through Silica gel anhydride groups. column to obtain a clear colorless Solution. The Solution was EXAMPLE 26 precipitated by addition of excess MeOH, collected by 50:50 Copolymer of t-BuNBEster/NB-COOH filtration and dried under vacuum. 6.54 g (77% yield) of To a 50 ml glass Vial equipped with a magnetic Stirring bar copolymer was recovered (Mw 244,000, Mn 182,000). The and under a nitrogen atmosphere was added the t-butyl ester glass transition temperature was measured using DSC meth of norbornene carboxylic acid (2 g, 10 mmol) and nor ods and determined to be 220 C. bornene carboxylic acid (1.38 g, 10 mmol). To this stirred 25 EXAMPLE 30 mixture was added, at ambient temperature,the initiator 50:50 Copolymer of t-BuNBEster/EtTDEster (t-butyl peroxide) (2.9 g) and the resulting mixture was To a 300 ml stainless steel reactor equipped with a heated to 130° C. and stirring was continued for 16 hours. mechanical Stirrer and containing nitrogen was added tolu The resulting polymer (soluble in both THF and toluene) ene (90 ml), t-butyl ester of norbornene carboxylic acid (3.9 was precipitated into hexane and filtered to afford the g, 20 mmol) and ethyl ester of tetracyclododecene carboxy product, which on drying weighed 2.91 g (86% conversion). lic acid (4.64 g, 20 mmol). To this stirred solution was The resulting solid polymer exhibited an Mw of 20,000, Mn added, at ambient temperature, a Solution of bis 3,000). IR, NMR and TGA analysis of the copolymers (tricyclohexylphosphine)benzylideneruthenium dichloride confirmed their composition to be random addition copoly (68 mg, 0.083 mmol) in 5 ml of toluene. After 2 hours ethyl mers of the two monomers. 35 vinyl ether (0.030 ml, 0.31 mmol) was added and stirred 16 EXAMPLE 27 hours. Hydrogen (350 psig) was added to reactor and the 50:50 Copolymer of t-BuNBEster/NB-MeNBEster temperature was maintained at 175 C. for 7 hours. Follow To a 50 ml glass Vial equipped with a magnetic Stirring bar ing reaction the Solution was passed through a Silica gel and under a nitrogen atmosphere was added the t-butyl ester column and the hydrogenated copolymer was isolated. NMR of norbornene carboxylic acid (2g, 10 mmol) and the methyl 40 methods were used to determine that the copolymer was ester of norbornene carboxylic acid (1.5g, 10 mmol). To this 95% hydrogenated (Mw 237,000, Mn 163,000). Stirred mixture was added, at ambient temperature,the ini tiator (t-butyl peroxide) (2.9 g) and the resulting mixture was EXAMPLE 31 heated to 130° C. and stirring was continued for 16 hours. 50:50 Copolymer of t-BuNBEster/EtTDEster The resulting polymer (Soluble in toluene) was precipitated 45 To a 300 ml stainless steel reactor equipped with a into methanol and filtered to afford the product, which on mechanical Stirrer and containing nitrogen was added tolu drying weighed 0.82 g (23% conversion). The resulting solid ene (90 ml), t-butyl ester of norbornene carboxylic acid (2.9 polymer exhibited an Mw of 35,000, Mn 6,000). IR, NMR g, 15 mmol) and ethyl ester of tetracyclododecene carboxy and TGA analysis of the copolymers confirmed their com lic acid (3.5g, 15 mmol). To this stirred solution was added, position to be random addition copolymers of the two 50 at ambient temperature, a Solution of b is OOCS. (tricyclohexylphosphine)benzylideneruthenium dichloride (50 mg, 0.060 mmol) in 5 ml of toluene. After 2 hours EXAMPLE 28 hydrogen (800 psig) was added to reactor and temperature 50:50 Copolymer of t-BuNBEster/EtTDEster maintained at 175 C. for 7 hours. Following reaction the To a 100 ml glass vial equipped with a magnetic Stirring 55 Solution was passed through Silica gel column and the bar and under a nitrogen atmosphere was added toluene (40 hydrogenated copolymer was isolated. NMR methods were ml), t-butyl ester of norbornene carboxylic acid (1.94 g, 10 used to determine that the copolymer was 96% hydroge mmol) and ethyl ester of tetracyclododecene carboxylic acid nated (Mw 278,000, Mn 172,000). (2.32 g, 10 mmol). To this stirred solution was added, at ambient temperature, a Solution of b is 60 EXAMPLE 32 (tricyclohexylphosphine)-benzylideneruthenium dichloride 50:50 Copolymer of t-BuNBEster/EtTDEster (34 mg., 0.042 mmol) in 5 ml of toluene. After 1 hour ethyl To a 100 ml glass vial equipped with a magnetic Stirring vinyl ether (0.015 ml, 0.156 mmol) was added and stirred 1 bar and containing nitrogen was added toluene (40 ml), hour. The polymer Solution was precipitated by addition to t-butyl ester of norbornene carboxylic acid (1.94 g, 10 excess MeOH, collected by filtration and dried under 65 mmol), ethyl ester of tetracyclododecene carboxylic acid vacuum. Recovered 3.46 g (81% yield) of copolymer was (2.32 g, 10 mmol) and 1-hexene (0.050 ml, 0.4 mmol). To recovered (Mw 221,000, Mn 133,000). this stirred Solution was added, at ambient temperature, a US 6,232,417 B1 65 66 Solution of bis(tricyclohexylphosphine) The Solution was precipitated by addition to exceSS benzylideneruthenium dichloride (34 mg., 0.042 mmol) in 5 methanol, collected by filtration and dried overnight at 80 ml of toluene. After 2 hours the polymer solution was added C. under vacuum. Approximately 5 g (59% yield) of poly to an excess of MeOH, collected by filtration and dried mer was recovered (Mw 30,000, Mn20,000). NMR methods under vacuum. 3.1 g (73% yield) of polymer was recovered were used to determine that the copolymer was greater than (Mw 35,000, Mn22,000). 99% hydrogenated. EXAMPLE 37 EXAMPLE 33 65:35 Copolymer of t-BuNBEster/EtTDEster 50:50 Copolymer of t-BuNBEster/EtTDEster To a 250 ml round bottomed flask equipped with a To a 100 ml glass vial equipped with a magnetic Stirring magnetic Stirring bar and containing nitrogen was added bar and containing nitrogen was added toluene (40 ml), toluene (160 ml), t-butyl ester of norbornene carboxylic acid t-butyl ester of norbornene carboxylic acid (1.94 g, 10 (10.1 g, 52 mmol), ethyl ester of tetracyclododecene car mmol), ethyl ester of tetracyclododecene carboxylic acid boxylic acid (6.5g, 28 mmol) and 1-hexene (0.176 ml, 1.4 (2.32 g, 10 mmol) and 1-hexene (0.275 ml, 2.2 mmol). To mmol). To this stirred solution was added, at ambient this stirred Solution was added, at ambient temperature, a temperature, a Solution of bis(tricyclohexylphosphine) Solution of bis(tricyclohexylphosphine) 15 benzylideneruthenium dichloride (131 mg, 0.160 mmol) in benzylideneruthenium dichloride (34 mg., 0.042 mmol) in 5 5 ml of toluene. After 16 hours ethyl vinyl ether (0.060 ml, ml of toluene. After 2 hours the polymer solution was added 0.62 mmol) was added and stirred 1.5 hours. The polymer to an excess of MeOH, collected by filtration and dried Solution was passed through Silica gel column to remove Rul. under vacuum. 3.45 g (81% yield) of polymer was recov The Solution was added to an excess of methanol, collected by filtration and dried under vacuum. 9.69 g (58% yield) of ered (Mw 8,000, Mn 6,000). polymer was recovered (Mw 42,000, Mn 31,000). DSC EXAMPLE 34 methods were used to measure the glass transition tempera 50:50 Copolymer of t-BuNBEster/EtTDEster ture (110° C.). To a 100 ml glass vial equipped with a magnetic Stirring 25 EXAMPLE 38 bar and containing nitrogen was added toluene (40ml), In a 100 ml glass vial containing nitrogen was dissolved t-butyl ester of norbornene carboxylic acid (1.94 g, 10 5.0 g of the polymer from Example 37 in THF (80 ml). The mmol), ethyl ester of tetracyclododecene carboxylic acid Solution was transferred to a 300 ml stainless steel reactor. (2.32 g, 10 mmol) and 1-hexene (0.62 ml, 5.0 mmol). To this 2.25 g of 5 wt % palladium on alumina catalyst (purchased Stirred Solution was added, at ambient temperature, a Solu from Aldrich) was added to reactor. The reactor was then tion of bis(tricyclohexylphosphine)benzylideneruthenium heated to 175 C. and pressurized with 800 psig hydrogen. dichloride (34 mg., 0.042 mmol) in 5 ml of toluene. After 2 Temperature and pressure were maintained for 9.5 hrs. The hours the polymer Solution was added to an excess of resulting polymer Solution was centrifuged and the colorless MeOH, collected by filtration and dried under vacuum. 2.75 Solution was separated and the polymer was precipitated in g (65% yield) of polymer was recovered. excess methanol. NMR methods showed the resulting 35 copolymer to be greater than 99% hydrogenated. EXAMPLE 35 EXAMPLE 39 50:50 Copolymer of t-BuNBEster/EtTDEster 50:50 Copolymer of t-BuNBEster/EtTDEster To a 100 ml glass vial equipped with a magnetic Stirring To a 100 ml glass vial equipped with a magnetic Stirring bar and containing nitrogen was added toluene (80 ml), bar and containing nitrogen was added toluene (80 ml), t-butyl ester of norbornene carboxylic acid (3.9 g, 20 mmol), 40 t-butyl ester of norbornene carboxylic acid (3.9 g, 20 mmol), ethyl ester of tetracyclododecene carboxylic acid (4.64 g, 20 ethyl ester of tetracyclododecene carboxylic acid (4.64 g, 20 mmol) and 1-hexene (0.088 ml, 0.7 mmol). To this stirred mmol) and 1-hexene (0.088 ml, 0.7 mmol). To this stirred Solution was added, at ambient temperature, a Solution of Solution was added, at ambient temperature, a Solution of bis(tricyclohexylphosphine)benzylideneruthenium dichlo bis(tricyclohexylphosphine)benzylideneruthenium dichlo ride (68 mg, 0.083 mmol) in 5 ml of toluene. After 2 hours 45 ride (68 mg, 0.084 mmol) in 5 ml of toluene. After 2 hours ethyl vinyl ether (0.030 ml, 0.31 mmol) was added and ethyl vinyl ether (30 ul) was added to the reaction to short stirred 2 hours. stop further reactions and the mixture was stirred for 1.5 The orange-amber polymer Solution was passed through hours. The polymer Solution was passed through a Silica gel silica gel column which removed the dark color (Ru). The column to remove Ru residues and the polymer was then solution was precipitated by addition to excess MeOH, 50 recovered as a clean white Solid by precipitating into metha collected by filtration and dried overnight at 80° C. under nol. The polymer was found to have an Mw of 46,600 (Mn vacuum. 2.6 g (30% yield) of polymer was recovered (Mw 33,700) and was fully characterized by IR, NMR and TGA 4,000, Mn 3,000). methods. EXAMPLE 36 55 EXAMPLE 40 50:50 Copolymer of t-BuNBEster/EtTDEster To a stainleSS Steel autoclave with an internal Volume of To a 300 ml stainless steel reactor equipped with a 300 ml was added ethyl 2-methyl-4-pentenoate (99 g, 0.7 mechanical Stirrer and containing nitrogen was added tolu mole) and freshly cracked cyclopentadiene (46.4 g., 0.7 ene (80 ml), t-butyl ester of norbornene carboxylic acid (3.9 mole). The stirred mixture was heated to 200° C. and left g, 20 mmol), ethyl ester of tetracyclododecene carboxylic 60 overnight. The reactor was then cooled and the contents acid (4.64 g, 20 mmol) and 1-hexene (0.088 ml, 0.7 mmol). removed. The resulting functionalized norbornene (NB To this stirred Solution was added, at ambient temperature, CHCH(CH)C(O)OCH) was purified by vacuum distil a Solution of bis(tricyclohexyl phosphine) lation and found to have a boiling point of about 46-7 C. benzylideneruthenium dichloride (68 mg, 0.042 mmol) in 5 at 0.02 mm Hg. The material was analyzed by GC methods ml of toluene. After 2 hours hydrogen (750 psig) was added 65 and found to have a purity of 98.4 to 99.3% (different to reactor and temperature maintained at 175 C. for 20 fractions). The isolated yield of high purity product was hours. around 33 g. US 6,232,417 B1 67 68 EXAMPLE 41 residues and allowed to evaporate. The resulting mixture 40:60 Copolymer of t-BuNBster (NB-CH-CH(CH)C(O) was dissolved in a minimum of THF and poured slowly into OCH) a 25:75 mixture of water:methanol to precipitate the poly To a 100 ml glass vial equipped with a magnetic Stirring mer. This procedure was repeated twice. The resulting white bar and under a nitrogen atmosphere was added toluene (50 polymer was filtered and dried at room temperature under ml), t-butyl ester of norbornene carboxylic acid (2.7 g., 14 vacuum. Yield=2.9 g. mmol) and the ester from Example 40 (NB-CHCH(CH) EXAMPLE 44 C(O)OCH) (4.4g, 21 mmol). To this stirred solution was added, at ambient temperature, a Solution of (toluene)Ni A deoxygenated, dried THF/methanol (35 ml/15 ml) (CFS) in toluene (1 ml) and the resulting Solution was solution of benzoquinone (0.43 g, 0.40 mmol), bipyridine heated to 50° C. and stirring was continued for 3 hours. The (0.0062 g, 0.0040 mmol), and Pd(MeCN)-(p- polymer was precipitated into methanol and filter ed. The toluenesulfonate)(0.0070 g, 0.0013 mmol) was added to a resulting solid was then redissolved in THF, filtered and dry 500 ml stainless steel reactor warmed to 50° C. To the precipitated again with methanol and filtered. The resulting 15 reactor was added norbornene-5-t-butylester (5.14g, 0.027 white Solid polymer was dried and found to weigh 2.66 g mol) in 100 ml of THF (deoxygenated and dried). The (Mw 70,000; Mn39,800), the Supernatant was evaporated to reactor was pressurized with carbon monoxide to 600 psig dryness to afford a further crop of white polymer which on and warmed to 65 C. After 12.5 hours, the reactor was drying weighed 1.52 g (Mw 60,650; Mn31,000). The total heated to 90° C. for 1.5 hours. Then the carbon monoxide yield of copolymer represented 59% conversion of the was vented and the reactor was allowed to cool. The purple monomers. IR, NMR and TGA analysis of the copolymers Solution from the reactor was filtered to remove palladium confirmed their composition to be random addition copoly residues and allowed to evaporate. The resulting mixture mers of the two monomers. was dissolved in a minimum of THF and poured slowly into 25 a 25:75 mixture of water:methanol to precipitate the poly EXAMPLE 42 mer. This procedure was repeated twice. The resulting white 40:60 Copolymer of t-BuNBEster (NB-CHCH(CH)C polymer was filtered and dried at room temperature under (O)OCH) vacuum. Yield=2.9 g. To a 250 ml glass vial equipped with a magnetic Stirring bar and under a nitrogen atmosphere was added dichloro EXAMPLES 45 to 51 ethane (200 ml), t-butyl ester of norbornene carboxylic acid Optical Density Measurements For Cyclic Olefin Based (7.76 g, 40 mmol) and the ester from Example 40 (NB Homo and Copolymers at 193 nm CHCH(CH)C(O)OCH) (12.5g, 60 mmol) and 2,6-di-t- Optical density is a critical characteristic of an effective butylpyridine (28.8 mg, 0.26 mmol). To this stirred solution 35 photoresist because it determines the uniformity of the was added, at ambient temperature, a Solution of the catalyst energy throughout the film thickness. A typical, lithographi resulting from mixing allylpalladium chloride dimer (0.183 cally useful, polymer backbone has an optical density of leSS g, 0.5 mmol) with Silver hexafluoroantimonate (equivalent than 0.2 absorbance units/micron prior to the addition of amount) in dichloroethane (3 ml) and filtering to remove the photoacid generators. (T. Neenan, E. Chandross, J. Komet Silver chloride precipitate. The resulting Solution was heated 40 ani and O. Nalamasu, “Styrylmethylsulfonamides: Versatile to 50° C. and stirring was continued for 16 hours. The Base-Solubilizing Components of Photoresist Resins' pg. polymer Solution was treated with carbon monoxide (4 psi 199 in Microelectronics Technology, Polymers for pressure) for 48 hours to precipitate the palladium residues, Advanced Imaging and Packaging, ACS Symposium Series filtered through a 0.45u filter, reduced in volume and pre 614, Eds: E. Reichmanis, C. Ober, S. MacDonald, T. Iway cipitated with excess methanol to afford 7.9 g of the copoly 45 anagai and T. Nishikubo, April, 1995). Polyhydroxystyrene, mer (39% conversion), Mw 11,600, Mn 7,000. The copoly the primary component of typical 248 nm DUV photoresists, mer was fully characterized using IR, NMR and TGA has an optical density of 2.8 absorbance units/micron at 193 methods. nm and hence is unusable as a resist backbone at this wave 50 length. EXAMPLE 43 Preparing Sample Solution Copolymerization of CO and Norbornene-5-t-butylester Samples of various polymerS Set forth in the foregoing A deoxygenated methanol Solution of bipyridine (0.025 g, examples (0.016+0.001 g of polymer) were weighed out and 0.16 mmol) was added to palladium (II) acetate (0.012 g, dissolved in 4 ml of chloroform. The Solutions of the 0.053 mmol) dissolved in deoxygenated methanol. To this 55 polymers were removed by pipette and thin films were cast solution was added p-toluenesulfonic acid (0.045 g, 0.27 on clean uniform quartz. Slides. The films were allowed to mmol) dissolved in deoxygenated methanol. The resulting dry overnight. The resulting circular films on the quartz brown Solution was added to a methanol (deoxygenated) slides were further dried at 70° C. in an oven for 10 minutes under a nitrogen purge. solution of benzoquinone (1.72 g, 1.59 mmol). This was 60 added to a stainless steel reactor preheated to 50° C. To this UV spectra of the films were obtained using a Perkin reactor was added norbornene-5-t-butylester (5.14g, 0.027 Elmer Lambda 9 UV/VIS/IR spectrophotometer, at a scan mol) in 100 ml of MeOH (deoxygenated with argon). The speed of 120 nm/minute. The spectrum range was set at 300 reactor was pressurized with carbon monoxide to 600 psig nm to 180 nm. By measuring the absorbance of the films at and warmed to 65 C. After 4.5 hours, the carbon monoxide 65 193 nm and normalizing them to the thickness of the films, was vented and the reactor was allowed to cool. The pink the optical density of the films at 193 nm were measured. Solution from the reactor was filtered to remove palladium The results are set forth in the table below: US 6,232,417 B1 69 70

Film Normalized Absorbance Thickness Absorbance at 193 Example Polymer at 193 nm(A) (microns) nm (A/micron) 45 50/50 Copolymer of bicyclo2.2.1]hept-5-ene-2- 1.0173 25.39 O.O400 methyl acetate?t-butylester of norbornene (polymer of Example 21) 46 50/50 Copolymer of bicyclo2.2.1]hept-5-ene-2-methyl O.1799 30.47 O.OO59 ethyl carbonate?t-butylester of norbornene (polymer of Example 22) 47 50/50 Copolymer of bicyclo2.2.1]hept-5-ene-2-methyl O.28O8 33.01 O.OO85 butyl carbonate?t-butylester of norbornene (polymer of Example 23) 48 Copolymer of maleicanhydride/t-butylester of norbornene 1.1413 38.09 O.O299 (polymer of Example 24) 49 Terpolymer of bicyclo2.2.1]hept-5-ene-2-methyl acetate/ O.8433 17.78 O.O4743 maleicanhydride/t-butylester of norbornene polymer of Example 25) 50 50/50 copolymer of t-butyl ester of norbornene/ethyl O.4693 33.01 O.O142 ester of tetracyclododecene (polymer of Example 29) 51 50/50 copolymer of t-butyl ester of norbornene/ethyl O.4146 35.55 O.O117 ester of tetracyclododecene (polymer of Example 30)

25 Preparation of Resist Solution, Exposure and Development: EXAMPLE 53 The polymers obtained in the above examples were Copolymerization of Bicyclo2.2.1]hept-5-ene-2-methyl dissolved in propylene glycol monomethyl ether acetate Ethyl Oxalate/t-butylester of Norbornene (PGMEA) at 15 w/v % of solids, to which was added the To a 50 ml glass vial equipped with a Teflon(R) coated stir onium salt set forth in the examples at 5 or 10 w/w % to the bar was added bicyclo2.2.1]hept-5-ene-2-methyl ethyl polymer. oxalate (8.57g, 0.0382 mol) and t-butylester of norbornene (7.42 g, 0.0392 mol) and 38 ml of toluene. A solution of the The solutions were filtered through a 0.2u Teflon(R) filter. nickel catalyst toluene complex of bisperfluorophenyl A resist layer was formed from each Solution by Spin coating nickel, (toluene)Ni(CFS) was prepared in the dry box by it onto a hexamethyldisilazane (HMDS) primed silicon dissolving 0.1854 g (0.382 mmol) of (toluene)Ni(CF) in wafer. The coated film was baked at 95 C. for 1 minute. The 35 5 ml of toluene. The active catalyst solution was added to the films were then exposed through a quartz mask to UV monomer Solution via a Syringe at ambient temperature. The radiation from a Karl Suss MJB3 UV 250 instrument reaction was allowed to Stir for 5 hours at room temperature. between the wave lengths of 230 to 250 nm. The exposed The solution was diluted with toluene and the polymer was films were heated to 125 C. to 150° C. for 1 minute. The precipitated in exceSS methanol. The precipitated polymer exposed and heated films were then developed in aqueous 40 was filtered, washed with acetone, and dried overnight under base to provide high resolution positive tone images without vacuum. The isolated yield of polymer was 7.62 g (48%). loSS of film thickness in the unexposed regions. The polymer was characterized using GPC for molecular The Systems can be easily made negative working by weight. Mn=28,000 and Mw =56,000. The NMR analysis of development in a nonpolar Solvent. These materials can be the copolymer indicated copolymer composition very close Sensitized to the longer wave lengths (365 nm) by adding a 45 to the feed ratio. IR analysis of the copolymer indicated Small amount of SensitizerS Such as pyrene, perylene, or absence of any acid groups. thioxanthones or to shorter wave lengths (193 nm), as these EXAMPLE 54 materials have been observed (as shown above) to have very low optical density at 193 nm. The copolymer of bicyclo2.2.1]hept-5-ene-2-methyl 50 acetate/t-butylester of norbornene (the polymer of Example EXAMPLE 52 21) (number average molecular weight 2 1,000) was dis Solved in propylene glycol monomethyl ether acetate The copolymer of bicyclo2.2.1]hept-5-ene-2-methyl (PGMEA) at 10 w/v % of solids. Diaryl iodonium hexafluo acetate/t-butylester of norbornene (the polymer of Example roantimonate (Sartomer 1012) was added at a loading of 10 21) number average molecular weight 21,000) was dis w/w % to the polymer. The resist film was filtered through Solved in propylene glycol monomethyl ether acetate 55 a 0.2u Teflon(R) filter and the filtered solution was spin coated (PGMEA) at 10 w/v % of solids. Triphenylsulfonium from the Solution onto a hexamethyldisilaZane primed sili hexafluoroarsenate was added at a loading of 10 w/w % to con wafer at 500 rpm for 30 seconds followed by 2000 rpm the polymer. The resist film was filtered through a 0.2u. for 25 seconds. This resulted in a 0.7u thick layer. The film Teflon(R) filter and the filtered solution was spin coated from was baked at 95 C. for 1 min over a hot plate and then the Solution onto a hexamethyldisilaZane primed Silicon 60 exposed through a quartz mask to UV radiation (240 nm) at wafer at 500 rpm for 30 seconds followed by 2000 rpm for a dose of 50 m.J/cm. After post-baking at 125° C. for 1 25 seconds. This resulted in a 0.7u thick layer. The film was minute, high resolution positive images were obtained by baked at 95 C. for 1 min over a hot plate and then exposed development in aqueous base for 60 Seconds. through a quartz mask to UV radiation (240 nm) at a dose of 50 m.J/cm. After post-baking at 125° C. for 1 minute, 65 EXAMPLE 55 high resolution positive images were obtained by develop Copolymer of bicyclo2.2.1]hept-5-ene-2-methyl acetate/ ment in aqueous base for 60 Seconds. t-butylester of norbornene (the polymer of Example 21) US 6,232,417 B1 71 72 (number average molecular weight 21,000) was dissolved in ethyldisilazane primed silicon wafer at 500 rpm for 30 propylene glycol monomethyl ether acetate (PGMEA) at 10 seconds followed by 2000 rpm for 25 seconds. This resulted w/v % of solids. Diaryl iodonium hexafluoroantimonate in a 0.7u thick layer. The film was baked at 95 C. for 1 (Sartomer 1012) was added at a loading of 10 w/w % to the minute over a hot plate and then exposed through a quartz polymer. The resist film was filtered through a 0.2u Teflon(R) mask to UV radiation (240 nm) at a dose of 30 m.J/cm°. After filter and the filtered solution was spin coated from the post-baking at 125 C. for 1 minute, high resolution positive Solution onto a hexamethyldisilaZane primed Silicon wafer at images were obtained by development in aqueous base for 500 rpm for 30 seconds followed by 2000 rpm for 25 60 seconds. seconds. This resulted in a 0.7u thick layer. The film was baked at 95 C. for 1 min over a hot plate and then exposed EXAMPLE 59 through a quartz mask to UV radiation (240 nm) at a dose Copolymerization of Bicyclo2.2.1]hept-5-ene-2-methyl of 100 m.J/cm'. After post-baking at 125 C. for 1 minute, Ethyl Oxalate/1-(1-ethoxy)ethyl 5-norbornene-2- high resolution positive images were obtained by develop carboxylated (50/50 Mole Ratio) Using NiArf catalyst ment in aqueous base for 60 Seconds. To a 50 ml glass vial equipped with a Teflon(R) coated stir 15 bar was added bicyclo2.2.1]hept-5-ene-2-methyl ethyl EXAMPLE 56 oxalate (0.5166 g, 2.304 mmol) and 1-(1-ethoxy)ethyl 5-norbornene-2-carboxylate (0.4885g, 2.304 mol) and 2.25 Copolymerization of Bicyclo2.2.1]hept-5-ene-2-methyl ml of cyclohexane. A Solution of the nickel catalyst toluene Ethyl Oxalate/t-butylester of Norbornene (70/30 Mole complex of bisperfluorophenyl nickel, (toluene)Ni(CFs). Ratio) was prepared in the dry box by dissolving 0.0112 g (0.023 To a 50 ml glass vial equipped with a Teflon(R) coated stir mmol) of (toluene)Ni(CF) in 0.65 ml of ethyl acetate. bar was added bicyclo2.2.1]hept-5-ene-2-methyl ethyl The active catalyst Solution was added to the monomer oxalate (14.8 g., 0.0663 mol) and t-butylester of norbornene Solution via a Syringe at ambient temperature. The reaction (5.52g, 0.0284 mol) and 113 ml of toluene. A solution of the was allowed to stir for 5 hours at room temperature. The nickel catalyst toluene complex of bisperfluorophenyl Solution was diluted with toluene and the polymer was nickel, (toluene)Ni(CFs) was prepared in the dry box by 25 precipitated in exceSS methanol. The precipitated polymer dissolving 0.2296 g (0.474 mmol) of (toluene)Ni(CF) in was filtered, washed with acetone, and dried overnight under 5 ml of toluene. The active catalyst solution was added to the vacuum. The isolated yield of polymer was 0.0315 g (3%). monomer Solution via a Syringe at ambient temperature. The The polymer was characterized using GPC for molecular reaction was allowed to Stir for 5 hours at room temperature. weight. Mn=52,000 and Mw = 100,000. The solution was diluted with toluene and the polymer was precipitated in exceSS methanol. The precipitated polymer EXAMPLE 60 was filtered, washed with acetone and dried overnight under The copolymer of maleicanhydride/t-butylester of nor vacuum. The isolated yield of polymer was 10.15 g (50%). bornene obtained via free radical polymerization (the poly The polymer was characterized using GPC for molecular mer of Example 24) (number average molecular weight weight. Mn=35,000 and Mw =98,000. The NMR analysis of 35 4,000) was dissolved in propylene glycol monomethyl ether the copolymer indicated copolymer composition very close acetate (PGMEA) at 15 w/v % of solids. Triarylsulfonium to the feed ratio. IR analysis of the copolymer indicated hexafluoroantimonate (Sartomer CD 1010, 50% solution in absence of any acid groups. propylene carbonate) was added at a loading of 5 W/w % to the polymer. The resist film was filtered through a 0.2u. EXAMPLE 57 40 Teflon(R) filter and the filtered solution was spin coated from the Solution onto a hexamethyldisilaZane primed Silicon Copolymer of bicyclo 2.2.1]hept-5-ene-2-methyl wafer at 500 rpm for 30 seconds followed by 2000 rpm for acetate/t-butylester of norbornene (the polymer of Example 25 seconds. This resulted in a 0.6ll thick layer. The film was 21) (number average molecular weight 21,000) was dis baked at 95 C. for 1 minute over a hot plate and then Solved in propylene glycol monomethyl ether acetate 45 exposed through a quartz mask to UV radiation (240 nm) at (PGMEA) at 10 w/v % of solids. Triphenylsulfonium a dose of 30 m.J/cm. After post-baking at 125° C. for 1 hexafluoroarsenate was added at a loading of 10 w/w % to minute, high resolution positive images were obtained by the polymer. The resist film was filtered through a 0.2u. development in aqueous base for 60 Seconds. Teflon(R) filter and the filtered solution was spin coated from the Solution onto a hexamethyldisilaZane primed Silicon 50 EXAMPLE 61 wafer at 500 rpm for 30 seconds followed by 2000 rpm for The copolymer of maleic anhydride/t-butylester of nor 25 seconds. This resulted in a 0.7u thick layer. The film was bornene obtained via free radical polymerization (the poly baked at 95 C. for 1 minute over a hot plate and then mer of Example 24) (number average molecular weight exposed through a quartz mask to UV radiation (240 mm) at 4,000) was dissolved in propylene glycol monomethyl ether a dose of 10 ml/cm. After post-baking at 125° C. for 1 55 acetate (PGMEA) at 15 w/v % of solids. Triarylsulfonium minute, high resolution positive images were obtained by hexafluoroantimonate (Sartomer CD 1010, 50% solution in development in aqueous base for 60 Seconds. propylene carbonate) was added at a loading of 5 W/w % to the polymer. The resist film was filtered through a 0.2u. EXAMPLE 58 Teflon(R) filter and the filtered solution was spin coated from Copolymer of bicyclo2.2.1]hept-5-ene-2-methyl acetate/ 60 the Solution onto a hexamethyldisilaZane primed Silicon t-butylester of norbornene (the polymer of Example 21) wafer at 500 rpm for 30 seconds followed by 2000 rpm for (number average molecular weight 21,000) was dissolved in 25 seconds. This resulted in a 0.6ll thick layer. The film was propylene glycol monomethyl ether acetate (PGMEA) at 10 baked at 95 C. for 1 minute over a hot plate and then w/v % of solids. Triphenylsulfonium hexafluoroarsenate was exposed through a quartz mask to UV radiation (240 nm) at added at a loading of 10 w/w % to the polymer. The resist 65 a dose of 30 m.J/cm. After post-baking at 95° C. for 1 film was filtered through a 0.2u Teflon(R) filter and the filtered minute, high resolution positive images were obtained by Solution was spin coated from the Solution onto a hexam development in aqueous base for 60 Seconds. US 6,232,417 B1 73 74 EXAMPLE 62 roethane and the Solution is degassed under argon atmo Sphere. A 10 ml glass Vial equipped with a Teflon(E) coated Copolymerization of Bicyclo2.2.1]hept-5-ene-2-methyl stir bar is charged with 0.0365 g (0.1 mmol) of allylpalla Ethyl Oxalate/trimethylsilyl Ester of Norbornene (50/50 dium chloride dimer in a monomer to catalyst ratio of 500/1 Mole Ratio) and 2 ml of dichloroethane. In another 10 ml glass vial is To a 50 ml glass vial equipped with a Teflon(R) coated stir charged with 0.0344 g (0.1 mmol) of silver hexafluoro bar was added bicyclo2.2.1]hept-5-ene-2-methyl ethyl antimonate and 2 ml of dichloroethane. The catalyst Solution oxalate (1.5484 g., 6.904 mmol) trimethyl silyl ester of is prepared by mixing the allylpalladium chloride dimer norbornene (1.4523 g, 6.905 mol) and 6.75 ml of cyclohex Solution with Silver hexafluoro antimonate Solution inside ane. A Solution of the nickel catalyst toluene complex of the dry box. Immediate precipitation of the silver chloride bisperfluorophenyl nickel, (toluene)Ni(CFs) was pre Salt is observed, which is filtered, to obtain active catalyst pared in the dry box by dissolving 0.0335 g (0.0691 mmol Solution. The active catalyst Solution is then added to the of (toluene)Ni(CF) in 1.95 ml of ethyl acetate. The active monomer Solution via a Syringe and the reaction mixture catalyst Solution was added to the monomer Solution via a allowed to stir for 20 hours at 60° C. The polymer Solution Syringe at ambient temperature. The reaction was allowed to 15 is cooled, concentrated in a rotovap, and precipitated into Stir for 5 hours at room temperature. The polymer was methanol. precipitated in exceSS methanol. The precipitated polymer was filtered, washed with acetone, and dried overnight under EXAMPLE 66 vacuum. The isolated yield of polymer was 0.2675 g (9%). The copolymer of bicyclo2.2.1]hept-5-ene-2-methyl It indicated the presence of acid functionality, arising from ethylcarbonate/t-butylester of norbornene (the polymer of the deprotection of the trimethyl silyl groups. Example 22) (number average molecular weight 22,000) EXAMPLE 63 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at 15 w/v % of solids. Triphenylsulfonium The terpolymer of maleic anhydride/bicyclo2.2.1]hept hexafluoroantimonate (Sartomer CD 1010, 50% solution in 5-ene-2-methyl acetate/t-butylester of norbornene obtained 25 propylene carbonate) was added at a loading of 5 W/w % to via free radical polymerization (the polymer of Example 25) the polymer. The resist film was filtered through a 0.2u. (number average molecular weight 3000) was dissolved in Teflon(R) filter and the filtered solution was spin coated from propylene glycol monomethyl ether acetate (PGMEA) at 10 the Solution onto a hexamethyldisilaZane primed Silicon w/v % of solids. Diaryl iodonium hexafluoroantimonate wafer at 500 rpm for 30 seconds followed by 2000 rpm for (Sartomer 1012) was added at a loading of 10 w/w % to the 25 seconds. This resulted in a 1.1 u thick layer. The film was polymer. The resist film was filtered through a 0.2u Teflon(R) baked at 95 C. for 1 minute over a hot plate and then filter and the filtered solution was spin coated from the exposed through a quartz mask to UV radiation (240 nm) at Solution onto a hexamethyldisilaZane primed silicon wafer at a dose of 15 m.J/cm. After post-baking at 95° C. for 1 500 rpm for 30 seconds followed by 2000 rpm for 25 minute, high resolution positive images were obtained by seconds. This resulted in a 0.5u thick layer. The film was 35 development in aqueous base for 60 Seconds. baked at 95 C. for 1 minute over a hot plate and then exposed through a quartz mask to UV radiation (240 nm) at EXAMPLE 67 a dose of 50 ml/cm'. After post-baking at 125 C. for 1 The copolymer of bicyclo 2.2.1]hept-5-ene-2-methyl minute, high resolution positive images were obtained by butylcarbonate/t-butylester of norbornene (the polymer of development in aqueous base for 60 Seconds. 40 Example 23) (number average molecular weight 22,000) EXAMPLE 64 was dissolved in propylene glycol monomethyl ether acetate The copolymer of bicyclo2.2.1]hept-5-ene-2-methyl (PGMEA) at 15 w/v % of solids. Triarylsulfonium hexafluo ethylcarbonate/t-butylester of norbornene (the polymer of roantimonate (Sartomer CD 1010, 50% solution in propy 45 lene carbonate) was added at a loading of 5 w/w % to the Example 22) (number average molecular weight 22,000) polymer. The resist film was filtered through a 0.2u Teflon(R) was dissolved in propylene glycol monomethyl ether acetate filter and the filtered solution was spin coated from the (PGMEA) at 15 w/v % of solids. Triarylsulfonium hexafluo Solution onto a hexamethyldisilaZane primed Silicon wafer at roantimonate (Sartomer CD 1010, 50% solution in propy 500 rpm for 30 seconds followed gby 2000 rpm for 25 lene carbonate) was added at a loading of 5 w/w % to the 50 seconds. This resulted in a 1.011 thick layer. The film was polymer. The resist film was filtered through a 0.2u Teflon(R) baked at 95 C. for 1 minute over a hot plate and then filter and the filtered solution was spin coated from the exposed through a quartz mask to UV radiation (240 nm) at Solution onto a hexamethyldisilaZane primed Silicon wafer at a dose of 30 m.J/cm°. After post-baking at 125° C. for 0.5 500 rpm for 30 seconds followed by 2000 rpm for 25 minute, high resolution positive images were obtained by seconds. This resulted in a 1.11u thick layer. The film was development in aqueous base for 60 Seconds. baked at 95 C. for 1 minute over a hot plate and then 55 exposed through a quartz mask to UV radiation (240 nm) at EXAMPLE 68 a dose of 30 m.J/cm. After post-baking at 95° C. for 1 minute, high resolution positive images were obtained by The copolymer of bicyclo2.2.1]hept-5-ene-2-methyl development in aqueous base for 60 Seconds. butylcarbonate/t-butylester of norbornene (the polymer of 60 Example 23) (number average molecular weight 22,000) EXAMPLE 65 was dissolved in propylene glycol monomethyl ether acetate Copolymerization of Bicyclo2.2.1]hept-5-ene-2-methyl (PGMEA) at 15 w/v % of solids. Triarylsulfonium hexafluo Ethyl Oxalate/t-butylester of Norbornene roantimonate (Sartomer CD 1010, 50% solution in propy To a 50 ml glass vial equipped with a Teflon(R) coated stir lene carbonate) was added at a loading of 5 w/w % to the bar is added 2.42 g (12.5 mmole) of t-butylester of 65 polymer. The resist film was filtered through a 0.2u Teflon(R) norbornene, 8.57 g (38.2 mmole) of bicyclo[2.2.1]hept-5- filter and the filtered solution was spin coated from the ene-2-methyl ethyl oxalate, 50 ml of freshly distilled dichlo Solution onto a hexamethyldisilaZane primed Silicon wafer at US 6,232,417 B1 75 76 500 rpm for 30 seconds followed by 2000 rpm for 25 to the feed ratio. IR analysis of the copolymer indicated seconds. This resulted in a 1.0u thick layer. The film was absence of any acid groups. baked at 95 C. for 1 minute over a hot plate and then exposed through a quartz mask to UV radiation (240 nm) at EXAMPLE 72 a dose of 30 m.J/cm°. After post-baking at 150° C. for 0.5 minute, high resolution positive images were obtained by Copolymerization of Bicyclo 2.2.1]hept-5-ene-2-methyl development in aqueous base for 60 Seconds. Acetate/t-butylester of Norbornene (Monomer/cat Ratio 100/1, 30 wt % Solids) EXAMPLE 69 To a 25 ml glass vial equipped with a Teflon(R) coated stir A35/65 mole % hydrogenated copolymer of ethylester of bar was added bicyclo2.2.1]hept-5-ene-2-methyl acetate tetracyclodecene/t-butylester of norbornene (the polymer of (1.399 g, 8.418 mmol) and t-butylester of norbornene Example 37) (number average molecular weight 23,000) (1.6217 g, 8.34 mmol) and 5 ml of toluene. A solution of the obtained via ring opening metathesis polymerization was nickel catalyst (toluene complex of bisperfluorophenyl dissolved in propylene glycol monomethyl ether acetate nickel, (toluene)Ni(CFs)) was prepared in the dry box by (PGMEA) at 15 w/v % of solids. Triarylsulfonium hexafluo 15 dissolving 0.0811 g (0.1673 mmol of (toluene)Ni(CF)) in roantimonate (Sartomer CD 1010, 50% solution in propy 3 ml of toluene. The active catalyst solution was added to the lene carbonate) was added at a loading of 5 w/w % to the monomer Solution via a Syringe at ambient temperature. The polymer. The resist film was filtered through a 0.2u Teflon(R) reaction was allowed to Stir for 6 hours at room temperature. filter and the filtered solution was spin coated from the The solution was diluted with toluene and the polymer was Solution onto a hexamethyldisilaZane primed Silicon wafer at precipitated in exceSS methanol. The precipitated polymer 500 rpm for 30 seconds followed by 2000 rpm for 25 was filtered, washed with acetone, and dried overnight under seconds. This resulted in a 1.11u thick layer. The film was vacuum. The isolated yield of polymer was 2.743 g (90%). baked at 95 C. for 1 minute over a hot plate and then The polymer was characterized using GPC for molecular exposed through a quartz mask to UV radiation (240 nm) at weight. Mn 33,000 and Mw =74,000. a dose of 30 m.J/cm°. After post-baking at 125° C. for 1.0 25 minute, high resolution positive images were obtained by EXAMPLE 73 development in aqueous base for 30 Seconds. Copolymerization of Bicyclo2.2.1]hept-5-ene-2-methyl acetate/t-butylester of Norbornene (Monomer/cat Ratio 200/ EXAMPLE 70 1, 30 wt % Solids) A 50/50 mole % nonhydrogenated copolymer of ethyl To a 25 ml glass vial equipped with a Teflon(R) coated stir ester of tetracyclodecene/t-butylester of norbornene (the bar was added bicyclo2.2.1]hept-5-ene-2-methyl acetate polymer of Example 39) (number average molecular weight (1.388 g, 8.353 mmol) and t-butylester of norbornene (1.6245 g, 8.3 mmol) and 5 ml of toluene. A solution of the 34,000) obtained via ring opening metathesis polymeriza nickel catalyst (toluene complex of bisperfluorophenyl tion was dissolved in propylene glycol monomethyl ether 35 acetate (PGMEA) at 15 w/v % of solids. Triarylsulfonium nickel, (toluene)Ni(CFs)) was prepared in the dry box by hexafluoroantimonate (Sartomer CD 1010, 50% solution in dissolving 0.0406 g (0.0836 mmol) of (toluene)Ni(CF)) propylene carbonate) was added at a loading of 5 W/w % to in 3 ml of toluene. The active catalyst solution was added to the polymer. The resist film was filtered through a 0.2u. the monomer Solution via a Syringe at ambient temperature. Teflon(R) filter and the filtered solution was spin coated from The reaction was allowed to stir for 6 hours at room the Solution onto a hexamethyldisilaZane primed Silicon 40 temperature. The solution was diluted with toluene and the wafer at 500 rpm for 30 seconds followed by 2000 rpm for polymer was precipitated in exceSS methanol. The precipi 25 seconds. This resulted in a 1.25u thick layer. The film was tated polymer was filtered, washed with acetone, and dried baked at 95 C. for 1 minute over a hot plate and then overnight under vacuum. The isolated yield of polymer was exposed through a quartz mask to UV radiation (240 nm) at 1.72 g (57%). The polymer was characterized using GPC for a dose of 50 m.J/cmi. After post-baking at 150° C. for 30 45 molecular weight. Mn=30,000 and Mw =68,000. Seconds, high resolution positive images were obtained by development in aqueous base for 60 Seconds. EXAMPLE 74 Copolymerization of Bicyclo2.2.1]hept-5-ene-2-methyl EXAMPLE 71 50 Acetate/t-butylester of Norbornene (Monomer/cat Ratio To a 50 ml glass vial equipped with a Teflon(R) coated stir 500/1, 30 wt.% Solids) bar was added bicyclo2.2.1]hept-5-ene-2-methyl ethyl To a 25 ml glass vial equipped with a Teflon(R) coated stir oxalate (8.57g, 0.0382 mol) and t-butylester of norbornene bar was added bicyclo2.2.1]hept-5-ene-2-methyl acetate (7.42 g, 0.0392 mol) and 38 ml of toluene. A solution of the (1.3957 g, 8.397 mmol) and t-butylester of norbornene nickel catalyst toluene complex of bisperfluorophenyl 55 (1.6235 g, 8.354 mmol) and 5 ml of toluene. A solution of nickel, (toluene)Ni(CFs) was prepared in the dry box by the nickel catalyst (toluene complex of bisperfluorophenyl dissolving 0.1854 g (0.382 mmol) of (toluene)Ni(CF) in nickel, (toluene)Ni(CFs)) was prepared in the dry box by 5 ml of toluene. The active catalyst solution was added to the dissolving 0.04162 g (0.0335 mmol) of (toluene)Ni(CF)) monomer Solution via a Syringe at ambient temperature. The in 3 ml of toluene. The active catalyst solution was added to reaction was allowed to Stir for 5 hours at room temperature. 60 the monomer Solution via a Syringe at ambient temperature. The solution was diluted with toluene and the polymer was The reaction was allowed to stir for 6 hours at room precipitated in exceSS methanol. The precipitated polymer temperature. The solution was diluted with toluene and the was filtered, washed with acetone, and dried overnight under polymer was precipitated in exceSS methanol. The precipi vacuum. The isolated yield of polymer was 7.62 g (48%). tated polymer was filtered, washed with acetone, and dried The polymer was characterized using GPC for molecular 65 overnight under vacuum. The isolated yield of polymer was weight. Mn=28,000 and Mw =56,000. The NMR analysis of 0.734 g (24%). The polymer was characterized using GPC the copolymer indicated copolymer composition very close for molecular weight. Mn=35,000 and Mw-75,000. US 6,232,417 B1 77 78 EXAMPLE 75 EXAMPLE 78 Copolymerization of Bicyclo2.2.1]hept-5-ene-2-methyl Copolymerization of Bicyclo2.2.1]hept-5-ene-2-methyl Acetate/t-butylester of Norbornene (Monomer/cat Ratio Acetate/t-butylester of Norbornene (Monomer/cat Ratio 100/1, 20 wt.% Solids) 200/1, 30 wt.% Solids) To a 25 ml glass vial equipped with a Teflon(R) coated stir To a 25 ml glass vial equipped with a Teflon(R) coated stir bar was added bicyclo2.2.1]hept-5-ene-2-methyl acetate bar was added bicyclo2.2.1]hept-5-ene-2-methyl acetate (1.3967 g, 8.404 mmol) and t-butylester of norbornene (1.3917 g, 8.373 mmol) and t-butylester of norbornene (1.6233 g, 8.356 mmol) and 4.5 ml of cyclohexane. A (1.6241 g, 8.36 mmol) and 9 ml of toluene. A solution of the Solution of the nickel catalyst (toluene complex of bisper nickel catalyst (toluene complex of bisperfluorophenyl fluorophenyl nickel, (toluene)Ni(C6F5)) was prepared in nickel, (toluene)Ni(CF)) was prepared in the dry box by the dry box by dissolving 0.0405 g (0.0836 mmol of dissolving 0.0811 g (0.167 mmol) of (toluene)Ni(CF)) in (toluene)Ni(CF)) in 3.5 ml of ethylacetate. The active 5 ml of toluene. The active catalyst solution was added to the catalyst Solution was added to the monomer Solution via a monomer Solution via a Syringe at ambient temperature. The Syringe at ambient temperature. The reaction was allowed to reaction was allowed to Stir for 6 hours at room temperature. 15 Stir for 6 hours at room temperature. The Solution was The solution was diluted with toluene and the polymer was diluted with toluene and the polymer was precipitated in precipitated in exceSS methanol. The precipitated polymer exceSS methanol. The precipitated polymer was filtered, was filtered, washed with acetone, and dried overnight under washed with acetone, and dried overnight under vacuum. vacuum. The isolated yield of polymer was 2.577 g (85.4%). The isolated yield of polymer was 1.7617 g (58%). The The polymer was characterized using GPC for molecular polymer was characterized using GPC for molecular weight. weight. Mn=27,000 and Mw =51,000. Mn=27,000 and Mw-71,000.

EXAMPLE 76 EXAMPLES 72-78 Copolymerization of Bicyclo2.2.1]hept-5-ene-2-methyl 25 Acetate/t-butylester of Norbornene (Monomer/cat Ratio 100/1, 10 wt.% Solids) Wt 9% of Theo Catalyst? Monomer retical To a 25 ml glass vial equipped with a Teflon(R) coated stir Monomer in Mn/Mw Mn Yield bar was added bicyclo2.2.1]hept-5-ene-2-methyl acetate Example Solvent Ratio Solution (10) (10) (%) (1.4041 g, 8.447 mmol) and t-butylester of norbornene 72 toluene 100/1 3O 33.4f74.2 18 91 (1.6251 g, 8.365 mmol) and 26 ml of toluene. A solution of 73 toluene 200/1 3O 30.5/68.6 36 57 the nickel catalyst (toluene complex of bisperfluorophenyl 74 toluene 500/1 3O 34.8/74.8 90 25 75 toluene 100/1 10 18.4f48 18 75 nickel, (toluene)Ni(CF)) was prepared in the dry box by 76 toluene 100/1 2O 27.3/51 18 85 dissolving 0.0811 g (0.167 mmol of (toluene)Ni(CF)) in 35 77 cyclo- 200/1 3O 31/68 36 71 5 ml of toluene. The active catalyst solution was added to the hexanef monomer Solution via a Syringe at ambient temperature. The ethyl acetate reaction was allowed to Stir for 6 hours at room temperature. (75/25) The solution was diluted with toluene and the polymer was 78 cyclo- 200/1 3O 27/71 36 58 precipitated in exceSS methanol. The precipitated polymer 40 hexanef ethyl was filtered, washed with acetone, and dried overnight under acetate vacuum. The isolated yield of polymer was 2.3035 g (50/50) (75.4%). The polymer was characterized using GPC for molecular weight. Mn=18,000 and Mw =40,000. 45 EXAMPLE 79 EXAMPLE 77 Copolymerization of Bicyclo2.2.1]hept-5-ene-2-methyl Copolymerization of Bicyclo2.2.1]hept-5-ene-2-methyl Acetate/t-butylester of Norbornene CHA/EtOAc (50/50) Acetate/t-butylester of Norbornene (Monomer/cat Ratio Solvent Mixture (Monomer/cat Ratio 100/1, 30 wt. % 200/1, 30 wt.% Solids) 50 Solids) To a 25 ml glass vial equipped with a Teflon(R) coated stir To a 25 ml glass vial equipped with a Teflon(R) coated stir bar was added bicyclo2.2.1]hept-5-ene-2-methyl acetate bar was added bicyclo2.2.1]hept-5-ene-2-methyl acetate (1.3881 g, 8.353 mmol) and t-butylester of norbornene (1.3933 g, 8.382 mmol) and t-butylester of norbornene (1.6265 g, 8.372 mmol) and 6.7 ml of cyclohexane. A (1.6230 g, 8.354 mmol) and 4.5 ml of cyclohexane. A Solution of the nickel catalyst (toluene complex of bisper 55 Solution of the nickel catalyst (toluene complex of bisper fluorophenyl nickel, (toluene)Ni(CF)) was prepared in fluorophenyl nickel, (toluene)Ni(CF)) was prepared in the dry box by dissolving 0.0405 g (0.0836 mmol of the dry box by dissolving 0.0405 g (0.0836 mmol) of (toluene)Ni(CF)) in 1.9 ml of ethylacetate. The active (toluene)Ni(CF)) in 3.9 ml of ethylacetate. The active catalyst Solution was added to the monomer Solution via a catalyst Solution was added to the monomer Solution via a Syringe at ambient temperature. The reaction was allowed to 60 Syringe at ambient temperature. The reaction was allowed to Stir for 6 hours at room temperature. The Solution was Stir for 6 hours at room temperature. The Solution was diluted with toluene and the polymer was precipitated in diluted with toluene and the polymer was precipitated in exceSS methanol. The precipitated polymer was filtered, exceSS methanol. The precipitated polymer was filtered, washed with acetone, and dried overnight under vacuum. washed with acetone, and dried overnight under vacuum. The isolated yield of polymer was 2.1345 g (70.8%). The 65 The isolated yield of polymer was 2.6918 g (89%). The polymer was characterized using GPC for molecular weight. polymer was characterized using GPC for molecular weight. Mn=31,000 and Mw 69,000. Mn=19,000 and Mw-48,000. US 6,232,417 B1 79 80 EXAMPLE 8O 4) Norbornene polymerization with 5 mole % of allyl Molecular Weight Control of Norbornene in the Presence of trifluoroacetate as chain transfer agent: an Ether Based Electron Donor And Using Allyl Trifluoro To a 100 ml glass vial equipped with a teflon coated stir acetate as Chain Transfer Agent 1) Norbornene polymerization with 1 mole % of allyl bar was added norbornene (25.0g, 265 mmol), cyclohexane trifluoroacetate as chain transfer agent: (280 ml) and allyltrifluoro acetate (2.04 g., 0.013 mol) as To a 100 ml glass vial equipped with a teflon coated stir chain transfer agent to control molecular weight. The Solu bar was added norbornene (5.0 g, 53 mmol), cyclohexane tion was heated to 50° C. and to this stirred solution, (55 ml) and allyltrifluoro acetate (0.082 g, 0.0005 mol) as dimethyl diethoxysilane (1.96 g, 13.2 mmol) was added as chain transfer agent to control molecular weight. The Solu an ether based electron donor ligand. To the above Solution tion was heated to 50° C. and to this stirred solution, a mixture of tris(pentafluorophenyl) boron (1.170 mmol in dimethyl diethoxysilane (0.392 g, 2.64 mmol) was added as petroleum naphtha) and triethylaluminum (0.77 ml of a 1.7 an ether based electron donor ligand. To the above Solution molar Solution in cyclohexane, 1.30 mmol) was added a mixture of tris(pentafluorophenyl) boron (234 umol in followed by nickel ethylhexanoate (0.1 ml of an 8 weight% petroleum naphtha) and triethylaluminum (0.154 ml of a 1.7 15 nickel Solution in mineral Spirits, 0.13 mmol). The reaction molar Solution in cyclohexane, 260 umol ) was added was allowed to run for 6 hours and then the reaction was followed by nickel ethylhexanoate (0.02 ml of an 8 weight quenched with methanol. The solution was diluted and the % nickel Solution in mineral Spirits, 26 umol). The reaction polymer was precipitated in exceSS acetone. The precipitated was allowed to run for 6 hours and then the reaction was polymer was filtered, washed with acetone and dried over quenched with methanol. The solution was diluted and the night under vacuum. The yield of polymer was 24 g (96%). polymer was precipitated in exceSS acetone. The precipitated The polymer was characterized using GPC and these results polymer was filtered, washed with acetone and dried over are provided in Table 1. night under vacuum. The yield of polymer was 4.45 g (89%). The polymer was characterized using GPC and these results 5) Norbornene polymerization with 10 mole % of allyl are provided in Table 1. 25 trifluoroacetate as chain transfer agent: 2) Norbornene polymerization with 2 mole % of allyl To a 100 ml glass vial equipped with a teflon coated stir trifluoroacetate as chain transfer agent: bar was added norbornene (25.0g, 265 mmol), cyclohexane To a 100 ml glass vial equipped with a teflon coated stir (280 ml) and allyltrifluoro acetate (4.08 g., 0.026 mol) as bar was added norbornene (5.0 g, 53 mmol), cyclohexane chain transfer agent to control molecular weight. The Solu (55 ml) and allyltrifluoro acetate (0.163 g, 0.0011 mol) as tion was heated to 50° C. and to this stirred solution, chain transfer agent to control molecular weight. The Solu dimethyl diethoxysilane (1.96 g, 13.2 mmol) was added as tion was heated to 50° C. and to this stirred solution, an ether based electron donor ligand. To the above Solution dimethyl diethoxysilane (0.392 g, 2.64 mmol) was added as a mixture of tris(pentafluorophenyl) boron (1.170 mmol in an ether based electron donor ligand. To the above Solution petroleum naphtha) and triethylaluminum (0.77 ml of a 1.7 a mixture of tris(pentafluorophenyl) boron (234 umol in 35 molar Solution in cyclohexane, 1.30 mmol) was added petroleum naphtha) and triethylaluminum (0.154 ml of a 1.7 followed by nickel ethylhexanoate (0.1 ml of an 8 weight% molar Solution in cyclohexane, 260 umol) was added fol nickel Solution in mineral Spirits, 0.13 mmol). The reaction lowed by nickel ethylhexanoate (0.02 ml of an 8 weight % was allowed to run for 6 hours and then the reaction was nickel Solution in mineral Spirits, 26.umol). The reaction was quenched with methanol. The solution was diluted and the allowed to run for 6 hours and then the reaction was 40 polymer was precipitated in exceSS acetone. The precipitated quenched with methanol. The solution was diluted and the polymer was precipitated in exceSS acetone. The precipitated polymer was filtered, washed with acetone and dried over polymer was filtered, washed with acetone and dried over night under vacuum. The yield of polymer was 21.7g (87%). night under vacuum. The yield of polymer was 4.9 g (97%). The polymer was characterized using GPC and these results The polymer was characterized using GPC and these results 45 are provided in Table 1. are provided in Table 1. 6) Norbornene polymerization with 20 mole % of allyl 3) Norbornene polymerization with 3 mole % of allyl trifluoroacetate as chain transfer agent: trifluoroacetate as chain transfer agent: To a 100 ml glass vial equipped with a teflon coated stir To a 100 ml glass vial equipped with a teflon coated stir bar was added norbornene (5.0 g, 53 mmol), cyclohexane bar was added norbornene (5.0 g, 53 mmol), cyclohexane 50 (55 ml) and allyltrifluoro acetate (1.63 g, 0.011 mol) as chain (55 ml) and allyltrifluoro acetate (0.245 g, 0.0016 mol) as transfer agent to control molecular weight. The Solution was chain transfer agent to control molecular weight. The Solu heated to 50° C. and to this stirred solution, dimethyl tion was heated to 50° C. and to this stirred solution, diethoxysilane (0.392 g, 2.64 mmol) was added as an ether dimethyl diethoxysilane (0.392 g, 2.64 mmol) was added as based electron donor ligand. To the above Solution a mixture an ether based electron donor ligand. To the above Solution 55 a mixture of tris(pentafluorophenyl) boron (234 umol in of tris(pentafluorophenyl) boron (234 umol in petroleum petroleum naphtha) and triethylaluminum (0.154 ml of a 1.7 naphtha) and triethylaluminum (0.154 ml of a 1.7 molar molar Solution in cyclohexane, 260 umol) was added fol solution in cyclohexane, 260 umol) was added followed by lowed by nickel ethylhexanoate (0.02 ml of an 8 weight % nickel ethylhexanoate (0.02 ml of an 8 weight 96 nickel nickel Solution in mineral spirits, 26 umol). The reaction was 60 Solution in mineral Spirits, 26.umol). The reaction was allowed to run for 6 hours and then the reaction was allowed to run for 6 hours and then the reaction was quenched with methanol. The solution was diluted and the quenched with methanol. The solution was diluted and the polymer was precipitated in exceSS acetone. The precipitated polymer was precipitated in exceSS acetone. The precipitated polymer was filtered, washed with acetone and dried over polymer was filtered, washed with acetone and dried over night under vacuum. The yield of polymer was 4.65 g (93%). 65 night under vacuum. The yield of polymer was 2.85 g (57%). The polymer was characterized using GPC and these results The polymer was characterized using GPC and these results are provided in Table 1. are provided in Table 1. US 6,232,417 B1 82 diethoxysilane (0.392 g, 2.64 mmol) was added as an ether TABLE 1. based electron donor ligand. To the above Solution a mixture of tris(pentafluorophenyl) boron (234 umol in petroleum Mole % of Yield of Molecular naphtha) and triethylaluminum (0.154 ml of a 1.7 molar Sample Allyl polymer weight (10 Poly solution in cyclohexane, 260 umol) was added followed by # trifluoroacetate (%) Mn Mw dispersity nickel ethylhexanoate (0.02 ml of an 8 weight 96 nickel Solution in mineral Spirits, 26 umol). The reaction was 1. 1. 89 Could not Could not allowed to run for 6 hours and then the reaction was leaSle leaSie 2 2 97 148 476 3.2 quenched with methanol. The solution was diluted and the 3 3 93 118 348 2.9 1O polymer was precipitated in exceSS acetone. The precipitated 4 5 97 93 281 3.0 polymer was filtered, washed with acetone and dried over 5 1O 87 65 196 3.0 night under vacuum. The yield of polymer was 4.28 g (86%). 6 2O 57 33 90 2.7 The polymer was characterized using GPC and these results are provided in Table 2. EXAMPLE 81 15 4) Norbornene polymerization with 5 mole % of allyl Molecular Weight Control of Norbornene in the Presence of chloride as chain transfer agent: an Ether Based Electron Donor And Using Allyl Chloride as To a 100 ml glass vial equipped with a teflon coated stir Chain Transfer Agent bar was added norbornene (5.0 g, 53 mmol), cyclohexane 1) Norbornene polymerization with 1 mole % of allyl (55 ml) and allyl chloride(0.203 g, 0.0026 mol) as chain chloride as chain transfer agent: transfer agent to control molecular weight. The Solution was To a 100 ml glass vial equipped with a teflon coated stir heated to 50° C. and to this stirred solution, dimethyl bar was added norbornene (5.0 g, 53 mmol), cyclohexane diethoxysilane (0.392 g, 2.64 mmol) was added as an ether (55 ml) and allyl chloride (0.04 g., 0.0005 mol) as chain based electron donor ligand. To the above Solution a mixture transfer agent to control molecular weight. The Solution was of tris(pentafluorophenyl) boron (234 umol in petroleum heated to 50° C. and to this stirred solution, dimethyl 25 naphtha) and triethylaluminum (0.154 ml of a 1.7 molar diethoxysilane (0.392 g, 2.64 mmol) was added as an ether solution in cyclohexane, 260umol) was added followed by based electron donor ligand. To the above Solution a mixture nickel ethylhexanoate (0.02 ml of an 8 weight 96 nickel of tris(pentafluorophenyl) boron (234 umol in petroleum Solution in mineral Spirits, 26.umol). The reaction was naphtha) and triethylaluminum (0.154 ml of a 1.7 molar allowed to run for 6 hours and then the reaction was solution in cyclohexane, 260 umol) was added followed by quenched with methanol. The solution was diluted and the nickel ethylhexanoate (0.02 ml of an 8 weight % nickel polymer was precipitated in exceSS acetone. The precipitated Solution in mineral Spirits, 26 umol). The reaction was polymer was filtered, washed with acetone and dried over allowed to run for 6 hours and then the reaction was night under vacuum. The yield of polymer was 4.05 g (81%). quenched with methanol. The solution was diluted and the The polymer was characterized using GPC and these results polymer was precipitated in exceSS acetone. The precipitated 35 are provided in Table 2. polymer was filtered, washed with acetone and dried over 5) Norbornene polymerization with 10 mole % of allyl night under vacuum. The yield of polymer was 4.55g (92%). chloride as chain transfer agent: The polymer was characterized using GPC and these results To a 100 ml glass vial equipped with a teflon coated stir are provided in Table 2. bar was added norbornene (5.0 g, 53 mmol), cyclohexane 2) Norbornene polymerization with 2 mole % of allyl 40 (55 ml) and allyl chloride (0.406 g., 0.0053 mol) as chain chloride as chain transfer agent: transfer agent to control molecular weight. The Solution was To a 100 ml glass vial equipped with a teflon coated stir heated to 50° C. and to this stirred solution, dimethyl bar was added norbornene (5.0 g, 53 mmol), cyclohexane diethoxysilane (0.392 g, 2.64 mmol) was added as an ether based electron donor ligand. To the above Solution a mixture (55 ml) and allyl chloride (0.081 g, 0.001 mol) as chain of tris(pentafluorophenyl) boron (234 umol in petroleum transfer agent to control molecular weight. The Solution was 45 naphtha) and triethylaluminum (0.154 ml of a 1.7 molar heated to 50° C. and to this stirred solution, dimethyl solution in cyclohexane, 260umol) was added followed by diethoxysilane (0.392 g, 2.64 mmol) was added as an ether nickel ethylhexanoate (0.02 ml of an 8 weight 96 nickel based electron donor ligand. To the above Solution a mixture Solution in mineral Spirits, 26.umol). The reaction was of tris(pentafluorophenyl) boron (234 umol in petroleum allowed to run for 6 hours and then the reaction was naphtha) and triethylaluminum (0.154 ml of a 1.7 molar 50 quenched with methanol. The solution was diluted and the solution in cyclohexane, 260 umol) was added followed by polymer was precipitated in exceSS acetone. The precipitated nickel ethylhexanoate (0.02 ml of an 8 weight % nickel polymer was filtered, washed with acetone and dried over Solution in mineral Spirits, 26 umol). The reaction was night under vacuum. The yield of polymer was 3.55 (71%). allowed to run for 6 hours and then the reaction was The polymer was characterized using GPC and these results quenched with methanol. The solution was diluted and the 55 are provided in Table 2. polymer was precipitated in exceSS acetone. The precipitated polymer was filtered, washed with acetone and dried over TABLE 2 night under vacuum. The yield of polymer was 4.25 g (85%). Mole % Yield of Molecular The polymer was characterized using GPC and these results Sample of Allyl polymer weight (10 are provided in Table 2. 60 3) Norbornene polymerization with 3 mole % of allyl # chloride (%) Mn Mw Polydispersity chloride as chain transfer agent: 1. 1. 91 2 2 85 109 294 2.7 To a 100 ml glass vial equipped with a teflon coated stir 3 3 86 51 148 2.9 bar was added norbornene (5.0 g, 53 mmol), cyclohexane 4 5 81 26 12O 4.7 (55 ml) and allyl chloride (0.121 g, 0.0016 mol) as chain 65 5 1O 71 2O 96 4.8 transfer agent to control molecular weight. The Solution was heated to 50° C. and to this stirred solution, dimethyl US 6,232,417 B1 83 84 EXAMPLE 82 mixture of tris(pentafluorophenyl)boron (196 umol in petro Alkyl Norbornene/norbornene Copolymers Using Tech II leum naphtha) and triethylaluminum (0.131 ml of a 1.7 Catalyst With And Without Ether as an Electron Donor molar Solution in cyclohexane, 218 umol) was added fol Ligand lowed by nickel ethylhexanoate (0.017 ml of an 8 weight% 1) Copolymer of norbornene/hexyl norbornene (95/5 nickel Solution in mineral Spirits, 21.8 umol). The reaction mole ratio). was allowed to run for 6 hours and then the reaction was To a 100 ml glass vial equipped with a teflon coated stir quenched with methanol. The solution was diluted and the bar was added norbornene (4.56 g., 48.4 mmol), cyclohexane polymer was precipitated in exceSS acetone. The precipitated (50 ml) and Hexyl norbornene (0.456 g, 2.5 mmol). The polymer was filtered, washed with acetone and dried over Solution was heated to 70° C. and to this stirred solution, a night under vacuum. The yield of polymer was 4.35 (87%). mixture of tris(pentafluorophenyl) boron (222umol in petro The polymer was characterized using GPC for molecular leum naphtha) and triethylaluminum (0.148 ml of a 1.7 weight and 'C NMR for copolymer composition and these molar Solution in cyclohexane, 247 umol) was added fol results are provided in Table 3. lowed by nickel ethylhexanoate (0.019 ml of an 8 weight% 5) Copolymer of norbornene/hexyl norbornene (75/25 nickel Solution in mineral Spirits, 24.7umol). The reaction 15 mole ratio). was allowed to run for 6 hours and then the reaction was To a 100 ml glass vial equipped with a teflon coated stir quenched with methanol. The solution was diluted and the bar was added norbornene (3.0 g, 31.9 mmol), cyclohexane polymer was precipitated in exceSS acetone. The precipitated (50 ml) and Hexyl norbornene(1.9 g, 10.6 mmol). The polymer was filtered, washed with acetone and dried over Solution was heated to 70° C. and to this stirred solution, a night under vacuum. The yield of polymer was 4.5 (90%). mixture of tris(pentafluorophenyl)boron (172 umol in petro The polymer was characterized using GPC for molecular leum naphtha) and triethylaluminum (0.12 ml of a 1.7 molar weight and 'C NMR for copolymer composition and these solution in cyclohexane, 192 umol) was added followed by results are provided in Table 3. nickel ethylhexanoate (0.015 ml of an 8 weight 9% nickel 2) Copolymer of norbornene/hexyl norbornene (90/10 Solution in mineral Spirits, 19.2 umol). The reaction was mole ratio). 25 allowed to run for 6 hours and then the reaction was To a 100 ml glass vial equipped with a teflon coated stir quenched with methanol. The solution was diluted and the bar was added norbornene (4.15g, 44.1 mmol), cyclohexane polymer was precipitated in exceSS acetone. The precipitated (50 ml) and Hexyl norbornene (0.877 g, 4.90 mmol). The polymer was filtered, washed with acetone and dried over Solution was heated to 70° C. and to this stirred solution, a night under vacuum. The yield of polymer was 4.2 g (87%). mixture of tris(pentafluorophenyl)boron (214 umol in petro The polymer was characterized using GPC for molecular leum naphtha) and triethylaluminum (0.143 ml of a 1.7 weight and mechanical properties of the copolymer and molar Solution in cyclohexane, 238 umol) was added fol these results are provided in Table 3. lowed by nickel ethylhexanoate (0.018 ml of an 8 weight % 6) Copolymer of norbornene/hexyl norbornene (50/50 nickel Solution in mineral Spirits, 23.8 umol). The reaction mole ratio). was allowed to run for 6 hours and then the reaction was 35 To a 100 ml glass vial equipped with a teflon coated stir quenched with methanol. The solution was diluted and the bar was added norbornene (1.7g, 18.1 mmol), cyclohexane polymer was precipitated in exceSS acetone. The precipitated (50 ml) and hexyl norbornene (3.3 g, 18.1 mmol). The polymer was filtered, washed with acetone and dried over Solution was heated to 70° C. and to this stirred solution, a night under vacuum. The yield of polymer was 4.15 (83%). mixture of tris(pentafluorophenyl)boron (149 umol in petro The polymer was characterized using GPC for molecular 40 leum naphtha) and triethylaluminum (0.10 ml of a 1.7 molar weight and 'C NMR for copolymer composition and these solution in cyclohexane, 166 umol) was added followed by results are provided in Table 3. nickel ethylhexanoate (0.013 ml of an 8 weight 9% nickel 3) Copolymer of norbornene/hexyl norbornene (85/15 Solution in mineral Spirits, 16.6 umol). The reaction was mole ratio). allowed to run for 6 hours and then the reaction was To a 100 ml glass vial equipped with a teflon coated stir 45 quenched with methanol. The solution was diluted and the bar was added norbornene (3.76 g., 39.9 mmol), cyclohexane polymer was precipitated in exceSS acetone. The precipitated (50 ml) and Hexyl norbornene (1.26 g, 7.0 mmol). The polymer was filtered, washed with acetone and dried over Solution was heated to 70° C. and to this stirred solution, a night under vacuum. The yield of polymer was 3.65 g (73%). mixture of tris(pentafluorophenyl) boron (214timol in petro The polymer was characterized using GPC for molecular leum naphtha) and triethylaluminum (0.143 ml of a 1.7 50 weight and mechanical properties of the copolymer and molar Solution in cyclohexane, 238 umol) was added fol these results are provided in Table 3. lowed by nickel ethylhexanoate (0.018 ml of an 8 weight% 7) Copolymer of norbornene/hexyl nobornene (75/25 nickel Solution in mineral Spirits, 23.8 umol). The reaction mole ratio). was allowed to run for 6 hours and then the reaction was To a 100 ml glass vial equipped with a teflon coated stir quenched with methanol. The solution was diluted and the 55 bar was added norbornene (0.7 g, 7.4 mmol), cyclohexane polymer was precipitated in exceSS acetone. The precipitated (50 ml) and Hexyl norbornene (4.0 g, 22.3 mmol). The polymer was filtered, washed with acetone and dried over Solution was heated to 70° C. and to this stirred solution, a night under vacuum. The yield of polymer was 4.35 (87%). mixture of tris(pentafluorophenyl)boron (126 umol in petro The polymer was characterized using GPC for molecular leum naphtha) and triethylaluminum (0.09 ml of a 1.7 molar weight and 'C NMR for copolymer composition and these 60 solution in cyclohexane, 140 umol) was added followed by results are provided in Table 3. nickel ethylhexanoate (0.011 ml of an 8 weight 9% nickel 4) Copolymer of norbornene/hexyl norbornene (80/20 Solution in mineral Spirits, 14 umol). The reaction was mole ratio). allowed to run for 6 hours and then the reaction was To a 100 ml glass vial equipped with a teflon coated stir quenched with methanol. The solution was diluted and the bar was added norbornene (3.39 g, 36 mmol), cyclohexane 65 polymer was precipitated in exceSS acetone. The precipitated (50 ml) and Hexyl norbornene (1.61 g, 9.0 mmol). The polymer was filtered, washed with acetone and dried over Solution was heated to 70° C. and to this stirred solution, a night under vacuum. The yield of polymer was 4.0 g (87%). US 6,232,417 B1 85 86 The polymer was characterized using GPC for molecular weight and mechanical properties of the copolymer and TABLE 3 these results are provided in Table 3. Mechanical 8) Homopolymer of hexyl norbornene (100 mole %). NB/Hex.NB con- Properties (% 5 Sam- NB/Hex.NB ratio in ver- elongation on To a 100 ml glass vial equipped with a teflon coated stir ple feed ratio polymer sion film cast from bar was added cyclohexane (50 ml) and hexyl norbornene # (moles) (moles) Mn/Mw(10) 7% CHCl) (3.0 g, 16.8 mmol). The solution was heated to 70° C. and 1. 95/5 95.5/4.5 165/482 90 Film Cracked to this stirred Solution, a mixture of tris(pentafluorophenyl) 2 90/10 91/9 70/426 83 Film Cracked boron (72.9 tumol in petroleum naphtha) and triethylalumi 3 85/15 86/14 149/8OO 87 Film Cracked num (0.049 ml of a 1.7 molar solution in cyclohexane, 81 4 80f2O 78/22 75/460 87 Film Cracked 5 75/25 157/546 87 2.8 O.3 umol) was added followed by nickel ethylhexanoate (0.006 6 50/50 188/524 73 12.5 O.7 ml of an 8 weight % nickel solution in mineral spirits, 8.1 7 25/75 151f470 59 34.8 - O umol). The reaction was allowed to run for 6 hours and then 8 Of1OO 165/482 87 40 9 the reaction was quenched with methanol. The Solution was 15 9: 50/50 346/1,269 73 22 4 diluted and the polymer was precipitated in exceSS acetone. 10* 50/50 124/382 60 24 3 The precipitated polymer was filtered, washed with acetone *9 & 10 were performed in the presence of an ether based electron donor and dried overnight under vacuum. The yield of polymer ligand. was 2.61 (87%). The polymer was characterized using GPC Film Preparation for DMA Analysis for molecular weight and mechanical properties of the Polynobornene copolymer films were cast from a dilute copolymer and these results are provided in Table 3. solution (10%) of the copolymer in chloroform onto a glass 9) Copolymer of norbornene/hexyl norbornene (50/50 plate and allowing the Samples to dry slowly at room mole ratio) in the presence of ether as an electron donor temperature for 15 hours. The samples were then removed ligand. from the glass plate and heated to 180° C. for 1 hour To a 100 ml glass vial equipped with a teflon coated stir 25 followed by heating the polymer films to 300° C. at 5 bar was added norbornene (1.7g, 18.1 mmol), cyclohexane C./min. and maintaining this temperature for 1 hour in a (50 ml) and hexyl norbornene (3.3 g, 18.1 mmol). The nitrogen atmosphere for complete removal of Solvent. The solution was heated to 70° C. and dimethyl diethoxysilane films were then cooled to room temperature and Samples (0.54g, 3.65 mmol) was added as an ether based electron were then cut for StreSS-Strain analysis. Thin film StreSS donor ligand. To the above Solution, a mixture of tris Strain analyses was performed on the above Samples using a (pentafluorophenyl) boron (149 umol in petroleum naphtha) portable universal tester at a Strain rate of 0.1 inches/min. and triethylaluminum (0.10 ml of a 1.7 molar solution in cyclohexane, 166 umol) was added followed by nickel EXAMPLE 83 ethylhexanoate (0.013 ml of an 8 weight 96 nickel solution Alkyl Norbornene/norbornene Copolymers in mineral spirits, 16.6 umol). The reaction was allowed to 35 1) Copolymer of norbornene/hexyl nobornene (50/50 run for 6 hours and then the reaction was quenched with mole ratio). methanol. The solution was diluted and the polymer was To a 50 ml glass vial equipped with a teflon coated stir bar precipitated in exceSS acetone. The precipitated polymer was was added norbornene (1.04 g, 11.1 mmol), cyclohexane (25 filtered, washed with acetone and dried overnight under ml) and hexyl norbornene (2.0 g, 11.2 mmol). A solution of vacuum. The yield of polymer was 4.75 (95%). The polymer 40 the nickel catalyst toluene complex of bisperfluorophenyl was characterized using GPC for molecular weight and nickel,(toluene)Ni(CFs) was prepared in the dry box by mechanical properties of the copolymer and these results are dissolving 0.0053 g (0.011 mmol of (toluene)Ni(CFS) in provided in Table 3. 5 ml of toluene. The active catalyst solution was added to the monomer Solution via a Syringe at ambient temperature. The 10) Copolymer of norbornene/hexyl norbornene (50/50 45 reaction was allowed to Stir for 6 hours at room temperature. mole ratio) in the presence of ether as an electron donor The solution was diluted with THF and the polymer was ligand and allyl trifluoro acetate as chain transfer agent. precipitated in exceSS acetone. The precipitated polymer was To a 100 ml glass vial equipped with a teflon coated stir filtered, washed with acetone and dried overnight under bar was added norbornene (1.7g, 18.1 mmol), cyclohexane vacuum. The yield of polymer was 2.9 (96%). The polymer (50 ml) and hexyl norbornene (3.3 g, 18.1 mmol). The 50 was characterized using GPC for molecular weight. solution was heated to 70° C. allyl trifluoroacetate (0.095 ml, Mn=348,000 and Mw- 1.061,000. 0.73 mmol) was added as chain transfer agent to control molecular weight and dimethyl diethoxysilane (0.54g, 3.65 EXAMPLE 84 mmol) was added as an ether based electron donor ligand. To Alkyl Norbornene/norbornene Methylacetate Copolymers the above Solution, a mixture of tris(pentafluorophenyl) 55 1) Copolymer of hexyl norbornene/norbornene methylac boron (149 umol in petroleum naphtha) and triethylalumi etate (bicyclo2.2.1]hept-5-ene-2-methyl acetate (80/20 num (0.10 ml of a 1.7 molar solution in cyclohexane, 166 mole ratio) in chlorinated Solvent. umol) was added followed by nickel ethylhexanoate (0.013 To a 50 ml glass vial equipped with a teflon coated stir bar ml of an 8 weight % nickel solution in mineral spirits, 16.6 was added hexyl norbornene (4.0g, 22.1 mmol), chloroben umol). The reaction was allowed to run for 6 hours and then 60 Zene (30 ml) and norbornene methylacetate (0.95 g, 5.7 the reaction was quenched with methanol. The Solution was mmol). The solution was heated to 70° C. and to the above diluted and the polymer was precipitated in exceSS acetone. solution, a mixture of tris(pentafluorophenyl) boron (120.6 The precipitated polymer was filtered, washed with acetone umol in petroleum naphtha) and triethylaluminum (0.08 ml and dried overnight under vacuum. The yield of polymer of a 1.7 molar Solution in cyclohexane, 134 umol) was added was 3.65 (73%). The polymer was characterized using GPC 65 followed by nickel ethylhexanoate (0.010 ml of an 8 weight for molecular weight and mechanical properties of the % nickel Solution in mineral Spirits, 13.4 umol). The reaction copolymer and these results are provided in Table 3. was allowed to run for 12 hours and then the reaction was US 6,232,417 B1 87 88 quenched with methanol. The solution was diluted and the night under vacuum. The yield of polymer was 2.1 g (39%). polymer was precipitated in exceSS acetone. The precipitated The polymer was characterized using GPC for molecular polymer was filtered, washed with acetone and dried over weight. Mn=122,000 and Mw-523,000. "H NMR indicated night under vacuum. The yield of polymer was 3.25 (63%). the presence of the methylacetate, and the copolymer com The polymer was characterized using GPC for molecular position was very close to that of the feed ratio. weight. Mn=231,000 and Mw-523,000. "H NMR indicated EXAMPLE 85 the presence of the methylacetate, and the copolymer com Alkyl Norbornene/norbornene Methylacetate Copolymers position was very close to that of the feed ratio. 1) Copolymer of hexyl norbornene/norbornene methylac 2) Copolymer of hexyl nobornene/nobornene methylac etate (bicyclo2.2.1]hept-5-ene-2-methyl acetate (80/20 etate (bicyclo2.2.1]hept-5-ene-2-methyl acetate (75/25 mole ratio) in hydrocarbon Solvent. mole ratio) in chlorinated Solvent. To a 50 ml glass vial equipped with a teflon coated stir bar To a 50 ml glass vial equipped with a teflon coated stir bar was added hexyl norbornene (2.44 g., 13.68 mmol), cyclo was added hexyl nobornene (39.6 g., 0.22 mol), chloroben hexane (25 ml) nobornene methylacetate (0.576 g., 3.47 Zene (175 ml) and nobornene methylacetate (12.3 g, 74 mmol). A Solution of the nickel catalyst toluene complex of mmol). The solution was heated to 70° C. and to the above 15 bisperfluorophenyl nickel, (toluene)Ni(CFs) was pre solution, a mixture of tris(pentafluorophenyl) boron (1206 pared in the dry box by dissolving 0.0041 g 0.0085 mmol mmol in petroleum naphtha) and triethylaluminum (0.85 ml of (toluene)Ni(CF) in 5 ml of toluene. The active catalyst of a 1.7 molar solution in cyclohexane, 1340 mmol ) was Solution was added to the monomer Solution via a Syringe at added followed by nickel ethylhexanoate (0.105 ml of an 8 ambient temperature. The reaction was allowed to stir for 20 weight% nickel solution in mineral spirits, 134 mmol). The hours at room temperature. The solution was diluted with reaction was allowed to run for 12 hours and then the THF and the polymer was precipitated in excess acetone. reaction was quenched with methanol. The Solution was The precipitated polymer was filtered, washed with acetone diluted and the polymer was precipitated in exceSS acetone. and dried overnight under Vacuum. The yield of polymer The precipitated polymer was filtered, washed with acetone was 2.4 (79.5%). The polymer was characterized using GPC and dried overnight under vacuum. The yield of polymer 25 for molecular weight. Mn=177,000 and Mw =401,000. H was 29 g (56%). The polymer was characterized using GPC NMR indicated the presence of the methylacetate, and the for molecular weight. Mn=167,000 and Mw-349,000. "H copolymer composition was very close to that of the feed NMR indicated the presence of the methylacetate, and the ratio. copolymer composition was very close to that of the feed 2) Copolymer of hexyl norbornene/nobornene methylac ratio. etate (bicyclo2.2.1]hept-5-ene-2-methyl acetate (70/30 3) Copolymer of hexyl nobornene/nobornene methylac mole ratio) in hydrocarbon Solvent. etate (bicyclo2.2.1]hept-5-ene-2-methyl acetate (70/30 To a 50 ml glass vial equipped with a teflon coated stir bar mole ratio) in chlorinated Solvent. was added hexyl norbornene (2.15g, 12.1 mmol), cyclo To a 50 ml glass vial equipped with a teflon coated stir bar hexane (25 ml) nobornene methylacetate (0.885 g, 5.32 was added hexyl nobornene (4.0g, 22.1 mmol), chloroben 35 mmol). A Solution of the nickel catalyst toluene complex of Zene (30 ml) and nobornene methylacetate (1.6 g., 9.6 bisperfluorophenyl nickel, (toluene)Ni(CFs) was pre mmol). The solution was heated to 70° C. and to the above pared in the dry box by dissolving 0.0042 g O.0086 mmol solution, a mixture of tris(pentafluorophenyl) boron (145 of (toluene)Ni(CF) in 5 ml of toluene. The active catalyst umol in petroleum naphtha) and triethylaluminum (0.092 ml Solution was added to the monomer Solution via a Syringe at of a 1.7 molar Solution in cyclohexane, 161 umol) was added 40 ambient temperature. The reaction was allowed to stir for 20 followed by nickel ethylhexanoate (0.010 ml of an 8 weight hours at room temperature. The solution was diluted with % nickel Solution in mineral Spirits, 16.1 umol). The reaction THF and the polymer was precipitated in excess acetone. was allowed to run for 12 hours and then the reaction was The precipitated polymer was filtered, washed with acetone quenched with methanol. The solution was diluted and the and dried overnight under Vacuum. The yield of polymer polymer was precipitated in exceSS acetone. The precipitated 45 was 1.82 g (60%). The polymer was characterized using polymer was filtered, washed with acetone and dried over GPC for molecular weight. Mn=197,000 and Mw-375,000. night under vacuum. The yield of polymer was 2.9 (53%). "H NMR indicated the presence of the methylacetate, and The polymer was characterized using GPC for molecular the copolymer composition was very close to that of the feed weight. Mn=52,000 and Mw =375,000. "H NMR indicated ratio. the presence of the methylacetate, and the copolymer com 50 position was very close to that of the feed ratio. EXAMPLE 86 4) Copolymer of hexyl norbornene/norbornene methylac Alkyl Norbornene/norbornene Methylacetate Copolymers etate (bicyclo2.2.1]hept-5-ene-2-methyl acetate (70/30 1) Copolymer of butyl norbornene/norbornene methylac mole ratio) in hydrocarbon Solvent. etate (bicyclo2.2.1]hept-5-ene-2-methyl acetate (70/30 To a 50 ml glass vial equipped with a teflon coated stir bar 55 mole ratio) catalyst in chlorinated Solvent. was added hexyl norbornene (4.0g, 22.1 mmol), cyclohex To a 50 ml glass vial equipped with a teflon coated stir bar ane (30 ml) and norbornene methylacetate (1.6 g., 9.6 mmol). was added butyl norbornene (3.0g, 20.0 mmol), chloroben The solution was heated to 70° C. and to the above solution, Zene (30 ml) and norbornene methylacetate (1.45 g, 8.7 a mixture of tris(pentafluorophenyl) boron (145 umol in mmol). The solution was heated to 70° C. and to the above petroleum naphtha) and triethylaluminum (0.092 ml of a 1.7 60 solution, a mixture of tris(pentafluorophenyl) boron (120.6 molar Solution in cyclohexane, 161 umol) was added fol umol in petroleum naphtha) and triethylaluminum (0.08 ml lowed by nickel ethylhexanoate (0.010 ml of an 8 weight% of a 1.7 molar Solution in cyclohexane, 134 umol) was added nickel Solution in mineral Spirits, 16.1 umol). The reaction followed by nickel ethylhexanoate (0.010 ml of an 8 weight was allowed to run for 12 hours and then the reaction was % nickel Solution in mineral Spirits, 13.4 umol). The reaction quenched with methanol. The solution was diluted and the 65 was allowed to run for 12 hours and then the reaction was polymer was precipitated in exceSS acetone. The precipitated quenched with methanol. The solution was diluted and the polymer was filtered, washed with acetone and dried over polymer was precipitated in exceSS acetone. The precipitated US 6,232,417 B1 89 90 polymer was filtered, washed with acetone and dried over cipitated in excess acetone. The precipitated polymer was night under vacuum. The yield of polymer was 2.1 g (49%). filtered, washed with acetone and dried overnight under The polymer was characterized using GPC for molecular vacuum. The yield of polymer was 2.25 g (75%). The weight. Mn=164,000 and Mw-383,000. "H NMR indicated polymer was characterized using GPC for molecular weight. the presence of the methylacetate, and the copolymer com Mn=389,000 and Mw-872,000. "H NMR indicated the position was very close to that of the feed ratio. presence of the methylbenzoate, and the copolymer compo 2) Copolymer of butyl norbornene/norbornene methylac etate (bicyclo2.2.1]hept-5-ene-2-methyl acetate (80/20 sition was very close to that of the feed ratio. mole ratio) in chlorinated Solvent. EXAMPLE 88 To a 50 ml glass vial equipped with a teflon coated stir bar Alkyl Norbornene/norbornene Methyl Ethylcarbonate was added butyl norbornene (3.0g, 20.0 mmol), chloroben Copolymer Zene (30 ml) and norbornene methylacetate (0.85 g, 5.1 1) Copolymer of hexyl nobornene/nobornene methyl eth mmol). The solution was heated to 70° C. and to the above ylcarbonate (bicyclo2.2.1]hept-5-ene-2-methyl ethylcar Solution, a mixture of tris(pentafluorophenyl) boron (116 bonate (80/20 mole ratio) in hydrocarbon solvent. umol in petroleum naphtha) and triethylaluminum (0.07 ml 15 To a 50 ml glass vial equipped with a teflon coated stir bar of a 1.7 molar Solution in cyclohexane, 129 umol) was added was added hexyl nobornene (2.35 g, 13.1 mmol), cyclohex followed by nickel ethylhexanoate (0.009 ml of an 8 weight ane (30 ml) nobornene methyl ethylcarbonate (0.64 g, 3.3 % nickel solution in mineral spirits, 12.9 umol). The reaction mmol). A Solution of the nickel catalyst toluene complex of was allowed to run for 12 hours and then the reaction was bisperfluorophenyl nickel, (toluene)Ni(CFs) was pre quenched with methanol. The solution was diluted and the pared in the dry box by dissolving 0.004 g0.0083 mmol of polymer was precipitated in exceSS acetone. The precipitated (toluene)Ni(CFS) in 5 ml of toluene. The active catalyst polymer was filtered, washed with acetone and dried over Solution was added to the monomer Solution via a Syringe at night under vacuum. The yield of polymer was 2.1 g (55%). ambient temperature. The reaction was allowed to stir for 5 The polymer was characterized using GPC for molecular hours at room temperature. The solution was diluted with weight. Mn=205,000 and Mw-507,000. "H NMR indicated 25 THF and the polymer was precipitated in excess acetone. the presence of the methylacetate, and the copolymer com The precipitated polymer was filtered, washed with acetone position was very close to that of the feed ratio. and dried overnight under Vacuum. The yield of polymer EXAMPLE 87 was 2.1 g (70%). The polymer was characterized using GPC Alkyl Norbornene/norbornene Methylbenzoate Copoly for molecular weight. Mn=356,000 and Mw =906,000. H CS. NMR indicated the presence of the methyl ethylcarbonate, 1) Copolymer of hexyl norbornene/norbornene methyl and the copolymer composition was very close to that of the benzoate (bicyclo2.2.1]hept-5-ene-2-methyl benzoate (90/ feed ratio. 10 mole ratio) in hydrocarbon Solvent. EXAMPLE 89 To a 50 ml glass vial equipped with a teflon coated stir bar Alkyl Norbornene/norbornene Methyl Methoxyacetate was added hexyl norbornene (2.63 g, 14.7 mmol), cyclo 35 Copolymer hexane (30 ml) and norbornene methylbenzoate (0.37 g, 1) Copolymer of hexyl norbornene/norbornene methyl 1.64 mmol). The solution was heated to 70° C. and to the methoxyacetate (bicyclo2.2.1 hept-5-ene-2-methyl meth above Solution, a mixture of tris(pentafluorophenyl) boron oxyacetate (80/20 mole ratio) in hydrocarbon solvent. (72 umol in petroleum naphtha) and triethylaluminum To a 50 ml glass vial equipped with a teflon coated stir bar (0.047 ml of a 1.7 molar solution in cyclohexane, 80 umol) 40 was added hexyl nobornene (2.35 g, 13.1 mmol), cyclohex was added followed by nickel ethylhexanoate (0.006 ml of ane (30 ml) nobornene methyl methoxyacetate (0.64g, 3.3 an 8 weight% nickel Solution in mineral spirits, 8.04 umol). mmol). A Solution of the nickel catalyst toluene complex of The reaction was allowed to run for 12 hours and then the bisperfluorophenyl nickel, (toluene)Ni(CFs) was pre reaction was quenched with methanol. The Solution was pared in the dry box by dissolving 0.004 g0.0083 mmol of diluted and the polymer was precipitated in exceSS acetone. 45 (toluene)Ni(CFS) in 5 ml of toluene. The active catalyst The precipitated polymer was filtered, washed with acetone Solution was added to the monomer Solution via a Syringe at and dried overnight under vacuum. The yield of polymer ambient temperature. The reaction was allowed to stir for 5 was 2.55 g (83%). The polymer was characterized using hours at room temperature. The solution was diluted with GPC for molecular weight. Mn=189,000 and Mw-523,000. THF and the polymer was precipitated in excess acetone. "H NMR indicated the presence of the methylbenzoate, and 50 The precipitated polymer was filtered, washed with acetone the copolymer composition was very close to that of the feed and dried overnight under Vacuum. The yield of polymer ratio. was 1.5 g (70%). The polymer was characterized using GPC 2) Copolymer of hexyl norbornene/norbornene methyl for molecular weight. Mn=312,000 and Mw =616,000. H benzoate (bicyclo2.2.1]hept-5-ene-2-methyl benzoate (90/ NMR indicated the presence of the methyl methoxyacetate, 10 mole ratio) in hydrocarbon solvent. 55 and the copolymer composition was very close to that of the To a 50 ml glass vial equipped with a teflon coated stir bar feed ratio. was added hexyl norbornene (2.63 g, 14.7 mmol), cyclo hexane (30 ml) norbornene methylbenzoate (0.37 g, 1.64 EXAMPLE 90 mmol) and and triethylaluminum (0.024 ml of a 1.7 molar Alkyl Nobornene/trimethyl Silyl Protected Norbornene Solution in cyclohexane). A Solution of the nickel catalyst 60 Methanol Copolymer toluene complex of bisperfluorophenyl nickel, (toluene)Ni 1) Copolymer of hexyl norbornene/trimethylsilyl pro (CFS) was prepared in the dry box by dissolving 0.004g tected nobornene methanol (trimethylsilyl protected bicyclo 0.0083 mmol of (toluene)Ni(CF) in 5 ml of toluene. The 2.2.1]hept-5-ene-2-methanol (80/20 mole ratio) in hydro active catalyst Solution was added to the monomer Solution carbon Solvent. via a Syringe at ambient temperature. The reaction was 65 To a 50 ml glass vial equipped with a teflon coated stir bar allowed to stir for 20 hours at room temperature. The was added hexyl norbornene (2.43 g, 13.6 mmol), cyclo solution was diluted with THF and the polymer was pre hexane (30 ml) trimethylsilyl protected norbornene metha US 6,232,417 B1 91 92 nol (0.57 g, 3.41 mmol). A solution of the nickel catalyst was filtered, washed with acetone and dried overnight under toluene complex of bisperfluorophenyl nickel, (toluene)Ni vacuum. The yield of polymer was 1.68 g (84%). The (CFS) was prepared in the dry box by dissolving 0.004g polymer was characterized using GPC for molecular weight. 0.0083 mmol of (toluene)Ni(CFS) in 5 ml of toluene. The Mn=132,000 and Mw-748,000. active catalyst Solution was added to the monomer Solution via a Syringe at ambient temperature. The reaction was EXAMPLE 94 allowed to stir for 20 hours at room temperature. The Homopolymerization of Bicyclo2.2.1]hept-5-ene-2-methyl solution was diluted with THF and the polymer was pre Acetate cipitated in excess acetone. The precipitated polymer was To a 50 ml glass vial equipped with a teflon coated stir bar filtered, washed with acetone and dried overnight under was added bicyclo2.2.1]hept-5-ene-2-methyl acetate (2.06 vacuum. The yield of polymer was 2.7 (90%). The polymer g, 12.2 mmol). A Solution of the nickel catalyst toluene was characterized using GPC for molecular weight. complex of bisperfluorophenyl nickel, (toluene)Ni(CFs). Mn=372,000 and Mw-660,000. "H NMR indicated the was prepared in the dry box by dissolving 0.0291 g 0.0602 presence of the trimethylsilyl groups, and the copolymer mmol of (toluene)Ni(CF) in 7 ml of toluene. The active composition was very close to that of the feed ratio. 15 catalyst Solution was added to the monomer Solution via a Syringe at ambient temperature. The reaction was allowed to EXAMPLE 91 Stir for 6 hours at room temperature. The Solution was Homopolymerization of Bicyclo2.2.1]hept-5-ene-2-methyl diluted with toluene and the polymer was precipitated in Butyl Ether exceSS methanol. The precipitated polymer was filtered, To a 50 ml glass vial equipped with a teflon coated stir bar washed with acetone and dried overnight under Vacuum. The was bicyclo[2.2.1]hept-5-ene-2-methyl butyl ether (3.0 g, yield of polymer was 1.76 (88%). The polymer was char 16.6 mmol), and cyclohexane (30 ml). A solution of the acterized using GPC for molecular weight. Mn=48,000 and nickel catalyst toluene complex of bisperfluorophenyl Mw-201,000. nickel, (toluene)Ni(CFS) was prepared in the dry box by EXAMPLE 95 dissolving 0.004 g0.0083 mmol of(toluene)Ni(CFS) in 5 25 ml of toluene. The active catalyst Solution was added to the Copolymerization of Bicyclo2.2.1]hept-5-ene-2-methyl monomer Solution via a Syringe at ambient temperature. The Acetate/t-butylester of Norbornene reaction was allowed to Stir for 20 hours at room tempera To a 50 ml glass vial equipped with a teflon coated stir bar ture. The solution was diluted with THF and the polymer was added bicyclo2.2.1]hept-5-ene-2-methyl acetate (4.63 was precipitated in exceSS acetone. The precipitated polymer g, 27.91 mmol)and t-butylester of norbornene (5.42 g, 27.93 was filtered, washed with acetone and dried overnight under mmol) and 15 ml of toluene. A solution of the nickel catalyst vacuum. The yield of polymer was 0.96 g (32%). The toluene complex of bisperfluorophenyl nickel, (toluene)Ni polymer was characterized using GPC for molecular weight. (C.F.) was prepared in the dry box by dissolving 0.1339 Mn=285,000 and Mw-721,000. g 0.276 mmol of (toluene)Ni(CFS) in 10 ml of toluene. The active catalyst Solution was added to the monomer EXAMPLE 92 35 Solution via a Syringe at ambient temperature. The reaction Homopolymerization of Trimethylsilyl Protected Bicyclo was allowed to stir for 6 hours at room temperature. The 2.2.1]hept-5-ene-2-methanol. Solution was diluted with toluene and the polymer was To a 50 ml glass vial equipped with a teflon coated stir bar precipitated in exceSS methanol. The precipitated polymer was bicyclo[2.2.1]hept-5-ene-2-methanol (3.0 g, 18.03 was filtered, washed with acetone and dried overnight under mmol), and cyclohexane (30 ml). A solution of the nickel 40 vacuum. The isolated yield of polymer was 5.5 g (55%). The catalyst toluene complex of bisperfluorophenyl nickel, polymer was characterized using GPC for molecular weight. (toluene)Ni(CFS) was prepared in the dry box by dissolv Mn=43,000 and Mw-89,000. ing 0.0044 g (0.0090 mmol of (toluene)Ni(CF) in 5 ml of toluene. The active catalyst Solution was added to the EXAMPLE 96 monomer Solution via a Syringe at ambient temperature. The 45 Comopolymerization of Bicyclo[2.2.1]hept-5-ene-2-methyl reaction was allowed to Stir for 20 hours at room tempera Ethylcarbonate/t-butylester of Norbornene ture. The solution was diluted with THF and the polymer To a 50 ml glass vial equipped with a teflon coated stir bar was precipitated in exceSS acetone. The precipitated polymer was added bicyclo2.2.1]hept-5-ene-2-methyl ethylcarbon was filtered, washed with acetone and dried overnight under ate (5.03 g, 25.65 mmol) and t-butylester of norbornene vacuum. The yield of polymer was 1.95 g (65%). The 50 (4.988 g, 25.68 mmol) and 15 ml of toluene. A solution of polymer was characterized using GPC for molecular weight. the nickel catalyst toluene complex of bisperfluorophenyl Mn=448,000 and Mw-650,000. nickel, (toluene)Ni(CFS) was prepared in the dry box by dissolving 0.1239 g (0.255 mmol of (toluene)Ni(CF) in EXAMPLE 93 10 ml of toluene. The active catalyst solution was added to Homopolymerization of Bicyclo2.2.1]hept-5-ene-2-methyl 55 the monomer Solution via a Syringe at ambient temperature. Ethylcarbonate The reaction was allowed to stir for 6 hours at room To a 50 ml glass vial equipped with a teflon coated stir bar temperature. The solution was diluted with toluene and the was added bicyclo2.2.1]hept-5-ene-2-methyl ethylcarbon polymer was precipitated in exceSS methanol. The precipi ate (2.06 g, 10.5 mmol). A solution of the nickel catalyst tated polymer was filtered, washed with acetone and dried toluene complex of bisperfluorophenyl nickel, (toluene)Ni 60 overnight under vacuum. The isolated yield of polymer was (C.F.) was prepared in the dry box by dissolving 0.0247 4.5 g (45%). The polymer was characterized using GPC for g 0.0525 mmol of (toluene)Ni(CF) in 7 ml of toluene. molecular weight. Mn=44,000 and Mw =87,000. The active catalyst Solution was added to the monomer Solution via a Syringe at ambient temperature. The reaction EXAMPLE 97 was allowed to stir for 6 hours at room temperature. The 65 Synthesis of (m-methallyl)nickel(norbornene) Chloride Solution was diluted with toluene and the polymer was This nickel Species was generated in a manner Similar to precipitated in exceSS methanol. The precipitated polymer that described by T. L. Hanlon et al., Journal of Organo US 6,232,417 B1 93 94 metallic Chemistry, Volume 33, 1971, pages C45-46. To a 0.017 mmol). The mixture was allowed to stir for 1 hour at solution of norbornene (0.52 g) dissolved in 2.5g of toluene 70° C. The resulting mixture was then poured into an excess was added all at once a solid (m-CHC(CH))NiCI) (0.012 of methanol to precipitate the polymer. The polymer was g). After Stirring overnight at room temperature for over filtered and dried in the vacuum oven overnight. Yield 0.27 night the Solution changed from a clear red orange to a g (11%). murky red orange brown Sludge. The red orange powder obtained by filtration was washed with dried pentane. If EXAMPLE 100 Stirring is stopped after addition and dissolution of the Solid NB-type Monomer Polymerization Using Catalyst E (m-CHC(CH))NiCl, bright red crystals are obtained by Norbornene (2.0g, 21 mmol) and triethoxysilylnobornene filtration. Yield 0.78 g (95%). Reaction of (m-methallyl) (1.6 g., 7.5 mmol) was added to a vial in the glove box nickel(norbornene) chloride with Zn(CF)-(dime). To (m- equipped with a stir bar. The vial was sealed with a Teflon CHC(CH))Ni(norbornene)C1 (0.102 g) stirring in lined rubber Septum cap. The norbornene monomers were d-benzene (0.6 ml) was added Zn(CFS)-(dime) (0.71 g). dissolved in cyclohexane to a total volume of 30 ml. To this The reaction mixture immediately turned from orange red vial was added (PhC(O)CHCH-PPh)Ni(CF5) (0.0102 g, Suspension to a dark brown mixture. The Solution was Stirred 15 0.014 mmol). The mixture was allowed to stir overnight. at room temperature for 48 hours and then filtered to yield The resulting mixture was then poured into an excess of a pale orange Solution. Analysis of the product by proton methanol to precipitate the polymer. The polymer was NMR indicated that the major reaction product was filtered and dried in the vacuum oven overnight. Yield 0.78 2-methyl-2-propenylpentafluorobenzene. A mass spectrum g (21%). recorded on the reaction product confirmed the major prod uct as 2-methyl-2-propenyl pentafluorobenzene (mw=222), EXAMPLE 1.01 and showed that mono-inserted product, CFs-norbornene NB-type Monomer Polymerization Using Catalyst J CHC(CH)=CH (mw-316), and bis-inserted product Norbornene (2.5g, 27 mmol) was added to a vial in the CFs-(norbornene)-CHC(CH)=CH (mw-410) were glove box equipped with a stir bar. The Vial was Sealed with also formed. This example provides evidence of pentafluo 25 a Teflon(R)-lined rubber septum cap. The norbornene mono rophenyl transfer from the Zinc reagent, nobornene insertion mer was dissolved in toluene to a total volume of 30 ml. To (as a way to polymerize monomer), and a reductive elimi this vial was added Ni(PPh)(C.F.) (0.012 g, 0.013 nation process, involving pentafluorophenyl, to yield the mmol). The mixture was allowed to stir for 2 hours at 70 product. C. The resulting mixture was then poured into an excess of methanol to precipitate the polymer. The polymer was EXAMPLE 98 filtered and dried in the vacuum oven overnight. Yield 0.15 NB Polymerization Using Catalyst A g (7%). Norbornene (5.0 g, 53 mmol) was added to a vial in the glove box equipped with a stir bar. The Vial was Sealed with EXAMPLES 102-144 a Teflon(R)-lined rubber septum cap. The nobornene was 35 Polymerization Procedure Using Catalyst B dissolved in the toluene to a total volume of 60 ml. To this Norbornene (5.0 g, 53 mmol) (or the appropriate amount vial was added a toluene solution (5 ml) (PhC(O)CH2PPh.) of norbornene-type monomer, see table below) was added to Ni(CFs). (0.018 g., 0.026 mmol). The mixture was allowed a vial in the glove box equipped with a Stir bar. The Vial was to Stir for 1 hour at room temperature. The resulting mixture sealed with a Teflon(R)-lined rubber septum cap. The nor was then poured into an excess of methanol to precipitate the 40 bornene was dissolved in the solvent of choice (see table polymer. The polymer was filtered and dried in the vacuum below) to a total volume of 30 ml. To this vial was added a oven overnight. Yield 1.94 g (39%). (minumum amount of the solvent of choice, either THF or toluene, see comments table below) Solution of an appro EXAMPLE 99 priate amount of the nickel catalyst (see table below). The NB Polymerization Using Catalyst D 45 mixture was allowed to stir for the allotted time at the Norbornene (2.5g, 27 mmol) was added to a vial in the temperature given in table below. The resulting mixture was glove box equipped with a stir bar. The Vial was Sealed with then poured into an excess of methanol to precipitate the a Teflon(R)-lined rubber septum cap. The nobornene was polymer. The polymer was filtered and dried in the vacuum dissolved in the toluene to a total volume of 30 ml. To this oven overnight. The conversions were then determined vial was added (PhNC(O)CH2PPh)Ni(CF) (0.010 g, gravimetrically.

NB-type monomer polymerizations using Catalyst B Exam- Ni Monomer: Tim e Temp Conv CTA Mw Mn ple (mM) Ni (monomer) Solw (h) ( C.) (%) (mol%) (x 10) (x 10) Comments 102 O.43 2000:1 CH 1. amb 97 Ni(THF) (CFs). (NB) delivered in THF 103 O.43 2000:1 CH 1. amb 93 Ni(THF) (CFs). (NB) delivered in THF 104 O.43 2000:1 CH amb 89 Ni(THF) (CF), (NB) delivered in THF 105 0.43 2000:1 (80:20 CH amb 1OO 709 252 Ni(THF) (CFs). NB:MeEsNB) delivered in THF 106 0.43 2000:1 (50:50 CH amb 19 428 138 Ni(THF) (CFs). NB:MeEsNB) delivered in THF US 6,232,417 B1 95 96

-continued NB-type monomer polymerizations using Catalyst B Exam Ni Monomer: Time Temp Conv CTA Mw Mn ple (mM) Ni (monomer) Solv (h) ( C.) (%) (mol%) (x 10) (x 10) Comments 3.43 200:1 (50:50 CH 16 50 50 64.7 33.7 Ni(THF) (CF). NB:t-BuEsNB) delivered in THF O.43 2000:1 (50:50 CH 16 50 5 105 51.6 Ni(THF) (CF). NB:t-BuEsNB) delivered in THF O.43 2100:1 (78:22 CH amb 83 1078 31.8 Ni(THF) (CF). NB:TESNB) delivered in THF O.21 4200:1 (78:22 CH amb 44 1148 392 Ni(THF) (CFs). NB:TESNB) delivered in THF O.11 8500:1 (78:22 CH amb 13 1029 374 Ni(THF) (CFs). NB:TESNB) delivered in THF O.11 8500:1 (78:22 CH 14.5 50 21 1071 392 Ni(THF) (CFs). NB:TESNB) delivered in THF O.11 17000:1 (78:22 CH 14.5 50 trace Ni(THF) (CFs). NB:TESNB) delivered in THF O.21 4200:1 (78:22 To 50 43 819 251 Ni(THF) (CFs). NB:TESNB) delivered in toluene O.21 4200:1 (78:22 To 50 47 1004 339 Ni(THF) (CFs). NB:TESNB) delivered in toluene O.21 4200:1 (78:22 To 1OO trace Ni(THF) (CFs). NB:TESNB) delivered in toluene O.9 1000:1 (78:22 To 70 87 646 170 Ni(THF) (CFs). NB:TESNB) delivered in toluene 1000:1 (78:22 To 50 89 855 157 Ni(THF) (CFs). NB:TESNB) delivered in toluene 8500:1 (78:22 To 60 29 969 356 Ni(THF) (CFs). NB:TESNB) delivered in toluene 8500:1 (78:22 To 70 25 924 349 Ni(THF) (CFs). NB:TESNB) delivered in toluene 21 2000:1 (78:22 To amb 83 1037 229 Ni(THF) (CFs). NB:TESNB) delivered in toluene 22 2000:1 (78:22 To 60 75 900 301 Ni(THF) (CFs). NB TESNB) delivered in toluene 23 2000:1 (78:22 To 70 73 846 222 Ni(THF), (CF), delivered in toluene 24 To al 73 hexene 708 205 Ni(THF) (CFs). (1) delivered in toluene 25 To al 64 hexene 511 2OO Ni(THF) (CFs). (3) delivered in toluene 26 To al 52 hexene 397 155 Ni(THF) (CFs).6 (5) delivered in toluene 27 To al allyl 117 52 Ni(THF) (CFs).6 bromide delivered in toluene (1) 28 To al trace allyl s B: fE SN B) bromide delivered in toluene (3) 29 To al trace allyl Ni(THF) (CFs). s B:f E SN B) bromide delivered in toluene (5) To al 50 betapinene 5O1 209 Ni(THF) (CFs).6 (1) delivered in toluene 31 To al 36 betapinene 214 89 Ni(THF) (CFs).6 (3) delivered in toluene 32 To al trace betapinene Ni(THF) (CFs). (5) delivered in toluene 33 CH 50 60 eXce 870 301 Ni(THF) (CFs). (1) delivered in THF 34 CH 50 56 eXce 540 2O1 Ni(THF) (CFs). (3) delivered in THF 35 O.43 CH 50 49 eXce 475 176 Ni(THF) (CFs). B E SN B) (5) delivered in THF 36 O.43 CH amb 79 eXce 878 269 Ni(THF) (CFs). (1) delivered in THF 37 O.43 CH amb 68 eXce 642 237 Ni(THF) (CFs). (3) delivered in THF 38 O.43 CH amb 57 eXce 524 212 Ni(THF) (CFs). (5) delivered in THF 39 CH amb 67 eXce 861 322 Ni(IHF) (CFs). (1) delivered in THF 40 CH amb 59 eXce 683 258 Ni(THF) (CFs). (3) delivered in THF 41 00:1 (78:22 CH amb 50 eXce 555 184 Ni(THF) (CFs). NB:TESNB) (5) delivered in THF US 6,232,417 B1 97 98

-continued NB-type monomer polymerizations using Catalyst B Exam- Ni Monomer: Time Temp Conv CTA Mw Mn ple (mM) Ni (monomer) Solv (h) ( C.) (%) (mol%) (x 10) (x 10) Comments 142 0.2100 4200:1 (78:22 CH 5 50 37 hexene 642 249 Ni(THF) (CFs). NB:TESNB) (1) delivered in THF 143 O.21 4200:1 (78:22 CH 5 50 34 hexene 736 233 Ni(THF) (CFs). NB:TESNB) (3) delivered in THF 144 O.21 4200:1 (78:22 CH 5 50 7 hexene Ni(THF) (CFs). NB:TESNB) (5) delivered in THF Toll = toluene, CH = cyclohexane, NB = norbornene, TESNB = 5-triethoxysilylnorbonene, MeEsNB = methylester of 5-norbornene carboxylic acid, t-BuEsNB = t-butylester of 5-norbornene carboxylic acid, amb = ambient temperature 15 EXAMPLES 145-162 (toluene)Ni(CFS) in a 60/40 mixture of cyclohexane and Generic Polymerization Procedure Using Catalyst C toluene, unless otherwise specified (see table below). The Norbornene (2.0 g) and triethoxysilylnorbornene (1.6 g), mixture was allowed to stir for the allotted time at the unless otherwise Specified, was added to a vial in the glove temperature given in the Table below. The resulting mixture box equipped with a stir bar. The vial was sealed with a was then poured into an excess of methanol to precipitate the Teflon(R)-lined rubber septum cap. The norbornene mono polymer. The polymer was filtered and dried in the vacuum mers were dissolved in cyclohexane to a total volume of 30 oven overnight. The conversions were then determined ml. To this vial was added an appropriate amount of gravimetrically.

NB-type monomer polymerizations using Catalyst C Ni monomer:Ni Time Temp Conv Example (mM) (monomer) Solv (h) ( C.) (%) Comments 145 0.23 4000:1 (78:22 CHA 5 amb. 46 Catalyst delivered as NB:TESNB) 0.02M solution (40% toluene in CHA) 146 0.11 8000:1 (78:22 CHA 5 amb. 29 Catalyst delivered as NB:TESNB) 0.02M solution (40% toluene in CHA) 147 O.O45 2OOOO:1 CHA ON amb. 12 Catalyst delivered as (78:22 0.02M solution (40% (NB:TESNB) toluene in CHA) 148 0.23 4000:1 (78:22 CHA 5 amb. 23 Catalyst delivered as NB:TESNB) 0.02M solution (40% toluene in CHA). CTA = 1 mol % (on monomers) allyltrifluoroacetate 149 0.11 8000:1 (8:22 CHA 5 amb. 11 Catalyst delivered as NB:TESNB) 0.02M solution (40% toluene in CHA). CTA = 1 mol % (on monomers) allyltrifluoroacetate 150 0.23 4000:1 (78:22 CHA 5 amb. 7 Catalyst delivered as NB:TESNB) 0.02M solution (40% toluene in CHA). CTA = 3 mol % (on monomers) allyltrifluoroacetate 151 0.45 2000:1 (50:50 CHA 4 amb. 54 Catalyst delivered as NB:MeEsNB) 0.02M solution (10% toluene in CHA) 152 0.45 2000:1 (50:50 CHA 4 amb. 22 Catalyst delivered as NB:BuEsNB) 0.02M solution (10% toluene in CHA) 153 0.47 2000:1 (78:22 CHA 3 amb. 32 Catalyst delivered as NB:TESNB) 0.02M solution (in toluene), CTA = mol % styrene on OOCS 154 0.47 2000:1 (78:22 CHA 3 amb. 29 Catalyst delivered as NB:TESNB) 0.02M solution (in toluene), CTA = 5 mol % styrene on OOCS US 6,232,417 B1 99 100

-continued NB-type monomer polymerizations using Catalyst C Ni monomer:Ni Time Temp Conv Example (mM) (monomer) Solv (h) ( C.) (%) Comments 155 0.47 2000:1 (78:22 CHA 21 amb. 59 Catalyst delivered as NB:TESNB) 0.02M solution (in toluene), CTA = 1 mol % styrene on monomers. Mw = 737,000, Min = 145,000 156 0.47 2000:1 (78:22 CHA 21 amb. 43 Catalyst delivered as NB:TESNB) 0.02M solution (in toluene), CTA = 5 mol % styrene on monomers. Mw = 499,000, Min = 239,000 157 0.47 2000:1 (78:22 CHA 3 amb. 84 Catalyst delivered as NB:TESNB) 0.02M solution (in toluene), CTA = 1 mol % cyclopentene on monomers. Mw = 690,000, Min = 247,000 158 0.47 2000:1 (78:22 CHA 3 amb. 40 Catalyst delivered as NB:TESNB) 0.02M solution (in toluene), CTA = 5 mol % cyclopentene on monomers. Mw = 355,000, Min = 135,000 159 0.47 2000:1 (78:22 CHA 3 amb. 83 Catalyst delivered as NB:TESNB) 0.02M solution (in toluene), CTA = 1 mol % cyclohexene on monomers. Mw = 707,000, Min = 220,000 160 0.47 2000:1 (78:22 CHA 3 amb. 54 Catalyst delivered as NB:TESNB) 0.02M solution (in toluene), CTA = 5 mol % cyclohexene on monomers. Mw = 472,000, Min = 223,000 161 0.47 2000:1 (78:22 CHA 3 amb. 62 Catalyst delivered as NB:TESNB) 0.02M solution (in toluene), CTA = 1 mol % cyclooctadiene on monomers. Mw = 605,000, Min = 255,000 162 0.47 2000:1 (78:22 CHA 3 amb. 10 Catalyst delivered as NB:TESNB) 0.02M solution (in toluene), CTA = 5 mol % cyclooctadiene on monomers. Mw = 292,000, Min = 122,000 Toll = toluene, CHA = cyclohexane, NB = norbornene, TESNB = 5-triethoxysilylnorbornene, MeEsNB = 5-methylester of 5-norbornene carboxylic acid, t-BuEsNB = t-butylester of 5-norbornene carboxylic acid, amb. = ambient temperature, ON = overnight, CTA = chain transfer agent. EXAMPLES 163-166 oven at ambient temperature for 24 hours (constant weight) Polymerization of NB-type Monomers Using Catalyst C 55 and weighed. To a 100 ml glass Vial fitted with an airtight crimptop cap and a Teflon(R) stir bar was added at ambient temperature Con nobornene (4.0 g, 42.4 mmol), triethoxysilylnobornene (2.8 ty sent Badise. Yi. version. Mw Mn ml, 10.4 mmol) and toluene or chlorobenzene (35 ml) and " o butadiene as MW control agent as indicated in the following E. then s s 5. 5. Oee s s table. Thereafter WS added (toluene)Ni(CFS) (6.3 mg, 13 165 chloro- 1.06 2.8 42 786,000 340,000 umol) dissolved in toluene (3 ml). After 120 min. reaction benzene time at ambient temperature the viscous solution was diluted as ' One 2.12 2.9 43 586,000 137,000 with toluene (50 ml) and poured into an excess of methanol. The precipitated copolymer was filtered, dried in a vacuum US 6,232,417 B1 101 102 EXAMPLES 1.67-175 EXAMPLE 1.79 Polymerization Procedure Using Catalysts B and C NB Polymerization Using Catalyst H Norbornene (2.0 g) and triethoxysilylnobornene (1.6 g) Approximately 10 mg of Catalyst H was dissolved in was added to a vial in the glove box equipped with a stir bar. about 2 ml of toluene to form a dark blue Solution. This The vial was sealed with a Teflon(R)-lined rubber septum cap. Solution was added to a Solution of nobornene (3.0 g) and The norbornene was dissolved in cyclohexane to a total triethoxysilylnobornene (2.0 g) in cyclohexane (50 ml). The volume of 30 ml. To this vial was added an appropriate resulting light blue Solution began to visibly increase in amount of a 0.02 MSolution of either (toluene)Ni(CF) or viscosity. After 1 hour the viscous solution was added to 300 cis-Ni(THF) (CFS) in a 90/10 mixture of cyclohexane and ml of methanol to precipitate the polymer. The polymer was toluene (see table below). The mixture was allowed to stir filtered and dried. Yield 2,72 g (54%). Mw-945,000 and for the allotted time at the temperature given in the table Mn=306,000 determined by GPC methods. below. The resulting mixture was then poured into an exceSS EXAMPLE 18O of methanol to precipitate the polymer. The polymer was NB Polymerization Using Catalyst I filtered and dried in the vacuum oven overnight. The con 15 Approximately 150 mg of Catalyst I in 5 ml of toluene versions were then determined gravimetrically. was added to a cyclohexane Solution (10 ml) of norbornene (1.0 g). After one hour the Solution was added to methanol (300 ml) to precipitate the polymer. NB (22% Conv Mw Example Catalyst TESNB):Ni (%) (103) Mw/Mn EXAMPLE 181 NB Polymerization Using Catalyst K 67 Catalyst C 2OOO: 79 676 2.42 0.45 mM To a 50 ml glass vial fitted with an airtight crimptop cap 68 Catalyst C 2OOO: 73 738 2.63 and a Teflon(R) stir bar was added at ambient temperature the 0.45 mM norbornene (4.0 g, 4.25 mmol and toluene (35 ml). There 69 Catalyst C 2OOO: 78 684 2.92 after was added Catalyst K (106.4 mg, 10.6 umol) dissolved 0.45 mM 25 70 Catalyst B 2OOO: 78 716 3.21 in toluene (5 ml). Within two minutes the solution became 0.45 mM So Viscous that Stirring Stopped. After 100 minutes the 71 Catalyst B 2OOO: 74 671 2.8 reaction was stopped by opening the Vial, diluting with 0.45 mM toluene and precipitating the polymer into exceSS methanol 72 Catalyst B 2OOO: 79 708 3.01 0.45 mM (400 ml). The polymer was filtered, washed with methanol 73 Catalyst C 4OOO: 55 757 2.17 and dried overnight in a vacuum oven at 80° C. The isolated O.23 mM yield of the polymer was 2.34 grams, representing 59% 74 Catalyst C 4OOO: 54 799 2.23 conversion. The polymer was characterized by NMR meth O.23 mM ods. 75 Catalyst C 4OOO: 53 810 2.28 O.23 mM 35 EXAMPLE 182 NB Polymerization Using Catalyst L To a 100 ml glass Vial fitted with an airtight crimptop cap EXAMPLE 176 and a Teflon(R) stir bar was added at ambient temperature NB Polymerization Using Catalyst F norbornene (5.0 g, 53.1 mmol) and toluene (35 ml). There Approximately 10 mg of Catalyst F was dissolved in 40 after was added (1,2-dimethoxyethane)Ni(2,4,6-tris about 2 ml of toluene. This solution was added to a Solution (trifluoromethyl)phenyl) (13 umol) dissolved in toluene (2 of norbornene (4.7g) in cyclohexane (50 ml). The resulting ml). Within three seconds the contents of the bottle became pale orange Solution began to visibly increase in Viscosity. a very Viscous, nonstirring mass and there was much heat After 1 hour the viscous Solution was added to 300 ml of evolution. When the bottle was opened, after 60 minutes, the methanol to precipitate the polymer. The polymer was 45 gel was So hard that it was almost impossible to remove it from the bottle. The gel was dried in a vacuum oven (80° C.) filtered and dried. Yield 1.21 g (26%). overnight and then cryogenically ground. The weight of EXAMPLE 177 dried, pulverized polymer indicated that the nobornene had been quantitatively converted. NB Polymerization Using Catalyst F 50 Approximately 10 mg of Catalyst F was dissolved in EXAMPLE 1.83 about 3 ml of toluene. This solution was added to a Solution NB-type Monomer Polymerization Using Catalyst L of nobornene (3.0 g) and triethoxysilylnobornene (2.0 g) in To a 100 ml glass Vial fitted with an airtight crimptop cap cyclohexane (50 ml). The resulting pale orange Solution and a Teflon(R) stir bar was added at ambient temperature began to visibly increase in Viscosity. After 1 hour the 55 nobornene (4.0 g, 42.4 mmol), triethylsilylnobornene (2.8 viscous Solution was added to 300 ml of methanol to ml, 10.6 mmol) and toluene (35 ml). Thereafter was added precipitate the polymer. The polymer was filtered and dried. (dimethoxyethane)Ni(2,4,6-tris(trifluoromethyl)phenyl) Yield 0.56 g (11%). Mw-907,000 and Mn=241,000 deter (13 umol) dissolved in toluene (2 ml). After 30 minutes there mined by GPC methods. was noticeable Viscosity, and after 90 minutes reaction time 60 the viscous solution was diluted with toluene (50 ml) and EXAMPLE 1.78 poured into an excess of methanol. The preciptated copoly NB Polymerization Using Catalyst G mer was filtered, dried in a vacuum oven at ambient tem Approximately 10 mg of Catalyst G was dissolved in perature for 24 hours (constant weight) and weighed. The about 2 ml of toluene. This solution was added to a Solution yield of copolymer was 2.5 g. The proton and carbon NMR of nobornene (5.0 g) in cyclohexane (50 ml). After one hour 65 Spectra revealed the product to be a copolymer. GPC analy the viscous Solution was added to 300 ml of methanol to sis showed the copolymer to have a very high molecular precipitate the polymer. The polymer was filtered and dried. weight (Mw 1,640,000, Mn 227,000). US 6,232,417 B1 103 104 EXAMPLE 1.84 mixture was stirred for 2 hours at room temperature. The Norbornene Polymerization Using Catalyst M mixture was poured into 300 ml of methanol. The resulting To a solution of nobornene (2.5 g) dissolved in 15 ml precipitated polymer was filtered and dried. Yield 0.47 g dichloromethane was added (EtN)Ni(CFs)Cl. (0.05g (9%). Mw-156,000 and Mn=71,000 determined by GPC dissolved in 2 ml of dichloromethane). The polymerization methods. occurred immediately to give an addition polymerized polynobornene which was recovered in 100% yield upon EXAMPLE 1.91 addition of the Solution to methanol. Norbornene (4.0 g) was dissolved in 50 ml of cyclohex ane. A solution of Ni(COD) (0.0058 g) and tri-tert EXAMPLE 1.85 butylphosphine (0.0043 g) in toluene (2 ml) was made. To NB Polymerization Using Catalyst N this mixture was added pentafluorobenzoyl chloride (0.0036 A quantity of (m-CHC(CH))Ni(PPh)(C.F.) (0.025 g) ml). Then this mixture was added to the nobornene solution. was added to a sample of hexylnorbornene (2 g) in toluene The mixture was allowed to stir for 1 hour at room tem (5 ml) and the reaction stirred for 16 hours. A yellow gelled perature and then poured into 300 ml of methanol. A small Solution was obtained. 15 amount of polymer was filtered and dried. EXAMPLE 1.86 EXAMPLE 1.92 NB Polymerization Using Catalyst O Norbornene (4.0 g) was dissolved in 50 ml of cyclohex A quantity of (m-CHC(CH))Ni(PCy)(C.F.) (0.025 g) ane. A solution of Ni(COD) (0.0058 g) and tris was added to a sample of hexylnorbornene (2 g) in toluene (pentafluorophenyl)phosphine (0.0112 g) in toluene (2 ml) (5 ml) and the reaction stirred for 16 hours. A yellow gelled was made. To this mixture was added pentafluorobenzoyl Solution was obtained after this time. chloride (0.0072 ml). Then this mixture was added to the norbornene Solution. The mixture was allowed to stir for 1 EXAMPLE 1.87 hour at room temperature and then poured into 300 ml of NB Polymerization Using Catalyst P 25 methanol. A Small amount of polymer was filtered and dried. To a 100 ml glass Vial fitted with an airtight crimptop cap and a Teflon(R) stir bar was added at ambient temperature EXAMPLE 1.93 norbornene (5.0 g, 53.1 mmol) and toluene (35 ml). There Norbornene (4.0 g) was dissolved in 50 ml of cyclohex after was added Ni(2,4,6-tris(trifluoromethyl)phenyl), the ane. A solution of Ni(COD) (0.0058 g) and trichlorophos catalyst from example 66 (13 umol), dissolved in toluene (3 phine (0.0018 ml) in toluene (2 ml) was made. To this ml). Within 5 seconds the contents of the bottle became a mixture was added pentafluorobenzoyl chloride (0.0036 ml). very Viscous, nonstirring mass and there was much heat Then this mixture was added to the norbornene Solution. The evolution. When the bottle was opened, after 60 minutes, the mixture was allowed to Stir for 1 hour at room temperature gel was So hard that it was almost impossible to remove it and then poured into 300 ml of methanol. A small amount of from the bottle. The gel was dried in a vacuum oven (80° C.) 35 polymer was filtered and dried. overnight and then cryogenically ground. The weight of EXAMPLE 1.94 dried, pulverized polymer indicated that the norbornene had been quantitatively converted. Ni(THF) (CFS) (0.020 g) was dissolved in about 2 ml of toluene containing 0.0079 ml of beta-pinene. The resulting EXAMPLE 1.88 mixture was stirred for about 30 min. during which time the 40 orange color changed to blue. This Solution was then added To a solution of norbornene (2.5 g) in toluene (30 ml) was to a cyclohexane solution (50 ml) or norbornene (3.85g). added a solution of catalyst B (0.05 ml of a 0.3 M solution Within 5 Sec. there was a noticeable increase in viscosity. in THF) which was made in situ from NiBrand pentafluo After 10-15 sec. the solution gelled. After 1 hour the mixture rophenylmagnesium bromide in THF. Within 10-15 s, an was transferred to a beaker after additional toluene was unstirrable mixture formed. After 15 m, the polymer was 45 added to aid in the transfer. Addition of methanol caused precipitated with ethanol, filtered, and dried overnight at 80 precipitation of the polymer. C. in a vacuum oven to give a quantitative yield of homopolynobornene. EXAMPLE 1.95 Norbornene (2.0 g) was dissolved in 50 ml of cyclohex EXAMPLE 1.89 50 ane. An ether solution of 2,4,6-trifluorobenzoyl chloride (0.708 g) was added to a THF (10 ml) of Ni(COD) (1.0 g). To a solution of nobornene (4.0 g) in cyclohexane (50 ml) The intially yellow solution became orange. After thirty was added a solution of Ni(COD) (0.0058 g) in about 2 ml minutes, the Volatiles were removed in vacuo to yield a of toluene, pentafluorobenzoyl chloride (0.003 ml) and yellow solid. A portion of this solid was dissolved in ether 0.048g of a 25 wt % Solution of AlEta in cyclohexane. The 55 Solution was allowed to stir for 1 hour after which time the and added to a nobornene (2.0 g, 57:1 norbornene: nickel solution was poured into methanol (300 ml). The polymer ratio) solution in cyclohexane (25 ml). After thirty minutes was filtered and dried. the mixture became black. After two days, addition of MeOH (300 ml) gave a grey solid which was redissolved in EXAMPLE 190 chlorobenzene warmed to 50° C. and stirred with a 95:5 60 water:acetic acid Solution. The layers were Separated and the To a cyclohexane solution (50 ml) of nobornene (3.0 g) organic layer was added to MeOH (300 ml) to yield white and triethoxylsilylnobornene (2.0 g) was added 0.13 g of powder. The powder was dried in vacuo at 70° C. Yield 1.30 nickel ethylhexanoate (8 wit % in mineral spirits). The mixture was then deoxygenated by bubbling argon through g (65%). Mw-170,000; Mn=78,900. the solution. A solution of pentafluorobenzoyl chloride 65 EXAMPLE 1.96 (0.025 ml in 2 ml of cyclohexane) was added followed by Norbornene (2.5 g) was dissolved in 30 ml of toluene. A 0.407 g of a 25 wt % Solution of triethylaluminum. The toluene solution (1 ml) of (PPh3)Ni(C,Cl)C1 (0.012 g) and US 6,232,417 B1 105 106 Cu(Mesityl)s (0.0024 g) was added to the norbornene allowed to Stir 5 min. at room temperature. After precipita solution. After stirring the mixture for 2 hours at 70° C., tion into acetone, filtration, and drying under Vacuum, 1.28 addition of 300 ml of methanol induced precipitation of g of polymer was isolated. Mw-1,076,000 and Mn=393,000 polymer in about 6% conversion after filtering and drying. by GPC methods. EXAMPLE 1.97 EXAMPLES 201-2O2 NB Polymerization using Catalyst C in the presence of a Norbornene (2.5 g) was dissolved in 30 ml of toluene. A ligand reagent. To a 100 ml glass vial fitted with an airtight toluene solution (1 ml) of (PPh)Ni(CF)Br (0.011 g) and crimptop cap and a Teflon(R) Stir bar was added at ambient Cu(Mesityl)s (0.0024 g) was added to the norbornene temperature norbornene (5.0 g, 53.1 mmol) and toluene (35 solution. After stirring the mixture for 2 hours at 70° C., ml). Thereafter was added (toluene)Ni(C.F.) (6.3 mg, 13 addition of 300 ml of methanol induced precipitation of umol) dissolved in toluene (3 ml) to which tris(2,2,2- polymer in about 31% conversion after filtering and drying. trifluoroethyl)phosphite had been added, the resulting Solu EXAMPLE 1.98 tion being allowed to stir at ambient temperature for 10 15 minutes prior to adding to the monomer Solution. In both NB-type monomer polymerization using Catalyst C in the cases the polymerization ensued very rapidly. After 60 presence of a ligand reagent. Norbornene (2.5 g) was minutes reaction time at ambient temperature the Viscous dissolved in 30 mL of toluene. A toluene solution (1 mL) of solution was diluted with toluene (50 ml) and poured into an Catalyst C (0.0065 g) and CF-CH=N-(o-NMe2)CH excess of methanol. The precipitated homopolymer was (0.0042 g) was added to the nobornene solution. After filtered, dried in a vacuum oven at 80°C. overnight (constant stirring the mixture for 14 hours, addition of 300 ml of weight) and weighed. methanol induced precipitation of polymer in about 20% conversion after filtering and drying. EXAMPLE 1.99 25 Phosp hite, NB-type monomer polymerization using Catalyst B and mol/mol Yield, Conversion, in the presence of a ligand reagent. Triphenylphosphine Example N S. % Mw Mn oxide (0.20 g) in 10 ml THF was added to a 20 ml THF 2O1 1. 4.9 98 1,242,000 607,000 solution of Ni(THF) (CFs). (0.20 g). The mixture was 2O2 2 4.4 88 1,213,000 591,000 allowed to stir for 30 min. The Solvent was removed in vacuo to give an orange oil. Approximately 17.5 ml of 1,2-dichloroethane was added to the oil. Removal of the EXAMPLE 203 Solvent in vacuo gave an orange powder. To this orange powder was added 17.5 ml of toluene to give a slurry. NB Polymerization using Catalyst C in the presence of a 35 ligand reagent. To a 100 ml glass vial fitted with an airtight Approximately 0.6 ml of this slurry was added to nobornene crimptop cap and a Teflon(R) Stirbar was added at ambient (2.0 g) and triethoxysilylnobornene (1.6 g) in 30 ml of temperature norbornene (5.0 g, 53.1 mmol) and toluene (35 cyclohexane. The mixture was heated to 50° C. for 1 hour. ml). Thereafter was added (toluene)Ni(C.F.) (6.3 mg, 13 The mixture was poured into 500 ml of acetone to precipitate umol) dissolved in toluene (3 ml) to which the ligand the polymer. After filtration and drying under vacuum 0.73 illustrated below had been added (13 umol. 1:1 mol/mol on g of polymer was isolated. 40 nickel), the resulting Solution being allowed to Stir at ambi EXAMPLE 200 ent temperature for 3 minutes prior to adding to the mono mer Solution. After 60 minutes reaction time at ambient NB-type monomer polymerization using Catalyst B in the temperature the Solution was poured into an excess of presence of a ligand reagent. Tri-n-butylphosphine oxide methanol. The precipitated homopolymer was filtered, dried (0.17 g) in 10 ml THF was added to a 20 ml THF solution 45 in a vacuum oven at 80 C. overnight (constant weight) and of Ni(THF) (CF) (0.20 g). The mixture was allowed to weighed, the polymer yield was 1.1 g (22% conversion). stir for 30 min. The solvent was removed in vacuo to give an orange oil. Approximately 17.5 ml of toluene was added to the oil to give an orange Solution. Three polymerization was carried out using this Solution. 50 Approximately 0.65 ml of this solution was added to added to nobornene (2.0 g) and triethoxysilylnobornene (1.6 g) in 30 ml of cyclohexane and was allowed to stir for 5 hours at room temperature. After precipitation into acetone, 55 filtration, and drying under vacuum, 1.0 g of polymer was isolated. EXAMPLE 2.04 Approximately 0.65 ml of the same solution was added to NB Polymerization using Catalyst C in the presence of a added to nobornene (2.0 g) and triethoxysilylnorbornene ligand reagent. To a 100 ml glass vial fitted with an airtight (1.6 g) in 30 ml of cyclohexane and was allowed to stir for 60 crimptop cap and a Teflon(R) Stir bar was added at ambient 5 hours at 50° C. After precipitation into acetone, filtration, temperature norbornene (5.0 g, 53.1 mmol) and toluene (35 and drying under Vacuum, 0.87 g of polymer was isolated. ml). Thereafter was added (toluene)Ni(C.F.) (6.3 mg, 13 Mw =710,000 and Mn=232,000 by GPC methods. umol) dissolved in toluene (3 ml) to which (C.H.S)P(o- Approximately 0.65 ml of the same solution was added to (OCH)CH) had been added (13 umol. 1:1 mol/mol on added to norbornene (2.0 g), triethoxysilylnobornene (1.6 g), 65 nickel) had been added, the resulting Solution being allowed and 0.063 g of methylaluminum bis(2,6-di-tert-butyl-4- to Stir at ambient temperature for 3 minutes prior to adding methylphenoxide) in 30 ml of cyclohexane and was to the monomer Solution. After 10 minutes reaction time at US 6,232,417 B1 107 108 ambient temperature the Viscous Solution was diluted with lined rubber septum cap. The norbornene was dissolved in toluene (50 ml) and poured into an excess of methanol. The toluene. To this vial was added the appropriate amount of precipitated homopolymer was filtered, dried in a vacuum catalyst and cocatalyst (see table below). The mixture was oven at 80 C. overnight (constant weight) and weighed, allowed to Stir for the allotted time at the temperature given indicating quantitative conversion. in table below. The resulting mixture was then poured into EXAMPLE 2.05-248 an excess of methanol to precipitate the polymer. The polymer was filtered and dried in the vacuum oven over The monomers were added to a vial in the glove box night. The conversions were then determined gravimetri equipped with a stir bar. The vial was sealed with a Teflon(R)- cally.

Monomer catalyst CO-cat mon:Ni: Conv Example (mmol) (mMol) (mMol) Zn Time/Temp (%) Comments 205 NB P(o-tol) PdCl, Zn(C.F.). DME 2001:1:1 18/65° C. 1.6 (26.6) (0.43) (0.43) 2O6 NB (NBD)PdCl, Zn(CFS). DME 3O (26.6) (0.43) (0.43) 2O7 NB (allyl-PdCI), Zn(CF). DME 1.6 (26.6) (0.43) (0.43) 208 NB (dime)NiCl, Zn(CFs). DME 18/80° C. 39 (26.6) (0.43) (0.43) 209 NB (dime)NiBr, Zn(CFs). DME 97 (26.6) (0.43) (0.43) 210 NB (dppe)NiCl, Zn(CFs). DME 5.6 (26.6) (0.43) (0.43) 211 NB (DPM).Ni Zn(CFs). DME 96 (26.6) (0.43) (0.43) 212 NB (t-Octdab)NiCl, Zn(CFs). DME 97 (26.6) (0.43) (0.43) 213 BuNB/TESNB (DPM).Ni Zn(CFs). DME 5/60° C. 83 90:10 (0.45) (0.45) 214 BuNB/TESNB (DPM).Ni Zn(CFs). DME 31 90:10 (0.45) (0.45) 215 BuNB/TESNB (DPM).Ni Zn(CFs). DME 15 90:10 (0.45) (0.45) 216 BuNB/TESNB (t-Octdab)NiCl, Zn(CFS). DME 87 90:10 (0.45) (0.45) 217 BuNB/TESNB (t-Octdab)NiCl, Zn(CFS). DME 41 90:10 (0.45) (0.45) 218 BuNB/TESNB (t-Octdab)NiCl, Zn(CFS). DME 34 90:10 (0.45) (0.45) 219 BuNB/TESNB (Pph-CHC Zn(CFs). DME 8.4 90:10 (OPh).Ni (0.45) (0.43) 220 BuNB/TESNB (t-Octdab)NiCl, Zn(CF). DME 2000:1:1 18/60° C. 65 90:10 (0.43) (0.43) 221 BuNB/TESNB (t-Octdab)NiCl, Zn(CFS). DME 4000:1:1 31.5 90:10 (0.23) (0.23) 222 BuNB/TESNB (t-Octdab)NiCl, Zn(CF). DME 4000:2:1 10.5 90:10 (0.12) (0.23) 223 BuNB/TESNB CpTiCl2 Zn(CFs). DME 1.6 90:10 (0.43) (0.23) 224 BuNB/TESNB Sm-Ethyl Zn(CFs). DME 5 90:10 hexanoate (0.23) (0.43) 225 BuNB/TESNB (dime)Zn(CFS), 2OOO:1:1 O control 90:10 (0.43) experiment 226 NB Cp2ZrCl Zn(CF). DME 4 (26.6) (0.43) (0.23) 227 NB Eu(DPM), Zn(CFs). DME 6 (26.6) (0.43) (0.23) 228 NB (t-budab)CoBr, Zn(CFs). DME 6 (26.6) (0.43) (0.23) 229 NB VO(acac), Zn(CF). DME 14f65° C. O.4 (26.6) (0.43) (0.23) 48.amb 230 NB SnBree, Zn(CFS). DME 200:1:5 24/90° C. 8 (26.6) (4.3) (22) 231 NB (NBD)RhCl, Zn(CFS). DME 18/65 C. 2 (26.6) (4.3) (22) 232 NB (t-budab (CuBr, Zn(CFs). DME 18/65 C. 8 (26.6) (4.3) (22) 233 NB (t-budab)FeBrs Zn(CFs). DME 1.5/65 C. O.4 (26.6) (4.3) (22) 234 NB GeBr. Zn(CFs). DME 1.5/65 C. 31 (26.6) (4.3) (22) US 6,232,417 B1 109 110

-continued

Monomer catalyst CO-cat mon:Ni: Conv Example (mmol) (mMol) (mMol) Zn Time/Temp (%) Comments 235 NB SiCl, Zn(CFs). DME 18/65 C. 2O (26.6) (4.3) (22) 236 NB/TESNB GeBr. Zn(CFs). DME 18/65° C. 11 (80:20) (4.3) (22) (27 mmol) 237 NB/TESNB SiCl Zn(CFs). DME 18/65° C. 16 (80:20) (4.3) (22) (27 mmol) 238 NB/MeEsNB SiCl Zn(CFs). DME 18/65 C. 9 (50:50) (4.3) (22) (27 mmol) 239 NB/MeEsNB GeBr. Zn(CFs). DME 18/65° C. 13 (50:50) (4.3) (22) (27 mmol) 240 NB Zn(CF). DME 40:1 18/65 C. O control (27 mmol) (4.3) experiment 241 NB SiBr. Zn(CFs). DME 64/65 C. O.8 (27 mmol) (4.3) (22) 242 NB MeSiBr Zn(CF). DME 64/65 C. O.4 (27 mmol) (4.3) (22) 243 NB SiBr. Zn(CFs)2eDME 64/65 C. 23 (27 mmol) (4.3) (22) 244 NB Sn(acac).Br. B(CFs). 18/65° C. 47 (27 mmol) (4.3) (22) 245 NB Pb(dpm), B(CFs). 40:1:1 18/65° C. 12 (27 mmol) (4.3) (22) 246 NB (CFs)SiCIMe, Zn(CF). DME 64/65 C. 8 (27 mmol) (4.3) (22) 247 NB Zn(CFs). DME B(CFs). 40:1:1 18/65 C. 6 (27 mmol) (22) (22) 248 NB B(CFs). 82:1:1 18/65 C. O control (27 mmol) (11) experiment P(o-tol) = P(orthotolyl), NBD = norbornadiene, dime = dimethoxyethane, dpm = 2.2,6,6-tetramethyl-3,5- heptanedionate or dipivaloylmethane, t-Octdab = tert-octyldiazabutadiene, t-budab = tert-butyldiazabutadiene, Cp* = pentamethylcyclopentadienyl, Cp = cyclopentadienyl, NB = norbornene, TESNB = 5-triethoxysilylnorbornene, MeEsNB = methylester of 5-norbornene carboxylic acid, acac = acetylacetonate

EXAMPLE 249 EXAMPLE 251 Polymerization of NB using reaction product of silicon tetrachoride and pentafluorophenyl Grignard. The reaction Polymerization of norbornene employing (m-methallyl) of SiCl, and (CF)MgBr as reported by Wittingham and 40 nickel chloride and Zn(2,4,6-tris(trifluoromethyl)phenyl). Jarvie (J. Organometal. Chem. 1968, 13, 125) was repeated. To a solution of norbornene (5 g) dissolved in toluene (25 According to this report, this reaction yields a mixture of ml) was added (m-CHC(CH))NiCl(0.0137 g). The Si(CFs), SiCl2(CF), and SiCl(CFs). Addition of this orange red Solution was stirred for 16 hours. To this Solution mixture to NB in toluene yields 54% conversion to was added a quantity of Solid (2,4,6-tris(trifluoromethyl) polynobornene after 3 h at 65 C. and Subsequent precipi 45 phenyl) (0.0166 g). Upon addition of the (2,4,6-tris tation from methanol and drying. Subsequent 'F NMR (trifluoromethyl)phenyl) there was an instant reaction and analysis of the initiator mixture showed resonances consis the Solution turned black and the reaction warmed as the tent with the formation of pentafluorophenyl silane polymerization proceeded. Within 2 minutes norbornene complexes, and Some unreacted Grignard reagent. was completely polymerized and the polymer Solution 50 gelled. This polynorbornene material could not be dissolved EXAMPLE 250 in boiling O-dichlorobenzene. Polymerization of norbornene employing (m-methallyl) nickel chloride. In a dry box, norbornene (2 g) admixed with EXAMPLE 252 (m-CHC(CH))NiCl) (0.012 g) was liquified by the addi Polymerization of norbornene employing (m-methallyl) tion of 0.15 ml of dried toluene. The Solution was then 55 nickel chloride and Zn(2,4,6-tris(trifluoromethyl)phenyl). Stirred with a magnetic Stir bar to dissolve the nickel To a solution of norbornene (1.24 g) dissolved in toluene (15 procatalyst. To this Solution was added Zn(CFS)-(dime) ml) was added (m-CHC(CH))NiCl, (0.0137 g). The dissolved in a minimum of toluene (0.25 ml). Upon addition orange red Solution was Stirred for 2 hours. To this Solution of the Zn(CF)-(dime) there was an instant reaction and the was added solid2,4,6-tris(trifluoromethyl)phenyl)(0.0166 polymer gelled and polymerized into a dark black foamy 60 g) and the Solution stirred for 2 hours at room temperature. mass with a thin film attached. The thin film was quite This polynorbornene material generated was precipitated in flexible. Given the boiling point of norbornene and toluene, evaporation of material from the vessel was expected to be methanol. Yield 1.20 (83%). caused by the Spontaneous polymerization exotherm. This EXAMPLE 253 polynorbornene material was dissolved in boiling 65 o-dichlorobenzene and precipitated into methanol. Yield 1.2 Norbornene polymerization employing (CH2)(C2H5) g (60%). NNiCl, and Zn(CFS).(dme). Norbornene (2.5 g) and US 6,232,417 B1 111 112 (CH4)(CH3)-N-NiCl(0.074 g) were dissolved in 1,2- for the allotted time (see table for time) at room temperature dichloromethane (40 ml). Upon injection of a Zn(CFS) (unless otherwise noted in table below). The resulting mix (dme) solution (0.024 g in 1,2-dichloroethane (2 ml)) a ture was then poured into an excess of ethanol to precipitate white polymer was generated immediately. The polymer was the polymer. The polymer was filtered and dried in the immediately recovered by precipitation into methanol. Yield Vacuum oven overnight. The conversions were then deter 1.44 g (58%). mined gravimetrically.

Conv. Time Tg Mw Mn Example Catalyst NB:Ni B(CFs):Ni (%) (h) ( C.) (x 10) (x 10) Comments 256 O 500: O 48 Control experiment 257 O 500: O 48 Control experiment, at 70° C. 258 O 500: O 48 added equimolar amount of Ni(COD) 259 O 500: 1: 50 24 987 450 260 O 500: 12 48 261 O 48 Control experiment, no nickel added; 500:1 monomer:B(CFs). 262 O 500: 1. 4 263 O 500: 1: 4 264 O 500: 1: 4 265 O 500: 1: 1. in dichloroethane 266 O 500: 1: 33 181 124 at 70° C. 267 O 500: 10: 89 349 805 384 268 O 500: 10: 90 351 675 3OO 269 R 500: 1: O 270 R 500: 10: 61 693 312 271 O 500: 10: 1OO 272 O 500: 10: 98 0.01 equiv of HO in toluene added to B(CFs). 273 O 5000: 100: 94 338 79.6 274 O 5000: 10: 96 542 242 275 O Control reaction, no Ni. NB:B(CFs) - 50:1 276 O 500: 10: 98 473 193 1 mol % of 1-hexane added to reaction 277 O 500: 10: 97 351 177 3 mol % of 1-hexane added to reaction

35 EXAMPLE 254 EXAMPLES 278-284 Norbornene (2.5g, 26.5 mmol) was added to a vial in the Norbornene polymerization employing (CH)(CH3) glove box equipped with a stir bar. The Vial was Sealed with NNiCl, and Zn(CFS).(dme). Norbornene (3.0 g) and a Teflon(R) lined rubber septum cap. The norbornene was ((CH4)(CHS)N).NiCl, (0.009 g) were dissolved in 40 dissolved in the Solvent of choice to a total volume of 30 ml. 1,2-dichloromethane (40 ml). After injection of a Zn(CFS) To this vial was added a toluene (minumum amount) Solu (dme) solution (0.003 g in 1,2-dichloroethane (2 ml)) the tion of an appropriate amount of the nickel catalyst (see table Solution was stirred at room temperature for 2 hours. The below). The n the appropriate amount of tris polymer was recovered by precipitation into methanol. Yield (perfluorophenyl)boron (as a 3.15 wt % solution in mineral 1.61 g (54%). spirits) was added. The mixture was allowed to stir for 1 45 hour at room temperature. The resulting mixture was then EXAMPLE 255 poured into an excess of methanol to precipitate the polymer. The polymer was filtered and dried in the vacuum oven Norbornene Polymerization Using Cd(CF)(dme). To a overnight. The conversions were then determined gravi solution of norbornene (2 g in 10 ml of toluene) was added metrically. (m-CHC(CH))NiCl) (0.055 g). After stirring the dark 50 red solution for 20 minutes CdCCF)-(dime) (0.036 g) was added. The reaction medium turned cloudy after 10 minutes Cata and a Solid precipitated was observed. The reaction mixture Exam- lys Cocatalyst Conv Mw Mn. Comments was reacted for 24 hours and then poured into ethanol to ple (mM) (mM) (%) (x 103) (x 103) 55 yield a white polymer. Yield=0.28 g (14%). 278 S B(CFs). 70 1900 571 (0.17 (1.7 mM) EXAMPLE 256-277 mM) 279 S B(CFs).3H2O 74 1698 615 Catalyst (0.17 (0.34 mM) CO Norbornene (2.5g, 26.5 mmol) was added to a vial in the mm) ponents glove box equipped with a stir bar. The Vial was Sealed with 60 premixed. a Teflon(R) lined rubber septum cap. The norbornene was 280 T B(CFs).3H2O 48 - Catalyst dissolved in the solvent of choice (see table below) to a total (0.17 (0.34 mM) CO mM) ponents volume of 30 ml. To this vial was added a toluene (minimum premixed. amount) Solution of the appropriate amount of the nickel 281 U B(CFs). 17 2239 545 compound (see table below). Then the appropriate amount 65 (0.17 (1.7 mM) of tris(perfluorophenyl)boron (as a 3.15 wt.% solution in mM) mineral spirits) was added. The mixture was allowed to stir US 6,232,417 B1 113 114 rubber septum cap. To this vial was added 1 ml of a 0.0055M -continued solution of (bpy)Ni(NBD) in chlorobenzene. Then the Cata appropriate amount of B(C.F.) (1.1 ml of a 0.043M solu Exam- lyst Cocatalyst Conv Mw Mn. Comments tion in naphtha, 0.000047 mol) was added. The mixture was ple (mM) (mM) (%) (x 10) (x 10) allowed to stir for the allotted time (see table below for time) 282 Q B(CFs).3H2O 86 1406 601 Catalyst at room temperature (unless otherwise noted in table below). (0.17 (0.34 mM) CO The resulting mixture was then poured into an excess of mM) ponents premixed. methanol to precipitate the polymer. The polymer was 283 Q B(CFs). 96 542 242 filtered and dried in the vacuum oven overnight. The con (0.17 (1.7 mM) versions were then determined gravimetrically. mM) 284 O B(CFs).3H2O 8 356 151 Catalyst (0.17 (0.34 mM) CO mM) ponents premixed. B(CFs). Time Conv 15 Examples :N NB:N (h) (%) 291 9:1 2OOO:1 O.25 22 EXAMPLES 286-290 292 9:1 2OOO:1 O.25 18 293 9:1 2OOO:1 0.5 26 Norbornene (25 ml of a 1.0M solution in chlorobenzene) 294 9:1 2OOO:1 0.5 3O was added vial equipped with a stirbar and a Teflon(R)-lined 295 9:1 2OOO:1 1. 36 rubber septum cap. To this vial was added 1 mL of a 296 9:1 2OOO:1 1. 36 0.0066M solution of (bpy)Ni(NBD) in chlorobenzene. 297 9:1 2001:1 2 37 Then the appropriate amount of B(C.F.) (1.35 ml of a 298 9:1 2001:1 2 52 0.043 M solution in naphtha) was added. The mixture was allowed to stir for the allotted time (see table below for time) at room temperature. The resulting mixture was then poured 25 into an excess of methanol to precipitate the polymer. The polymer was filtered and dried in the vacuum oven over EXAMPLES 299-318 night. The conversions were then determined gravimetri cally. Norbornene (5.0 g, 53 mmol) was added to a vial in the glove box equipped with a stir bar. The Vial was Sealed with a Teflon(R)-lined rubber septum cap. The norbornene was Exam- Norbornene Time Conv. Mw Mn dissolved in the solvent of choice (see table below) to a total ples B(CFs):Ni N (h) (%) (x 10) (x 10) volume of 60 ml. To this vial was added a (minumum 286 9:1 4000:1 1. O 35 amount of the Solvent of choice) Solution of an appropriate 287 9:1 4OOO1 2 2.3 296 155 amount of the nickel catalyst (see table below). Then the 288 9:1 4000:1 4 7 823 492 289 9:1 4000:1 8 13.2 449 168 appropriate amount of FAB (as a 3.15 wt % solution in 290 9.1 4000:1 24 46 685 353 mineral spirits) or the Lewis acid listed in table below was added. The mixture was allowed to stir for 1 hour at room 40 temperature. The resulting mixture was then poured into an EXAMPLES 291-298 excess of methanol to precipitate the polymer. The polymer Norbornene (10 ml of a 1.1M solution in chlorobenzene) was filtered and dried in the vacuum oven overnight. The was added vial equipped with a stirbar and a Teflon(R)-lined conversions were then determined gravimetrically.

Temp Time Conv Example Catalyst Cocatalyst Sol ( C.) (h) (%) Comments 299 Ni(DPM), B(CFs). DCE RT 97 2.16 mM O.22 mM 1.95 mM triethylaluminum 3OO Ni(DPM), B(CFs). DCE amb 95 O.22 mM 1.95 mM 3O1 N B(CFs). DCE amb 1.5 97 ethylhexanoate 1.95 mM O.22 mM 3O2 N B(CFs). DCE amb 1.5 99 ethylhexanoate 1.95 mM O.22 mM 303 Ni(DPM), B(CFs). DCE amb 23 O.22 mM O.22 mM 304 Ni(DPM), B(CFs). CHA amb 73 O.22 mM O.22 mM 305 Ni(DPM), B(CFs). DCE amb 34 O.22 mM O.22 mM 306 Ni(DPM), B(CFs). DCE amb 42 2 equiv. HO added O.22 mM O.22 mM to Ni 307 Pd(DPM), B(CFs). DCE amb 95 O.22 mM 1.95 mM US 6,232,417 B1 115 116

-continued Temp Time Conv Example Catalyst Cocatalyst Sol ( C.) (h) (%) Comments 3O8 Ni(acac), B(CFs). DCE amb 98 O.22 mM 1.95 mM 309 Ni(tfacac).2H2O B(CFs). DCE amb 99 O.22 mM 1.95 mM 310 Ni(DPM), B(CFs).3H2O DCE amb 86 O.22 mM 1.25 mM 311 Ni(DPM).2HO B(CFs). DCE amb 67 O.22 mM O.22 mM 312 Ni(DPM), B(CFs). DCE amb 48 O.22 mM O.22 mM 313 Ni(DPM), B(CFs). DCE amb 54 O.22 mM O.22 mM 314 Ni(DPM), B(CFs). DCE amb 46 O.22 mM O.22 mM 315 Ni(DPM), dimethylanilinium DCE amb 6 O.22 mM tetrakisperfluorophenylborate 316 Ni(acac)Et(Pphs) B(CFs). DCE amb 1OO O.22 mM 1.95 mM 317 Nik(DPM), B(CF).3H2O DCE amb 91 O.22 mM O.22 mM 318 Ni(DPM), B(CFs).3H2O DCE amb 87 O.22 mM O.22 mM

25 EXAMPLE 319 norbornene (5.0 g, 53.1 mmol) dissolved in cyclohexane (35 This reaction was carried out in a 10 ml Stainless Steel, ml) followed by nickel ethylhexanoate (13 umol). To this high pressure, cylindrical reactor with Sapphire windows at Stirred Solution, at ambient temperature, was added a mix each end. The reactor was placed in a horizontal position and ture of tris(perfluorophenyl)boron (117 umol, in 2 ml Stirred using a magnetic stirbar. The norbornene (1.8 g., 19 octanes) and dimethyldiethoxysilane (0.041 ml, 234 umol) mmol) and nickel (II) 2,2,6,6-tetramethyl-3,5- which had been allowed to stand at ambient temperature for heptanedionate (2 mg, 4.7 umol) were added to the open end 5 minutes, finally followed by triethylaluminum (130 umol, of the argon purged reactor after which the window was 0.13 ml of a 1.0 Molar solution in cyclohexane). There was immediately replaced and tightened to Seal the reactor. an immediate exotherm and viscosity increase. Within 5 Carbon dioxide was charged to 1000 psig dissolving the 35 minutes the whole Solution had set up to afford a nonflowing norbornene and forming a homogeneous liquid layer in the colorless gel. After 60 minutes the vial was opened and the vessel. To this solution was added a solution of tris contents were dissolved in an excess of toluene (300 ml) and (perfluorophenyl)boron (22 umol) in octanes (0.5 ml) using then poured into exceSS methanol to afford the product as a additional carbon dioxide pressure to afford a Supercritical pure white polymer which was isolated by filtration, washed condition in the reactor. There ensued an exothermic reac with exceSS methanol and dried overnight in a vacuum oven tion (temperature increased from 20° C. to 31 C. within 2 40 at 80° C. The isolated yield of the poly(norbornene) was 5 minutes) and the pressure stabilized at 1800 psig. The grams, representing quantitative conversion. GPC showed reactor was vented after 30 minutes and the white polymer the polymer to have a high molecular weight (M 790,000, was dissolved in toluene and then poured into exceSS M, 236,000). acetone to afford the product which was isolated by filtration, washed with exceSS acetone and dried overnight in 45 EXAMPLE 322 a vacuum oven at 80° C. The isolated yield of the poly To a 100 ml glass Vial fitted with an airtight crimptop cap (norbornene) was 0.73 grams, representing 41% conversion. and a Teflon(E) stirbar was added at ambient temperature norbornene (5.0 g, 53.1 mmol) dissolved in cyclohexane (35 EXAMPLE 32O ml) followed by nickel ethylhexanoate (13 umol), NB-type monomer polymerization using (toluene)Ni 50 tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane (0.20 (SiCl) and B(CF). To a 100 ml glass vial fitted with an ml, 0.53 mmol), tris(perfluorophenyl)boron (117 umol, in 2 airtight crimptop cap and a Teflon(R) Stir bar was added at ml octanes), followed by triethylaluminum (130 umol, 0.13 ambient temperature norbornene (4.0 g, 42.4 mmol), tri ethoxy silylnorbornene (2.8 ml, 10.6 mmol) and toluene (35 ml of a 1.0 Molar solution in cyclohexane). ml). Thereafter was added (toluene)Ni(SiCl) (13 umol) There was an immediate exotherm and Viscosity increase. dissolved in toluene (3 ml) and tris(pentafluorophenyl)boron 55 Within 30 seconds the whole solution had set up to afford a (13 umol). After 24 hours reaction time at ambient tempera nonflowing colorless gel. After 60 minutes the Vial was ture the viscous solution was diluted with toluene (50 ml) opened and the contents were dissolved in an excess of and poured into an excess of methanol. The preciptated toluene (200 ml) and then poured into excess acetone to copolymer was filtered, dried in a vacuum oven at ambient afford the product as a pure white polymer which was temperature for 24 hours (constant weight) and weighed. 60 isolated by filtration, washed with excess acetone and dried The yield of copolymer was 1.4g. GPC analysis showed the overnight in a vacuum oven at 80° C. The isolated yield of copolymer to have a very high molecular weight (Mw the poly(norbornene) was 5 grams, representing quantitative 1437,000, Mn 195,000). conversion. EXAMPLE 321 65 EXAMPLE 323 To a 100 ml glass Vial fitted with an airtight crimptop cap To a 100 ml glass Vial fitted with an airtight crimptop cap and a Teflon(R) stir bar was added at ambient temperature and a Teflon(E) stirbar was added at ambient temperature US 6,232,417 B1 117 118 norbornene (5.4g, 57.3 mmol) dissolved in cyclohexane (35 norbornene (5.0 g, 53.1 mmol) dissolved in cyclohexane (35 ml) followed by nickel ethylhexanoate (13 umol), dimeth ml) followed by tetraethoxysilane (0.11 ml, 0.53 mmol), yldiethoxysilane (0.09 ml, 0.53 mmol), tris nickel ethylhexanoate (13 umol), boron trifluoride etherate (perfluorophenyl)boron (117 umol, in 2 ml octanes), fol (104 umol), tris(perfluorophenyl)boron (13 umol, in 0.3 ml lowed by triethylaluminum (130 umol, 0.077 ml of a 1.7 octanes), followed by triethylaluminum (130 umol, 0.077ml Molar Solution in cyclohexane). There was an immediate of a 1.7 Molar solution in cyclohexane). The solution exotherm and viscosity increase. Within 30 seconds the became noticeably Viscous within 3 minutes and stopped whole Solution had set up to afford a nonflowing colorleSS gel. After 60 minutes the vial was opened and the contents stirring after 10 minutes. After 60 minutes the vial was were dissolved in an excess of toluene (200 ml) and then opened and the contents were dissolved in an excess of poured into excess acetone to afford the product as a pure toluene (100 ml) and then poured into excess acetone to white polymer which was isolated by filtration, washed with afford the product as a pure white polymer which was excess acetone and dried overnight in a vacuum oven at 80 isolated by filtration, washed with excess acetone and dried C. The isolated yield of the poly(norbornene) was 5.4 g overnight in a vacuum oven at 80° C. The isolated yield of representing quantitative conversion. the poly(norbornene) was 2.1 grams, representing 42% 15 isolated conversion. EXAMPLE 324 To a 100 ml glass Vial fitted with an airtight crimptop cap EXAMPLE 328 and a Teflon(R) stir bar was added at ambient temperature To a 100 ml glass Vial fitted with an airtight crimptop cap norbornene (5.0 g, 53.1 mmol) dissolved in cyclohexane (35 and a Teflon(E) stirbar was added at ambient temperature ml) followed by nickel ethylhexanoate (13 umol), tetra norbornene (5.0 g, 53.1 mmol) dissolved in 1,2- ethoxysilane (0.0275 ml, 0.132 mmol), tris(perfluorophenyl) dichloroethane (35 ml) followed by tetraethoxysilane (0.11 boron (117 umol, in 2 ml octanes), followed by triethylalu ml, 0.53 mmol), m-crotylnickelbromide (26 umol) dis minum (130 umol, 0.077 ml of a 1.7 Molar solution in solved in 1,2-dichloroethane (1.5 ml) and tris cyclohexane). There was an immediate exotherm and vis (perfluorophenyl)boron (117 umol, in 2.3 ml octanes. The cosity increase. Within 30 seconds the whole solution had 25 Solution immediately developed a large exotherm and Set up to afford a nonflowing colorless gel. After 60 minutes formed a solid mass of white polymer. After 60 minutes the the vial was opened and the contents were dissolved in an Vial was opened and the contents were dissolved in an exceSS excess of toluene (200 ml) and then poured into excess of toluene (100 ml) and then poured into excess acetone to acetone to afford the product as a pure white polymer which afford the product as a pure white polymer which was was isolated by filtration, washed with excess acetone and isolated by filtration, washed with excess acetone and dried dried overnight in a vacuum oven at 80° C. The isolated overnight in a vacuum oven at 80° C. The isolated yield of yield of the poly(norbornene) was 4.8 grams, representing the poly(norbornene) was 4.3 grams, representing 86% 96% isolated conversion. isolated conversion. EXAMPLE 325 EXAMPLE 329 The procedure used in Example 324 was duplicated 35 except the amount of tetraethoxysilane was reduced to To a 100 ml glass Vial fitted with an airtight crimptop cap 0.0137 ml (0.066 mmol). Within 30 seconds the whole and a Teflon(E) stirbar was added at ambient temperature Solution had set up to afford a nonflowing colorleSS gel. norbornene (5.0 g, 53.1 mmol) dissolved in 1,2- After 60 minutes the vial was opened and the contents were dichloroethane (35 ml) followed by tetraethoxysilane (0.11 dissolved in an excess of toluene (200 ml) and then poured 40 ml, 0.53 mmol), nickel ethylhexanoate (13 umol), tris into exceSS acetone to afford the product as a pure white (perfluorophenyl)boron (117 umol, in 2.3 ml octanes), fol polymer which was isolated by filtration, washed with lowed by triethylaluminum (130 umol, 0.077 ml of a 1.7 excess acetone and dried overnight in a vacuum oven at 80 Molar Solution in cyclohexane). There was an immediate C. The isolated yield of the poly(norbornene) was 5.0 grams, exotherm and precipitation of polymer within a Second. 45 After 60 minutes the vial was opened and the contents were representing quantitative conversion. poured into excess acetone to afford the product as a pure EXAMPLE 326 white polymer which was isolated by filtration, washed with To a 100 ml glass Vial fitted with an airtight crimptop cap excess acetone, and dried overnight in a vacuum oven at 80 and a Teflon(R) stir bar was added at ambient temperature C. The isolated yield of the poly(norbornene) was 5g decylnorbornene (14.5 ml, 53.1 mmol) dissolved in cyclo 50 representing quantitative conversion. hexane (40 ml) followed by nickel ethylhexanoate (13 EXAMPLE 330 umol), tetraethoxysilane (0.11 ml, 0.53 mmol), tris (perfluorophenyl)boron (117 umol, in 2 ml octanes), fol The procedure used in Example 329 was followed except lowed by triethylaluminum (130 umol, 0.077 ml of a 1.7 that a higher level of tetraethoxysilane was employed (2.25 Molar Solution in cyclohexane). There was an exotherm and 55 ml, 10.8 mmol). The reaction was slower than Example 329 gradual Viscosity increase. After 120 minutes the Vial was with polymer precipitating from Solution after 10 minutes opened and the contents were dissolved in an excess of and the reactor contents becoming a Solid mass after 15 toluene (100 ml) and then poured into excess acetone to minutes. After 60 minutes the vial was opened and the afford the product as a pure white polymer which was contents were poured into exceSS acetone to afford the isolated by filtration, washed with excess acetone and dried 60 product as a pure white polymer which was isolated by overnight in a vacuum oven at 80 C. The isolated yield of filtration, washed with exceSS acetone and dried overnight in the poly(decylnorbornene) was 7.4 grams, representing 59% a vacuum oven at 80° C. The isolated yield of the poly isolated conversion. (norbornene) was 4.6 g representing 92% conversion. EXAMPLE 331 EXAMPLE 327 65 To a 100 ml glass Vial fitted with an airtight crimptop cap To a 100 ml glass Vial fitted with an airtight crimptop cap and a Teflon(E) stirbar was added at ambient temperature and a Teflon(R) stir bar was added at ambient temperature US 6,232,417 B1 119 120 norbornene (5.0 g, 53.1 mmol) dissolved in cyclohexane (35 ethylhexanoate (13 umol), tris(perfluorophenyl)boron (117 ml) followed by nickel ethylhexanoate (13 umol), tetra almol, in 2 ml octanes) and triethylaluminum (130 umol, ethoxygermane (0.1 ml, 0.53 mmol), tris(perfluorophenyl) 0.077 ml of a 1.7 Molar solution in cyclohexane). There was boron (117 umol, in 2 ml octanes), followed by triethylalu an immediate exotherm and Viscosity increase. Within 2 minum (130 umol, 0.077 ml of a 1.7 Molar solution in minutes the whole Solution had set up to afford a nonflowing cyclohexane). After 60 minutes the vial was opened and then colorless gel. After 60 minutes the vial was opened and the poured into excess acetone to afford the product as a pure contents were dissolved in an excess of toluene (200 ml) and white polymer which was isolated by filtration, washed with then poured into exceSS acetone to afford the product as a excess acetone and dried overnight in a vacuum oven at 80 pure white polymer which was isolated by filtration, washed C. The isolated yield of the poly(norbornene) was 0.25 with excess acetone and dried overnight in a vacuum oven grams, representing 5% conversion. at 80°C. The isolated yield of the poly(norbornene) was 5.0 grams, representing quantitative conversion. EXAMPLE 332 EXAMPLE 336 To a 100 ml glass Vial fitted with an airtight crimptop cap and a Teflon(R) stir bar was added at ambient temperature 15 To a 100 ml glass Vial fitted with an airtight crimptop cap norbornene (5.0 g, 53.1 mmol) dissolved in cyclohexane (35 and a Teflon(R) stir bar was added at ambient temperature ml) followed by nickel ethylhexanoate (13 umol), bis norbornene (5.0 g, 53.1 mmol) dissolved in cyclohexane (35 (dimethylamino)dimethylsilane (0.53 mmol), tris ml) followed by dimethoxyethane (0.055 ml, 0.53 mmol), (perfluorophenyl)boron (117 umol, in 2 ml octanes), fol nickel ethylhexanoate (13 umol), tris(perfluorophenyl)boron lowed by triethylaluminum (130 umol, 0.13 ml of a 1.0 (117 umol, in 2 ml octanes) and triethylaluminum (130 Molar solution in cyclohexane). After 60 minutes the vial umol, 0.077 ml of a 1.7 Molar solution in cyclohexane). was opened and then poured into exceSS acetone to afford the There was an exotherm and gradual Viscosity increase. After product as a pure white polymer which was isolated by 60 minutes the Vial was opened and the contents were filtration, washed with exceSS acetone and dried overnight in dissolved in an excess of toluene (100 ml) and then poured a vacuum oven at 80° C. The isolated yield of the poly 25 into exceSS acetone to afford the product as a pure white (norbornene) was 0.1 grams, representing 2% conversion. polymer which was isolated by filtration, washed with excess acetone and dried overnight in a vacuum oven at 80 EXAMPLE 333 C. The isolated yield of the poly(norbornene) was 1.6 grams, The procedure used in Example 322 was duplicated representing 32% conversion. except that trimethylorthoformate was used (0.058 ml, 0.53 EXAMPLE 337 mmol,1 mol % on monomer) in place of tridecafluoro-1,1, 2,2-tetrahydrooctyltriethoxysilane. Within 5 minutes the To a 100 ml glass Vial fitted with an airtight crimptop cap whole Solution had set up to afford a nonflowing colorleSS and a Teflon(R) stir bar was added at ambient temperature gel. After 60 minutes the vial was opened and the contents 35 norbornene (5.0 g, 53.1 mmol) dissolved in cyclohexane (35 were dissolved in an excess of toluene (200 ml) and then ml) followed by nickel ethylhexanoate (13 umol), tris poured into excess acetone to afford the product as a pure (perfluorophenyl)boron (117 umol, in 2 ml octanes) and white polymer which was isolated by filtration, washed with di-n-butylmagnesium (130 umol, 0.13 ml of a 1.0 Molar excess acetone and dried overnight in a vacuum oven at 80 Solution in heptane). There was an immediate exotherm and C. The isolated yield of the poly(norbornene) was 5.0 grams, 40 viscosity increase. Within 3 minutes the whole solution had representing quantitative conversion. Set up to afford a nonflowing colorless gel. After 60 minutes the Vial was opened and the contents were dissolved in an EXAMPLE 334 excess of toluene (200 ml) and then poured into excess acetone to afford the product as a pure white polymer which To a 100 ml glass Vial fitted with an airtight crimptop cap 45 was isolated by filtration, washed with excess acetone and and a Teflon(R) stir bar was added at ambient temperature dried overnight in a vacuum oven at 80° C. The isolated norbornene (5.0 g, 53.1 mmol) dissolved in 1,2- yield of the poly(norbornene) was 4.1 grams, representing dichloroethane (35 ml) followed by trimethylorthoformate 82% isolated conversion. (1.16 ml, 10.6 mmol), nickel ethylhexanoate (13 umol), tris(perfluorophenyl)boron (117 umol, in 2 ml octanes) and EXAMPLE 338 triethylaluminum (130 umol, 0.077 ml of a 1.7 Molar 50 Solution in cyclohexane). There was an immediate exotherm To a 5 ml serum bottle fitted with an airtight crimptop cap and polymer precipitated as a white mass. Within 30 seconds at ambient temperature was added tetraethoxysilane (0.11 the vial was filled with a Solid white mass. After 60 minutes ml, 0.53 mmol), nickel ethylhexanoate (13 umol), tris the vial was opened and the contents were poured into (perfluorophenyl)boron (117 umol, in 2 ml octanes) and excess acetone to afford the product as a pure white polymer 55 triethylaluminum (130 umol, 0.077 ml of a 1.7 Molar which was isolated by filtration, washed with exceSS acetone Solution in cyclohexane). The resulting mixture comprised a and dried overnight in a vacuum oven at 80° C. The isolated viscous brown oil dispersed in colorless solvent. The mix yield of the poly(norbornene) was 5.0 grams, representing ture was Shaken Vigorously for 30 Seconds and then injected quantitative conversion. GPC indicated the polymer to have into a 100 ml glass Vial fitted with an airtight crimptop cap 60 and a Teflon(R) stir bar containing norbornene (5.0 g, 53.1 a high molecular weight (Mw 625,000, Mn 191,000). mmol) dissolved in toluene (35 ml). There were immediate EXAMPLE 335 Signs of catalyst encapsulation due to the catalysts high activity. However after 10 minutes the contents became To a 100 ml glass Vial fitted with an airtight crimptop cap Viscous and nonflowing indicating high conversion to poly and a Teflon(R) stir bar was added at ambient temperature 65 mer. After 60 minutes the Vial was opened and a Sample of norbornene (5.0 g, 53.1 mmol) dissolved in cyclohexane (35 the contents were dissolved in toluene and then poured into ml) followed by triethoxyboron (0.09 ml, 0.53 mmol), nickel exceSS acetone to afford the product as a pure white polymer US 6,232,417 B1 121 122 which was isolated by filtration, washed with exceSS acetone norbornene (5.0 g, 53.1 mmol) dissolved in cyclohexane (35 and dried overnight in a vacuum oven at 80 C. ml) followed by trimethylethoxysilane (0.083 ml, 0.53 There remained a very small amount of the brown oil in mmol), nickel ethylhexano ate (13 u mol), tris the serum bottle. This oil was dissolved in chlorobenzene (2 (perfluorophenyl)boron (117 umol, in 2 ml octanes) and ml) and allowed to stand at ambient temperature for 10 triethylaluminum (130 umol, 0.077 ml of a 1.7 Molar minutes. This solution was then added to a 50 ml glass vial Solution in cyclohexane). There was an immediate exotherm fitted with an airtight crimptop cap and a Teflon(R) stir bar and Viscosity increase. After 60 minutes the Vial was opened containing norbornene (2.5 g, 26.5 mmol) dissolved in and the contents were dissolved in an excess of toluene (200 chlorobenzene (35 ml). There were immediate signs of catalyst encapsulation due to the catalysts very high activity. ml) and then poured into excess acetone to afford the product The reaction was obviously extremely fast and eXothermic. as a pure white polymer which was isolated by filtration, After 60 minutes the Vial was opened and a Sample of the washed with exceSS acetone and dried overnight in a vacuum contents were dissolved in toluene and then poured into oven at 80° C. The isolated yield of the poly(norbornene) excess acetone to afford the product as a pure white polymer was 5.0 grams, representing quantitative conversion. A very which was isolated by filtration, washed with exceSS acetone high molecular weight (Mw 1,006,000 Mn 160,000) poly and dried overnight in a vacuum oven at 80 C. The small 15 mer was obtained. quantity of catalyst used and the rapidity of the reaction emphasizes the high activity of this premixed catalyst Sys EXAMPLE 343 tem. To a 100 ml glass Vial fitted with an airtight crimptop cap and a Teflon(E) stirbar was added at ambient temperature EXAMPLE 339 norbornene (5.0 g, 53.1 mmol) dissolved in cyclohexane (35 To a 100 ml glass Vial fitted with an airtight crimptop cap ml) followed by B-pinene (1.0 ml, 6.3 mmol), tetraethox and a Teflon(R) stir bar was added at ambient temperature ysilane (011 ml, 0.53 mmol), nickel ethylhexanoate (13 norbornene (5.0 g, 53.1 mmol) dissolved in cyclohexane (35 almol), tris(perfluorophenyl)boron (117 umol, in 2 ml ml) followed by nickel ethylhexanoate (13 umol), anhydrous octanes) and triethylaluminum (130 umol, 0.077 ml of a 1.7 n-propanol (0.04 ml, 0.53 mmol), tris(perfluorophenyl) 25 Molar solution in cyclohexane). After 48 hours the vial was boron (117 umol, in 2 ml octanes) and triethylaluminum opened and the contents were dissolved in an excess of (130 umol, 0.077 ml of a 1.7Molar solution in cyclohexane). toluene (100 ml) and then poured into excess acetone to There was an immediate exotherm and Viscosity increase. afford the product as a pure white polymer which was After 60 minutes the vial was opened and the contents were isolated by filtration, washed with excess acetone and dried dissolved in an excess of toluene (200 ml) and then poured overnight in a vacuum oven at 80° C. The isolated yield of into exceSS acetone to afford the product as a pure white the poly(norbornene) was 1.3 grams, representing 26% polymer which was isolated by filtration, washed with conversion. The polymer had a greatly reduced molecular excess acetone and dried overnight in a vacuum oven at 80 weight (M, 65,300 M26,000). C. The isolated yield of the poly(norbornene) was 4.95 grams, representing 99% conversion. 35 EXAMPLE 344 EXAMPLE 340 The above experiment was repeated except chloroben To a 100 ml glass Vial fitted with an airtight crimptop cap Zene was used in place of cyclohexane. After 6 hours the Vial and a Teflon(E) stirbar was added at ambient temperature was opened and the contents were dissolved in an excess of norbornene (5.0 g, 53.1 mmol) dissolved in cyclohexane (35 toluene (200 ml) and then poured into excess acetone to ml) followed by diethylether (0.055 ml, 0.53 mmol), nickel 40 afford the product as a pure white polymer which was ethylhexanoate (13 umol), tris(perfluorophenyl)boron (117 isolated by filtration, washed with excess acetone and dried almol, in 2 ml octanes) and triethylaluminum (130 umol, overnight in a vacuum oven at 80° C. The isolated yield of 0.077 ml of a 1.7 Molar solution in cyclohexane). There was the poly(norbornene) was 4.4 grams, representing 88% an immediate exotherm and Viscosity increase. After 60 conversion. A greatly reduced molecular weight (M, 81,000 minutes the Vial was opened and the contents were dissolved 45 M. 33.900) polymer was obtained. in an excess of toluene (200 ml) and then poured into excess EXAMPLE 345 acetone to afford the product as a pure white polymer which was isolated by filtration, washed with excess acetone and To a 100 ml glass Vial fitted with an airtight crimptop cap dried overnight in a vacuum oven at 80° C. The isolated and a Teflon(R) stir bar was added at ambient temperature 50 norbornene (5.0 g, 53.1 mmol) dissolved in cyclohexane (35 yield of the poly(norbornene) was 3.9 grams, representing ml) followed by 4-methylcyclohexene (1.0 ml), tetraethox 78% conversion. ysilane (0.11 ml, 0.53 mmol), nickel ethylhexanoate (13 EXAMPLE 341 almol), tris(perfluorophenyl)boron (117 umol, in 2 ml The same procedure was used as in Example 340 except octanes) and triethylaluminum (130 umol, 0.077 ml of a 1.7 that a higher level of diethylether was applied (0.55 ml, 5.3 55 Molar solution in cyclohexane). After 60 minutes the vial mmol). There was an immediate exotherm and Viscosity was opened and the contents were dissolved in an excess of increase. After 60 minutes the Vial was opened and the toluene (100 ml) and then poured into excess acetone to contents were dissolved in an excess of toluene (200 ml) and afford the product as a pure white polymer which was then poured into exceSS acetone to afford the product as a isolated by filtration, washed with excess acetone and dried pure white polymer which was isolated by filtration, washed 60 overnight in a vacuum oven at 80° C. The isolated yield of with excess acetone and dried overnight in a vacuum oven the poly(norbornene) was 4.1 grams, representing 82% at 80°C. The isolated yield of the poly(norbornene) was 4.1 conversion. A polymer having a greatly reduced molecular grams, representing 82% conversion. weight (Mw 312,000 Mn 96,000) was obtained. EXAMPLE 346 EXAMPLE 342 65 To a 100 ml glass Vial fitted with an airtight crimptop cap To a 100 ml glass Vial fitted with an airtight crimptop cap and a Teflon(R) stir bar was added at ambient temperature and a Teflon(R) stir bar was added at ambient temperature US 6,232,417 B1 123 124 7-methylnorbornene (2.15g, 19.5 mmol) dissolved in cyclo the norbornene ring (CHCH(CH2)C(O)OCHs in this hexane (35 ml) followed by tetraethoxysilane (0.04 ml, example)) it is to be understood that R' is attached to the 0.195 mmol), nickel ethylhexanoate (26 umol), tris carbon atom in the 5 position on the norbornene moeity and (perfluorophenyl)boron (234 umol, in 2 ml octanes) and is in the form of a mixture of the endo and eXo isomers triethylaluminum (260 umol, 0.077 ml of a 1.7 Molar thereof. solution in cyclohexane). After 90 minutes the vial was opened and the contents were dissolved in an excess of EXAMPLE 350 toluene (100 ml) and then poured into excess methanol to To a 100 ml glass Vial fitted with an airtight crimptop cap afford the product as a pure white polymer which was and a Teflon(R) stir bar was added at ambient temperature the isolated by filtration, washed with exceSS methanol and monomer from example 30 (2.0 g, 10.0 mmol) dissolved in dried overnight in a vacuum oven at 80° C. The isolated dichloroethane (50 ml) followed by nickel ethylhexanoate yield of the poly(7-methylnorbornene) was 0.47 g. (0.01 mmol). Thereafter was added tris(perfluorophenyl) EXAMPLE 347 boron (0.09 mmol), triethylaluminum (0. 1 mmol). The vessel was heated to 50 C. and allowed to stir for 16 hours. To a 100 ml glass Vial fitted with an airtight crimptop cap 15 The Solution remained freeflowing throughout the polymer and a Teflon(R) stir bar was added at ambient temperature ization. The Solution was concentrated by removing half of norbornene (5.0 g, 53.1 mmol) dissolved in cyclohexane (35 the Solvent by vacuum methods and then added to hexane ml) followed by nickel ethylhexanoate (13 umol), tris which caused the homopolymer to precipitate. The polymer (perfluorophenyl)boron (117 umol, in 2 ml octanes) and was filtered, washed with hexane and dried overnight in a diethylzinc (130 umol, 0.013 ml). There was an immediate vacuum oven at 80°C. The isolated yield of the polymer was pink hue, exotherm and viscosity increase. Within 20 min 1.23 grams, representing 63% conversion. The molecular utes the whole Solution had set up to afford a nonflowing weight was determined using GPC methods (M 700,000, cement. After 60 minutes the vial was opened and the M. 242,000). contents were dissolved in an excess of toluene (200 ml) and then poured into exceSS acetone to afford the product as a 25 EXAMPLE 351 pure white polymer which was isolated by filtration, washed with excess acetone and dried overnight in a vacuum oven To a 100 ml glass Vial fitted with an airtight crimptop cap at 80°C. The isolated yield of the poly(norbornene) was 5.0 and a Teflon(R) stirbar was added at ambient temperature the grams, representing quantitative conversion. The polymer monomer from Example 349 (2.0 g, 10.0 mmol) dissolved in dichloroethane (50 ml) followed by nickel (II) bis(2.2, was found to have a very high molecular weight (Mw 6,6-tetramethyl-3,5-heptanedionate) (4.3 mg, 0.01 mmol). 1,107,000, Mn323,000). Thereafter was added tris(perfluorophenyl)boron (0.09 EXAMPLE 348 mmol). The vessel was heated to 50° C. and allowed to stir for 16 hours. The solution remained freeflowing throughout To a 100 ml glass Vial fitted with an airtight crimptop cap 35 the polymerization. The Solution was concentrated by and a Teflon(R) stir bar was added at ambient temperature norbornene (5.0 g, 53.1 mmol) dissolved in cyclohexane (35 removing half of the solvent by vacuum methods and then ml) followed by nickel ethylhexanoate (13 umol). Thereafter added to hexane which caused the homopolymer to precipi was added a mixture (which had first been allowed to stand tate. The polymer was filtered, washed with hexane and at ambient temperature for 5 minutes) of tris dried overnight in a vacuum oven at 80° C. The isolated (perfluorophenyl)boron (117 umol, in 2 ml octanes), triethy 40 yield of the polymer was 1.5 grams, representing 75% laluminum (97.5 umol, 0.058 ml) and diethylzinc (32.5 conversion. The molecular weight was determined using umol, 0.0032 ml). There was an immediate color change to GPC methods (M, 500,000, M 171,000). a tan/yellow, large exotherm and Viscosity increase. The EXAMPLE 352 Solution remained freeflowing throughout the polymeriza tion. After 60 minutes the Vial was opened and the contents 45 To a stainleSS Steel autoclave with an internal Volume of were dissolved in an excess of toluene (200 ml) and then 300 ml was added 5-hexene-2-one (69 g, 0.7 Mole) and poured into excess acetone to afford the product as a pure freshly cracked cyclopentadiene (46.4 g., 0.7 mole). The white polymer which was isolated by filtration, washed with stirred mixture was heated to 150 C. for 3 hours and then excess acetone and dried overnight in a vacuum oven at 80 the temperature was raised to 170° C. and the reaction was C. The isolated yield of the poly(norbornene) was 5.0 grams, 50 left overnight. The reactor was then cooled and the contents representing quantitative conversion. removed. The resulting norbornene (NBCHCHC(O)CH) was purified by vacuum distillation and found to have a EXAMPLE 349 boiling point of about 46-49 C. at 0.2 mm Hg. The material To a stainless Steel autoclave with an internal volume of 55 was analyzed by GC methods and found to have a purity of 300 ml was added ethyl 2-methyl-4-pentenoate (99 g, 0.7 99 to 99.3% (different fractions). The isolated yield of high Mole) and freshly cracked cyclopentadiene (46.4 g., 0.7 purity product was around 32 g. Mole). The stirred mixture was heated to 200° C. and left overnight. The reactor was then cooled and the contents EXAMPLE 353 removed. The resulting norbornene (NBCHCH(CH)C(O) 60 To a stainleSS Steel autoclave with an internal Volume of OCH) was purified by vacuum distillation and found to 300 ml was added 4-penten-1-ylacetate (96.13 g, 0.75 mole) have a boiling point of about 467 C at 0.02 mm Hg. The and freshly cracked cyclopentadiene (24.81 g, 0.375 mole). material was analyzed by GC methods and found to have a The stirred mixture was heated to 170° C. for 2 hours and purity of 98.4 to 99.3% (different fractions). The isolated then the temperature was raised to 190° C. and the reaction yield of high purity product was around 33 g. 65 was left overnight. The reactor was then cooled and the Note: In this and all Subsequent examples where reference contents removed. The resulting norborne ne is made to NBR' (where R' refers to a substituent attached to (NBCHCHOC(O)CH) was purified by vacuum distilla US 6,232,417 B1 125 126 tion and found to have a boiling point of about 40-50 C. at raised to 200 C. and the reaction was left overnight. The 0.080.14 mm Hg. The material was analyzed by GC meth reactor was then cooled and the contents removed. The ods and found to have a purity of 92.5 to 93.1% (different resulting norbornene was purified by vacuum distillation and fractions). The isolated yield of the relatively high purity found to have a boiling point of about 85°C. at 0.03 mm Hg. product was around 22 g. The material was analyzed by GC methods and found to have a purity of 98%. The isolated yield of high purity EXAMPLE 354 product was around 31 g. To a stainless Steel autoclave with an internal volume of 300 ml was added ethyl undecylenate (138g, 0.65 Mole) and EXAMPLE 359 freshly cracked cyclopentadiene (21.45 g, 0.325 mole). The To a 100 ml glass Vial fitted with an airtight crimptop cap stirred mixture was heated to 170° C. for 2 hours and then and a Teflon(R) stir bar was added at ambient temperature the the temperature was raised to 190° C. and the reaction was monomer from Example 352 (0.85g, 5.3 mmol), norbornene left overnight. The reactor was then cooled and the contents (2.0g, 21.25 mmol) in toluene (2 ml) and toluene (35 ml). removed. The resulting norbornene (NB(CH2)C(O) Thereafter was added (toluene)Ni(C.F.) (catalyst from OCH-CH-) was purified by vacuum distillation and found to 15 example 33; 6.44 mg, 13.3 umol) dissolved in toluene (1 have a boiling point of about 97 C. at 0.01 mm Hg. The ml). The vessel was heated to 50° C. and allowed to stir for material was analyzed by GC methods and found to have a 2.5 hours. The resulting polymer Solution was diluted with purity of 92 to 97% (different fractions). The isolated yield further toluene and then precipitated from Solution by add of high purity product was around 40 g. ing to a large excess of methanol. The polymer was filtered, washed with methanol and dried overnight in a vacuum oven EXAMPLE 355 at 80° C. The isolated yield of the polymer was 1.2 grams, To a stainless Steel autoclave with an internal volume of representing 41% conversion. The molecular weight was 300 ml was added allylglycidyl ether (91.4g, 0.8 Mole) and determined using GPC methods (M 745,000, M238,000). freshly cracked cyclopentadiene (52.8 g., 0.8 mole). The 25 stirred mixture was heated to 190° C. for 2 hours and then EXAMPLE 360 the temperature was raised to 200 C. and the reaction was To a 100 ml glass Vial fitted with an airtight crimptop cap left overnight. The reactor was then cooled and the contents and a Teflon(R) stirbar was added at ambient temperature the removed. The resulting nor born ene monomer from Example 353 (1.05 g, 5.3 mmol), norbornene (NBCHO.CHCHOCH) was purified by vacuum distilla (2.0g, 21.25 mmol) in toluene (2 ml) and toluene (35 ml). tion and found to have a boiling point of about 50-51 C. at Thereafter was added (toluene)Ni(CFs)(6.44 mg, 13.3 0.02 mm Hg. The material was analyzed by GC methods and umol) dissolved in toluene (1 ml). The vessel was heated to found to have a purity of 94 to 95% (different fractions). The 50° C. and allowed to stir for 3 hours. The resulting isolated yield of high purity product was around 71 g. sparingly Soluble polymer was precipitated with methanol 35 and then redissolved in hoto-dichlorobenzene. The polymer EXAMPLE 356 was then reprecipitated in methanol, filtered, washed with To a stainless Steel autoclave with an internal volume of methanol and dried overnight in a vacuum oven at 80° C. 300 ml was added allyl butyl ether (73.1 g, 0.64 mole) and The isolated yield of the polymer was 1.37 grams, repre freshly cracked cyclopentadiene (42.2 g, 0.64 mole). The senting 45% conversion. The relatively poor solubility of the stirred mixture was heated to 190° C. for 6 hours and 40 Sample precluded determining the molecular weight using Samples were taken as a function of time to follow the course GPC methods. NMR analysis indicated that the resulting of the reaction by GC methods. After 6 hours the reaction polymer contained roughly 10 mol % of the ester monomer. was essentially complete in that the cyclopentadiene was almost completely reacted and the ether was roughly 70% EXAMPLE 361 converted. The reactor was then cooled and the contents 45 To a 100 ml glass Vial fitted with an airtight crimptop cap removed. The resulting norbornene (NBCHO(CH-)-CH) and a Teflon(R) stirbar was added at ambient temperature the was purified by vacuum distillation in the usual way. monomer from Example 357 (0.05 g, 0.265 mmol), nor EXAMPLE 357 bornene (2.45 g, 26.25 mmol) in toluene (2.3 ml) and 50 toluene (35 ml). Thereafter was added (toluene)Ni(CF). To a stainless Steel autoclave with an internal volume of (6.43 mg, 13.3 umol) dissolved in toluene (1 ml). The vessel 300 ml was added allyl succinic anhydride (100 g, 0.71 was heated to 50° C. and allowed to stir for 3 hours. The mole) and dicyclopentadiene (47g, 0.35 mole). The stirred resulting polymer Solution was diluted with further toluene mixture was heated to 190° C. for 2 hours and then the and then precipitated from Solution by adding to a large temperature was raised to 200 C. and the reaction was left 55 excess of methanol. The polymer was filtered, washed with overnight. The reactor was then cooled and the contents methanol and dried overnight in a vacuum oven at 80° C. removed. The resulting norbornene was purified by vacuum The yield of polymer was 0.63 g, representing a conversion distillation and found to have a boiling point of about 130 of 25%. The relatively poor solubility of the sample pre C. at 0.05 mm Hg. The material was analyzed by GC cluded determining the molecular weight using GPC meth methods and found to have a purity of 89%. The isolated ods. yield of relatively high purity product was around 38 g. 60 EXAMPLE 362 EXAMPLE 358 To a 100 ml glass Vial fitted with an airtight crimptop cap To a stainless Steel autoclave with an internal volume of and a Teflon(R) stirbar was added at ambient temperature the 300 ml was added diethyl allyl malonate (88 g., 0.44 mole) 65 monomer from Example 352 (0.44g, 2.7 mmol), butylnor and dicyclopentadiene (0.26 Mole). The stirred mixture was bornene (3.65g, 24.3 mmol) and toluene (35 ml). Thereafter heated to 190° C. for 2 hours and then the temperature was was added (toluene)Ni(CFs)(6.54 mg, 13.5 umol) dis US 6,232,417 B1 127 128 solved in toluene (1 ml). The vessel was heated to 60° C. and allowed to stir for 3 hours. The resulting polymer Solution allowed to stir for 3 hours. The resulting polymer Solution was diluted with further toluene and then precipitated from was diluted with further toluene and then precipitated from Solution by adding to a large excess of methanol. The Solution by adding to a large excess of methanol. The polymer was filtered, washed with methanol and dried polymer was filtered, washed with methanol and dried overnight in a vacuum oven at 80° C. The isolated yield of overnight in a vacuum oven at 80 C. The isolated yield of the polymer was 1.02 grams, representing 23.3% conver the polymer was 0.73 grams, representing 18% conversion. Sion. The molecular weight was determined using GPC The molecular weight was determined using GPC methods methods (Mw 537,000, Mn 230,000). NMR spectroscopy (Mw 408,000, Mn 165,000). showed the copolymer to contain approximately 8% of the eSter monomer. EXAMPLE 363 To a 100 ml glass Vial fitted with an airtight crimptop cap EXAMPLE 367 and a Teflon(R) stirbar was added at ambient temperature the To a 100 ml glass Vial fitted with an airtight crimptop cap monomer from Example 353 (0.52g, 2.7 mmol), butylnor and a Teflon(R) stir bar was added at ambient temperature the bornene (3.65g, 24.3 mmol) and toluene (35 ml). Thereafter 15 methyl ester of 5-norbornenecarboxylic acid (0.41 g, 2.7 was added (toluene)Ni(C.F.) (6.5 mg, 13.5umol) dissolved mmol), butylnorbornene (3.65 g, 24.3 mmol) and toluene in toluene (1 ml). The vessel was heated to 60° C. and (35 ml). Thereafter was added (toluene)Ni(CF)(6.54 mg, allowed to stir for 3 hours. The resulting polymer Solution 13.5 umol) dissolved in toluene (1 ml). The vessel was was diluted with further toluene and then precipitated from heated to 60° C. and allowed to stir for 3 hours. The resulting Solution by adding to a large excess of methanol. The polymer solution was diluted with further toluene and then polymer was filtered, washed with methanol and dried precipitated from Solution by adding to a large excess of overnight in a vacuum oven at 80 C. The isolated yield of methanol. The polymer was filtered, washed with methanol the polymer was 1.3 grams, representing 31.2% conversion. and dried overnight in a vacuum oven at 80° C. The isolated The molecular weight was determined using GPC methods yield of the polymer was 0.47 grams, representing 12% (Mw 541,000, Mn 223,000). 25 conversion. The molecular weight was determined using GPC methods (M. 204,000, M., 82,000). NMR spectros EXAMPLE 364 copy showed the copolymer to contain approximately 8% of To a 100 ml glass Vial fitted with an airtight crimptop cap the ester monomer. and a Teflon(R) stir bar was added at ambient temperature the monomer from Example 354 (0.75g, 2.7 mmol), butylnor EXAMPLE 368 bornene (3.65g, 24.3 mmol) and toluene (35 ml). Thereafter To a 100 ml glass Vial fitted with an airtight crimptop cap was added (toluene)Ni(CF)(6.5 mg, 13.5 limol) dissolved and a Teflon(E) stirbar was added at ambient temperature the in toluene (1 ml). The vessel was heated to 60° C. and monomer from Example 355 (0.49 g, 2.7 mmol), butylnor allowed to stir for 3 hours. The resulting polymer Solution 35 bornene (3.65g, 24.3 mmol) and toluene (35 ml). Thereafter was diluted with further toluene and then precipitated from was added (toluene)Ni(CF5)(6.54 mg, 13.5 umol) dis Solution by adding to a large excess of methanol. The solved in toluene (1 ml). The vessel was heated to 60° C. and polymer was filtered, washed with methanol and dried allowed to stir for 3 hours. The resulting polymer Solution overnight in a vacuum oven at 80 C. The isolated yield of was diluted with further toluene and then precipitated from the polymer was 0.57 grams, representing 13% conversion. 40 Solution by adding to a large excess of methanol. The The molecular weight was determined using GPC methods polymer was filtered, washed with methanol and dried (Mw 367,000, Mn 158,000). overnight in a vacuum oven at 80° C. The isolated yield of the polymer was 1.33 grams, representing 32% conversion. EXAMPLE 365 The molecular weight was determined using GPC methods To a 100 ml glass Vial fitted with an airtight crimptop cap 45 (Mw 528,000, Mn222,000). IR analysis showed the copoly and a Teflon(R) stirbar was added at ambient temperature the mer to contain Significant levels of epoxide functionality. monomer from Example 349 (0.56 g, 2.7 mmol), butylnor EXAMPLE 369 bornene (3.65g, 24.3 mmol) and toluene (35 ml). Thereafter iwas added (toluene)Ni(CF)(6.54 mg, 13.5 umol) dis To a 100 ml glass Vial fitted with an airtight crimptop cap solved in toluene (1 ml). The vessel was heated to 60° C. and 50 and a Teflon(R) stirbar was added at ambient temperature the allowed to stir for 3 hours. The resulting polymer Solution monomer from Example 353 (0.52g, 2.7 mmol), hexylnor was diluted with further toluene and then precipitated from bornene (4.33 g, 24.3 mmol) and toluene (35 ml). Thereafter Solution by adding to a large excess of methanol. The was added (toluene)Ni(CFs)(6.44 mg, 13.3 umol) dis polymer was filtered, washed with methanol and dried solved in toluene (1 ml). The vessel was heated to 60° C. and overnight in a vacuum oven at 80 C. The isolated yield of 55 allowed to stir for 3 hours. The resulting polymer Solution the polymer was 0.81 grams, representing 19% conversion. was diluted with further toluene and was then reprecipitated The molecular weight was determined using GPC methods in methanol, filtered, washed with methanol and dried (Mw 460,000, Mn 188,000). overnight in a vacuum oven at 80° C. The isolated yield of the polymer was 2.61 grams, representing 54% conversion. EXAMPLE 366 60 The molecular weight was determined using GPC methods To a 100 ml glass Vial fitted with an airtight crimptop cap (Mw 1,185,000, Mn 518,000). and a Teflon(R) stir bar was added at ambient temperature the monomer from Example 358 (0.72 g, 2.7 mmol), butylnor EXAMPLE 370 bornene (3.65g, 24.3 mmol) and toluene (35 ml). Thereafter 65 To a 100 ml glass Vial fitted with an airtight crimptop cap was added (toluene)Ni(CFs)(6.54 mg, 13.5 umol) dis and a Telfon(R) stir bar was added at ambient temperature solved in toluene (1 ml). The vessel was heated to 60° C. and norbornene (4.0 g, 42.5 mmol) dissolved in cyclohexane (4 US 6,232,417 B1 129 130 ml), the monomer from Example 349 (2.20 g, 10.6 mmol) norbornene (4.0 g, 42.5 mmol) dissolved in cyclohexane (4 dissolved in cyclohexane (35 ml) followed by nickel ethyl ml) and the methyl ester of 5-norbornene carboxylic acid hexanoate (0.026 mmol). Thereafter was added tris (1.6 g., 10.6 mmol) dissolved in cyclohexane (35 ml) fol (perfluorophenyl)boron (0.234 mmol) and triethylaluminum lowed by allyl bromide (16 mg, 0.13 mmol) and nickel (0.26 mmol). The vessel was heated to 50° C. and allowed ethylhexanoate (0.026 mmol). Thereafter was added tris to stir for 3 hours. The solution became so viscous during the (perfluorophenyl)boron (0.234 mmol) and triethylaluminum polymerization that the entire mass became gelled. The (0.26 mmol). The vessel was heated to 50° C. and allowed resulting polymer was dissolved in THF and precipitated by to Stir for 3 hours. The copolymer produced was precipitated adding to a large exceSS of methanol. The copolymer was by adding to a large excess of acetone. The copolymer was filtered, washed with methanol and dried overnight in a filtered, washed with acetone and dried overnight in a vacuum oven at 80° C. The isolated yield of the copolymer vacuum oven at 80° C. The isolated yield of the copolymer was 5.25 grams, representing 85% conversion. was 3.85 grams, representing 69% conversion. The molecu lar weight was determined using GPC methods (Mw 89,600, EXAMPLE 371 Mn37.400). To a 100 ml glass Vial fitted with an airtight crimptop cap 15 and a Telfon(R) stir bar was added at ambient temperature EXAMPLE 375 butylnorbornene (3.2g, 21.3 mmol) and the monomer from To a 100 ml glass Vial fitted with an airtight crimptop cap Example 349 (1.1 g, 5.3 mmol) dissolved in cyclohexane (35 and a Teflon(R) stir bar was added at ambient temperature ml) followed by nickel ethylhexanoate (0.013 mmol). There norbornene (4.5g, 47.8 mmol) dissolved in cyclohexane (4 after was added tris(perfluorophenyl)boron (0.117 mmol) ml) and the methyl ester of 5-norbornene carboxylic acid and triethylaluminum (0.136 mmol). The vessel was heated (0.8 g., 5.3 mmol) dissolved in cyclohexane (35 ml) followed to 50° C. and allowed to stir for 3 hours. The polymer by allyl bromide (16 mg, 0.13 mmol) and nickel ethylhex produced remained in Solution and was precipitated by anoate (0.026 mmol). Thereafter was added tris adding to a large exceSS of acetone. The copolymer was (perfluorophenyl)boron (0.234 mmol) and triethylaluminum filtered, washed with acetone and dried overnight in a 25 (0.26 mmol). The vessel was heated to 50° C. and allowed vacuum oven at 80° C. The isolated yield of the copolymer to Stir for 3 hours. The copolymer produced was precipitated was 1.31 grams, representing 30% conversion. The molecu by adding to a large excess of methanol. The copolymer was lar weight was determined using GPC methods (M. 269, filtered, washed with methanol and dried overnight in a 000, M. 138,000). vacuum oven at 80° C. The isolated yield of the copolymer was 4.51 grams, representing 85% conversion. The molecu EXAMPLE 372 lar weight was determined using GPC methods (Mw 173, To a 100 ml glass Vial fitted with an airtight crimptop cap 000, Mn 65,400). and a Teflon(E) stir bar was added at ambient temperature butylnorbornene (1.6 g., 10.63 mmol), decylnorbornene (2.5 EXAMPLE 376 g, 10.63 mmol) and the monomer from Example 349 (1.1 g, 35 To a 100 ml glass Vial fitted with an airtight crimptop cap 5.3 mmol) dissolved in cyclohexane (35 ml) followed by and a Telfon(R) stir bar was added at ambient temperature nickel ethylhexanoate (0.013 mmol). Thereafter was added norbornene (3.5g, 37.2 mmol) dissolved in cyclohexane (4 tris(perfluorophenyl)boron (0.117 mmol) and triethylalumi ml) and the methyl ester of 5-norbornene carboxylic acid num (0.136 mmol). The vessel was heated to 50° C. and (1.9 g, 15.9 mmol) dissolved in cyclohexane (35 ml) fol allowed to stir for 3 hours. The polymer produced remained 40 lowed by allyl bromide (16 mg, 0.13 mmol) and nickel in Solution and was precipitated by adding to a large exceSS ethylhexanoate (0.026 mmol). Thereafter was added tris of acetone. The copolymer was filtered, washed with (perfluorophenyl)boron (0.234 mmol) and triethylaluminum acetone and dried overnight in a vacuum oven at 80°C. The (0.26 mmol). The vessel was heated to 50° C. and allowed isolated yield of the copolymer was 0.93 grams, representing to Stir for 3 hours. The copolymer produced was precipitated 23% conversion. The molecular weight was determined 45 by adding to a large excess of methanol. The copolymer was using GPC methods (Mw 334,000, Mn 175,000). filtered, washed with methanol and dried overnight in a vacuum oven at 80° C. The isolated yield of the copolymer EXAMPLE 373 was 2.4 grams, representing 44% conversion. The molecular To a 100 ml glass Vial fitted with an airtight crimptop cap weight was determined using GPC methods (MW 114,000, and a Teflon(E) stirbar was added at ambient temperature 50 Mn 48,000). norbornene (4.0 g, 42.5 mmol) dissolved in cyclohexane (4 ml) and the monomer from Example 349 (2.2g, 10.6 mmol) EXAMPLE 377 dissolved in cyclohexane (35 ml) followed by allyl bromide To a 100 ml glass Vial fitted with an airtight crimptop cap (64 mg., 0.53 mmol) and nickel ethylhexanoate (0.026 and a Teflon(E) stirbar was added at ambient temperature mmol). Thereafter was added tris(perfluorophenyl)boron 55 norbornene (4.7g, 50.4 mmol) dissolved in cyclohexane (4 (0.234 mmol) and triethylaluminum (0.26 mmol). The ves ml) and the monomer described in Example 357 (0.5g, 2.6 sel was heated to 50° C. and allowed to stir for 3 hours. The mmol) dissolved in cyclohexane (35 ml) followed by nickel copolymer produced was precipitated by adding to a large ethylhexanoate (0.026 mmol). Thereafter was added tris excess of acetone. The copolymer was filtered, washed with (perfluorophenyl)boron (0.234 mmol) and triethylaluminum acetone and dried overnight in a vacuum oven at 80°C. The 60 (0.26 mmol). The vessel was heated to 50° C. and allowed isolated yield of the copolymer was 2.53 grams, representing to Stir for 3 hours during which time the reactor contents Set 41% conversion. The molecular weight was determined up to form a Solid mass. The copolymer produced was using GPC methods (Mw 224,000, Mn 110,000). insoluble in toluene, THF and dichlorobenzene. EXAMPLE 374 EXAMPLE 378 65 To a 100 ml glass Vial fitted with an airtight crimptop cap To a 100 ml glass Vial fitted with an airtight crimptop cap and a Telfon(R) stirbar was added at ambient temperature and a Teflon(R) stir bar was added at ambient temperature US 6,232,417 B1 131 132 norbornene (4.9 g, 52.5 mmol) dissolved in cyclohexane (4 colorless gel. After 60 minutes the vial was opened and the ml) and the monomer described in Example 357 (0.1 g, 0.53 contents were dissolved in an excess of toluene (300 ml) and mmol) dissolved in cyclohexane (35 ml) followed by then poured into exceSS methanol to afford the product as a (toluene)Ni(CFS).(6.43 mg, 13.3 umol) dissolved in tolu pure white polymer which was isolated by filtration, washed ene (1 ml). The vessel was heated to 50° C. and allowed to with exceSS methanol and dried overnight in a vacuum oven Stir for 3 hours during which time the reactor contents at 80° C. The isolated yield of the polymer was 8.08 grams, became Viscous. The copolymer produced was diluted in representing 96% conversion. GPC showed the polymer to toluene and precipitated into methanol, filtered and washed with methanol followed by drying overnight in a vacuum have a high molecular weight (Mw 1,120,000, Mn 285,000) oven at 80° C. The isolated yield of the copolymer was 0.9 and NMR showed the polymer to be a terpolymer of all three grams, representing 18% conversion. Infrared analysis OOCS. showed the copolymer to contain low levels of anhydride functionality (stretches at 1792 and 1868 cm). EXAMPLE 382

15 To a 100 ml glass vial fitted with an air-tight crimp-top EXAMPLE 379 cap and a Teflon(R) Stir bar was added at ambient temperature To a 100 ml glass Vial fitted with an airtight crimptop cap norbornene (5.1 g, 54.2 mmol) and toluene (50 ml). There and a Telfon(R) stir bar was added at ambient temperature after the solution was flushed with ethylene and pressurized endo nadic anhydride (0.646g, 4.25 mmol), norbornene (3.6 to 5 psi with ethylene, then was added (toluene)Ni(CFS) g, 38.2 mmol) and chlorobenzene (35 ml). Thereafter was (52.7 mg, 108 umol) dissolved in toluene (10 ml). The added (toluene)Ni(C.F.) (20.4 mg., 42.5 umol) dissolved in solution was stirred at ambient temperature for 1 hour. The chlorobenzene (1 ml). The solution became so viscous that resulting solution was poured into methanol (300 ml) and Stirring Stopped within 12 minutes. The resulting polymer the precipitated low molecular weight polymer was isolated Solution precipitated from Solution by adding to a large and dried (yield 400 mg, 7.8%) and characterized a polynor excess of acetone. The polymer was filtered, washed with 25 bornene by NMR methods. The methanol soluble fraction acetone and dried overnight in a vacuum oven at 80°C. The was isolated by evaporation of the methanol Solution to isolated yield of the polymer was 3.66 grams, representing dryneSS affording approximately 50 mg of low oligomers. 86% conversion. The molecular weight was determined These oligomers were characterized by proton and 'C using GPC methods (Mw867,000, Mn331,000). NMR and NMR methods and also by mass spectrometry. These oli IR characterization indicated that the resulting polymer was gomers were found to comprise dimers, trimers, tetramers, a copolymer of norbornene and nadic anhydride. pentamers, hexamers and heptamers of norbornene. Further more each oligomer was found to bear one pentafluorophe EXAMPLE 380 nyl head group and one vinyl end group. To a 100 ml glass Vial fitted with an airtight crimptop cap 35 and a Telfon(R) stir bar was added at ambient temperature EXAMPLE 383 butylnorbornene 6.375 g, 42.5 mmol), 5-phenylnorbornene (1.35 g, 7.95 mmol) and 5-triethoxysilylnorbornene (0.7g, (Toluene)Ni(C.F.) (1.5 g) was dissolved in toluene (3 2.65 mmol) dissolved in toluene (50 ml) followed by nickel ml). This solution was added to the methyl ester of ethylhexanoate (26 umol). To this stirred Solution, at ambi 40 5-norbornene carboxylic acid (1.0 g) which was dissolved in ent temperature, was added a mixture of tris cyclohexane (10 ml). After Stirring overnight, the resulting (perfluorophenyl)boron (238 umol, in 4 ml octanes) and polymer (MW-10,700, Mn=6.800) was isolated and Sub triethylaluminum (265 umol). There was an immediate jected to matrix assisted laser desorption ionization - time of exotherm and viscosity increase. Within 5 minutes the whole flight mass spectrometry which showed that each polymer Solution had set up to afford a nonflowing colorleSS gel. 45 chain contained a CFs end group. Broad resonances (-130 After 60 minutes the vial was opened and the contents were to 142 and -155 to -165 ppm) were observed in the 19F dissolved in an excess of toluene (300 ml) and then poured NMR spectrum of the polymer consistent with the presence into exceSS methanol to afford the product as a pure white of CFs end groups. polymer which was isolated by filtration, washed with What is claimed is: exceSS methanol and dried overnight in a vacuum oven at 50 1. A method for preparing a polycyclic polymer compris 80 C. The isolated yield of the polymer was 8.22 grams, ing polymerizing a monomeric reaction composition com representing virtually quantitative conversion. GPC showed prising at least two types of polycyclic monomers one of the polymer to have a high molecular weight (Mw 865,000, which containing a pendant acid labile group and another of Mn 143,000) and NMR showed the polymer to be a ter which containing a pendant polar functional group in the polymer of all three monomers. 55 presence of a catalyst represented by the formula: EXAMPLE 381 E.M.(Q), (R), To a 100 ml glass Vial fitted with an airtight crimptop cap wherein M is a Group VIII transition metal, Q is an electron and a Teflon(E) stirbar was added at ambient temperature 60 withdrawing ligand Selected from the group consisting of butylnorbornene 6.375 g, 42.5 mmol), 5-phenylnorbornene linear and branched (C to Co) perhaloalkyl, (C7 to C.) (1.35 g, 7.95 mmol) and 5-triethoxysilylnorbornene (0.7g, perhaloalkaryl and perhaloaryl groups, n is an integer of 0, 2.65 mmol) dissolved in toluene (50 ml). To this stirred 1, 2 or 3., f is an integer of 1, 2 or 3; g is an integer of 0 or Solution, at ambient temperature, was added (toluene)Ni 1; when f is 1, R must be present; and E when present is (CFS)-(26 mg, 53.1 umol) in toluene (3 ml). There was an 65 Selected from a monodentate or bidentate ligand wherein immediate exotherm and viscosity increase. Within 5 min Said monodentate ligand is Selected from the group consist utes the whole Solution had set up to afford a nonflowing ing of p-arenes, ethers and thioethers of the formulae US 6,232,417 B1 133 134 R-O-R and R-S-R wherein R can be the same or different and represents a linear and branched (C to Co) alkyl group, the R groups that are connected to the oxygen or Sulfur heteroatom can be taken together to represent heterocyclic ring containing 4 to 8 carbon atoms, cyclic diethers containing 3 to 6 carbon atoms, ketones represented by the formula R-C(O)-R wherein R is as defined p above, Substituted or unsubstituted cyclic ketones contain ing 5 to 8 carbon atoms wherein Said Substituents are 1O Selected from linear or branched (C to Co) alkyl and (C to C.) aryl groups; amines of the formula N(R)s wherein wherein R' to R' independently represent a substituent R" independently represents linear or branched (C, to Co) Selected from the group consisting of hydrogen, linear and alkyl, (C7 to Co) aralyl, (C. to C) aryland cycloaliphatic branched (C to Co) alkyl, -(A),C(O)OR*, -(A), C(O) groups containing 5 to 8 carbon atoms, wherein Said alkyl, 15 OR, -(A), OR, -(A), OC(O)R, -(A)-C(O)R, aryl and cycloaliphatic Substituents optionally contain halo -(A), OC(O)OR, -(A), OCHC(O)OR*, -(A), C gen atoms Selected from chlorine, bromine, fluorine and (O)O-A-OCHC(O)OR*, -(A), OC(O)-A-C(O) iodine, pyridine, and Substituted pyridine containing linear OR*,-(A),C(R)-CH(R)(C(O)OR**), and -(A),C(R)-CH and branched (C to Co) alkyl groups; phosphines of the (C(O)OR**) wherein n is 0 or 1, m is an integer from 0 to formula P(R), phosphine oxides of the formula (R)-PO; 5, -A- and -A- independently represent a divalent phosphites of the formula P(OR), wherein R in each of the radical Selected from the group consisting of linear and phosphine, phosphine oxide and phosphite formulae is as branched (C to Co) alkylene, (C. to Co) alkylene ethers, defined above; ester compounds of the formula RC(O)OR polyethers, or a divalent cyclic group of the formula: wherein R is defined above; lactones and linear and 25 branched (C to C) alkyl and (Cs to Cs) aryl Substituted 1N lactones wherein the lactone ring contains 3 to 8 carbon -CH (CH2) 3. atoms, and Said bidentate ligand is Selected from a hemila bile chelating ligand containing phosphorus, oxygen, nitro gen and Sulfur represented by the formula: wherein a is an integer from 2 to 7, and the diagonal bond -Y projecting from the center of the cyclic Structure represents K the divalent nature of the cyclic moiety and can be connected Nz to anyone of the carbocyclic atoms (-CH-) in the ring 35 with the proviso that the carbocyclic atom to which the bond is connected will have one less hydrogen atom to Satisfy the wherein Y and Z independently represent phosphorus, Valance of carbon, R represents hydrogen or linear and oxygen, carbonyl, nitrogen and Sulfur which are optionally branched (C to Co) alkyl, and R represents an acid labile substituted with linear and branched(C. to C) alkyl and (C group that is cleavable by a photoacid initiator and is to C) aryl groups and K represents an unsubstituted and 40 Selected from the group consisting of -C(CH), -Si Substituted hydrocarbon backbone moiety containing from 2 (CH), —CH(R)OCHCH, -CH(R)OC(CH), or the to 25 carbon atoms, or a divalent alkylene ether moiety following cyclic groups: wherein the alkylene radicals independently contain from 1 to 10 carbon atoms, said Substituents if present are Selected from linear and branched (C to Co) alkyl, (Cs to Cs) 45 C HCA V-CH alicyclic and (Cs to Caryl), halides, and amine; and R is a Substituted or unsubstituted allyl ligand represented by the RP - formula: RP RP 50 o Ya R21 ( 55 RP R22 wherein R', R', and Rif independently represent c)O hydrogen, linear or branched (C to Cs) alkyl, (C. to C.) 60 aryl, (C, to Co) aralkyl such as benzyl, -COOR, wherein R represents hydrogen or a linear or branched (C, -(CH), OR, CI and (Cs to C.) cycloaliphatic, wherein to C) alkyl group, R** independently represents R and R* R is linear and branched (C. to C) alkyl, and n is 1 to 5, and at least one of R' to R' must be selected from a any two of R', R', and R* may be linked together to form 65 Substituent containing said acid labile group; and wherein R an alicyclic group and wherein Said polycyclic monomers to Rindependently represent a substituent selected from the are represented by the formulae: group consisting of hydrogen, linear and branched (C to US 6,232,417 B1 135 136 Co) alkyl, and a polar Substituent represented as follows: 6. The method of claim 5 wherein the reaction composi -(A), C(O)OR", -(A), OR", -(A), OC(O)R", tion further comprises a mixed Solvent System comprising a -(A), OC(O)OR", -(A), C(O)R", -(A), OC(O)C dual component Solvent System containing a non-polar (O)OR", -(A), O-A-C(O)OR", -(A), OC(O)- hydrocarbon diluent in combination with a polar organic A-C(O)OR", -(A), C(O)O-A-C(O)OR", -(A)- 5 Solvent in a ratio of non-polar hydrocarbon Solvent to polar C(O)-A'-OR", -(A)-C(O)O-A'-OC(O)OR", organic solvent ranging from 75:25 w/w to 25:75 w/w. -(A), C(O)O-A'-O-A-C(O)OR", -(A), C(O) 7. The method of claim 6 wherein the monomer to solvent O-A'-OC(O)C(O)OR", -(A)-C(R")-CH(R")(C(O) concentration ranges from 5 to 50 weight percent (monomer OR"), and -(A), C(R")-CH(CO)OR"), wherein n is 0 in Solvent). or 1, p is an integer from 0 to 5, R" represents a Substituent 8. The method of claim 7 wherein the monomer to catalyst ratio ranges from 500:1 to 100:1 and the monomer to solvent Selected from hydrogen, linear and branched (C to Co) concentration ranges from 10 weight percent to 30 weight alkyl, linear and branched (C to Co) alkoxyalkylene, percent (monomer in Solvent). polyethers, monocyclic and polycyclic (C. to Co) 9. A method of appending an electron withdrawing ligand cycloaliphatic moieties, cyclic ethers, cyclic diethers, cyclic onto a terminal end of a polycyclic polymer comprising ketones, and cyclic esters (lactones), with the proviso that 15 homopolymerizing or copolymerizing a polycyclic mono when R" is an alkyl, lactone, cycloaliphatic or cyclic ketone mer of the formula: group -A- must be present and can not represent an alkylene radical. 2. The method of claim 1 wherein said monomer com position further includes one or more monomers represented by the following structures:

25

in the presence of a catalyst of the formula: E.M.(Q), (R), R10 R11 R14 R15 wherein M is a Group VIII transition metal, Q is an electron withdrawing ligand Selected from the group consisting of wherein R to R' independently represent hydrogen and linear and branched (C. to Co) perhaloalkyl, (C7 to C.) linear and branched (C to Co) alkyl, with the proviso that perhaloalkaryl and perhaloaryl groups, n is an integer of 0, at least one of R to R' is -(CH2), SOH, -(CH),C(O) 35 1, 2 or 3., f is an integer of 1, 2 or 3; g is an integer of 0 or O", -(CH), SOX", or -(CH),C(O)OH wherein X 1; when f is 1, R must be present; and E when present is represents a tetraalkylammonium cation; n is an integer from Selected from a monodentate or bidentate ligand wherein 0 to 10; and q and rare integers from 0 to 5. Said monodentate ligand is Selected from the group consist 3. The method of claim 1 or 2 wherein M is selected from ing of p-arenes, ethers and thioethers of the formulae the group consisting of nickel, palladium, platinum, iron, 40 R-O-R and R-S-R wherein R' can be the same or rhodium and cobalt, Q is Selected from a ligand Selected different and represents a linear and branched (C to Co) from the group consisting of trifluoromethyl, alkyl group, the R groups that are connected to the oxygen pent a flu or op he nyl, p ent a chlorophenyl, and or Sulfur heteroatom can be taken together to represent pentabromophenyl, 2,4,6-tris(trifluoromethylphenyl); and E heterocyclic ring containing 4 to 8 carbon atoms, cyclic is Selected from the group consisting of benzene, toluene, 45 diethers containing 3 to 6 carbon atoms, ketones represented and mesitylene, methyltertbutylether, diethylether, furan, by the formula R-C(O)-R wherein R is as defined glyme, diglyme, triglyme, tetraglyme, tetrahydrofuran, above, Substituted or unsubstituted cyclic ketones contain thiophene, tetrahydrothiophene, dioxane, acetone, methyl ing 5 to 8 carbon atoms wherein Said Substituents are ethylketone and methylphenylketone, pyridine, trialkyl, Selected from linear or branched (C to Co) alkyl and (C triperfluoroalkyl, and triaryl phosphines phosphites and 50 to C.) aryl groups; amines of the formula N(R)s wherein phosphine oxides, ethyl acetate, B-propiolactone and R" independently represents linear or branched (C, to Co) Y-butyrolactone, and allyl. alkyl, (C7 to Co) aralyl, (C. to C.) aryl and cycloaliphatic 4. The method of claim 2 wherein said catalyst is selected groups containing 5 to 8 carbon atoms, wherein Said alkyl, from the group consisting of bis(2,4,6-tris aryl and cycloaliphatic Substituents optionally contain halo (trifluoromethylphenyl)) nickel, (toluene) bis 55 gen atoms Selected from chlorine, bromine, fluorine and (perfluorophenyl) nickel, (mesitylene)bis(perfluorophenyl) iodine, pyridine, and Substituted pyridine containing linear nickel, (benzene)bis(perfluorophenyl) nickel, bis and branched (C to Co) alkyl groups; phosphines of the (tetrahydrofuran) bis(perfluorophenyl) nickel, formula P(R); phosphine oxides of the formula (R)-PO; (dimethylethoxyethane)bis(perfluorophenyl) nickel, phosphites of the formula P(OR), wherein R in each of the (dimethoxyethane)bis(2,4,6-tris(trifluoromethylphenyl)) 60 phosphine, phosphine oxide and phosphite formulae is as nickel bis(dioxane)bis(perfluorophenyl) nickel, bis defined above; ester compounds of the formula RC(O)OR (diethylether)bis(perfluorophenyl) nickel, (methallyl)nickel wherein R is defined above; lactones and linear and (pentafluorophenyl)(triphenylphosphine), (methalyl) nickel branched (C to C) alkyl and (Cs to Cs) aryl Substituted (pentafluorophenyl)(tricyclohexylphosphine), and the lactones wherein the lactone ring contains 3 to 8 carbon compound Ni(CFs)Cl]. 65 atoms, and Said bidentate ligand is Selected from a hemila 5. The method of claim 4 wherein the monomer to catalyst bile chelating ligand containing phosphorus, oxygen, nitro ratio ranges from 2000:1 to 50:1. gen and Sulfur represented by the formula: US 6,232,417 B1 137 138 from 0 to 5, -A- and -A- independently represent a -Y divalent radical Selected from the group consisting of linear K and branched (C to Co) alkylene, (C. to Co) alkylene NZ ethers, polyethers, or a cyclic group of the formula: wherein Y and Z independently represent phosphorus, oxygen, carbonyl, nitrogen and Sulfur which are optionally Substituted with linear and branched(C to Co) alkyl and -CH (CH2) 3. (C. to C) aryl groups and K represents an unsubstituted and Substituted hydrocarbon backbone moiety containing from 2 to 25 carbon atoms, or a divalent alkylene ether moiety wherein the alkylene radicals independently contain from 1 to 10 carbon atoms, Said Substituents if present are wherein a is an integer from 2 to 7, R" represents hydrogen Selected from linear and branched (C to Co) alkyl, (Cs to or linear and branched (C to Co) alkyl, -C(CH), -Si Cs) alicyclic and (C to Caryl), halides, and amine; and (CH), -CH(R)OCHCH, -CH(R)OC(CH), R is a substituted or unsubstituted allyl ligand represented 15 by the formula: HC CH R20 RP R21 ( RP RP

R22 wherein R', R', and R’ independently represent 25 oric hydrogen, linear or branched (C to Cs) alkyl, (C. to g) aryl, (C, to Co) aralkyl such as benzyl, -COOR, - (CH), OR, CI and (Cs to C.) cycloaliphatic, wherein R is linear and branched (C, to Cs) alkyl, and n is 1 to 5, any two of R', R, and R* may be linked together to form OH analicyclic group, wherein R", R', R', and R' indepen dently represent hydrogen, linear and branched (C to Co) alkyl, hydrocarbyl Substituted and unsubstituted (Cs to C.) cycloalkyl, (C7 to Cs) aralkyl, (C. to Co) alkynyl, linear and branched (C. to Co) alkenyl, vinyl; any of R' and R' or R' and R' can be taken together to form a (C. to Co) 35 alkylidenyl group, R' and R' can be taken together with wherein R represents hydrogen or a linear or branched (C, the two ring carbon atoms to which they are attached can to Cs) alkyl group; linear and branched (C to Co) represent Saturated and unsaturated cyclic groups containing alkoxyalkylene, polyethers, monocyclic and polycyclic (C 4 to 12 carbon atoms or an aromatic ring containing 6 to 17 to Co) cycloaliphatic moieties, cyclic ethers, cyclic carbon atoms, or an anhydride or dicarboxyimide group; 40 diethers, cyclic ketones, and cyclic esters (lactones), when —(B), SiRRR wherein B is a divalent bridging or any of R' to R' represent a succinic or carboxyimide Spacer radical Selected from linear and branched (C to g) moiety and n is 1A can only represent a linear or branched alkylene, n is an integer of 0 or 1, R, R, and R' (C. to Co) alkylene group. independently represent halogen, linear or branched (C to 10. The catalyst of claim 9 wherein said catalyst is Co) alkyl, linear or branched (C to Co) alkoxy, Substituted 45 Selected from the group consisting of bis(2,4,6-tris or unsubstituted (C to Co) aryloxy, linear or branched (C (trifluoromethylphenyl)) nickel, (toluene) bis to Co) alkyl carbonyloxy, and (C to Co) alkyl peroxy, (perfluorophenyl) nickel, (mesitylene)bis(perfluorophenyl) -(A), C(O)OR", -(A), OR", -(A), OC(O)R", nickel, (benzene)bis(perfluorophenyl) nickel, bis -(A), OC(O)OR", -(A), C(O)R", -(A), OCHC (tetrahydrofuran) bis(perfluorophenyl) nickel, (O)OR*, -(A), C(O)O-A-OCHC(O)OR*, -(A) - 50 OC(O)C(O)OR", -(A), O-A-C(O)OR", -(A), OC (dimethylethoxyethane)bis(perfluorophenyl) nickel, (O)-A'-C(O)OR, -(A)-C(O)O-A'-C(O)OR", (dimethoxyethane)bis(2,4,6-tris(trifluoromethylphenyl)) nickel bis(dioxane)bis(perfluorophenyl) nickel, bis (diethylether)bis(perfluorophenyl) nickel, (methallyl)nickel (pentafluorophenyl)(triphenylphosphine), (methallyl) nickel 55 (pentafluorophenyl)(tricyclohexylphosphine), and the compound Ni(CF)Cl]. 11. The method of claim 6 wherein at least one of R', - (A) -CC(O)OC(O)CH, R", R', and R' of said polycyclic monomer represents the 60 group -(A), C(O)OR", wherein R" is a lactone. 12. The method of claim 11 wherein m and n are 0. 13. The method of claim 9 wherein said ligand is a perfluorophenyl group. wherein R is hydrogen, linear and branched (C, to Co) alkyl, or (C. to Cs) aryl, wherein n is 0 or 1, m is an integer k k k k k UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION

PATENT NO. : 6.232,417 B1 Page 1 of 1 DATED : May 15, 2001 INVENTOR(S) : Rhodes et al.

It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:

Title page, Please add: -- Related U.S. Application Data 60 Continuation-in-part of Application No. 08/812,418, March 6, 1997, now Patent No. 6,136,499, which claims benefit of Provisional Application No. 60,025,174, March 7, 1996. --

Signed and Sealed this Nineteenth Day of November, 2002

Attest.

JAMES E ROGAN Attesting Officer Director of the United States Patent and Trademark Office