United States Patent (19) 11 Patent Number: 5,939,504 Woodson, Jr

USOO5939504A United States Patent (19) 11 Patent Number: 5,939,504 Woodson, Jr. et al. (45) Date of Patent: Aug. 17, 1999

54 METHOD FOR EXTENDING THE POT LIFE Burrell, Anthony, et al., “Synthesis and Reactions of Ru OF AN OLEFIN METATHESIS (=CH-) Cl (NO) (PPh), a Stable Terminal Methylene POLYMERIZATION REACTION complex and the Crystal Structure of Ru (CH2PPh3) 75 Inventors: Charles S. Woodson, Jr., Monroe, La., (m°-CF) Cl (NO) PPH)”, J. Chem. Soc. Dalton Trans. , Robert H. Grubbs, South Pasadena, pp. 609-614 (1991). Calif. E.L. Dias et al. (1997) J. Am. Chem. Soc. 119,3887-3897. 73 Assignee: Advanced Polymer Technologies, J.P. Collman et al. “Principles and Applications of Organ Monroe, La. otransition Metal Chemistry, pp. 475-485, University Sci ence Books, Mill Valley, 1987. 21 Appl. No.: 08/759,018 22 Filed: Dec. 2, 1996 Primary Examiner Mark Nagumo Related U.S. Application Data Attorney, Agent, or Firm-Limbach & Limbach L.L.P. 57 ABSTRACT 60 Provisional application No. 60/008,356, Dec. 7, 1995. (51) Int. Cl...... C08F 4/80 Compositions and methods for catalyzing and controlling 52 U.S. Cl...... 526/145; 526/147; 526/146; the rate of olefin metathesis reactions including Ring Open 526/135; 526/171; 526/283; 502/152; 502/155; ing Metathesis Polymerization (ROMP) reactions. The 502/156; 556/22; 556/136; 585/366; 585/645 molding of polymer articles using ROMP polymers. The 58 Field of Search ...... 502/155, 156, composition includes a Ruthenium or OSmium carbene 502/152; 556/22, 136; 526/145, 147; 585/366, complex catalyst and a gel modification additive. The Ruthe 645 nium or OSmium carbene complex catalyst having the formula 56) References Cited U.S. PATENT DOCUMENTS 4,380,617 4/1983 Minchak et al. . ... 526/161 4,400,340 8/1983 Klosiewicz ...... 264/328.6 4,418,179 11/1983 DeWitt et al...... 525/249 4,426,502 1/1984 Minchak ...... 526/172 4,507,453 3/1985 Tom ...... 526/283 4,520,181 5/1985 Klosiewicz ...... 525/247 where M may be Os or Ru; R and R' may be the same or 4.584,425 4/1986 Tom ...... 585/827 different and may be hydrogen or a Substituent group includ 4,661,575 4/1987 Tom ...... 526/283 ing C-Co alkenyl, C-Co alkynyl, C-Co alkyl, aryl, 4,701,510 10/1987 Minchak et al. . ... 526/283 C-C20 carboxylate, C-Co alkoxy, Ca-Co alkenyloxy, 4,703,098 10/1987 Matlack ...... 526/283 C-Co alkynyloxy, aryloxy, C-Co alkoxycarbonyl, 4,748.216 5/1988 Tom ...... 526/77 C-C alkylthio, C-C alkylsulfonyl and C-C alkyl 4,899,005 2/1990 Lane et al...... 585/360 4,906,797 3/1990 Lane, Jr. et al...... 585/1 sulfinyl; X and X may be the same or different and may be 4,943,621 7/1990 Janda et al...... 526/127 any anionic ligand; and L and L' may be the same or different and may be neutral electron donor. The gel modi 5,312,940 5/1994 Grubbs et al...... 526/136 5,331,057 7/1994 Brekner et al...... 525/289 fication additive may be a neutral electron donor or a neutral 5,342,909 8/1994 Grubbs et al...... 526/171 Lewis base including phosphine, Sulfonated phosphine, FOREIGN PATENT DOCUMENTS phosphite, phosphinite, phosphonite, arsine, Stibine, ether, amine, amide, Sulfoxide, carboxyl, nitroSyl, pyridine, or WO 96/20235 7/1996 WIPO. thioether. The gel modification additive may be a trialky WO 96/04289 2/1997 WIPO. lphosphine or triarylphosphine. Examples of gel modifica OTHER PUBLICATIONS tion additives include P(cyclohexyl), P(cyclopentyl), P(isopropyl), P(phenyl), and pyridine. Schwab, Peter, et al., “Synthesis and Applications of RuCl (=CHR) (PR): The Influence of the Alkylidene Moiety on Metathesis Activity”, J. Am. Chem. Soc. 118:100-10 (1996). 69 Claims, No Drawings 5,939.504 1 2 METHOD FOR EXTENDING THE POT LIFE by controlling the temperature of the monomer or the mold. OF AN OLEFIN METATHESIS Such control would be useful, for example, to produce a POLYMERIZATION REACTION catalyst/monomer mixture in which the catalyst is Substan tially deactivated at room temperature. This mixture may This application claims the benefit of U.S. Provisional then be poured, cast, or injected into a mold and the application No. 60/008,356, filed Dec. 7, 1995; titled polymerization may then be initiated by heating the mixture. “Method for Extending the Pot Life of an Olefin Metathesis There therefore exists a need for an olefin metathesis Reaction'; inventors Charles S. Woodson and Robert H. catalyst System that can be used to catalyze olefin metathesis Grubbs. reactions and control the rate of the catalyzed metathesis reaction. There is also a need for an olefin metathesis BACKGROUND catalyst System that can be used to control the pot life of a monomer/catalyst mixture in a ROMP reaction. The present invention relates to compositions and meth ods for catalyzing and controlling the rate of olefin metathe SUMMARY sis reactions. More particularly, the present invention relates The present invention addresses these needs by providing to compositions and methods for catalyzing and controlling 15 a composition which may be used for catalyzing and con the rate of Ring Opening Metathesis Polymerization trolling the rate of olefin metathesis reactions. The invention (ROMP) reactions and the molding of polymer articles using also provides a method for controlling an olefin metathesis ROMP polymers. reaction using the composition, a process for Ring Opening The molding of thermoset polymerS is a technologically Metathesis Polymerization using the composition, and a important processing technique. In one version of this method for molding polymer articles using ROMP catalyzed technique, a liquid monomer (e.g., an olefin) and a poly and controlled by the composition. merization catalyst are mixed and poured, cast or injected In one embodiment of the invention, the composition into a mold. The polymerization proceeds (the article includes a Ruthenium or OSmium carbene complex catalyst “cures”) and on completion the molded part is removed from and a gel modification additive. The Ruthenium or Osmium the mold for any post cure processing that is required. The 25 carbene complex catalyst includes a Ruthenium or OSmium polymerization reaction mixture may optionally contain metal center that is in a +2 oxidation State, has an electron added modifiers, fillers, reinforcements, pigments, etc. count of 16, and is pentacoordinated and the gel modifica To mold Successfully, the reaction mixture must not cure tion additive is an electron donor or Lewis base. More So quickly that the liquid monomer/catalyst mixture poly Specifically, the Ruthenium or OSmium carbene complex merizes before the mixture can be introduced in to the mold. catalyst may have the formula In addition, the mixture must not cure So quickly that it has polymerized before the mold is completely filled or before the catalyst has had time to completely dissolve. For con Venience and expedient cycle time, it is also important that the catalyst activate within a reasonable time after the mold 35 is filled. The time during which the liquid monomer/catalyst mix where M may be Os or Ru; R and R' may be the same or ture can be worked after the monomer and catalyst is mixed different and may be hydrogen or a Substituent group includ is called the “pot life” of the polymerization reaction mix 40 ing C-Co alkenyl, C-Co alkynyl, C-Co alkyl, aryl, ture. The ability to control the “pot life” becomes even more C-C20 carboxylate, C-Co alkoxy, Ca-Co alkenyloxy, important in the molding of large parts. The monomer/ C-Co alkynyloxy, aryloxy, C-Co alkoxycarbonyl, catalyst mixture may also be applied to articles as a coating, C-C alkylthio, C-C alkylsulfonyl and C-C alkyl and in this case it is also important to be able to control the sulfinyl; X and X may be the same or different and may be “pot life” of the mixture. Generally, it would be useful to be 45 any anionic ligand; and L and L' may be the same or able to control the rate of reaction of catalyzed metathesis different and may be neutral electron donor. The substituent reactions including ROMP reactions. groups may be Substituted with one or more groups includ Reaction Injection Molding (“RIM”) has previously been ing C-C alkyl, halide, C-C alkoxy, and phenyl. The used for the molding of polymer articles using a polymer phenyl group may be Substituted with one or more groups ization catalyst and olefin monomer (U.S. Pat. Nos. 4,400, 50 including halide, C-C alkyl and C-C alkoxy. In addition 340 and 4,943,621). In these previous processes, a metal (W to the above groups, the Substituent group may be Substi or Mo) containing compound is dissolved in a first monomer tuted with one or more functional groups Selected from the Stream and an alkyl aluminum compound is dissolved in a group consisting of hydroxyl, thiol, ketone, aldehyde, ester, Second monomer Stream. The monomer Streams are then ether, amine, imine, amide, nitro, carboxylic acid, disulfide, mixed and the metal containing compound and the alkyl 55 carbonate, isocyanate, carbodiimide, carboalkoxy, and halo aluminum compound react to form an active catalyst which gen. In a preferred embodiment, the R and R' groups may then catalyzes the polymerization reaction. In the previous be the same or different and may be hydrogen, Substituted processes, the alkyl aluminum compound Stream may also aryl, unsubstituted aryl, Substituted vinyl, and unsubstituted include an inhibitor, usually a Lewis base, which inhibits the vinyl; where the substituted aryl and substituted vinyl may rate of formation of the catalyst; however, in these previous 60 be Substituted with one or more groups Selected from the processes, once the catalyst is formed, the polymerization group consisting of hydroxyl, thiol, ketone, aldehyde, ester, reaction is extremely fast and there is no method to control ether, amine, imine, amide, nitro, carboxylic acid, disulfide, the rate of polymerization initiated by the active catalyst carbonate, isocyanate, carbodiimide, carboalkoxy, halogen, Species. C-C alkyl, C-C alkoxy, unsubstituted phenyl, and phe Previously, there has been few methods for producing a 65 nyl Substituted with a halide, C-C alkyl or C-C alkoxy. mixture of active catalyst Species and monomer and con In a preferred embodiment, the gel modification additive trolling the rate of polymerization of the mixture other than is a neutral electron donor or a neutral Lewis base. The gel 5,939.504 3 4 modification additive may be a phosphine, Sulfonated cyclooctene, cyclononene, cyclodecene, cyclooctadiene, phosphine, phosphite, phosphinite, phosphonite, arsine, cyclononadiene, norbornene and dicyclopentadiene; each of Stibine, ether, amine, amide, Sulfoxide, carboxyl, nitroSyl, which may be functionalized or unfunctionalized. In a more pyridine, or thioether. More specifically, the gel modification preferred embodiment, the cyclic olefin is dicyclopentadi additive may be a trialkylphosphine or triarylphosphine. CC. Preferred gel modification additives include P(cyclohexyl), The invention also includes a proceSS for molding poly P(cyclopentyl), P(isopropyl), P(phenyl), and pyridine. mer articles in which a mixture comprising a functionalized In a preferred embodiment of the invention, the compo or unfunctionalized cyclic olefin and a composition accord Sition includes a catalyst of the formula ing to the present invention is provided in a mold. The mixture may either be prepared in the mold or prepared outside of the mold and then introduced into the mold. The mixture is then left to at least partially polymerize to form a polymer article and the polymer article is removed from the mold. Alternatively, the mixture may be coated onto an article and left to at least partially polymerize to form a 15 coating. The mixture may be made by preparing a mixture of monomer and gel modification additive and adding the catalyst. The process may also include heating the mold and heating the mixture. The process may also include adding a crosslinking initiator to the mixture. If the cyclic olefin is functionalized, it may contain one or more functional groups including of hydroxyl, thiol, ketone, aldehyde, ester, ether, amine, amide, nitro acid, carboxylic acid, disulfide, carbonate, carboalkoxy acid, isocyanate, carbodiimide, where Cy is cyclohexyl or cyclopentyl, and a gel modifica carboalkoxy, and halogen. In a preferred embodiment, the tion additive having the formula P(Phenyl). cyclic olefin is cyclobutene, cycloheptene, cyclooctene, In another embodiment of the invention the composition cyclononene, cyclodecene, cyclooctadiene, cyclononadiene, includes a catalyst of the formula norbornene and dicyclopentadiene; each of which may be functionalized or unfunctionalized. In a more preferred C PPh3 H / embodiment, the cyclic olefin is dicyclopentadiene. Ru Ph The invention also includes a method for controlling the rate of an olefin metathesis reaction that is catalyzed by a Cl PPh. y =\= metathesis catalyst having an open coordination site. This H Ph method includes the Step of contacting an active catalyst O having an open coordination Site with an olefin in the 35 presence of a means for coordinating the catalyst open C. PPh3 H / coordination site. The means may be an electron donor or RC Lewis base. Cl/ PPh3 Ph DETAILED DESCRIPTION 40 We have found that it is possible to control the rate of and a gel modification additive of the formula olefin metathesis reactions that are catalyzed by certain P(cyclohexyl)- or P(cyclopentyl). Ruthenium and OSmium carbene complex catalysts. More The invention also includes a method for olefin metathesis generally, we have found that it is possible to control the rate which includes the Step of contacting an olefin with a of polymerization in those reactions in which the polymer composition according to the present invention. The olefin 45 ization mechanism involves an open coordination Site at a may be unfunctionalized or functionalized to contain one or catalyst metal center. more functional groups Selected from the group consisting The Ruthenium and OSmium carbene complex catalysts of hydroxyl, thiol, ketone, aldehyde, ester, ether, amine, that may be used in the present invention and methods of amide, nitro acid, carboxylic acid, disulfide, carbonate, Synthesizing these catalysts are taught in this Specification carboalkoxy acid, isocyanate, carbodiimide, carboalkoxy, 50 and the following references, all of which are incorporated and halogen. The olefin may be a Strained cyclic olefin, herein by reference: U.S. Pat. Nos. 5,312,940 and 5,342,909; unstrained cyclic olefin, acyclic olefin, diene, or unsaturated U.S. patent application Ser. Nos. 08/282,827 (filed Jul. 29, polymer; each of which may be functionalized or unfunc 1994), 08/282,826 (filed Jul. 29, 1994), and 08/693,789 tionalized. (filed Jul. 31, 1996); and U.S. provisional patent application The invention also includes a process for the ring opening 55 titled “Synthesis of Ruthenium Metathesis Catalysts from metathesis polymerization of functionalized or unfunction Ruthenium Hydride complexes”, filed Nov. 15, 1996, inven alized cyclic olefins. This process includes contacting a tors Robert H. Grubbs, Tomas Belderrain, and Seth Brown, functionalized or unfunctionalized cyclic olefin with a com Attorney Docket No. CTCH-8600. In the compounds position according to the present invention. The cyclic according to the general formulae Set forth in these patents olefins may be Strained or unstrained and may be 60 and applications: monocyclic, bicyclic, or multicyclic olefins. If the cyclic alkenyl can include 1-propenyl, 2-propenyl, 3-propenyl olefin is functionalized, it may contain one or more func and the different butenyl, pentenyl and hexenyl tional groups including of hydroxyl, thiol, ketone, aldehyde, isomers, 1,3-hexadienyl and 2,4,6-heptatrienyl, and ester, ether, amine, amide, nitro acid, carboxylic acid, cycloalkenyl; disulfide, carbonate, carboalkoxy acid, isocyanate, 65 alkenyloxy can include HC=CHCHO, (CH) carbodiimide, carboalkoxy, and halogen. In a preferred C=CHCHO, (CH) CH=CHCHO, (CH) CH=C embodiment, the cyclic olefin is cyclobutene, cycloheptene, (CH) CHO and CH=CHCHCHO; 5,939.504 S 6 alkoxide can include methoxide, t-butoxide, and phenox Sulfonate can include trifluoromethaneSulfonate, tosylate, ide; and meSylate; alkoxy can include methoxy, ethoxy, n-propyloxy, isopro sulfoxide can include CHS(=O)CH, (CH3)SO; and pyloxy and the different butoxy, pentoxy and hexyloxy thioether can include CH-SCH, CHS CH, isomers, cycloalkoxy can include cyclopentyloxy and CHOCHCH-SCH, and tetrahydrothiophene. cyclohexyloxy; A neutral electron donor is any ligand which, when alkoxyalkyl can include CHOCH, CHOCH2CH, removed from a metal center in its closed shell electron CHCHO CH, CHCHCHCHOCH and configuration, has a neutral charge, i.e., is a Lewis base. CHCHOCHCH; and An anionic ligand is any ligand which when removed alkoxycarbonyl can include CHOC(=O); CHCHOC 1O from a metal center in its closed shell electron con (=O), CHCHCHOC(=O), (CH)-CHOC(=O) figuration has a negative charge. An important feature and the different butoxy-, pentoxy- or hexyloxycarbo of the carbene compounds of this invention is the presence of the ruthenium or osmium in the formal +2 nyl isomers, Oxidation State (the carbene fragment is considered to alkyl can include primary, Secondary and cycloalkyl iso 15 be neutral), an electron count of 16 and pentacoordi merS, nation. A wide variety of ligand moieties X, X', L, and alkylsulfinyl can include CHSO, CHCHSO, L' can be present and the carbene compound will still CHCHCHSO, (CH)-CHSO and the different exhibit its catalytic activity. butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers; In one embodiment of the invention, olefin metathesis alkylsulfonyl can include CHSO, CHCHSO, reactions are catalyzed and the rate of reaction is controlled CHCHCHSO, (CH)-CHSO and the different by a composition that includes a Ruthenium or OSmium butylsulfonyl, pentylsulfonyl and hexylsulfonyl iso carbene complex catalyst as described above and a gel merS, modification additive. We have chosen to name this second alkylthio can include, methylthio, ethylthio, and the Sev component a “Gel Modification Additive” because in certain eral propylthio, butylthio, pentylthio and hexylthio 25 reactions this component modifies the time in which the isomers, catalyst/monomer mixture gels, i.e. the time in which the alkynyl can include ethynyl, 1-propynyl, 3-propynyl and mixture partially polymerizes. Generally however, by “Gel the Several butynyl, pentynyl and heXynyl isomers, Modification Additive” we mean any substance that coop 2,7-octadiynyl and 2.5,8-decatriynyl, erates with the catalyst to change the rate of the catalyzed reaction. Most generally, we have found that the gel modi alkynyloxy can include HC=CCHO, CHC=CCHO fication additive may be any electron donor or Lewis base. and CHC=CCHOCHO; The Ruthenium or OSmium carbene complex catalyst and amide can include HC(=O)N(CH) and (CH) C(=O) gel modification additive composition may be used to cata N (CH), lyze and control the rate of reaction in a variety of olefin amine can include tricyclohexylamine, triisopropylamine 35 metathesis reactions. Examples of olefin metathesis reac and trineopentylamine; tions that may be catalyzed include Ring Opening Metathe arSine can include triphenylarSine, tricyclohexylarSine sis Polymerization of Strained and unstrained cyclic olefins, and triisopropylarSine, aryl can include phenyl, p-tolyl Ring Closing Metathesis, croSS- and Self-metathesis of acy and p-fluorophenyl, clic olefins, telechelic polymerization, and depolymerization 40 of unsaturated polymers. These metathesis reactions are carboxylate can include CH-CO2CHCH2CO, described in the following U.S. patent applications, all of CHSCO, (CH) CHCO; which are incorporated herein by reference: application Ser. cycloalkenyl can include cyclopentenyl and cyclohex Nos. 08/550,679 (filed Oct. 31, 1995); 08/548,915 (filed Oct. enyl. cycloalkyl can include cyclopropyl, cyclobutyl, 26, 1995); 08/548.445 (filed Oct. 26, 1995); 08/550,300 cyclopentyl, and cyclohexyl, 45 (filed Oct. 30, 1995), and 08/705,064 (filed Aug. 29, 1996). diketonates can include acetylacetonate and 2,4- The Ruthenium and OSmium carbene complex catalysts hexanedionate; of the present invention are stable in the presence of a ether can include (CH) CCHOCH2CH, THF, variety of functional groups including hydroxyl, thiol, (CH) COC (CH), CHOCH2CHOCH, and ketone, aldehyde, ester, ether, amine, amide, nitro acid, CHOCHs; 50 carboxylic acid, disulfide, carbonate, carboalkoxy acid, “halogen' or “halide', either alone or in compound words isocyanate, carbodiimide, carboalkoxy, and halogen. Since Such as "haloalkyl, denotes fluorine, chlorine, bromine the catalysts are stable in the presence of these groups, the or iodine, olefin Substrate, the gel modification additive, and any phosphine can include triphenylphosphine, Substituent groups on the catalyst may include one or more tricyclohexylphosphine, triisopropylphosphine, trine 55 of the above listed groups without deactivating the catalysts. opentylphosphine and methyldiphenylphosphine; Preferred catalysts used in the polymerization reactions phosphinite can include triphenylphosphinite, described here are of the general Structure: tricyclohexylphosphinite, triisopropylphosphinite, and methyldiphenylphosphinite, phosphite can include triphenylphosphite, 60 tricyclohexylphosphite, tri-t-butylphosphite, triisopro pylphosphite and methyldiphenylphosphite, Secondary alkyl includes ligands of the general formula -CHRR' where R and R' are carbon moieties; 65 where M is Ru; R' is hydrogen; R is substituted or unsub Stibine can include triphenylstibine, tricyclohexylstibine stituted aryl or substituted or unsubstituted vinyl; X and X" and trimethylstibine; are Cl; and Land L'are triphenylphosphines or tricycloalky 5,939.504 7 8 lphosphines Such as tricyclopentylphosphine and tricyclo triphenylphosphine is used, the pot life can be decreased hexylphosphine. The Substituted aryl and substituted vinyl (i.e., the reaction rate increased) by adding a gel modifica may each be Substituted with one or more groups including tion additive Such as tricyclohexylphosphine or tricyclopen C-C alkyl, halide, C-C alkoxy, and a phenyl group tylphosphine (see Table 3, samples 29–31). In this case, we which may be optionally substituted with one or more hypothesize that the tricycloalkylphosphine gel modification halide, C-C alkyl, or C-C alkoxy groups. The Substi additive exchanges with the triphenylphosphine L and L' tuted aryl and substituted vinyl may also be substituted with ligands leading to a more active catalyst. Generally, a gel one or more functional groups including hydroxyl, thiol, modification additive increases the rate of reaction if the ketone, aldehyde, ester, ether, amine, amide, nitro acid, catalyst becomes more active when its L and L' ligands are carboxylic acid, disulfide, carbonate, carboalkoxy acid, eXchanged with the gel modification additive. However in isocyanate, carbodiimide, carboalkoxy, and halogen. The this case, as the concentration of gel modification additive is preferred gel modification additives are neutral electron increased, the additive will compete with the monomer for donorS Such as phosphines. Aparticularly preferred embodi coordination sites on the metal center and the additive may ment of the present invention includes the ruthenium cata lyst where L and L' are both tricyclopentylphosphine and eventually act to decrease the rate of reaction. 15 For the change in ligand and ligand structure to affect the the gel modification additive is triphenylphosphine (PPh). overall rate of reaction and the time between mixing and gel GEL MODIFICATION ADDITIVE point, there must be Sufficient time for the ligands and gel The rate of metathesis reaction may be controlled by modification additive to totally equilibrate between being varying the amount of gel modification additive (see Table bound by the catalyst and being in Solution in the monomer. 2) and the gel modification additive itself (see Table 3). As In Some cases, to obtain the maximum effect of a gel is conventional, the metathesis reaction rate may also be modification additive, it may be necessary to allow the gel controlled by varying the reaction temperature. Gel modi modification additive and the catalyst complex to equilibrate fication additives that may be used in the present invention in a non reactive solvent before the monomer is added. This include phosphines, Sulfonated phosphines, phosphites, is particularly important where exchange of the ligands and phosphinites, phosphonites, arsines, Stibines, ethers, amines, 25 gel modification additive appears to be slow relative to the amides, Sulfoxides, carboxyls, nitroSyls, pyridines, onset of polymerization Such as cases where a very bulky gel thioethers, nitriles, thiophenes, and furans. Specific gel modification additive Such as tricyclohexylphosphine is modification additives include tricyclopentylphosphine, being exchanged on to the catalyst complex. For an example tricyclohexylphosphine, triphenylphosphite, pyridine, of this, see the results for samples 30 and 33 in Table 3 propylamine, tributylphosphine, ben Zonitrile, below. triphenylarSine, anhydrous acetonitrile, thiophene, and Since the gel modification additive is assumed to modify furan. Preferred gel modification additives include the coordination environment of the catalyst, we hypoth tricyclopentylphosphine, tricyclohexylphosphine, eSize that any Substance capable of coordinating with the triisopropylphosphine, triphenylphosphine, and pyridine. catalyst metal center will modify the rate of catalyzed Without being bound by theory, we hypothesize that the 35 reaction. This holds true not only for the specific Ruthenium gel modification additive operates by modifying the coor and OSmium catalysts discussed above but also for any dination environment of the catalyst. The gel modification catalysts that initiate reaction through an open coordination additives of the present invention may be used to either Site at a metal center. In the present invention, the gel enhance or reduce the rate of polymerization. The Specific modification additive may therefore be any Species that is action of the gel modification additive will depend on both 40 capable of coordinating with an open coordination site at a the additive used and the catalyst. The magnitude of the catalyst metal center. Examples of gel modification additives reduction or enhancement of the reaction will also depend that may be used include electron donors, Lewis bases, and on the concentration of the gel modification additive. Below nucleophiles. we describe how to Select a gel modification additive to If it is desired to Speed up the reaction after the gel achieve a specific desired action. 45 modification additive has been used, one may increase the Triphenylphosphine is an example of a gel modification reaction and/or mold temperature. By adjusting the amount additive that acts to retard the rate of reaction when the of gel modification additive and the temperature, the pot life catalyst has tricycloalkylphosphine Land L' ligands. In this can be varied to the desired time. The amount of the additive case, the catalyst where L and L' are tricycloalkylphos required to achieve the desired pot life may depend on the phines is much more active in ROMP than the catalyst where 50 coordinating ability of the gel modification additive used L and L are triphenylphosphines. When L and L are and the resulting catalyst activity of the Substituted catalyst. tricycloalkylphosphines and the gel modification additive is AS is shown in Table 3, Some Lewis basic gel modification triphenylphosphine, we therefore hypothesize that the added additives Such as phosphites and propylamine completely triphenylphosphine Substitutes for the tricycloalkylphos inhibit the catalyst while Some gel modification additives phine in the coordination sphere of the ruthenium and 55 Such as triphenylarSine, nitrites, ethers and thiols have little decreases the activity of the catalyst. Generally, a gel modi effect on polymerization rate at the low levels explored. In fication additive decreases the rate of reaction if the catalyst addition to the phosphines examined, pyridine was unex becomes less active when its Land L' ligands are exchanged pectedly effective in controlling pot life. with the gel modification additive. Since monomer coordi To help determine the dependence of the reaction rate on nation is required for polymerization, the gel modification 60 the amount of gel modification additive, we can turn to Some additive can also slow the polymerization reaction by com recent Studies on the mechanistic pathways by which the Ru peting with the monomer for coordination Sites on the metal and OS carbene catalysts operate. A Scientific article titled center. Hence, increasing the concentration of the gel modi “Well-defined Ruthenium Olefin Metathesis Catalysts: fication additive will decrease the rate of polymerization Mechanism and Activity” by Eric L. Dias, Son Binh T. reaction (See Table 3, samples 13-17). 65 Nguyen, and Robert H. Grubbs, summarizes the results of Conversely, if the pot life (reaction time) is too long, as these Studies and has recently been accepted for publication may be the case if a catalyst in which L and L' are in the Journal of the American Chemical Society. This article 5,939.504 10 is incorporated herein by reference. Among other things, catalyst and gel modification additive dissolved in the these Studies investigated the effect of adding phosphines on monomer). In this regard, we have Surprisingly also found the rate of a Ring Closing Metathesis (“RCM”) reaction that adding the gel modification additive and lowering the catalyzed by ruthenium catalysts of the type used in the temperature will allow the catalytic activity of the catalyst to present invention. The mechanistic pathways for other met be inhibited for extended periods of time (days or longer) athesis reactions such as ROMP are not expected be much and that the catalyst can then be “reactivated” by heating. different than those for the RCM reactions. In these studies, Further, the addition of the gel modification additives the added phosphine was the same as the L and L' ligands according to the present invention have an unexpected on the catalyst and therefore, by the arguments presented desirable effect on the properties of the resulting polymers. above, the added phosphine can only act to reduce the For example, when triphenylphosphine was used as the gel reaction rate by competing with the monomer for the open modification additive, the heat distortion temperature (HDT) coordination site. These studies did in fact find that the of the resulting DCPD part was significantly higher and the added phosphine reduced the reaction rate, they further Surface appearance of the resulting part was improved when determined that the reaction rate was the Sum of a term compared to parts produced in the absence of a gel modi independent of the concentration of the added phosphine and 15 fication additive. We therefore deduce that a polyIDCPD a term inversely proportional to the concentration of the material that includes the gel modification additive of the added phosphine. Since we expect the mechanism for met present invention can have Superior material properties athesis reactions in general (and ROMP in particular) to be compared to the material produced without any gel modi similar to that for RCM, the dependence of metathesis fication additive present. reaction rate on concentration of gel modification additive is EXPERIMENTAL expected to be Similar to that found in the above Study, at Synthesis of Ruthenium Complex Catalyst ClaRu(PCy) least in the case where the gel modification additive retards (=CHCH=CPh). the reaction. Therefore an estimate of the dependence of the A Ruthenium complex catalyst of the present invention ROMP rate of reaction on the gel modification additive may be prepared in a one Step synthesis as illustrated in the concentration could be achieved by performing just two 25 reaction Sequence below. Separate reactions at different additive concentrations. In practice one may wish to run additional reactions at different additive concentrations to determine the best fit for the reaction rate. Ph Ph > CHRuO ROMP OF DICYCLOPENTADIENE 0.5 CV y +2 PCys - or - ROMP reactions have been used in the formation of high polymers by the ring-opening of cyclic olefins. The reaction Ru-CI has been used effectively for Reaction Injection Molding of thermosets. For these Systems, techniques have been devel 35 oped for controlling the gel time of the polymer by control ling the rate of catalyst formation after the catalyst compo nents are mixed. In the present invention, the ROMP catalysts are the ruthenium or oSmium carbene complex Ph catalysts described above. In contrast to catalysts used in 40 CPCy3 earlier RIM and Resin Transfer Molding (“RTM”) processes, these catalysts may be added to the monomer in (" Ph the molding proceSS in their “active' form. Also in contrast C PCys to the earlier RIM processes, the polymerization rate of the 45 active catalyst can be controlled by adding a gel modifica In a typical reaction, (Cymene)RuCl dimer complex tion additive according to the present invention. (0.53 g, 1.73 mmol Ru) and PCya (0.91 g, 2 equiv) were ROMP of dicyclopentadiene (“DCPD") is catalyzed by loaded under inert atmosphere into a 100 mL Schlenk flask the above described catalysts. Cross-linking of the resulting equipped with a magnetic Stirbar. Benzene (40 mL) was then poly DCPD has been explored commercially. See for 50 added followed by 3,3-diphenylcyclopropene (0.33 g, 1 example U.S. patent application Ser. No. 08/678,397 (filed equiv). The reaction flask was then attached to a reflux Jul. 2, 1996) now allowed which is incorporated herein by condenser under an inert atmosphere and heated in an reference. oilbath at 83-85 C. for 6 hours. The solvent was then In one aspect of the invention, the pot life of the ROMP removed to complete dryneSS in vacuo and the remaining red of DCPD is controlled by the addition of a gel modification 55 solid washed with pentane (4x25 mL) under inert atmo additive to the reaction mixture. By adding the gel modifi Sphere. The remaining red powder was dried under Vacuum cation additive, the room temperature pot life of the poly for 12 h and Stored under an inert atmosphere yielding 1.4 merization mixture may be extended from about 1-9 min g of ClaRu(PCy)(=CHCH=CPh) in 88% yield. utes with no gel modification additive to greater than 2.5 hrs Purification and Degassing of DCPD Monomer or more with the gel modification additive present. 60 500 mL DCPD was filtered under vacuum into a one liter The present invention provides numerous advantages, round bottom flask through a 150 mL medium porosity most importantly, the ability to control the gel time or pot Sintered glass fritted funnel containing one inch of alumi life while still being able to completely polymerize the num oxide. Lower grades of DCPD with lower freezing monomer in a short period of time. The present invention points can be used after Similar purifying treatment. further provides the ability to completely stop the polymer 65 To the round bottom flask, containing purified DCPD as ization reaction through decreasing the temperature of a above, was added a 1-inch magnetic Stir bar. The flask was catalyst concentrate (i.e., a concentrated mixture of the placed in a water bath 30-35 C. and under 0.10 mm Hg 5,939.504 11 12 vacuum with stirring for from 20 minutes to 1 hour. The about 19 minutes at a temperature of about 69.5 C. The degassed DCPD was then stored under vacuum and pro mold was then allowed to cool to room temperature and the tected from light to prevent premature free radical polymer polymer removed from the mold and post cured at 190° C. ization. for 1 hour. We have found that due to the functional group tolerance The experimental procedure described above was carried of the catalysts of the present invention, we do not need to out for different concentrations of the gel modification purify and degass the DCPD monomer before carrying out additive and the results are Summarized in Table 1. the polymerization. DCPD Polymerization Without Gel Modification Additive TABLE 1. using P(CyPentyl))C1Ru(=CHCH=CPh) catalyst Peak To a 250 mL Erlenmeyer flask containing a 1-inch mag Monomer? Exotherm netic stir bar, DCPD, purified and degassed, as described Sample Catalyst PPhs (g) Catalyst (g) Pot Life time (min) above, (147.9 g, 150 mL, 1.12 mol, 5000 eq) and (P(CyPentyl))C1Ru(=CHCH=CPh) (188.5 mg, 0.224 1. SOOO:1 2O3 O74 >3 hr 20 min 19 2 SOOO:1 O79 O71 2 hr 14 min -6 mmol, 1 eq) were added. Stirring was initiated and option 15 ally a slow flow of argon was introduced into the flask. The 3 SOOO:1 .044 O71 49 min ~4/2 orange Solution was Stirred at room temperature for 8 "The pot life for samples 2 and 3 is the time at which the polymerization minutes under argon until it became highly viscous. The mixture is becoming viscous but can still be poured. Solution was then poured open to air into a crystallization dish (14.6 cm in diameter) that had been previously stored DEPENDENCE OF GEL TIME ON at 120° C. After 2 minutes, the Solution began to gel, and the CONCENTRATION OF GEL MODIFICATION production of Smoke was observed over the following 2 ADDITIVE: TABLE 2 minutes. At this point, the polymerization appeared complete, and the crystallization dish cooled to room tem Using Catalyst (P(CyHexyl)-ClaRuCHPh perature. The polymer Separated from the Sides of the 25 The following reactions were carried out using a catalyst crystallization dish easily. The polymer was post-cured at of the formula (P(CyHexyl)). ClaRuCHPh the results of 120° C. for 3 hours, resulting in poly(DCPD) (141.1 g, which are summarized in Table 2. The sample numbers 95.4% yield). relate to the entries in Table 2. DCPD Polymerization with Gel Modification Additive using Sample #4 P(CyPentyl))C1Ru(=CHCH=CPh) catalyst. Pour into a 250 ml flask with stir bar approximately 64.6 To a flask containing a stir bar, triphenylphosphine (95 g of Velsicol VHPDCPD that has been filtered and degassed mg), and DCPD, purified and degassed, as described above, with vacuum. (Note: filtering and degassing are optional). (63.991 g) were added. The flask was stirred under vacuum Add 0.054g of catalyst (P(CyHexyl)). ClRuCHPh and stir for about 5 minutes. (P(Cy Penty 1)). C1Ru for about 3 minutes. Pour into mold. Mold temperature was (=CHCH=CPh) (71 mg) was then added to the mixture 35 34.4° C. and the DCPD monomer temperature 31.5° C. Gel and a slow flow of argon was introduced into the flask. The time was <2 minutes & 45 Seconds with peak exotherm at 4 Solution was then Stirred at room temperature under argon. minutes & 11 seconds and a peak temperature of 133.8 C. After 59 minutes, the acetone test (See below) gave a “Flat Note: Gel time is defined as a) the time at which a stir bar Ball” result. The solution was then poured open to air into ceases turning in a 250-ml flask during mixing of the a mold that had been previously stored at 60.2 C. The peak 40 catalyst/monomer; or b) the time at which a glass pipet temperature of the reaction occurred about 10 minutes after lowered or pushed into a very high Viscosity poured pouring, with a peak temperature of about 158 C. Sample will no longer pick up or have “cling to the Acetone Test pipet any of the polymerizing Sample. The acetone test was a Subjective test used to measure the Sample #5 extent of the polymerization reaction. In this test, a few 45 Pour into a 250-ml flask with stir bar approximately 64.0 drops of the catalyzed DCPD were removed with a small g of Velsicol VHPDCPD that has been filtered and degassed pipet and dropped into a test tube of acetone. Visual inspec with vacuum. (Note: filtering and degassing are optional). tion yielded a qualitative measure of the extent of polymer Add 0.030 g of triphenylphosphine and mix for about 5 formation. The visual results were described as “Nothing” minutes. Add 0.054 g of catalyst (P(Cy Hexyl)) (no polymerization), “Cloud”, “Flat Ball” (some 50 ClaRuCHPh and stir for about 3 minutes. Pour into mold. polymerization), and “Ball.” Mold temperature was 35.0° C. and the DCPD monomer Dependence of pot life on concentration of Gel Modification temperature 31.5° C. Additive using P(CyPentyl))C1Ru(=CHCH=CPh.) Sample #6 catalyst: TABLE 1. Pour into a 250-ml flask with stir bar approximately 64.0 203 mg of triphenylphosphine was added to 4.052 g of 55 g of Velsicol VHPDCPD that has been filtered and degassed 95% DCPD in a test tube and the test tube shaken until the with vacuum. (Note: filtering and degassing are optional). triphenylphosphine was dissolved. 74 mg of (P(Cy Add 0.065 g of triphenylphosphine and mix for about 5 Pentyl))C1Ru(=CHCH=CPh) was then added, shaken minutes. Add 0.054g of catalyst (P(Cy Hexyl)) by hand and then mixed with a stir bar for about 1-2 ClRuCHPh and stir for about 3 minutes. Pour into mold. minutes. The mixture was then set aside. After 3 hours 20 60 Mold temperature was 37.8° C. and the DCPD monomer minutes, the mixture was still fluid, i.e. only partial poly temperature 33 C. merization had occurred. The pot life of this reaction mix Sample #7 ture is therefore greater than 3 hours 20 minutes. The Pour into a 250-ml flask with stir bar approximately 64.0 reaction mixture was added to 60.06 g of DCPD. The g of Velsicol VHPDCPD that has been filtered and degassed mixture was stirred slowly under Vacuum (this is optional) 65 with vacuum. (Note: filtering and degassing are optional). for a further 5 minutes and then poured into a mold that had Add 0.200 g of triphenylphosphine and mix for about 5 been preheated to 60.8 C. The peak exotherm occurred after minutes. Add 0.054 g of catalyst (P(Cy Hexyl)) 5,939.504 13 14 ClaRuCHPh and stir for about 3 minutes. Pour into mold. Using Catalyst P(CyHexyl))C1RuCHPh: Sample Mold temperature was 36.3° C. and the DCPD monomer is 13–28 temperature 31 C. Sample #8 In a 250-mL flask approximately 64.0 g of filtered and In a 25x150mm test tube, add approximately 8.132 g of 5 degassed Velsicol VHP DCPD was added. The gel modifi Velsicol VHP DCPD that has been filtered and degassed cation additive was added. After mixing until dissolved or 5 with vacuum. (Note: filtering and degassing are optional). minutes, the catalyst (P(CyHexyl)-). ClRuCHPh was Add 0.060 g of triphenylphosphine and mix until added. After mixing for about 3 minutes (or less if gelation dissolved-about 3-5 minutes. Add 0.054 g of catalyst had occurred) the mixture was poured into a mold. (P(CyHexyl)). ClRuCHPh and stir for about 3 minutes. Then put test tube into a dry ice/acetone bath for approxi Using Catalyst (PPh)C1Ru(=CHCH=CMe): mately 30 seconds to cool, and then put sample into a 35 F. Sample is 29–33 refrigeration and leave overnight. The following reactions were carried out using the The following day, weigh out about 56 g of Velsicol VHP (PPh)C1Ru(=CHCH=CMe) catalyst. that has been filtered and degassed with vacuum. (Note: 15 filtering and degassing are optional). Add the frozen Sample 29 Catalyst/TPP/DCPD concentrate pellet to the 56 g of DCPD Pour into a 250-ml flask with stir bar approximately 64.0 monomer and mix until dissolved-about 49 seconds. Resin g of Velsicol VHP DCPD that has been filtered and temperature is 35 C. Mix for 3 minutes longer and pour into degassed with vacuum. (Note: filtering and degassing a 33.8 C. mold. Resin temperature at pour=35.4 C. are optional). Add 0.020 g of tricyclohexylphosphine Sample #9 and mix for about 5 minutes. Add 0.049 g of catalyst In a 250-ml flask with stir bar add approximately 64.0 g (PPh)C1Ru(=CHCH=CMe) and mix for 3 min of Lyondell 10894.04% DCPD that has been filtered and utes. Pour into mold. Mold temperature was 39.2 C. degassed with vacuum. Add 0.055 g of Triphenylphosphine and the Resin temperature 33.6 C. and mix for about 5 minutes. Add 0.054 g of catalyst 25 Sample 30 (P(CyHexyl)). ClaRuCHPh and mix for about 3 minutes. Pour into a 250-ml flask with stir bar approximately 64.0 Pour into mold. Mold temperature is 38° C. and the DCPD g of Velsicol VHPDCPD that has been filtered and degassed monomer temperature 32 C. with vacuum. (Note: filtering and degassing are optional). Sample #10 Add 0.054 g of tricyclohexylphosphine and mix for about 5 In a 250-ml flask with stir bar add approximately 64.0 g minutes. Add 0.049 g of catalyst (PPh3)2C1Ru of Lyondell 10894.04% DCPD that has been filtered and (=CHCH=CMe) and mix for 3 minutes. Pour into mold. degassed with vacuum. Add 0.054g of catalyst (P(CyHexyl) Mold temperature was 37.5 C. and the resin temperature a), CIRuCHPh and mix for 3 minutes. Pour into mold. s32.O. C. Mold temperature is 38 C. and the DCPD monomer tem Sample #31 perature 32° C. 35 Pour into a 250-ml flask with stir bar approximately 64.0 Sample #11 g of Velsicol VHPDCPD that has been filtered and degassed Pour into a 250-ml flask with stir bar approximately 64.1 with vacuum. (Note: filtering and degassing are optional). g of Velsicol VHPDCPD that has been filtered and degassed Add 0.032 g of tricyclohexylphosphine and mix for about 5 with vacuum. (Note: filtering and degassing is optional). minutes. Add 0.049 g of catalyst (PPh)C1Ru Add 0.200 g of triphenylphosphine and mix for about 5 40 (=CHCH=CMe) and mix for 3 minutes. Pour into mold. minutes. Add 0.080 g of catalyst (P(Cy Hexyl)) Mold temperature was 39.3 C. and the resin temperature ClRuCHPh and stir for about 3 minutes. Pour into mold. 32.0° C. Mold temperature was 32 C. and the DCPD monomer temperature 33 C. Sample 32 Sample #12 45 Pour into a 250-ml flask with stir bar approximately 64.0 In a 25x150mm test tube, add approximately 6.0 g of g of Velsicol VHPDCPD that has been filtered and degassed Velsicol VHP DCPD that has been filtered and degassed with vacuum. (Note: filtering and degassing are optional). with vacuum. (Note: filtering and degassing are optional). Add 0.049 g of catalyst (PPh)C1Ru(=CHCH=CMe) Add 0.011 g of triphenylphosphine and mix until and mix for 3 minutes. Pour into mold. Mold temperature dissolved-about 3-5 minutes. Add 0.054 g of catalyst 50 was 40.6° C. and the Resin temperature 34.0° C. (P(CyHexyl)). ClRuCHPh and stir for about 3 minutes. Sample #33 Put 58 g of Velsicol VHP DCPD into a flask and mix in test In a 25x150 mm test tube, add 0.051 g of catalyst tube with Catalyst/Monomer/TPP mix for one minute. Pour (PPh)C1Ru(=CHCH=CMe) and 4-6 g of dichlo into mold. Mold temperature is 37.9° C. Resin temperature romethane. Add stir bar and mix for about 5 minutes or until about 31.8 C. 55 catalyst appears to dissolve. Then add 0.052 g tricyclohexy lphosphine and purge test tube with argon. Cap test tube and DEPENDENCE OF GEL TIME ON GEL mix at room temperature for 2 hours. After 2 hours, pull off MODIFICATION ADDITIVE: TABLE 3 dichloromethane with a vacuum and wash catalyst mixture The following experiments use a similar format to those with another dichloromethane wash. Now add approxi set forth in Table 2, but the gel modification additive was 60 mately 10.0 g of Velsicol VHP DCPD that has not been varied. The results of these experiments are Summarized in filtered or degassed, to the test tube and mix rapidly for Table 3. These experiments used two different catalysts: about 1 minute or until the catalyst mixture is dissolved in (P(Cy Hexyl)). C1Ru CHPh and (PPh). C1Ru the DCPD. Add the DCPD/catalyst mixture to a flask (=CHCH=CMe). Other than for the five specific experi containing 54.0 g of Velsicol VHP DCPD that has not been ments described below (Sample is 29–33), all results pre 65 filtered or degassed. Continue mixing for about 3 minutes sented in Table 3 are for the (P(CyHexyl)). ClaRuCHPh total mix time. Pour into mold. Mold temperature was 38.3 catalyst. The Sample numbers relate to the entries in table 3. C. and the resin temperature 32.0 C. 5,939.504 15 16

TABLE 2 Triphenylphosphine Level vs. Gel Time Peak Peak Part Sample Monomer? Weight Mold Resin Gel Time Exotherm Exotherm Cure 264 ps # Catalyst DCPD (g) PPhs (g) Catalyst (g) Temp. C. Temp. C. (min) Time (min) Temp. C. Schedule HDT C. 4 7SOO:1 64.6 O O54 34.4 31.5 2.75 4.18 133.8 al 59 5 7SOO:1 64.O O3O O54 35.O 31.5 11.OO 16.28 143.6 al 122.5 6 7SOO:1 64.O O65 O54 37.8 33.O 25.OO 27.00 42.O al 126.5 7 7SOO:1 64.O 2OO O54 36.3 31.0 >99.OO 53.OO 37.6 al 69 8 7SOO:1 64.O O60 O54 33.8 35.4 16.OO 17.OO 38.2 al 130 9 7SOO:1 64.O O55 O54 38.0 32.O >109.OO al 114 1O 7500:1 64 g O O54 38.0 32.O 7.OO 18.58 68.3 al 109 11 5000:1 64.1 g 2OO O8O 32.O 33.O >154.00 al 128 12 7SOO:1 64.O O11 O54 37.9 31.8 &4.OO 9.56 1611

Cure Schedule a: 1 hour and 15 minutes G 130 C.

TABLE 3

Gel Modification Additives vs. Giel Time

Ge: Weight of Weight of Modification Additive Mold Resin Gel Time Peak Exotherm Sample # Catalyst (g) DCPD (g) Additive Amount Temp C. Temp. C. (min) Time (min) Temp. C. 13 O54 64.O #1 .010 g 36.4 31.O 6.OO 7.33 1603 14 O54 64.O #1 .028 g 36.2 31.O 9.OO 10.83 173.2 15 O54 64.O #1 .073 g 36.3 31.O 21.00 38.30 91.5 16 O54 64.1 #2 .069 g 38.6 33.3 6.OO 7.20 1904 17 O54 64.O #2 .150 g 36.3 33.2 11.OO 13.75 1849 18 O54 64.O #3 .084 g 35.9 32.5 Ole Ole Ole 19 O54 64.O #4 .061 g 37.1 31.O 1O.OO 15.10 145.1 2O O54 64.O #5 .046 g 36.6 32.O Ole Ole Ole 21 O54 64.6 #6 .062 g 35.O 31.O Ole Ole Ole 22 O56 64.O #7 .066 g 33.1 32.O 1.50 too fast to measure 23 O54 64.O #7 .150 g 33.O 32.O s2.50 4.03 148.4 24 O54 64.3 #8 .062 g 34.O 32.O 1.50 too fast to measure 25 O54 64.O #8 .290 g s35.0 32.O 2.75 26 O54 64.O #9 150 ml 35.6 32.O 1.23 too fast to measure 27 O54 64.O #10 150 ml 33.9 32.O 188 too fast to measure 28 O54 64.O #11 150 ml 33.6 32.O 1.32 too fast to measure 29 O49 64.O #2 .020 g 39.2 33.6 9.OO 15.OO 44.2O 3O O49 64.O #2 .054g 37.5 32.O 12.OO 21.00 48.00 31 O49 64.O #1 .032 g 39.3 32.O >16.OO 14.OO 14.00 32 O49 64.O Ole Ole 40.6 34.O >6O.O 33 O51 64.O #2 .052 g 38.3 32.O 13.OO 20.75 111.7

Gel Modification Additives *#1 Tricyclopentylphosphine *#2 Tricyclohexylphosphine *#3 Triphenylphosphite *#4 Pyridine *#5 Propylamine *#6 Tributylphosphine *#7 Benzonitrile *#8 Triphenylarsine *#9 Anhydrous Acetonitrile *#10 Thiophene #11 Furan

55 The results for samples 4-7 (Table 2) demonstrate that The gel time, peak exotherm characteristics, and HDT test when using a (P(CyHexyl)-). ClRuCHPh catalyst, increas results are very similar for samples 8 and 6 (Table 2). Since ing the concentration of the gel modification additive PPh these Samples were prepared by Similar methods except that increases the gel time (i.e., decreases the reaction rate). This in Sample 8 a catalyst/gel modification additive/monomer is as expected: the catalyst used in Samples 4-7 includes 6 O concentrate was prepared and frozen overnight, this dem trihexylphosphine L and L' ligands and since exchanging onstrates that the catalyst may be inhibited for long periods these ligands for PPh yields a less active catalyst, the added of time and then be “reactivated” by heating. PPh may only act to retard the reaction. These results also The results for samples 13-15 (Table 3) demonstrate that show that polymer articles molded with DCPD containing a when using a (P(CyHexyl)-). ClRuCHPh catalyst, increas gel modification additive possess Superior heat deflection 6 ing the concentration of the gel modification additive temperature properties as compared with an article molded P(cyclopentyl) increases the gel time (i.e., decreases the with DCPD that does not contain a gel modification additive. reaction rate). This demonstrates that the gel modification 5,939.504 17 18 additive may decrease the reaction rate by competing with 5. A composition according to claim 2, wherein the the monomer for the open coordination Site. Substituent group is Substituted with one or more functional The results for samples 16 and 17 (Table 3) further groupS Selected from the group consisting of hydroxyl, thiol, demonstrate that increasing the concentration of the gel ketone, aldehyde, ester, ether, amine, imine, amide, nitro, modification additive increases the gel time (i.e., decreases 5 the reaction rate). In this case, the gel modification additive carboxylic acid, disulfide, carbonate, isocyanate, is the same as the L and L' ligands (both carbodiimide, carboalkoxy, and halogen. tricyclohexylphosphine). Since the gel modification additive 6. A composition according to claim 2, wherein R and R' and the L and L' ligands are the same, ligand exchange are independently Selected from the group consisting of cannot effect the rate of reaction and we expect the additive hydrogen, Substituted aryl, unsubstituted aryl, Substituted to retard the reaction by competing with the monomer for the Vinyl, and unsubstituted vinyl; and open coordination Site. Finally, the results for samples 29-33 (Table 3) demon wherein the substituted aryland substituted vinyl are each strate that when using a (PPh)C1Ru(=CHCH=CMe) Substituted with one or more groups Selected from the catalyst, adding either P(cyclopentyl) or P(cyclohexyl) as group consisting of hydroxyl, thiol, ketone, aldehyde, a gel modification additive decreases the gel time (i.e., 15 ester, ether, amine, imine, amide, nitro, carboxylic acid, increases the reaction rate) compared to the gel time for the disulfide, carbonate, isocyanate, carbodiimide, reaction with no additive (sample 32). This result is as carboalkoxy, halogen, C-C alkyl, C-C alkoxy, expected since the catalyst with P(cyclopentyl) or P(cyclopentyl)s L and L' ligands is more active than that unsubstituted phenyl, and phenyl Substituted with a with PPha ligands. halide, C-C alkyl or C-C alkoxy. What is claimed is: 7. A composition according to claim 2, wherein Land L' 1. A composition, comprising: are independently Selected from the group consisting of (a) a Ruthenium or OSmium carbene complex catalyst that phosphine, Sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, Stibine, ether, amine, amide, Sulfoxide, includes a Ruthenium or OSmium metal center that is in 25 a +2 oxidation State, has an electron count of 16, and is carboxyl, nitroSyl, pyridine, and thioether. pentacoordinated; 8. A composition according to claim 7, wherein L and L' (b) an olefin which may be functionalized or unfunction are phosphines independently selected from PRR'R' alized; and wherein R is selected from the group consisting of second (c) an electron donor or Lewis base in a concentration ary alkyl and cycloalkyl and wherein R' and R are inde Sufficient to change the rate of an olefin metathesis pendently Selected from the group consisting of aryl, C-Co catalyzed by Said carbene complex catalyst in the primary alkyl, Secondary alkyl, and cycloalkyl. absence of Said electron donor or Lewis base. 9. A composition according to claim 8, wherein Land L' 2. A composition according to claim 1, wherein the are independently Selected from the group consisting of Ruthenium or OSmium carbene complex catalyst has the 35 -P(cyclohexyl)-, -P(cyclopentyl), and -P(isopropyl). formula 10. A composition according to claim 7, wherein Land L' are both-P(phenyl). 11. A composition according to claim 7, wherein Land L' are the Same. 40 12. A composition according to claim 2, wherein X and X' are independently Selected from the group consisting of halogen, hydrogen; C1-Co alkyl, aryl, C-Co alkoxide, where: aryloxide, C-C alkyldiketonate, aryldiketonate, C-Co M is Selected from the group consisting of OS and Ru; 45 carboxylate, aryl or C-C alkylsulfonate, C-Co R and R' are independently selected from the group alkylthio, C-C alkylsulfonyl, or C-Co alkylsulfinyl, consisting of hydrogen and a Substituent group Selected each optionally Substituted with C-C alkyl, halogen, from the group consisting of vinyl, C-C alkenyl, C-C alkoxy or with a phenyl group optionally Substituted C-Co alkynyl, C-Co alkyl, aryl, C-Co with halogen, C-C alkyl or C-C alkoxy. carboxylate, C-Co alkoxy, C-Co alkenyloxy, 50 13. A composition according to claim 12, wherein X and C-C alkynyloxy, aryloxy, C-C alkoxycarbonyl, X' are independently selected from Cl, Br, I, H; benzoate, C-C alkylthio, C-C alkylsulfonyl and C-Co C-C carboxylate, C-C alkyl, phenoxy, C-C alkoxy, alkylsulfinyl, wherein each of Said Substituents is Sub C-C alkylthio, aryl, or C-C alkyl Sulfonate; each option Stituted or unsubstituted; ally Substituted with C-C alkyl, halogen or a phenyl group X and X’ are independently selected from any anionic 55 ligand; and optionally Substituted with halogen, C1-C5 alkyl or C-Cs L and L' are independently selected from any neutral alkoxy. electron donor. 14. A composition according to claim 13, wherein X and 3. A composition according to claim 2, wherein the X' are independently selected from the group consisting of Substituent group is Substituted with one or more groups 60 Cl, CFCO, CHCO, CFHCO, (CH) CO, (CF)(CH) Selected from the group consisting of C-C alkyl, halide, CO, (CF)(CH3)2CO, PhO, MeO, EtO, tosylate, mesylate, C-C alkoxy, and phenyl, wherein Said phenyl is Substi and trifluoromethaneSulfonate. tuted or unsubstituted. 15. A composition according to claim 14, wherein X and 4. A composition according to claim3, wherein the phenyl X' are both Cl. group is Substituted with one or more groups Selected from 65 16. A composition according to claim 1, wherein the the group consisting of halide, C-C alkyl, and C-C, Ruthenium or OSmium carbene complex catalyst has the alkoxy. formula 5,939.504 19 20 -continued X R1 \ Y=/ RucC / X'( 1 \R C PPh3 Ph where: 23. A composition according to claim 1, wherein compo nent (c) is a neutral electron donor or neutral Lewis base. M is Ru; 24. A composition according to claim 1, wherein compo R" is hydrogen; nent (c) is selected from the group consisting of phosphines, R is substituted aryl, unsubstituted aryl, Substituted vinyl, Sulfonated phosphines, phosphites, phosphinites, or unsubstituted vinyl; phosphonites, arsines, Stibines, ethers, amines, amides, X and X’ are Cl; and Sulfoxides, carboxyls, nitroSyls, pyridines, thioethers, L and L are triphenylphosphines or tricycloalkylphos 15 nitriles, thiophenes, and furans. phines. 25. A composition according to claim 24, wherein com 17. A composition according to claim 16, wherein the ponent (c) is a trialkyl or triaryl phosphine. Substituted aryl is Substituted with one or more groups 26. A composition according to claim 1, wherein compo Selected from the group consisting of C-C alkyl, halide, nent (c) is selected from the group consisting of C-C alkoxy, unsubstituted phenyl, and phenyl Substituted P(cyclohexyl), P(cyclopentyl), P(isopropyl), and pyri with a halide, C-C alkyl or C-C alkoxy. dine. 18. A composition according to claim 16, wherein the 27. A composition according to claim 1, wherein compo Substituted Vinyl is Substituted with one or more groups nent (c) is P(phenyl). Selected from the group consisting of C-C alkyl, halide, 28. A composition according to claim 1, wherein compo C-C alkoxy, unsubstituted phenyl, and phenyl Substituted 25 nent (c) is selected from the group consisting of with a halide, C-C alkyl or C-C alkoxy. tricyclope ntylphosphine, tricyclohexylphosphine, 19. A composition according to claim 16, wherein the triphenylphosphite, pyridine, propylamine, substituted aryl is substituted with one or more functional tributylphosphine, benzonitrile, triphenylarSine, anhydrous groupS Selected from the group consisting of hydroxyl, thiol, acetonitrile, thiophene, and furan. ketone, aldehyde, ester, ether, amine, imine, amide, nitro, 29. A composition according to claim 1, wherein compo carboxylic acid, disulfide, carbonate, isocyanate, nent (c) contains one or more functional groups selected carbodiimide, carboalkoxy, and halogen. from the group consisting of hydroxyl, thiol, ketone, 20. A composition according to claim 16, wherein the aldehyde, ester, ether, amine, amide, nitro acid, carboxylic substituted vinyl is substituted with one or more functional acid, disulfide, carbonate, carboalkoxy acid, isocyanate, groupS Selected from the group consisting of hydroxyl, thiol, 35 carbodiimide, carboalkoxy, and halogen. ketone, aldehyde, ester, ether, amine, imine, amide, nitro, 30. A Composition, comprising: carboxylic acid, disulfide, carbonate, isocyanate, (a) a compound Selected from the group consisting of carbodiimide, carboalkoxy, and halogen. 21. A composition according to claim 1, wherein the catalyst is Selected from the group consisting of Ph 40 H Ph Cl fy o Ru Ph /

Ph and C PCy3 H \ / Ru 50 / and

wherein Cy is cyclohexyl or cyclopentyl and 55 wherein Cy is cyclohexyl or cyclopentyl. (b) triphenylphosphine or pyridine. 22. A composition according to claim 1, wherein the 31. A composition, comprising: catalyst is Selected from the group consisting of (a) a compound Selected form the group consisting of

60 C. PPh3 H / o Ph \ / Ph c/ C / C Y PPh PPh 3 / \ H = Ph H Ph 65 and 5,939.504 21 22 -continued 42. A method according to claim 38, wherein the com position comprises: \ Ru (a) a compound Selected from the group consisting of / C PPh3 Ph C PPh3 H and /RucC M / Ph (b) tricyclohexylphosphine or tricyclopentylphosphine. Cl PPh3 y=SN 32. A composition according to claim 1, further compris H Ph ing an olefin monomer having a ring of at least four and members, wherein members of Said ring are bonded with a double bond of said olefin. 33. A composition according to claim 2, wherein Said RuC olefin monomer is Selected from the group consisting of 15 Strained cyclic olefins, unstrained cyclic olefins, acyclic C PPh Ph olefins, dienes and unsaturated polymers, each of which may and be functionalized or unfunctionalized. 34. A composition according to claim 33, wherein Said functionalized olefin monomer contains a functional group (b) P(cyclohexyl)- or P(cyclopentyl). Selected from the group consisting of alcohol, thiol, ketone, aldehyde, ester, ether, amine, amide, nitro acid, imine, 43. A proceSS for the ring opening metathesis polymer carboxylic acid, disulfide, carbonate, isocyanate, ization of functionalized or unfunctionalized cyclic olefins, carbodiimide, carboalkoxy and halogen. the proceSS comprising the Step of contacting a functional 35. A composition according to claim 34, wherein Said 25 ized or untunctionalized cyclic olefins with the composition functional group is a Substituent on Said olefin. of (a) and (c) as recited in claim 1. 36. A composition according to claim 34, wherein Said 44. A process according to claim 43, wherein the cyclic functional group is part of a carbon chain of Said olefin. 37. A composition according to claim 32, wherein Said olefin is a functionalized cyclic olefin that contains one or olefin monomer is a member Selected from the group more functional groupS. Selected from the group consisting consisting of cyclobutene, cycloheptene, cyclooctene, of hydroxyl, thiol, ketone, aldehyde, ester, ether, amine, cyclononene, cyclodecene, cyclooctadiene, cyclononadiene, amide, nitro acid, carboxylic acid, disulfide, carbonate, norbornene and dicyclopentadiene. carboalkoxy acid, isocyanate, carbodiimide, carboalkoxy, and halogen. 38. A method for olefin metathesis, the method compris 35 ing contacting a functionalized or unfunctionalized olefin 45. A process according to claim 43, wherein the cyclic with the composition of (a) and (c) as recited in claim 1. olefin is Selected from the group consisting of cyclobutene, 39. A method according to claim 38, wherein the olefin is cycloheptene, cyclooctene, cyclononene, cyclodecene, functionalized and contains one or more functional groups Selected from the group consisting of hydroxyl, thiol, cyclooctadiene, cyclononadiene, norborne ne and ketone, aldehyde, ester, ether, amine, amide, nitro acid, 40 dicyclopentadiene, each of which may be functionalized or carboxylic acid, disulfide, carbonate, carboalkoxy acid, unfunctionalized. isocyanate, carbodiimide, carboalkoxy, and halogen. 46. A process according to claim 43, wherein the cyclic 40. A method according to claim 38, wherein the olefin is olefin is dicyclopentadiene. Selected from the group consisting of Strained cyclic olefins, 45 47. A proceSS according to claim 43, wherein the com unstrained cyclic olefins, acyclic olefins, dienes, and unsat position comprises: urated polymers, each of which may be functionalized or unfunctionalized. (a) a compound Selected from the group consisting of 41. A method according to claim 38, wherein the com position comprises: 50 H Ph (a) a compound Selected from the group consisting of C PCy3 o \lRu Ph / Cl fy o 55 and Ph C PCy3 Ph \lRu / 60

wherein Cy is cyclohexyl or cyclopentyl; and

65 (b) P(Phenyl) or pyridine. wherein Cy is cyclohexyl or cyclopentyl; and 48. A proceSS according to claim 43, wherein the com (b) P(Phenyl) or pyridine. position comprises: 5,939.504 23 24 (a) a catalyst Selected from the group consisting of 61. A process according to claim 49, wherein the cyclic olefin is Selected from the group consisting of cyclobutene, C. PPh3 H cycloheptene, cyclooctene, cyclononene, cyclodecene, / Ru Ph cyclooctadiene, cyclononadiene, norborne ne and / dicyclopentadiene, each of which may be functionalized or Cl PPh y=Q unfunctionalized. H Ph 62. A process according to claim 49, wherein the cyclic and olefin is dicyclopentadiene. C. PPh3 H 1O 63. A proceSS according to claim 49, wherein the com / position comprises: Ru (a) a compound Selected from the group consisting of Cl PPh3 Ph and H Ph 15 C \lPCy3 o (b) P(cyclohexyl) or P(cyclopentyl). Ru Ph 49. A proceSS for molding polymer articles, comprising / the Steps of: (a) providing, in a mold, a mixture comprising the com and position as recited in claim 1, (b) waiting until the mixture at least partially polymerizes Cl fy Ph to give a polymer article; and Ru (c) removing the polymer article from the mold. / 50. A process according to claim 49, wherein step (a) 25 comprises the Steps of: (i) preparinq said mixture, wherein said functionalized or unfunctionalized olefin is cyclic, and wherein Cy is cyclohexyl or cyclopentyl; and (ii) introducing the mixture into a mold. (b) P(Phenyl) or pyridine. 51. A process according to claim 50, wherein step (i) 64. A process according to claim 63, wherein the cyclic comprises the Steps of: olefin is dicyclopentadiene. (1) preparing a mixture comprising said cyclic function 65. A process according to claim 49, wherein the com alized or unfunctionalized olefin and said component position comprises, (c); and (2) adding to said mixture said complex catalyst, compo 35 (a) a compound Selected from the group consisting of nent (a). 52. A process according to claim 50, further comprising C PPh3 H the step of heating the mold before the mixture is introduced into the mold. RuC Ph 53. A process according to claim 50, further comprising 40 the Step of heating the mold after the mixture is introduced Cl PPh3 y=SV into the mold. H Ph 54. A process according to claim 50, further comprising and the Step of heating the mixture before it is introduced into the C PPh3 H mold. 45 55. A process according to claim 50, further comprising RucC the Step of heating the mixture after it has been introduced / into the mold. C PPh3 Ph 56. A process according to claim 50, further comprising and adding a crosslinking initiator to the mixture before the mixture is introduced into the mold. 50 57. A process according to claim 49, further comprising (b) P(cyclohexyl)- or P(cyclopentyl). the Step of heating the mold. 58. A process according to claim 49, further comprising 66. A process according to claim-96, wherein the cyclic the Step of heating the mixture. olefin is dicyclopentadiene. 59. A process according to claim 49, further comprising 55 67. A process according to claim 49, wherein the com the Step of adding a crosslinking initiator to the mixture. position as recited in claim 1 further comprises a reinforcing 60. A process according to claim 49, wherein the cyclic material. olefin is a functionalized cyclic olefin containing one or 68. A method according to claim 38, further comprising more functional groups Selected from the group consisting contacting Said olefin with a reinforcing material. of hydroxyl, thiol, ketone, aldehyde, ester, ether, amine, 60 69. a composition of matter according to claim 1, further amide, nitro acid, carboxylic acid, disulfide, carbonate, comprising a reinforcing material as a component (d). carboalkoxy acid, isocyanate, carbodiimide, carboalkoxy, and halogen. k k k k k