USOO6171995B1 (12) United States Patent (10) Patent No.: US 6,171,995 B1 Miihlebach et al. (45) Date of Patent: *Jan. 9, 2001
(54) CATALYST MIXTURE FOR RING-OPENING C. Grunwald et al., Organometallics, Vol. 15, No. 8, pp. METATHESIS POLYMERIZATION 1960-1962, 1996.* Journal of Molecular Catalysis, 76, (1992) pp. 123-132, A. (75) Inventors: Andreas Miihlebach, Belfaux; Paul Demonceau et al. Adriaan Van Der Schaaf, Fribourg; Andreas Hafner, Laupen, all of (CH) Primary Examiner Mark L. Bell Assistant Examiner J. Pasterczyk (73) Assignee: Ciba Specialty Chemcials (74) Attorney, Agent, or Firm Michele A. Kovaleski; Corporation, Tarrytown, NY (US) David R. Crichton; Luther A. R. Hall (*) Notice: This patent issued on a continued pros (57) ABSTRACT ecution application filed under 37 CFR 1.53(d), and is subject to the twenty year A composition, comprising patent term provisions of 35 U.S.C. (a) a compound of formula I 154(a)(2). (RRRP), LM'ZZ, (I), Under 35 U.S.C. 154(b), the term of this wherein R, R2 and R are each independently of one patent shall be extended for 0 days. another H, C-Coalkyl, C-Co-alkoxy; C-Cacycloalkyl This patent is Subject to a terminal dis which is unsubstituted or substituted by C-C-alkyl, claimer. C-Chaloalkyl or C-C alkoxy; C-Cacycloalkoxy which is unsubstituted or substituted by C-C-alkyl, C-Chaloalkyl or C-C alkoxy; Co-Caryl which is (21) Appl. No.: 08/970,989 unsubstituted or substituted by C-Calkyl, C-Chaloalkyl (22) Filed: Nov. 14, 1997 or C-Calkoxy; Co-Caryloxy which is unsubstituted or Substituted by C-C alkyl, C-Chaloalkyl or C-C alkoxy, (30) Foreign Application Priority Data C7-C-aralkyloxy which is unsubstituted or Substituted by Nov. 15, 1996 (CH) ...... 2826/96 C-C alkyl, C-Chaloalkyl or C-C alkoxy; or C7-Caralkyloxy which is unsubstituted or substituted by (51) Int. Cl." ...... B01J 31/00 C-C alkyl, C-C-haloalkyl or C-Calkoxy, or R and R (52) U.S. Cl...... 502/162; 502/152; 502/150; together are tetra- or pentamethylene which is unsubstituted 502/156; 502/158; 502/169; 502/172 or Substituted by C-C alkyl, C-Chaloalkyl or (58) Field of Search ...... 502/150, 152, C-C alkoxy, tetra- or pentamethylenedioxyl which is 502/155, 156, 158, 161, 169, 170, 172, unsubstituted or substituted by C-Calkyl, C-Chaloalkyl 162 or C-C alkoxy, tetra- or pentamethylene which is con densed with one or two 1,2-phenylene radicals and which is (56) References Cited unsubstituted or substituted by C-Calkyl, C-Chaloalkyl or C-Calkoxy, tetra- or pentamethylenedioxyl which is U.S. PATENT DOCUMENTS condensed with one or two 1,2-phenylene radicals and 3,855,323 : 12/1974 Lyons ...... 260/666 A which is unsubstituted or substituted by C-C alkyl, 3,957,827 : 5/1976 Lyons ...... 502/155 C-Chaloalkyl or C-Calkoxy; or tetramethylenedioxyl 3,962,294 : 6/1976 Lyons ...... 502/155 which is condensed in the 1,2- and 3,4-positions with 5,312.940 : 5/1994 Grubbs et al...... 556/136 1,2-phenylene and which is unsubstituted or substituted by (List continued on next page.) C-C alkyl, C-Chaloalkyl or C-C alkoxy; and R has the meaning cited above; L is a neutral ligand; M is Ru or FOREIGN PATENT DOCUMENTS OS, Z and Z are each a singly charged anion, or Z and O 839 821 * 10/1997 (EP). Z together are a doubly charged anion; X is a number from 9313171 7/1993 (WO). 1 to 3, and y is a number from 0 to 3, wherein 2s x+y s4; 96/16100 5/1996 (WO). and 9620235 7/1996 (WO). (b) a compound of formula II WO 97/40934 * 11/1997 (WO). WO 98/39346 * 9/1998 (WO). R-C=C-H (II), OTHER PUBLICATIONS wherein R is hydrogen or a monovalent organic radical of C. Grunwald et al., Advances ACS Abstracts, vol. 4, No. 6, up to 30 carbon atoms which may contain one or Several p. 140, Apr. 15, 1996.* Silicon, phosphorus, nitrogen, oxygen, Sulfur or halogen P. Schwab et al., Angew. Chem. Int. Ed. Engl., vol. 34, No. atoms, is Suitable as Storage-Stable two-component catalyst 18, pp. 2039–2041, 1995.* for the ring-opening metathesis polymerisation of cyclopen P. Schwab et al., J. Am. Chem. Soc., vol. 118, No. 1, pp. tadiene adducts and makes it possible to polymerise dicy 100-110, 1996.* clopentadiene and other cydopentadiene adducts within a A. Stumpf et al., J. Chem. Soc., Chem. Commun., pp. Short time and with high enthalpy of reaction and only little 1127-1128, 1995.* weight loSS. L. Porri et al., Die Makromolekulare Chemie, vol. 175, pp. 3097-301.15, 1974.* 6 Claims, No Drawings US 6,171,995 B1 Page 2
U.S. PATENT DOCUMENTS 5,912,376 * 6/1999 Van Der Schaaf et al...... 502/155 5,342,909 * 8/1994 Grubbs et all 556/136 5,917,071 * 6/1999 Grubbs et al...... 502/152 5550.262 9/1996 Beatty et all ------502/155 5,939,504 * 8/1999 Woodson, Jr. et al...... 502/152
5.599,962 * 2/1997 N et al. 556/137 6,043,380 3/2000 Okeda et al...... 502/162 2- - - 2 - - - 6,048,993 * 4/2000 Grubbs et al...... 502/162 5,710,298 * 1/1998 Grubbs et al. . 502/155 6,077.805 3/2000 Van Der Schaaf et all 502/155 5,726,334 * 3/1998 Beatty et al. .. 502/155 2Y------5,728,785 * 3/1998 Grubbs et al. . 526/142 5,831,108 11/1998 Grubbs et al...... 502/152 * cited by examiner US 6,171,995 B1 1 2 CATALYST MIXTURE FOR RING-OPENING butyl groups as well as the different isomeric halogenated METATHESIS POLYMERIZATION pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, The present invention relates to a catalyst composition octadecyl, nonadecyl and eicosyl groups. consisting of a ruthenium or osmium phosphine complex Cycloalkyl is preferably C-C cycloalkyl, in particular and an alkyne; to a mixture comprising a Diels-Alder adduct Cs- or Cecycloalkyl. Typical examples are cyclopropyl, of cyclopentadiene and Such a catalyst composition; to a dimethylcyclopropyl, cyclobutyl, cyclope nty 1, proceSS for the preparation of a metathesis polymer as well methylcyclopentyl, cyclohexyl, cycloheptyl and cydooctyl. as to the use of the polymerisable composition as casting Cycloalkoxy groups are, for example, cyclopentyloxy, resin, impregnating resin or as encapsulating material for methylcyclopentyloxy and cydohexyloxy. electrical or electronic components. Aryl preferably contains 6 to 10 carbon atoms and may WO 93/13171 describes air- and water-stable one- and typically be phenyl, pentalinyl, indenyl, naphtyl, azulinyl two-component catalysts based on carbonyl group and anthryl. containing molybdenum and tungsten compounds as well as Aryloxy groups are, for example, phenyloxy, naphthyloxy ruthenium and OSmium compounds having at least one 15 and anthryloxy. polyene ligand for the thermal and photoactivated ring Aralkyl preferably contains 7 to 12 carbon atoms and, opening metathesis polymerisation (ROMP) of strained particularly preferably, 7 to 10 carbon atoms. Aralkyl may cycloolefins, in particular norbornenes and norbornene typically be benzyl, phenethyl, 3-phenylpropyl, derivatives. C.-methylbenzyl, 4-phenylbutyl and C.C.-dimethylbenzyl. 1-Alkynes are, inter alia, recommended as co-catalysts Illustrative examples of aralkyloxy groups are benzyloxy, for the two-component catalysts. phenethyloxy, 3-phenylpropyloxy, C.-methylbenzyloxy, Demonceau et al. A. Demonceau, A. F. Noels, E. Saive 4-phenylbutyloxy and C.C.-dimethylbenzyloxy. and A. J., Hubert: J. Mol. Catal. 76, 123–132 (1992) Preferred components (a) are compounds of formula I, describe (C6Hs). PRuCl, (CHS)PRuHCl and wherein Me is ruthenium. (p-cymene)RuCl2P(CH) as thermal catalysts for the 25 Other preferred components (a) are compounds of for ring-opening metathesis polymerisation of norbornene. The mula I, wherein R, R and R are each independently of one relatively low activity of these catalysts is increased by another C-C alkyl, C-C alkoxy, C-Cacycloalkyl, addition of diaZO esters. It is also mentioned that only C-Cacycloalkoxy, Co-Caryl or C-Caryloxy. (p-cymene)RuOlP(CH) is able to polymerise nor Particularly preferred compounds of formula I are those, bornene in relatively short time at 60° C. Another monomer wherein R, R and R are each independently of one mentioned is cyclooctene. No other cycloolefins suitable for another isopropyl, Sec-butyl, phenyl, tolyl, cyclopentyl or the metathesis polymerisation are mentioned. cyclohexyl. WO 96/20235 describes ruthenium and osmium complex L in formula I is preferably benzene, thiophene, benzoni compounds as excellent catalysts for the metathesis poly trile or acetonitrile which are unsubstituted or substituted by merisation of di- and oligocyclopentadienes. 35 1 to 3 C-C alkyl, nitrogen (N), unsubstituted or partially Surprisingly, it has now been found that the addition of or completely fluorinated C-C alcohol, CO, HO or NH. 1-alkynes increases the catalytic activity of the ruthenium Those compounds of formula I are also preferred, wherein and OSmium phosphines very Substantially and improves the Z and Z are each independently of the other H, F, Cl, properties of the polymers considerably. In this manner it is Br, I, or cyclopentadienyl which is unsubstituted or Sub possible to prepare polymers having excellent physical and 40 Stituted by one or Several hydroxide groups, amino groups, mechanical properties within Shorter polymerisation times. halogen atoms, C-Coalkyl groups, C-Coalkoxy groups, Moreover, the catalyst System is latent and Storage-Stable C-C cycloalkyl groups, C-Cacycloalkoxy groups, and not Susceptible to air and moisture, which also permits Co-Caryl group, Co-Caryloxy groups or C7-Caralkyl marketing formulated polymerisable compositions. groupS. This invention relates to a composition, comprising 45 The complex compounds of formula I are known and are (a) a compound of formula I described, inter alia, in WO 96/16100 and WO 96/20235. The alkyl groups in formulae I and II may be Straight Typical examples of ruthenium and osmium compounds chain or branched. This also applies to the, or every, alkyl of of formula I are tos denotes tosylate, Cp is moiety of alkoxy- or haloalkyl-containing groupS and other cyclopentadienyl, and C.His cyclohexyl: (CH)HPRu groups containing alkyl. These alkyl groups preferably con 50 (p-cymene)Cl., (CH)-PRu(p-cymene)Cl., (CH)-PRu tain 1 to 12, particularly preferably 1 to 8 and, most (p-cymene) (tos), (CH), PRu(p-cyme ne) Br, preferably, 1 to 4, carbon atoms. (CH)4PRu(p-cymene)CIF, (CH)4PRu(C.H.2, Alkyl typically includes methyl, ethyl, isopropyl, (CH)-PRu(CH-CH5)(tos), (C)PRu(CoH) (tos), n-propyl, n-butyl, isobutyl, Sec-butyl, tert-butyl as well as (i-CH-)PRu(p-cymene)Cl., (CH)PRu(p-cymene)Cl, the different isomeric pentyl, hexyl, heptyl, octyl, nonyl, 55 (CH)PRu(CH-CN)(CH-OH)(tos), (CH)PRu decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, (p-cymene)(CH-CN) (PF), (CH)PRu(p-cymene) hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl (CH-CN)(tos), (n-CHo).PRu(p-cymene)(CH-CN) groupS. (tos), (CH)PRu(CHCN)Cl., (CH)PRu(CH Alkoxy is typically methoxy, ethoxy, propyloxy, -CN)2Cl2, (n-CCHo).PRu(p-cymene)Cl., (CH)PRu isopropyloxy, n-butyloxy, isobutyloxy, Sec-butyloxy and 60 (p-cymene)(C2H5OH)2(BF), (CH)PRu(p-cymene) tert-butyloxy. (CHOH) (PF), (i-CH,). POS (p-cymene) Cl, Halo alkyl typically comprises fluoromethyl, (CH-)POS(p-cymene)Cl., (CHS)-POS(p-cymene)Cl, difluoromethyl, trifluoromethyl, chloromethyl, (C.H.)PRu(CH-CN), (CHo).PRu(p-cymene)C1, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, (CH)PRu(p-cymene)HCl, (CH)PRu1,2,4,5-(CH), 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl as well as 65 CH2Cl2, (CH) PRu1,3,5-(i-CH7)3CHCl2, halogenated, in particular fluorinated or chlorinated, (CH)-PRu(CHo)-CHCl2, (CH)-POS(p-cymene) isopropyl, n-propyl, n-butyl, isobutyl, Sec-butyl and tert Cl, (CH3)PRu(p-cymene)HCl, (CH)PRu(CH US 6,171,995 B1 3 4 -CN) (tos), Ru Cl (p-cyme me)(CH)PCHCHP Particularly Suitable components (b) are compounds of (CH), (CH)PRu(p-cymene)(C2H5OH)(BF), formula II, wherein R is a hydroxyl group-containing (CH)PRu(CH)(CH3OH) (tos), (CH)PRu(i- radical. The use of Such co-catalysts Surprisingly results in CH7-CH5)(tos),(CH)PRu(CH)(p-cymene) Br, (CH)PRu(biphenyl)(tos), (CH)-PRu(anthracene) a very uniform liberation of the enthalpy of reaction, i.e. (tos), (2-CH-CH)-POS(p-cymene)Cl and CH)-PRu there are no high peak temperatures during polymerisation. (chrysene)(tos). By adding hydroxyl group-containing acetylenes, it is Particularly preferred compounds of formula I are possible, for example, to lower the peak temperature when (CH)PRuCl, (CH)P RuCl, (CHS)P (CO) polymerising dicyclopentadiene from the usual c. 180 C. to RuH., (CHs). P. Ru ClCp, (CH) P(CHOH) <100 C., resulting in improved mechanical properties. Ru(tos), (o-tolyl)-PRuCl2, (CH3)2CHP(p-cymene) Accordingly, this invention also relates to a composition RuCl2 and, in particular, (CH) P(p-cymene)RuOl. comprising components (a) and (b) defined above and, The compounds of formula II are also known and some of additionally, them are commercially available. Illustrative examples of (c) a Diels-Alder adduct of cyclopentadiene. these compounds are ethyne, phenylethyne, 4-tert 15 butylphenylethyne, trimethylsilylethyne, triethylsilylethyne, Components (c) are preferably compounds of formula III trii Sopropyl Sily lethyne, ethylethy nyl ether, 2 - e thy nylpy ridine, 4e thy nyl to lue ne, (III) 1-ethynylcyclohexylamine, propyne, 3-cyclohexyl-1- propyne, 1-bromo-2-propyne, 1-chloro-2-propyne, 1-dimethylamino-2-propyne, 1-diethylamino-2-propyne, 3-trimethylsilyl-1-propyne, 3-trimethylsilyloxy-1-propyne, propargylacrylate, propargylacetate, dipropargyl ether, pro pargyl aldehyde diethylacetal, N-propargyloxyphthalimide, propargylpropionate, propargyl-p-toluenesulfonate, propy 25 noic acid, methyl propiolate, ethyl propiolate, 1-butyne, wherein Rs and R are each independently of the other 3-methyl-1-butyne, 4-phenyl-1-butyne, 3,3-dimethyl-1- hydrogen, C-C alkyl, phenyl, tolyl, cyclohexyl, butyne, 1-cyano-4-butyne, 2-methyl-1-buten-3-yne, cyclohexenyl, halogen, cyano, C-C-hydroxyalkyl or 4-trimethylsilyloxy-1-butyne, 3-trimethylsilyloxy-1-butyne, 3-methyl-3 trimethylsilyloxy-1-butyne, 1-pentyne, C-Chaloalkyl, or Rs and R, together with the linking 3-methyl-1-pentyne, 5chloro-1-pentyne, 1-triethylsilyloxy carbon atoms, are a five- or six-membered ring. 4-pentyne, 1,4-pentadiyne, 1-trimethylsilyl-1,4-pentadiyne, Suitable Diels-Alder adducts are, for example, the fol 4-pentinic acid, 1-hexyne, 1,5heXadiyne, 5-heXinic acid, lowing compounds: 5heXinic acid nitrile, 1-heptyne, 1,6heptadiyne, 1-octyne, 1,7-octadiyne, 1-nonyne, 8-noninic acid, 1,8nonadiyne, 35 (1) 1-decyne, 1,9-decadiyne, 1-dodecyne, 1-undecyne, 10unde cinic acid, methyl 10-undecinate, 1-tride cyne, 1-tetrade cyne, 1-pentade cyne, 1-hexadecyne and 1-octadecyne. At 7 Component (b) in the novel compositions is preferably a 40 (2) compound of formula II, wherein R is a C-Coalkyl, C-Coalkoxy, C-Cacycloalkyl, C-Cacycloalkoxy, Co-Caryl, C-Caryloxy or C7-Caralkyl group which / is unsubstituted or Substituted by one or Several amino groups or halogen atoms. 45 R in formula II is particularly preferably C-C alkyl or (3) Co-Co aryl. Component (b) is particularly preferably 1-heptyne, O 1-octyne, 1-decyne or phenylethyne. The amounts of components (a) and (b) in the novel 50 / compositions can vary within a wide range. O The weight ratio of components (a):(b) is preferably from 25:1 to 1:10, more preferably from 10:1 to 1:2 and, very O s particularly preferably, from 7:1 to 2:1. (4) Particularly Suitable compositions are those containing 55 about equimolar amounts of components (a) and (b), i.e. O compositions, wherein the molar ratio of components (a):(b) is from 1.1:1 to 1:1.1. / AS has been mentioned at the outset, the novel composi tions are Suitable as Storage-Stable two-component catalysts 60 for the ring-opening metathesis polymerisation of cyclopen O s tadiene adducts. With this novel catalyst system it is possible (5) to polymerise dicyclopentadiene and other cyclopentadiene adducts in Substantially shorter time and with high enthalpy CN of reaction and only little weight loSS. The polymers are 65 distinguished by a high glass transition temperature and by W s generally good mechanical properties. US 6,171,995 B1 S 6 -continued -continued (6) (15)
(7) CO
o (8) 15 (16) CHNHCH
At CHNHCH (9) CO (17) OCH
25 (10)
AsOCH (18)
(11) 35 AO (19)
(11) 40 (20)
T. (12) 45
2. (21) 50 Ayr (13) (22) 55
(14) (23) 60 G. 65 US 6,171,995 B1 7 8 -continued examples are: ethers (dibutyl ether, tetrahydrofuran, (24) dioxane, 2-methoxyethanol or ethylene glycol dimethyl ether, 2-ethoxyethanol or ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether), halogenated hydrocarbons (methylene chloride, chloroform, 1,2-dichloroethane, 1,1,1trichloroethane, 1,1,2, 2-tetrachloroethane), carboxylates and lactones (ethyl acetate, methyl propionate, ethylbenzoate, 2-methoxyethyl (25) acetate, 2-butyro-lactone, Ö-Valerolactone, pivalolactone), 1O carboxamides and lactams (N,N-dimethylformymide, N,N- diethyl form amide, N,N-dimethyl acetamide, tetramethylu rea, hexamethylphosphoric triamide, Ö-butyrolactam, 6-caprolactam, N-methylpyrrollidone, / N-acetylpyrrollidone, N-methylcaprolactam), Sulfoxides 15 (dimethylsulfoxide), sulfones (dimethylsulfone, Preferred Diels-Alder adducts are norbornene (1), nor diethylsulfone, trime thylene Sulfone, bornadiene (6), cyclohexenyinorbornene (25), tetracy tetra methylene Sulf one), tertiary a mines clododecene (14), methyltetracyclododecene (11) and, in (N-methylpiperidine, N-methylmorpholine), aliphatic and particular, dicyclopentadiene (18). aromatic hydrocarbons, typically petroleum ether, pentane, The amounts of components (a), (b) and (c) in the novel hexane, cyclohexane, methylcyclohexane, benzene or Sub compositions can vary within a wide range. Stituted benzenes (chlorobenzene, O-dichlorobenzene, 1,2,4- Preferred compositions are those containing 0.001-10.0% trichlorobenzene, nitrobenzene, toluene, xylene) and nitriles by weight, particularly preferablyy 0.01-5.0% by weight, (acetonitrile, propionitrile, benzonitrile, phenylacetonitrile). most preferably 0.1-2.0% by weight, of component (a), Preferred Solvents are aprotic polar and nonpolar Solvents. 0.001-10.0%; by weight, particularly preferably 25 Preferred Solvents are aliphatic and aromatic hydrocar 0.005–2.0% by weight, most preferably 0.01–1.0% by bons as well as mixtures of Such Solvents. weight, of component (b), and 85.0-99.99% by weight, It is a particular advantage of the novel compositions that particularly preferably 90.0-99.9% by weight, most prefer in the case of liquid monomers a metathesis polymerisation ably 95.0-99.8% by weight, of component (c), based on the can be carried out without using a Solvent. entire composition (a)+(b)+(c). The novel composition can be prepared directly before The weight ratio of monomer (component c) to catalyst polymerisation or can be used in the form of a preformulated mixture (components a+b) can also vary within a wide mixture. The mixture can be Stored for an extended period range, of time as ready-to-use formulation before polymerisaion, The novel compositions preferably contain 85.0-99.99% which is advantageous for large Scale industrial application. by weight, in particular 90.0-99.9% by weight, of monomer, 35 However, it is advisable to store the mixture with the and 0.01-15.0% by weight, in particular 0.1-10.0% by exclusion of light if the catalyst contains photoSensitive weight, of catalyst mixture, based on the entire composition. ligands. The desired viscosity of the curable mixture can be In another of its aspects, this invention relates to a process adjusted by adding thermoplastic materials. Typical for the preparation of a metathesis polymer, which com examples of Suitable thermoplasts are polystyrene, polynor 40 prises heating a composition comprising components (a) to bornene (e.g. NorSorex(R) NS , of Nippon Zeon), hydrated (c) to a temperature of >40° C. polynorbornene derivatives (e.g. ZeoneXOR), of Nippon The process of this invention is conveniently carried out Zeon), polycyclooctene (e.g. Vestenamer(R), of Hills), and at a temperature of at least 60° C. The novel process is polybutadiene. carried out in particular in the temperature range from 60 to The curable mixtures can also comprise tougheners, for 45 300° C., preferably from 60 to 250° C., more preferably example core/shell polymers or the elastomers or elastomer from 60 to 200° C. and, most preferably, from 70 to 160° C. containing graft polymers known to the skilled perSon as After polymerisation it may be useful to after-bake the rubber tougheners. mixture at elevated temperatures, typically in the range from Suitable tougheners are described, interalia, in EP-A-449 80 to 200° C. 776. 50 If component (a) is a compound of formula I with To improve the electrical properties (dielectric constant, photosensitive ligands, the metathesis polymersiation may loss factor) of the curable mixtures, Silanes, Such as the also be carried out photochemically. In this case, a compo compounds provided by Osi Specialties under the registered Sition comprising components (a) to (c) is irradiated with trademark Silcquest(R) Silan, may be added. Suitable silanes UV radiation or visible light and is then heat-postcured, if are typically octyltriethoxysilane , methyltriethoxysilane, 55 required. Vinyltrie thoxy Silane, methyltrime thoxy Silane, The polymerisation can involve moulding processes, for Vinyltrimethoxysilane, 2-amino-propyltrimethoxysilane and example calendering, casting, compression moulding, injec 2 glycidyloxypropyltrimethoxysilane. tion moulding or extruding processes. Using the novel In addition to the above-mentioned additives, the novel process it is possible to prepare materials for the preparation compositions can contain further customary additives, typi 60 of moulded articles of all kinds as well as coatings. Moul cally antioxidants, light Stabilisers, plasticisers, colourants, ding and polymerisation are usefully combined in Solvent pigments, thixotropitc agents, antifoams, antistatic agents, free reactive Systems, in which case it is possible to use lubricants and mould release agents. processing techniqueS Such as injection moulding, extrusion, The novel compositions can also contain inert Solvents. polymerisations in given moulds (if required under Suitable inert Solvents are, for example, protic-polar and 65 pressure). aprotic Solvents which can be used by themselves or in The mixtures prepared according to the novel proceSS can mixtures consisting of at least two Solvents. Typical additionally contain homopolymers, copolymers with ran US 6,171,995 B1 dom distribution of the Structural units, graft polymers, block polymers or crosslinked polymers. The polymers may TABLE 1. have an average molecular weight of 500 up to 2 000 000 dalton, preferably of 1000 to 1000 000 dalton (determined T -AH Weight loss by gel permeation chromatography). Component (b) C. J/g % Remark n.b. 48 n.b. semi-solid The mixtures prepared in accordance with the novel composition, proceSS are particularly distinguished by their high heat strong smell Stability, excellent toughness and mechanical Strength as of dicyclo pentadiene well as by good electrical properties (low dielectric constant, 2 mg of 1-octyne 35 262 11.7 good solid low loss factor or tano value) and are particularly Suitable for 4 mg of 1-octyne n.b. 300 n.b. good solid applications in Vacuum casting technology, as casting resins, 6 mg of 1-octyne 48 -300 n.b. good solid 8 mg of 1-octyne 53 3OO 13.4 good solid impregnating resins and especially as encapsulating mate 10 mg of 1-octyne 57 300 11.6 good solid rials for electrical and electronic components. The cured 15 mg of 1-octyne 6O >300 n.b. good solid casting compounds have good mechanical and dielectrical 15 20 mg of 1-octyne 58 3OO 15.O good solid properties and long durability. 50 mg of 1-octyne 53 288 21.6 good solid 100 mg of 1-octyne 26 n.b. n.b. soft solid Accordingly, this invention also relates to the use of the 9 mg of phenylethyne 127 289 3.5 excellent solid novel compositions as casting resin, impregnating resin and 13 mg of phenylethyne 125 284 5.2 excellent solid as encapsulating material for electrical or electronic com ponents. n.b.: not determined
EXAMPLES TABLE 2 The following abbreviations are used in the Working Component (b) Tmax C. T? C. Reaction?% Examples: 25 52 mg of phenylethyne 170 (40 min) 115 93 56 mg of 1-octyne 189 (24 min) 130 95 DSC: differential scanning calorimetry TGA: thermogravimetrical analysis What is claimed is: RT: room temperature 1. A composition, comprising (a) (CH)HPRu(p-cymene)Cl., (CH,)PRu(p- T. glass transition temperature cymene)Cl., (CH)PRu(p-cymene)(tosylate), AH: enthalpy of reaction (CH)PRu(p-cymene) Bra, (CH)PRu(p-cymene) Commercially available dicyclopentadiene (BF Goodrich, CIF, (CH)PRu(CH)(tosylate), (CH)PRu USA) having a purity of 98.4% (determined by gas (CH-CH) (tosylate), (CH)PRu(CHH) chromatography) is used in all the Examples. 35 (tosylate), (i-CH7)PRu(p-cymene)Cl., (CH-)PRu The ROMP catalyst is (CH) P(p-cymene)RuOl (p-cymene)Cl.(CH)PRu(CH-CN)(CH-OH) (catalyst A). (tosylate), (CH), PRu(p-cymene)(CH-CN)2 (PF),(CH)PRu(p-cymene)(CH-CN) (tosy Example 1 late), (n-CHo). PRu(p - cymene)(CH-CN)2 40 (tosylate), (CH)PRu(CHCN)Cl., (CH)PRu (CH -CN)Cl., (N-CHo).PRu(p-cymene)Cl, 200 g of dicyclopentadiene are liquefied by heating to 40 (CHPRu(p-cymene)(C2H5OH)2), (CH4). C. 50 mg each of catalyst A are then added to 10 g of the PRu(p-cymene)(C2H5OH)(PF), (i-CH-)POs(p-cy liquid dicyclopentadiene and dissolved by Stirring with a mene)Cl., (CH)POS(p-cymene)Cl., (CH)POS magnetic stirrer at 40 C. The corresponding amount (See 45 (P= cymene)C12, (CHP), Ru(CHs-CN), Table 1) of 1-octyne or phenylethyne is added and dissolved. (CSH)PRu(p-cymene)Cl., (CH)PRu(p-cymene) A Small Sample (about 10 mg) is taken to determine the H C 1, enthalpy of reaction AH by DSC (heating rate: 10°C/min). (CH)PRu1,2,4,5-(CH), CHCl, (CH) The mixture is then polymerised in a hot air oven (curing PRu1,3,5-(i-CH2)CHCl, (CH)POs(p- cy me ne) Cl, (CHs). PRu(p-cyme ne) HCl, cycle: 1 h/80° C., 1 h/100° C., 2 h/120° C.). The glass 50 (CH)PRu(CH-CN)(tosylate), RuCl2(p-cym transition temperature of the polymer is determined by DSC ene)(CH)PCHCHP(CH)), (CH)PRu(p- (heating rate 10° C./min). The weight loss between RT and cymene)(C2H5OH)(BF), (CH)PRu(CH.) 300 C. is determined by TGA. The results are compiled in (CHOH)2(tosylate), (CH)PRu(i-CH-CH) Table 1. (tosylate). (CH)PRu(CH)PRu(biphenyl) 55 (tosylate), (CH)PRu-(anthracene)(tosylate), Example 2 (2-CHCH)POs(p-cymene)C1 or (CH)PRu (chrysene)(tosylate) a compound of formula I 0.2 g of catalyst A is dissolved in 100 g of liquid dicyclopentadiene (heated to 40° C). The corresponding (RRRP), LM'ZZ, (1), amount (see Table 2) of 1-octyne or phenylethyne is then 60 wherein R, R2 and R are each independently of one added and dissolved by stirring. The mixture is then poly another H, C-Coalkyl, C1-Co-alkoxy, C-Cacycloalkyl merised (curing cycle: 1 h/80° C., 1 h/100° C., 2 h/120° C.) which is unsubstituted or substituted by C-C-alkyl, and the peak temperature T, obtained during the first C-Chaloalkyl or C-C alkoxy; C-Cacycloalkoxy which curing phase at 80 C., is measured (in brackets the time in is unsubstituted or substituted by C-C-alkyl, minutes to reaching the peak temperature) which is given in 65 C-Chaloalkyl or C-C alkoxy; Co-Caryl which is Table 2 together with the glass transition temperature deter unsubstituted or substituted by C-Calkyl, C-Chaloalkyl mined by DSC and the reaction determined by TGA. or C-Calkoxy; Co-Caryloxy which is unsubstituted or US 6,171,995 B1 11 12 Substituted by C-C alkyl, C-Chaloalkyl or C-C alkoxy, X is a number from 1 to 3, and y is a number from 0 to 3, C-C-aralkyl which is unsubstituted or substituted by wherein 2s X+ys4; and C-C alkyl, C-C-haloalkyl or C-C alkoxy; or C7-Caralkyloxy which is unsubstituted or substituted by (b) a compound of formula II C-C alkyl, C-C-haloalkyl or C-C alkoxy, R-C=C-H (II), or R and R together are tetra- or pentamethylene which is unsubstituted or substituted by C-C alkyl, wherein R is hydrogen or a monovalent organic radical of C-Chaloalkyl or C-C alkoxy, tetra- or pentameth up to 30 carbon atoms which may contain one or Several ylenedioxyl which is unsubstituted or substituted by Silicon, phosphorus, nitrogen, oxygen, Sulfur or halogen C-C alkyl, C-Chaloalkyl or C-C alkoxy, tetra- or pentamethylene which is condensed with one or two atOmS. 1,2-phenylene radicals and which is unsubstituted or 2. A composition according to claim 1, wherein compo Substituted by C-C alkyl, C-Chaloalkyl or nent (b) is a compound of formula II, wherein R is a C-C alkoxy, tetra- or pentamethylenedioxyl which is C-C2 oalkyl, C-Coalkoxy, C-C 2 cycloalkyl, condensed with one or two 1,2-phenylene radicals and 15 C-C2 cycloalkoxy, Co-Caryl, Co-Caryloxy or which is unsubstituted or substituted by C1-Calkyl, C7-Caralkyl group which is unsubstituted or Substituted C-Chaloalkyl or C-Calkoxy; or tetramethylene by one or Several amino groups or halogen atoms. dioxyl which is condensed in the 1,2- and 3,4-positions 3. A composition according to claim 1, wherein compo with 1,2-phenylene and which is unsubstituted or Sub Stituted by C-C alkyl, C-Chaloalkyl or nent (b) is a compound of formula II, wherein R is C-C alkoxy; and R has the meaning cited above; C-C alkyl or C-Caryl. L is a neutral ligand Selected from benzene, thiophene, 4. A composition according to claim 1, wherein compo benzonitrile or acetonitrile which are unsubstituted or nent (b) is 1-heptyne, 1-octyne, 1-decyne or phenylethyne. Substituted by 1 to 3 C-C alkyl; nitrogen (N); unsub 5. A composition according to claim 1, wherein the molar Stituted or partially or completely fluorinated 25 ratio of components (a):(b) is from 25:1 to 1:10. C-C alcohol; CO; HO; or NH; 6. A composition according to claim 1, wherein compo M is Ru or Os; nent (a) is (CH)P(p-cymene)RuCl2. Z and Z are each a singly charged anion, or Z and Z together are a doubly charged anion;