# US 5,344,900 A · Process for producing a norbornene polymer > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,344,900 A - Document ID: US5344900A - Status: Granted - Kind: A - Application number: 08/056,587 - Filed: 1993-04-30 - Granted: 1994-09-06 - Earliest claimed: 1990-03-06 - Assignees: Idemitsu Kosan Co., Ltd. - Inventors: Hiroshi Maezawa; Junichi Matsumoto; Hideki Aiura; Satoshi Asahi - Web page: https://patentgrep.com/patent/US5344900A ## CPC - C08G 61/08: of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring - Y10S 526/943: Polymerization with metallocene catalysts - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS ## Abstract A process for producing a norbornene polymer consisting essentially of a repeating unit of the formula (I) ##STR1## wherein R.sup.1 to R.sup.12 are the same or different and are hydrogen, C.sub.1 -C.sub.20 hydrocarbon, or a group having a halogen, oxygen or nitrogen, R.sup.5 and R.sup.7 may combine to form a ring, and n is an integer of 0 or more; and having a weight average molecular weight as determined by GPC of 1.times.10.sup.5 to 1.times.10.sup.7. The process comprises polymerizing a norbornene monomer of the formula (II) ##STR2## wherein R.sup.1 to R.sup.12 are the same or different and are independently hydrogen, C.sub.1 -C.sub.20 hydrocarbon, or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom; R.sup.5 and R.sup.7 may combine together to form a ring; and n is an integer of 0 or more, in the presence of a catalyst containing a transition metal compound component containing a transition metal belonging to Group VB, VIB, VIIB or VIII of the Periodic Table, and an aluminoxane components. ## Claims ### Claim 1 A process for producing a norbornene polymer consisting essentially of a repeating unit of formula (I): ##STR11## wherein R.sup.1 to R.sup.12 are the same or different and are independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom; R.sup.5 and R.sup.7 may combine together to form a ring; and n is an integer of 0 or more, and having a weight average molecular weight of 1.times.10.sup.5 to 1.times.10.sup.7 as determined by gel permeation chromatography, which process comprises polymerizing a norbornene monomer of the formula (II): ##STR12## wherein R.sup.1 to R.sup.12 are the same or different and are independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom; R.sup.5 and R.sup.7 may combine together to form a ring; and n is an integer of 0 or more, in the presence of a catalyst comprising a transition metal compound component containing a transition metal selected from the group consisting of manganese, nickel and palladium, and an aluminoxane component. ### Claim 2 (depends on 1) The process as claimed in claim 1, wherein the aluminoxane component is a compound obtained by contacting an organoaluminum compound and water. ### Claim 3 (depends on 2) The process as claimed in claim 2, wherein the organoaluminum compound is a compound of the formula AlR.sub.3.sup.17, wherein R.sup.17 is at least one alkyl group having 1 to 8 carbon atoms. ### Claim 4 (depends on 3) The process as claimed in claim 3, wherein the organoaluminum compound is trimethylaluminum, triethylaluminum or triisobutylaluminum. ### Claim 5 (depends on 1) The process as claimed in claim 1, wherein the molar ratio of aluminum in the aluminoxane component to the transition metal in the transition metal compound component is 1 to 10.sup.1. ### Claim 6 (depends on 1) The process as claimed in claim 1, wherein the catalyst further comprises an organoaluminum compound. ### Claim 7 (depends on 1) The process as claimed in claim 1, wherein the transition metal is nickel. ### Claim 8 (depends on 1) The process as claimed in claim 1, wherein R.sup.1 to R.sup.12 are the same or different and are a hydrogen atom, an unsubstituted alkyl group having 1 to 20 carbon atoms; an aryl or an alkylaryl group having 6 to 20 carbon atoms; an alkylidene group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine; and an alkyl group having 1 to 20 carbon atoms and being substituted with a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine; an alkoxy group having 1 to 20 carbon atoms; a cyano group; an alkylamino group having 1 to 20 carbon atoms; with the proviso that R.sup.1, R.sup. 2, R.sup.9 and R.sup.10 is not an alkylidene group and when any of R.sup.3 to R.sup.8 or R.sup.12 is an alkylidene group, the carbon atom to which the alkylidene group is connected does not have another substituent. ### Claim 9 (depends on 1) The process as claimed in claim 1, wherein R.sup.1 to R.sup.12 are the same or different and are a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a phenyl group, a tolyl group, a benzyl group, a methylidene group, an ethylidene, a propylidene group, a vinyl group, an allyl group, a chloromethyl group, a bromomethyl group, a chloroethyl group, a methoxy group, an ethoxy group, a propoxy group, a phenoxy, a methoxycarbonyl group, an ethoxy carbonyl group, a dimethylamino group or a diethylamino group ### Claim 10 (depends on 1) The process as claimed in claim 1, wherein the polymer is selected from the group consisting of polynorbornene, poly(5-methylnorbornene), poly(5-ethylnorbornene), poly(5-propylnorbornene), poly(5,6-dimethylnorbornene), poly(1-methylnorbornene), poly(7-methylnorbornene), poly(5,5,6-trimethylnorbornene), poly(5-phenylnorbornene), poly(5-benzylnorbornene), poly(5-ethylidenenorbornene), poly(5-vinylnorbornene), poly(1,4,5,8,-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene), poly(2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene), poly(2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene), poly(2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene ), poly(1,2-dihydrodicyclopentadiene), poly(5-chloronorbornene), poly(5,5-dichloronorbornene), poly(5-fluoronorbornene), poly(5,5,6-trifluoro-6-trifluoromethylnorbornene), poly(5-chloromethylnorbornene), poly(5-methoxynorbornene), poly(5-dimethylaminobornene), and poly5-cyanonorbornene). ### Claim 11 (depends on 4) The process as claimed in claim 4, wherein the transition metal compound component is of the formula MR.sub.a.sup.13 R.sub.b.sup.14 R.sub.c.sup.15 R.sub.d.sup.16 wherein M is a transition metal selected from the group consisting of manganese, nickel and palladium, a, b, c and d are integers from 0 to 7, R.sup.13 to R.sup.16 are the same or different are hydrogen, fluorine, chlorine, bromine, oxygen, methyl, ethyl, n-propyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl, octyl, 2-ethylhexyl, methoxy, ethoxy, propoxy, butoxy, phenoxy, phenyl, tolyl, xylyl, benzyl, heptadecylcarbonyloxy, indenyl, fluorenyl, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, 1,2-dimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, .pi.-allyl, allyl substituted with alkyl, acetylocetonate, acetylocetonate substituted with alkyl, trimethylsilyl, (trimethyl silyl)methyl, nitrogen, ethylene, diethyl ether, tetrahydrofuran, dimethyl ether, ethyl benzoate, acetonitrile, benzonitrite, triethylamine, 2,2'-bipyridene, phenanethroline, triethylphosphine, triphenylphosphine, isocyanide, phosphoric acid, thiocyanate, benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatrine and cyclooctetraene. ### Claim 12 (depends on 4) The process as claimed in claim 4, wherein the transition metal compound component is selected from the group consisting of tricarbonyl(cyclopentadienyl)manganese, pentacarbonylmethylmanganese, bis(cyclopentadienyl)manganese, manganese bis(acetylacetonate) dicarbonylbis(triphenylphosphine)nickel, dibromobis(triphenylphosphine)nickel, dinitrogenbis[bis(tricyclohexylphosphine)nickel], chlorohydridobis(tricyclohexylphosphine)nickel, chloro(phenyl)bis(triphenylphosphine)nickel, dimethylbis(trimethylphosphine)nickel, diethyl(2,2'-bipyridyl)nickel, bis(allyl)nickel, bis(cyclopentadienyl)nickel, bis(methylcyclopentadienyl)nickel, bis(pentamethylcyclopentadienyl)nickel, allyl(cyclopentadienyl)nickel, (cyclopentadienyl)(cyclooctadiene)nickel tetrafluoroborate, bis(cyclooctadiene)nickel, nickel bisacetylacetonate, allylnickel chloride, tetrakis(triphenylphosphine)nickel, nickel chloride, (C.sub.6 H.sub.5)Ni{OC(C.sub.6 H.sub.5)CH.dbd.P(C.sub.6 H.sub.5).sub.2 } {P(C.sub.6 H.sub.5).sub.3 } and (C.sub.6 H.sub.5)Ni{OC(C.sub.6 H.sub.5)C(SO.sub.3 Na).dbd.P(C.sub.6 H.sub.5).sub.2 } {P(C.sub.6 H.sub.5).sub.3 } dichlorobis(benzonitrile)palladium, carbonyltris(triphenylphosphine)palladium, dichlorobis(triethylphosphine)palladium, bis(tert-butyl-iso-cyanide) palladium, palladium bis(acetylacetonate), dichloro(tetraphenylcyclobutadiene)palladium, dichloro(1,5-cyclooctadiene)palladium, allyl(cyclopentadienyl)palladium, bis(allyl)palladium, allyl(1,5-cyclooctadiene)palladium tetrafluoroborate, (acetylacetonate) (1,5-cyclooctadiene)palladium tetrafluoroborate and tetrakis (acetonitrile)palladium bis(tetrafluoroborate). ### Claim 13 (depends on 12) The process as claimed in claim 12, wherein the molar ratio of aluminum in the aluminoxane component to the transition metal is 10 to 10.sup.4 ; and the process is carried out at a temperature of -10.degree. C. to +120.degree. C. ### Claim 14 (depends on 1) The process as claimed in claim 1, which further comprises forming a solution of said norbornene polymer and an organic solvent and evaporating the organic solvent to form a film. ### Claim 15 (depends on 14) The process as claimed in claim 14, wherein the organic solvent is at least one solvent selected from the group consisting of aromatic hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons. ### Claim 16 (depends on 15) The process as claimed in claim 15, wherein the concentration of the norbornene polymer in the solution is 0.1 to 20% by weight. ### Claim 17 (depends on 15) The process as claimed in claim 15, wherein the norbornene polymer is poly(1,4,5,8-dimethano-1,2,3,4,4a,5,8,8-octahydronaphthalene). ### Claim 18 (depends on 15) The process as claimed in claim 15, wherein the norbornene polymer is poly(5-ethylidene-2-norbornene). ### Claim 19 (depends on 1) The process as claimed in claim 1, wherein the transition metal is palladium. ### Claim 20 (depends on 1) The process as claimed in claim 1, wherein the transition metal is manganese. ### Claim 21 (depends on 4) The process as claimed in claim 4, wherein the transition metal component is selected from the group consisting of nickel bisacetylacetonate, biscyclooctadienylnickel, biscyclopentadienylnickel, tetrakis (triphenylphosphine)nickel, chloro(phenyl)bis(triphenylphosphine)nickel, (C.sub.6 H.sub.5)Ni{OC(C.sub.6 H.sub.5).sub.2 CH.dbd.P(C.sub.6 H.sub.5).sub.2 } {P(C.sub.6 H.sub.5).sub.3, nickel chloride, dichloro(1,5-cyclooctadiene)palladium, dichlorobis(benzonitrile)palladium, tetrakis(triphenylphosphine)palladium, palladium bis(acetylacetonate), palladium chloride and manganese bis(acetylacetonate).