# US RE35,717 E · Cycloolefin copolymerization method, feed composition and product > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US RE35,717 E - Document ID: USRE35717E - Status: Granted - Kind: E - Application number: 08/122,176 - Filed: 1993-09-17 - Granted: 1998-01-20 - Earliest claimed: 1986-04-11 - Assignees: Metton America, Inc. - Inventors: Steven H. Nahm - Web page: https://patentgrep.com/patent/USRE35717E ## Abstract A cycloolefin copolymerization method, feed composition and product made from the feed which includes: a nonpolar cycloolefin, a polar cycloolefin and a catalyst. Preferably, the nonpolar cycloolefin is dicyclopentadiene, the catalyst comprises WCl.sub.6, the polar cycloolefin is an ester, and the composition also includes an activator. ## Claims ### Claim 1 A .›.substantially.!. cross-linked copolymer product comprising polymerized units of dicyclopentadiene and a comonomer selected from the group consisting of bis( 2-hydroxymethyl-5-norbornene ) adipate; .›.methyl-5-norbornene-2-carboxylate;.!. ethylene.›.-.!.bis.›.-.!.(5-norbornene-2-carboxylate); 2-hydroxymethyl-5-norbornene acetate ; and ethylene.›.-.!.bis.›.-.!.( 2-methyl- 5-norbornene-2-carboxylat e).›.; and, said copolymer product having a glass transition temperature of at least 145.degree. C., and a swell of less than about 245% in toluene after for 16 hours.!.. ### Claim 2 A method of rate moderated dicyclopentadiene polymerization comprising: contacting dicyclopentadiene, cycloolefin comonomer, an .›.aluminum containing.!. alkylaluminum activator and a tungsten containing catalyst, to form a polymerization mixture, said mixture being 50% by weight or less of said cycloolefin, said cycloolefin being bis( 2-hydroxymethyl-5-norbornene ) adipate; .›.methyl-5-norbornene-2-carboxylate;.!. ethylene.›.-.!.bis.›.-.!.(5-norbornene-2-carboxylate); 2-hydroxymethyl-5-norbornene acetate ; or ethylene.›.-.!.bis.›.-.!.(2-methyl-5-norbornene-2-carboxylate) ; and polymerizing said polymerization mixture, said cycloolefin being present in a concentration effective to increase the time from said contacting to the maximum temperature of the exotherm of polymerization. .›. ### Claim 3 (depends on 1, 7) The composition of claim 1 wherein said glass transition temperature is at least 153.degree. C..!..›.4. The composition of claim 1 wherein said glass transition temperature is at least 160.degree. C..!..›.5. The composition of claim 1 wherein said glass transition temperature is at least 165.degree. C..!..›.6. The composition of claim 1 wherein said glass transition temperature is at least 175.degree. C..!..›.7. A substantially cross-linked copolymer product comprising polymerized units of dicyclopentadiene and a polar cycloolefin monomer, said cycloolefin being; 2-hydroxymethyl-5-norbornene adipate; methy-5-norbornene-2-carboxylate; 2-hydroxymethyl-5-norbornene acetate; ethylene-bis-(5-norbornene-2-carboxylate); or ethylene-bis-(2-methyl-5-norbornene-2-carboxylate) said copolymer product having a glass transition temperature of at least 145.degree. C., and a swell of less than about 245% in toluene after reflex for 16 hours..!..›.8. The composition of claim 7 wherein said copolymer product composition has a glass transition temperature of at least 153.degree. C..!. ### Claim 9 A solid, infusible, crosslinked copolymer, prepared by metathesis-catalyzed, ring-opening polymerization of a cycloolefin monomer having a norbornene group, in admixture with a comonomer selected from the group consisting of ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxylate), bis-(2-hydroxymethyl-5-norbornene) adipate, trimethylolpropane-tris-(5-norbornene-2-carboxylate), and 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene. ### Claim 10 (depends on 9) The copolymer of claim 9, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 30% by weight. ### Claim 11 (depends on 9) The copolymer of claim 9, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is from about 1% to 30% by weight. ### Claim 12 (depends on 9) The copolymer of claim 9, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 20% by weight. ### Claim 13 (depends on 9) The copolymer of claim 9, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is from 5% to 20% by weight. ### Claim 14 (depends on 9) The copolymer of claim 9, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is from about 10% to 20% by weight. ### Claim 15 (depends on 9) The copolymer of claim 9, wherein the comonomer comprises 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene. ### Claim 16 A solid, infusible, crosslinked copolymer, prepared by metathesis-catalyzed, ring-opening polymerization of a cycloolefin monomer having a norbornene group in admixture with a comonomer selected from the group consisting of ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxylate), and bis-(2-hydroxymethyl-5-norbornene) adipate. ### Claim 17 (depends on 16) The copolymer of claim 16, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 30% by weight. ### Claim 18 (depends on 16) The copolymer of claim 16, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the metathesis polymerizable comonomer is from about 1% to 30% by weight. ### Claim 19 (depends on 16) The copolymer of claim 16, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the metathesis polymerizable comonomer is up to about 20% by weight. ### Claim 20 (depends on 16) The copolymer of claim 16, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the metathesis polymerizable comonomer is from about 5% to 20% by weight. ### Claim 21 (depends on 16) The copolymer of claim 16, wherein the cyclolefin monomer is dicyclopentadiene and the amount of the metathesis polymerizable comonomer is from about 10% to 20% by weight. ### Claim 22 A process for preparing a solid, infusible crosslinked copolymer, the process comprising the step of polymerizing a cycloolefin monomer having a norbornene group, in the presence of a metathesis catalyst system and a comonomer selected from the group consisting of ethylene-bis-(5-norbornene-2-carboxylate), ethyelene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxylate), bis-(2-hydroxymethyl-5-norbornene adipate), trimethylolpropane-tris-(5-norbornene-2-carboxylate), and 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene. ### Claim 23 (depends on 22) The process of claim 22, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 30% by weight. ### Claim 24 (depends on 22) The process of claim 22, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the metathesis polymerizable comonomer is from about 1% to 30% by weight. ### Claim 25 (depends on 22) The process of claim 22, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 20% by weight. ### Claim 26 (depends on 22) The process of claim 22, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is from about 5% to 20% by weight. ### Claim 27 (depends on 22) The process of claim 22, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is from about 10% to 20% by weight. ### Claim 28 (depends on 22) The process of claim 22, wherein the comonomer is 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene. ### Claim 29 (depends on 22) The process of claim 22, wherein the metathesis catalyst system comprises an activator selected from the group consisting of tetraalkyl tin compounds and trialkylaluminum compounds. ### Claim 30 A process for preparing a solid, infusible crosslinked copolymer, the process comprising the step of polymerizing a cycloolefin monomer having a norbornene group, in the presence of a metathesis catalyst system and a comonomer comprising a 1:1 Diels-Alder adduct of cyclopentadiene with 1,5-cyclooctadiene. ### Claim 31 A process for preparing a solid, infusible crosslinked copolymer, the process comprising the step of polymerizing a cycloolefin monomer having a norbornene group, in the presence of a metathesis catalyst system and a comonomer selected from the group consisting of ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxylate), and bis-(2-hydroxymethyl-5-norbornene) adipate. ### Claim 32 (depends on 31) The process of claim 31, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 30% by weight. ### Claim 33 (depends on 31) The process of claim 31, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the metathesis polymerizable comonomer is from about 1% to 30% by weight. ### Claim 34 (depends on 31) The process of claim 31, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 20% by weight. ### Claim 35 (depends on 31) The process of claim 31, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is from about 5% to 20% by weight. ### Claim 36 (depends on 31) The process of claim 31, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is from about 10% to 20% by weight. ### Claim 37 A process for preparing a solid, infusible crosslinked copolymer comprising the step of polymerizing a cycloolefin monomer selected from the group consisting of: ##STR17## where R and R.sup.1 are independently selected from hydrogen, alkyl groups of 1 to 20 carbon atoms, and saturated and unsaturated cyclic groups formed by R and R.sup.1 together with the two ring carbon atoms connected thereto, and where R.sup.2 and R.sup.3 are independently selected from hydrogen and alkyl groups containing 1 to 20 carbon atoms, in the presence of a metathesis catalyst system and a comonomer selected from the group consisting of ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxylate), and bis-(2-hydroxymethyl-5-norbornene) adipate. ### Claim 38 A process for preparing a solid, infusible, crosslinked copolymer comprising the step of polymerizing a cycloolefin monomer selected from the group consisting of: ##STR18## where R and R.sup.1 are independently selected from hydrogen, alkyl groups of 1 to 20 carbon atoms, and saturated and unsaturated cyclic groups formed by R and R.sup.1 together with the two ring carbon atoms connected thereto, and where R.sup.2 and R.sup.3 are independently selected from hydrogen and alkyl groups containing 1 to 20 carbon atoms, in the presence of a metathesis catalyst system and a comonomer selected from the group consisting of 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene, ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxylate), and bis-(2-hydroxymethyl-5-norbornene adipate). ### Claim 39 (depends on 38) The process of claim 38, wherein the cycloolefin monomer is dicyclopentadiene. ### Claim 40 (depends on 38) The process of claim 38, wherein the amount of comonomer is between about 1 and 25 weight percent, based on total weight of monomers. ### Claim 41 A solid, infusible, crosslinked copolymer, prepared by metathesis-catalyzed, ring-opening polymerization of a cycloolefin monomer selected from the group consisting of: ##STR19## where R and R.sup.1 are independently selected from hydrogen, alkyl groups of 1 to 20 carbon atoms, and saturated and unsaturated cyclic groups formed by R and R.sup.1 together with the two ring carbon atoms, and where R.sup.2 and R.sup.3 are independently selected from hydrogen and alkyl groups containing 1 to 20 carbon atoms, in admixture with a comonomer selected from the group consisting of ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxylate), bis-(2-hydroxymethyl-5-norbornene adipate), trimethylolpropane-tris-(5-norbornene-2-carboxylate), and 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene. ### Claim 42 A solid, infusible, crosslinked copolymer, prepared by metathesis-catalyzed, ring-opening polymerization of a cycloolefin monomer selected from the group consisting of: ##STR20## where R and R.sup.1 are independently selected from hydrogen, alkyl groups of 1 to 20 carbon atoms, and saturated and unsaturated cyclic groups formed by R and R.sup.1 together with the two ring carbon atoms, and where R.sup.2 and R.sup.3 are independently selected from hydrogen and alkyl groups containing 1 to 20 carbon atoms, in admixture with a comonomer selected from the group consisting of 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene, ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxylate), and bis-(2-hydroxymethyl-5-norbornene) adipate. ### Claim 43 (depends on 42) The copolymer of claim 42, wherein the cycloolefin monomer is dicyclopentadiene and the amount of comonomer is up to about 50 weight percent, based on the total weight of monomers. ### Claim 44 (depends on 42) The copolymer of claim 42, wherein the cycloolefin monomer is dicyclopentadiene. ### Claim 45 (depends on 42) The copolymer of claim 42, wherein the cycloolefin monomer is dicyclopentadiene and the amount of comonomer is from about 1 to 25 weight percent, based on total weight of monomers. ### Claim 46 A process for increasing the glass transition temperature of polymerized dicyclopentadiene by producing a crosslinked copolymer, comprising polymerizing a monomer charge comprising dicyclopentadiene in the presence of a metathesis catalyst system and metathesis polymerizable comonomer selected from the group consisting of ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), trimethylolpropane-tris-(5-norbornene-2-carboxylate), and 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene. ### Claim 47 A process for preparing a crosslinked polymer, the process comprising polymerizing dicyclopentadiene in the presence of a metathesis catalyst system and a comonomer selected from the group consisting of ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornen-2-carboxylate), bis-(2-hydroxymethyl-5-norbornene adipate), trimethylolpropane-tris-(5-norbornene-2-carboxylate), and 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene. ### Claim 48 (depends on 47) The process of claim 47, wherein the crosslinked polymer has a percent swell, determined after the polymer is immersed in toluene for two hours at 100.degree. C., of less than about 200. ### Claim 49 (depends on 48) The process of claim 48, wherein the crosslinked polymer has a percent swell of less than 150. ### Claim 50 (depends on 47, 49) The process of claim 49, wherein the crosslinked polymer has a percent swell of less than 100. The process of claim 47, wherein the comonomer is present in an amount of from about 1 to 25 percent, based on total weight of monomers. ### Claim 52 (depends on 47) The process of claim 47, wherein the comonomer comprises etheylene-bis-(5-norbornene-2-carboxylate). ### Claim 53 (depends on 47) The process of claim 47, wherein the comonomer comprises ethylene-bis-(2-methyl-5-norbornene-2-carboxylate). ### Claim 54 (depends on 47) The process of claim 47, wherein the comonomer comprises 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxyalte). ### Claim 55 (depends on 47) The process of claim 47, wherein the comonomer comprises bis-(2-hydroxymethyl-5-norbornene adipate). ### Claim 56 (depends on 47) The process of claim 47, wherein the comonomer comprises trimethylolpropane-tris-(5-norbornene-2-carboxylate). ### Claim 57 (depends on 47) The process of claim 47, wherein the comonomer comprises dimethanohexahydronaphthalene. ### Claim 58 (depends on 9) The copolymer of claim 9, wherein said polymerization is in the presence of (a) a catalyst that is a tungsten compound and (b) an activator selected from the group consisting of tetraalkyl tin compounds and alkylaluminum compounds; and wherein said cycloolefin monomer is selected from the following monomers: ##STR21## where R and R.sup.1 are independently selected from hydrogen, alkyl groups of 1 to 20 carbon atoms, and saturated and unsaturated cyclic groups formed by R and R.sup.1 and the two ring carbon atoms connected thereto, and where R.sup.2 and R.sup.3 are independently selected from hydrogen and alkyl groups containing 1 to 20 carbon atoms. ### Claim 59 (depends on 58) The copolymer of claim 58, wherein the activator comprises at least one member selected from the group consisting of a tetraalkyl tin compound and a trialkylaluminum compound. ### Claim 60 A solid, infusible, crosslinked copolymer, prepared by metathesis-catalyzed, ring-opening polymerization of a cyclolefin monomer having a norbornene group in admixture with a comonomer comprising a 1:1 Diels-Alder adduct of cyclopentadiene with 1,5-cyclooctadiene. ### Claim 61 (depends on 22) The process of claim 22, wherein said metathesis catalyst system includes a catalyst and an activator, said catalyst being a tungsten compound and said activator being selected from the group consisting of tetraalkyl tin compounds and alkylaluminum compounds; wherein said cycloolefin monomer is selected from the following monomers: ##STR22## where R and R.sup.1 are independently selected from hydrogen, alkyl groups of 1 to 20 carbon atoms, and saturated and unsaturated cyclic groups formed by R and R.sup.1 and the two ring carbon atoms, and R.sup.2 and R.sup.3 are independently selected from hydrogen and alkyl groups containing 1 to 20 carbon atoms. ### Claim 62 A solid, infusible, crosslinked copolymer, prepared by metathesis-catalyzed, ring-opening polymerization of a monomer charge comprising a cycloolefin monomer having a norbornene group in admixture with a comonomer selected from the group consisting of ethylene-bis-(5-norbornene-2-carboxylate), ethylene-bis-(2-methyl-5-norbornene-2-carboxylate), 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxylate), bis-(2-hydroxymethyl-5-norbornene adipate), trimethylolpropane-tris-(5-norbornene-2-carboxylate), and 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene; wherein said polymerization is in the presence of (a) a catalyst that is a tungsten compound and (b) an activator comprising at least one member selected from the group consisting of tetraalkltin compounds and trialkylaluminum compounds. ### Claim 63 (depends on 62) The copolymer of claim 62, wherein the cyclolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 30% by weight. ### Claim 64 (depends on 62) The copolymer of claim 62, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is from about 1% to 30% by weight. ### Claim 65 (depends on 62) The copolymer of claim 62, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 20% by weight. ### Claim 66 (depends on 62) The copolymer of claim 62, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is from about 5% to 20% by weight. ### Claim 67 (depends on 62) The copolymer of claim 62, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is from about 10% to 20% by weight.