Cycloolefin copolymerization method, feed composition and product

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 6 , the polar cycloolefin is an ester, and the composition also includes an activator.

What I claim and desire to protect by Letters Patent is: 
     
       1. A . .substantially.!. cross-linked copolymer product comprising polymerized units of dicyclopentadiene and a comonomer selected from the group consisting of .Iadd.bis(.Iaddend.2-hydroxymethyl-5-norbornene.Iadd.) .Iaddend.adipate;   . .methyl-5-norbornene-2-carboxylate;.!.   ethylene. .-.!.bis. .-.!.(5-norbornene-2-carboxylate);   2-hydroxymethyl-5-norbornene acetate.Iadd.; and .Iaddend.   ethylene. .-.!.bis. .-.!.(.Iadd.2-methyl-.Iaddend.5-norbornene-2-carboxylate). .; and, said copolymer product having a glass transition temperature of at least 145° C., and a swell of less than about 245% in toluene after for 16 hours.!..   
     
     
       2. A method of rate moderated dicyclopentadiene polymerization comprising: contacting dicyclopentadiene, cycloolefin comonomer, an . .aluminum containing.!. .Iadd.alkylaluminum .Iaddend.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   .Iadd.bis(.Iaddend.2-hydroxymethyl-5-norbornene.Iadd.) .Iaddend.adipate;   . .methyl-5-norbornene-2-carboxylate;.!.   ethylene. .-.!.bis. .-.!.(5-norbornene-2-carboxylate);   2-hydroxymethyl-5-norbornene acetate.Iadd.; .Iaddend.or   ethylene. .-.!.bis. .-.!.(2-methyl-5-norbornene-2-carboxylate).Iadd.; and .Iaddend.   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. . .   
     
     
       3.  The composition of claim 1 wherein said glass transition temperature is at least 153° C..!.. .4. The composition of claim 1 wherein said glass transition temperature is at least 160° C..!.. .5. The composition of claim 1 wherein said glass transition temperature is at least 165° C..!.. .6. The composition of claim 1 wherein said glass transition temperature is at least 175° 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° 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° C..!..Iadd.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..Iaddend..Iadd.10. The copolymer of claim 9, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 30% by weight..Iaddend..Iadd.11. 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..Iaddend..Iadd.12.  The copolymer of claim 9, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 20% by weight..Iaddend..Iadd.13. The copolymer of claim 9, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is from 5% to 20% by weight..Iaddend..Iadd.14. 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..Iaddend..Iadd.15. The copolymer of claim 9, wherein the comonomer comprises 
     
     
        1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene..Iaddend..Iadd.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..Iaddend..Iadd.17.  The copolymer of claim 16, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 30% by weight..Iaddend..Iadd.18. 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..Iaddend..Iadd.19. 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..Iaddend..Iadd.20. 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..Iaddend..Iadd.21. 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..Iaddend..Iadd.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..Iaddend..Iadd.23. The process of claim 22, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 30% by weight..Iaddend..Iadd.24. 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..Iaddend..Iadd.25. The process of claim 22, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 20% by weight..Iaddend..Iadd.26. 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..Iaddend..Iadd.27.  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..Iaddend..Iadd.28. The process of claim 22, wherein the comonomer is 1,4,5,8-dimethano-1,4,4a,5,8,8a-hexahydronaphthalene..Iaddend..Iadd.29. 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..Iaddend..Iadd.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..Iaddend..Iadd.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..Iaddend..Iadd.32. The process of claim 31, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 30% by weight..Iaddend..Iadd.33. 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..Iaddend..Iadd.34. The process of claim 31, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 20% by weight..Iaddend..Iadd.35. 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..Iaddend..Iadd.36. 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..Iaddend..Iadd.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 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 1  together with the two ring carbon atoms connected thereto, and where R 2  and R 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..Iaddend..Iadd.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 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 1  together with the two ring carbon atoms connected thereto, and where R 2  and R 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)..Iaddend..Iadd.39.  The process of claim 38, wherein the cycloolefin monomer is dicyclopentadiene..Iaddend..Iadd.40. The process of claim 38, wherein the amount of comonomer is between about 1 and 25 weight percent, based on total weight of monomers..Iaddend..Iadd.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 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 1  together with the two ring carbon atoms, and where R 2  and R 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..Iaddend..Iadd.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 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 1  together with the two ring carbon atoms, and where R 2  and R 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..Iaddend..Iadd.43.  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..Iaddend..Iadd.44. The copolymer of claim 42, wherein the cycloolefin monomer is dicyclopentadiene..Iaddend..Iadd.45. 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..Iaddend..Iadd.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..Iaddend..Iadd.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..Iaddend..Iadd.48. 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° C., of less than about 200..Iaddend..Iadd.49. The process of claim 48, wherein the crosslinked polymer has a percent swell of less than 150..Iaddend..Iadd.50. The process of claim 49, wherein the crosslinked polymer has a percent swell of less than 
     
     
        100..Iaddend..Iadd.     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..Iaddend..Iadd.52. The process of claim 47, wherein the comonomer comprises etheylene-bis-(5-norbornene-2-carboxylate)..Iaddend..Iadd.53. The process of claim 47, wherein the comonomer comprises ethylene-bis-(2-methyl-5-norbornene-2-carboxylate)..Iaddend..Iadd.54. The process of claim 47, wherein the comonomer comprises 1,4-butane-bis-(2-methyl-5-norbornene-2-carboxyalte)..Iaddend..Iadd.55. The process of claim 47, wherein the comonomer comprises bis-(2-hydroxymethyl-5-norbornene adipate)..Iaddend..Iadd.56. The process of claim 47, wherein the comonomer comprises trimethylolpropane-tris-(5-norbornene-2-carboxylate)..Iaddend..Iadd.57. The process of claim 47, wherein the comonomer comprises 
     
     
        dimethanohexahydronaphthalene..Iaddend..Iadd.58.  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 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 1  and the two ring carbon atoms connected thereto, and where R 2  and R 3  are independently selected from hydrogen and 
     
     
        alkyl groups containing 1 to 20 carbon atoms..Iaddend..Iadd.59.  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..Iaddend..Iadd.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..Iaddend..Iadd.61. 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 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 1  and the two ring carbon atoms, and R 2  and R 3  are independently selected from hydrogen and alkyl groups 
     
     
        containing 1 to 20 carbon atoms..Iaddend..Iadd.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..Iaddend..Iadd.63. The copolymer of claim 62, wherein the cyclolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 30% by weight..Iaddend..Iadd.64. 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..Iaddend..Iadd.65. The copolymer of claim 62, wherein the cycloolefin monomer is dicyclopentadiene and the amount of the comonomer is up to about 20% by weight..Iaddend..Iadd.66. 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..Iaddend..Iadd.67.  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..Iaddend.