Cycloolefin copolymerization method, feed composition and product

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.

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.

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.

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.

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.

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.

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).

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.

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.

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.

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.

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.

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.