Stereoregular cyclopolymers and method

Claim 1

A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR6## where C 1 ,C 2 , and C 3 designate respectively the first, second, and third carbon in the ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of: (a) providing nonconjugated diolefins having the following structural formula: ##STR7## where n is an integer between about 0 and 3 and R 1 and R 2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R 1 is connected to R 2 by a chain of atoms; and (b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) an achiral metallocene derivative (C 5 R' 5 ) 2 MX 2 , where (C 5 R' 5 ) is a substituted or nonsubstituted cyclopentadienyl ligand, R' is a hydrogen or hydrocarbyl substituent, M is Zr, Hf, or Ti, and X is any uninegative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound wherein the polymers synthesized are predominately atactic.

Claim 2

A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR6## where C 1 ,C 2 , and C 3 designate respectively the first, second, and third carbon in the ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of: (a) providing nonconjugated diolefins having the following structural formula: ##STR7## where n is an integer between about 0 and 3 and R 1 and R 2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R 1 is connected to R 2 by a chain of atoms; and (b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) an achiral metallocene derivative (C 5 R' 5 ) 2 MX 2 , where (C 5 R' 5 ) is a substituted or nonsubstituted cyclopentadienyl ligand, R' is a hydrogen or hydrocarbyl substituent, M is Zr, Hf, or Ti, and X is any uninegative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound wherein the polymers synthesized are predominately atactic.

Claim 3

A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR8## where C 1 ,C 2 , and C 3 designate respectively the first, second, and third carbon int he ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of: (a) providing nonconjugated diolefins having the following structural formula: ##STR9## where n is an integer between about 0 and 3 and R 1 and R 2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R 1 is connected to R 2 by a chain of atoms; and (b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) an achiral metallocene derivative (C 5 R' 5 ) 2 MX 2 , where (C 5 R' 5 ) is a substituted or nonsubstituted cyclopentadienyl ligand, R' is a hydrogen or hydrocarbyl substituent, M is Zr, Hf, or Ti, and X is any uninegative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound; and (c) controlling the temperature of the diolefins and catalyst system to regulate the trans selectivity in the cyclopolymerization.

Claim 4

A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR8## where C 1 ,C 2 , and C 3 designate respectively the first, second, and third carbon int he ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of: (a) providing nonconjugated diolefins having the following structural formula: ##STR9## where n is an integer between about 0 and 3 and R 1 and R 2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R 1 is connected to R 2 by a chain of atoms; and (b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) an achiral metallocene derivative (C 5 R' 5 ) 2 MX 2 , where (C 5 R' 5 ) is a substituted or nonsubstituted cyclopentadienyl ligand, R' is a hydrogen or hydrocarbyl substituent, M is Zr, Hf, or Ti, and X is any uninegative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound; and (c) controlling the temperature of the diolefins and catalyst system to regulate the trans selectivity in the cyclopolymerization.

Claim 5

A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR10## where C 1 ,C 2 , and C 3 designate respectively the first, second, and third carbon int he ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of: (a) providing nonconjugated diolefins having the following structural formula: ##STR11## where n is an integer between about 0 and 3 and R 1 and R 2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R 1 is connected to R 2 by a chain of atoms; and (b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) an achiral metallocene derivative (C 5 R' 5 ) 2 MX 2 , where (C 5 R' 5 ) is a substituted or nonsubstituted cyclopentadienyl ligand, R' is a hydrogen or hydrocarbyl substituent, M is Zr, Hf, or Ti, and X is any uninegative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound wherein the polymers synthesized are predominately isotactic.

Claim 6

A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR10## where C 1 ,C 2 , and C 3 designate respectively the first, second, and third carbon int he ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of: (a) providing nonconjugated diolefins having the following structural formula: ##STR11## where n is an integer between about 0 and 3 and R 1 and R 2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R 1 is connected to R 2 by a chain of atoms; and (b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) an achiral metallocene derivative (C 5 R' 5 ) 2 MX 2 , where (C 5 R' 5 ) is a substituted or nonsubstituted cyclopentadienyl ligand, R' is a hydrogen or hydrocarbyl substituent, M is Zr, Hf, or Ti, and X is any uninegative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound wherein the polymers synthesized are predominately isotactic.

Claim 7

A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR12## where C 1 ,C 2 , and C 3 designate respectively the first, second, and third carbon int he ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of: (a) providing nonconjugated diolefins having the following structural formula: ##STR13## where n is an integer between about 0 and 3 and R 1 and R 2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R 1 is connected to R 2 by a chain of atoms; and (b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) an achiral metallocene derivative (C 5 R' 5 ) 2 MX 2 , where (C 5 R' 5 ) is a substituted or nonsubstituted cyclopentadienyl ligand, R' is a hydrogen or hydrocarbyl substituent, M is Zr, Hf, or Ti, and X is any uninegative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound wherein the substituents of C 1 and C 3 of the monomers in the polymers synthesized are predominately in the trans position.

Claim 8

A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR12## where C 1 ,C 2 , and C 3 designate respectively the first, second, and third carbon int he ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of: (a) providing nonconjugated diolefins having the following structural formula: ##STR13## where n is an integer between about 0 and 3 and R 1 and R 2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R 1 is connected to R 2 by a chain of atoms; and (b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) an achiral metallocene derivative (C 5 R' 5 ) 2 MX 2 , where (C 5 R' 5 ) is a substituted or nonsubstituted cyclopentadienyl ligand, R' is a hydrogen or hydrocarbyl substituent, M is Zr, Hf, or Ti, and X is any uninegative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound wherein the substituents of C 1 and C 3 of the monomers in the polymers synthesized are predominately in the trans position.

Claim 9

A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR14## where C 1 ,C 2 , and C 3 designate respectively the first, second, and third carbon in the ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of: (a) providing nonconjugated diolefins having the following structural formula: ##STR15## where n is an integer between about 0 and 3 and R 1 and R 2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R 1 is connected to R 2 by a chain of atoms; and (b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) a chiral stereorigid metallocene described by the formula: R"(C.sub.5 (R').sub.4).sub.2 MX.sub.2 wherein (C 5 (R') 4 ) is a cyclopentadienyl or substituted cyclopentadienyl ring, including indenyl and tetrahydroindenyl rings; each R' is a hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms; R" is an organic or inorganic group providing a structural bridge between the two (C 5 (R') 4 ) rings imparting stereorigidity to the said catalyst; M is Zr, Hf, or Ti; and X is any uni-negative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound wherein the polymers synthesized are predominately atactic.

Claim 10

A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR14## where C 1 ,C 2 , and C 3 designate respectively the first, second, and third carbon in the ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of: (a) providing nonconjugated diolefins having the following structural formula: ##STR15## where n is an integer between about 0 and 3 and R 1 and R 2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R 1 is connected to R 2 by a chain of atoms; and (b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) a chiral stereorigid metallocene described by the formula: R"(C.sub.5 (R').sub.4).sub.2 MX.sub.2 wherein (C 5 (R') 4 ) is a cyclopentadienyl or substituted cyclopentadienyl ring, including indenyl and tetrahydroindenyl rings; each R' is a hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms; R" is an organic or inorganic group providing a structural bridge between the two (C 5 (R') 4 ) rings imparting stereorigidity to the said catalyst; M is Zr, Hf, or Ti; and X is any uni-negative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound wherein the polymers synthesized are predominately atactic.

Claim 11

A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR16## where C 1 ,C 2 , and C 3 designate respectively the first, second, and third carbon int he ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of: (a) providing nonconjugated diolefins having the following structural formula: ##STR17## where n is an integer between about 0 and 3 and R 1 and R 2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R 1 is connected to R 2 by a chain of atoms; (b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) a chiral stereorigid metallocene described by the formula: R"(C.sub.5 (R').sub.4).sub.2 MX.sub.2 wherein (C 5 (R') 4 ) is a cyclopentadienyl or substituted cyclopentadienyl ring, including indenyl and tetrahydroindenyl rings; each R' is a hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms; R" is an organic or inorganic group providing a structural bridge between the two (C 5 (R') 4 ) rings imparting stereorigidity to the said catalyst; M is Zr, Hf, or Ti; and X is any uni-negative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound; and (c) controlling the temperature of the diolefins and catalyst system to regulate the trans selectivity in the cyclopolymerization.

Claim 12

A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR16## where C 1 ,C 2 , and C 3 designate respectively the first, second, and third carbon int he ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of: (a) providing nonconjugated diolefins having the following structural formula: ##STR17## where n is an integer between about 0 and 3 and R 1 and R 2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R 1 is connected to R 2 by a chain of atoms; (b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) a chiral stereorigid metallocene described by the formula: R"(C.sub.5 (R').sub.4).sub.2 MX.sub.2 wherein (C 5 (R') 4 ) is a cyclopentadienyl or substituted cyclopentadienyl ring, including indenyl and tetrahydroindenyl rings; each R' is a hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms; R" is an organic or inorganic group providing a structural bridge between the two (C 5 (R') 4 ) rings imparting stereorigidity to the said catalyst; M is Zr, Hf, or Ti; and X is any uni-negative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound; and (c) controlling the temperature of the diolefins and catalyst system to regulate the trans selectivity in the cyclopolymerization.

Claim 13

A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR18## where C 1 ,C 2 , and C 3 designate respectively the first, second, and third carbon int he ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of: (a) providing nonconjugated diolefins having the following structural formula: ##STR19## where n is an integer between about 0 and 3 and R 1 and R 2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R 1 is connected to R 2 by a chain of atoms; and (b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) a chiral stereorigid metallocene described by the formula: R"(C.sub.5 (R').sub.4).sub.2 MX.sub.2 wherein (C 5 (R') 4 ) is a cyclopentadienyl or substituted cyclopentadienyl ring, including indenyl and tetrahydroindenyl rings; each R' is a hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms; R" is an organic or inorganic group providing a structural bridge between the two (C 5 (R') 4 ) rings imparting stereorigidity to the said catalyst; M is Zr, Hf, or Ti; and X is any uni-negative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound wherein the polymers synthesized are predominately isotactic.

Claim 14

A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR18## where C 1 ,C 2 , and C 3 designate respectively the first, second, and third carbon int he ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of: (a) providing nonconjugated diolefins having the following structural formula: ##STR19## where n is an integer between about 0 and 3 and R 1 and R 2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R 1 is connected to R 2 by a chain of atoms; and (b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) a chiral stereorigid metallocene described by the formula: R"(C.sub.5 (R').sub.4).sub.2 MX.sub.2 wherein (C 5 (R') 4 ) is a cyclopentadienyl or substituted cyclopentadienyl ring, including indenyl and tetrahydroindenyl rings; each R' is a hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms; R" is an organic or inorganic group providing a structural bridge between the two (C 5 (R') 4 ) rings imparting stereorigidity to the said catalyst; M is Zr, Hf, or Ti; and X is any uni-negative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound wherein the polymers synthesized are predominately isotactic.

Claim 15

A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR20## where C 1 ,C 2 , and C 3 designate respectively the first, second, and third carbon int he ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of: (a) providing nonconjugated diolefins having the following structural formula: ##STR21## where n is an integer between about 0 and 3 and R 1 and R 2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R 1 is connected to R 2 by a chain of atoms; and (b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) a chiral stereorigid metallocene described by the formula: R"(C.sub.5 (R').sub.4).sub.2 MX.sub.2 wherein (C 5 (R') 4 ) is a cyclopentadienyl or substituted cyclopentadienyl ring, including indenyl and tetrahydroindenyl rings; each R' is a hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms; R" is an organic or inorganic group providing a structural bridge between the two (C 5 (R') 4 ) rings imparting stereorigidity to the said catalyst; M is Zr, Hf, or Ti; and X is any uni-negative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound wherein the substituents of C 1 and C 3 of the monomers in the polymers synthesized are predominately in the trans position.

Claim 16

A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR20## where C 1 ,C 2 , and C 3 designate respectively the first, second, and third carbon int he ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of: (a) providing nonconjugated diolefins having the following structural formula: ##STR21## where n is an integer between about 0 and 3 and R 1 and R 2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R 1 is connected to R 2 by a chain of atoms; and (b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) a chiral stereorigid metallocene described by the formula: R"(C.sub.5 (R').sub.4).sub.2 MX.sub.2 wherein (C 5 (R') 4 ) is a cyclopentadienyl or substituted cyclopentadienyl ring, including indenyl and tetrahydroindenyl rings; each R' is a hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms; R" is an organic or inorganic group providing a structural bridge between the two (C 5 (R') 4 ) rings imparting stereorigidity to the said catalyst; M is Zr, Hf, or Ti; and X is any uni-negative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound wherein the substituents of C 1 and C 3 of the monomers in the polymers synthesized are predominately in the trans position.