Process of producing polyolefins using metallocene polymerization catalysts and copolymers therefrom

Patent metadata

Field	Value
Publication number	US-9611348-B2
Application number	US-201414248671-A
Country	US
Kind code	B2
Filing date	Apr 9, 2014
Priority date	Apr 11, 2013
Publication date	Apr 4, 2017
Grant date	Apr 4, 2017

Abstract

An ethylene copolymer, a Group 4 transition metal catalyst compound, and methods for polymerization using such a compound, said compound represented by the formula: (L) p (R′) z T(Cp)(A)MX 2 , where M is a Group 4 metal; z is 0 to 8; p is 1 to 3; X is an anionic leaving group; T is a bridging group; R 1 to R 4 are hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, aryl group, substituted aryl group, or a heteroatom-containing group (where adjacent R groups can form rings); R′ is hydrogen, a C 1 to C 10 alkyl group, a C 6 to C 24 aryl group, or a C 7 to C 40 alkylaryl group; and L is a heteroatom or heteroatom-containing group bound to T, Cp is a cyclopentadienyl ring substituted with 0 to 4 substituent groups (where adjacent groups can form C 4 to C 20 rings); A is Cp or (JS′ z*-1-y ), where J is a Group 15 or 16 element; S′ is a hydrocarbyl, substituted hydrocarbyl, or heteroatom; z* is 2 or 3, and y is 0 or 1, is provided.

First claim

The invention claimed is:

1. A process for producing a polyolefin comprising contacting one or more olefin monomers with a catalyst system comprising:
1) an activator; and
2) a catalyst compound represented by the formula: (L) p (R′) z T(Cp)(A)MX 2 ,
wherein:
Cp is a cyclopentadienyl ring substituted with 0, 1, 2, 3, or 4 substituent groups R 1 , R 2 , R 3 , and/or R 4 , each substituent group R 1 , R 2 , R 3 , and/or R 4 being, independently, hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, an aryl group, or a substituted aryl group, provided that any of adjacent R 1 , R 2 , R 3 , and R 4 groups optionally form a fused ring or multicenter fused ring system where the rings are aromatic, partially saturated or saturated, where A is bound to M and T, Cp is bound to M and T, and L and R′ are bound to T;
M is a Group 4 transition metal;
z is 0, 1, 2, 3, 4, 5, 6, 7, or 8 indicating the number of R′ groups bound to the bridging group T;
p is 1, indicating the number of L groups bound to the bridging group T;
each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof, provided that two X's optionally form a part of a fused ring or a ring system;
T is a bridging group;
each R′ is, independently, hydrogen, a C 1 to C 10 alkyl group, a C 6 to C 24 aryl group, or a C 7 to C 40 alkylaryl group;
A is Cp or (JS′ z*-1-y ), where JS′ z*-1-y is a heteroatom ligand in which J is an element from Group 15 with a coordination number of 3 or an element from Group 16 with a coordination number of 2; S′ is a radical group which is a hydrocarbyl, substituted hydrocarbyl, or heteroatom; and z* is the coordination number of the element J, and y is 0 or 1; and
L is a heteroatom or heteroatom-containing group bound to T comprising perfluoroethyl, pentafluorophenyl, 2-fluorophenyl, 2,6-difluorophenyl, 2,4,6-trifluorophenyl, 2-dimethylaminophenyl, 2,3-bis(dimethylamino)phenyl, 2,4-bis(dimethylamino)phenyl, 2,5-bis(dimethylamino)phenyl, 2,6-bis(dimethylamino)phenyl, 2,4,6-tris(dimethylamino)phenyl, 2-diethylaminophenyl, 2,3-bis(diethylamino)phenyl, 2,4-bis(diethylamino)phenyl, 2,5-bis(diethylamino)phenyl, 2,6-bis(diethylamino)phenyl, 2,4,6-tris(diethylamino)phenyl, 2-diisopropylaminophenyl, 2,3-bis(diisopropylamino)phenyl, 2,4-bis(diisopropylamino)phenyl, 2,5-bis(diisopropylamino)phenyl, 2,6-bis(diisopropylamino)phenyl, 2,4,6-tris(diisopropylamino)phenyl, 2-dimethylphosphinophenyl, 2,3-bis(dimethylphosphino)phenyl, 2,4-bis(dimethylphosphino)phenyl, 2,5-bis(dimethylphosphino)phenyl, 2,6-bis(dimethylphosphino)phenyl, 2,4,6-tris(dimethylphosphino)phenyl, 2-diethylphosphinophenyl, 2,3-bis(diethylphosphino)phenyl, 2,4-bis(diethylphosphino)phenyl, 2,5-bis(diethylphosphino)phenyl, 2,6-bis(diethylphosphino)phenyl, 2,4,6-tris(diethylphosphino)phenyl, 2-diisopropylphosphinophenyl, 2,3-bis(diisopropylphosphino)phenyl, 2,4-bis(diisopropylphosphino)phenyl, 2,5-bis(diisopropylphosphino)phenyl, 2,6-bis(diisopropylphosphino)phenyl, 2,4,6-tris(diisopropylphosphino)phenyl, 2-hydroxyphenyl, 2,3-dihydroxyphenyl, 2,4-dihydroxyphenyl, 2,5-dihydroxyphenyl, 2,6-dihydroxyphenyl, 2,4,6-trihydroxylphenyl, 2,3,5,6-tetrahydroxyphenyl, 2,3,4,5,6-pentahydroxyphenyl, 2-methoxyphenyl, 2-methoxy-5-fluorophenyl, 2,3-dimethoxyphenyl, 2,4-dimethoxyphenyl, 2,5-dimethoxyphenyl, 2,6-dimethoxyphenyl, 2,4,6-trimethoxylphenyl, 2,3,5,6-tetramethoxyphenyl, 2,3,4,5,6-pentamethoxyphenyl, 2-ethoxyphenyl, 2-ethoxy-5-fluorophenyl, 2,3-diethoxyphenyl, 2,4-diethoxyphenyl, 2,5-diethoxyphenyl, 2,6-diethoxyphenyl, 2,4,6-triethoxylphenyl, 2,3,5,6-tetrathoxyphenyl, 2,3,4,5,6-pentaethoxyphenyl, 2-isopropoxyphenyl, 2-isopropoxy-5-fluorophenyl, 2,3-diisopropoxyphenyl, 2,4-diisopropoxyphenyl, 2,5-diisopropoxyphenyl, 2,6-diisopropoxyphenyl, 2,4,6-triisopropoxylphenyl, 2,3,5,6-tetraisoproxyphenyl, 2,3,4,5,6-pentaisopropoxyphenyl, 2-methylthiophenyl, 2-methylthio-5-fluorophenyl, 2,3-dimethylthiophenyl, 2,4-dimethylthiophenyl, 2,5-dimethylthiophenyl, 2,6-dimethylthiophenyl, 2,4,6-trimethylthiolphenyl, 2,3,5,6-tetramethylthiophenyl, 2,3,4,5,6-pentamethylthiophenyl, 2-ethylthiophenyl, 2-ethylthio-5-fluorophenyl, 2,3-diethylthiophenyl 2,4-diethylthiophenyl, 2,5-diethylthiophenyl, 2,6-diethylthiophenyl, 2,4,6-triethylthiolphenyl, 2,3,5,6-tetraethylthiophenyl, 2,3,4,5,6-pentaethylthiophenyl, 2-isopropylthiophenyl, 2-isopropylthio-5-fluorophenyl, 2,3-dimthylthiophenyl, 2,4-diisopropylthiophenyl, 2,5-diisopropylthiophenyl, 2,6-diisopropylthiophenyl, 2,4,6-triisopropylthiolphenyl, 2,3,5,6-tetraisopropylthiophenyl, 2,3,4,5,6-pentaisopropylthiophenyl, 2-tert-butylthiophenyl, 2-tert-butylthio-5-fluorophenyl, 2,3-dimthylthiophenyl, 2,4-ditert-butylthiophenyl, 2,5-ditert-butylthiophenyl, 2,6-ditert-butylthiophenyl, 2,4,6-tritert-butylthiolphenyl, 2,3,5,6-tetratert-butylthiophenyl, 2,3,4,5,6-pentatert-butylthiophenyl, dimethylaminomethyl, diethylaminomethyl, di-n-propylaminomethyl, di-isopropylaminomethyl, diphenylaminomethyl, 2-dimethylaminoethyl, 2-diethylaminoethyl, 2-di-n-propylaminoethyl, 2-di-iso-propyl amino ethyl, 2-diphenyl amino ethyl, 3-dimethylaminopropyl, 3-diethylaminopropyl, 3-di-n-propylaminopropyl, 3-di-isopropylaminopropyl, 3-diphenylaminopropyl, dimethylphosphinomethyl, diethylphosphinomethyl, di-n-propylphosphinomethyl, di-isopropylphosphinomethyl, diphenylphosphinomethyl, 2-dimethylphosphinoethyl, 2-diethylphosphinoethyl, 2-di-n-propylphosphinoethyl, 2-di-iso-propylphosphinoethyl, 2-diphenylphosphinoethyl, 3-dimethylphosphinopropyl, 3-diethylphosphinopropyl, 3-di-n-propylphosphinopropyl, 3-di-isopropylphosphinopropyl, 3-diphenylphosphinopropyl, methoxymethyl, ethyoxymethyl, propoxymethyl, isopropoxymethyl, tert-butoxymethyl, phenoxymethyl 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-tert-butoxyethyl, 2-phenoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-n-propoxypropyl, 3-isopropoxypropyl, 3-diphenoxypropyl, methylthiomethyl, ethylthiomethyl, propylthiomethyl, isopropylthiomethyl, tert-butylthiomethyl, phenylthiomethyl, 2-methylthioethyl, 2-propylthioethyl, 2-isopropylthioethyl, 2-tert-butylthioethyl, 2-phenylthioethyl, 3-methylthiopropyl, 3-ethylthiopropyl, 3-n-propylthiopropyl, 3-isoprylthiopropyl, 3-diphenylthiopropyl, 2-dimethylphosphinophenyl, 2-diphenylphosphinophenyl, 2-dicyclohexylphosphinophenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-(4-dimethylaminopyridyl), 3-(4-dimethylaminopyridyl), 4-(4-dimethylaminopyridyl), 2-pyrimidyl, 4-pyrimidyl, 5-pyrimidyl, 6-pyrimidyl, 2-quinolyl, 2-isoquinolyl, 2-tetrahydroisoquinolyl, 4-acridinyl, or 4-(5-methylacridinyl).

2. The process of claim 1 wherein the catalyst compound is represented by the formula:

where M is a Group 4 transition metal; z is 0, 1, 2, 3, 4, 5, 6, 7, or 8 indicating the number of R′ groups bound to the bridging group T;
p is 1, indicating the number of L groups bound to the bridging group T;
each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof, provided that two X's optionally form a part of a fused ring or a ring system;
T is a bridging group bound to each of the cyclopentadienyl groups;
each R 1 , R 2 , R 3 , and R 4 is, independently, hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, an aryl group, or a substituted aryl group, provided that any of adjacent R 1 , R 2 , R 3 , and R 4 groups optionally form a fused ring or multicenter fused ring system where the rings are aromatic, partially saturated, or saturated; and
each R′ is, independen

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Stewart Ian C
• Brown Steven D
• Atienza Crisita Carmen H
• Harris David T
• Hollas Aaron M

Classifications

• C08F4/6592

  containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring · CPC title

• C08F210/14

  Monomers containing five or more carbon atoms · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F10/00

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title