Multiple non-coordinating anion activators for propylene-ethylene-diene monomer polymerization reactions

Patent metadata

Field	Value
Publication number	US-11053329-B2
Application number	US-201916356826-A
Country	US
Kind code	B2
Filing date	Mar 18, 2019
Priority date	Mar 19, 2018
Publication date	Jul 6, 2021
Grant date	Jul 6, 2021

Abstract

This invention relates to production of propylene-predominant copolymers using a transition metal complex and at least two different non-coordinating anion activators. An olefinic feed comprising a C 3 -C 40 alpha olefin, ethylene, and a diene monomer is contacted under polymerization reaction conditions with a catalyst system comprising a first non-coordinating anion activator, a second non-coordinating borate activator differing from the first non-coordinating anion activator, and a transition metal complex comprising a tetrahydro-s-indacenyl or tetrahydro-as-indacenyl group bound to a group 3-6 transition metal. A molar ratio of the first non-coordinating anion activator to the second non-coordinating anion activator is sufficient to produce a melt flow rate under the polymerization reaction conditions for the resulting copolymer of about 30 g/10 min or below as determined by ASTM D-1238 (230° C., 2.16 kg).

First claim

What is claimed is:

1. A method comprising:
1) contacting a catalyst system with an olefinic feed comprising a C 3 -C 40 alpha olefin, ethylene, and a diene monomer under polymerization reaction conditions where the C 3 -C 40 alpha olefin is present in the olefinic feed in a molar excess relative to a combined molar amount of the ethylene and the diene monomer, the catalyst system comprising a first non-coordinating anion activator, a second non-coordinating anion activator differing from the first non-coordinating anion activator, and a transition metal complex represented by the formula:
T y C p′ m MG n X q

wherein:
M is a group 3, 4, 5, or 6 transition metal;
Cp′ is an optionally substituted tetrahydro-s-indacenyl or tetrahydro-as-indacenyl group;
G is a heteroatom containing group having a formula of JR′ z-y ;
wherein J is N, P, O or S, R′ is a C 1 to C 100 optionally substituted hydrocarbyl, halocarbyl, silylcarbyl, or germylcarbyl group, and z is 2 when J is N or P, and z is 1 when J is O or S;
T is a bridging group and y is 0 or 1 indicating an absence (y=0) or a presence (y=1) of T, wherein when y is 1 Cp′ and G are bonded to the bridging group;
each X is, independently, a leaving group, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene;
m=1;
n=1, 2 or 3;
q=1, 2 or 3;
wherein a sum of m+n+q is equal to the oxidation state of M; and
2) obtaining a copolymer comprising 1 to 35 mol. % ethylene, 98.9 to 65 mol. % C 3 -C 40 olefin, and 0.1 to 10 mol. % diene monomer having an MFR of 30 g/10 min or below,
wherein the first non-coordinating anion activator and the second non-coordinating anion activator interact synergistically under the polymerization reaction conditions such that melt flow rate of the copolymer changes non-linearly as a function of molar ratio of the first non-coordinating anion activator to the second non-coordinating anion activator, when measured under same polymerization conditions, except for having different activator ratios.

2. The method of claim 1 , wherein the transition metal complex comprises a tetrahydro-as-indacenyl group represented by the formula:

wherein:
M is a group 4 transition metal;
each R d , R e and R f is independently hydrogen or a C 1 -C 10 alkyl group;
each R 2 , R 3 , R 6 , and R 7 is independently hydrogen or a C 1 -C 50 optionally substituted hydrocarbyl, halocarbyl, silylcarbyl or germylcarbyl group; and
J is N, P, O or S, and z is 2 when J is N or P, and z is 1 when J is O or S, R′ is a C 1 to C 100 optionally substituted hydrocarbyl, halocarbyl, silylcarbyl or germylcarbyl group.

3. The method of claim 1 , wherein the transition metal complex comprises a tetrahydro-s-indacenyl group represented by the formula:

wherein:
M is a group 4 transition metal;
each R a is independently a C 1 -C 10 alkyl group;
each R b and R c is independently hydrogen or a C 1 -C 50 alkyl group;
each R 2 , R 3 , R 4 and R 7 is independently hydrogen or a C 1 -C 50 optionally substituted hydrocarbyl, halocarbyl, silylcarbyl or germylcarbyl group, optionally provided that:
1) R 3 and/or R 4 are not aryl or substituted aryl,
2) R 3 is not directly bonded to a group 15 or 16 heteroatom, and
3) adjacent R 4 , R c , R a R b , or R 7 do not join together to form a fused ring system; and

J is N, P, O or S, and z is 2 when J is N or P, and z is 1 when J is O or S, R′ is a C 1 to C 100 optionally substituted hydrocarbyl, halocarbyl, silylcarbyl or germylcarbyl group.

4. The method of claim 1 , wherein the polymerization reaction occurs at 80° C. or more.

5. The method of claim 1 , wherein the molar ratio of the first non-coordinating anion activator to the second non-coordinating anion activator ranges from 1:99 to 99:1.

6. The method of claim 3 , wherein each R a is methyl and each R b and R c are hydrogen.

7. The method of claim 3 , wherein R 2 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof, and R 3 , R 4 and R 7 are all hydrogen.

8. The method of claim 2 , wherein each R d is methyl and each R c and R f are hydrogen.

9. The method of claim 2 , wherein R 2 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or an isomer thereof, and R 3 , R 6 , and R 7 are all hydrogen.

10. The method of claim 2 , wherein R 2 is methyl and y is 1.

11. The method of claim 1 , wherein y is 1 and T is (CR 8 R 9 ) x , SiR 8 R 9 , or GeR 8 R 9 ;
wherein x is 1 or 2, and R 8 and R 9 are independently hydrogen or an optionally substituted hydrocarbyl, halocarbyl, silylcarbyl, or germylcarbyl group and R 8 and R 9 are optionally bonded together to form a ring structure.

12. The method of claim 1 , wherein M is Ti.

13. The method of claim 1 , wherein J is N.

14. The method of claim 1 , wherein R′ is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, phenyl or an isomer thereof.

15. The method of claim 1 , wherein R′ is t-butyl, neopentyl, cyclohexyl, cyclooctyl, cyclododecyl, adamantyl, or norbornyl.

16. The method of claim 1 , wherein each X is independently selected from the group consisting of a C 1 -C 20 hydrocarbyl group, an aryl group, a hydride, an amide, an alkoxide, a sulfide, a phosphide, and a halide.

17. The method of claim 1 , wherein each X is independently selected from the group consisting of a C 1 -C 5 alkyl group, a halide, and an aryl group.

18. The method of claim 1 , wherein the transition metal complex is selected from the group consisting of dimethylsilylene(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R) 2 ; dimethylsilylene(6,6-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R) 2 ; dimethylsilylene(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R) 2 ; dimethylsilylene(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R) 2 ; dimethylsilylene(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(cyclododecylamido)M(R) 2 ; dimethylsilylene(6,6-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(cyclododecylamido)M(R) 2 ; dimethylsilylene(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclododecylamido)M(R) 2 ; dimethylsilylene(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclododecylamido)M(R) 2 ; dimethylsilylene(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(cyclohexylamido)M(R) 2 ; dimethylsilylene(6,6-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(cyclohexylamido)M(R) 2 ; dimethylsilylene(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclohexylamido)M(R) 2 ; dimethylsilylene(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclohexylamido)M(R) 2 ; dimethylsilylene(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(adamantylamido)M(R) 2 ; dimethylsilylene(6,6-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(adamantylamido)M(R) 2 ; dimethylsilylene(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(adamantylamido)M(R) 2 ; dimethylsilylene(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(adamantylamido)M(R) 2 ; dimethylsilylene(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(neopentylamido)M(R) 2 ; dimethylsilylene(6,6-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(neopentylamido)M(R) 2 ; dimethylsilylene(2

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Shah Rhutesh K
• Canich Jo Ann M
• Blok Edward J

Classifications

• C08L23/16

  Ethylene-propylene or ethylene-propylene-diene copolymers · CPC title

• C09J123/16 Primary

  Elastomeric} ethylene-propylene or ethylene-propylene-diene copolymers {, e.g. EPR and EPDM rubbers · CPC title

• C08J3/24

  Crosslinking, e.g. vulcanising, of macromolecules (mechanical aspects B29C35/00; crosslinking agents C08K) · CPC title

• B60C1/0025

  Compositions of the sidewalls · CPC title

• C08F2800/10

  as molar percentages · CPC title