High propylene content EP having low glass transition temperatures

Patent metadata

Field	Value
Publication number	US-12305028-B2
Application number	US-202017626601-A
Country	US
Kind code	B2
Filing date	Jul 17, 2020
Priority date	Jul 17, 2019
Publication date	May 20, 2025
Grant date	May 20, 2025

Abstract

The present disclosure provides methods for producing an olefin polymer by contacting a C 3 -C 40 olefin and ethylene with a catalyst system including an activator and a metallocene catalyst compound comprising a substituted or unsubstituted tetrahydro-s-indacenyl group and obtaining a C 3 -C 40 olefin-ethylene copolymer typically comprising from 0.5 to 43 wt % ethylene, and from 99.5 to 57 wt % C 3 to C 40 comonomer wherein the Tg of the terpolymer is from 0 to −60° C.

First claim

What is claimed is:

1. A method for producing a C 3 -C 40 olefin-ethylene copolymer comprising:
contacting a C 3 -C 40 olefin and ethylene with a catalyst system comprising an activator and a catalyst compound represented by formula (I):
T y Cp′ m MG n X q   (I)

wherein: Cp′ is a tetrahydroindacenyl group, wherein the tetrahydroindacenyl group tetrahydro-s-indacenyl or tetrahydro-as-indacenyl, and wherein the tetrahydroindacenyl group is optionally substituted or unsubstituted, provided that when Cp′ is tetrahydro-s-indacenyl: 1) the 3 and/or 4 positions are not aryl or substituted aryl, 2) the 3 position is not directly bonded to a group 15 or 16 heteroatom, 3) there are no additional rings fused to the tetrahydroindacenyl ligand, 4) T is not bonded to the 2-position, and 5) the 5, 6, or 7-position is geminally disubstituted;
M is a group 3, 4, 5, or 6 transition metal;
T is a bridging group;
y is 0 or 1, indicating the absence or presence of T;
G is a heteroatom group represented by the formula JR i z-y where J is N, P, O or S,
R i is a C 1 to C 100 hydrocarbyl group, and z is 2 when J is N or P, and z is 1 when J is O or S;
X is a leaving group;

m=1; n=1, 2 or 3; q=1, 2 or 3; and the sum of m+n+q is equal to the oxidation state of the transition metal; and
obtaining the a C 3 -C 40 olefin-ethylene copolymer comprising from 0.5 to 43 wt % of ethylene, and from 99.5 to 57 wt % C 3 -C 40 olefin, and wherein the copolymer has a T g (° C.) is from 0 to −60° C.

2. The method of claim 1 , wherein the catalyst compound is represented

by formula (II):
where M is a group 4 metal;
J is N, O, S or P;
p is 2 when J is N or P, and is 1 when J is O or S;
each R a is independently C 1 -C 10 alkyl;
each R b and each R c is independently hydrogen or a C 1 -C 10 alkyl;
each R 2 , R 3 , R 4 , and R 7 is independently hydrogen, or a C 1 -C 50 substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl or germylcarbyl, 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 b , R a , or R 7 do not join together to form a fused ring system;
each R′ is independently a C 1 -C 100 substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl or germylcarbyl;
T is a bridging group and y is 0 or 1 indicating the absence (y=0) or presence (y=1) of T;
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.

3. The method of claim 2 , wherein both R a are methyl and all R b and R c are hydrogen.

4. 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 4 , and R 7 are hydrogen.

5. The method of claim 1 , wherein the catalyst compound is represented by formula (III):

where M is a group 4 metal;
J is N, O, S or P;
p is 2 when J is N or P, and is 1 when J is O or S;
each R d , R e and R f is independently hydrogen or a C 1 -C 10 alkyl;
each R 2 , R 3 , R 6 , and R 7 is independently hydrogen, or a C 1 -C 50 substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl or germylcarbyl;
each R′ is, independently, a C 1 -C 100 substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl or germylcarbyl;
T is a bridging group and y is 0 or 1 indicating the absence (y=0) or presence (y=1) of T;
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.

6. The method of claim 5 , wherein both R d are methyl and all R e and R f are hydrogen.

7. The method of claim 5 , 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 hydrogen.

8. The method of claim 2 , wherein R 2 is methyl.

9. The method of claim 2 , wherein y is 1 and T is (CR 8 R 9 ) x , SiR 8 R 9 , or GeR 8 R 9 where x is 1 or 2, and R 8 and R 9 are independently selected from hydrogen or substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl and germylcarbyl and R 8 and R 9 may optionally be bonded together to form a ring structure.

10. The method of claim 5 , wherein y is 1 and T is (CR 8 R 9 ) x , SiR 8 R 9 , or GeR 8 R 9 where x is 1 or 2, and R 8 and R 9 are independently selected from hydrogen or substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl and germylcarbyl and R 8 and R 9 may optionally be bonded together to form a ring structure.

11. The method of claim 1 , wherein each X is, independently, selected from hydrocarbyl radicals having from 1 to 20 carbon atoms, aryls, hydrides, amides, alkoxides, sulfides, phosphides, halides, amines, phosphines, ethers, or a combination thereof, and wherein two X's optionally form a part of a metallocycle ring, or two X's are joined to form a chelating ligand, diene ligand or alkylidene.

12. The method of claim 1 , wherein each X is independently selected from halides, aryls or C 1 to C 5 alkyl groups.

13. The method of claim 1 , wherein the catalyst compound is one or more 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(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(neopentylamido)M(R) 2 ;
dimethylsilylene(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(neopentylamido)M(R) 2 ;
dimethylsilylene(2-methyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R) 2 ;
dimethylsilylene(6,6-diethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R) 2 ;
dimeth

Assignees

• Exxonmobil Chemical Patents Inc
• Exxonmobil Engineering & Tech Company

Inventors

• Bai Zhifeng
• Canich Jo Ann M
• Zhang Jingwen
• Jiang Peijun
• Barry Adrian Garcia
• Eckert Chase A
• Mattler Sarah J

Classifications

• C08F210/16

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

• C09J2467/006

  in the substrate · CPC title

• C09J2423/16

  Presence of ethen-propene or ethene-propene-diene copolymers · CPC title

• C08L2205/025

  containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure · CPC title

• C08J3/24

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