Processes for producing high propylene content PEDM having low glass transition temperatures using tetrahydroindacenyl catalyst systems

Patent metadata

Field	Value
Publication number	US-10894841-B2
Application number	US-201916356772-A
Country	US
Kind code	B2
Filing date	Mar 18, 2019
Priority date	Mar 19, 2018
Publication date	Jan 19, 2021
Grant date	Jan 19, 2021

Abstract

The present disclosure provides methods for producing an olefin polymer by contacting a C 3 -C 40 olefin, ethylene and a diene with a catalyst system including an activator and a metallocene catalyst compound comprising a substituted or unsubstituted indacenyl group and obtaining a C 3 -C 40 olefin-ethylene-diene terpolymer typically comprising from 30 to 55 mol % ethylene, from 69.09 to 45 mol % C 3 to C 40 comonomer, and from 0.01 to 7 mol % diene wherein the Tg of the terpolymer is −28° C. or less. Preferably, a propylene-ethylene-ethylidene norbornene is obtained.

First claim

What is claimed is:

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

wherein:
Cp′ is a tetrahydro-s-indacenyl group which 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 a C 3 -C 40 olefin-ethylene-diene terpolymer comprising from 30 to 55 mol % of ethylene, from 70 to 55 mol % C 3 -C 40 olefin, and from 0.01 to 7 mol % diene, and wherein the T g of the terpolymer is −28° C. or lower, and the terpolymer produced has a T g (° C.) greater than or equal to −6.886−(87.98*E)+294*D) and less than or equal to −1.886−(87.98*E)+(294*D) and E is the mole fraction of ethylene in the polymer and D is the mole fraction of diene in the terpolymer.

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 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 , R 2 , and R 7 are hydrogen.

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

6. 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 or germylcarbyl.

7. The method of claim 1 wherein M is Ti.

8. The method of claim 1 wherein J is N.

9. The method of claim 2 wherein R′ is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, phenyl or an isomer thereof.

10. 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.

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

12. The method of claim 1 , wherein the catalyst 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-y1)(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 ;
dimethylsilylene(2-methyl-7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R) 2 ;
dimethylsilylene(7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R) 2 ;
dimethylsilylene(2-methyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacen-1-y1)(cyclododecylamido)M(R) 2 ;
dimethylsilylene(6,6-diethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(cyclododecylamido)M(R) 2 ;
dimethylsilylene(2-methyl-7,7-diethyl-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 ;
diethylsilylene(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R) 2 ;
diethylsilylene(6,6-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R) 2 ;
diethylsilylene(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R) 2 ;
diethylsilylene(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R) 2 ;
dimethylsilylene(2-methyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclohexylamido)M(R) 2 ;
dimethylsilylene(2-methyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclododecylamido)M(R) 2 ;
dimethylsilylene(2-methyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(adamantylamido)M(R) 2 ; and
dimethylsilylene(2-methyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R) 2 ;
where M is selected from a group consisting of Ti, Zr, and Hf and R is selected from halogen or C 1 to C 5 alkyl.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Canich Jo Ann M
• Hagadorn John R
• Shah Rhutesh K
• Barsan Florin
• Mattler Sarah J
• Eckert Chase A
• Bai Zhifeng

Classifications

• C08F236/20

  unconjugated · CPC title

• C09J123/16 Primary

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

• C08F2420/02

  Cp or analog bridged to a non-Cp X anionic donor · CPC title

• B60C1/00

  Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition · CPC title

• C08J3/24

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