Group 4 Catalyst Compounds and Process for Use Thereof

Patent metadata

Field	Value
Publication number	US-2018237559-A1
Application number	US-201815877143-A
Country	US
Kind code	A1
Filing date	Jan 22, 2018
Priority date	Feb 20, 2017
Publication date	Aug 23, 2018
Grant date	—

Abstract

This invention relates to metallocene compounds having a group substituted at the 3 position of at least one cyclopentadienyl ring represented by the formula —CH2—SiR′3 or —CH2—CR′3 and R′ is a C1 to C20 substituted or unsubstituted hydrocarbyl.

First claim

We claim:

1 . A catalyst compound represented by the formula (A):

where:
M is Hf or Zr;
each R 1 , R 2 , and R 4 is independently hydrogen, alkoxide or a C 1 to C 40 substituted or unsubstituted hydrocarbyl group;
R 3 is independently hydrogen, alkoxide or a C 1 to C 40 substituted or unsubstituted hydrocarbyl group or is —CH 2 —SiR′ 3 or —CH 2 —CR′ 3 , and each R′ is independently a C 1 to C 20 substituted or unsubstituted hydrocarbyl, provided that at least one R′ is not H;
each R 7 , R 8 , and R 10 is independently hydrogen, alkoxide or a C 1 to C 40 substituted or unsubstituted hydrocarbyl group;
R 9 is —CH 2 —SiR′ 3 or —CH 2 —CR′ 3 , and each R′ is independently a C 1 to C 20 substituted or unsubstituted hydrocarbyl, provided that at least one R′ is not H;
T is a bridging group; and
each X is, independently, a univalent anionic ligand, or two X are joined and bound to the metal atom to form a metallocycle ring, or two X are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand.

2 . The catalyst compound of claim 1 , wherein M is Hf and Zr.

3 . The catalyst compound of claim 1 , wherein R 9 and R 3 are, independently, —CH 2 —SiR′ 3 or —CH 2 —CR′ 3 , and each R′ is independently a C 1 to C 20 substituted or unsubstituted hydrocarbyl, provided that at least one R′ is not H.

4 . The catalyst compound of claim 1 , wherein R 3 is hydrogen, alkoxide or a C 1 to C 40 substituted or unsubstituted hydrocarbyl group

5 . The catalyst compound of claim 1 , wherein the catalyst compound is at least 50% racemic, preferably at least 90% racemic, preferably at least 97% racemic.

6 . The catalyst compound of claim 1 , wherein R 9 and optionally R 3 are, independently, —CH 2 —CMe 3 , or —CH 2 —SiMe 3 where.

7 . A catalyst system comprising activator and the catalyst of claim 1 .

8 . The catalyst system of claim 7 , wherein the activator comprises alumoxane or non-coordinating anion.

9 . The catalyst system of claim 7 , wherein the catalyst system further comprises a support.

10 . A process to polymerize olefins comprising contacting one or more olefins with the catalyst system claim 7 .

11 . The process of claim 10 , wherein the olefins and catalyst system are contacted in the gas phase.

12 . The process of claim 10 , wherein the olefins and catalyst system are contacted in the slurry phase.

13 . The process of claim 10 , wherein the olefins and catalyst system are contacted in the solution phase.

14 . The process of claim 10 , wherein the olefins and catalyst system are contacted in a slurry loop reactor.

15 . The process of claim 10 , wherein the polymerization is a continuous process.

16 . The process of claim 10 , wherein the catalyst compound comprises one or more of: rac/meso Me 2 Si(Me 3 SiCH 2 Cp) 2 HfMe 2 ; racMe 2 Si(Me 3 SiCH 2 Cp) 2 HfMe 2 ; rac/meso Ph 2 Si(Me 3 SiCH 2 Cp) 2 HfMe 2 ; Me 2 Si(Me 4 Cp)(Me 3 SiCH 2 Cp)HfMe 2 ; Ph 2 Si(Me 4 Cp)(Me 3 SiCH 2 Cp)HfMe 2 ; rac/meso Me 2 Si(Me 3 SiCH 2 Cp) 2 ZrMe 2 ; Me 2 Si(Me 4 Cp)(Me 3 SiCH 2 Cp)ZrMe 2 ; Ph 2 Si(Me 4 Cp)(Me 3 SiCH 2 Cp)ZrMe 2 ; rac/meso (CH 2 ) 3 Si(Me 3 SiCH 2 Cp) 2 HfMe 2 ; rac/meso (CH 2 ) 4 Si(Me 3 SiCH 2 Cp) 2 HfMe 2 ; rac/meso (C 6 F 5 ) 2 Si(Me 3 SiCH 2 Cp) 2 HfMe 2 ; rac/meso (CH 2 ) 3 Si(Me 3 SiCH 2 Cp) 2 ZrMe 2 ; rac/meso (CH 2 ) 4 Si(Me 3 SiCH 2 Cp) 2 ZrMe 2 ; rac/meso (C 6 F 5 ) 2 Si(Me 3 SiCH 2 Cp) 2 ZrMe 2 ; (CH 2 ) 4 Si(Me 4 Cp)(Me 3 SiCH 2 Cp)HfMe 2 ; (CH 2 ) 4 Si(Me 4 Cp)(Me 3 SiCH 2 Cp)ZrMe 2 ; (CH 2 ) 3 Si(Me 4 Cp)(Me 3 SiCH 2 Cp)HfMe 2 ; (CH 2 ) 3 Si(Me 4 Cp)(Me 3 SiCH 2 Cp)ZrMe 2 ; (C 6 F 5 ) 2 Si(Me 4 Cp)(Me 3 SiCH 2 Cp)HfMe 2 ; (C 6 F 5 ) 2 Si(Me 4 Cp)(Me 3 SiCH 2 Cp)ZrMe 2 ; rac/meso Me 2 Ge(Me 3 SiCH 2 Cp) 2 HfMe 2 ; rac/meso Me 2 Si(Me 2 PhSiCH 2 Cp) 2 HfMe 2 ; rac/meso Ph 2 Si(Me 2 PhSiCH 2 Cp) 2 HfMe 2 ; Me 2 Si(Me 4 Cp)(Me 2 PhSiCH 2 Cp)HfMe 2 ; Ph 2 Si(Me 4 Cp)(Me 2 PhSiCH 2 Cp)HfMe 2 ; rac/meso Me 2 Si(Me 2 PhSiCH 2 Cp) 2 ZrMe 2 ; Me 2 Si(Me 4 Cp)(Me 2 PhSiCH 2 Cp)ZrMe 2 ; Ph 2 Si(Me 4 Cp)(Me 2 PhSiCH 2 Cp)ZrMe 2 ; rac/meso (CH 2 ) 3 Si(Me 2 PhSiCH 2 Cp) 2 HfMe 2 ; rac/meso (CH 2 ) 4 Si(Me 2 PhSiCH 2 Cp) 2 HfMe 2 ; rac/meso (C 6 F 5 ) 2 Si(Me 2 PhSiCH 2 Cp) 2 HfMe 2 ; rac/meso (CH 2 ) 3 Si(Me 2 PhSiCH 2 Cp) 2 ZrMe 2 ; rac/meso (CH 2 ) 4 Si(Me 2 PhSiCH 2 Cp) 2 ZrMe 2 ; rac/meso (C 6 F 5 ) 2 Si(Me 2 PhSiCH 2 Cp) 2 ZrMe 2 ; (CH 2 ) 4 Si(Me 4 Cp)(Me 2 PhSiCH 2 Cp)HfMe 2 ; (CH 2 ) 4 Si(Me 4 Cp)(Me 2 PhSiCH 2 Cp)ZrMe 2 ; (CH 2 ) 3 Si(Me 4 Cp)(Me 2 PhSiCH 2 Cp)HfMe 2 ; (CH 2 ) 3 Si(Me 4 Cp)(Me 2 PhSiCH 2 Cp)ZrMe 2 ; (C 6 F 5 ) 2 Si(Me 4 Cp)(Me 2 PhSiCH 2 Cp)HfMe 2 ; (C 6 F 5 ) 2 Si(Me 4 Cp)(Me 2 PhSiCH 2 Cp)ZrMe 2 ; rac/meso Me 2 Ge(Me 2 PhSiCH 2 Cp) 2 HfMe 2 ; rac/meso Me 2 Si(MePh 2 SiCH 2 Cp) 2 HfMe 2 ; rac/meso Ph 2 Si(MePh 2 SiCH 2 Cp) 2 HfMe 2 ; Me 2 Si(Me 4 Cp)(MePh 2 SiCH 2 Cp)HfMe 2 ; Ph 2 Si(Me 4 Cp)(MePh 2 SiCH 2 Cp)HfMe 2 ; rac/meso Me 2 Si(MePh 2 SiCH 2 Cp) 2 ZrMe 2 ; Me 2 Si(Me 4 Cp)(MePh 2 SiCH 2 Cp)ZrMe 2 ; Ph 2 Si(Me 4 Cp)(MePh 2 SiCH 2 Cp)ZrMe 2 ; rac/meso (CH 2 ) 3 Si(MePh 2 SiCH 2 Cp) 2 HfMe 2 ; rac/meso (CH 2 ) 4 Si(MePh 2 SiCH 2 Cp) 2 HfMe 2 ; rac/meso (C 6 F 5 ) 2 Si(MePh 2 SiCH 2 Cp) 2 HfMe 2 ; rac/meso (CH 2 ) 3 Si(MePh 2 SiCH 2 Cp) 2 ZrMe 2 ; rac/meso (CH 2 ) 4 Si(MePh 2 SiCH 2 Cp) 2 ZrMe 2 ; rac/meso (C 6 F 5 ) 2 Si(MePh 2 SiCH 2 Cp) 2 ZrMe 2 ; (CH 2 ) 4 Si(Me 4 Cp)(MePh 2 SiCH 2 Cp)HfMe 2 ; (CH 2 ) 4 Si(Me 4 Cp)(MePh 2 SiCH 2 Cp)ZrMe 2 ; (CH 2 ) 3 Si(Me 4 Cp)(MePh 2 SiCH 2 Cp)HfMe 2 ; (CH 2 ) 3 Si(Me 4 Cp)(MePh 2 SiCH 2 Cp)ZrMe 2 ; (C 6 F 5 ) 2 Si(Me 4 Cp)(MePh 2 SiCH 2 Cp)HfMe 2 ; (C 6 F 5 ) 2 Si(Me 4 Cp)(MePh 2 SiCH 2 Cp)ZrMe 2 ; rac/meso Me 2 Ge(MePh 2 SiCH 2 Cp) 2 HfMe 2 ; rac/meso Me 2 Si(Ph 3 SiCH 2 Cp) 2 HfMe 2 ; rac/meso Ph 2 Si(Ph 3 SiCH 2 Cp) 2 HfMe 2 ; Me 2 Si(Me 4 Cp)(Ph 3 SiCH 2 Cp)HfMe 2 ; Ph 2 Si(Me 4 Cp)(Ph 3 SiCH 2 Cp)HfMe 2 ; rac/meso Me 2 Si(Ph 3 SiCH 2 Cp) 2 ZrMe 2 ; Me 2 Si(Me 4 Cp)(Ph 3 SiCH 2 Cp)ZrMe 2 ; Ph 2 Si(Me 4 Cp)(Ph 3 SiCH 2 Cp)ZrMe 2 ; rac/meso (CH 2 ) 3 Si(Ph 3 SiCH 2 Cp) 2 HfMe 2 ; rac/meso (CH 2 ) 4 Si(Ph 3 SiCH 2 Cp) 2 HfMe 2 ; rac/meso (C 6 F 5 ) 2 Si(Ph 3 SiCH 2 Cp) 2 HfMe 2 ; rac/meso (CH 2 ) 3 Si(Ph 3 SiCH 2 Cp) 2 ZrMe 2 ; rac/meso (CH 2 ) 4 Si(Ph 3 SiCH 2 Cp) 2 ZrMe 2 ; rac/meso (C 6 F 5 ) 2 Si(Ph 3 SiCH 2 Cp) 2 ZrMe 2 ; (CH 2 ) 4 Si(Me 4 Cp)(Ph 3 SiCH 2 Cp)HfMe 2 ; (CH 2 ) 4 Si(Me 4 Cp)(Ph 3 SiCH 2 Cp)ZrMe 2 ; (CH 2 ) 3 Si(Me 4 Cp)(Ph 3 SiCH 2 Cp)HfMe 2 ; (CH 2 ) 3 Si(Me 4 Cp)(Ph 3 SiCH 2 Cp)ZrMe 2 ; (C 6 F 5 ) 2 Si(Me 4 Cp)(Ph 3 SiCH 2 Cp)HfMe 2 ; (C 6 F 5 ) 2 Si(Me 4 Cp)(Ph 3 SiCH 2 Cp)ZrMe 2 ; rac/meso Me 2 Ge(Ph 3 SiCH 2 Cp) 2 HfMe 2 ; rac/meso Me 2 Si(Cy 3 SiCH 2 Cp) 2 HfMe 2 ; racMe 2 Si(Cy 3 SiCH 2 Cp) 2 HfMe 2 ; rac/meso Ph 2 Si(Cy 3 SiCH 2 Cp) 2 HfMe 2 ; Me 2 Si(Me 4 Cp)(Cy 3 SiCH 2 Cp)HfMe 2 ; Ph 2 Si(Me 4 Cp)(Cy 3 SiCH 2 Cp)HfMe 2 ; rac/meso Me 2 Si(Cy 3 SiCH 2 Cp) 2 ZrMe 2 ; Me 2 Si(Me 4 Cp)(Cy 3 SiCH 2 Cp)ZrMe 2 ; Ph 2 Si(Me 4 Cp)(Cy 3 SiCH 2 Cp)ZrMe 2 ; rac/meso (CH 2 ) 3 Si(Cy 3 SiCH 2 Cp) 2 HfMe 2 ; rac/meso (CH 2 ) 4 Si(Cy 3 SiCH 2 Cp) 2 HfMe 2 ; rac/meso (C 6 F 5 ) 2 Si(Cy 3 SiCH 2 Cp) 2 HfMe 2 ; rac/meso (CH 2 ) 3 Si(Cy 3 SiCH 2 Cp) 2 ZrMe 2 ; rac/meso (CH 2 ) 4 Si(Cy 3 SiCH 2 Cp) 2 ZrMe 2 ; rac/meso (C 6 F 5 ) 2 Si(Cy 3 SiCH 2 Cp) 2 ZrMe 2 ; (CH 2 ) 4 Si(Me 4 Cp)(Cy 3 SiCH 2 Cp)HfMe 2 ; (CH 2 ) 4 Si(Me 4 Cp)(Cy 3 SiCH 2 Cp)ZrMe 2 ; (CH 2 ) 3 Si(Me 4 Cp)(Cy 3 SiCH 2 Cp)HfMe 2 ; (CH 2 ) 3 Si(Me 4 Cp)(Cy 3 SiCH 2 Cp)ZrMe 2 ; (C 6 F 5 ) 2 Si(Me 4 Cp)(Cy 3 SiCH 2 Cp)HfMe 2 ; (C 6 F 5 ) 2 Si(Me 4 Cp)(Cy 3 SiCH 2 Cp)ZrMe 2 ; rac/meso Me 2 Ge(Cy 3 SiCH 2 Cp) 2

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Kuppuswamy Subramaniam
• Holtcamp Matthew W
• Fiscus David M
• Bedoya Matthew S
• Mccullough Laughlin G
• Ye Xuan

Classifications

• C07F17/00

  Metallocenes · CPC title

• C08F10/02 Primary

  Ethene · CPC title

• C08F2800/10

  as molar percentages · CPC title

• C08F210/16 Primary

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

• C08F2420/07

  Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom · CPC title