Tetrahydroindacenyl catalyst composition, catalyst system, and processes for use thereof

Patent metadata

Field	Value
Publication number	US-9796795-B2
Application number	US-201615145314-A
Country	US
Kind code	B2
Filing date	May 3, 2016
Priority date	Jan 14, 2015
Publication date	Oct 24, 2017
Grant date	Oct 24, 2017

Abstract

This invention relates to a compound represented by the formula: T y Cp′ m MG n X q wherein: Cp′ is a tetrahydroindacenyl group which may be 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; G is a heteroatom group represented by the formula JR i z where J is N, P, O or S, R i is a C 1 to C 20 hydrocarbyl group, and z is 1 or 2; T is a bridging group; y is 0 or 1; 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.

First claim

What is claimed is:

1. A compound represented by the formula: T y Cp′ m MG n X q
wherein: Cp′ is a tetrahydroindacenyl 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;
G is a heteroatom group represented by the formula JR i z where J is N, P, O or S, R i is a C 1 to C 20 hydrocarbyl group, and z is 1 or 2;
T is a bridging group;
y is 0 or 1;
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.

2. A compound represented by the formula (I):

where:
M is a group 4 metal;
J is N, O, S or P;
p is 1 when J is N or P, and is 0 when J is O or S;
each R a is independently a C 1 -C 10 alkyl;
each R c is independently hydrogen or a C 1 -C 10 alkyl;
R 2 , R 3 , R 4 , and R 7 are independently hydrogen, or a C 1 -C 50 substituted or unsubstituted hydrocarbyl, halocarbyl or silylcarbyl, provided that: 1) R 3 and/or R 4 are not aryl or substituted aryl, 2) R 3 is not substituted with a group 15 or 16 heteroatom; and 3) that adjacent R 4 , R c , R a , and 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, or silylcarbyl;
T is (CR 8 R 9 ) x , SiR 8 R 9 or GeR 8 R 9 where x is 1 or 2, 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 are optionally bonded together to form a ring structure;
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. A compound represented by the formula (III):

where M is group 3, 4, 5, or 6 transition metal;
B is the oxidation state of M, and is 3, 4, 5 or 6;
c is B-2;
J is N, O, S or P;
p is 1 when J is N or P, and is 0 when J is O or S;
R 2 , R 3 , R 6 , and R 7 , are independently hydrogen, or a C 1 -C 50 substituted or unsubstituted hydrocarbyl, halocarbyl or silylcarbyl;
each R b and R c is independently C 1 -C 10 alkyl, or hydrogen;
each R′ is, independently, a C 1 -C 100 substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl or germycarbyl;
T is (CR 8 R 9 ) x , SiR 8 R 9 or GeR 8 R 9 where x is 1 or 2, R 8 and R 9 are independently selected from hydrogen, substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl and germylcarbyl, and R 8 and R 9 may optionally be bonded together to form a ring structure;
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.

4. The catalyst compound of claim 1 , wherein M is Ti.

5. The compound of claim 1 , where J is N, and R′ is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl or an isomer thereof.

6. The catalyst compound of claim 2 wherein R 2 , R 3 , R 4 , and/or R 7 , are not aryl or substituted aryl.

7. The catalyst compound of claim 3 , wherein R 2 , R 3 , R 6 , and/or R 7 , are not aryl or substituted aryl.

8. The compound of claim 2 , wherein each R a is independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl and isomers thereof.

9. The compound of claim 1 , wherein the sum of m+n+q is equal to 3, 4, 5, or 6.

10. The compound of claim 1 , wherein the Cp′ is tetrahydro-s-indacenyl and the 6 position is geminally disubstituted with two C 1 -C 10 alkyl groups.

11. The compound of claim 1 , wherein the Cp′ is tetrahydro-s-indacenyl and the 6 position is geminally disubstituted with two alkyl groups selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl and isomers thereof.

12. The compound of claim 1 , wherein the Cp′ is tetrahydro-s-indacenyl and the 3 and 4 positions are not aryl or substituted aryl.

13. The compound of claim 3 , wherein each R b is independently a C 1 -C 10 alkyl.

14. The compound of claim 1 , where J is N, and R i is t-butyl, hexyl, neopentyl, cyclohexyl, cyclooctyl, cyclododecyl, adamantyl, or norbornyl.

15. A composition comprising one or more of:
dimethylsilylene(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(cyclododecylamido)M(R) 2 ;
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)(cyclododecylamido)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)(cyclododecylamido)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)(cyclododecylamido)M(R) 2 ;
dimethylsilylene(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(1-adamantylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(6,6-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(1-adamantylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(2-methyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(1-adamantylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(6,6-diethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(1-adamantylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(1-adamantylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(1-adamantylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(2-methyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(1-adamantylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(2-methyl-7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(1-adamantylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(1-adamantylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(6,6-dimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(2-methyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(6,6-diethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(2-methyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(2-methyl-7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(t-butylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(cyclododecylamido)M(R) 2 ;
μ-(CH 3 ) 2 Si(6,6-dimethyl-1,5,6,7-tet

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Canich Jo Ann M
• Atienza Crisita Carmen H
• Izmer Vyatcheslav V
• Kononovich Dmitry S
• Voskoboynikov Alexander Z

Classifications

• C07F7/28 Primary

  Titanium compounds · CPC title

• C08F4/6592

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

• C08F210/02

  Ethene · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/76 Primary

  selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum · CPC title