Granted Patent B2

US 9,796,795 · App. 15/145,314 · Granted Oct 24, 2017

Inventors: Jo Ann M. Canich (Houston, TX); Crisita Carmen H. Atienza (Houston, TX); Vyatcheslav V. Izmer (Moscow, RU); Dmitry S. Kononovich (Moscow, RU); Alexander Z. Voskoboynikov (Moscow, RU)

Assignee: ExxonMobil Chemical Patents Inc.

C08F4/76C07F7/28C07F17/00C08F4/6592C08F4/65912C08F110/02C08F110/06C08F210/02C08F4/65908C08F2420/02

Abstract

Claims (101)

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-tetrahydro-s-indacen-1-yl)(cyclododecylamido)M(R) 2 ;

μ-(CH 3 ) 2 Si(2-methyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(cyclododecylamido)M(R) 2 ;

μ-(CH 3 ) 2 Si(6,6-diethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(cyclododecylamido)M(R) 2 ;

μ-(CH 3 ) 2 Si(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclododecylamido)M(R) 2 ;

μ-(CH 3 ) 2 Si(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclododecylamido)M(R) 2 ;

μ-(CH 3 ) 2 Si(2-methyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclododecylamido)M(R) 2 ;

μ-(CH 3 ) 2 Si(2-methyl-7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclododecylamido)M(R) 2 ;

μ-(CH 3 ) 2 Si(7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclododecylamido)M(R) 2 ;

μ-(CH 2 ) 3 Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R) 2 ;

μ-(CH 2 ) 4 Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R) 2 ;

μ-(CH 2 ) 5 Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R) 2 ;

μ-(CH 3 ) 2 C(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R) 2 ;

μ-(CH 2 ) 3 Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R) 2 ;

μ-(CH 2 ) 4 Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R) 2 ;

μ-(CH 2 ) 5 Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R) 2 ;

μ-(CH 3 ) 2 C(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(t-butylamido)M(R) 2 ; and

μ-(CH 3 ) 2 Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(neopentylamido)M(R) 2 ;

where M is selected from a group consisting of Ti, Zr, and Hf and R is selected from halogen and C 1 to C 5 alkyl.

16. The compound of claim 3 , wherein the compound is represented by the formula:

where M, B, c, J, p, R 2 , R 3 , R 6 , R 7 , R′, T, y and X are as defined in claim 3 and each R b , R c , and R d is independently C 1 -C 10 alkyl, or hydrogen, provided that both R b , both R c , or both R d are not hydrogen.

17. A catalyst system comprising the compound of claim 1 and an activator.

18. The catalyst system of claim 17 , wherein the activator comprises a non-coordinating anion activator and/or an alumoxane.

19. The catalyst system of claim 17 , where the catalyst system is supported.

20. A process to produce olefin polymer comprising contacting olefin monomer with the catalyst system of claim 17 .

21. The process of claim 20 , wherein the monomer comprises ethylene and/or propylene.

22. The process of claim 20 , wherein the catalyst system comprises one catalyst compound.

23. The process of claim 20 , wherein the process occurs at a temperature of from about 0° C. to about 300° C., at a pressure in the range of from about 0.35 MPa to about 16 MPa, and at a time up to 300 minutes.

24. The process of claim 20 , wherein the monomer comprises two or more of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, or dodecene.

25. The process of claim 20 , wherein the monomer comprises ethylene, propylene and 5-ethylidene-2-norbornene.

Assignments (1)

Continuity (9)