Bisphenolate transition metal complexes, production and use thereof

Patent metadata

Field	Value
Publication number	US-9745327-B2
Application number	US-201615051421-A
Country	US
Kind code	B2
Filing date	Feb 23, 2016
Priority date	Mar 24, 2015
Publication date	Aug 29, 2017
Grant date	Aug 29, 2017

Abstract

Bis phenolate transition metal complexes are disclosed for use in alkene polymerization, with optional chain transfer agent, to produce polyolefins.

First claim

What is claimed is:

1. A transition metal complex represented by the formula (I):

wherein M is a Group 4 transition metal;
X 1 and X 2 are, independently, a univalent C 1 to C 20 hydrocarbyl radical, a C 1 to C 20 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group, or X 1 and X 2 join together to form a C 4 to C 62 cyclic or polycyclic ring structure;
each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is, independently, a hydrogen, a C 1 -C 40 hydrocarbyl radical, a C 1 -C 40 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group, or two or more of R 1 to R 10 may independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof; and
Q is a neutral donor group;
J is a C 7 to C 60 fused polycyclic group, which optionally comprises up to 20 atoms from Groups 15 and 16, where at least one ring is aromatic and where at least one ring, which may or may not be aromatic, has at least five members;
G is as defined for J or may be hydrogen, a C 1 -C 60 hydrocarbyl radical, a C 1 -C 60 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group, or may independently form a C 4 to C 60 cyclic or polycyclic ring structure with R 6 , R 7 , or R 6 or a combination thereof; and
Y is a divalent C 1 to C 20 hydrocarbyl or divalent C 1 to C 20 substituted hydrocarbyl.

2. The transition metal complex of claim 1 , wherein the complex is represented by the formula (II) or (III):

wherein M, X 1 , X 2 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and Y are as defined in claim 1 ;
each R*, R″, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 is, independently, a hydrogen, a C 1 -C 40 hydrocarbyl radical, a C 1 -C 40 substituted hydrocarbyl radical a functional group comprising elements from Groups 13-17 of the periodic table of the elements, or two or more of R 1 to R 28 may independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof, or R 1 and R* may independently join together to form a five- to eight-membered heterocycle; and
Q* is a group 15 or 16 atom;
z is 0 or 1;
J* is CR″ or N; and
G* is CR″ or N.

3. The complex of claim 1 , wherein M is Hf or Zr or Ti.

4. The complex of claim 1 , wherein G and J are carbazolyl, substituted carbazolyl, indolyl, substituted indolyl, indolinyl, substituted indolinyl, imidazolyl, substituted imidazolyl, indenyl, substituted indenyl, indanyl, substituted indanyl, fluorenyl, or substituted fluorenyl.

5. The complex of claim 1 , wherein Q is a neutral donor group comprising at least one atom from Group 15 or Group 16 and the -(-Q-Y—)— fragment optionally form a substituted or unsubstituted heterocycle which may or may not be aromatic and may have multiple fused rings.

6. The complex of claim 1 , wherein Q is NR′ 2 , OR′, SR′, PR′ 2 , where R′ is as defined for R 1 .

7. The complex of claim 1 , wherein G and J are the same.

8. The complex of claim 1 , wherein G is a hydrogen, a C 1 -C 60 hydrocarbyl radical, a substituted hydrocarbyl radical, a heteroatom, or a heteroatom-containing group, or may independently form a C 4 to C 60 cyclic or polycyclic ring structure with R 6 , R 7 , or R 6 , or a combination thereof.

9. The complex of claim 1 , wherein the complex is represented by formula (IV) or (V):

where Y is a divalent C 1 to C 3 hydrocarbyl, Q 1 is NR′ 2 , OR′, SR′, PR′ 2 , where R′ is as defined for R 1 in claim 1 , M is Zr, Hf or Ti and each X is, independently, as defined for X 1 in claim 1 .

10. The complex of claim 2 , wherein Q* is N, O, S or P, and when Q* is a N or P, z is 1 and when Q* is a S or O z is 0, and G* and J* are N or CR′″, where each R′″ is H or a C 1 to C 12 alkyl.

11. A catalyst system comprising an activator and the complex of claim 1 .

12. The catalyst system of claim 11 , wherein G and J are, independently, carbazolyl, substituted carbazolyl, indolyl, substituted indolyl, indolinyl, substituted indolinyl, imidazolyl, substituted imidazolyl, indenyl, substituted indenyl, indanyl, substituted indanyl, fluorenyl, or substituted fluorenyl.

13. The catalyst system of claim 11 , wherein the catalyst complex is represented by formula (IV) or (V):

where Y is a divalent C 1 to C 3 hydrocarbyl, Q 1 is NR′ 2 , OR′, SR′, PR′ 2 , where R′ is as defined for R 1 in claim 1 , M is Zr, Hf or Ti and each X is, independently, as defined for X 1 in claim 1 .

14. The catalyst system of claim 11 , wherein G and J are the same.

15. The catalyst system of claim 11 , wherein the catalyst system further comprises chain transfer agent.

16. The catalyst system of claim 11 , wherein the catalyst system further comprises chain transfer agent represented by the formula R 3 Al or R 2 Zn, where R is a C 1 to C 20 alkyl group.

17. The catalyst system of claim 11 , wherein the activator is an alumoxane.

18. The catalyst system of claim 11 , wherein the activator is a non-coordinating anion.

19. The catalyst system of claim 11 , wherein the activator is selected from the group consisting of: methylalumoxane, ethylalumoxane, isobutyl alumoxane, N,N-dimethylanilinium tetra(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetra(perfluorophenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium, tetrakis(pentafluorophenyl)borate, and 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

20. A polymerization process to produce polyolefin comprising:
a) contacting one or more olefin monomers with the catalyst system of claim 11 , and
b) obtaining olefin polymer.

21. The process of claim 20 , wherein the activator is an alumoxane or a non-coordinating anion.

22. The process of claim 20 , wherein the activator is selected from the group consisting of: methylalumoxane, ethylalumoxane, isobutyl alumoxane, N,N-dimethylanilinium tetra(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetra(perfluorophenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Atienza Crisita Carmen H
• Cano David A
• Hagadorn John R
• Shah Rhutesh K

Classifications

• C08F2410/01

  Additive used together with the catalyst, excluding compounds containing Al or B · CPC title

• C08F4/64158

  ONO · CPC title

• C08F210/16

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

• C08F210/18

  with non-conjugated dienes, e.g. EPT rubbers · CPC title

• C08F4/64124

  ONO · CPC title