Asymmetric fluorenyl-substituted salan catalysts

Patent metadata

Field	Value
Publication number	US-9975973-B2
Application number	US-201615241997-A
Country	US
Kind code	B2
Filing date	Aug 19, 2016
Priority date	Oct 2, 2015
Publication date	May 22, 2018
Grant date	May 22, 2018

Abstract

Catalyst compounds and catalyst systems including an asymmetric Salan ligands having a fluorenyl moiety are disclosed. Methods of preparing such catalyst compounds and catalyst systems, polymerization processes using such catalysts systems and olefin polymers prepared according to such processes using the catalysts systems are described.

First claim

What is claimed is:

1. A catalyst compound represented by the Formula (I):

wherein each solid line represents a covalent bond and each dotted line represents a bond having a varying degree of covalency and a varying degree of coordination;
wherein M is a Group 3, 4, 5, or 6 transition metal;
N 1 and N 2 are nitrogen;
O is oxygen;
each of X 1 and X 2 is, independently, a univalent C 1 to C 20 hydrocarbyl radical, a univalent substituted C 1 to C 20 , hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of elements or X 1 and X 2 join together to form a C 4 to C 62 cyclic or polycyclic ring structure, provided that when M is trivalent X 2 is not present;
each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , and R* 1 , is, independently, hydrogen, a C 1 to C 40 hydrocarbyl radical, or a substituted C 1 to C 40 hydrocarbyl radical;
or a functional group comprising elements from Groups 13 to 17 of the periodic table of elements optionally, wherein two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , and R 21 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof;
wherein R* 1 comprises a group other than a substituted or unsubstituted fluorenyl group; and
wherein Y is a C 1 to C 40 divalent hydrocarbylene radical comprising a linker backbone comprising from 1 to 18 carbon atoms bridging between nitrogen atoms N 1 and N 2 .

2. The catalyst compound of claim 1 , wherein R* 1 comprises a substituted or unsubstituted C 4 to C 20 aliphatic radical, a substituted or unsubstituted C 4 to C 20 alicyclic radical, a substituted or unsubstituted C 5 to C 40 aryl radical, or an electron withdrawing functional group selected from the group consisting of —NO 2 , —CF 3 , —CCl 3 , —CBr 3 , —CI 3 , —CN, —NCR α , 13 SO 3 H, —COOH, —CHO, —F, —Cl, —Br, —I, —COOR α , —COR α , —NRa α 3 + , wherein each R α is independently hydrogen, or a C 1 to C 20 alkyl radical.

3. The catalyst compound of claim 1 , wherein R* 1 comprises a substituted or unsubstituted cyclopentadienyl radical represented by the Formula:

wherein C* indicates an attachment carbon of the radical;
each of R 22 , R 23 , R 24 , R 25 , and R 26 is, independently, hydrogen, a C 1 to C 40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, optionally, wherein two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , 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 , and R 26 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof.

4. The catalyst compound of claim 1 , wherein R* 1 comprises a substituted or unsubstituted pyrrole radical represented by the Formula:

wherein N* indicates an attachment nitrogen of the radical;
each of R 22 , R 23 , R 24 , and R 25 is, independently, hydrogen, a C 1 to C 40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, optionally, wherein two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , 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 , and R 25 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof.

5. The catalyst compound of claim 1 , wherein at least one of R 5 and/or R 11 is C 1 to C 10 alkyl, C 1 to C 10 alkoxy, C 6 to C 15 aryl, or an electron withdrawing functional group selected from the group consisting of —NO 2 , —CF 3 , —CCl 3 , —CBr 3 , —CI 3 , —CN, —NCR α , —SO 3 H, —COOH, —CHO, —F, —Cl, —Br, —I, —COOR α , —COR α , —NR α 3 + , wherein each R α is independently hydrogen, or a C 1 to C 20 alkyl radical.

6. The catalyst compound of claim 1 , wherein R 5 is a C 1 to C 10 alkyl radical, C 1 to C 10 alkoxy radical, and each of R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , and R* 1 is, independently, hydrogen, a halogen, or a C 1 to C 10 hydrocarbyl radical.

7. The catalyst compound of claim 1 , wherein R 5 is a C 1 to C 10 alkyl radical, C 1 to C 10 alkoxy radical, R 11 is a C 1 to C 10 alkyl radical, and each of R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , and R* 1 is, independently, hydrogen, a halogen, or a C 1 to C 10 hydrocarbyl radical.

8. The catalyst compound of claim 1 , wherein R 5 is a C 1 to C 10 alkyl radical, C 1 to C 10 alkoxy radical, R 11 and R* 1 , independently is a C 1 to C 10 alkyl radical, and each of R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , and R 21 , is, independently, hydrogen, a halogen, or a C 1 to C 10 hydrocarbyl radical.

9. The catalyst compound of claim 1 , wherein R 13 is C 1 to C 10 alkyl, C 1 to C 10 alkoxy or C 6 to C 15 aryl.

10. The catalyst compound of claim 1 , wherein Y is a C 1 to C 40 divalent hydrocarbylene radical comprising O, S, S(O), S(O) 2 , Si(R′) 2 , P(R′), N, N(R′), or a combination thereof, wherein each R′ is independently a C 1 to C 18 hydrocarbyl radical.

11. The catalyst compound of claim 1 , wherein Y is a divalent C 1 to C 20 hydrocarbyl radical.

12. The catalyst compound of claim 1 , wherein Y is —CH 2 CH 2 CH 2 —, 1,2-cyclohexylene, or —CH 2 CH 2 —.

13. The catalyst compound of claim 1 , wherein M is Ti, Zr, or Hf and/or at least one of X 1 and X 2 is, independently, a halogen or a C 1 to C 7 hydrocarbyl radical.

14. The catalyst compound of claim 1 , wherein M is Ti, Zr, or Hf and each of X 1 and X 2 is a benzyl radical.

15. The catalyst compound of claim 1 , wherein M is Ti, Zr, or Hf; R 5 is a C 1 to C 10 alkyl radical, C 1 to C 10 alkoxy radical; R 11 is a C 1 to C 10 alkyl radical; R 13 is C 1 to C 10 alkyl, C 1 to C 10 alkoxy or C 6 to C 15 aryl.

16. The catalyst compound of claim 1 , wherein:
M is Zr or Hf;
X 1 and X 2 are benzyl radicals;
R 5 and R 11 are independently a methyl or t-butyl radical;
R 13 is a methyl, or 4-methylphenyl radical;
R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , and R 21 are hydrogen; and
Y is —CH 2 CH 2 —.

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

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

19. The catalyst system of claim 17 , wherein the activator is selected from the group consisting of: methylalumoxane, ethylalumoxane, isobutyl alumoxane, N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimet

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Atienza Crisita Carmen H
• Cano David A
• Evans Meagan E

Classifications

• C08F210/16 Primary

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

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/60189

  ONNO · CPC title

• C08F4/64189

  ONNO · CPC title

• C08F2500/01

  High molecular weight, e.g. >800,000 Da. · CPC title