Cyclopentadienyl-substituted salan catalysts

Patent metadata

Field	Value
Publication number	US-9290589-B2
Application number	US-201414557813-A
Country	US
Kind code	B2
Filing date	Dec 2, 2014
Priority date	Dec 13, 2013
Publication date	Mar 22, 2016
Grant date	Mar 22, 2016

Abstract

A cyclopentadienyl-substituted Salan catalyst, a catalyst system comprising an activator and the cyclopentadienyl-substituted Salan catalyst, a process comprising contacting one or more olefins with the catalyst system, and polymers produced by the process are disclosed herein.

First claim

What is claimed is:

1. A catalyst compound represented by the formula:

wherein each solid line represents a covalent bond and each arrow 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 functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, or X 1 and X 2 join together to form a C 4 to C 62 cyclic or polycyclic ring structure, provided however when M is trivalent X 2 is not present;
wherein each of R* 1 and R* 2 independently comprises a bulky functional group, an electron withdrawing group, or a combination thereof, and wherein at least one of R* 1 and R* 2 independently comprises a cyclopentadienyl radical having the structure:

wherein C* indicates an attachment carbon of the radical;
each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 is, independently, hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof;
R 7 is a C 1 -C 40 hydrocarbyl radical or a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements; and
Y is a divalent C 1 to C 20 hydrocarbyl radical.

2. The catalyst compound of claim 1 , wherein each of R* 1 and R* 2 independently comprises a substituted or unsubstituted cyclopentadienyl radical, and wherein one of R* 1 and R* 2 independently comprises a substituted or unsubstituted cyclopentadienyl radical represented by the formula:

wherein C* indicates an attachment carbon of the radical;
wherein each of R 18 , R 19 , R 20 , R 21 , and R 22 is, independently, hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, two or more of R 19 , R 20 , R 21 , and R 22 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof.

3. The catalyst compound of claim 2 , wherein each of R 7 and R 18 is a C 1 -C 12 aliphatic radical or a phenyl radical.

4. The catalyst compound of claim 1 , wherein at least one of R* 1 and R* 2 independently comprises a substituted or unsubstituted C 4 -C 20 aliphatic radical or a C 4 -C 20 alicyclic radical.

5. The catalyst compound of claim 1 , wherein at least one of R* 1 and R* 2 independently comprises an electron withdrawing functional group comprising —NO 2 , —CF 3 , —CCl 3 , —CBr 3 , —CI 3 , —CN, —SO 3 H, —COOH, —CHO, —F, —Cl, —Br, —I, —COOR α , —COR α , —NR α 3 + , or a combination thereof, wherein each R α is independently hydrogen or a C 1 -C 20 alkyl radical.

6. The catalyst compound of claim 1 , wherein Y is a divalent cyclic, branched or linear C 1 to C 12 aliphatic radical.

7. The catalyst compound of claim 1 , wherein Y is selected from the group consisting of methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, nonylene, decylene, undecylene, dodecylene, cyclohexylene, phenylene, and isomers thereof.

8. The catalyst compound of claim 1 , wherein Y is ethylene (—CH 2 CH 2 —), 1,2-cyclohexylene, 1,2-phenylene, or 2-benzylene.

9. The catalyst compound of claim 1 , wherein M is Hf, Ti, or Zr.

10. The catalyst compound of claim 1 , wherein each of X 1 and X 2 is, independently, a halogen or a C 1 to C 7 hydrocarbyl radical, provided however when M is trivalent, X 2 is not present.

11. The catalyst compound of claim 1 , wherein each of X 1 and X 2 is a benzyl radical, provided however when M is trivalent, X 2 is not present.

12. The catalyst compound of claim 1 , wherein each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 is, independently, hydrogen, a halogen, or a C 1 to C 30 hydrocarbyl radical.

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

14. The catalyst compound of claim 1 , wherein at least one of R* 1 and R* 2 independently comprises a 6-membered aromatic ring.

15. The catalyst compound of claim 1 , wherein at least one of R* 1 and R* 2 independently comprises an indenyl ring system or a fluorenyl ring system.

16. The catalyst compound of claim 1 , wherein R 1 and R 12 are independently selected from the group consisting of methyl, trifluoromethyl and 2,2,2-trifluoroethyl, wherein at least one of R 1 and R 12 is trifluoromethyl or 2,2,2-trifluoroethyl.

17. The catalyst compound of claim 1 , represented by the formula:

wherein each R 39 and R 40 is, independently, hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, R 39 and R 40 join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof.

18. The catalyst compound of claim 1 , represented by the formula:

and wherein each of R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 , and R 54 is, independently, hydrogen, a C 1 -C 40 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, two or more of R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 , and R 54 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof.

19. A catalyst compound represented by the formula:

wherein each solid line represents a covalent bond and each arrow 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 functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, or X 1 and X 2 join together to form a C 4 to C 62 cyclic or polycyclic ring structure, provided however when M is trivalent X 2 is not present;
each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 19 , R 20 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 ,

Assignees

• Exxonmobil Chem Patents Inc
• Univ Ramot

Inventors

• Evans Meagan E
• Cano David A
• Kol Moshe
• Press Konstantin

Classifications

• C08F10/00 Primary

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C08F110/06 Primary

  Propene · CPC title

• C08F4/659

  Component covered by group C08F4/64 containing a transition metal-carbon bond {(C08F4/64003 - C08F4/64196 take precedence)} · CPC title

• C08F4/64189

  ONNO · CPC title

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title