Supported Salan catalysts

Patent metadata

Field	Value
Publication number	US-10000593-B2
Application number	US-201615242198-A
Country	US
Kind code	B2
Filing date	Aug 19, 2016
Priority date	Oct 2, 2015
Publication date	Jun 19, 2018
Grant date	Jun 19, 2018

Abstract

A catalyst system including the reaction product of a fluorided support, an activator, and at least a first transition metal catalyst compound; methods of making such catalyst systems, polymerization processes using such catalyst systems, and polymers made therefrom.

First claim

What is claimed is:

1. A catalyst system comprising the reaction product of a fluorided support, an activator, and a catalyst compound represented by Formula I:

wherein:
each solid line represents a covalent bond and each dashed line represents a coordinative link;
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, or a univalent C 1 to C 20 hydrocarbyl radical, a univalent substituted C 1 to C 20 hydrocarbyl radical, 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 12 , R 13 , R 14 , R 15 , R 16 , and R 17 is, independently, hydrogen, a C 1 to C 40 hydrocarbyl radical, or a substituted C 1 to C 40 hydrocarbyl radical, optionally, two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , 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;
wherein R* 1 and R* 2 independently comprise a bulky functional group, an electron withdrawing group, or a combination thereof; and
Y is a divalent C 1 to C 20 hydrocarbylene radical.

2. The catalyst system of claim 1 , wherein the fluorided support comprises fluorided silica.

3. The catalyst system of claim 2 , wherein the fluorided silica has not been calcined at a temperature of 400° C. or more.

4. The catalyst system of claim 3 , wherein X 1 and X 2 are benzyl radicals and Y is selected from the group consisting of —CH 2 CH 2 —, 1,2-cyclohexylene, and —CH 2 CH 2 CH 2 —.

5. The catalyst system of claim 1 , wherein X 1 and X 2 are benzyl radicals and Y is selected from the group consisting of —CH 2 CH 2 —, 1,2-cyclohexylene, and —CH 2 CH 2 CH 2 —.

6. The catalyst system of claim 1 , wherein R* 1 and R* 2 each comprises a cyclopentadienyl radical represented by Formula II:

wherein:
C* indicates an attachment carbon of the radical;
R 7 is a C 1 to C 40 hydrocarbyl radical or a substituted C 1 to C 40 hydrocarbyl radical; and
each of R 8 , R 9 , R 10 , and R 11 is, independently, a hydrogen, a C 1 to C 40 hydrocarbyl radical, or a substituted C 1 to C 40 hydrocarbyl radical, optionally, 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 , and R 17 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure.

7. The catalyst system of claim 1 , wherein the catalyst compound is represented by Formula III:

wherein:
each of R 7 and R 26 is, independently, a C 1 -C 40 hydrocarbyl radical or a substituted C 1 to C 40 hydrocarbyl radical;
wherein each of R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , and R 34 is, independently, hydrogen, a C 1 to C 40 hydrocarbyl radical, or a substituted C 1 to C 40 hydrocarbyl radical,
M is a Group 3, 4, 5, or 6 transition metal;
Y is a divalent C 1 to C 20 hydrocarbylene radical;
N 1 and N 2 are nitrogen;
O is oxygen;
each of X 1 and X 2 is, independently, or a univalent C 1 to C 20 hydrocarbyl radical, a univalent substituted C 1 to C 20 hydrocarbyl radical, 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 12 , R 13 , R 14 , R 15 , R 16 , and R 17 is, independently, hydrogen, a C 1 to C 40 hydrocarbyl radical, or a substituted C 1 to C 40 hydrocarbyl radical; and
wherein two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , 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 may independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or.

8. The catalyst system of claim 7 , wherein X 1 and X 2 are benzyl radicals and Y is selected from the group consisting of —CH 2 CH 2 —, 1,2-cyclohexylene, and —CH 2 CH 2 CH 2 —.

9. The catalyst system of claim 2 , wherein R* 1 and R* 2 each comprise a pyrrole radical is represented by Formula IV:

wherein:
N* indicates an attachment nitrogen of the radical;
each of R 8 , R 9 , R 10 , and R 11 is, independently, a hydrogen, a C 1 to C 40 hydrocarbyl radical, or a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, optionally, 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.

10. The catalyst system of claim 1 , wherein the catalyst compound is represented by Formula V:

wherein:
each of R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , and R 33 is, independently, a hydrogen, a C 1 to C 40 hydrocarbyl radical, or a substituted C 1 to C 40 hydrocarbyl radical, optionally two or more of R 1 to R 6 and R 12 to R 33 may independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure;
M is a Group 3, 4, 5, or 6 transition metal;
Y is a divalent C 1 to C 20 hydrocarbylene radical;
N 1 , N 2 , N 3 , and N 4 are nitrogen;
O is oxygen;
each of X 1 and X 2 is, independently, or a univalent C 1 to C 20 hydrocarbyl radical, a or univalent substituted C 1 to C 20 hydrocarbyl radical, 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; and
each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 is, independently, hydrogen, a C 1 to C 40 hydrocarbyl radical, or a substituted C 1 to C 40 hydrocarbyl radical.

11. The catalyst system of claim 10 , wherein X 1 and X 2 are benzyl radicals and Y is selected from the group consisting of —CH 2 CH 2 —, 1,2-cyclohexylene, and —CH 2 CH 2 CH 2 —.

12. The catalyst system of claim 1 , wherein the catalyst compound is represented by Formula VI:

wherein:
each of 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 to C 40 hydrocarbyl radical, or a substituted C 1 to C 40 hydrocarbyl radical, optionally two or more of R 1 to R 6 and R 12 to R 27 may independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure, or a combination thereof;
M is a Group 3, 4, 5, or 6 transition metal;
Y is a divalent C 1 to C 20 hydrocarbylene radical;
N 1 and N 2 are nitrogen;
O is oxygen;
each of X 1 and X 2 is, independently, or a univalent C 1 to C 20 hydroca

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Ye Xuan
• Atienza Crisita Carmen H
• Holtcamp Matthew W
• Sanders David F
• Day Gregory S
• Titone Michelle E
• Cano David A
• Bedoya Matthew S

Classifications

• C08F4/64189

  ONNO · CPC title

• C07F7/00 Primary

  Compounds containing elements of Groups 4 or 14 of the Periodic Table · CPC title

• C08F4/64

  Titanium, zirconium, hafnium or compounds thereof · CPC title

• C08F4/60189

  ONNO · CPC title

• C08F210/16 Primary

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