Polymerization process using bis phenolate compounds supported on organoaluminum treated layered silicate supports

Patent metadata

Field	Value
Publication number	US-9994657-B2
Application number	US-201615242337-A
Country	US
Kind code	B2
Filing date	Aug 19, 2016
Priority date	Oct 2, 2015
Publication date	Jun 12, 2018
Grant date	Jun 12, 2018

Abstract

This invention relates to a process to polymerize olefins comprising: i) contacting one or more olefins with a catalyst system comprising: 1) a support comprising an organoaluminum treated layered silicate and an inorganic oxide; and 2) a bisphenolate compound; and ii) obtaining olefin polymer having high molecular weight and layered silicate dispersed therein. Preferably the support is in the form of spheroidal particles.

First claim

What is claimed is:

1. A catalyst system comprising:
1) support comprising inorganic oxide and an organoaluminum treated layered silicate, and 2) catalyst compound represented by Formula (A):

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, a univalent C 1 to C 20 hydrocarbyl radical, or 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 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 -C 40 hydrocarbyl radical, or a functional group comprising elements from groups 13 to 17 of the periodic table of the elements, wherein 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 support is present in the form of spheroidal particles, has an average aspect ratio (L/W) of 1 to 1.7; has an average particle size (D50) of 20 to 180 microns, has a surface area of about 100 to about 200 m 2 /g and has a pore volume of about 0.1 to about 0.4 cc/g.

3. The catalyst system of claim 1 , wherein the catalyst system has an average aspect ratio (L/W) of 1 to 1.7, has an average particle size (D50) of 20 to 180 microns, and has a pore volume of about 0.1 to about 0.4 cc/g.

4. The catalyst system of claim 1 , wherein the support comprises particles of an agglomerate of an inorganic oxide and treated layered silicate, where the particles have been spray dried prior to contact with the organo aluminum.

5. The catalyst system of claim 4 , wherein the support is obtained by spray drying an aqueous slurry of layered silicate and an inorganic oxide, where a pH of the slurry is from about 3 to 7; a dry solids content of the slurry is from about 20 to 30 wt % based on a weight of the slurry and a weight of the dry solids; a ratio of inorganic oxide to layered silicate in the slurry is from 1:5 to 1:20; and the support has an average particle size of from 20 to 125 microns and is free flowing.

6. A process to polymerize olefins comprising:
i) contacting olefins with a catalyst system comprising: 1) support comprising inorganic oxide and an organoaluminum treated layered silicate and 2) catalyst compound represented by Formula (A):

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, a univalent C 1 to C 20 hydrocarbyl radical, or 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 that however 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 functional group comprising elements from groups 13 to 17 of the periodic table of the elements, wherein 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 may 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, and
ii) obtaining polyolefin.

7. The process 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 —.

8. The process of claim 1 , wherein R *1 and R *2 each comprises a cyclopentadienyl radical having a structure according to Formula II:

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

9. The process of claim 1 , wherein the catalyst compound has a structure according to Formula III:

wherein each of R 7 and R 26 is, independently, 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;
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 , R 33 , and R 34 is, independently, 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,
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.

10. The process of claim 1 , wherein the catalyst compound has a structure according to Formula V:

wherein:
N 3 and N 4 are nitrogen;
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 -C 40 hydrocarbyl radical, or a functional group comprising elements from groups 13 to 17 of the periodic table of the elements, or 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.

11. The process of claim 1 , wherein the catalyst compound has a structure according to 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 functional group comprising elements from groups 13 to 17 of the periodic table of the elements, or two or more of R 1 to R 6 and R 12 to R 27 may independently joi

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Atienza Crisita Carmen H
• Holtcamp Matthew W
• Ye Xuan
• Day Gregory S
• Cano David A
• Titone Michelle E
• Mertens Machteld M W
• Majano Sanchez Gerardo J

Classifications

• C08F210/16 Primary

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

• C08F4/60189

  ONNO · CPC title

• C08F4/64

  Titanium, zirconium, hafnium or compounds thereof · CPC title

• C08F4/64189

  ONNO · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title