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

Patent metadata

Field	Value
Publication number	US-9994658-B2
Application number	US-201615242366-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 an inorganic oxide and organoaluminum treated layered silicate and 2) bisphenolate compound represented by Formula (A):

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 to C 40 hydrocarbyl radical, a C 1 to 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; 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 to C 60 hydrocarbyl radical, a C 1 to 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 8 ; and
Y is a divalent C 1 to C 20 hydrocarbylene or divalent C 1 to C 20 substituted hydrocarbylene.

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 organoaluminum.

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. The catalyst system of claim 1 , wherein the bisphenolate compound is represented by Formula (IV) or (V):

where Y is a divalent C 1 to C 3 hydrocarbylene, Q 1 is NR′ 2 , OR′, SR′, PR′ 2 , where each R′ is independently, a hydrogen, a C 1 to C 40 hydrocarbyl radical, a C 1 to 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, M is Zr, Hf or Ti and each X is, 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.

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

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 to C 40 hydrocarbyl radical, a C 1 to 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; 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 to C 60 hydrocarbyl radical, a C 1 to 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 8 ; and
Y is a divalent C 1 to C 20 hydrocarbylene or divalent C 1 to C 20 substituted hydrocarbylene and

ii) obtaining polyolefin.

8. The process of claim 7 , wherein M is Hf or Zr.

9. The process of claim 7 , 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.

10. The process of claim 7 , wherein Q is a neutral donor group comprising at least one atom from Group 15 or Group 16 and the -(-Q-Y—)— fragment can form a substituted or unsubstituted heterocycle which may aromatic and may have multiple fused rings.

11. The process of claim 7 , wherein Q is NR′ 2 , OR′, SR′, PR′ 2 , where each R′ is independently, a hydrogen, a C 1 to C 40 hydrocarbyl radical, a C 1 to 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.

12. The process of claim 7 , wherein G is a hydrogen, a C 1 to 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 .

13. The process of claim 7 wherein the bisphenolate compound is represented by Formula (IV) or (V):

where Y is a divalent C 1 to C 3 hydrocarbylene, Q 1 is NR′ 2 , OR′, SR′, PR′ 2 , where each R′ is independently, a hydrogen, a C 1 to C 40 hydrocarbyl radical, a C 1 to 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, M is Zr, Hf or Ti and each X is, 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.

14. The process of claim 7 , wherein the support comprises spheroida

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

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

Classifications

• C08F4/65916

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title

• C08F210/16 Primary

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

• C08F4/60189

  ONNO · CPC title

• C08F4/64013

  NN · CPC title

• C08F2500/03

  Narrow molecular weight distribution, i.e. Mw/Mn < 3 · CPC title