Supported bis phenolate transition metals complexes, production and use thereof

Patent metadata

Field	Value
Publication number	US-9982076-B2
Application number	US-201615242357-A
Country	US
Kind code	B2
Filing date	Aug 19, 2016
Priority date	Oct 2, 2015
Publication date	May 29, 2018
Grant date	May 29, 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 of Formula I:

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 -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;
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 -C 60 hydrocarbyl radical, a C 1 -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 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 1 , 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 and 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 or may not be aromatic and may have multiple fused rings.

5. The catalyst system of claim 1 , wherein G is 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 8 .

6. The catalyst system of claim 1 , wherein the catalyst complex 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 M is Zr, Hf, or Ti
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 both X groups join together to form a C 4 to C 62 cyclic or polycyclic ring structure;
each R′ is, independently, a hydrogen, a C 1 to C 40 hydrocarbyl radical, a C 1 -C 40 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group, or two or more of R′ may 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 system further comprises a chain transfer agent.

8. The catalyst system of claim 1 , wherein the catalyst system further comprises chain transfer agent represented by the formula R 3 Al or R 2 Zn, where R is a C 1 to C 20 alkyl group.

9. The catalyst system of claim 1 , wherein the activator comprises an alkylalumoxane.

10. The catalyst system of claim 1 , wherein the activator is selected from the group consisting of: methylalumoxane, ethylalumoxane, isobutyl alumoxane, N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium, and 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

11. The catalyst system of claim 1 , 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 and 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 -C 40 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group.

12. A method of preparing a catalyst system according to claim 1 , comprising:
combining a fluoride compound with water, then combining with a slurry of a non-polar solvent and a support,
removing the non-polar solvent,
thereafter combining the support with a second solvent, which may be the same as or different from the non-polar solvent, an activator, and at least a first catalyst compound according to Formula I:

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 -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;
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.

13. The method of claim 12 , wherein the support comprises silica.

14. The method of claim 12 , wherein the support is calcined at a temperature from 100° to less than 400° C., before or after combination with the activator and/or catalyst compounds.

15. The method of claim 12 , wherein a ratio (by weight) of water to non-polar solvent is between 1:10 to 1:1000.

16. The method of claim 12 , wherein the non-polar solvent is toluene, pentane, hexane, or benzene.

17. The method of claim 12 , wherein the fluoride compound is one or more of

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

• C08F4/64

  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

• C08F4/64189

  ONNO · CPC title

• C08F2410/07

  Catalyst support treated by an anion, e.g. Cl-, F-, SO42- · CPC title