Production of polyolefins with internal unsaturation structures using a metallocene catalyst system

Patent metadata

Field	Value
Publication number	US-9926396-B2
Application number	US-201615249021-A
Country	US
Kind code	B2
Filing date	Aug 26, 2016
Priority date	Oct 23, 2015
Publication date	Mar 27, 2018
Grant date	Mar 27, 2018

Abstract

This invention relates to a process to polymerize olefins, particularly to produce ethylene polymers with internal unsaturation structures.

First claim

What is claimed is:

1. A process to polymerize olefins comprising:
1) contacting olefin monomers with a catalyst system comprising an activator and a bis-cyclopentadienyl metallocene compound represented by the formula:

wherein:
M is Hf;
each X 1 and X 2 is, independently, a hydrocarbyl radical having from 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine, phosphine, ether, or X 1 and X 2 optionally form a part of a fused ring or a ring system;
each of R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , and R 9 is, independently, hydrogen, halide, alkoxide or a C 1 to C 40 substituted or unsubstituted hydrocarbyl group, provided that at least one of R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , and R 9 is a linear C 3 to C 20 substituted or unsubstituted hydrocarbyl group;
T is a group 14 atom;
each R a and R b is, independently, a C 1 to C 40 substituted or unsubstituted hydrocarbyl;
and
wherein the bis-cyclopentadienyl metallocene compound generates hydrogen and the polymerization occurs in the presence of hydrogen;
2) obtaining a polymer having:
a) an internal unsaturation of 50% or more;
b) a melt index of less than 20 g/10 min; and
c) a g′vis of 0.95 or more.

2. The process of claim 1 , wherein each X 1 and X 2 is, independently, a halide or a C 1 to C 5 alkyl group.

3. The process of claim 1 , wherein each R a and R b is, independently, a C 6 to C 20 substituted or unsubstituted aryl.

4. The process of claim 1 , wherein at least one of R 6 , R 7 , R 8 , and R 9 and at least one of R 1 , R 2 , R 3 , R 4 , is a linear C 3 to C 20 substituted or unsubstituted hydrocarbyl group.

5. The process of claim 1 , wherein each R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , and R 9 is, independently, a linear C 3 to C 20 alkyl group.

6. The process of claim 1 , wherein at least one of R 7 and R 8 and at least one of R 2 and R 3 is, independently, a n-propyl, n-butyl, n-pentyl, or n-hexyl group.

7. The process of claim 1 , wherein each R a and R b comprises a phenyl or substituted phenyl group.

8. The process of claim 1 , wherein the metallocene compound comprises one or more of: diphenylsilylbis(n-propylcyclopentadienyl)hafnium X 1 X 2 , diphenylsilylbis(n-butylcyclopentadienyl)hafniumX 1 X 2 , diphenylsilylbis(n-pentylcyclopentadienyl)hafniumX 1 X 2 , diphenylsilyl(n-propyl cyclopentadienyl)(n-butyl cyclopentadienyl)hafniumX 1 X 2 , diphenylsilylbis[(2-trimethylsilylethyl)cyclopentadienyl]hafniumX 1 X 2 , dimethylsilylbis(n-propylcyclopentadienyl)hafniumX 1 X 2 , dimethylsilylbis(n-butylcyclopentadienyl)hafniumX 1 X 2 , dimethylsilylbis(n-pentylcyclopentadienyl)hafniumX 1 X 2 , dimethylsilyl(n-propyl cyclopentadienyl)(n-butyl cyclopentadienyl)hafniumX 1 X 2 , dimethylsilylbis[(2-trimethylsilylethyl)cyclopentadienyl]hafniumX 1 X 2 ,
wherein each X 1 and X 2 is, independently, selected from the group consisting of chlorides, fluorides, methyl, ethyl, propyl, and butyl groups.

9. The process of claim 1 , wherein the activator comprises alumoxane and/or a non-coordinating anion activator.

10. The process of claim 9 , wherein the activator comprises alumoxane present at a molar ratio of aluminum to transition metal of the metallocene compound of 100:1 or more.

11. The process of claim 1 , wherein the activator is represented by the formula:
(Z) d + (A d− )
wherein Z is (L-H) or a reducible Lewis Acid, L is a neutral Lewis base; H is hydrogen; (L-H) + is a Bronsted acid; A d− is a non-coordinating anion having the charge d−; and d is an integer from 1 to 3.

12. The process of claim 1 , wherein the activator is one or more of: N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorophenyl)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, [Me3NH+][B(C6F5)4-], 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium, tetrakis(pentafluorophenyl)borate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine, triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate), trialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N-dialkylanilinium tetrakis(perfluoronaphthyl)borate, trialkylammonium tetrakis(perfluorobiphenyl)borate, N,N-dialkylanilinium tetrakis(perfluorobiphenyl)borate, trialkylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di -(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,
wherein alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl, or t-butyl.

13. The process of claim 1 , wherein the olefin monomer comprises ethylene.

14. The process of claim 1 , wherein the catalyst system is supported on an inert support material.

15. The process of claim 1 , wherein the catalyst system is supported on support material selected from the group consisting of talc, inorganic oxides, zeolites, clays, organoclays and mixtures thereof.

16. The process of claim 1 , wherein step 1) occurs at a temperature of from about 0° C. to about 300° C., at a pressure in the range of from about 0.35 MPa to about 10 MPa, and at a time of up to 300 minutes.

17. The process of claim 1 , wherein step 1) occurs at a temperature of from about 0° C. to about 300° C., at a pressure in the range of from about 0.35 MPa to about 10 MPa, and at a time of up to 300 minutes.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Holtcamp Matthew W
• Bedoya Matthew S
• Ye Xuan
• Sanders David F
• Day Gregory S
• Mattler Sarah J

Classifications

• C08F4/65925

  two cyclopentadienyl rings being mutually non-bridged · CPC title

• C08F2800/20

  as weight or mass percentages · CPC title

• C08F210/16 Primary

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

• C08F4/65916

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

• C08F2500/18

  Bulk density · CPC title