Polymers produced via use of vinyl transfer agents

Patent metadata

Field	Value
Publication number	US-10829569-B2
Application number	US-201615744513-A
Country	US
Kind code	B2
Filing date	Aug 10, 2016
Priority date	Aug 31, 2015
Publication date	Nov 10, 2020
Grant date	Nov 10, 2020

Abstract

Catalyst systems with single site transition metal complexes (such as pyridyldiamido transition metal complexes), an activator, and a metal hydrocarbenyl chain transfer agent (preferably an aluminum vinyl-transfer agent) are disclosed for use in alkene polymerization.

First claim

What is claimed is:

1. A catalyst system comprising a pyridyldiamido transition metal complex represented by the formula:

wherein:
M is a Group 3, 4, 5, 6, 7, 8, or metal;
E is selected from carbon, silicon, or germanium;
X is an anionic leaving group;
L is a neutral Lewis base;
R 1 and R 13 are each independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;
R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are each independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino;
n is 1 or 2;
m is 0, 1, or 2; and
two X groups may be joined together to form a dianionic group;
two L groups may be joined together to form a bidentate Lewis base;
an X group may be joined to an L group to form a monoanionic bidentate group;
R 7 and R 8 may be joined to form a ring;
R 10 and R 11 are joined to form a ring;
an activator; and
a metal hydrocarbenyl chain transfer agent.

2. The catalyst system of claim 1 , wherein the metal hydrocarbenyl chain transfer agent is an aluminum vinyl transfer agent, AVTA.

3. The catalyst system of claim 1 , wherein M is Ti, Zr, or Hf.

4. The catalyst system of claim 1 , wherein E is carbon.

5. The catalyst system of claim 1 , wherein X is an alkyl, aryl, hydride, alkylsilane, fluoride, chloride, bromide, iodide, triflate, carboxylate, or alkylsulfonate.

6. The catalyst system of claim 1 , wherein L is an ether, amine, or thioether.

7. The catalyst system of claim 1 , wherein the activator comprises an alumoxane and or a non-coordinating anion.

8. The catalyst system of claim 7 , wherein the activator comprises one or more of:
trimethylammonium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, trimethylammonium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Me 3 NH + ][B(C 6 F 5 ) 4 − ], 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridinium, triphenylcarbenium tetraphenylborate, and triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate.

9. The catalyst system of claim 1 , wherein the metal hydrocarbenyl chain transfer agent is represented by the formula:
Al(R′) 3-v (R″) v or E[Al(R′) 2-y (R″) y ] 2

wherein each R′, independently, is a C 1 -C 30 hydrocarbyl group;
each R″, independently, is a C 4 -C 20 hydrocarbenyl group having an allyl chain end;
E is a group 16 element;
v is from 0.01 to 3; and
y is from 0.01 to 2.

10. The catalyst system of claim 9 , wherein R″ is butenyl, pentenyl, heptenyl, or octenyl and or R′ is methyl, ethyl, propyl, isobutyl, or butyl.

11. The catalyst system of claim 1 , wherein the catalyst system does not comprise a metallocene.

12. The catalyst system of claim 9 , wherein v=2.

13. A polymerization process comprising contacting one or more alkene monomers with the catalyst system of claim 1 .

14. The process of claim 13 , wherein the activator comprises an alumoxane.

15. The process of claim 13 , wherein the activator comprises a non-coordinating anion.

16. The process of claim 13 , wherein the one or more monomers comprises ethylene or propylene.

17. The process of claim 13 , wherein the one or more monomers comprise at least two of ethylene, propylene, and an alkyl diene.

18. The process of claim 13 , wherein the pyridyldiamido transition metal complex is supported.

19. The process of claim 18 , wherein the support is silica.

20. The process of claim 13 , wherein the metal hydrocarbenyl chain transfer agent is represented by the formula:
Al(R′) 3-v (R″) v or E[Al(R′) 2-y (R″) y ] 2

wherein each R′, independently, is a C 1 -C 30 hydrocarbyl group;
each R″, independently, is a C 4 -C 20 hydrocarbenyl group having an allyl chain end;
E is a group 16 element;
v is from 0.01 to 3; and
y is from 0.01 to 2.

21. The process of claim 20 , wherein R″ is butenyl, pentenyl, heptenyl, or octenyl, R′ is methyl, ethyl, propyl, isobutyl, or butyl and v=2.

22. The process of claim 13 , further comprising adding a metallocene after contacting one or more alkene monomers with the catalyst system.

23. The process of claim 22 , wherein the adding a metallocene is conducted in a second reactor.

24. The process of claim 22 , wherein the contacting one or more alkene monomers with the catalyst system and the adding a metallocene are performed in a continuous stirred tank reactor.

25. A polymerization process to produce polyolefin having allyl chain ends, and optionally a g′vis of 0.95 or more, comprising contacting one or more alkene monomers with the catalyst system of claim 1 where moles of metal hydrocarbenyl chain transfer agent added to the reactor relative to an amount of polymer produced is 500,000 or more.

26. A polymerization process to produce polyolefin having a g′vis of 0.95 or less comprising contacting one or more alkene monomers with the catalyst system of claim 1 where moles of metal hydrocarbenyl chain transfer agent added to a reactor relative to an amount of polymer produced is less than 500,000.

27. A catalyst system comprising a pyridyldiamido transition metal complex represented by the formula:

wherein:
M is a Group 3, 4, 5, 6, 7, 8, or 9 metal;
E is selected from carbon, silicon, or germanium;
X is an anionic leaving group;
L is a neutral Lewis base;
R 1 and R 13 are each independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;
R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino;
n is 1 or 2;
m is 0, 1, or 2; and
two X groups may be joined together to form a dianionic group;
two L groups may be joined together to form a bidentate Lewis base;
an X group may be joined to an L group to form a monoanionic bidentate group;
R 7 and R 8 may be joined to form a ring;
R 10 and R 11 are joined to form a ring;
an activator; and
aluminum vinyl transfer agent represented by the formula: Al(R′) 3-v (R″) v , wherein each R′, independently, is a C 1 to C 30 hydrocarbyl group; each R″, independently, is a C 4 to C 20 hydrocarbenyl group having an allyl chain end; v is from 0.01 to 3.

28. The catalyst system of claim 27 , wherein the aluminum vinyl

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Hagadorn John R
• Canich Jo Ann M
• Holtcamp Matthew W
• Palafox Patrick J
• Mathialagan Ramyaa

Classifications

• C08F4/659

  Component covered by group C08F4/64 containing a transition metal-carbon bond {(C08F4/64003 - C08F4/64196 take precedence)} · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F10/02 Primary

  Ethene · CPC title

• C08F2420/02

  Cp or analog bridged to a non-Cp X anionic donor · CPC title

• C08F4/64 Primary

  Titanium, zirconium, hafnium or compounds thereof · CPC title