Polymers Produced via Use of Vinyl Transfer Agents

Patent metadata

Field	Value
Publication number	US-2018201698-A1
Application number	US-201615744513-A
Country	US
Kind code	A1
Filing date	Aug 10, 2016
Priority date	Aug 31, 2015
Publication date	Jul 19, 2018
Grant date	—

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, 9, 10, 11, or 12 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 may be 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(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Ph 3 C + ][B(C 6 F 5 ) 4 − -], [Me 3 NH + ][B(C 6 F 5 ) 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, 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 monomer comprises ethylene or propylene.

17 . The process of claim 13 , wherein the 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 the step of adding a metallocene in a second step.

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

24 . The process of claim 22 , wherein the steps are performed in a continuous stirred tank reactor.

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

wherein:
M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 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 may be 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.

26 . The catalyst system of claim 25 , wherein the aluminum vinyl transfer agent comprises one or more of tri(but-3-en-1-yl)aluminum, tri(pent-4-en-1-yl)aluminum, tri(oct-7-en-1-yl)aluminum, tri(non-8-en-1-yl)aluminum, tri(dec-9-en-1-yl)aluminum, dimethyl(oct-7-en-1-yl)aluminum, diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum, diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminum, diisobutyl(dec-8-en-1-yl)aluminum, and diisobutyl(dodec-10-en-1-yl)aluminum.

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

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

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

Classifications

• C08F8/42

  Introducing metal atoms or metal-containing groups · CPC title

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title

• C08F2420/02

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

• C08F10/02 Primary

  Ethene · CPC title

• C08F4/65927 Primary

  two cyclopentadienyl rings being mutually bridged · CPC title