Polymers produced via use of quinolinyldiamido transition metal complexes and vinyl transfer agents

Patent metadata

Field	Value
Publication number	US-10562987-B2
Application number	US-201815869984-A
Country	US
Kind code	B2
Filing date	Jan 12, 2018
Priority date	Jun 30, 2016
Publication date	Feb 18, 2020
Grant date	Feb 18, 2020

Abstract

Catalyst systems with single site transition metal complexes (such as quinolinyldiamide transition metal complexes), an activator, and a metal hydrocarbenyl 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 quinolinyldiamido transition metal complex represented by the Formula I:

wherein:
M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal;
J is a three-atom-length bridge between the quinoline and the amido nitrogen;
X is an anionic leaving group;
L is a neutral Lewis base;
R 1 and R 13 are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;
R 2 , R 3 , R 4 , R 5 , and R 6 are 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
n+m is not greater than 4; and
any two adjacent R groups (e.g., R 1 & R 2 , R 2 & R 3 , etc.) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic ring, or unsubstituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings;
any two X groups may be joined together to form a dianionic group;
any two L groups may be joined together to form a bidentate Lewis base; and
an X group may be joined to an L group to form a monoanionic bidentate group;
an activator; and
and a metal hydrocarbenyl transfer agent.

2. The catalyst system of claim 1 , wherein J is selected from the following structures:

where indicates connection to the complex.

3. The catalyst system of claim 1 , wherein the complex is further represented by Formula (II):

wherein M, L, X, m, n, R 2 , R 3 , R 4 , R 5 , R 6 , and R 13 are as defined in claim 1 , and E is carbon, silicon, or germanium;
R 7 through R 12 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and
any two adjacent R groups may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings.

4. The catalyst system of claim 3 , wherein R 11 and R 12 are independently selected from hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, and trimethylsilyl.

5. The catalyst system of claim 3 , wherein E is carbon.

6. The catalyst system of claim 3 , wherein R 7 , R 8 , R 9 , and R 10 are independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy, and trimethylsilyl.

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

8. The catalyst system of claim 1 , wherein R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls, and halogen.

9. The catalyst system of claim 1 , wherein each L is independently selected from Et 2 O, MeOtBu, Et 3 N, PhNMe 2 , MePh 2 N, tetrahydrofuran, and dimethylsulfide and each X is independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

10. The catalyst system of claim 1 , wherein R 1 is 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2,6-diisopropyl-4-methylphenyl, 2,6-diethylphenyl, 2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl, 2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl; and/or R 13 is phenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, 2-isopropylphenyl, 4-methylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorophenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl.

11. The catalyst system of claim 1 , wherein J is dihydro-1H-indenyl and R 1 is 2,6-dialkylphenyl or 2,4,6-trialkylphenyl.

12. The catalyst system of claim 1 , wherein R 1 is 2,6-diisopropylphenyl and R 13 is a hydrocarbyl group containing 1, 2, 3, 4, 5, 6, or 7 carbon atoms.

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

14. The catalyst system of claim 1 , 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.

15. The catalyst system of claim 1 , wherein the metal hydrocarbenyl transfer agent is represented by the formula:
Al(R′) 3-v (R″) v

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; and
v is from 0.01 to 3.

16. The catalyst system of claim 15 , wherein R″ is butenyl, pentenyl, hexenyl, heptenyl, octenyl or decenyl, and/or R′ is methyl, ethyl, propyl, isobutyl, or butyl.

17. The catalyst system of claim 1 , wherein the metal hydrocarbenyl 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, dimethyl(dec-9-en-1-yl)aluminum, diethyl(dec-9-en-1-yl)aluminum, dibutyl(dec-9-en-1-yl)aluminum, diisobutyl(dec-9-en-1-yl)aluminum, and diisobutyl(dodec-11-en-1-yl)aluminum.

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

19. The process of claim 18 , wherein the monomer comprises ethylene or propylene.

20. The process of claim 18 , wherein the monomers comprise at least two of ethylene, propylene, and an alkyl diene.

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

22. The process of claim 21 , wherein the support is silica.

23. The process of claim 18 , wherein the polymerization is performed in one or more continuous stirred tank reactors in series or in parallel.

24. The process of claim 18 , wherein the monomer comprises ethylene and octene.

25. The process

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Canich Jo Ann M
• Hagadorn John R

Classifications

• C08F110/14

  Monomers containing five or more carbon atoms · CPC title

• C08F4/6498

  containing another heteroatom · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/6495 Primary

  containing nitrogen · CPC title

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title