Long chain branched polypropylene via polymerization with aluminum vinyl transfer agent

Patent metadata

Field	Value
Publication number	US-10927196-B2
Application number	US-201816026196-A
Country	US
Kind code	B2
Filing date	Jul 3, 2018
Priority date	Jun 30, 2016
Publication date	Feb 23, 2021
Grant date	Feb 23, 2021

Abstract

The present disclosure provides the use of quinolinyldiamido transition metal complexes, an activator and a metal hydrocarbenyl chain transfer agent, such as an aluminum vinyl-transfer agent, to produce long chain branched propylene polymers.

First claim

What is claimed is:

1. A process to produce branched propylene polymers comprising:
1) contacting, at a temperature of from 70° C. to 150° C., monomer comprising propylene with a catalyst system comprising: a) an activator, b) a metal hydrocarbenyl chain transfer agent 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, and c) non-metallocene olefin polymerization transition metal complex that readily undergoes reversible polymeryl group chain transfer with the metal hydrocarbenyl chain transfer agent and is also capable of incorporating the allyl chain end of the metal hydrocarbenyl chain transfer agent to form a long-chain branched polymer,
wherein the non-metallocene polymerization catalyst transition metal complex undergoes reversible polymeryl group chain transfer with the metal hydrocarbenyl transfer agent and incorporates the allyl chain end of the metal hydrocarbenyl transfer agent to form a long-chain branched polymer; and
2) obtaining a branched propylene polymer comprising from about 90 wt % or greater propylene, wherein said branched propylene polymer: a) has a g′ vis of 0.97 or less;

b) has strain hardening ratio of 1 or greater; c) has an Mw of 50,000 g/mol or more; and d) has a Mw/Mn of 4 or less.

2. A process to produce branched propylene polymers comprising:
1) contacting monomer comprising propylene with a catalyst system comprising an activator, a metal hydrocarbenyl chain transfer agent, and a non-metallocene complex represented by Formula (I):

wherein:
M is a group 3, 4, or 5 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 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, and
wherein the metal hydrocarbenyl chain 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 0.1 to 3;
2) obtaining a branched propylene polymer comprising from about 90 wt % or greater propylene, wherein said branched propylene polymer: a) has a g′ vis of 0.97 or less;

b) has strain hardening ratio of 1 or greater; c) has an Mw of 50,000 g/mol or more; and d) has a Mw/Mn of 4 or less.

3. The process of claim 1 , wherein the propylene polymer has (at 190° C.) one or more of:
a power law index of from about 0.38 to about 0.63;
transition index of from about 0.24 to about 0.52;
consistency (characteristic time) of from about 7s to about 1.5s;
infinite-rate viscosity of from about −181.8 to about −143 Pa·s; and
zero-shear viscosity of from about 117 kPa·s to about 3.9 kPa·s.

4. The process of claim 1 , wherein the propylene polymer has a g′ vis of 0.95 or less.

5. The process of claim 1 , wherein the propylene polymer has a Tc of 63° C. or more.

6. The process of claim 1 , wherein the propylene polymer has a shear thinning index at 190° C. of from 1 to 11.

7. The process of claim 2 , wherein the propylene polymer has a shear thinning index at 190° C. of from 4 to 7.

8. The process of claim 1 , wherein the propylene polymer has a terminal unsaturation of 80% or more, based upon the number of the total unsaturations.

9. The process of claim 1 , wherein the polymerization is performed in one or more continuous stirred tank reactors in series or in parallel.

10. The process of claim 9 , wherein conversion of monomers is 20% or more.

11. The process of claim 1 , wherein the polymerization is performed at a temperature of from 75° C. to 150° C.

12. The process of claim 2 , wherein the polymerization is performed at a temperature of from 80° C. to 120° C.

13. The process of claim 3 , wherein the polymerization is performed at a temperature of from 90° C. to 100° C.

14. The process of claim 1 , wherein the catalyst compound has an efficiency greater than 50,000 g Polymer/g catalyst.

15. The process of claim 2 , wherein M is Ti, Zr, or Hf.

16. The process of claim 2 , wherein J is selected from:

wherein indicates connection to the catalyst compound.

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

18. The process of claim 2 , wherein the catalyst compound is represented by Formula (II):

wherein M, L, X, m, n, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 13 are as defined in claim 2 , and
E is carbon, silicon, or germanium;
R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are independently selected from hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, or any two adjacent R groups are joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, wherein the ring has 5, 6, 7, or 8 ring atoms and wherein substitutions on the ring can join to form additional rings.

19. The process of claim 18 , wherein R 11 and R 12 are independently selected from hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, and trimethylsilyl.

20. The process of claim 18 , wherein E is carbon.

21. The process of claim 18 , 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.

22. The process of claim 18 , wherein R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from hydrogen, hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls, and halogen.

23. The process of claim 18 , 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.

24. The process of claim 18 , 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-dicyclopentylphe

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Hagadorn John R
• Canich Jo Ann M
• Jiang Peijun
• Shivokhin Maksim E

Classifications

• C08F110/06 Primary

  Propene · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F110/14

  Monomers containing five or more carbon atoms · CPC title

• C08F110/02

  Ethene · CPC title

• C08F4/64148

  NN(R)N · CPC title