Branched EPDM polymers produced via use of vinyl transfer agents and processes for production thereof

Patent metadata

Field	Value
Publication number	US-10626200-B2
Application number	US-201815906861-A
Country	US
Kind code	B2
Filing date	Feb 27, 2018
Priority date	Feb 28, 2017
Publication date	Apr 21, 2020
Grant date	Apr 21, 2020

Abstract

This invention relates to the use of quinolinyldiamido transition metal complexes and catalyst systems with an activator and a metal hydrocarbenyl chain transfer agent, such as an aluminum vinyl-transfer agent (AVTA), to produce branched propylene-ethylene-diene terpolymers.

First claim

What is claimed is:

1. A process to produce branched ethylene, propylene-diene terpolymers comprising:
1) contacting monomers comprising propylene, ethylene and diene with a catalyst system comprising an activator, a metal hydrocarbenyl chain transfer agent, and one or more catalyst complexes represented by the Formula (Ia) or (IIa):

wherein:
M is a Group 3, 4, 5, 6, 7, 8, 9, or 10 metal;
J is a three-atom-length bridge between the quinoline and the amido nitrogen;
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 independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;
R 2* and R 3 through R 12 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;
any two adjacent R groups (e.g., R 1 & R 2 , R 2 & R 3 , etc.) 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;
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; wherein
the metal hydrocarbenyl chain transfer agent is one or more aluminum vinyl transfer agents, AVTA, represented by 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 end-vinyl group; and v is from 0.1 to 3; and
2) obtaining propylene copolymers comprising from about 98.9 to 30 wt % propylene, from 1 to 70 wt % ethylene, from 0.5 to 20 wt % diene monomer, and a remnant of the metal hydrocarbenyl chain transfer agent, wherein said branched propylene copolymer: a) has a g′ vis of less than 0.90; b) is essentially gel free; c) has an Mw of 250,000 g/mol or more; d) has a Mw/Mn of greater than 3.0; and e) has an Mz of 850,000 g/mol or more;

wherein the process has a diene conversion of at least 15% and the ratio of the metal hydrocarbenyl chain transfer agent to the one or more catalyst complexes is at least 100:1.

2. The process of claim 1 , wherein M is Ti, Zr, or Hf.

3. The process of claim 1 wherein E is carbon.

4. The process of claim 1 , wherein J is selected from the following structures);

5. The process of claim 1 , wherein the catalyst complex is represented by Formula (6b):

wherein
M is a group 4 metal;
R 54 and R 55 , are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen and phosphino, and R 54 and R 55 may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings;
R 51 and R 52 are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, silylcarbyls and substituted silylcarbyl groups;
each X* is independently a univalent anionic ligand, or two X*s are joined and bound to the metal atom to form a metallocycle ring, or two X*s are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand;
R 61 , R 62 , R 63 , R 64 , R 65 , and R 66 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and wherein any one or more adjacent R 61 -R 66 may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, wherein the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings;
R 70 and R 71 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and wherein R 70 and R 71 may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, wherein the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings; and
t is 2 or 3.

6. The process of claim 5 , wherein M is Hf and t is 3.

7. The process of claim 6 wherein:
R 61 to R 66 are hydrogen;
R 70 and R 71 are independently hydrogen;
one or both R 54 or R 55 is hydrogen, or one of R 54 or R 55 is hydrogen and the other is an aryl group or substituted aryl group; and
R 52 and R 51 are independently aryl or substituted aryl.

8. The process of claim 6 wherein R 51 is 2,6-diisopropylphenyl, 2,6-diethylphenyl, 2,6-dimethylphenyl, or mesityl, and R 52 2-tolyl, 2-ethylphenyl, 2-propylphenyl, 2-trifluoromethylphenyl, 2-fluorophenyl, mesityl, 2,6-diisopropylphenyl, 2,6-diethylphenyl, 2,6-dimethylphenyl, or 3,5-di-tert-butylphenyl.

9. The process of claim 6 wherein R 54 , R 55 , R 61 to R 66 , R 70 and R 71 are hydrogen, R 52 is phenyl, R 51 is 2,6-diisopropylphenyl and t is 2.

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

11. The process of claim 1 , wherein the activator comprises one or more of: alumoxane, 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, 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.

12. The process of claim 1 , wherein v is from 0.1 to 3.

13. The process of claim 1 , wherein R″ is butenyl, pentenyl, heptenyl, or octenyl and or wherein R′ is methyl, ethyl, propyl, isobutyl, or butyl.

14. The process of claim 1 , 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-9-en-1-yl)aluminum, diisobutyl(dodec-11-en-1-yl)aluminum, methyl-di(oct-7-en-1-yl)aluminum, ethyl-di(oct-7-en-1-yl)aluminum, butyl-di(oct-7-en-1-yl)aluminum, isobutyl-di(oct-7-en-1-yl)aluminum, isobutyl-di(non-8-en-1-yl)aluminum, isobutyl-di(dec-9-en-1-yl)aluminum, and isobutyl-di(dodec-11-en-1-yl)aluminum.

15. The process of claim 1 , wherein v=2.

16.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Hagadorn John R
• Canich Jo Ann M
• Tsou Andy H
• Dharmarajan Narayanaswami
• Jiang Peijun
• Shah Rhutesh K

Classifications

• C08F4/65908

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

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F210/18

  with non-conjugated dienes, e.g. EPT rubbers · CPC title

• C08F210/02 Primary

  Ethene · CPC title

• C08F236/20

  unconjugated · CPC title