Long chain branched polypropylene via polymerization with aluminum vinyl transfer agent

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-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl; and/or R13 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.

25. The process of claim 18 , 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.

26. The process of claim 18 , wherein the activator comprises an alumoxane and/or a non-coordinating anion.

27. The process of claim 26 , 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, trimethylammonium tetrakis(perfluorophenyl)borate, 1 (4 (tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium, dimethylanilinium tetrakis(pentafluorophenyl)borate, 4 (tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine, triphenylcarbenium tetraphenylborate, and triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, methyldidodecylammonium tetrakis(pentafluorophenyl)borate, trihexadecylammonium tetrakis(pentafluorophenyl)borate.

28. The process of claim 1 , wherein v is from 1.1 to 3.

29. The process of claim 28 , wherein R″ is butenyl, pentenyl, hexenyl, heptenyl, octenyl, decenyl, or dodecenyl, and/or R′ is methyl, ethyl, propyl, isobutyl, or butyl.

30. The process of claim 28 , 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, tri(dodec-11-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-i-yl)aluminum, dibutyl(dec-9-en-1-yl)aluminum, diisobutyl(dec-9-en-1-yl)aluminum, and 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, methyl-di(dec-9-en-1-yl)aluminum, ethyl-di(dec-9-en-1-yl)aluminum, butyl-di(dec-9-en-1-yl)aluminum, isobutyl-di(dec-9-en-1-yl)aluminum, and isobutyl-di(dodec-11-en-1-yl)aluminum.

31. The process of claim 1 , wherein the branched propylene polymer has 5 wt % or less of xylene insoluble material.

32. The process of claim 1 , wherein the branched propylene polymer comprises 95 wt % or more propylene.

33. The process of claim 1 , wherein the branched propylene polymer comprises 100 wt % propylene, not including the remnant of any metal hydrocarbenyl chain transfer agent.

34. The process of claim 1 , wherein the propylene polymer has a g′ vis of 0.90 or less.

35. The process of claim 1 , wherein the non-metallocene polymerization catalyst transition metal complex is a late transition metal pyridylbisimine complex.

36. The process of claim 1 , wherein the non-metallocene polymerization catalyst transition metal complex is a pyridylamido complex.

37. The process of claim 1 , wherein the non-metallocene polymerization catalyst transition metal complex is a phenoxyimine complex.

38. The process of claim 1 , wherein the non-metallocene polymerization catalyst transition metal complex is a bridged bi-aromatic complex.

39. The process of claim 1 , wherein the non-metallocene polymerization catalyst transition metal complex is selected from the group consisting of iron complexes of tridentate pyridylbisimine ligands, zirconium and hafnium complexes of pyridylamido ligands, zirconium and hafnium complexes of tridentate pyridyldiamido ligands, zirconium and hafnium complexes of tridentate quinolinyldiamido ligands, zirconium and hafnium complexes of bidentate phenoxyimine ligands, and zirconium and hafnium complexes of bridged bi-aromatic ligands.

40. The process of claim 1 , wherein the non-metallocene polymerization catalyst transition metal complex is selected from the group consisting of group 4 non-metallocene complexes including: 1) two anionic donor atoms and one or two neutral donor atoms, or 2) an anionic amido donor, or 3) an anionic aryloxide donor atom, or 4) two anionic aryloxide donor atoms and two additional neutral donor atoms.

41. The process of claim 1 , wherein the non-metallocene polymerization catalyst transition metal complex is a group 4 pyridyldiamido complex.