Branched ethylene copolymers produced via use of vinyl transfer agents and processes for production thereof

1. A process to produce a branched ethylene copolymer comprising:

1) contacting monomer comprising ethylene and C 4 to C 8 alpha-olefin comonomer with a catalyst system comprising an activator, a metal hydrocarbenyl chain transfer agent, and one or more catalyst complexes represented by formula I or II:

wherein:

M is a Group 3, 4, 5, 6, 7, 8, 9, or 10 metal;

E is C(R 2 ) or C(R 3 )(R 3′ );

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 is a group containing 1-10 carbon atoms that is optionally joined with R 4 to form an aromatic ring;

R 3 , 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, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyl, halogen, and phosphino groups;

J is a divalent group that forms a three-atom-length bridge between the pyridine ring and the amido nitrogen;

n is 1 or 2;

m is 0, 1, or 2;

two X groups optionally join together to form a dianionic group;

two L groups optionally join together to form a bidentate Lewis base;

an X group optionally joins to an L group to form a monoanionic bidentate group;

where adjacent R 3 , R 3′ , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 groups are optionally joined to form a ring;

where the metal hydrocarbenyl chain transfer agent is one or more aluminum vinyl transfer agents 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 end-vinyl group; and v is from 0.1 to 3; and

2) obtaining branched ethylene copolymer comprising greater than 50 mol % ethylene, and one or more C 4 to C 8 alpha-olefin comonomers, and a remnant of the metal hydrocarbenyl chain transfer agent,

wherein said branched ethylene copolymer:

a) has a g′ vis of less than 0.97;

b) is essentially gel free;

c) has an Mw of 60,000 g/mol or more; and

d) has a Mw/Mn of less than 4.0.

2. A process to produce branched copolymer comprising:

1) contacting monomer comprising ethylene and C 4 to C 8 alpha-olefin comonomer with a catalyst system comprising an activator, a metal hydrocarbenyl chain transfer agent, and one or more catalyst complexes represented by the formula:

wherein: (1) M is a group 4 metal; (2) N is nitrogen; (3) L 7 is group that links R 50 to Z′ by a three-atom-length bridge with the central of the three atoms being a group 15 or 16 element that optionally forms a dative bond to M, and is a C 5 -C 20 heteroaryl group containing a Lewis base functionality; (4) Z′ is a divalent linker group, (R 56 ) p C—C(R 57 ) q , where each R 56 and R 57 is independently selected from the group consisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl groups, and wherein adjacent R 56 and R 57 groups may be joined to form an aromatic or saturated, substituted or unsubstituted hydrocarbyl ring, wherein the ring has 5, 6, 7, or 8 ring carbon atoms and where the substituents on the substituted ring can join to form additional rings, and p is 1 or 2 and q is 1 or 2; (5) R 50 and R 53 are each, independently, ER 54 R 55 wherein each E is independently carbon, silicon or germanium, and each R 54 and R 55 is independently selected from the group consisting of: hydrogen, hydrocarbyl, substituted hydrocarbyl, alkoxy, silyl, amino, aryloxy, halogen and phosphino groups, 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 saturated substituted heterocyclic ring optionally join to form additional a ring or rings; (6) R 51 and R 52 are independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, silylcarbyl, and substituted silylcarbyl groups; and (7) each X is independently a univalent anionic ligand, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand;

where the metal hydrocarbenyl chain transfer agent is one or more aluminum vinyl transfer agents 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 end-vinyl group; and v is from 0.1 to 3; and

2) obtaining branched ethylene copolymer comprising greater than 50 mol % ethylene and one or more C 4 to C 8 alpha-olefin comonomer, and a remnant of the metal hydrocarbenyl chain transfer agent,

wherein said branched ethylene copolymer: a) has a g′ vis of less than 0.97; b) is essentially gelfree; c) has an Mw of 60,000 g/mol or more; and d) has a Mw/Mn of less than 4.0.

3. The process of claim 1 , wherein the catalyst complex is represented by the formula:

wherein:

M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal;

E is carbon, silicon, or germanium;

X is an anionic group;

L is a neutral Lewis base;

R 1 and R 13 are each independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, and silyl groups;

R 2 through R 12 are each independently selected from the group consisting of hydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyl, halogen, and phosphino groups;

n is 1 or 2;

m is 0, 1, or 2;

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; and

R 10 and R 11 may be joined to form a ring.

4. The process of claim 1 , wherein the catalyst complex is represented by 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 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 hydrocarbyl, substituted hydrocarbyl, and silyl groups;

R 2 * through R 12 are independently selected from the group consisting of hydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyl, halogen, and phosphino groups;

n is 1 or 2;

m is 0, 1, or 2

n+m is not greater than 4;

wherein 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 an additional ring or 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.

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

6. The process of claim 1 , wherein E is carbon.

7. A process to produce branched ethylene copolymer comprising:

contacting monomer comprising ethylene and a C 4 to C 8 alpha-olefin comonomer with a catalyst system comprising an activator, a metal hydrocarbenyl chain transfer agent, and one or more catalyst complexes represented by the formula:

wherein:

M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal;

E is carbon, silicon, or germanium;

X is an anionic group;

L is a neutral Lewis base;

R 1 and R 13 are each independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, and silyl groups;

R 5 through R 12 and R 14 through R 16 are each independently selected from the group consisting of hydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyl, halogen, and phosphino groups;

n is 1 or 2;

m is 0, 1, or 2;

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;

where the metal hydrocarbenyl chain transfer agent is one or more aluminum vinyl transfer agents 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 end-vinyl group; and v is from 0.1 to 3; and

2) obtaining branched ethylene copolymer comprising greater than 50 mol % ethylene and one or more C 4 to C 8 alpha-olefin comonomers, and a remnant of the metal hydrocarbenyl chain transfer agent,

wherein said branched ethylene copolymer: a) has a g′ vis of less than 0.97; b) is essentially gel free; c) has an Mw of 60,000 g/mol or more; and d) has a Mw/Mn of less than 4.0.

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

9. The process of claim 1 , wherein v is from 1.1 to 2.9.

10. The process of claim 1 , wherein R″ is butenyl, pentenyl, heptenyl, octenyl, or decenyl.

11. 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-11l-en-1-yl)aluminum.

12. The process of claim 1 , wherein v is 2.

13. The process of claim 1 , wherein the C 4 to C 8 alpha-olefin comonomer comprises 1-butene, 1-hexene and/or 1-octene.

14. The process of claim 1 , wherein the C 4 to C 8 alpha-olefin comonomer comprises 1-hexene.

15. The process of claim 1 , wherein the catalyst complex is supported.

16. The process of claim 1 , wherein the branched ethylene copolymer has a complex viscosity of at least 500 Pa·s measured at 0.1 rad/sec and a temperature of 190° C. 10 alternately at least 5000 Pa.

17. The process of claim 1 , wherein the branched ethylene copolymer comprises 5 wt % or less of xylene insoluble material.

18. The process of claim 2 , wherein M is Hf.

19. The process of claim 2 , wherein the Lewis base functionality is a divalent pyridinyl, substituted pyridinyl, quinolinyl, or substituted quinolinyl group.

20. The process of claim 2 , wherein the branched ethylene copolymer comprises 5 wt % or less of xylene insoluble material.

21. The process 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)b orate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine, triphenylcarbenium tetraphenylborate, and triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate.

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

23. The process of claim 1 , wherein R′ is methyl, ethyl, propyl, isobutyl, or butyl.

24. The process of claim 1 , wherein the branched ethylene copolymer has a complex viscosity of at least 5000 Pa·s measured at 0.1 rad/sec and a temperature of 190° C.