Polymers produced via use of vinyl transfer agents
Catalyst systems with single site transition metal complexes (such as pyridyldiamido transition metal complexes), an activator, and a metal hydrocarbenyl chain transfer agent (preferably an aluminum vinyl-transfer agent) are disclosed for use in alkene polymerization.
1. A catalyst system comprising a pyridyldiamido transition metal complex represented by the formula:
wherein:
M is a Group 3, 4, 5, 6, 7, 8, or metal;
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 each independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;
R 2 , 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, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino;
n is 1 or 2;
m is 0, 1, or 2; and
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 are joined to form a ring;
an activator; and
a metal hydrocarbenyl chain transfer agent.
2. The catalyst system of claim 1 , wherein the metal hydrocarbenyl chain transfer agent is an aluminum vinyl transfer agent, AVTA.
3. The catalyst system of claim 1 , wherein M is Ti, Zr, or Hf.
4. The catalyst system of claim 1 , wherein E is carbon.
5. The catalyst system of claim 1 , wherein X is an alkyl, aryl, hydride, alkylsilane, fluoride, chloride, bromide, iodide, triflate, carboxylate, or alkylsulfonate.
6. The catalyst system of claim 1 , wherein L is an ether, amine, or thioether.
7. The catalyst system of claim 1 , wherein the activator comprises an alumoxane and or a non-coordinating anion.
8. The catalyst system of claim 7 , 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(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Me 3 NH + ][B(C 6 F 5 ) 4 − ], 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridinium, triphenylcarbenium tetraphenylborate, and triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate.
9. The catalyst system of claim 1 , wherein the metal hydrocarbenyl chain transfer agent is represented by the formula:
Al(R′) 3-v (R″) v or E[Al(R′) 2-y (R″) y ] 2
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;
E is a group 16 element;
v is from 0.01 to 3; and
y is from 0.01 to 2.
10. The catalyst system of claim 9 , wherein R″ is butenyl, pentenyl, heptenyl, or octenyl and or R′ is methyl, ethyl, propyl, isobutyl, or butyl.
11. The catalyst system of claim 1 , wherein the catalyst system does not comprise a metallocene.
12. The catalyst system of claim 9 , wherein v=2.
13. A polymerization process comprising contacting one or more alkene monomers with the catalyst system of claim 1 .
14. The process of claim 13 , wherein the activator comprises an alumoxane.
15. The process of claim 13 , wherein the activator comprises a non-coordinating anion.
16. The process of claim 13 , wherein the one or more monomers comprises ethylene or propylene.
17. The process of claim 13 , wherein the one or more monomers comprise at least two of ethylene, propylene, and an alkyl diene.
18. The process of claim 13 , wherein the pyridyldiamido transition metal complex is supported.
19. The process of claim 18 , wherein the support is silica.
20. The process of claim 13 , wherein the metal hydrocarbenyl chain transfer agent is represented by the formula:
Al(R′) 3-v (R″) v or E[Al(R′) 2-y (R″) y ] 2
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;
E is a group 16 element;
v is from 0.01 to 3; and
y is from 0.01 to 2.
21. The process of claim 20 , wherein R″ is butenyl, pentenyl, heptenyl, or octenyl, R′ is methyl, ethyl, propyl, isobutyl, or butyl and v=2.
22. The process of claim 13 , further comprising adding a metallocene after contacting one or more alkene monomers with the catalyst system.
23. The process of claim 22 , wherein the adding a metallocene is conducted in a second reactor.
24. The process of claim 22 , wherein the contacting one or more alkene monomers with the catalyst system and the adding a metallocene are performed in a continuous stirred tank reactor.
25. A polymerization process to produce polyolefin having allyl chain ends, and optionally a g′vis of 0.95 or more, comprising contacting one or more alkene monomers with the catalyst system of claim 1 where moles of metal hydrocarbenyl chain transfer agent added to the reactor relative to an amount of polymer produced is 500,000 or more.
26. A polymerization process to produce polyolefin having a g′vis of 0.95 or less comprising contacting one or more alkene monomers with the catalyst system of claim 1 where moles of metal hydrocarbenyl chain transfer agent added to a reactor relative to an amount of polymer produced is less than 500,000.
27. A catalyst system comprising a pyridyldiamido transition metal complex represented by the formula:
wherein:
M is a Group 3, 4, 5, 6, 7, 8, or 9 metal;
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 each independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;
R 2 , 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, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino;
n is 1 or 2;
m is 0, 1, or 2; and
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 are joined to form a ring;
an activator; and
aluminum vinyl transfer agent represented by the formula: Al(R′) 3-v (R″) v , wherein each R′, independently, is a C 1 to C 30 hydrocarbyl group; each R″, independently, is a C 4 to C 20 hydrocarbenyl group having an allyl chain end; v is from 0.01 to 3.
28. The catalyst system of claim 27 , 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, and diisobutyl(dodec-11-en-1-yl)aluminum.
29. A polymerization process comprising contacting one or more alkene monomers with the catalyst system of claim 27 .
30. A catalyst system comprising an activator; and aluminum vinyl transfer agent represented by the formula: Al(R′) 3-v (R″) v , wherein each R′, independently, is a C 1 to C 30 hydrocarbyl group; each R″, independently, is a C 7 to C 20 hydrocarbenyl group having an allyl chain end; v is from 0.01 to 3; and a transition metal complex represented by the formula:
where: (1) J* is a divalent bridging group comprising C, Si, or both; (2) M is a group 4 metal; (3) O is oxygen; (4) 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; and (5) L 4 and L 5 are independently, a substituted monocyclic or polycyclic aromatic group.