Polymers produced via use of quinolinyldiamido transition metal complexes and vinyl transfer agents
Catalyst systems with single site transition metal complexes (such as quinolinyldiamide transition metal complexes), an activator, and a metal hydrocarbenyl transfer agent (preferably an aluminum vinyl-transfer agent) are disclosed for use in alkene polymerization.
1. A catalyst system comprising a quinolinyldiamido transition metal complex represented by the Formula I:
wherein:
M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 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 (e.g., R 1 & R 2 , R 2 & R 3 , etc.) 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;
an activator; and
and a metal hydrocarbenyl transfer agent.
2. The catalyst system of claim 1 , wherein J is selected from the following structures:
where indicates connection to the complex.
3. The catalyst system of claim 1 , wherein the complex is further represented by Formula (II):
wherein M, L, X, m, n, R 2 , R 3 , R 4 , R 5 , R 6 , and R 13 are as defined in claim 1 , and E is carbon, silicon, or germanium;
R 7 through R 12 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and
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 additional rings.
4. The catalyst system of claim 3 , wherein R 11 and R 12 are independently selected from hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, and trimethylsilyl.
5. The catalyst system of claim 3 , wherein E is carbon.
6. The catalyst system of claim 3 , 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.
7. The catalyst system of claim 1 , wherein M is Ti, Zr, or Hf.
8. The catalyst system of claim 1 , wherein R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls, and halogen.
9. The catalyst system of claim 1 , 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.
10. The catalyst system of claim 1 , 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 R 13 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.
11. The catalyst system of claim 1 , wherein J is dihydro-1H-indenyl and R 1 is 2,6-dialkylphenyl or 2,4,6-trialkylphenyl.
12. The catalyst system of claim 1 , 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.
13. The catalyst system of claim 1 , wherein the activator comprises an alumoxane and/or a non-coordinating anion.
14. The catalyst system 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)borate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine, triphenylcarbenium tetraphenylborate, and triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate.
15. The catalyst system of claim 1 , wherein the metal hydrocarbenyl 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 0.01 to 3.
16. The catalyst system of claim 15 , wherein R″ is butenyl, pentenyl, hexenyl, heptenyl, octenyl or decenyl, and/or R′ is methyl, ethyl, propyl, isobutyl, or butyl.
17. The catalyst system of claim 1 , 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, 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-1-yl)aluminum, dibutyl(dec-9-en-1-yl)aluminum, diisobutyl(dec-9-en-1-yl)aluminum, and diisobutyl(dodec-11-en-1-yl)aluminum.
18. A polymerization process comprising contacting one or more alkene monomers with the catalyst system of claim 1 .
19. The process of claim 18 , wherein the monomer comprises ethylene or propylene.
20. The process of claim 18 , wherein the monomers comprise at least two of ethylene, propylene, and an alkyl diene.
21. The process of claim 18 , wherein the transition metal complex is supported.
22. The process of claim 21 , wherein the support is silica.
23. The process of claim 18 , wherein the polymerization is performed in one or more continuous stirred tank reactors in series or in parallel.
24. The process of claim 18 , wherein the monomer comprises ethylene and octene.
25. The process of claim 18 , wherein the monomer comprises ethylene.
26. A polymerization process comprising contacting one or more alkene monomers with the catalyst system of claim 3 .
27. The catalyst system of claim 1 , wherein the metal hydrocarbenyl 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=2.
28. The catalyst system of claim 15 , wherein R″ is butenyl, pentenyl, hexenyl, heptenyl, octenyl or decenyl, and R′ is methyl, ethyl, propyl, isobutyl, or butyl.