Process using substituted metallocene catalysts and products therefrom
This invention relates to a process to produce propylene polymer using a bridged hafnium transition metal metallocene catalyst compounds having two indenyl ligands substituted at the 4 positions with a C 1 to C 10 alkyl, where the 3 positions are hydrogen (assuming the bridge position is counted as the one position) and the bridging atom is carbon or silicon which is incorporated into a cyclic group comprising 3, 4, 5, or 6 silicon and/or carbon atoms that make up the cyclic ring, where the propylene polymer has 1) greater than 40% vinyl chain ends, relative to the total unsaturated chain ends, 2) a Tm of 70° C. or more; an Mw of 3000 to 300,000 g/mol, and 4) a g′ vis of 0.90 or less.
1. A process for polymerization, comprising:
(i) contacting one or more monomers comprising propylene and optionally ethylene, with a catalyst system comprising a metallocene catalyst compound and an activator, wherein the metallocene catalyst compound is represented by the formula:
where each R 3 is hydrogen; each R 4 is independently a C 1 -C 10 alkyl; each R 2 and R 7 is independently hydrogen or C 1 -C 10 alkyl; each R 5 and R 6 is independently hydrogen, C 1 -C 50 substituted or unsubstituted hydrocarbyl, or C 1 -C 50 substituted or unsubstituted halocarbyl; and R 4 and R 5 , R 5 and R 6 and/or R 6 and R 7 are optionally bonded together to form a ring structure; J is a bridging group represented by the formula R a 2 J′, where J′ is C or Si, and each R a is, independently, C 1 to C 20 substituted or unsubstituted hydrocarbyl, and the two R a form a cyclic structure incorporating J′ and the cyclic structure is optionally a saturated or partially saturated cyclic or fused ring system; and each X is 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
(ii) obtaining a polymer having: 1) greater than 40% vinyl chain ends, relative to the total unsaturated chain ends, 2) a Tm of 70° C. or more; 3) an Mw of 3000 to 300,000 g/mol, and 4) a g′ vis of 0.90 or less.
2. The process of claim 1 , wherein step (i) occurs at a temperature of greater than 60° C.
3. The process of claim 1 , wherein the polymer produced has 1) greater than 70% vinyl chain ends, relative to total unsaturated chain ends, and 2) an Mw of 3000 to 200,000 g/mol.
4. The process of claim 1 , wherein the polymer produced is isotactic polypropylene having a Tm of 115° C. or more.
5. The process of claim 1 , wherein the polymer produced is a propylene-ethylene copolymer containing 30 wt % or less of ethylene.
6. The process of claim 1 , wherein the polyolefin produced has a g′ vis of 0.85 or less.
7. The process of claim 1 , wherein the polyolefin produced has at least X % vinyl chain ends (relative to total unsaturations as measured by 1 H NMR, where X=47.8*g′ vis +45.1.
8. The process of claim 1 wherein R 2 , R 4 and R 7 are, independently, selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl and an isomers thereof.
9. The process of claim 1 wherein R 2 and R 4 are, independently, a C 1 to C 10 alkyl.
10. The process of claim 1 wherein R 4 and R 7 are, independently, a C 1 to C 10 alkyl.
11. The process of claim 1 wherein each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof and two X's optionally form a part of a fused ring or a ring system.
12. The process of claim 1 wherein J is represented by the formula:
wherein J′ is a carbon or silicon atom, x is 1, 2, 3, or 4, and each R′ is, independently, hydrogen or C 1 -C 10 hydrocarbyl.
13. The process of claim 1 wherein J is cyclopentamethylenesilylene, cyclotetramethylenesilylene, cyclotrimethylenesilylene.
14. The process of claim 1 wherein the activator comprises alumoxane.
15. The process of claim 1 wherein alumoxane is present at a molar ratio of aluminum to catalyst compound transition metal of 100:1 or more.
16. The process of claim 1 wherein the activator comprises a non-coordinating anion activator.
17. The process of claim 1 wherein activator is represented by the formula:
(Z) d + (A d− )
wherein Z is (L-H) or a reducible Lewis Acid, L is an neutral Lewis base; H is hydrogen; (L-H) + is a Bronsted acid; A d− is a non-coordinating anion having the charge d−; and d is an integer from 1 to 3.
18. The process of claim 1 wherein activator is represented by the formula:
(Z) d + (A d− )
wherein A d− is a non-coordinating anion having the charge d−; d is an integer from 1 to 3, and Z is a reducible Lewis acid represented by the formula: (Ar 3 C + ), where Ar is aryl or aryl substituted with a heteroatom, a C 1 to C 40 hydrocarbyl, or a substituted C 1 to C 40 hydrocarbyl.
19. The process of claim 1 wherein the activator is one or more of:
N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,
triphenylcarbenium tetrakis(pentafluorophenyl)borate,
trimethylammonium tetrakis(perfluoronaphthyl)borate,
triethylammonium tetrakis(perfluoronaphthyl)borate,
N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,
N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate,
tropillium tetrakis(perfluoronaphthyl)borate,
triphenylcarbenium tetrakis(perfluoronaphthyl)borate,
triphenylphosphonium tetrakis(perfluoronaphthyl)borate,
triethylsilylium tetrakis(perfluoronaphthyl)borate,
benzene(diazonium) tetrakis(perfluoronaphthyl)borate,
trimethylammonium tetrakis(perfluorobiphenyl)borate,
triethylammonium tetrakis(perfluorobiphenyl)borate,
tripropylammonium tetrakis(perfluorobiphenyl)borate,
tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate,
tri(t-butyl)ammonium tetrakis(perfluorobiphenyl)borate,
N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,
N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate,
N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(perfluorobiphenyl)borate,
tropillium tetrakis(perfluorobiphenyl)borate,
triphenylcarbenium tetrakis(perfluorobiphenyl)borate,
triphenylphosphonium tetrakis(perfluorobiphenyl)borate,
triethylsilylium tetrakis(perfluorobiphenyl)borate,
benzene(diazonium) tetrakis(perfluorobiphenyl)borate,
[4-t-butyl-PhNMe 2 H][(C 6 F 3 (C 6 F 5 ) 2 ) 4 B],
trimethylammonium tetrakis(pentafluorophenyl)borate,
tripropylammonium tetrakis(pentafluorophenyl)borate,
tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,
N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,
N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,
tropillium tetrakis(pentafluorophenyl)borate,
triphenylcarbenium tetrakis(pentafluorophenyl)borate,
triphenylphosphonium tetrakis(pentafluorophenyl)borate,
triethylsilylium tetrakis(pentafluorophenyl)borate,
benzene(diazonium) tetrakis(pentafluorophenyl)borate,
trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,
dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
benzene(diazonium) tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
trimethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
tri(t-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
tropillium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
benzene(diazonium) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)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, and
triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).
20. The process of claim 1 wherein the process occurs at a temperature of from about 0° C. to about 300° C., at a pressure in the range of from about 0.35 MPa to about 10 MPa, and at a time up to 300 minutes.
21. The process of claim 1 further comprising obtaining polymer having at least 90% allyl chain ends.
22. The process of claim 1 wherein the monomers comprise ethylene and propylene.