Asymmetric polypropylene catalysts
This invention relates to unsymmetrical metallocenes, catalyst systems therefrom and their use to make highly isotactic polypropylene.
1. A catalyst compound represented by the formula:
wherein
M is a transition metal atom selected from group 3, 4, or 5 of the Periodic Table of Elements;
T is a bridging group;
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;
R 2 is a substituted or unsubstituted C 1 to C 20 hydrocarbyl group;
R 3 , R 5 , R 6 and R 7 are each independently a hydrogen atom or a substituted or unsubstituted C 1 to C 20 hydrocarbyl group, and, optionally, any two of R 5 , R 6 , and R 7 can be joined to form a cyclic structure;
R 4 is a substituted or unsubstituted aryl group; and
R 8 , R 9 , R 10 , and R 11 are each independently a substituted or unsubstituted C 1 to C 6 hydrocarbyl group and, optionally, R 9 and R 10 are joined to form a cyclic structure.
2. The catalyst compound of claim 1 , wherein R 2 is a primary substituted or unsubstituted C 1 -C 12 alkyl group.
3. The catalyst compound of claim 1 , wherein R 4 is selected from phenyl, 1-naphthyl, 2-naphthyl, 9-anthracenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,5-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5,6-pentamethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 2,6-diethylphenyl, 3,4-diethylphenyl, 3,5-diethylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 3,5-di-isopropylphenyl, 2,5-di-isopropylphenyl, 2-tert-butylphenyl, 3-tert-butylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 2-trimethylsilylphenyl, 3-trimethylsilylphenyl, 4-trimethylsilylphenyl, 3,5-bis(trimethylsilyl)phenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 3,5-bis(trifluoromethyl)phenyl, cyclopropyl, carbazolyl, indolyl, pyrrolyl, or 2-furanyl, 3-furanyl, 5-methyl-2-furanyl, 5-ethyl-2-furanyl, 4,5-dimethyl-2-furanyl, 2-methyl-3-furanyl, 5-methyl-3-furanyl, 2-thiophenyl, 3-thiophenyl, 5-methyl-2-thiophenyl, 2-methyl-3-thiophenyl, or 5-methyl-3-thiophenyl.
4. The catalyst compound of claim 1 , wherein R 3 is a hydrogen atom.
5. The catalyst compound of claim 1 , wherein T is represented by the formula, (R* 2 G) g , where each G is C, Si, or Ge, g is 1 or 2, and each R* is, independently, hydrogen, halogen, C 1 to C 20 hydrocarbyl or a C 1 to C 20 substituted hydrocarbyl, and two or more R* can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system.
6. The catalyst compound of claim 1 , wherein R 5 , R 6 , and R 7 are independently a hydrogen atom or a substituted or unsubstituted C 1 to C 6 hydrocarbyl group, and any two of R 5 , R 6 , and R 7 can be joined to form a cyclic structure.
7. A catalyst system comprising an activator and a catalyst represented by the formula:
wherein
M is a transition metal atom selected from group 3, 4, or 5 of the Periodic Table of Elements;
T is a bridging group;
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;
R 2 is a substituted or unsubstituted C 1 to C 20 hydrocarbyl group;
R 3 , R 5 , R 6 , and R 7 are each independently a hydrogen atom or a substituted or unsubstituted C 1 to C 20 hydrocarbyl group, and, optionally, any two of R 5 , R 6 , and R 7 can be joined to form a cyclic structure;
R 4 is a substituted or unsubstituted aryl group; and
R 8 , R 9 , R 10 , and R 11 are each independently a substituted or unsubstituted C 1 to C 6 hydrocarbyl group and, optionally, R 9 and R 10 are joined to form a cyclic structure.
8. The catalyst system of claim 7 , wherein R 2 is a primary substituted or unsubstituted C 1 -C 12 alkyl group.
9. The catalyst system of claim 7 , wherein R 4 is selected from phenyl, 1-naphthyl, 2-naphthyl, 9-anthracenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,5-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5,6-pentamethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 2,6-diethylphenyl, 3,4-diethylphenyl, 3,5-diethylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 3,5-di-isopropylphenyl, 2,5-di-isopropylphenyl, 2-tert-butylphenyl, 3-tert-butylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 2-trimethylsilylphenyl, 3-trimethylsilylphenyl, 4-trimethylsilylphenyl, 3,5-bis(trimethylsilyl)phenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 3,5-bis(trifluoromethyl)phenyl, cyclopropyl, carbazolyl, indolyl, pyrrolyl, or 2-furanyl, 3-furanyl, 5-methyl-2-furanyl, 5-ethyl-2-furanyl, 4,5-dimethyl-2-furanyl, 2-methyl-3-furanyl, 5-methyl-3-furanyl, 2-thiophenyl, 3-thiophenyl, 5-methyl-2-thiophenyl, 2-methyl-3-thiophenyl, or 5-methyl-3-thiophenyl.
10. The catalyst system of claim 7 , wherein R 3 is a hydrogen atom.
11. The catalyst system of claim 7 , wherein T is represented by the formula, (R* 2 G) g , where each G is C, Si, or Ge, g is 1 or 2, and each R* is, independently, hydrogen, halogen, C 1 to C 20 hydrocarbyl or a C 1 to C 20 substituted hydrocarbyl, and two or more R* can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system.
12. The catalyst system of claim 7 , wherein R 5 , R 6 , and R 7 are independently a hydrogen atom or a substituted or unsubstituted C 1 to C 6 hydrocarbyl group, and any two of R 5 , R 6 , and R 7 can be joined to form a cyclic structure.
13. The catalyst system of claim 7 , wherein the activator comprises methylalumoxane.
14. The catalyst system of claim 7 , wherein the activator comprises a non-coordinating anion.
15. A catalyst composition comprising a support and the catalyst compound of claim 1 .
16. The catalyst composition of claim 15 , wherein the support is silica.
17. A process to prepare isotactic polypropylene comprising contacting propylene with the catalyst system of claim 7 and obtaining isotactic polypropylene.
18. The catalyst system of claim 7 , further comprising a support.
19. The catalyst system of claim 18 , wherein the support is silica.
20. A process to prepare isotactic polymer comprising contacting C2 to C40 olefin monomers and optional C2 to C40 olefin comonomers with the catalyst system of claim 7 and obtaining polymer.
21. The process of claim 20 , wherein the monomer comprises propylene and the comonomer comprises one or more of ethylene or C4 to C40 olefins.