Patent EA-004039-B1 (EA)
Title: Olefins polymerization process
Inventor: DEVORE DAVID D
IPC: C08F2/34
Filed: 1999-09-08
Abstract: 1. An olefin polymerization process comprising contacting one or more olefin monomers under gas phase polymerization conditions with a catalyst composition comprising a metal complex corresponding to the following formulas: wherein: M is titanium, zirconium, or hafnium in the +4, +3, or +2 oxidation state; Y<1>and Y<2> are independently an anionic, cyclic or non-cyclic, pi-bonded group, NR<1>, PR<1>; NR<12> or PR<12>; Z is boron or aluminum; Q is a neural, anionic or dianionic ligand group depending on the oxidation state of M; j is 1,2 or 3 depending on the oxidation state of M and the electronic nature of Q; T independently each occurrence is: R<1> is independently each occurrence hydrogen, a hydrocarbyl group, a tri (hydrocarbyl) silyl group, or a tri (hydrocarbyl) silylhydrocarbyl group, said R<1> groups containing up to 20 atoms not counting hydrogen; R<5> is R<1> or N (R<1>)2; and two R<1> groups together or one or more R<1> groups together with R<5> may optionally be joined to form a ring structure. 2. The process of claim 1 wherein the metal complex corresponding to formula 1 is represented by formula 4,5,6,7,8 or 9: Formula 4 Formula 5 Formula 6 Formula 7 Formula 8 or Formula 9 wherein M, Z, T, R<1>, Q and j are as defined in claim 1; R<2> is hydrogen, or a hydrocarbyl, halohydrocarbyl, dihydrocarbylaminohydrocarbyl, tri (hydrocarbylsilyl) hydrocarbyl, Si (R<3>) 3, N (R<3>) 2, or OR<3> group of up to 20 carbon or silicon atoms, and optionally two adjacent R<2> groups can be joined together, thereby forming a fused ring structure, especially an indenyl ligand or a substituted indenyl ligand; and R<3> is independently hydrogen, a hydrocarbyl group, a trihydrocarbylsilyl group or a trihydrocarbylsilylhydrocarbyl group, said R<3> having up to 20 atoms not counting hydrogen. 3. A process according to claim 2 wherein M is in the +4 oxidation state, j = 2 and Q independently each occurrence is halide, hydride, hydrocarbyl, silylhydrocarbyl, hydrocarbyloxide, or dihydrocarbylamide, said Q having up to 20 atoms not counting hydrogen, or two Q groups together form an alkanediyl group or a conjugated C4-40 diene ligand that together with M form a metallocyclopentene. 4. A process according to claim 2 wherein M is in the +3 oxidation state, j = 1 and Q is either 1) a monovalent anionic stabilizing ligand selected from the group consisting of alkyl, cycloalkyl, aryl, silyl, amido, phosphido, alkoxy, aryloxy, sulfido groups, and mixtures thereof, said Q being further substituted with an amine, phosphine, ether, or thioether containing substituent able to form a coordinatecovalent bond or chelating bond with M said ligand having up to 50 atoms not counting hydrogen; or 2) a C3-10 hydrocarbyl group comprising an ethylenic unsaturation able to form an eta<3>-bond with M. 5. A process according to claim 2 wherein M is in the +2 oxidation state, j = 1 and Q is a neutral conjugated diene, optionally substituted with one or more tri (hydrocarbyl) silyl or tri (hydrocarbylsilyl) hydrocarbyl groups, said Q having up to 40 carbon atoms and forming a eta-complex with M. 6. A process according to claim 3 wherein the metal complex corresponds to Formula 4a, 5a, 6a, 7a, 8a, or 9a, wherein the definitions of M, Z, R<1>, R<2>, and R<3> are as defined in claim 3: Formula 4a, Formula 5a, Formula 6a Formula 8a, Formula9a, Formula7a, and Q, independently each occurrence is a halide, hydrocarbyl, hydrocarbyloxy, or dihydrocarbylamide group of up to 10 atoms not counting hydrogen, or two Q groups together form a C4-20 diene ligand that together with M forms a metallocyclopentene. 7. A process according to claim 4 wherein the metal complex corresponds to Formula 4b, 5b, 6b, 7b, 8b, or 9b, wherein the definitions of M, Z, R<1>, R<2>, and R<3> are as defined in claim 4: Formula 4b, Formula 5b, Formula 6b Formula 7b, Formula 8b, or Formula 9b, and Q, each occurrence is a monovalent anionic stabilizing ligand selected from the group consisting of alkyl, cycloalkyl, aryl, and silyl groups, said group being further substituted with one or more amine, phosphine, or ether substituents able to form a coordinate-covalent bond or chelating bond with M, and said Q having up to 30 nonhydrogen atoms; or Q is a C3-10 hydrocarbyl group comprising an ethylenic unsaturation able to form an eta<3> bond with M. 8. A process according to claim 5 wherein the metal complex corresponds to Formula 4c, 5c, 6c, 7c, 8c, or 9c, wherein the definitions of M, Z, R1, R<2>, and R<3> are as defined in claim 5: Formula 4c, Formula 5c, Formula 6c Formula 7c, Formula 8c, Formula 9c and Q, each occurrence is a neutral conjugated diene, optionally substituted with one or more tri (hydrocarbyl) silyl groups or tri (hydrocarbyl) silylhydrocarbyl groups, said Q having up to 30 atoms not counting hydrogen and forming a eta-complex with M. 9. A process according to any of claims 1-8 wherein M is zirconium or hafnium. 10. A process according to claim 9 wherein Z is boron. 11. A process according to claim 1 wherein the metal complex is dimethylamidoborane-bis (eta<5>-cyclopentadienyl) zirconium dichloride, dimethylamidoboranebis (eta<5>-inden-1-yl) zirconium dichloride, dimethylamidoboranebis(eta<5>-2-methyl-4-phenylinden-1-yl) zirconium dichloride, dimethylamidoborane-bis (eta<5>-2-ethyl-4-phenylinden-1-yl) zirconium dichloride, dimethylamidoborane-bis (eta<5>-2isopropyl-4-phenylinden-1-yl) zirconium dichloride, dimethylamidoborane-bis (eta<5>-2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-1-yl) zirconium dichloride, dimethylamidoborane-bis (eta<5>-3-t-butylinden-1-yl) zirconium dichloride, diisopropylamidoborane-bis (eta<5>-cyclopentadienyl) zirconium dichloride, diisopropylamidoboranebis (eta<5>-inden-1-yl) zirconium dichloride, diisopropylamidoborane-bis (eta<5>-2-methyl-4-phenylinden-1-yl) zirconium dichloride, diisopropylamidoborane-bis (eta<5>-2-ethyl-4-phenylinden-1-yl) zirconium dichloride, diisopropylamidoborane-bis(eta<5>-2-isopropyl-4-phenylinden-1-yl) zirconium dichloride, diisopropylamidoborane-bis(eta<5>-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl) zirconium dichloride, diisopropylamidoborane-bis (eta<5>-3-t-butylinden-1-yl) zirconium dichloride, diphenylamidoborane-bis (eta<5>-cyclopentadienyl) zirconium dichloride, diphenylamidoboranebis (eta<5>-inden-1-yl) zirconium dichloride, diphenylamidoborane-bis (eta<5>-2-methyl-4-phenylinden-1-yl) zirconium dichloride, diphenylamidoborane-bis (eta<5>-2-ethyl-4-phenylinden-1-yl) zirconium dichloride, diphenylamidoborane-bis (eta<5>-2-isopropyl-4-phenylinden-1-yl) zirconium dichloride, diphenylamidoborane-bis (eta<5>-2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-1-yl) zirconium dichloride, diphenylamidoborane-bis (eta<5>-3-t-butylinden-1-yl) zirconium dichloride, dimethylamidoborane-bis (eta<5>-cyclopentadienyl) zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis (eta<5>-inden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis (eta<5>-2-methyl-4-phenylinden-1-yl) zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis (eta<5>-2-ethyl-4-phenylinden-1-yl) zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis (eta<5>-2-isopropyl-4phenylinden-1-yl) zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis (eta<5>-2-methyl-4-bis (3,5-trffluoromethyl) phenylinden-1-yl) zirconium 1,4-diphenyl-1,3-butadiene, dimethylamidoborane-bis (eta<5>-3-t-butylinden-1-yl) zirconium 1,4-diphenyl-1,3-butadiene, diisopropylamidoborane-bis (eta<5>-cyclopentadienyl) zirconium 1,4-diphenyl-1,3-butadiene, diisopropylamidoborane-bis (eta<5>-inden-1-yl) zirconium 1,4-diphenyl-1,3-butadiene, iisopropylamidoborane-bis (eta<5>-2-methyl-4-phenylinden-1-yl) zirconium 1,4-diphenyl-1,3-butadiene, diisopropylamidoborane-bis (eta<5>-2-ethyl-4-phenylinden-1-yl) zirconium 1,4-diphenyl-1,3-butadiene, diisopropylamidoborane-bis (eta<5>-2-isopropyl4-phenylinden-1-yl) zirconium 1,4-diphenyl-1,3-butadiene, diisopropylamidoborane-bis (eta<5>-2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-1-yl) zirconium 1,4-diphenyl-1,3-butadiene, diisopropylamidoborane-bis (eta<5>-3-t-butylinden-1-yl) zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis (eta<5>-cyclopentadienyl) zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis (eta<5>-inden-1-yl) zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis (eta<5>-2-methyl-4-phenylinden-1-yl) zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis (eta<5>-2-ethyl-4-phenylinden-1-yl) zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis (eta<5>-2-isopropyl-4- phenylinden-1-yl) zirconium 1,4-diphenyl-1,3-butadiene, diphenylamidoborane-bis (eta<5>-2-methyl-4-bis (3,5-trifluoromethyl) phenylinden-1-yl) zirconium 1,4-diphenyl-1,3-butadiene, or diphenylamidoborane-bis (eta<5>-3-t-butylinden-1-yl) zirconium 1,4-diphenyl-1,3-butadiene. 12. A process according to claim 1 wherein the catalyst additionally comprises a support material. 13. The process of claim 1 which is a continuous gas phase polymerization. 14. The process of claim 13 wherein ethylene is homopolymerized, or a mixture of C2-6 olefins is copolymerized. 15. The process of any of the foregoing claims wherein the resulting polymer contains long chain branching.