Claims
- 1. A process for the preparation of a syndiotactic propylene copolymer comprising 99.9 to 50% by weight, relative to the entire polymer, of propylene units and 0.1 to 50% by weight, relative to the entire polymer, of units derived from ethylene or an olefin having at least 4 carbon atoms of the formula R.sup.a --CH.dbd.CH--R.sup.b, in which R.sup.a and R.sup.b are identical or different and are a hydrogen atom or an alkyl radical having 1 to 20 carbon atoms or R.sup.a and R.sup.b together with the carbon atoms linking them form a ring of 4 to 10 carbon atoms, said process comprising polymerization of 50 to 99.5% by weight, relative to the total amount of the monomers, of propylene and 0.5 to 50% by weight, relative to the total amount of the monomers, of at least one representative from the group comprising ethylene and olefins having at least 4 carbon atoms of the formula R.sup.a --CH.dbd.CH--R.sup.b, in which
- R.sup.a and R.sup.b have the above mentioned meaning, at a temperature of -40.degree. C. to 150.degree. C. and a pressure of 0.5 to 100 bar in solution, in suspension or in the gas phase,
- in the presence of a catalyst which comprises a metallocene as the transition metal component and an aluminoxane of the formula II ##STR13## for the linear type and/or the formula III ##STR14## for the cyclic type, R.sup.9 in formulae II and III being a C.sub.1 -C.sub.6 -alkyl group or phenyl or benzyl and n an integer from 2 to 50, which comprises carrying out the polymerization in the presence of a catalyst whose transition metal component is a metallocene compound of the formula I ##STR15## in which M.sup.1 is titanium, zirconium, hafnium, vanadium, niobium or tantalum,
- R.sup.l and R.sup.2 are identical or different and are a hydrogen atom, a halogen atom, a C.sub.1 -C.sub.10 -alkyl group, a C.sub.1 -C.sub.10 -alkoxy group, a C.sub.6 -C.sub.10 -aryl group, a C.sub.6 -C.sub.10 -aryloxy group, a C.sub.2 -C.sub.10 -alkenyl group, a C.sub.7 -C.sub.10 -arylalkyl group, a C.sub.7 -C.sub.40 -alkylaryl group or a C.sub.8 -C.sub.40 -arylalkenyl group,
- R.sup.3 and R.sup.4 are different and are a mono- or polynuclear hydrocarbon radical which together with the central atom M.sup.1 can form a sandwich structure,
- R.sup.5 is ##STR16## in which R.sup.6 and R.sup.7 are identical or different and R.sup.6 is a C.sub.6 -C.sub.10 aryl group and R.sup.7 is a hydrogen atom, a halogen atom, a C.sub.1 -C.sub.10 -alkyl group, a C.sub.1 -C.sub.10 -fluoroalkyl group, a C.sub.6 -C.sub.10 -fluoroaryl group, a C.sub.6 -C.sub.10 -aryl group, a C.sub.1 -C.sub.10 -alkoxy group, a C.sub.2 -C.sub.10 -alkenyl group, a C.sub.7 -C.sub.40 -arylalkyl group, a C.sub.8 -C.sub.40 -arylalkenyl group or a C.sub.7 -C.sub.40 -alkylaryl group or R.sup.6 and R.sup.7 in each case together with the atoms linking them form a ring.
- 2. A process for the preparation of a syndiotactic propylene copolymer comprising 99.9 to 50% by weight, relative to the entire polymer, of propylene units and 0.1 to 50% by weight, relative to the entire polymer, of units derived from ethylene or an olefin having at least 4 carbon atoms of the formula R.sup.a --CH.dbd.CH--R.sup.b, in which R.sup.a and R.sup.b are identical or different and are a hydrogen atom or an alkyl radical having 1 to 20 carbon atoms or R.sup.a and R.sup.b together with the carbon atoms linking them form a ring of 4 to 10 carbon atoms, said process comprising polymerization of 50 to 99.5% by weight, relative to the total amount of the monomers, of propylene and 0.5 to 50% by weight, relative to the total amount of the monomers, of at least one representative from the group comprising ethylene and olefins having at least 4 carbon atoms of the formula R.sup.a --CH.dbd.CH--R.sup.b, in which R.sup.a and R.sup.b have the above mentioned meaning, at a temperature of -40.degree. C. to 150.degree. C. and a pressure of 0.5 to 100 bar in solution, in suspension or in the gas phase, in the presence of a catalyst which comprises a metallocene as the transition metal component and an aluminoxane of the formula II ##STR17## for the linear type and/or the formula III ##STR18## for the cyclic type, R.sup.9 in formulae II and III being a C.sub.1 -C.sub.6 -alkyl group or phenyl or benzyl and n an integer from 2 to 50, which comprises carrying out the polymerization in the presence of a catalyst whose transition metal component is a metallocene, wherein said metallocene compound is (arylalkylidene)(9-fluorenyl)(cyclopentadienyl) zirconium dichloride, (diarylmethylene)(9-fluorenyl)(cyclopentadienyl)zirconium dichloride or (dialkylmethylene)(9-fluorenyl)(cyclopentadienyl) zirconium dichloride or the corresponding hafnium analogs of said metallocene compounds.
- 3. A process for the preparation of a syndiotactic propylene copolymer comprising 99.9 to 50% by weight, relative to the entire polymer, of propylene units and 0.1 to 50% by weight, relative to the entire polymer, of units derived from ethylene or an olefin having at least 4 carbon atoms of the formula R.sup.a --CH.dbd.CH--R.sup.b, in which R.sup.a and R.sup.b are identical or different and are a hydrogen atom or an alkyl radical having 1 to 20 carbon atoms or R.sup.a and R.sup.b together with the carbon atoms linking them form a ring of 4 to 10 carbon atoms, said process comprising polymerization of 50 to 99.5% by weight, relative to the total amount of the monomers, of propylene and 0.5 to 50% by weight, relative to the total amount of the monomers, of at least one representative from the group comprising ethylene and olefins having at least 4 carbon atoms of the formula R.sup.a --CH.dbd.CH--R.sup.b, in which R.sup.a and R.sup.b have the above mentioned meaning, at a temperature of -40.degree. C. to 150.degree. C. and a pressure of 0.5 to 100 bar in solution, in suspension or in the gas phase, in the presence of a catalyst which comprises a metallocene as the transition metal component and an aluminoxane of the formula II ##STR19## for the linear type and/or the formula III ##STR20## for the cyclic type, R.sup.9 in formulae II and III being a C.sub.1 -C.sub.6 -alkyl group or phenyl or benzyl and n an integer from 2 to 50, which comprises carrying out the polymerization in the presence of a catalyst whose transition metal component is a metallocene, wherein said metallocene compound is (methyl(phenyl)methylene)(9-fluorenyl)(cyclopentadienyl) zirconium dichloride, (diphenylmethylene)(9-fluorenyl)(cyclopentadienyl) zirconium dichloride, or (dimethylmethylene)(9-fluorenyl)(cyclopentadienyl)zirconium chloride or the corresponding hafnium analogs of said metallocene compounds.
- 4. The process as claimed in claim 1, wherein, in said formula (I), R.sup.3 or R.sup.4 is fluorenyl.
- 5. The process as claimed in claim 4, wherein, in said formula (I), R.sup.3 and R.sup.4 are fluorenyl and cyclopentadienyl.
- 6. The process as claimed in claim 4, wherein, in said formula (I), M.sup.1 is zirconium or hafnium.
- 7. The process as claimed in claim 3, wherein said metallocene compound is (methyl(phenyl)methylene)(9-fluorenyl)(cyclopentadienyl) hafnium dichloride, (diphenylmethylene)(9-fluorenyl)(cyclopentadienyl) zirconium dichloride, or (dimethylmethylene)(9-fluorenyl)(cyclopentadienyl) zirconium dichloride.
Priority Claims (1)
Number |
Date |
Country |
Kind |
39 42 366.2 |
Dec 1989 |
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Parent Case Info
This application is a continuation of 08/203,514 filed Feb. 28, 1994, now abandoned, which was a continuation of 07/996,868 filed Dec. 16, 1992, now abandoned, which was a continuation of application Ser. No. 07/630,263 filed Dec. 19, 1990, now abandoned.
US Referenced Citations (3)
Number |
Name |
Date |
Kind |
4892851 |
Ewen et al. |
Jan 1990 |
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5086134 |
Antberg et al. |
Feb 1992 |
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5132381 |
Winter et al. |
Jul 1992 |
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Foreign Referenced Citations (4)
Number |
Date |
Country |
302424 |
Aug 1987 |
EPX |
0387691 |
Sep 1990 |
EPX |
0395055 |
Oct 1990 |
EPX |
0426645 |
May 1991 |
EPX |
Non-Patent Literature Citations (1)
Entry |
Ewen, J.A. et al., J. Am. Chem. Soc. 110:6255-6256 (1988). |
Continuations (3)
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Number |
Date |
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Parent |
203514 |
Feb 1994 |
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Parent |
996868 |
Dec 1992 |
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Parent |
630263 |
Dec 1990 |
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