Claims
- 1. A process for the preparation of copolymers of ethylene with minor amounts of C.sub.3 -C.sub.8 -.alpha.-monoolefins by polymerization of the monomers at from 50.degree. to 125.degree. C. and under a pressure of from 5 to 60 bar, the improvement which comprises using a Ziegler catalyst system comprising
- (1) a transition metal catalyst component,
- (2) an organoaluminum catalyst component of the formula
- AIR.sub.3
- where R is C.sub.2 -C.sub.8 -alkyl, and
- (3) an organohalogen catalyst component (cocatalyst), selected from the group consisting of those of the formulae CFCl.sub.3, CCl.sub.4, CHCl.sub.3, CH.sub.2 Cl.sub.2, CF.sub.2 Cl.sub.2, CH.sub.2 .dbd.CH--CH.sub.2 Cl, CCl.sub.2 .dbd.CCl--CCl.sub.3, CH.tbd.C--CH.sub.2 Cl, .alpha.-chlorotoluene, .alpha.,.alpha.-dichlorotoluene, .alpha.,.alpha.,.alpha.-trichlorotoluene, methyl perchlorocrotonate and n-butyl 2,3, 4, 4-tetrachlorobut-2-enoate
- with the provisos that the atomic ratio of the transition metal from the catalyst component (1) to aluminum from the catalyst component (2) is from 1:0.2 to 1:50, and the molar ratio of the organoaluminum catalyst component (2) to the organohalogen catalyst component (3) is from 1:0.01 to 1:10, wherein the transition metal catalyst component (1) used is a solid-phase product (VI), obtained by a method in which
- (1.1) first
- (1.1.1) a finely divided, porous silicon dioxide (I), which has a particle diameter of from 1 to 400 .mu.m, a pore volume of from 1 to 2.5 cm.sup.3 /g and a specific surface area of from 200 to 400 m.sup.2 / g and
- (1.1.2) a solution (II), as obtained on combining
- (11a) 100 parts by weight of a saturated alicyclic oxahydrocarbon of 1 oxa oxygen atom and 4 to 6 carbon atoms an
- (11b) from 1 to 50 parts by weight of a mixture of
- (11b1) 100 molar parts of a vanadium trihalide/alcohol complex of the formula VY.sub.3.nZ-OH, wherein Y is chlorine, n is from 1 to 6, and Z is an alkyl of not more than 6 carbon atoms,
- (IIb2) from 0.5 to 100 molar parts of a titanium trichloride or of a titanium trihalide/alcohol complex of the formula TiY.sub.3.nZOH, where Y is chlorine, n is from 1 to 6 and Z is an alkyl of not more than 4 carbon atoms and
- (IIb3) from 3 to 200 molar parts of a zirconium tetrachloride, are brought into contact with one another to form a suspension (III), with the proviso that the weight ratio of silicon dioxide (I) to transition metal composition (IIb) is from 1:0.2 to 1:1.5, the suspension (III) is evaporated to dryness at below 160.degree. C. and above the melting point of the oxahydrocarbon (IIa) used, a solid-phase intermediate (IV) being formed, and
- (1.2) thereafter
- (1.2.1) the solid-phase intermediate (IV) obtained from stage (1.1) and
- (1.2.2) a solution, in an organic solvent, of an aluminum compound (V) of the formula
- AIR.sub.m X.sub.3-m
- where X is chlorine, R is C.sub.2 -C.sub.8 -alkyl, and m is the number 2,
- are brought into contact with one another to form a suspension, with the proviso that the weight ratio of the solid-phase intermediate (IV) to the aluminum compound (V) is from 1:0.1 to 1:1, and the resulting suspended solid-phase product (VI) is the transition metal catalyst component (1).
- 2. The process of claim 1 wherein component IIa is tetrahydrofuran; in component IIb1 n is 3 or 4; and in component IIb2 n is 3 or 4.
- 3. The process of claim 1 wherein component (IIb2) consists solely of a titanium trihalide/alcohol complex of the formula TiY.sub.3 -nZOH, where Y is chlorine, n is from 1 to 6, and Z is an alkyl of not more than 4 carbon atoms.
Priority Claims (1)
Number |
Date |
Country |
Kind |
3417238 |
May 1984 |
DEX |
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Parent Case Info
This application is a continuation of application Ser. No. 666,480, filed on Oct. 30, 1984 abandoned.
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3723348 |
Apotheker et al. |
Mar 1973 |
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Maemoto et al. |
Jul 1978 |
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4151337 |
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Apr 1979 |
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4508842 |
Beran et al. |
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716176 |
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DEX |
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Continuations (1)
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Number |
Date |
Country |
Parent |
666480 |
Oct 1984 |
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