Patent EP-0010741-B1 (EP)
IPC: C08F10/00
Filed: 1979-10-26
Granted: 1982-07-28
Abstract: 1. A process for the production of homopolymers and copolymers of C2 -C6 -monoolefins by polymerization of the monomer(s) at a temperature of from 30 degrees to 200 degrees C and a pressure of from 0.1 to 200 bar using a Ziegler catalyst system consisting of (1) a titanium-containing catalyst component and (2) a metal compound of the general formula Me Am-n Xn where Me is the metal aluminium, magnesium or zinc, A is a C1 -C12 -hydrocarbon radical, X is chlorine, bromine, iodine or hydrogen, m is the number of the valency of the metal Me, and n is a number form 0 to m-1, with the proviso that the atomic ratio of titanium form catalyst component (1) to metal (Me) from catalyst component (2) is from 1 : 0.1 to 1 : 500, characterized in that there is used as titanium-containing catalyst component (1) the solide-phase product (VI) which has been obtained by bringing into contact with one another, with the formation of a suspension (III), (1.1) in a first stage (1.1.1) a particulate, porous, inorganic oxidic material (I) exhibiting a particle diameter of from 1 to 1000 mu m, a pore volume of from 0.3 to 3 cm**3 /g and a surface area of from 100 to 1000 m**2 /g, and having the formula SiO2 .aAl2 O3 , where a is a number from 0 to 2, and (1.1.2) a solution (II) formed by combining (IIa) 100 parts by weight of an alcohol of the general formula Z-OH where Z is a saturated C1 -C8 -hydrocarbon radical, (IIb) 0.01 to 6 parts by weight (calculated as titanium) of a titanium trihalide, it being possible for the halogen to be chlorine and/or bromine, and (IIc) 0.01 to 4 parts by weight (calculated as magnesium) of a magnesium compound soluble in the alcohol (IIa) and selected from the series of (A) magnesium alcoholates of the formulae Mg(OD)2 , MgX(OD) and Mgw [Ek.x (OD)y ]z where D is a monovalent C1 -C10 -hydrocarbon radical of saturated aliphatic and/or aromatic nature, X is chlorine, bromine or iodine, E is the element lithium, boron, aluminium or titanium, w is an integer from 1 to 6, k ist the number of the valency of the element E, x is an integer from 1 to 4, y is k.x + 1, 1 is an integer from 1 to 5, and z is 2w:(y-k.x) ; or (B) magnesium carboxylates of the formula Mg(OCOD')2 where D' is a monovalent C1 -C18 -hydrocarbon radical of saturated aliphatic and/or aromatic nature ; or (C) magensium salts of CH-acidic compounds, with the proviso that the weight ratio of inorganic oxidic material (I) to titanium in the titanium trihalide (IIb) is from 1 : 0.01 to 1 : 0.2 and the weight ratio of inorganic oxidic material (I) to magnesium in the magnesium compound (IIc) is from 1 : 0.01 to 1 : 0.25 ; the suspension (III) is evaporated, at a temperature below 200 degrees C and above the melting point of the alcohol (IIa) used, to dry consistency, a solid-phase intermediate product (IV) thus being formed, and then by bringing into contact with one another, with the formation of a suspension, (1.2) in a second stage (1.2.1) the solid-phase intermediate product (IV) obtained from step (1.1), and (1.2.2) an acyl halide (V), optionally dissolved in an organic solvent, of the general formula D"-CO-X where D" is a saturated C1 -C18 -hydrocarbon radical, with the proviso that up to 3 hydrogen atoms in the said radical can be substituted by chlorine or bromine, and X is F, Cl, Br or I, with the proviso that the molar ratio of titanium from the solid-phase intermediate product IV to acryl halide (V) is from 1 : 0.01 to 1 : 100, the solid-phase product VI thus obtained as suspended material being the titanium-containing catalyst component (1).