Patent EP-0041139-B1 (EP)
IPC: C08F10/00
Filed: 1981-05-07
Granted: 1983-06-08
Abstract: 1. A process for the preparation of homopolymers and copolymers of C2 -alpha-monoolefins, at from 20 to 160 degrees C, under a pressure of from 1 to 100 bar, by means of a Ziegler-Natta catalyst system comprising (1) a titanium-III component, in the preparation of which (1.1) a titanium-containing compound (a) of the formula TiCl3 .nAlCl3 , where n is a number from 0.01 to 1, and (1.2) an ester (b), which contains a total of from 2 to 34 carbon atoms and has the formula R**1 -O-CO-R**2 or  see diagramm : EP0041139,P12,F2  where R**1 is (I) alkyl of 1 to 16 carbon atoms or (II) phenylalkyl of a total of 7 to 23 carbon atoms, in which up to 5 hydrogen atoms of the phenyl radical can be substituted by alkyl of 1 to 4 carbon atoms, and R**2 is (I) hydrogen, (II) alkyl of 1 to 18 carbon atoms, (III) phenylalkyl of a total of 7 to 23 carbon atoms, in which up to 5 hydrogen atoms of the phenyl radical can be substituted by alkyl having 1 to 4 carbon atoms, (IV) phenyl or (V) alkylphenyl of a total of 7 to 23 carbon atoms, in which up to 5 hydrogen atoms of the phenyl radical can be substituted by alkyl of 1 to 4 carbon atoms, are subjected to a milling treatment, wherein (A) a vibratory ball mill having a milling acceleration of from 30 to 80 m . sec**-2 is used, (B) the mill is first charged with the titanium-containing compound (a) and - if desired - is run at from -50 to +100 degrees C for a period of from 0.5 to 100 hours in the absence of a diluent, thereafter (C) the amount of the ester (b) which corresponds to a molar ratio of titanium in the titanium-containing compound (a) : ester (b) of from 1:1.5 to 1:0.01 is added at a rate of 0.01-200 ml/min per 2.5 kg of titanium-containing compound (a), continuously or in small portions, and in the absence of a diluent, whilst milling the mixture at from -50 to +80 degrees C, thereupon (D) the material is kept for a period of from 1 to 120 hours at from +15 to +100 degrees C whilst being milled, following this (E) - if desired - the product obtained from (D) is milled further for a period of from 0.5 to 60 minutes at from -50 to +5 degrees C in the absence of a diluent, then (F) - if desired, and advantageously - the product obtained from (D) or (E) is kept for a period of from 0.25 to 300 hours at from +20 to +150 degrees C without being milled, and thereafter (G) - if desired - the product obtained from (F) is milled again, for a period of from 0.5 to 60 minutes, at from -50 to +5% C, in the absence of a diluent, (2) an aluminium-alkyl component of the formula  see diagramm : EP0041139,P12,F1  where R**3 and R**4 are identical or different and each is alkyl of 1 to 8 carbon atoms, and (3) - if desired - a phenolic compound of the formula  see diagramm : EP0041139,P12,F3  or  see diagramm : EP0041139,P12,F4  where R**5 is C1 -C6 -alkyl, R**6 is hydrogen or C1 -C6 -alkyl, R**7 is hydrogen or a saturated hydrocarbon radical of not more than 30 carbon atoms, which may or may not contain up to a total of 6 ether groups and/or ester groups, R**7 ' is C2 -C24 -alkyl and o is an integer from 1 to 6, with the proviso that the atomic ratio of titanium from the titanium-III component (1) : aluminium from the aluminium-alkyl component (2) is from 1:1 to 1:20 and that, where relevant, the molar ratio of aluminium-alkyl component (2) : phenolic compound (3) is from 1:1 to 40:1, in which process a titanium-III component (1) is employed which has been prepared in the following manner : - (H) a suspension is prepared from (H1 ) 1 part by weight of the product obtained according to (D), (E), (F) or (G), (H2 ) from 0.5 to 20 parts by weight of a hydrocarbon (c) which is liquid under standard conditions of temperature and pressure and boils below 150 degrees C, and (H3 ) an oxygen-containing compound (d), consisting of an alcohol of 1 to 20 carbon atoms, which has the general formula X(OH)y where y is 1 or 2 and X is the radical of an aromatic or saturated aliphatic or cycloaliphatic hydrocarbon, in such as amount that the molar ratio of titanium from the titanium-containing compound (a) : oxygen-containing compound (d) is from 1:0.01 to 1:2, thereafter (I) the suspension obtained according to (H) is kept at from +40 to +140 degrees C for a period of from 5 to 120 minutes, with vigorous agitation, and is then brought to from +15 degrees C to +25 degrees C, thereupon (J) - if desired - the suspension obtained according to (I) is mixed with an aluminium-containing compound (e) of the general formula AIRx-8 Y3-x , where x is 1, 2 or 3, Y is chlorine or R**8 , and the R**8 's are identical or different alkyl groups of 1 to 12 carbon atoms, in such as amount that the molar ratio of hydroxyl groups of the oxygen-containing compound (d) : alkyl groups of the aluminium-containing compound (e) is from 1:0.005 to 1:2, and finally, (K) - if desired - the solid is isolated from the suspension obtained according to (I) or (J), if desired, washed with a hydrocarbon which is liquid under standard conditions of temperature and pressure and boils below 150 degrees C and dried, the solid in suspension obtained according to (I) or (J), or the isolated solid obtained according to (K), constituting the novel titanium-III component (1).