公开(公告)号：DE3210003A1

公开(公告)日：1983-09-22

申请号：DE3210003

申请日：1982-03-19

Applicant: BASF AG

Inventor： JAGGARD JAMES F R DIPL CHEM DR ,  SCHWEIER GUENTHER DIPL CHEM DR ,  KLAERNER PETER DIPL CHEM DR

IPC: C08F2/34 ,  C08F4/64 ,  C08F297/08 ,  C08F4/52

Abstract: The method relates to a process for the preparation of propylene-ethylene polymers of the block copolymer type, in which, in each case in an agitated bed of finely divided polymer, from the gas phase, first I) in a first polymerisation zone propylene is homopolymerised by the feed of a Ziegler-Natta catalyst system comprising 1) a titanium (III) component, 2) a dialkylaluminium chloride component and 3) optionally a further catalyst component, and then II) in a second polymerisation zone a mixture of propylene and ethylene is polymerised onto the propylene homopolymer present in the reaction product obtained from the first polymerisation zone by the feed thereof, characterised in that, in the Ziegler-Natta catalyst system, a titanium (III) component 1) is employed for whose preparation 1.1) a titanium-containing compound a) of the formula TiCl3 . nAlCl3 and 1.2) an electron donor b) comprising an ester of a certain class, is subjected to a special grinding treatment which is distinguished, in particular, by particular metering and temperature conditions, and the resultant intermediate is suspended in a mixture of a liquid hydrocarbon c) and an oxygen-containing compound d) comprising an alcohol of a certain class, and the resultant suspension is then subjected to heat treatment, where the solid, which is then in the form of suspended material, is the titanium (III) component 1) employed for the polymerisation. The result is a polymer having improved morphological properties.

公开(公告)号：DE3020863A1

公开(公告)日：1981-12-10

申请号：DE3020863

申请日：1980-06-02

Applicant: BASF AG

Inventor： JAGGARD JAMES F R DIPL CHEM DR ,  KLAERNER PETER DIPL CHEM DR ,  STAIGER GERHARD DIPL CHEM DR

IPC: C08F4/64 ,  C08F10/00

Abstract: Milling of a Ti cpd. (I) of formula TiCl3.nAlCl3 (where n is 0.01-1) and a 2-34C ester (II) of formulae R10-C(O)R2 or R10-C(O)-CR2=CHR2 (where R1 is 1-16C alkyl or 7-23C phenylalkyl where phenyl gp. is opt. substd. R2 is H, 1-18C alkyl, 7-23C phenylalkyl where phenyl gp. is opt. substd. by 1-4C alkyl, phenyl or 7-23C alkyb phenyl is carried out (1) at a milling acceleration of 30-80 m/sec-sec, (2) filling the mill first with (I) and opt. milling at -50 to 100 deg.C for 0.5-100 hrs. in the absence of diluant, (3) adding (II) in the absence of diluents continuously or in small amts. at -50 to 80 deg.C in a mol. ratio of Ti in (I) to (II) of 1:1.5-1: 0.1 at a rate of 0.01-200 ml/min per 2.5 (I), (4) milling for 1-120 hrs. at 15-100 deg.C, (5) opt. milling for 0.5-60 min. at -50 to 5 deg.C in the absence of diluants, (6) opt. maintaining the prod. from step (4) or (5) at 20-150 deg.C for 0.25-300 hrs. without milling and (7) opt. past-milling the prod. from step (6) for 0.5-60 min. at -50 to 5 deg.C in the absence of diluant, a suspension is formed from 1 pt.wt. the prod. obtd. from steps (4), (5), (6) or (7), 0.5-20 pts.wt. hydrocarbon with a b.pt. below 150 deg.C and which is liq. an ambient conditions and an ether (III) of formula R8-O-R8 (where R8 is 1-15C alkyl, phenyl or 7-14C alkylphenyl and/or 2-34C ester (IV) of formulae R3- R3-OC(O)-R4 or R3-OC(O)-C(R4)=CH(R9) (where R4 is H, 1-12C alkyl, 7-14C phenylalkyl with one alkyl substituent, phenyl or 7-14C alkylphenyl and R3 is 1-8C alkyl, phenyl of 7-14C phenyalkyl) such that the mol ratio of Ti from (I) to (III) or (IV) is 1:0.01-1.2. The suspension is maintained under vigorous stirring at 40-140 deg.C for 5-120 min and then at 15-25 deg.C, opt. separating off the solids, washing with a hydrocarbon liq. at ambient conditions and a b.pt. below 150 deg.C, drying and isolating the Ti component. The polymers have high stereoregularity and good morphological properties.

公开(公告)号：DE2909603A1

公开(公告)日：1980-09-25

申请号：DE2909603

申请日：1979-03-12

Applicant: BASF AG

Inventor： KLAERNER PETER DIPL CHEM DR ,  STAIGER GERHARD DIPL CHEM DR ,  SCHWEIER GUENTHER DIPL CHEM DR ,  JAGGARD JAMES F R DIPL CHEM DR

IPC: C08F4/16 ,  C08F10/00

Abstract: TiCl3 componens for Ziegler-Natta polymerisation catalysts are prepd. by (1) wetting a standard catalyst component consisting of or contg. TiCl3 with hydrocarbon mixt. contg. (A) 100 pts. vol. pentane, hexane and/or heptane and (B) 10-1000 pts. wt. benzene or alkylbenzene having b. pt. 80-270 degrees C under standard conditions, provided catalyst component: wetting hydrocarbon mixt. is 1: x (where x is no. 0.01-0.5) and (2) drying under constant mixing. The catalyst components are used in alpha-olefin polymerisation, in gas- or liq. phase. The polymers have optimum morphological properties, e.g. narrow grain-size distribution. Catalyst component conditioning suppresses the formation of very fine grains having dia. 200 mu. Alkaline (A) is esp. n-hexane or n-heptane. The benzene hydrocarbon (B) is esp. toluene, a xylene or ethylbenzene. (B) can be a light oil mixt. having b. pt. 80-170 degrees c. Drying can take place (a) under an inert gas, in a rotary evaporator, for 0.5-5 hrs., under pressure 0.9-1.1 bar, at 5-50 degrees C above the highest-boiling hydrocarbon b. pt., or (b) in a ball mill under increasing vacuum.

公开(公告)号：DE2739382A1

公开(公告)日：1979-03-15

申请号：DE2739382

申请日：1977-09-01

Applicant: BASF AG

Inventor： MUELLER-TAMM HEINZ DIPL CHEM D ,  JAGGARD JAMES F R DIPL CHEM DR ,  SCHICK HANS DIPL CHEM DR

IPC: C08F4/00 ,  C07F7/00 ,  C08F4/60 ,  C08F4/64 ,  C08F10/00

Abstract: A process for the manufacture of a titanium-containing component of a catalyst for the Ziegler-Natta polymerization of alpha -monoolefins, by (a) milling a titanium-containing compound of the general formula TiCl3.nAlCl3 (where n is a number from 0.01 to 1) with (b) an ether of a particular type or an ester of a particular type, wherein (1) a vibratory ball mill giving a relatively high milling acceleration is used, (2) the mill is first charged with the titanium-containing compound (a), after which it may or may not be run for a certain period, thereafter (3) while milling, the amount of the ether or ester (b) which corresponds to a particular molar ratio of aluminum in the titanium-containing compound (a) to ether or ester (b) is added continuously or in small portions, then (4) the batch is milled for a certain period, after which (5) the product obtained from stage (4) may or may not be washed with a hydrocarbon and dried, and following which (6) the product obtained from stage (4) or (5) may or may not be milled for a certain period at a low temperature, next (7) the product obtained from stage (4), (5) or (6) is brought together with a liquid silicon compound of a particular type or a liquid tin compound of a particular type (these compounds acting as promoters) and the batch is left for a certain period and is then separated into a solid-phase product and into a liquid-phase product, and thereafter (8) the solid-phase product obtained from stage (7) is washed with a hydrocarbon or with one of the promoters mentioned under (7) and is dried, following which (9) the product obtained from stage (8) may or may not be milled for a certain period at a low temperature. Using the titanium-containing catalyst components thus obtainable makes it possible to produce polymers, having a high stereoregularity, in high specific yields.