Patent GB-929191-A (GB)
Title: Improvements in and relating to processes for the preparation of catalytic crystalline materials of aluminium, titanium and chlorine
Inventor: CAUNT ANTHONY DAVID
IPC: B01J27/06
Filed: 1959-07-06
Abstract: A crystalline compound containing trivalent titanium, aluminium and chlorine, generally having an Al:Ti:Cl ratio of 1:3:12, as described in Specification 877,050, is prepared by reacting titanium tetrachloride and aluminium on which fresh surfaces are formed during the reaction; this may be achieved by effecting the reaction in a ball-mill or by employing "pigment" grade aluminium in the presence of a hydrocarbon liquid such as petroleum ether or benzene, such pigment grade aluminium having a fatty acid coating which dissolves off in the reaction medium to give the fresh aluminium surfaces. Titanium tetrachloride is employed in greater than stoichometric amounts at a reaction temperature of above 100 DEG  to below 200 DEG C. and unreacted titanium tetrachloride is finally separated off. The crystalline material may be employed to prepare catalyst suspensions for polymerizing olefines according to Specification 927,785 by admixture with a dialkyl aluminium chloride or bromide. The catalyst preparation is preferably effected in an atmosphere of dry nitrogen. According to examples (1) a nitrogen-purged autoclave was charged with petroleum ether, pigment grade aluminium and titanium tetrachloride and the mixture heated to 125 DEG C. to effect reaction.  On completion the slurry was filtered, washed with petroleum ether and dried in nitrogen.  The crystalline product, of formula Al Ti3Cl12 was ball-milled with diethyl aluminium chloride in petroleum ether, after which propylene was added at 70 DEG C. whereupon polymerization occurred.  On treating with methanol, polypropylene, 91% of which was ether in soluble, was obtained. Benzene may replace the petroleum ether.  (4) A nitrogen-purged ball-mill was charged with aluminium and titanium tetrachloride whilst being heated on an oil bath at 148 DEG -152 DEG C. Excess tetrachloride was distilled off and the crystalline product was ball-milled and added to an auto-clave containing petroleum ether, dimethyl aluminium chloride and propylene.  Polymerization was effected at 70 DEG C. to produce a polymer 10% of which was soluble in ether.ALSO:A crystalline compound containing trivalent titanium, aluminium and chlorine, generally having an Al:Ti:Cl ratio of 1:3:12, as described in Specification 877,050, is prepared by reacting titanium tetrachloride and aluminium on which fresh surfaces are formed during the reaction; this may be achieved by effecting the reaction in a ball-mill or by employing "pigment" grade aluminium in the presence of a hydrocarbon liquid such as petroleum ether or benzene, such pigment grade aluminium having a fatty acid coating which dissolves off in the reaction medium to give the fresh aluminium surfaces.  Titanium tetrachloride is employed in greater than stoichometric amounts at a reaction temperature of above 100 DEG C. to below 200 DEG C. and unreacted titanium tetrachloride is finally separated off.  The crystalline material may be employed to prepare catalyst suspensions for polymerizing olefines according to Specification 927,785 by admixture with a dialkyl aluminium chloride or bromide.  The catalyst preparation is preferably effected in an atmosphere of dry nitrogen. According to examples (1) a nitrogen-purged autoclave was charged with petroleum ether, pigment grade aluminium and titanium tetrachloride and the mixture heated to 125 DEG C. to effect reaction. On completion the slurry was filtered, washed with petroleum ether and dried in nitrogen.  The crystalline product, AlTi3Cl12, was ball-milled with diethyl aluminium chloride in petroleum ether, after which propylene was added at 70 DEG C. whereupon polymerization occurred.  On treating with methanol, polypropylene, 91% of which was ether insoluble, was obtained. Benzene may replace the petroleum ether.  (4) A nitrogen-purged ball-mill was charged with aluminium and titanium tetrachloride and whilst being heated in an oil bath at 148 DEG -152 DEG C.  Excess tetrachloride was distilled off and the crystalline product was ball-milled and added to an autoclave containing petroleum ether, dimethyl aluminium chloride and propylene.  Polymerization was effected at 70 DEG C. to produce a polymer 10% of which was soluble in ether.