Patent GB-864352-A (GB)
Title: Polmerisation catalyst and process for polymerising olefins with said catalyst
IPC: C08F10/00
Filed: 1957-07-11
Abstract: a -Olefines, especially those having up to 6 carbon atoms are polymerized in the presence of a catalyst composition comprising the reaction product of aluminium chloride and aluminium powder in a weight ratio of from 10 : 1 to 1 : 1 with an olefine having 2-5 carbon atoms and a compound of a metal of Group IVA, VA or VIA, (see Group III).  Preferably the aluminium chloride, which may be anhydrous or partially, e.g. about one-third, hydrolized, metal and olefine are reacted first in the presence of 0,5 to 1% of anhydrous hydrogen chloride, based on the weight of aluminium chloride, in benzene or n-heptane at 50 DEG -200 DEG C. and super-atmospheric pressure, and the metal compound, e.g. TiCl4, Ti Cl3 or VO Cl3, subsequently added in an amount corresponding to equimolar proportion with the aluminium chloride at less than 50 DEG C.  The lower olefine may be the olefine to be polymerized or different.  The olefines, which may be polymerized at up to 100 DEG C. and normal, sub- or super-atmospheric pressure, give high molecular weight linear polymers; they may also be copolymerized with each other.  In typical Examples (1) anhydrous aluminium chloride, aluminium powder, anhydrous hydrogen chloride and titanium tetrachloride are mixed in n-heptane in an autoclave and ethylene pumped in at 60 atmospheres and about 35 DEG C. for 1 hour; a linear polymer of m.w. 31,000 is obtained; (2) titanium tetrachloride is added to a prereacted mixture of aluminium chloride, aluminium powder, hydrogen chloride and ethylene in n-heptane and ethylene polymerized in contact therewith at 75 DEG C. and 10-12 atmospheres; (4) propylene is polymerized in the presence of a catalyst as in (2) using titanium trichloride instead of the tetrachloride at 70 DEG C. and 7 atmospheres; (5) a mixture of 1- and 2-butenes is polymerized at 70 DEG C. in the presence of a catalyst as in (4) using benzene as solvent; (6) a mixture of 1- and 2-butenes and ethylene is copolymerized at 60 DEG C. and 7 atmospheres in the presence of a catalyst as in (2) except that vanadium oxychloride replaces titanium tetrachloride. Specification 810,023 is referred to.ALSO:A catalyst for polymerizing olefines comprises the reaction product of aluminium chloride and powdered aluminium, in a weight ratio of from 10 : 1 to 1 : 1, with an olefine having 2-5 carbon atoms and a compound of a metal of Group IVa, Va or VIa.  The catalyst is preferably prepared by contacting the aluminium chloride and aluminium with the olefine and simultaneously or subsequently adding the metal compound.  The aluminium chloride may be anhydrous or partially hydrolysed, e.g. about 1/3 ; preferably the aluminium chloride and metal are contacted with the olefine at 50-200 DEG C. and super-atmospheric pressure in the presence of 0.5 to 1% of anhydrous hydrogen chloride, and based on the weight of aluminium chloride, and in a non - polymerizable solvent such as a liquid saturated aliphatic hydrocarbon or a C6-C10 non-olefinic aromatic hydrocarbon.  Benzene and n-heptane are preferred solvents.  The olefine may be the olefine to be polymerized or a different olefine.  The metal compound added may be titanium tetra- or tri-chloride or vanadium oxychloride in an amount corresponding to about equimolar proportions with the aluminium chloride and at below 50 DEG C. Specification 810,023 is referred to.