Patent GB-1001699-A (GB)
Title: A process for polymerizing propylene, and a catalyst therefor
IPC: C08F110/06
Filed: 1963-11-25
Abstract: Propylene is polymerized in the absence of any free aluminium trialkyl or alkyl aluminium halide using as catalyst a black solid reaction product containing titanium, aluminium and antimony in the atomic ratio of 1 : 0.05-0.5 : 0.001-0.1 and being prepared by reacting (A) titanium trichloride with (B) the compound or the complex compound selected from antimony pentalkyls SbR5 and organometallic complex compounds containing antimony and aluminium having the general formulae SbAlR8, SbAl2R11 and [SbR4] [AlmRnX3m-n+1], where R is an aliphatic hydrocarbon group having 1 to 7 carbon atoms, X is one or more of the halogens other than fluorine, m is 1 or 2 and n is 0, 1, 2 or 3 when m=1 and an integer of 1 to 6 when m=2, in a molar ratio of 0.001 to 1 mole per 1 mole of titanium trichloride in an inert reaction medium at a temperature between room temperature and 150 DEG  C.  Thereafter the inert reaction medium is removed from the solid part of the resulting product and the resulting product is subsequently reacted with an aluminium trialkyl AlR13, where R1 is an aliphatic hydrocarbon group having 1 to 7 carbon atoms, in an amount of 1-6 moles per 1 mole of titanium trichloride in the absence of an inert reaction medium at a temperature between 30 DEG  and 100 DEG  C. and separating only the solid reaction product at room temperature from the resulting reaction product.  This solid reaction product is washed with a hot aromatic hydrocarbon to remove any free aluminium compounds.  Lists of components (B), aluminium trialkyls and solvents are given.  In the examples, the catalysts, containing titanium, aluminium and antimony, employed are the reaction products of (1) TiCl3, [Sb(C2H5)4] [Al(C2H5)Cl3] and Al(C2H5)3; (2) TiCl3, Sb(C2H5)5 and Al(C2H5)3; (3) TiCl3, SbAl(C2H5)8 and Al(C2H5)3; (4) TiCl3, SbAl2(C2H5)11 and Al(n-C3H7)3 and (5) TiCl3, [Sb(C2H5)4] [Al2(C2H5)5Cl2] and Al(C2H5)3.ALSO:Pentalkyls antimony compounds SbR5 where R is an alkyl group having 1 to 7 carbon atoms may be prepared by reacting a trialkyl antimony halide or stibonium tetralkyl halide with a dialkyl magnesium, dialkyl zinc or alkyl lithium.  In an example pentaethyl antimony is prepared by reacting a diethyl magnesium solution with triethylantimonydichloride. Organometallic complex compounds containing antimony and aluminium and having the general formulae SbAlR8 and SBAL2R11 where R is as above, may be prepared by reacting a pentalkyl antimony with a trialkyl aluminium AlR3 at a temperature between - 40 DEG  C. and 100 DEG  C.  In an example the complexes SbAl(C2H5)8 and SbAl2(C2H5)11 are prepared by reacting triethyl aluminium with an excess of pentaethyl antimony in the presence of n-hexane.  Antimony complex compounds having the general formula <FORM:1001699/C2/1> where R is as above, X is one or more of chlorine, bromine or iodine and when m = 1, n is 0, 1, 2 or 3 and when m = 2, n is an integer 1 to 6, may be prepared as follows:- (a) [Sb(C2H5)4][AlCl4] by reacting SbCl3 with an excess of Al(C2H5)2Cl;  (b) [Sb(C2H5)4][AlC2H5Cl3] by reacting Sb(C2H5)4Cl with AlC2H5Cl2;  (c) [Sb(C2H5)4] [Al(C2H5)2Cl2 by reacting Sb(C2H5)4Cl with Al(C2H5)2Cl;  (d) [Sb(C2H5)4][Al(C2H5)3Cl] by reacting Sb(C2H5)4Cl with Al(C2H5)3;  (e) [Sb(C2H5)4] [Al2(C2H5)5Cl2] by reacting SbCl3 with excess of Al(C2H5)3; and  (f) [Sb(C2H5)4] [Al2(C2H5)6Cl] by reacting Sb[C2H5)4Cl with Al(C2H5)3.