Mono:olefin (co)polymerisation using Ziegler catalyst - with solid titanium component on silica or silica-alumina support, giving high constant yield

摘要

(Co)polymerisation of 2-6C alpha-monoolefins at 30-200 degrees C and 0.1-200 bar employs Ziegler catalyst contg. a component (I) contg. Ti and a metal cpd. (II) of the formula MAm-nXn (where M is Al, Mg or Zn. A is a 1-12C hydrocarbyl gp. X is Cl, Br, I or H. m is the valency of Me. n is 0 to m-1), the atomic ratio of Ti:Me being 1:0.1:500. In the prodn. of (I) a finely-divided porous inorganic oxide (III) of particle size of 1-100 mu m pore vol. of 0,3-3 cm3/g and surface area of 100-1000 m2/g, having the formula SiO2.aAl2O3 (in which a is 0-2) is contacted with a soln., in an organic solvent, of an Al cpd. (IV) of the formula AlB3-pYp (in which B is a 1-12C hydrocarbyl gp. Y is Cl, Br, I, H or OR; R is a 1-12C hydrocarbon gp. p= 0-3), in a (III):(IV) wt. ratio of 1:0.05-10. (2) The intermediate solid obtd. is dispersed in a soln. contg. 100 pts. wt. alcohol of the formula Z-OH (in which Z is a satd. 1-8C hydrocarbon gp.), 0.01-6 pts. (as Ti) of TiCl3 and/or TiBr3 and 0.01-4 pts. (as Mg) of a Mg cpd. which is soluble in the alcohol, using a (III):Ti wt. ratio of 1:0.01-0.2 and a (III):Mg wt. ratio of 1:0.01:0.25. This dispersion is evaporated to dryness at a temp. below 200 degrees C and above the m.pt. of the alcohol used. (3) The second intermediate solid (V) is dispersed in a soln., in an organic solvent, of a metal cpd. (VI) of the formula MtGs-tEt (in which Mt is Al or Si. G is a 1-12C hydrocarbon gp. E is Cl, Br, I, H or an OD gp.; D is a 1-12C hydrocarbon gp. s is the valency of Mt. t is 0 to s-1 if Mt is Al and 0 to 4 if Mt is Si), using a wt. ratio of (V):(VI) of 1:0.05-2. The polymer is obtd. in a high and constant specific yield and has esp. favourable morphological properties, such as high bulk density and good powder flow.