PROCESS FOR POLYMERIZINING ALPHA-OLEFINS

摘要

1333759 Polymerization catalyst for α-olefins FARBWERKE HOECHST AG 16 Nov 1970 [17 Nov 1969] 54405/70 Heading C3P [Also in Division C2] Olefins of formula RCH = CH 2 , where R is hydrogen or a hydrocarbon group, especially C 1 -C 10 alkyl, are polymerized using a catalyst comprising (A) the reaction product of a tetravalent, halogen-containing titanium compound with a complex metal alkoxide, optionally mixed with a simple alkoxide, or with two simple alkoxides in succession, and (B) an organoaluminium compound. The complex alkoxides may be of the general formula where each of M1, M11 and M111 represents a metal of main- or sub-groups I to V, Fe, Co or Ni, R represents one or more C 1 to C 20 hydrocarbon groups, y is 2 to 6, z is 0 or 1, (v+w) is at least 1 and x is 1 to 5. The complex alkoxides, which need not be isolated before treatment with the titanium compound, may be prepared by (i) reaction between the simple alkoxides of M1 and M11, (ii) dissolving one metal in an alcohol in the presence of a simple alkoxide of the other, (iii) dissolving both metals together in an alcohol, (iv) reacting the acid of the anion [M1 x (OR) y ] with an alkaline simple alkoxide of M11 or (v) reacting an anhydrous metal halide, M1X n , with an alkali metal alkoxide, M11(OR). In the examples, complex alkoxides are obtained by reacting (i) Mg(OEt) 2 with Ti(Oi-Pr) 4 or Al(Oi-Pr) 3 or Al(O sec-Bu) 3 ; (ii) Ti(Oi-Pr) 4 with Li(Oi-Pr) and Mg(OEt) 2 or Al(Oi-Pr) 3 and Mg(OEt) 2 ; (iii) lithium metal with an isopropanol solution of Al(Oi-Pr) 3 , followed by addition of Mg(OEt) 2 ; (iv) titanium glycolate with Mg(OEt) 2 and Al(Oi-Pr) 3 ; and (v) ZrCl 4 with Mg(OEt) 2 . The complex alkoxides are then treated with TiCl 4 , washed, activated with Et 3 Al, Et 2 AlCl or (i-Bu) 3 Al and used to catalyse the homopolymerization of ethylene or copolymerization of ethylene and 1-butene in a hydrocarbon diluent. The gas-phase polymerization of ethylene is also described.