Patent GB-824374-A (GB)
Title: Process and catalyst for polymerization of polymerizable hydrocarbons
IPC: C08F4/42
Filed: 1956-12-13
Abstract: A catalyst for polymerizing olefines consists of a mixture of three components: (1) a metal halide containing Ti, Zr, Hf, Ge; (2) an alkoxide or aryl oxide of a metal comprising Li, Rb, Cs, Na, K, Mg, Ca, Zn, Si, Ca, Ba, Al, Ga, In or Tl; and (3) one or more members of the three groups (a) an organo metallic halide containing Al, In, Ga, Tl or Be; (b) a mixture of an organic halide preferably containing eight C atoms or less, and a metal selected from the group Na, K, Li, Rb, Cs, Be, Mg, Zn, Cd, Hg, Al, Ga, In, or Tl ; and (c) a complex hydride containing two metals one selected from the groups Al, Ga, In, Tl and the other being an alkali metal.  The organic radical present in compounds (2) and (3, a) may contain up to 20 carbon atoms but preferably 1 to 10, e.g. alkyl, aryl, cycloaryl, cycloalkenyl or cycloalkynyl groups. Numerous examples given, the following are the preferred mixtures: (a) titanium tri- or tetra chloride, sodium ethoxide, and diethyl aluminium chloride containing ethyl aluminium dichloride; (b) titanium tetrachloride, aluminium ethoxide or sodium propoxide and lithium aluminium hydrate; (c) zirconium tetrachloride, calcium phenoxide and diethyl aluminium chloride containing ethyl aluminium dichloride; 1-olefines, di- or polyolefines may be treated, and the components of the catalyst changed in any order or simultaneously.ALSO:Olefines including branched chain olefines, di- and poly-olefines, and cyclic olefines are polymerized with a catalyst consisting of a mixture of 3 components (1) a metal halide of Ti, Zr, Hf, Ge; (2) a compound M1(OR1)x where R1 is alkyl, alkenyl, cycloalkyl, cycloalkenyl, or aryl, and M1 is Li, Rb, Cs, Na, K, Mg, Ca, Zn, Sr, Ca, Ba, Al, Ga, In, or Tl, and (3) one or more members of the following 3 groups: (a) an organo-metallic halide containing Al, In, Ga, Be, Tl; (b) a mixture of an organic halide preferably containing up to 8 C atoms, and a metal Na, K, Li, Rb, Cs, Be, Mg, Zn, Cd, Hg, Ga, In or Tl; or (c) a complex hydride containing 2 metals, one being an alkali metal and the other Al, Ga, In or Tl. The organic radical present in (2) and (3a) may contain up to 20 C atoms., preferably 1 to 10. The preferred mixtures from a range of example are: (1) titanium tri- or tetrachloride, sodium ethoxide and diethyl aluminium chloride containing ethyl aluminium di-chloride; (2) titanium tetra chloride, aluminium ethoxide and lithium aluminium hydride; (3) zirconium tetrachloride, calcium phenoxide or sodium propoxide and diethyl aluminium chloride.  The olefines polymerized include ethylene, propylene, 1-octene, isobutylene; di-alkyl substituted olefines, e.g. hexene-2, 2-methyl-butene-1; non-conjugated di- or poly-olefines, e.g. butadiene, isoprene, 1,4-pentadiene; cyclic olefines, e.g. cyclohexene; aryl olefines, e.g. styrene, or mixtures of these.  Co-polymers may be formed, using compounds with CH2=C< group, e.g. acrylonitrile, methyl acrylate or methacrylate, vinyl chloride, and 2-vinyl pyridine.  Polymerization is effected in a continuous or batch process, using diluents, preferably low molecular paraffins, but aromatic, halogenated and cycloparaffin hydrocarbons are referred to.  The components of the catalyst may be changed in any order or simultaneously.