Patent GB-833478-A (GB)
Title: Improvements in or relating to catalytic olefin polymerisation
IPC: C08F10/00
Filed: 1957-02-04
Abstract: Catalyst systems suitable for low pressure olefin polymerization (see Group IV (a)) comprise a suspension in an inert liquid of a pyrophoric multivalent metal having an effective surface of at least 25 sq.m./g. and, as an activator therefor, at least 0.01 mol. of a metal hydride alkyl, or aryl or a Grignard reagent for each mol. of pyrophoric metal.  Metals mentioned are Fe, Ni, Co, Pt, Ti, Pb, Ce, U, Th, Zr and Cr, which may be produced under any conditions which result in a pyrophoric product.  Methods of obtaining the pyrophoric metal of the required surface area include: (i) reducing their oxides or salts in a finely-divided form (less than 50m  particles); (ii) forming a monomolecular layer on a porous carrier, e.g. alumina, silica, other metal oxides or carbon; and (iii) dissolution of one metal from an alloy, e.g. by dissolving out Al from its alloy with Ni, Co, Ti or Zr by means of NaOH.  The metal surface must be rendered completely dry, e.g. by washing with an oxygen-free hydrocarbon solvent and distilling off the solvent and it must be protected from oxygen.  When the metal is prepared by reduction with hydrogen some metal hydride may also be present.  The second component is an alkyl, aryl, or hydride of a metal (e.g. Al, Zn, Mg, Li, K, Na) or (when the metal is polyvalent) a Grignard reagent. Examples include tri-methyl, ethyl, propyl or octyl aluminium; di-methyl, ethyl or propyl zinc or magnesium; lithium ethyl or butyl; and ethyl, benzyl or tolyl magnesium chloride or bromide.  The two components are suspended in an inert liquid such as an aliphatic, cycloaliphatic, aromatic or hydroaromatic hydrocarbon, e.g. hexane, heptane, petroleum ether, cyclohexane, decalin, benzene, xylene or tetraline; a halogenated hydrocarbon, e.g. carbon tetrachloride; or an ether, e.g. dioxane.  The gaseous or liquid monomeric olefin is then added to the suspension. Highly polished small steel balls may be added constantly to grind the catalyst and expose a fresh surface. Examples describe the preparation of large surface area, pyrophoric iron, cobalt, nickel, platinum and zirconium which are used in the following combinations of components, inert liquid, and monomers: (i) Fe/diethyl zinc, heptane ethylene; (ii) Ni/lithium ethyl, decalin, ethylene and styrene; (iii) Co/EtMgBr, octane, ethylene; (iv) Fe/aluminium triethyl, tetralin, propylene; (v) Ni/aluminium Tri-iso-butyl, heptane, ethyene; (vi) Pt/zinc diethyl, heptane, ethylene; (vii) Zr or Ti/aluminium triethyl, heptane, ethylene and propylene; and (viii) Co/aluminium triethyl, ethylene and propylene.ALSO:A process for the polymerization of an alpha-beta ethylenically unsaturated monomer comprises maintaining the monomer in contact with a suspension in an inert organic liquid of a catalytically-active system (see Group III) comprising a pyrophoric multi-valent metal having an effective surface of at least 25 sq. m./g., and at least 0.01 mol. (per mol. of pyrophoric metal) of a metal hydride, alkyl, aryl or Grignard reagent as an activator therefor.  Pyrophoric metals mentioned are Fe, Ni, Co, Pt, Ti, Pb, Ce, U, Th, Zr and Cr; they may be in the form of a mono-molecular layer on a carrier of the required surface area. The activators may be compounds of Al, Zn, Mg, Li, K or Na.  Inert liquids specified are hydrocarbons, e.g. hexane, heptane, petroleum ether, cyclohexane, decalin, benzene, xylene, and tetralin; carbon tetrachloride; and ethers, e.g. dioxane. Monomers specified are ethylene, propylene, styrene and acrylates. The polymerization may be effected in a closed vessel or autoclave with agitation in the presence of highly polished small steel balls.