Patent GB-868909-A (GB)
Title: Improvements in or relating to the production of ethylene polymers
IPC: C08F110/02
Filed: 1960-01-21
Abstract: Polymers of ethylene having a branched chain structure are made by polymerizing ethylene in the presence of a catalyst comprising a chromyl halide, an aluminium halide and a compound selected from (a) an organometallic compound of sodium, potassium, lithium, rubidium, caesium, beryllium, magnesium, zinc, cadmium, mercury, aluminium, gallium, indium or thallium; (b) an organometal halide of one of the metals aluminium, gallium, indium, thallium, and beryllium, and (c) a mixture of an organic halide and at least one metal selected from sodium, potassium, lithium, rubidium, caesium, beryllium, magnesium, zinc, cadmium, mercury, aluminium, gallium, indium and thallium.  The chromyl halides may be CrO2Cl2, CrO2F2, CrO2Br2, CrO2I2 and mixtures thereof.  Compound (a) has the general formula MRx where M is one of the metals previously specified, R is a monovalent saturated acylic, cyclic, or aromatic radical or a combination thereof and x is equal to the valency of the metal.  Specified (a) compounds are C2H5Na, C3H7K, C4H9Li, Al (C2H5)3, Al(CH3)3, Be(CH3)2, Ga(C3H7)3, In (CH3)3, Be(C6H5)2, Al(C6H13)3, Al(CH2-(CH2)18CH3)3, Ga(C6H5)3 and In(C6H5)3. Compound (b) has the formula RM1mXx where R is as previously specified, M1 is a metal selected from (b) above), X is a halogen and m and n are integers equal to the valency of the metal.  Specific examples of (b) are CH3AlCl2, (CH3)2 AlCl, C2H5AlCl2, (C2H5)2 AlCl, (C2H5)2 AlBr, (C4H9)2AlBr, C8H17AlI2, (C3H7)2GaF, (C6H11)2GaCl, C6H5GaBr2, C20H41GaBr2, (C14H29)2GaF, (C6H5)2 InCl, C8H17InF2, C6H11 InBr2, C17H35BeI, and CH3BeBr.  The organic halide may be ethyl bromide, propyl chloride, butyl iodide, pentyl fluoride, 1, 2-dibromoethane, 1, 3-dibromopropane, 1, 2, 3-tribromopropane, 1, 2, 3-trichloro-propane, 1, 1-difluoro-ethane, 1, 4-diidobutane, 1, 3-dichlorocyclohexane, benzyl chloride, 1, 4-dichlorobenzene, 1-bromodecane, 1- or 2-chloro-octane, 2-chloro-4-methyl-octane, cyclopentyl chloride, 1-chloro-3-phenyl propane, 1-bromo-3-phenylhexane, cyclohexyl chloride, phenyl chloride, or propargyl chloride.  The process may be effected continuously or batchwise, and the polymerization effected in the presence of a diluent, e.g. a hydrocarbon or a halogenated hydrocarbon, or in bulk. The polymer may be purified by conventional techniques.ALSO:A polymerization catalyst comprises a chromyl halide, an aluminium halide and a compound selected from (a) an organometallic compound of sodium, potassium, lithium, rubidium, caesium, beryllium, magnesium, zinc, cadmium, mercury, aluminium, gallium, indium and thallium, (b) an organometal halide of one of the metals aluminium, gallium, indium, thallium, and beryllium, and (c) a mixture of an organic halide and at least one metal selected from sodium, potassium, lithium, rubidium, caesium, beryllium, magnesium, zinc, cadmium, mercury, aluminium, gallium, indium and thallium.  The chromyl halide may be CrO2Cl2, CrO2F2, CrO2Br2, CrO2I2 or a mixture thereof.  Com pound (a) has the general formula MRx where M is one of the metals previously specified, R is a mono-valent saturated acylic, cyclic, or aromatic radical or a combination thereof and x is equal to the valency of the metal.  Specified (a) compounds are C2H5Na, C3H7K, C4H9Li, Al(C2H5)3, Al(CH3)3, Be(CH3)2, Ga(C3H7)3, In(CH3)3, Be(C6H5)2, Al(C6H13)3, Al(CH2-(CH2)18CH3)3, Ga(C6H5)3 and In(C6H5)3. Compound (b) has the formula RmM1Xx where R is as above, M1 is a metal selected from (b) above, X is a halogen and m and n are integers equal to the valency of the metal.  Specific examples of (b) are CH3AlCl2, (CH3)2AlCl, C2H5AlCl2, (C2H5)2AlCl, (C2H5)2AlBr, (C4H9)2AlBr, C8H17AlI2, (C3H7)2 GaF, (C6H11)2GaCl, C6H5GaBr2, C20H41GaBr2, (C14H29)2GaF, (C6H5)2InCl, C8H17InF2, C6H11 InBr2, C17H35BeI, and CH3BeBr.  The organi halide may be ethyl bromide, propyl chloride, butyl iodide, pentyl fluoride, 1,2-dibromoethane, 1,3-dibromopropane, 1,2,3-tribromopropane, 1,2,3-trichloropropane, 1,1-difluoroethane, 1,4-diiodobutane, 1,3-dichlorocyclohexane, benzyl chloride, 1,4-dichlorobenzene, 1-bromodecane, 1- or 2-chlorooctane, 2-chloro-4-methyloctane, cyclopentyl chloride, 1-chloro-3-phenylpropane, 1-bromo-3-phenylhexane, cyclohexyl chloride, phenyl chloride, or propargyl chloride.