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    51.
    发明专利
    未知

    公开(公告)号：FI56191B

    公开(公告)日：1979-08-31

    申请号：FI290171

    申请日：1971-10-15

    Applicant: SOLVAY

    Inventor： DELBOUILLE ANDRE ,  DERROITTE JEAN-LOUIS

    IPC: C08F4/42 ,  C08F4/64 ,  C08F4/68 ,  C08F10/00 ,  C08F4/02 ,  C08F110/02

    Abstract: This invention relates to the polymerization of alpha -olefins and to catalysts and to cocatalysts for that purpose wherein the polymerization is carried out in the presence of a catalyst comprising an organometallic compound of a metal of Groups IA, IIA, IIB, IIIA, and IVA of the Periodic Table and a cocatalyst comprising a reaction product of a halogenated derivative of a transition metal of Groups IVB, VB, and VIB of the Periodic Table and a hydrous divalent metal salt of a carboxylic acid, the cocatalyst having a gram equivalent ratio of halogen/divalent metal plus transition metal greater than 0.5. The invention also comprises the method of making the cocatalysts.

    58.
    发明专利
    未知

    公开(公告)号：DE1770907A1

    公开(公告)日：1972-02-17

    申请号：DE1770907

    申请日：1968-07-18

    Applicant: SOLVAY

    Inventor： DELBOUILLE ANDRE ,  TOUSSAINT HENRI

    IPC: C08F4/68 ,  C08F10/00 ,  C08F3/06

    Abstract: 1,162,079. Stereospecific polymerization. SOLVAY & CIE. 22 July 1968 [31 Aug., 1967], No. 34876/68. Heading C3P. Alpha olefins are stereospecifically polymerized in the presence of a solid catalyst coinprising a combination of an organic comprund of a metal of group 1, 2 or 3 of the Periodic Table and a reduced crystalline halide of a metal of group 4A, 5A or 6A deposited on an inert porous solid support, wherein the halide is obtained by reducing, under an anhydrous and oxygen-free atmosphere at a temperature lower than 0‹ C. in the absence of any liquid diluent, a halide of a group 4A, 5A or 6A metal in its maximum valence state, by means of an organolithium compound which may be the same as the one forming the polymerization catalyst, the quantities of support, unreduced halide and organometallic compound being such that during reduction, the volume of reactants is not higher than the total volume of the pores which could absorb the reactants so that the mixture is maintained pulverulent. The reduceable halide may be titanium or vanadium tetrachloride, the reducing agent may be a trialkyl or halo-alkyl aluminium, the support may be alumina, silica, an aluminum silicate, a magnesium silicate, magnesia, titania or a polyolefin, and the alpha-olefin may be ethylene, propylene, butene-1, pentene-1, methyl butene-1, hexene-1, 3- or 4-methyl pentene-1, a C 1-12 olefin or styrene. In the examples, titanium tetrachloride, deposited on various supports, is reduced with aluminium diethyl chloride, aluminium ethyl dichloride or aluminium diisobutyl chloride, and the resultant catalyst, activated with aluminium diethyl chloride, is used to polymerize propylene, 4-methyl pentene-1, or butene-1, to polymers of a high isotactic content.

    POLYMERIZATION CATALYSTS AND A PROCESS FOR THEIR PREPARATION
    59.
    发明专利
    POLYMERIZATION CATALYSTS AND A PROCESS FOR THEIR PREPARATION 未知

    公开(公告)号：GB1259962A

    公开(公告)日：1972-01-12

    申请号：GB968569

    申请日：1969-02-24

    Applicant: SOLVAY

    Inventor： DERROITTE JEAN LOUIS ,  DELBOUILLE ANDRE

    IPC: C08F4/00 ,  C08F4/02 ,  C08F4/42 ,  C08F4/60 ,  C08F4/68 ,  C08F10/00

    Abstract: 1,259,962. Polymerisation catalysts. SOLVAY & CIE. 24 Feb., 1969 [22 March, 1968], No. 9685/69. Heading B1E. [Also in Divisions C1 and C3] An olefin polymerisation catalyst comprises (a) an organometallic compound or an organosilicon compound having at least one siliconhydrogen bond and (b) a solid catalytic component comprising a product of the reaction between a compound of a transition metal and solid support material, the solid catalytic component having been prepared by a process which comprises partially hydrolysing a halide having the formula MX 2 .mH 2 O, wherein M is a bivalent metal, for example magnesium, calcium, chromium, manganese, iron, cobalt, nickel, copper, zinc or cadmium, each X is a halogen atom, for example a fluorine, chlorine, bromine or iodine atom, and m is equal to or greater than O, under reaction conditions such as to provide solid support material at least the surface of which has the formula M(OH) x Xy.nH 2 O, wherein the sum of x and y is 2, x is greater than 0 but less than 1, preferably greater than 0.1 but less than 0.8, and n is equal to or greater than 0, and thereafter reacting, in the liquid phase and whilst preventing overheating, the solid support material and a transition metal compound. The partial hydrolysis may be carried out prior to the contact between the metal halide and the transition metal compound, for example either by contacting anhydrous metal halide with water vapour at a temperature of for example above 100‹C or simply by heating hydrated metal hydride at a temperature of between 50 and 350‹C, the water of hydration providing the water required for the partial hydrolysis; alternatively and especially when the metal halide is hydrated, the partial hydrolysis may be carried out simultaneously with the contact between the metal halide and the transition metal compound, the solid support material being formed in the medium in which the solid support material is reacted with the transition metal compound. The transition metal compound may be a halide, oxyhalide, alkoxyhalide, alkoxide or oxyalkoxide of a metal selected from Groups IVa, Va and VIa; exemplified compounds are TiCl 4 . TiCl 2 (OC 2 H 5 ) 2 , Ti(OC 4 H 9 ) 4 , VCl 4 , VOCl 3 , VO(OC 4 H 9 ) 3 and CrO 2 Cl 2 . The organometallic compound may be an alkyl, alkyl hydride or alkyl halide of a metal selected from Groups I, II, III and IV, for example a trialkyl aluminium, an alkyl aluminium hydride, an alkyl tin hydride, an alkyl magnesium halide or an alkyl aluminium halide. Examples relate to catalysts which comprise triisobutylaluminium and a solid component comprising a product of the reaction between TiCl 4 and solid support material obtained from MgF 2 and water (Example 1) or MgBr 2 .6H 2 O (Examples 2, 3 and 4) or MgCl 2 .H 2 O (Examples 5, 6, 7 and 8) or MgI 2 .8H 2 O (Example 11) or FeCl 2 .4H 2 O (Example 12) or NiCl 2 .6H 2 O (Example 13) or CoCl 2 .6H 3 O (Example 14) or MnCl 2 .4H 2 O (Examples 15, 19 and 20); triisobutylaluminium and a solid component comprising a product of the reaction between TiCl 2 (OC 2 H 5 ) 2 (Example 9) or CrO 2 Cl 2 (Example 10) and solid support material obtained from MgCl 2 .H 2 O; diethylaluminium chloride (Example 16) or diethyl zinc (Example 17) and a solid component comprising a product of the reaction between TiCl 4 and solid support material obtained from MnCl 2 .4H 3 O; and triisobutylaluminium and a solid component comprising a product of the reaction between VOCl 3 and solid support material obtained from MnCl 2 .4H 2 O (Example 18).

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