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    33.
    发明专利
    未知

    公开(公告)号：DE1180522B

    公开(公告)日：1964-10-29

    申请号：DEB0068568

    申请日：1962-08-25

    Applicant: BASF AG

    Inventor： KASTNING DR ERNST-GUENTHER ,  NAARMANN DR HERBERT ,  BERDING DR CHRISTOPH ,  REIS DR HERMANN

    IPC: C08F2/00 ,  C08F2/02 ,  C08F4/06 ,  C08F36/04

    Abstract: Polymers of ethylenically unsaturated monomeric compounds are prepared using a catalyst comprising (a) at least one metal chelate compound of a Group IVb, Va, Vb, VIb, VIb or VIII metal (for Periodic Table see Handbook of chemistry and Physics) and a b -diketone, b -ketocarboxylic ester, ester of diacetoacetic acid, amino acid having 2 to 6 carbon atoms, salicylaldehyde, chloromalonodialdehyde, o-amino phenol, o-aminobenzoic acid or 2,21-hydroxyazobenzene and (b) at least one aliphatic, aromatic or heterocyclic chlorine, bromine or iodine compound having 1 to 12 carbon atoms. The catalyst contains component (a) in an amount between 0.001 and 5% by weight based on the weight of monomeric compounds, and 0.01 to 50 parts of component (b) to 1 part of component (a). The polymerization may be in bulk or the monomers may be dissolved or suspended in inert auxiliary liquids for the polymerization such as hydrocarbons, ethers, alcohols and ketones. Lists of catalyst components (a) and (b), monomers and auxiliary liquids are given. In the Examples: (I) styrene is homopolymerized using carbon tetrachloride and one of the following: manganic acetylacetonate, manganic anthranilate, manganic acetoacetic ethyl ester, cobaltic acetylacetonate, cobaltic histidinate, cobaltic acetoacetic ethyl ester, chromic glycinate and molybdenum acetylacetonate; (2) styrene is homopolymerized using manganic acetylacetonate and one of the following: bromobenzene, hexachloroethane, chlorobenzene, 1,3,5-trichlorobenzene, cyanuric chloride, trichloroethylene, 1,2-dibromoethane, carbon tetrachloride, pentachloropropanol, n-amylchloride, a -bromocaproic acid and 2-amino-5-iodopyrimidine; (3) ethylene is copolymerized with vinylethylether using carbon tetrachloride and manganic acetylacetonate; (4) diisobutylene is copolymerized with acrylic acid using hexachloroethane and manganic acetylacetonate; (5) propylene is copolymerized with acrylamide and ethyl acrylate using amyl chloride and nickelous acetoacetic propargyl ester; (6) styrene is copolymerized with vinyl chloride using manganic anthrilate and amyl chloride; (7) butadiene is copolymerized with dibutyl fumarate using manganic acetylacetonate and chloroform; (8) styrene is compolymerized with vinyl acetate using cobaltic anthranilate and 1,4-dichlorobutane; (9) butadiene is copolymerized with acrylic acid using nickeleous acetylacetonate and butyl chloride; (10) ethylene is homopolymerized using cobaltic acetylacetonate or cobaltic acetylacetonimide and carbon tetrachloride or amyl chloride; (11) butadiene or isoprene is homopolymerized using manganic diacetoacetic ethyl ester and n-lauryl chloride; (12) methylmethacrylate is homopolymerized using cobaltic salicylaldehyde and carbon tetrachloride; (13) vinylisobutyl ether is homopolymerized using chloroform and manganic ortho-aminophenolate, antimony tetrachloroacetylacetonate or titanium dichloroacetylacetonate; (14) acrylic acid is homopolymerized using carbon tetrachloride and manganic acetylacetonate; (15) acrylamide is homopolymerized using cobaltic chloromalonodialdehyde and bromoform; (16) N-methylol methacrylamide, N-vinylimidazole or N-vinyl-carbazole are homopolymerized using vanadium acetylacetonate, manganic acetoacetic ester and n-amyl chloride and (17) styrene is copolymerized with acrylonitrile using methylene chloride and manganic 2,2-hydroxyazobenzene.

    35.
    发明专利
    未知

    公开(公告)号：DE1023013B

    公开(公告)日：1958-01-23

    申请号：DEB0041407

    申请日：1956-08-16

    Applicant: BASF AG

    Inventor： WISSEROTH DR KARL ,  KASTNING DR ERNST-GUENTHER

    IPC: B01J19/00 ,  C08F2/00 ,  C08F10/00

    Abstract: Exothermic polymerization reactions are conducted in the presence of a solution of a gas in a solvent in which it dissolves with evolution of heat, after said solution has been cooled, and p allowing said gas to escape by decompression during the course of the reaction so that the gas withdraws the reaction heat. The gas serving as a heat carrier may be an active participant in the polymerization thus in the polymerization of a gaseous olefin the olefin (e.g. ethylene) may be the heat carrier. The process which may be continuous may especially be employed in the polymerization of gaseous monomers e.g. propylene, isobutylene, vinyl chloride or fluorinated ethylenes and may be used for both the high and low pressure polymerization of ethylene, an example of each being given. Catalysts specified for the polymerization of ethylene are alpha, alpha'- azobisisobutyronitrile, peroxides, e.g. benzoyl peroxide, and normal amyl sodium with titanium tetrachloride and diluents specified are cyclohexane and benzene.

    38.
    发明专利
    未知

    公开(公告)号：DE1013870B

    公开(公告)日：1957-08-14

    申请号：DEB0039038

    申请日：1956-02-08

    Applicant: BASF AG

    Inventor： WISSEROTH DR KARL ,  PIETSCH DR-ING WALTER ,  KASTNING DR ERNST-GUENTHER

    IPC: B01J8/10 ,  B01J19/00 ,  B01J19/18 ,  C08F2/00 ,  C08F10/00 ,  C08F10/02

    Abstract: In a process for withdrawing polymerization heat in continuous olefin polymerization processes in which gaseous olefins are used, which comprises supplying gaseous olefin reactant, with or without an additional non-polymerizable gaseous component under a pressure substantially higher than the pressure that prevails in the reactor, and expanding said compressed olefin (or olefin and said additional non-polymerizable component) through a throttle valve into the reactor, the reactor being arranged in a circulatory path for said olefin, whereby heat of polymerization is withdrawn by heat exchange after the olefin has left the reactor and before it is again supplied through said valve into the reactor, according to the parent Specification, the olefin is introduced into the reaction space immediately after pressure release in the form of directed jets continuously moving in the reaction space while the layer of polymer arising in powder form is simultaneously agitated by mechanical means. Apparatus suitable for carrying out the process of the invention is described and illustrated and may comprise a rotating stirrer and rotating nozzle heads secured to a common shaft the hollow base of which running in a hollow bearing provides a passage for supplying the monomer. Catalyst may be added either continuously or incrementally, and the product may be recovered by passing the material withdrawn from the reactor through a cyclone separator. The polymerization of ethylene is described in an example.

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