公开(公告)号：GB1092477A

公开(公告)日：1967-11-22

申请号：GB1052365

申请日：1965-03-12

Applicant: BASF AG

Inventor： NAARMANN HERBERT ,  KASTNING ERNST-GUENTHER

IPC: C08F36/04

Abstract: 1,3-Dienes having four to ten carbon atoms are polymerized in aqueous emulsion using 0.001 to 3% of a catalyst comprising (a) complex compounds of cobalt in which the cobalt is at least trivalent and which bears ligands containing nitrogen atoms selected from ammonia, hydrazine, derivatives of ammonia carrying cycloaliphatic hydrocarbon radicals, derivatives of hydrazine carrying aliphatic hydrocarbon radicals, and derivatives of hydrazine carrying cycloaliphatic hydrocarbon radicals all these hydrocarbon radicals containing one to ten carbon atoms together with (b) halogenated hydrocarbons, indifferent to water, containing one to ten halogen atoms and having molecular weights of from 35 to 128, the molar ratio of halogenated hydrocarbon to cobalt complex compound being between 0.5 to 1 and 40 to 1. Specified dienes are butadiene, isoprene, 2-3-dimethylbutadiene and 2-phenylbutadiene while specified comonomers are the methyl up to 2-ethyl hexyl esters of acrylic, methacrylic, fumaric or maleic acids, especially butyl acrylate, acrylo and methacrylonitrile, styrene, alphastyrene, o-, m- and p-methyl styrene, p-ethyl-styrene and vinyl-methyl, ethyl, isopropyl, n-butyl or isobutyl ethers. Amongst the listed cobalt compounds are octarine-mu-aminoperoxocobalt (III)-cobalt (IV) chloride, tetraethylenediamine - mu -aminoperoxocobalt (II)-cobalt (V) nitrate, hexamminetriodicobalt (II) oxalate, sulphatooctammine - mu - iminodi-cobalt (III) nitrate, nitratoaquotetrahydrazine-mu-aminodicobalt (III) chloride, the cobalt complex compounds en being an alkylene diamine, and Specified halogenated hydrocarbons include n-amyl chloride, carbon tetrachloride, chloroform, and chlorobenzene. Stabilizers e.g. trinonylphenyl phosphite, chain transfer agents, and emulsifying agents may be present, and the polymerization take place by batch or continuous methods with continuous addition of reactants.

公开(公告)号：GB1092137A

公开(公告)日：1967-11-22

申请号：GB1032165

申请日：1965-03-11

Applicant: BASF AG

Inventor： NAARMANN HERBERT ,  KASTNING ERNST-GUENTHER ,  SCHNELL GEORG

IPC: C08F2/00 ,  C08F10/00 ,  C08F210/00

Abstract: Copolymers of mono-olefines and aromatic compounds are made by reacting at least one mono-olefin with at least one aromatic compound selected from aromatic hydrocarbons, thiophene and substitution products of thiophene at a temperature higher than - 100 DEG C. in the presence of a catalyst comprising (a) at least one halide of a metal of Groups III and/or IV of the Mendeleef Periodic System having an atomic weight up to 120; and (b) at least one metal compound containing metal ions having a redox potential of at least + 0.16 volt, and optionally (c) at least one organometallic compound of a metal of Groups I to IV. Suitable mono-olefines are ethylene, propylene, butene-1, 4-methylpentene-1, and octene-1. The aromatic compound may be benzene, toluenes, xylenes, diisopropylbenzene, diphenyl, terphenyl, naphthalene, alpha-methylnaphthalene, anthracene, thiophene, ethyl and methyl-substituted thiophenes, and benzothiazole. Compound (a) may be BF3 and its etherates, AlBr3, AlCl3, TiCl4, TiI4, TiCl3, SnCl4, and complexes of TiCl3 and AlCl3. Compound (b) may be MoCl5, MnCl4, FeCl3, CeCl4, PbCl4, VOCl3, cobalt tri(acetylacetone), copper dipyridyl, or potassium hexacyanomanganate. Compound (c) may be an alkyl, aryl and/or aralkyl compound of Na, K, Be, Mg, Cd, Sn, or Al. The aromatic compounds and/or the monoolefins may function as diluents for the polymerization. The polymers are recovered conventionally.

公开(公告)号：CA769805A

公开(公告)日：1967-10-17

申请号：CA769805D

Applicant: BASF AG

Inventor： KASTNING ERNST-GUENTHER ,  NAARMANN HERBERT

公开(公告)号：GB1074260A

公开(公告)日：1967-07-05

申请号：GB4187764

申请日：1964-10-14

Applicant: BASF AG

Inventor： NAARMANN HERBERT ,  KASTNING ERNST-GUENTHER

IPC: C08F8/48 ,  C08K3/16

Abstract: Polymers of vinyl methyl ketone or isopropenyl ketone or the cyclization products of such polymers are heated to a temperature of from 30 DEG C. to 800 DEG C. in the presence of a metal halide of a metal of Groups IIIA, IVB, VB, VIB, or VIIB of the Periodic Table (defined) or of iron or zinc in the presence of a dehydrogenating agent, to produce aromatized high-molecular weight compounds. Copolymers of the above ketones containing at least 50% by weight of ketone may also be used. The cyclization products are formed by intramolecular condensation by the action of acid or alkali. The treatment of copolymers with styrene, vinyl chloride, butadiene, isoprene, acrylonitrile, and methacrylonitrile are exemplified.

公开(公告)号：GB1065406A

公开(公告)日：1967-04-12

申请号：GB3067964

申请日：1964-08-04

Applicant: BASF AG

Inventor： NAARMANN HERBERT ,  KASTNING ERNST-GUENTHER

IPC: C08F36/04

Abstract: Elastomeric diene polymers are prepared by aqueous emulsion polymerization of conjugated dienes in the presence of a catalyst comprising (A) a chelate complex of trivalent chromium, manganese or cobalt, tetravalent cerium or divalent copper with a 1,3-dicarbonyl compound and (B) an organic halogen compound inert to water. Specified dienes are butadiene, isoprene, chloroprene, 2,3 - dimethylbutadiene, cyclo-octadiene- 1,3 1 -cyclohexyl butadiene and 2-phenylbutadiene, which may be copolymerized with minor proportions of other monomers such as acrylic and methacrylic acids, esters and nitriles, maleic and fumaric esters, vinyl ethers and vinyl aromatic compounds. Many suitable dicarbonyl compounds and organic halogen compounds are listed. Polymerization may be effected batchwise or continuously, preferably to a conversion of 55 to 60%, in the presence of conventional emulsifiers, e.g. salts of paraffin sulphonates, sulphonated alkyl phenols and fatty acids, and protective colloids, e.g. dextrans, cellulose ethers and polyvinyl alcohol; regulators, e.g. dodecyl mercaptan; and stabilizers for the polymers, e.g. trinonyl phosphite. The polymers may be precipitated with complex-forming compounds, e.g. alkali metal cyanides and phosphates and ethylene diamine tetra-acetic acid, to give catalyst-free products. Examples describe emulsion polymerizations using (1) butadiene, cobaltic acetoacetate, n-amyl chloride and sodium paraffin sulphonate; (2) butadiene manganic acetoacetate, n-amyl chloride and sodium paraffin sulphonate; (3) butadiene, styrene or (4) butadiene, vinyl ethyl ether with cobaltic acetoacetate, n-amyl chloride and sodium paraffin sulphonate; (5) butadiene, styrene or (6) butadiene, styrene, acrylonitrile with cobaltic salicylate, carbon tetrachloride and potassium rosin soap; (7) butadiene, manganic methylbutenyl acetoacetate, chloroform and fatty acid soap; (8) 2,3-dimethyl butadiene, n-butyl acrylate, di-n-butyl fumarate, ceric acetylacetonate, cupric acetoacetic ethyl ester trichlorethylene, ammonium oleate and octylphenol/ethylene oxide condensate; (9) as (8) using isoprene as monomer; (10) butadiene, acrylic acid, 2-ethylhexyl acrylate, methyl methacrylate, cobaltic malono dialdehyde, chromic acetoacetic ethyl ester, chloral, potassium rosin soap and oleic acid/ethylene oxide condensate; and (11) butadiene, t.-butyl acrylate, vinyl methyl ether, cobaltic benzoylacetonate, nickelous acetoacetic ethyl ester, n-butyl chloride, bromoform and potassium stearate.

公开(公告)号：GB1045800A

公开(公告)日：1966-10-19

申请号：GB3185163

申请日：1963-08-13

Applicant: BASF AG

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

公开(公告)号：GB1043360A

公开(公告)日：1966-09-21

申请号：GB210164

申请日：1964-01-17

Applicant: BASF AG

Inventor： KASTNING ERNST-GUENTHER ,  NAARMANN HERBERT

IPC: C08F10/00 ,  C08F36/04 ,  C08G61/00 ,  H01B1/12

Abstract: Homopolymers and copolymers of unsaturated cyclic hydrocarbons (other than aromatic hydrocarbons) are produced by polymerizing them under oxidizing conditions alone or with another unsaturated cyclic hydrocarbon and/or an open-chain diolefin and/or a compound having an aromatic ring system at temperatures of from -30 DEG to 150 DEG C. and in the presence of a Friedel-Crafts catalyst. Cyclic unsaturated hydrocarbons specified are cyclooctene, cyclopentadiene, dicyclopentadiene, cyclohexadiene, cycloheptatriene, cyclooctadiene-1,3, cyclooctadiene-1,5, cyclooctatriene, cyclooctatetraene, and cyclododecatriene. Comonomers exemplified are benzene, thiophene, isoprene, quinaldine, anthracene and phenanthracene. A number of catalyst components are specified; those exemplified are Friedel Crafts catalysts-AlCl3 and TiCl4, oxidizing agents-CuCl2, FeCl3, PbCl4 and PbNO3. Polymerization may be effected in a diluent or preferably in bulk. Traces of water or alcohols may advantageously be present in the reaction mixture. The polymers formed have semiconductor properties.

公开(公告)号：GB1042467A

公开(公告)日：1966-09-14

申请号：GB2805363

申请日：1963-07-16

Applicant: BASF AG

Inventor： NAARMANN HERBERT ,  KASTNING ERNST-GUENTHER

IPC: C08F10/00 ,  C08F16/00

Abstract: In a process for the production of ethylene copolymers containing hydroxyl groups, ethylene is polymerized using free radical forming catalysts at temperatures between 30 DEG and 300 DEG C. and pressures of more than 10 atmospheres in admixture with up to 50% by weight of the monomers of an ethylenically unsaturated alcohol of formula where R1 and R2 are hydrocarbon radicals which may together form components of a carbocyclic ring. Specified alcohols are 3-methylbuten-1-ol-3, 3 - methylpenten - 1 - ol - 3, 3 - methylhexen - 1 - ol - 3, 3 - methylhepten - 1 - ol - 3, 3 - phenylbuten - 1 - ol - 3, 3 - ethylpenten-1-ol-3, 3 - phenylpenten - 1 - ol - 3, diphenylvinyl carbinol, 1 - vinylcyclohexanol - 1, 3 - n - butylbuten - 1 - ol - 3 and 3 - n - butylpenten - 1 - ol-3. Additional comonomers may also be present, many suitable compounds being listed including vinyl esters, vinyl ethers, acrylic and methacrylic esters, amides and N-methylol amides, maleic acid or anhydride, fumaric acid, itaconic acid, vinyl sulphonic acids and their aryl esters. Specified catalysts are benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, t-butyl perbenzoate, azodiisobutyronitrile, azo bis-cyclohexanecarboxylic nitrile, azo bis-dimethylbutyronitrile, methyl azo bis-isobutyrate, azo bis-isobutyramide, redox systems of potassium or ammonium persulphate and ascorbic acid or sodium hydrosulphite, or benzoyl peroxide and dimethyl aniline, and oxygen. Polymerization may be effected in bulk, in emulsion or in the presence of organic solvents, e.g. methanol, ethanol, propanol, t-butanol, glycol, acetone, methyl ethyl ketone, diisobutyl ether, tetrahydrofuran, dioxane, cyclohexane, benzene, toluene, xylene, ethylbenzene, isopropylbenzene, formamide and dimethylformamide. The copolymers may be mixed with polyethylene, polyacrylates, polyamides, copolymers of ethylene and vinyl acetate, natural and synthetic rubbers, cellulose acetate and fillers, e.g. diatomaceous earth, titanium dioxide and carbon black, and used for moulding, coating and improving paper and textiles. The polymers may be cross-linked with diisocyanates and dicarboxylic acids. Examples describe the copolymerization of ethylene with (1) and (2) 3-methylbuten-1-ol-3, 3-phenylbuten - 1 - ol - 3, 3 - ethylpenten - 1 - ol - 3, 1-vinylcyclohexanol - 1 and 3 - methylocten - 1 -ol-3; (3) 3 - methylpenten - 1 ol - 3; (4) 3-methylbuten-1-ol-3 and the curing of the product with hexamethylene diisocyanate; (5) 3-methylbuten-1-ol-3 and acrylic acid; (6) 3-phenylbuten-1-ol-3 and vinyl acetate; (7) 3,4-dimethylpenten-1-ol-3 and the cross-linking of the product with tolylene diisocyanate; (8) 3-phenylbuten-1-ol-3, the cross-linking of the product with hexamethylene diisocyanate and the formation of sulphur vulcanizable products by treating with acetic acid; (9) 3-methylbuten-1-ol-3 and vinyl acetate; (10) 3-isobutylbuten-1-ol - 3; (11) 3 - n - butylbuten - 1 - ol - 3 and n-butyl acrylate and the cross-linking of the product with hexamethylene diisocyanate; and (12) 3-cyclohexylbuten-1-ol-3 and vinyl acetate.

公开(公告)号：FR1444438A

公开(公告)日：1966-07-01

申请号：FR26660

申请日：1965-07-30

Applicant: BASF AG

Inventor： NAARMANN HERBERT ,  KASTNING ERNST-GUENTHER

IPC: C08C3/00 ,  C08J3/09 ,  C08J3/11

公开(公告)号：GB982916A

公开(公告)日：1965-02-10

申请号：GB1500363

申请日：1963-04-17

Applicant: BASF AG

Inventor： BERDING CHRISTOPH ,  HOFMANN HERMANN PANKRAZ ,  KASTNING ERNST-GUENTHER ,  KUTEPOW NIKOLAUS VON ,  NAARMANN HERBERT ,  REIS HERMANN

IPC: C08F2/00 ,  C08F4/06 ,  C08F12/08 ,  C08F36/04

Abstract: Polymers of olefins are obtained by the use as sole catalystic material of metal chelates of Group IVb, Vb, VIb, VIIb, or VIII metals and b -diketones, b -ketocarboxylic esters, acetylacetonimide, salicylaldehyde, chloromalondialdehyde, a -hydroxypropionic acid, dihydroxymalonic acid, histidine or 1,3-diaminobutyric acid. Copolymers with a wide variety of monomers may be obtained. Optional ingredients are catalyst carriers, such as charcoal, carbon black, aluminium oxide, silica gel and aluminium silicate, and organic amines or carboxylic acids or amides. The reaction may be in bulk, in water, or preferably in an organic medium. Most of the examples illustrate the use of acetylacetonate complexes. The products may be of high crystallinity or enhanced 1,4-cis or 1,4-trans structure.