Improvements in the crosslinking of polymers

    公开(公告)号:GB862869A

    公开(公告)日:1961-03-15

    申请号:GB3905959

    申请日:1959-11-18

    Applicant: BASF AG

    Abstract: 862,869. Cross-linking copolymers of ethylenically unsaturated compounds. BADISCHE ANILIN- & SODA-FABRIK A.G. Nov. 18, 1959 [Nov. 28, 1958], No. 39059/59. Class 2(6). Copolymers of at least one α, #-ethylenically unsaturated carboxylic acid, at least one α, #- ethylenically unsaturated carboxylic acid nitrile and at least one α, #-ethylenically unsaturated carboxylic acid ester which contain 0À5 to 12% by weight of said acid component and at least 30% by weight of said nitrile component are cross-linked by reacting with a compound of formula: where R 1 , R 2 , R 4 and R 5 represent hydrogen, alkyl radicals or methylol groups, R 3 represents - (CH 2 )xin which x is 0 to 12, -CH=CH-, arylene or cycloalkylene, m is 3 to 11, n is 4 to 10 and y is 1 or 2. The monomers may be acrylic, methacrylic and crotonic acids, nitriles and esters of these acids with methanol, ethanol, propanol, butanol, hexanol, octanol and cyclohexanol. Cross-linking may be effected with N, N 1 -bismethylol diamides of oxalic, malonic, glutaric, succinic, adipic, suberic, sebacic, heptadecane dicarboxylic, phthalic, isophthalic, terephthalic, diphenyl dicarboxylic, maleic and fumaric acids; N-methylol substituted lactams of α-aminobutyric, α-aminovaleric, α-aminocaproic, α- aminocaprylic, α aminooenanthic and α-aminooundecanic acids; and the 2, 21-methylene and 2, 2 1 -ethylene bis caprolactams, their N-methylol derivatives and the corresponding derivatives of caprylic, oenanthic and undecanic lactams. The polymers may be prepared by polymerisation in aqueous media in the presence of catalysts, e.g. potassium persulphate, and emulsifiers, e.g. sodium octylphenylsulphonate and the sodium sulphonate of C 15 paraffins. Examples describe the cross-linking of acrylonitrile-butyl acrylateacrylic acid terpolymers with (1, 2 and 3) N, N 1 - bis-methyloladipamide, (4) 2, 2 1 -methylene-biscaprolactam, (5) N-methylolcaprolactam and (6) N, N 1 -bis-methylol-2, 2 1 -methylene-biscaprolactam; and of (2) acrylonitrile-ethylhexyl acrylate-methacrylic acid terpolymer, methacrylonitrile-isobutyl acrylate-acrylic acid terpolymer and acrylonitrile-butyl acrylate-butyl methacrylate-acrylic acid copolymer with N, N 1 -bismethyloladipamide. The products may be used in making films and coatings, e.g. on metal, wood, glass, paper, fabrics and leather, and lacquers, e.g. in solvents such as cyclohexanone, glycol, dimethylformamide, dimethyl sulphoxide and tetramethylene sulphone.

    Production of non-dusting coal products

    公开(公告)号:GB953778A

    公开(公告)日:1964-04-02

    申请号:GB3256062

    申请日:1962-08-24

    Applicant: BASF AG

    Abstract: Three examples are given of aqueous dispersions of polymers or copolymers that form tacky films in the region of 0 DEG C., on coal surfaces. In the first, (all parts by weight) 190 parts butyl acrylate and 10 parts vinyl isobutyl ether are emulsified in a solution of 8 parts of a sulphonated condensation product derived from 1 mole sperm oil alcohol and 15 moles ethylene oxide, in 200 parts water. 0.4 part potassium persulphate is added and the mixture polymerized. In the second, 180 parts ethylhexyl acrylate and 20 parts "Lorol" acrylate ("Lorol" is a trade name applied to mixtures of aliphatic alcohols obtained by high pressure hydrogenation of coconut oil) are emulsified in a solution of 7 parts of the sulphonated condensation product derived from 1 mole iso octyl phenol and 20 moles ethylene oxide in 200 parts water, 0.4 part potassium persulphate being added before polymerizing. In the third, 100 parts vinyl propionate and 100 parts vinyl octanoate are emulsified in an aqueous solution containing 8 parts of the sulphonated condensation product derived from 1 mole stearyl alcohol and 10 moles ethylene oxide, potassium persulphate being added and polymerization being carried out as above. Specification 842,672 is referred to.ALSO:Coal and coal products are made dustless or non-dusting by spraying them with an electrolyte-resistant, i.e. non-coagulating, aqueous dispersion of a polymer or copolymer that forms on the surface of the coal a coating that will remain soft and tacky at temperatures down to 0 DEG C. Polymers and copolymers made by the methods described in Specification 842,672 may be used, preferably those using oxyethylated and sulphonated alkyl phenols or fatty alcohols as dispersing agents. Glycols may be added for anti-freezing purposes. Polymers and copolymers mentioned are: acrylates of alcohols having at least four carbon atoms, e.g. straight-chained or branched butyl, hexyl, octyl, decyl, stearyl acrylate and corresponding methacrylates; vinyl esters of fatty acids having at least three carbon atoms, e.g. vinyl propionate, laurate, stearate; vinyl ethers of alcohols having up to eight carbon atoms, or butadiene or isoprene. Three specific examples are described giving parts by weight.ALSO:Coal and coal products are made dustless or non-dusting by spraying them with an electrolyte-resistant, i.e. non-coagulating, aqueous dispersion of a polymer or copolymer that forms on the surface of the coal a coating that will remain soft and tacky at temperatures down to 0 DEG C. Polymers and copolymers made by the methods described in Specification 842,672 may be used, preferably those using oxyethylated and sulphonated alkyl phenols or fatty alcohols as dispersing agents. Glycols may be added for anti-freezing purposes. Polymers and copolymers mentioned are: acrylates of alcohols having at least four carbon atoms, e.g. straightchained or branched butyl, hexyl, octyl, decyl, stearyl acrylate and corresponding methacrylates; vinyl esters of fatty acids having at least three carbon atoms, e.g. vinyl propionate, laurate, stearate, vinyl ethers of alcohols having up to eight carbon atoms, or butadiene or isoprene. Three specific examples are described giving parts by weight.

    A process for the production of polymer dispersions which are stable to frost and electrolytes

    公开(公告)号:GB842672A

    公开(公告)日:1960-07-27

    申请号:GB1268958

    申请日:1958-04-22

    Applicant: BASF AG

    Abstract: Aqueous polymer suspension stable to frost and electrolytes are prepared by processes comprising polymerizing monomeric ethylenically unsaturated compounds in a aqueous media with water-soluble catalysts in the presence of 2 to 10%, by weight of the monomers, of an emulsifier which has a carbon chain of at least 6 carbon atoms, the hydrocarbon chain bearing a group containing at least one reactive hydrogen atom and which has been reacted with at least 5 mols of an alkylene oxide per mol and then sulphated, and adjusting the pH after polymerization to between 2 and 9. The monomer may be a conjugated diene, vinyl ester, vinyl ketone, vinyl ether, ethylene, styrene and its homologues, acrylic esters, acrylonitrile and their homologues, maleic and fumaric esters and nitrile, vinyl and vinylidene halides and vinyl lactams, optionally together with small amounts of acrylic acid, acrylamide and their homologues, vinyl pyrrolidone and vinyl imidazole. The catalyst may be a persulphate, hydrogen peroxide or peracetic acid, optionally together with sulphurous acid salts, alkylamines or hydroxyalkylamines. The emulsifiers may be prepared by reacting with ethylene or propylene oxide and sulphating fatty alcohols, fatty acids, resin acids, sulphuric acids, their amides and imides, monoalkylated and polyalkylated phenols and naphthols. Many suitable compounds are listed and examples describe the use of emulsifiers derived from sperm oil alcohol, coconut oil alcohol, decyl alcohol, C12-C18 alkyl sulphamides hexadecyl sulphamide of aminomethyl cyclohexane, octadecyl sulphamide, octadecyl sulphanilide, sperm oil acid monoethanolamide, octyl phenol, iso octyl phenol, ethyhexyl phenol, decyl phenol, iso decyl phenol, dodecyl phenol, octyl naphthol, decyl naphthol and dodecyl naphthol; and the copolymerization of methyl acrylate, methyl methacrylate and acrylic acid; ethyl acrylate, methyl methacrylate and acrylic acid; butyl acrylate, acrylonitrile and acrylic acid; vinyl propionate and butyl acrylate; vinylidene chloride, methylacrylate and acrylic acid; vinyl propionate, methyl methacrylate and acrylic acid; styrene, butyl acrylate and acrylic acid; butyl acrylate, methacrylamide, acrylic acid and vinyl chloride; butyl acrylate and vinyl acetate; vinyl propionate and dimethyl maleate; and methyl acrylate, acrylonitrile and acrylic acid. The dispersions may be used for coating and making films, treating leather and textiles, and in floor coverings.

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