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    Production of block-graft polymers from polyolefines and synthetic polyamides
    1.
    发明专利
    Production of block-graft polymers from polyolefines and synthetic polyamides 未知

    公开(公告)号：GB927968A

    公开(公告)日：1963-06-06

    申请号：GB3572861

    申请日：1961-10-04

    Applicant: BASF AG

    Inventor： CRAUBNER HANS ,  ILLING GERHARD

    IPC: C08G69/00 ,  C08G81/02 ,  C08L23/02 ,  C08L77/00

    Abstract: In a process for the production of block-graft polymers, a mixture of (a) one or more polyolefines or copolymers of olefines with other unsaturated monomers and (b) one or more synthetic linear polyamides is homogenized at a temperature between 50 DEG and 350 DEG C. with addition of 0,05 to 10% by weight, with reference to the total weight of the mixture of all components of a free radical-forming catalyst. Specified polyolefines are those derived from ethylene, propylene, styrene, iso-butylene, butene-1 and butene-2 and optionally butadiene, isoprene, acrylic acid, methacrylic acid, esters of acrylic and methacrylic acid, acrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, a -methyl styrene, vinyl toluenes and vinyl isobutyl ether. Specified catalysts are cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, 2:5-di-t-butyl-peroxy-2:5-dimethyl hexane, dibenzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, azo-bis-iso-butyronitrile and azo disulphonates which may be dissolved in benzene, toluene, xylene, dioxane, cyclohexane, butanone, dimethyl formamide, carbon tetrachloride or tetrahydrofurane and hydrogen peroxide, sodium peroxide and ammonium persulphate. The examples describe the preparation of block-graft polymers from:-(1) polyethylene and poly-S -caprolactam; (2) polyethylene and polyhexamethylene adipamide; (3) polypropylene and poly-S -caprolactam; (4) polypropylene and poly-caprylic lactam; (5) polypropylene and polyhexamethylene adipamide; (6) polypropylene and polyhexamethylene sebacamide; (7) polystyrene, polyethylene and poly-S -caprolactam; (8) poly-iso-butylene, polyethylene and poly-S -caprolactam and (9) an acrylonitrilestyrene copolymer and poly-S -caprolactam.

    Graft copolymers from olefinically unsaturated monomers and polycondensates and a process for their production
    5.
    发明专利
    Graft copolymers from olefinically unsaturated monomers and polycondensates and a process for their production 未知

    公开(公告)号：GB899567A

    公开(公告)日：1962-06-27

    申请号：GB47961

    申请日：1961-01-05

    Applicant: BASF AG

    Inventor： CRAUBNER HANS ,  HRUBESCH ADOLPH

    IPC: C08F283/00 ,  C08F283/04

    Abstract: Graft polymers are formed by a process in which a polycondensate containing -CONHgroups is nitrosated at some or all of the amide nitrogen atoms and the resulting N-nitrosopolycondensate is copolymerized with one or more olefinically unsaturated monomers, e.g. acrylic and methacrylic acids and their C1-C12 esters, nitriles and amides, styrene, methylstyrenes, divinylbenzene, isobutylene, vinyl esters with C2-C18 acids, vinyl and vinylidene chlorides, butadiene, chloroprene, isoprene, dimethylbutadiene, vinyl ethers of C1-C12 alcohols, vinyl sulphonic acids, and vinyl pyridine, imidazole, pyrrolidone and carbazole. Polycondensates speeified are polycaprolactam, condensates of hexamethylene diamine with adipic or sebacic acid, a condensate of sebacic acid with p,p1diamino-diphenylmethane, a polyurethane prepared from a mixture of hexamethylene diamine and 1,4-butanediol dichlorocarbonate, and also polyesteramides, polyureas and polythioureas. The polycondensates are nitrosated by treatment with nitrosating agents such as dinitrogen trioxide, nitrosyl chloride, nitrous acid or alkyl nitrites, the reaction being carried out with the polycondensate in powder form or in solution, dispersion or in swollen form. In one mode of operation the polycondensate is nitrosated whilst dissolved, swollen or dispersed in the olefincally unsaturated monomer, in which case graft polymerization occurs simultaneously if the temperature of the reaction is in excess of room temperature. The graft polymerization of the unsaturated monomer may be accelerated by means of catalysts such as alkali and alkaline earth hydroxides, alkali carbonates, amines, heavy metal salts, benzoyl peroxide and, when employing photochemical excitation of the reaction, azobisisobutyronitrile, anthracene or perchloromethyl mercaptan. The polymerization may be carried out in bulk, solution or dispersion. The examples describe the production of graft polymers from nitrosated polycondensates with: (1) and (2) vinyl acetate+ acrylic acid, (3) acrylonitrile, (4) acrylonitrile+ styrene, (5) acrylonitrile, (6) and (7) methyl methacrylate, (8) methyl methacrylate+vinyl acetate, (9) butyl acrylate+vinyl pyrrolidone, (10) styrene, (11) styrene+isoprene or isobutylene, (12) vinyl chloride+vinyl carbazole, (13) vinyl propionate+vinyl isobutyl ether and (15) styrene.

    Production of graft copolymers from olefinically unsaturated monomers and nitrosated copolymers
    6.
    发明专利
    Production of graft copolymers from olefinically unsaturated monomers and nitrosated copolymers 未知

    公开(公告)号：GB891758A

    公开(公告)日：1962-03-21

    申请号：GB47861

    申请日：1961-01-05

    Applicant: BASF AG

    Inventor： CRAUBNER HANS ,  HRUBESCH ADOLF

    IPC: C08F8/30 ,  C08F291/12

    Abstract: Graft polymers are obtained by nitrosating all or part of the amide nitrogen atoms of copolymers with other unsaturated monomers of olefinically unsaturated aliphatic, cycloaliphatic and/or heterocyclic acylamines which are monosubstituted on the amide nitrogen atoms by alkyl, alkenyl aralkyl, cycloalkyl, cycloalkenyl, alkylene and/or cycloalkylene groups, and then grafting the nitrosated copolymers with olefinically unsaturated monomers. Unsaturated acylamines specified are the N- monosubstituted amides of acrylic, methacrylic and crotonic acids, N-monosubstituted monoamides of maleic and fumaric acids and esters thereof, N,N1-substituted diamides of maleic, fumaric, itaconic and mesaconic acids, N,N1-alkylene or -cycloalkylene substituted bis-acrylic, -methacrylic and -crotonic amides, N-methyl cyclohexen-1-yl carboxylamide, N,N1-methylene-bis-cyclohexenyl carboxylamide, N,N1-hexamethylene-bis-maleic monoamide and esters thereof, N-allyl acetamide, propionamide and butyramide, N,N1-diallylhexahydroterephthalamide, mono- and diureides of unsaturated acids, e.g. acrylic, methacrylic, maleic and fumaric acids, such compounds being substituted at one or more ureide nitrogen atoms, and barbituric acid derivatives substituted at the 5-position on the ring by a C2-C6 alkenyl group. Monomers specified for use either as comonomers with the unsaturated amides or as grafting monomers are acrylic and methacrylic acids and their nitriles, amides or ester with C1-C12 alkanols or cycloalkanols, styrene, methyl styrenes, ethylene, propylene, butene-1, butene-2, isobutylene, butadiene, isoprene, chlorobutadiene, vinyl acetate and propionate, vinyl and vinylidene chloride, vinyl ethers of C1-C12 alcohols, vinyl sulphonic acid, vinyl pyridine, pyrrolidone and carbazole and unsaturated polyesters. The nitrosation of the amide copolymers is accomplished by means of agents such as dinitrogen trioxide, nitrosyl chloride, alkyl nitrites and nitrous acid. The grafting of the unsaturated monomer on to the nitrosated copolymer may be effected in bulk, solution, emulsion or suspension, and may be accelerated by means of alkali metal carbonates and/or hydroxides, amines, e.g. triethanolamine, salts of iron, nickel, cobalt and manganese, peroxides or azodiisobutyronitrile. The Examples describe grafting of: (1) acrylic acid on to a nitrosated styrene-N-benzyl maleic monoamide copolymer, (2) a mixture of vinyl acetate and methyl methacrylate on to a copolymer as in (1), (3) butyl acrylate on to a nitrosated methyl methacrylate-N-(2-ethylhexyl)-maleic monoamide copolymer, (4) a mixture of vinyl acetate and acrylonitrile on to a nitrosated acrylonitrile-N,N1-methylene dimethacrylamide copolymer, (5) a mixture of styrene, butyl acrylate and acrylonitrile on to a nitrosated styrene-N,N1-methylene dimethacrylamide copolymer, (6) methyl methacrylate on to a nitrosated acrylonitrile-butadiene-N-benzyl maleic monoamide copolymer, (7) acrylonitrile on to a nitrosated styrene-butadiene-N-stearyl maleic monoamide copolymer, (8) methyl methacrylate on to a nitrosated styrene-N-allyl propionamide copolymer, (9) acrylonitrile on to a nitrosated N-methyl methacrylamide-N-isopropyl acrylamide copolymer, (10) acrylonitrile on to a nitrosated vinylidene chloride-styrene-N-lauryl maleic monoamide copolymer, (11) acrylonitrile on to a nitrosated methyl methacrylate-N,N-dimethyl maleic acid monureide copolymer, (12) a mixture of vinylidene chloride and vinyl pyrrolidone on to a nitrosated copolymer of styrene, N-cyclohexyl maleic monoamide and a polyester derived from maleic and phthalic acids and propylene glycol, (13) acrylonitrile on to a nitrosated methyl methacrylate-N-iso-octyl maleic monoamide copolymer, (14) acrylic acid on to a nitrosated styrene-N,N1-methylene dimethacrylamide copolymer, and (15) acrylonitrile on to a nitrosated vinyl chloride-vinyl propionate-N-allyl maleic amide copolymer. Specification 546,459 is referred to.

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