公开(公告)号：CA684478A

公开(公告)日：1964-04-14

申请号：CA684478D

Applicant: BASF AG

Inventor： MAHLING DIETER ,  WEIDINGER HANS ,  LANGE GUENTER ,  SCHWINDT WOLFGANG ,  LOUIS GERD ,  KREHBIEL GUENTER ,  CRAEMER KARL ,  WILHELM HANS

公开(公告)号：GB949404A

公开(公告)日：1964-02-12

申请号：GB1774461

申请日：1961-05-16

Applicant: BASF AG

Inventor： WILHELM HANS ,  PENNING ERNST ,  LOUIS GERD ,  LANGE GUENTER ,  WEIDINGER HANS

IPC: C08F2/04 ,  C08F2/22 ,  C08F2/44 ,  C08F16/12 ,  C08F20/62 ,  C08F28/00 ,  C09B69/10 ,  D06L3/12 ,  D06L4/60 ,  D06M15/39 ,  D06P1/00

Abstract: Coloured cross-linked or cross-linkable copolymers are obtained by copolymerizing at least one olefinic monomer dyestuff, containing, in addition to the unsaturated at least one olefinic monomer polymerizable group, a group capable of condensation or addition, and, if desired, at least one further copolymerizable monomer, and then, if desired, cross-linking the resulting copolymers by way of the groups capable of condensation or addition. The dyestuff monomers may be of the azo, anthraquinone, phthalocyanine, triarylmethane, phenazine, or oxazine type, such dyestuffs being described in Specifications 779,781, 830,876, 858,183, 875,946 and 879,071. The examples describe the following processes: (1) emulsion copolymerizing butyl acrylate, N-methylol methacrylamide and an unsaturated azo dyestuff to yield a copolymer which cross-links on drying; (2) emulsion copolymerizing acrylonitrile, butyl acrylate, N-methyldimethacrylamide and an unsaturated azo dyestuff; (3) as in (2) but using an unsaturated anthraquinone dyestuff; (4) emulsion copolymerizing styrene, methylolacrylamide, butyl acrylate, N-methylolacryloylurea and acryloylaminobenzene, and cross-linking the resulting polymer by heating in the presence of ammonium nitrate; (5) emulsion polymerizing ethyl acrylate, vinyl propionate, N-methylolmethacrylamide, N-methylol maleimide and an unsaturated azo dyestuff and cross-linking the resulting copolymer by heating; (6) emulsion copolymerizing butyl acrylate, acrylonitrile, butane-diol monoacrylate and an unsaturated azo dyestuff, and cross-linking the resulting copolymer with hexamethylene diisocyanate; (7) emulsion copolymerizing butyl acrylate, methacrylamide and an unsaturated azo dyestuff and cross-linking the product by heating with dimethylol urea; (8) cross-linking the copolymer of (7) by heating with N,N1-dimethylolbutane-(1,4)-diurethane; (9) emulsion copolymerizing butyl acrylate, acrylonitrile, acrylic acid and an unsaturated azo dyestuff, neutralising the carboxyl groups in the product with ammonia, and heating it with a polyepoxide derived from pentaerythritol and epichlorohydrin; (10) emulsion copolymerizing butyl acrylate, N-methylolacrylamide and an unsaturated azo dyestuff, mixing the resulting dispersion with an acrylamide/methacrylamide copolymer, sawdust and a mixture of N,-N1 dimethylolurea monomethyl and dimethyl ethers, drying the composition and moulding at 150 DEG C.; (11) emulsion copolymerizing butyl and ethyl acrylates, methyl methacrylate methacrylamide and an azo dyestuff containing vinyl ether groups, adding a mixture of N,N1-dimethylol urea monomethyl and dimethyl ethers and heating in the presence of ammonium nitrate; (12) emulsion copolymerizing butyl acrylate, N-methylol methacrylamide, a triazine derivative of acrylamide and an unsaturated azo dyestuff, mixing the dispersion with N,N1-dimethylolbutane-(1, 4)-diurethane and ammonium nitrate and subjecting the mixture to heat; (13) emulsion copolymerizing butyl acrylate, acrylamide, vinyl chloride and an unsaturated azo dyestuff, mixing the dispersion with N,N1-dimethylol urea and cross-linking at 130 DEG C.; (14) solution copolymerizing butyl acrylate, acrylamide, methyl methacrylate, butanediol monoacrylate and an azo dyestuff containing vinyl ether groups and cross-linking the product with hexamethylene diisocyanate; (15) solution copolymerizing methyl methacrylate butyl acrylate, acrolein and an unsaturated azo dyestuff, and cross-linking the product with the glycol ester of bisacetoacetic acid; (16) solution copolymerizing butyl acrylate, vinyl propionate, methacrylamide, N-methylol methacrylamide and an unsaturated anthraquinone dyestuff, and heating the product after the addition thereto of phosphoric acid; (17) as in (3) but with the use of tetramethylolacetylene diurea tetrabutyl ether at the cross-linking stage and with the addition of wood pulp to the curable mixture; (18) bulk copolymerizing methyl methacrylate, butanediol monoacrylate and an unsaturated azo dyestuff in the presence of dibutylphthalate until the product is syrupy, discontinuing polymerization and then heating the product with hexamethylene diisocyanate; (19) solution copolymerizing vinyl pyrrolidone, methyl methacrylate, butyl acrylate, N-methylol methacrylamide and a copper phthalocyanine dyestuff containing sulphonic groups which have been reacted with N-acryloyl - p - phenylene diamene, and heating the product with tetramethylolacetylenediure tetrabutyl ether; and (20) solution copolymerizing acrylamide ethyl acrylate, N-methylol methacrylamide and an unsaturated azo dyestuff, and heating the product with tetramethylolacetylene diurea.ALSO:Surfaces of paper, wood and metal are coated with coloured copolymers obtained from olefinic monomer dyestuffs, monomers containing cross-linkable groups, and, if desired, other copolymerizable monomers. In examples: (2) wood and paper are coated with an aqueous dispersion of a copolymer of butyl acrylate, N-methylol methacrylamide and an unsaturated azo dyestuff, and the coating is dried at 180 DEG C.; (13) paper and a metal plate are coated with an aqueous dispersion containing a copolymer of butyl acrylate, vinyl chloride, acrylamide and an unsaturated azo dyestuff, N,N1-dimethylolurea and ammonium nitrate, the coating is dried at room temperature and cross-linked at 130 DEG C.; (15) a toluene-ethanol solution containing a copolymer of methyl methacrylate, acrolein and an unsaturated azo dyestuff, the glycol ester of bisacetoacetic acid, phosphoric acid and piperidine is brushed or sprayed on to bleached wood, and the coating is dried at 80-90 DEG C.; and (19) a tolueneethanol solution containing a copolymer of vinyl pyrrolidone, methyl methacrylate, butyl acrylate, N-methylol methacrylamide and a copper phthalocyanine dyestuff containing sulphonic groups which have been reacted with N-acryloyl-p-phenylene diamine, tetramethylolacetylenediurea tetrabutyl ether and glacial acetic acid is brushed on to wood or paper and dried at 140 DEG C. Specifications 779,781, 830,876, 858,183, 875,946 and 879,071 are referred to.

公开(公告)号：GB947463A

公开(公告)日：1964-01-22

申请号：GB2501062

申请日：1962-06-29

Applicant: BASF AG

Inventor： KREHBIEL GUENTER ,  LANGE GUENTER ,  WILHELM HANS ,  LOUIS GERD ,  WEIDINGER HANS

IPC: C08F2/22 ,  C08F2/44 ,  C08F16/12 ,  C08F20/62 ,  C08F28/00 ,  C09B69/10 ,  D06L3/12 ,  D06L4/60 ,  D06L4/614 ,  D06L4/657 ,  D06L4/679 ,  D06M15/39 ,  D06P1/00

Abstract: 4,6-Dimethyl -7- acryloyl - hydroxyethyl - amino-coumarin of the formula: is produced from 4,6-dimethyl -7- b-hydroxyethylamino-coumarin by esterification with acrylic acid. ALSO: Fluorescent copolymers are obtained by emulsion, solution, bulk, suspension or precipitation polymerization of fluorescent dyes containing a polymerizable olefinic group outside of the fluorescent system with non-coloured, non-fluorescent compounds containing a polymerizable olefinic group and groups which are accessible to condensation or addition reactions and, optionally, with other polymerizable non-coloured, non-fluorescent compounds. Suitable fluorescent dyes are of the stilbene, triarylmethane coumarin, aminonaphthalimide, aminoterephthalic diamide and azomonomethinecyanine series; their polymerizable groups, e.g. acryloyl or allyl, may be introduced by way of acid, hydroxy or amino groups. In the examples (1) an emulsion polymer of butyl acrylate, N-methylolmethacrylamide, methacrylamide and 4, 6 - dimethyl - 7 - acryloyl - hydroxyethylaminocoumarin is prepared by emulsion polymerization and (2) a copolymer of butyl acrylate, N-methylolmethacrylamide and 4, 6-dimethyl-7-acryloylhydroxyethylamino-coumarin is prepared in ethanol solution. ALSO: Textiles, e.g. of cotton or polypropylene, are simultaneously dyed in fluorescent shades and/or optically brightened and finished by applying thereto a solution or dispersion of a cross-linkable copolymer obtained by copolymerization of fluorescent dyes containing a polymerizable olefinic group outside of the fluorescent system with non-coloured, non-fluorescent compounds containing polymerizable olefinic groups which are accessible to condensation or addition reactions and optionally with other polymerizable non-coloured, non-fluorescent compounds and cross-linking the copolymer either directly or with the aid of suitable bi-or poly-functional compounds. Specified fluorescent dyes are from the stilbene, triarylmethane, coumarin, aminonaphthalimide, aminoterephthalic diamide and azomonomethinecyanine series. The polymerizable olefinic groups, e.g. acryloyl or allyl, may be attached by way of acid, hydroxy or amino groups. The copolymer may be obtained by the methods of emulsion, solution, bulk, suspension or precipitation polymerization. Examples are given.

公开(公告)号：FR1348650A

公开(公告)日：1964-01-10

申请号：FR919995

申请日：1962-12-28

Applicant: BASF AG

Inventor： BEYER KARL HEINZ ,  GULBINS KLAUS ,  LANGE GUENTER ,  LOUIS GERD ,  WEIDINGER HANS ,  WILHELM HANS

IPC: C08F2/22 ,  C08F2/44 ,  C08F20/52 ,  C08F291/00 ,  C09B1/40 ,  C09B62/467 ,  C09B69/10 ,  D06L3/12 ,  D06L4/657 ,  D06P1/00

Abstract: Polymeric substances are coloured by graft polymerizing thereon a dye bearing a polymerizable olefinic group and, if desired, other monomers which are colourless. Polymers specified are polymers and copolymers of olefinic monomers, polyaldehydes, polymers of lactams, lactones, cyclic ethers sulphides and amines, phenol, urea, melamine and alkyd resins, polyesters, polyamides, polycarbonates, polyurethanes, epoxy resins, cellulose, proteins and rubber. The polymerizable dyes may be of the azo, anthraquinone, triarylmethane, azomethane or phthalocyanine type. Grafting may be effected by means of a free-radical initiator or high-energy irradiation. The substrate monomer may be dissolved in the grafting monomer, or may be used in the form of a solution in an organic solvent or as an aqueous emulsion, or may be in the form of a film or fibre. The examples describe: (1) grafting by means of X-rays isobutyl 1 - amino - 4 - acryloylaminoanthraquinone - 2 - carboxylate and butyl acrylate on to an aqueous dispersion of a copolymer of butyl acrylate and methylol methacrylamide, followed by cross-linking the product with the dimethylol compound of butanediol-1, 4-diurethane; (2) as in (1), but using as the grafting monomer the coupling product of diazotized 2-amino-4-sulphonic acid-41-acryloylaminodiphenyl sulphone and 3-sulphonic acid-7-aminonaphthol-1; (3) grafting by means of X-rays the coupling product of diazotized 1-acryloylamino-4-aminobenzene and 1-phenyl-(21-chloro-41-sulphonic acid)-3-methylpyrazolone-5 on to an aqueous dispersion of a copolymer of butyl acrylate acrylonitrile and methylol methacrylamide, and cross-linking the product with the dimethylol compound of butanediol-1, 4-diurethane; (4) as in (3), but grafting by means of potassium persulphate; and (5) as in (3), but using a copolymer of butyl acrylate and methacrylamide as the grafting substrate. The resulting products are used for colouring cotton fabrics. Specifications 877,402, 914,354, 946,472, 948,694, and 952,810 are referred to.ALSO:Fibrous materials or films of polymeric organic substances are coloured by graft-polymerizing a dye containing olefinic unsaturated groups with the substance of the fibres or films. Alternatively the materials, e.g. fabrics, are dyed by applying thereto an aqueous dispersion of a polymeric substance on which has been grafted a dye bearing a polymerizable olefinic group. The examples describe the application to cotton fabrics of aqueous dispersions of graft copolymers containing the dimethylol compound of butanediol-1, 4-diurethane as a cross-linking agent, followed by drying at 140 DEG C., the graft copolymers specified being obtained by graftin: (1) isobutyl 1-amino-4-acryloylaminoanthraquinone 2-carboxylate and butyl acrylate on to a copolymer of butyl acrylate and methylol methacrylamide; (2) the coupling product of diazotized 2-amino-4-sulphonic acid-41-acryloylamino-diphenyl sulphone and 3-sulphonic acid-7-aminonaphthol-1 on to a copolymer as in (1); (3) the coupling product of diazotized 1-acryloylamino-4-aminobenzene and 1-phenyl-(21-chloro-41-sulphonic acid)-3-methylpyrazolone-5 on to a copolymer of butyl acrylate, acrylonitrile and methylol methacrylamide; and (5) a dye as in (3) on to a copolymer of butyl acrylate and methacrylamide. The dyeing of textiles such as polypropylene textiles by direct graft-polymerization with polymerizable dyes is referred to. Specifications 877,402, 914,354, 946,472, 948,694 and 952,810 are referred to.

公开(公告)号：GB946182A

公开(公告)日：1964-01-08

申请号：GB2202862

申请日：1962-06-07

Applicant: BASF AG

Inventor： WILH LM HANS ,  LOUIS GERD ,  LANGE GUENTER ,  WEIDINGER HANS ,  MAHLING DIETER

Abstract: Coloured copolymers are obtained by solution, bulk, suspension or precipitation polymerization of dyes containing polymerizable olefinic groups with non-coloured compounds containing polymerizable olefinic groups and groups which are accessible to condensation or addition reactions and, optionally, with other polymerizable non-coloured compounds. In the examples copolymers are prepared from (1) butyl acrylate, acrylamide, methyl methacrylate, butanediol monoacrylate and 2,4-dichloraniline--->N-ethyl-N-b -vinyl-hydroxy-ethylaniline in ethanol solution, (2) methyl methacrylate, butyl acrylate, acrolein and 2,4-dichloraniline--->N-b -acryloylhydroxyethyl-N-ethylaniline in ethanol/toluene solution, (3) butyl acrylate, methacrylamide, N-methylol-methacrylamide, vinyl propionate and 1 -acryloylamino - 5 - benzoylamino - anthraquinone in butanol/toluene solution, (4) same as (3) using a different dye, viz. the isobutyl ester of 1-amino-4-acryloylamino-anthraquinone -2- carboxylic acid, (5) butyl acrylate, methyl methacrylate, N-methylol-methacrylamide and copper phthalocyanine tetra sulphonic acid of which 2 sulphonic acid groups have been reacted with N - acryloyl - p - phenylenediamine in ethanol/ toluene solution and (6) acrylamide, ethyl acrylate, N-methylol-methacrylamide and the dye of (2) by precipitation from butanol.ALSO:Textiles are simultaneously dyed and finished by applying solutions, emulsions or suspensions of coloured copolymers obtained by solution, bulk, suspension or precipitation polymerization of (a) dyes containing polymerizable olefinic groups, (b) non-coloured compounds containing polymerizable olefinic groups and groups which are accessible to condensation or addition reactions and, optionally, (c) further polymerizable non-coloured compounds and thereafter cross-linking the copolymers either directly or with the aid of bi- or poly-functional cross-linking agents. The preferred copolymers contain inert monomers, (c) and the solutions or dispersions thereof preferably have a solids content of 10-40%. Examples of treating cellulose textiles are given.

公开(公告)号：GB848660A

公开(公告)日：1960-09-21

申请号：GB1966259

申请日：1959-06-09

Applicant: BASF AG

Inventor： KUEHN ERICH ,  LOUIS GERD ,  PENNING ERNST ,  SENNINGER RUDOLF ,  WILHELM HANS

IPC: C08G2/00

Abstract: Ethers of highly polymeric formaldehyde are obtained by reacting the latter with an alphachoralkyl ether of an aliphatic, cycloaliphatic, heterocyclic or aromatic hydroxyl compound, preferably in the presence of a basic compound, or with a quaternary salt of the alpha-chloralkyl ether with a tertiary amine. Alpha-chloralkyl ethers mentioned are chlormethyl methyl ether, chlormethyl ethyl ether, bis-(chlormethyl) ethylene glycol ether, bis-(chlormethyl) butane-diol-(1,4) ether, chlormethyl cyclohexyl ether, chlormethyl benzyl ether and chlormethyl cyclohexyl ether. In Examples polyformaldehyde is reacted with quaternary salts of dimethylcyclohexylamine with chlormethyl methyl ether, 1,4-bis (chlormethoxy) butane, alpha-chlorethyl isobutyl ether, alpha-chlorethyl benzyl ether and 2,3-dichlordioxane.