NO133049B - - Google Patents
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- Publication number
- NO133049B NO133049B NO207070A NO207070A NO133049B NO 133049 B NO133049 B NO 133049B NO 207070 A NO207070 A NO 207070A NO 207070 A NO207070 A NO 207070A NO 133049 B NO133049 B NO 133049B
- Authority
- NO
- Norway
- Prior art keywords
- polymer
- naphthol
- component
- base
- vinyl
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 24
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 14
- 230000008878 coupling Effects 0.000 claims description 10
- 238000010168 coupling process Methods 0.000 claims description 10
- 238000005859 coupling reaction Methods 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 4
- 150000003931 anilides Chemical class 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 150000005673 monoalkenes Chemical class 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000002585 base Substances 0.000 description 34
- OCISOSJGBCQHHN-UHFFFAOYSA-N 3-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC(O)=CC2=C1 OCISOSJGBCQHHN-UHFFFAOYSA-N 0.000 description 18
- 239000000975 dye Substances 0.000 description 12
- 239000003086 colorant Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- -1 aryl olefins Chemical class 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- JFGQHAHJWJBOPD-UHFFFAOYSA-N 3-hydroxy-n-phenylnaphthalene-2-carboxamide Chemical compound OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=CC=C1 JFGQHAHJWJBOPD-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- IRPXADUBAQAOKL-UHFFFAOYSA-N chembl1408927 Chemical compound C1=CC=C2C(N=NC3=C4C=CC(=CC4=CC(=C3O)S(O)(=O)=O)S(O)(=O)=O)=CC=C(S(O)(=O)=O)C2=C1 IRPXADUBAQAOKL-UHFFFAOYSA-N 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- QMMMCTXNYMSXLI-UHFFFAOYSA-N fast blue B Chemical compound C1=C([N+]#N)C(OC)=CC(C=2C=C(OC)C([N+]#N)=CC=2)=C1 QMMMCTXNYMSXLI-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- VENDXQNWODZJGB-UHFFFAOYSA-N n-(4-amino-5-methoxy-2-methylphenyl)benzamide Chemical compound C1=C(N)C(OC)=CC(NC(=O)C=2C=CC=CC=2)=C1C VENDXQNWODZJGB-UHFFFAOYSA-N 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 239000012209 synthetic fiber Substances 0.000 description 3
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 2
- ZGHFDIIVVIFNPS-UHFFFAOYSA-N 3-Methyl-3-buten-2-one Chemical compound CC(=C)C(C)=O ZGHFDIIVVIFNPS-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- MVEOHWRUBFWKJY-UHFFFAOYSA-N 7-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=CC(S(O)(=O)=O)=CC2=CC(O)=CC=C21 MVEOHWRUBFWKJY-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- MRQIXHXHHPWVIL-ISLYRVAYSA-N Sudan I Chemical compound OC1=CC=C2C=CC=CC2=C1\N=N\C1=CC=CC=C1 MRQIXHXHHPWVIL-ISLYRVAYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000004815 dispersion polymer Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- DSWNVYFFLCPXEW-UHFFFAOYSA-N (2,4-diamino-3,6-diethoxyphenyl)-phenylmethanone Chemical compound CCOC1=CC(N)=C(OCC)C(N)=C1C(=O)C1=CC=CC=C1 DSWNVYFFLCPXEW-UHFFFAOYSA-N 0.000 description 1
- ZALVJCYWUBQENP-UHFFFAOYSA-N (2,5-dichlorophenyl)azanium;chloride Chemical compound Cl.NC1=CC(Cl)=CC=C1Cl ZALVJCYWUBQENP-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- YJJYGKTWCPEFMD-UHFFFAOYSA-N 2,5-dichloroaniline;sulfuric acid Chemical compound OS(O)(=O)=O.NC1=CC(Cl)=CC=C1Cl YJJYGKTWCPEFMD-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- DRGIDRZFKRLQTE-UHFFFAOYSA-N 2-chloroaniline;hydron;chloride Chemical compound Cl.NC1=CC=CC=C1Cl DRGIDRZFKRLQTE-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical class ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- QQBUHYQVKJQAOB-UHFFFAOYSA-N 2-ethenylfuran Chemical compound C=CC1=CC=CO1 QQBUHYQVKJQAOB-UHFFFAOYSA-N 0.000 description 1
- FCYVWWWTHPPJII-UHFFFAOYSA-N 2-methylidenepropanedinitrile Chemical compound N#CC(=C)C#N FCYVWWWTHPPJII-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 1
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- XQVCBOLNTSUFGD-UHFFFAOYSA-N 3-chloro-4-methoxyaniline Chemical compound COC1=CC=C(N)C=C1Cl XQVCBOLNTSUFGD-UHFFFAOYSA-N 0.000 description 1
- NMGHWHCTRGZZOP-UHFFFAOYSA-N 3-chloroaniline;hydron;chloride Chemical compound Cl.NC1=CC=CC(Cl)=C1 NMGHWHCTRGZZOP-UHFFFAOYSA-N 0.000 description 1
- FBLAHUMENIHUGG-UHFFFAOYSA-N 3-hydroxy-n-(2-methylphenyl)naphthalene-2-carboxamide Chemical compound CC1=CC=CC=C1NC(=O)C1=CC2=CC=CC=C2C=C1O FBLAHUMENIHUGG-UHFFFAOYSA-N 0.000 description 1
- PMYDPQQPEAYXKD-UHFFFAOYSA-N 3-hydroxy-n-naphthalen-2-ylnaphthalene-2-carboxamide Chemical compound C1=CC=CC2=CC(NC(=O)C3=CC4=CC=CC=C4C=C3O)=CC=C21 PMYDPQQPEAYXKD-UHFFFAOYSA-N 0.000 description 1
- VKYZDCTWJGBFDW-UHFFFAOYSA-N 4-chloro-2-methylaniline;hydron;chloride Chemical compound Cl.CC1=CC(Cl)=CC=C1N VKYZDCTWJGBFDW-UHFFFAOYSA-N 0.000 description 1
- ASEYMHNCCXSHIL-UHFFFAOYSA-N 5-chloro-2-methoxyaniline;hydrochloride Chemical compound Cl.COC1=CC=C(Cl)C=C1N ASEYMHNCCXSHIL-UHFFFAOYSA-N 0.000 description 1
- QYFYIOWLBSPSDM-UHFFFAOYSA-N 6-aminonaphthalen-1-ol Chemical compound OC1=CC=CC2=CC(N)=CC=C21 QYFYIOWLBSPSDM-UHFFFAOYSA-N 0.000 description 1
- ZYSOYLBBCYWEMB-UHFFFAOYSA-N 7-aminonaphthalen-1-ol Chemical compound C1=CC=C(O)C2=CC(N)=CC=C21 ZYSOYLBBCYWEMB-UHFFFAOYSA-N 0.000 description 1
- HMNPDEGBVWDHAR-UHFFFAOYSA-N 8-aminonaphthalen-1-ol Chemical compound C1=CC(O)=C2C(N)=CC=CC2=C1 HMNPDEGBVWDHAR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical class OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940051881 anilide analgesics and antipyretics Drugs 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- AWJZTPWDQYFQPQ-UHFFFAOYSA-N methyl 2-chloroprop-2-enoate Chemical compound COC(=O)C(Cl)=C AWJZTPWDQYFQPQ-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- CNXZLZNEIYFZGU-UHFFFAOYSA-N n-(4-amino-2,5-diethoxyphenyl)benzamide Chemical compound C1=C(N)C(OCC)=CC(NC(=O)C=2C=CC=CC=2)=C1OCC CNXZLZNEIYFZGU-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- ICMWSAALRSINTC-UHFFFAOYSA-N penta-1,4-dien-3-ol Chemical class C=CC(O)C=C ICMWSAALRSINTC-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G15/00—Apparatus for electrographic processes using a charge pattern
- G03G15/06—Apparatus for electrographic processes using a charge pattern for developing
- G03G15/08—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer
- G03G15/09—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer using magnetic brush
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Magnetic Brush Developing In Electrophotography (AREA)
- Dry Development In Electrophotography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Fremgangsmåte til fremstilling av farvbare vinylpolymere. Process for the production of dyeable vinyl polymers.
Foreliggende oppfinnelse angår en fremgangsmåte til fremstilling av farvbare vinylpolymere. The present invention relates to a method for producing dyeable vinyl polymers.
De nyere syntetiske fibre, særlig de som er laget av vinylpolymere, er ikke lett farvbare. Man har antatt at dette skyldes mangel på reaktive plasser i molekylet hvor adsorpsjonen av f arvestoff molekylene kan finne sted, samt mangel på porer eller amorfe regioner som gjør det mulig for farvestoffene å diffumdere inn i fibrene i rimelig grad. Der er funnet forskjellige metoder til å øke antallet av farve-«plasser» i de syntetiske fibres molekylstruktur for å aksellerere graden av farvning. I en annen retning førte betydningsfull forskning til innføringen av hydrofile grupper i fiber-molekylet, noe som fremmer svellingen av fibrene i farvebadet og således gir mulighet for en bedre inntrengning av farvestoffet i fiber strukturen. Et annet kjent middel til å bedre gjennomtrengningen av farvestoffet er å åpne fiberstrukturen ved hjelp av svellingsmidler. The newer synthetic fibers, especially those made from vinyl polymers, are not easily dyed. It has been assumed that this is due to a lack of reactive sites in the molecule where the adsorption of the dye molecules can take place, as well as a lack of pores or amorphous regions that enable the dyes to diffuse into the fibers to a reasonable extent. Various methods have been found to increase the number of dye "places" in the molecular structure of the synthetic fibers in order to accelerate the degree of dyeing. In another direction, significant research led to the introduction of hydrophilic groups in the fiber molecule, which promotes the swelling of the fibers in the dye bath and thus provides the opportunity for a better penetration of the dye into the fiber structure. Another known means of improving the penetration of the dye is to open the fiber structure using swelling agents.
I US patent nr. 2 431 956 er der beskrevet en fremgangsmåte til å farve en syn-tetisk tråd ved å behandle en gel av poly-akrylnitriltråd med et fairvestoff av naft-holtypen og derefter å utvikle en farve i trådene ved å koble farvestoffet med en diazotert base. Fordi de er i gelform kan trådene lettere gjennomtrenges av farve-eminene. Ennskjønt denne patenterte metode betyr en forbedring overfor tråder som In US patent no. 2 431 956 there is described a method for dyeing a synthetic thread by treating a gel of polyacrylonitrile thread with a dyestuff of the naphthol type and then developing a color in the threads by coupling the dye with a diazotized base. Because they are in gel form, the threads can be more easily penetrated by the color emins. Although this patented method means an improvement over threads that
er sluttfarvet med tilsvarende farvestof-fer, er uheldigvis ikke lysektheten til trå- is finished colored with corresponding dyes, unfortunately the lightfastness of the
dene som er behandlet på denne måte helt tilfredsstillende. those treated in this way completely satisfactorily.
Syntetiske fibre har vært farvet ved den såkalte oppsugmngsfarvnimgsprosess hvorved et uoppløselig farvet pigment inn-arbeides i polymeren under dens polymeri-sasjon eller mens polymeren er i smeltet tilstand. Med demme farvningsmetode er det vanskelig å oppnå ensartet spredning av pigmentet i polymeren, og antallet farver som kan brukes er begrenset. Synthetic fibers have been dyed by the so-called absorption dyeing process, whereby an insoluble colored pigment is incorporated into the polymer during its polymerization or while the polymer is in a molten state. With this dyeing method, it is difficult to achieve uniform dispersion of the pigment in the polymer, and the number of colors that can be used is limited.
Ved hjelp av oppfinnelsen skaffes der nu en fremgangsmåte tdl fremstilling av farvbare polymere fra monomere som inneholder vinylgrupper, hvilken fremgangsmåte utmerker seg ved at man polymeriserer én eller flere vimylmonomere eller blandinger av sådanne med andre mono-olefiner med hvilke de er blandbare, ii nærvær av en koblende naftholkomponent som er istand til å kobles med diazoterte baser under dannelse av azofarvede materialer. With the help of the invention, a method is now provided for the production of dyeable polymers from monomers containing vinyl groups, which method is characterized by polymerizing one or more vimyl monomers or mixtures thereof with other mono-olefins with which they are miscible, in the presence of a coupling naphthol component capable of coupling with diazotized bases to form azo colored materials.
Selve polymeriseringen kan utføres efter i og for seg kjente metoder, slik at man oppnår et polymerisat med ønsket sammensetning. The polymerization itself can be carried out according to methods known per se, so that a polymer with the desired composition is obtained.
Når det erholdte polymerisat anbrin-ges i et bad' som. inneholder en diazotert base, kobles maftholet med denne, hvorved der dannes farver med meget god lysekthet. When the resulting polymer is placed in a bath which. contains a diazotized base, the mafthole is connected with this, whereby colors with very good light fastness are formed.
I betraktning av de mange kombina-sjonsmuligheter for base- og farvestoffkomponenter, kan der ved fremgangsmå-ten ifølge oppfinnelsen fåes mange forskjellige farver, idet variasjoner innen et nesten ubegrenset område er mulige. In consideration of the many combination possibilities for base and dye components, many different colors can be obtained by the method according to the invention, as variations within an almost unlimited range are possible.
Eksempler på klassen vinylmonomere som beskrevet ovenfor innbefatter: aryl-olefinene som styren, klorstyrenene, p-methoxystyren, a-methylstyren, vinylnaft-halen og lignende; akrylsyre og substitu-erte akrylsyrer og deres estere, nitriler og amider som akrylsyre, metakrylsyre, methyl&krylat, ethylakrylat, isobutylakrylat, methyl-a-kloraikrylat, methylmetakrylat, ethylmietakrylat, butylmetakrylat, met-akrylamid og lignende; methyl-isoprope-nylketon, methylvinylketon, methylvinyl-ether, vinylethenylcarbinoler, vinylidenklorid, vinylpyriidin, vinylacetat, vinylklorid, vinylfuran, vinylcarbazol, fumarsyre-estere, diallylmaleat, vinylacetylen, samt estere, alkoholer, syrer, ethere og lågnende av den beskrevne type. Examples of the class of vinyl monomers as described above include: the aryl olefins such as styrene, the chlorostyrenes, p-methoxystyrene, α-methylstyrene, vinyl naphthalene and the like; acrylic acid and substituted acrylic acids and their esters, nitriles and amides such as acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, isobutyl acrylate, methyl α-chloro acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, meth-acrylamide and the like; methyl isopropenyl ketone, methyl vinyl ketone, methyl vinyl ether, vinyl ethenyl carbinols, vinylidene chloride, vinyl pyridine, vinyl acetate, vinyl chloride, vinyl furan, vinyl carbazole, fumaric acid esters, diallyl maleate, vinyl acetylene, as well as esters, alcohols, acids, ethers and the like of the type described.
Koblende maftholkomponenter som ligger innenfor rammen av oppfinnelsen innbefatter koblende komponenter som brukes i naftholfarvningsprosessene og er beskrevet f. eks. i «The Chemical Technolo-gy of Dyeing and Printing» sider 348-363, av dr. Louis Diserens, utgitt av Reinhold Pub-lishing Corporation (1948). Blant disse komponenter er [3-na.fthol; 2-nafthol-7-sulfonsyre; 6-amino- og 7-amlno-a-nafthol; en blanding av 2,3-oxynafthosyre, |3-nafthol og 2-nafthol-7-sulifonsyre; 6-amino-a-nafthol; 8-amino-a-nafthol, acetyl-derlvatene av 4-amino-a-nafthol; anilid av 2,3-oxynafthosyre; p-nitranilM av 2,3-oxy-naftbosyre; o-toluidid av 2,3-oxynafthosyre; o-aniisidid av 2,3-oxynafthosyre; p-ariisidid av 2,3-oxynafthosyre; m-nitrani-lid av 2,3-oxynafthosyre; a-nafthalid av 2,3-oxynafthosyre; 4-klor-o-toluidid av 2,3-oxynafthosyre; p-nafthalid av 2,3-oxynafthosyre; m-klor-o-anisidid av 2,3-oxynafthosyre; o-kloranllid av 2,3-oxynafthosyre; p-methoxy-o-toluidid av 2,3-oxynafthosyre; 2,5-dimethoxyanilid av 2-oxydibenzo-furan-3-karboxylsyre; 2,5-dimetoxyanilid av 2,3-oxynafthosyre; samt andre av den type forbindelser som er istand til å pro-dusere uoppløselige azofarvestoffer uten selv å være diazotert. Blandinger av disse niaftholer er spesielt nyttige ved fremstil-lingen av visse ønskelige farver. Av disse koblende forbindelser gir derivatene av oxynafthosyre, og da spesielt anilidene av 2,3-oxynafthosyre, god gjennomgående fasthet overfor lys. Coupling naphthol components which are within the scope of the invention include coupling components which are used in the naphthol dyeing processes and are described e.g. in "The Chemical Technology of Dyeing and Printing" pages 348-363, by Dr. Louis Diserens, published by Reinhold Publishing Corporation (1948). Among these components are [3-na.fthol; 2-naphthol-7-sulfonic acid; 6-amino- and 7-amino-α-naphthol; a mixture of 2,3-oxynaphthoic acid, 3-naphthol and 2-naphthol-7-sulfonic acid; 6-amino-α-naphthol; 8-amino-α-naphthol, the acetyl derivatives of 4-amino-α-naphthol; anilide of 2,3-oxynaphthoic acid; p-nitranilM of 2,3-oxy-naphthoic acid; o-toluidide of 2,3-oxynaphthoic acid; o-anisidide of 2,3-oxynaphthoic acid; p-Aricidide of 2,3-oxynaphthoic acid; m-nitranilide of 2,3-oxynaphthoic acid; α-naphthalide of 2,3-oxynaphthoic acid; 4-chloro-o-toluidide of 2,3-oxynaphthoic acid; p-naphthalide of 2,3-oxynaphthoic acid; m-chloro-o-anisidide of 2,3-oxynaphthoic acid; o-chloroanlide of 2,3-oxynaphthoic acid; p-methoxy-o-toluidide of 2,3-oxynaphthoic acid; 2,5-dimethoxyanilide of 2-oxydibenzo-furan-3-carboxylic acid; 2,5-dimethoxyanilide of 2,3-oxynaphthoic acid; as well as other compounds of the type that are capable of producing insoluble azo dyes without being diazotized themselves. Mixtures of these niaphthols are particularly useful in the preparation of certain desirable colors. Of these connecting compounds, the derivatives of oxynaphthoic acid, and especially the anilides of 2,3-oxynaphthoic acid, provide good through-fastness to light.
Den basiske komponent innbefatter de kjente naftholbaser som brukes i naft-holfaivnmigstekniktoen og er beskrevet i den ovennevnte bok på sider 364—409. Blant disse basiske komponenter er o-kloranilin-hydroklorid; o-kloranilin, m-kloranilin-hydrokloriid, m-klorandlin, o-nitr-anilin, m-nitramilin, o-klor-p-anisidin, 2,5-dikloraniilin-hydroklorid, 2,5-dikloranilin-sulfat, p-iiiitro-o-toluidin, m-hitro-o-anisidin, 5-amino-2-benzoyla.mino-l, 4-dieth-oxybenzen1, o-klor-o-anlisidin-hydroklorid, 6-benzoylamino-4-methoxy-m-toluidln, p-klor-o-toluidin-hydroklprid, dianisidin, samt andre av den type forbindelser som er istand til å diazoteres og kobles med de ovenfor beskrevne koblende nafholkom-ponenter. Fortrinnsvis anvendes en hvil-kensomhelst kombinasjon av en slik koblende naftholkomponent og en slik basisk naftholkomponenit som' overhodet vil kobles og derved gi en brukbar farve i polymer em. The basic component includes the known naphthol bases which are used in the naphthol-holoil synthesis technique and are described in the above-mentioned book on pages 364-409. Among these basic components are o-chloroaniline hydrochloride; o-Chloraniline, m-Chloraniline hydrochloride, m-Chlorandlin, o-Nitr-aniline, m-Nitramyline, o-Chloro-p-anisidine, 2,5-Dichloraniline hydrochloride, 2,5-Dichloroaniline sulfate, p- iiiitro-o-toluidine, m-hitro-o-anisidine, 5-amino-2-benzoyla.mino-l, 4-dieth-oxybenzene1, o-chloro-o-anlisidine hydrochloride, 6-benzoylamino-4-methoxy- m-toluidln, p-chloro-o-toluidine hydrochloride, dianisidine, as well as other compounds of the type which are capable of being diazotized and coupled with the above-described coupling naphthol components. Preferably, any combination of such a linking naphthol component and such a basic naphthol component is used which will be linked at all and thereby give a usable color in polymer etc.
Den anvendte mengde koblende naftholkomponent kan varieres avhengig av den kjemiiske sammensetning og molekylvekten av polymeren og den ønskede slutt-farves intensitet. Det er klart at bruken av koblende naftholkomponent i stort overskudd av det som vil forbinde seg i polymeren vil medføre tap av stoff siden den The amount of linking naphthol component used can be varied depending on the chemical composition and molecular weight of the polymer and the desired final color intensity. It is clear that the use of connecting naphthol component in large excess of what will connect in the polymer will result in a loss of substance since it
del av komponenten som ikke forbinder seg, heller ikke frembringer noen farve part of the component that does not connect, nor does it produce any color
som er så ekte som den farve som dannes which is as real as the color that is formed
når den koblende komponent forbinder seg when the connecting component connects
kjemisk i polymeren. Det er funnet at mengder på fra 0,5 til 6,0 pst. av den koblende komponent basert på vekten av polymeren i alminnelighet gir de beste resul-tater. chemically in the polymer. It has been found that amounts of from 0.5 to 6.0 percent of the linking component based on the weight of the polymer generally give the best results.
Skjønt oppfinnelsen er til nytte ved produksjon av farvede polymerar tikler inkl1, polymere med relativ lav molekylvekt som kan være nyttige ved fabrikasjon av maling, lakk og lignende, har den sin stør-ste verdi når vinylpolymeren har film- og fiber dannende egenskaper eller kan støpes, f. eks. ved sprøytestøpningsteknikken, til formede gjenstander. Eksempler på disse vinylpolymere innbefatter polymere av po-lystyren og beslektede stoffer; polymere av metakryl- og akryl-estere; polymere av akrylnitril, akrylsyre og beslektede stoffer; polymere av vinylacetat; polymere av vinylklorid; polymere av vinylidenklorid; polymere av vinylidenfluorid, polymere av vlnylidencyanld, polymere av ethylen og propylen; polytetrafluorethylen og lignende. Videre kan sampolymere, terpolymere og blandinger av disse vinylpolymere med polymere som igj en er sampolymerisert med andre polymeriserbare olefiner, farves tilfredsstillende ved denne metode. Although the invention is useful in the production of colored polymer articles incl1, polymers with a relatively low molecular weight which can be useful in the manufacture of paints, varnishes and the like, it has its greatest value when the vinyl polymer has film and fiber forming properties or can be molded , e.g. by the injection molding technique, into shaped objects. Examples of these vinyl polymers include polymers of polystyrene and related materials; polymers of methacrylic and acrylic esters; polymers of acrylonitrile, acrylic acid and related substances; polymers of vinyl acetate; polymers of vinyl chloride; polymers of vinylidene chloride; polymers of vinylidene fluoride, polymers of vinylidene cyanide, polymers of ethylene and propylene; polytetrafluoroethylene and the like. Furthermore, copolymers, terpolymers and mixtures of these vinyl polymers with polymers that have also been copolymerized with other polymerizable olefins can be dyed satisfactorily by this method.
Vinylpolymerene kan, fremstilles efter kjente metoder. Imidlertid blir i denne oppfinnelse den. koblende naftholkomponent innarbeidet i polymerisasjonsmassen før polymerisasjonen har begynt, eller før den har funnet sted i vesentlig grad. En polymer kan fremstilles ved forskjellige typer reaksj onsteknikk ut fra oppløsnin-gen, vandige emulsjoner, vandige suspen-sjoner eller faste masser. Den foretrukne polymer har en molekylvekt på minst 10 000 og kan være så høy som 250 000 eller høyere, idet molekylvekten bestemmes ved vanlige viskositetsmiålinger. The vinyl polymers can be produced according to known methods. However, in this invention it becomes. linking naphthol component incorporated into the polymerization mass before polymerization has begun, or before it has taken place to a significant extent. A polymer can be produced by different types of reaction techniques from the solution, aqueous emulsions, aqueous suspensions or solid masses. The preferred polymer has a molecular weight of at least 10,000 and may be as high as 250,000 or higher, the molecular weight being determined by conventional viscosity measurements.
Analyse av polymeren viser at den koblende naftholkomponent utgjør en integrerende del av polymerens molekylkjede, og at komponenten øyensynlig er kjemisk bundet til molekylkjedens ender og fun-gerer som sluttledd for kjeden. En annen indikasjon på at den koblende komponent er kjemisk bundet i polymermolekylet er at komponenten ikke skilles fra polymeren i oppløsningsmidler for polymeren og den koblende komponent. Polymerproduktene man får ved metoden ifølge oppfinnelsen kan anvendes til forming, støpning og fremstilling av tråder på plastikområdet efter konvensjonelle metoder. Under slike betingelser vedblir den koblende komponent å være en integrerende del av mole-kylkj eden. Analysis of the polymer shows that the connecting naphthol component forms an integral part of the polymer's molecular chain, and that the component is apparently chemically bound to the ends of the molecular chain and functions as the end link for the chain. Another indication that the linking component is chemically bound in the polymer molecule is that the component does not separate from the polymer in solvents for the polymer and the linking component. The polymer products obtained by the method according to the invention can be used for shaping, casting and producing threads in the plastics area according to conventional methods. Under such conditions, the linking component remains an integral part of the molecular chain.
Efter polymerisasjonen blir den med den koblende komponent modifiserte polymer renset og bleket om nødvendig. Derefter bringes polymeren, enten før eller efter den er formet som fiber, tråd, hinner, overtrekk, rør eller lignende, i kontakt med den basiske komponent under slike betingelser at den koblende naftholkomponent forbinder seg med den, og der derved ut-vikles i polymeren en farve som er ytterst motstandsdyktig overfor lysets skadelige innvirkning. For å unngå en slik forbin-delse må den basiske komponent omgjøres til en diazoforbindelse ved hjelp av fri salpetersyre. Denne diazotering av den basiske komponent kan utføres i nærvær eller ikke av polymeren som inneholder den koblende komponent. Der må tas hen-syn til at mengden av basisk komponent avhenger av den mengde koblende komponent som er tilsatt polymeren. Vanligvis er det best å anvende ca. 0,85—1,5 deler base pr. del naftholkomponent. After polymerization, the polymer modified with the linking component is cleaned and bleached if necessary. Then the polymer, either before or after it has been shaped as a fiber, thread, membrane, coating, tube or the like, is brought into contact with the basic component under such conditions that the connecting naphthol component connects with it, and is thereby developed in the polymer a color that is extremely resistant to the harmful effects of light. To avoid such a connection, the basic component must be converted to a diazo compound using free nitric acid. This diazotization of the basic component can be carried out in the presence or not of the polymer containing the linking component. Consideration must be given to the fact that the amount of basic component depends on the amount of linking component added to the polymer. Generally, it is best to use approx. 0.85-1.5 parts base per part naphthol component.
Ifølge en utførelsesform for oppfinnelsen fremstilles et vandig bad som inneholder en diazoterbar basisk komponent ved å dispergere komponenten i vann sammen med et passende dispergeringsmiddel om nødvendig. En oppløsning surgjøres ved hjelp av en organisk eller uorganisk syre som vil<1> spalte et passende metallnitrit til salpetersyre. Den fremkomne oppløsning bør ha en pH på 3,5—4,5. Polymeren sen-kes så i badet sammen med basen som er bragt til en temperatur fortrinnsvis på eller nær badets kokepunkt, i minst 20— 30 minutter eller lenger. Efter avkjøling av badet til 49°C eller under, helst til under 27°C, tisettes et alkalimetallhitrit, fortrinnsvis natriumnitrit, i en mengde på omtrent 7—9 pst., basert på polymerens vekt. Temperaturen i badet heves så lang-somt til mellom 82 og 88°C elUer til kokepunktet, og denne temperatur oppretthol-des i omtrent 15 minutter eller lenger for According to one embodiment of the invention, an aqueous bath containing a diazotizable basic component is prepared by dispersing the component in water together with a suitable dispersing agent if necessary. A solution is acidified using an organic or inorganic acid which will<1> split a suitable metal nitrite into nitric acid. The resulting solution should have a pH of 3.5-4.5. The polymer is then immersed in the bath together with the base, which has been brought to a temperature preferably at or near the boiling point of the bath, for at least 20-30 minutes or longer. After cooling the bath to 49°C or below, preferably below 27°C, an alkali metal nitrite, preferably sodium nitrite, is added in an amount of about 7-9 percent, based on the weight of the polymer. The temperature in the bath is then slowly raised to between 82 and 88°C or to the boiling point, and this temperature is maintained for approximately 15 minutes or longer for
å fullføre koblingen av nafthO'lkomponen-ten med basekomponenten og således utvikle farven. Tilslutt vaskes den farvede polymer med varm sepe og vann for å fjerne ikke forbundet eller løst festet f arvestoff komponent. to complete the coupling of the naphthol component with the base component and thus develop the colour. Finally, the colored polymer is washed with warm soap and water to remove unconnected or loosely attached dye components.
Ifølge en annen utførelsesform for oppfinnelsen bringes polymeren inneholdende den koblende naftholkomponent i kontakt med en diazotert basekomponent i vandig medium ved høy temperatur til-strekkelig lenge til at den koblende komponent forbinder seg med basekomponenten. According to another embodiment of the invention, the polymer containing the linking naphthol component is brought into contact with a diazotized base component in an aqueous medium at a high temperature long enough for the linking component to connect with the base component.
I det følgende beskrives som eksempler noen utførelsesformer for oppfinnelsen. In the following, some embodiments of the invention are described as examples.
Eksempel 1. Example 1.
En del «Nafthol AS», anilidet av 2,3-oxynafthosyre (3, 5 g) ble blandet med 94 deler akrylnitril (334 g) og 6 deler vinylacetat (21 g). Blandingen ble utsatt for polymerisasjonsbetingelser av suspensjons-typen, idet man brukte et kaliumpersulfat-svoveldioxyd- og jern-katalysatorsystem. Polymerisasjonen ble utført ved at blandingen ble tilsatt til et vandig medium som ble holdt ved 50°C i 2 timer. Kataly-satoren ble likeledes tilsatt 1 løpet av 2 timer. Polymeren som ble dannet på denne måte ble gjenvunnet ved filtrering, vasket omhyggelig med vann, alkohol og aceton, og derpå tørket ved 50°C til konstant vekt. One part "Naphthol AS", the anilide of 2,3-oxynaphthoic acid (3.5 g) was mixed with 94 parts of acrylonitrile (334 g) and 6 parts of vinyl acetate (21 g). The mixture was subjected to suspension type polymerization conditions using a potassium persulfate-sulfur dioxide and iron catalyst system. The polymerization was carried out by adding the mixture to an aqueous medium which was kept at 50°C for 2 hours. The catalyst was likewise added 1 over 2 hours. The polymer thus formed was recovered by filtration, washed thoroughly with water, alcohol and acetone, and then dried at 50°C to constant weight.
Polymeren i granulert form ble disper-gert i vann inneholdende edddksyre og med en pH på 4,0. Basekomponenten, «Fast Orange GC» base (metakloranilln-hydroklorid) i litet overskudd av den nødvendige mengde for å kobles med «Nafthol AS», ble blandet for seg med det ikke-ioniske dispergeringsmiddel «Diazopon AN» (polyoxyethylen fettalkohol) og oppløst i ethanol. Denne oppløsning ble tilsatt til poly-merdispersj onen: den resulterende blanding ble kokt 30 minutter og derpå avkjølt til romtemperatur. Maursyre og natriumnitrit ble tilsatt til denne blanding, og temperaturen øket til kokepunktet. En vakker orange-rød farve dannet seg øyeblikkelig og nådde full farvedybde efter 30 minutter. The polymer in granulated form was dispersed in water containing acetic acid and with a pH of 4.0. The base component, "Fast Orange GC" base (metachloranilln hydrochloride) in a slight excess of the amount necessary to couple with "Naphthol AS", was mixed separately with the non-ionic dispersant "Diazopon AN" (polyoxyethylene fatty alcohol) and dissolved in ethanol. This solution was added to the polymer dispersion: the resulting mixture was boiled for 30 minutes and then cooled to room temperature. Formic acid and sodium nitrite were added to this mixture, and the temperature was raised to the boiling point. A beautiful orange-red color formed instantly and reached full color depth after 30 minutes.
Ovennevnte fremgangsmåte ble utført med følgende baser: «Fast Scarlet RC» base (m-nitro-o-anisidim-hydroklorid); The above procedure was carried out with the following bases: "Fast Scarlet RC" base (m-nitro-o-anisidim hydrochloride);
«Fast Blue BB» base (5-amino-2-benzoyl-amino-l,4-dietoxybenzen) og «Fast Red RC» base (p- klor-o-anisidinhydroklorid) i stedet for Orange-basem. De farvede polymere i dette eksempel har en meget god lysekthetsverdi på 5—6. Denne verdi er basert på American Association of Textile Chemists' og Colorists' skala på fra én til åtte, som. er definert efter antall timer før merkbar forringelse efter anbringelse i et såkalt Fadometer. Eksempelvis tilsvarer 1 1,25—2,5 timer; 2 tilsvarer 2,5—5,0 timer; 3 tilsvarer 5—10 timer og videre fordobles tallene opp til 8 <A>som tilsvarer 160—320 timer. "Fast Blue BB" base (5-amino-2-benzoyl-amino-1,4-diethoxybenzene) and "Fast Red RC" base (p-chloro-o-anisidine hydrochloride) instead of Orange basem. The colored polymers in this example have a very good light fastness value of 5-6. This value is based on the American Association of Textile Chemists' and Colorists' scale of one to eight, which. is defined by the number of hours before noticeable deterioration after placement in a so-called Fadometer. For example, 1 corresponds to 1.25-2.5 hours; 2 corresponds to 2.5-5.0 hours; 3 corresponds to 5-10 hours and further the numbers double up to 8 <A> which corresponds to 160-320 hours.
I stedet for å utvikle farvene i små polymerkorn (granuler), ble den med koblende komponent modifiserte polymer opp-løst i N,N-dimethylacetamdd. Andre passende oppløsningsmidler kunne også ha vært brukt. Oppløsningen som inneholdt 18 vektpst. fast stoff ble ekstrudert gjen-nom passende åpninger i en spinnedyse som var senket i et utfelhingsbad bestående av vann. Trådene som ble dannet på denne måte ble trukket ut av badet og renset ved vaskninig for å fjerne all le rester av oppløsningsmiddel. Trådene ble senket i en oppløsning inneholdende et overskudd av «Fast Orange GC» base og ca. 8 pst. natriumnitrit og gjort svakt sur med eddiksyre. Denne oppløsning ble holdt ved en temperatur nær dens kokepunkt, og efter 30 minutter hadde der utviklet seg en full-god farve i trådene. Tilslutt ble trådene-renset med vann og tørket. Disse tråder var meget lys ekte. Instead of developing the colors in small polymer grains (granules), the linking component modified polymer was dissolved in N,N-dimethylacetamdd. Other suitable solvents could also have been used. The solution which contained 18 wt. solid was extruded through suitable openings in a spinning die which was immersed in a precipitation bath consisting of water. The threads formed in this way were withdrawn from the bath and cleaned by washing to remove all residual solvent. The threads were immersed in a solution containing an excess of "Fast Orange GC" base and approx. 8 per cent sodium nitrite and made slightly acidic with acetic acid. This solution was kept at a temperature close to its boiling point, and after 30 minutes a full color had developed in the threads. Finally, the threads were cleaned with water and dried. These threads were very light genuine.
Til sammenligning ble samme slags tråder fremstillet uten innføring av nafthol-komponenten i reaksjonsblandingen av momomiere. Trådene ble farvet med samme slags farvestoffkomponenter. Det ble funnet at tråder fremstillet av polymeren med polymerkjeden modifisert med nafthol-komponenten viste helt overlegen mot-stand mot falming. For comparison, the same kind of threads were produced without introducing the naphthol component into the reaction mixture of momomiers. The threads were dyed with the same type of dye components. It was found that threads made from the polymer with the polymer chain modified with the naphthol component showed superior resistance to fading.
Eksempel 2. Example 2.
20 mil akrylnitril og 0,2 g «Nafthol AS» ble oppløst i 100 ml N,N-dimethylacetamid med 0,1 g azo-bisisobutyrnitril tilsatt som katalysator. Oppløsningen ble oppvarmet til en temperatur på 62°C og holdt ved denne for å polymerisere reaktantene. 20 mils of acrylonitrile and 0.2 g of "Naphthol AS" were dissolved in 100 ml of N,N-dimethylacetamide with 0.1 g of azo-bisisobutyrnitrile added as catalyst. The solution was heated to a temperature of 62°C and held there to polymerize the reactants.
Den således dannede polymer ble koagulert i methylalkohol, filtrert, omhyggelig vasket med vann, alkohol og aceton, og derefter tørket ved 50°C til konstant vekt. Utbyttet av polymer var 9,3 g. The polymer thus formed was coagulated in methyl alcohol, filtered, carefully washed with water, alcohol and acetone, and then dried at 50°C to constant weight. The yield of polymer was 9.3 g.
Polymeren i granulert form ble disper-gert i vann inneholdende eddiksyre og med en pH på 4,0. Basekomponenten, «Fast Violet B» base (6-benzylamino-4-rn.ethoxy-m-toluidin) i lite overskudd av den nød-vendige mengde for kobling med det anvendte «Nafthol<1> AS», ble blandet for seg med polyoxyethylen fettalkohol og opp-løst i ethanol. Denne oppløsning bie tilsatt til polymerdispersjonen; den resulterende blanding ble kokt i 30 minutter og derefter avkjølet til romtemperatur. Maursyre og natriumnitrit ble tilsatt til blandingen, og temperaturen, øket til kokepunktet. En vakker rødligbrun farve dannet seg øyeblikkelig og nådde full farvedybde efter 30 minutter,. The polymer in granulated form was dispersed in water containing acetic acid and with a pH of 4.0. The base component, "Fast Violet B" base (6-benzylamino-4-rn.ethoxy-m-toluidine) in a small excess of the necessary amount for coupling with the "Naphthol<1> AS" used, was mixed separately with polyoxyethylene fatty alcohol and dissolved in ethanol. This solution was added to the polymer dispersion; the resulting mixture was boiled for 30 minutes and then cooled to room temperature. Formic acid and sodium nitrite were added to the mixture and the temperature raised to the boiling point. A beautiful reddish-brown color formed instantly and reached full color depth after 30 minutes.
Ovennevnte fremgangsmåte ble utført med følgende baser: «Fast Red KR» base (p-klor-o-toluidini) og «Fast Blue B» base (dianisidin). Henholdsvis orange og rødllg-brune farver utvikler seg. Lysektheten av de farvede polymere i dette eksempel var meget god. The above procedure was carried out with the following bases: "Fast Red KR" base (p-chloro-o-toluidini) and "Fast Blue B" base (dianisidine). Orange and reddish-brown colors respectively develop. The lightfastness of the colored polymers in this example was very good.
Eksempel 3. Example 3.
Den i eksempel 2 beskrevne fremgangsmåte ble gjentatt med unntagelse av at «Nafthol AS-SW» (p-nafthalidet av 2,3-oxynafthosyre) ble benyttet som koblende komponent. Med «Fast Violet» base, «Fast Red KB» base og «Fast Blue B» base ble fremstillet polymere med ekte farver, henholdsvis rødlig-brun, rødlig-orange og mørkerød. The procedure described in example 2 was repeated with the exception that "Naphthol AS-SW" (the p-naphthalide of 2,3-oxynaphthoic acid) was used as the linking component. With "Fast Violet" base, "Fast Red KB" base and "Fast Blue B" base, polymers with real colors were produced, respectively reddish-brown, reddish-orange and dark red.
Eksempel 4. Example 4.
Den i eksempel 2 beskrevne fremgangsmåte ble gjentatt med unntagelse av at «Nafthol AS-D» (o-toluidid av 2,3-oxynafthosyre) ble brukt som koblende komponent. Med «Fast Violet B» base, «Fast Red KB» base og «Fast Blue B» base ble fremstillet polymere med ekte farver, henholdsvis rød-brun, lys orange og mørkerød. The procedure described in example 2 was repeated with the exception that "Naphthol AS-D" (o-toluidide of 2,3-oxynaphthoic acid) was used as the connecting component. With "Fast Violet B" base, "Fast Red KB" base and "Fast Blue B" base, polymers with real colors were produced, respectively red-brown, light orange and dark red.
Eksempel 5. Example 5.
20 ml methylmetakrylat og 0,2 g «Nafthol AS» ble polymerisert under de i eksempel 1 beskrevne betingelser. Den resulterende polymer ble renset, og porsjoner av polymeren ble behandlet med «Fast Violet B» base, «Fast Red KB» base og 20 ml of methyl methacrylate and 0.2 g of "Naphthol AS" were polymerized under the conditions described in example 1. The resulting polymer was purified, and portions of the polymer were treated with "Fast Violet B" base, "Fast Red KB" base and
«Fast Blue B» base på samme måte som beskrevet i eksempel 1. Ekte farver utvikler seg i polymeren. "Fast Blue B" base in the same way as described in example 1. True colors develop in the polymer.
Eksempel 6. 20 ml vinylidenklorid og 0,2 g «Nafthol AS» bile polymerisert under de i eksempel 1 beskrevne betingelser. Polymeren ble renset, og porsjoner av polymeren ble behandlet med «Fast Violet B» base, «Fast Red KB» base og «Fast Blue B» base på samme måte som1 beskrevet i eksempel 1. Meget lysekte farver utvikler seg i polymeren. Example 6. 20 ml vinylidene chloride and 0.2 g "Naphthol AS" polymerized under the conditions described in example 1. The polymer was purified, and portions of the polymer were treated with "Fast Violet B" base, "Fast Red KB" base and "Fast Blue B" base in the same manner as described in Example 1. Very fast colors develop in the polymer.
Eksempel 7. Example 7.
10 g vinylacetat, 1,0 g «Naphtol AS», 0,5 g azobisisobutyronitril og 500 ml toluen ble anbragt i en autoklav ved 0°C. Systemet ble påsatt et trykk på omtrent 21 kg/cm2 ved innledning av 110 g propylen og derefter oppvarmet til 65°C. Til å begynne med øket trykket, hvoretter det avtok ved konstant temperatur efter hvert som polymerisasjonen skred frem. Efter at reaksjo-nen var fullført og det gjenværende trykk var avlastet, ble reaksjonsproduktet (ca. 90/10 propylen/vinylacetat) isolert og far- 10 g vinyl acetate, 1.0 g "Naphtol AS", 0.5 g azobisisobutyronitrile and 500 ml toluene were placed in an autoclave at 0°C. The system was pressurized to approximately 21 kg/cm 2 by introducing 110 g of propylene and then heated to 65°C. At first the pressure increased, after which it decreased at a constant temperature as the polymerization progressed. After the reaction was complete and the remaining pressure was relieved, the reaction product (approx. 90/10 propylene/vinyl acetate) was isolated and
vet under de i eksempel II angitte betingelser. Det ble oppnådd en noe lysere farve-tone som oppviste utmerket lysekthet. knows under the conditions stated in example II. A somewhat lighter color tone was achieved which exhibited excellent light fastness.
Claims (3)
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US83028569A | 1969-06-04 | 1969-06-04 | |
US83043769A | 1969-06-04 | 1969-06-04 |
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NO133049B true NO133049B (en) | 1975-11-17 |
NO133049C NO133049C (en) | 1976-02-25 |
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NO207070A NO133049C (en) | 1969-06-04 | 1970-05-29 |
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BE (1) | BE751486A (en) |
CH (1) | CH509614A (en) |
CS (1) | CS168528B2 (en) |
DE (1) | DE2027551C3 (en) |
ES (1) | ES380378A1 (en) |
FR (1) | FR2049827A5 (en) |
GB (1) | GB1251477A (en) |
NL (1) | NL166137C (en) |
NO (1) | NO133049C (en) |
SE (1) | SE359664B (en) |
SU (1) | SU419061A3 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US3724422A (en) * | 1970-12-14 | 1973-04-03 | Xerox Corp | Magnetic brush developing apparatus |
JPS5843739B2 (en) * | 1974-10-10 | 1983-09-28 | キヤノン株式会社 | developing device |
DE2756368A1 (en) * | 1977-12-17 | 1979-06-28 | Magnetfab Bonn Gmbh | Toner carrier tube for electrophotographic copiers - consists of ferromagnetic material homogenising field of pole pieces on magnetic roller |
JPS55142369A (en) * | 1979-04-23 | 1980-11-06 | Canon Inc | Developing device |
-
1970
- 1970-05-28 GB GB1251477D patent/GB1251477A/en not_active Expired
- 1970-05-29 SE SE743970A patent/SE359664B/xx unknown
- 1970-05-29 CH CH810370A patent/CH509614A/en not_active IP Right Cessation
- 1970-05-29 SU SU1445313A patent/SU419061A3/en active
- 1970-05-29 NO NO207070A patent/NO133049C/no unknown
- 1970-06-01 NL NL7007881A patent/NL166137C/en not_active IP Right Cessation
- 1970-06-02 CS CS384770A patent/CS168528B2/cs unknown
- 1970-06-03 ES ES380378A patent/ES380378A1/en not_active Expired
- 1970-06-03 FR FR7020260A patent/FR2049827A5/fr not_active Expired
- 1970-06-04 BE BE751486D patent/BE751486A/en not_active IP Right Cessation
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NL166137B (en) | 1981-01-15 |
GB1251477A (en) | 1971-10-27 |
CS168528B2 (en) | 1976-06-29 |
SU419061A3 (en) | 1974-03-05 |
NL7007881A (en) | 1970-12-08 |
NO133049C (en) | 1976-02-25 |
DE2027551A1 (en) | 1970-12-10 |
NL166137C (en) | 1981-06-15 |
BE751486A (en) | 1970-12-04 |
DE2027551B2 (en) | 1978-12-14 |
SE359664B (en) | 1973-09-03 |
DE2027551C3 (en) | 1979-09-20 |
ES380378A1 (en) | 1973-04-16 |
CH509614A (en) | 1971-06-30 |
FR2049827A5 (en) | 1971-03-26 |
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