CN1083864C - 含有氟磺酰基的单偶氮类染料及其应用 - Google Patents
含有氟磺酰基的单偶氮类染料及其应用 Download PDFInfo
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- CN1083864C CN1083864C CN96180204A CN96180204A CN1083864C CN 1083864 C CN1083864 C CN 1083864C CN 96180204 A CN96180204 A CN 96180204A CN 96180204 A CN96180204 A CN 96180204A CN 1083864 C CN1083864 C CN 1083864C
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- 239000000975 dye Substances 0.000 title claims abstract description 31
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 title description 4
- 239000000463 material Substances 0.000 claims abstract description 26
- 229920002994 synthetic fiber Polymers 0.000 claims abstract description 12
- 239000004758 synthetic textile Substances 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 5
- 238000004040 coloring Methods 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- DXBICNXFLXEILE-UHFFFAOYSA-N ClNC1=CC=C(C=C1)S(=O)(=O)F Chemical compound ClNC1=CC=C(C=C1)S(=O)(=O)F DXBICNXFLXEILE-UHFFFAOYSA-N 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 11
- -1 Phenyl Chemical group 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- 150000004982 aromatic amines Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 4
- 238000010168 coupling process Methods 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
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- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 150000001989 diazonium salts Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 2
- 125000001424 substituent group Chemical group 0.000 abstract 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 abstract 1
- 229910006095 SO2F Inorganic materials 0.000 abstract 1
- 125000005236 alkanoylamino group Chemical group 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 10
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- 150000001875 compounds Chemical class 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000176 photostabilization Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
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- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RXLDQNGVCXRJOO-UHFFFAOYSA-N N,1-diethylcyclohexa-2,4-dien-1-amine Chemical compound CCC1(CC=CC=C1)NCC RXLDQNGVCXRJOO-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
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- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
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- 229920006304 triacetate fiber Polymers 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical group OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- 229940061334 2-phenylphenol Drugs 0.000 description 1
- WYRNRZQRKCXPLA-UHFFFAOYSA-N 3-(n-ethylanilino)propanenitrile Chemical compound N#CCCN(CC)C1=CC=CC=C1 WYRNRZQRKCXPLA-UHFFFAOYSA-N 0.000 description 1
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Chemical group 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical group O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010014 continuous dyeing Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 238000010017 direct printing Methods 0.000 description 1
- 238000010018 discharge printing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- IDSJYFJVPKCVLM-UHFFFAOYSA-N ethyl 3-(n-ethylanilino)propanoate Chemical compound CCOC(=O)CCN(CC)C1=CC=CC=C1 IDSJYFJVPKCVLM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000009635 nitrosylation Effects 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
- C09B29/0805—Amino benzenes free of acid groups
- C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
- C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
- C09B29/0811—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino
- C09B29/0815—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino substituted by -C(=O)-
- C09B29/0816—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino substituted by -C(=O)- substituted by -COOR
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/922—Polyester fiber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/924—Polyamide fiber
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
一种不含水溶性基团、结构式(1)所示的单偶氮染料，式中：Q是-Br或Cl、R1和R2各自表示H或是选自C1-6烷基或芳基的基团；各个基团可以是非取代的或被一个或多个非离子取代基取代；和R3、R4、R5和R6各自表示H、F、Cl、Br、I、-SO2F，或是选自C1-6烷基、C1-6烷氧基、C1-4链烷酰氨基、-NHSO2烷基、-NHCOC1-4烷基和-O苯基的有机基团，每个有机基团是非取代的或被一个或多个非离子取代基取代。这些染料可染色合成纤维纺织品材料。
Description
本发明涉及含有氟磺酰基的偶氮类染料、特别是涉及水不溶性单偶氮类染料，其制备方法及其用于合成纤维纺织品和其它材料的染色的用途。
公开于WO95/20014的国际专利申请描述了含有至少一个氟磺酰基且不含水溶性基团的偶氮美化合物。其中还描述了这些化合物用于合成纤维纺织品材料的染色和用于塑料的本体染色的用途。
当作为合成纤维纺织品材料的分散染料时，我们发现一些染料显示出优越性能，它们属于WO95/20014中所概述的化合物，但没有在其中具体公开。
因此，本发明提供不含水溶性基团的单偶氮类染料，其结构式如下：
其中：
Q是-Br或-Cl
R1和R2各自表示H或选自C1-6烷基或芳基，各个基团可以是非取代的或被一个或多个非离子取代基取代；和
R3、R4、R5和R6各自表示H、F、Cl、Br、I、-SO2F或选自C1-6烷基、C1-6烷氧基、C1-4链烷酰氨基、-NHSO2烷基、-NHCOC1-4烷基和-O苯基的有机基团，每个有机基团是非取代的或被一个或多个非离子取代基取代。
式(1)的染料必须不含水溶性基团，水溶性基团特别包括-SO3H、-CO2H、-PO3H和季铵基及它们的盐。
当R1和R2二者中的一个或两个表示C3-6烷基时，该烷基基团可以是直链的或支链的，当烷基基团是支链基团时，可以支化形成仲基或叔基。其中可以存在一或两个支化点。可以在N原子和R1或R2中的任意碳原子之间形成C-N键。
当R1和R2二者中的一个或两个表示芳基基团时，该芳基基团可以是苯基或萘基，它可在相对于N原子键的任何位置被取代。当R1和R2二者中的一个或两个表示苯基基团时，优选在苯基-N键的邻和/或对位进行任意取代。在某些实验方案中，R1和R2可以与N原子一起稠合形成芳族或共轭的杂环基、特别是5元或6元环，或者形成饱和的杂环基、特别是5、6或7元环。
R1-R6表示的基团上可有可无的非离子取代基特别包括-CN、-OH、-OC1-6-烷基、-OCOC1-6-烷基、-COOC1-6-烷基、苯基、苯氧基、-OCO苯基、-OCO苯基SO2F、苯基SO2F、-O苯基SO2F、-CO2苯基SO2F、-COOC1-6-烷基OCOC1-6-烷基和-COOC1-6-烷基COOC1-6-烷基。
优选的一类式(1)染料包括下式的化合物：
其中Q如上述所定义，R1和R2各自为可被取代的C1-6-烷基。
在式(2)所示的染料中，特别可提到的是其中R1和R2各自为可被取代的乙基的染料，例如R1是-C2H5和R2是-C2H4X的染料，其中X选自-H、-CN、-COOC2H5、-OCOCH3和-OC6H5。
式1的染料可以通过重氮化6-溴2，5-二氯-4-氟磺酰基苯胺或2，3，6-三氯-4-氟磺酰基苯胺，并且用芳香胺偶联得到的重氮化合物而制备，该芳香胺的结构式为：
其中R1-R6如上文所定义。
重氮化和偶联反应可以使用所用反应试剂的通常采用的反应条件来进行。典型地是，在-10℃-10℃的温度下在酸性介质(如乙酸，丙酸或盐酸)中，使用亚硝基化试剂(如亚硝基硫酸、亚硝酸钠或亚硝酸甲酯)将6-溴-2，5-二氯-4-氟磺酰基苯胺或2，3，6-三氯-4-氟磺酰基苯胺重氮化。可以在0℃-10℃的温度下在链烷醇如甲醇中，通过往式3的胺中加入重氮化的6-溴-2，5-二氯-4-氟磺酰基苯胺或2，3，6-三氯-4-氟磺酰基苯胺实现与式3的芳香胺的偶联。偶联后，可以用任意简便方法(如过滤)从反应混合物中回收式1的化合物。
通过2，5-二氯-4-氟磺酰基苯胺的溴化反应或氯化反应分别得到6-溴-2，5-二氯-4-氟磺酰基苯胺或2，3，6-三氯-4-氟磺酰基苯胺。
式(1)的偶氮化合物可用作分散染料，它对于合成纺织品材料和含有此材料的混合纤维的着色很重要。
合成纤维纺织品材料可以选自二级乙酸纤维素、三乙酸纤维素、聚酰胺、聚丙烯腈和芳族聚酯。合成纤维纺织品材料优选为聚酰胺如聚亚己基己二酰胺，或芳族聚酯、特别是聚对苯二甲酸乙二醇酯。混合纤维可以包括不同合成纤维纺织品材料的混合物或合成和天然纤维纺织品材料的混合物。优选的混合纤维包括聚酯-纤维素如聚酯-棉混合纤维。纺织品材料或其混合物可以呈长丝、散纤维、纱或织物或针织物的形式。
式1的偶氮化合物或其混合物，以及可以选择地加入的其它分散染料可以通过使用常规方法施用于合成纤维纺织品材料或其混合纤维上。
适宜的工艺条件如下：1)在压力为1-2巴，温度为125℃-140℃，pH为4-6.5的条件下浸染10-120分钟；可选择地加入螯合剂；2)在温度为190℃-225℃，pH为4-6.5的条件下连续染色15秒-5分钟；可选择地加入迁移抑制剂；3)在pH为4-6.5，温度为160℃-185℃的高温汽蒸的条件下直接印花4-15分钟，或在190℃-225℃、用干热烘干固色15秒-5分钟或在120℃-140℃和1-2巴压力下汽蒸10-45分钟；可选择地加入染料重量的5-100％的润湿剂和增稠剂(如藻酸盐类)；4)在pH为4-6.5的条件下拔染印花(在纺织品材料上浸轧染料，干燥并套印)；可选择地加入迁移抑制剂和增稠剂；5)在pH为4-6.5，温度为95℃-100℃的条件下，使用如甲基萘、二苯胺或2-苯基苯酚为染色载体进行载体染色；可选择地加入螯合剂；和6)在pH为4-6.5，醋酯纤维为85℃或三醋酸纤维和尼龙为90℃的条件下常压染色醋酯纤维、三醋酸酯纤维和尼龙15-90分钟；可选择地加入螯合剂。
在所有的上述工艺中，式1的化合物或其混合物适于用作在含水介质中的分散体，它包含0.001％-4％重量的偶氮化合物或其混合物。
染料分散体可进一步包括通常用于着色应用中的成分，例如分散剂如木素磺酸盐、萘磺酸/甲醛缩合物或苯酚/甲酚/对氨基苯磺酸/甲醛缩合物，表面活性剂，润湿剂如可被磺化或磷酸盐化的烷芳基乙氧基化物，无机盐类，消泡剂如矿物油或壬醇，有机液体和缓冲剂。分散剂可以为式1的偶氮化合物重量的10％-200％。使用的润湿剂可为式1的偶氮化合物重量的0％-20％。
适宜的分散体可在含水介质中通过用玻璃小珠或砂子小球研磨式1的化合物而制备。
式1的化合物能提供呈现耐洗、耐光和耐热的黄褐色的合成纤维纺织品材料。
式1的偶氮化合物也可用于塑料材料的本体染色。偶氮化合物通常与粒状或粉状塑料材料掺和混用，例如使用干法滚抛(dry tumbling)或高速混合接着在螺杆机上注塑或用常规混合/母炼胶的工艺加工。通常，本发明染料溶解或快速分散在热的塑料熔融物中并提供具有良好透明度和良好耐光性的明亮颜色。可用这种方法染色的塑料包括聚苯乙烯、聚丙烯酸类、聚苯乙烯/丙烯腈混合物、聚丙烯腈/丁二烯/苯乙烯混合物、聚碳酸酯、聚醚砜、尼龙、硬质PVC(uPVC)和聚丙烯。
式1的偶氮化合物也可作为用于基于溶剂的喷墨印花工艺中的油墨的色料。一般地，这些基于酮类和/或醇类的油墨用于疏水基质(如塑料和金属)上的印花。
本发明用下列实施例说明，但不限于此，除另外指出，实施例中所有份数指重量份。所有λmax值是在CH2Cl2中测定的。
实施例1
在室温下搅拌2，5-二氯-4-氟磺酰基苯胺(4.9份)在乙酸(30份)中的溶液，向该溶液中加入溴(3.52份)在乙酸(10份)中的溶液。在70℃下搅拌该混合物2小时，将其冷却到室温并加入水(75份)。搅拌1小时后，通过过滤分离产物并干燥，得到6-溴-2，5-二氯-4-氟磺酰基苯胺(6.0份)。
在0-5℃搅拌6-溴-2，5-二氯-4-氟磺酰基苯胺(2.6份)和乙酸/丙酸混合物(15份，86/14体积/体积)的混合物，往该混合物中滴加亚硝基硫酸溶液(5份)。在此温度下进一步搅拌该混合物30分钟。
在0-5℃搅拌下，将上述重氮溶液缓慢加入到N，N-二乙基苯胺(1.2份)、甲醇(20份)、水(10份)和氨基磺酸(0.5份)的混合物中。在此温度搅拌3小时后，通过过滤分离产物，用水洗涤并干燥，得到4-(6-溴-2，5-二氯-4-氟磺酰基苯偶氮基)-N，N-二乙基苯胺(1.3份)。
当从水分散体中施用于聚酯材料上时，染料呈现出具有极好的耐光性和极好的耐湿处理性的黄褐色色调。λmax＝452nm。
实施例2
用N-乙基-N-(2-氰基乙基)-苯胺(1.4份)代替实施例1中的N，N-二乙基苯胺(1.2份)，得到4-(6-溴-2，5-二氯-4-氟磺酰基苯偶氮基)-N-乙基-N-(2-氰基乙基)苯胺(1.6份)。当从水分散体中施用于聚酯材料上时，染料呈现出具有极好的耐光性和极好的耐湿处理性的黄褐色色调。λmax＝418nm。
实施例3
用N-乙基-N-(2-乙氧基羰基乙基)苯胺(1.5份)代替实施例1中的N，N-二乙基苯胺(1.2份)，得到4-(6-溴-2，5-二氯-4-氟磺酰基苯偶氮基)-N-乙基-N-(2-乙氧基羰基乙基)苯胺(1.4份)。
当从水分散体中施用于聚酯材料上时，染料呈现出具有极好的耐光性和极好的耐湿处理性的黄褐色色调。λmax＝436nm。
实施例4
用N-乙基-N-(2-乙酰氧基乙基)-苯胺(1.4份)代替实施例1中的N，N-二乙基苯胺(1.2份)，得到4-(6-溴-2，5-二氯-4-氟磺酰基苯偶氮基)-N-乙基-N-(2-乙酰氧基乙基)苯胺(1.3份)。当从水分散体中施用于聚酯材料上时，染料呈现出具有极好的耐光性和极好的耐湿处理性的黄褐色色调。λmax＝434nm。
实施例5
用N-乙基-N-(2-苯氧基乙基)-苯胺(1.7份)代替实施例1中的N，N-二乙基苯胺(1.2份)，得到4-(6-溴-2，5-二氯-4-氟磺酰基苯偶氮基)-N-乙基-N-(2-苯氧基乙基)苯胺(1.8份)。当从水分散体中施用于聚酯材料上时，染料呈现出具有极好的耐光性和极好的耐湿处理性的黄褐色色调。λmax＝446nm。
Claims (7)
1.一种不含水溶性基团、结构式如下的单偶氮染料：
其中：
Q是-Br或-Cl；
R1和R2各自表示H或选自C1-6烷基和芳基，各个C1-6烷基和芳基可以是非取代的或被一个或多个非离子取代基取代，所述芳基选自苯基、萘基、包含5-或6-元环的芳族和共轭的杂环基以及包含5-、6-或7-元环的饱和杂环基，所述杂环由基团R1、R2和所连的氮原子一起形成，所述非离子取代基选自-CN、-OH、-OC1-6-烷基、-OCOC1-6-烷基、-COOC1-6-烷基、苯基、苯氧基、-OCO苯基、-OCO苯基SO2F、苯基SO2F、-O苯基SO2F、-CO2苯基SO2F、-COOC1-6-烷基OCOC1-6-烷基和-COOC1-6-烷基COOC1-6-烷基；和
R3、R4、R5和R6各自表示H、F、Cl、Br、I、-SO2F，或是选自C1-6烷基、C1-6烷氧基、C1-4链烷酰氨基、-NHSO2烷基、-NHCOC1-4烷基和-O苯基的有机基团，每个有机基团是非取代的或被一个或多个上述非离子取代基取代。
2按照权利要求1的单偶氮染料，其中R1和R2各自是非取代的或被一个或多个权利要求1所定义的非离子取代基取代的C1-6烷基，并且R3、R4、R5和R6均是H。
3按照权利要求2的单偶氮染料，其中R1和R2各自是非取代的或被一个或多个权利要求1所定义的非离子取代基取代的乙基。
4.按照权利要求3的单偶氮染料，其中R1是-C2H5和R2是-C2H4X，其中X选自-H、-CN、-COOC2H5、-OCOCH3和-OC6H5。
5.权利要求1的单偶氮染料的制备方法，它包括，重氮化6-溴-2，5-二氯-4-氟磺酰基苯胺或2，3，6-三氯-4-氟磺酰基苯胺，并用芳香胺偶联得到的重氮化合物，该芳香胺的结构式为：
其中R1-R6如权利要求1所定义。
6.一种将合成纤维纺织品材料或其混合纤维染色的方法，它包括将权利要求1-4中任何一项的单偶氮染料施用于合成纤维纺织品材料或其混合纤维上。
7.一种将塑料本体染色的方法，它包括将权利要求1-4中任何一项的单偶氮染料掺入到塑料材料中。
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| Application Number | Priority Date | Filing Date | Title |
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| GBGB9602741.2A GB9602741D0 (en) | 1996-02-10 | 1996-02-10 | AZO dyes |
| GB9602741.2 | 1996-02-10 |
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| CN1083864C true CN1083864C (zh) | 2002-05-01 |
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| CN (1) | CN1083864C (zh) |
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| BR (1) | BR9612491A (zh) |
| DE (1) | DE69607989T2 (zh) |
| GB (1) | GB9602741D0 (zh) |
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| CN103319380B (zh) * | 2013-05-28 | 2015-11-25 | 江苏之江化工有限公司 | 一种含氟元素的染料 |
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| WO1995020014A1 (en) * | 1994-01-19 | 1995-07-27 | Zeneca Limited | Monoazo dyes containing a fluorosulphonyl group and use thereof |
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1996
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- 1996-12-16 PT PT96942454T patent/PT888405E/pt unknown
- 1996-12-16 CN CN96180204A patent/CN1083864C/zh not_active Expired - Fee Related
- 1996-12-16 BR BR9612491A patent/BR9612491A/pt not_active IP Right Cessation
- 1996-12-16 KR KR10-1998-0706103A patent/KR100420543B1/ko not_active IP Right Cessation
- 1996-12-16 US US09/125,021 patent/US6048370A/en not_active Expired - Lifetime
- 1996-12-16 WO PCT/GB1996/003094 patent/WO1997029155A1/en active IP Right Grant
- 1996-12-16 JP JP52825197A patent/JP3989549B2/ja not_active Expired - Fee Related
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| WO1995020014A1 (en) * | 1994-01-19 | 1995-07-27 | Zeneca Limited | Monoazo dyes containing a fluorosulphonyl group and use thereof |
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| Publication number | Publication date |
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| DE69607989D1 (de) | 2000-05-31 |
| PT888405E (pt) | 2000-08-31 |
| GB9602741D0 (en) | 1996-04-10 |
| KR100420543B1 (ko) | 2005-10-31 |
| JP2000505832A (ja) | 2000-05-16 |
| CN1214065A (zh) | 1999-04-14 |
| BR9612491A (pt) | 1999-07-20 |
| WO1997029155A1 (en) | 1997-08-14 |
| DE69607989T2 (de) | 2001-03-15 |
| US6048370A (en) | 2000-04-11 |
| AU1182397A (en) | 1997-08-28 |
| ID15879A (id) | 1997-08-14 |
| KR19990082373A (ko) | 1999-11-25 |
| JP3989549B2 (ja) | 2007-10-10 |
| EP0888405A1 (en) | 1999-01-07 |
| EP0888405B1 (en) | 2000-04-26 |
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