CN1060493C - 一类含双活性基的蒽醌型艳蓝色活性染料 - Google Patents
一类含双活性基的蒽醌型艳蓝色活性染料 Download PDFInfo
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 9
- 239000000975 dye Substances 0.000 claims description 27
- 238000009833 condensation Methods 0.000 claims description 17
- 230000005494 condensation Effects 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 5
- MMNWSHJJPDXKCH-UHFFFAOYSA-N 9,10-dioxoanthracene-2-sulfonic acid Chemical compound C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 MMNWSHJJPDXKCH-UHFFFAOYSA-N 0.000 claims description 4
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims description 3
- BEHLMOQXOSLGHN-UHFFFAOYSA-N benzenamine sulfate Chemical compound OS(=O)(=O)NC1=CC=CC=C1 BEHLMOQXOSLGHN-UHFFFAOYSA-N 0.000 claims description 3
- -1 halo triazines Chemical class 0.000 claims description 3
- 125000001475 halogen functional group Chemical group 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 2
- 239000000835 fiber Substances 0.000 abstract description 11
- 229920000742 Cotton Polymers 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 210000004243 sweat Anatomy 0.000 abstract description 2
- 244000025254 Cannabis sativa Species 0.000 abstract 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 abstract 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 abstract 1
- 229920003043 Cellulose fiber Polymers 0.000 abstract 1
- 235000009120 camo Nutrition 0.000 abstract 1
- 235000005607 chanvre indien Nutrition 0.000 abstract 1
- 239000011487 hemp Substances 0.000 abstract 1
- 102000004169 proteins and genes Human genes 0.000 abstract 1
- 108090000623 proteins and genes Proteins 0.000 abstract 1
- 210000002268 wool Anatomy 0.000 abstract 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 238000004043 dyeing Methods 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229940056729 sodium sulfate anhydrous Drugs 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KXXFHLLUPUAVRY-UHFFFAOYSA-J [Na+].[Na+].[Na+].[Cu++].[O-]C(=O)C1=CC=C(C=C1N=N[C-](N=NC1=C([O-])C(NC2=NC(F)=NC(NCCOCCS(=O)(=O)C=C)=N2)=CC(=C1)S([O-])(=O)=O)C1=CC=CC=C1)S([O-])(=O)=O Chemical compound [Na+].[Na+].[Na+].[Cu++].[O-]C(=O)C1=CC=C(C=C1N=N[C-](N=NC1=C([O-])C(NC2=NC(F)=NC(NCCOCCS(=O)(=O)C=C)=N2)=CC(=C1)S([O-])(=O)=O)C1=CC=CC=C1)S([O-])(=O)=O KXXFHLLUPUAVRY-UHFFFAOYSA-J 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010016 exhaust dyeing Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- INVZMZZUHLNNHA-UHFFFAOYSA-N phenyl(sulfo)sulfamic acid Chemical compound OS(=O)(=O)N(S(O)(=O)=O)C1=CC=CC=C1 INVZMZZUHLNNHA-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009941 weaving Methods 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
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
- C09B62/06—Anthracene dyes
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Abstract
本发明涉及一类含双活性基的蒽醌型艳蓝色活性染料，具有下列通式结构：
这类染料在棉、麻等纤维素纤维或毛、丝等蛋白质纤维上染色后，呈鲜艳的红光蓝色，有较好的上色率、固色率和耐洗、耐汗等湿处理坚牢度及耐日晒牢度。也可用于上述纤维的直接印花。
Description
本发明涉及一类含双活性基的蒽醌型艳蓝色活性染料。
目前市场上在纤维素纤维上呈红光艳蓝色的染色用活性染料尚无满意的商品应市。以1-氨基-4-(2′，6′二甲基-3′-氨基-5′-磺基-苯胺基-)蒽醌-2-磺酸及其衍生物(Ⅰ)为发色体骨架的染料，因苯环2′，6′二个甲基的空间障碍，使染料具有十分鲜艳的红光蓝色，例如C．I．活性蓝74(Ⅱ)：
式中：R=H或CH3
(Ⅱ)用于纤维素纤维印花呈艳蓝色，λmax在580nm附近，易洗涤性好，牢度高，但在纤维素纤维上直接性较差，上色率和固色率很低。
Eur．Pat 584045和Eur．Pat 625429中，涉及过以(Ⅰ)为母体骨架的染料，通过一个脂肪族二氨基化合物间苯二胺双磺酸或对苯二胺双磺酸为桥基相连的双活性基染料，例如，(Ⅲ)和(Ⅳ)：引入桥基后，由于分子加大，直接性有所提高，但由于脂肪链柔性过大，苯胺双磺酸的水溶性太大，作为染色用染料仍不理想。
本发明中的双活性基活性染料，在两个三嗪环之间连结直接性相对较大的桥基，当用于纤维素纤维的竭染染色时，具有较高的上染率和固色率。染料结构的通式如下：
上述染料可以通过两条路线合成：
(1)染料母体1-氨基-4-(2′，6′-二甲基-3′-氨基-5′-磺基-苯胺基)-蒽醌-2-磺酸或其4′甲基衍生物先与卤代均三嗪进行第一次缩合后，再与作为桥基的二氨基化合物进行第二次缩合反应。第一次缩合温度-5～10℃，反应pH2-6；第二次缩合温度0-50℃，反应pH3-7。即： 
(2)两分子卤代三嗪先与作为桥基的二氨基化合物缩合，然后再与两分子母体染料1-氨基-4-(2′，6′-二甲基-3′-氨基-5′-磺基苯胺基)蒽醌-2-磺酸或其4′-甲基衍生物反应而得。第一次缩合的温度为0～10℃，反应pH2-6；第二次缩合温度为30～55℃，缩合pH5-7。即：
本发明所涉及的染料在20～80g／L元明粉促染下，中性介质中对棉、麻等纤维素纤维于85～100℃竭染染色，然后用10～35g／L纯碱固色染料，具有较高的上色率和固色率，被染纤维呈红光艳蓝色，耐皂洗、耐汗渍、耐水浸坚牢度好。由于其艳丽的色泽和透染性相对较好，特别在麻纤维上比较适用。该系列染料在毛、丝纤维染色也有较满意的结果。
本发明所述的双活性基蒽醌型艳蓝色活性染料的特点为：
(1)以芳胺2′，6′位有甲基存在的1-氨基-4-芳胺基蒽醌衍生物为发色基骨架，由于2′，6′位的空间障碍使芳胺和蒽醌共平面性遭到破坏，从而赋予被染织物具艳丽红光蓝色和一定的耐晒牢度。
(2)以亲和力和反应性较强的卤代均三嗪为活性基同时由于两个活性基团具有一致的反应活性，使染料具有较高的反应率和湿处理牢度。
(3)以相对刚性较大的芳香二胺为桥基，在桥基上引入(或不引入)适量的水溶性基，以保证染料具有较好的直接性，从而保证了较高的上色率和固色率。
本文实施例中涉及的份数均为重量份数，除专门标明浓度的溶液外，均折算成纯品计。
实施例1
1-氨基-4-(2′，4′，6′三甲基-3-氨基-5-磺基苯胺基)-蒽醌-2-磺酸双钠盐57．5份(0．1摩尔)加300份水溶解，冷至5℃以下，此蓝色基溶液备下步缩合用。
18．45份三聚氯氰(0．1摩尔)和100份冰、20份水混合，搅拌20分钟后，将上述蓝色基溶液加入，在0～5℃下反应，缩合过程中用150g／L碳酸钠溶液控制反应液为6-6．5，用色层法鉴定至蓝色基全部消失为终点。
18．5份4，4′-二氨基-二苯乙烯-2，2′二磺酸(0．05摩尔)加100mL水，用150g／L碳酸钠溶液调至溶液pH为7，使之全溶。将溶液倒入上述一次缩合液中，在5～10℃反应，缩合过程中用150g／L碳酸钠调节反应液pH为6．5-7，用色层法控制至4，4′二氨基-二苯乙烯2，2′二磺酸基本消失为终点。用氯化钠盐析，过滤，干燥。得到的艳蓝色染料具下述结构，染棉或麻织物呈鲜艳的红光蓝色和良好的耐湿处理及耐日晒牢度。
实施例2-5
分别用下列表1不同的二氨基芳胺作为桥基代替实施例1中的4，4′-二氨基-二苯乙烯-2，2′二磺酸钠盐溶液，得到了下列结构的艳蓝色活性染料：(合成方法同实施例1，桥基的用量均为0．05摩尔)。
实施例6
实施例1所得染料按3％o．w．f．用量，液比1∶20，在60g／L元明粉促染下，染予先煮练过的亚麻织物，95～98℃下用20g／L碳酸钠固色、水洗、皂煮、水洗、干燥。在麻上呈鲜艳的红光蓝色。固色率约70％。耐皂洗、汗渍、日晒。
表1用不同桥基合成的艳蓝色活性染料
Claims (3)
1．一类含双活性基的蒽醌型艳蓝色活性染料，其特征在于这类染料具有下列结构通式：
式中R=H或CH3X=Cl或FM=H，Na，K或NH4
2．一类含双活性基的蒽醌型艳蓝色活性染料的制备方法，其特征在于染料可用1-氨基-4(2′，6′-二甲基-3′-氨基-5′-磺基苯胺基)-蒽醌-2-磺酸或其4′-甲基衍生物先与卤代均三嗪，进行第一次缩合后，再与作为桥基的二氨基化合物进行第二次缩合反应而制得，第一次缩合温度为-5～10℃，pH=2～6；第二次缩合温度为0～50℃，pH=3～7，即：式中的R、X、Y、M与权利要求1中给出的定义相同。
3．一类含双活性基的蒽醌型艳蓝色活性染料的制备方法，其特征在于可用两分子卤代三嗪先与作为桥基的二氨基化合物缩合，然后再与两分子母体染料1-氨基-4-(2′，6′-二甲基-3′-氨基-5′-磺基苯胺基)蒽醌-2-磺酸或其4′-甲基衍生物反应而制得，第一次缩合温度为0～10℃，pH=2～6；第二次缩合温度为30～55℃，pH=5～7，即：
式中R、X、Y、M的含义同权利要求1。
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| CN1060493C true CN1060493C (zh) | 2001-01-10 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101007909B (zh) * | 2007-01-19 | 2010-05-19 | 武汉海图特先导材料有限公司 | 一种大分子量染料及其制备纯化方法以及使用该染料的喷墨墨水 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102337045B (zh) * | 2011-07-13 | 2014-03-26 | 丽源(湖北)科技有限公司 | 蓝色活性染料混合物及其制备和应用 |
| CN102504583B (zh) * | 2011-09-29 | 2014-10-08 | 刘卫斌 | 一种大红偶氮染料及其制备和使用 |
| CN102532937A (zh) * | 2011-12-15 | 2012-07-04 | 丽源(湖北)科技有限公司 | 一种蓝色活性染料及其制备和应用 |
| CN104693836B (zh) * | 2014-12-08 | 2017-07-21 | 大连理工大学 | 蒽醌偶氮型活性染料 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0625549A1 (de) * | 1993-05-17 | 1994-11-23 | Ciba-Geigy Ag | Reaktivfarbstoffe, Verfahren zu deren Herstellung und deren Verwendung |
| CN1095389A (zh) * | 1992-09-24 | 1994-11-23 | 山道士有限公司 | 纤维活性单偶氮铜配合物 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095389A (zh) * | 1992-09-24 | 1994-11-23 | 山道士有限公司 | 纤维活性单偶氮铜配合物 |
| EP0625549A1 (de) * | 1993-05-17 | 1994-11-23 | Ciba-Geigy Ag | Reaktivfarbstoffe, Verfahren zu deren Herstellung und deren Verwendung |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007909B (zh) * | 2007-01-19 | 2010-05-19 | 武汉海图特先导材料有限公司 | 一种大分子量染料及其制备纯化方法以及使用该染料的喷墨墨水 |
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| CN1170737A (zh) | 1998-01-21 |
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