CN1170737A - 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 PDF

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CN1170737A
CN1170737A CN 97111397 CN97111397A CN1170737A CN 1170737 A CN1170737 A CN 1170737A CN 97111397 CN97111397 CN 97111397 CN 97111397 A CN97111397 A CN 97111397A CN 1170737 A CN1170737 A CN 1170737A
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condensation
dyestuff
anthraquinone
amino
dye
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吴祖望
王桂娟
林莉
李鹏
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Dalian University of Technology
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02Reactive 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
    • C09B62/04Reactive 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
    • C09B62/06Anthracene 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,具有右列通式结构,这类染料在棉、麻等纤维素纤维或毛、丝等蛋由质纤维上染色后,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

一类含双活性基的蒽醌型艳蓝色活性染料
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):
Figure A9711139700051
Eur.Pat.584045例28
Figure A9711139700052
                        Eur.Pat 625549例1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:
Figure A9711139700061
式中R=H或CH3X=Cl或F
M=H,Na,K或NH4
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:
式中R,X,Y,M的含义同前。
(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:
式中R,X,Y,M的含义同前。
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。
Figure A9711139700091
                    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 (2)

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:
Figure A9711139700021
式中R=H或CH3X=Cl或F
Figure A9711139700022
M=H,Na,K或NH4
该类染料结构的特点为:
(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,由于2′,6′位存在空间障碍,使芳胺与蒽醌环的共平面性遭到破坏,从而赋予被染织物具有艳丽的红光蓝色和较好的耐晒坚牢度;
(2)由于染料结构上有亲和力和反应性较强的两个反应一致的卤代均三嗪活性基,使染料具有较高的反应率和湿处理牢度;
(3)由于以相对刚性较大的芳香二胺作为桥基,从而保证染料具有较好的直接性及较高的上色率和固色率。
2.根据权利要求1所述的活性染料,其特征在于染料的合成既可由染料母体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(I)先与卤代均三嗪,在-5~10℃,pH=2~6进行第一次缩合,再与作为桥基的芳香二胺在0~5℃,pH=3~7进行第二次缩合而制得;又可用两分子卤代均三嗪先与芳香二胺在0~10℃,pH=2~6进行第一次缩合,然后再与两分子母体染料(I)在30~55℃,pH=5~7进行第二次缩合而制得。
CN97111397A 1997-06-18 1997-06-18 一类含双活性基的蒽醌型艳蓝色活性染料 Expired - Fee Related CN1060493C (zh)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102337045A (zh) * 2011-07-13 2012-02-01 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
CN102504583A (zh) * 2011-09-29 2012-06-20 丽源(湖北)科技有限公司 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
CN104693836A (zh) * 2014-12-08 2015-06-10 大连理工大学 蒽醌偶氮型活性染料

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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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GB2270923B (en) * 1992-09-24 1995-11-08 Sandoz Ltd Fibre-reactive monoazo copper complexes
MY116477A (en) * 1993-05-17 2004-02-28 Ciba Sc Holding Ag Reactive dyes, processes for their preparation and their use

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102337045A (zh) * 2011-07-13 2012-02-01 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
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
CN102504583A (zh) * 2011-09-29 2012-06-20 丽源(湖北)科技有限公司 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
CN104693836A (zh) * 2014-12-08 2015-06-10 大连理工大学 蒽醌偶氮型活性染料

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