WO2019223015A1 - 一种蓝色蒽醌活性分散染料的前驱体及其制备方法 - Google Patents

一种蓝色蒽醌活性分散染料的前驱体及其制备方法 Download PDF

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WO2019223015A1
WO2019223015A1 PCT/CN2018/088526 CN2018088526W WO2019223015A1 WO 2019223015 A1 WO2019223015 A1 WO 2019223015A1 CN 2018088526 W CN2018088526 W CN 2018088526W WO 2019223015 A1 WO2019223015 A1 WO 2019223015A1
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precursor
disperse dye
dyeing
temperature
blue
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PCT/CN2018/088526
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English (en)
French (fr)
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龙家杰
樊月
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苏州大学张家港工业技术研究院
苏州大学
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Priority to PCT/CN2018/088526 priority Critical patent/WO2019223015A1/zh
Publication of WO2019223015A1 publication Critical patent/WO2019223015A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/24—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings
    • C07C225/26—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings
    • C07C225/32—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings of condensed quinone ring systems formed by at least three rings
    • C07C225/34—Amino anthraquinones
    • 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
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/16—Amino-anthraquinones
    • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
    • C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
    • C09B1/32—Dyes with amino groups substituted by hydrocarbon radicals substituted by aryl groups
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a precursor of anthraquinone reactive disperse dye for supercritical CO 2 dyeing and its synthesis, and belongs to the technical field of dye synthesis.
  • Supercritical CO 2 dyeing technology is a new dyeing and finishing technology for dyeing textiles with supercritical CO 2 fluid as the dyeing medium. It began in the 1980s and is characterized by the absence of additional additives and no waste water generation. .
  • the dyeing technology of textiles in supercritical CO 2 fluid has entered the pilot scale of laboratory research and is expected to replace the traditional water bath process in the future. It greatly eases the demand for water, and also greatly reduces the discharge of sewage, which fundamentally solves the environmental pollution problem of the dyeing process.
  • the dyeing products obtained in the supercritical (: 0 2 body) have good leveling properties and can achieve the same effect as traditional water bath dyeing. After the dyeing is completed, the residual dye is in the form of powder.
  • the dye and CO 2 gas can be recycled. It is dry and does not require drying treatment, etc. Compared with the traditional water bath dyeing method, it can save energy by more than 20%, the dyeing speed is increased by 3 to 6 times compared with the water bath, and the processing time can be shortened by 1 to 2 hours.
  • active groups are directly introduced on the basis of existing disperse dyes, and there are fewer varieties. Therefore, how to diversify the structure of reactive disperse dyes and solve the problems of few types of reactive disperse dyes and poor applicability has become the key to breaking through the bottleneck.
  • the present invention addresses the shortcomings of the prior art, and provides an anthraquinone-structured active disperse dye precursor suitable for supercritical CO 2 fluid dyeing and a preparation method thereof.
  • the precursor can be prepared into a dye, which can solve the current problem.
  • Anthraquinone reactive disperse dyes have a single structure and few varieties, which cannot meet the shortcomings of natural fiber dyeing.
  • the dyes prepared from the precursors provided by the present invention are used in supercritical CO 2 anhydrous dyeing or traditional printing and dyeing processes. Natural fibers such as cotton, wool, and silk, and their blended textiles have good dyeing properties, the speed of dye diffusion and dyeing into the fiber is fast, the dyeing quality is good, and the manufacturing cost is low.
  • a technical solution to achieve the objective of the present invention is to provide a precursor of a blue anthraquinone active disperse dye, which has a general structural formula:
  • the characteristic absorption peak is in the range of 550 ⁇ 650nm; the maximum absorption wavelength is
  • the technical solution of the present invention further includes a method for preparing a precursor of the blue anthraquinone active disperse dye, and the steps are as follows:
  • the temperature was raised to 108 ° C. After stirring for 3 hours, the temperature was lowered to 95 ° C, copper acetate and piperidine catalyst were added, and the temperature was raised to 108 ° C.
  • the molar ratio of 1,4-dihydroxyanthraquinone to copper acetate was 1: 1.5 ⁇ 1: 6;
  • reaction equation involved in preparing the precursor of the blue anthraquinone reactive disperse dye of the present invention is as follows:
  • the precursor for a blue anthraquinone reactive disperse dye provided by the present invention contains a highly reactive amino group, and can react with an active group;
  • the raw materials were selected to change the length of the carbon chain, and blue anthraquinone reactive disperse dyes with different structures were obtained.
  • the precursor of the blue anthraquinone active disperse dye provided by the present invention has a simple structure and is easy to handle and control the reaction process; the amino group contained in the precursor structure has strong reactivity and can be used for supercritical (: 0 2) Dyeing of natural fibers in fluid dyeing or printing and dyeing of natural fibers and their blended fabrics in traditional printing and dyeing processes.
  • the anthraquinone reactive disperse dye obtained by using the precursor system of the anthraquinone reactive disperse dye provided by the present invention has good dyeing performance on natural fibers such as cotton, silk, wool, etc., and has good dyeing quality and low manufacturing cost. Has a good application prospect.
  • Example 1 is a UV-visible absorption spectrum of a precursor provided by Example 1 of the present invention measured with a U3010 ultraviolet spectrophotometer.
  • FIG. 2 is a spectrogram of infrared spectrum measurement of a precursor provided in Embodiment 1 of the present invention by using Fourier infrared spectrum.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • reaction with ethylenediamine is taken as an example, and the structural formula of the product is:
  • the specific method is as follows: take 0.24 g of 1,4-dihydroxyanthraquinone and 0.619 g of its leuco 1,4-diaminoanthraquinone and 0.462 m of 1 isobutanol in a three-necked flask, while placing 6.840 mL Aniline and 1 ml of ethylenediamine were dissolved in 15 ml of a 20% isobutanol solution, and kept under stirring at 60 ° C under nitrogen for 2 hours; after 2 hours of incubation, the temperature was raised to 108 ° C, and the mixture was boiled and stirred for 3 hours at this temperature; lowered to 95 ° C
  • Add the catalyst copper acetate and piperidine, the molar ratio of 1,4-dihydroxyanthraquinone to copper acetate is 1: 1.5, the proper amount of piperidine, heat to 108 ° C and boil for 3h; charge with oxygen for 3h; cool to room temperature, react
  • the concentration of the precursor 3x10 - at 5 mol / L conditions, measured by a spectrophotometer U3010 type precursor with an ultraviolet UV - visible absorption spectroscopy as a result see FIG. 1 .
  • the characteristic absorption peak of the blue anthraquinone reactive disperse dye precursor is in the range of 550 to 650 nm, the maximum absorption wavelength is 610 nm, and the precursor is blue.
  • the results in FIG. 1 indicate that the absorption band for the blue anthraquinone reactive disperse dye precursor provided in this embodiment is wide, and the color of the precursor is relatively dark.
  • FIG. 2 Fourier infrared spectroscopy is used to perform an infrared spectroscopy test on the precursor provided in this embodiment, and the results are shown in FIG. 2.
  • IR spectra FIG. 2, 3460.34cm - 1 and 1567.09cm - at 1 is an amino group and an imino group stretching vibration respectively; 2924.19cm - 1 at the peak of stretching vibration of methylene, 1644.58cm - 1 at the The carbonyl stretching vibration peak on the anthraquinone ring.
  • Embodiment 2 Embodiment 2:
  • 1,4-butanediamine is used as a reactant to prepare a blue anthraquinone active disperse dye precursor.
  • the specific steps are as follows:
  • the column was separated and purified by using petroleum ether and dichloromethane (l: 3, v / v) as eluents to obtain a blue solid, which is a blue anthraquinone reactive disperse dye precursor. Its structural formula is:
  • reaction with 1,6-hexanediamine is taken as an example to prepare a blue anthraquinone active disperse dye precursor.
  • the specific steps are as follows:
  • the column was separated and purified by using petroleum ether and dichloromethane (1: 3, v / v) as eluents to obtain a blue solid, which is a blue anthraquinone reactive disperse dye precursor with the structural formula:
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • Example 1 The precursor provided in Example 1 was used to prepare an anthraquinone reactive disperse dye with dichloromesinetriazine as an active group.
  • reaction formula is:
  • the blue anthraquinone reactive disperse dyes of the present embodiment provides for the supercritical (: 02 fluid, cotton, silk and wool dyeing process, specific process: taking knitted cotton, wool and silk fabrics each lg were placed in a supercritical (: 0 2 fluid dyeing kettle, the amount of reactive disperse dye was 2% omf, and an appropriate amount of catalyst was added. The temperature was maintained at 25 MPa and 130 ° C for 40 minutes, and the heating rate was 2 ° C / min. [0046] After the dyeing is finished, the fabric is taken out for testing of dyeing performance.
  • the anthraquinone active disperse dye provided in this embodiment has good dyeing performance on natural fibers such as cotton, silk, and wool, and has good dyeing quality.
  • the various dyeing fastness indexes are good, among them, the soaping fastness is good, the fading grade can reach 3 to 4 grades; the staining of other fabrics is less, and the staining grade can reach Grade 4 ⁇ 5; Fastness to dry rubbing can reach 3 ⁇ 4, Fastness to wet rubbing can reach 4 ⁇ 5.
  • the precursor for the anthraquinone reactive dye provided by the present invention has outstanding characteristics, the amino group in the structure is highly reactive, and it is easy to react with the reactive part; and the precursor structure is simple, the reaction process is easy to operate and control, and the manufacturing cost Low; using the precursor provided by the present invention to prepare anthraquinone reactive disperse dye, suitable for supercritical CO 2 fluid dyeing, especially for natural fibers such as cotton, silk, wool, etc., has good dyeing performance and dyeing quality, and therefore has good application prospect.

Abstract

一种用于蓝色蒽醌活性分散染料的前驱体及其制备方法。所述前驱体母体结构为蒽醌结构，且带有可与活性基反应的氨基，可用于制备蒽醌活性分散染料，其合成工艺简单，易于操作，制造成本低；制备的蒽醌活性分散染料可应用于超临界CO 2流体染色中天然纤维的染色及其混纺织物的染色加工，尤其是对棉、羊毛、蚕丝等天然纤维有很好的染色效果。

Description

一种蓝色蒽醌活性分散染料的前驱体及其制备方法 技术领域
[0001] 本发明涉及一种用于超临界 co 2染色的蒽醌活性分散染料的前驱体及其合成， 属于染料合成技术领域。
背景技术
[0002] 超临界 CO 2染色技术是以超临界 CO 2流体为染色介质对纺织品进行染色加工的 染整新技术， 始于 20世纪 80年代， 其特点是不需添加助剂， 也无废水产生。 纺 织品在超临界 C0 2流体中的染色技术， 已在实验室进入中试阶段的规模研究， 有 望在将来替代传统的水浴工艺。 它大大缓解了对水的需求量， 同时也大大减少 了污水的排放量， 从根本上解决了染色工艺对环境的污染问题。 在超临界（：0 2体 中得到的染色产品匀染性好， 能达到传统水浴染色的同等效果， 而且染色完成 后， 残余染料呈粉末状， 染料及 C0 2气体可回收利用， 且染色物呈干燥状态， 无 需烘干处理等。 与传统水浴染色法相比， 可节约能量达到 20%以上， 染色速度比 水浴提高 3〜 6倍， 加工时间可缩短 1〜 2h。
[0003] 涤纶等合成纤维的超临界染色技术相对成熟， 而天然纤维的染色还存在着诸多 问题， 适用的染料品种少。 活性分散染料由于自身的特殊性质， 可以较好的解 决天然纤维在超临界 CO 2流体中难以染色的问题， 且逐步朝着混纺织物超临界无 水染色应用方向发展。 为超临界 co 2无水染色开发专用染料， 尤其是应用于棉、 真丝、 羊毛等天然纤维的染料， 增加染料品种， 扩大适用范围， 是目前亟待解 决的问题。 在活性分散染料合成方面， 现有技术中关于蒽醌结构的报道较少， 方法也比较单一。 一般是在现有的分散染料的基础上直接引入活性基， 品种较 少。 因此， 如何使活性分散染料的结构多元化， 解决活性分散染料种类少、 应 用性不强等不足， 已成为突破瓶颈的关键。
发明概述
技术问题
问题的解决方案 技术解决方案
[0004] 本发明针对现有技术存在的不足， 提供一种适用于超临界 CO 2流体染色的蒽醌 结构的活性分散染料前驱体及其制备方法， 将该前驱体制备成染料， 可解决目 前蒽醌活性分散染料结构单一、 品种少， 无法满足天然纤维的染色所存在的不 足； 将以本发明提供的前驱体制备成的染料应用于超临界 CO 2无水染色或传统印 染加工中， 对棉、 毛、 真丝等天然纤维及其混纺织品具有良好的染色性能， 染 料向纤维内扩散和上染的速度快， 染色质量好， 制造成本低。
[0005] 实现本发明目的的技术方案是提供一种蓝色蒽醌活性分散染料的前驱体， 它的 结构通式为：
[0006]
Figure imgf000004_0001
[0007] 式中： 2。
[0008] 本发明所述的前驱体在浓度为 3x10 - 5
mol/L的二氯甲烷介质中， 特征吸收峰处于 550〜 650nm范围内； 最大吸收波长为
610nm°
[0009] 本发明技术方案还包括所述蓝色蒽醌活性分散染料的前驱体的制备方法， 其步 骤如下：
[0010] ( 1) 将 1,4 -二羟基蒽醌、 1,4 -二氨基蒽醌隐色体按摩尔比 1: 1.5〜 1:3加入到反应 容器中， 再将苯胺、 碳链长度! 1^2的二胺溶解于异丁醇溶液后加入到所述的反应 容器中， 得到反应液， 1,4 -二羟基蒽醌与苯胺的摩尔比为 1:2〜 1:7.5 ;
[0011] (2) 在氮气保护、 温度为 55〜 90°C的条件下， 搅拌反应液反应 2h后
， 升温至 108°C， 搅拌反应 3h后， 降温至 95°C， 加入乙酸铜和哌啶催化剂， 再升 温至 108°C; 1,4 -二羟基蒽醌与乙酸铜的摩尔比为 1: 1.5〜 1:6;
[0012] (3) 在温度为 108°C的条件下， 通入氧气， 氧化反应 2〜 5h; 冷却至室温后， 经分离纯化处理， 得到一种蓝色固体， 即为用于蒽醌活性分散染料的前驱体。
[0013] 本发明制备蓝色蒽醌活性分散染料的前驱体所涉及的反应方程式如下：
[0014]
Figure imgf000005_0001
[0015] 式中： 2。
[0016] 本发明提供的用于蓝色蒽醌活性分散染料的前驱体， 其结构中的碳链末端含有 反应性较强的氨基， 且可与活性基团进行反应； 在制备中， 可通过选择原料改 变碳链的长度， 得到不同结构的蓝色蒽醌型活性分散染料。
发明的有益效果
有益效果
[0017] 与现有技术相比， 本发明的有益效果在于：
[0018] 1.本发明提供的蓝色蒽醌活性分散染料的前驱体， 结构简单， 反应过程易于操 作和控制； 前驱体的结构中含有的氨基反应活性强， 可用于超临界（：0 2流体染色 中天然纤维的染色或传统印染加工中天然纤维及其混纺织物的印染加工。
[0019] 2.利用本发明提供的蒽醌活性分散染料的前驱体制得的蒽醌活性分散染料， 对 棉、 真丝、 羊毛等天然纤维具有很好的染色性能， 染色质量好， 制造成本低， 具有良好的应用前景。
对附图的简要说明
附图说明
[0020] 图 1为用 U3010紫外分光光度计测得本发明实施例 1提供的前驱体的紫外-可见吸 收光谱。
[0021] 图 2为采用傅里叶红外光谱对本发明实施例 1提供的前驱体进行红外光谱测试的 光谱图。
发明实施例 本发明的实施方式
[0022] 下面结合附图和实施例， 对本发明技术方案做进一步的具体描述。
[0023] 实施例 1 :
[0024] 本实施例以与乙二胺的反应为例， 得到产物的结构式为：
[0025]
Figure imgf000006_0001
[0026] 其中， n=2。
[0027] 具体方法是： 取 1,4 -二羟基蒽醌 0.24g及其隐色体 1,4 -二氨基蒽醌 0.619g和 0.462m 1异丁醇置于三口瓶中， 同时将 6.840mL苯胺和 lml乙二胺溶于 15ml20%的异丁醇 溶液中， 在 60°C氮气保护条件下保温搅拌 2h; 保温 2h后升温至 108°C在此温度下 沸腾搅拌 3h; 降温至 95°C加入催化剂乙酸铜和哌啶， 1,4 -二羟基蒽醌与乙酸铜的 摩尔比为 1: 1.5 , 哌啶适量， 升温至 108°C沸腾 3h; 充入氧气氧化 3h; 冷却至室温 ， 反应完成。 以石油醚和二氯甲烷 （1:3, v/v） 为洗脱剂进行层析柱分离纯化， 获 得蓝色固体， 产物即为蓝色蒽醌活性分散染料前驱体。
[0028] 以二氯甲烷作为溶剂， 在前驱体浓度为 3x10 - 5mol/L的条件下， 用 U3010型紫外 分光光度计测得前驱体的紫外-可见吸收光谱， 其结果参见图 1所示。 由图 1可以 看出， 采用二氯甲烷作为溶剂时， 蓝色蒽醌活性分散染料前驱体的特征吸收峰 处于 550〜 650nm范围内， 最大吸收波长为 610nm， 所述前驱体为蓝色。 图 1结果 表明， 本实施例提供的用于蓝色蒽醌活性分散染料前驱体的吸收带较宽， 前驱 体的颜色比较暗。
[0029] 采用傅里叶红外光谱对本实施例提供的前驱体进行红外光谱测试， 其结果参见 图 2所示。 图 2的红外光谱图中， 3460.34cm - 1和 1567.09cm -1处分别为氨基和亚氨 基的伸缩振动峰； 2924.19cm - 1处为亚甲基的伸缩振动峰， 1644.58cm -1处为的蒽 醌环上羰基伸缩振动峰。 [0030] 实施例 2:
[0031] 本实施例以 1,4 -丁二胺为反应物， 制备蓝色蒽醌活性分散染料前驱体， 具体步 骤如下：
[0032] 取 1,4 -二羟基蒽醌 0.24g及其隐色体 1,4 -二氨基蒽醌 0.619g和 0.462ml异丁醇置于 三口瓶中， 同时将6.84011^苯胺和1.5 1111 1,4 -丁二胺溶于 15ml20%的异丁醇溶液中 ， 在 60°C氮气保护条件下保温搅拌 2h; 保温 2h后升温至 108°C在此温度下沸腾搅 拌 3h; 降温至 95°C加入乙酸铜和哌啶催化剂， 1,4 -二羟基蒽醌与乙酸铜的摩尔比 为 1:3 , 哌啶适量， 升温至 108°C沸腾 3h; 充入氧气氧化 3h; 冷却至室温， 反应完 成。 以石油醚和二氯甲烷 ( l:3,v/v) 为洗脱剂进行层析柱分离纯化， 获得蓝色固 体， 即为蓝色蒽醌活性分散染料前驱体， 其结构式为：
[0033]
Figure imgf000007_0001
[0034] 其中， n=4。
[0035] 实施例 3:
[0036] 本实施例以与 1,6 -己二胺的反应为例， 制备蓝色蒽醌活性分散染料前驱体， 具 体步骤如下：
[0037] 取 1,4 -二羟基蒽醌 0.24g及其隐色体 1,4 -二氨基蒽醌 0.619g和 0.462ml异丁醇置于 三口瓶中， 同时将 6.840mL苯胺和 3.3 ml 1， 6 -己二胺溶于 15ml20%的异丁醇溶液 中， 在 60°C氮气保护条件下保温搅拌 2h; 保温 2h后升温至 108°C在此温度下沸腾 搅拌 3h; 降温至 95°C加入乙酸铜和哌啶催化剂， 1,4 -二羟基蒽醌与乙酸铜的摩尔 比为 1:5 , 哌啶适量， 升温至 108°C沸腾 3h; 充入氧气氧化 3h; 冷却至室温， 反应 完成。 以石油醚和二氯甲烷 ( 1:3, v/v) 为洗脱剂进行层析柱分离纯化， 获得蓝色 固体， 即为蓝色蒽醌活性分散染料前驱体， 结构式为：
[0038]
Figure imgf000008_0001
[0039] 其中， n=6。
[0040] 实施例 4:
[0041] 将实施例 1提供的前驱体用于制备以二氯均三嗪为活性基的蒽醌活性分散染料
， 其反应式为：
[0042]
Figure imgf000008_0002
[0043] 具体步骤如下：
[0044] 将 1.5mmol (0.277g) 三聚氯氰溶解于 5ml 1,4 -二氧六环中， 并将其置于低温反 应浴中， 温度控制在 0〜 5°C范围内。 取 lmmol (0.357g) 实施例 1提供的染料前 驱体溶于 15mL 1,4 -二氧六环中， lmmol (0.106g) Na 2C0 3溶于 15mL水， 两者同 时滴加至反应体系中， 搅拌 3h。 反应结束后， 加水 (约 350mL) 稀释， 析出絮状 沉淀， 抽滤， 水洗， 真空干燥， 获得蓝色固体。 再以石油醚和二氯甲烷 ( 1: 1, v/v ) 为洗脱剂进行层析柱分离纯化， 获得蓝色固体， 即为蒽醌活性分散染料， 分 离收率为 63%。
[0045] 将本实施例提供的蓝色蒽醌活性分散染料用于超临界 (：0 2流体中， 对棉、 羊毛 以及蚕丝进行染色处理， 具体工艺为： 取针织棉布、 羊毛和蚕丝织物各 lg分别 置于超临界 (：0 2流体染色釜中， 活性分散染料的用量为 2%omf， 并加入适量的催 化剂。 在 25MPa， 130°C的条件下保温 40min， 升温速率为 2°C/min。 [0046] 染色结束后取出织物用于染色性能检测， 结果表明， 本实施例提供的蒽醌活性 分散染料， 对棉、 真丝、 羊毛等天然纤维具有良好的染色性能， 染色质量好。 在织物上染色后， 各项染色牢度指标好， 其中， 耐皂洗牢度良好， 褪色级数可 达到 3〜 4级； 对其他织物的沾色情况均较少， 沾色级数可达到 4〜 5级； 耐干摩 擦牢度可达到 3〜 4级， 耐湿摩擦牢度可达到 4〜 5级。
[0047] 本发明提供的用于蒽醌活性染料的前驱体具有突出的特点， 结构中的氨基反应 性强， 易与活性部分反应； 且前驱体结构简单， 反应过程易于操作和控制， 制 造成本低； 利用本发明提供的前驱体制备蒽醌活性分散染料， 适用于超临界 co 2 流体染色， 尤其是对棉、 真丝、 羊毛等天然纤维， 染色性能和染色质量好， 因 此， 具有良好的应用前景。

Claims

权利要求书 [权利要求 1] 一种蓝色蒽醌活性分散染料的前驱体， 其特征在于它的结构通式为: 式中： 2。 [权利要求 2] 根据权利要求 1所述的一种蓝色蒽醌活性分散染料的前驱体， 其特征 在于： 所述前驱体在浓度为 3x10 - 5mol/L的二氯甲烷介质中， 特征吸 收峰处于 550〜 650nm范围内； 最大吸收波长为 610nm。 [权利要求 3] 一种如权利要求 1所述的蓝色蒽醌活性分散染料的前驱体的制备方法 ， 其特征在于包括如下步骤：
( 1) 将 1,4 -二羟基蒽醌、 1,4 -二氨基蒽醌隐色体按摩尔比 1: 1.5〜 1:3加 入到反应容器中， 再将苯胺、 碳链长度！ 1^2的二胺溶解于异丁醇溶液 后加入到所述的反应容器中， 得到反应液， 1,4 -二羟基蒽醌与苯胺的 摩尔比为 1:2〜 1:7.5 ;
(2) 在氮气保护、 温度为 55〜 90°C的条件下， 搅拌反应液反应 2h后 ， 升温至 108°C， 搅拌反应 3h后， 降温至 95°C， 加入乙酸铜和哌啶催 化剂， 再升温至 108°C; 1,4 -二羟基蒽醌与乙酸铜的摩尔比为 1: 1.5〜 1:
6；
(3) 在温度为 108°C的条件下， 通入氧气， 氧化反应 2〜 5h; 冷却至 室温后， 经分离纯化处理， 得到一种蓝色固体， 即为用于蒽醌活性分 散染料的前驱体。
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GB1475081A (en) * 1974-05-14 1977-06-01 Yorkshire Chemicals Ltd Water-soluble anthraquinone dyes
US4088661A (en) * 1974-12-20 1978-05-09 Sandoz Ltd. Cationic 1,4-diamino-anthraquinone dyestuffs
CH616441A5 (en) * 1973-07-02 1980-03-31 Sandoz Ag Process for the preparation of sulphonic acid group-free basic anthraquinone dyestuffs
US4503224A (en) * 1979-07-07 1985-03-05 Bayer Aktiengesellschaft Halogenotriazinyl dyestuffs
JPS62124152A (ja) * 1985-11-25 1987-06-05 Dainippon Printing Co Ltd 染料
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GB1074028A (en) * 1964-12-04 1967-06-28 Allied Chem Dyestuffs of the amino-anthraquinone series
CH616441A5 (en) * 1973-07-02 1980-03-31 Sandoz Ag Process for the preparation of sulphonic acid group-free basic anthraquinone dyestuffs
GB1475081A (en) * 1974-05-14 1977-06-01 Yorkshire Chemicals Ltd Water-soluble anthraquinone dyes
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