CN116253856A - Water-based polyurethane wet rubbing fastness improver with catechol group and preparation method thereof - Google Patents
Water-based polyurethane wet rubbing fastness improver with catechol group and preparation method thereofDownload PDFInfo
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- CN116253856A CN116253856ACN202310222813.4ACN202310222813ACN116253856ACN 116253856 ACN116253856 ACN 116253856ACN 202310222813 ACN202310222813 ACN 202310222813ACN 116253856 ACN116253856 ACN 116253856A
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Classifications
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5285—Polyurethanes; Polyurea; Polyguanides
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
Translated fromChinese技术领域technical field
本发明涉及纺织印染助剂技术领域，具体涉及一种具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂及其制备方法。The invention relates to the technical field of textile printing and dyeing auxiliaries, in particular to a water-based polyurethane wet rubbing fastness improving agent with catechol groups and a preparation method thereof.
背景技术Background technique
活性染料具有色泽鲜艳、色谱全、匀染性好、使用简便且廉价等特点，广泛应用于纤维素纤维的染色，但是活性染料染深浓色织物的湿摩擦牢度较低。因此，研究用于固色的新型绿色环保纺织助剂已成为热点。近年来，水性聚氨酯类活性染料湿摩擦牢度提升剂以其无毒无害的特点逐渐成为湿摩擦牢度提升剂的主要产品。Reactive dyes have the characteristics of bright color, complete chromatogram, good level dyeing, easy to use and low cost, etc., and are widely used in the dyeing of cellulose fibers, but the wet rubbing fastness of reactive dyes dyed deep-colored fabrics is low. Therefore, it has become a hot spot to study new green environmental protection textile auxiliaries for color fixing. In recent years, water-based polyurethane reactive dye wet rubbing fastness improver has gradually become the main product of wet rubbing fastness improver due to its non-toxic and harmless characteristics.
目前水性聚氨酯类湿摩擦牢度提升剂主要依赖于在织物表面形成一层高分子保护膜，来防止染料在摩擦时掉落。例如专利申请CN 113563560 A公开了一种水性聚氨酯湿摩擦色牢度提升剂及制备方法，它是由聚酯多元醇、氨基改性硅油、小分子多元醇、多异氰酸酯、胺类扩链剂、氨基磺酸盐型亲水单体在催化加热条件下聚合而成，经其处理的织物湿摩擦牢度可提升1级，并且水性聚氨酯湿摩擦色牢度提升剂乳液具有优异的分散稳定性。又如申请专利CN 112341597 A公开了一种水性聚氨酯湿摩擦色牢度提升剂的制备方法，以异氟尔酮二异氰酸酯、甲苯2,4-二异氰酸酯、聚己内酯三元醇、一缩二乙二醇、二羟甲基丁酸为主要原料，制备了具有交联网状结构的水性聚氨酯，可有效提高织物的湿摩擦牢度1级。上述技术方案单纯通过提升交联密度增加成膜性，虽然会使织物湿摩擦牢度有所提升，但是会导致其手感变硬，破坏织物自身手感风格。At present, water-based polyurethane wet rubbing fastness improvers mainly rely on the formation of a polymer protective film on the surface of the fabric to prevent dyes from falling off during rubbing. For example, patent application CN 113563560 A discloses a water-based polyurethane wet rubbing color fastness improving agent and a preparation method thereof, which is composed of polyester polyol, amino-modified silicone oil, small molecule polyol, polyisocyanate, amine chain extender, The sulfamate-type hydrophilic monomer is polymerized under catalytic heating conditions, and the wet rubbing fastness of the treated fabric can be improved by one level, and the water-based polyurethane wet rubbing color fastness improver emulsion has excellent dispersion stability. Another example is the patent application CN 112341597 A which discloses a preparation method of a water-based polyurethane wet rubbing color fastness improving agent, using isophorone diisocyanate, toluene 2,4-diisocyanate, polycaprolactone triol, Diethylene glycol and dimethylol butyric acid were used as the main raw materials to prepare water-based polyurethane with a cross-linked network structure, which can effectively improve the wet rubbing fastness of the fabric to grade 1. The above-mentioned technical solution simply increases the film-forming property by increasing the crosslinking density, although the wet rubbing fastness of the fabric will be improved, but it will cause its hand feeling to become hard and destroy the fabric's own hand feel style.
发明内容Contents of the invention
本发明的目的是为了克服现有的活性染料染色中染深浓色织物时的湿摩擦牢度差的问题，提供一种具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂及其制备方法。The purpose of the present invention is to provide a kind of water-based polyurethane wet rubbing fastness improving agent with catechol group and its Preparation.
为了实现上述目的，本发明一方面提供一种制备具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂的方法，所述方法包括以下步骤：In order to achieve the above object, the present invention provides a method for preparing a water-based polyurethane wet rubbing fastness improving agent with catechol groups, the method may further comprise the steps:
(1)原料准备：所述原料含有聚合单体、有机溶剂、催化剂和中和剂；其中，聚合单体包括二异氰酸酯、扩链剂A、聚醚二元醇和扩链剂B；(1) Raw material preparation: the raw material contains polymerized monomers, organic solvents, catalysts and neutralizers; wherein, the polymerized monomers include diisocyanate, chain extender A, polyether diol and chain extender B;
二异氰酸酯为异佛尔酮二异氰酸酯或1,6-己二异氰酸酯；The diisocyanate is isophorone diisocyanate or 1,6-hexamethylene diisocyanate;
扩链剂A为N-(3,4-二羟基苯基)二乙醇胺、N-(3,4-二羟基苯基)二异丙醇胺或N-(3,4-二羟基苯基)二正丁醇胺；Chain extender A is N-(3,4-dihydroxyphenyl)diethanolamine, N-(3,4-dihydroxyphenyl)diisopropanolamine or N-(3,4-dihydroxyphenyl) Di-n-butanolamine;
聚醚二元醇为聚四氢呋喃二醇；Polyether diol is polytetrahydrofuran diol;
扩链剂B为N-甲基二乙醇胺；Chain extender B is N-methyldiethanolamine;
中和剂为醋酸；The neutralizing agent is acetic acid;
聚合单体中各组分的摩尔份数为：扩链剂A为0.5-1.5、二异氰酸酯为4.5、聚醚二元醇为2.4-2.7，扩链剂A与扩链剂B的摩尔分数之和为1.7；The mole fraction of each component in the polymerized monomer is: chain extender A is 0.5-1.5, diisocyanate is 4.5, polyether diol is 2.4-2.7, the mole fraction of chain extender A and chain extender B is and is 1.7;
中和剂的用量为扩链剂A和扩链剂B的重量之和的60-80重量％；The amount of neutralizing agent is 60-80% by weight of the sum of the weight of chain extender A and chain extender B;
(2)脱水处理：将聚醚二元醇加入到反应器中进行脱水处理；(2) Dehydration treatment: adding polyether glycol into the reactor for dehydration treatment;
(3)预聚：将二异氰酸酯、脱水处理后的聚醚二元醇、部分有机溶剂和催化剂进行反应，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂预聚体；(3) Prepolymerization: react diisocyanate, polyether diol after dehydration treatment, part of organic solvent and catalyst to prepare water-based polyurethane wet rubbing fastness improving agent prepolymer with catechol groups;
(4)扩链：将具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂预聚体、扩链剂A、扩链剂B和剩余有机溶剂进行反应，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂分子；(4) Chain extension: react the water-based polyurethane wet rubbing fastness improving agent prepolymer with catechol groups, chain extender A, chain extender B and the remaining organic solvents to obtain catechol-containing Molecules of water-based polyurethane wet rubbing fastness enhancer;
(5)成品化：将具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂分子与中和剂混合，然后与水混合，脱除有机溶剂，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂。(5) Finished product: mix the water-based polyurethane wet rubbing fastness improving agent molecules with catechol groups with neutralizing agent, then mix with water, remove organic solvents, and obtain catechol groups Water-based polyurethane wet rubbing fastness improver.
优选地，步骤(2)中，脱水处理的条件包括：温度为100-110℃，真空度为-0.08MPa至-0.1MPa。Preferably, in step (2), the conditions for the dehydration treatment include: a temperature of 100-110° C., and a vacuum of -0.08 MPa to -0.1 MPa.
优选地，步骤(3)的具体过程包括：Preferably, the concrete process of step (3) comprises:
(3.1)将二异氰酸酯和总量20-30重量％的有机溶剂投入反应器，升温至70-80℃；(3.1) Put diisocyanate and a total amount of 20-30% by weight of organic solvent into the reactor, and heat up to 70-80°C;
(3.2)维持体系温度为70-80℃，投入脱水处理后的聚醚二元醇；(3.2) Maintain the system temperature at 70-80°C, and put in the dehydration-treated polyether glycol;
(3.3)维持温度为70-80℃，保温反应50-60min，然后在10-20min内投入催化剂；(3.3) Maintain the temperature at 70-80°C, keep the temperature for 50-60 minutes, and then put in the catalyst within 10-20 minutes;
(3.4)升温至80-90℃，保温反应60-90min，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂的预聚体。(3.4) Raise the temperature to 80-90° C., heat-preserve and react for 60-90 minutes, and prepare a prepolymer of a water-based polyurethane wet rubbing fastness improving agent having a catechol group.
优选地，步骤(4)的具体过程包括：Preferably, the concrete process of step (4) comprises:
(4.1)控制反应温度为50-60℃，将扩链剂A、扩链剂B和剩余有机溶剂加入到步骤(3)的得到的物料中；(4.1) Control the reaction temperature to be 50-60°C, and add chain extender A, chain extender B and the remaining organic solvent to the obtained material in step (3);
(4.2)升温并控制反应温度为60-65℃，搅拌反应90-120min，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂分子。(4.2) Raise the temperature and control the reaction temperature to 60-65° C., and stir for 90-120 minutes to prepare the water-based polyurethane wet rubbing fastness improving agent molecules with catechol groups.
优选地，步骤(5)的具体过程包括：Preferably, the concrete process of step (5) comprises:
(5.1)向步骤(4)得到的物料中加入中和剂并搅拌30-40min；(5.1) Add neutralizing agent to the material obtained in step (4) and stir for 30-40min;
(5.2)加水混合30-60min，在不高于100℃的条件下真空干燥至固含量≥30％，得到具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂。(5.2) Add water and mix for 30-60 minutes, and vacuum-dry under the condition of not higher than 100° C. until the solid content is ≥ 30%, to obtain a water-based polyurethane wet rubbing fastness improving agent with catechol groups.
优选地，聚四氢呋喃二醇的分子量为1000-4000。Preferably, the polytetrahydrofuran diol has a molecular weight of 1000-4000.
优选地，有机溶剂选自丙酮、甲乙酮和乙基吡咯烷酮中的一种。Preferably, the organic solvent is selected from one of acetone, methyl ethyl ketone and ethyl pyrrolidone.
优选地，催化剂为辛酸亚锡或二月桂酸二丁基锡。Preferably, the catalyst is stannous octoate or dibutyltin dilaurate.
优选地，催化剂的用量为聚合单体总重量的0.04-0.05重量％。Preferably, the catalyst is used in an amount of 0.04-0.05% by weight based on the total weight of polymerized monomers.
本发明第二方面提供前文所述的方法制备的具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂。The second aspect of the present invention provides the water-based polyurethane wet rubbing fastness improving agent having a catechol group prepared by the aforementioned method.
与现有技术相比，本发明所述的方法具有以下优点和特点：Compared with prior art, method described in the present invention has following advantages and characteristics:
1、在本发明中，从仿生学角度出发，模拟贻贝中对水环境中粘附性能起到关键作用的邻苯二酚结构，引入到水性聚氨酯分子结构中，可以得到具有优异湿粘接性能的水性聚氨酯湿摩擦牢度提升剂，可以应用于织物的活性染料固色工艺过程中，提高水解的活性染料与织物之间的湿粘接强度，从而得到具有优异湿摩擦牢度的织物。1. In the present invention, from the perspective of bionics, the catechol structure that plays a key role in the adhesion performance in the water environment is simulated in mussels, and introduced into the molecular structure of water-based polyurethane to obtain excellent wet adhesion. The high-performance water-based polyurethane wet rubbing fastness improver can be used in the reactive dye fixing process of fabrics to improve the wet bonding strength between hydrolyzed reactive dyes and fabrics, thereby obtaining fabrics with excellent wet rubbing fastness.
2、在本发明中，原料中使用了含有邻苯二酚基团的扩链剂，进而对水性聚氨酯成膜性需求降低，因此对整理后织物的手感风格影响较少。2. In the present invention, a chain extender containing a catechol group is used in the raw material, thereby reducing the demand for film-forming property of the water-based polyurethane, so it has less influence on the handle style of the finished fabric.
具体实施方式Detailed ways
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.
本发明的发明人在研究过程中发现，使用具有邻苯二酚基团的扩链剂对水性聚氨酯预聚体进行扩链，可以将邻苯二酚基团引入了水性聚氨酯分子中，从而使得产品具有更好的湿粘接性能，进而表现出更好的湿摩擦牢度。基于此，完成了本发明。The inventors of the present invention found in the course of research that using a chain extender with a catechol group to extend the chain of the water-based polyurethane prepolymer can introduce a catechol group into the water-based polyurethane molecule, thereby making The product has better wet bonding performance, which in turn shows better wet rubbing fastness. Based on this, the present invention has been accomplished.
本发明第一方面提供一种制备具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂的方法，所述方法包括以下步骤：A first aspect of the present invention provides a method for preparing a water-based polyurethane wet rubbing fastness improving agent with catechol groups, the method comprising the following steps:
(1)原料准备：所述原料含有聚合单体、有机溶剂、催化剂和中和剂；其中，聚合单体包括二异氰酸酯、扩链剂A、聚醚二元醇和扩链剂B；(1) Raw material preparation: the raw material contains polymerized monomers, organic solvents, catalysts and neutralizers; wherein, the polymerized monomers include diisocyanate, chain extender A, polyether diol and chain extender B;
二异氰酸酯为异佛尔酮二异氰酸酯或1,6-己二异氰酸酯；The diisocyanate is isophorone diisocyanate or 1,6-hexamethylene diisocyanate;
扩链剂A为N-(3,4-二羟基苯基)二乙醇胺、N-(3,4-二羟基苯基)二异丙醇胺或N-(3,4-二羟基苯基)二正丁醇胺；Chain extender A is N-(3,4-dihydroxyphenyl)diethanolamine, N-(3,4-dihydroxyphenyl)diisopropanolamine or N-(3,4-dihydroxyphenyl) Di-n-butanolamine;
聚醚二元醇为聚四氢呋喃二醇；Polyether diol is polytetrahydrofuran diol;
扩链剂B为N-甲基二乙醇胺；Chain extender B is N-methyldiethanolamine;
中和剂为醋酸；The neutralizing agent is acetic acid;
聚合单体中各组分的摩尔份数为：扩链剂A为0.5-1.5、二异氰酸酯为4.5、聚醚二元醇为2.4-2.7，扩链剂A与扩链剂B的摩尔分数之和为1.7；The mole fraction of each component in the polymerized monomer is: chain extender A is 0.5-1.5, diisocyanate is 4.5, polyether diol is 2.4-2.7, the mole fraction of chain extender A and chain extender B is and is 1.7;
中和剂的用量为扩链剂A和扩链剂B的重量之和的60-80重量％；The amount of neutralizing agent is 60-80% by weight of the sum of the weight of chain extender A and chain extender B;
(2)脱水处理：将聚醚二元醇加入到反应器中进行脱水处理；(2) Dehydration treatment: adding polyether glycol into the reactor for dehydration treatment;
(3)预聚：将二异氰酸酯、脱水处理后的聚醚二元醇、部分有机溶剂和催化剂进行反应，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂预聚体；(3) Prepolymerization: react diisocyanate, polyether diol after dehydration treatment, part of organic solvent and catalyst to prepare water-based polyurethane wet rubbing fastness improving agent prepolymer with catechol groups;
(4)扩链：将具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂预聚体、扩链剂A、扩链剂B和剩余有机溶剂进行反应，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂分子；(4) Chain extension: react the water-based polyurethane wet rubbing fastness improving agent prepolymer with catechol groups, chain extender A, chain extender B and the remaining organic solvents to obtain catechol-containing Molecules of water-based polyurethane wet rubbing fastness enhancer;
(5)成品化：将具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂分子与中和剂混合，然后与水混合，脱除有机溶剂，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂。(5) Finished product: mix the water-based polyurethane wet rubbing fastness improving agent molecules with catechol groups with neutralizing agent, then mix with water, remove organic solvents, and obtain catechol groups Water-based polyurethane wet rubbing fastness improver.
在本发明所述的方法中，N-(3,4-二羟基苯基)二乙醇胺、N-(3,4-二羟基苯基)二异丙醇胺和N-(3,4-二羟基苯基)二正丁醇胺均可以通过实验室自制获得，例如可以参考发明专利CN110028467B中记载的方法进行制备。In the method of the present invention, N-(3,4-dihydroxyphenyl)diethanolamine, N-(3,4-dihydroxyphenyl)diisopropanolamine and N-(3,4-dihydroxyphenyl) Hydroxyphenyl)di-n-butanolamine can be obtained by laboratory self-made, for example, it can be prepared by referring to the method described in the invention patent CN110028467B.
在本发明中，N-(3,4-二羟基苯基)二乙醇胺的结构式如式(1)所示；In the present invention, the structural formula of N-(3,4-dihydroxyphenyl)diethanolamine is shown in formula (1);
N-(3,4-二羟基苯基)二异丙醇胺的结构式如式(2)所示；The structural formula of N-(3,4-dihydroxyphenyl) diisopropanolamine is shown in formula (2);
N-(3,4-二羟基苯基)二正丁醇胺的结构式如式(3)所示；The structural formula of N-(3,4-dihydroxyphenyl) di-n-butanolamine is shown in formula (3);
在具体的实施方式中，聚合单体中各组分的摩尔份数可以为：扩链剂A可以为0.5、0.6、0.7、0.8、0.9、1、1.1、1.2、1.3、1.4或1.5、二异氰酸酯为4.5、聚醚二元醇可以为2.4、2.5、2.6或2.7，扩链剂A与扩链剂B的摩尔分数之和为1.7。In a specific embodiment, the mole fraction of each component in the polymerized monomer can be: chain extender A can be 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4 or 1.5, two The isocyanate is 4.5, the polyether diol can be 2.4, 2.5, 2.6 or 2.7, and the sum of the mole fractions of chain extender A and chain extender B is 1.7.
在具体的实施方式中，中和剂的用量可以为扩链剂A和扩链剂B的重量之和的60重量％、65重量％、70重量％、75重量％或80重量％。In a specific embodiment, the amount of neutralizing agent can be 60 wt%, 65 wt%, 70 wt%, 75 wt% or 80 wt% of the sum of the weight of chain extender A and chain extender B.
在优选的实施方式中，步骤(2)中，脱水处理的条件包括：温度为100-110℃，真空度为-0.08MPa至-0.1MPa；具体的，脱水处理时的温度可以为100℃、101℃、10℃、103℃、104℃、105℃、106℃、107℃、108℃、109℃或110℃，真空度可以为-0.08MPa、-0.09MPa或-0.1MPa。In a preferred embodiment, in step (2), the conditions for dehydration treatment include: the temperature is 100-110°C, and the degree of vacuum is -0.08MPa to -0.1MPa; specifically, the temperature during dehydration treatment can be 100°C, 101°C, 10°C, 103°C, 104°C, 105°C, 106°C, 107°C, 108°C, 109°C or 110°C, the vacuum can be -0.08MPa, -0.09MPa or -0.1MPa.
优选地，步骤(3)的具体过程包括：Preferably, the concrete process of step (3) comprises:
(3.1)将二异氰酸酯和总量20-30重量％的有机溶剂投入反应器，升温至70-80℃；(3.1) Put diisocyanate and a total amount of 20-30% by weight of organic solvent into the reactor, and heat up to 70-80°C;
(3.2)维持体系温度为70-80℃，投入脱水处理后的聚醚二元醇；(3.2) Maintain the system temperature at 70-80°C, and put in the dehydration-treated polyether glycol;
(3.3)维持温度为70-80℃，保温反应50-60min，然后在10-20min内投入催化剂；(3.3) Maintain the temperature at 70-80°C, keep the temperature for 50-60 minutes, and then put in the catalyst within 10-20 minutes;
(3.4)升温至80-90℃，保温反应60-90min，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂的预聚体。(3.4) Raise the temperature to 80-90° C., heat-preserve and react for 60-90 minutes, and prepare a prepolymer of a water-based polyurethane wet rubbing fastness improving agent having a catechol group.
在本发明所述的方法中，在步骤(3.2)中，在70-80℃的温度下投入脱水处理后的聚醚二元醇；优选地，在10min内完成聚醚二元醇的投入过程。In the method of the present invention, in step (3.2), the polyether glycol after the dehydration treatment is put into at a temperature of 70-80°C; preferably, the process of putting in the polyether glycol is completed within 10min .
在具体的实施方式中，在步骤(3.3)中，反应温度可以为70℃、71℃、72℃、73℃、74℃、75℃、76℃、77℃、78℃、79℃或80℃；保温反应时间可以为50min、52min、54min、56min、58min或60min。In a specific embodiment, in step (3.3), the reaction temperature can be 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C or 80°C ; The heat preservation reaction time can be 50min, 52min, 54min, 56min, 58min or 60min.
在具体的实施方式中，在步骤(3.4)中，升温至80-90℃，保温反应60-90min，即在80-90℃的温度下反应60-90min；具体的，反应的温度可以为80℃、81℃、83℃、84℃、85℃、86℃、87℃、88℃、89℃或90℃，反应的时间可以为60min、65min、70min、75min、80min、85min或90min。In a specific embodiment, in step (3.4), the temperature is raised to 80-90° C., and the heat preservation reaction is carried out for 60-90 minutes, that is, the reaction is carried out at a temperature of 80-90° C. for 60-90 minutes; specifically, the reaction temperature can be 80 °C, 81 °C, 83 °C, 84 °C, 85 °C, 86 °C, 87 °C, 88 °C, 89 °C or 90 °C, the reaction time can be 60 min, 65 min, 70 min, 75 min, 80 min, 85 min or 90 min.
优选地，步骤(4)的具体过程包括：Preferably, the concrete process of step (4) comprises:
(4.1)控制反应温度为50-60℃，将扩链剂A、扩链剂B和剩余有机溶剂加入到步骤(3)的得到的物料中；(4.1) Control the reaction temperature to be 50-60°C, and add chain extender A, chain extender B and the remaining organic solvent to the obtained material in step (3);
(4.2)升温并控制反应温度为60-65℃，搅拌反应90-120min，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂分子。(4.2) Raise the temperature and control the reaction temperature to 60-65° C., and stir for 90-120 minutes to prepare the water-based polyurethane wet rubbing fastness improving agent molecules with catechol groups.
在具体的实施方式中，在步骤(4.2)中，反应温度可以为60℃、61℃、62℃、63℃、64℃或65，搅拌反应时间可以为90min、95min、100min、105min、110min、115min或120min。In a specific embodiment, in step (4.2), the reaction temperature can be 60°C, 61°C, 62°C, 63°C, 64°C or 65°C, and the stirring reaction time can be 90min, 95min, 100min, 105min, 110min, 115min or 120min.
优选地，步骤(5)的具体过程包括：Preferably, the concrete process of step (5) comprises:
(5.1)向步骤(4)得到的物料中加入中和剂并搅拌30-40min；(5.1) Add neutralizing agent to the material obtained in step (4) and stir for 30-40min;
(5.2)加水混合30-60min，在不高于100℃的条件下真空干燥至固含量≥30％，得到具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂。(5.2) Add water and mix for 30-60 minutes, and vacuum-dry under the condition of not higher than 100° C. until the solid content is ≥ 30%, to obtain a water-based polyurethane wet rubbing fastness improving agent with catechol groups.
在具体的实施方式中，在步骤(5.2)中，加水混合进行乳化的过程中，对于水的用量没有特殊的要求，能够实现充分乳化即可。In a specific embodiment, in step (5.2), in the process of adding water and mixing for emulsification, there is no special requirement for the amount of water, as long as sufficient emulsification can be achieved.
在具体的实施方式中，在步骤(5.2)中，采用真空干燥的方式脱除有机溶剂，并控制真空干燥后的物料的固含量≥30％。In a specific embodiment, in step (5.2), vacuum drying is used to remove the organic solvent, and the solid content of the vacuum-dried material is controlled to be ≥ 30%.
在优选的实施方式中，聚四氢呋喃二醇的分子量为1000-4000。In a preferred embodiment, the polytetrahydrofuran diol has a molecular weight of 1000-4000.
在具体的实施方式中，聚四氢呋喃二醇的分子量可以为1000、2000、3000或4000。In a specific embodiment, the polytetrahydrofuran diol may have a molecular weight of 1000, 2000, 3000 or 4000.
在本发明所述的方法中，对于有机溶剂的用量没有特殊的要求，可使聚合反应正常进行即可。In the method of the present invention, there is no special requirement on the amount of the organic solvent, as long as the polymerization reaction can proceed normally.
在优选的实施方式中，对于有机溶剂的选择没有特殊的要求，可以使反应正常进行即可。在具体的实施方式中，有机溶剂选自丙酮、甲乙酮和乙基吡咯烷酮中的一种。In a preferred embodiment, there is no special requirement for the selection of the organic solvent, as long as the reaction can proceed normally. In a specific embodiment, the organic solvent is selected from one of acetone, methyl ethyl ketone and ethyl pyrrolidone.
在优选的实施方式中，所述催化剂为本领域常规使用的聚合催化剂，具体的，催化剂为辛酸亚锡或二月桂酸二丁基锡。In a preferred embodiment, the catalyst is a polymerization catalyst commonly used in the art, specifically, the catalyst is stannous octoate or dibutyltin dilaurate.
在优选的实施方式中，催化剂的用量为聚合单体总重量的0.04-0.05重量％；具体的，可以为0.04重量％、0.041重量％、0.042重量％、0.043重量％、0.044重量％、0.045重量％、0.046重量％、0.047重量％、0.048重量％、0.049重量％或0.05重量％。In a preferred embodiment, the amount of the catalyst is 0.04-0.05% by weight of the total weight of the polymerized monomers; specifically, it can be 0.04% by weight, 0.041% by weight, 0.042% by weight, 0.043% by weight, 0.044% by weight, 0.045% by weight %, 0.046% by weight, 0.047% by weight, 0.048% by weight, 0.049% by weight or 0.05% by weight.
本发明第二方面提供前文所述的方法制备的具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂。The second aspect of the present invention provides the water-based polyurethane wet rubbing fastness improving agent having a catechol group prepared by the aforementioned method.
以下将通过实施例对本发明进行详细描述，但本发明的保护范围并不局限于此。The present invention will be described in detail through examples below, but the protection scope of the present invention is not limited thereto.
表1Table 1
实施例1Example 1
(1)原料准备，所述原料的主要成分和用量如表1所示；(1) Raw material preparation, the main components and consumption of said raw material are as shown in Table 1;
(2)脱水处理：将聚醚二元醇加入到反应器中进行脱水处理，脱水处理温度为108℃，真空度为-0.09MPa；(2) Dehydration treatment: Add polyether glycol into the reactor for dehydration treatment, the dehydration treatment temperature is 108°C, and the vacuum degree is -0.09MPa;
(3)预聚：将二异氰酸酯、脱水处理后的聚醚二元醇、部分有机溶剂和催化剂进行反应，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂预聚体；(3) Prepolymerization: react diisocyanate, polyether diol after dehydration treatment, part of organic solvent and catalyst to prepare water-based polyurethane wet rubbing fastness improving agent prepolymer with catechol groups;
(3.1)将二异氰酸酯和总量30重量％的有机溶剂投入反应器，升温至72℃；(3.1) Put diisocyanate and a total amount of 30% by weight of organic solvent into the reactor, and heat up to 72°C;
(3.2)维持体系温度为78℃，在10min内投入脱水处理后的聚醚二元醇；(3.2) Maintain the system temperature at 78°C, and put in the dehydration-treated polyether diol within 10 minutes;
(3.3)维持温度为78℃，保温反应560min，然后在10min内匀速投入催化剂；(3.3) Maintain the temperature at 78°C, keep the temperature for 560 minutes, and then put in the catalyst at a constant speed within 10 minutes;
(3.4)升温至85℃，保温反应90min，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂的预聚体；(3.4) heating up to 85° C., and heat preservation reaction for 90 minutes to prepare a prepolymer of a water-based polyurethane wet rubbing fastness improving agent having a catechol group;
(4)扩链：将具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂预聚体、扩链剂A、扩链剂B、剩余有机溶剂进行反应，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂分子；(4) Chain extension: react the water-based polyurethane wet rubbing fastness improving agent prepolymer with catechol groups, chain extender A, chain extender B, and the remaining organic solvents to obtain catechol-containing Molecules of water-based polyurethane wet rubbing fastness enhancer;
(4.1)控制反应温度为55℃，将扩链剂A、扩链剂B和剩余有机溶剂加入到步骤(3.4)的得到的物料中；(4.1) Control the reaction temperature to 55° C., and add chain extender A, chain extender B and the remaining organic solvent to the obtained material in step (3.4);
(4.2)升温并控制反应温度为65℃，搅拌反应100min，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂分子；(4.2) Heating up and controlling the reaction temperature to be 65° C., stirring and reacting for 100 minutes to prepare the water-based polyurethane wet rubbing fastness improving agent molecules having catechol groups;
(5)成品化：将具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂分子与中和剂混合，然后与水混合，脱除有机溶剂，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂。(5) Finished product: mix the water-based polyurethane wet rubbing fastness improving agent molecules with catechol groups with neutralizing agent, then mix with water, remove organic solvents, and obtain catechol groups Water-based polyurethane wet rubbing fastness improver.
(5.1)向步骤(4.2)得到的物料中加入中和剂并搅拌30min；(5.1) Add neutralizing agent to the material obtained in step (4.2) and stir for 30min;
(5.2)加水混合乳化40min，在不高于100℃的条件下真空干燥至固含量为32％，得到具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂。(5.2) Add water, mix and emulsify for 40 minutes, and vacuum-dry under the condition of not higher than 100° C. to a solid content of 32%, to obtain a water-based polyurethane wet rubbing fastness improver with catechol groups.
实施例2Example 2
(1)原料准备，所述原料的主要成分和用量如表1所示；(1) Raw material preparation, the main components and consumption of said raw material are as shown in Table 1;
(2)脱水处理：将聚醚二元醇加入到反应器中进行脱水处理，脱水处理温度为106℃，真空度为-0.09MPa；(2) Dehydration treatment: Add polyether glycol into the reactor for dehydration treatment, the dehydration treatment temperature is 106°C, and the vacuum degree is -0.09MPa;
(3)预聚：将二异氰酸酯、脱水处理后的聚醚二元醇、部分有机溶剂和催化剂进行反应，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂预聚体；(3) Prepolymerization: react diisocyanate, polyether diol after dehydration treatment, part of organic solvent and catalyst to prepare water-based polyurethane wet rubbing fastness improving agent prepolymer with catechol groups;
(3.1)将二异氰酸酯和总量28重量％的有机溶剂投入反应器，升温至75℃；(3.1) Put diisocyanate and a total amount of 28% by weight of organic solvent into the reactor, and heat up to 75°C;
(3.2)维持体系温度为80℃，在10min内投入脱水处理后的聚醚二元醇；(3.2) Maintain the system temperature at 80°C, and put in the dehydration-treated polyether diol within 10 minutes;
(3.3)维持温度为80℃，保温反应55min，然后在15min内匀速投入催化剂；(3.3) Maintain the temperature at 80°C, keep the temperature for 55 minutes, and then put in the catalyst at a constant speed within 15 minutes;
(3.4)升温至87℃，保温反应90min，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂的预聚体；(3.4) heating up to 87° C., and heat preservation reaction for 90 minutes to prepare a prepolymer of a water-based polyurethane wet rubbing fastness improving agent having a catechol group;
(4)扩链：将具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂预聚体、扩链剂A、扩链剂B、剩余有机溶剂进行反应，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂分子；(4) Chain extension: react the water-based polyurethane wet rubbing fastness improving agent prepolymer with catechol groups, chain extender A, chain extender B, and the remaining organic solvents to obtain catechol-containing Molecules of water-based polyurethane wet rubbing fastness enhancer;
(4.1)控制反应温度为53℃，将扩链剂A、扩链剂B和剩余有机溶剂加入到步骤(3.4)的得到的物料中；(4.1) Control the reaction temperature to be 53° C., and add chain extender A, chain extender B and the remaining organic solvent to the obtained material in step (3.4);
(4.2)升温并控制反应温度为58℃，搅拌反应90min，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂分子；(4.2) Heating up and controlling the reaction temperature to be 58° C., stirring and reacting for 90 minutes to prepare the water-based polyurethane wet rubbing fastness improving agent molecule having catechol groups;
(5)成品化：将具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂分子与中和剂混合，然后与水混合，脱除有机溶剂，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂。(5) Finished product: mix the water-based polyurethane wet rubbing fastness improving agent molecules with catechol groups with neutralizing agent, then mix with water, remove organic solvents, and obtain catechol groups Water-based polyurethane wet rubbing fastness improver.
(5.1)向步骤(4.2)得到的物料中加入中和剂并搅拌40min；(5.1) Add neutralizer to the material obtained in step (4.2) and stir for 40min;
(5.2)加水混合乳化30min，在不高于100℃的条件下真空干燥至固含量为33％，得到具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂。(5.2) Add water, mix and emulsify for 30 minutes, and vacuum-dry under the condition of not higher than 100° C. to a solid content of 33%, to obtain a water-based polyurethane wet rubbing fastness improving agent with catechol groups.
实施例3Example 3
(1)原料准备，所述原料的主要成分和用量如表1所示；(1) Raw material preparation, the main components and consumption of said raw material are as shown in Table 1;
(2)脱水处理：将聚醚二元醇加入到反应器中进行脱水处理，脱水处理温度为102℃，真空度为-0.09MPa；(2) Dehydration treatment: Add polyether glycol into the reactor for dehydration treatment, the dehydration treatment temperature is 102°C, and the vacuum degree is -0.09MPa;
(3)预聚：将二异氰酸酯、脱水处理后的聚醚二元醇、部分有机溶剂和催化剂进行反应，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂预聚体；(3) Prepolymerization: react diisocyanate, polyether diol after dehydration treatment, part of organic solvent and catalyst to prepare water-based polyurethane wet rubbing fastness improving agent prepolymer with catechol groups;
(3.1)将二异氰酸酯和总量25重量％的有机溶剂投入反应器，升温至74℃；(3.1) Put diisocyanate and a total amount of 25% by weight of organic solvent into the reactor, and heat up to 74°C;
(3.2)维持体系温度为74℃，在10min内投入脱水处理后的聚醚二元醇；(3.2) Maintain the system temperature at 74°C, and put in the dehydration-treated polyether diol within 10 minutes;
(3.3)维持温度为78℃，保温反应60min，然后在10min内匀速投入催化剂；(3.3) Maintain the temperature at 78°C, keep the temperature for 60 minutes, and then put in the catalyst at a constant speed within 10 minutes;
(3.4)升温至85℃，保温反应80min，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂的预聚体；(3.4) heating up to 85° C., heat preservation reaction for 80 minutes, to prepare a prepolymer of water-based polyurethane wet rubbing fastness improving agent having catechol groups;
(4)扩链：将具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂预聚体、扩链剂A、扩链剂B、剩余有机溶剂进行反应，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂分子；(4) Chain extension: react the water-based polyurethane wet rubbing fastness improving agent prepolymer with catechol groups, chain extender A, chain extender B, and the remaining organic solvents to obtain catechol-containing Molecules of water-based polyurethane wet rubbing fastness enhancer;
(4.1)控制反应温度为55℃，将扩链剂A、扩链剂B和剩余有机溶剂加入到步骤(3.4)的得到的物料中；(4.1) Control the reaction temperature to 55° C., and add chain extender A, chain extender B and the remaining organic solvent to the obtained material in step (3.4);
(4.2)升温并控制反应温度为65℃，搅拌反应105min，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂分子；(4.2) Heating up and controlling the reaction temperature to be 65° C., stirring and reacting for 105 minutes to prepare the water-based polyurethane wet rubbing fastness improving agent molecules having catechol groups;
(5)成品化：将具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂分子与中和剂混合，然后与水混合，脱除有机溶剂，制得具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂。(5) Finished product: mix the water-based polyurethane wet rubbing fastness improving agent molecules with catechol groups with neutralizing agent, then mix with water, remove organic solvents, and obtain catechol groups Water-based polyurethane wet rubbing fastness improver.
(5.1)向步骤(4.2)得到的物料中加入中和剂并搅拌40min；(5.1) Add neutralizer to the material obtained in step (4.2) and stir for 40min;
(5.2)加水混合乳化40min，在不高于100℃的条件下真空干燥至固含量为31％，得到具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂。(5.2) Add water, mix and emulsify for 40 minutes, and vacuum-dry under the condition of not higher than 100° C. to a solid content of 31%, to obtain a water-based polyurethane wet rubbing fastness improving agent with catechol groups.
对比例1Comparative example 1
按照实施例1所述的方法进行实施，与之不同的是，不使用扩链剂A，扩链剂B的用量为202.5g(1.7mol)。The implementation was carried out according to the method described in Example 1, the difference was that the chain extender A was not used, and the amount of the chain extender B was 202.5 g (1.7 mol).
测试例1test case 1
将实施例和对比例得到的产物分别与水混合，配置成浓度为30g/L的处理液，分别记为处理液S1、S2、S3和D1。使用水溶液作为空白对照处理液，记为S0。The products obtained in Examples and Comparative Examples were mixed with water respectively to form treatment liquids with a concentration of 30 g/L, which were respectively designated as treatment liquids S1, S2, S3 and D1. Use an aqueous solution as a blank control solution, denoted as S0.
湿摩擦牢度测试：Wet rubbing fastness test:
将未固色的活性蓝染色牛仔织物在处理液中经过两浸两轧(轧液率80％)、100℃烘干和140℃焙烘5min的处理过程后，依据国标GB/T3920-2008进行湿摩擦牢度性能测试。After the unfixed reactive blue dyed denim fabric has been subjected to two dipping and two rolling treatments in the treatment solution (rolling rate 80%), drying at 100°C and baking at 140°C for 5 minutes, it is carried out according to the national standard GB/T3920-2008 Wet rubbing fastness performance test.
柔软度测试：Softness Test:
将未固色的活性蓝染色牛仔织物在处理液中经过两浸两轧(轧液率80％)、100℃烘干和140℃焙烘5min的处理过程后，剪成20cm×5cm的布条，采用LFY-208摆动式柔软度测试仪进行检测，测试时布条的一端被固定在仪器旋杆上并自然下垂，启动转盘，柔软度为布条另一端脱离旋杆时指针指示的刻度(单位：mm)。Cut the unfixed reactive blue denim fabric into strips of 20cm×5cm after two immersions and two rollings (rolling rate 80%), drying at 100°C and baking at 140°C for 5 minutes in the treatment solution , using LFY-208 swing-type softness tester for testing. During the test, one end of the cloth strip is fixed on the rotating rod of the instrument and hangs down naturally. When the turntable is started, the softness is the scale indicated by the pointer when the other end of the cloth strip is detached from the rotating rod ( Unit: mm).
结果如表2所示。The results are shown in Table 2.
表2Table 2
由表2可知，采用本发明所述的具有邻苯二酚基团的水性聚氨酯湿摩擦牢度提升剂对织物进行处理，可有效提高织物的湿摩擦牢度，且不会影响织物的手感。It can be seen from Table 2 that the wet rubbing fastness of the fabric can be effectively improved by using the water-based polyurethane wet rubbing fastness improving agent having a catechol group according to the present invention to treat the fabric without affecting the feel of the fabric.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.
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