CN105566595B - 一种用于极性表面涂层的水性聚氨酯乳液及其制备方法 - Google Patents

一种用于极性表面涂层的水性聚氨酯乳液及其制备方法 Download PDF

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CN105566595B
CN105566595B CN201511017731.8A CN201511017731A CN105566595B CN 105566595 B CN105566595 B CN 105566595B CN 201511017731 A CN201511017731 A CN 201511017731A CN 105566595 B CN105566595 B CN 105566595B
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aqueous polyurethane
monomer
polyurethane emulsion
modified polymeric
chitin modified
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CN105566595A (zh
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张建森
罗楠
张冬海
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Cangzhou meiuite New Material Technology Co., Ltd
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Environmental Science & Technology (beijing) Co Ltd
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Abstract

本发明属于水性功能高分子乳液技术领域，具体涉及一种用于极性表面涂层的水性聚氨酯乳液及其制备方法。所述用于极性表面涂层的水性聚氨酯乳液由以下成分组成：壳聚糖改性大单体，多元醇，异氰酸酯，亲水性扩链剂，醇类扩链剂，胺类扩链剂，成盐剂，催化剂，溶剂和去离子水。本发明制备得到的水性聚氨酯乳液对极性基材具有很好的附着力，同时也可以作为非极性基材的转移涂层使用。本发明中的壳聚糖改性大单体的结构具有可调节性，通过丙烯酸单体及功能性硅烷单体改变，可以对最终产品的性能进行调控，从而满足对不同产品性能的要求。

Description

一种用于极性表面涂层的水性聚氨酯乳液及其制备方法
技术领域
本发明属于水性功能高分子乳液技术领域，具体涉及一种用于极性表面涂层的水性聚氨酯乳液及其制备方法。
背景技术
随着我国经济的飞速发展，环境污染的情况也越来越严重。近几年来，国家不断推出一系列节能减排政策，绿色化工的发展力度也逐步加大。涂料是全球消耗量最大的化工产品之一。油性涂料在过去占据了涂料生产的主要地位，但是其生产过程会产生大量的有机溶剂，给环境和人类生活带来了巨大威胁。因此随着科学技术的进步以及人们环保意识的增强，油性涂料行业正逐步被新兴的水性涂料所取代。水性涂料安全无毒，且不会燃烧爆炸，已被广泛应用于建筑、胶黏剂、织物涂层与整理剂、皮革涂饰剂、纸张表面整理剂和纤维表面处理剂等领域。水性聚氨酯乳液作为其中的一大类，是目前的研究热点之一，其乳液性能已经可以跟油性乳液媲美。
水性聚氨酯乳液的应用非常广泛，但是其作为不同基材的涂层使用时，由于其本身原料及制备方法的限制，润湿能力不尽相同。水性聚氨酯涂料的涂层具有一定的极性，但是在一些极性基材上的剥离性能仍不理想，不能实现完美的涂覆。主要原因是水性聚氨酯分子链中多是酯键、醚键等极性不高的基团，且基团数量并不多，主要分布在大分子链中间，使得最终产品的极性也不是很高。
为了提高水性聚氨酯涂层的极性，研究者做了很多尝试。201210408829.6利用水性丙烯酸乳液与水性聚氨酯乳液混合或改性，再加入固化剂或进行UV固化，可提高对PET薄膜的附着力。但是单纯的混合方法并不能实现有效均匀的涂覆，而且UV固化的活性能量很难渗透完全涂层，使其最终的粘合效果变差。201280034728.5在水性聚氨酯原料中加入一种亲水性化合物及单羟基乙烯基醚化合物，制备的组合物可以跟不同极性的基材进行涂覆。涂层粘合力高，抗粘连性好，透明度高，并且具有可交联的硬涂层成分，交联后不会雾化。这种方法得到的涂层在电晕后的聚丙烯薄膜上粘合性好、透明、且抗粘连。但是仅通过加入一种多羟基的亲水性化合物对最终产品的极性提高程度有限。此外，多羟基亲水化合物的加入会导致产品耐水性的下降，虽然可通过UV交联来改善，但是由于能量渗透及交联点浓度问题，最终结果不尽理想。
发明内容
为克服现有技术的不足，本发明提供了一种用于极性表面涂层的水性聚氨酯乳液及其制备方法，具体技术方案如下：
一种用于极性表面涂层的水性聚氨酯乳液，其组成及质量份数如下：
进一步地，所述多元醇为聚对苯二甲酸乙二醇酯多元醇、聚对苯二甲酸丁二醇酯多元醇、聚己二酸乙二醇酯多元醇、聚对苯二甲酸己二醇酯多元醇、聚环氧乙烷多元醇、聚四氢呋喃醚多元醇、聚环氧丙烷多元醇、聚碳酸酯多元醇、聚己内酯多元醇中的一种或一种以上；所述多元醇的分子量为500-5000，优选为1000-4000，进一步优选为2000-4000。
所述异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、四甲基苯二甲基二异氰酸酯中的一种或一种以上；
所述亲水性扩链剂为二羟甲基丙酸、二羟甲基丁酸、非离子二元醇、乙二胺基乙磺酸钠、1,4-丁二醇-2-磺酸钠中的一种或一种以上；
所述醇类扩链剂为三羟甲基丙烷、季戊四醇、丙三醇、乙二醇、1,4-丁二醇、1,6-己二醇、新戊二醇、二乙二醇、二丙二醇、三乙二醇中的一种或一种以上；所述胺类扩链剂为乙二胺、氨水、异佛尔酮二胺、水合肼、二乙烯三胺、三乙烯四胺中的一种或一种以上；
所述成盐剂包括三乙胺、氢氧化钠、氢氧化钾中的一种或一种以上；
所述引发剂包括二丁基二月桂酸锡，辛酸亚锡中的一种或一种以上；
所述溶剂包括丙酮、N，N二甲基甲酰胺、N，N二甲基乙酰胺、丁酮、甲苯、二甲苯、乙酸乙酯、乙酸丁酯中的一种或一种以上。
进一步地，所述壳聚糖改性大单体的结构组成包括壳聚糖、异氰酸酯、丙烯酸类单体、甲基丙烯酸类单体、非丙烯酸类单体及功能性硅烷类单体。所述壳聚糖改性大单体的分子量为800-10000，优选为1000-8000，进一步优选为1000-4000；羟值为100-1000mgKOH/g，优选为100-900mgKOH/g，进一步优选为200-600mgKOH/g。
所述壳聚糖改性大单体的结构如下：
其中，R为由异氰酸酯连接的丙烯酸类单体、甲基丙烯酸类单体、非丙烯酸类单体以及功能性硅烷类单体组成的聚合分子链，聚合度n＝2-2000，其中，优选为2-1000，进一步优选为2-500；异氰酸酯与壳聚糖反应的取代度在0.2-3.0之间，优选为0.5-2.5，进一步优选为0.8-2.0；丙烯酸类单体、甲基丙烯酸类单体、非丙烯酸类单体、功能性硅烷单体在R聚合分子链中的质量百分数依次为5-90％、5-90％、5-30％、1-30％，优选为10-80％、10-80％、5-25％、1-25％，进一步优选为20-70％、20-70％、10-25％、5-20％。
所述异氰酸酯为带有两个或三个异氰酸酯官能团，包括异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、四甲基苯二甲基二异氰酸酯、上述物质的二聚体或三聚体中的一种或一种以上。
所述丙烯酸类单体为丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸仲丁酯、丙烯酸异丁酯、丙烯酸正丙酯、丙烯酸环己酯、丙烯酸月桂酯、丙烯酸-2-乙基己酯、丙烯酸羟甲酯、丙烯酸羟乙酯、丙烯酸羟丙酯中的一种或一种以上；
所述甲基丙烯酸类单体为甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸异冰片酯、甲基丙烯酸月桂酯、甲基丙烯酸羟甲酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸三氟乙酯中的一种或一种以上；
所述非丙烯酸类单体包含丙烯酰胺、N-羟甲基丙烯酰胺、N-丁氧基甲基丙烯酰胺、苯乙烯、丙烯腈、醋酸乙烯酯、氯乙烯、二乙烯基苯中的一种或一种以上；
所述功能性硅烷类单体带有可聚合的双键，为乙烯基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三异丙氧基硅烷、γ-氨丙基三乙氧基硅烷中的一种或一种以上。
如上所述的水性聚氨酯乳液的制备方法，包括以下步骤：
(1)将异氰酸酯、多元醇及壳聚糖改性大单体在60-100℃下反应2-4小时；
(2)加入亲水性扩链剂、醇类扩链剂、催化剂及溶剂，在50-90℃下反应3-5小时，得到预聚体；
(3)降温至30-50℃，加入成盐剂及溶剂，搅拌30-60分钟；
(4)降温至10-30℃，加入适量去离子水，同时高速搅拌分散30-60分钟，得到水性聚氨酯乳液。
进一步地，步骤(4)加入去离子水并高速搅拌分散后，还可以加入胺类扩链剂，进一步扩链，得到水性聚氨酯乳液。
进一步地，所述水性聚氨酯乳液中，水性聚氨酯的分子量为2-25万，优选为5-20万，进一步优选为5-15万；乳液固含量为10-50％，优选为10-45％，进一步优选为15-40％。
本发明在水性聚氨酯乳液中引入了一种带有多种极性官能团的化合物——壳聚糖改性大单体，它既可以参与水性聚氨酯乳液的合成，又保留了本身带有的大量极性官能团，使最终产品的极性升高。同时，在支链末端可引入功能性硅烷，硅烷本身以及水解后形成的交联结构可以进一步改善产品的耐水性、耐溶剂性、耐热性、力学性能等。该乳液可以广泛用于极性基材的涂覆，或作为非极性及低极性基材电晕后的涂层使用，也可以直接作为其转移涂层使用。
在乳液中，壳聚糖改性大单体的极性基团向水中分散，硅烷单体部分向乳胶粒内部伸展，从而帮助乳胶粒更加稳定地分散于水介质中；而当乳液涂覆在极性基体上时，壳聚糖改性大单体的极性基团会与极性基体结合，而低极性的硅烷部分会向膜表面扩散，从而形成一层疏水的保护层；功能性硅烷本身也可以进一步交联。
本发明的有益效果为：
(1)本发明制备得到的水性聚氨酯乳液具有高固含量、低粘度的特点，对极性基材具有很好的附着力，其乳液固含量、耐热性、耐水性、耐溶剂性、力学性能均有提高；同时也可以作为非极性基材的转移涂层使用。
(2)本发明中的壳聚糖改性大单体的结构具有可调节性，通过丙烯酸单体及功能性硅烷单体改变，可以对最终产品的性能进行调控，从而满足对不同产品性能的要求。
具体实施方式
以下结合实施例对本发明作进一步详细的描述，但是本发明的实施方式并不仅局限于此。
实施例1
选用壳聚糖改性大单体结构：壳聚糖聚合度n＝10；异佛尔酮二异氰酸酯在壳聚糖分子链上的取代度为1.0；选用的单体为：丙烯酸羟乙酯、丙烯酸、甲基丙烯酸乙酯、苯乙烯、乙烯基三甲氧基硅烷，单体分别占R分子链质量分数的10％、30％、40％、5％、10％。
将6份分子量为3000的聚对苯二甲酸丁二醇酯多元醇、6份壳聚糖改性大单体和16份异佛尔酮二异氰酸酯投入干燥的反应釜中，在90℃，200-350rpm搅拌速度下反应3-4小时；
加入3份二羟甲基丁酸、5份非离子二元醇、0.5份三羟甲基丙烷、0.03份催化剂二丁基二月桂酸锡和溶剂N,N-二甲基甲酰胺，继续反应2-3小时；
降低温度至50℃，加入0.5份三乙胺，继续在300-400rpm转速下反应30-60分钟；
降温至30℃以下，在1200-1500rpm转速下加入70份去离子水，快速分散30-60分钟；
加入2份乙二胺，在300-400rpm转速下继续反应60-90分钟，即得到水性聚氨酯乳液。
性能测试：将所得水性聚氨酯乳液用80％乙醇稀释到12％(wt％)，再用4μm的线棒将稀释后的乳液直接涂覆在PET膜上；干燥后用胶带粘在涂层上测量涂层剥离性，涂层完整无脱落；用电晕笔测量膜表面达因值可达52；PET膜前后透明度没有变化，热压不粘连。
实施例2
选用壳聚糖改性大单体结构：壳聚糖聚合度n＝20；甲苯二异氰酸酯在壳聚糖分子链上的取代度为1.5；选用的单体为：甲基丙烯酸三氟乙酯、甲基丙烯酸甲酯、N-羟甲基丙烯酰胺、丙烯酸乙酯、乙烯基三异丙氧基硅烷，分别占R分子链质量分数的10％、40％、5％、35％、5％。
将8份分子量为1000的聚对苯二甲酸乙二醇酯多元醇、4份壳聚糖改性大单体和20份异佛尔酮二异氰酸酯投入干燥的反应釜中，在90℃，200-350rpm搅拌速度下反应3-4小时；
加入3份二羟甲基丙酸、3份1,4-丁二醇-2-磺酸钠、1份三羟甲基丙烷、0.1份催化剂二丁基二月桂酸锡和溶剂N-甲基吡咯烷酮，继续反应2-3小时；
降低温度至50℃，加入0.5份三乙胺继续在300-400rpm转速下反应30-60分钟；
降温至30℃以下，在1200-1500rpm转速下加入80份去离子水，快速分散30-60分钟，即得到水性聚氨酯乳液。
性能测试：将所得水性聚氨酯乳液用80％乙醇稀释到12％(wt％)，再用4μm的线棒直接将稀释后的乳液涂覆在聚酯膜上；干燥后用胶带粘在涂层上测量涂层剥离性，涂层完整无脱落；用电晕笔测量膜表面达因值可达50；聚酯膜前后透明度没有变化，热压不粘连。
实施例3
选用壳聚糖改性大单体结构：壳聚糖聚合度n＝100；4,4'-二环己基甲烷二异氰酸酯在壳聚糖分子链上的取代度为1.8；选用的单体为：甲基丙烯酸羟甲酯、丙烯酸正丁酯、N-丁氧基甲基丙烯酰胺、丙烯酸、苯乙烯，分别占R分子链质量分数的15％、30％、10％、10％、30％。
将10份分子量为1500的聚聚己内酯多元醇、25份二苯基甲烷二异氰酸酯和5份壳聚糖改性大单体投入干燥的反应釜中，在85℃，200-350rpm搅拌速度下反应3-4小时；
加入4份二羟甲基丙酸、4份非离子二元醇、1.5份三羟甲基丙烷、0.15份催化剂二丁基二月桂酸锡和溶剂丁酮，继续反应2-3小时；
降低温度至50℃，加入1份三乙胺继续在300-400rpm转速下反应30-60分钟；
降温至30℃以下，在1200-1500rpm转速下加入80份去离子水，快速分散30-60分钟；
加入3份水合肼，在300-400rpm转速下继续反应60-90分钟，即得到水性聚氨酯乳液。
性能测试：将所得水性聚氨酯乳液用80％乙醇稀释到12％(wt％)，再用4μm的线棒将稀释后的乳液直接涂覆在电晕后的BOPP膜上；干燥后用胶带粘在涂层上测量涂层剥离性，涂层完整无脱落；用电晕笔测量膜表面达因值可达50；BOPP膜前后透明度没有变化，热压不粘连。
实施例4
选用壳聚糖改性大单体结构：壳聚糖聚合度n＝500；六亚甲基二异氰酸酯在壳聚糖分子链上的取代度为0.8；选用的单体为：丙烯酸羟甲酯、丙烯酸-2-乙基己酯、N-丁氧基甲基丙烯酰胺、丙烯酸、乙烯基三乙氧基硅烷，分别占R分子链质量分数的5％、40％、15％、30％、5％。
将5份分子量为2000的聚四氢呋喃醚多元醇、30份异佛尔酮二异氰酸酯和8份壳聚糖改性大单体投入干燥的反应釜中，在90℃，200-350rpm搅拌速度下反应3-4小时；
加入3份二羟甲基丁酸、5份1,4-丁二醇-2-磺酸钠、1份季戊四醇、0.2份催化剂二丁基二月桂酸锡和溶剂乙酸乙酯，继续反应2-3小时；
降低温度至50℃，加入0.2份三乙胺继续在300-400rpm转速下反应30-60分钟；
降温至30℃以下，在1200-1500rpm转速下加入80份去离子水，快速分散30-60分钟；
加入2份异佛尔酮二胺，在300-400rpm转速下继续反应60-90分钟，即得到水性聚氨酯乳液。
性能测试：将所得水性聚氨酯乳液用80％乙醇稀释到12％(wt％)，再用4μm的线棒直接将稀释后的乳液涂覆在聚酯膜上；干燥后用胶带粘在涂层上测量涂层剥离性，涂层完整无脱落；用电晕笔测量膜表面达因值可达48；聚酯膜前后透明度没有变化，热压不粘连。
实施例5
选用壳聚糖改性大单体结构：壳聚糖聚合度n＝2000；六亚甲基二异氰酸酯在壳聚糖分子链上的取代度为0.5；选用的单体为：甲基丙烯酸羟乙酯、丙烯酸-2-乙基己酯、丙烯酰胺、甲基丙烯酸正丁酯，分别占R分子链质量分数的5％、45％、5％、40％。
将10份分子量为800的聚四氢呋喃醚多元醇、20份异佛尔酮二异氰酸酯和2份壳聚糖改性大单体投入干燥的反应釜中，在95℃，200-350rpm搅拌速度下反应3-4小时；
加入8份二羟甲基丙酸、1份三羟甲基丙烷、0.1份催化剂二丁基二月桂酸锡和溶剂乙酸丁酯，继续反应2-3小时；
降低温度至50℃，加入0.5份三乙胺继续在300-400rpm转速下反应30-60分钟；
降温至30℃以下，在1200-1500rpm转速下加入60份去离子水，快速分散30-60分钟；
加入3份水合肼，在300-400rpm转速下继续反应60-90分钟，即得到水性聚氨酯乳液。
性能测试：将所得水性聚氨酯乳液用80％乙醇稀释到12％(wt％)，再用4μm的线棒将稀释后的乳液直接涂覆在PC膜上涂膜，干燥后用胶带粘在涂层上测量涂层剥离性，涂层完整无脱落；用电晕笔测量膜表面达因值可达50；PC膜前后透明度没有变化，热压不粘连。
实施例6
选用壳聚糖改性大单体结构：壳聚糖聚合度n＝1000；六亚甲基二异氰酸酯在壳聚糖分子链上的取代度为0.15；选用的单体为：甲基丙烯酸羟甲酯、甲基丙烯酸正丁酯、丙烯酸乙酯、丙烯酰胺、乙烯基三乙氧基硅烷，分别占R分子链质量分数的10％、35％、20％、10％、20％。
将6份分子量为1000的聚碳酸酯多元醇、17份甲苯二异氰酸酯和3份壳聚糖改性大单体投入干燥的反应釜中，在70℃，200-350rpm搅拌速度下反应3-4小时；
加入4份二羟甲基丙酸、1份季戊四醇、0.2份催化剂二丁基二月桂酸锡和溶剂二甲苯，继续反应2-3小时；
降低温度至50℃，加入0.2份三乙胺继续在300-400rpm转速下反应30-60分钟；
降温至30℃以下，在1200-1500rpm转速下加入70份去离子水，快速分散30-60分钟；
加入5份氨水，在300-400rpm转速下继续反应60-90分钟，即得到水性聚氨酯乳液。
性能测试：将所得水性聚氨酯乳液用80％乙醇稀释到12％(wt％)，再用4μm的线棒直接将稀释后的乳液涂覆在PBT膜上；干燥后用胶带粘在涂层上测量涂层剥离性，涂层完整无脱落；用电晕笔测量膜表面达因值可达48；PBT膜前后透明度没有变化，热压不粘连。
实施例7
选用壳聚糖改性大单体结构：壳聚糖聚合度n＝800；二苯基甲烷二异氰酸酯在壳聚糖分子链上的取代度为0.25；选用的单体为：丙烯酸羟乙酯、甲基丙烯酸乙酯、N-羟甲基丙烯酰胺、乙烯基三异丙氧基硅烷，分别占R分子链质量分数的10％、50％、15％、15％。
将5份分子量为3000的聚对苯二甲酸己二醇酯多元醇、16份异佛尔酮二异氰酸酯和3份壳聚糖改性大单体投入干燥的反应釜中，在80℃，200-350rpm搅拌速度下反应3-4小时；
加入4份二羟甲基丁酸、2份非离子二元醇、2份季戊四醇、0.2份催化剂二丁基二月桂酸锡和溶剂二甲苯，继续反应2-3小时；
降低温度至50℃，加入0.5份三乙胺继续在300-400rpm转速下反应30-60分钟；
降温至30℃以下，在1200-1500rpm转速下加入85份去离子水，快速分散30-60分钟；
加入2份三乙胺，在300-400rpm转速下继续反应60-90分钟，即得到水性聚氨酯乳液。
性能测试：将所得水性聚氨酯乳液用80％乙醇稀释到12％(wt％)，再用4μm的线棒直接将稀释后的乳液涂覆在PET膜上；干燥后用胶带粘在涂层上测量涂层剥离性，涂层完整无脱落；用电晕笔测量膜表面达因值可达48；PET膜前后透明度没有变化，热压不粘连。
实施例8
选用壳聚糖改性大单体结构：壳聚糖聚合度n＝1500；甲苯二异氰酸酯在壳聚糖分子链上的取代度为0.11；选用的单体为：丙烯酸羟乙酯、甲基炳烯酸甲酯、甲基丙烯酸、丙烯酰胺、乙烯基三异丙氧基硅烷，分别占R分子链质量分数的5％、35％、30％、20％、5％。
将3份2000分子量的聚碳酸酯多元醇、15份二苯基甲烷二异氰酸酯和6份壳聚糖改性大单体投入干燥的反应釜中，在80℃，200-350rpm搅拌速度下反应3-4小时；
加入3份二羟甲基丙酸、1份1,4-丁二醇-2-磺酸钠、2份三羟甲基丙烷、0.15份催化剂二丁基二月桂酸锡和溶剂甲苯，继续反应2-3小时；
降低温度至50℃，加入0.1份三乙胺继续在300-400rpm转速下反应30-60分钟；
降温至30℃以下，在1200-1500rpm转速下加入80份去离子水，快速分散30-60分钟；
加入2份三乙胺，在300-400rpm转速下继续反应60-90分钟，即得到水性聚氨酯乳液。
性能测试：将所得水性聚氨酯乳液用80％乙醇稀释到12％(wt％)，再用4μm的线棒直接将稀释后的乳液涂覆在PA膜上，干燥后用胶带粘在涂层上测量涂层剥离性，涂层完整无脱落；用电晕笔测量膜表面达因值可达52；PA膜前后透明度没有变化，热压不粘连。
以上实施例对用于极性表面的水性聚氨酯涂层的设计原理及其制备方法进行了详细介绍。以上实施例的说明只适用于帮助理解本发明的制备方法及其核心技术思想，不应理解为对本发明的限制。其他任何未违背本发明的技术实质与原理下所做的任何改变、修饰、替代、组合或简化，均应包含在本发明的保护范围之内。

Claims (8)

1.一种用于极性表面涂层的水性聚氨酯乳液，其特征在于，所述水性聚氨酯乳液的组成及质量份数如下：
所述壳聚糖改性大单体的结构组成包括壳聚糖、异氰酸酯、丙烯酸类单体、甲基丙烯酸类单体、非丙烯酸类单体及功能性硅烷类单体；所述壳聚糖改性大单体的结构如下：
其中，R为由异氰酸酯连接的丙烯酸类单体、甲基丙烯酸类单体、非丙烯酸类单体以及功能性硅烷类单体组成的聚合分子链，聚合度n＝2-2000；异氰酸酯与壳聚糖反应的取代度为0.5-2.5，丙烯酸类单体、甲基丙烯酸类单体、非丙烯酸类单体、功能性硅烷单体在R聚合分子链中的质量百分数依次为5-90％、5-90％、5-30％、1-30％；
所述壳聚糖改性大单体中的非丙烯酸类单体包含丙烯酰胺、N-羟甲基丙烯酰胺、N-丁氧基甲基丙烯酰胺、苯乙烯、丙烯腈、醋酸乙烯酯、氯乙烯、二乙烯基苯中的一种或一种以上。
2.根据权利要求1所述的水性聚氨酯乳液，其特征在于，所述壳聚糖改性大单体中的异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、四甲基苯二甲基二异氰酸酯、上述物质的二聚体或三聚体中的一种或一种以上。
3.根据权利要求1所述的水性聚氨酯乳液，其特征在于，所述壳聚糖改性大单体中的丙烯酸类单体为丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸仲丁酯、丙烯酸异丁酯、丙烯酸正丙酯、丙烯酸环己酯、丙烯酸月桂酯、丙烯酸-2-乙基己酯、丙烯酸羟甲酯、丙烯酸羟乙酯、丙烯酸羟丙酯中的一种或一种以上；
所述壳聚糖改性大单体中的甲基丙烯酸类单体为甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸异冰片酯、甲基丙烯酸月桂酯、甲基丙烯酸羟甲酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸三氟乙酯中的一种或一种以上；
所述壳聚糖改性大单体中的功能性硅烷类单体为乙烯基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三异丙氧基硅烷、γ-氨丙基三乙氧基硅烷中的一种或一种以上。
4.根据权利要求1所述的水性聚氨酯乳液，其特征在于，所述壳聚糖改性大单体的分子量为800-10000，羟值为100-1000mgKOH/g；所述多元醇的分子量为500-5000。
5.根据权利要求1所述的水性聚氨酯乳液，其特征在于，所述水性聚氨酯乳液中的多元醇为聚对苯二甲酸乙二醇酯多元醇、聚对苯二甲酸丁二醇酯多元醇、聚己二酸乙二醇酯多元醇、聚对苯二甲酸己二醇酯多元醇、聚环氧乙烷多元醇、聚四氢呋喃醚多元醇、聚环氧丙烷多元醇、聚碳酸酯多元醇、聚己内酯多元醇中的一种或一种以上；
所述水性聚氨酯乳液中的异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、四甲基苯二甲基二异氰酸酯中的一种或一种以上；
所述水性聚氨酯乳液中的亲水性扩链剂为二羟甲基丙酸、二羟甲基丁酸、非离子二元醇、乙二胺基乙磺酸钠、1,4-丁二醇-2-磺酸钠中的一种或一种以上；
所述水性聚氨酯乳液中的醇类扩链剂为三羟甲基丙烷、季戊四醇、丙三醇、乙二醇、1,4-丁二醇、1,6-己二醇、新戊二醇、二乙二醇、二丙二醇、三乙二醇中的一种或一种以上；所述胺类扩链剂为乙二胺、氨水、异佛尔酮二胺、水合肼、二乙烯三胺、三乙烯四胺中的一种或一种以上；
所述水性聚氨酯乳液中的成盐剂包括三乙胺、氢氧化钠、氢氧化钾中的一种或一种以上；
所述水性聚氨酯乳液中的引发剂包括二丁基二月桂酸锡，辛酸亚锡中的一种或一种以上；
所述水性聚氨酯乳液中的溶剂包括丙酮、N，N二甲基甲酰胺、N，N二甲基乙酰胺、丁酮、甲苯、二甲苯、乙酸乙酯、乙酸丁酯中的一种或一种以上。
6.权利要求1-5任一项所述的水性聚氨酯乳液的制备方法，其特征在于，包括以下步骤：
(1)将异氰酸酯、多元醇及壳聚糖改性大单体在60-100℃下反应2-4小时；
(2)加入亲水性扩链剂、醇类扩链剂、催化剂及溶剂，在50-90℃下反应3-5小时，得到预聚体；
(3)降温至30-50℃，加入成盐剂及溶剂，搅拌30-60分钟；
(4)降温至10-30℃，加入适量去离子水，同时高速搅拌分散30-60分钟，得到水性聚氨酯乳液。
7.根据权利要求6所述的制备方法，其特征在于，步骤(4)加入去离子水并高速搅拌分散后，还可以加入胺类扩链剂，进一步扩链，得到水性聚氨酯乳液。
8.根据权利要求6所述的制备方法，其特征在于，所述水性聚氨酯乳液中，水性聚氨酯的分子量为2-25万；乳液固含量为10-50％。
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