CN105968309B - 一种用于合成革面料的水性聚氨酯树脂及其制备方法 - Google Patents

一种用于合成革面料的水性聚氨酯树脂及其制备方法 Download PDF

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CN105968309B
CN105968309B CN201610494902.4A CN201610494902A CN105968309B CN 105968309 B CN105968309 B CN 105968309B CN 201610494902 A CN201610494902 A CN 201610494902A CN 105968309 B CN105968309 B CN 105968309B
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polyurethane resin
diisocyanate
waterborne polyurethane
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汪飞
戴家兵
李维虎
赵曦
赵春娥
花亮亮
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Lnzhou Ketian Aqueous Polymer Material Co Ltd
Hefei Scisky Technology Co Ltd
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Abstract

本发明提供一种用于合成革面料的水性聚氨酯树脂及其制备方法，包括以下原料组分及重量份：多元醇120～150份；多异氰酸酯20～35份；第一扩链剂3～6份；第二扩链剂1～8份；第三扩链剂1～8份；成盐剂2～6份，其中，所述多元醇包括聚碳酸酯多元醇和聚硅氧烷多元醇，所述聚碳酸酯多元醇与所述聚硅氧烷多元醇的重量比例为(9‑13):(0.1‑0.4)。本发明获得的水性聚氨酯树脂制备成的合成革面料不仅软而不粘，而且具有优异的耐水解性、耐折性等优点。

Description

一种用于合成革面料的水性聚氨酯树脂及其制备方法
技术领域
本发明涉及高分子聚合物领域，具体公开了一种用于合成革面料的水性聚氨酯树脂及其制备方法。
背景技术
水性聚氨酯树脂是以水为分散介质，在加工过程中无需有机溶剂，而且产品体系中不含有有毒的NCO基团，避免了对环境的污染和对操作人员的健康危害。水性聚氨酯树脂广泛应用到合成革面料领域，水性合成革面料不含苯系物、DMF等有机溶剂，具有无毒环保的优点，受到越来越多消费者的喜爱。但由于受合成革采用水性聚氨酯树脂技术上限制，导致水性合成革发展受到限制，尤其在软合成革面料上，一方面手感没有溶剂型面料丰满，塑胶感严重，另一方面，如果将合成革的手感做软，往往合成革表面会出现发粘的问题。因此，亟需研究出一种水性聚氨酯树脂解决合成革面料存在的手感问题。
发明内容
本发明的目的在于克服现有技术的缺陷，提供一种用于合成革面料的水性聚氨酯树脂及其制备方法，由该水性聚氨酯树脂制备的合成革面料不仅软而不粘，而且具有优异的耐水解性、耐折性。
为了实现以上目的及其他目的，本发明是通过包括以下技术方案实现的：一种水性聚氨酯树脂，包括以下原料组分及重量份：
优选地，所述多元醇为130～140份。
优选地，所述多异氰酸酯为25～30份。
优选地，所述第一扩链剂为4～5份。
优选地，所述第二扩链剂为4～7份。
优选地，所述第三扩链剂为4～7份。
优选地，所述成盐剂为3～5份。
优选地，所述多元醇包括聚碳酸酯多元醇和聚硅氧烷多元醇，所述聚碳酸酯多元醇与所述聚硅氧烷多元醇的重量比例为(9-13):(0.1-0.4)。
更优选地，所述多元醇还包括聚环氧丙烷多元醇和/或聚四氢呋喃多元醇。
更优选地，所述聚碳酸酯多元醇通过己内酯与1,6-己二醇聚合反应而获得，所述聚碳酸酯多元醇的分子量为1800-2100。
优选地，所述多异氰酸酯选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、4,4-二环己基甲烷二异氰酸酯、二苯基甲烷二异氰酸酯、1,6-己二异氰酸酯、苯二亚甲基二异氰酸酯、萘-1,5-二异氰酸酯、多亚甲基多苯基异氰酸酯、四甲基苯二亚甲基二异氰酸酯、甲基环己基二异氰酸酯和二环己基甲烷二异氰酸酯中的任意一种或多种。
优选地，所述第一扩链剂选自二羟甲基丙酸、二羟甲基丁酸、二羟甲基戊酸和二羟甲基辛酸中的一种或多种。
优选地，所述第二扩链剂选自乙二醇、一缩二乙二醇、1,4-丁二醇、2,3-丁二醇、1,6-己二醇、新戊二醇、二甘醇、甘油、山梨醇、三羟甲基丙烷和二羟甲基环己烷中的一种或多种。
优选地，所述第三扩链剂选自乙二胺、异佛尔酮二胺、1,6-己二胺、1,3-环己二甲胺和间苯二甲胺中的任意一种或多种。
优选地，所述成盐剂为三乙胺。
本发明公开一种制备如上述所述的水性聚氨酯树脂的方法，包括以下步骤：将所述多元醇和所述多异氰酸酯在85～95℃下反应2～3h；再加入所述第一扩链剂和所述第二扩链剂在75～85℃下反应5～8h；降温至0～5℃加入所述成盐剂中和；加水后再加入所述第三扩链剂，减压蒸馏，获得水性聚氨酯树脂。
优选地，加入所述第一扩链剂和所述第二扩链剂的同时加入丙酮。
丙酮的作用为调整反应溶液的粘度。丙酮的添加量可根据反应需要酌情添加。所述丙酮在减压蒸馏阶段被蒸馏除去。
本发明还公开一种如上述所述的水性聚氨酯树脂或上述所述的方法制备的水性聚氨酯树脂在合成革面料中的用途。
综上所述，本发明提供一种用于合成革面料的水性聚氨酯树脂及其制备方法，其有益效果为：
本发明在水性聚氨酯制备过程中加入聚碳酸酯多元醇和聚硅氧烷多元醇，而聚碳酸酯多元醇是通过己内酯与1,6-己二醇反应而获得，由于己内酯具有较低的玻璃化温度，本身非常柔软，具有极大的伸展性，使得由获得水性聚氨酯制备的合成革面料不仅手感柔软，而且具有优异的耐水解性、常温及低温耐曲挠性，在耐磨、耐溶剂性能方面也非常优异；聚硅氧烷多元醇能够给由水性聚氨酯树脂制备的合成革带来柔软性能、滑爽的手感，同时避免水性合成革面料的粘连的问题；由获得的水性聚氨酯树脂制备的合成革面料不仅软而不粘，而且具有优异的耐水解性、马丁代尔耐磨性能和耐溶剂性。
具体实施方式
下面结合实施例进一步阐述本发明。应理解，实施例仅用于说明本发明，而非限制本发明的范围。
实施例1
将130g聚碳酸酯多元醇(分子量为2000)和3g聚硅氧烷多元醇在100℃脱水一小时，然后降温至50℃，加入23g的甲苯二异氰酸酯，升温至90℃保温反应2小时，两小时测定NCO含量，达到理论值后降温至50℃，加入4.68g的二羟甲基丙酸和1.8g的1,4-丁二醇和少量丙酮调整粘度，升温至80℃反应6小时，反应结束测定NCO含量，然后降温至5℃，加入3.53g的三乙胺进行中和，中和30分钟后，高速剪切下加入去离子水，分散2分钟，然后缓慢加入用冰水稀释的2g的乙二胺，减压蒸馏除去体系中的丙酮，即得到样品1。
实施例2
将110g聚碳酸酯多元醇(分子量为2000)、32g聚氧化丙烯二元醇(分子量为2000)和2g聚硅氧烷二元醇在110℃脱水一小时，然后降温至50℃，加入32g的异佛尔酮二异氰酸酯，升温至90℃保温反应3小时，两小时测定NCO含量，达到理论值后降温至50℃，加入3.2g的二羟甲基丙酸和6.2g的1,4-丁二醇和少量丙酮调整粘度，升温至80℃反应6小时，反应结束测定NCO含量，然后降温至5℃，加入2.41g的三乙胺进行中和，中和30分钟后，高速剪切下加入去离子水，分散2分钟，然后缓慢加入用冰水稀释的4g的异佛尔酮二胺，减压蒸馏除去体系中的丙酮，即得到样品2。
实施例3
将90g聚碳酸酯多元醇(分子量为2000)、40g聚四氢呋喃多元醇(分子量为2000)和2g聚硅氧烷二元醇在105℃脱水一小时，然后降温至50℃，加入32g的甲苯二异氰酸酯，升温至90℃保温反应3小时，两小时测定NCO含量，达到理论值后降温至50℃，加入5.86g的二羟甲基丙酸和3g的一缩二乙二醇和少量丙酮调整粘度，升温至80℃反应6小时，反应结束测定NCO含量，然后降温至5℃，加入4.41g的三乙胺进行中和，中和30分钟后，高速剪切下加入去离子水，分散2分钟，然后缓慢加入用冰水稀释的2.1g的乙二胺，减压蒸馏除去体系中的丙酮，即得到样品3。
实施例4
将120g聚碳酸酯多元醇(分子量为2000)、18g聚四氢呋喃多元醇(分子量为3000)和2g聚硅氧烷二元醇在105℃脱水一小时，然后降温至50℃，加入35g的异佛尔酮二异氰酸酯，升温至90℃保温反应3小时，两小时测定NCO含量，达到理论值后降温至50℃，加入5.33g的二羟甲基丙酸和2g的1,4-丁二醇和少量丙酮调整粘度，升温至80℃反应6小时，反应结束测定NCO含量，然后降温至5℃，加入4.01g的三乙胺进行中和，中和30分钟后，高速剪切下加入去离子水，分散2分钟，然后缓慢加入用冰水稀释的1.2g的乙二胺，减压蒸馏除去体系中的丙酮，即得到样品4。
对比例1
将120g聚碳酸酯多元醇(分子量为2000)和18g聚四氢呋喃多元醇(分子量为3000)在105℃脱水一小时，然后降温至50℃，加入35g的异佛尔酮二异氰酸酯，升温至90℃保温反应3小时，两小时测定NCO含量，达到理论值后降温至50℃，加入5.33g的二羟甲基丙酸和2g的1,4-丁二醇和少量丙酮调整粘度，升温至80℃反应6小时，反应结束测定NCO含量，然后降温至5℃，加入4.01g的三乙胺进行中和，中和30分钟后，高速剪切下加入去离子水，分散2分钟，然后缓慢加入用冰水稀释的1.2g的乙二胺，减压蒸馏除去体系中的丙酮，即得到样品5。
测试结果
(1)使用涂四杯测试本发明实施例1～4以及对比例1中获得的水性聚氨酯树脂在25℃下的粘度分别为：75S、67S、70S、72S、84S。
(2)将上述实施例中获得的5个水性聚氨酯样品以及两种市面销售的水性聚氨酯树脂以相同的工艺制成合成革面料，然后进行柔软度、粘度、耐醇性和耐水性测试。
其中，柔软度：很柔软为5级，柔软4级，较柔软为3级，较硬为2级，硬为1级；
粘度：很粘为5级，粘4级，较粘为3级，较不粘为2级，不粘1级。
表1 由实施例1-4、对比例1及市面销售的水性聚氨酯制成的合成革面料的性能测试结果
表1为实施例1至4、对比例1及市面销售的水性聚氨酯树脂制成的合成革面料的性能测试结果。从表1中看出，由实施例1至4以及对比例1获得水性聚氨酯树脂制成的合成革面料的柔软性较好，对粘度性能也有大大的改善，实施例1至4的合成革面料的粘度优于对比例1，说明加入聚硅氧烷多元醇提高了合成革的粘度性能；并且由实施例1至4以及对比例1获得水性聚氨酯制成的合成革面料在常温、低温耐折性、以及耐水解性上均不低于由市场销售中水性聚氨酯制成的合成革面料。所以，由实施例1至4获得水性聚氨酯制成的合成革面料在柔软度、粘度、耐水解性和耐折性方面的性能优异，尤其在柔软度、粘度方面可以做到软而不粘，大大改善了合成革面料的产品质量。
以上所述，仅为本发明的较佳实施例，并非对本发明任何形式上和实质上的限制，应当指出，对于本技术领域的普通技术人员，在不脱离本发明方法的前提下，还将可以做出若干改进和补充，这些改进和补充也应视为本发明的保护范围。凡熟悉本专业的技术人员，在不脱离本发明的精神和范围的情况下，当可利用以上所揭示的技术内容而做出的些许更动、修饰与演变的等同变化，均为本发明的等效实施例；同时，凡依据本发明的实质技术对上述实施例所作的任何等同变化的更动、修饰与演变，均仍属于本发明的技术方案的范围内。

Claims (5)

1.一种用于合成革面料的水性聚氨酯树脂，其特征在于：包括以下原料组分及重量份：
其中，所述多元醇包括聚碳酸酯多元醇和聚硅氧烷多元醇，所述聚碳酸酯多元醇通过己内酯与1,6-己二醇聚合反应而获得，所述聚碳酸酯多元醇的分子量为1800-2100，所述聚碳酸酯多元醇与所述聚硅氧烷多元醇的重量比例为(9-13):(0.1-0.4)，所述第一扩链剂选自二羟甲基丙酸、二羟甲基丁酸、二羟甲基戊酸和二羟甲基辛酸中的一种或多种，所述第二扩链剂选自乙二醇、一缩二乙二醇、1,4-丁二醇、2,3-丁二醇、1,6-己二醇、新戊二醇、二甘醇、甘油、山梨醇、三羟甲基丙烷和二羟甲基环己烷中的一种或多种，所述第三扩链剂选自乙二胺、异佛尔酮二胺、1,6-己二胺、1,3-环己二甲胺和间苯二甲胺中的任意一种或多种。
2.如权利要求1所述水性聚氨酯树脂，其特征在于：所述多元醇还包括聚环氧丙烷多元醇和/或聚四氢呋喃多元醇。
3.如权利要求1所述的阴离子水性聚氨酯树脂，其特征在于：所述多异氰酸酯选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、4,4-二环己基甲烷二异氰酸酯、二苯基甲烷二异氰酸酯、1,6-己二异氰酸酯、苯二亚甲基二异氰酸酯、萘-1,5-二异氰酸酯、多亚甲基多苯基异氰酸酯、四甲基苯二亚甲基二异氰酸酯、甲基环己基二异氰酸酯和二环己基甲烷二异氰酸酯中的任意一种或多种。
4.一种制备如权利要求1至3任一所述的水性聚氨酯树脂的方法，其特征在于：包括以下步骤：将所述多元醇和所述多异氰酸酯在85～95℃下反应2～3h；再加入所述第一扩链剂和所述第二扩链剂在75～85℃下反应5～8h；降温至0～5℃加入所述成盐剂中和；加水后再加入所述第三扩链剂，减压蒸馏，获得水性聚氨酯树脂。
5.如权利要求4所述的水性聚氨酯树脂的制备方法，其特征在于：加入所述第一扩链剂和所述第二扩链剂的同时加入丙酮。
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