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CN109180900A - 一种可提升与pvc人造革涂层附着力的水基聚氨酯及制备方法 - Google Patents

一种可提升与pvc人造革涂层附着力的水基聚氨酯及制备方法 Download PDF

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CN109180900A
CN109180900A CN201810964473.1A CN201810964473A CN109180900A CN 109180900 A CN109180900 A CN 109180900A CN 201810964473 A CN201810964473 A CN 201810964473A CN 109180900 A CN109180900 A CN 109180900A
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范浩军
徐佳丽
颜俊
陈意
孙哲
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Sichuan University
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Abstract

本发明公开了一种可提升与PVC人造革涂层附着力的水基聚氨酯及制备方法。将含有氰基的端羟基化合物作为扩链剂，与异氰酸酯反应嵌入到水性聚氨酯的结构单元中，提升了水性聚氨酯与PVC人造革涂层的附着力。同时，该水基聚氨酯干燥时，在乳胶粒相互融合的过程中，屏蔽在乳胶粒内部的叔胺基与乳胶粒表面的羧基发生阴阳离子交联作用，进一步提升了其抗溶剂性、抗粘性和耐水解性。该水性聚氨酯综合性能优异，且以水代替有机溶剂，可从源头消除有机溶剂污染，具有环境友好性，尤其适合用作各种软质PVC材料的表面处理剂的基础树脂。

Description

一种可提升与PVC人造革涂层附着力的水基聚氨酯及制备 方法
技术领域
本发明涉及一种可提升与PVC人造革涂层附着力的水基聚氨酯及制备方法，属于高分子材料合成技术领域。
背景技术
在我国，人们习惯将用PVC树脂为原料生产的人造革称为PVC人造革(简称人造革)。我国是世界人造革生产和消费大国，截至2017年，我国人造革、合成革生产线和产量已占据世界总产量的2/3，是塑料行业重点发展的产业。
人造革主要由3层构成，粘接层、中间发泡层、表面效应层（表面处理剂）。表处剂一般由聚氨酯和特殊助剂复配而成，其作为人造革顶层，要求具有较好的物理性能，如耐水解、耐溶剂、与PVC人造革涂层有良好的附着力等。
传统人造革表面处理过程使用溶剂型树脂，其中有机溶剂的挥发会造成严重的环境污染，这些溶剂主要是二甲基甲酰胺（DMF）、甲苯、环己酮、丁酮、乙酸乙酯和乙酸丁酯等。根据测算，在有溶剂回收设备的企业中，每一条人造革生产线每年排放甲苯、丁酮、乙酸酯类溶剂24.5吨。因此，人造革行业长期面临着环境治理成本高、资源浪费严重、环境污染的严峻挑战，如何开发水性树脂替代传统的溶剂型树脂，是维系人造革产业可持续发展的关键。
但对于水性聚氨酯树脂而言，根据二元醇的种类可分为聚酯型聚氨酯和聚醚型聚氨酯。对于聚酯型水性聚氨酯，其结构中的酯键有利于提升聚氨酯与PVC涂层的附着力，但分子内的酯键本身不耐水解，而且水性聚氨酯中的亲水基还会加速这种水解作用；聚醚型水性聚氨酯耐水解优良，但耐溶剂和与PVC涂层间的附着力差，拉伸时易出现拉白和折白现象。因此，表处剂的耐水解性与附着力难以平衡。
发明内容
本发明的目的是为了克服现有技术存在的缺点和不足，而提供一种可提升与PVC人造革涂层附着力的水基聚氨酯及制备方法。该水基聚氨酯低模量、高弹性、软而不粘、耐水解、耐溶剂，且提升了与PVC人造革涂层的附着力，适合作为PVC表处剂的基础树脂；采用水性聚氨酯代替传统的溶剂型聚氨酯作为表处树脂，可减少有机溶剂的使用，减少环境污染，具有环境友好性。
通过如下工艺步骤制备（其中所述物料的份数均为重量份数）：
（1）小分子扩链剂N-(2-腈基乙基)二乙醇胺的制备
将50～70份二乙醇胺置于带有控温、搅拌、恒压滴液漏斗和回流冷凝装置的250～500ml干燥四口瓶中，通氮气保护，并加热到35～50℃；然后开始滴加40～50份丙烯腈，保持温度稳定在50～55℃，1～1.5小时滴加完毕，继续保温3～5小时，然后减压蒸馏脱除残留的丙烯腈，即得到扩链剂N-(2-腈基乙基)二乙醇胺；
（2）水基聚氨酯的制备
将耐水解型二元醇30-80份、二异氰酸酯10-20份、三羟甲基丙烷0.1-0.2份和催化剂0.02-0.04份加入反应容器，在持续搅拌和氮气气氛保护下，升温至75-85℃反应50-70分钟，加入小分子扩链剂N-(2-腈基乙基)二乙醇胺0.5-3份，并维持在75-85℃反应50-70分钟制得预聚体；
将2-3份含羧基的短链脂肪族二元醇溶解于5-20份溶剂中，再加入1.8-2.5份三乙胺进行中和，然后将其加入所得的预聚体中，降温至50-55℃持续反应3-4小时，制得含亲水基的预聚体；
降温至45 ℃以下，高剪切速率下加入去离子水乳化（此过程中由于体系呈碱性，COO-离子在乳胶粒表面提供亲水性，而扩链剂中的叔胺无法电离被屏蔽在乳胶粒内部），然后加入0.3-0.8份后交联剂或后扩链剂室温下反应2-3小时，即得到可提升与PVC人造革涂层附着力的水基聚氨酯乳液。
水基聚氨酯固含量为25%-35%，羧基的质量分数为1.0%-1.5%，异氰酸根指数为1.3-1.4。
耐水解型二元醇为数均分子量为1000-4000的共聚氧化乙烯氧化丙烯醚二醇、共聚氧化乙烯四氢呋喃醚二醇、聚丙二醇、聚碳酸酯二醇、共聚氧化丙烯四氢呋喃醚二醇中的一种或其组合。
二异氰酸酯为异佛二酮二异氰酸酯、2,4-甲苯二异氰酸酯、4,4 ， -二苯甲烷二异氰酸酯、六亚甲基二异氰酸酯、对苯二异氰酸酯或碳化二亚胺和脲酮亚胺改性的4,4 ， -二苯甲烷二异氰酸酯中的一种或其组合。
催化剂为月桂酸二丁基锡、辛酸亚锡、月桂酸铋、新癸酸铋、异辛酸铋、环烷酸铋、二甲基环己胺或N-乙基吗啡啉中的任一种。
含羧基的短链脂肪族二元醇为二羟甲基丙酸或二羟甲基丁酸中的任一种。
后交联剂或后扩链剂为正硅酸乙酯、γ-氨丙基三乙氧基硅烷、N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷、二乙烯三胺和乙二胺中的至少一种。
小分子扩链剂N-(2-腈基乙基)二乙醇胺具有如下结构式：
。
小分子扩链剂N-(2-腈基乙基)二乙醇胺的具体合成路线为：
。
本发明与现有技术相比，具有以下积极效果：
（1）本发明的水基聚氨酯以N-(2-腈基乙基)二乙醇胺作为小分子扩链剂，在分子中引入了强极性基团-CN，提升了其与强极性的PVC人造革涂层的附着力，尤其适用于PVC人造革表处剂的基础聚氨酯树脂，且-CN耐热性和耐溶剂性优良；
（2）本发明提供的水基聚氨酯在干燥过程中乳胶粒之间相互融合，屏蔽在乳胶粒内部的叔胺基与乳胶粒表面的羧基发生阴阳离子交联作用，有效地提升了其附着力、抗粘性和抗溶剂性；同时，阴阳离子相互作用而失去亲水性，进一步改善了耐水解性能；
（3）本发明使用的N-(2-腈基乙基)二乙醇胺扩链剂，其端羟基结构对称、反应活性相同，有利于化学反应的进行和聚合物性能的调控；
（4）采用本发明的水性聚氨酯替代传统的溶剂型聚氨酯作为表处树脂，从源头消除有机溶剂污染，消除安全隐患，节约资源，改善就业者工作环境，提升了人造革的生态等级和国际市场竞争力。
附图说明
图1是实施例1使用N-(2-腈基乙基)二乙醇胺作为扩链剂与对比例1使用一缩二乙二醇作为扩链剂的水性聚氨酯的红外光谱对比图。与对比例1相比，实施例1在2247 cm-1处出现了明显的-CN特征吸收峰，表明扩链剂N-(2-腈基乙基)二乙醇胺成功接入了水性聚氨酯中。
具体实施方式
下面通过实施例对本发明进行具体的描述，只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限定，该领域的技术工程师可根据上述发明的内容对本发明作出一些非本质的改进和调整。
实施例1：
（1）将数均分子量为2000的聚丙二醇30份、共聚氧化丙烯四氢呋喃醚二醇、数均分子量为1000的共聚氧化乙烯四氢呋喃醚二醇20份、异佛二酮二异氰酸酯9份、六亚甲基二异氰酸酯9份、三羟甲基丙烷0.2份和月桂酸铋0.04份加入反应容器，在持续搅拌和氮气气氛保护下，升温至85℃反应1小时，加入小分子扩链剂N-(2-腈基乙基)二乙醇胺0.9份，并维持在85℃反应1小时制得预聚体；
（2）将2.6份二羟甲基丙酸溶解于15份丙酮中，再加入2.15份三乙胺进行中和，然后将其加入所得的预聚体中，降温至55℃持续反应3小时，制得含亲水基的预聚体；
（3）降温至45 ℃以下，高剪切速率下加入200份去离子水乳化，然后加入0.4份N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷室温下反应3小时，即得到可提升与PVC人造革涂层附着力的水基聚氨酯乳液。
实施例2
（1）将数均分子量为2000的聚丙二醇40份、共聚氧化乙烯四氢呋喃醚二醇10份、数均分子量为1000的共聚氧化乙烯四氢呋喃醚二醇10份、异佛二酮二异氰酸酯14份、六亚甲基二异氰酸酯4份、三羟甲基丙烷0.2份和月桂酸铋0.04份加入反应容器，在持续搅拌和氮气气氛保护下，升温至85℃反应1小时，加入小分子扩链剂N-(2-腈基乙基)二乙醇胺1份，并维持在85℃反应1小时制得预聚体；
（2）将2.5份二羟甲基丙酸溶解于15份丙酮中，再加入2份三乙胺进行中和，然后将其加入所得的预聚体中，降温至55℃持续反应3小时，制得含亲水基的预聚体；
（3）降温至45 ℃以下，高剪切速率下加入180份去离子水乳化，然后加入0.1份正硅酸乙酯、0.5份二乙烯三胺室温下反应2小时，即得到可提升与PVC人造革涂层附着力的水基聚氨酯乳液。
实施例3：
（1）将数均分子量为2000的聚丙二醇20份、聚碳酸酯二醇16份、2,4-甲苯二异氰酸酯7.5份、六亚甲基二异氰酸酯2.5份、三羟甲基丙烷0.1份和月桂酸二丁基锡0.02份加入反应容器，在持续搅拌和氮气气氛保护下，升温至65℃反应1小时，加入小分子扩链剂N-(2-腈基乙基)二乙醇胺0.8份，并维持在75℃反应1小时制得预聚体；
（2）将2.3份二羟甲基丙酸溶解于15份丙酮中，再加入1.9份三乙胺进行中和，然后将其加入所得的预聚体中，降温至55℃持续反应3小时，制得含亲水基的预聚体；
（3）降温至45 ℃以下，高剪切速率下加入110份去离子水乳化，然后加入0.8份正硅酸乙酯室温下反应2小时，即得到可提升与PVC人造革涂层附着力的水基聚氨酯乳液。
实施例4：
（1）将数均分子量为4000的聚碳酸酯二醇15份、数均分子量为1000的共聚氧化乙烯氧化丙烯醚二醇25份、2,4-甲苯二异氰酸酯9份、六亚甲基二异氰酸酯3份、三羟甲基丙烷0.2份和月桂酸二丁基锡0.03份加入反应容器，在持续搅拌和氮气气氛保护下，升温至65℃反应1小时，加入小分子扩链剂N-(2-腈基乙基)二乙醇胺0.7份，并维持在75℃反应1小时制得预聚体；
（2）将2.1份二羟甲基丙酸溶解于15份丙酮中，再加入1.8份三乙胺进行中和，然后将其加入所得的预聚体中，降温至55℃持续反应3小时，制得含亲水基的预聚体；
（3）降温至45 ℃以下，高剪切速率下加入120份去离子水乳化，然后加入0.4份γ-氨丙基三乙氧基硅烷室温下反应2小时，即得到可提升与PVC人造革涂层附着力的水基聚氨酯乳液。
对比例1：
（1）将数均分子量为2000的聚丙二醇30份、共聚氧化丙烯四氢呋喃醚二醇、数均分子量为1000的共聚氧化乙烯四氢呋喃醚二醇20份、异佛二酮二异氰酸酯9份、六亚甲基二异氰酸酯9份、三羟甲基丙烷0.2份和月桂酸铋0.04份加入反应容器，在持续搅拌和氮气气氛保护下，升温至85℃反应1小时，加入一缩二乙二醇0.9份，并维持在85℃反应1小时制得预聚体；
（2）将2.6份二羟甲基丙酸溶解于15份丙酮中，再加入2.15份三乙胺进行中和，然后将其加入所得的预聚体中，降温至55℃持续反应3小时，制得含亲水基的预聚体；
（3）降温至45 ℃以下，高剪切速率下加入200份去离子水乳化，然后加入0.4份N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷室温下反应3小时，即得到水基聚氨酯乳液。
测试结果：
（1）将各实施例及对比例所得水性聚氨酯乳液添加增稠剂、流平剂复配后涂覆于PVC基材上，120℃下烘干冷却后按照GB/T 9286-1998 标准进行附着力测试，结果以0-5级评价，0级最好，5级最差，对于一般性的用途，前三级是令人满意的；
（2）将各实施例及对比例所得水性聚氨酯乳液先置于聚四氟乙烯模板中，室温下缓慢风干，再放入60℃真空干燥箱中干燥至胶膜质量不再变化，得到厚度为3.0mm的透明、无气泡、表面平整的聚氨酯乳胶膜，再进行柔软度、粘度、耐水解性、耐溶剂性测试：
根据ASTM D412-Diec标准测定胶膜的力学性能，结果以1-5级表示柔软度：很柔软为5级，柔软为4级，较柔软为3级，较硬为2级，硬为1级；
根据HG/T 3828-2006标准进行抗粘连性测试，结果以A-F表示粘连等级，0-5表示表面损坏等级，等级越小，防粘性越好；
根据QB/T 4671-2014标准A法进行耐水解性测试，结果以胶膜水解前后拉伸强度的保留率来定量表示；
将薄膜剪成2 cm×2 cm正方形，称重，浸入25℃甲苯中，24 h后再称重，以浸泡后增重率表示耐溶剂性。
表1 一种可提升与PVC人造革涂层附着力的水基聚氨酯性能测试结果
项目 实例 对比例1 实施例1 实施例2 实施例3 实施例4
附着力/级 4 2 2 1 1
柔软度/级 5 5 4 5 4
粘度/级 C-0 B-0 B-0 B-0 B-0
耐水解性/% 88 92 94 90 95
耐溶剂性/% 149 121 116 125 109
由表1可知，实施例1-4均表现出与PVC涂层较好的附着力，且成膜软而不粘、耐水解、耐溶剂，综合性能优异。与对比例1相比较，实施例1在PVC上的附着力有了明显的提高，说明分子中引入强极性基团-CN对改善水性聚氨酯的附着力有显著效果，同时，由于该水性聚氨酯在干燥过程中乳胶粒之间相互融合，屏蔽在乳胶粒内部的叔胺基与乳胶粒表面的羧基发生阴阳离子交联作用，不同程度上提升了其抗粘性、耐水解性和耐溶剂性，但由于腈基乙基在分子侧链，柔软度基本保持不变。

Claims (7)

1.一种可提升与PVC人造革涂层附着力的水基聚氨酯及制备方法，其特征在于通过如下工艺制备，其中物料的份数均为重量份数：
（1）小分子扩链剂N-(2-腈基乙基)二乙醇胺的制备
将50～70份二乙醇胺置于带有控温、搅拌、恒压滴液漏斗和回流冷凝装置的250～500ml干燥四口瓶中，通氮气保护，并加热到35～50℃；然后开始滴加40～50份丙烯腈，保持温度稳定在50～55℃，1～1.5小时滴加完毕，继续保温3～5小时，然后减压蒸馏脱除残留的丙烯腈，即得到扩链剂N-(2-腈基乙基)二乙醇胺；
（2）水基聚氨酯的制备
将耐水解型二元醇30-80份、二异氰酸酯10-20份、三羟甲基丙烷0.1-0.2份和催化剂0.02-0.04份加入反应容器，在持续搅拌和氮气气氛保护下，升温至75-85℃反应50-70分钟，加入小分子扩链剂N-(2-腈基乙基)二乙醇胺0.5-3份，并维持在75-85℃反应50-70分钟制得预聚体；
将2-3份含羧基的短链脂肪族二元醇溶解于5-20份溶剂中，再加入1.8-2.5份三乙胺进行中和，然后将其加入所得的预聚体中，降温至50-55℃持续反应3-4小时，制得含亲水基的预聚体；
降温至45 ℃以下，高剪切速率下加入去离子水乳化，然后加入0.3-0.8份后交联剂或后扩链剂室温下反应2-3小时，即得到可提升与PVC人造革涂层附着力的水基聚氨酯乳液。
2.根据权利要求1所述的一种可提升与PVC人造革涂层附着力的水基聚氨酯及制备方法，其特征在于所述水基聚氨酯固含量为25%-35%，羧基的质量分数为1.0%-1.5%，异氰酸根指数为1.3-1.4。
3.根据权利要求1所述的一种可提升与PVC人造革涂层附着力的水基聚氨酯及制备方法，其特征在于所述耐水解型二元醇为数均分子量为1000-4000的共聚氧化乙烯氧化丙烯醚二醇、共聚氧化乙烯四氢呋喃醚二醇、聚丙二醇、聚碳酸酯二醇、共聚氧化丙烯四氢呋喃醚二醇中的一种或其组合。
4.根据权利要求1所述的一种可提升与PVC人造革涂层附着力的水基聚氨酯及制备方法，其特征在于所述二异氰酸酯为异佛二酮二异氰酸酯、2,4-甲苯二异氰酸酯、4,4 ， -二苯甲烷二异氰酸酯、六亚甲基二异氰酸酯、对苯二异氰酸酯或碳化二亚胺和脲酮亚胺改性的4,4 ， -二苯甲烷二异氰酸酯中的一种或其组合。
5.根据权利要求1所述的一种可提升与PVC人造革涂层附着力的水基聚氨酯及制备方法，其特征在于所述催化剂为月桂酸二丁基锡、辛酸亚锡、月桂酸铋、新癸酸铋、异辛酸铋、环烷酸铋、二甲基环己胺或N-乙基吗啡啉中的任一种。
6.根据权利要求1所述的一种可提升与PVC人造革涂层附着力的水基聚氨酯及制备方法，其特征在于所述含羧基的短链脂肪族二元醇为二羟甲基丙酸或二羟甲基丁酸中的任一种。
7.根据权利要求1所述的一种可提升与PVC人造革涂层附着力的水基聚氨酯及制备方法，其特征在于所述后交联剂或后扩链剂为正硅酸乙酯、γ-氨丙基三乙氧基硅烷、N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷、二乙烯三胺和乙二胺中的至少一种。
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CN113150732B (zh) * 2021-03-09 2021-10-22 四川大学 一种对基材表面能具有互识性的水基胶粘剂的制备方法
CN117701138A (zh) * 2023-12-25 2024-03-15 福建汇得新材料有限公司 一种高附着低光泽pvc人造革表处剂用水性聚氨酯分散体及其制备方法和应用
CN117701138B (zh) * 2023-12-25 2025-12-09 福建汇得新材料有限公司 一种高附着低光泽pvc人造革表处剂用水性聚氨酯分散体及其制备方法和应用

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