CN113462343A - 一种双组份水性聚氨酯粘合剂及其制备方法 - Google Patents

一种双组份水性聚氨酯粘合剂及其制备方法 Download PDF

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CN113462343A
CN113462343A CN202110574158.XA CN202110574158A CN113462343A CN 113462343 A CN113462343 A CN 113462343A CN 202110574158 A CN202110574158 A CN 202110574158A CN 113462343 A CN113462343 A CN 113462343A
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朱立芳
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Anhui Dasong Resin Co ltd
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Abstract

本发明公开了一种双组份水性聚氨酯粘合剂及其制备方法，涉及粘合剂技术领域，包括A组分和B组分；所述A组分由以下重量份的原料制成：蓖麻油15～20份、聚碳酸酯二醇15～20份、聚己二酸‑1,4‑丁二醇酯二醇80～100份、N‑(2‑氨基乙基)‑2‑氨基乙烷磺酸钠盐6～10份、三羟甲基丙烷3～8份、二异氰酸酯20～30份、二月桂酸二丁基锡0.02～0.05份、乙二胺2.5～4份；所述B组分为六亚甲基二异氰酸酯三聚体。本发明制备工艺简单，制得的粘合剂综合性能优异，具有良好的耐水解性、剥离强度高、贮存稳定性好，对胶鞋、运动鞋、皮鞋等多种鞋材均具有很好的粘结能力，可以满足鞋用耐水性胶粘剂高湿环境下的应用要求。

Description

一种双组份水性聚氨酯粘合剂及其制备方法
技术领域
本发明涉及粘合剂技术领域，尤其涉及一种双组份水性聚氨酯粘合剂及其制备方法。
背景技术
水性聚氨酯粘合剂是指将聚氨酯溶于水或分散于水中而形成的胶黏剂，与溶剂型相比具有无溶剂、无污染、成膜性好、粘接力强等优点。随着人们的安全和环保意识的加强，水性聚氨酯胶黏剂的研究得以迅速发展，由于其优良的粘接性、耐磨性，良好的弹性和工艺性，被广泛地应用于制鞋工业和其它工业领域。然而，水性聚氨酯的机械性能、耐水性不佳，从而难以满足鞋用胶粘剂高湿环境下的应用需求。
发明内容
基于背景技术存在的技术问题，本发明提出了一种双组份水性聚氨酯粘合剂及其制备方法，制得的粘合剂具有良好的耐水解性、剥离强度高、贮存稳定性好，可以满足鞋用耐水性胶粘剂高湿环境下的应用要求。
本发明提出的一种双组份水性聚氨酯粘合剂，包括A组分和B组分；
所述A组分由以下重量份的原料制成：蓖麻油15～20份、聚碳酸酯二醇15～20份、聚己二酸-1,4-丁二醇酯二醇80～100份、N-(2-氨基乙基)-2-氨基乙烷磺酸钠盐6～10份、三羟甲基丙烷3～8份、二异氰酸酯20～30份、二月桂酸二丁基锡0.02～0.05份、乙二胺2.5～4份；
所述B组分为六亚甲基二异氰酸酯三聚体。
优选地，所述聚己二酸-1,4-丁二醇酯二醇的分子量为1000-2000。
优选地，所述二异氰酸酯由异氟尔酮二异氰酸酯和甲苯二异氰酸酯按照2～3：2～3组成的。
优选地，所述A组分和B组分的重量比为9～10：1。
本发明还提出了上述双组份水性聚氨酯粘合剂的制备方法，包括以下步骤：
S1、A组分制备：将蓖麻油、聚碳酸酯二醇、聚己二酸-1,4-丁二醇酯二醇、N-(2-氨基乙基)-2-氨基乙烷磺酸钠盐、三羟甲基丙烷加入到反应容器中，升温搅拌，然后加入二异氰酸酯和二月桂酸二丁基锡，降温，搅拌反应，反应过程中加入丙酮调节体系粘度；降温，加入三乙胺中和成盐，然后加入去离子水乳化，再加入乙二胺进行扩链，搅拌反应，减压蒸出丙酮，即得聚氨酯分散液，作为A组分；
S2、配胶：将A组分和B组分按比例混合均匀，即可使用。
优选地，将蓖麻油、聚碳酸酯二醇、聚己二酸-1,4-丁二醇酯二醇、N-(2-氨基乙基)-2-氨基乙烷磺酸钠盐、三羟甲基丙烷加入到反应容器中，升温至80～90℃，搅拌30～40min，然后加入二异氰酸酯和二月桂酸二丁基锡，降温至70～80℃，搅拌反应4～5h，反应过程中加入丙酮调节体系粘度；降温至50～60℃，加入三乙胺中和成盐，然后加入去离子水乳化，再加入乙二胺进行扩链，搅拌反应50～60min，减压蒸出丙酮，即得聚氨酯分散液。
优选地，A组分中固含量为40～45％。
有益效果：本发明提出了一种双组份水性聚氨酯粘合剂，通过对组分的优化选择，以蓖麻油、聚碳酸酯二醇、聚己二酸-1,4-丁二醇酯二醇作为混合软段，以异氟尔酮二异氰酸酯和甲苯二异氰酸酯作为硬段，采用预聚体分散法制备获得具有良好剥离强度和耐水性的磺酸型水性聚氨酯分散体；亲水单体采用N-(2-氨基乙基)-2-氨基乙烷磺酸钠盐和三羟甲基丙烷复配，提高聚氨酯耐水解性的同时还获得一定的内交联结构提高机械性能。
本发明制备工艺简单，制得的粘合剂综合性能优异，具有良好的耐水解性、剥离强度高、贮存稳定性好，对胶鞋、运动鞋、皮鞋等多种鞋材均具有很好的粘结能力，可以满足鞋用耐水性胶粘剂高湿环境下的应用要求。
具体实施方式
下面，通过具体实施例对本发明的技术方案进行详细说明。
实施例1
本发明提出的一种双组份水性聚氨酯粘合剂，包括A组分和B组分；
其中，A组分由以下重量份的原料制成：蓖麻油15份、聚碳酸酯二醇15份、聚己二酸-1,4-丁二醇酯二醇PBA1000 100份、N-(2-氨基乙基)-2-氨基乙烷磺酸钠盐6份、三羟甲基丙烷8份、异氟尔酮二异氰酸酯12份、甲苯二异氰酸酯18份、二月桂酸二丁基锡0.05份、乙二胺2.5份；
A组分的制备如下：将蓖麻油、聚碳酸酯二醇、聚己二酸-1,4-丁二醇酯二醇、N-(2-氨基乙基)-2-氨基乙烷磺酸钠盐、三羟甲基丙烷加入到反应容器中，升温至80℃，搅拌30min，然后加入异氟尔酮二异氰酸酯、甲苯二异氰酸酯和二月桂酸二丁基锡，降温至70℃，搅拌反应4h，反应过程中加入丙酮调节体系粘度；降温至50℃，加入三乙胺中和成盐，然后加入去离子水乳化，再加入乙二胺进行扩链，搅拌反应50min，减压蒸出丙酮，即得聚氨酯分散液。
所述B组分为六亚甲基二异氰酸酯三聚体。
使用时，将A组分和B组分按照10：1的重量比混合均匀即可。
实施例2
本发明提出的一种双组份水性聚氨酯粘合剂，包括A组分和B组分；
其中，A组分由以下重量份的原料制成：蓖麻油17份、聚碳酸酯二醇15份、聚己二酸-1,4-丁二醇酯二醇PBA1000 95份、N-(2-氨基乙基)-2-氨基乙烷磺酸钠盐7份、三羟甲基丙烷6份、异氟尔酮二异氰酸酯12份、甲苯二异氰酸酯15份、二月桂酸二丁基锡0.05份、乙二胺3份；
A组分的制备如下：将蓖麻油、聚碳酸酯二醇、聚己二酸-1,4-丁二醇酯二醇、N-(2-氨基乙基)-2-氨基乙烷磺酸钠盐、三羟甲基丙烷加入到反应容器中，升温至85℃，搅拌30min，然后加入异氟尔酮二异氰酸酯、甲苯二异氰酸酯和二月桂酸二丁基锡，降温至75℃，搅拌反应4h，反应过程中加入丙酮调节体系粘度；降温至50℃，加入三乙胺中和成盐，然后加入去离子水乳化，再加入乙二胺进行扩链，搅拌反应50min，减压蒸出丙酮，即得聚氨酯分散液。
所述B组分为六亚甲基二异氰酸酯三聚体。
使用时，将A组分和B组分按照10：1的重量比混合均匀即可。
实施例3
本发明提出的一种双组份水性聚氨酯粘合剂，包括A组分和B组分；
其中，A组分由以下重量份的原料制成：蓖麻油18份、聚碳酸酯二醇18份、聚己二酸-1,4-丁二醇酯二醇PBA1000 90份、N-(2-氨基乙基)-2-氨基乙烷磺酸钠盐8份、三羟甲基丙烷5份、异氟尔酮二异氰酸酯12份、甲苯二异氰酸酯12份、二月桂酸二丁基锡0.05份、乙二胺3.5份；
A组分的制备如下：将蓖麻油、聚碳酸酯二醇、聚己二酸-1,4-丁二醇酯二醇、N-(2-氨基乙基)-2-氨基乙烷磺酸钠盐、三羟甲基丙烷加入到反应容器中，升温至85℃，搅拌35min，然后加入异氟尔酮二异氰酸酯、甲苯二异氰酸酯和二月桂酸二丁基锡，降温至75℃，搅拌反应4.5h，反应过程中加入丙酮调节体系粘度；降温至55℃，加入三乙胺中和成盐，然后加入去离子水乳化，再加入乙二胺进行扩链，搅拌反应1h，减压蒸出丙酮，即得聚氨酯分散液。
所述B组分为六亚甲基二异氰酸酯三聚体。
使用时，将A组分和B组分按照10：1的重量比混合均匀即可。
实施例4
本发明提出的一种双组份水性聚氨酯粘合剂，包括A组分和B组分；
其中，A组分由以下重量份的原料制成：蓖麻油20份、聚碳酸酯二醇20份、聚己二酸-1,4-丁二醇酯二醇PBA1000 80份、N-(2-氨基乙基)-2-氨基乙烷磺酸钠盐10份、三羟甲基丙烷3份、异氟尔酮二异氰酸酯12份、甲苯二异氰酸酯8份、二月桂酸二丁基锡0.05份、乙二胺4份；
A组分的制备如下：将蓖麻油、聚碳酸酯二醇、聚己二酸-1,4-丁二醇酯二醇、N-(2-氨基乙基)-2-氨基乙烷磺酸钠盐、三羟甲基丙烷加入到反应容器中，升温至90℃，搅拌40min，然后加入异氟尔酮二异氰酸酯、甲苯二异氰酸酯和二月桂酸二丁基锡，降温至80℃，搅拌反应5h，反应过程中加入丙酮调节体系粘度；降温至60℃，加入三乙胺中和成盐，然后加入去离子水乳化，再加入乙二胺进行扩链，搅拌反应1h，减压蒸出丙酮，即得聚氨酯分散液。
所述B组分为六亚甲基二异氰酸酯三聚体。
使用时，将A组分和B组分按照10：1的重量比混合均匀即可。
对本发明实施例1-4制备的双组份水性聚氨酯粘合剂的性能进行检测。
检测方法：将制备的双组份水性聚氨酯粘合剂的A组分和B组分混合均匀，然后将其涂布到经打磨清理后的150×25mm的丁苯橡胶条表面，涂布量为25g/m2，开放时间1分钟；按照GB 19340-2003测试粘接性能；具体检测项目如下：
1.剥离强度：将试样条于25℃、相对湿度50％下存放7d，测T-剥离强度；
2.耐热老化性：将试样条于25℃、相对湿度50％下存放7d，再在50℃、相对湿度50％下存放7d，然后室温下放置24h后测试试样条的T-剥离强度；
3.剪切强度：将试样条于25℃、相对湿度50％下存放7d，测剪切强度；
检测结果如表1所示。
表1双组份水性聚氨酯粘合剂的性能数据
实施例1 实施例2 实施例3 实施例4
剥离强度N/mm 6.9 7.3 7.1 7.0
耐热老化性N/mm 6.9 7.2 7.1 6.9
剪切强度MPa 2.6 2.8 2.9 2.6
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。

Claims (7)

1.一种双组份水性聚氨酯粘合剂，其特征在于，包括A组分和B组分；
所述A组分由以下重量份的原料制成：蓖麻油15～20份、聚碳酸酯二醇15～20份、聚己二酸-1,4-丁二醇酯二醇80～100份、N-(2-氨基乙基)-2-氨基乙烷磺酸钠盐6～10份、三羟甲基丙烷3～8份、二异氰酸酯20～30份、二月桂酸二丁基锡0.02～0.05份、乙二胺2.5～4份；
所述B组分为六亚甲基二异氰酸酯三聚体。
2.根据权利要求1所述的双组份水性聚氨酯粘合剂，其特征在于，所述聚己二酸-1,4-丁二醇酯二醇的分子量为1000-2000。
3.根据权利要求1所述的双组份水性聚氨酯粘合剂，其特征在于，所述二异氰酸酯由异氟尔酮二异氰酸酯和甲苯二异氰酸酯按照2～3：2～3组成的。
4.根据权利要求1所述的双组份水性聚氨酯粘合剂，其特征在于，所述A组分和B组分的重量比为9～10：1。
5.一种基于权利要求1-4任一项所述的双组份水性聚氨酯粘合剂的制备方法，其特征在于，包括以下步骤：
S1、A组分制备：将蓖麻油、聚碳酸酯二醇、聚己二酸-1,4-丁二醇酯二醇、N-(2-氨基乙基)-2-氨基乙烷磺酸钠盐、三羟甲基丙烷加入到反应容器中，升温搅拌，然后加入二异氰酸酯和二月桂酸二丁基锡，降温，搅拌反应，反应过程中加入丙酮调节体系粘度；降温，加入三乙胺中和成盐，然后加入去离子水乳化，再加入乙二胺进行扩链，搅拌反应，减压蒸出丙酮，即得聚氨酯分散液，作为A组分；
S2、配胶：将A组分和B组分按比例混合均匀，即可使用。
6.根据权利要求5所述的双组份水性聚氨酯粘合剂的制备方法，其特征在于，将蓖麻油、聚碳酸酯二醇、聚己二酸-1,4-丁二醇酯二醇、N-(2-氨基乙基)-2-氨基乙烷磺酸钠盐、三羟甲基丙烷加入到反应容器中，升温至80～90℃，搅拌30～40min，然后加入二异氰酸酯和二月桂酸二丁基锡，降温至70～80℃，搅拌反应4～5h，反应过程中加入丙酮调节体系粘度；降温至50～60℃，加入三乙胺中和成盐，然后加入去离子水乳化，再加入乙二胺进行扩链，搅拌反应50～60min，减压蒸出丙酮，即得聚氨酯分散液。
7.根据权利要求5所述的双组份水性聚氨酯粘合剂的制备方法，其特征在于，A组分中固含量为40～45％。
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