CN106634785B - 一种强耐水性水性聚氨酯胶黏剂的制备方法 - Google Patents

一种强耐水性水性聚氨酯胶黏剂的制备方法 Download PDF

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CN106634785B
CN106634785B CN201611030352.7A CN201611030352A CN106634785B CN 106634785 B CN106634785 B CN 106634785B CN 201611030352 A CN201611030352 A CN 201611030352A CN 106634785 B CN106634785 B CN 106634785B
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汪逸凡
徐越
赵玲玲
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Lu'anyi New Material Technology Co.,Ltd.
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Abstract

本发明涉及一种强耐水性水性聚氨酯胶黏剂的制备方法，属于胶黏剂技术领域。本发明先利用硬脂酸、脂肪酶和双氧水对棉籽油和蓖麻油进行环氧改性，改性后再和KH‑550混合，即可得到改性油，利用改性油对水性聚氨酯乳液进行改性提高水性聚氨酯的耐水性，最后将改性后的水性聚氨酯乳液和减水剂、交联剂等物质混合后即可得到耐水性水性聚氨酯胶黏剂，本发明制得的强耐水性水性聚氨酯胶黏剂耐水性能良好，属于高固含量产品，发挥快，干燥时间短，粘度适中，具有良好的流动性与贮存稳定性。

Description

一种强耐水性水性聚氨酯胶黏剂的制备方法
技术领域
本发明涉及一种强耐水性水性聚氨酯胶黏剂的制备方法，属于胶黏剂技术领域。
背景技术
聚氨酯胶黏剂是分子链中含有氨酯基和异氰酸酯基类的胶黏剂。聚氨酯由于具有优良的弹性、耐低温性、耐磨、耐化学药品和对各种基材良好的黏附性等特点，使其广泛应用于涂料、胶黏剂、油墨等领域。以往在胶黏剂和涂料方面，溶剂型产品占较大比例。但是溶剂型聚氨酯由于含有挥发性有机化合物而污染环境，使得其应用受到限制。随着人们环保意识的加强，水性聚氨酯获得快速发展，水性聚氨酯以水为溶剂，具有环境友好、无毒、不易燃等优点而被广泛用于环境友好型涂料和胶黏剂中，并显示出一系列优良的性质。
水性聚氨酯胶黏剂目前可分为3类：（1）可水分散性多异氰酸酯胶黏剂，其主要成分为含亲水基团、可自动分散于水的多异氰酸酯，其主要用于人造板制造和其他类型水性聚氨酯胶黏剂的固化剂；（2）乙烯基聚氨酯水性胶黏剂，其是乙烯基水性高分子乳液-多异氰酸酯双组分胶黏剂，主要用于木材粘接；（3）水分散性聚氨酯，其是高相对分子质量聚氨酯树脂溶于或分散于水中形成的稳定的水分散液为主体成分的胶黏剂，这一类是真正意义上以水分散性聚氨酯树脂为基础的水性聚氨酯胶黏剂，是一般溶剂型聚氨酯胶黏剂的替代品。
水性聚氨酯胶黏剂由于综合性能优良而被广泛地应用于民用、体育、航天、军事等领域，成为不可缺少的重要材料之一。现有的聚氨酯胶黏剂主要存在成膜速度较慢，固化时间长，大约需要4～6小时，耐水性不好以及固含相对较低，目前市场聚氨酯胶黏剂的固含量大约都在30%～40%。因此，对于水性聚氨酯胶黏剂的研究，显得尤为重要。
发明内容
本发明主要解决的技术问题是：针对传统水性聚氨酯胶黏剂存在干燥速度慢，初黏性低以及耐水性不好的问题，提供了一种利用环氧化油提高水性聚氨酯胶黏剂耐水性的方法，本发明先利用硬脂酸、脂肪酶和双氧水对棉籽油和蓖麻油进行环氧改性，改性后再和KH-550混合，即可得到改性油，利用改性油对水性聚氨酯乳液进行改性提高水性聚氨酯的耐水性，最后将改性后的水性聚氨酯乳液和减水剂、交联剂等物质混合后即可得到耐水性水性聚氨酯胶黏剂，本发明制得的强耐水性水性聚氨酯胶黏剂耐水性能良好，属于高固含量产品，发挥快，干燥时间短，粘度适中，具有良好的流动性与贮存稳定性。
为了解决上述技术问题，本发明所采用的技术方案是：
（1）称取10～20g硬脂酸加入到三口烧瓶中，再加入80～120mL甲苯，搅拌混合15～25min后放入水浴锅中，升温至60～65℃，在此温度下依次称取50～60g棉籽油和50～60g蓖麻油加入到三口烧瓶中，搅拌2～4min后加入0.1～0.3g脂肪酶和25～35mL质量分数30%双氧水，搅拌反应3～5h；
（2）上述反应结束后静置分层，得油相，用质量分数10%氢氧化钠溶液调节pH值为中性，调节后用去离子水洗涤油相2～4次，洗涤后放入真空烘箱中，在60～70℃温度下干燥3～5h后向油中加入0.1～0.3g硅烷偶联剂KH-550，搅拌20～30min得改性油；
（3）分别称取20～30g异弗尔酮二异氰酸酯和50～60g聚四氢呋喃醚二醇放入真空干燥箱中，干燥20～30min后混合，并加入反应釜中，向反应釜中用胶头滴管滴加2～3滴二月桂酸二丁基锡，搅拌混合后升温至80～90℃，保温搅拌反应2～3h，反应后滴加8～10g上述改性油，滴加结束后继续搅拌反应3～4h；
（4）称取0.8～1.0g二羟甲基丙酸加入到5～6gN-甲基吡咯烷酮中，搅拌至溶解得溶解液，待上述反应结束后滴加溶解液，滴加速度为2～3滴/s，滴加结束后在70～80℃温度下搅拌反应3～4h，反应结束后加入5～10g三乙胺和20～30g丙酮，搅拌15～20min，搅拌后冷却至室温得反应物，向反应物中加入200～300g去离子水，加入速度为5～10mL/min，加入同时以1000～1200r/min转速，高速乳化30～50min，得乳液后在56～60℃温度下蒸馏30～40min，蒸馏后即可得改性水性聚氨酯乳液；
（5）按重量份数计，分别选取70～80份上述改性聚氨酯乳液、1～3份磺化木质素、2～4份羧甲基纤维素、0.6～0.8份柠檬酸钠和8～10份聚碳化二亚胺XR-201，混合后在600～800W功率下超声搅拌30～50min，搅拌后即可得到强耐水性水性聚氨酯胶黏剂。
本发明的应用方法：首先将皮鞋表面处理干净，再将皮鞋开裂处进行打磨，打磨10～20s，打磨后将本发明制备的强耐水性水性聚氨酯胶黏剂施用于皮鞋开裂处，并按压5～6s，静置3～5min，即可，经检测，本发明制备的强耐水性水性聚氨酯胶黏剂干燥时间短，固含量为58～65%，粘度为0.2～0.3pa·s，pH值为7.8～8.2，且制备过程无异味，具有良好的耐水性与光泽性。
本发明的有益效果是：
（1）本发明制备的强耐水性水性聚氨酯胶黏剂具有高固含量，稳定分散性好，高初粘强度，耐水耐热性能良好的优点；
（2）本发明制得的强耐水性水性聚氨酯胶黏剂制备工艺简单，操作简便，制备过程无污染，无异味，对人体无伤害，具有优异的环保性能。
具体实施方式
称取10～20g硬脂酸加入到三口烧瓶中，再加入80～120mL甲苯，搅拌混合15～25min后放入水浴锅中，升温至60～65℃，在此温度下依次称取50～60g棉籽油和50～60g蓖麻油加入到三口烧瓶中，搅拌2～4min后加入0.1～0.3g脂肪酶和25～35mL质量分数30%双氧水，搅拌反应3～5h；上述反应结束后静置分层，得油相，用质量分数10%氢氧化钠溶液调节pH值为中性，调节后用去离子水洗涤油相2～4次，洗涤后放入真空烘箱中，在60～70℃温度下干燥3～5h后向油中加入0.1～0.3g硅烷偶联剂KH-550，搅拌20～30min得改性油；分别称取20～30g异弗尔酮二异氰酸酯和50～60g聚四氢呋喃醚二醇放入真空干燥箱中，干燥20～30min后混合，并加入反应釜中，向反应釜中用胶头滴管滴加2～3滴二月桂酸二丁基锡，搅拌混合后升温至80～90℃，保温搅拌反应2～3h，反应后滴加8～10g上述改性油，滴加结束后继续搅拌反应3～4h；称取0.8～1.0g二羟甲基丙酸加入到5～6gN-甲基吡咯烷酮中，搅拌至溶解得溶解液，待上述反应结束后滴加溶解液，滴加速度为2～3滴/s，滴加结束后在70～80℃温度下搅拌反应3～4h，反应结束后加入5～10g三乙胺和20～30g丙酮，搅拌15～20min，搅拌后冷却至室温得反应物，向反应物中加入200～300g去离子水，加入速度为5～10mL/min，加入同时以1000～1200r/min转速，高速乳化30～50min，得乳液后在56～60℃温度下蒸馏30～40min，蒸馏后即可得改性水性聚氨酯乳液；按重量份数计，分别选取70～80份上述改性聚氨酯乳液、1～3份磺化木质素、2～4份羧甲基纤维素、0.6～0.8份柠檬酸钠和8～10份聚碳化二亚胺XR-201，混合后在600～800W功率下超声搅拌30～50min，搅拌后即可得到强耐水性水性聚氨酯胶黏剂。
实例1
称取10g硬脂酸加入到三口烧瓶中，再加入80mL甲苯，搅拌混合15min后放入水浴锅中，升温至60℃，在此温度下依次称取50g棉籽油和50g蓖麻油加入到三口烧瓶中，搅拌2min后加入0.1g脂肪酶和25mL质量分数30%双氧水，搅拌反应3h；上述反应结束后静置分层，得油相，用质量分数10%氢氧化钠溶液调节pH值为中性，调节后用去离子水洗涤油相2次，洗涤后放入真空烘箱中，在60℃温度下干燥3h后向油中加入0.1g硅烷偶联剂KH-550，搅拌20min得改性油；分别称取20g异弗尔酮二异氰酸酯和50g聚四氢呋喃醚二醇放入真空干燥箱中，干燥20min后混合，并加入反应釜中，向反应釜中用胶头滴管滴加2滴二月桂酸二丁基锡，搅拌混合后升温至80℃，保温搅拌反应2h，反应后滴加8g上述改性油，滴加结束后继续搅拌反应3h；称取0.8g二羟甲基丙酸加入到5gN-甲基吡咯烷酮中，搅拌至溶解得溶解液，待上述反应结束后滴加溶解液，滴加速度为2滴/s，滴加结束后在70℃温度下搅拌反应3h，反应结束后加入5g三乙胺和20g丙酮，搅拌15min，搅拌后冷却至室温得反应物，向反应物中加入200g去离子水，加入速度为5mL/min，加入同时以1000r/min转速，高速乳化30min，得乳液后在56℃温度下蒸馏30min，蒸馏后即可得改性水性聚氨酯乳液；按重量份数计，分别选取70份上述改性聚氨酯乳液、1份磺化木质素、2份羧甲基纤维素、0.6份柠檬酸钠和8份聚碳化二亚胺XR-201，混合后在600W功率下超声搅拌30min，搅拌后即可得到强耐水性水性聚氨酯胶黏剂。
首先将皮鞋表面处理干净，再将皮鞋开裂处进行打磨，打磨10s，打磨后将本发明制备的强耐水性水性聚氨酯胶黏剂施用于皮鞋开裂处，并按压5s，静置3min，即可，经检测，本发明制备的强耐水性水性聚氨酯胶黏剂干燥时间短，固含量为58%，粘度为0.2pa·s，pH值为7.8，且制备过程无异味，具有良好的耐水性与光泽性。
实例2
称取20g硬脂酸加入到三口烧瓶中，再加入120mL甲苯，搅拌混合25min后放入水浴锅中，升温至65℃，在此温度下依次称取60g棉籽油和60g蓖麻油加入到三口烧瓶中，搅拌4min后加入0.3g脂肪酶和35mL质量分数30%双氧水，搅拌反应5h；上述反应结束后静置分层，得油相，用质量分数10%氢氧化钠溶液调节pH值为中性，调节后用去离子水洗涤油相4次，洗涤后放入真空烘箱中，在70℃温度下干燥5h后向油中加入0.3g硅烷偶联剂KH-550，搅拌30min得改性油；分别称取30g异弗尔酮二异氰酸酯和60g聚四氢呋喃醚二醇放入真空干燥箱中，干燥30min后混合，并加入反应釜中，向反应釜中用胶头滴管滴加3滴二月桂酸二丁基锡，搅拌混合后升温至90℃，保温搅拌反应3h，反应后滴加10g上述改性油，滴加结束后继续搅拌反应4h；称取1.0g二羟甲基丙酸加入到6gN-甲基吡咯烷酮中，搅拌至溶解得溶解液，待上述反应结束后滴加溶解液，滴加速度为3滴/s，滴加结束后在80℃温度下搅拌反应4h，反应结束后加入10g三乙胺和30g丙酮，搅拌20min，搅拌后冷却至室温得反应物，向反应物中加入300g去离子水，加入速度为10mL/min，加入同时以1200r/min转速，高速乳化30min，得乳液后在60℃温度下蒸馏40min，蒸馏后即可得改性水性聚氨酯乳液；按重量份数计，分别选取80份上述改性聚氨酯乳液、3份磺化木质素、4份羧甲基纤维素、0.8份柠檬酸钠和10份聚碳化二亚胺XR-201，混合后在800W功率下超声搅拌50min，搅拌后即可得到强耐水性水性聚氨酯胶黏剂。
首先将皮鞋表面处理干净，再将皮鞋开裂处进行打磨，打磨15s，打磨后将本发明制备的强耐水性水性聚氨酯胶黏剂施用于皮鞋开裂处，并按压6s，静置5min，即可，经检测，本发明制备的强耐水性水性聚氨酯胶黏剂干燥时间短，固含量为65%，粘度为0.3pa·s，pH值为8.2，且制备过程无异味，具有良好的耐水性与光泽性。
实例3
称取15g硬脂酸加入到三口烧瓶中，再加入100mL甲苯，搅拌混合20min后放入水浴锅中，升温至63℃，在此温度下依次称取55g棉籽油和55g蓖麻油加入到三口烧瓶中，搅拌3min后加入0.2g脂肪酶和30mL质量分数30%双氧水，搅拌反应4h；上述反应结束后静置分层，得油相，用质量分数10%氢氧化钠溶液调节pH值为中性，调节后用去离子水洗涤油相3次，洗涤后放入真空烘箱中，在65℃温度下干燥4h后向油中加入0.2g硅烷偶联剂KH-550，搅拌25min得改性油；分别称取25g异弗尔酮二异氰酸酯和55g聚四氢呋喃醚二醇放入真空干燥箱中，干燥25min后混合，并加入反应釜中，向反应釜中用胶头滴管滴加3滴二月桂酸二丁基锡，搅拌混合后升温至85℃，保温搅拌反应3h，反应后滴加9g上述改性油，滴加结束后继续搅拌反应4h；称取0.9g二羟甲基丙酸加入到6gN-甲基吡咯烷酮中，搅拌至溶解得溶解液，待上述反应结束后滴加溶解液，滴加速度为2滴/s，滴加结束后在75℃温度下搅拌反应4h，反应结束后加入8g三乙胺和25g丙酮，搅拌18min，搅拌后冷却至室温得反应物，向反应物中加入250g去离子水，加入速度为8mL/min，加入同时以1100r/min转速，高速乳化40min，得乳液后在58℃温度下蒸馏35min，蒸馏后即可得改性水性聚氨酯乳液；按重量份数计，分别选取75份上述改性聚氨酯乳液、2份磺化木质素、3份羧甲基纤维素、0.7份柠檬酸钠和9份聚碳化二亚胺XR-201，混合后在700W功率下超声搅拌40min，搅拌后即可得到强耐水性水性聚氨酯胶黏剂。
首先将皮鞋表面处理干净，再将皮鞋开裂处进行打磨，打磨20s，打磨后将本发明制备的强耐水性水性聚氨酯胶黏剂施用于皮鞋开裂处，并按压6s，静置4min，即可，经检测，本发明制备的强耐水性水性聚氨酯胶黏剂干燥时间短，固含量为61%，粘度为0.3pa·s，pH值为8，且制备过程无异味，具有良好的耐水性与光泽性。

Claims (1)

1.一种耐水性水性聚氨酯胶黏剂的制备方法，其特征在于具体制备步骤为：
（1）称取10～20g硬脂酸加入到三口烧瓶中，再加入80～120mL甲苯，搅拌混合15～25min后放入水浴锅中，升温至60～65℃，在此温度下依次称取50～60g棉籽油和50～60g蓖麻油加入到三口烧瓶中，搅拌2～4min后加入0.1～0.3g脂肪酶和25～35mL质量分数30%双氧水，搅拌反应3～5h；
（2）上述反应结束后静置分层，得油相，用质量分数10%氢氧化钠溶液调节pH值为中性，调节后用去离子水洗涤油相2～4次，洗涤后放入真空烘箱中，在60～70℃温度下干燥3～5h后向油中加入0.1～0.3g硅烷偶联剂KH-550，搅拌20～30min得改性油；
（3）分别称取20～30g异弗尔酮二异氰酸酯和50～60g聚四氢呋喃醚二醇放入真空干燥箱中，干燥20～30min后混合，并加入反应釜中，向反应釜中用胶头滴管滴加2～3滴二月桂酸二丁基锡，搅拌混合后升温至80～90℃，保温搅拌反应2～3h，反应后滴加8～10g上述改性油，滴加结束后继续搅拌反应3～4h；
（4）称取0.8～1.0g二羟甲基丙酸加入到5～6gN-甲基吡咯烷酮中，搅拌至溶解得溶解液，待上述反应结束后滴加溶解液，滴加速度为2～3滴/s，滴加结束后在70～80℃温度下搅拌反应3～4h，反应结束后加入5～10g三乙胺和20～30g丙酮，搅拌15～20min，搅拌后冷却至室温得反应物，向反应物中加入200～300g去离子水，加入速度为5～10mL/min，加入同时以1000～1200r/min转速，高速乳化30～50min，得乳液后在56～60℃温度下蒸馏30～40min，蒸馏后即可得改性水性聚氨酯乳液；
（5）按重量份数计，分别选取70～80份上述改性聚氨酯乳液、1～3份磺化木质素、2～4份羧甲基纤维素、0.6～0.8份柠檬酸钠和8～10份聚碳化二亚胺XR-201，混合后在600～800W功率下超声搅拌30～50min，搅拌后即可得到耐水性水性聚氨酯胶黏剂。
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