CN105462536B - 一种水性硅烷改性聚氨酯粘合剂及其制备方法 - Google Patents
一种水性硅烷改性聚氨酯粘合剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种水性硅烷改性聚氨酯粘合剂及其制备方法，由以下重量份的原料制备而成：15～20份聚醚二元醇、8～10份二异氰酸酯、1～2份酸、2～5份硅烷偶联剂、8～10份环氧树脂、5～10份丙酮、0.5～1份催化剂、2～5份封端剂、1～2份三乙胺、10～15份氮甲基呲咯烷酮和45～50份去离子水。发明提供的水性硅烷改性聚氨酯粘合剂通过将硅烷偶联剂和聚氨酯树脂进行复合，利用硅烷偶联剂固化快、固化时不起泡、耐湿热、耐老化性能优异等特性来提高聚氨酯粘合剂的性能，并加入四甲基间苯二亚甲基二异氰酸酯提高水性聚氨酯粘合剂的强度、粘附力、外观、柔韧性和耐久性，研制出的水性硅烷改性聚氨酯粘合剂，可耐100℃水煮60min，对各种亲水和疏水性的基材都具有高粘接强度。
Description
技术领域
本发明属于粘合剂制备技术领域，涉及一种水性硅烷改性聚氨酯粘合剂及其制备方法。
背景技术
水性胶粘剂以水为基本介质，具有不易燃、气味小、不污染环境、节能、操作加工方便等特点，用水性胶粘剂来取代溶剂型胶粘剂，对改善工作环境减少污染，降低工作强度，避免火灾的危险非常有效。水性胶粘剂替代溶剂型产品已大势所趋。水性聚氨酯粘合剂具有无溶剂、无污染、成膜性好、粘接力强等特性，但聚氨酯树脂固化较慢，且固化时易和空气中的水气反应使树脂固化物产生气泡甚至裂缝，不能长期耐湿热和耐老化。
因此有必要发明一种能长期耐湿热和耐老化的水性聚氨酯粘合剂。
发明内容
本发明的目的在于克服现有技术的缺陷，提供一种耐湿热和耐老化性能优异的水性硅烷改性聚氨酯粘合剂。
本发明的另一目的在于提供该水性硅烷改性聚氨酯粘合剂的制备方法。
上述目的是通过如下技术方案实现的：
一种水性硅烷改性聚氨酯粘合剂，由以下重量份的原料制备而成：15～20份聚醚二元醇、8～10份二异氰酸酯、1～2份酸、2～5份硅烷偶联剂、8～10份环氧树脂、5～10份丙酮、0.5～1份催化剂、2～5份封端剂、1～2份三乙胺、10～15份氮甲基呲咯烷酮和45～50份去离子水。
优选地，所述酸选用二羟甲基丙酸。
优选地，所述催化剂选用二月桂酸二丁基锡。
优选地，所述封端剂选用丙烯酸羟乙酯和正丁醇按照体积比1:0.5～1的混合物。
优选地，所述聚醚二元醇选用聚四氢呋喃二醇。
优选地，所述二异氰酸酯选用四甲基间苯二亚甲基二异氰酸酯。
上述水性硅烷改性聚氨酯粘合剂的制备方法，包括如下步骤：
(1)将聚四氢呋喃二醇、四甲基间苯二亚甲基二异氰酸酯、二月桂酸二丁基锡以及丙烯酸羟乙酯和正丁醇的混合物分别在在80～100℃真空下减压脱水0.5～1h；将环氧树脂溶解在丙酮中，制成环氧树脂与丙酮混合溶液；
(2)将聚四氢呋喃二醇、四甲基间苯二亚甲基二异氰酸酯放入装有温度计、搅拌器及回流冷凝管的三口容器中，加热到60～80℃，缓慢滴加环氧树脂与丙酮混合溶液，同时缓慢均匀滴加二月桂酸二丁基锡，反应2～3h后滴加二羟甲基丙酸，继续反应2～3h，降温到30～50℃之间，得到聚氨酯预聚体Ⅰ，该步骤始终在氮气保护下进行；
(3)在聚氨酯预聚体Ⅰ中滴加封端剂，滴加后加热到60～80℃反应2～3h，得到聚氨酯预聚体Ⅱ；
(4)在聚氨酯预聚体Ⅱ中滴加硅烷偶联剂，滴加后反应1～2h，检测异氰酸酯基至异氰酸酯基消失后降温至40～50℃，得到硅烷改性的聚氨酯齐聚物；
(5)在40～50℃搅拌条件下，往硅烷改性的聚氨酯齐聚物中滴加三乙胺进行成盐反应，同时往硅烷改性的聚氨酯齐聚物中滴加氮甲基呲咯烷酮以及去离子水进行乳化；剧烈搅拌下搅拌20～30min使齐聚物乳化，得到水性硅烷改性聚氨酯粘合剂
本发明的有益效果：
1、本发明将硅烷偶联剂和聚氨酯树脂进行复合，利用硅烷偶联剂固化快、固化时不起泡、耐湿热、耐老化性能优异等特性来提高聚氨酯粘合剂的性能，并加入四甲基间苯二亚甲基二异氰酸酯提高水性聚氨酯粘合剂的强度、粘附力、外观、柔韧性和耐久性，研制出的水性硅烷改性聚氨酯粘合剂，可耐100℃水煮60min，对各种亲水和疏水性的基材都具有高粘接强度。
2、本发明提供的制备方法简单、可控，易于推广。
具体实施方式
下面结合具体实施例详细说明本发明的技术方案。
实施例1：水性硅烷改性聚氨酯粘合剂的制备
包括如下步骤：
(1)将聚四氢呋喃二醇、四甲基间苯二亚甲基二异氰酸酯、二月桂酸二丁基锡以及丙烯酸羟乙酯和正丁醇的1:1混合物分别在80℃真空下减压脱水0.5h，待用；
(2)将15g聚四氢呋喃二醇、8g四甲基间苯二亚甲基二异氰酸酯放入装有温度计、搅拌器及回流冷凝管的三口烧瓶中，加热到60℃，缓慢滴加5g丙酮溶解的8g环氧树脂，同时缓慢均匀滴加0.5g二月桂酸二丁基锡，反应2h后滴加1g二羟甲基丙酸，继续反应2h，过程始终在氮气保护下进行，降温到30℃，得到聚氨酯预聚体Ⅰ；
(3)在聚氨酯预聚体Ⅰ中滴加2g丙烯酸羟乙酯和正丁醇体积比1:1的混合物，加热到60℃反应2h，得到聚氨酯预聚体Ⅱ；
(4)在聚氨酯预聚体Ⅱ滴加2g硅烷偶联剂，反应1h，用丁二胺法测定异氰酸酯基含量，当不再含有异氰酸酯基时降温至40℃，得到硅烷改性的聚氨酯齐聚物；
(5)在40℃条件下搅拌，往齐聚物中滴加1g三乙胺进行成盐反应，同时往齐聚物中滴加10g氮甲基呲咯烷酮以及45g去离子水进行乳化；在剧烈搅拌下搅拌20min使齐聚物乳化，得到水性硅烷改性聚氨酯粘合剂。
实施例2：水性硅烷改性聚氨酯粘合剂的制备
(1)将聚四氢呋喃二醇、四甲基间苯二亚甲基二异氰酸酯、二月桂酸二丁基锡以及丙烯酸羟乙酯和正丁醇的1:0.5混合物分别在100℃真空下减压脱水1h，待用；
(2)将20g聚四氢呋喃二醇、10g四甲基间苯二亚甲基二异氰酸酯放入装有温度计、搅拌器及回流冷凝管的三口烧瓶中，加热到80℃，缓慢滴加10g丙酮溶解的10g环氧树脂，同时缓慢均匀滴加1g二月桂酸二丁基锡，反应3h后滴加2g二羟甲基丙酸，继续反应3h，过程始终在氮气保护下进行，降温到50℃，得到聚氨酯预聚体Ⅰ；
(3)在聚氨酯预聚体Ⅰ中滴加5g丙烯酸羟乙酯和正丁醇体积比1:0.5的混合物，加热到80℃反应3h，得到聚氨酯预聚体Ⅱ；
(4)在聚氨酯预聚体Ⅱ滴加5g硅烷偶联剂，反应2h，用丁二胺法测定异氰酸酯基含量，当不再含有异氰酸酯基时降温至50℃，得到硅烷改性的聚氨酯齐聚物；
(5)在50℃条件下搅拌，往齐聚物中滴加2g三乙胺进行成盐反应，同时往齐聚物中滴加15g氮甲基呲咯烷酮以及50g去离子水进行乳化；在剧烈搅拌下搅拌30min使齐聚物乳化，得到水性硅烷改性聚氨酯粘合剂。
实施例3：水性硅烷改性聚氨酯粘合剂的制备
包括如下步骤：
(1)将聚四氢呋喃二醇、四甲基间苯二亚甲基二异氰酸酯、二月桂酸二丁基锡以及丙烯酸羟乙酯和正丁醇的1:0.8混合物分别在90℃真空下减压脱水0.8h，待用；
(2)将18g聚四氢呋喃二醇、9g四甲基间苯二亚甲基二异氰酸酯放入装有温度计、搅拌器及回流冷凝管的三口烧瓶中，加热到70℃，缓慢滴加8g丙酮溶解的9g环氧树脂，同时缓慢均匀滴加0.8g二月桂酸二丁基锡，反应2.5h后滴加1.5g二羟甲基丙酸，继续反应2.5h，过程始终在氮气保护下进行，降温到40℃，得到聚氨酯预聚体Ⅰ；
(3)在聚氨酯预聚体Ⅰ中滴加3.5g丙烯酸羟乙酯和正丁醇体积比1:0.8的混合物，加热到70℃反应2.5h，得到聚氨酯预聚体Ⅱ；
(4)在聚氨酯预聚体Ⅱ滴加3.5g硅烷偶联剂，反应1.5h，用丁二胺法测定异氰酸酯基含量，当不再含有异氰酸酯基时降温至45℃，得到硅烷改性的聚氨酯齐聚物；
(5)在45℃条件下搅拌，往齐聚物中滴加1.5g三乙胺进行成盐反应，同时往齐聚物中滴加12.5g氮甲基呲咯烷酮以及47.5g去离子水进行乳化；在剧烈搅拌下搅拌25min使齐聚物乳化，得到水性硅烷改性聚氨酯粘合剂。
实施例4：效果实施例
测试实施例1所研制的水性硅烷改性聚氨酯粘合剂的性能指标，见表1。
表1水性聚氨酯胶粘剂的一般性能指标
| 固含量/％ | 45 | 拉伸强度/MPa | 50 |
| 平均粒径/μm | <0.15 | 断裂伸长率/％ | 500 |
| 粘度(为增稠)/mPa.s | 200 | 邵氏A硬度 | 55 |
| 表面张力/N.m-1 | 55 | PH值 | 6.8 |
实施例2和3制备的水性硅烷改性聚氨酯粘合剂的性能指标与实施例1相似。
本发明提供的水性硅烷改性聚氨酯粘合剂通过将硅烷偶联剂和聚氨酯树脂进行复合，利用硅烷偶联剂固化快、固化时不起泡、耐湿热、耐老化性能优异等特性来提高聚氨酯粘合剂的性能，并加入四甲基间苯二亚甲基二异氰酸酯提高水性聚氨酯粘合剂的强度、粘附力、外观、柔韧性和耐久性，研制出的水性硅烷改性聚氨酯粘合剂，可耐100℃水煮60min，对各种亲水和疏水性的基材都具有高粘接强度。
上述实施例的作用在于说明本发明的实质性内容，但并不以此限定本发明的保护范围。本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和保护范围。
Claims (2)
1.一种水性硅烷改性聚氨酯粘合剂，其特征在于：由以下重量份的原料制备而成：15~20份聚醚二元醇、8~10份二异氰酸酯、1~2份酸、2~5份硅烷偶联剂、8 ~10份环氧树脂、5~10份丙酮、0.5~1份催化剂、2~5份封端剂、1~2份三乙胺、10~15份氮甲基呲咯烷酮和45~50份去离子水；所述聚醚二元醇为聚四氢呋喃二醇；所述二异氰酸酯为四甲基间苯二亚甲基二异氰酸酯；所述封端剂为丙烯酸羟乙酯和正丁醇按照体积比1:0.5~1的混合物；所述酸为二羟甲基丙酸；所述催化剂为二月桂酸二丁基锡。
2.权利要求1所述水性硅烷改性聚氨酯粘合剂的制备方法，其特征在于包括如下步骤：
（1）将聚四氢呋喃二醇、四甲基间苯二亚甲基二异氰酸酯、二月桂酸二丁基锡以及丙烯酸羟乙酯和正丁醇的混合物分别在在80~100℃真空下减压脱水0.5~1h；将环氧树脂溶解在丙酮中，制成环氧树脂与丙酮混合溶液；
（2）将聚四氢呋喃二醇、四甲基间苯二亚甲基二异氰酸酯放入装有温度计、搅拌器及回流冷凝管的三口容器中，加热到60~80℃，缓慢滴加环氧树脂与丙酮混合溶液，同时缓慢均匀滴加二月桂酸二丁基锡，反应2~3h后滴加二羟甲基丙酸，继续反应2~3h，降温到30~50℃之间，得到聚氨酯预聚体Ⅰ，该步骤始终在氮气保护下进行；
（3）在聚氨酯预聚体Ⅰ中滴加封端剂，滴加后加热到60~80℃反应2~3h，得到聚氨酯预聚体Ⅱ；
（4）在聚氨酯预聚体Ⅱ中滴加硅烷偶联剂，滴加后反应1~2h，检测异氰酸酯基至异氰酸酯基消失后降温至40~50℃，得到硅烷改性的聚氨酯齐聚物；
（5）在40~50℃搅拌条件下，往硅烷改性的聚氨酯齐聚物中滴加三乙胺进行成盐反应，同时往硅烷改性的聚氨酯齐聚物中滴加氮甲基呲咯烷酮以及去离子水进行乳化；剧烈搅拌下搅拌20~30 min使齐聚物乳化，得到水性硅烷改性聚氨酯粘合剂。
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