CN108467702A - 一种用于车灯的湿固化聚氨酯热熔胶及制备方法 - Google Patents
一种用于车灯的湿固化聚氨酯热熔胶及制备方法 Download PDFInfo
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Abstract
本发明涉及一种用于车灯的湿固化聚氨酯热熔胶及制备方法，按质量份数计，其原料包括聚酯多元醇，10－45份；聚醚多元醇，20－55份；聚丙烯酸树脂，10－45份；扩链剂，0.01‑5份；异氰酸酯，10－20份；催化剂，0.0001－0.001份。本发明用于车灯的湿固化聚氨酯热熔胶是由含有活性基团（羟基）的多元醇与异氰酸酯基团（NCO）共聚制备，聚合物链末端含有活性基团NCO，而NCO会与空气中或者被粘物中的水分发生不可逆的交联反应，从而最终获得高的粘接强度。
Description
技术领域
本发明涉及一种用于车灯的湿固化聚氨酯热熔胶及制备方法，属于一种反应型聚氨酯热熔胶，属于聚氨酯热熔胶制备技术领域。
背景技术
中国发明专利申请公开说明书CN102585753A公开了一种用于汽车灯具密封用的聚氨酯热熔胶。其将高结晶性聚酯二醇、聚酯多元醇、增粘树脂在搅拌下真空脱水，然后降温；取二异氰酸酯预热，加入反应釜搅拌均匀，进行预聚反应；预聚完成后在氮气环流下依次加入计量好的催化剂、抗氧剂、偶联剂、粘度稳定剂、灰色浆搅拌至混合均匀；在通入氮气保护条件下出料，密封包装，即得产物车灯粘接用聚氨酯热熔胶。但是其优点在于粘接强度高、耐震动性好、对环境友好，但该热熔胶的多元醇全部用聚酯多元醇为原料，制备的聚氨酯热熔胶粘度较高，对于使对温度相对敏感的基材易受损伤，如ABS，PVC和TPU膜材等。
中国发明专利申请公开说明书CN103740316A公开了一种用于汽车灯具密封用的聚氨酯热熔胶。 将聚酯多元醇与异氰酸酯在一定温度搅拌下进行预聚反应，预聚完成后加入催化剂和炭黑，抽真空脱除气泡30min，在通入氮气保护条件下倒出产物，密封包装，得到车灯用湿固化聚氨酯热熔胶。但该热熔胶开放时间较短，而大型复杂设备的粘接工艺相对要较长时间，其操作时间不能满足。
发明内容
本发明提供了一种用于车灯的湿固化聚氨酯热熔胶及制备方法。
本发明提供的技术方案为：一种用于车灯的湿固化聚氨酯热熔胶，其特征在于：按质量份数计，其原料包括聚酯多元醇，10－45份；聚醚多元醇，20－55份；聚丙烯酸树脂，10－45份；扩链剂，0.01-5份；异氰酸酯，10－20份；催化剂，0.0001－0.001份。本发明用于车灯的湿固化聚氨酯热熔胶是由含有活性基团（羟基）的多元醇与异氰酸酯基团（NCO）共聚制备，聚合物链末端含有活性基团NCO，而NCO会与空气中或者被粘物中的水分发生不可逆的交联反应，从而最终获得高的粘接强度。
本发明所述聚丙烯酸树脂的分子量Mn为1000-1000000，玻璃化转变温度Tg为30-120℃。
本发明所述聚丙烯酸树脂的分子量Mn为5000-90000，玻璃化转变温度Tg为40-90℃。
本发明所述扩链剂为1，4-丁二醇、乙二醇、丙二醇、一缩二乙二醇、新戊二醇、丙三醇、三羟甲基丙烷（TMP）、3,3'-二氯-4,4'-二氨基二苯基甲烷（MOCA）、乙醇胺、二乙醇胺、三乙醇胺、三异丙醇胺和N，N'-双（2-羟丙基）苯胺中的一种或几种。这些是目前主要扩链剂的产品，目的是涵盖广。
本发明所述催化剂为二月桂酸二丁基锡、辛酸亚锡、辛酸铅、三乙胺、三亚乙基二胺、辛酸钴、辛酸铁、环烷酸辛、钛酸四异丁酯、二吗啉基二乙基醚中的一种或几种。这些是目前主要催化剂的产品，目的是涵盖广。
一种用于车灯的湿固化聚氨酯热熔胶的制备方法，其特征在于：包括如下步骤：按重量份数计，将10－45份的聚酯多元醇、20－55份的聚醚多元醇、10－45份的聚丙烯酸树脂和0.01-5份的扩链剂置于反应釜中，加热至120－150 ℃，在搅拌下真空脱水1-2小时，然后加入10－20份的异氰酸酯，搅拌下反应1-5 h，并抽真空，当NCO达到理论值时，加入0.0001－0.001份的催化剂，抽真空搅拌30 min，在通入氮气保护条件下倒出产物，密封包装，得到用于车灯的湿固化聚氨酯热熔胶。
相比现有技术，本发明优点为：（1）优异的初始剥离强度：大于100N/25mm。（2）优异的最终剥离强度：大于900N/25mm。（3）长的开放时间：大于4min。（4）优异的耐高温性：190℃下无软化流淌。（5）优异的耐低温性：－50℃下无开裂。（6）较低的施胶温度：110℃粘度小于10000cps，施胶温度低，可以对温度敏感的基材很好的保护。（7）不含石油等含有易挥发小分子的树脂，胶体的没有刺激性味道。（8）方法工艺简便易行，设备简单，易于规模化生产。
具体实施方式
下面结合实施例对本发明做进一步的详细说明，以下实施例是对本发明的解释而本发明并不局限于以下实施例。
实施例1。
本实施例提供了用于车灯的湿固化聚氨酯热熔胶的制备方法，具体包括如下步骤：按质量份数计，将39份的己二酸-1,4-丁二醇（PBA）、20份的聚丙二醇、20份的聚丙烯酸树脂（分子量20000，Tg为70℃）和1份作为扩链剂的1,4-丁二醇置于反应釜中，加热至120℃，在搅拌下真空脱水1小时，然后加入20份的MDI，搅拌下反应2h，并抽真空，当NCO达到理论值时，加入0.001份的辛酸亚锡作为催化剂，抽真空搅拌30 min，在通入氮气保护条件下倒出产物，密封包装，得到用于车灯的湿固化聚氨酯热熔胶。
实施例2。
本实施例提供了用于车灯的湿固化聚氨酯热熔胶的制备方法，具体包括如下步骤：按质量份数计，将29份的己二酸-1,6-己二醇酯（PHA）、35份的聚四氢呋喃二醇、25份的聚丙烯酸树脂（分子量50000，Tg为50℃） 和1份作为扩链剂的1,4-丁二醇置于反应釜中，加热至120℃，在搅拌下真空脱水1小时，然后加入10份的MDI，搅拌下反应2h，并抽真空，当NCO达到理论值时，加入0.01份的辛酸亚锡作为催化剂，抽真空搅拌20 min，在通入氮气保护条件下倒出产物，密封包装，得到用于车灯的湿固化聚氨酯热熔胶。
实施例3。
本实施例提供了用于车灯的湿固化聚氨酯热熔胶的制备方法，具体包括如下步骤：按质量份数计，将23份的癸二酸-1,6-己二醇酯多元醇、40份的聚丙二醇、25份的聚丙烯酸树脂（分子量3000，Tg为85℃） 和2份作为扩链剂的一缩二乙二醇置于反应釜中，加热至130℃，在搅拌下真空脱水1小时，然后加入10份的MDI，搅拌下反应2h，并抽真空，当NCO达到理论值时，加入0.001份的二吗啉基二乙基醚作为催化剂，抽真空搅拌20 min，在通入氮气保护条件下倒出产物，密封包装，得到用于车灯的湿固化聚氨酯热熔胶。
实施例4。
本实施例提供了用于车灯的湿固化聚氨酯热熔胶的制备方法，具体包括如下步骤：按质量份数计，将40份的己二酸-1,4-丁二醇（PBA）、20份的聚丙二醇、20份的聚丙烯酸树脂（分子量70000，Tg为40℃） 和1份作为扩链剂的三乙醇胺置于反应釜中，加热至125℃，在搅拌下真空脱水1小时，然后加入19份的MDI，搅拌下反应2h，并抽真空，当NCO达到理论值时，加入0.001份的钛酸四异丁酯作为催化剂，抽真空搅拌10 min，在通入氮气保护条件下倒出产物，密封包装，得到用于车灯的湿固化聚氨酯热熔胶。
表1为实施例1－4与目前汽车灯用某国进口外湿固化聚氨酯热熔胶测试对比数据。
表1
通过表1可以看到，实施例1-4以异氰酸酯、聚醚二元醇、聚酯二元醇、聚丙烯酸树脂等为反应原料，得到车灯用湿固化聚氨酯热熔胶，获得的用于车灯的湿固化聚氨酯热熔胶具有高的初始和最终粘接强度，施胶温度低，开放时间长，优异的耐高低温等性能。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员，在不脱离本发明构思的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围内。虽然本发明已以实施例公开如上，但其并非用以限定本发明的保护范围，任何熟悉该项技术的技术人员，在不脱离本发明的构思和范围内所作的变动与润饰，均应属于本发明的保护范围。
Claims (6)
1.一种用于车灯的湿固化聚氨酯热熔胶，其特征在于：按质量份数计，其原料包括聚酯多元醇，10－45份；聚醚多元醇，20－55份；聚丙烯酸树脂，10－45份；扩链剂，0.01-5份；异氰酸酯，10－20份；催化剂，0.0001－0.001份。
2.根据权利要求1所述的用于车灯的湿固化聚氨酯热熔胶，其特征在于：所述聚丙烯酸树脂的分子量Mn为1000-1000000，玻璃化转变温度Tg为30-120℃。
3.根据权利要求2所述的用于车灯的湿固化聚氨酯热熔胶，其特征在于：所述聚丙烯酸树脂的分子量Mn为5000-90000，玻璃化转变温度Tg为40-90℃。
4.根据权利要求1所述的用于车灯的湿固化聚氨酯热熔胶，其特征在于：所述扩链剂为1，4-丁二醇、乙二醇、丙二醇、一缩二乙二醇、新戊二醇、丙三醇、三羟甲基丙烷、3,3'-二氯-4,4'-二氨基二苯基甲烷、乙醇胺、二乙醇胺、三乙醇胺、三异丙醇胺和N，N'-双（2-羟丙基）苯胺中的一种或几种。
5.根据权利要求1所述的用于车灯的湿固化聚氨酯热熔胶，其特征在于：所述催化剂为二月桂酸二丁基锡、辛酸亚锡、辛酸铅、三乙胺、三亚乙基二胺、辛酸钴、辛酸铁、环烷酸辛、钛酸四异丁酯、二吗啉基二乙基醚中的一种或几种。
6.一种如权利要求1-5任一权利要求所述的用于车灯的湿固化聚氨酯热熔胶的制备方法，其特征在于：包括如下步骤：按重量份数计，将10－45份的聚酯多元醇、20－55份的聚醚多元醇、10－45份的聚丙烯酸树脂和0.01-5份的扩链剂置于反应釜中，加热至120－150℃，在搅拌下真空脱水1-2小时，然后加入10－20份的异氰酸酯，搅拌下反应1-5 h，并抽真空，当NCO达到理论值时，加入0.0001－0.001份的催化剂，抽真空搅拌30 min，在通入氮气保护条件下倒出产物，密封包装，得到用于车灯的湿固化聚氨酯热熔胶。
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| CN111040717A (zh) * | 2019-12-25 | 2020-04-21 | 惠州市远安新材料有限公司 | 一种湿气固化反应型聚氨酯热熔胶及其制备方法 |
| CN112592687A (zh) * | 2020-12-15 | 2021-04-02 | 南通恒华粘合材料科技有限公司 | 一种汽车车灯用反应型聚氨酯热熔胶 |
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