CN109971007B - 一种常温固化聚氨酯类防雾薄膜及其制备方法 - Google Patents

一种常温固化聚氨酯类防雾薄膜及其制备方法 Download PDF

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CN109971007B
CN109971007B CN201910257367.4A CN201910257367A CN109971007B CN 109971007 B CN109971007 B CN 109971007B CN 201910257367 A CN201910257367 A CN 201910257367A CN 109971007 B CN109971007 B CN 109971007B
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东为富
刘晓锦
李婷
杨铄冰
贾睿
马丕明
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Abstract

本发明提供了一种常温固化聚氨酯类防雾薄膜及其制备方法，属于高分子材料技术领域。所述防雾薄膜包括聚氨酯预聚体和固化交联剂，重量比为100:(1～20)，优选100:(15～20)。本发明防雾薄膜主要利用羧基与氮丙啶基团在常温下进行交联固化，不消耗能源，薄膜含有聚合的表面活性剂，不迁移不脱落。本发明防雾薄膜的透光率高、防雾效果稳定持久、表面耐刮擦、与基材黏附力高、耐水性优异且制备方法简单，适于大规模工业化生产。

Description

一种常温固化聚氨酯类防雾薄膜及其制备方法
技术领域
本发明属于高分子材料技术领域，特别是涉及一种常温固化聚氨酯类防雾薄膜及其制备方法。
背景技术
透明材料的生产与使用已渗透在人们生活的各个方面，但是透明材料(例如眼镜、面罩、浴室玻璃、汽车前挡玻璃、相机镜头、落地窗、展示柜)在一定环境下会结雾、干扰视线，这种现象给人们带来很多困扰，甚至造成安全隐患和重大的经济损失。
国内市场防雾材料多为喷雾式，其主要成分为表面活性剂类，防雾持效性短，不耐擦拭；通过电加热玻璃升温除雾和除霜需要耗用大量的电和金属；其他防雾产品大多生产过程复杂，制作成本高昂且防雾效果稳定性和持久性差、耐水性差。
ACS Appl.Mater.Interfaces,2016,8:8737一文中制备了一种具有防雾功能的聚合物涂层，然而其耐水性与附着力差；美国FSI公司的
Figure BDA0002014170290000011
Premium系列产品，但其固化温度需高达150℃以上，在资源与能源消耗上补课持续发展，且其防雾效果在泡水后急剧下降，价格高昂。所以，目前市场开发的防雾涂层材料存在附着力低、生产工艺复杂、防雾时间短、成本高、不可持续发展等缺点。
发明内容
为解决现有技术所存在的问题，本发明提供了一种常温固化聚氨酯类防雾薄膜及其制备方法。这种防雾薄膜在常温下进行交联固化，不消耗能源，薄膜含有聚合的表面活性剂，不迁移不脱落，薄膜的透光率高、防雾效果稳定持久、表面耐刮擦、与基材黏附力高、耐水性优异且制备方法简单，适于大规模工业化生产。
本发明的技术方案：
一种常温固化聚氨酯类防雾薄膜，所述防雾薄膜是由固化交联剂的氮丙啶基团在常温下与聚氨酯预聚体的羧基交联固化得到的；所述聚氨酯预聚体与固化交联剂的重量比为100:(1～20)，优选100:(15～20)。
所述的聚氨酯预聚体主要由异氰酸酯或异氰酸酯多聚体、聚氧乙烯醚、二羟甲基脂肪酸、含羟基的表面活性剂聚合制成，重量比为100:(10～60):(40～80):(10～50)，优选100:(10～30):(50～65):(10～25)。
所述的固化交联剂为三官能团氮丙啶，包括季戊四醇三(3-氮丙啶基)丙酸酯、三羟甲基丙烷-三[3-(2-甲基吖丙啶基)丙酸酯、三羟甲基丙烷-三(3-吖丙啶基丙酸酯)中的一种或两种以上混合。
所述的异氰酸酯或异氰酸酯多聚体包括异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、萘二异氰酸酯、二苯甲烷二异氰酸酯、1,6-己二异氰酸酯、苯二亚甲基二异氰酸酯、1,4-环己烷二异氰酸酯、间苯二异氰酸酯、异佛尔酮二异氰酸酯三聚体、六亚甲基二异氰酸酯三聚体中的一种或两种以上混合
所述的聚氧乙烯醚为直链聚氧乙烯醚或含双酚A聚氧乙烯醚；所述直链聚氧乙烯醚的分子量在200g/mol至1000g/mol范围内；所述含双酚A聚氧乙烯醚的分子量在300g/mol至2600g/mol范围内。
所述的二羟甲基脂肪酸为二羟甲基丙酸或二羟甲基丁酸。
所述的含羟基的表面活性剂为OP-4、OP-10、OP-20、OP-50、曲拉通X-100、曲拉通X-114、吐温20中的一种或两种以上混合。
一种常温固化聚氨酯类防雾薄膜的制备方法，包括以下步骤：
(1)将异氰酸酯或异氰酸酯多聚体与聚氧乙烯醚按配比混合，加溶剂稀释，升温，加引发剂引发聚合；
(2)将二羟甲基脂肪酸按配比加入步骤(1)聚合后的体系中，进一步升温聚合；
(3)再将含羟基的表面活性剂按配比加入到步骤(2)聚合后的体系中进行封端，得到聚氨酯预聚体；
(4)将聚氨酯预聚体与固化交联剂按配比混合均匀，涂膜并置于常温下交联固化成膜。
本发明的有益效果：
(1)本发明防雾薄膜主要利用羧基与氮丙啶基团在常温下进行交联固化，可通过调节固化交联剂的用量调节薄膜的交联密度，进而调节防雾薄膜的综合性能，包括防雾效果的稳定性与持久性、硬度、与基材间的黏附力、表面耐刮擦性和耐水性；
(2)本发明所述的防雾薄膜无需加热固化，节省能源，符合可持续发展，成本低廉，适用于大规模工业化生产。
具体实施方式
下面结合实施例，进一步说明本发明。
除特殊说明外，其他试剂均购置于国药集团化学试剂有限公司。
一、聚氨酯预聚体的制备
实施例1
将100份异佛尔酮二异氰酸酯置于三口烧瓶中，加入适量丙酮溶解，再加入10份直链聚氧乙烯醚(分子量约为200g/mol)，在催化剂二月桂酸二丁基锡作用下，升温到50℃并搅拌，反应2h；再加入80份二羟甲基丙酸，60℃搅拌反应2h；随后加入50份OP-4，70℃搅拌2h停止加热反应，得到聚氨酯预聚体1。
实施例2
将100份六亚甲基二异氰酸酯置于三口烧瓶中，加入适量丙酮溶解，再加入20份直链聚氧乙烯醚(分子量约为400g/mol)，在催化剂二月桂酸二丁基锡作用下，升温到50℃并搅拌，反应2h；再加入60份二羟甲基丁酸，60℃搅拌反应2h；接着加入25份曲拉通X-114，70℃搅拌2h后停止加热反应，得到聚氨酯预聚体2。
实施例3
将50份赖氨酸二异氰酸酯、50份甲苯二异氰酸酯置于三口烧瓶中，加入适量丙酮溶解，再加入30份直链聚氧乙烯醚(分子量约为1000g/mol)，在催化剂二月桂酸二丁基锡作用下，升温到50℃并搅拌，反应2h；再加入40份二羟甲基丁酸，60℃搅拌反应2h；接着加入50份吐温20，70℃搅拌2h后停止加热反应，得到聚氨酯预聚体3。
实施例4
将100份1,4-环己烷二异氰酸酯置于三口烧瓶中，加入适量丙酮溶解，再加入30份双酚A聚氧乙烯醚(分子量约为1548g/mol)，在催化剂二月桂酸二丁基锡作用下，升温到50℃并搅拌，反应2h；再加入50份二羟甲基丁酸，60℃搅拌反应2h；随后加入10份曲拉通X-114，70℃搅拌2h停止加热反应，得到聚氨酯预聚体4。
实施例5
将100份异佛尔酮二异氰酸酯三聚体置于三口烧瓶中，加入适量丙酮溶解，再加入10份双酚A聚氧乙烯醚(分子量约为2516g/mol)，在催化剂二月桂酸二丁基锡作用下，升温到50℃并搅拌，反应2h；再加入65份二羟甲基丁酸，60℃搅拌反应2h；随后加入25份OP-20，70℃搅拌2h停止加热反应，得到聚氨酯预聚体5。
二、防雾薄膜的制备
实施例6
将100份实施例1中制备得到的聚氨酯预聚体1与1份季戊四醇三(3-氮丙啶基)丙酸酯混合，涂膜后置于常温下交联固化形成防雾薄膜1。
实施例7
将100份实施例2中制备得到的聚氨酯预聚体2与5份三羟甲基丙烷-三[3-(2-甲基吖丙啶基)丙酸酯、5份三羟甲基丙烷-三(3-吖丙啶基丙酸酯)混合，涂膜后置于常温下交联固化形成防雾薄膜2。
实施例8
将100份实施例3中制备得到的聚氨酯预聚体3与15份三羟甲基丙烷-三[3-(2-甲基吖丙啶基)丙酸酯混合，涂膜后置于常温下交联固化形成防雾薄膜3。
实施例9
将100份实施例4中制备得到的聚氨酯预聚体4与18份三羟甲基丙烷-三(3-吖丙啶基丙酸酯)混合，涂膜后置于常温下交联固化形成防雾薄膜4。
实施例10
将100份实施例5中制备得到的聚氨酯预聚体5与20份季戊四醇三(3-氮丙啶基)丙酸酯酯混合，涂膜后置于常温下交联固化形成防雾薄膜5。
对比例1
将100份1,4-环己烷二异氰酸酯置于三口烧瓶中，加入适量丙酮溶解，再加入30份双酚A聚氧乙烯醚(分子量约为1548g/mol)，在催化剂二月桂酸二丁基锡作用下，升温到50℃并搅拌，反应2h；再加入50份二羟甲基丁酸，60℃搅拌反应2h；随后加入10份曲拉通X-114，70℃搅拌2h停止加热反应，涂膜后置于常温下干燥。
对比例2
将100份异佛尔酮二异氰酸酯三聚体置于三口烧瓶中，加入适量丙酮溶解，再加入10份双酚A聚氧乙烯醚(分子量约为2516g/mol)，在催化剂二月桂酸二丁基锡作用下，升温到50℃并搅拌，反应2h；再加入65份二羟甲基丁酸，60℃搅拌反应2h；随后加入25份OP-20，70℃搅拌2h停止加热反应，涂膜后置于常温下干燥。
将制备的防雾薄膜在70-100℃的蒸汽中放置，并保证温度持续，观察表面是否有起雾现象，放置时间>2min，结果列于表1。
参照GB/T 6739-2006，使用QHQ-A型铅笔硬度计测定涂膜的铅笔硬度，结果列于表1。
参照GB/T 1733-1993，将防雾产品浸泡于去离子水中，观察是否出现起泡、泛白、脱落现象，结果列于表1。
参照GB/T 9286-1998，使用HGQ型漆膜划格器通过划格实验的方法测定涂膜的附着力，结果列于表1。
表1
Figure BDA0002014170290000051
从表1看出，未添加固化剂的薄膜耐水性极差，防雾效果也受到影响，本发明调控聚氧乙烯醚、二羟甲基脂肪酸、含羟基的表面活性剂三者的配比，可获得综合性能最优的防雾薄膜，防雾效果优异，表面硬度高、耐磨耐刮擦、耐水性好且与基材的附着力高。
通过本发明获得的防雾薄膜可在常温下固化成膜，通过调节固化交联剂的用量调节薄膜的交联密度，进而调节防雾薄膜的综合性能，包括防雾效果的稳定性与持久性、硬度、与基材间的黏附力、表面耐刮擦性和耐水性；无需加热固化，节省能源，符合可持续发展，成本低廉，适用于大规模工业化生产。
所属领域的普通技术人员应当理解：以上所述仅为本发明的具体实施例而已，并不用于限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

1.一种常温固化聚氨酯类防雾薄膜，其特征在于，所述防雾薄膜是由固化交联剂的氮丙啶基团在常温下与聚氨酯预聚体的羧基交联固化得到的；所述的聚氨酯预聚体主要由异氰酸酯或异氰酸酯多聚体、聚氧乙烯醚、二羟甲基脂肪酸、含羟基的表面活性剂聚合制成；所述的固化交联剂为三官能团氮丙啶；所述的二羟甲基脂肪酸为二羟甲基丙酸或二羟甲基丁酸。
2.一种如权利要求1所述的常温固化聚氨酯类防雾薄膜的制备方法，其特征在于，包括以下步骤：
(1)将异氰酸酯或异氰酸酯多聚体与聚氧乙烯醚按配比混合，加溶剂稀释，升温，加引发剂引发聚合；
(2)将二羟甲基脂肪酸按配比加入步骤(1)聚合后的体系中，进一步升温聚合；
(3)再将含羟基的表面活性剂按配比加入步骤(2)聚合后的体系中进行封端，得到聚氨酯预聚体；
(4)将聚氨酯预聚体与固化交联剂按配比混合均匀，涂膜并置于常温下交联固化成膜。
3.根据权利要求2所述的一种常温固化聚氨酯类防雾薄膜的制备方法，其特征在于，所述聚氨酯预聚体与固化交联剂的重量比为100:(1～20)，所述聚氨酯预聚体中异氰酸酯或异氰酸酯多聚体、聚氧乙烯醚、二羟甲基脂肪酸、含羟基的表面活性剂之间的重量比为100:(10～60):(40～80):(10～50)。
4.根据权利要求2或3所述的一种常温固化聚氨酯类防雾薄膜的制备方法，其特征在于，所述聚氨酯预聚体与固化交联剂的重量比为100:(15～20)，所述聚氨酯预聚体中异氰酸酯或异氰酸酯多聚体、聚氧乙烯醚、二羟甲基脂肪酸、含羟基的表面活性剂之间的重量比为100:(10～30):(50～65):(10～25)。
5.根据权利要求2或3所述的一种常温固化聚氨酯类防雾薄膜的制备方法，其特征在于，所述的固化交联剂包括季戊四醇三(3-氮丙啶基)丙酸酯、三羟甲基丙烷-三[3-(2-甲基吖丙啶基)丙酸酯、三羟甲基丙烷-三(3-吖丙啶基丙酸酯)中的一种或两种以上混合。
6.根据权利要求4所述的一种常温固化聚氨酯类防雾薄膜的制备方法，其特征在于，所述的固化交联剂包括季戊四醇三(3-氮丙啶基)丙酸酯、三羟甲基丙烷-三[3-(2-甲基吖丙啶基)丙酸酯、三羟甲基丙烷-三(3-吖丙啶基丙酸酯)中的一种或两种以上混合。
7.根据权利要求2、3或6所述的一种常温固化聚氨酯类防雾薄膜的制备方法，其特征在于，所述的异氰酸酯或异氰酸酯多聚体包括异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、萘二异氰酸酯、1,6-己二异氰酸酯、苯二亚甲基二异氰酸酯、1,4-环己烷二异氰酸酯、间苯二异氰酸酯、异佛尔酮二异氰酸酯三聚体、六亚甲基二异氰酸酯三聚体中的一种或两种以上混合；所述的聚氧乙烯醚为直链聚氧乙烯醚或含双酚A聚氧乙烯醚；所述的含羟基的表面活性剂为OP-4、OP-10、OP-20、OP-50、曲拉通X-100、曲拉通X-114、吐温20中的一种或两种以上混合。
8.根据权利要求4所述的一种常温固化聚氨酯类防雾薄膜的制备方法，其特征在于，所述的异氰酸酯或异氰酸酯多聚体包括异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、萘二异氰酸酯、1,6-己二异氰酸酯、苯二亚甲基二异氰酸酯、1,4-环己烷二异氰酸酯、间苯二异氰酸酯、异佛尔酮二异氰酸酯三聚体、六亚甲基二异氰酸酯三聚体中的一种或两种以上混合；所述的聚氧乙烯醚为直链聚氧乙烯醚或含双酚A聚氧乙烯醚；所述的含羟基的表面活性剂为OP-4、OP-10、OP-20、OP-50、曲拉通X-100、曲拉通X-114、吐温20中的一种或两种以上混合。
9.根据权利要求5所述的一种常温固化聚氨酯类防雾薄膜的制备方法，其特征在于，所述的异氰酸酯或异氰酸酯多聚体包括异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、萘二异氰酸酯、1,6-己二异氰酸酯、苯二亚甲基二异氰酸酯、1,4-环己烷二异氰酸酯、间苯二异氰酸酯、异佛尔酮二异氰酸酯三聚体、六亚甲基二异氰酸酯三聚体中的一种或两种以上混合；所述的聚氧乙烯醚为直链聚氧乙烯醚或含双酚A聚氧乙烯醚；所述的含羟基的表面活性剂为OP-4、OP-10、OP-20、OP-50、曲拉通X-100、曲拉通X-114、吐温20中的一种或两种以上混合。
10.根据权利要求7所述的一种常温固化聚氨酯类防雾薄膜的制备方法，其特征在于，所述直链聚氧乙烯醚的分子量在200g/mol至1000g/mol范围内；所述含双酚A聚氧乙烯醚的分子量在300g/mol至2600g/mol范围内。
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