CN105419620A - 一种改性聚氨酯树脂涂料及其制备方法 - Google Patents
一种改性聚氨酯树脂涂料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种改性聚氨酯树脂涂料，所述涂料由以下原料按照重量配比制成：甲苯二异氰酸酯60-80份、二环己基甲烷二异氰酸酯5-10份、六亚甲基二异氰酸酯5-10份、己二酸4-8份、醇酸树脂1-5份、环氧树脂2-4份、丙二醇1-3份、甲基二乙醇胺1-3份、二酯酸二丁基锡1-4份、醋酸乙酯5-10份，磷酸0.5-1份，去离子水10-30份；以及聚合物纳米粒子8-16份，本发明将聚合物纳米粒子与涂料相结合，分散于改性聚氨酯树脂中，形成有效的防腐蚀复合涂层，具有耐油性、耐海水、耐磨损和耐冲击等优良性能。
Description
技术领域
本发明涉及一种改性聚氨酯树脂涂料及其制备方法。
背景技术
聚氨酯树脂的水性化已逐步取代溶剂型，成为聚氨酯工业发展的重要方向。聚氨酯可广泛应用于涂料、胶粘剂、织物涂层与整理剂、皮革涂饰剂、纸张表面处理剂和纤维表面处理剂。水性聚氨酯乳液不仅是比较环保的涂料，而且具有耐油性、耐海水、耐磨损和耐冲击等优良性能。现有对聚氨酯进行配方设计与调整以满足实际使用的要求，并可结合纳米杂化技术制备高性能的水性聚氨酯。以聚氨酯或改性聚氨酯为主要成膜物，添加适量的辅助成膜物组分、助剂溶剂的涂料通常为聚氨酯涂料。聚氨酯树脂涂料具有明显优于其他涂料的特定，聚氨酯涂料的优点是漆膜耐磨性强，装饰性能好，涂膜附着力强，涂膜弹性高，涂膜耐腐蚀性能强，烘干温度范围宽，耐高温低温性能突出，绝缘性能优异，花色品种多，但其也有明显的缺点，例如保光保色性差，树脂乳液稳定性差，容易损坏涂层，施工要求高。
当应用到冶金金属处理时，所形成的涂层容易受到腐蚀而产生破坏，例如金属铜如果处于含离子的腐蚀溶液中时(比如氯离子、硫酸根离子等)，容易发生点蚀(即在金属表面局部出现纵深发展的腐蚀小孔。大量实践证明，混合型缓蚀剂苯并三氮唑及其衍生物对铜的防腐蚀效果比较理想，应用比较广泛，其作用机理是能在铜表面形成一层苯并三氮唑和铜离子的络合物保护膜，并且既能在阳极成膜，也能在阴极成膜，阻止水与水中溶解氧向金属表面的扩散，降低铜的腐蚀速度。
如前所述，随着外界腐蚀介质的变化，需要缓蚀剂能够长效地释放到受腐蚀破坏区域，比较有效的方法是将缓蚀剂直接加入到金属处理涂层中，涂层主要起到的是物理阻隔的作用。然而，这种直接掺入的方法有时候不能起到足够的保护作用，缓蚀剂与涂层直接接触，在大多数情况下，这种体系不具备刺激响应性释放缓蚀剂的能力，如果缓蚀剂在涂层中的溶解度比较高时，快速释放的缓蚀剂会使得涂层发生起泡现象，并且会破坏涂层的完整性。
发明内容
本发明的目的在于提供一种改性聚氨酯树脂涂料，其将预先制备好的负载包覆有缓蚀剂的纳米粒子分散于聚氨酯树脂中，从而将负载材料包覆缓蚀剂掺入涂层中，这些载体不仅可以避免缓蚀剂不必要的流失，以及缓蚀剂对涂层直接的破坏，而且具有一定环境刺激响应性，比如机械破坏、PH改变和光照等。
本发明的技术方案为：一种改性聚氨酯树脂涂料，所述涂料由以下原料按照重量配比制成：甲苯二异氰酸酯60-80份、二环己基甲烷二异氰酸酯5-10份、六亚甲基二异氰酸酯5-10份、己二酸4-8份、醇酸树脂1-5份、环氧树脂2-4份、丙二醇1-3份、甲基二乙醇胺1-3份、二酯酸二丁基锡1-4份、醋酸乙酯5-10份，磷酸0.5-1份，去离子水10-30份；以及聚合物纳米粒子8-16份。
该涂料的制备方法如下：
1)将甲苯二异氰酸酯60-80份、二环己基甲烷二异氰酸酯5-10份、六亚甲基二异氰酸酯5-10份、醋酸乙酯5-10份加入反应釜，使用搅拌机进行充分搅拌，升温至90-100℃，缓慢加入己二酸4-8份；
2)继续加入醇酸树脂1-5份，环氧树脂2-4份，充分搅拌1h以上，
3)加入扩链剂、活化剂以及催化剂：按照均分四次间隔30min加入丙二醇1-3份、甲基二乙醇胺1-3份、二酯酸二丁基锡1-4份，磷酸0.5-1份，然后保温80摄氏度4h以上，加离子水进行乳化30min以上；
4)将包覆有苯并三氮唑的聚合物纳米粒子通过超声分散混合于上述乳液中，在保温50℃充分搅拌反应1h以上，得到改性聚氨酯树脂-纳米粒子复合涂料。
与现有技术相比，本发明的聚合物纳米颗粒包覆缓蚀剂，这种聚合物纳米颗粒能够在腐蚀介质中，具有PH值响应性，在外界刺激涂层或者损坏涂层时，由于腐蚀局部酸碱变化，依据情况不同释放出缓蚀剂，在金属表面吸附成膜，起到主动修复涂层的作用，同时本发明采用的多步乳液聚合得到包覆缓蚀剂的聚合物纳米粒子具有优越的包覆功能和稳定性，成品率较高，将聚合物纳米粒子与涂料相结合，分散于改性聚氨酯树脂中，形成有效的防腐蚀复合涂层，具有耐油性、耐海水、耐磨损和耐冲击等优良性能。
具体实施方式
以下实施例用于说明本发明，但不用来限制本发明的范围。
一种改性聚氨酯树脂-纳米粒子复合涂料，所述涂料由以下原料按照重量配比制成：甲苯二异氰酸酯60-80份、二环己基甲烷二异氰酸酯5-10份、六亚甲基二异氰酸酯5-10份、己二酸4-8份、醇酸树脂1-5份、环氧树脂2-4份、丙二醇1-3份、甲基二乙醇胺1-3份、二酯酸二丁基锡1-4份、醋酸乙酯5-10份，磷酸0.5-1份，去离子水10-30份；以及聚合物纳米粒子8-16份。
该涂料的制备方法如下：
1)将甲苯二异氰酸酯60-80份、二环己基甲烷二异氰酸酯5-10份、六亚甲基二异氰酸酯5-10份、醋酸乙酯5-10份加入反应釜，使用搅拌机进行充分搅拌，升温至90-100℃，缓慢加入己二酸4-8份；
2)继续加入醇酸树脂1-5份，环氧树脂2-4份，充分搅拌1h以上，
3)加入扩链剂、活化剂以及催化剂：按照均分四次间隔30min加入丙二醇1-3份、甲基二乙醇胺1-3份、二酯酸二丁基锡1-4份，磷酸0.5-1份，然后保温80摄氏度4h以上，加离子水进行乳化30min以上；
4)将包覆有苯并三氮唑的聚合物纳米粒子通过超声分散混合于上述乳液中，在保温50℃充分搅拌反应1h以上，得到改性聚氨酯树脂-纳米粒子复合涂料。
该包覆有苯并三氮唑的聚合物纳米粒子的制备方法如下：
步骤1)：将正丁基丙烯酸酯2.5重量份(或克)，甲基丙烯酸甲酯1.1重量份，甲基丙烯酸0.4重量份，肌醇六磷酸酯0.25重量份的混合单体加入到1L容量的反应容器中，然后将按照每升水中含有过硫酸钾0.23重量份、十二烷基硫酸钠0.22重量份比例制得的水溶液200ml加入反应器中，在反应器中通入氮气，温度升高至85-90℃，使用永磁直流电动机进行机械搅拌反应24-36小时，得到初级乳液；
步骤2)：将含有过硫酸钾0.2重量份、十二烷基硫酸钠0.45重量份的水溶液150mL加入到上述初级乳液中，然后缓慢滴入丙烯酸丁酯2重量份、甲基丙烯酸甲酯30重量份，甲基丙烯酸14重量份的混合单体，滴加时间为40min，反应温度保持在85-90℃，使用永磁直流电动机进行机械搅拌反应8小时，得到一级核心乳液；配置质量浓度为4％的苯并三氮唑水溶液400ml置于另一反应器中(容量可为1L)，取上述合成的一级核心乳液50ml加入到苯并三氮唑水溶液中，温度升高至85-90℃，保持3h以上，得到吸附有一定量苯并三氮唑的一级核心乳液。
步骤3)：将0.5重量份过硫酸钾加入到上述含有吸附有一定量苯并三氮唑的一级核心乳液，随后缓慢滴入丙烯酸丁酯3.8重量份、甲基丙烯酸甲酯40重量份，甲基丙烯酸2重量份的混合单体，滴加过程持续40min，反应温度保持在85-90℃，持续反应至少8h以上，得到包覆有苯并三氮唑的二级核心乳液；
步骤4)：取上述合成的二级核心乳液100ml，加入含有0.2重量份过硫酸钾的水溶液200ml，反应温度保持在85-90℃，按照滴加速度为0.04g/min的速度非常缓慢地滴入苯乙烯0.5重量份，然后用氢氧化钠水溶液(10wt％)调节反应溶液的PH值至10左右，最后再次缓慢滴入苯乙烯15重量份，滴加时间不少于40min，恒温保持85-90℃持续至少8小时，完成上述步骤后通过离心机进行分离，先使用无水乙醇洗涤两次，后用去离子水洗涤三次以上，置于50℃的鼓风干燥箱中干燥24小时，得到包覆有苯并三氮唑的聚合物纳米粒子。
实施例1
聚氨酯树脂-纳米粒子复合涂料由以下原料按照重量配比制成：甲苯二异氰酸酯60份、二环己基甲烷二异氰酸酯5份、六亚甲基二异氰酸酯5份、己二酸4份、醇酸树脂1份、环氧树脂2份、丙二醇1份、甲基二乙醇胺1份、二酯酸二丁基锡1份、醋酸乙酯6份，磷酸0.5份，去离子水15份；以及聚合物纳米粒子8份。制备方法如前所述。
实施例2
聚氨酯树脂-纳米粒子复合涂料由以下原料按照重量配比制成：甲苯二异氰酸酯70份、二环己基甲烷二异氰酸酯10份、六亚甲基二异氰酸酯10份、己二酸8份、醇酸树脂3份、环氧树脂4份、丙二醇3份、甲基二乙醇胺2份、二酯酸二丁基锡4份、醋酸乙酯10份，磷酸0.5份，去离子水30份；以及聚合物纳米粒子10份。制备方法如前所述。
实施例3
聚氨酯树脂-纳米粒子复合涂料由以下原料按照重量配比制成：甲苯二异氰酸酯60份、二环己基甲烷二异氰酸酯8份、六亚甲基二异氰酸酯7份、己二酸5份、醇酸树脂4份、环氧树脂4份、丙二醇3份、甲基二乙醇胺1份、二酯酸二丁基锡3份、醋酸乙酯5份，磷酸1份，去离子水25份；以及聚合物纳米粒子12份。制备方法如前所述。
实施例4
聚氨酯树脂-纳米粒子复合涂料由以下原料按照重量配比制成：甲苯二异氰酸酯80份、二环己基甲烷二异氰酸酯10份、六亚甲基二异氰酸酯8份、己二酸8份、醇酸树脂5份、环氧树脂4份、丙二醇2份、甲基二乙醇胺3份、二酯酸二丁基锡1份、醋酸乙酯6份，磷酸1份，去离子水30份；以及聚合物纳米粒子14份。制备方法如前所述。
实施例5
聚氨酯树脂-纳米粒子复合涂料由以下原料按照重量配比制成：甲苯二异氰酸酯60份、二环己基甲烷二异氰酸酯8份、六亚甲基二异氰酸酯5份、己二酸6份、醇酸树脂2份、环氧树脂2份、丙二醇2份、甲基二乙醇胺3份、二酯酸二丁基锡4份、醋酸乙酯10份，磷酸0.5份，去离子水25份；以及聚合物纳米粒子16份。制备方法如前所述。
将上述实施例1-5得到的涂料对同一金属工件进行表面处理，效果参数比较如下：
实施例1-5性能测试结果对比分析表
尽管上文对本发明的具体实施方式给予了详细描述和说明，但是应该指明的是，我们可以依据本发明的构想对上述实施方式进行各种等效改变和修改，其所产生的功能作用仍未超出说明书所涵盖的精神时，均应在本发明的保护范围之内。例如，重量份可以选择为克或其他重量单位。以上所述，仅为本发明的较佳实施例，并不用以限制本发明，凡是依据本发明的技术实质对以上实施例所作的任何细微修改、等同替换和改进，均应包含在本发明技术方案的保护范围之内。
Claims (2)
1.一种改性聚氨酯树脂涂料，所述涂料由以下原料按照重量配比制成：甲苯二异氰酸酯60-80份、二环己基甲烷二异氰酸酯5-10份、六亚甲基二异氰酸酯5-10份、已二酸4-8份、醇酸树脂1-5份、环氧树脂2-4份、丙二醇1-3份、甲基二乙醇胺1-3份、二酯酸二丁基锡1-4份、醋酸乙酯5-10份，磷酸0.5-1份，去离子水10-30份；以及聚合物纳米粒子8-16份。
2.一种如权利要求1所述的改性聚氨酯树脂涂料的制备方法如下：
1)将甲苯二异氰酸酯60-80份、二环己基甲烷二异氰酸酯5-10份、六亚甲基二异氰酸酯5-10份、醋酸乙酯5-10份加入反应釜，使用搅拌机进行充分搅拌，升温至90-100℃，缓慢加入已二酸4-8份；
2)继续加入醇酸树脂1-5份，环氧树脂2-4份，充分搅拌1h以上，
3)加入扩链剂、活化剂以及催化剂：按照均分四次间隔30min加入丙二醇1-3份、甲基二乙醇胺1-3份、二酯酸二丁基锡1-4份，磷酸0.5-1份，然后保温80摄氏度4h以上，加离子水进行乳化30min以上；
4)将包覆有苯并三氮唑的聚合物纳米粒子通过超声分散混合于上述乳液中，在保温50℃充分搅拌反应1h以上，得到改性聚氨酯树脂-纳米粒子复合涂料。
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Effective date of registration: 20180327 Address after: 528463 Zhongshan City, Guangdong Province, three villages and towns Baishi industrial area Applicant after: Zhongshan new Longchang Chemical Co., Ltd. Address before: 322013 Zhejiang province Yiwu Niansanli East Village No. 50 Applicant before: Dong Xiaona |
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Granted publication date: 20180605 Termination date: 20201210 |