CN114381196A - 一种光致变色水性聚氨酯涂料的制备方法 - Google Patents

一种光致变色水性聚氨酯涂料的制备方法 Download PDF

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CN114381196A
CN114381196A CN202011111382.7A CN202011111382A CN114381196A CN 114381196 A CN114381196 A CN 114381196A CN 202011111382 A CN202011111382 A CN 202011111382A CN 114381196 A CN114381196 A CN 114381196A
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黄文青
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Guangzhou Shengse Technology Co ltd
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Abstract

本发明公开了一种光致变色水性聚氨酯涂料的制备方法，具体方法如下：(1)一定温度下聚合物多元醇与异氰酸酯反应制备预聚体；(2)加入小分子醇、二羟基丙酸进行扩链，反应过程中使用有机溶剂降低体系粘度；(3)加入光致变色染料和助溶剂，搅拌均匀；(4)加入中和剂中和；(5)高速搅拌条件下缓慢加入去离子水，形成均匀的水乳液；(6)加入胺类扩链剂进行扩链；(7)进行减压蒸馏去除有机溶剂，得到光致变色水性聚氨酯涂料。本方法适用于多种光致变色染料，制得的光致变色水性聚氨酯涂料产品变色性能稳定，并且制备方法简单，为市场提供一种新型的水性聚氨酯涂料，具有很好的市场前景。

Description

一种光致变色水性聚氨酯涂料的制备方法
技术领域
本发明涉及一种水性聚氨酯涂料的制备方法，具体是涉及一种光致变色水性聚氨酯涂料的制备方法。
背景技术
现在市面上的光致变色染料在涂料中的应用一般通过两种方式：一种方法是利用微胶囊技术对光致变色染料进行包覆，然后将微胶囊分散在油性涂料或水性涂料中，形成光致变色涂料；另一种方法是在油性涂料中均匀混入融有光致变色染料的有机溶剂，制得光致变色油性涂料。光致变色染料直接应用在水性涂料中的商品化涂料较少，并且颜色品种也比较单一，不能满足市场需求。
专利文献CN 110627965 A公开了一种光致变色水性聚氨酯涂层剂及其制备方法。这种具有变色功能的水性聚氨酯是以聚丙二醇、甲苯二异氰酸酯与二羟甲基丙酸等为主要原料，在制备过程中，加入单羟基丙烯酸进行扩链并引入双键；在引发剂偶氮二异丁腈的作用下聚氨酯分子与制备的含乙烯基光致变色单体发生聚合反应；然后乳化、脱溶剂，得到光致变色水性聚氨酯涂层剂。光致变色材料是通过聚合的方式连接到树脂主体上，从而制备出的光致变色水性聚氨酯涂料。
文献显示鲍利红等人(水性光致变色聚氨酯的制备及其性能研究[J].涂料工业,2015,45(12):7-13)使用聚四氢呋喃二醇、IPDI、有机锡催化剂、二羟甲基丙酸、1,4-丁二醇、三羟甲基丙烷合成水性聚氨酯，然后将带有羟基的螺吡喃光致变色染料接枝到树脂主体上，形成具有光致变色功能的水性聚氨酯乳液。
现有的制备光致变色水性聚氨酯涂料的方法中，要求所用的光致变色染料具有一定的反应基团或者不饱和双键，具有这种结构的光致变色染料较少，限制了通过这种方法制备的光致变色涂料的种类。
发明内容
本发明提供的一种光致变色水性聚氨酯涂料的制备方法，对光致变色染料结构要求低，适用于多种染料，操作简单，产品颜色鲜艳，色牢度好。
一种光致变色水性聚氨酯涂料的制备方法，各组分以质量份数计算，其特征在于包括以下步骤：(1)将反应用的聚合物多元醇、小分子醇、二羟甲基丙酸、光致变色染料，真空条件下脱水；(2)将100份聚合物多元醇、15～120份异氰酸酯、5～10份有机溶剂搅拌均匀，在50～80℃、氮气保护条件下反应1～4小时形成预聚体；(3)加4～10份小分子醇、10～20份二羟甲基丙酸进行扩链，继续反应1～4小时；(4)升温至80～90℃继续反应1～4小时，反应过程中添加5～10份有机溶剂降低粘度；(5)加入0.1～7份光致变色染料和5～10份有机溶剂，搅拌均匀；(6)加入9～20份中和剂进行中和；(7)在搅拌条件下缓慢加入200～400份去离子水，进行反相乳化得到均匀的水乳液；(8)20～40℃条件下加入2～20份多元胺扩链剂扩链，搅拌0.5～1小时；(9)减压蒸馏去除水乳液中的有机溶剂，得到光致变色水性聚氨酯涂料。
所述异氰酸酯为甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、二苯基甲烷二异氰酸酯(MDI)、二环己基甲烷二异氰酸酯(HMDI)、六亚甲基二异氰酸酯(HDI)中的至少一种。
所述聚合物多元醇为聚酯多元醇、聚醚多元醇中的至少一种。
所述小分子醇为1,4-丁二醇、乙二醇、丙二醇、一缩二乙二醇、丙三醇中的至少一种。
所述有机溶剂为丙酮、丁酮、二甲基甲酰胺(DMF)、N-甲基吡咯烷酮或乙酸乙酯中的至少一种。
所述光致变色染料为螺吡喃类化合物、螺唔嗓类化合物、六苯基双咪哇类化合物、偶氮苯类化合物、稠环芳香类化合物、哗嗓类二芳基乙烯类化合物中的至少一种。
所述中和剂为三乙胺、三乙醇胺、二乙醇胺、三丙胺中的至少一种。
所述多元胺扩链剂为异佛尔酮二胺、乙二胺、二乙烯三胺、三乙烯四胺中的至少一种。
本发明的优点在于将光致变色染料溶解在树脂中，在后期乳化、扩链的过程中，树脂在水中形成一个个实心球，将光致变色染料固定在其中，所以可以使用的光致变色染料种类非常多，颜色品种也非常多，并且操作方法非常简单，适合工业生产和产品商品化。
附图说明
图1为实施例1样品变色前后对比图。
具体实施方式
下面结合具体实施例对本发明作进一步说明，以下所述的具体实施方式，是为了对本发明的目的、技术方案和有益效果进行了进一步详细说明，并不是用于限制本发明，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。
实施例1
一种光致变色水性聚氨酯涂料的制备方法，以质量份数进行计算，其包括以下步骤：(1)将反应用的聚丙二醇1000、一缩二乙二醇、二羟甲基丙酸、1,3,3-三甲基吲哚-β-萘基二氢呋喃，真空脱水；(2)将100份聚丙二醇1000、15份甲苯二异氰酸酯、5份N-甲基吡咯烷酮搅拌均匀，在50℃、氮气保护条件下反应4小时形成预聚体；(3)加4份一缩二乙二醇、10份二羟甲基丙酸进行扩链，继续反应1小时；(4)升温至90℃继续反应1小时，反应过程中添加5份N-甲基吡咯烷酮降低粘度；(5)加入0.1份1,3,3-三甲基吲哚-β-萘基二氢呋喃和5份乙酸乙酯，搅拌均匀；(6)加入9份三乙胺进行中和；(7)在搅拌条件下缓慢加入200份去离子水，进行反相乳化得到均匀的水乳液；(8)20℃条件下加入2份二乙烯三胺扩链，搅拌0.5小时；(9)减压蒸馏去除水乳液中的有机溶剂，得到光致变色水性聚氨酯涂料。
得到光致变色水性聚氨酯涂料在无光条件下具有轻微底色，属于正常现象，在阳光照射下能够变色，颜色鲜艳。
实施例2
一种光致变色水性聚氨酯涂料的制备方法，以质量份数进行计算，其包括以下步骤：(1)将反应用的聚四氢呋喃二醇1000、聚丙二醇1000、聚醚多元醇DL1000、一缩二乙二醇、二羟甲基丙酸、1,2-双(2,4,5-三甲基-3-噻吩基)-顺-1,2-二氰基乙烯，真空脱水；(2)将60份聚四氢呋喃二醇1000、20份聚丙二醇1000、20份聚醚多元醇DL1000、10份甲苯二异氰酸酯、40份异氟尔酮二异氰酸酯、5份N-甲基吡咯烷酮搅拌均匀，在80℃、氮气保护条件下反应1小时形成预聚体；(3)加10份一缩二乙二醇、20份二羟甲基丙酸进行扩链，继续反应4小时；(4)升温至90℃继续反应4小时，反应过程中添加10份N-甲基吡咯烷酮降低粘度；(5)加入7份1,2-双(2,4,5-三甲基-3-噻吩基)-顺-1,2-二氰基乙烯和10份乙酸乙酯，搅拌均匀；(6)加入20份三乙胺进行中和；(7)在搅拌条件下缓慢加入400份去离子水，进行反相乳化得到均匀的水乳液；(8)30℃条件下加入20份二乙烯三胺扩链，搅拌0.8小时；(9)减压蒸馏去除水乳液中的有机溶剂，得到光致变色水性聚氨酯涂料。
得到光致变色水性丙烯酸涂料在无光条件下具有轻微底色，属于正常现象，在阳光照射下能够变色，颜色鲜艳。
实施例3
一种光致变色水性聚氨酯涂料的制备方法，以质量份数进行计算，其包括以下步骤：(1)将反应用的四氢呋喃二醇1000、聚酯二醇PBA1000、一缩二乙二醇、二羟甲基丙酸、1,2-双(2,4-二甲基-5-苯基-3-噻吩基)-3,3,4,4,5,5-六氟-1-环戊烯，真空条件下脱水；(2)将60份聚四氢呋喃二醇1000、40份聚酯二醇PBA1000、80份甲苯二异氰酸酯、40份异氟尔酮二异氰酸酯、8份N-甲基吡咯烷酮搅拌均匀，在60℃、氮气保护条件下反应2小时形成预聚体；(3)加6份一缩二乙二醇、15份二羟甲基丙酸进行扩链，继续反应2小时；(4)升温至80℃继续反应2小时，反应过程中添加6份N-甲基吡咯烷酮降低粘度；(5)加入5份1,2-双(2,4-二甲基-5-苯基-3-噻吩基)-3,3,4,4,5,5-六氟-1-环戊烯和8份乙酸乙酯，搅拌均匀；(6)加入15份三乙胺进行中和；(7)在搅拌条件下缓慢加入300份去离子水，进行反相乳化得到均匀的水乳液；(8)25℃条件下加入12份二乙烯三胺扩链，搅拌1小时；(9)减压蒸馏去除水乳液中的有机溶剂，得到光致变色水性聚氨酯涂料。
得到光致变色水性丙烯酸涂料在无光条件下具有轻微底色，属于正常现象，在阳光照射下能够变色，颜色鲜艳。
实施例4
一种光致变色水性聚氨酯涂料的制备方法，以质量份数进行计算，其包括以下步骤：(1)将反应用的聚四氢呋喃二醇1000、聚酯多元醇PUD L3025、丙三醇、二羟甲基丙酸、8-甲氧基-1',3',3'-三甲基-6-硝基螺[苯并吡喃-2,2'-吲哚]，真空条件下脱水；(2)将60份聚四氢呋喃二醇1000、40份聚酯多元醇PUD L3025、40份甲苯二异氰酸酯、35份异氟尔酮二异氰酸酯、6份N-甲基吡咯烷酮搅拌均匀，在80℃、氮气保护条件下反应3小时形成预聚体；(3)加8份丙三醇、6份二羟甲基丙酸进行扩链，继续反应3小时；(4)升温至85℃继续反应1.5小时，反应过程中添加7份N-甲基吡咯烷酮降低粘度；(5)加入2.5份8-甲氧基-1',3',3'-三甲基-6-硝基螺[苯并吡喃-2,2'-吲哚]和8份乙酸乙酯，搅拌均匀；(6)加入16份三乙胺进行中和；(7)在搅拌条件下缓慢加入250份去离子水，进行反相乳化得到均匀的水乳液；(8)30℃条件下加入8份二乙烯三胺扩链，搅拌1小时；(9)减压蒸馏去除水乳液中的有机溶剂，得到光致变色水性聚氨酯涂料。
得到光致变色水性聚氨酯涂料在无光条件下具有轻微底色，属于正常现象，在阳光照射下能够变色，颜色鲜艳。

Claims (8)

1.一种光致变色水性聚氨酯涂料的制备方法，各组分以质量份数计算，其特征在于包括以下步骤：(1)将反应用的聚合物多元醇、小分子醇、二羟甲基丙酸、光致变色染料，真空条件下脱水；(2)将100份聚合物多元醇、15～120份异氰酸酯、5～10份有机溶剂搅拌均匀，在50～80℃、氮气保护条件下反应1～4小时形成预聚体；(3)加4～10份小分子醇、10～20份二羟甲基丙酸进行扩链，继续反应1～4小时；(4)升温至80～90℃继续反应1～4小时，反应过程中添加5～10份有机溶剂降低粘度；(5)加入0.1～7份光致变色染料和5～10份有机溶剂，搅拌均匀；(6)加入9～20份中和剂进行中和；(7)在搅拌条件下缓慢加入200～400份去离子水，进行反相乳化得到均匀的水乳液；(8)20～40℃条件下加入2～20份多元胺扩链剂扩链，搅拌0.5～1小时；(9)减压蒸馏去除水乳液中的有机溶剂，得到光致变色水性聚氨酯涂料。
2.根据权利要求1所述一种光致变色水性聚氨酯涂料的制备方法，其特征在于所述异氰酸酯为甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、二苯基甲烷二异氰酸酯(MDI)、二环己基甲烷二异氰酸酯(HMDI)、六亚甲基二异氰酸酯(HDI)中的至少一种。
3.根据权利要求1所述一种光致变色水性聚氨酯涂料的制备方法，其特征在于所述聚合物多元醇为聚酯多元醇、聚醚多元醇中的至少一种。
4.根据权利要求1所述一种光致变色水性聚氨酯涂料的制备方法，其特征在于所述小分子醇为1,4-丁二醇、乙二醇、丙二醇、一缩二乙二醇、丙三醇中的至少一种。
5.根据权利要求1所述一种光致变色水性聚氨酯的制备方法，其特征在于所述有机溶剂为丙酮、丁酮、二甲基甲酰胺(DMF)、N-甲基吡咯烷酮或乙酸乙酯中的至少一种。
6.根据权利要求1所述一种光致变色水性聚氨酯涂料的制备方法，其特征在于所述光致变色染料为螺吡喃类化合物、螺唔嗓类化合物、六苯基双咪哇类化合物、偶氮苯类化合物、稠环芳香类化合物、哗嗓类二芳基乙烯类化合物中的至少一种。
7.根据权利要求1所述一种光致变色水性聚氨酯涂料的制备方法，其特征在于所述中和剂为三乙胺、三乙醇胺、二乙醇胺、三丙胺中的至少一种。
8.根据权利要求1所述一种光致变色水性聚氨酯涂料的制备方法，其特征在于所述多元胺扩链剂为异佛尔酮二胺、乙二胺、二乙烯三胺、三乙烯四胺中的至少一种。
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