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CN106977690B - 一种环三磷腈型光固化聚氨酯树脂及其制备的自修复涂层 - Google Patents

一种环三磷腈型光固化聚氨酯树脂及其制备的自修复涂层 Download PDF

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CN106977690B
CN106977690B CN201710330211.5A CN201710330211A CN106977690B CN 106977690 B CN106977690 B CN 106977690B CN 201710330211 A CN201710330211 A CN 201710330211A CN 106977690 B CN106977690 B CN 106977690B
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刘敬成
曹建诚
周珍
刘仁
刘晓亚
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Abstract

本发明公开了一种环三磷腈型光固化聚氨酯树脂及其制备的自修复涂层，首先二元醇、二异氰酸酯进行反应；再与光固化单体反应，引入双键；最后与环三磷腈单体发生反应，制得所述环三磷腈型光固化聚氨酯树脂；将光固化聚氨酯树脂、光引发剂、活性稀释剂、溶剂混合制成自修复涂层。本发明制备方法简单，反应条件温和，所含有的碳碳双键可用于涂层的光固化性能，异氰酸酯间的氢键可用于自修复性能，环三磷腈内核的引入使其具有较好的硬度及机械性能，同时又使其具有自修复性能，各原料间相互配合制得性能优异的自修复涂层。

Description

一种环三磷腈型光固化聚氨酯树脂及其制备的自修复涂层
技术领域
本发明涉及光固化材料技术领域，尤其是涉及一种环三磷腈单体与聚氨酯预聚物反应制备环三磷腈型光固化聚氨酯树脂，及其在自修复中的应用。
背景技术
自修复涂层是指在涂层破坏后，具有自我修复能力，或者在一定的外界环境下具有自我修复能力的功能涂层。自修复聚合物材料作为一种新颖的智能结构功能材料，通过实现微裂纹的自愈合，避免材料进一步遭到破坏。自修复原理主要包括非本征型(微胶囊修复型，中空纤维型)和本征型(可逆共价键类，可逆非共价键类)两大类。外援型自修复只能实现一次修复，因此大大限制了其在涂层领域的广泛应用，而本征型自修复由于其修复特点可用于多次复，然而之前的涂层大多选用单臂或少臂结构，导致其具有较低的硬度及较差的机械性能，使其在实际应用中大大受限。
环三磷腈是一类由磷原子和氮原子通过单双建交替排列的有机-无机杂化材料，可分为环磷腈和聚磷腈，环三磷腈是环磷腈化合物中最有代表性的化合物，结构上，磷原子连接可被取代的两个活性基团，容易受到亲核试剂进攻而被取代，可以赋予材料优异的硬度和热稳定性能。因此将其改性作为合成聚氨酯的多元醇结构并引入苯环结构，在保证其自修复性能的同时，提高其制备自修复涂层的硬度及机械性能。
发明内容
针对现有技术存在的上述问题，本发明申请人提供了一种环三磷腈型光固化聚氨酯树脂及其制备的自修复涂层。本发明将可光固化的双键基团接枝到环三磷腈上，制备了环三磷腈型光固化聚氨酯树脂，在保证较好自修复性能的同时，大大提高了自修复涂层的硬度；引入的光敏基团，不仅可以实现高效率的紫外光固化作用，而且还可以提高涂层的机械性能。
本发明的技术方案如下：
一种环三磷腈型光固化聚氨酯树脂，所述树脂的制备方法包括如下步骤：
(1)采用无水溶剂将二异氰酸酯、催化剂二月桂酸二丁基锡稀释后置于反应器中，然后向反应器中滴加无水溶剂稀释的二元醇，在40～50℃下反应2～4h，制得异氰酸基封端的预聚物；
(2)然后，向步骤(1)所得异氰酸基封端的预聚物中滴加光固化单体，60-70℃搅拌反应5-7h，得到光敏聚氨酯溶液；
(3)最后，将环三磷腈单体和催化剂二月桂酸二丁基锡溶于无水溶剂中，缓慢滴加到步骤(2)所得光敏聚氨酯溶液中，50-70℃搅拌反应10-12h，反应结束，产物在去离子水中沉淀、抽滤、真空干燥，得到所述环三磷腈型光固化聚氨酯树脂。
步骤(1)中所述二异氰酸酯为二苯基甲烷二异氰酸酯、聚合二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、苯二亚甲基二异氰酸酯中的一种或多种；所述二元醇为PEG-400、PEG-800、PEG-1000、PEG-2000、PEG-10000、T5650E、T5650J、T5651、T5652、聚环氧乙烷(聚乙二醇)二醇、聚环氧丙烷(聚丙二醇)二醇、聚四氢呋喃二醇、聚己二酸乙二醇酯二醇、聚己二酸-1,4-丁二醇酯二醇中的一种或多种；所述二异氰酸酯与二元醇的摩尔比为2～2.2:1。
步骤(1)中所述催化剂二月桂酸二丁基锡的用量为二元醇和二异氰酸酯总质量的0.5～1％。
步骤(2)中所述光固化单体为(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸羟丁酯中的一种或多种；所述光固化单体与异氰酸基封端的预聚物的摩尔比为1～1.1:1。
步骤(3)中所述环三磷腈单体为六对羟甲基苯氧基环三磷腈、十二羟基环三磷腈中的一种或两种的混合；所述环三磷腈单体与光敏聚氨酯的摩尔比为1～1.1:1。
所述的无水溶剂为N,N-二甲基甲酰胺、丙酮、无水丁酮、四氢呋喃、乙酸乙酯中的一种或多种；所述无水溶剂的用量为使反应体系中反应物的浓度为20～30wt％。
一种所述环三磷腈型光固化聚氨酯树脂的应用，该光固化聚氨酯树脂可用于自修复技术领域。
一种含有所述环三磷腈型光固化聚氨酯树脂的自修复涂层，该涂层所含原料及各原料的质量百分数为：
将各原料按上述比例混合，避光超声30～60min后，旋涂于铝板上，厚度为0.1～1mm，在40～100℃条件下，预烘60～120min，然后在500-800mJ/cm2的能量下进行曝光固化，制得环三磷腈型光固化聚氨酯自修复涂层。
所述活性稀释剂为三羟甲基丙烷三丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯中的一种或多种；所述光引发剂为2-羟基-2-甲基-1-苯基-1-丙酮、1-羟基环已基苯基甲酮、2-羟基-4’-(2-羟乙氧基)-2-甲基苯丙酮、2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮中的一种或多种；所述溶剂为N,N-二甲基甲酰胺、丁酮、二甲基乙酰胺、环己酮、乙酸乙酯中的一种或多种。
本发明有益的技术效果在于：
(1)本发明中的聚氨酯树脂以环三磷腈为硬核，通过逐步加成在环三磷腈上接枝多条直线型聚氨酯软链，形成一种“硬核软臂”的结构，六对羟甲基苯氧基环三磷腈中的苯环结构可以大大提高的硬度，同时，聚氨酯的多臂结构不仅能够接枝更多的自修复基团，同时可以在加热下保持链的移动性，保证具有较好的自修复性能。
(2)本发明中采用的环三磷腈单体，合成原料简单易得，合成工艺成熟，制备方法简单。
(3)本发明中光固化聚氨酯树脂分子链末端含有的光敏基团，通过采用固化温度低、固化速度快、固化效率高、操作简便、节能环保的紫外光固化技术，制备环三磷腈型光固化聚氨酯自修复，既简化了传统的成膜工艺，提高了生产效率，同时也可以通过形成交联网络来增强的机械性能。
附图说明
图1为本发明反应过程示意图；
图2为实施例1所述涂层修复前(A)和修复后(a)的超景深显微镜图片；
图3为实施例1所述涂层的TGA曲线图。
具体实施方式
下面结合附图和实施例，对本发明进行具体描述。
实施例1
一种环三磷腈型光固化聚氨酯树脂，通过如下步骤制得：
(1)采用12.5g无水N,N-二甲基甲酰胺(DMF)将2.445g(0.011mol)异氟尔酮二异氰酸酯、0.024g二月桂酸二丁基锡稀释后置于带有搅拌和冷凝的三口烧瓶中，然后向三口烧瓶中缓慢滴加12.5g无水DMF和2.5g(0.005mol)PCDL500的混合物，在45℃下反应2h，制得异氰酸基封端的预聚物；
(2)将0.651g(0.005mol)甲基丙烯酸羟乙酯溶于4.4g无水DMF中，滴加入步骤(1)制得的异氰酸基封端的预聚物中，在60℃下反应6h，制得光敏聚氨酯溶液；
(3)将0.728g(0.000833mol)六对羟甲基苯氧基环三磷腈与0.01g二月桂酸二丁基锡溶于3.0g无水DMF中，滴加入步骤(2)制得的光敏聚氨酯溶液中，在70℃下反应12h，反应结束，产物在去离子水中沉淀、抽滤、真空干燥，制得所述环三磷腈型光固化聚氨酯树脂。
将60wt％本发明实施例制备的环三磷腈型聚氨酯树脂、3wt％的1-羟基环己基苯基甲酮和37wt％的DMF混合，避光超声30min后，旋涂于铝板上，厚度为0.3mm，在70℃条件下，预烘120min，然后在600mJ/cm2的能量下进行曝光固化，制得环三磷腈型光固化聚氨酯自修复涂层。
采用划痕仪将制备的环三磷腈型光固化聚氨酯自修复涂层表面进行划伤后，利用热风枪使涂层的表面在100℃下加热10min，并且通过三维超景深光学显微镜观察了涂层的自修复性能，涂层修复前后的对比如图2所示，涂层的摆杆硬度(avg)为147±3，铅笔硬度为2H。
由图2可以看出，涂层被破坏后的划痕消失较为明显，呈现出了良好的自修复效果。
由图3可以看出涂层主要分为三个热失重过程，分别在220-280℃，300-400℃和420-500℃之间，分别对应着硬段结构、软段结构及其他键的分解，表明制备的聚氨酯自修复涂层具有较好的热稳定性。
实施例2
一种环三磷腈型光固化聚氨酯树脂，通过如下步骤制得：
(1)使用12g无水乙酸乙酯将3.532g(0.021mol)六亚甲基二异氰酸酯和0.037g二月桂酸二丁基锡稀释后加入到带有搅拌和冷凝的三口烧瓶中，然后向三口烧瓶中缓慢滴加15g无水乙酸乙酯和4.0g(0.01mol)PEG400的混合物，反应在45℃下搅拌2h，制备出异氰酸基封端的预聚物；
(2)将1.301g(0.01mol)丙烯酸羟丙酯溶于5.0g无水乙酸乙酯中，缓慢滴加入步骤(1)制得的异氰酸基封端的预聚物中，反应在60℃下搅拌6h，制得光敏聚氨酯溶液；
(3)将1.449g(0.00166mol)六对羟甲基苯氧基环三磷腈和0.017g二月桂酸二丁基锡溶于5.0g无水乙酸乙酯中，滴加入步骤(2)制得的光敏聚氨酯溶液中，反应在70℃下搅拌12h，反应结束，将产物滴加到去离子水中沉淀，抽滤，真空干燥，制备出所述环三磷腈型光固化聚氨酯树脂。
将50wt％本发明实施例所制备的光固化聚氨酯、20wt％的三乙氧基化三羟甲基丙烷三丙烯酸酯、27wt％的乙酸乙酯和3wt％的2-羟基-2-甲基-1-苯基-1-丙酮混合，避光超声45min后，旋涂于铝板上，厚度为0.2mm，在40℃条件下，预烘120min，然后在700mJ/cm2的能量下进行曝光固化，制备出环三磷腈型光固化聚氨酯自修复涂层。
实施例3
一种环三磷腈型光固化聚氨酯树脂，通过如下步骤制得：
(1)使用10g无水丁酮将2.753g(0.011mol)二苯基亚甲基二异氰酸酯和0.035g二月桂酸二丁基锡稀释后加入到带有搅拌和冷凝的三口烧瓶中；然后向三口烧瓶中缓慢滴加15g无水丁酮与5.0g(0.005mol)PCDL1000的混合物，反应在40℃下搅拌3h，制备出异氰酸基封端的预聚物；
(2)将0.581g(0.005mol)丙烯酸羟乙酯溶于3.5g无水丁酮中，缓慢滴加入步骤(1)制得的异氰酸基封端的预聚物中，反应在60℃下搅拌4h，制得光敏聚氨酯溶液；
(3)将1.570g(0.000833mol)十二羟基环三磷腈和0.01g二月桂酸二丁基锡溶于5g无水丁酮中，滴加入步骤(2)制得的光敏聚氨酯溶液中，反应在70℃下搅拌12h，反应结束，将产物滴加到去离子水中沉淀，抽滤，真空干燥，制备出所述环三磷腈型光固化聚氨酯树脂。
将50wt％本发明实施例中所制备的环三磷腈型聚氨酯树脂、10wt％九乙氧基化三羟甲基丙烷三丙烯酸酯、37wt％乙酸乙酯、3wt％1-羟基环已基苯基甲酮混合，避光超声60min后，旋涂于铝板上，厚度为0.15mm，在50℃条件下，预烘100min，然后在800mJ/cm2的能量下进行曝光固化，制备出环三磷腈型光固化聚氨酯自修复涂层。

Claims (7)

1.一种环三磷腈型光固化聚氨酯树脂，其特征在于所述树脂的制备方法包括如下步骤：
(1)采用无水溶剂将二异氰酸酯、催化剂二月桂酸二丁基锡稀释后置于反应器中，然后向反应器中滴加无水溶剂稀释的二元醇，在40～50℃下反应2～4h，制得异氰酸基封端的预聚物；
(2)然后，向步骤(1)所得异氰酸基封端的预聚物中滴加光固化单体，60-70℃搅拌反应5-7h，得到光敏聚氨酯溶液；所述光固化单体为(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸羟丁酯中的一种或多种；所述光固化单体与异氰酸基封端的预聚物的摩尔比为1～1.1:1；
(3)最后，将环三磷腈单体和催化剂二月桂酸二丁基锡溶于无水溶剂中，缓慢滴加到步骤(2)所得光敏聚氨酯溶液中，50-70℃搅拌反应10-12h，反应结束，产物在去离子水中沉淀、抽滤、真空干燥，得到所述环三磷腈型光固化聚氨酯树脂；所述环三磷腈单体为六对羟甲基苯氧基环三磷腈、十二羟基环三磷腈中的一种或两种的混合；所述环三磷腈单体与光敏聚氨酯的摩尔比为1～1.1:1。
2.根据权利要求1所述的环三磷腈型光固化聚氨酯树脂，其特征在于步骤(1)中所述二异氰酸酯为二苯基甲烷二异氰酸酯、聚合二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、苯二亚甲基二异氰酸酯中的一种或多种；所述二元醇为PEG-400、PEG-800、PEG-1000、PEG-2000、PEG-10000、T5650E、T5650J、T5651、T5652、聚环氧乙烷二醇、聚环氧丙烷二醇、聚四氢呋喃二醇、聚己二酸乙二醇酯二醇、聚己二酸-1,4-丁二醇酯二醇中的一种或多种；所述二异氰酸酯与二元醇的摩尔比为2～2.2:1。
3.根据权利要求1所述的环三磷腈型光固化聚氨酯树脂，其特征在于步骤(1)中所述催化剂二月桂酸二丁基锡的用量为二元醇和二异氰酸酯总质量的0.5～1％。
4.根据权利要求1所述的环三磷腈型光固化聚氨酯树脂，其特征在于所述的无水溶剂为N,N-二甲基甲酰胺、丙酮、无水丁酮、四氢呋喃、乙酸乙酯中的一种或多种；所述无水溶剂的用量为使反应体系中反应物的浓度为20～30wt％。
5.一种权利要求1～4任一项所述环三磷腈型光固化聚氨酯树脂的应用，其特征在于该光固化聚氨酯树脂可用于自修复技术领域。
6.一种含有权利要求1～4任一项所述环三磷腈型光固化聚氨酯树脂的自修复涂层，其特征在于该涂层所含原料及各原料的质量百分数为：
将各原料按上述比例混合，避光超声30～60min后，旋涂于铝板上，厚度为0.1～1mm，在40～100℃条件下，预烘60～120min，然后在500-800mJ/cm2的能量下进行曝光固化，制得环三磷腈型光固化聚氨酯自修复涂层。
7.根据权利要求6所述的自修复涂层，其特征在于所述活性稀释剂为三羟甲基丙烷三丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯中的一种或多种；所述光引发剂为2-羟基-2-甲基-1-苯基-1-丙酮、1-羟基环已基苯基甲酮、2-羟基-4’-(2-羟乙氧基)-2-甲基苯丙酮、2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮中的一种或多种；所述溶剂为N,N-二甲基甲酰胺、丁酮、二甲基乙酰胺、环己酮、乙酸乙酯中的一种或多种。
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