CN116199844B - 一种含氟丙烯酸树脂及其合成方法和在uv防污涂料中的应用 - Google Patents
一种含氟丙烯酸树脂及其合成方法和在uv防污涂料中的应用 Download PDFInfo
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Abstract
本发明提供了一种新的含氟丙烯酸树脂，同时，提供了其合成方法，具体为采用2‑(全氟辛基)乙醇在催化剂下与二异氰酸酯反应；通过NCO含量的测定达到设定转化率时，进行第二步反应，加入PETA和催化剂，直至NCO的含量为零，反应结束，合成F‑PUA；把合成的含氟丙烯酸树脂加入UV涂料中，具有优良的防污性能。
Description
技术领域
本发明涉及一种丙烯酸树脂，具体涉及含氟丙烯酸树脂，同时，涉及其合成方法及其UV防污涂料中的应用。
背景技术
现在防污涂料已经广泛应用在工业和生活中，比如玻璃的防污，防冰霜，天线的防冻，以及野外电线的防冰雪。还有运用在衣服鞋子上防雨水和污渍。这些防污涂料有着低表面能，可以作为疏水性涂料。这种材料有着疏水疏油的性能，且稳定性能好，化学惰性强。
含氟防污涂料具有低表面能，氟碳长链化合物氟原子和碳原子由于范德华力作用导致碳氟键非常牢固。全氟烷基的分子骨架像锯齿形碳链，由于氟原子的范德华力半径比较大，氟原子刚好可以将碳骨架完全的包裹住。氟碳链会形成一个刚性的聚集体，所以具备高熔点和难溶性。还有氟碳链具有非常低的表面张力。同时氟碳链越长疏水疏油效果越好。
UV涂料具有无VOCs排放，对环境友好型，固化的速度快，施工操作简单，成本低经济效益高，在其中加入适宜的含氟树脂可能得到优异的疏水疏油性能，从而具有耐污作用。所以，选择一种适宜的含氟树脂是亟待解决的一个问题。
发明内容
为了解决以上技术问题，本发明提供了一种含氟丙烯酸树脂，其加入UV涂料中具有优良的耐污性能。
本发明提供的含氟丙烯酸树脂，其结构式如下式所示：
进一步的，其结构式为以下结构中的任意一种：
同时，本发明提供了含氟丙烯酸树脂的合成方法，具体合成方法为：
1)2-(全氟辛基)乙醇在催化剂下与二异氰酸酯反应；
2)通过NCO含量的测定达到设定转化率时，进行第二步反应，加入PETA和催化剂，直至NCO的含量为零，反应结束，合成F-PUA；
具体合成路线为：
进一步的，所述的催化剂为DBTDL。
进一步的，步骤1)的具体反应条件为：在空冷的条件下，在40℃时向2-(全氟辛基)乙醇中滴加二异氰酸酯，滴加十分钟，滴加完后，升高温度至60℃保温1h，升高温度至75℃保温2h，至转化率到达50-55％。
进一步的，40℃向反应体系中流加PETA，流加十分钟，然后升温至80℃反应至NCO完全消失。
同时，本发明还提供了含氟丙烯酸树脂在制备UV防污涂料中的应用。
进一步的，所述UV防污涂料的具体组成为：
本发明提供的含氟丙烯酸树脂，为一新合成的化合物，把制备成的含氟丙烯酸树脂加入到UV涂料中，具有防污的作用。
附图说明
图1为F-PUA在合成过程中NCO的转化率；
图2为F-PUA的红外谱图。
具体实施方式
下面结合实施例对本发明进行进一步的说明。
含氟树脂及其总合成路线如下
合成的化合物路线如下所示，2-(全氟辛基)乙醇在催化剂的条件下与二异氰酸酯反应，通过NCO含量的测定达到设定转化率时，进行第二步反应，加入PETA和催化剂，直至NCO的含量为零，反应结束。合成F-PUA。
实施例1
树脂F-PUA-1的合成
合成的化学物结构如下所示，在250ml的四口烧瓶中，加入88g的2-(全氟辛基)乙醇，0.11g的DBTDL，40℃慢慢滴加38.32g IPDI，通过冰水控制温度在38-42℃以内，滴加完后，慢慢升温到60℃保温1h，再慢慢升温至75℃保温2h，通过NCO的转化率测定反应程度。直至转化率到50-55％，然后进行下一步，加0.11g DBTDL，40℃缓慢流加90g PETA，通过冷水控制温度在58-60℃，10min流完，然后在慢慢升温至80℃保温，通过测定NCO的含量，监测反应程度，直至NCO完全消失，反应结束。得到黄色透明液体。
实施例2
树脂F-PUA-2的合成
合成的化学物结构如下所示，在250ml的四口烧瓶中，加入88g的2-(全氟辛基)乙醇，0.11g的DBTDL，40℃慢慢滴加30.02g TDI，通过冰水控制温度在38-42℃以内，滴加完后，慢慢升温到60℃保温1h，再慢慢升温至75℃保温2h，通过NCO的转化率测定反应程度。直至转化率到50-55％，然后进行下一步，加0.11g DBTDL，40℃缓慢流加90g PETA，通过冷水控制温度在58-60℃，10min流完，然后在慢慢升温至80℃保温，通过测定NCO的含量，监测反应程度，直至NCO完全消失，反应结束。得到白色结晶物。
实施例3
树脂F-PUA-3的合成
合成的化学物结构如下所示，在250ml的四口烧瓶中，加入91.56g的2-(全氟辛基)乙醇，0.11g的DBTDL，40℃慢慢滴加44.08g HMDI，通过冰水控制温度在38-42℃以内，滴加完后，慢慢升温到60℃保温1h，再慢慢升温至75℃保温2h，通过NCO的转化率测定反应程度。直至转化率到50-55％，然后进行下一步，加0.11g DBTDL，40℃缓慢流加65.13g PETA，通过冷水控制温度在58-60℃，10min流完，然后在慢慢升温至80℃保温，通过测定NCO的含量，监测反应程度，直至NCO完全消失，反应结束。得到黄色透明液体。
实施例4
合成树脂的反应过程
F-PUA在合成过程中NCO的转化率随时间变化如图1所示，第一阶段是0-190min，在空冷的条件下，在40℃时向2-(全氟辛基)乙醇中滴加二异氰酸酯，滴加十分钟，这个阶段会有轻微的放热，滴加完后，升高温度至60℃保温1h，以防止反应有放热和温度太高导致副反应太多，这个时候NCO的转化率达到30％左右。由于羟基含量的减少，导致转化率增长速率太慢，升高温度至75℃保温2h，转化率到达50-550％。
第二阶段是190-380min，40℃向反应体系中流加PETA，流加十分钟。放热不明显，然后升温至80℃保温3h。因为第二步封端反应的异氰酸酯中NCO的空间位阻比第一步反应的较大。同时PETA也拥有比较大的空间位阻，需要较高的温度和较长的时间。特别是后期，当NCO转化率到达95％，NCO含量太少，而PETA的空间位阻大，这个时候反应速率明显降低。
结构和表征
合成物的红外谱图如图2所示，其中3330cm-1是N-H特征吸收峰，1530cm-1处是N-H伸缩振动和C-N伸缩振动吸收峰的和频，说明有酰胺键；1720cm-1是羰基(C＝O)的伸缩振动；1200cm-1,1060cm-1处分别是C-O的伸缩振动；2980cm-1、2900cm-1、2890cm-1是烷基-CH3、-CH2的C-H的特征吸收峰，1200cm-1是C-O-C非对称伸缩振动，说明有丙烯酸酯键，1060cm-1是C-F伸缩振动，说明含有氟碳链结构。综上分析FT-IR表明3种F-PUA都合成功。
实施例5
防污涂料的制备
防污涂料的组成，选用了6官的聚氨酯B-619W，具备高感光度快速固化，高硬度不黄变，耐划伤耐钢丝绒性能好，高性价比。DPHA是6官单体具有高速固化，高硬度，高沸点。TMPTA作为三官单体，高沸点，低挥发，低粘度的特性，而且具有良好的相容性，同时提供耐磨和硬度以及光泽。并以本发明制备的产品为改善添加剂，并加入适量的光引发剂1173。各样品具体配方如表1所示。
成膜方式：涂膜厚度15μm；辐照光源：高压汞灯；辐照剂量：300-400mJ/cm2；基材：PC塑料板。分别测试其中的接触角和耐污等性能。
测试方法：采用接触角测试仪测试各样品水接触角(water contact angle：WCA)，并选取各样品指定区域进行耐油性笔擦拭性能测试(ASTM D6578/D6578M-2013)。国标测试各样铅笔硬度(国标GB/T 6739-2006)，附着力测试(国标GB/T 9286-88)。
表1各种样品配方表Table 1Formula table of different sample
防污涂料性能测试
硬度和附着力的测试如下表
表2硬度和附着力的测试Table 2Testing of hardness and adhesion
纯含氟树脂，硬度均为F，附着力均为1，性能一般。不含氟树脂硬度达到2H，附着力为0，性能优异。在不含氟树脂中个添加4％的三种含氟树脂，测试硬度和附着力，均不影响硬度和附着力。
接触角测试
不同的二异氰酸酯有着不同的接触角，异佛尓酮二异氰酸酯合成树脂接触角最大，比甲苯二异氰酸酯合成的树脂高31.79°，比4,4'-二环己基甲烷二异氰酸酯合成的树脂高24.11°。表明IPDI合成的树脂表面张力更小。由于IPDI的不同NCO基团有着不同空间位阻。
表3F-PUAs的接触角测试结果Table 3Water contact angle test of F-PUAs
耐污性能测试
耐污测试结果如表2所示。测试方法，采用脱脂棉擦拭，以油性笔划痕可擦去的次数来，来确定涂料的耐污性能。普通的树脂不具备耐油性笔性能，掺杂4％的F-PUA树脂，耐擦拭性均到达100次以上。表明F-PUA系列均可以明显提高材料耐污性能，并且不同的异氰酸酯，对同一树脂的影响基本一样，这是因为耐污性能主要是氟碳长链基团，在表面形成一层，这样就只需要少量的含氟树脂就可以达到一个较强的耐污性能。
表3耐污性能测试Table 3The result of stain resistance testing
通过把制备成的三种氟树脂，并把他们做为助剂4％的含量添加到普通的涂料中，制备出三种UV防污涂料F-PUA，保持着硬度(2H)、附着力(0)不变，极大的改善耐油性笔耐污性能，F-PUA-1具有较高的水滴角性能，F-PUA-3更加具备耐油性笔擦拭性能。三种UV防污涂料有望在防污、防水材料等领域应用。
本具体实施例仅仅是对本发明的解释，其并不是对本发明的限制，本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改，但只要在本发明的权利要求范围内都受到专利法的保护。
Claims (3)
1.一种含氟丙烯酸树脂的UV防污涂料，其特征在于，所述UV防污涂料的具体组成为：
聚氨酯B-619W 20g
三羟甲基丙烷三丙烯酸酯TMPTA 20g
季戊四醇丙烯酸酯DPHA 60g
F-PUA 4g
光引发剂 1173 4g；
所述的F-PUA为含氟丙烯酸树脂，其结构通式如下式所示：
；
所述的含氟丙烯酸树脂其结构式为以下任意一种：
、
、
。
2.根据权利要求1所述的含氟丙烯酸树脂的UV防污涂料，其特征在于，所述的含氟丙烯酸树脂的合成方法为：
1) 2-(全氟辛基)乙醇在催化剂下与二异氰酸酯反应；
2) 通过NCO含量的测定达到设定转化率时，进行第二步反应，加入PETA和催化剂，直至NCO的含量为零，反应结束，合成F-PUA；
具体合成路线为：
；
步骤1）的具体反应条件为：在空冷的条件下，在40 ℃时向2-(全氟辛基)乙醇中滴加二异氰酸酯，滴加十分钟，滴加完后，升高温度至60℃保温1h，升高温度至75 ℃保温2 h，至转化率到达50-55 %；
步骤2）的具体反应条件为：40 ℃向反应体系中流加PETA，流加十分钟，然后升温至80℃反应至NCO完全消失。
3.根据权利要求2所述的含氟丙烯酸树脂的UV防污涂料，其特征在于，所述的催化剂为DBTDL。
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