CN107488244B - 一种poss改性苯丙乳液共聚物、制备方法及应用 - Google Patents
一种poss改性苯丙乳液共聚物、制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种POSS改性苯丙乳液共聚物、制备方法及应用,所述共聚物,按重量计,包括以下组分:40~60份去离子水,15~20份苯乙烯,15~20份丙烯酸丁酯,3~5份乳化剂,2~7份POSS,1~2份水溶性引发剂,0.1~0.3份pH值调节剂,3~5份其他助剂。本发明得到的POSS改性的苯丙乳液做外外墙涂料,具有表面张力低,抗污性强,自洁性强的优点。共聚物中POSS可以和墙体形成Si‑O‑Si键,提高苯丙乳液做外外墙涂料的附着力。
Description
技术领域
本发明涉及一种建筑材料外墙涂料及其制备方法,尤其涉及的是一种POSS改性苯丙乳液共聚物、制备方法及应用。
背景技术
苯丙乳液主要是有苯乙烯和丙酸酯进行乳液聚合得到的乳液,具有成本低和吸水率低的性能,由于丙烯酸酯类的引入改善了其冲击性能,提高了共聚物的韧性。同时使其具有很好的粘结力,耐化学药品性,光泽度高,一定的抗污能力,广泛应用于建筑外墙涂料等领域。作为外墙涂料使用,随着环境污染的加重,空气中的颗粒物的增加,颗粒物在建筑物外墙涂料的粘附,使建筑物的表面变得不美观,需要对建筑物的表面进行清理,现代建筑多为高层建筑,这给清理工作带来很多麻烦。因此需要具有自洁性能高、抗污能力强的建筑物外墙涂料,苯丙乳液外墙涂料由于其特殊的性价比在外墙涂料中广泛采用,但苯丙乳液抗污能力在环境污染加重的情况下需要进一步提高其抗污能力和自洁能力。
目前对苯丙乳液外墙涂料抗污和自洁能力的提高,国内外很多专家学者都在做深入研究。主要是降低苯丙乳液外墙涂料的表面张力,降低粉尘的吸附能力。有机硅改性苯丙乳液是一种重要的方法,例如:改性苯丙乳液的合成与表征及涂料研究,硕士论文,江苏科技大学,2009.12,通过在苯丙乳液聚合过程中加入含双键的有机硅功能单体参与聚合,在提高苯丙乳液耐水性的同时降低苯丙乳液的表面张力,提高涂料的抗污性。中国发明专利201410605314.4,通过在苯丙乳液聚合过程中加入含有机硅功能单体,提高苯丙乳液结合力的同时降低苯丙乳液的表面张力,提高涂料的抗污性。多面体低聚倍半硅氧烷(POSS)是一类具有纳米分子尺寸和有机-无机杂化结构的化合物。这种以无机Si-O-Si键组成的框架为核,***被有机取代基所包围的特殊结构,具有独特的物理性质。由于POSS具有独特的纳米级尺寸可以赋予涂料表面一定的纳米级粗糙度,且随着POSS含量的增加,粗糙度变大,接触角显著增加。含有疏水基团的POSS单体的能降低涂料表面张力,有助于提高涂料的疏水性,提高抗污性。中国发明专利:201510547051.0,公开了含POSS嵌段丙烯酸酯共聚物超疏水涂层及其制备方法,该专利采用溶液聚合方法,存在溶剂对环境的污染,在目前对环境的苛刻要求条件下,该方法不适于大规模生产。中国发明专利:200910107167.7,采用含氟的POSS与丙烯酸酯共聚物得到的涂料的具有低表面能,高防污能力。乙烯基POSS-丙烯酸酯共聚乳液性能研究,涂料工业,2007,37(2):10-13,成功合成了八乙烯基POSS与丙烯酸酯制备共聚乳液,因此采用乳液聚合方法,POSS改性苯丙乳液是完全可行的。
发明内容
本发明的目的在于克服现有技术的不足,提供了一种POSS改性苯丙乳液共聚物、制备方法及应用,采用乳液聚合的方法将含一个乙烯基的POSS与苯乙烯、丙烯酸酯等进行共聚,得到含POSS的苯丙乳液。
本发明是通过以下技术方案实现的:一种POSS改性苯丙乳液共聚物,所述共聚物的结构如下:
其中,R2为甲基、乙基、丙基、丁基、苯基、异丁基中的任一种。
所述共聚物中的POSS含一个乙烯基的多面体低聚倍半硅氧烷,其结构式如下:
其中,R1为乙烯基、烯丙基、甲基丙烯酰氧基丙基、甲基丙烯酸酯基中的任一种。
一种POSS改性苯丙乳液共聚物,包括以下组分:40~60份去离子水,15~20份苯乙烯,15~20份丙烯酸丁酯,3~5份乳化剂,2~7份POSS,1~2份水溶性引发剂,0.1~0.3份pH值调节剂,3~5份其他助剂。所述乳化剂选自十二烷基硫酸钠盐、十二烷基磺酸钠盐、OP-10、司盘系列、烷基糖苷、烷基酚聚氧乙烯醚系列、脂肪醇聚氧乙烯醚、失水山梨醇脂肪酸酯聚氧乙烯醚、失水山梨醇脂肪酸酯、椰子油二乙醇酰胺、渗透剂系列、十二烷基苯磺酸、脂肪醇聚氧乙烯醚AES、油酸、三乙醇胺、椰油酰胺丙基甜菜碱CAB-35、聚醚系列、聚乙二醇系列、乳化剂酯醚系列中的一种或多种。
作为本发明的优选方式之一,所述其他助剂为流平剂、滑爽剂中的至少一种。
作为本发明的优选方式之一,所述水溶性引发剂为过硫酸铵或过硫酸钾。
一种POSS改性苯丙乳液共聚物在外墙涂料中的应用。
一种POSS改性苯丙乳液共聚物的制备方法,包括以下步骤:
(1)在低速的条件下,将20~30份水,7.5-~10份苯乙烯,7.5~10份丙烯酸丁酯,1.5~3份乳化剂混合均匀,升温至70~80℃,搅拌25~40分钟;
(2)将1~2份水溶性引发剂加十倍水混合均匀;
(3)准备2~7份POSS;
(4)将20~30份水,7.5~10份苯乙烯,7.5~10份丙烯酸丁酯,1.5~3份乳化剂混合均匀;
(5)将步骤(2)和步骤(4)的混合物同时滴加到步骤(1)的混合物中,在2.5小时内滴加完,保持反应温度83~87℃;(6)将步骤(3)的POSS在步骤(5)反应1小时后加入一半,滴加时长为10~30分钟,剩余一半在反应2小时后加入,加入时长为10~30分钟;
(7)滴加结束后,在75~80℃下继续反应1小时,降温至40~45℃时加入pH值调节剂,调节pH值至7~8,降至常温出料。
作为本发明的优选方式之一,所述步骤(1)中,低速搅拌为60~80转/分钟。
由于POSS具有独特的纳米级尺寸可以赋予涂料表面一定的纳米级粗糙度,且随着POSS含量的增加,粗糙度变大,接触角显著增加,同时含有疏水基团的POSS单体的能降低涂料表面张力,有助于提高涂料的疏水性,提高涂料抗污性和自洁性。本发明采用含一个乙烯基的POSS与苯乙烯、丙烯酸酯单体采用乳液聚合的方法进行共聚,得到含POSS的苯丙乳液,以该乳液为基础制备的含POSS的苯丙乳液外墙涂料。
本发明相比现有技术具有以下优点:本发明的聚合方法符合环保要求,本发明采用乳液聚合方法,用水作为分散介质,不对环境造成污染。聚合方法简单,生产条件温和,生产效率高,适合大规模生产。POSS对苯丙乳液的改性,目前国内外还没有报道,得到的POSS改性的苯丙乳液做外外墙涂料,具有表面张力低,抗污性强,自洁性强的优点。共聚物中POSS可以和墙体形成Si-O-Si键,提高苯丙乳液做外外墙涂料的附着力。
附图说明
图1是实施例2制备的乳液进行氢质谱检测示意图。
具体实施方式
下面对本发明的实施例作详细说明,本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
实施例1
制备空白样:
(1)在低速(60~80转/分钟)的条件下,将25份水,10份苯乙烯,10份丙烯酸丁酯,1.5-3份乳化剂混合均匀,升温至75℃,搅拌30分钟;
(2)将1~2份水溶性引发剂加十倍水混合均匀;
(3)将25份水,10份苯乙烯,10份丙烯酸丁酯,1.5~3份乳化剂(OP-10)混合均匀;
(4)将步骤(2)和步骤(3)的混合物同时滴加到步骤(1)的产物中,控制在2.5小时滴加完,保持反应温度85℃;
(5)滴加结束后,在80℃下继续反应1小时,降温至45℃时加入pH值调节剂,调节pH值至7~8,降温出料。
(6)取以上制备的乳液30份,加入成膜助剂0.5份,颜料(如钛白粉)3g,搅拌均匀,80目过滤,将滤液均匀涂在玻璃板上,待测试。
实施例2
(1)在低速的条件下,将25份水,10份苯乙烯,10份丙烯酸丁酯,1.5~3份乳化剂混合均匀,升温至75℃,搅拌30分钟;
(2)将1~2份水溶性引发剂加十倍水混合均匀;
(3)准备1份POSS(一乙烯基七甲基POSS);
(4)将25份水,10份苯乙烯,10份丙烯酸丁酯,1.5~3份乳化剂(OP-10)混合均匀;
(5)将步骤(2)和步骤(4)的混合物滴加到步骤(1)中,控制在2.5小时滴加完,保持反应温度85℃;
(6)将步骤(3)的POSS在反应1小时后加入一半,滴加时长为10~30分钟,剩余一半在反应2小时后加入,加入时长为10~30分钟;
(7)滴加结束后,在80℃下继续反应1小时,降温至45℃时加入pH值调节剂,调节pH值至7~8,降温出料;
(8)取以上制备的乳液30份,加入成膜助剂0.5份,颜料(如钛白粉)3g,搅拌均匀,80目过滤,将滤液均匀涂在玻璃板上,待测试。
实施例3
(1)在低速的条件下,将25份水,10份苯乙烯,10份丙烯酸丁酯,1.5~3份乳化剂混合均匀,升温至75℃,搅拌30分钟;
(2)将1~2份水溶性引发剂加十倍水混合均匀;
(3)3份POSS(一乙烯基七甲基POSS);
(4)将25份水,10份苯乙烯,10份丙烯酸丁酯,1.5~3份乳化剂(OP-10)混合均匀;
(5)将步骤(2)和步骤(4)的混合物同时滴加到步骤(1)中,控制在2.5小时滴加完,保持反应温度85℃;
(6)将步骤(3)的POSS在反应1小时后加入一半,滴加时长为10~30分钟,剩余一半在反应2小时后加入,加入时长为10~30分钟;
(7)滴加结束后,在80℃下继续反应1小时,降温至45℃时加入pH值调节剂,调节pH值至7~8,降温出料;
(8)取以上制备的乳液30份,加入成膜助剂0.5份,颜料(如钛白粉)3g,搅拌均匀,80目过滤,将滤液均匀涂在玻璃板上,待测试。
实施例4
(1)在低速的条件下,将25份水,10份苯乙烯,10份丙烯酸丁酯,1.5~3份乳化剂混合均匀,升温至75℃,搅拌30分钟;
(2)将1~2份水溶性引发剂加十倍水混合均匀;
(3)准备5份POSS(一乙烯基七甲基POSS);
(4)将25份水,10份苯乙烯,10份丙烯酸丁酯,1.5~3份乳化剂(OP-10)混合均匀;
(5)将步骤(2)和步骤(4)的混合物同时滴加到步骤(1)中,控制在2.5小时滴加完,保持反应温度85℃;
(6)将步骤(3)的POSS在反应1小时后加入一半,滴加时长为10~30分钟,剩余一半在反应2小时后加入,加入时长为10~30分钟;
(7)滴加结束后,在80℃下继续反应1小时,降温至45℃时加入pH值调节剂,调节pH值至7~8,降温出料;
(8)取以上制备的乳液30份,加入成膜助剂0.5份,颜料(如钛白粉)3g,搅拌均匀,80目过滤,将滤液均匀涂在玻璃板上,待测试。
实施例5
(1)在低速的条件下,将25份水,10份苯乙烯,10份丙烯酸丁酯,1.5~3份乳化剂混合均匀,升温至75℃,搅拌30分钟;
(2)将1~2份水溶性引发剂加十倍水混合均匀;
(3)7份POSS(一乙烯基七甲基POSS);
(4)将25份水,10份苯乙烯,10份丙烯酸丁酯,1.5~3份乳化剂(OP-10)混合均匀;
(5)将步骤(2)和步骤(4)的混合物同时滴加到步骤(1)中,控制在2.5小时滴加完,保持反应温度85℃;
(6)将步骤(3)的POSS在反应1小时后加入一半,滴加时长为10~30分钟,剩余一半在反应2小时后加入,加入时长为10~30分钟;
(7)滴加结束后,在80℃下继续反应1小时,降温至45℃时加入pH值调节剂,调节pH值至7~8,降温出料;
(8)取以上制备的乳液30份,加入成膜助剂0.5份,颜料(如钛白粉)3g,搅拌均匀,80目过滤,将滤液均匀涂在玻璃板上,待测试。
实施例2所得的聚合物经过破乳,水洗,干燥。然后用氘代试剂(DMSO),400兆赫兹核磁做氢质谱,氢质图如图1所示。
对实施例1~5进行附着力、硬度、VOC和接触角测试,结果如表1所示。
由上表可知,在实施例2~5中,分步加入了POSS进行聚合反应,得到的最终产物,能够提高附着力和VOC浓度,一定程度上提高了硬度,极大的增大了接触角,将其用作建筑外墙涂料,共聚物中POSS可以和墙体形成Si-O-Si键,提高乳液的附着力。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (6)
1.一种POSS改性苯丙乳液共聚物,其特征在于,所述共聚物的结构如下:
其中,R2为甲基、乙基、丙基、丁基、苯基、异丁基中的任一种;
所述共聚物中的POSS含一个乙烯基的多面体低聚倍半硅氧烷,其结构式如下:
其中,R1为乙烯基、烯丙基中的任一种;R2为甲基、乙基、丙基、丁基、苯基、异丁基中的任一种;
一种POSS改性苯丙乳液共聚物的制备方法,包括以下步骤:
(1)在60~80转/分钟的低速条件下,将20~30份水,7.5~10份苯乙烯,7.5~10份丙烯酸丁酯,1.5~3份乳化剂混合均匀,升温至70~80℃,搅拌25~40分钟;
(2)将1~2份水溶性引发剂加十倍水混合均匀;
(3)准备2~7份POSS;
(4)将20~30份水,7.5~10份苯乙烯,7.5~10份丙烯酸丁酯,1.5~3份乳化剂混合均匀;
(5)将步骤(2)和步骤(4)的混合物同时滴加到步骤(1)的混合物中,在2.5小时内滴加完,保持反应温度83~87℃;
(6)将步骤(3)的POSS在步骤(5)反应1小时后加入一半,滴加时长为10~30分钟,剩余一半在反应2小时后加入,加入时长为10~30分钟;
(7)滴加结束后,在75~80℃下继续反应1小时,降温至40~45℃时加入pH值调节剂,调节pH值至7~8,降至常温出料。
2.根据权利要求1所述的一种POSS改性苯丙乳液共聚物,其特征在于,所述共聚物,按重量计,原料包括以下组分:40~60份去离子水,15~20份苯乙烯,15~20份丙烯酸丁酯,3~5份乳化剂,2~7份POSS,1~2份水溶性引发剂,0.1~0.3份pH值调节剂,3~5份其他助剂。
3.根据权利要求2所述的一种POSS改性苯丙乳液共聚物,其特征在于,所述乳化剂选自十二烷基硫酸钠盐、十二烷基磺酸钠盐、OP-10、烷基糖苷、烷基酚聚氧乙烯醚系列、脂肪醇聚氧乙烯醚、失水山梨醇脂肪酸酯聚氧乙烯醚、失水山梨醇脂肪酸酯、椰子油二乙醇酰胺、十二烷基苯磺酸、AES、油酸、三乙醇胺、椰油酰胺丙基甜菜碱CAB-35、聚乙二醇系列中的一种或多种。
4.根据权利要求2所述的一种POSS改性苯丙乳液共聚物,其特征在于,所述水溶性引发剂为过硫酸铵或过硫酸钾。
5.根据权利要求2所述的一种POSS改性苯丙乳液共聚物,其特征在于,所述其他助剂为流平剂、滑爽剂中的至少一种。
6.如权利要求1~5任一项所述的一种POSS改性苯丙乳液共聚物在外墙涂料中的应用。
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