CN108219618B - 一种高防流挂型丙烯酸涂料的制备方法 - Google Patents
一种高防流挂型丙烯酸涂料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种高防流挂型丙烯酸涂料的制备方法,涉及涂料技术领域,包括以下步骤:(1)水性丙烯酸乳液合成,(2)辅料制备,(3)丙烯酸涂料制备。本发明通过水性丙烯酸乳液的制备使涂料以水作为稀释剂,避免使用有机溶剂作为稀释剂存在的易挥发污染环境的问题;所制丙烯酸涂料在力学性能满足使用需求的基础上同时具有优异的防流挂性能,能有效避免常规丙烯酸涂料在喷涂后由于重力原因向下产生流动堆积从而出现“流泪”的外观流痕,进而提高漆膜的外观质量。
Description
技术领域:
本发明涉及涂料技术领域,具体涉及一种高防流挂型丙烯酸涂料的制备方法。
背景技术:
在涂料领域中,丙烯酸树脂具有许多优良的性能,并且随着技术的发展,对丙烯酸涂料的使用性能也提出了更高的要求,特别是涂料的触变性能。良好的触变性能使漆膜即使在较厚的情况下,也不会出现流挂现象。
流挂现象,是涂料施工中经常遇到的一种缺陷。当涂料通过喷涂或其他工艺涂覆到垂直放置的表面上时,由于重力的原因,较厚的涂料湿膜或者粘度过稀的涂料湿膜会向下产生流动堆积,并出现“流泪”的外观流痕,严重影响漆膜的外观。
目前,提高涂料触变性的常用方法包括:(1)将触变剂添加到涂料中。触变剂由于性能、副作用等原因,添加量有限,对于涂料流变特性的改变非常有限,从而所制涂料的防流挂性能差。(2)在基体树脂存在的情况下合成流变控制剂,最终混合形成触变树脂。流变控制剂和基体树脂之间是物理混合,在树脂中的分散需要通过物理搅拌来实现,无法得到更为稳定均匀的产物,并且触变性仍旧较差,导致防流挂性能差。
发明内容:
本发明所要解决的技术问题在于提供一种操作简单易行、环保性强且产品使用性能优异的高防流挂型丙烯酸涂料的制备方法。
本发明所要解决的技术问题采用以下的技术方案来实现:
一种高防流挂型丙烯酸涂料的制备方法,包括以下步骤:
(1)水性丙烯酸乳液合成:向引发剂中加入丙酮,搅拌使引发剂完全溶解,再加入链转移剂和混合好的单体,搅拌下加热至回流状态保温反应,反应结束后将所得混合物降温至30-40℃,然后加入三乙胺中和搅拌,待中和完成后加入去离子水搅拌水化,并蒸馏回收丙酮溶剂,即得水性丙烯酸乳液;
(2)辅料制备:将纳米碳酸钙、超细聚四氟乙烯粉末、十二碳醇酯、防流挂剂、聚合硫酸铝、六羟甲基三聚氰胺六甲醚混合,即得辅料;
(3)丙烯酸涂料制备:向水中加入水性丙烯酸乳液和辅料,使所得混合物的质量含水量达到30-40%,搅拌均匀,并转入5-10℃环境中密封静置12h,自然恢复至室温,充分搅拌,即得丙烯酸涂料。
所述引发剂选自偶氮二异丁腈、偶氮二异庚腈中的一种。
所述引发剂用量占单体总质量的4.5-5%。
所述单体由甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸、丙烯酸羟乙酯组成。
所述甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸、丙烯酸羟乙酯的摩尔比为1:1:1:0.5-1。
所述链转移剂选用β-巯基乙醇。
所述链转移剂的用量为每合成1mol丙烯酸酯聚合物需要1mol链转移剂。
所述纳米碳酸钙、超细聚四氟乙烯粉末、十二碳醇酯、防流挂剂、聚合硫酸铝、六羟甲基三聚氰胺六甲醚与单体总质量的比值为10-15:5-10:3-8:3-8:1-5:1-5:50-80。
所述防流挂剂选自氢化蓖麻油、气相二氧化硅中的一种。
所述防流挂剂由如下重量份数的原料制成:氢化蓖麻油20-40份、多聚谷氨酸10-15份、4A分子筛原粉5-10份、无水乙醇100-200份。
所述防流挂剂的制备方法包括如下步骤:
(1)酯化改性:将多聚谷氨酸溶于20-25℃去离子水中制成多聚谷氨酸饱和溶液,并滴加5%稀硫酸调节溶液pH值至4.5-5,再加入氢化蓖麻油,加热至回流状态保温搅拌反应,酯化反应结束后将所得混合物减压浓缩制成膏体,所制膏体经自然冷却至室温后送入冷冻干燥机中,干燥所得固体经超微粉碎机制成微粉,即得改性氢化蓖麻油;
(2)载体助分散:将所制多聚谷氨酸改性氢化蓖麻油加入无水乙醇中,并加热至50-55℃保温搅拌5-10min,再加入4A分子筛原粉,继续加热至回流状态保温搅拌0.5-1h,所得混合物经减压浓缩回收乙醇,浓缩剩余物送入55-60℃烘箱中干燥至恒重,所得固体经超微粉碎机制成微粉,即得防流挂剂。
所述多聚谷氨酸选用水处理级多聚谷氨酸。
通过多聚谷氨酸对氢化蓖麻油的酯化改性,以解决氢化蓖麻油应用于涂料时易形成凝胶的问题,改善氢化蓖麻油在涂料中的分散性;并通过载体的助分散作用来进一步促使氢化蓖麻油均匀分散于涂料中,提高防流挂剂与涂料原料的共混相容性,从而使防流挂剂充分发挥其防流挂性能。
所述4A分子筛原粉经过改性处理,其改性方法为:向4A分子筛原粉中加入三羟甲基丙烷三缩水甘油醚和二茂铁,加热至120-125℃保温搅拌0.5-1h,再加入水解聚马来酸酐,继续在120-125℃下保温搅拌0.5-1h,所得混合物自然冷却至室温,最后经超微粉碎机制成微粉,即得改性4A分子筛。
所述4A分子筛原粉、三羟甲基丙烷三缩水甘油醚、二茂铁、水解聚马来酸酐的质量比为15-25:5-10:0.05-0.5:1-5。
4A分子筛原粉经上述改性处理后,显著增强其与涂料原料的共混相容性,从而促使氢化蓖麻油均匀分散于涂料中,以充分发挥其抗流挂性能。
触变值:是指在室温情况下,转速5rpm下的粘度值与50rpm下的粘度值的比值。
本发明的有益效果是:本发明所述丙烯酸涂料的制备方法具有操作简单易行、环保性强的特点,通过水性丙烯酸乳液的制备使涂料以水作为稀释剂,避免使用有机溶剂作为稀释剂存在的易挥发污染环境的问题;所制丙烯酸涂料在力学性能满足使用需求的基础上同时具有优异的防流挂性能,能有效避免常规丙烯酸涂料在喷涂后由于重力原因向下产生流动堆积从而出现“流泪”的外观流痕,进而提高漆膜的外观质量。
具体实施方式:
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面结合具体实施例,进一步阐述本发明。
实施例1
涂料的制备:
(1)水性丙烯酸乳液合成:向引发剂偶氮二异丁腈中加入丙酮,搅拌使引发剂完全溶解,再加入链转移剂β-巯基乙醇和80kg混合好的单体,搅拌下加热至回流状态保温反应,反应结束后将所得混合物降温至30-40℃,然后加入三乙胺中和搅拌,待中和完成后加入去离子水搅拌水化,并蒸馏回收丙酮溶剂,即得水性丙烯酸乳液;
(2)辅料制备:将15kg纳米碳酸钙、8kg超细聚四氟乙烯粉末、5kg十二碳醇酯、5kg防流挂剂氢化蓖麻油、3kg聚合硫酸铝、2kg六羟甲基三聚氰胺六甲醚混合,即得辅料;
(3)丙烯酸涂料制备:向水中加入水性丙烯酸乳液和辅料,使所得混合物的质量含水量达到30-40%,搅拌均匀,并转入5-10℃环境中密封静置12h,自然恢复至室温,充分搅拌,即得丙烯酸涂料。
其中,引发剂用量占单体总质量的5%,单体由摩尔比为1:1:1:0.7甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸、丙烯酸羟乙酯组成,链转移剂的用量为每合成1mol丙烯酸酯聚合物需要1mol链转移剂。
实施例2
涂料的制备:
(1)水性丙烯酸乳液合成:向引发剂偶氮二异丁腈中加入丙酮,搅拌使引发剂完全溶解,再加入链转移剂β-巯基乙醇和80kg混合好的单体,搅拌下加热至回流状态保温反应,反应结束后将所得混合物降温至30-40℃,然后加入三乙胺中和搅拌,待中和完成后加入去离子水搅拌水化,并蒸馏回收丙酮溶剂,即得水性丙烯酸乳液;
(2)辅料制备:将15kg纳米碳酸钙、8kg超细聚四氟乙烯粉末、5kg十二碳醇酯、5kg防流挂剂气相二氧化硅、3kg聚合硫酸铝、2kg六羟甲基三聚氰胺六甲醚混合,即得辅料;
(3)丙烯酸涂料制备:向水中加入水性丙烯酸乳液和辅料,使所得混合物的质量含水量达到30-40%,搅拌均匀,并转入5-10℃环境中密封静置12h,自然恢复至室温,充分搅拌,即得丙烯酸涂料。
其中,引发剂用量占单体总质量的5%,单体由摩尔比为1:1:1:0.7甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸、丙烯酸羟乙酯组成,链转移剂的用量为每合成1mol丙烯酸酯聚合物需要1mol链转移剂。
实施例3
涂料的制备:
(1)水性丙烯酸乳液合成:向引发剂偶氮二异丁腈中加入丙酮,搅拌使引发剂完全溶解,再加入链转移剂β-巯基乙醇和80kg混合好的单体,搅拌下加热至回流状态保温反应,反应结束后将所得混合物降温至30-40℃,然后加入三乙胺中和搅拌,待中和完成后加入去离子水搅拌水化,并蒸馏回收丙酮溶剂,即得水性丙烯酸乳液;
(2)辅料制备:将15kg纳米碳酸钙、8kg超细聚四氟乙烯粉末、5kg十二碳醇酯、5kg防流挂剂、3kg聚合硫酸铝、2kg六羟甲基三聚氰胺六甲醚混合,即得辅料;
(3)丙烯酸涂料制备:向水中加入水性丙烯酸乳液和辅料,使所得混合物的质量含水量达到30-40%,搅拌均匀,并转入5-10℃环境中密封静置12h,自然恢复至室温,充分搅拌,即得丙烯酸涂料。
其中,引发剂用量占单体总质量的5%,单体由摩尔比为1:1:1:0.7甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸、丙烯酸羟乙酯组成,链转移剂的用量为每合成1mol丙烯酸酯聚合物需要1mol链转移剂。
防流挂剂的制备:
(1)酯化改性:将15g水处理级多聚谷氨酸溶于20-25℃去离子水中制成多聚谷氨酸饱和溶液,并滴加5%稀硫酸调节溶液pH值至4.5-5,再加入40g氢化蓖麻油,加热至回流状态保温搅拌反应,酯化反应结束后将所得混合物减压浓缩制成膏体,所制膏体经自然冷却至室温后送入冷冻干燥机中,干燥所得固体经超微粉碎机制成微粉,即得改性氢化蓖麻油;
(2)载体助分散:将所制多聚谷氨酸改性氢化蓖麻油加入200g无水乙醇中,并加热至50-55℃保温搅拌10min,再加入8g 4A分子筛原粉,继续加热至回流状态保温搅拌1h,所得混合物经减压浓缩回收乙醇,浓缩剩余物送入55-60℃烘箱中干燥至恒重,所得固体经超微粉碎机制成微粉,即得防流挂剂。
实施例4
涂料的制备:
(1)水性丙烯酸乳液合成:向引发剂偶氮二异丁腈中加入丙酮,搅拌使引发剂完全溶解,再加入链转移剂β-巯基乙醇和80kg混合好的单体,搅拌下加热至回流状态保温反应,反应结束后将所得混合物降温至30-40℃,然后加入三乙胺中和搅拌,待中和完成后加入去离子水搅拌水化,并蒸馏回收丙酮溶剂,即得水性丙烯酸乳液;
(2)辅料制备:将15kg纳米碳酸钙、8kg超细聚四氟乙烯粉末、5kg十二碳醇酯、5kg防流挂剂、3kg聚合硫酸铝、2kg六羟甲基三聚氰胺六甲醚混合,即得辅料;
(3)丙烯酸涂料制备:向水中加入水性丙烯酸乳液和辅料,使所得混合物的质量含水量达到30-40%,搅拌均匀,并转入5-10℃环境中密封静置12h,自然恢复至室温,充分搅拌,即得丙烯酸涂料。
其中,引发剂用量占单体总质量的5%,单体由摩尔比为1:1:1:0.7甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸、丙烯酸羟乙酯组成,链转移剂的用量为每合成1mol丙烯酸酯聚合物需要1mol链转移剂。
防流挂剂的制备:
(1)酯化改性:将15g水处理级多聚谷氨酸溶于20-25℃去离子水中制成多聚谷氨酸饱和溶液,并滴加5%稀硫酸调节溶液pH值至4.5-5,再加入40g氢化蓖麻油,加热至回流状态保温搅拌反应,酯化反应结束后将所得混合物减压浓缩制成膏体,所制膏体经自然冷却至室温后送入冷冻干燥机中,干燥所得固体经超微粉碎机制成微粉,即得改性氢化蓖麻油;
(2)载体助分散:将所制多聚谷氨酸改性氢化蓖麻油加入200g无水乙醇中,并加热至50-55℃保温搅拌10min,再加入8g 4A分子筛原粉,继续加热至回流状态保温搅拌1h,所得混合物经减压浓缩回收乙醇,浓缩剩余物送入55-60℃烘箱中干燥至恒重,所得固体经超微粉碎机制成微粉,即得防流挂剂。
4A分子筛原粉的改性:向25g 4A分子筛原粉中加入8g三羟甲基丙烷三缩水甘油醚和0.25g二茂铁,加热至120-125℃保温搅拌1h,再加入3g水解聚马来酸酐,继续在120-125℃下保温搅拌0.5h,所得混合物自然冷却至室温,最后经超微粉碎机制成微粉,即得改性4A分子筛。
对照例1
涂料的制备:
(1)水性丙烯酸乳液合成:向引发剂偶氮二异丁腈中加入丙酮,搅拌使引发剂完全溶解,再加入链转移剂β-巯基乙醇和80kg混合好的单体,搅拌下加热至回流状态保温反应,反应结束后将所得混合物降温至30-40℃,然后加入三乙胺中和搅拌,待中和完成后加入去离子水搅拌水化,并蒸馏回收丙酮溶剂,即得水性丙烯酸乳液;
(2)辅料制备:将15kg纳米碳酸钙、8kg超细聚四氟乙烯粉末、5kg十二碳醇酯、5kg防流挂剂氢化蓖麻油、3kg聚合硫酸铝、2kg六羟甲基三聚氰胺六甲醚混合,即得辅料;
(3)丙烯酸涂料制备:向水中加入水性丙烯酸乳液和辅料,使所得混合物的质量含水量达到30-40%,搅拌均匀,即得丙烯酸涂料。
其中,引发剂用量占单体总质量的5%,单体由摩尔比为1:1:1:0.7甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸、丙烯酸羟乙酯组成,链转移剂的用量为每合成1mol丙烯酸酯聚合物需要1mol链转移剂。
对照例2
涂料的制备:
(1)水性丙烯酸乳液合成:向引发剂偶氮二异丁腈中加入丙酮,搅拌使引发剂完全溶解,再加入链转移剂β-巯基乙醇和80kg混合好的单体,搅拌下加热至回流状态保温反应,反应结束后将所得混合物降温至30-40℃,然后加入三乙胺中和搅拌,待中和完成后加入去离子水搅拌水化,并蒸馏回收丙酮溶剂,即得水性丙烯酸乳液;
(2)辅料制备:将15kg纳米碳酸钙、8kg超细聚四氟乙烯粉末、5kg十二碳醇酯、5kg防流挂剂氢化蓖麻油、3kg聚合硫酸铝混合,即得辅料;
(3)丙烯酸涂料制备:向水中加入水性丙烯酸乳液和辅料,使所得混合物的质量含水量达到30-40%,搅拌均匀,并转入5-10℃环境中密封静置12h,自然恢复至室温,充分搅拌,即得丙烯酸涂料。
其中,引发剂用量占单体总质量的5%,单体由摩尔比为1:1:1:0.7甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸、丙烯酸羟乙酯组成,链转移剂的用量为每合成1mol丙烯酸酯聚合物需要1mol链转移剂。
对照例3
涂料的制备:
(1)水性丙烯酸乳液合成:向引发剂偶氮二异丁腈中加入丙酮,搅拌使引发剂完全溶解,再加入链转移剂β-巯基乙醇和80kg混合好的单体,搅拌下加热至回流状态保温反应,反应结束后将所得混合物降温至30-40℃,然后加入三乙胺中和搅拌,待中和完成后加入去离子水搅拌水化,并蒸馏回收丙酮溶剂,即得水性丙烯酸乳液;
(2)辅料制备:将15kg纳米碳酸钙、8kg超细聚四氟乙烯粉末、5kg十二碳醇酯、3kg聚合硫酸铝、2kg六羟甲基三聚氰胺六甲醚混合,即得辅料;
(3)丙烯酸涂料制备:向水中加入水性丙烯酸乳液和辅料,使所得混合物的质量含水量达到30-40%,搅拌均匀,并转入5-10℃环境中密封静置12h,自然恢复至室温,充分搅拌,即得丙烯酸涂料。
其中,引发剂用量占单体总质量的5%,单体由摩尔比为1:1:1:0.7甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸、丙烯酸羟乙酯组成,链转移剂的用量为每合成1mol丙烯酸酯聚合物需要1mol链转移剂。
实施例5
分别利用实施例1-4、对照例1-3制备丙烯酸涂料,并测试所制丙烯酸涂料的流挂性能,测试结果如表1所示。
测试方法:将一块40mm×15×(0.1-0.3)mm的马口铁样板自上而下用胶带分为5个区域,然后进行喷涂,自上而下分别喷涂1遍、2遍、3遍、4遍和5遍,即膜厚自上而下逐渐变厚。将胶带撕掉,保持竖直状态放置表干,然后入烘箱高温烘烤一定时间取出后观察从哪个区域开始出现轻微流挂现象,并记录下此区域下边缘的膜厚,此数值定义为湿膜的流挂极限膜厚。
表1本发明丙烯酸涂料的流挂性能测试结果
由表1可知,自制防流挂剂具有优于常规防流挂剂氢化蓖麻油和气相二氧化硅的防流挂性能,自制防流挂剂所用助分散载体4A分子筛原粉的改性能进一步提高防流挂性能;未经5-10℃低温冷却处理的涂料防流挂性能下降,未添加六羟甲基三聚氰胺六甲醚的涂料防流挂性能也会下降。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (8)
1.一种高防流挂型丙烯酸涂料的制备方法,其特征在于,包括以下步骤:
(1)水性丙烯酸乳液合成:向引发剂中加入丙酮,搅拌使引发剂完全溶解,再加入链转移剂和混合好的单体,搅拌下加热至回流状态保温反应,反应结束后将所得混合物降温至30-40℃,然后加入三乙胺中和搅拌,待中和完成后加入去离子水搅拌水化,并蒸馏回收丙酮溶剂,即得水性丙烯酸乳液;
(2)辅料制备:将纳米碳酸钙、超细聚四氟乙烯粉末、十二碳醇酯、防流挂剂、聚合硫酸铝、六羟甲基三聚氰胺六甲醚混合,即得辅料;
(3)丙烯酸涂料制备:向水中加入水性丙烯酸乳液和辅料,使所得混合物的质量含水量达到30-40%,搅拌均匀,并转入5-10℃环境中密封静置12h,自然恢复至室温,充分搅拌,即得丙烯酸涂料;
所述防流挂剂由如下重量份数的原料制成:氢化蓖麻油20-40份、多聚谷氨酸10-15份、4A分子筛原粉5-10份、无水乙醇100-200份,其制备方法包括如下步骤:
(1)酯化改性:将多聚谷氨酸溶于20-25℃去离子水中制成多聚谷氨酸饱和溶液,并滴加5%稀硫酸调节溶液pH值至4.5-5,再加入氢化蓖麻油,加热至回流状态保温搅拌反应,酯化反应结束后将所得混合物减压浓缩制成膏体,所制膏体经自然冷却至室温后送入冷冻干燥机中,干燥所得固体经超微粉碎机制成微粉,即得改性氢化蓖麻油;
(2)载体助分散:将所制多聚谷氨酸改性氢化蓖麻油加入无水乙醇中,并加热至50-55℃保温搅拌5-10min,再加入4A分子筛原粉,继续加热至回流状态保温搅拌0.5-1h,所得混合物经减压浓缩回收乙醇,浓缩剩余物送入55-60℃烘箱中干燥至恒重,所得固体经超微粉碎机制成微粉,即得防流挂剂。
2.根据权利要求1所述的高防流挂型丙烯酸涂料的制备方法,其特征在于:所述引发剂选自偶氮二异丁腈、偶氮二异庚腈中的一种。
3.根据权利要求1所述的高防流挂型丙烯酸涂料的制备方法,其特征在于:所述引发剂用量占单体总质量的4.5-5%。
4.根据权利要求1所述的高防流挂型丙烯酸涂料的制备方法,其特征在于:所述单体由甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸、丙烯酸羟乙酯组成。
5.根据权利要求4所述的高防流挂型丙烯酸涂料的制备方法,其特征在于:所述甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸、丙烯酸羟乙酯的摩尔比为1:1:1:0.5-1。
6.根据权利要求1所述的高防流挂型丙烯酸涂料的制备方法,其特征在于:所述链转移剂选用β-巯基乙醇。
7.根据权利要求1所述的高防流挂型丙烯酸涂料的制备方法,其特征在于:所述链转移剂的用量为每合成1mol丙烯酸酯聚合物需要1mol链转移剂。
8.根据权利要求1所述的高防流挂型丙烯酸涂料的制备方法,其特征在于:所述纳米碳酸钙、超细聚四氟乙烯粉末、十二碳醇酯、防流挂剂、聚合硫酸铝、六羟甲基三聚氰胺六甲醚与单体总质量的比值为10-15:5-10:3-8:3-8:1-5:1-5:50-80。
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