CN110003381B - 一种防流挂树脂及其制备方法 - Google Patents
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Abstract
本发明涉及一种防流挂树脂及其制备方法。本发明的防流挂树脂,包括按重量份计的以下组分:丙烯酸酯类单体65‑160份、丙烯酸1‑5份、苯乙烯20‑40份、引发剂1‑10份、含有‑NCO基团的单体5‑20份、溶剂30‑80份。本发明的树脂具有防流挂功能,可一次性厚涂,降低用工成本以及减少挥发性有机物排放,同时具有良好的光泽度和透明度,综合性能优异。本发明的制备工艺路线简单,易于操作,生产所需溶剂少,对环境污染少。
Description
技术领域
本发明涉及一种防流挂树脂及其制备方法。
背景技术
一次性厚涂的树脂主要用于制备高端清漆、色漆,用于木器、家装、五金上面的涂装,市场需求极大。然而目前市场上的树脂,无论固含高或低,都存在着不能一次性厚涂的问题。如果一次性喷涂的树脂过厚,很容易引起流挂、缩边、起暗泡、针孔等漆膜弊病。一般解决的方法是多次喷涂,这样不光增加了人工量,从而变相的增加了成本,还延长了工期,也增加了挥发性有机物的排放。
为了使树脂能一次性厚涂,目前的一种解决办法是向油漆里面添加一些具有防流挂功能的材料,比如膨润土、气相二氧化硅等,这类材料的添加往往会对其光泽度、透明度有严重的影响,不能应用于高光产品。
发明内容
针对现有技术的不足,本发明的目的在于提供一种防流挂树脂及其制备方法。本发明的树脂具有防流挂功能,可一次性厚涂,避免流挂、缩边、起暗泡等弊病、降低用工成本以及减少挥发性有机物排放,同时具有良好的光泽度和透明度。
本发明采用以下技术方案。
一种防流挂树脂,包括按重量份计的以下组分:丙烯酸酯类单体65-160份、丙烯酸1-5份、苯乙烯20-40份、引发剂1-10份、含有-NCO基团的单体5-20份、溶剂30-80份。
本发明中加入的苯乙烯除了为产品提供硬度外,还可以使产品具有良好的光泽。
优选地,所述丙烯酸酯类单体包括以下组分:甲基丙烯酸甲酯10-30份、甲基丙烯酸丁酯10-20份、丙烯酸羟丙酯10-35份、丙烯酸丁酯5-10份、丙烯酸异辛酯25-50份、甲基丙烯酸异冰片酯5-15份。
本发明使用的丙烯酸酯类单体包括甲基丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸羟丙酯、丙烯酸丁酯、丙烯酸异辛酯、甲基丙烯酸异冰片酯;所用的甲基丙烯酸甲酯和甲基丙烯酸异冰片酯可以为产品提供硬度以及更好的溶剂释放性,所用的丙烯酸丁酯和丙烯酸异辛酯为产品提供良好的柔韧性。
优选地,所述引发剂为BPO(过氧化苯甲酰)、TBPB(过氧化苯甲酸叔丁酯)、CHPO(过氧化环己酮)、TBHP(叔丁基过氧化氢)、DCP(过氧化二异丙苯)、过硫酸盐中的一种或多种。
优选地,所述含有-NCO基团的单体为TDI(甲苯二异氰酸酯)、HDI(1,6-六亚甲基二异氰酸酯)、MDI(二苯基甲烷二异氰酸酯)、IPDI(异佛尔酮二异氰酸酯)中的一种或多种。
优选地,所述溶剂为醋酸丁酯、醋酸乙酯、二甲苯中的一种或多种。
本发明的溶剂一方面作为介质,承载反应;另一方面为产品提供溶解作用。
上述的防流挂树脂的制备方法,包括以下步骤:
(1)将丙烯酸酯类单体、丙烯酸、苯乙烯、50%-70%所用量的引发剂混合均匀,形成混合料A;
(2)往混合料A加入50%-70%所用量的溶剂,搅拌均匀;加热至温度125-135℃,回流2-3小时,形成混合料B;
(3)30-40分钟内,往混合料B加入剩余的引发剂、溶剂;在温度125-135℃下,回流2-3小时,形成混合料C;
(4)在低速下,1-1.5小时内,往混合料C加入含有-NCO基团的单体,然后在高速下、温度为60-70℃、搅拌3-4小时,即得到防流挂树脂。
优选地,所述低速为800-1000转/分钟的搅拌速度;所述高速为5000-6000转/分钟的搅拌速度。
本发明的有益效果:
(1)本发明通过不同的种类、重量份配比的丙烯酸酯类单体与丙烯酸、苯乙烯搭配,可以得到理想TG值(玻璃化转变温度)的产品,使得产品具有极佳的干燥速度,有效减少产品流挂;本发明采用了包括醋酸丁酯、醋酸乙酯、二甲苯的溶剂,通过与本发明的其它成分搭配,极大地加快了有机溶剂的排放速度,降低了产品流挂的可能性;本发明通过后期加入含有-NCO基团的单体来扩大分子量,使产品产生触变性,在没有剪切力的情况下不易流动,从而达到优异的性能;
(2)本发明的防流挂树脂性能优异,可一次性厚涂;本发明的防流挂树脂一次性施工即可达到普通油漆四至五次的施工厚度,不但可以降低用户使用成本,还可以降低挥发性有机溶剂的使用量,是一款性能卓越的环保型产品;
(3)本发明的制备工艺路线简单,易于操作,生产所需溶剂少,对环境污染少。
具体实施方式
下面通过实施例详细说明本发明。
实施例1
一种防流挂树脂,包括按重量份计的以下组分:甲基丙烯酸甲酯15份、甲基丙烯酸丁酯10份、丙烯酸羟丙酯30份、丙烯酸丁酯10份、丙烯酸异辛酯25份、甲基丙烯酸异冰片酯5份、丙烯酸1.8份、苯乙烯20份、BPO 10份、TDI 15份、二甲苯40份、醋酸丁酯30份。
上述的防流挂树脂的制备方法,包括以下步骤:
(1)将甲基丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸羟丙酯、丙烯酸丁酯、丙烯酸异辛酯、甲基丙烯酸异冰片酯、丙烯酸、苯乙烯、70%所用量的BPO混合均匀,形成混合料A;
(2)往混合料A加入70%所用量的二甲苯、醋酸丁酯,搅拌均匀;加热至温度125℃,回流3小时,形成混合料B;
(3)30分钟内,往混合料B加入剩余的BPO、二甲苯、醋酸丁酯;在温度125℃下,回流3小时,形成混合料C;
(4)在800转/分钟的搅拌速度下,1小时内,往混合料C加入TDI,然后在5000转/分钟的搅拌速度下、温度为60℃、搅拌4小时,即得到防流挂树脂。
实施例2
一种防流挂树脂,包括按重量份计的以下组分:甲基丙烯酸甲酯10份、甲基丙烯酸丁酯18份、丙烯酸羟丙酯10份、丙烯酸丁酯5份、丙烯酸异辛酯30份、甲基丙烯酸异冰片酯10份、丙烯酸3份、苯乙烯30份、DCP 3份、IPDI 5份、二甲苯10份、醋酸丁酯10份、醋酸乙酯10份。
上述的防流挂树脂的制备方法,包括以下步骤:
(1)将甲基丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸羟丙酯、丙烯酸丁酯、丙烯酸异辛酯、甲基丙烯酸异冰片酯、丙烯酸、苯乙烯、50%所用量的DCP混合均匀,形成混合料A;
(2)往混合料A加入50%所用量的二甲苯、醋酸丁酯、醋酸乙酯,搅拌均匀;加热至温度130℃,回流2小时,形成混合料B;
(3)35分钟内,往混合料B加入剩余的DCP、二甲苯、醋酸丁酯、醋酸乙酯;在温度135℃下,回流2小时,形成混合料C;
(4)在900转/分钟的搅拌速度下,1小时内,往混合料C加入IPDI,然后在6000转/分钟的搅拌速度下、温度为70℃、搅拌3小时,即得到防流挂树脂。
实施例3
一种防流挂树脂,包括按重量份计的以下组分:甲基丙烯酸甲酯30份、甲基丙烯酸丁酯20份、丙烯酸羟丙酯35份、丙烯酸丁酯8份、丙烯酸异辛酯48份、甲基丙烯酸异冰片酯15份、丙烯酸5份、苯乙烯40份、CHPO 10份、HDI 20份、二甲苯20份、醋酸丁酯30份、醋酸乙酯30。
上述的防流挂树脂的制备方法,包括以下步骤:
(1)将甲基丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸羟丙酯、丙烯酸丁酯、丙烯酸异辛酯、甲基丙烯酸异冰片酯、丙烯酸、苯乙烯、65%所用量的CHPO混合均匀,形成混合料A;
(2)往混合料A加入65%所用量的二甲苯、醋酸丁酯、醋酸乙酯,搅拌均匀;加热至温度135℃,回流2小时,形成混合料B;
(3)40分钟内,往混合料B加入剩余的CHPO、二甲苯、醋酸丁酯、醋酸乙酯;在温度130℃下,回流2小时,形成混合料C;
(4)在1000转/分钟的搅拌速度下,1.5小时内,往混合料C加入HDI,然后在6000转/分钟的搅拌速度下、温度为70℃、搅拌3小时,即得到防流挂树脂。
对比例1
一种防流挂树脂,包括按重量份计的以下组分:甲基丙烯酸甲酯50份、甲基丙烯酸丁酯40份、丙烯酸1.8份、苯乙烯20份、BPO 10份、TDI 15份、二甲苯40份、醋酸丁酯30份。
上述的防流挂树脂的制备方法,包括以下步骤:
(1)将甲基丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸、苯乙烯、70%所用量的BPO混合均匀,形成混合料A;
(2)往混合料A加入70%所用量的二甲苯、醋酸丁酯,搅拌均匀;加热至温度125℃,回流3小时,形成混合料B;
(3)30分钟内,往混合料B加入剩余的BPO、二甲苯、醋酸丁酯;在温度125℃下,回流3小时,形成混合料C;
(4)在800转/分钟的搅拌速度下,1小时内,往混合料C加入TDI,然后在5000转/分钟的搅拌速度下、温度为60℃、搅拌4小时,即得到防流挂树脂。
对比例2
一种防流挂树脂,包括按重量份计的以下组分:甲基丙烯酸甲酯15份、甲基丙烯酸丁酯10份、丙烯酸羟丙酯30份、丙烯酸丁酯50份、丙烯酸异辛酯80份、甲基丙烯酸异冰片酯5份、丙烯酸1.8份、苯乙烯20份、BPO 10份、TDI 15份、二甲苯40份、醋酸丁酯30份。
上述的防流挂树脂的制备方法,包括以下步骤:
(1)将甲基丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸羟丙酯、丙烯酸丁酯、丙烯酸异辛酯、甲基丙烯酸异冰片酯、丙烯酸、苯乙烯、70%所用量的BPO混合均匀,形成混合料A;
(2)往混合料A加入70%所用量的二甲苯、醋酸丁酯,搅拌均匀;加热至温度125℃,回流3小时,形成混合料B;
(3)30分钟内,往混合料B加入剩余的BPO、二甲苯、醋酸丁酯;在温度125℃下,回流3小时,形成混合料C;
(4)在800转/分钟的搅拌速度下,1小时内,往混合料C加入TDI,然后在5000转/分钟的搅拌速度下、温度为60℃、搅拌4小时,即得到防流挂树脂。
对比例3
一种高固体份树脂,包括按重量份计的以下组分:甲基丙烯酸甲酯20份、丙烯酸羟丙酯20份、丙烯酸丁酯15份、丙烯酸异辛酯20份、丙烯酸1份、苯乙烯30份、BPO 15份、二甲苯40份、醋酸丁酯30份。
上述的高固体份树脂的制备方法,包括以下步骤:
(1)将甲基丙烯酸甲酯、丙烯酸羟丙酯、丙烯酸丁酯、丙烯酸异辛酯、丙烯酸、苯乙烯、70%所用量的BPO混合均匀,形成混合料A;
(2)往混合料A加入70%所用量的二甲苯、醋酸丁酯,搅拌均匀;加热至温度125℃,回流3小时,形成混合料B;
(3)30分钟内,往混合料B加入剩余的BPO、二甲苯、醋酸丁酯;在温度125℃下,回流3小时,得到高固体份树脂。
实验例1
对上述实施例1-3、对比例1-3的树脂进行性能测试,测试结果如表1所示:
表1实施例1-3、对比例1-3的树脂的性能测试结果
由表1可知,实施例1-3的防流挂树脂具有防流挂功能,可一次性厚涂,综合性能优异。对比例1-2的防流挂树脂的部分组分不在本发明的范围内,与实施例相比,丰满度、透明度、版面效果、一次性施工厚度、耐冲击、曲折、防流挂等性能具有明显差异,综合性能不如实施例的防流挂树脂。对比例4的高固体份树脂综合性能较差,一次性施工厚度较低。对比例1-3的树脂表干时间较长,表明产品干燥速度慢。由对比例的树脂的实验数据可知,本发明的组分及其配比对树脂性能具有重要影响。
Claims (6)
1.一种防流挂树脂,其特征在于,包括按重量份计的以下组分:丙烯酸酯类单体65-160份、丙烯酸1-5份、苯乙烯20-40份、引发剂1-10份、含有-NCO基团的单体5-20份、溶剂30-80份;
所述丙烯酸酯类单体包括以下组分:甲基丙烯酸甲酯10-30份、甲基丙烯酸丁酯10-20份、丙烯酸羟丙酯10-35份、丙烯酸丁酯5-10份、丙烯酸异辛酯25-50份、甲基丙烯酸异冰片酯5-15份。
2.根据权利要求1所述的防流挂树脂,其特征在于,所述引发剂为BPO、TBPB、CHPO、TBHP、DCP、过硫酸盐中的一种或多种。
3.根据权利要求1所述的防流挂树脂,其特征在于,所述含有-NCO基团的单体为TDI、HDI、MDI、IPDI中的一种或多种。
4.根据权利要求1所述的防流挂树脂,其特征在于,所述溶剂为醋酸丁酯、醋酸乙酯、二甲苯中的一种或多种。
5.根据权利要求1-4中任一项所述的防流挂树脂的制备方法,其特征在于,包括以下步骤:
(1)将丙烯酸酯类单体、丙烯酸、苯乙烯、50%-70%所用量的引发剂混合均匀,形成混合料A;
(2)往混合料A加入50%-70%所用量的溶剂,搅拌均匀;加热至温度125-135℃,回流2-3小时,形成混合料B;
(3)30-40分钟内,往混合料B加入剩余的引发剂、溶剂;在温度125-135℃下,回流2-3小时,形成混合料C;
(4)在低速下,1-1.5小时内,往混合料C加入含有-NCO基团的单体,然后在高速下、温度为60-70℃、搅拌3-4小时,即得到防流挂树脂。
6.根据权利要求5所述的防流挂树脂的制备方法,其特征在于,所述低速为800-1000转/分钟的搅拌速度;所述高速为5000-6000转/分钟的搅拌速度。
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