CN116948140A - 零voc丙烯酸聚氨酯改性醇酸树脂乳液的制备方法 - Google Patents
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Abstract
本发明公开了一种零VOC丙烯酸聚氨酯改性醇酸树脂乳液的制备方法:(1)将植物油不饱和脂肪酸32‑50份、对苯二甲酸20‑30份、三羟甲基丙烷20‑25份、季戊四醇2‑6份酯化反应制得长油醇酸树脂;(2)将羟乙基丙烯酸酯10‑30份、丙烯酸1‑5份、苯乙烯20‑50份、反应型阴离子乳化剂1‑3份、反应型非离子乳化剂1‑3份、引发剂2‑8份、二甲苯10‑20份合成自乳化羟基丙烯酸树脂;(3)将该两个步骤得到的物料按质量分数(10‑50份):(40‑10份)搅拌后滴加异氰酸酯单体1‑10份合成丙烯酸聚氨酯改性醇酸树脂;(4)将步骤(3)得到的物料抽真空除去有机溶剂,在70℃高速搅拌下加入去离子水,制得零VOC丙烯酸聚氨酯改性醇酸树脂乳液。本发明制得的产品硬度高、表干与实干快、初期耐水好且不含VOC。
Description
技术领域
本发明涉及涂料树脂制备方法技术领域,特别是零VOC丙烯酸聚氨酯改性醇酸树脂乳液的制备方法。
背景技术
醇酸树脂涂料具有氧化自交联、涂层丰满、装饰性好和易施工的特点。然而,传统的溶剂型醇酸树脂涂料在施工状态中约含有60%的有机溶剂,在施工过程中大量的VOC被排放到大气中,直接危害人们的身体健康。因此,水性醇酸涂料由于其安全环保、施工方便、成本低等优势越来越被广大消费者所接受。
醇酸树脂的水性化目前常用的方法有以下几种:一是采用添加非活性乳化剂的外乳化法,这种方法由于加入大量的转相乳化剂,游离的乳化剂使得漆膜耐水性差;二是在醇酸分子结构中引入亲水基团,在助溶剂的帮助下分散于水溶液中,这种方法得到的漆膜耐水性依旧不能很好地满足市场需求;三是利用成盐法制备水性醇酸,将过量的羧基引入醇酸树脂的分子中,并用有机胺中和成盐以获得水溶性的醇酸树脂,此方法存在乳液固含量低、储存稳定性差、漆膜硬度低等缺点;四是丙烯酸改性法,在先行合成的醇酸树脂的基础上,通过滴加丙烯酸单体的方式将水溶性丙烯酸树脂嫁接到醇酸树脂上,用胺中和后在助溶剂的帮助下分散于水中,该方法由于导入了水溶性丙烯酸树脂,分布在外壳的丙烯酸树脂将内部核的醇酸树脂包裹在其中,提高了整体树脂的硬度和耐水解性,但是由于助溶剂的导入,增加了VOC,胺的存在增加了醇酸树脂水解风险,影响了涂料的储存稳定性,而且丙烯酸树脂嫁接到醇酸上损耗了一部分醇酸树脂上不饱和键,影响了树脂后期的氧化交联。
因此,很有必要开发一种硬度高、表干与实干快、耐水性好的不含VOC的改性醇酸树脂乳液。
发明内容
本发明的目的是提供一种硬度高、表干与实干快、初期耐水好且不含VOC的零VOC丙烯酸聚氨酯改性醇酸树脂乳液的制备方法。
为实现上述目的,本发明零VOC丙烯酸聚氨酯改性醇酸树脂乳液的制备方法按如下步骤操作:
(1)长油醇酸树脂的合成:按质量分数的原料配比为:植物油不饱和脂肪酸32-50份、对苯二甲酸20-30份、三羟甲基丙烷20-25份、季戊四醇2-6份;将该配比原料加入带有冷凝器与分水器的四口瓶中,升温至物料融化,搅拌,通入氮气,再升温至230-260℃进行高温酯化反应,直至酸值<5mgKOH/g,制得长油醇酸树脂;
(2)自乳化羟基丙烯酸树脂的合成:按质量分数的物料配比为:羟乙基丙烯酸酯10-30份、丙烯酸1-5份、苯乙烯20-50份、反应型阴离子乳化剂1-3份、反应型非离子乳化剂1-3份、引发剂2-8份、二甲苯10-20份;将二甲苯加入带有冷凝器与分水器的四口瓶中,升温至140℃,再把其余成分搅拌均匀加入滴加釜中,缓慢滴加入四口瓶中,3小时滴完,保温1小时,制得自乳化羟基丙烯酸树脂;
(3)丙烯酸聚氨酯改性醇酸树脂的合成:将步骤(1)得到的长油醇酸树脂和步骤(2)得到的自乳化羟基丙烯酸树脂,按质量分数(10-50份):(40-10份)加入四口瓶中并升温至80℃,搅拌均匀后缓慢滴加异氰酸酯单体1-10份,保温2小时;
(4)丙烯酸聚氨酯改性醇酸树脂乳液的去除VOC处理:将步骤(3)得到的物料移至配有加温及高速搅拌机的抽真空系统的容器中,抽真空以除去物料中的有机溶剂;在70℃,高速搅拌下缓慢加入去离子水,制得质量比浓度50%的零VOC丙烯酸聚氨酯改性醇酸树脂乳液。
所述步骤(1)中植物油不饱和脂肪酸为亚麻油酸、豆油酸、亚油酸、桐油酸中的至少一种。
所述长油醇酸树脂是醇过量长油醇酸树脂,以提供异氰酸酯TDI交联用的足够的羟基,提供常温快速氧化交联的双键。
上述步骤(2)中所述反应型阴离子乳化剂和反应型非离子乳化剂的分子结构为:
式中:反应型阴离子乳化剂X为SO3NH4,反应型非离子乳化剂X为H;
所述自乳化羟基丙烯酸树脂的分子结构为:
上述步骤(3)中所述丙烯酸聚氨酯改性醇酸树脂的反应式和分子结构为:
上述零VOC丙烯酸聚氨酯改性醇酸树脂乳液的制备方法,具有以下技术特点和有益效果:
1、通过异氰酸酯TDI的交联手段,保留了不饱和油中充足的双键,缩短了实干时间;增大了目标树脂的分子量,缩短了表干时间;增加了树脂的交联密度,提高了成膜的硬度。
2、通过交联乳化剂的使用,避免了常规水溶性树脂需要的胺中和,缩短了表干时间。
具体实施方式
下面结合具体实施方式对本发明零VOC丙烯酸聚氨酯改性醇酸树脂乳液的制备方法作进一步详细说明。
实施例1
本发明零VOC丙烯酸聚氨酯改性醇酸树脂乳液的制备方法按如下步骤操作:
(1)醇过量长油醇酸树脂的合成:按质量分数的原料配比为:亚麻油酸49份,对苯二甲酸25份,三羟甲基丙烷22份,季戊四醇4份;将该配比原料加入带有冷凝器与分水器的四口瓶中,升温至物料融化,搅拌,通入氮气,再升温至230-260℃进行高温酯化反应,直至酸值<5mgKOH/g,制得醇过量长油醇酸树脂;
(2)自乳化羟基丙烯酸树脂的合成:按质量分数的物料配比为:羟乙基丙烯酸酯15份,丙烯酸1份,苯乙烯55份,反应型阴离子乳化剂2份,反应型非离子乳化剂2份,过氧化苯甲酸叔丁酯5份,二甲苯20份;将二甲苯加入带有冷凝器与分水器的四口瓶中,升温至140℃,再把其余成分搅拌均匀加入滴加釜中,缓慢滴加入四口瓶中,3小时滴完,保温1小时,制得自乳化羟基丙烯酸树脂;
(3)丙烯酸聚氨酯改性醇酸树脂的合成:将步骤(1)得到的长油醇酸树脂和步骤(2)得到的自乳化羟基丙烯酸树脂,按质量分数47.5份比47.5份的比例加入四口瓶中升温至80℃,搅拌均匀后,缓慢滴加异氰酸酯TDI单体5份,1个小时滴完,保温2个小时;
(4)丙烯酸聚氨酯改性醇酸树脂乳液的去除VOC处理:将步骤(3)得到的物料移至配有加温及高速搅拌机的抽真空系统的容器中,抽真空以除去物料中的有机溶剂;在70℃,高速搅拌下缓慢加入去离子水100份,制得质量比浓度50%的零VOC丙烯酸聚氨酯改性醇酸树脂乳液。
实施例2
(1)醇过量长油醇酸树脂的合成:按质量分数的原料配比为:亚麻油酸49份,对苯二甲酸25份,三羟甲基丙烷22份,季戊四醇4份;
(2)自乳化羟基丙烯酸树脂的合成:按质量分数的物料配比为:羟乙基丙烯酸酯15份,丙烯酸1份,苯乙烯55份,反应型阴离子乳化剂2份,反应型非离子乳化剂2份,过氧化苯甲酸叔丁酯5份,二甲苯20份;
(3)丙烯酸聚氨酯改性醇酸树脂的合成:将步骤(1)得到的长油醇酸树脂和步骤(2)得到的自乳化羟基丙烯酸树脂,按质量分数49份比49份的比例加入四口瓶中升温至80℃,搅拌均匀后,缓慢滴加异氰酸酯TDI单体2份,1个小时滴完,保温2个小时;
其他操作同实施例1。
实施例3
(1)醇过量长油醇酸树脂的合成:按质量分数的原料配比为:亚麻油酸49份,对苯二甲酸25份,三羟甲基丙烷22份,季戊四醇4份;
(2)自乳化羟基丙烯酸树脂的合成:按质量分数的物料配比为:羟乙基丙烯酸酯15份,丙烯酸1份,苯乙烯55份,反应型阴离子乳化剂2份,反应型非离子乳化剂2份,过氧化苯甲酸叔丁酯5份,二甲苯20份;
(3)丙烯酸聚氨酯改性醇酸树脂的合成:将步骤(1)得到的长油醇酸树脂和步骤(2)得到的自乳化羟基丙烯酸树脂,按质量分数49.5份比49.5份的比例加入四口瓶中升温至80℃,搅拌均匀后,缓慢滴加异氰酸酯TDI单体1份,1个小时滴完,保温2个小时;
其他操作同实施例1。
实施例4
(1)醇过量长油醇酸树脂的合成:按质量分数的原料配比为:亚麻油酸49份,对苯二甲酸25份,三羟甲基丙烷22份,季戊四醇4份;
(2)自乳化羟基丙烯酸树脂的合成:按质量分数的物料配比为:羟乙基丙烯酸酯15份,丙烯酸1份,苯乙烯55份,反应型阴离子乳化剂2份,反应型非离子乳化剂2份,过氧化苯甲酸叔丁酯5份,二甲苯20份;
(3)丙烯酸聚氨酯改性醇酸树脂的合成:将步骤(1)得到的长油醇酸树脂和步骤(2)得到的自乳化羟基丙烯酸树脂,按质量分数49份比49份的比例加入四口瓶中升温至80℃,搅拌均匀后,缓慢滴加异氰酸酯TDI单体2份,1个小时滴完,保温2个小时;
其他操作同实施例1。
比较例
该比较例是现有技术,一种水性丙烯酸改性醇酸树脂乳液的制备方法,按如下步骤操作:
(1)醇酸树脂的合成:按质量分数的原料配比为:亚麻油酸49份,对苯二甲酸25份,三羟甲基丙烷22份,季戊四醇4份;将该配比原料加入带有冷凝器与分水器的四口瓶中,升温至物料融化,搅拌,通入氮气,再升温至230-260℃进行高温酯化反应,直至酸值<5mgKOH/g,制得醇酸树脂;
(2)自乳化羟基丙烯酸改性醇酸树脂的合成:按质量分数的物料配比为:丙烯酸5份,苯乙烯70份,过氧化苯甲酸叔丁酯5份;将步骤(1)制得的醇酸树脂80份和20份的乙二醇丁醚加入带有冷凝器与分水器的四口瓶中,升温至140℃,其余成分搅拌均匀加入滴加釜中,缓慢滴加入四口瓶中,3小时滴完,保温1小时,制得自乳化羟基丙烯酸改性醇酸树脂;
(3)丙烯酸改性醇酸乳液的后续处理:将步骤(2)制得的自乳化丙烯酸改性醇酸树脂100份移至配有加温及高速搅拌机的容器中,加入适量的二甲基乙醇胺或者三乙胺中和树脂中自带的羧基;在70℃高速搅拌下缓慢加入适量的去离子水,制得质量比浓度50%的丙烯酸改性醇酸乳液。
以上实施例制得的零VOC丙烯酸聚氨酯改性醇酸树脂乳液产品与现有技术比较例制得的产品综合技术性能指标对比见下表:
从上表可以看出,实施例由于使用了交联型乳化剂和异氰酸酯单体,涂膜的表干时间和实干时间都有明显缩短,硬度增高,同时体系维持在PH值为7的中性范围,这也有利于后续涂料制作时的材料使用。
Claims (3)
1.一种零VOC丙烯酸聚氨酯改性醇酸树脂乳液的制备方法,其特征是:按如下步骤操作:
(1)长油醇酸树脂的合成:按质量分数的原料配比为:植物油不饱和脂肪酸32-50份、对苯二甲酸20-30份、三羟甲基丙烷20-25份、季戊四醇2-6份;将该配比原料加入带有冷凝器与分水器的四口瓶中,升温至物料融化,搅拌,通入氮气,再升温至230-260℃进行高温酯化反应,直至酸值<5mgKOH/g,制得长油醇酸树脂;
(2)自乳化羟基丙烯酸树脂的合成:按质量分数的物料配比为:羟乙基丙烯酸酯10-30份、丙烯酸1-5份、苯乙烯20-50份、反应型阴离子乳化剂1-3份、反应型非离子乳化剂1-3份、引发剂2-8份、二甲苯10-20份;将二甲苯加入带有冷凝器与分水器的四口瓶中,升温至140℃,再把其余成分搅拌均匀加入滴加釜中,缓慢滴加入四口瓶中,3小时滴完,保温1小时,制得自乳化羟基丙烯酸树脂;
(3)丙烯酸聚氨酯改性醇酸树脂的合成:将步骤(1)得到的长油醇酸树脂和步骤(2)得到的自乳化羟基丙烯酸树脂,按质量分数(10-50份):(40-10份)加入四口瓶中并升温至80℃,搅拌均匀后缓慢滴加异氰酸酯单体1-10份,保温2小时;
(4)丙烯酸聚氨酯改性醇酸树脂乳液的去除VOC处理:将步骤(3)得到的物料移至配有加温及高速搅拌机的抽真空系统的容器中,抽真空以除去物料中的有机溶剂;在70℃,高速搅拌下缓慢加入去离子水,制得质量比浓度50%的零VOC丙烯酸聚氨酯改性醇酸树脂乳液。
2.如权利要求1所述零VOC丙烯酸聚氨酯改性醇酸树脂乳液的制备方法,其特征是:所述步骤(1)中植物油不饱和脂肪酸为亚麻油酸、豆油酸、亚油酸、桐油酸中的至少一种。
3.如权利要求1所述零VOC丙烯酸聚氨酯改性醇酸树脂乳液的制备方法,其特征是:所述长油醇酸树脂是醇过量长油醇酸树脂,以提供异氰酸酯TDI交联用的足够的羟基,提供常温快速氧化交联的双键。
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