CN105754461A - 一种水性预混乳液及其抗污涂料 - Google Patents

一种水性预混乳液及其抗污涂料 Download PDF

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CN105754461A
CN105754461A CN201610154613.XA CN201610154613A CN105754461A CN 105754461 A CN105754461 A CN 105754461A CN 201610154613 A CN201610154613 A CN 201610154613A CN 105754461 A CN105754461 A CN 105754461A
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CN105754461B (zh
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张武
许钧强
康伦国
姚东生
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Shandong Pompeii New Material Co.,Ltd.
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Shaoguan Union Chemical Co Ltd
Union Foshan Chemical Co Ltd
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Abstract

本发明涉及一种水性预混乳液及其抗污涂料，其成分由聚氨酯改性丙烯酸树脂、氟改性水性醇酸树脂、水性硅氧烷树脂、正丁醇、聚氨酯增稠流平剂、分散剂、消泡剂和润湿剂组成；其中，所述的氟改性水性醇酸树脂由植物油或脂肪酸、有机酸酐、多元醇、环氧树脂、含氟单体、丙烯类单体和去离子水通过反应制得；所述的聚氨酯改性丙烯酸树脂，由二异氰酸酯单体、聚乙二醇或聚醚二醇、二羟甲基丙酸、丙烯酸类单体和多元醇通过反应制得；本发明制得的一种抗污涂料，特点是硬度高，防水性能好、交联密度高、耐温耐化学性能好，无污染，当被污染物污染或被溶液类物质污染时，能有效达到防水，防污的优良效果。

Description

一种水性预混乳液及其抗污涂料
技术领域
本发明涉及一种水性预混乳液的制备，及其用于水泥混凝土、金属、木材等各种表面的一种抗污涂料，属于合成树脂乳液和水性涂料技术领域。
背景技术
以往涂料对基材保护层的要求，往往只要求外观美观、光泽鲜艳，而对涂层的抗污性能却没有严格的要求。随着工业的发展，社会环境日趋恶劣，我们日常生活中充斥着各种污染源，如空气中的尘埃、汽车排放尾气中的颗粒物、工业酸雨等，这些常常对基材表面造成污染且不易清洗，同时损害涂层的外观及其保护性能。
在实际应用中，现有的防水抗污涂料对环境和人体有较大的危害，其涂料的VOC排放量较大，这对施工人员的身体健康与自然环境都造成危害，特别是在石油资源日益紧张的情况下，不可避免地导致此类防水涂料和防污涂料的成本不断攀升，因此开发出性能突出，且对环境友好型的抗污涂料刻不容缓。
涂料是多组分物质，通常包含溶剂、树脂、颜料和添加剂。传统的涂料中只含有一种树脂，其结构性能受到了一定的限制，可能会造成本身结构形态不佳、表面硬度太低，交联密度不大，从而导致涂层对于外界污染源的抗污性能不强等问题。因此，涂料界中亟需寻求具有良好抗污性能且对环境友好的涂料，以满足社会的需求，水性预混乳液能有效解决单一树脂所遇到的问题，由于都是水性乳液，其VOC排放量几乎为零，对环境无污染。同时水性预混乳液能有效发挥出每种树脂的特性，扬长避短，有效解决抗污性能。
发明内容
本发明的目的旨在提供一种性能全面的水性预混树脂乳液及其一种性能突出、环境友好的抗污涂料。
为解决所述的上述问题，本发明采用水性树脂的预混再进行抗污涂料的制备，利用树脂侧链的氟段和硅段能有效降低涂层的表面张力，同时提高涂层的抗污性；利用聚氨酯丙烯酸树脂的高硬度，可以增强涂料的硬度，并能形成致密的保护膜，防止液体类物质渗入涂层破坏涂层的结构，使涂层具有良好的耐化学性，力学性能及耐久性。
为了解决上面所述的技术问题，本发明采取以下技术方案：本发明涉及一种抗污涂料，按重量百分比计,其组成为：聚氨酯改性丙烯酸树脂10～35份、氟改性水性醇酸树脂25～60份、水性硅氧烷树脂12～30份、正丁醇4～10份、聚氨酯增稠流平剂0.5～1.5份、分散剂0.5～1份、消泡剂0.5～1份、润湿剂0.2～0.6份。
本发明所述的氟改性水性醇酸树脂，由植物油或脂肪酸、有机酸酐、多元醇、环氧树脂、含氟单体、丙烯类单体和去离子水组成；其制备工艺是先在较高温度下醇解，然后进行酯化，再加入烯类单体进行聚合，中和，然后加水分散。
所述的氟改性水性醇酸树脂，其特征在于：按重量百分比计，其组成为：植物油脂肪酸8.0～15.0份、甘油2.0～5.0份、石油酐1.5～4.0份、苯酐1.5～4.0份、三羟甲基丙烷1.0～5.0份、二甲苯2.0～10.0份、苯甲酸2.0～5.0份、环氧树脂6.0～12.0份、氟烯类单体6.0～15.0份、丙烯类单体3.0～15.0份、碱2.0～6.0份、去离子水40.0～60.0份。
所述的的丙烯类单体为丙烯酸甲酯、2-甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸羟丙酯、丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基乙酯、丙烯酸叔丁酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸异辛酯、甲基丙烯酸环己酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、丙烯酸、甲基丙烯酸、2-丙基庚基丙烯酸酯、甲基丙烯酸月桂醇酯、丙烯酸月桂酯、甲基丙烯酸十八酯、丙烯酸十八酯、甲基丙烯酸缩水甘油酯、环三羟甲基丙烷甲缩醛丙烯酸酯、丙烯酸四氢糠醇酯、甲基丙烯酸四氢糠醇酯或其混合物的一种或几种的组合。
所述的氟烯类单体为丙烯酸六氟丁酯、甲基丙烯酸六氟丁酯、丙烯酸六氟异丙酯、甲基丙烯酸六氟异丙酯、丙烯酸八氟戊酯、甲基丙烯酸八氟戊酯、全氟己基乙基丙烯酸酯、全氟己基乙基甲基丙烯酸酯、全氟辛基乙基丙烯酸酯、全氟辛基乙基甲基丙烯酸酯、全氟烷基乙基丙烯酸酯、全氟烷基乙基甲基丙烯酸酯或其混合物的一种或几种的组合。
所述的植物油脂肪酸为精制亚麻油、大豆油、蓖麻油、妥尔油、椰子油、菜籽油的一种或几种的组合；所述的环氧树脂为双酚A型环氧树脂。
本发明所述的聚氨酯改性丙烯酸树脂，按重量百分比计，由以下成分组成：甲苯二异氰酸酯(TDI)或异佛尔酮二异氰酸酯(IPDI)12～30份、聚乙二醇或聚醚二醇6～18份、二羟甲基丙酸6～15份、丙烯酸类单体4～25份、一缩二乙二醇0.4～3.0份、三羟甲基丙烷0.5～3.0份、三乙胺1.0～3.0份、去离子水45～65份；所述的丙烯酸类单体为N-羟甲基丙烯酰胺、丙烯酸羟丙酯、丙烯酸羟乙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丁酯的一种或几种的组合。
本发明制得的一种抗污涂料，特点是硬度高，防水性能好、交联密度高、耐温耐化学性能好，无污染，当被污染物污染或被溶液类物质污染时，能有效达到防水，防污的优良效果。
具体实施方式
本发明结合以下实例对抗污涂料的制备做进一步的描述。
实施例1
一种氟改性水性醇酸树脂，其制备工艺如下：
a、在装有温度计、冷凝管、分水器、搅拌器的四口反应器中，按配方的重量百分比依次加入精制亚麻油10份、甘油2份、石油酐2份、苯酐3份、三羟甲基丙烷2份、二甲苯3份、苯甲酸2.5份、环氧树脂6份，加热升温至一定温度使物料溶解，继续搅拌和升温，直到出现回流，继续保温反应一段时间；
b、取样检测反应物的酸值，直到与理论值接近为止；降温，加入全氟己基乙基丙烯酸酯10份、丙烯酸羟丙酯5份、甲基丙烯酸3份，控制一定温度下进行聚合反应；
c、聚合反应完毕，开真空抽出回流的溶剂二甲苯，降低温度加碱2.5份进行中和，加入49份去离子水搅拌分散，制得一种氟改性水性醇酸树脂A。
实施例2
一种氟改性水性醇酸树脂，其制备工艺如下：
a、在装有温度计、冷凝管、分水器、搅拌器的四口反应器中，按配方的重量百分比依次加入精制蓖麻油11份、甘油2.5份、石油酐2.5份、苯酐3.5份、苯甲酸3.2份、三羟甲基丙烷1.5份、苯甲酸2.8份、二甲苯3.0份、环氧树脂6.0份，加热升温至一定温度使物料溶解，继续搅拌和升温，直到出现回流，继续保温反应一段时间；
b、取样检测反应物的酸值，直到与理论值接近为止；降温，加入丙烯酸八氟戊酯7.6份、甲基丙烯酸异丁酯1.4份、甲基丙烯酸3.2份、丙烯酸叔丁酯2.6份，控制一定温度下进行聚合反应；
c、聚合反应完毕，开真空抽出回流的溶剂二甲苯，降低温度加碱2.2份进行中和，加入47份去离子水搅拌分散，制得一种氟改性水性醇酸树脂B。
实施例3
一种聚氨酯改性丙烯酸树脂，其制备工艺如下：在反应容器中加入聚醚二醇10份，加热真空脱水，N2保护下加入甲苯二异氰酸酯22份、二羟甲基丙酸7份、N-羟甲基丙烯酰胺6.5份、一缩二乙二醇0.5份、三羟甲基丙烷0.5份，在75～90℃下保温反应3～4h，降温冷却后加入少许的对苯二酚，然后加入三乙胺1.8份中和，然后加入去离子水51.7份搅拌分散，制备一种聚氨酯改性丙烯酸酯树脂C。
实施例4
一种聚氨酯改性丙烯酸酯树脂的制备，其制备工艺如下：在反应容器中加入聚醚二醇12.5份，加热真空脱水，N2保护下加入异佛尔酮二异氰酸酯20份、二羟甲基丙酸6.0份、N-羟甲基丙烯酰胺5份、一缩二乙二醇0.5份、三羟甲基丙烷0.5份，在75～90℃下保温反应3～4h，降温冷却后加入少许的对苯二酚，然后加入三乙胺1.5份中和，然后加入去离子水54份搅拌分散，制备一种聚氨酯改性丙烯酸酯树脂D。
实施例5
一种预混乳液E，重量百分比组成：69.7份氟改性水性醇酸树脂A、30份聚氨酯改性丙烯酸酯树脂C，0.3份乳化剂。
实施例6
一种预混乳液F，重量百分比组成：44份聚氨酯改性丙烯酸酯C、55.6份氟改性水性醇酸树脂A，0.4份乳化剂。
实施例7
一种预混乳液G，重量百分比组成：35份聚氨酯改性丙烯酸酯D、64.5份氟改性水性醇酸树脂B，0.5份乳化剂。
在上述实施例5、6、7制备的预混乳液中，不仅只限于两种树脂，还可以是三种或者三种以上树脂的预混，其预混乳液的树脂中，可以只是简单的物体混合，也可以是复杂的化学混合。
实施例8
一种环境友好型抗污涂料，按重量百分比，其组成为：预混乳液E73份、水性硅氧烷树脂16份、正丁醇8份、聚氨酯增稠流平剂1.2份、分散剂0.6份、消泡剂0.8份、润湿剂0.4份。
实施例9
一种抗污涂料，按重量百分比，其组成为：预混乳液F70份、水性硅氧烷树脂20份、正丁醇7.2份、聚氨酯增稠流平剂0.8份、分散剂0.8份、消泡剂0.7份、润湿剂0.5份。
实施例10
一种抗污涂料，按重量百分比，其组成为：预混乳液G70份、水性硅氧烷树脂20份、正丁醇8份、聚氨酯增稠流平剂0.4份、分散剂0.5份、消泡剂0.6份、润湿剂0.5份。
尽管本发明已作了详细说明并引证了实施例，但对于本领域的普通技术人员，显然可以按照上述说明而做出的各种方案、修改和改动，都应该包括在权利要求的范围之内。

Claims (5)

1.一种抗污涂料，其特征在于：按重量百分比计，其组成为：聚氨酯改性丙烯酸树脂10～35份、氟改性水性醇酸树脂25～60份、水性硅氧烷树脂12～30份、正丁醇4～10份、聚氨酯增稠流平剂0.5～1.5份、分散剂0.5～1份、消泡剂0.5～1份、润湿剂0.2～0.6份；
其中，所述的氟改性水性醇酸树脂，由植物油或脂肪酸、有机酸酐、多元醇、环氧树脂、含氟单体、丙烯类单体和去离子水组成；其制备工艺是先在较高温度下醇解，然后进行酯化，再加入烯类单体进行聚合，中和，然后加水分散；
所述的聚氨酯改性丙烯酸树脂，按重量百分比计，由以下成分组成：甲苯二异氰酸酯(TDI)或异佛尔酮二异氰酸酯(IPDI)12～30份、聚乙二醇或聚醚二醇6.0～18份、二羟甲基丙酸6.0～15份、丙烯酸类单体4.0～25份、一缩二乙二醇0.4～3.0份、三羟甲基丙烷0.5～3.0份、三乙胺1.0～3.0份、去离子水45～65份；所述的丙烯酸类单体为N-羟甲基丙烯酰胺、丙烯酸羟丙酯、丙烯酸羟乙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丁酯的一种或几种的组合。
2.一种如权利要求1所述的氟改性水性醇酸树脂，其特征在于：按重量百分比计，其组成为：植物油脂肪酸8.0～15.0份、甘油2.0～5.0份、石油酐1.5～4.0份、苯酐1.5～4.0份、三羟甲基丙烷1.0～5.0份、二甲苯2.0～10.0份、苯甲酸2.0～5.0份、环氧树脂6.0～12.0份、氟烯类单体6.0～15.0份、丙烯类单体3.0～15.0份、碱2.0～6.0份、去离子水40.0～60.0份。
3.如权利要求2所述的一种氟改性水性醇酸树脂，其特征在于：所述的丙烯类单体为丙烯酸甲酯、2-甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸羟丙酯、丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基乙酯、丙烯酸叔丁酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸异辛酯、甲基丙烯酸环己酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、丙烯酸、甲基丙烯酸、2-丙基庚基丙烯酸酯、甲基丙烯酸月桂醇酯、丙烯酸月桂酯、甲基丙烯酸十八酯、丙烯酸十八酯、甲基丙烯酸缩水甘油酯、环三羟甲基丙烷甲缩醛丙烯酸酯、丙烯酸四氢糠醇酯、甲基丙烯酸四氢糠醇酯或其混合物的一种或几种的组合。
4.如权利要求2所述的一种氟改性水性醇酸树脂，其特征在于：所述的氟烯类单体为丙烯酸六氟丁酯、甲基丙烯酸六氟丁酯、丙烯酸六氟异丙酯、甲基丙烯酸六氟异丙酯、丙烯酸八氟戊酯、甲基丙烯酸八氟戊酯、全氟己基乙基丙烯酸酯、全氟己基乙基甲基丙烯酸酯、全氟辛基乙基丙烯酸酯、全氟辛基乙基甲基丙烯酸酯、全氟烷基乙基丙烯酸酯、全氟烷基乙基甲基丙烯酸酯或其混合物的一种或几种的组合。
5.如权利要求2所述的一种氟改性水性醇酸树脂，其特征在于：所述的植物油脂肪酸为精制亚麻油、大豆油、蓖麻油、妥尔油、椰子油、菜籽油的一种或几种的组合；所述的环氧树脂为双酚A型环氧树脂。
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