CN107446458A - 一种高耐水性的丙烯酸改性聚氨酯杂化树脂水性涂料 - Google Patents
一种高耐水性的丙烯酸改性聚氨酯杂化树脂水性涂料 Download PDFInfo
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- CN107446458A CN107446458A CN201710659967.4A CN201710659967A CN107446458A CN 107446458 A CN107446458 A CN 107446458A CN 201710659967 A CN201710659967 A CN 201710659967A CN 107446458 A CN107446458 A CN 107446458A
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- water
- modified polyurethane
- acrylic acid
- hybrid resin
- acrylic
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Abstract
本发明涉及一种高耐水性的丙烯酸改性聚氨酯杂化树脂水性涂料，其成分由水性丙烯酸改性聚氨酯杂化树脂、硅溶胶、丙二醇单丁醚、色浆、助剂和去离子水组成；所述的水性丙烯酸改性聚氨酯杂化树脂，由聚氨酯共聚物链段和丙烯酸共聚物链段组成的纳米水分散体，由二异氰酸酯、多元醇、丙烯酸羟乙酯、低聚物多元醇、二羟甲基丙酸、丙烯酸单体、过硫酸铵、中和剂通过反应制得；本发明制得的一种高耐水性丙烯酸改性聚氨酯水性涂料，其交联密度高，具有优异的附着力、耐磨性、机械强度和柔韧性，并赋于其优良的耐水性、耐盐雾性、耐腐蚀性和耐老化性；广泛用于木器家具、汽车、工程机械、钢结构、混凝土、五金、塑胶等制品的涂装和防护。
Description
技术领域
本发明涉及一种改性聚氨酯树脂水性涂料，尤其涉及到一种高耐水性的丙烯酸改性聚氨酯杂化树脂水性涂料，属于水性特种涂料技术领域。
背景技术
涂料在生产和生活中的作用非常大，广泛应用与各个领域，涂料形成的涂膜可对物体起到装饰、保护和标致作用，目前市面上的大部分涂料虽然制作简单、售价便宜但同时功能比较单一，只能简单的作为装饰之用，而在一些特殊的作业环境中，简单的涂料的并不能满足人们的所需。
聚氨酯具有优异的耐腐性、附着力、耐化学药品性、耐候性，在胶粘剂、涂料等领域得到广泛的应用。但是溶剂型的聚氨酯含有大量的溶剂，如甲苯、二甲基酰胺等，都会造成严重的环境污染。近年来随着各国环保法规的确立和环保意识的增强，以溶剂为分散介质的聚氨酯越来越来越受到限制，而目前广泛使用的溶剂型涂料中含有大量的可挥发有机化合物(VOC)，有机化合物(VOC)有毒、易燃，污染大气层，对环境和人体都造成危害。因此，为了减少这些有机溶剂对环境的污染，我国已将水性涂料列入今后工业涂料的发展方向。可是我国目前应用在地板涂料、金属防锈漆和船舶涂料上的水性工业涂料其耐水性、耐化学性、耐磨性和耐候性不理想。
水性聚氨酯(WPU)以水为溶剂，不仅具有溶剂型聚氨酯胶粘剂所具有的耐寒、耐候、弹性好、光泽高、软硬段温度可调等基本特性外，还具有不燃、无毒、无污染等优点，但是，水性聚氨酯采用水作为溶剂，在存储或者运输过程中的稳定性较差，易出现分层现象，粘结性较差。而且，当水性聚氨酯与基材结合后，由于介质水的表面张力太大，聚氨酯在基材表面成膜后的耐水性较差易吸水，成膜牢度较低易与基材相分离，而且喷涂后的产品手感较硬，同时水性聚氨酯还存在固含量低、物理机械性能差、耐水性差等缺点，这影了水性聚氨酯的推广和应用。丙烯酸树脂具有机械强度高、耐老化、抗黄变、耐水性好等优点，但又存在着耐有机溶剂性较差、耐热性差、软化点较低、耐磨性差等缺点。因此聚氨酯和聚丙烯酸酯两者在性能上具有很大的互补性，若将两者复合可以使水性聚氨酯的性能得到明显改善。
中国专利CN 104559505 A公开了一种耐水性涂料，包括如下重量份的组分：甲基丙烯酸-2-羟乙酯75～125份、甲基丙烯酸20～40份、甲基丙烯酸甲酯100～150份、甲基丙烯酸月桂酯80～100份、苯乙烯200～300份、甲基丙烯酸丁酯150～200份；该发明提供一种耐水性涂料，制作简单，采用的生产原料选择无毒性的，涂料的使用效果好，环保，可形成坚韧涂层；但其为纯的丙烯酸树脂涂料，存在耐磨性不佳、耐溶剂较差等缺点。
因此，开发一种环境友好型的高耐水性丙烯酸改性聚氨酯水性涂料，使其具备漆膜硬度高、优异的耐水性、耐磨性、耐盐雾性、耐化品性等功能，满足环境的严要求和涂装水性化。
发明内容
为了克服上述现有技术中存在的不足，提供一种无污染、耐水性、耐磨性和耐候性好的丙烯酸改性聚氨酯水性涂料。
本发明的目的提供一种高耐水性的丙烯酸改性水性聚氨酯杂化树脂水性涂料。
为了解决上面所述的技术问题，本发明采取以下技术方案：本发明涉及一种高耐水性的丙烯酸改性水性聚氨酯杂化树脂水性涂料，按重量百分比计，其组成为：水性丙烯酸改性聚氨酯杂化树脂50.0～80.0％、硅溶胶2.0～6.0％、水性色浆0～10.0％、二丙二醇单丁醚3.0～8.0％、助剂0.6～5.0％、去离子水10.0～25.0％。
其中，所述的水性丙烯酸改性聚氨酯杂化树脂，由聚氨酯共聚物链段和丙烯酸共聚物链段组成纳米水分散体，其分子结构式如下所示：
其中，分子式中的R为二异氰酸酯取代基团；R1、R2为H、-CH3及其它烷基类取代基团；R3、R4为及其他酯基；
所述的聚氨酯共聚物链段为分子结构式中的h链段，由硬段m和软段n组成；所述的丙烯酸共聚物链段为分子结构式中的i链段，由硬段x和软段y组成。
所述的水性丙烯酸改性聚氨酯杂化树脂，其玻璃化温度Tg为35～70℃、分子量为4500～5500、乳液粒径为150～280nm、pH值7.5～8.5。
所述的水性丙烯酸改性聚氨酯杂化树脂，其制备工艺如下：
a)、在装有温度计、冷凝管、搅拌器的四口反应器中，按配方重量百分比，依次加入低聚物多元醇、多元醇、二羟甲基丙酸，升温至95～110℃，真空下脱水1.5～2.0h；
b)、降温至60～70℃，加入二异氰酸酯后通入N2，滴加配方量的二月桂酸二丁基锡，然后升温到80～82℃反应2～2.5h，得所述的亲水性聚氨酯预聚物；
c)、按配方量配制好丙烯酸软、硬混合单体，取其40～50％量的混合单体加入到所述的亲水性聚氨酯预聚物至粘度适中，降温至70℃，加入丙烯酸羟乙酯，继续反应1.5h，检测，当NCO值达到规定的设计值时为止；
d)、将温度降至40℃以下，缓慢滴加中和剂至pH值8.5～9.0，继续搅拌反应10～20min，加入计算量的水，继续搅拌15min，得丙烯酸与聚氨酯的预聚物；
e)、预先配制好5％过硫酸铵水溶液，取其20％量加入上述的预聚物中，升温至80℃，搅拌0.5h；然后滴加剩下的丙烯酸混合单体和过硫酸铵水溶液，控制滴加时间为3～4h；然后升温至85℃，保温反应2h，加水至规定的固含量，降温至40℃，过滤，得所述的水性丙烯酸改性聚氨酯杂化树脂。
所述的水性丙烯酸改性聚氨酯杂化树脂，已申请了发明专利“无溶剂法制备水性丙烯酸改性聚氨酯杂化树脂”，并作了详细描述。
所述的助剂至少包括基材润湿剂、润湿分散剂、杀菌剂、消泡剂、流平剂、增稠剂、pH调节剂、消光剂、手感剂、抗划伤剂、闪锈剂、耐水剂、抗紫外线剂，纳米添加剂的一种或几种的组合。
本发明制得的一种高耐水性丙烯酸改性聚氨酯水性涂料，其交联密度高，具有优异的附着力、耐磨性、机械强度和柔韧性，并赋于其优良的耐水性、耐盐雾性、耐腐蚀性和耐老化性；广泛用于木器家具、汽车、工程机械、钢结构、混凝土、五金、塑胶等制品的涂装和防护。
具体实施方式
本发明结合以下实施例对高耐水性丙烯酸改性聚氨酯水性涂料做进一步的描述。
实施例1
制备水性丙烯酸改性聚氨酯杂化树脂A，其步骤如下：
a)、在装有温度计、冷凝管、搅拌器的四口反应器中，按配方的重量百分比依次加入聚四氢呋喃二元醇6.0份、丁二醇3.0份、三羟甲基丙烷1.5份、二羟甲基丙酸2.6份，升温至95～110℃，真空下脱水1.5～2.0h；
b)、降温至60～70℃，加入六亚甲基二异氰酸酯16.0份，通入N2，滴加二月桂酸二丁基锡0.05份，然后升温至80～82℃反应2～2.5h，得所述的亲水性聚氨酯预聚物；
c)、预先配好甲基丙烯酸甲酯与丙烯酸丁酯混合单体16.0份，取其8份加到所述的亲水性聚氨酯预聚物至粘度适中，降温至70℃，加入丙烯酸羟乙酯1.5份，继续反应1.5h，检测，当NCO值达到规定的设计值时为止；
d)、将温度降至40℃以下，缓慢滴加中和剂1.5份至pH值8.5～9.0，继续搅拌反应10～20min，加入计算量水30.0份，继续搅拌15min，得丙烯酸与聚氨酯的预聚物；
e)、预先配制好5％过硫酸铵水溶液1.5份，取其0.3份加入上述的预聚物中，升温至80℃，搅拌0.5h；然后滴加剩下的8份丙烯酸混合单体和1.2份过硫酸铵水溶液，控制滴加时间为3～4h；然后升温至85℃，保温反应2h，加水20.35份，降温至40℃，过滤，得固含45.6％、pH值7.5～8.0的所述水性丙烯酸改性聚氨酯杂化树脂A。
实施例2
制备水性丙烯酸改性聚氨酯杂化树脂B，其步骤如下：
a)、在装有温度计、冷凝管、搅拌器的四口反应器中，按配方的重量百分比依次加入聚碳酸酯二元醇6.0份、一缩二丙二醇4.0份、三羟甲基丙烷2.0份、、二羟甲基丙酸3.0份，升温至95～110℃，真空下脱水1.5～2.0h；
b)、降温至60～70℃，加入异佛尔酮二异氰酸酯17.0份，通入N2，滴加二月桂酸二丁基锡0.05份，然后升温至80～82℃反应2～2.5h，得所述的亲水性聚氨酯预聚物；
c)、取8份甲基丙烯酸甲酯单体加到所述的亲水性聚氨酯预聚物至粘度适中，降温至70℃，加入丙烯酸羟乙酯1.8份，继续反应1.5h，检测，当NCO值达到规定的设计值时为止；
d)、将温度降至40℃以下，缓慢滴加中和剂2.5份至pH值8.5～9.0，继续搅拌反应10～20min，加入计算量水25.0份，继续搅拌15min，得丙烯酸与聚氨酯的预聚物；
e)、预先配制好5％过硫酸铵水溶液1.5份，取其0.3份加入上述的预聚物中，升温至80℃，搅拌0.5h；然后滴加剩下的8份甲基丙烯酸甲酯单体和1.2份过硫酸铵水溶液，控制滴加时间为3～4h；然后升温至85℃，保温反应2h，加水21.15份，降温至40℃，过滤，得固含50.2％、pH值7.5～8.0的所述水性丙烯酸改性聚氨酯杂化树脂B。
实施例3
一种高耐水性的丙烯酸改性聚氨酯水性钢构涂料，按重量百分比计，其组成为：水性丙烯酸改性聚氨酯杂化树脂A 70％、硅溶胶6.0％、二丙二醇单丁醚5.8％、防水剂0.8％、闪锈剂1.0％、基材润湿剂0.2％、pH调节剂0.2％、流平剂0.3％、增稠剂0.3％、消泡剂0.2％、杀菌剂0.2％、去离子水15.0％。
实施例4
一种高耐水性的丙烯酸改性聚氨酯水性木器涂料，按重量百分比计，其组成为：水性丙烯酸改性聚氨酯杂化树脂B 75％、硅溶胶4.0％、二丙二醇单丁醚6.0％、基材润湿剂0.2％、手感剂0.8％、pH调节剂0.2％、流平剂0.3％、增稠剂0.3％、消泡剂0.2％、杀菌剂0.2％、去离子水12.8％。
按照相关标准，对本发明的实施例与对比例1(丙烯酸水性涂料)、对比例2(聚氨酯水性涂料)进行对比，检测的性能指标如表1所示。
表1：本发明的实施例与对比例性能对比
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 (3)
1.一种高耐水性的丙烯酸改性聚氨酯杂化树脂水性涂料，其特征在于，所述的高耐水性的丙烯酸改性聚氨酯水性涂料，按重量百分比计，其组成为：水性丙烯酸改性聚氨酯杂化树脂50.0～80.0％、硅溶胶2.0～6.0％、水性色浆0～10.0％、二丙二醇单丁醚3.0～8.0％、助剂0.6～5.0％、去离子水10.0～25.0％；
所述的水性丙烯酸改性聚氨酯杂化树脂，由聚氨酯共聚物链段和丙烯酸共聚物链段组成纳米水分散体，其分子结构式如下所示：
其中，分子式中的R为二异氰酸酯取代基团；R1、R2为H、-CH3及其它烷基类取代基团；R3、R4为及其他酯基；
所述的聚氨酯共聚物链段为分子结构式中的h链段，由硬段m和软段n组成；所述的丙烯酸共聚物链段为分子结构式中的i链段，由硬段x和软段y组成；
所述的水性丙烯酸改性聚氨酯杂化树脂，其玻璃化温度Tg为35～70℃、分子量为4500～5500、乳液粒径为150～280nm、pH值7.5～8.5。
2.根据权利要求1所述的高耐水的性丙烯酸改性聚氨酯水性涂料，其特征在于，所述的助剂至少包括基材润湿剂、润湿分散剂、杀菌剂、消泡剂、流平剂、增稠剂、pH调节剂、消光剂、手感剂、抗划伤剂、闪锈剂、耐水剂、抗紫外线剂，纳米添加剂的一种或几种的组合。
3.根据权利要求1所述的高耐水性的丙烯酸改性聚氨酯水性涂料，其特征在于，所述的水性丙烯酸改性聚氨酯杂化树脂，由以下步骤制成：
a)、在装有温度计、冷凝管、搅拌器的四口反应器中，按配方重量百分比，依次加入低聚物多元醇、多元醇、二羟甲基丙酸，升温至95～110℃，真空下脱水1.5～2.0h；
b)、降温至60～70℃，加入二异氰酸酯后通入N2，滴加配方量的二月桂酸二丁基锡，然后升温到80～82℃反应2～2.5h，得所述的亲水性聚氨酯预聚物；
c)、按配方量配制好丙烯酸软、硬混合单体，取其40～50％量的混合单体加入到所述的亲水性聚氨酯预聚物至粘度适中，降温至70℃，加入丙烯酸羟乙酯，继续反应1.5h，检测，当NCO值达到规定的设计值时为止；
d)、将温度降至40℃以下，缓慢滴加中和剂至pH值8.5～9.0，继续搅拌反应10～20min，加入计算量的水，继续搅拌15min，得丙烯酸与聚氨酯的预聚物；
e)、预先配制好5％过硫酸铵水溶液，取其20％量加入上述的预聚物中，升温至80℃，搅拌0.5h；然后滴加剩下的丙烯酸混合单体和过硫酸铵水溶液，控制滴加时间为3～4h；然后升温至85℃，保温反应2h，加水至规定的固含量，降温至40℃，过滤，得所述的水性丙烯酸改性聚氨酯杂化树脂。
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Cited By (6)
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| CN109554057A (zh) * | 2018-10-31 | 2019-04-02 | 韶关市合众化工有限公司 | 一种持久防腐水性金属底漆及其制备方法 |
| CN109608956A (zh) * | 2018-11-06 | 2019-04-12 | 青岛展辰新材料有限公司 | 一种水性单组分零voc漆及其制备方法 |
| CN109796866A (zh) * | 2019-02-14 | 2019-05-24 | 天津通用科技有限公司 | 一种地面防水涂料及其制备方法 |
| CN110452609A (zh) * | 2019-09-11 | 2019-11-15 | 山东七维新材料有限公司 | 轨道交通低VOCs排放中涂涂料及制备方法 |
| CN111620984A (zh) * | 2020-06-12 | 2020-09-04 | 湖南湘江关西涂料有限公司 | 改性聚氨酯树脂及其制备方法、水性涂料及涂膜制品 |
| CN116333552A (zh) * | 2023-03-31 | 2023-06-27 | 华南理工大学 | 核壳结构水性聚氨酯/丙烯酸酯杂化消光涂料及其制备方法与应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109554057A (zh) * | 2018-10-31 | 2019-04-02 | 韶关市合众化工有限公司 | 一种持久防腐水性金属底漆及其制备方法 |
| CN109608956A (zh) * | 2018-11-06 | 2019-04-12 | 青岛展辰新材料有限公司 | 一种水性单组分零voc漆及其制备方法 |
| CN109796866A (zh) * | 2019-02-14 | 2019-05-24 | 天津通用科技有限公司 | 一种地面防水涂料及其制备方法 |
| CN110452609A (zh) * | 2019-09-11 | 2019-11-15 | 山东七维新材料有限公司 | 轨道交通低VOCs排放中涂涂料及制备方法 |
| CN111620984A (zh) * | 2020-06-12 | 2020-09-04 | 湖南湘江关西涂料有限公司 | 改性聚氨酯树脂及其制备方法、水性涂料及涂膜制品 |
| CN111620984B (zh) * | 2020-06-12 | 2022-11-08 | 湖南湘江关西涂料有限公司 | 改性聚氨酯树脂及其制备方法、水性涂料及涂膜制品 |
| CN116333552A (zh) * | 2023-03-31 | 2023-06-27 | 华南理工大学 | 核壳结构水性聚氨酯/丙烯酸酯杂化消光涂料及其制备方法与应用 |
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