CN107903357B - 含氟聚氨酯改性丙烯酸水性树脂及其制备方法 - Google Patents

含氟聚氨酯改性丙烯酸水性树脂及其制备方法 Download PDF

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CN107903357B
CN107903357B CN201710917112.7A CN201710917112A CN107903357B CN 107903357 B CN107903357 B CN 107903357B CN 201710917112 A CN201710917112 A CN 201710917112A CN 107903357 B CN107903357 B CN 107903357B
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CN107903357A (zh
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张武
许钧强
谢义鹏
康伦国
姚东生
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Foshan Xiance Resin Co ltd
Shaoguan Union Chemical Co Ltd
Union Foshan Chemical Co Ltd
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Abstract

本发明涉及一种含氟聚氨酯改性丙烯酸水性树脂，其成分由多异氰酸酯、多元醇、六氟异丙醇、低聚物多元醇、二羟甲基丙酸、丙烯酸单体、中和剂和去离子水组成；本发明还提供一种含氟聚氨酯改性丙烯酸水性树脂的无溶剂绿色制备方法。本发明制得的含氟聚氨酯改性丙烯酸水性树脂，其玻璃化温度为45～75℃、数均分子量为5000～6000、粒径为200～300nm、零VOC，具有优异的附着力、耐沾污性、疏水性、耐化品性、耐老化性、耐盐雾性和耐腐蚀性；可配制成单组分、双组分水性涂料，广泛用于水性木器涂料、水性自洁涂料、水性防污涂料、水性防腐涂料、水性防大气腐蚀涂料、水性工程涂料等。

Description

含氟聚氨酯改性丙烯酸水性树脂及其制备方法
技术领域
本发明涉及一种改性丙烯酸树脂的制备方法，尤其涉及到一种表面张力极低、具有良好的疏水防污功能的含氟聚氨酯改性丙烯酸水性树脂，属于合成水性树脂技术领域。
背景技术
目前作用于塑料、木材、金属等表面进行防污防水处理的表面处理剂，由于存在涂抹后涂层表面分散不均、表面张力过大，这使得基材涂层表面极易被污染且不易清洁，因此低表面能疏水涂料在科学研究领域受到了广泛关注。
水性聚氨酯是一种环境友好型高分子材料，具备优异的粘结性、弹性、耐寒性、高光泽以及软硬度随温度变化不大等优点，拥有良好的通用性。相对于溶剂型聚氨酯，水性聚氨酯是以水代替有机溶剂，具有节约资源，防止污染等特点，由于聚氨酯拥有独特的微相分离结构，所以具有优异的弹性、耐磨性、抗冲击和拉伸等性能，已经广泛应用于涂料、橡胶、黏合剂、纤维、软质泡沫塑料、硬质泡沫塑料、保温材料、合成皮革、防水材料、铺装材料等。随着世界环保法规的日益严格和人们环保意识的逐渐增强，溶剂型聚氨酯的使用越来越受到限制，以水为分散介质的水性聚氨酯日益成为开发研究的方向。
丙烯酸树脂通常由自由基聚合方法而制备，需外加乳化剂，制造这类树脂可用的单体很多，包括丙烯酸的烷基酯、羟烷基酯以及乙烯基单体，如苯乙烯等。丙烯酸树脂的最终性能可通过选择适当的单体种类加以控制，通过调整硬性单体和软性单体的比例可以达到硬度、耐冲击和柔韧性的统一。
中国专利CN102432768A公开了一种含氟硅聚氨酯-丙烯酸酯乳液的制备方法：将含氢硅油、含氟丙烯酸酯、双烯基丙烯酸酯、无水乙醇制得含氟硅油；将异氰酸酯、聚醚二元醇和聚酯二元醇反应制得的预聚体与含氟二元醇和扩链剂、亲水扩链剂进行扩链反应，再加水分散乳化，减压蒸馏除去有机溶剂得到水性聚氨酯乳液，然后再加入丙烯酸酯、含氟硅油，高速分散，加入催化剂升温聚合得到含氟硅聚氨酯-丙烯酸酯乳液，所制得的复合材料的乳液均一、稳定，固化膜具有较好的力学性能；该发明是通过含氟丙酸酸单体引入氟原子，其制备过程中需要用有机溶剂，增加了减压蒸馏除去有机溶剂过程，这对环境有一定污染。
近年来，我国水性树脂的研制得到了快速的发展，基本上满足了国民经济建设的需要，但是在品种、数量、技术方面和世界先进国家还存在较大的差距。本发明开发出一种含氟聚氨酯改性丙烯酸水性树脂，这不仅能发挥聚氨酯硬度大、耐磨损、柔韧性好、附着性能及保光保色性优良等性能，还能结合氟原子半径小、具有很低的表面张力等优良性能以及丙烯酸树脂原料成本低等特点。这不仅能满足低表面能防水防污的需求，更能保证对环境无污染，适应可持续发展路线。
发明内容
本发明的目的旨在提供一种含氟聚氨酯改性丙烯酸水性树脂。
本发明的另一目的提供一种含氟聚氨酯改性丙烯酸水性树脂的无溶剂制备方法。
含氟聚合物中的氟原子沿碳链螺旋分布，由于氟原子半径比其它元素子半径小，并具有很强的电负性，可以把碳链严密地包住并向外伸展，起到屏蔽保护作用，提高了C-C主链结构的稳定性，这使得氟聚合物具有优异的热稳定性、耐候性和化学惰性，以及独特的低表面张力、低表面自由能和低摩擦系数，这赋予了氟聚合物拥有优异的憎水、憎油性、耐腐蚀性是低表面能材料领域中的一类重要聚合物。
本发明是在聚氨酯改-丙烯酸分子结构中的聚氨酯硬段链上用小分子含氟醇以扩链剂的方式引入氟原子，通过这种方式引入氟原子可以避免聚氨酯出现相对分子量低、脆性大的缺点。
本发明采用无溶剂绿色法生产。由于反应过程中先合成可反应型乳化剂--亲水性聚氨酯预聚物，能自乳法合成含氟聚氨酯改性丙烯酸水性树脂，该树脂能稳定均匀分散在水溶液中，零VOC，是真正意义的环保产品。
本发明的一种含氟聚氨酯改性丙烯酸水性树脂，由含氟聚氨酯共聚物链段和丙烯酸共聚物链段组成，其分子结构式如下所示：
Figure BDA0001426007250000031
所述的含氟聚氨酯共聚物链段为分子结构式中的h链段，具有亲水性；其中R0为聚氨酯硬段：
Figure BDA0001426007250000032
所述的含氟聚氨酯共聚物h链段，其分子结构式如下所示：
Figure BDA0001426007250000041
其中，分子式中的R为二异氰酸酯取代基团，m为硬段、n为软段；m/n的摩尔比为1:0.5～1.0；通过调整m/n摩尔比来控制聚氨酯共聚物链段分子结构、玻璃化温度、分子量及其分布；所述的含氟聚氨酯共聚物链段的玻璃化温度Tg为25℃～35℃、数均分子量Mn为2200～2500。
所述的丙烯酸共聚物链段为分子结构式中的i链段，其分子结构式如下所示：
Figure BDA0001426007250000042
其中，R1、R2可以是H、-CH3及其它烷基类取代基团；R3、R4可以是
Figure BDA0001426007250000043
及其他酯基；x为硬段、y为软段；y/x的摩尔比为1:0.1～1；通过调整y/x摩尔比来控制丙烯酸共聚物链段分子结构、玻璃化温度、分子量及其分布；所述的丙烯酸共聚物链段玻璃化温度Tg为50～80℃、数均分子量Mn为1800～3000。
本发明的一种含氟聚氨酯改性丙烯酸水性树脂，h/i的摩尔比为1:0.2～1；其玻璃化温度Tg为45℃～75℃、数均分子量Mn为5000～6000、乳液粒径为160～300nm、pH值7.5～8.5。
本发明所述的含氟聚氨酯改性丙烯酸水性树脂，采取以下技术方案：按重量百分比计,其组分为：多异氰酸酯8.0～15.0％、多元醇2.0～5.0％、低聚物多元醇5.0～12.0％、二羟甲基丙酸1.5～3.5％、二月桂酸二丁基锡0.01～0.1％、过硫酸铵0.05～0.2％、丙烯酸羟乙酯2.0～4.0％、丙烯酸软硬单体5.0～15.0％、六氟异丙醇1.0～3.0％、中和剂1.0～2.5％、去离子水50.0～68.0％。
其中，所述的多异氰酸酯为甲苯二异氰酸酯TDI、异佛尔酮二异氰酸酯IPDI、六亚甲基二异氰酸酯HDI、苯二亚甲基二异氰酸酯XDI、环己烷二亚甲基二异氰酸酯H6XDI、四甲基苯二亚甲基二异氰酸酯TMXDI中的一种或几种的组合。
所述的多元醇为乙二醇、丙二醇、丁二醇、己二醇、新戊二醇、二缩二乙二醇、一缩二丙二醇、2-丁基-2-乙基-1,3-丙二醇、2,4-二乙基-1,5-戊二醇、2-乙基-1,3-己二醇、三羟甲基丙烷、甘油、三羟甲基乙烷、季戊四醇、木糖醇、山梨醇中的一种或几种的组合。
所述的低聚物多元醇为聚四氢呋喃多元醇、聚碳酸酯多元醇、聚己内酯多元醇、聚环氧乙烷多元醇、聚醚二元醇、聚乙二醇、聚环氧丙烷多元醇中的一种或几种的组合；所述的低聚物多元醇数均分子量为1000～4000。
所述的丙烯硬单体为丙烯酸甲酯、2-甲基丙烯酸甲酯、丙烯酰胺、丙烯腈、甲基丙烯酸叔丁酯、甲基丙烯酸-2-羟基乙酯、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、甲基丙烯酸的中一种或几种的组合。
所述的丙烯软单体为丙烯酸-2-乙基己酯、丙烯酸丁酯、甲基丙烯酸丁酯、甲基丙烯酸异辛酯、甲基丙烯酸十三碳酯、甲基丙烯酸正己酯、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的中一种或几种的组合。
所述的中和剂为三乙胺、氨水、二甲基乙醇胺中的一种或几种的组合。
本发明提供一种含氟聚氨酯改性丙烯酸水性树脂的制备方法，包括以下步骤：
a)、在装有温度计、冷凝管、搅拌器的四口反应器中，按配比计，依次加入多元醇、低聚物多元醇、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℃，通入N2，加入多异氰酸酯，按配方量滴加二月桂酸二丁基锡，然后升温至80～82℃反应1.5～2.0h，得所述的亲水性聚氨酯预聚物；
c)、取预先按配方重量比配制好丙烯酸软、硬混合单体总量的40～50％加入到所述的亲水性聚氨酯预聚物，降温至70℃，加入丙烯酸羟乙酯，反应1.5h，再加入六氟异丙醇，继续反应1～1.5h，取样检测，当NCO值达到规定的设计值时，停止反应；
d)、将温度降至40℃以下，关闭N2，缓慢滴加中和剂至pH值8.5～9.0，搅拌10～20min，加入配方量的去离子水，继续搅拌15min，得含氟聚氨酯与丙烯酸的预聚物；
e)、取预先配制好5％过硫酸铵水溶液总量的20％加入上述的预聚物中，升温至80℃，搅拌0.5h；再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；滴加完之后升温至85℃，保温反应2h，加去离子水至规定的固含量，降温至40℃，过滤，得所述的含氟聚氨酯改性丙烯酸水性树脂。
本发明提供一种含氟聚氨酯改性丙烯酸水性树脂及其制备方法，采用无溶剂、无乳化剂制备，符合绿色生产要求。本发明制得的含氟聚氨酯改性丙烯酸水性树脂，具有优异的附着力、耐沾污性、疏水性、耐化品性、耐老化性、耐盐雾性和耐腐蚀性；由于含有低表面张力的氟基团，赋于其疏水和自洁功能，可配制成单组分、双组分水性涂料，广泛用于水性木器涂料、水性自洁涂料、水性防污涂料、水性防腐涂料、水性防大气腐蚀涂料、水性工程涂料等。
具体实施方式
下面结合实施例对本发明的一种含氟聚氨酯改性丙烯酸水性树脂做进一步的描述。可以理解的是，此处所描述的具体实施例仅仅用于解释相关发明，而非对该发明的限定。
实施例1
一种含氟聚氨酯改性丙烯酸水性树脂A1，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，按配方重量份计依次加入丁二醇3.0份、三羟甲基丙烷1.5份、聚四氢呋喃多元醇7.0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℃，通入N2，加入异佛尔酮二异氰酸酯10.0份，滴加二月桂酸二丁基锡0.05份，然后升温至80～82℃反应1～1.5h，得所述的亲水性聚氨酯预聚物；
c)、预先准备甲基丙烯酸甲酯12.0份，取其6.0份加到所述的亲水性聚氨酯预聚物，降温至70℃，加入丙烯酸羟乙酯2.0份，反应1.5h，再加入六氟异丙醇2.0份，继续反应1～1.5h，取样检测，当NCO值达到规定的设计值时，停止反应；
d)、将温度降至40℃以下，关闭N2，缓慢滴加中和剂1.5份至pH值8.5～9.0，搅拌10～20min，加入去离子水35.0份，继续搅拌15min，得所述含氟聚氨酯与丙烯酸的预聚物；
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；再滴加剩下的6.0份丙烯酸混合单体和1.2份过硫酸铵水溶液，保温反应3～4h；滴加完之后升温至85℃，保温反应2h，加去离子水23.28份，降温至40℃，过滤，得所述的含氟聚氨酯改性丙烯酸水性树脂。
实施例2
一种含氟聚氨酯改性丙烯酸水性树脂B1，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，按配方重量份计依次加入一缩二丙二醇4.0份、三羟甲基丙烷1.0份、聚碳酸酯多元醇8.0份、二羟甲基丙酸2.5份，升温至95～110℃，真空下脱水1.5～2.0h；
b)、降温至60～70℃，通入N2，加入异佛尔酮二异氰酸酯12.0份，滴加二月桂酸二丁基锡0.05份，然后升温至80～82℃反应1～1.5h，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甲基丙烯酸乙酯混合单体15.0份，取其7.0份加到所述的亲水性聚氨酯预聚物，降温至70℃，加入丙烯酸羟乙酯2.5份，反应1.5h，再加入六氟异丙醇2.0份，继续反应1～1.5h，取样检测，当NCO值达到规定的设计值时，停止反应；
d)、将温度降至40℃以下，关闭N2，缓慢滴加中和剂1.8份至pH值8.5～9.0，搅拌10～20min，加入去离子水30.0份，继续搅拌15min，得所述含氟聚氨酯与丙烯酸的预聚物；
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；再滴加剩下的8.0份丙烯酸混合单体和1.2份过硫酸铵水溶液，反应3～4h；滴加完之后升温至85℃，保温反应2h，加水21.08份，降温至40℃，过滤，得所述的含氟聚氨酯改性丙烯酸水性树脂。
实施例3
一种含氟聚氨酯改性丙烯酸水性树脂C1，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，按配方重量份计依次加入丁二醇3.0份、甘油1.5份、聚碳酸酯多元醇6.0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℃，通入N2，加入异佛尔酮二异氰酸酯11.0份，滴加二月桂酸二丁基锡0.05份，然后升温至80～82℃反应1～1.5h，得所述的亲水性聚氨酯预聚物；
c)、预先准备甲基丙烯酸甲酯10.0份，取其5.0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3.0份，反应1.5h，再加入六氟异丙醇3.0份，继续反应1～1.5h，取样检测，当NCO值达到规定的设计值时，停止反应；
d)、将温度降至40℃以下，关闭N2，缓慢滴加中和剂2.0份至pH值8.5～9.0，搅拌10～20min，加入去离子水32.0份，继续搅拌15min，得所述含氟聚氨酯与丙烯酸的预聚物；
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；再滴加剩下的5.0份甲基丙烯酸甲酯单体和1.2份过硫酸铵水溶液，保温反应3～4h；滴加完之后升温至85℃，保温反应2h，加水25.38份，降温至40℃，过滤，得所述的含氟聚氨酯改性丙烯酸水性树脂。
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)

1.一种含氟聚氨酯改性丙烯酸水性树脂的制备方法，其特征在于，所述的制备方法，其步骤如下：
a）、按配方重量份计，在装有温度计、冷凝管、搅拌器的四口反应器中，依次加入丁二醇3.0份、三羟甲基丙烷1.5份、聚四氢呋喃多元醇7.0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℃，通入N2，加入异佛尔酮二异氰酸酯10.0份，滴加二月桂酸二丁基锡0.05份，然后升温至80～82℃反应1～1.5h，制得亲水性聚氨酯预聚物；
c）、预先准备甲基丙烯酸甲酯12.0份，取其6.0份加入到上述的亲水性聚氨酯预聚物中，降温至70℃，加入丙烯酸羟乙酯2.0份，反应1.5h，再加入六氟异丙醇2.0份，继续反应1～1.5h，取样检测，当NCO值达到规定的设计值时，停止反应；
d）、将温度降至40℃以下，关闭N2，缓慢滴加中和剂1.5份至pH值8.5～9.0，搅拌10～20min，加入去离子水35.0份，继续搅拌15 min，制得含氟聚氨酯与丙烯酸的预聚物；
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；再滴加剩下的6.0份丙烯酸混合单体和1.2份过硫酸铵水溶液，保温反应3～4h；滴加完之后升温至85℃，保温反应2h，加去离子水23.28份，降温至40℃，过滤，得所述的含氟聚氨酯改性丙烯酸水性树脂；
其中，所述的聚四氢呋喃多元醇数均分子量为1000～4000；所述的中和剂为三乙胺、氨水、二甲基乙醇胺中的一种或几种的组合。
2.一种含氟聚氨酯改性丙烯酸水性树脂的制备方法，其特征在于，所述的制备方法，其步骤如下：
a）、按配方重量份计，在装有温度计、冷凝管、搅拌器的四口反应器中，依次加入一缩二丙二醇4.0份、三羟甲基丙烷1.0份、聚碳酸酯多元醇8.0份、二羟甲基丙酸2.5份，升温至95～110℃，真空下脱水1.5～2.0h；
b）、降温至60～70℃，通入N2，加入异佛尔酮二异氰酸酯12.0份，滴加二月桂酸二丁基锡0.05份，然后升温至80～82℃反应1～1.5h，制得亲水性聚氨酯预聚物；
c）、预先配好甲基丙烯酸甲酯与甲基丙烯酸乙酯混合单体15.0份，取其7.0份加入到上述的亲水性聚氨酯预聚物中，降温至70℃，加入丙烯酸羟乙酯2.5份，反应1.5h，再加入六氟异丙醇2.0份，继续反应1～1.5h，取样检测，当NCO值达到规定的设计值时，停止反应；
d）、将温度降至40℃以下，关闭N2，缓慢滴加中和剂1.8份至pH值8.5～9.0，搅拌10～20min，加入去离子水30.0份，继续搅拌15 min，制得含氟聚氨酯与丙烯酸的预聚物；
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；再滴加剩下的8.0份丙烯酸混合单体和1.2份过硫酸铵水溶液，反应3～4h；滴加完之后升温至85℃，保温反应2h，加水21.08份，降温至40℃，过滤，得所述的含氟聚氨酯改性丙烯酸水性树脂；
其中，所述的聚碳酸酯多元醇数均分子量为1000～4000；所述的中和剂为三乙胺、氨水、二甲基乙醇胺中的一种或几种的组合。
3.一种含氟聚氨酯改性丙烯酸水性树脂的制备方法，其特征在于，所述的制备方法，其步骤如下：
a）、按配方重量份计，在装有温度计、冷凝管、搅拌器的四口反应器中，依次加入丁二醇3.0份、甘油1.5份、聚碳酸酯多元醇6.0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℃，通入N2，加入异佛尔酮二异氰酸酯11.0份，滴加二月桂酸二丁基锡0.05份，然后升温至80～82℃反应1～1.5h，制得亲水性聚氨酯预聚物；
c）、预先准备甲基丙烯酸甲酯10.0份，取其5.0份加入到上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3.0份，反应1.5h，再加入六氟异丙醇3.0份，继续反应1～1.5h，取样检测，当NCO值达到规定的设计值时，停止反应；
d）、将温度降至40℃以下，关闭N2，缓慢滴加中和剂2.0份至pH值8.5～9.0，搅拌10～20min，加入去离子水32.0份，继续搅拌15 min，制得含氟聚氨酯与丙烯酸的预聚物；
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；再滴加剩下的5.0份甲基丙烯酸甲酯单体和1.2份过硫酸铵水溶液，保温反应3～4h；滴加完之后升温至85℃，保温反应2h，加水25.38份，降温至40℃，过滤，得所述的含氟聚氨酯改性丙烯酸水性树脂；
其中，所述的聚碳酸酯多元醇数均分子量为1000～4000；所述的中和剂为三乙胺、氨水、二甲基乙醇胺中的一种或几种的组合。
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