CN106832138B - 一种石墨烯-氟改性水性聚氨酯树脂及其制备方法 - Google Patents

一种石墨烯-氟改性水性聚氨酯树脂及其制备方法 Download PDF

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CN106832138B
CN106832138B CN201710036115.XA CN201710036115A CN106832138B CN 106832138 B CN106832138 B CN 106832138B CN 201710036115 A CN201710036115 A CN 201710036115A CN 106832138 B CN106832138 B CN 106832138B
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张武
许钧强
康伦国
姚东生
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Shaoguan Union Chemical Co Ltd
Union Foshan Chemical Co Ltd
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Abstract

本发明涉及一种石墨烯‑氟改性水性聚氨酯树脂，由多异氰酸酯、多元醇、多元胺类扩链剂、低聚物多元醇、二羟甲基丙酸、石墨烯、羟基丙烯酸、氟烯类单体、丙烯酸类单体、中和剂和去离子水通过化学反应制得；本发明还提供一种石墨烯‑氟改性水性聚氨酯树脂的制备方法；本发明制得的石墨烯‑氟改性水性聚氨酯树脂具有良好的附着力、耐沾污性、高硬度、防腐性、耐久性、疏水性、防静电和自洁等性能，可用于单组分水性涂料、双组分水性涂料、常温固化涂料；广泛用于水性木器涂料、水性工业涂料、水性防污涂料、水性防腐涂料、水性抗静电涂料以及水性特种工程涂料如风能发电、核电、船舶涂料等。

Description

一种石墨烯-氟改性水性聚氨酯树脂及其制备方法
技术领域
本发明涉及一种改性水性聚氨酯树脂的制备方法，尤其涉及到一种表面张力极低、具有良好的疏水防污抗静电功能的石墨烯-氟改性水性聚氨酯树脂，属于合成树脂技术领域。
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。
聚氨酯主要由醇和异氰酸酯反应而成，反应原料及工艺因素对聚氨酯材料形态有很大影响，能够根据不同使用要求对软段、硬段进行有机结合，从而达到研究者对特殊聚合物的设计，为了综合聚氨酯和石墨烯的优良性能，现有技术对两者形成复合材料的方法性能进行了大量研究。通过添加石墨烯可以改进涂料的防腐性，导电导热性，以及阻燃性和力学性能，但基于石墨烯在水性体系中容易发生团聚而沉降，限制其应用，因此，采用化学方法共性石墨烯与聚氨酯树脂成为发展潮流。
中国专利号CN103467676A公开了一种水性氧化石墨烯改性聚(氨酯-丙烯酸酯)复合材料的制备方法。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，但是其表面张力较大，难以适应特殊涂层的应用。
随着科技水平的不断进步和人们环保意识的不断增强，不含或少含挥发性物质的树脂己成为新的发展方向，溶剂型树脂正逐步被水性树脂所替代，水性树脂的开发与研究越来越受到人们的重视。
发明内容
由于氟原子半径小且具有很强的电负性，因此其对碳链具有屏蔽保护作用，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，是低表面能材料研究领域的一类重要聚合物。
而石墨烯具有优异的综合性能，如高导电性、导热性、高强度等特性，而且石墨烯是已知的世上最薄、最坚硬的纳米材料，石墨烯被称为“黑金”，是“新材料之王”，它是一种由单层sp2杂化碳原子组成的二维片状材料，其特殊的结构决定了它具有特殊的性能，石墨烯经强氧化剂氧化后可以制备成氧化石墨烯，氧化石墨烯片层含有大量羟基等活性基团。近年来以氧化石墨烯制备的纳米复合材料表现出非常优越的性能，越来越受到人们的热捧。
本发明结合了聚氨酯树脂、石墨烯和氟原子的特种性能，这能充分发挥聚氨酯硬度大、耐磨损、柔韧性好、附着性能及保光保色性能优良等特点，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石墨烯优良的导电性能，这不仅能满足低表面能防水防污的需求，也满足防静电要求，更能保证其对环境无污染，适应可持续发展路线。
本发明在聚氨酯树脂中引入二羟甲基丙酸DMPA，这使得其能与中和剂中和后形成稳定的水性树脂。
为了解决上述所述的技术问题，本发明在聚氨酯树脂中分子结构上引入有氟元素以及石墨烯对其改性，改性后的聚氨酯树脂具有良好的耐候性，抗污、防静电等性能，改善了聚氨酯树脂性能的不足。
本发明的目的旨在提供一种石墨烯-氟改性水性聚氨酯树脂。
本发明的另一目的在于提供一种石墨烯-氟改性水性聚氨酯树脂的制备方法。
为了解决上面所述的技术问题，本发明采取以下技术方案：本发明涉及一种石墨烯-氟改性水性聚氨酯树脂，按重量百分比计,其组成为：多异氰酸酯8.0～22.0份、多元醇2.0～5.0份、多元胺类扩链剂0.5～2.0份、低聚物多元醇4.0～12.0份、二羟甲基丙酸1.5～3.5份、二月桂酸二丁基锡0.01～0.1份、偶氮二异丁腈0.05～0.2份、石墨烯0.1～1.5份、丙酮3.0～8.0份、羟基丙烯酸2.0～5.0份、氟烯类单体2.0～6.0份、丙烯酸类单体3.0～8.0份、中和剂1.0～2.5份、去离子水40.0～68.0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中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组合。
所述的低聚物多元醇为分子量在1000～4000之间的聚四氢呋喃多元醇、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。
所述的石墨烯为羟基氧化石墨烯，由Hummers法、Staudemaier法、电化学法或Brodie法制备；进一步地，为Hummers法制备的氧化石墨烯。
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。
所述的多元胺类扩链剂为乙二胺、己二酸二肼、水合肼、N，N-二羟基(二异丙基)苯胺中的一种或几种的组合。
所述的羟基丙烯酸为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、甲基丙烯酸羟丁酯中的一种或几种的组合。
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。
所述的石墨烯-氟改性水性聚氨酯树脂的制备方法，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，按配方的重量百分比依次加入多元醇、低聚物多元醇、石墨烯、二羟甲基丙酸，加热升温至95～110℃真空脱水1.5～2.0h；
b、降温至60～70℃条件下滴加多异氰酸酯，在0.5～1h内滴加完毕；然后滴加配方量的二月桂酸二丁基锡，升温至80～82℃反应2～2.5h，视体系粘度补加丙酮；降温至65℃，滴加羟基丙烯酸，继续反应1～2h，测定NCO值，当测定的值与理论设计值接近时终止反应；
c、将温度降至40℃以下，在搅拌下缓慢滴加中和剂，搅拌反应10～20min；加入计算量的水，继续搅拌15min后加入多元胺类扩链剂，高速搅拌1h，然后低速搅拌0.5h，减压下蒸脱丙酮，过滤，得一种石墨烯改性水性聚氨酯树脂；
d、在带有搅拌、滴液装置的反应器中，按配方要求加入丙烯酸类单体、氟烯类单体和催化剂偶氮二异丁腈，搅拌均匀得单体混合物，待用；
e、将石墨烯改性聚氨酯树脂加入反应器，升温至80～82℃，在搅拌下，匀速滴加上述单体混合物，滴加时间为3～5h，滴加完毕继续升温至85℃，保温反应1h，降温40℃，过滤，即制得到一种石墨烯-氟改性水性聚氨酯树脂。
本发明提供一种性能优良、无环境污染、VOC含量极低的石墨烯-氟改性水性聚氨酯树脂及其制备方法。本发明制得的石墨烯-氟改性水性聚氨酯树脂可调配出单组分水性涂料、双组分水性涂料、常温固化涂料。本发明制得的石墨烯-氟改性水性聚氨酯树脂具有良好的附着力、耐沾污性、耐水性、耐碱性、耐久性、疏水性、低表面张力和良好的防静电能力等特点，广泛用于海洋领域、木器涂料、防污防水涂料和防静电涂料，其应用潜力都非常巨大。
具体实施方式
下面结合实施例对本发明的石墨烯-氟改性水性聚氨酯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
一种石墨烯-氟改性水性聚氨酯树脂，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，按配方的重量百分比依次加入聚四氢呋喃多元醇5.0份、丁二醇2.0份、石墨烯0.8份、甘油1.5份、二羟甲基丙酸2.0份，加热升温至95-110℃之间真空脱水1.5～2.0h；
b、降温至60～70℃条件下滴加甲苯二异氰酸酯12.0份，在0.5～1h内滴加完毕；然后滴加二月桂酸二丁基锡0.04份，升温至80～82℃反应2～2.5h，视体系粘度补充丙酮4.0份；降温至65℃，滴加丙烯酸羟乙酯3.0份，继续反应1～2h，测定NCO值，当测定NCO值与理论设计值接近时终止反应；
c、将温度降至40℃以下，在搅拌下缓慢滴加中和剂三乙胺1.5份，继续搅拌反应10～20min；加入计算量的水58.06份，继续搅拌15min后加入乙二胺1.0份，高速搅拌1h，然后低速搅拌0.5h，减压下蒸脱丙酮，得一种石墨烯改性聚氨酯树脂A；
d、在带有搅拌、滴液装置的反应器中，按配方要求加入甲基丙烯酸甲酯4.0份、丙烯酸六氟丁酯5.0份和催化剂偶氮二异丁腈0.1份，搅拌均匀得单体混合物B，待用；
e、将石墨烯改性聚氨酯树脂A加入反应器，升温至80～82℃，在搅拌下，匀速滴加单体混合物B，滴加时间为3～5h；滴加完毕继续升温至85℃，保温反应1h，降温40℃，过滤，即制得一种石墨烯-氟改性水性聚氨酯树脂。
实施例2
一种石墨烯-氟改性水性聚氨酯树脂，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，按配方的重量百分比依次加入聚四氢呋喃多元醇5.0份、丁二醇2.2份、石墨烯0.9份、三羟甲基丙烷2.0份、二羟甲基丙酸2.0份，加热升温至95～110℃之间真空脱水1.5～2.0h；
b、降温至60～70℃条件下滴加异佛尔酮二异氰酸酯14.0份，在0.5～1h内滴加完毕；然后滴加二月桂酸二丁基锡0.05份，升温至80～82℃反应2～2.5h，视体系粘度补充丙酮5.0份；降温至65℃，滴加甲基丙烯酸羟丙酯3.5份，继续反应1～2h，测定NCO值，当测定NCO值与理论设计值接近时终止反应；
c、将温度降至40℃以下，在搅拌下缓慢滴加中和剂三乙胺1.5份，继续搅拌反应10～20min；加入计算量的水56.45份，继续搅拌15min后加入乙二胺0.8份，高速搅拌1h，然后低速搅拌0.5h，减压下蒸脱丙酮，得一种石墨烯改性聚氨酯树脂C；
d、在带有搅拌、滴液装置的反应器中，按配方要求加入丙烯酸甲酯3.0份、甲基丙烯酸六氟丁酯3.5份和催化剂偶氮二异丁腈0.1份，搅拌均匀得单体混合物D，待用；
e、将石墨烯改性聚氨酯树脂C加入反应器，升温至80～82℃，在搅拌下，匀速滴加单体混合物D，滴加时间为3～5h；滴加完毕继续升温至85℃，保温反应1h，降温40℃，过滤，即制得一种石墨烯-氟改性水性聚氨酯树脂。
实施例3
一种石墨烯-氟改性水性聚氨酯树脂，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，按配方的重量百分比依次加入聚四氢呋喃多元醇6.0份、丁二醇3.0份、石墨烯1.0份、三羟甲基丙烷1.5份、二羟甲基丙酸2.0份，加热升温至95～110℃之间真空脱水1.5～2.0h；
b、降温至60～70℃条件下滴加六亚甲基二异氰酸酯18.0份，在0.5～1h内滴加完毕；然后滴加二月桂酸二丁基锡0.06份，升温至80～82℃反应2～2.5h，视体系粘度补充丙酮6.0份；降温至65℃，滴加甲基丙烯酸羟丙酯4.0份，继续反应1～2h，测定NCO值，当测定NCO值与理论设计值接近时终止反应；
c、将温度降至40℃以下，在搅拌下缓慢滴加中和剂三乙胺1.5份，继续搅拌反应10～20min；加入计算量的水47.94份，继续搅拌15min后加入乙二胺0.9份，高速搅拌1h，然后低速搅拌0.5h，减压下蒸脱丙酮，得一种石墨烯改性聚氨酯树脂E；
d、在带有搅拌、滴液装置的反应器中，按配方要求加入甲基丙烯酸环己酯3.5份、甲基丙烯酸六氟异丙酯4.5份和催化剂偶氮二异丁腈0.1份，搅拌均匀得单体混合物F，待用；
e、将石墨烯改性聚氨酯树脂E加入反应器，升温至80～82℃，在搅拌下，匀速滴加单体混合物F，滴加时间为3～5h；滴加完毕继续升温至85℃，保温反应1h，降温40℃，过滤，即制得一种石墨烯-氟改性水性聚氨酯树脂。
以上描述仅为本申请的较佳实施例以及对所运用技术原理的说明；本领域技术人员应当理解，本申请中所涉及的发明范围，并不限于上述技术特征的特定组合而成的技术方案，同时也应涵盖在不脱离所述发明构思的情况下，由上述技术特征或其等同特征进行任意组合而形成的其它技术方案。例如上述特征与本申请中公开的(但不限于)具有类似功能的技术特征进行互相替换而形成的技术方案。

Claims (5)

1.一种石墨烯-氟改性水性聚氨酯树脂的制备方法，其特征在于：所述制备方法，步骤如下：
a)、在装有温度计、冷凝管、搅拌器的四口反应器中，按配方重量百分比依次加入多元醇、低聚物多元醇、石墨烯、二羟甲基丙酸，加热升温至95～110℃下真空脱水1.5～2.0h；
b)、降温至60～70℃下滴加多异氰酸酯，在0.5～1h内滴加完毕；然后滴加二月桂酸二丁基锡，升温至80～82℃反应2～2.5h，视体系粘度补加丙酮；降温至65℃，滴加羟基丙烯酸，继续反应1～2h，测定NCO值，当测定的NCO值与理论设计值接近时终止反应；
c)、将温度降至40℃以下，在搅拌下缓慢滴加中和剂，搅拌反应10～20min；加入去离子水，继续搅拌15min后加入多元胺类扩链剂，高速搅拌1h，然后低速搅拌0.5h，减压下蒸脱丙酮，过滤，得石墨烯改性水性聚氨酯树脂；
d)、在带有搅拌、滴液装置的反应器中，按配方要求加入丙烯酸类单体、氟烯类单体和偶氮二异丁腈，搅拌均匀，得单体混合物；
e)、将石墨烯改性聚氨酯树脂加入反应器中，升温至80～82℃，在搅拌下，匀速滴加单体混合物，滴加时间为3～5h，滴加完毕继续升温至85℃，保温反应1h，降温40℃，过滤，得所述的石墨烯-氟改性水性聚氨酯树脂；
按重量份数计，各原料组分为：
多异氰酸酯8.0～22.0份
多元醇2.0～5.0份
多元胺类扩链剂0.5～2.0份
低聚物多元醇4.0～12.0份
二羟甲基丙酸1.5～3.5份
二月桂酸二丁基锡0.01～0.1份
偶氮二异丁腈0.05～0.2份
石墨烯0.1～1.5份
丙酮3.0～8.0份
羟基丙烯酸2.0～5.0份
氟烯类单体2.0～6.0份
丙烯酸类单体3.0～8.0份
中和剂1.0～2.5份
去离子水40.0～68.0份；
其中，所述多元醇为乙二醇、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、聚环氧丙烷多元醇中的一种或几种的组合；所述低聚物多元醇的分子量为1000～4000；
所述羟基丙烯酸为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、甲基丙烯酸羟丁酯中的一种或几种的组合；所述丙烯酸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、丙烯酸四氢糠醇酯、甲基丙烯酸四氢糠醇酯中的一种或几种的组合；
所述石墨烯由Hummers法、Staudenmaier法、电化学法、Brodie法制备的任一种含羟基的氧化石墨烯。
2.根据权利要求1所述的制备方法，其特征在于：所述多异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、苯二亚甲基二异氰酸酯、环己烷二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯中的一种或几种的组合。
3.根据权利要求1所述的制备方法，其特征在于：所述多元胺类扩链剂为乙二胺、己二酸二肼、水合肼中的一种或几种的组合。
4.根据权利要求1所述的制备方法，其特征在于：所述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中的一种或几种的组合。
5.根据权利要求1所述的制备方法，其特征在于：所述中和剂为三乙胺、氨水、二甲基乙醇胺中的一种或几种的组合。
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