CN107778449A - 一种石墨烯改性水性聚氨酯树脂及其制备方法 - Google Patents

一种石墨烯改性水性聚氨酯树脂及其制备方法 Download PDF

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CN107778449A
CN107778449A CN201710855021.5A CN201710855021A CN107778449A CN 107778449 A CN107778449 A CN 107778449A CN 201710855021 A CN201710855021 A CN 201710855021A CN 107778449 A CN107778449 A CN 107778449A
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polyurethane resin
aqueous polyurethane
graphene
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耿光强
李智璐
刘贝贝
车云霞
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Special Novel Material Science And Technology Ltd Of Qingdao Rayleigh
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Abstract

本发明公开了一种石墨烯改性水性聚氨酯树脂及其制备方法，具体步骤包括：采用Hummers法获得的氧化石墨烯经功能化改性、分散后得到高浓度石墨烯水分散液；在石墨烯水分散液中加入加入配方量的聚酯多元醇(或聚醚多元醇)及亲水扩链剂，搅拌均匀后，在真空条件下去除水分；停真空后立即通氮气，加入配方量的二异氰酸酯，加热搅拌反应一定时间后停止通氮气，加入中和剂；后加入去离子水高速分散一定时间后，加入小分子扩链剂反应，出料。其操作过程简便可控，易于大批量制备及合成；通过该方法制备的石墨烯改性水性聚氨酯树脂具有良好的附着力、耐腐蚀及抗冲击性能，可广泛应用于海洋领域、钢构、防静电涂料、导电涂料、防污防水涂料等领域。

Description

一种石墨烯改性水性聚氨酯树脂及其制备方法
技术领域
本发明属于水性树脂合成技术领域，涉及一种石墨烯改性水性聚氨酯树脂及其制备方法。
背景技术
随着人们环保意识的增强，材料安全问题越加重视。传统溶剂型材料在应用时存在有机融合剂的污染，这给生产工人以及生态环境带来严重的影响，水性聚氨酯是采用水作为分散介质的聚氨酯乳液，除具有溶剂型聚氨酯优异性能外，还具有使用简单、无毒、无环境污染等优点，但是由于水性聚氨酯乳液采用水作为稀释剂，介质水的表面张力较大，使得其成膜过程中表面铺展较差、力学性能低等缺点，而促使水性聚氨酯稳定分散在介质水中的亲水性基团，会引起水性聚氨酯在成膜后耐水性差且易吸水，造成涂膜易起泡等缺点。
石墨稀是一种由单层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奇特的电学性能、良好的力学性能、优异的物理机械性能以及气体阻隔性能，石墨经由强氧化剂氧化后可以制备成氧化石墨，氧化石墨片层含有大量的羟基基团，具有较高的比表面积。石墨烯经过氧化，其共扼结构遭到了破坏，片层容易剥离，因此氧化石墨烯很容易的在水溶液中形成均一稳定的水溶液，这为石墨烯改性水性聚氨酯树脂提供了天然条件。
发明内容
本发明针对上述的问题，提供了一种石墨烯改性水性聚氨酯树脂及其制备方法。
为了达到上述目的，本发明采用的技术方案为，
一种石墨烯改性水性聚氨酯树脂，具体包括以下组分：
所述石墨烯水分散液是采用Hummers法获得的氧化石墨烯并经功能化改性、分散后得到高浓度石墨烯水分散液。
作为优选，所述聚酯多元醇或聚醚多元醇为有机二元羧酸或氧化烯烃类与多元醇、多元胺聚合而成的低聚物；其中，二元酸有苯二甲酸或苯二甲酸酐或其酯、己二酸、卤代苯二甲酸等；多元醇有乙二醇、丙二醇、一缩二乙二醇、三羟甲基丙烷、季戊四醇等。
作为优选，所述亲水扩链剂为羧酸盐或硫酸盐型扩链剂。
作为优选，所述二异氰酸酯为甲苯2,4-二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、二苯基甲烷二异氰酸酯(MDI)中的一种或几种。
作为优选，所述中和剂为三乙胺、氨水、氢氧化钠、二甲基乙醇胺中的一种或几种。
作为优选，所述的小分子扩链剂为1,4-丁二醇、乙二醇、1,6-己二醇中的一种或几种。
作为优选，所述中和剂为乙二胺、乙二酸二肼、水合肼、N,N-二羟基(二异丙基)苯胺中的一种或几种。
一种制备石墨烯改性水性聚氨酯树脂的方法，具体包括以下步骤：
a、在装有温度计、冷凝管、搅拌器的四口瓶中，按配方的重量百分比，加入聚酯多元醇或聚醚多元醇、亲水扩链剂、石墨烯水分散液，在真空条件下加热到90-120℃，搅拌1.5h去，充分除去原料中的水分；
b、停真空后立即通氮气，将四口瓶降温至60-80℃，加入配方量的二异氰酸酯反应3-5h；视体系粘度补充丙酮，测定NCO值，当测定的值与理论计算值接近时，停止反应；
c、停止通入氮气，继续搅拌，降温至30-40℃，加入中和剂反应10-20min，在剧烈搅拌下加入计算量的水，继续高速搅拌10-20min；
d、在搅拌条件下缓慢滴加小分子扩链剂的去离子水溶液，滴完后再搅拌30-50min，停止反应；然后低速搅拌30min，减压蒸脱丙酮，即制得石墨烯改性水性聚氨酯树脂。
与现有技术相比，本发明的优点和积极效果在于，
本发明制备的石墨烯改性水性聚氨酯树脂漆膜硬度高、具有良好的防静电性、耐老化、耐磨、耐紫外线以及抗腐蚀等性能，可广泛应用于海洋领域、钢构、防静电涂料、导电涂料、防污防水涂料等领域。
具体实施方式
为了能够更清楚地理解本发明的上述目的、特征和优点，下面结合实施例对本发明做进一步说明。需要说明的是，在不冲突的情况下，本申请的实施例及实施例中的特征可以相互组合。
在下面的描述中阐述了很多具体细节以便于充分理解本发明，但是，本发明还可以采用不同于在此描述的其他方式来实施，因此，本发明并不限于下面公开说明书的具体实施例的限制。
实施例1
一种石墨烯改性水性聚氨酯树脂及其制备方法，其制备工艺如下：
a、在装有温度计、冷凝管、搅拌器的四口瓶中，加入聚酯多元醇10份，二羟甲基丙酸2份，石墨烯水分散液1份，在真空条件下加热到100℃，搅拌1.5h去，充分除去原料中的水分；
b、停真空后立即通氮气，将四口瓶降温至60℃，加入TDI 10份，反应3h；补充丙酮7份，测定NCO值，当测定的值与理论计算值接近时，停止反应；
c、停止通入氮气，继续搅拌，降温至40℃，加入三乙胺1份反应10min，在剧烈搅拌下加入去离子水67份，继续高速搅拌10min；
d、在搅拌条件下缓慢滴加1,4-丁二醇的去离子水溶液2份，滴完后再搅拌30min，停止反应；然后低速搅拌30min，减压蒸脱丙酮，即制得一种石墨烯改性水性聚氨酯树脂1。
实施例2
一种石墨烯改性水性聚氨酯树脂及其制备方法，其制备工艺如下：
a、在装有温度计、冷凝管、搅拌器的四口瓶中，加入聚酯多元醇18份，甲基二乙醇胺3份，石墨烯水分散液2份，在真空条件下加热到105℃，搅拌1.5h去，充分除去原料中的水分；
b、停真空后立即通氮气，将四口瓶降温至65℃，加入HDI 13份，反应3.5h；补充丙酮12份，测定NCO值，当测定的值与理论计算值接近时，停止反应；
c、停止通入氮气，继续搅拌，降温至38℃，加入氨水1.5份反应13min，在剧烈搅拌下加入去离子水48份，继续高速搅拌15min；
d、在搅拌条件下缓慢滴加乙二胺的去离子水溶液2.5份，滴完后再搅拌40min，停止反应；然后低速搅拌30min，减压蒸脱丙酮，即制得一种石墨烯改性水性聚氨酯树脂2。
实施例3
一种石墨烯改性水性聚氨酯树脂及其制备方法，其制备工艺如下：
a、在装有温度计、冷凝管、搅拌器的四口瓶中，加入聚醚多元醇18份，乙二胺基乙磺酸钠3份，石墨烯水分散液3份，在真空条件下加热到115℃，搅拌1.5h去，充分除去原料中的水分；
b、停真空后立即通氮气，将四口瓶降温至80℃，加入IPDI 15份，反应4h；补充丙酮13份，测定NCO值，当测定的值与理论计算值接近时，停止反应；
c、停止通入氮气，继续搅拌，降温至40℃，加入二甲基乙醇胺2.5份反应20min，在剧烈搅拌下加入去离子水41.5份，继续高速搅拌20min；
d、在搅拌条件下缓慢滴加1,6-己二醇的去离子水溶液4份，滴完后再搅拌50min，停止反应；然后低速搅拌30min，减压蒸脱丙酮，即制得一种石墨烯改性水性聚氨酯树脂3。
采用相同的技术配方将上述实施例中的改性聚氨酯树脂制备成防腐涂料，并与普通水性聚氨酯树脂制备的防腐涂料性能进行对比，结果表1所示。
其中，附着力：按照GB/T9286-1988的规定，使用划格法进行测试；
硬度：按照GB/T6739-2006色漆和清铅笔法测定漆膜硬度；
干燥时间：按照GB/T1728-1979的规定进行检测，其中表干按甲法进行，实干按乙法进行；
耐水性：按照GB/T1733-1993的规定进行检测；
耐盐雾性：按照GB/T1771-1991的规定进行检测；
耐老化性：按照GB/T1865-1997的规定进行检测。
表1.本发明的实施例所制备防腐涂料与普通水性聚氨酯树脂防腐涂料性能对比
检测项目 实施例1 实施例2 实施例3 普通对比样
附着力 0级 0级 0级 1级
硬度 2H 2H 3H HB
表干 ≤1.5h ≤1.5h ≤1.5h 2h
实干 ≤12h ≤12h ≤12h 18h
耐水性 500h 800h 800h 200h
耐盐雾性 720h 1080h 1100h 200h
耐老化性 500h 1200h 1272h 300h
以上所述，仅是本发明的较佳实施例而已，并非是对本发明作其它形式的限制，任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例应用于其它领域，但是凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型，仍属于本发明技术方案的保护范围。

Claims (8)

1.一种石墨烯改性水性聚氨酯树脂，其特征在于，具体包括以下组分：
所述石墨烯水分散液是采用Hummers法获得的氧化石墨烯并经功能化改性、分散后得到高浓度石墨烯水分散液。
2.根据权利要求1所述的一种石墨烯改性水性聚氨酯树脂，其特征在于，所述聚酯多元醇或聚醚多元醇为有机二元羧酸或氧化烯烃类与多元醇、多元胺聚合而成的低聚物。
3.根据权利要求1所述的一种石墨烯改性水性聚氨酯树脂，其特征在于，所述亲水扩链剂为羧酸盐或硫酸盐型扩链剂。
4.根据权利要求1所述的一种石墨烯改性水性聚氨酯树脂，其特征在于，所述二异氰酸酯为甲苯2,4-二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、二苯基甲烷二异氰酸酯(MDI)中的一种或几种。
5.根据权利要求1所述的一种石墨烯改性水性聚氨酯树脂，其特征在于，所述中和剂为三乙胺、氨水、氢氧化钠、二甲基乙醇胺中的一种或几种。
6.根据权利要求1所述的一种石墨烯改性水性聚氨酯树脂，其特征在于，所述的小分子扩链剂为1,4-丁二醇、乙二醇、1,6-己二醇中的一种或几种。
7.根据权利要求1所述的一种石墨烯改性水性聚氨酯树脂，其特征在于，所述中和剂为乙二胺、乙二酸二肼、水合肼、N,N-二羟基(二异丙基)苯胺中的一种或几种。
8.一种制备权利要求1-7中所述的石墨烯改性水性聚氨酯树脂的方法，其特征在于，具体包括以下步骤：
a、在装有温度计、冷凝管、搅拌器的四口瓶中，按配方的重量百分比，加入聚酯多元醇或聚醚多元醇、亲水扩链剂、石墨烯水分散液，在真空条件下加热到90-120℃，搅拌1.5h去，充分除去原料中的水分；
b、停真空后立即通氮气，将四口瓶降温至60-80℃，加入配方量的二异氰酸酯反应3-5h；视体系粘度补充丙酮，测定NCO值，当测定的值与理论计算值接近时，停止反应；
c、停止通入氮气，继续搅拌，降温至30-40℃，加入中和剂反应10-20min，在剧烈搅拌下加入计算量的水，继续高速搅拌10-20min；
d、在搅拌条件下缓慢滴加小分子扩链剂的去离子水溶液，滴完后再搅拌30-50min，停止反应；然后低速搅拌30min，减压蒸脱丙酮，即制得石墨烯改性水性聚氨酯树脂。
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