表面修饰GO改性无胺型水性聚氨酯-丙烯酸酯乳液制备与性能

doi:10.16085/j.issn.1000-6613.2019-1120

化工进展 ›› 2020, Vol. 39 ›› Issue (4): 1389-1395.DOI: 10.16085/j.issn.1000-6613.2019-1120

表面修饰GO改性无胺型水性聚氨酯-丙烯酸酯乳液制备与性能

赖小娟^1,²(),张引引¹(),刘佳慧¹,王磊^1,²

^1.陕西科技大学陕西省轻化工助剂重点实验室，陕西西安 710021
^2.陕西农产品加工技术研究院，陕西西安 710021

收稿日期:2019-07-15 出版日期:2020-04-05 发布日期:2020-04-28
通讯作者: 张引引
作者简介:赖小娟（1984—），女，博士，教授，研究方向为功能高分子材料的合成和油田化学品。E-mail：3578466@163.com。
基金资助:
陕西省青年科技新星项目(2018KJXX-023);西安市科技计划(201805024YD2CG8)

Preparation and properties of surface modified GO modified amine-free waterborne polyurethane-acrylate emulsion

Xiaojuan LAI^1,²(),Yinyin ZHANG¹(),Jiahui LIU¹,Lei WANG^1,²

^1.Shaanxi Key Laboratory of Chemical Additives for Industry, Shaanxi University of Science and Technology, Xi’an 710021, Shaanxi, China
^2.Shaanxi Research Institute of Agricultural Products Processing Technology, Xi’an 710021, Shaanxi, China

Received:2019-07-15 Online:2020-04-05 Published:2020-04-28
Contact: Yinyin ZHANG

摘要/Abstract

摘要：

以异佛尔酮二异氰酸酯（IPDI）、聚己内酯二元醇（PCL）、甲基丙烯酸甲酯（MMA）为主要原料，合成水性聚氨酯-丙烯酸酯乳液（WPUA）预聚体，利用十二烷基三甲基溴化铵对氧化石墨烯进行插层改性，改性产物与预聚体进行机械共混，同时引入羧酸型亲水扩链剂和磺酸型亲水扩链剂，采用自乳化法合成无溶剂、零VOC型改性的水性聚氨酯-丙烯酸酯复合乳液（DTGO/WPUA），研究改性氧化石墨烯（DTGO）用量，并对复合乳液和胶膜进行测试和表征。研究结果表明：DTGO复合材料改性水性聚氨酯涂料表现出较好的力学性能和耐热性。当DTGO用量为质量分数0.8%时，相比未改性的水性聚氨酯胶膜，复合胶膜拉伸强度提高到48.5MPa，热分解温度提高21℃。

关键词: 水性聚氨酯-丙烯酸酯, 氧化石墨烯, 插层改性, 机械共混, 热分解

Abstract:

A waterborne polyurethane-acrylate emulsion (WPUA) prepolymer was synthesized using isophorone diisocyanate (IPDI), polycaprolactone diol (PCL) and methyl methacrylate as main raw materials. The graphene oxide was intercalated with dodecyltrimethylammonium bromide to mechanically blend the modified product with the prepolymer, and the carboxylic acid type hydrophilic chain extender and the sulfonic acid type hydrophilic group were simultaneously introduced. The self-emulsification method was used to synthesize solvent-free, zero VOC-modified waterborne polyurethane-acrylate composite emulsion (DTGO/WPUA), and then the amount of modified graphene oxide (DTGO) was studied, and the composite emulsion and film were tested and characterized. The results indicated that the DTGO composite modified waterborne polyurethane coatings showed good mechanical properties and heat resistance. When the amount of DTGO was 0.8%, the tensile strength of the composite film was increased to 48.5MPa compared to the unmodified waterborne polyurethane film, and the thermal decomposition temperature was increased by 21℃.

Key words: waterborne polyurethane-acrylate, graphene oxide, intercalation modification, mechanical blending, thermal decomposition

中图分类号:

TQ323.8

赖小娟,张引引,刘佳慧,王磊. 表面修饰GO改性无胺型水性聚氨酯-丙烯酸酯乳液制备与性能[J]. 化工进展, 2020, 39(4): 1389-1395.

Xiaojuan LAI,Yinyin ZHANG,Jiahui LIU,Lei WANG. Preparation and properties of surface modified GO modified amine-free waterborne polyurethane-acrylate emulsion[J]. Chemical Industry and Engineering Progress, 2020, 39(4): 1389-1395.

图/表 10

图1 DTAB改性氧化石墨烯反应路线

图2 DTGO/WPUA复合涂料反应路线

图3 GO、DTGO、WPUA、0.8%DTGO/WPUA的红外光谱图

表1 DTGO/WPUA复合乳液的稳定性

编号	乳液外观	贮存稳定性（＞30d）	胶膜状态
DTGO/WPUA-0%	透明蓝光	稳定	光滑平整、柔软
DTGO/WPUA-0.3%	浅黑	稳定	光滑平整、柔软
DTGO/WPUA-0.6%	浅黑	稳定	光滑平整、稍硬
DTGO/WPUA-0.8%	浅黑	稳定	光滑平整、较硬
DTGO/WPUA-1%	浅黑出现沉淀	不稳定	不成膜

图4 不同DTGO含量的DTGO/WPUA复合乳液粒径分布曲线

图5 WPUA、DTGO/WPUA乳液TEM图及胶膜SEM图

图6 GO、DTGO、WPUA和DTGO/WPUA的XRD谱图

图7 不同DTGO质量分数复合胶膜的力学性能

图8 不同DTGO质量分数胶膜的TG曲线

图9 不同DTGO质量分数胶膜的接触角

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表面修饰GO改性无胺型水性聚氨酯-丙烯酸酯乳液制备与性能

Preparation and properties of surface modified GO modified amine-free waterborne polyurethane-acrylate emulsion

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