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第 36 卷第 6 期 精 细 化 工 Vol.36, No.6
201 9 年 6 月 FINE CHEMICALS June 2019

橡塑助剂
有机硅丙烯酸酯改性水性聚氨酯的合成与性能

刘信胜 1,2,3 ，刘伟区 1,2* ，石红义 1,2,3 ，刘春华 1,2,3 ，王政芳 1,2

（1. 中国科学院广州化学研究所，广东 广州 510650；2. 中国科学院纤维素化学重点实验室，广东 广
州 510650；3. 中国科学院大学，北京 101408）

摘要：以异佛尔酮二异氰酸酯（IPDI）、-氨丙基三乙氧基硅烷（KH550）、甲基丙烯酸甲酯（MMA）、-（甲基
丙烯酰氧基）丙基三甲氧基硅烷（KH570）为原料，分别合成了水性聚氨酯预聚体（WPU）、聚丙烯酸酯（PA）、
有机硅改性的水性聚氨酯预聚体（SiWPU）和有机硅改性的聚丙烯酸酯（SiPA），然后以 WPU、SiWPU、PA、
SiPA 为原料，采用互穿网络聚合法合成了有机硅-丙烯酸酯双重改性水性聚氨酯。通过测定吸水率和水接触角考
察了 PA、SiPA、SiWPU 含量对胶膜耐水性能的影响并分析了反应机理。结果表明：SiWPU-40%-SiPA-37.5%〔40%
为 SiWPU 的含量（以 WPU 和 SiWPU 总质量为基准，下同）；37.5%为 SiPA 占膜总质量百分数〕胶膜吸水率从
改性前样品 WPU 的 37.8%降低至改性后的 6.8%，接触角从 56.8°增至 86.4°，铅笔硬度从改性前的 2B 提升至 H。
热重分析显示，T max （样品热分解速率最大时的温度）从改性前的 340.2 ℃提升至 412.4 ℃；TEM 表明，改性
后的乳胶粒形成了核壳结构；XRD 和断面 SEM 显示，PA 和有机硅改性均增加了聚合物的交联度。
关键词：水性聚氨酯；双重改性；有机硅；互穿聚合物网络；核壳结构；橡塑助剂
中图分类号：TQ317 文献标识码：A 文章编号：1003-5214 (2019) 06-1241-08

Synthesis and Properties of Silicone Acrylate Modified
Waterborne Polyurethane

1,2
LIU Xin-sheng 1,2,3 , LIU Wei-qu 1,2* , SHI Hong-yi 1,2,3 , LIU Chun-hua 1,2,3 , WANG Zheng-fang
（1. Guangzhou Institute of Chemistry, Chinese Academy of Sciences, Guangzhou 510650, Guangdong, China; 2. Laboratory of
Cellulose and Lignocellulosics Chemistry, Chinese Academy of Sciences, Guangzhou 510650, Guangdong, China;
3. University of Chinese Academy of Sciences, Beijing 101408, China）

Abstract: Waterborne polyurethane prepolymer (WPU), polyacrylate (PA), silicone modified waterborne
polyurethane prepolymer (SiWPU) and polyacrylate (SiPA) were synthesized using isophorone diisocyanate
(IPDI), γ-aminopropyltriethoxysilane (KH550), methyl methacrylate (MMA) and γ-(methacryloyloxy)
propyltrimethoxysilane (KH570) as main raw materials. Then, silicone acrylate double modified waterborne
polyurethane (SiWPUA) emulsions were synthesized by interpenetrating network polymerization using
WPU, SiWPU and SiPA as raw materials. The effects of PA addition amount, SiPA addition amount and
SiWPU addition amount on the water resistance of the emulsion films were investigated by measuring
water absorption rate and water contact angle and the mechanism was analyzed. The results showed that the
water absorption rate of SiWPU-40%-SiPA-37.5%(40% is the content of SiWPU based on the total mass of
WPU and SiWPU, the same below, and 37.5% is the mass fraction of SiPA in the system) film was reduced
from 37.8% before modification to 6.8%, the contact angle was increased from 56.8° to 86.4°, and pencil
hardness was increased from 2B to H. Thermogravimetric analysis demonstrated that the T max (the
temperature at which the decomposition reaction occurs) of SiWPU-40%-SiPA-37.5% was 412.4 ℃,
higher than that of WPU (340.2 ℃). TEM results revealed that the modified latex particles had a core-shell
structure. SEM of film section and XRD results showed that both PA and silicone modification increased
the crosslinking degree of the polymer.

收稿日期：2018-11-16; 定用日期：2019-02-21; DOI: 10.13550/j.jxhg.20180850
基金项目：广东省应用型科技研发专项资金项目（2015B09090019）
作者简介：刘信胜（1991—），男，硕士生。联系人：刘伟区（1963—），男，研究员，电话：020-85231269，E-mail：liuwq@gic.ac.cn。