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第 36 卷第 1 期 精 细 化 工 Vol.36, No.1
201 9 年 1 月 FINE CHEMICALS Jan. 2019

功能材料
对羟基苯甲酸-壳寡糖改性水性聚氨酯

任龙芳 1,2 ，赵永霞 1,2 ，郭旭东 1,2 ，强涛涛 1,2

（1. 陕西科技大学 轻工科学与工程学院，陕西 西安 710021；2. 轻化工程国家级实验教学示范中心 陕
西科技大学，陕西 西安 710021）

摘要：用对羟基苯甲酸（p-HBzA）对壳寡糖（OCS）进行接枝改性，得到了对羟基苯甲酸接枝壳寡糖
（p-HBzA-g-OCS）。将 p-HBzA-g-OCS 作为交联剂，与水性聚氨酯预聚体（PPU）聚合，合成了对羟基苯甲酸-
壳寡糖改性水性聚氨酯（HOCS-WPU）。通过 FTIR 和 UV-Vis 证实了样品的结构；分别用 DLS、力学性能分析、
XRD、TGA、ABTS 和 DPPH 自由基清除率对 HOCS-WPU 的性能进行了考察。结果显示：当加入质量分数为
2%的 p-HBzA-g-OCS（以合成 PPU 原料的总质量计）时，HOCS-WPU 乳液粒径较小，为 57.85 nm，相比未改
性 WPU，HOCS-WPU 胶膜的拉伸强度从 14.03 MPa 提高到 16.85 MPa，结晶度从 3.57%下降到 3.45%；初始分
解温度从 204.6 ℃提高到 216.7 ℃。自由基清除率测定结果显示：当 HOCS-WPU 的质量浓度为 2.5 g/L 时，该聚
合物的 ABTS 和 DPPH 自由基的清除率分别达到了 62%和 35%，抗氧化活性相比未改性 WPU 明显提高。
关键词：水性聚氨酯；对羟基苯甲酸；壳寡糖；抗氧化；功能材料
中图分类号：TQ323.8 文献标识码：A 文章编号：1003-5214 (2019) 01-0037-07

Modification of Waterborne Polyurethane by
p-Hydroxybenzoic Acid-Oligochitosan

1,2
1,2
1,2
1,2
REN Long-fang , ZHAO Yong-xia , GUO Xu-dong , QIANG Tao-tao
（1. College of Bioresources Chemical and Materials Engineering, Shaanxi University of Science and Technology, Xi'an
710021, Shaanxi, China; 2. National Demonstration Center for Experimental Light Chemistry Engineering Education,
Shaanxi University of Science and Technology, Xi'an 710021, Shaanxi, China）
Abstract: p-Hydroxybenzoic acid grafted oligochitosan (p-HBzA-g-OCS) was obtained by graft
copolymerization of p-hydroxybenzoic acid (p-HBzA) and oligochitosan (OCS). Then, it reacted with
polyurethane prepolymer (PPU) to produce p-HBzA-g-OCS modified waterborne polyurethane
(HOCS-WPU). The structure of the sample was confirmed by FTIR and UV-Vis. The properties were
analyzed by DLS, mechanical properties measurement, XRD, TGA and radical scavenging assay of ABTS
and DPPH. The results demonstrated that when the mass fraction of p-HBzA-g-OCS was 2% (based on the
total mass of raw materials for synthesis of PPU), the resulting HOCS-WPU emulsion showed smaller
particle size of 57.85 nm. Compared with those of unmodified WPU film, the tensile strength of
HOCS-WPU film increased from 14.03 MPa to 16.85 MPa, the crystallinity declined from 3.57% to 3.45%,
and the initial decomposition temperature increased from 204.6 ℃ to 216.7 ℃. The free radical scavenging
assay results showed that ABTS and DPPH radical scavenging assay of the polymer reached 62% and 35%
when the mass concentration of HOCS-WPU was 2.5 g/L. The antioxidant activity of HOCS-WPU was
significantly better than that of the unmodified WPU.
Key words: waterborne polyurethane; p-hydroxybenzoic acid; oligochitosan; antioxidant; functional materials
Foundation items: National Science and Technology Major Project of China (2017YFB0308500); Science
and Technology Planning Project of Shaanxi Province (2018JM5164)

收稿日期：2018-06-06; 定用日期：2018-09-12; DOI: 10.13550/j.jxhg.20180416
基金项目：国家重点研发计划项目（2017YFB0308500）；陕西省科技计划项目（2018JM5164）
作者简介：任龙芳（1981—），女，教授，博士，E-mail：renlf1010@163.com。