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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
桐油基光引发剂的制备及性能
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李翠华,周宏勇,王家喜
(河北工业大学 化工学院,天津 300130)
摘要:以桐油(TO)、桐酸(TA)和马来酸酐(MA)为原料,经 Diels-Alder 反应,得到桐油酸酐(TOM1~3)
及桐酸酸酐(TAM)。在三乙胺催化下,TOM、TAM 分子中酸酐分别与 Irgacure2959〔2-羟基-4-(2-羟乙氧基)
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-2-甲基苯丙酮〕的羟基反应,合成了 4 种裂解型光引发剂(TOMG1~3,TAMG)。用 FTIR、 HNMR 及 HRMS
表征了其结构,利用 UV-vis 考察了引发剂的光分解过程,用实时红外光谱探究了引发剂引发 1,6-己二醇二丙
烯酸酯(HDDA)的聚合过程。结果表明,在 Irgacure2959 和桐油改性的几种光引发剂中,TOMG3 光引发性能最
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优。在紫外光强度为 28 mW/cm 的光照下,以 HDDA、PUA(聚氨酯丙烯酸酯)及 TOMG3 按质量比 46 : 46 : 8
复配的胶液的光固化表干时间为 60 s,凝胶率为 96%,固化膜的硬度及柔韧性分别为 6H 和 5 mm,对玻璃的附
着力为 0 级。
关键词:桐油;Diels-Alder;光引发剂;自由基聚合;紫外光固化;功能材料
中图分类号:O632.12 文献标识码:A 文章编号:1003-5214 (2019) 01-0012-07
Preparation and Properties of Tung Oil-based Photoinitiators
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LI Cui-hua, ZHOU Hong-yong, WANG Jia-xi
(School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China)
Abstract: Tung oil anhydrides (TOM1~TOM3) and tung acid anhydride (TAM) were synthesized from
tung oil (TO) and tung acid (TA) with maleic anhydride (MA) via the Diels-Alder reaction. Then, the
obtained compounds reacted with the hydroxyl groups of 2-hydroxy-4-(2-hydroxyethoxy)-2-
methylpropiophenone (Irgacure2959) to produce four cleavage photoinitiators (TOMG1~TOMG3, TAMG)
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in the presence of catalytic amount of triethylamine. Theses initiators were characterized by FTIR, HNMR
and HRMS spectroscopy. Their decomposition processes were investigated by UV visible spectroscopy. The
photopolymerization dynamics of 1, 6-hexanediol diacrylate (HDDA) initiated photoinitiators were studied
using real-time FTIR technology. The results showed that initator TOMG3 had the best photoinitiation
performance among Irgacure 2959 and the tung oil modified photoinitiators. The mixture of HDDA, PUA
(polyurethane acrylate) and TOMG3 in a mass ratio of 46 : 46 : 8 could be cured within 60 s under
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ultraviolet light irradiation with an intensity of 28 mW/cm , and the gelation rate reached 96%. The
hardness, flexibility and adhesion to glass of the cured film was 6H, 5 mm, grade 0, respectively.
Key words: tung oil; Diels-Alder; photoinitiator; radical polymerization; UV curing; functional materials
为促进工业可持续发展并减轻日益严峻的环境问 子中的共轭三烯结构,将马来酸酐、马来亚酰胺等
题,可再生资源的使用越来越受到人们的重视 [1-3] 。 基团引入到桐油分子上,制得了热固性、光固性甚
桐油作为储量丰富的可再生资源,可以直接作为添 至生物学特性的功能单体,从而拓宽了桐油的应用
加剂加入清漆、涂料等相关材料中使用,但所得产 范围,提高桐油产品附加值的研究已成为桐油综合
品附加值低,应用领域较窄。近年来,利用桐油分 应用的重要方向 [4-10] 。
收稿日期:2018-01-31; 定用日期:2018-05-24; DOI: 10.13550/j.jxhg.20180093
作者简介:李翠华(1991—),女,硕士生。联系人:王家喜(1965—),男,教授,博士生导师,电话:022-60200441,E-mail:
wangjiaxi@hebut.edu.cn。