Page 97 - 《精细化工》2020年第7期

第 37 卷第 7 期 精 细 化 工 Vol.37, No.7
202 0 年 7 月 FINE CHEMICALS July 2020

功能材料
紫外光固化环氧聚硅氧烷树脂的制备与性能

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于昕仪 1,2 ，李小全 1,2 ，黄振祝 ，冯 超 ，林树东 1,2* ，胡继文 1,2*
（1. 中国科学院广州化学研究所 广东省电子有机聚合物材料重点实验室 中国科学院新型特种精细化学
品工程实验室，广东 广州 510650；2. 中国科学院大学，北京 100049）

摘要：以 1,2-环氧-9-癸烯和双侧氢封端的聚二甲基硅氧烷为反应物，在卡斯特催化剂〔铂(0)-1,3-二乙烯基-1,1,3,3-
四甲基二硅氧烷〕的催化下发生硅氢加成反应，成功制备了双端环氧基聚硅氧烷预聚物，并使用阳离子型光引
发剂对其进行紫外光固化，制得紫外光固化环氧聚硅氧烷树脂。对合成双端环氧基聚硅氧烷预聚物的反应条件
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进行优化。利用 FTIR 和 HNMR 对所合成预聚物的结构进行了表征，采用热失重分析、差示扫描量热法、接触
角、耐碱性、耐醇性、凝胶率、邵氏 A 硬度和断裂面微观形貌对固化膜的性能和形貌进行了测试与表征。结果
表明：在反应温度为 75 ℃、催化剂有效成分添加量为 0.009‰（以双端含氢聚硅氧烷和 1,2-环氧-9-癸烯的质量
和为基准，下同）条件下，8 h 时反应程度达 93.95%；当使用光引发剂 BL9380 用量为 3%（以预聚体质量为基
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准，下同）、固化时间为 20 s 时，制得的树脂表面自由能为 18.4~18.8 mJ/m ，耐碱性、耐醇性良好，凝胶率为
93.9%，邵氏 A 硬度为 37，空气气氛下两个最大分解速率的对应温度分别为 437.6 和 511.3 ℃，780 ℃下残炭
率为 13.9%，固化膜的综合性能较好。
关键词：紫外光固化；环氧基；聚硅氧烷；硅氢加成；涂料改性；功能材料
中图分类号：TQ322.41 文献标识码：A 文章编号：1003-5214 (2020) 07-1379-08

Preparation and properties of UV-curable epoxy-polysiloxane resin

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YU Xinyi , LI Xiaoquan , HUANG Zhenzhu , FENG Chao , LIN Shudong 1,2* , HU Jiwen 1,2*
（1. Guangdong Provincial Key Laboratory of Organic Polymer Materials for Electronics, CAS Engineering
Laboratory for Special Fine Chemicals, Guangzhou Institute of Chemistry, Chinese Academy of Sciences, Guangzhou
510650, Guangdong, China; 2. University of Chinese Academy of Sciences, Beijing 100049, China）
Abstract: Epoxy-siloxaneprepolymer was synthesized through hydrosilylation between 1,2-epoxy-9-
decene and hydrogen-terminated polydimethylsiloxane in the presence of a catalytic amount of Karstedt's
catalyst [platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane], then cured with cationic light initiator
under ultraviolet light to obtain UV-curable epoxy-polysiloxane resin. The reaction conditions for the
synthesis of the prepolymer were optimized. The structure of the synthesized prepolymer was characterized
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by FTIR and HNMR. The properties and morphology of the cured film were tested by TGA, DSC, contact
angle, alkali resistance and alcohol resistance, gel rate, Shore A hardness, and fracture surface morphology.
The results showed that under the conditions of reaction temperature 75 ℃, reaction time 8 h, dosage of
catalyst's active ingredient 0.009‰ (based on the total mass of hydrogen-terminated polydimethylsiloxane
and 1,2-epoxy-9-decene, the same below), the reaction degree was 93.95%. When the dosage of
photoinitiator BL9380 was 3% (based on the mass of the epoxy-siloxaneprepolymer, the same below), and
the curing time was 20 s, the cured resin had the best comprehensive performance. The surface activity
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energy was 18.4~18.8 mJ/m , the gel rate was 93.9%, and exhibited good dalkali resistance and alcohol
resistance with Shore A hardness of 37. The cured resins exhibited good thermal stability with
corresponding temperatures of maximum decomposition rate of 437.6 and 511.3 ℃ in air, and 13.9% of
carbon yield at 780 ℃.

收稿日期：2020-01-16; 定用日期：2020-02-10; DOI: 10.13550/j.jxhg.20200052
基金项目：国家自然科学基金（21404121）；广州市科技计划重点项目（201904020019）
作者简介：于昕仪（1996—），女，硕士生。联系人：林树东（1980—），男，硕士生导师，E-mail：linsd@gic.ac.cn；胡继文（1966—），
男，博士生导师，E-mail：hujiwen@gic.ac.cn。