脂环族环氧官能化十字型MDQ硅树脂的合成及UV固化性能研究  

Synthesis and UV Curing Properties of Cycloaliphatic Epoxy Functionalized Cross-type MDQ Silicone Resins

作　　者：蔡亮 夏远乾 金晨 呼雪 许银根 陈昱 张瑞 瞿志荣[1,2] 董红 伍川[1,2] CAI Liang;XIA Yuanqian;JIN Chen;HU Xue;XU Yingen;CHEN Yu;ZHANG Rui;QU Zhirong;DONG Hong;WU Chuan(College of Material,Chemistry and Chemical Engineering,Key Laboratory of Organosilicon Chemistry and Material Technology,Ministry of Education,Hangzhou Normal University,Hangzhou 311121,China;Collaborative Innovation Center for Fluorosilicon Fine chemical and Materials Manufacturing,Hangzhou 311121,China;Ningbo Runhe High-tech Materials Co.,Ltd.,Ningbo 315600,China)

机构地区：[1]杭州师范大学材化学院,有机硅化学及材料技术教育部重点实验室,浙江杭州311121 [2]氟硅精细化学品与材料制造协同创新中心,浙江杭州311121 [3]宁波润禾高新材料科技股份有限公司,浙江宁波315600

出　　处：《塑料工业》2023年第11期34-42,共9页China Plastics Industry

基　　金：宁波市重大科技任务攻关项目(2021Z074)。

摘　　要：以α-二甲基氢基-ω-硅醇锂封端的聚二甲基硅氧烷(HSiOLi)为原料,四氯化硅(SiCl_(4))为止链剂,在四氢呋喃(THF)促进剂的作用下通过缩聚反应先制备得到端氢封端的十字型MDQ硅树脂(H-PDMS),再将H-PDMS与1,2-环氧-4-乙烯基环己烷(VCHO)在铂的乙烯基络合物催化剂作用下发生硅氢加成反应制备得到十字型脂环族环氧官能化MDQ硅树脂(VCHO-PDMS),通过核磁共振波谱(NMR)、傅里叶红外光谱(FTIR)以及凝胶渗透色谱(GPC)等手段对改性硅树脂的结构进行了表征。对合成的脂环族环氧官能化MDQ硅树脂进行UV固化实验,探究了光引发剂用量、脂环族环氧基含量以及有机硅含量等因素对硅树脂材料性能的影响。结果表明,当UV光照时间为20 s、光引发剂质量分数为2%时,制备得到的固化树脂材料的综合性能良好,凝胶率大于70%,吸水率小于4.7%,水接触角大于100°,5%失重温度大于320℃,玻璃化转变温度(T_g)为-100℃左右,铅笔硬度值为HB左右。A series of cross-type hydrogen-terminated MDQ silicone resins had been prepared by means of condensation reaction conducted betweenα-dimethylhydrogen-ω-lithium siliconate end-capped polydimethylsiloxane(HSiOLi)and silicon tetrachloride(SiCl_(4))in presence of THF.Cross-type cycloaliphatic epoxy group functionalized MDQ silicone resins(VCHO-PDMS)were then prepared by hydrosilylation reaction of H-PDMS and 1,2-epoxy-4-vinylcyclohexane(VCHO)under the catalysis of platinum vinyl complex.The structure of the modified silicone resin was characterized by nuclear magnetic resonance spectroscopy(NMR),Fourier transform infrared spectroscopy(FTIR)and gel permeation chromatography(GPC).Ultraviolet(UV)curing experiments were carried out on the synthesized cycloaliphatic epoxy-functionalized MDQ silicone resins,and the effects of factors,such as,the amount of photo initiator,the contents of cycloaliphatic epoxy group and the contents of silicone on the properties of the modified silicone resin material were explored.The results indicate when the UV irradiation time is 20 s and the amount of photo initiator is about 2%,a cured resin material with the excellent comprehensive performance could be achieved with a gel rate greater than 70%,the water absorption rate less than 4.7%,the water contact angle greater than 100°,the 5%weight loss temperature greater than 320℃,the glass transition temperature Tg at about-100℃,and the pencil hardness value about HB.

关 键 词：端氢树脂 环氧树脂 缩聚反应 硅氢加成 UV阳离子固化 

分 类 号：TQ323.5[化学工程—合成树脂塑料工业]