低气味高透光率含硫改性UV固化硅树脂的研制  

Development of Sulphur Modified UV Silicone Resin with Low Odor and High Refractive Index

作　　者：欧阳冲 向洪平 刘晓暄 刘珠 肖定书 刘国聪 卢明 强娜 丁小卫 陈康辉 张祥龙 OUYANG Chong;XIANG Hong-ping;LIU Xiao-xuan;LIU Zhu;XIAO Ding-shu;LIU Guo-cong;LU Ming;QIANG Na;DING Xiao-wei;CHEN Kang-hui;ZHANG Xiang-long(Research Institute of Daya Bay Chemical Engineering,Huizhou University,School of Chemistry and Materials Engineering,Huizhou University,Technology Development Center of Advanced Materials Surface Interface,Guangdong Province,Team of Advanced Material Coating and Surface Interface Technology,Research Center of Advanced Coating Material Engineering Technology,Huizhou 516007,Guangdong;不详;Shenzhen Anpin Silicone Material Co.Ltd.,Shenzhen 518000,Guangdong)

机构地区：[1]惠州学院大亚湾化工研究院,惠州学院化学与材料工程学院,广东省先进材料表界面工程技术开发中心,广东省教育厅先进材料涂层与表界面技术开发团队,惠州市先进涂层材料工程技术研究中心,广东惠州516007 [2]广东工业大学材料与能源学院,广东省功能软凝聚态物质重点实验室,广州510006 [3]深圳市安品有机硅材料有限公司,广东深圳518000

出　　处：《有机硅材料》2021年第5期1-10,20,共11页Silicone Material

基　　金：国家自然科学基金(21604014,51162026);惠州市科技计划(2017X0202012);大亚湾科技计划项目(2020020001);惠州学院博士启动项目(2020JB051)。

摘　　要：以γ-巯丙基三乙氧基硅烷、二苯基二甲氧基硅烷、1,3-二噻戊环-2-基甲醇及六甲基二硅氧烷等为原料,三氟甲烷磺酸为催化剂,二氯乙酸为环硫稳定剂,通过水解-缩聚法制得不同结构的含硫改性巯基MDT硅树脂(MDT-DS),通过红外光谱、核磁共振波谱及凝胶渗透色谱对其结构进行了表征,并对其气味、黏度、密度、折射率和可见光透过率进行了测试。然后将MDT-DS、乙烯基硅油和光引发剂混合均匀后经紫外光固化制得固化物,并研究了其光固化动力学、力学性能、热稳定性和透光率。结果表明,成功制得了MDT-DS,且当有机取代基与硅原子的量之比(R/Si值)为1.61、巯基含量为0.3871 mol/100 g时,MDT-DS的摩尔质量分布系数为1.15,产率为93.16%,折射率为1.5685;此外,在2,4,6-三甲基苯甲酰基膦酸乙酯质量分数为0.80%、辐照强度为70 mW/cm 2的条件下,选用R/Si值为1.61的MDT-DS且巯基与乙烯基量之比为1.5∶1时,硅树脂可在40 s内快速固化,双键转化率为94.60%,固化物的拉伸强度为2.41 MPa,拉断伸长率为87.71%,最大热分解速率时的温度为416.30℃,玻璃化转变温度为85.05℃,可见光透过率高于95%。The sulphur-modified MDT silicone resins(MDT-DS)have been synthesized by hydrolysis polycondensation withγ-(methacryloyloxy)-propyltrimethoxysilane,diphenyldimethoxysilane,1,3-dithiolan-2-ylmethanol and hexamethyldisiloxane,triflic acid as catalyst and dichloroacetic acid as epithio-stabilizer.Their structures were characterized by Fourier transform infrared spectroscopy,nuclear magnetic resonance spectroscopy and gel permeation chromatography.Then the silicone resin has been analyzed its odour,viscosities,densities,refractive index and visible light transmittance.Then MDT-DS,vinyl silicone oil and photoinitiator have been mixed uniformly and cured by ultraviolet light to get a cured MDT-DS,and its photocuring kinetics,mechanical properties,thermal stability and light transmittance are studied.The results show that MDT-DS is prepared successfully,at R/Si value of 1.61 and thiol content of 0.3871 mol/100 g,MDT-DS has a yield of 93.2%,with PDI of 1.15 and the refractive index of 1.5685.In addition,when the mass fraction of ethyl in 2,4,6-trimethylbenzoylphosphonate is 0.80%and the irradiation intensity is 70 mW/cm 2,the MDT-DS with R/Si value is 1.61,and the molar ratio of thiol group to vinyl is 1.5∶1,the silicone resin can be cured quickly within 40 s,the double bond conversion rate is 94%,the tensile strength of the cured MDT-DS is 2.41 MPa,the elongation at break is 87.71%,the temperature at the maximum thermal decomposition rate is 416.30℃,the glass transition temperature is 85.05℃,and the visible light transmittance is higher than 95%.

关 键 词：紫外光固化 水解-缩聚法 含硫改性MDT硅树脂 巯基-烯光聚合 高折射率 低气味 

分 类 号：TQ324.21[化学工程—合成树脂塑料工业]