【作者】 甘禄铜；

【导师】 张军营；

【作者基本信息】 北京化工大学 ， 材料科学与工程， 2011， 硕士

【摘要】 聚硅氧烷树脂可以通过硅羟基缩合及硅氢加成反应进行交联固化,同时固化产物具有优良的耐高低温性能和弹性的可调节性,广泛用于粘接、密封领域,在航天、电子等领域是不可或缺的材料。研究和开发有机硅材料的新固化方式是有机硅开发的重要方向之一。本论文通过结构设计,合成具有双固化特点的新型官能化聚硅氧烷树脂(ATPS),综合了紫外光固化技术快速固化和湿气固化方便的特点,同时解决了紫外光固化存在的阴影及湿固化定位速度慢的难题,扩展了有机硅材料的应用。因此,研究新型官能化聚硅氧烷树脂(ATPS)不仅具有重要的现实应用意义,而且对新型紫外光固化预聚物的研发具有指导意义。本论文研究了各种反应条件及原料配比对合成反应的影响,同时采用IR、1H-NMR、13C-NMR、29Si-NMR等方法研表征了树脂的结构,通过平板-小刀法、实时红外(RTIR)等方法对双固化机理进行了考察,用DSC、TG方法研究了树脂双固化物的热性能。主要工作如下：1.设计反应路线,由端羟基聚二甲基硅氧烷与甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)通过脱醇缩合反应得到端甲基丙烯酰氧基烷氧基的线形有机硅长链分子(ATPS),并且建立了实现这种反应路线所需的工艺体系。2.通过IR、NMR等手段表征了ATPS树脂,从结构上确定了其具备双固化特性,且证明了该树脂结构为线形长链聚合物。3.研究了ATPS的双固化行为,结果表明,在紫外光固化过程中,光引发剂添加量、光照强度、光引发剂种类均受与双固化预聚物相容性影响；在湿气过程中,通过测定湿气固化过程的凝胶时间,经Arrhenius公式推导计算,在28%相对湿度的环境测试下,双固化预聚物的湿气固化反应表观活化能为23.2kJ/mol,频率指数lnA=-5.466。4.考察了通过添加胺类促进剂和加入活性含硅稀释剂两种提高ATPS树脂光固化速率的方法,结果表明,胺类促进剂在该体系中自身的阻聚作用强于对氧阻聚的抑制作用,而使光固化速率降低；活性含硅稀释剂的加入能在一定程度上加快光固化速率。5.研究了双固化树脂固化后的热力学性能,通过DSC测试双固化物的玻璃化转变温度Tg为-81.4℃,TGA测试该固化物的热失重10%的温度为427.8℃,经过公式推算,可以得出其热分解活化能为129.3kJ/mol。6.设计反应路线,将光引发剂1173与侧基为氢基的线形有机硅长链分子(PMHS)进行脱氢取代反应,合成了侧基含有光引发剂基团的长链聚硅氧烷树脂。相容性实验表明,其与ATPS树脂的相容性较好。更多还原

【Abstract】 Polysiloxane resin can be cured by condensation of Si-OH or hydrosilylation, and their cured product has excellent resistance, high and low temperature performace and adjustable flexibility. They are widely used in the area of bonding and sealing, which become essential materials in the aerospace, electronics and other fields. Research and development of the new curing method is an important direction in the area of silicone materials. The functionalized polysiloxane resin (Acrylate and alkoxy-terminated polysiloxane, ATPS) was designed and synthesized, which combined fast curing of UV curing technology and convenient moisture curing. The problems of the existence of the shadow in the UV curing and slow positioning in the moisture curing were solved by the synthesis of ATPS, which extending the application of silicone materials. Therefore, the study of the new functionalized polysiloxane resin (ATPS) has not only very important practical applications, but also has instructive development of UV curable prepolymer.In this thesis, the reaction conditions and raw materials ratio on the synthesis were investigated, the structure of the resin was characterized by IR,1H-NMR,13C-NMR and 29Si-NMR. The dual cure mechanisms were studied by real-time infrared (RTIR) and plane-knife method, and also thermal properties were considerred by DSC and TG.1. ATPS with acrylate and alkoxy-terminated groups was synthesized by transesterification reaction ofγ-(methacryloyloxy)propyltrimeth oxysilane with hydroxyl-terminated polydimethylsiloxane, and the reaction route system was also established.2. ATPS was characterized by IR and NMR, its characteristics of dual curing and long linear structure were proved and determined.3. Dual curing behavior of ATPS was studied, the addition of photoinitiator, light intensity and different photoinitiator types were influenced by the compatibility of dual-curing prepolymer in the UV curing process. In Moisture curing process, the gel time was measured, according to the formula of Arrhenius, the moisture curing apparent activation energy was 23.2kJ/mol, frequency index lnA=-5.466, which was tested at 28% relative humidity.4. Adding the amine accelerator and activity diluent to increased ATPS’ UV curing rate were investigated. The results showed that the amine accelerator in this system was its own inhibitor stronger than the inhibition of oxygen inhibition, leaving the curing rate decrease; By adding the Si-contained diluents, the curing rate can be accelerated at a certain extent.5. Thermal properties of dual curing product were studied by DSC and TG. The results show that the Tg was -81.4℃, the temperature of thermal decomposition of cured product 10% was 427.8℃. After the formula projections, the thermal decomposition activation energy was 129.3kJ/mol, which can be drawn from the projected formula.6. polysiloxane modified Photoinitiator was synthesized from polymethylhydrosiloxane(PMHS) by dehydrocoupling reaction. The experiments showed that the Si-contained photoinitiator had good compatibility with ATPS.更多还原