3D打印用光固化笼状硅树脂的分子设计、制备及混杂光固化机理研究

This project is continuously research and development basis about photo-curing 3D printing POSS precursor and dual curing mechanism by the National Fund Emergency Management Program (NO：51641302), with further usage of the organic-inorganic structural characteristics of photo curable precursor POSS with cage structure, the screw ring structure’s volume expansively of expansion monomer, and the interpenetrating network (IPN) structure built by hybrid photo-curing system, a library of new photosensitive silicon resin with cage structure are prepared. Its hybrid photo-curing mechanism, influence of expansion monomer and dynamic change of photo-curing are detailed studied. The photo-curing silicon resin with cage structure is further combined with the inorganic filler modified by photo-curable silane coupling agent, to build effective IPN and prepare 3D printing photosensitive resin with high precision and excellent mechanical performance. The research mainly focuses on the following aspects: the preparation and characterization of snail functional monomer with high expansion; the preparation of photo-curable POSS precursor modified by expansion monomer and the study of kinetics and mechanism of hybrid photo-curing; construction and morphology characterization of IPNs and multidimensional curing network structure; the study on the performance of inorganic fillers with photo-curable silane coupling agent and the building of reaction kinetics, product performance and network structure are effectively assisted by modern analytical techniques. Finally，effectively applied in the research and development of photo-curing 3D printing entity, which will have important theoretical value and application guidance significance for the breakthrough 3D printing function consumables.

本项目结合国家基金应急管理项目（NO：51641302）关于光固化3D打印POSS前驱体及双固化机理的研究基础，进一步利用笼状POSS光固化前驱体兼具有机-无机杂化结构、膨胀螺环单体的膨胀性以及混杂光固化体系构建的互穿网络（IPN）结构，制备出一系列新型笼状光固化硅树脂，并对其混杂光固化机理、膨胀单体的影响及动力学变化规律进行详细研究，并进一步与光固化硅烷偶联剂改性无机填料结合，构建有效的IPN制备出高精度及力学性能优越的3D打印光敏树脂。重点研究内容包括：膨胀效果较高的螺环类功能化单体制备及表征；膨胀单体改性光固化POSS前驱体的制备、混杂光固化动力学及机理的研究；IPNs及多维固化网络结构构建和形貌表征；光固化硅烷偶联剂处理无机填料的性能研究以及利用现代分析技术手段有效辅助各反应动力学、产物性能以及网络结构构建等，最后应用于光固化3D打印实体，对突破3D打印功能耗材具有重要的理论价值。

本项目结合国家基金应急管理项目（NO：51641302）关于光固化3D打印POSS前驱体及双固化机理的研究基础，进一步利用笼状POSS光固化前驱体兼具有机-无机杂化结构、膨胀螺环单体的膨胀性以及混杂光固化体系构建的互穿网络（IPN）结构，制备出一系列新型笼状光固化硅树脂，并对其混杂光固化机理、膨胀单体的影响及动力学变化规律进行详细研究，并进一步与光固化硅烷偶联剂改性无机填料结合，构建有效的IPN制备出高精度及力学性能优越的3D打印光敏树脂。重点研究内容包括：膨胀效果较高的螺环类功能化单体制备及表征；膨胀单体改性光固化POSS前驱体的制备、混杂光固化动力学及机理的研究；IPNs及多维固化网络结构构建和形貌表征；光固化硅烷偶联剂处理无机填料的性能研究以及利用现代分析技术手段有效辅助各反应动力学、产物性能以及网络结构构建等，最后应用于光固化3D打印实体，对突破3D打印功能耗材具有重要的理论价值。本项目执行期间，共发表论文30篇，其中SCI收录19篇，SCI JCR二区以上9篇（一区7篇l；二区2篇），获授权发明专利8件。培养博士研究生6人，硕士研究生12人。荣获2022年度广东省科技进步二等奖（第一完成单位），圆满地完成了本项目的各项预期成果和指标。