天然生漆液相界面结构与多相多组分漆酶催化聚合反应及漆膜结构性能关系研究

In this study, Chinese specialty resources lacquer sap was investigated by TEM, SEM, SAXS, and fluorescence microscopy to understand the distribution and arrangement of its compositions in the lacquer emulsion phase, and to determine the phase interfacial micro-environmental structure of the lacquer sap. Under not destroying its phase structure, lacquer sap was also modified by lacquer ingredients, the amphiphilic polymers and modified nanoparticles to study the phase interfacial micro-environmental structure's changes and investigate the structure-function relationships. Then, the multiphase-multicomponent laccase catalyzed polymerization process of lacquer sap during the drying was investigated by GPC, TLC, GC /MS, LC / MS, NMR and FT-IR, ESR and Py-GC/MS, and the effect of lacquer sap phase interfacial micro-environmental structure changes on the polymerization was studied to explore their relationships and film-forming mechanism. In addition, the drying, structure and performance of lacquer film was also investigated to clarify the relationship between film structure and properties. It is put forward the first that the multiphase and multicomponent laccase catalyzed polymerization process, the film structure and properties of lacquer sap are regulated through subtle changes in lacquer phase interfacial micro-environmental structure, for the purpose of design and development of lacquer coatings, promotion of lacquer resource utilization, and exploration of enzyme-catalyzed reaction in the complex system to provide the theoretical and practical basis.

本研究以中国特产资源生漆液为对象，以TEM、SEM、SAXS、荧光显微等技术研究生漆乳液各成份在生漆乳液各相中的分布和排列，确定生漆乳液相界面微环境结构，以及在不破坏生漆乳液相结构的前提下采用生漆成分、两亲高分子和纳米粒子等修饰生漆，研究生漆乳液相界面微环境结构的变化，考察构效关系，然后采用GPC、TLC、GC/MS、LC/MS、NMR、FT-IR、ESR和Py-GC/MS等手段研究生漆乳液多相多组分漆酶催化聚合反应过程，以及生漆乳液相界面微环境结构改变对聚合反应的影响，探究二者之间的关系和成膜机理；同时考察生漆的干燥成膜、膜结构及性能，阐明漆膜结构和性能之间的关系。本研究首次提出通过生漆相界面结构微环境的微调来改变或调控其多相多组分漆酶催化聚合反应过程及漆膜结构和性能的新的研究思路，为有目的设计开发生漆涂料,促进生漆资源利用以及探索复杂体系的酶催化反应提供理论和实践依据。

本研究针对中国特产资源生漆这一复杂体系，主要研究了生漆液的相结构及对生漆相结构的修饰。通过研究搞清了生漆液中组分漆酶、漆多糖、星青素和水不溶性糖蛋白在乳液相中的分布，获得了相界面结构的信息，建立了相结构模型；以均质的方法和修饰剂如多糖和表面活性剂修饰生漆，探索了生漆相界面微环境的变化，初步建立了探索相界面微环境的方法，获得了部分多糖和表面活性剂等引起相界面微环境变化和生漆乳液性能之间的关系，同时也初步阐明了生漆中漆多糖和微量星青素在生漆成膜过程中的作用，这些为仿生生漆和其他水性合成涂料的开发提供了理论支撑。采用多糖、表面活性剂、热预聚生漆及各种纳米粒子对生漆进行修饰，研究了这些修饰剂存在下的生漆酶催化聚合干燥机理，搞清了这些修饰对生漆及其漆膜性能的影响以及漆膜结构和性能之间的关系，也研究了生漆纯氧气氛中的预聚合和生漆相反转的对生漆和漆膜结构性能的影响，这些为有目的解决生漆应用的瓶颈问题，改善生漆性能提供了新的思路。此外，以少量的生漆成分漆酚对丙烯酸酯乳液的进行修饰，制备获得了线型桥架聚合物粒子，大大提升了乳液的性能，拓展了生漆成分的用途。