萜烯基聚硅氧烷改性水性聚氨酯的多层次结构对其性能的影响

As one of environmentally-friendly resin, waterborne polyurethane (WPU) has been widely concerned in all industry. The key approach to developing the application of it is the functional modification of WPU. In this project, Novel terpene based organic silane functional monomers will be prepared with terpene and its derivatives of distinctive forestry resource by hydrosilylation. Polysiloxane with side chain or main chain containing terpene structure will be prepared by chemical grafting. Moreover, the effective way of synthesis of waterborne polyurethane modified by polysiloxane containing terpene structure will be explored. The performances of modified WPU, including microstructure, thermal property and mechanical property will be investigated by means of Differential Scanning Calorimetry (DSC), Thermal Gravimetric Analysis (TG), Dynamic Mechanical Analysis (DMA), Scanning Electron Microscope (SEM), Atomic Force Microscopy (AFM), X-ray Photoelectron Spectroscopy (XPS) and other analysis instruments. It will focus on the relationship between different multilayer structure of terpene based polysiloxane and performances including mechanical properties, high temperature resistance, surface energy, water resistance of WPU in this proposal. The effects of different terpene ring structure on properties of terpene based WPU, such as hardness, heat resistance, mechanical property and so on, will also be studied. This project can provide theoretical guidance for the development and innovation of biomass-based WPU, as well as open up a new way for the high value utilization of turpentine.

水性聚氨酯作为环保型树脂，已受到各行业广泛关注，而通过功能化改性提高应用性是其发展的关键。本项目以生物质资源松节油及其衍生物为原料，利用硅氢加成反应设计、合成一系列新型萜烯基有机硅烷功能性单体，制备主链或侧链含有萜烯基结构单元的聚硅氧烷。深入研究萜烯基聚硅氧烷改性水性聚氨酯的有效途径，利用差示扫描量热（DSC）、热重分析（TG）、动态热机械分析（DMA）、扫描电镜（SEM）、原子力显微镜（AFM）、X射线光电子能谱（XPS）等对其微观结构、热学性能及力学性能等进行表征，重点研究萜烯环结构对水性聚氨酯不同层次结构的影响机制，探索萜烯基聚硅氧烷改性水性聚氨酯的多层次结构对其力学性能、耐高温性能、表面能、耐水性等性能的影响规律，为新型水性聚氨酯的开发提供理论指导，同时也为松节油的高值化利用开辟新的途径。

水性聚氨酯是高分子材料行业的重要产品之一，水性聚氨酯虽然可以降低VOC的排放，但是由于亲水基团的引入，使得水性聚氨酯的力学性能、耐水性和耐候性明显减弱。因此，研究高品质水性聚氨酯的改性方法，以满足产业需求是急需解决的关键问题。松节油为我国的特色生物质资源，本项目以松节油为原料，将其特有的单环、双环及三环结构与有机硅烷进行结合，制备了多种松节油改性有机硅烷化合物，并深入研究了松节油衍生物丙烯酸异冰片酯改性聚硅氧烷对水性聚氨酯热稳定性、机械性能、耐水性等性能的影响；探讨了丙烯酸异冰片酯和甲基丙烯酸异冰片酯在水性聚氨酯体系中的分散行为，及其作为光固化组分对水性聚氨酯力学性能、热稳定性、耐水性等性能的影响；同时进一步讨论了松节油主要成分α-蒎烯、β-蒎烯、双戊烯与含氢硅烷的硅氢加成反应条件，以及松节油刚性结构和聚硅氧烷柔性链段对聚合物网络结构和材料性能的影响。通过本项目的研究，获得了一种松节油及其衍生物与有机硅烷基于硅氢加成反应的高效结合技术，成功制备了多种松节油改性有机硅烷，并实现了松节油改性聚硅氧烷在制备高性能水性聚氨酯中的应用，改性后的水性聚氨酯水接触角从74.7°提高到102.1°，拉伸强度提高了47%。松节油改性聚硅氧烷有效提升了水性聚氨酯的力学性能、热稳定性和耐水性，初步解决了聚氨酯水性化导致的材料性能缺陷问题，丰富了高性能水性聚氨酯制备方法，也进一步拓展了林业生物质资源松节油及其衍生物的高值、高效利用。