松香基聚氨酯微球构建及功能化研究

Polyurethane (PU) microspheres possess excellent adsorption, ion exchange and chelation, and are prepared with oil-based products. . Natural renewable resource rosin is used as the raw material for this project. After it is modified by acrylic acid, rosin can be esterified with glycidyl methacrylate (GMA), thus a rosin-based polyester diol (RAG) containing hydroxyl groups and double bonds is obtained which reacts with diisocyanate and chain extender to prepare a rosin-based polyurethane resin with suspending double bonds. Based on the study of oily and waterborne rosin-based polyurethane resins, hydrophilic and hydrophibic rosin-based polyurethane microspheres will be prepared by different polymerization methods through self-polymerization or copolymerization with other monomer, including porous microspheres, surface hydrophilic microspheres, molecular-imprint microspheres and organicsilica modified microspheres. The effects of raw material composition, preparation and modification methods on the composition, structure and properties of the polyurethane microspheres are investigated. The structure and properties of the bio-based polyurethane microspheres are optimized. Thus the polyurethane microspheres with excellent comprehensive properties are controlled prepared. The products will be widely used in the field of drug release, ion adsorption, coating and ink. This project will provide a theoretical basis for the development of new high value-added rosin products, expanding the application scope of the polyurethane microspheres.

聚氨酯微球具有良好的吸附、离子交换、螯合等特性，通常采用石油产品为主要原料制备。本项目利用天然可再生资源松香为主要原料，经丙烯酸改性得到丙烯酸松香，然后与甲基丙烯酸缩水甘油酯进行酯化反应，得到含有羟基和双键的松香酯多元醇，再与二异氰酸酯和扩链剂反应制备含有悬挂双键的生物基聚氨酯树脂，在此基础上，通过不同聚合方法自聚或共聚构建功能化的亲油性和亲水性的松香基聚氨酯微球，包括多孔微球、表面亲水的微球、分子印迹微球和有机硅改性微球，探索原料组成、制备方法和条件等对聚氨酯微球的结构、形态和性能的影响规律，优化生物基聚氨酯微球的结构和性能，实现微球功能化和粒径的可控，得到综合性能优良的生物基聚氨酯微球。产物将在药物释放、废水离子吸附、涂料和油墨等领域得到广泛应用。本项目研究将为开发新型高附加值松香产品，扩大聚氨酯微球的应用范围奠定理论基础。

松香是一种宝贵的天然可再生资源，含有三个六元环菲骨架结构，可用于合成结构均一的网状高分子材料。聚氨酯微球是一种新型的聚氨酯产品，由于微球的表面和内部有较多的褶皱和孔道，使其具有良好的吸附、离子交换等特点。本项目以松香为主要原料，通过改性得到含有两个羟基和双键的松香基二元醇，然后与二异氰酸酯反应制备了水性或溶剂性聚氨酯，通过双键自由基聚合制备了松香基功能性聚氨酯微球，探索了原料组成、制备条件等对聚氨酯及微球的结构、形态和性能的影响，并将产物应用于离子吸附、pH测定等。研究结果表明：（1）制备了松香基溶剂型聚氨酯，随着RAG含量的增加，聚氨酯的热稳定性、玻璃化转变温度升高，耐水性增强；有机硅的引入可改善聚氨酯涂膜的光泽度、硬度和耐水性。（2）制备了松香基亲水性聚氨酯，随着R值增大，水性聚氨酯热稳定性降低，玻璃化转变温度升高，耐水性随着亲水扩链剂DMPA用量增加而逐渐降低；有机硅材料的引入，可以降低聚氨酯的表面能，增强聚氨酯的抑菌性能；荧光剂的引入，使聚氨酯具有荧光性能和紫外防护性能。（3）通过分散聚合法制备了松香基芳香族型亲水性聚氨酯微球，微球的平均粒径为120.0 nm，微球对金橙Ⅱ的吸附量为17.53 mg·g-1。（4）通过悬浮聚合法制备了松香基聚氨酯多孔微球，微球比表面积为 63.7 m2·g-1（BJH），孔容为0.200 cm3·g-1，孔径为12.7 nm。微球对苯酚的吸附量为24.53 mg·g-1。（5）通过悬浮聚合法制备了松香基聚氨酯印迹微球，其对BPA具备良好的选择识别能力，吸附后微球的形态没有改变。（6）通过悬浮聚合法制备了有机硅改性松香基聚氨酯微球和pH响应性聚氨酯微球，微球内部空心，表面多孔，具有疏水性，有机硅改性微球对刚果红溶液的吸附量为28.92 mg·g-1；pH响应性微球的酸碱缓冲体积为1.6 mL。（8）通过悬浮聚合法制备了松香基荧光聚氨酯微球，微球平均粒径为49.3 μm，荧光强度为3662 a.u.，具有较好的抗干扰性、可回复性，可用于溶液pH检测；对Fe3+的检测具有高选择性和低检测限，检测限为6.63 μM。