异海松酸UV光固化产物组成、性能与形成机理研究

With a deeper development of study on the refinery and purification of resin acids from rosin, the isolation and fine utilization of major resin acids, and so on, it becomes possible to exploit the new usage in the fields such as a new-type UV-curing materials of pimaric type acids, which is essentially different from traditional way on usage of rosin, while keeping the dominant characters of rosin. Based on the achievement of the accomplished foundation project and the latest developments, this project will focus on studying the constituents and their distibution of the UV-cured products from isopimaric acid as well as methyl and allyl isopimarate, according to some significant discoveries such as that exocyclic vinyl group may occur UV-curing reaction, that there is not UV-responsivity on the UV-cured product, and that the HPLC with Evaporative Light-Scattering Detector (HPLC-ELSD) would be applied on detecting solid materials. Based on an initially establishment of the new technology for tracing UV-curing reaction of isopimaric acid and for detecting constituents of the UV-cured products, the project will also further explain the mechanism of UV-curing reaction of pimaric type acid by isolation, purifying, and identifying the key constituents. And then the preparation method, the application performance, and the application technology of UV-cured products of pimaric type acids will be explored. This project will lay a massy theoretical and practical foundation for utilization of slash pine (Pinus elliottii Engelm) rosin with reasonability, high efficiency, and high value. It also has a significant directive function for developing utilization approach of new UV-curing materials of pimaric type acids.

随着松香树脂酸提纯精制、主要树脂酸单离与精细利用等研究工作的展开与深入，在保持松香优势特性基础上开发与传统松香利用方式具有本质区别的海松酸型树脂酸成分在诸如光固化新材料等领域中的新兴用途成为可能。本项目将在已完成基金项目取得成果及最新进展基础上，依据树脂酸分子中环外乙烯基可发生UV光固化反应、固化产物缺乏UV响应性能、蒸发光检测技术可用于检测固化产物等重要发现，在初步建立了跟踪检测和研究异海松酸光固化反应及产物组成变化新技术方法的基础上，着重研究异海松酸及主要改性物UV光固化产物的组成及其分布，通过关键组分的分离、纯化与鉴定，进一步阐明海松酸型树脂酸的UV光固化反应机理。进而探索海松酸酸型树脂酸及改性物的UV光固化产物制备方法、应用性能与应用技术。本项目研究将为合理、高效、高附加值利用湿地松松香奠定坚实的理论和应用基础，对开发海松酸型树脂酸的UV光固化新材料利用途径具有重要指导作用。

松香是我国重要的天然资源，湿地松松香是其重要品种。湿地松松香中的重要成分异海松酸含有较活泼的环外乙烯基双键，分离纯化后可进行UV固化反应。探明异海松酸及其酯化衍生物的UV 光固化产物组成、分布特征、形成机理及应用性能，对异海松酸乃至湿地松松香资源的合理、高效、高附加值利用具有重要理论意义。.通过本项目研究取得了如下重要创新成果：.（1）研制了适用于UV光固化反应的石英反应器，解决了马口铁片薄膜反应制备效率低下的难题。.（2）探明了异海松酸及其甲基酯/烯丙基酯UV固化为自由基引发的低聚反应，封闭羧基使得UV固化反应时间延长，但是烯丙基化封闭可增大聚合度。通过设计合成羧基被封闭的异海松酸甲酯、引入1个活泼乙烯基的异海松酸烯丙酯、只含有1个活泼乙烯基的枞酸烯丙酯及含有两个活泼乙烯基的丙烯酸海松酸双烯丙酯等，对比研究了UV固化反应性能及组成分布差异特征。结果表明，异海松酸的羧基进行甲基封闭降低了UV光固化反应速度，异海松酸及其甲基酯由于空间位阻作用形成的主要是聚合度在2~3的低聚物。引入活泼乙烯基可显著提高UV光固化性能及产物聚合度，异海松酸烯丙酯形成以长链状为主体但分子间有一定交联度的、聚合度约为28的聚合物。.（3）探明了异海松酸及其甲酯化衍生物的UV光固化产物组成的组成及分布特征，即固化产物中以含二聚体和三聚体等低聚物为主，而较高聚合度的多聚体成分则比较少且分散，同时还含有少量空气氧化副产物。通过透析袋分离技术，获得到了分子量500～1000中间的异海松酸及其甲酯的UV固化产物中的二聚、三聚物质。通过制备型TLC结合透析袋分离技术，从异海松酸及其甲酯化衍生物的UV固化产物中得到并鉴定了7-羰基-8,15-异海松酸及7-羰基-8,15-异海松酸甲酯，进一步阐明其在发生UV光固化反应的同时还伴有空气氧化副反应的机理。.（4）制备所得异海松酸及其甲基酯/烯丙基酯改性产物的UV光固化产物具有较好柔韧性和热稳定性，初始热分解温度均高于200℃，玻璃化温度Tg在3.64℃（异海松酸甲酯聚合物）～50.72℃（异海松酸聚合物）之间。异海松酸及其衍生物有可能作为光固化反应预聚体应用于涂料、胶黏剂、油墨等。.（5）探索了异海松酸酰腙和异海松酰（胺）基硫脲两大类衍生物的生物活性，研究发现酰腙结构和酰氨基硫脲结构的引入，对赋予异海松酸抗癌活性具有一定的作用，酰基硫脲则没有作用。