松香基功能分离材料的合成及应用技术研究

本项目属林学学科林产化学与加工领域。松脂是重要的林化特色资源，经加工生产松 香和松节油，目前全球年生产松香约 80 万吨，我国约占世界总产量的 60%，广西松香产量 居全国第一位。然而，我国松脂行业“科技含量低、附加值低，从而造成经济效益低”的 现象比较严重，在资源高质化利用方面有较大的提升空间，实现经济和社会可持续发展、 充分发挥特色优势资源的重要途径之一就是依靠科学技术实现资源的高质化利用。本项目 在 6 项国家自然科学基金项目和 13 项省部级项目的资助下，针对松香含有三元菲环骨架、 双键和-COOH 的特殊结构进行改性，合成系列松香基功能材料，研究其构效关系及在分离生物碱、天然药物、去除环境污染物、烯烃的催化氧化、酶的固定化等方面的应用，为其 高质化综合利用奠定了基础。 1.以松香为原料通过 D-A 加成、酯化等反应，合成了含菲环骨架的松香基交联剂-马 来松香丙烯酸乙二醇酯，自由基悬浮聚合制备了系列新型松香基大孔吸附树脂、采用加入 模板分子的微悬浮聚合方法制备了松香基高分子印迹微球，并用于分离盐酸小檗碱、盐酸 川芎嗪和葛根素等药物。 2.以松香基高分子印迹微球为高效液相色谱柱的填充材料和固相萃取材料，用于分离 药物、食品及化妆品检测。研究了吸附分离过程的热力学数据和动力学方程，建立了松香 基高分子印迹色谱柱分离盐酸小檗碱、分子印迹固相萃取-高效液相色谱检测食品中的罗 丹明 B 等分析新方法。 3.以松香及其衍生物为原料，合成了含菲环骨架的 N，N-二甲基脱氢枞胺氧化物、脱氢 枞胺 Schiff 碱-金属配合物等功能材料，研究了在环境污染物（有机染料和重金属离子） 的吸附去除和对有机物（枞酸、苯乙烯、环己烯、异戊二烯和茴香油）烯烃的催化氧化。 4.以松香为原料合成了系列松香基大孔吸附树脂，用于固定化酶的载体，创建了一种 新的固定化酶方法，即“高分子配位键法”，金属离子与松香基功能高分子中的羧基配位， 生成配合物，再与酶蛋白中的氨基酸配位连接，达到固定化酶的目的。

This project belongs to the field of forest product chemistry and processing under forestry discipline. Pine resin is an important characteristic forestry chemical resource, which can be processed to produce rosin and turpentine. At present, the global annual production of rosin is approximately 800,000 metric tons, with China accounting for about 60% of the world's total output, and Guangxi ranks first in China in terms of rosin production. However, the Chinese pine resin industry faces severe problems of low technological content, low added value, and consequently low economic benefits, leaving large room for improvement in the high-value utilization of resources. Relying on science and technology to achieve high-value utilization of resources is one of the important approaches to realizing economic and social sustainable development and giving full play to the advantages of characteristic resources. Funded by 6 National Natural Science Foundation of China projects and 13 provincial and ministerial-level projects, this project focuses on modifying rosin with its special structure containing tricyclic phenanthrene skeleton, double bonds and -COOH groups, synthesizing a series of rosin-based functional materials, studying their structure-activity relationships and applications in the separation of alkaloids, natural medicines, removal of environmental pollutants, catalytic oxidation of olefins, enzyme immobilization and other aspects, laying a foundation for its high-value comprehensive utilization. 1. Using rosin as raw material, through Diels-Alder addition, esterification and other reactions, a phenanthrene skeleton-containing rosin-based crosslinking agent—maleinated rosin ethylene glycol acrylate was synthesized. A series of novel rosin-based macroporous adsorption resins were prepared via free radical suspension polymerization, and rosin-based molecularly imprinted microspheres were prepared via micro-suspension polymerization with template molecules added, which were used for separating drugs such as berberine hydrochloride, ligustrazine hydrochloride and puerarin. 2. Taking rosin-based molecularly imprinted microspheres as packing materials for high performance liquid chromatography (HPLC) columns and solid phase extraction (SPE) materials, they were used for drug separation and detection in food and cosmetics. The thermodynamic data and kinetic equations of the adsorption and separation process were studied, and new analytical methods were established, including the separation of berberine hydrochloride using rosin-based molecularly imprinted HPLC columns and the detection of rhodamine B in food via molecularly imprinted solid phase extraction-high performance liquid chromatography. 3. Using rosin and its derivatives as raw materials, functional materials such as N,N-dimethyl dehydroabietylamine oxide and dehydroabietylamine Schiff base-metal complex containing phenanthrene skeleton were synthesized, and their applications in adsorption and removal of environmental pollutants (organic dyes and heavy metal ions) and catalytic oxidation of organic olefins (abietic acid, styrene, cyclohexene, isoprene and anise oil) were studied. 4. Using rosin as raw material, a series of rosin-based macroporous adsorption resins were synthesized as carriers for immobilized enzymes, and a new immobilized enzyme method named "polymer coordination bond method" was established. Specifically, metal ions coordinate with the carboxyl groups in rosin-based functional polymers to form complexes, and then coordinate with amino acids in enzyme proteins to achieve enzyme immobilization.

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该数据集围绕松香基功能分离材料的合成与应用技术展开研究，旨在提升松香资源的高质化利用水平。研究内容包括合成松香基交联剂、大孔吸附树脂和高分子印迹微球等材料，应用于药物分离、环境污染物去除、催化氧化和酶固定化等多个领域，为林产化工提供科学基础和技术支持。数据集属于植物学学科，数据量较小（4.86 KB），完全公开共享，发布时间为2019年。