摘要
从松脂或松香单离树脂酸、利用其不饱和双键进行氧化改性能够以低成本方式合成多功能基树脂酸衍生物,是具有发展潜力的松香深加工利用研究的重要方向之一。目前松香树脂酸的分离效率低、氧化反应选择性差,已成为制约其氧化改性研究和工业化应用的“瓶颈”问题。
本论文以左旋海松酸和枞酸为研究对象,从绿色化学角度,系统研究了简化树脂酸分离工艺,提高树脂酸氧化反应选择性的方法与技术。结果表明,乙酸乙酯可以替代丙酮为溶剂,改善左旋海松酸丁醇铵盐沉淀晶形和过滤性能,简化分离工艺,提高产品收率;在95 %乙醇中,在常压加热条件下,固体酸全氟磺酸离子交换树脂能够催化松香树脂酸异构化反应,直接结晶分离纯化得到纯度为94 %、得率为35 %的枞酸;采用良溶剂溶解松香或松脂,与非良溶剂混合,能够沉淀分离混合树脂酸、精制松香,并简化左旋海松酸和枞酸的分离工艺;左旋海松酸丁醇铵盐可以直接进行光敏氧化反应,从而缩减了从松脂分离左旋海松酸、制备左旋海松酸环过氧化物的工艺;枞酸及其甲酯在不同的杂多酸季铵盐/H2O2催化体系中均能够发生温和的氧化反应,通过反应条件的优化与调控,可以实现高选择性环氧化。
The research on separation of rosin acids from gum rosin or pine oleoresin and low cost synthesis of rosin acids derivatives having multiple functional groups by oxidation of the C=C double bonds is one of the important directions having good prospects in deep-processing of gum rosin. The low yield and complicated separation process and oxidation selectivity of rosin acids has become the bottle-neck problem in the basic research and industrial application of oxidation modification of rosin acids.
The paper takes levopimaric acid and abietic acid as representative rosin acids to study the method for simplifying the separation processing of rosin acids and improving the selectivity of oxidation reaction according to the green chemistry principles. The results showed that ethyl acetate could be used as a substitute for acetone to yield more butanolamine salt of levopimaric acid and levopimaric acid products by improving the crystal phase and filtration performance of butanolamine salt precipitates;Perfluorinated sulphonate resin membrane could be used as solid acid to catalyze the isomerization reaction of rosin acids in 95 % alcohol and to obtain abietic acid in 94 % purity and 35 % yield by direct cool crystallization; the process of separating rosin acids mixtures from gum rosin or Pine Oleoresin for purifying rosin and preparing abietic acid could be simplified by a precipitation separation method, in which Gum rosin or Pine Oleoresin were dissolved in a good solvent and added a poor solvent; Photo-sensitized oxidation reaction of 2-amino-2-methyl-1-propanol salt of levopimaric acid in 95 % ethanol could be carried out in order to simplify the process of separating levopimaric acid from pine oleoresin and preparing levopimaric acid transannular peroxide; oxidation reaction of abietic acid and its methyl esters could be easily carried out by using quaternary ammonium salts of heteropoly acids as catalyst and 30 % H2O2 as oxidant, and gave epoxides in good yield and selectivity at the optimized reaction conditions.
引文
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