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详细研究了在溶液状态下酸催化作用引起松香中海松酸型树脂酸组成变化的特征及规律,以甲苯、醋酸等作为溶剂,醋酸、盐酸、硫酸等作为催化剂,反应温度为保持良好回流,反应时间1～8h。研究结果表明,松香中的海松酸型树脂酸在醋酸作用下比较稳定,其组成没有发生明显的变化。在盐酸、硫酸作用下,松香中原有的海松酸、异海松酸、山达海松酸明显减少,初始质量分数越高、酸作用时间越长,减少越明显,与此同时产生了原料中没有的8,15-异海松酸、8,15-海松酸和7,15-海松酸,且随酸作用时间延长而增多。在质量分数为51.4%的硫酸催化作用下于甲苯中回流8h后,湿地松松香中的海松酸型树脂酸质量分数变化为:异海松酸由13.77%降至10.53%,山达海松酸由1.78%升至1.98%,8,15-异海松酸则从0升至5.05%;马尾松松香中的海松酸型树脂酸质量分数变化为:海松酸由7.45%降至3.02%,7,15-海松酸由0升至0.67%,8,15-海松酸则从0升至3.99%。海松酸型树脂酸主要发生以环内双键位置变化为主的异构反应,很少发生分解反应,而环外乙烯基则没有参与反应,松香中各海松酸型树脂酸总质量分数基本不变。对海松酸型树脂酸各成分的立体结构分析及异构体之间的相关性分析结果表明,8,15-异海松酸应来源于异海松酸和山达海松酸的异构化,而8,15-海松酸和7,15-海松酸应来源于海松酸的异构化反应。
The characteristics and rules of the changes of the pimaric acid resin composition in rosin caused by acid catalysis were studied in detail. Toluene, acetic acid and other solvents were used as the solvent. Acetic acid, hydrochloric acid and sulfuric acid were used as the catalysts. The reaction temperature was kept well and the reaction Time 1 ~ 8h. The results showed that the pimaric acid resin in rosin is relatively stable under the action of acetic acid, and its composition has not changed obviously. Under the action of hydrochloric acid and sulfuric acid, the original pimaric acid, isopimaric acid and sandaracopimaric acid in the rosin are obviously reduced. The higher the initial mass fraction, the longer the acid action time, the more obvious the decrease is. At the same time, 8,15-isopimaric acid, 8,15-pimaric acid and 7,15-pimaric acid, and increased with prolonged acid action. After refluxing in toluene for 8h under the catalysis of 51.4% sulfuric acid, the content of pimaric acid resin in the rosin of Pinus elliottii decreased from 13.77% to 10.53%, while that of sandaracopimaric acid from 1.78 % Rose to 1.98%, 8,15-isopimaric acid rose from 0 to 5.05%; Masson pine gum in the pimaric acid resin acid content changes: from 7.45% to 3.02% pimaric acid, 7,15- Pimaric acid increased from 0 to 0.67% while 8,15-pimaric acid rose from 0 to 3.99%. Pimalic acid type resin acid mainly occurs in the isomerization reaction with the change of the position of the double bond in the ring, the decomposition reaction is seldom occurred, and the vinyl group outside the ring does not participate in the reaction. The total mass fraction of each of the pimaric acid resin acids in the rosin is basically not change. The structural analysis of the components of the pimaric acid resin acid and the correlation analysis between the isomers showed that 8,15-isopimaric acid should be derived from the isomerization of isopimaric acid and sandaracopimaric acid, while 8 , 15-pimaric acid and 7,15-pimaric acid should be derived from isomerization of pimaric acid.