文献类型：期刊文献

中文题名：马来海松酸三烯丙酯的制备与表征

英文题名：Preparation and Characterization of Tri-Allyl Maleopimarate

作者：卢言菊[1,2] 刘娟娟[1] 赵振东[1,2] 陈玉湘[1,2] 古研[1,2]

第一作者：卢言菊

通信作者：Zhao, Zhendong

机构：[1]中国林业科学研究院林产化学工业研究所,生物质化学利用国家工程实验室,国家林业和草原局林产化学工程重点开放性实验室,江苏省生物质能源与材料重点实验室,南京210042;[2]中国林业科学研究院林业新技术研究所,北京100091

年份：2018

卷号：54

期号：10

起止页码：108-115

中文期刊名：林业科学

外文期刊名：Scientia Silvae Sinicae

收录：CSTPCD;;EI(收录号：20184706117263);Scopus;北大核心:【北大核心2017】；CSCD:【CSCD2017_2018】；

基金：国家自然科学基金面上项目(31370575);中央级公益性科研院所基本科研业务费专项资金(CAFYBB2017QA018).

语种：中文

中文关键词：马来海松酸酐;微波辅助;合成;马来海松酸三烯丙酯;表征

外文关键词：maleopimaric acid anhydride（MPA）;microwave-assisted;synthesis;tri-allyl maleopimarate;characteristic

分类号：TQ351

摘要：【目的】通过Diels-Alder反应将马来酸酐引入松香结构单元,在微波辅助条件下在马来海松酸分子结构中引入含有3个活性碳碳双键的马来海松酸三烯丙酯,为我国松香基精细化学品的精深加工提供一条新路径。【方法】分别以水和乙醇为溶剂,通过中和反应制备马来海松酸钠盐,在微波辅助条件下,以N,N-二甲基甲酰胺为溶剂,以马来海松酸钠与氯丙烯为原料,通过相转移催化法制备马来海松酸三烯丙酯。基于FT-IR、GC及MS等手段对产物结构进行表征。【结果】确定优化反应条件为:微波功率400 W,反应温度55℃,反应时间4 h,氯丙烯与马来海松酸钠物质的量之比为3,催化剂用量5%,在此条件下产物的收率为93.2%。从色谱分析结果可以看出,反应进行比较彻底,原料峰已完全消失,而且生成的产物纯度较高,优化条件下所得产物GC含量为96.1%。红外光谱表征中红外特征吸收峰的消失和生成说明马来海松酸三烯丙酯3个羧基均发生了酯化反应,且反应较为彻底。质谱分析确认了以乙醇为溶剂制备的钠盐为原料所得的马来海松酸三烯丙酯的副产物经甲酯化后主要有马来松香酸酐单烯丙酯及马来松香酸二烯丙酯,以水为溶剂制备的钠盐为原料所得产物主要为马来海松酸三烯丙酯,副产物只有马来海松酸酐单烯丙酯。质谱分析中m/z 538为马来海松酸三烯丙酯的分子离子峰,m/z 481的碎片峰为[M-OCH_2CHCH_2]^+是脱去1分子酯基部分生成的峰,m/z 439的碎片峰为脱去酯基后形成的稳定的马来海松酸酐结构,质谱碎片峰m/z 342为马来海松酸三烯丙烯酯的质谱分裂逆Diels-Alder反应,碎片离子197的基峰是稳定的三环菲骨架结构。制备的马来海松酸三烯丙酯为白色黏稠液体,其酸值为2.5 mg·g^(-1),密度为1.109 7×10~3 kg·cm^(-3),黏度为8.5×10~3mPa·s。【结论】开发了具有3个活性双键的马来海松酸三烯丙酯聚合单体,以水为溶剂制备的钠盐为原料所得马来海松酸三烯丙酯的纯度较高。
【Objective】 A novel monomer, tri-allyl maleopimarate with three functional C C bonds, was synthesized by introduction of maleic anhydride in rosin structure under microwave irradiation through Diels-Alder reaction. The newly synthesized monomer, consisting of three functional C C bonds, is proposed to have plenty of reactive functionalities during free radical polymerization. Then the rosin structure can be directly introduced into polymers. The successful synthesis of the new multi-functional polymerization monomer provides a new path for the deep processing in China.【Method】 Sodium maleopimarate was prepared from maleopimaric acid and sodium hydroxide through neutralization reaction using ethanol or water as solvent respectively. Then tri-allyl maleopimarate was synthesized from sodium maleopimarate followed by phase transfer reaction with allyl choloride under microwave-assisted conditions. The structure of the product was characterized by FT-IR, GC and MS.【Result】 The optimized reaction conditions were as follows： microwave power 400 W, reaction temperature 55 ℃, reaction time 4 h, n （allyl chloride） ∶ n （sodium malaypimarate）=3 ∶1, and the amount of catalyst 5%. Under the above conditions the yield of the product was 93.2%, and the purity of tri-allyl maleopimarate was 96.1%. FT-IR analysis showed that three carboxyl groups were successfully introduced in the rosin structure through esterification reaction. The byproducts identified in this reaction are allyl maleopimarate and di-allyl maleopimarate using ethanol as solvent. Only single byproduct can be observed using water as solvent. The physical and chemical properties of the synthesized products were tested. The products appeared as a viscous liquid at room temperature, with a viscosity of 8.5×10 3 mPa ·s at 25 ℃. The density and the acid value of the product were determined as 1.109 7×10 3 kg ·cm -3 and 2.5 mg KOH ·g ^-1 sample, respectively.【Conclusion】 Tri-allyl maleopimarate is proposed as a new type of natural rosin-derived reactive monomer. The purity of tri-allyl maleopimarate using water as solvent was higher than that of using ethanol as solvent.