Page 199 - 《精细化工》2022年第8期

第 39 卷第 8 期 精 细 化 工 Vol.39, No.8
2022 年 8 月 FINE CHEMICALS Aug. 2022

橡塑助剂
生物基甘油酯类增塑剂的合成及性能

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沈一蕊 1,2,3 ，周津君 ，沈曙光 ，周文斌 ，刘德开 ，蒋平平
（1. 宁波工程学院 材料与化学工程学院，浙江 宁波 315211；2. 江南大学 化学与材料工程学院，江苏
无锡 214122；3. 浙江镇洋发展股份有限公司，浙江 宁波 315200；4. 南开大学 电子信息与光学工程
学院，天津 300350）

摘要：以甘油和不同结构脂肪酸（正辛酸、2-乙基己酸、正戊酸和 2-甲基丁酸）为原料，采用直接酯化法制备
了甘油酯类生物基增塑剂〔甘油三辛酸酯、甘油三(2-乙基己酸)酯、甘油三戊酸酯和甘油三(2-甲基丁酸)酯〕。利
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用 FTIR 和 HNMR 对其结构进行了表征。对比了 4 种增塑剂塑化的聚氯乙烯（PVC）试片与邻苯二甲酸二(2-
乙基己)酯（DEHP）塑化的 PVC 试片的性能。结果表明，与 DEHP 塑化的 PVC 试片相比，甘油三戊酸酯/PVC
试片的断裂伸长率提高 151.0%；甘油三辛酸酯/PVC 试片的初始降解温度（T 5% ）提高 12.3 ℃；甘油三(2-甲基
丁酸)酯/PVC 试片的耐抽出性更好，均具有替代 DEHP 的潜力。增塑剂的构效关系表明，在相同相对分子质量
下分子结构中支链多的增塑剂与 PVC 之间的相容性和耐抽出性更好，但热稳定性和耐挥发性降低。
关键词：生物基增塑剂；聚氯乙烯；甘油基酯；构效关系
中图分类号：TQ414 文献标识码：A 文章编号：1003-5214 (2022) 08-1699-07

Synthesis and properties of bio-based glyceryl ester plasticizers

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SHEN Yirui 1,2,3 , ZHOU Jinjun , SHEN Shuguang , ZHOU Wenbin ,
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LIU Dekai , JIANG Pingping
(1. College of Materials and Chemical Engineering, Ningbo University of Technology, Ningbo 315211, Zhejiang, China;
2. School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, Jiangsu, China; 3. Zhejiang
Oceanking Development Co., Ltd., Ningbo 315200, Zhejiang, China; 4. Department of Electronic Science and
Engineering, Nankai University, Tianjin 300350, China)
Abstract: A series of bio-based gester plasticizers [glycerol trioctanoate, glycerol tri(2-ethylhexanoate),
glycerol trivalericate, glycerol tri(2-methylbutyrate)] were synthesized by direct esterification of glycerol
with different fatty acids (octanoic acid, 2-ethylhexanoic acid, valeric acid and 2-methylbutyric acid), and
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then characterized by FTIR and HNMR. The plasticizing effects of the prepared plasticizers on polyvinylchloride
(PVC) formulations were investigated with commercial plasticizer bis(2-ethylhexyl) phthalate (DEHP) used
as control. The results showed that compared with those of the PVC test sheet plasticized by DEHP , the
elongation at break of PVC test sheet plasticized glycerol trivalerate was increased by 151.0%, the initial
degradation temperature of PVC test sheet plasticized by glycerol trioctanoate displayed an improvement of 12.3
℃, and the volatility resistance of the one plasticized by glycerol tri(2-methylbutyrate) was also enhanced,
indicating that the obtained plasticizers show the promise to fully or partially replace DEHP. Furthermore, the
structure-activity relationship analysis for the plasticizers demonstrated that plasticizers with more branched
chains in molecular structure at the same relative molecular mass had better compatibility and extraction
resistance with PVC, but with reduced thermal stability and volatility resistance.
Key words: bio-based plasticizers; polyvinyl chloride; glyceryl esters; structure-activity relationship

增塑剂是塑料制品中最重要的助剂之一，已被 装、涂料和电气绝缘等领域的塑料制品。邻苯二甲
广泛用于医疗器械、汽车制造、儿童玩具、食品包 酸二(2-乙基己)酯（DEHP）、邻苯二甲酸二丁酯

收稿日期：2022-02-17; 定用日期：2022-04-20; DOI: 10.13550/j.jxhg.20220133
基金项目：中央高校基本科研业务费专项资金资助项目（JUSRP51623A）；宁波工程学院科研启动金基金资助项目
作者简介：沈一蕊（1992—），女，讲师，E-mail：shenyr@nbut.edu.cn。联系人：蒋平平（1957—），男，教授，E-mail：ppjiang@jiangnan.edu.cn。