摘要
以油酸甲酯与硬脂酸甲酯混合物为原料,经高碳醇酯交换、环氧化处理,制备了一系列环氧脂肪酸高碳醇酯生物基增塑剂。在此基础上,将核磁共振、气相色谱-质谱分析技术联用,确定了产物组成和结构,并将实验与分子模拟相结合,对比了高碳醇烷基链长及支链结构对这类增塑剂在聚氯乙烯(PVC)中耐迁移性的影响。结果表明,随着高碳醇烷基链增长,环氧脂肪酸酯增塑剂的耐挥发性显著提高,耐萃取性呈逐渐下降趋势。其中,环氧脂肪酸甲酯塑化PVC膜的雾化值约为环氧脂肪酸正辛酯塑化PVC膜的2倍,而前者萃取质量损失率约为后者的一半。此外,高碳醇烷基链长对酯交换后增塑剂产物耐析出性能的影响规律则较复杂。最后,高碳醇烷基支链结构对这类增塑剂的耐挥发、耐萃取和耐析出性能的影响均较小。上述实验结果可为PVC用高物性增塑剂的分子设计与开发提供参考。
Herein,a series of bio-plasticizers,epoxidized fatty acid long-chain alcohol esters,were prepared by transesterification between fatty acid methyl esters(containing 85%methyl oleate and 15%methyl stearate)and long-chain alcohols,followed by epoxidation.The structure and composition of the products were confirmed by ^(1)H nuclear magnetic resonance(^(1)H NMR)and gas chromatography-mass spectrometry(GC-MS),whose migration resistance as a function of the long-chain alcohol structure were evaluated via a combination of experiment and molecular simulation.The results demonstrates that the volatility resistance of the resulting bio-plasticizers increases substantially and the extraction resistance decreases gradually with increasing alkyl carbon number of the long-chain alcohol.The fogging value of epoxidized fatty acid methyl ester in polyvinyl chloride(PVC)is twice that of epoxidized fatty acid n-octyl ester,while the extraction made loss rate of the former decreases by 50%compared with that of the latter.Furthermore,the exudation resistance of the resulting bio-plasticizers varies in a complicated manner as a function of alkyl carbon number of the long-chain alcohol,and the branched-chain structure of the long-chain alcohol shows no obvious impact on volatility resistance,extraction resistance,and exudation resistance of the products.The present effort may provide guidance for other researchers to develop high performance plasticizers for PVC industry to replace conventional but toxic di-(2-ethylhexyl)phthalate plasticizer.
作者
王松杭
潘思宇
赵东方
赵敏仲
陈意
范浩军
Wang Songhang;Pan Siyu;Zhao Dongfang;Zhao Minzhong;Chen Yi;Fan Haojun(College of Biomass Science and Engineering,Sichuan University,Chengdu 610065,China;Shandong Chengwu Yixin Environmental Technology Co.,Ltd.,Heze 274200,China;Hebei Jingu Recycling Resources Development Co.,Ltd.,Xinji 052371,China)
出处
《工程塑料应用》
CAS
CSCD
北大核心
2022年第3期113-119,共7页
Engineering Plastics Application
基金
皮革化学与工程教育部重点实验室开放课题基金项目(SCU2021D005)
四川大学合成革及高性能纤维工科特色团队基金项目(2020SCUNG122)。
关键词
环氧脂肪酸甲酯
增塑剂
高碳醇
迁移
聚氯乙烯
epoxidized fatty acid methyl ester
plasticizers
long-chain alcohol
migration
polyvinyl chloride
