环保型增塑剂油酸基聚酯的合成及增塑性能研究  

Synthesis and plasticizing performance study of environmentally friendly oleic acid-based polyester plasticizer

作　　者：张超 于二雷[1] 王贺云[1] 王自庆 熊新阳 黄东 宋晓玲 魏忠[1,2] ZHANG Chao;YU Erlei;WANG Heyun;WANG Ziqing;XIONG Xinyang;HUANG Dong;SONG Xiaoling;WEI Zhong(State Key Laboratory Incubation Base for Green Processing of Chemical Engineering,School of Chemistry and Chemical Engineering,Shihezi University,Shihezi 832003,Xinjiang,China;Xinjiang Tianye(Group)Co.,Ltd.,Shihezi 832000,Xinjiang,China)

机构地区：[1]石河子大学化学化工学院化工绿色过程国家重点实验室孵化基地,新疆石河子832003 [2]新疆天业(集团)有限公司,新疆石河子832000

出　　处：《低碳化学与化工》2024年第12期60-67,共8页Low-Carbon Chemistry and Chemical Engineering

基　　金：国家自然科学基金(22068033);兵团南疆重点产业创新发展支撑计划(2021DB004);天山英才培养计划——青年科技拔尖人才(2022TSYCCX0115)。

摘　　要：增塑剂邻苯二甲酸二辛酯(DOP)存在生殖毒性和耐迁移性差的问题。选用油酸甲酯作为主要原料,通过双键环氧化、环氧基水解和本体酯交换反应合成了超支化聚酯(HBPE),随后通过丁酰化合成了IA-HBPE聚酯,可作为绿色低毒的生物基增塑剂。采用FTIR和1H-NMR对不同增塑剂样品化学结构进行了表征。随后通过溶液铸膜法制备了聚氯乙烯(PVC)复合材料,测试了不同PVC复合材料的玻璃化转变温度、力学性能、热稳定性和耐迁移性等。结果表明,IA-HBPE聚酯与PVC有良好的相容性,IA-HBPE聚酯增塑的PVC材料玻璃化转变温度从75.0℃下降到-5.0℃。IA-HBPE聚酯增塑的PVC材料断裂伸长率高达402.0%,而DOP增塑的PVC材料断裂伸长率仅为289.5%。相较于DOP,IA-HBPE聚酯在PVC材料中的抽出率和挥发率分别降低了22.99%和7.08%,IA-HBPE聚酯的耐迁移性更加优良。IA-HBPE增塑的PVC材料在220℃以下可以保持良好的热稳定性,满足实际热加工的要求。基于油酸的超支化聚酯是一种高效、环保的新型增塑剂,有望成为DOP的替代品。The plasticizer dioctyl phthalate(DOP)has issues of reproductive toxicity and poor migration resistance.Methyl oleate was selected as the primary raw material to synthesize hyperbranched polyethylene(HBPE)through processes including double bond epoxidation,epoxy group hydrolysis and bulk transesterification.This was followed by butyrylation to synthesize IA-HBPE polyester,which can serve as a green,low-toxicity bio-based plasticizer.The chemical structures of different plasticizer samples were characterized using FTIR and 1H-NMR.Subsequently,polyvinyl chloride(PVC)composites were prepared using the solution casting method,and the glass transition temperature,mechanical properties,thermal stability and migration resistance of different PVC composites were tested.The results show that IA-HBPE polyester has good compatibility with PVC,and the glass transition temperature of PVC material plasticized with IA-HBPE polyester decreases from 75.0℃to-5.0℃.The elongation at break of PVC material plasticized with IA-HBPE polyester reach 402.0%,compared to 289.5%for PVC material plasticized with DOP.Compared to DOP,the extraction rate and volatilization rate of IA-HBPE polyester in PVC materials are reduced by 22.99%and 7.08%,respectively,indicating superior migration resistance of IA-HBPE polyester.PVC materials plasticized with IA-HBPE can maintain good thermal stability below 220℃,meeting the requirements for practical thermal processing.The hyperbranched polyester based on oleic acid is an efficient,environmentally friendly new plasticizer,showing promise as a replacement for DOP.

关 键 词：PVC 增塑剂 油酸 超支化聚酯 

分 类 号：TQ414.6[化学工程]