两步酯化法合成皮革加脂剂及其应用性能研究  

Synthesis of Leather Fatliquor Using Two-step Esterification Reaction and its Application Properties

作　　者：霍文凯 周继博 廖学品[1,2] 石碧[1,2] HUO Wenkai;ZHOU Jibo;LIAO Xuepin;SHI Bi(Nationa Engineering Laboroi-ory for Clean Technology of Leather Manufacture.,Sichuan University,Chengdu 610065,China;Key Laboratory of Leather Chemistry and Engineering of Ministry of Education,Sichuan University,Chengdu 610065,China)

机构地区：[1]制革清洁技术国家工程实验室(四川大学),四川成都610065 [2]四川大学皮革化学与工程教育部重点实验室(四川大学),四川成都610065

出　　处：《皮革科学与工程》2020年第3期7-14,共8页Leather Science and Engineering

基　　金：国家重点研发计划(2017YFB0308500)。

摘　　要：以马来酸酐(MAH)为起始材料,依次与二乙二醇乙醚、十八醇进行反应,然后经过磺化制得一种新型加脂剂MADO-SUL。通过单因素实验确定了最佳反应条件,第一步酯化反应生成中间产物MADG的反应温度为90℃,时间为5 h,马来酸酐与二乙二醇乙醚反应摩尔比为1∶1;第二步酯化反应生成MADO的反应温度为190℃,时间为7 h,MADG与十八醇反应摩尔比为1∶1,催化剂亚磷酸用量为反应体系总质量的0.5%;磺化反应温度为80℃,时间为5 h,MADO与亚硫酸钠反应摩尔比为1∶1。通过傅里叶变换红外光谱(FT-IR)和核磁共振氢谱(1H-NMR)表征分析了MADO-SUL的结构,并将MADO-SUL应用于牛皮蓝湿革加脂实验,同时与市售加脂剂SF做对比。结果表明,MADO-SUL加脂性能良好,MADO-SUL加脂后坯革的二氯甲烷萃取物含量为3.224%,挥发性有机物(VOCs)含量为92.484μg C/g。市售加脂剂加脂后坯革的二氯甲烷萃取物含量为5.485%,挥发性有机物(VOCs)含量为173.348μg C/g,均高于MADO-SUL。A new leather-making fatliquoring agent MADO-SUL was prepared using maleic anhydride(MAH)as starting material.It was reacted in order with diethylene glycol diethyl ether,stearyl alcohol and sodium sulfite respectively,which involved two-step esterification and a sulfonation reaction.A series of single factor experiments were carried out to explore the optimum synthesis conditions.It was found that the optimum synthesis temperature of MADG,the product of first esterification,was 90℃and the reaction time was 5 h with the molar ratio of maleic anhydride to diethylene glycol diethyl ether to be 1∶1.Additionally,the product of second esterification reaction was named MADO and the optimum reaction temperature was 190℃,the reaction time was 7 h and the molar ratio of MADG to stearyl alcohol was 1∶1.Furthermore,phosphorous acid was selected as catalyst and its dosage was 0.5%of total reaction system on weight basis.As for sulfonation reaction,its optimum temperature was 80℃,the optimum time was 5 h,and the molar ratio of MADO to sodium sulfite was 1∶1.The structure of MADO-SUL was analyzed by FTIR and1 H-NMR.Moreover,MADO-SUL was applied to fatliquoring experiment of cowhide blue wet leather and compared with commercial fatliquoring agent SF.It was found that the prepared MADO-SUL exhibited promising performances,and the dichloromethane extracted content of leather fatliquored by MADO-SUL was 3.224%and the content of volatile organic compounds(VOCs)was 92.484μg C/g,both lower than that of leather fatliquored by commercial fatliquoring agent,which were 5.4855%and 173.348μgC/g,respectively.

关 键 词：马来酸酐 二乙二醇乙醚 十八醇 加脂剂 VOCS 

分 类 号：TS529.4[轻工技术与工程—皮革化学与工程]