聚乙二醇化多环氧共聚物的清洁化铬鞣应用  

Cleaner Chrome Tanning Application based on PEGylated Multi-epoxy Copolymer

作　　者：陈勇波 王俊超 李开军[1,2] 马维宁 刘公岩 CHEN Yongbo;WANG Junchao;LI Kaijun;MA Weining;LIU Gongyan(National Engineering Laboratory 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;Jingyi Fur Products Co.,Ltd.Wuzhong 751100,China)

机构地区：[1]四川大学制革清洁技术国家工程实验室,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,四川成都610065 [3]精艺裘皮制品股份有限公司,宁夏吴忠751100

出　　处：《皮革科学与工程》2023年第3期37-43,共7页Leather Science and Engineering

基　　金：宁夏回族自治区重点研发计划重点项目“基于封闭胶原侧链氨基改性的滩羊皮无害化鞣制新技术”(2022ZDYF0354)。

摘　　要：传统铬鞣的低铬利用率以及鞣制过程中大量含铬、含盐废水的排放严重危害生态环境和人类健康,制约了制革工业的可持续发展。研究采用自由基共聚设计并制备了一种聚乙二醇化多环氧基共聚物,将其作为预鞣剂考察了其在无盐、少铬、高吸收清洁化铬鞣过程中的应用。基于碱性条件下环氧基与胶原氨基的反应,共聚物预鞣能够封闭胶原氨基并在皮胶原纤维之间产生预交联,赋予坯革无盐浸酸性能。此外,聚乙二醇链段的引入能够在纤维表面形成水化层惰化胶原纤维,防止铬鞣初期鞣剂在皮表面的快速结合,促进铬鞣剂在皮中的均匀渗透。同时,环氧基开环反应所产生的羟基为后续铬鞣剂提供额外的结合位点,有助于提高铬鞣剂的吸收率。结果表明,共聚物预鞣能够实现无盐浸酸,能使少铬鞣法的铬吸收率由80.5%提高至95%,并显著提高成革热稳定性、力学性能和感官性能。The low chrome utilization efficiency and the discharge of large amounts of effluent containing chromium and salt during the traditional chrome tanning process gravely impair the natural environment and human health,and limit the sustainable development of leather industry.In this study,a copolymer with multi-epoxy groups was designed and synthesized by using the free radical copolymerization.The salt-free,chrome-less,high-exhaustion clean chrome tanning application of the prepared copolymer were studied.Based on the interaction between the epoxy group and amino group of collagen under alkaline condition,the copolymer pre-tanning could block the collagen amino group and create pre-crosslinking between collagen fibers,resulting in salt-free pickling in the crust leather.Furthermore,the introduction of polyethylene glycol chain segments could form hydration layer on the fiber surface and inert collagen fibers,prevent the rapid binding of chrome tanning agent on the skin surface during the initial tanning process and promote the uniform penetration of chrome tanning agent inside the skin.Simultaneously,the hydroxyl groups generated by the ring-opening reaction of epoxy groups gave extra binding sites for the following chrome tanning agent,which is beneficial to improve the absorption rate of chrome tanning agent.Results showed that the copolymer pre-tanning could achieve salt-free pickling,and the chrome absorption rate in the chrome-less tanning was improved from 80.5%to 95%.At the same time,the thermal stability,mechanical and sensory properties of resulting leather were significantly improved.

关 键 词：多环氧基共聚物 无盐浸酸 高吸收铬鞣 清洁化鞣制技术 

分 类 号：TS543[轻工技术与工程—皮革化学与工程]