Page 142 - 201811

第 35 卷第 11 期 精 细 化 工 Vol.35, No.11
2018 年 11 月 FINE CHEMICALS Nov. 2018

皮革化学品
催化剂对双氧水氧化淀粉-锆配合物结构

及鞣制性能的影响

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余 跃 ，王亚楠 1,2* ，丁 伟 1,3 ，周建飞 ，石 碧 1,2
（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. 四川亭江新材料股份有限公司, 四川 什邡 618412）

摘要：分别用钨酸盐、偏钒酸盐和铜-铁盐催化双氧水氧化淀粉，制得氧化淀粉配体，测定了氧化淀粉的氧化度
和双氧水分解率，采用核磁共振碳谱、红外光谱和凝胶渗透色谱等分析了氧化淀粉的官能团结构和相对分子质
量。考察了氧化淀粉-锆配合物的鞣制性能。铜-铁盐可催化葡萄糖单元 C-2，C-3 和 C-6 位的羟基氧化为羰基和
羧基，同时打断 α-1，4-糖苷键，制得低相对分子质量（14628）、高氧化度（72.5%）的氧化淀粉，用作配体可
明显提高锆配合物在皮革中的分布均匀度（97.8%）和结合量（ZrO 2 质量分数 8.0%），皮革收缩温度达 89.7 ℃，
鞣制效果最佳。钨酸盐催化氧化淀粉的相对分子质量高（465095），氧化度低（15.0%），形成的锆配合物鞣制性
能差。偏钒酸盐催化氧化淀粉的鞣制性能介于上述两者之间。
关键词：催化剂；双氧水；氧化淀粉；制革；锆鞣；皮革化学品
中图分类号：TS23; TS543 文献标识码：A 文章编号：1003-5214 (2018) 11-1928-07

Effect of Catalyst on Structure of Hydrogen Peroxide Oxidized Starch and Its

Performance as a Ligand in Zirconium Tanning of Leather

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YU Yue , WANG Ya-nan 1,2* , DING Wei , ZHOU Jian-fei , SHI Bi
（1. National Engineering Laboratory for Clean Technology of Leather Manufacture, Sichuan University, Chengdu
610065, Sichuan, China; 2. Key Laboratory of Leather Chemistry and Engineering, Ministry of Education, Sichuan
University, Chengdu 610065, Sichuan, China; 3. Sichuan Tingjiang New Material, Inc., Shifang 618412, Sichuan,
China)
Abstract: Oxidation of starch with hydrogen peroxide was catalyzed by tungstate, metavanadate and
copper-iron salts, respectively. The oxidation degree of oxidized starch and the decomposition rate of
hydrogen peroxide were determined. The functional groups and relative molecular weight of oxidized starch
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were characterized by CNMR, FTIR, gel permeation chromatography (GPC) and so on. The tanning
performance of oxidized starch as a ligand for zirconium tanning of leather was investigated. The hydroxyl
groups at the positions C-2, C-3 and C-6 in the glucose unit were oxidized to carbonyl and carboxyl groups,
and the α-1, 4-glycosidic bonds were broken during oxidation using cooper-iron salts as catalyst.
Subsequently, the oxidized starch with a relatively low molecular weight (14628) and a high oxidation
degree (72.5%) was used as a ligand of zirconium tanning agent. The Zr distribution (97.8%) and fixation
〔w(ZrO 2)=8.0%〕in leather were remarkably improved, and the shrinkage temperature of leather reached
89.7 ℃, leading to better tanning performances. Oxidized starch by using tungstate as catalyst had a higher
molecular weight (465095) and a lower oxidation degree (15.0%), and was poorer in tanning performances
when it coordinated with zirconium salt. While, the tanning performances of oxidized starch obtained by
using metavanadate as catalyst was between the above two kind of oxidized starch.
Key words: catalyst; hydrogen peroxide; oxidized starch; leather-making; zirconium tanning; leather
chemicals

收稿日期：2017-09-08; 定用日期：2018-02-12; DOI: 10.13550/j.jxhg.20170727
基金项目：国家重点研发计划（2017YFB0308500）；四川大学德阳校市科技合作专项资金（XSHZ201613）
作者简介：余 跃（1991—），男，博士生。联系人：王亚楠（1986—），男，副教授，E-mail：wangyanan@scu.edu.cn。