多羧基聚合物-锆配合物在无铬鞣制中的应用
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摘要
以锆鞣坯革的收缩温度、柔软度、锆含量分布及纤维分散状况为评价指标,研究了不同相对分子质量及羧基含量的多羧基聚合物(OP)作为锆盐配体在无铬鞣制中的应用性能。当羧基含量相当时,OP配体的相对分子质量越小,锆配合物的鞣制性能越好。相比于相对分子质量,OP的羧基含量对锆配合物鞣制性能的影响更大。在本研究中,羧基含量适中的OP4-2(羧基含量4.65 mmol/g,Mn 3986 g/mol)作为锆盐配体,所得坯革的性能最佳,收缩温度达到86℃,柔软度最好,且坯革中的锆分布最均匀,纤维分散度也最高。
A series of multi-carboxyl polymer(OP) with varying molecular weights and carboxyl contents were used as ligands of zirconium salt in chrome-free tanning. The tanning performance of OP-Zr complex was evaluated by shrinkage temperature, softness, zirconium distribution and extent of fiber dispersion of the leather. When the carboxyl content of OP was similar, the lower molecular weight of OP resulted in better tanning performance. However, the carboxyl content of OP played a more essential role in the tanning performance compared with its molecular weight. In this study, OP4-2 with medium carboxyl content(carboxyl content 4.65 mmol/g, Mn 3986 g/mol) was chosen as the best ligand of zirconium sulfate, leading to the best comprehensive properties of the crust leather. The shrinkage temperature reached 86 ℃. Meanwhile, the crust leather showed the highest softness, the most uniform zirconium distribution and the highest extent of fiber dispersion.
A series of multi-carboxyl polymer(OP) with varying molecular weights and carboxyl contents were used as ligands of zirconium salt in chrome-free tanning. The tanning performance of OP-Zr complex was evaluated by shrinkage temperature, softness, zirconium distribution and extent of fiber dispersion of the leather. When the carboxyl content of OP was similar, the lower molecular weight of OP resulted in better tanning performance. However, the carboxyl content of OP played a more essential role in the tanning performance compared with its molecular weight. In this study, OP4-2 with medium carboxyl content(carboxyl content 4.65 mmol/g, Mn 3986 g/mol) was chosen as the best ligand of zirconium sulfate, leading to the best comprehensive properties of the crust leather. The shrinkage temperature reached 86 ℃. Meanwhile, the crust leather showed the highest softness, the most uniform zirconium distribution and the highest extent of fiber dispersion.
引文
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[17] Liu B H,Wang Y N,Ding W,et al.Preparation of oxidized polyvinyl alcohol using hydrogen peroxide and its application for collagen modification[J].Journal of the Society of Leather Technologists and Chemists,2019,103(1):1-7.
[18] IUP 36.Measurement of leather softness[J].Journal of the Society of Leather Technologists and Chemists,2000,84:377-379.
[19] IUP 6.Measurement of tensile strength and percentage elongation[J].Journal of the Society of Leather Technologists and Chemists,2000,84:317-321.
[20] IUP 8.Measurement of tear load-double edge tear[J].Journal of the Society of Leather Technologists and Chemists,2000,84:327-329.
[2]兰云军,刘建国,周建飞,等.无铬鞣技术离规模化推广到底还有多远[J].中国皮革,2008,37(1):38-41.
[3] Wang Y N,Huang W L,Zhang H S,et al.Surface charge and isoelectric point of leather:a novel determination method and its application in leather making[J].Journal of the American Leather Chemists Association,2019,112(7):224-231.
[4]兰云军,许晓红,周建飞.锆盐的鞣性分析及其发展前景[J].皮革科学与工程,2009,19(4):21-23.
[5] Cai S W,Zeng Y H,Zhang W H,et al.Inverse chrome tanning technology based on wet white tanned by Al-Zr complex tanning agent[J].Journal of the American Leather Chemists Association,2015,110(4):114-120.
[6]周永香,李闻欣.锆盐在皮革工业中的应用及展望[J].皮革与化工,2005,22(3):9-12.
[7] Sreeram K J,Kanthimathi M,Rao J R,et al.Development of an organo-zirconium complex-organozir as a possible alternative to chromium[J].Journal of the American Leather Chemists Association,2000,95(9):324-332.
[8]余洁,兰云军,沈晓军.没食子酸与锆离子的相互作用及其鞣制性能研究[J].中国皮革,2014,43(19):11-16.
[9] Sundarrajan A,Madhan B,Rao J R,et al.Studies on tanning with zirconium oxychloride:Part I:Standardization of tanning process[J].Journal of the American Leather Chemists Association,2003,98(3):101-106.
[10]宋新娅,熊静,沈晓军,兰云军.硫酸锆与乙醇、PEG-200、乙二醇的相互作用研究[J].皮革科学与工程,2016,26(4):10-15.
[11]刘洪娣,熊静,沈晓军,兰云军.硫酸锆与苦杏仁酸的相互作用研究[J].皮革科学与工程,2018,2(28):30-34.
[12]陈树,兰云军,沈晓军.原儿茶酸与锆离子的相互作用及其鞣制性能研究[J].中国皮革,2018,10(47):22-26.
[13]余洁,兰云军,沈晓军.没食子酸与锆离子的相互作用及其鞣制性能研究[J].中国皮革,2014,43(19):11-16.
[14]余跃,王亚楠,丁伟,等.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[J].精细化工,2018,35(11):1928-1934.
[15] Yu Y,Wang Y N,Ding W,et al.Preparation of highly-oxidized starch using hydrogen peroxide and its application as a novel ligand for zirconium tanning of leather[J].Carbohydrate Polymers,2017,174:823-829.
[16] Liu B H,Wei Z,Wang Y N,et al.Preparation of oxidized poly(2-hydroxyethyl acrylate)with multiple aldehyde groups by TEMPO-mediate oxidation for gelatin crosslinking[J].Journal of the American Leather Chemists Association,2019,In press.
[17] Liu B H,Wang Y N,Ding W,et al.Preparation of oxidized polyvinyl alcohol using hydrogen peroxide and its application for collagen modification[J].Journal of the Society of Leather Technologists and Chemists,2019,103(1):1-7.
[18] IUP 36.Measurement of leather softness[J].Journal of the Society of Leather Technologists and Chemists,2000,84:377-379.
[19] IUP 6.Measurement of tensile strength and percentage elongation[J].Journal of the Society of Leather Technologists and Chemists,2000,84:317-321.
[20] IUP 8.Measurement of tear load-double edge tear[J].Journal of the Society of Leather Technologists and Chemists,2000,84:327-329.