【作者】 栾世方；

【导师】 范浩军；

【作者基本信息】 四川大学 ， 皮革化学与工程， 2003， 硕士

【摘要】 本论文研究工作分三部分，在第一部分中，制备了两种高吸收铬鞣助剂ECPA和OXD。采用自由基聚合方法制备的含有羧基、胺基、醛基、羟基、苯环等多官能团大分子铬鞣助剂ECPA，其官能团质量百分数为：羧基38.0％-44.O％、羟基2.0％、醛基2.0％、叔胺基1.5％-2.0％、苯基5.0-7.0％时，有较优良的促进铬、染料和油脂吸收作用。ECPA助剂Tg较低，能改善皮革的柔韧性和耐折性。ECPA在-40～280℃范围内不会发生降解，其水溶液在pH 1～8范围内稳定性良好。采用特殊的合成方法制备了带有羧基、醛基及羟基等多种基团的（口恶）唑烷基小分子杂环类铬鞣助剂OXD，应用实验表明，其具有优良的助铬吸收能力，并能显著提高皮革的收缩温度。该助剂水溶液在pH 1～14范围内均具有良好的稳定性。 在论文第二部分中，对助剂进行了应用和工艺平衡研究，ECPA和OXD-Ⅰ的最适宜用量分别为3％和2％。ECPA宜在铬鞣前加入，而OXD-Ⅰ既可在铬鞣前加入，也可于铬鞣后加入，鞣制终点pH值均控制在4.0左右。同常规铬鞣相比，铬粉节省40％，废液中Cr₂O₃含量从1.68 g／l左右降至0.2 g／l以下，铬吸收率从70％左右提高到96％以上，基本上达到了行业直接排放标准。将1.0％的OXD-Ⅰ和1.5％的ECPA结合使用，也可得到上述相似结论。采用高吸收铬鞣法制革，工艺简单，成革丰满性和染色性能优良，抗张强度、撕裂强度等机械性能均明显优于行业标准。对于某些软革的生产可以实现主-复鞣一体化，节省了水的用量，缩短了鞣制周期。 本论文第三部分中，采用紫外分析、DSC分析及铬结合牢度分析方法从不同角度探讨了ECPA和OXD-Ⅰ助剂的高吸收机理。DSC研究表明，ECPA和OXD-Ⅰ上的醛基和唑烷基均可与胶原上活性基团发生化学反应，从而将羧基、羟基以及胺基等基团引入蛋白质分子链上。紫外研究表明，ECPA和OXD-Ⅰ上羧基能与铬形成有效配合物，为铬的高吸收提供了理论依据。在铬揉过程中，助剂分子上的梭基及胶原侧链梭基会与铬配位，形成配位交联结合、单点配位结合及环状鳌合等不可逆结合，这些作用协同使助剂具有很强的助铬吸收能力。这也是该类助剂能助铬高吸收的本质原因所在。更多还原

【Abstract】 Two kinds of polymer chrome tanning auxiliaries ECPA and OXD- I were prepared. ECPA with various functional groups such as -COOH, -CHO, -OH and -NR2 was synthesized by means of copolymerization from acrylic monomers and vinyl monomers, while OXD-1 was prepared via special chemical synthesis method. ECPA containing 38.0-44.0% carboxyl group, 2.0% hydroxyl group, 2.0 % aldehyde group, 1.5-2.0% tertiary amino group and 5.0-7.0% benzene ring exhibited high exhaustion of both chromium and dyestuff as well as oil. Because of lower glass transition temperature (Tg) and containing a great deal of activity groups of ECPA, leather tanned with ECPA and chrome can be imparted with good fullness , elasticity and flexibility. At the temperature range of -40℃ to 280℃, ECPA showed no decomposition and its solution exhibited good stability between pH value 1-8. Similarly, OXD-1 with carboxyl group, hydroxyl group and tertiary amino group possessed excellent property of improving absorption of chrome. Most of all, it can raise the shrinkage temperature of leather obviously.The optimum application conditions of the auxiliaries were achieved via a series of leather making experiments. The results showed that 3% ECPA or 2% OXD- I was combined with 5% KMC in leather tanning, final pH of the chrome tanning was adjusted to 4.0 or so by urotropin, the content of Cr2O3 in the wastewater will bedecreased to 0.2g/l and chromium uptake will reach to 96.8%. Furthermore, the treated leather was imparted with good fullness and dyeing performance. The tensile strength and tear strength of leather were better than those of industry standard. When 1.0% OXD-I and 1.5% ECPA were used together, the similar results were achieved. Comparing with traditional chrome tanning, the tensile strength of leather increased 45%, and the dosage of chromium was decreased by 40%, the content of Cr2O3 in the wastewater was decreased from 1.68 g/l to below 0.2 g/l and chromium uptake was raised from 70% or so to 97.0%. Meanwhile, a large amount of water was saved and leather making time was reduced.The high exhaustion chrome tanning mechanisms of ECPA and OXD-I were respectively studied via approaches of UV, DSC and so on. The DSC study indicated that the aldehyde group of ECPA or oxazolidine group of OXD-I can react with the amino group in the side-chain of collagen and formed covalent bond. As a result, plenty of carboxyl group, hydroxyl group and tertiary amino group of ECPA or OXD-I can be introduced onto the backbone of collagen. UV study showed that carboxyl group of ECPA or OXD-I coordinating with Cr(III) provided a possibility of high chromium uptake. The carboxyl groups in both the auxiliaries and side-chain of collagen could coordinate with chrome and thus formed cross-linking and single-point reaction, producing irreversible fixation of chrome which were suggested to be the key reason contributing to the complete absorption of chrome.更多还原