Preparation and assistant-dyeing of formaldehyde-free amphoteric acrylic retanning agent

With the enhancement of environmental protection consciousness,concerns have been raised about non-toxic and biodegradable leather retanning agents.According to the European standard 2002/231/EC,the free formaldehyde content of leather products should be less than 150 mg/kg.As one of the retanning agents in the market,the content of free formaldehyde in the Multifunctional retanning agent(MTA)is 372.22 mg/kg and higher than the limit value.In this work,glutaraldehyde as an alternative of formaldehyde was used to modify acrylic polymer and an amphoteric acrylic retanning agent was prepared.Then it was used in retanning process,and its retanning and assistant-dyeing properties were investigated.The results showed that the free formaldehyde content of amphoteric acrylic retanning agent modified with glutaraldehyde was only 4.17mg/kg.Meanwhile,the presence of amino groups in the amphoteric acrylic retanning agent improved the dyeing properties of leather by electrostatic attraction.Compared with the leather treated with anionic acrylic retanning agent,the residual dye concentration of the dyeing effluent of the retanned leather with amphoteric acrylic retanning agent decreased from 17.4mg/L to 10.0mg/L,and the dyed leather had better resistances to friction and water-washing.In addition,the BOD 5/COD value of the wastewater after Mannich base polymer retanning was only 0.32,indicating that the retanning agent was biodegradable.Moreover,the leather retanned with amphoteric acrylic retanning agent had good thermal stability,fullness and physical and mechanical properties.

Interaction between retanning agents and wet white tanned by a novel bimetal complex tanning agent

A promising and practical chrome-free tanning system has been developed based on a novel Al–Zr bimetal complex tanning agent.However,to achieve satisfactory resultant leather,the retanning process that is compatible with this emerging tannage needs to be investigated systematically.This paper aims to explore the interaction between the bimetal complex tanned wet white and retanning agents.The isoelectric point(pI)of wet white was 7.2,which was nearly the same as wet blue.The electropositivity of wet white was even higher than that of wet blue during post-tanning processes,resulting in higher uptake rate of retanning agents.The distribution of various retanning agents in wet white was analyzed by pI measurement of layered leather and fluorescent tracing technique.The retanning agents were unevenly distributed throughout the cross-section,which might be an important restriction factor in obtaining satisfactory organoleptic properties of the crust leather.This fact is mainly due to the strong electrostatic interaction between anionic retanning agents and wet white.Applying a high dosage of multiple retanning agents in a proper sequence of addition benefited the full penetration of retanning agents in leather matrix and thus improved the organoleptic properties of crust leather.This work provides guidance for optimizing retanning process of the wet white leather.

含铬合成鞣剂的结构和性能的关系(Ⅰ)

铬-合成单宁铬合合成鞣剂目前在制革界颇受欢迎。国际上有多种牌号的这类鞣剂,其制法、形态、结构和性能都有所不同。有的是机械混合物;有的是铬和合成单宁铬合的:有的络合后完全变成了黄绿色,铬离子本身的兰绿色完全消失;有的溶解于水后呈清亮、透明的溶液;有的则不完全溶于水,水溶液呈浑浊状态。

Investigations on the general properties of biomass-based aldehyde tanned sheep fur for its selective post-tanning processing

Dialdehyde sodium alginate(DSA)is an alternative chrome-free tanning material for fur production.To obtain satisfactory resultant fur and provide suggestions for the usage of DSA in fur making,the general properties of DSA tanned sheep fur were systematically investigated.The tanning mechanism of DSA was analyzed and it was verified that DSA was mainly combined with collagen fiber by forming Schiff base covalent bonds while supplemented by a small number of hydrogen bonds and ionic bonds.Due to the acid sensitivity of Schiff base structure,DSA tanned fur had poor resistance to acid rinsing but had excellent resistance to washing and good fatliquoring performance.Also,it had good resistances to yellowing and reductant.After being retanned by chrome tanning agent,the fur was capable of enduring a high-temperature dyeing process(68°C for 8 h).Overall,DSA tanned sheep fur had favorable properties under appropriate post-tanning processing conditions to manufacture light-colored or dark-colored fur products with desirable physical properties.

Effect of cationic monomer structure on the aggregation behavior of amphoteric acrylic polymer around isoelectric point

Amphoteric polymer can be used as retanning agent in leather manufacture. It is particularly useful in chrome-free tanning systems since it can regulate the charge properties of chrome-free leather and enhance the fixation of anionic post-tanning chemicals in leather. However, the aggregation and precipitation of amphoteric polymer retanning agents around the isoelectric point (pI) hinder their wide application. Herein, we synthesized five amphoteric acrylic polymers (AAPs) by free radical copolymerization with acrylic acid and five different cationic acrylic monomers. The effect of cationic monomer structure on the aggregation behavior of AAPs was investigated. The aggregation of AAPs in aqueous solution showed pH and concentration dependence. Light scattering analysis showed that Poly (AA-co-MAPTAC) and Poly (AA-co-DMAPMA) were in the shape of coiled linear flexible chains with small particle size (Rg 7.6 nm and 14.8 nm, respectively) near the pI. However, Poly (AA-co-DAC), Poly (AA-co-DMC) and Poly (AA-co- DMAEMA) were in the shape of hollow spheres and exhibited serious aggregation. Quantum chemical calculations suggested that the amide groups in the cationic monomers MAPTAC and DMAPMA enhanced the nucleophilicity of AAPs. Thus the corresponding AAPs could carry a large number of cationic charges to slow their aggregation when the pH just climbed over the pI. The results are expected to provide theoretical reference for the synthesis and widespread application of AAPs.