Preparation and application of a novel sucrose-based amphoteric retanning agent for sustainable leather making

Abstract

The reliance on fossil-derived compounds in most conventional retanning agents faces a challenge to the sustainable development of the leather industry. Consequently, the development of environmentally friendly biomass-based retanning agents is urgently needed. In this research, a novel sucrose-based amphoteric retanning agent (GLS) was synthesized with a weight-average molecular weight of 3.48 × 10⁴ g/mol. The molecular structure of GLS was determined using FT-IR, ¹³C-NMR, XPS, and EA. The GLS exhibited a favorable isoelectric point (pI = 4.68) as a retanning agent. At a 10% dosage, GLS retanning of wet-blue resulted in a 14.42% thickness increase, substantially greater than that achieved with commercial amino resin (CML, 6.77%) and acrylic resin (LP, 10.8%) retanning agents. GLS also exhibited superior absorption (87.13%) compared to CML (75.27%) and absorption comparable to LP (89.2%). Notably, GLS improved the uptake of subsequent anionic fatliquoring agents compared to CML and LP. Moreover, GLS-retanned leather displayed good thermal stability and commendable physical and mechanical properties. The BOD₅/COD value of the GLS retanning wastewater was 0.48, indicating its excellent biodegradability. Life cycle assessment further highlighted the environmental benefits of GLS compared to LP and CML. These findings position GLS as a promising biomass-derived amphoteric retanning agent with the potential to displace conventional fossil-derived alternatives.

Keywords

Sucrose / Amphoteric retanning agent / Leather retanning performances / Life cycle assessment

References

[1] Bai ZX, Wang XC, Zheng MH, Yue OY, Xie L, Zha SY, Tong L, Song YY, Huang MC, Liu XH. Leather for flexible multifunctional bio-based materials: A review. J Leather Sci Eng, 2022, 4(1): 16

[2] Wei C, Wang X, Wang W, Sun S, Liu X. Bifunctional amphoteric polymer-based ecological integrated retanning/fatliquoring agents for leather manufacturing: simplifying processes and reducing pollution. J Clean Prod, 2022, 369: 133229

[3] Wang YX, Xiao YH, Ren KS, Wang CH, Sun HY, Lin W. Insights into the development of dyeing-assisting amphoteric acrylic retanning/fatliquoring agents for ecological chrome-free tanned leather production. Ind Eng Chem Res, 2024, 63(16): 7206-15

[4] Ferraris S, Gamna F, Luxbacher T, Maculotti G, Giorio L, Kholkhujaev J, Genta G, Galetto M, Sarnataro A, Nogarole M, Florio C. Comparative characterization of leather from different tanning processes as a contribution to a sustainable development of the leather industry. Sci Rep, 2025, 15(1): 10608

[5] Ren KS, Sang J, Bu QQ, Zhou JF, Lin W. Research on constructing standard system for carbon peaking and carbon neutrality in leather industry. J Leather Sci Eng, 2024, 34(1): 41-6

[6] Ozkan CK, Ozgunay H. Retanning performance of carboxymethyl starch and its effects on dyeing. J Am Leather Chem Assoc, 2022, 117(2): 71-81

[7] Ozkan CK, Ozgunay H. Production of carboxymethyl starches from oxidized starches and determination of their tanning characteristics. J Am Leather Chem Assoc, 2021, 116(6): 187-97

[8] Guan XY, Zhang BY, Liu SY, An M, Han QX, Li DP, Rao P. Facile degradation of chitosan-sodium alginate-chromium (III) gel in relation to leather re-tanning and filling. Int J Biol Macromol, 2023, 240: 124437

[9] Yuan LL, Yao QD, Liang YX, Dan Y, Wang YX, Wen HT, Yang YQ, Dan WH. Chitosan based antibacterial composite materials for leather industry: a review. J Leather Sci Eng, 2021, 3(12): 1-18

[10] Quaratesi I, Badea E, Călinescu I, Sardroudi NP, Zengin G, Casas C, Bacardit A. Eco-friendly alternatives in leather production: performance of biodegradable alginate-based retanned leather compared to conventional leathers and plant-based materials. Appl Sci, 2024, 14(22): 10263

[11] Ding W, Wang YT, Sun J, Bao LH, Pang XY. Dialdehyde sodium alginate bonded Dicyandiamide for formaldehyde-free leather production with enhanced properties. Carbohydr Polym, 2022, 295: 119838

[12] Liang S, Wang XC, Sun SW, Hao DY, Xie L, Yang J, Dang XG. Polysaccharides for sustainable leather production: a review. Environ Chem Lett, 2024, 22(5): 2553-72

[13] Yu Y, Wang H, Zeng YH, Zhou JF, Zhang Y, Shi B, Wang YN. Biomass-derived polycarboxylate–aluminum–zirconium complex tanning system: A sustainable and practical approach for chrome-free eco-leather manufacturing. J Clean Prod, 2024, 452: 142261

[14] Hao DY, Wang XC, Liu XH, Su RR, Duan ZJ, Dang XG. Chrome-free tanning agent based on epoxy-modified dialdehyde starch towards sustainable leather making. Green Chem, 2021, 23(23): 9693-703

[15] Gao M, Tang YD, Ding W, Jiang ZC, Shi B. Oxidized oligosaccharides for chrome-free metal tanning: utilization of food waste for the sustainability of the leather industry. Ind Crops Prod, 2022, 187: 115549

[16] Jiang ZC, Ding W, Fan JJ, Liao YH, Remón J, Shi B. Biomass derived oligosaccharides for potential leather tanning. Collagen Leather, 2023, 5(1): 7

[17] Queneau Y, Jarosz S, Lewandowski B, Fitremann J. Sucrose chemistry and applications of sucrochemicals. Adv Carbohydr Chem Biochem, 2007, 61: 217-92

[18] Yang HX, Tan XP, Du GB, Ni KL, Wu YC, Li Z, Ran X, Gao W, Li J, Yang L. Development of biomass adhesives based on aminated cellulose and oxidized sucrose reinforced with epoxy functionalized wood interface. Compos Part B, 2023, 263: 110872

[19] Kunz T, Lee EJ, Schiwek V, Methner FJ. Glucose—A reducing sugar? Reducing properties of sugars in beverages and food. Brew Sci, 2011, 64: 61-7

[20] Ding W, Remón J, Jiang ZC. Biomass-derived aldehyde tanning agents with in situ dyeing properties: a ‘Two birds with one stone’ strategy for engineering chrome-free and dye-free colored leather. Green Chem, 2022, 24: 3750-8

[21] Ding W, Liu HT, Pang XY, Ding ZW. Engineering a pioneering melamine resin based on saccharide-derived aldehyde: structure characterization and application for eco-leather production. Ind Crops Prod, 2022, 185: 115133

[22] Ding W, Wang XY, Remón J, Jiang ZC, Pang XY, Ding ZW, Wu YB. Engineering an epoxy tanning agent via facile functionalization of sucrose with silane coupling agent for sustainable leather production. Collagen Leather, 2025, 7: 18

[23] Krishnamoorthy G, Sadulla S, Sehgal PK, Mandal AB. Greener approach to leather tanning process: D-Lysine aldehyde as novel tanning agent for chrome-free tanning. J Clean Prod, 2013, 42: 277-86

[24] Jin YY, Wang JC, Li XZ, Hu Y, Han Y, Zhang YX, Wu YB, Lei ZQ, Lu DD. Biomimetic and multifunctional polypeptides for green leather processing: design, preparation, and properties. ACS Appl Polym Mater, 2024, 6: 5530-43

[25] Pan F, Xiao Y, Zhang LH, Zhang L, Zhou JJ, Wang CH, Lin W. Leather wastes into high-value chemicals: keratin-based retanning agents via UV-initiated polymerization. J Clean Prod, 2023, 383: 135492

[26] Zhang C, Zhou JB, Sun N, Liao XP, Shi B. A novel approach for Preparing aldehyde-free melamine resin and investigation of its retanning performance. Collagen Leather, 2024, 6(1): 10

[27] Sun N, Zhou JB, Liao XP, Shi B. Synthesis and retanning performance of a novel melamine resin with ultralow formaldehyde content. J Am Leather Chem Assoc, 2023, 118(1): 23-35

[28] Hou X, Yang J, Tang JC, Chen XM, Wang XK, Yao KD. Preparation and characterization of crosslinked polysucrose microspheres. React Funct Polym, 2006, 66(12): 1711-7

[29] Li X, Zeng WC, Zhu DY, Feng JL, Tian CC, Liao XP, Shi B. Investigation of collagen hydrolysate used as carbon and nitrogen source in the fermentation of Bacillus pumilus. Process Biochem, 2017, 55: 11-6

[30] Liu X, Yuan QW, Yang Y, Li K, Pang NJ, Wang JT, Yang M, Li X, Guo JL, Liao XP, Shi B. Self-assembled Gallic acid-rare Earth nanocomplexes against MRSA with multi-targeting antibacterial mechanisms robustly combating bacterial resistance. Chem Eng J, 2025, 510: 161698

[31] Li X, Li MF, Guo JL, Liu X, Liao XP, Shi B. Collagen peptide provides streptomyces coelicolor CGMCC 4.7172 with abundant precursors for enhancing undecylprodigiosin production. J Leather Sci Eng, 2021, 3(1): 17

[32] Yang M, Li X, Wang B, Liu X, Zhang B, Liao XP. Collagen peptide protects Saccharomyces cerevisiae from furfural stress for enhancing bioethanol synthesis. Collagen Leather, 2025, 7(1): 4

[33] IUP 6. Measurement of tensile strength and percentage elongation. J Soc Leather Technol Chem, 2000, 84(7): 317-21

[34] IUP 8. Measurement of tear load-double edge tear. J Soc Leather Technol Chem, 2000, 84(7): 327-9

[35] IUP 36. Measurement of leather softness. J Soc Leather Technol Chem, 2000, 84(7): 377-9

[36] Navarro D, Wu JH, Lin W, Fullana-i-Palmer P, Puig R. Life cycle assessment and leather production. J Leather Sci Eng, 2020, 2: 1-13

[37] Zhang YY, Yuan KZ, Magagnin L, Wu XS, Jiang ZC, Wang W. Selective adsorption of Pb (II) and Cu (II) on mercapto-functionalized aerogels: experiments, DFT studies and LCA analysis. J Clean Prod, 2023, 393: 136126

[38] Chaloulos A, Catti P, Nikolakis N, Alexopoulos K. A process-level LCA for evaluating the contribution of digitalization in the greening of a manufacturing system. Procedia CIRP, 2024, 126: 904-8

[39] Li GL, Shang Y, Wang YH, Wang LS, Chao YS, Qi Y. Reaction mechanism of etherification of rice straw with epichlorohydrin in alkaline medium. Sci Rep, 2019, 9(1): 14307

[40] Song Y, Wang YN, Zeng YH, Wu HP, Shi B. Quantitative determinations of isoelectric point of retanned leather and distribution of retanning agent. J Am Leather Chem Assoc. 2018;113(7):232–8.

[41] Fathima NN, Kumar MP, Rao JR, Nair BU. A DSC investigation on the changes in pore structure of skin during leather processing. Thermochim Acta, 2010, 501(1–2): 98-102

[42] Song Y, Zeng YH, Xiao KL, Wu HP, Shi B. Effect of molecular weight of acrylic resin retanning agent on properties of leather. J Am Leather Chem Assoc, 2017, 112(04): 128-34

[43] Tian ZH, Ma JZ, Liu QW, Zhang H. Preparation and application of novel amphoteric acrylic retanning agents to improve dye absorption. React Chem Eng, 2023, 8(3): 645-55

[44] Wang YN, Hu LY. Essential role of isoelectric point of skin/leather in leather processing. J Leather Sci Eng, 2022, 4(1): 25

[45] Dang XG, Yu ZF, Wang XC, Du YM, Wang CH. Sustainable one-pot synthesis of novel soluble cellulose-based nonionic biopolymers for natural antimicrobial materials. Chem Eng J, 2023, 468: 143810

[46] Madhu V, Mayakrishnan S, Muthu J, Sekar K, Madurai S. Win–win approach toward Chrome-free and Chrome-less tanning with waterborne epoxy polymers: a sustainable way to curb the use of Chrome. ACS Sustainable Chem Eng, 2024, 12(16): 6082-92

[47] Liu XH, Wang YY, Wang XC, Jiang H. Development of hyperbranched poly-(amine-ester) based aldehyde/chrome-free tanning agents for sustainable leather resource recycling. Green Chem, 2021, 23(16): 5924-35

[48] Ren LF, Sun X, Miao J, Li RL, Liu HQ, Yu SJ, Yang L, Zhang XC, Qiang TT. A highly compatible polylysine-based chrome-free tanning agent: achieving the double benefit of superior adsorption to anionic materials and ecological leather manufacturing. ACS Sustainable Chem Eng, 2025, 13(43): 18810-20

[49] Raczuk E, Dmochowska B, Samaszko-Fiertek J, Madaj J. Different schiff bases—structure, importance and classification. Molecules, 2022, 27(3): 787

[50] Lou JF, Wang D, Fan XR. Preparation, characterization of carboxyl polyaldehyde sugars and application as innovative anti-crease finishing agents for cotton fabric. J Nat Fibers, 2022, 19(15): 10564-71

[51] Riera GCS, Azurmendi HF, Ramia ME, Bertorello HE, Martin CA. Synthesis of cross-linked polymers by reaction of sucrose and diepoxide monomers: characterization and nuclear magnetic resonance study. Polymer, 1998, 39(15): 3515-21

[52] Hao DY, Wang XC, Liang S, Yue OY, Liu XH, Hao DY, Dang XG. Sustainable leather making—an amphoteric organic chrome-free tanning agents based on recycling waste leather. Sci Total Environ, 2023, 867: 161531

[53] Makal A, Schilf W, Kamieński B, Szady-Chelmieniecka A, Grech E, Woźniak K. Hydrogen bonding in schiff bases–NMR, structural and experimental charge density studies. Dalton Trans, 2011, 40(2): 421-30

[54] Matuana LM, Balatinecz JJ, Sodhi RNS, Park CB. Surface characterization of esterified cellulosic fibers by XPS and FTIR spectroscopy. Wood Sci Technol, 2001, 35(3): 191-201

[55] Wang LH, Mo HZ, Li HB, Xu D, Gao DG, Liu ZB, Zhang JY, Yao LS, Hu LB. Preparation and application of tremella polysaccharide based Chrome free tanning agent for sheepskin processing. Int J Biol Macromol, 2023, 241: 124493

[56] Ma JZ, Liu QW, Wu MX, Tian ZH. Preparation and assistant-dyeing of formaldehyde-free amphoteric acrylic retanning agent. J Leather Sci Eng, 2021, 3(1): 26

[57] Dang XG, Han SY, Du YM, Fei YF, Guo BY, Wang XC. Engineered environment-friendly multifunctional food packaging with superior nonleachability, polymer miscibility and antimicrobial activity. Food Chem, 2025, 466: 142192

[58] Gohy JF, Creutz S, Garcia M, Mahltig B, Stamm M, Jérôme R. Aggregates formed by amphoteric diblock copolymers in water. Macromol, 2000, 33(17): 6378-87

[59] Li QJ, Yi YD, Wang YN, Li J, Shi B. Effect of cationic monomer structure on the aggregation behavior of amphoteric acrylic polymer around isoelectric point. J Leather Sci Eng, 2022, 4(1): 4

[60] Kamely N. Fatliquors for leathers: an application of microemulsion—a review. Polym Bull, 2022, 79(3): 1977-2002

[61] Arcibar-Orozco JA, Barajas-Elias BS, Caballero-Briones F, Nielsen L, Rangel-Mendez JR. Hybrid carbon nanochromium composites prepared from chrome-tanned leather shavings for dye adsorption. Water Air Soil Pollut, 2019, 230(7): 142

[62] Mandal S, Venkatramani J. A review of plant-based natural dyes in leather application with a special focus on color fastness characteristics. Environ Sci Pollut Res, 2023, 30(17): 48769-77

[63] Zhou JB, Zhou JF, Li PL, Liao XP, Shi B. Preparation of formaldehyde-free melamine resin using furfural as condensation agent and its retanning performances investigation. J Am Leather Chem Assoc, 2018, 113(6): 198-206

[64] Ning GQ, Zhou JB, Liao XP, Shi B. Synthesis of a waterborne melamine resin and its retanning behaviors investigation. J Am Leather Chem Assoc, 2022, 117(7): 288-95

[65] Qiao PF, Liu J, Jin LQ, Zhang FF, Feng ZH, Wang YL. Ecofriendly and sustainable metal-free leather tanning using novel poly (carbamoyl sulfonate) technology. Collagen Leather, 2025, 7(1): 9

[66] Sun N, Gao Y, Cheng JL, Li X, Liao XP. Synthesis and retanning performance of hollow polymer microspheres for lightweight leather processing. Collagen Leather, 2025, 7(1): 20

[67] Yi YD, Li QJ, Sun QY, Wang YN, Shi B. Aggregation behavior of cationic amphiphilic polymers and their application in metal-free leather retanning. Polymer, 2024, 295: 126738

[68] Yu Y, Lin YR, Zeng YH, Wang YN, Zhang WH, Zhou JF, Shi B. Life cycle assessment for Chrome tanning, Chrome-free metal tanning, and metal-free tanning systems. ACS Sustainable Chem Eng, 2021, 9(19): 6720-31

[69] Lisiecka MZ. Biological effects of epoxy resins on the human body: toxicity and allergic reactions. Drug Chem Toxicol. 2025;1–11. https://doi.org/10.1080/01480545.2025.2557405.

[70] Ahmed T, Verma A, Patterson AT, Styczynski MP, Takayama S. Compositional dependence of DNA partitioning in a poly (ethylene glycol)–ficoll aqueous two-phase system. Chemistry, 2024, 6(6): 1680-91

[71] Abid S, Khalid S, Khawar MT, Nawab Y, Riaz S. Comparison between BOD and COD of auxiliaries used in conventional and enzymatic pretreatment of textiles polluting the aquatic environment. Chem Pap, 2024, 78(14): 7791-9

[72] Jiang Y, Li J, Li D, Ma YK, Zhou SC, Wang Y, Zhang DH. Bio-based hyperbranched epoxy resins: synthesis and recycling. Chem Soc Rev, 2024, 53(2): 624-55

Funding

National Natural Science Foundation of China(22278279)

RIGHTS & PERMISSIONS

The Author(s)