A novel self-colored waterborne polyurethane (SCPU) was synthesized and used in the preparation of a microfiber synthetic leather (MS-Leather) base in order to reduce the pollution caused by N,N-dimethylformamide (DMF) and dyes. The SCPU was prepared using the reaction of a reactive brilliant red K-2G with a waterborne polyurethane which was then extended via a first generation of hyperbranched poly(amine-ester). With the introduction of the dye, new absorption peaks at 1118 cm−1 [S=O], 1413 cm−1 [N=N], and 1635 cm−1 [C=N] appeared in the Fourier transform infrared (FTIR) spectrum of SCPU, and SCPU mean particle size increased to 162 nm. The X-ray diffraction (XRD) peak intensity of SCPU at 19.27° was 1310 cts. The thermal stability of SCPU at 200–280 °C was inferior to that of the control sample; however, it improved at temperatures above 360 °C. Finally, a free-dyeing MS-Leather base prepared by using SCPU without DMF was manufactured. It was found that the dyes were distributed mainly in the polyurethane matrix rather than in the microfibers. Moreover, the color changes of the base before and after being washed in both a water and a soap solution were 0.93 and 4.21, respectively. This indicated that the base’s washing color fastness to water was better than to a soap solution.
The demand for waterproof leather has been increasing, and environmentally friendly waterproof fatliquors have recently received increasing attention. In this work, two polymer nanoemulsions containing carboxyl groups were synthesized and used as waterproof fatliquors for chrome-tanned leather. First, a reactive emulsifier (C12-Na) was prepared using itaconic anhydride and lauryl alcohol. Subsequently, two polymer nanoemulsions were prepared through mini-emulsion polymerization with C12-Na as the emulsifier, 4,4′-azobis (4-cyanovaleric acid) as the initiator, and lauryl acrylate (LA)/stearyl acrylate (SA) as monomers; these were named PLA and PSA. PLA and PSA were characterized using FT-IR, a Zetasizer, and GPC. It was found that the critical micellar concentration (CMC) of C12-Na was 2.34 mmol/L, which could reduce the surface tension of water to 26.61 mN/m. The average particle sizes of PLA and PSA were 53.39 and 67.90 nm, respectively. The maeser flexes of leather treated with PLA and PSA were 13928 and 19492 at a 5% dosage, respectively, and the contact angles reached 148.4° and 150.3°, respectively; these values were both higher than for a conventional fatliquor. Compared with PLA, the leather treated with PSA exhibited better fullness, and tensile and tearing strength. The prepared nanoemulsions have prospective applications in leather manufacturing as waterproof fatliquors.
Fatliquoring is one of the most important processes in leather making, in which the collagen fibers are split effectively, while the crust acquires a good softness and mechanical strength. The effectiveness of fatliquoring depends not only on the variety and dosage of fatliquoring agent but also on its distribution in hierarchical collagen fiber layers. Up to now, the research about the mass transfer of fatliquoring agent in leather is very limited because quantifying the distribution of invisible fatliquor in leather is very difficult. In this paper, a fluorescent tracing technique based on modified castor oil was established and send used to investigate the mass transfer of fatliquor in leather. The crucial fluorescent tracer was synthesized favorably by the reaction of castor oil, successively with maleic anhydride and 5-aminofluorescein, which was confirmed by FTIR, 1H NMR and DSC. The fluorescent tracer was pH-sensitive and emitted an intense fluorescent signal at pH 8–10. Then, it was applied to monitor the fatliquoring process in real-time. Compared with Sudan IV or Nile Blue sulphate dyeing tests, this fluorescent tracing technique could conveniently visualize and quantify the penetration and distribution of fatliquor in leather process.
In order to elucidating the exact effect mechanism of polyphenols on the assembly of collagen, the assembled architectures of collagen treated with different amounts of procyanidin (PA) were investigated in details. The assembled morphologies of collagen were greatly influenced by the content of PA according to atomic force microcopy (AFM) images. When the content of PA was more than 20% (w/w), the fibrillar morphologies were substituted by globular aggregates, which were driven by the intense hydrogen bonding action originating from PA. While the formation of the non-fibrous aggregates was due to the coiling and entangling of flexible collagen molecules rather than their gelatinization based on the appearance of typical adsorption peaks at 222nm and 197nm on circular dichroism (CD) spectra. After being crosslinked by glutaraldehyde (GA), not only the diameters but also the lengths of fibrils increased. Unfortunately, the fibrillogenesis was still inhibited when the collagen suffered from 20% PA firstly and then 4% GA. Conversely, the fibrous morphologies of the fibrils stabilized by 4% GA and then underwent 20% PA maintained well, in spite of accompanying with grievous intertwining. This difference was derived from the change of flexibilities of collagen before and after being crosslinked by GA. Additionally, the differential scanning calorimeter (DSC) analysis confirmed the PA had no positive effect on the improvement of thermal stability of hydrous collagen, whereas the denaturation temperature of hydrated collagen stabilized by 4% GA increased from 40 °C to 80 °C.
Solar-driven interfacial evaporation is a promising strategy for alleviating freshwater scarcity and water pollution. However, developing efficient evaporators using eco-friendly, renewable biomass remains a significant challenge. Herein, we report a bio-derived solar-driven interfacial evaporator (CSIE) based on iron–tannin modified collagen, further enhanced via mechanical micro-perforations to induce the Marangoni effect (EN-CSIE). The influence of pore size and open-area ratio on the Marangoni-driven flow was systematically investigated. The optimized EN-CSIE (with 1.2 mm pore size and 6.1% open-area ratio) achieved a superior evaporation rate of 2.5 kg m−2 h−1 with an energy conversion efficiency of 93.5% under 1 sun illumination. Furthermore, the system demonstrated exceptional purification capabilities, removing over 99.9% of metal ions and organic impurities. Long-term durability tests in 3.5 wt% saline water confirmed a stable evaporation rate of 2.3 kg m−2 h−1 over 15 continuous cycles. This low-cost and sustainable collagen-based evaporator presents a robust solution for solar-powered water desalination, particularly for decentralized clean water production in sun-rich regions.