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Tannin and carbohydrates based non-isocyanate polyurethane for foams, surface finishes and adhesives

Abstract : This research was focus on bioresources, including tannin, lignin, soybean protein, humins, to prepare bio-based wood adhesives and foams. There are four main parts, including two kinds of wood adhesives preparation by using bio-resources, i.e., bio-sourced NIPU wood adhesives and bio-based (tannin, SPI, and lignin) wood adhesives without toxic formaldehyde; two kinds of tannin-foam products, i.e., typical tannin-furanic foam and non-isocyanate polyurethane foams. (1) Commercial humins, soybean protein isolation (SPI), and mimosa tannin have been utilized to prepare wood adhesives, based on the formulation of non-isocyanate polyurethanes (NIPU). The basic properties of the adhesives were determined. Techniques such as MALDI-ToF and FTIR were used to detect the products obtained and for analyzing the reaction mechanisms involved. Thermomechanical analysis (TMA) was utilized to investigate the thermal behavior of the adhesives. Finally, the laboratory plywood or particleboard were prepared for evaluating the bonding performances of adhesives. (2) A novel biomass-based wood adhesive was prepared with commercial mimosa tannin extract and glycerol diglycidyl ether (GOE) by convenient mechanical mixing. GOE served as the crosslinker of the tannin without any aldehyde addition yielding hardened three­dimensional networks. Oifferent weight ratios of tannin/GOE were investigated by several techniques to determine their influence on final properties. Two kinds of lignin-based adhesives were prepared, i.e., ( i ) glyoxal modified lignin and dialdehyde starch cross-linked by urea; ( ii ) periodate oxidation by two-steps. The molecular species formed and the reactions mechanism involved were determined by FT-IR, 13C NMR and MALDI-ToF mass spectrometry. The adhesives based on this reaction were tested by bonding laboratory plywood or particleboard, by differential scanning calorimetry (DSC), and thermomechanical analysis (TMA). (3) A tannin-based non-isocyanate polyurethane (NIPU) rigid foam was obtained. Citric acid and glutaraldehyde mixture served as a blowing and crosslinker agent used to provide foaming energy and cross-link the tannin-based resin to prepare the NIPU foams. The reaction mechanism of the tannin-based NIPU foams were investigated by FT-IR, MALDI-TOF, and 13C NMR. Additionally, tannin was also used as a natural tire-retardant to improve the final properties of glucose-­based NIPU foams, including fire retardancy and compression strength. (4) A biorefinery waste, humins, and soybean protein insolate (SPI) were selected as formaldehyde substitute bio-sourced crosslinkers for two kinds of tannin-based foam formulations. As expected, the properties were improved by using these bio-sourced crosslinkers. The basic properties of series tannin foams were investigated. The morphology and structure characteristics were observed by scanning electron microscopy (SEM). Additionally, the crosslinking reaction mechanisms between tannin with the two bio-sourced crosslinkers, i.e., humins and SPI, were determined by MALDE-ToF and FTIR spectrometry. Finally, the thermal stability, mechanical properties, fire retardancy and formaldehyde emission were evaluated by the relevant techniques.
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Submitted on : Thursday, June 23, 2022 - 12:03:11 PM
Last modification on : Friday, June 24, 2022 - 3:39:55 AM


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Xinyi Chen. Tannin and carbohydrates based non-isocyanate polyurethane for foams, surface finishes and adhesives. Chemical Sciences. Université de Lorraine, 2021. English. ⟨NNT : 2022LORR0286⟩. ⟨tel-03702716⟩



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