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Soy protein isolate was reacted first with maleic anhydride and then hexamethylenediamine to synthesis soy protein isolate-based polyamides (SPIPA). Its bonding properties were measured by preparing laboratory three-layer plywood. Furthermore, a silane coupling agent (KH560), citric acid and maleic anhydride were added as cross-linkers to the SPIPA glue mix before hot pressing the panels. ATR FT-MIR and MALDI-ToF were used to determine the structures of the SPIPA, and thermomechanical analysis was used to analyze its thermomechanical properties. The results show that maleic anhydride reacts with amino acids in the soy protein molecule and then reacts with hexamethylenediamine to form carbamate-structured polyamides. This is confirmed by the ATR FT-MIR and MALDI-ToF results. Moreover, structural analysis indicates that a large number of branched structures are formed and occur in the SPIPA, rendering possible the formation of a network during curing, ensuring the bonding performance of the adhesive. The SPIPA adhesive presented good bonding strength and water resistance above the standard requirements of China National Standard GB/T 9846-2015. In particular, when maleic anhydride was added as a cross-linking agent, namely the SPIPA-MA adhesive, the panels’ dry and wet shear strengths were improved so that it can be considered as a suitable soy protein-based wood adhesive.

Lignin was successfully modified to prepare a bio-based wood adhesive by just two synthesis steps: demethylation and periodate oxidation. Fourier Transform Infrared Spectroscopy (FT-IR), Matrix Assisted Laser Desorption Ionization Time of Flight (MALDI-TOF) Mass Spectrometry and Thermomechanical Analysis (TMA) were combined to characterize the bio-based adhesives obtained. Furthermore, the adhesion performance of the bio-based lignin adhesive was measured by testing the tensile shear strength of the bonded joints. The results show that demethylated lignin gives to the wood joint acceptable dry shear strength, but no wet shear strength. Thus, sodium peroxide (NaIO4) oxidant was used to improve the bonding performance of lignin-based adhesives. The optimal formulation for oxidized demethylated lignin adhesives was found to be by 20% addition of NaIO4. The adhesive presented is a lignin-derived non- aldehyde addition, high biomass content, and its preparation is convenient, low-cost product and can be applied to wood bonding.

To prepare a natural tannin-based adhesive with good water resistance, an environment friendly furfuryl alcohol-glyoxal resin (FG) synthesized in the laboratory was developed as a cross-linker for tannin-based adhesives. 13C Nuclear Magnetic Resonance (NMR) and Matrix-Assisted Laser Desorption-Ionization Time-of-Flight (MALDI-TOF) mass spectroscopy results indicated that furfuryl alcohol and glyoxal reacted under acidic conditions and that the -CH-(OH)- groups could be shown to be the ones involved in the cross-linking of the tannin-furfuryl-glyoxal adhesive (TFG). The results for the wet shear strength of TFG-bonded plywood showed that the cured TFG was improved and better than that bonded with a tannin-furfuryl alcohol (TF) adhesive. Moreover, the TFG adhesive cross-linked with 12% epoxy resin (EPR) presented a good water resistance. It had a modulus of elasticity (MOE) higher than that of tannin-furfuryl alcohol-formaldehyde (TFF), TF and phenol-formaldehyde (PF) adhesives.

To guide the preparation of soy protein-based adhesives, the reaction between protein and formaldehyde as a possible cross-linker was studied in this paper under different pHs. To simplify the investigations, dipeptide N-(2)-l-alanyl-l-glutamine (AG) was used as a model compound for protein. Based on the analysis of the results of ESI-MS and 13C-NMR of the reaction products between AG and formaldehyde prepared under different pHs, it was found that the pH has strong effects on these reactions. Under strong acid conditions, such as pH 1–3, the methylolation reaction mainly occurred at the aliphatic amino groups of AG. However, it was very difficult for the resulted methylolated AG to be further condensed. Under weak acid conditions, such as pH 5, both the methylolation reaction between amido groups and formaldehyde and the further condensation reaction were possible. However, the condensation reaction was still rather weak under these conditions. At alkaline conditions, the methylolation reaction occurred between all of the three types of amino groups of AG and formaldehyde with both methylene bonds and methylene–ether bonds present in the system. Methylene bonds were mainly from the reaction between AG methylols and amido groups and aliphatic amino groups of AG. Ether bridges were formed between two methylolated AG mainly from amido groups.

Environmental concerns about natural adhesive materials are leading to an increasing interest towards the development of ecological products. The development of new value-added uses for wheat proteins led us to develop protein-based wood adhesives. Different protein cold-setting resins were formulated by reacting the protein hydrolysates with different aldehydes (formaldehyde, glyoxal and glutaraldehyde). Wood bonded with cold-setting protein adhesive with different aldehydes met the requirements for interior and exterior conditions, and the characterization was similar to those of conventional PRF (phenol–resorcinol–formaldehyde) adhesives. As the results indicate, both glyoxal and glutaraldehyde are able to react with wheat protein hydrolysates and are viable alternatives to formaldehyde and prospectively seem more environmentally friendly. Matrix-assisted laser desorption ionisation time-of-flight (MALDI-TOF) analysis allowed the identification of the main oligomer species obtained. The analysis showed that resin prepared with glutaraldehyde is not a simple mix of resorcinol–glutaraldehyde oligomers and amino acid, but a much more complex combination of various species including amino acid-glutaraldehyde and amino acid-resorcinol oligomers.

International audience; Soy-protein isolate (SPI) was used to prepare non-isocyanate polyurethane (NIPU) thermosetting adhesives for wood panels by reacting it with dimethyl carbonate (DMC) and hexamethylene diamine. Both linear as well as branched oligomers were obtained and identified, indicating how such oligomer structures could further cross-link to form a hardened network. Unusual structures were observed, namely carbamic acid-derived urethane linkages coupled with lactam structures. The curing of the adhesive was followed by thermomechanical analysis (TMA). It appeared to follow a two stages process: First, at a lower temperature (maximum 130°C), the growth of linear oligomers occurred, finally forming a physically entangled network. This appeared to collapse and disentangle, causing a decrease of MOE, as the temperature increases. This appears to be due to the ever more marked Brownian movements of the linear oligomer chains with the increase of the temperature. Second, chemi- cal cross-linking of the chains appeared to ensue, forming a hardened network. This was shown by the thermo- mechanical analysis (TMA) showing two distinct MOE maxima peaks, one around 130°C and the other around 220°C, with a very marked MOE decrease between the two. Plywood panels were prepared and bonded with the SPI-NIPU wood adhesive and the results obtained are presented. The adhesive appeared to pass comfortably the requirements for dry strength of relevant standards, showing to be suitable for interior grade plywood panels. It did not pass the requirements for wet tests. However, addition of 15% of glycerol diglycidyl ether improved the wet tests results but still not enough to satisfy the standards requirements.

International audience; Wheat gluten protein hydrolysate was used as a biomass feedstock to prepare environmentally friendly protein-based adhesives, with hydrolyzed wheat protein as control. Glutaraldehyde was used to modify it to obtain a glutaraldehyde-wheat protein (GP) adhesive. Polyethylenimine (PEI) was also used as a crosslinking agent. Plywood has been prepared and tested, and its performance was used to measure the wheat gluten protein hydrolysate adhesive bonding performance. Differential scanning calorimetry (DSC) and thermomechanical analysis (TMA) were used to analyze the adhesive thermal properties and the microstructures of the cured adhesives by scanning electron microscopy (SEM). The results show that modification by glutaraldehyde can effectively improve the bonding performance of wheat protein adhesives, the plywood bonded strength having been improved by its addition. The effect of PEI as a crosslinking agent became evident. It can greatly improve the bonding properties of glutaraldehyde-modified wheat protein adhesives. TMA analysis indicates that the glutaraldehydemodified GP adhesive has a higher storage modulus than the unmodified one. The modulus of the adhesive increased after adding the PEI cross-linking agent.

Furfuryl alcohol, a biosourced material, is widely used in the foundry industry, and also as additive or modifier in the adhesives field. However, furanic resins have not been reported as being use...

Broussonetiapapyrifera leaf protein was used as a biomass feedstock to prepare wood adhesives, and the influence of cutting modes (cutting frequencies and cutting heights) on leaf protein content and reactivity was studied in this paper. Bonding performance of Broussonetiapapyrifera leaf protein-based adhesives were evaluated by shear strength of plywood. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetry (TG), and scanning electron microscope (SEM) were used to analyze them. The results indicated that: (1) the leaf protein content gradually increased as the cutting height increased, but it presented a decreasing trend as the cutting frequency increased. When the cutting frequency is two times per year and the cutting height is 30 cm, this leaf protein-based adhesive exhibited the best bonding strength with 0.75 MPa. (2) Cutting frequency and cutting height have no significant correlations to the reactivity of leaf protein with the crosslinker. (3) DSC and FTIR indicated that both leaf protein content and reactivity appeared to exert an influence on the bonding properties of the protein adhesives, and the latter is more pronounced. (4) TG and SEM analyses indicated that under different cutting modes, leaf protein content, especially protein reactivity, had a great effect on the thermal properties of the adhesives. (5) Contact angle analysis showed that Broussonetiapapyrifera leaf protein-based adhesives had good wettability on wood surfaces. Under different cutting modes with the difference of leaf protein content and reactivity, the crosslinking degree of the adhesives with crosslinker and compactness of the cured adhesives were different and thus affect their bonding strength and water resistance.

International audience

By using only glyoxal instead of formaldehyde to prepare environment-friendly amino resin for wood adhesives is a hot topic in the wood industry. However, the existing reports on UG resin present a poor bonding performance, and especially an almost complete absence of water resistance. Thus, to explore new synthetic processes to prepare UG resins with good water resistance is a work of considerable interest. In this work a novel formulation is developed by reacting hexamethylene diamine (H) and urea (U) via first deamination and then polymerization with glyoxal (G) to obtain HUGs green resins. These resins were used to prepare well bonded wood panels. The effect of different H/U ratios on resin performance was also investigated. At a H/U molar ratio of 1, the HUG resin presents the best performance, dry strength, 24h wet strength, and 63℃ hot water soaking wet strength of the plywood bonded with it, these being respectively 1.18MPa, 1.70MPa, 0.92MPa respectively. This means that the HUG resin has potential as an industrial adhesive to replace urea-formaldehyde or melamine-urea- formaldehyde resins in the production of wood composites.

Chitosan is a biomass material with abundant reserves. It has been used in this work to prepare an environmentally friendly wood adhesive. By employing carbohydrates, namely glucose, sucrose and starch modified by specific oxidation as hardeners, petroleum-based aldehydes were eliminated due to their unsustainability, volatility, and toxicity. Three-layer laboratory plywood was prepared to measure the bonding performance of the chitosan adhesives prepared. The effect of different levels of oxidation by different sodium periodate additions on their bonding performance was also studied. The thermal properties of the chitosan adhesives were analyzed by differential scanning calorimetry (DSC) and thermomechanical analysis (TMA). Fourier-transform infrared (FTIR) spectrometry and matrix assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry were used to explain the reaction mechanisms involved. Oxidized carbohydrates have been shown to effectively improve the bond strength and water resistance of chitosan adhesives, with oxidized starch showing a better improvement than glucose and sucrose. The best chitosan-oxidized starch (CS) adhesive is obtained by treatment with 8 mass% of oxidized starch mixed with a chitosan solution at ambient temperature, when 10% sodium periodate on starch weight is used for its specific oxidation. Thermal analysis shows that the chitosan-oxidized starch (CS) adhesive cures at a lower temperature than the other adhesives in this work, this being one of the reasons for CS having a better bonding performance. MALDI and FTIR showed oxidized glucose, taken as a model, to form aldehydes and condensation products due to water elimination between two aldehyde groups, followed then by their reaction with the chitosan.

International audience

Sucrose-based non-isocyanate polyurethanes (S-NIPU) were synthesized by the already codified reaction of sucrose, dimethyl carbonate and hexamethylene diamine and used for the first time as adhesives for bonding particleboard. To decrease the NIPU adhesive curing temperature, a silane coupling agent was used as a crosslinking promoter. The performance of particleboards prepared at a press temperature of 230 °C, 200 °C and 180 °C and a press time of 8 min, 10 min and 12 min was tested and evaluated. The structure of the oligomers obtained was detected by matrix-assisted laser desorption ionization time-of-flight mass spectrometry. Thermomechanical analysis and differential scanning calorimetry were also used to analyze their behavior. The particleboards bonded with the S-NIPU adhesive at 230 °C showed excellent properties, which, however, decreased as the press time was reduced. The silane coupling agent used as a crosslinking promoter significantly reduced the curing temperature of the adhesive and allowed to obtain good bonding at a lower press temperature. The results obtained confirmed that coupling the S-NIPU adhesive with a silane used as a crosslinking promoter can yield sufficiently improved results to function as a suitable adhesive for particleboard, medium density fiberboard and other types of particulate wood panels. It was also the first time that a NIPU adhesive was used for wood bonding.

To find the effects of cross-linker phenol-formaldehyde (PF) resin on the performance of soy-based adhesives, the reaction between model compounds hydroxymethyl phenol (HPF) and glutamic acid were studied in this paper. HPF prepared in laboratory conditions showed higher content of hydroxymethyl groups than normal PF resin, which was proved by the results of Electrospray Ionization Mass Spectrometry (ESI-MS) and 13C Nuclear Magnetic Resonance (13C-NMR). The results of ESI-MS, Fourier transform infrared spectroscopy (FT-IR), and 13C-NMR based on resultant products obtained from model compounds showed better water resistance of the soy protein-based adhesive modified by PF-based resin, which indicated the reaction between PF resin and soy protein. However, it seemed that the soy-based adhesive cross-linked by HPF with the maximum content of hydroxymethyl groups did not show the best water resistance.

(1) A compound protectant was prepared using manganese chloride, phosphoric acid, boric acid and ammonium chloride, and then a veneer was immersed in the prepared protectant to prepare plywood in this paper. Great attention was paid to discussing influences of such protectant on fire resistance, decay resistance, anti-mold property and bonding performance of plywood. Results demonstrated that after protectant treatment, the plywood showed not only good fire resistance and smoke inhibition, but also strong char-formation ability, slow flame spreading, long time to ignition, small fire risk and high safety level. (2) The mass loss rates of plywood with protectant treatment after infection and erosion in wood-destroying Coriolus versicolor and Gloeophyllum trabeum were 19.73% and 17.27%, reaching the II-level corrosion grade. (3) There is not a significant difference with Aspergillus niger V., however, it was possible to observe a strong difference with Trichoderma viride Pers. ex Fr., indicating that the protectant acted as a good anti-mold product for plywood. (4) The protectant influenced the bonding interface of wood and bonding conditions of the adhesive. The bonding strength of plywood was weakened, but it still met the requirements on bonding strength of GB/T 9846-2015. (5) The protectant changed the thermal decomposition and thermal degradation of plywood, inhibiting the generation of inflammable goods, blocking transmission of heats and lowering the thermal decomposition temperature of plywood. These promoted dehydrations and charring of wood and the generated carbon had a high thermal stability. (6) Compared with untreated plywood, the prepared protectant treatment significantly enhanced the fire resistance of plywood, reduced its biodegradability by wood-decaying fungi and showed good mold resistance.

To develop a soy-based adhesive with good water resistance, non-toxic melamine–glyoxal resin (MG) prepared in the laboratory was used as a cross-linker of soy-based adhesive. The FT-IR and ESI-MS results showed that there was a reaction between melamine and glyoxal. The resulted –CH–OH– groups could be the possible reactive groups for the cross-linking of soy-based adhesive. The wet shear strength of soy-based plywood indicated that the water resistance of soy adhesive cross-linked by MG improved with respect to that with no cross-linker, although it was not good enough to satisfy the relative standard. With the optimized preparation procedures for plywood, specifically, press temperature 180 °C, press time 3 min and resin loading 280 g m−2, type I soy-based plywood could be prepared with a hybrid cross-linker, namely 12%MG + 2% epoxy resin (EPR). The DSC results showed that the reaction between soy-based adhesive and the hybrid cross-linker MG + EPR was very complex.

Sodium periodate has been shown to cleave glucose by specific oxidation to yield a number of non-volatile aldehydes which can react with the phenolic compounds in tannin extract and lead to tannin cross-linking and hardening. This approach to prepare a tannin resin useable for wood adhesives can be used by either treating with periodate a mixture of tannin and glucose, or to treat glucose beforehand with periodate to cleave it and generate the aldehydes, and only afterwards to mix it with the tannin. The results obtained with these two methods are identical, but the latter method avoids oxidation of tannin. The aldehydes were generated either by direct cleavage of glucose C–C bonds carrying vicinal oriented hydroxyls, or by recombination of the aldehydes so formed by aldol condensation or by water elimination between two aldehyde groups. MALDI ToF analysis indicated that all the three types of aldehydes appeared to react with the polyphenols in the tannin. Thermomechanical analysis (TMA) and plywood bonded with the tannin + glucose + periodate mixes gave good bonding results, with dry, 24 h cold water soaking and 3 h at 63 °C shear strength values improving concomitantly to the proportion of periodate used for the oxidation step.

To guide the preparation of protein-based adhesive, especially the soy-based adhesive, the reaction between a simple dipeptide N-(2)-l-alanyl-l-glutamine (AG), being used as a model compound of protein, and its cross-linker furfuryl alcohol were studied in this paper. The products that were prepared with furfuryl alcohol and AG under different pHs were analyzed by ESI-MS, 13C NMR, and FT-IR. It was found that the medium environment had great effects on the competition of the co-condensation reaction between furfuryl alcohol and AG and self-condensation reaction of furfuryl alcohol molecules in the mixing system with furfuryl alcohol and AG. Under alkaline conditions, both co- and self-condensation were not obviously detected. Only when the value of pH was higher than 11, were a few co-condensation reaction products gotten. The reaction occurred mainly between furfuryl alcohol and the primary amido groups of AG. Under acid conditions, both co- and self-condensation were observed. The more acid the preparation conditions were, the easier to be observed the self-condensation of furfuryl alcohol molecules would be than the co-condensation between furfuryl alcohol and AG. When the value of pH was higher than 5, both co- and self-condensation were not outstanding. In this study, under pH 3, the co- and self-condensation found equilibrium. There was a great possibility for the primary amido and aliphatic amino groups of AG molecules to react with furfuryl alcohol molecules. No reaction was detected between the secondary amido groups of AG and furfuryl alcohol.

To improve the water resistance of soy-based adhesive for wood panels, three kinds of cross-linkers, namely, epoxy resin (EPR), melamine–formaldehyde (MF) and their mixture EPR+MF were used in this paper. The results indicated that all the three cross-linkers improved the water resistance of soy-based adhesive and the hybrid cross-linker EPR+MF, was the best. With press temperature 160 °C and press time 8 min, type II and even type I plywood could be prepared when 6.4%EPR+6.4%MF is used as cross-linker of soy-based adhesive. FT-IR indicated that the great improvement of water resistance of soy-based adhesive modified with EPR and MF might be caused by the reaction between epoxy and –OH, and that between MF and –NH.

To prepare a low-formaldehyde soy-based adhesive with good water resistance, phenol-formaldehyde modified with glutaraldehyde (PFG) with lower free phenol and free formaldehyde contents was used to cross-link the soy-based adhesive. The results showed that the mechanical properties and water resistance of plywood prepared with soy-based adhesive with PFG was better than that of plywood with the same amount of phenol-formaldehyde (PF). The reaction between phenol and glutaraldehyde was proved by 13C-NMR. Under the optimized preparation conditions for plywood, that is to say, press temperature 160 °C, press time 4 min and resin loading 320 g·m−2, type I plywood could be prepared with 9% PFG as a cross-linker of soy-based adhesive. The Differential Scanning Calorimetry (DSC) result confirmed the cross-linking reaction between soy-based adhesive and PFG or PF. The activation energy of soy-based adhesive with cross-linker PFG was higher than that with PF resin.