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In this study, the rotating welding process of Chinese fir (Keteleeriafortunei) in Guizhou, China, was systematically analyzed. The effects of rotating welding conditions, including the dowel-to-guide hole diameter ratio, welding time, depth, base surface, angle, and dowel type, on the performance of welded Chinese fir were explored. Moreover, the physical and chemical changes oftheChinese fir interface during welding were revealed by Fourier-Transform Infrared Spectroscopy (FT-IR), X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD), and Scanning Electron Microscopy (SEM). The results indicated the following: (1) The rotating welding technology can quickly achieve a strong connection between wood through friction heat without chemical adhesives and compared with traditional wood connection technology such as gluing or mechanical fixing;it has the advantages of simple operation, high production efficiency; and environmental friendliness. (2) Aftertherotating welding, the wood underwent significant pyrolysis, especially the degradation of hemicellulose. The heat generated in the welding process caused good melting and mechanical interlocking between the dowel and the wall of the guide hole, but it was also accompanied by afriction loss of the dowel and the substrate. (3) The welding parameters affected the wood's connection strength and stability by altering heat production, distribution, transfer, and frictional losses. The impact of the dowel-to-guide hole diameter ratio had a great influence on the connection strength. When the diameter ratio was 1:0.7, the tensile strength was the highest, reaching 2.27 MPa. (4) The analyses of XPS, FTIR, XRD, and SEM proved thatthechemical composition changes at the interface, leading to a more structured crystalline bond and enhanced connection strength due to fiber entanglement and interlocking. This research providesatheoretical and experimental basis forthefurther innovation and development of wood processing technology and provides a new technical path forthegreen manufacturing of wood structure buildings. [ABSTRACT FROM AUTHOR]

This study focuses on the competition reaction rules of a system containing resorcinol (as a tannin model compound) and dimethylol urea (as a urea–formaldehyde resin model compound) under various alkaline and acidic environments. The aim is to investigate the crosslinked modification mechanism of urea–formaldehyde resin with tannin adhesive. The study delves into the competitive relationship between self-condensation polymerization reactions and co-condensation polymerization reactions. It specifically highlights the conditions for the copolycondensation reaction of dimethylolurea and resorcinol and validates its rationality through an examination of the resorcinol–urea–formaldehyde system's reaction rules. The results show that (1) under strongly acidic conditions, the activity of carbocation intermediates produced by hydroxymethyl resorcinol for the resorcinol phenol ring is higher than the electrophilic reactivity of nitrogen atoms on hydroxymethyl urea, which is more beneficial for the resorcinol–formaldehyde self-polycondensation reaction, and the co-polycondensation structures do not play a dominant role. (2) Under weakly acidic conditions, the co-polycondensation structures are evidently advantageous over self-polycondensation structures, and the degree of the co-polycondensation reaction is positively correlated with pH below the neutral point of resorcinol. (3) Under alkaline conditions, the self-polycondensation between resorcinol and formaldehyde is dominant in the system. (4) The concentration of hydroxymethyl urea carbocation is the key factor to determine the degree of the co-polycondensation reaction. [ABSTRACT FROM AUTHOR]

The wettability, bonding strength and flexibility of modified melamine–urea–formaldehyde resin adhesive with hydroxymethyl lignin (LMUF) were investigated. Moreover, the curing performance, thermal properties and chemical structure of LMUF were analyzed by differential scanning calorimetry (DSC), thermogravimetry (TG), scanning electronmicroscopy (SEM), X–ray diffraction (XRD), Fourier–transform infrared spectroscopy (FTIR) and 13C nuclear magnetic resonance (13C–NMR). The synthesis mechanism of LMUF was also discussed. The results demonstrated that: (1) LMUF resin is characterized by low free formaldehyde and a short pot life. (2) With the increase in hydroxymethyl lignin, the bonding strength and flexibility of the LMUF increased first and then decreased. They reached their maximum when the hydroxymethyl lignin content was 6%–8%, which represented increases of 36% and 102%, respectively. (3) The DSC and TG analyses showed that the LMUF resin had a high hot-pressing temperature, but its thermostability was increased. (4) The XRD and SEM analyses proved that the LMUF resin was characterized by flexibility failure, especially at 6% of hydroxymethyl lignin. (5) Hydroxymethyl lignin is a type of flexible long-chain molecule, which was introduced into spaces between the rigid triazine rings through adhesion and penetration, thus improving the regular single structural form of MUF resin and increasing the compactness of the system. As a result, the resin had stronger deformability and cohesion in the molecules. The bonding strength and flexibility were improved to different degrees. [ABSTRACT FROM AUTHOR]

Rosin has a great influence on the bonding of Pinus massoniana wood, and surface modification is an important way to solve this problem. In this study, Pinus massoniana wood was treated by plasma, and the effects of plasma treatment on the bonding performance and surface characteristics were investigated. The results showed the following: (1) After plasma treatment, the contact angle of Pinus massoniana wood was significantly reduced and the surface energy was significantly increased from 28.42 × 10−7 to 74.75 × 10−7 J·cm−2, and the surface wettability was also greatly improved. (2) Plasma high-energy particles experience simultaneous physical and chemical effects on the surface of Pinus massoniana wood. The former formed a micro-etched roughness on the wood surface and led to the increase in surface dispersion force, while the latter increased the aggregation and activity of polar groups on the wood surface and the degradation of some wood components and rosin, resulting in the increase in surface polar force and the enhancement of wettability. (3) After plasma treatment, the reactivity of wood was enhanced, and the cross-linking degree with adhesive and the heat release were increased. The bonding strength of Pinus massoniana wood could be improved: dry bonding from 5.08 to 5.38 MPa, boiling-water bonding strength from 4.12 to 4.53 MPa, cold-water bonding strength from 3.84 to 4.51 MPa, and the bonding stability and reliability of glued specimens were also improved. [ABSTRACT FROM AUTHOR]

Whole-biomass adhesives are the research hotspot of wood adhesives andcan improve the competitiveness of adhesives. The tannin–sucrose adhesive studied by our research group shows good bonding performance, but poor bonding stability induced by low viscosity. In this study, the tannin–sucrose adhesive was modified by isolated soybean protein (SPI), the effect of the SPI substitution ratio for tannin on the properties of the tannin–sucrose–SPI composite adhesive was investigated, and the bonding mechanism was explored using Fourier-transform infrared spectroscopy (FT-IR), thermogravimetry (TG), X-ray diffraction (XRD), and gas chromatography–mass spectroscopy (GC–MS). The results showed that: (1) when the SPI substitution ratio was above 40%, the viscosity of the composite adhesive increased significantly, which effectively avoided adhesive leakage. (2) The tannin–sucrose–SPI composite adhesive displayed high bonding performance and water resistance. (3) The FTIR and GC–MS results revealed that the curing mechanism of the tannin–sucrose–SPI adhesive was very complicated, but it was certain that the conversion of sucrose into furan compounds, especially 5-hydroxymethylfurfural (5-HMF), was the core of the cross-linking reaction of the adhesive when elevating temperature. (4) The macromolecules and high reactivity of SPI compensated for the shortage of high temperature required for the conversion of sucrose into furanic cross-linkers so that the tannin–sucrose–SPI adhesive experienced an efficient curing reaction at a low temperature, and the reaction degree and thermal stability of the curing product increased. [ABSTRACT FROM AUTHOR]

Fully bio-based adhesives are beneficial to reduce the dependence of the wood adhesive industry on synthetic resins based on petrochemical resources and enhance the market competitiveness of adhesives. A fully bio-based wood adhesive composed of tannin and sucrose was developed and successfully used in the preparation of plywood. Effects of the preparation technology on the bonding strength and water resistance of plywood were investigated, and the properties of the adhesive were analyzed by Fourier transform infrared spectroscopy (FT-IR), thermogravimetry (TG) and X-ray diffraction (XRD) in this study. The results showed that: (1) Compared with other biomass adhesives, tannin–sucrose adhesive had the characteristics of high-solid content and low viscosity, which had the potential to prepare particleboard and fiberboard. (2) A proper mass ratio of tannin to sucrose was key to obtaining a tannin–sucrose adhesive with better properties. (3) The optimum preparation process of tannin–sucrose adhesive for plywood was as follows: hot-pressing temperature of 210 °C, hot-pressing time of 1.2 min/mm, m(tannin):m(sucrose) of 60:40 and adhesive loading of 160 g/m2. Under these conditions, the water-resistant bonding strength of the plywood was 0.89 MPa, which met the strength requirements of the Type II standard of plywood in GB/T 17657-2013. (4) The hot-pressing temperature played a decisive role in the tannin–sucrose adhesive, and the good performance of the plywood was maintained when the temperature was 210 °C or above. Thus, the prepared tannin–sucrose adhesive had high-bonding strength, good water resistance and thermal stability. [ABSTRACT FROM AUTHOR]

In order to improve the initial viscosity and stability of Camellia oleifera cake-protein adhesive, Camellia oleifera cake-protein was blended with defatted soybean protein (DSP), soybean protein isolate (SPI), and casein, followed by adhesive preparation through degradation and crosslinking methods. The performance of Camellia oleifera cake-protein adhesive was investigated by Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), scanning electron microscopic (SEM), and thermogravimetric (TG) and X-ray diffraction (XRD). The results showed that DSP, SPI, and casein likely promoted the effective degradation of Camellia oleifera cake-protein, and, thus, more active groups were formed in the system, accompanied by more reactivity sites. The prepared adhesive had a lower curing temperature, and higher initial viscosity and stability, but the storage time was shortened. Moreover, DSP, SPI, and casein, themselves, were degraded into peptide chains with lower molecular weights; thus, improving the overall flexibility of the adhesive, facilitating a better elastic contact and regular array between crosslinking products, and further strengthening the crosslinked structure and density of the products. After curing, a compact and coherent reticular structure was formed in the adhesive layer, with both bonding strength and water resistance being significantly improved. According to the results obtained, the next step will be to study the DSP-modified Camellia oleifera cake-protein adhesive in depth. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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, 13 C 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., Competing Interests: The authors declare no conflict of interest.

The base-catalyzed resorcinol-formaldehyde condensation reactions were theoretically investigated in this study by employing a quantum chemistry method. The condensation reaction includes two steps: (1) formation of the quinonemethide (QM) intermediate from hydroxymethylresorcinol; (2) Michael addition between the quinonemethide and resorcinol anion. The first step is the rate-determining step. Two mechanisms, unimolecular elimination of the conjugate base (E1cb) and water-aided elimination (WAE), were identified for the formation of QM. The hydroxymethylresorcinol anion produces neutral QM while the dianion produces a quinonemethide anion (QMA). The calculated potential energy barriers suggested that the QMA formation is much more favorable. Although resorcinol-formaldehyde and phenol-formaldehyde condensations share a common mechanism, the former would be faster if the QMA participates in condensations. The potential energy barriers for formation of 2-QM, 4-QM, 6-QM, 2-QMA, and 4-QMA were calculated. The results show that the formations of 6-QM and 4-QMA have relatively lower energy barriers. This rationalized previous experimental observations that the 2,4-(2,6-) and 6,6'-(4,4'-) methylene linkages were dominant, whereas the 2,2'-linkage was almost absent. The resorcinol-phenol-formaldehyde co-condensations were also calculated. The cold-setting characteristic of phenol-resorcinol-formaldehyde co-condensed resin can be attributed to participation of resorcinol quinonemethides in condensations., Competing Interests: The authors declare no conflict of interest.

Base-catalyzed urea⁻formaldehyde condensation reactions were investigated by using a quantum chemistry method. It was found that monomethylolurea or N , N '-dimethylolurea can produce the methyleneurea intermediate (⁻HN⁻CO⁻N=CH₂) with the catalysis of base. The E1cb (unimolecular elimination of conjugate base) mechanism was identified for the formation of such an intermediate. The potential energy barrier was theoretically predicted to be 59.6 kJ/mol for the E1cb step, which is about half of that of previously proposed S N 2 (bimolecular nucleophilic substitution) mechanism. In the subsequentcondensation reactions, Michael addition reactions that lead to different condensed structures can occur between the methyleneurea intermediate and the anions produced from methylolureas under alkaline conditions. Based on the theoretical calculations on the kinetics and thermodynamics of the selected reactions, the competitive formations of methylene linkages, ether linkages and uron were discussed in combination with our previous experimental observations., Competing Interests: The authors declare no conflict of interest.

1,3-dimethylurea (DMU) was used to mimic urea and to model melamine-urea-formaldehyde (MUF) co-condensation reactions. The products of 1,3-dimethylurea-formaldehyde (DMUF), melamine-formaldehyde (MF), and melamine-1,3-dimethylurea-formaldehyde (MDMUF) reactions under alkaline and weak acidic conditions were compared by performing quantitative carbon-13 nuclear magnetic resonance ( 13 C-NMR) analysis. The effect of pH on the co-condensation reactions was clarified. With the presence of the methyl groups in DMU, the appearance or absence of the featured signal at 54⁻55 ppm can be used to identify the co-condensed methylene linkage ⁻N(⁻CH₃) ⁻CH₂⁻NH⁻. Under alkaline condition, MDMUF reactions produced primarily MF polymers and the featured signal at 54⁻55 ppm was absent. Even though the co-condensations concurrently occurred, undistinguishable and very minor condensed structures with ether linkage were formed. Differently, under weak acidic condition, the relative content of co-condensed methylene carbons accounts for over 40%, indicating the MDMUF co-condensation reactions were much more competitive than the self-condensations. The formation of reactive carbocation intermediate was proposed to rationalize the results.

The mechanisms for the base-catalyzed condensation reactions in phenol-formaldehyde resin synthesis were investigated by using the density functional theory method. The structures of the intermediates and transition states, as well as the potential energy barriers of the involved reactions, were obtained. The hypothesis of quinine methide (QM) formation was theoretically confirmed. Two mechanisms were identified for QM formation, namely E1cb (elimination unimolecular conjugate base) and water-aided intra-molecular water elimination. The latter is energetically more favorable and is proposed for the first time in this work. Based on the QM mechanism, the condensation should be a unimolecular reaction because the following condensation between an ionized species (dissociated phenol or hydroxymethylphenol) with QM is much faster. The previously proposed S N 2 condensation mechanism was found to be not competitive over the QM mechanism due to a much higher energy barrier. The condensation reaction between neutral phenol or hydroxymethylphenol and QM was also found to be possible. The energy barrier of this reaction is close to or higher than that of QM formation. Therefore, the overall condensation reaction may appear to be bimolecular if such a reaction is incorporated. The theoretical calculations in this work rationalized the discrepant results reported in previous kinetics studies well.

The reactions of di-hydroxymethylurea with phenol under alkaline (pH = 10), weak (pH = 6) and strong acidic (pH = 2) conditions were investigated via the 13 C-NMR method. Based on the proposed reaction mechanisms, the variations of the structures of different condensed products were analyzed and the competitive relationship between self- and co-condensation reactions was elucidated. The required experimental conditions for co-condensations were clearly pointed out. The main conclusions include: (1) the self-condensation between urea formaldehyde (UF) or phenol formaldehyde (PF) monomers were dominant while the co-condensations were very limited under alkaline conditions. This is because the intermediates produced from urea, methylolurea and phenol are less reactive in co-condensations with respect to self-condensations; (2) under weak acidic conditions, the self-condensations occurred exclusively among the UF monomers. The co-condensation structures were not observed; and (3) the co-condensations became much more competitive under strong acidic conditions as the relative content of the co-condensed methylenic carbon accounts for 53.3%. This result can be rationalized by the high reactivity of the methylolphenol carbocation intermediate toward urea and methylolurea. The revealed reaction selectivity and mechanisms may also be applied to the synthesis of those more complex co-condensed adhesives based on natural phenolic and amino compounds.