Soy Protein Isolate Non-Isocyanates Polyurethanes(NIPU)Wood Adhesives

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℃),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,chemical cross-linking of the chains appeared to ensue,forming a hardened network.This was shown by the thermomechanical analysis(TMA)showing two distinct MOE maxima peaks,one around 130℃ and the other around 220℃,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.

No-Aldehydes Glucose/Sucrose-Triacetin-Diamine Wood Adhesives for Particleboard

A three reagents adhesive system for wood particleboards not containing any aldehyde was developed by the reaction of glucose or sucrose with triacetin(glycerin triacetate)and with hexamethylene diamine.The system was found to be based on the mix of three reactions,namely the reaction of(i)glucose with triacetin,(ii)of the diamine with triacetin,and(iii)of glucose with the diamine.The chemical species formed were identified by Matrix Assisted Laser Desorption Ionization Time of Flight(MALDI-ToF)mass spectrometry.Wood particleboard panels were prepared with this adhesive system and gave good internal bond(IB)strength results suitable for interior grade panels and with extremely low formaldehyde emission.

Adhesion of Technical Lignin-Based Non-Isocyanate Polyurethane Adhesives for Wood Bonding

Lignin is the most abundant aromatic natural polymer,and receiving great attention in replacing various petro-leum-based polymers.The aim of this study is to investigate the feasibility of technical lignin as a polyol for the synthesis of non-isocyanate polyurethane(NIPU)adhesives to substitute current polyurethane(PU)adhesives that have been synthesized with toxic isocyanate and polyols.Crude hardwood kraft lignin(C-HKL)was extracted from black liquor from a pulp mill followed by acetone fractionation to obtain acetone soluble-HKL(AS-HKL).Then,C-HKL,AS-HKL,and softwood sodium lignosulfonate(LS)were used for the synthesis of technical lignin-based NIPU adhesives through carbonation and polyamination and silane as a cross-linker.Their adhesion per-formance was determined for plywood.FTIR spectra showed the formation of urethane bonds and the reaction between lignin and silane.The NIPU adhesives prepared with C-HKL showed the highest adhesion strength among the three lignin-based NIPU adhesives.As the silane addition level increased,the adhesion strength of NIPU adhesives increased whereas formaldehyde emission decreased for all NIPU adhesives prepared.These results indicate that NIPU adhesives based on technical kraft lignin have a great potential as polyol for the synth-esis of bio-based NIPU adhesives for wood bonding.

MUF Resins Improved by Citric Acid as Adhesives for Wood Veneer Panels

This article presents the first applied results of using citric acid in combinations with a melamine-urea-formal-dehyde(MUF)resin for bonding wood veneers.The chemical reactions involved are shown based on a MALDI ToF analysis of the reaction of the MUF resin with citric acid.The preliminary results of the physical and mechanical properties of the LVL prepared are also presented.Veneers from Populus sp were used to manufacture 5-layer laminated veneer lumber(LVL)of small dimensions.Five combinations of the amount of citric acid,MUF spread rate and pressing parameters were tested.LVL bonded with 20%of citric acid+100 g/m^(2)of MUF,hot-pressed using a 3-step process with maximum 1.5 MPa of pressure yielded the board with better dimensional stability and mechanical properties.It could be concluded that citric acid in combination with MUF can be used for bonding wood veneer and the research should be continued to study further the parameters involved and to enhance the results.

Overview of the Synthesis, Characterization, and Application of Tannin-Glyoxal Adhesive for Wood-Based Composites

More than a century after its initial synthesis,urea-formaldehyde(UF)resins still have dominant applications as adhesives,paints,and coatings.However,formaldehyde in this industry produces formaldehyde emissions that are dangerous to health.Scientists have spent the last decade replacing formaldehyde and phenol with environmentally friendly substances such as glyoxal and tannin to create bio-based adhesives.This review covers recent advances in synthesizing glyoxal tannin-based resins,especially those made from sustainable raw material substitutes and changes made to synthetic processes to improve mechanical properties.The efficacy of using tannin-glyoxal adhesives in producing wood-based composites has been proven.The glyoxylate reaction forms cross-linked bridges between the aromatic sites of the tannin and glyoxal molecular structures.Glyoxal tannin adhesive with a greater percentage of glyoxal than tannin will produce an adhesive with better characteristics.The gel time reduces as the hardener concentration rises from 7.5%to 15%when glyoxal is used in adhesives.However,excessive amounts of glyoxal will result in a decrease in viscosity values.Glyoxal exhibits faster delivery degradation when it reaches a maximum temperature of approximately 130°C,although it initiates the curing process slightly slower at 110°C.Adding glyoxal to tannin-based adhesives can improve the mechanical properties of composite boards.The wet shear strength of the resulting plywood is increased by 105.4%with the addition of 5-weight percent tannin-based resin with glyoxal as a cross-linker in Soy Protein Adhesive.With glyoxal as a hardener,the panels produced showed good internal bond strengths(>0.35 MPa)and met the international standard specifications for interior-grade panels.

Preparation of Environmentally Friendly Urea-Hexanediamine-Glyoxal(HUG)Resin Wood Adhesive

Using non-toxic,low-volatile glyoxal to completely replace formaldehyde for preparing urea-glyoxal(UG)resin adhesive is a hot research topic that could be of great interest for the wood industry.However,urea-glyoxal(UG)resins prepared by just using glyoxal instead of formaldehyde usually yields a lower degree of polymerization.This results in a poorer bonding performance and water resistance of UG resins.A good solution is to pre-react urea to preform polyurea molecules presenting already a certain degree of polymerization,and then to condense these with glyoxal to obtain a novel UG resin.Therefore,in this present work,the urea was reacted with hexamethylene diamine to form a polyurea named HU,and then this was used to react it with different amounts of glyoxal to synthesize hexamethylenediamine-urea-glyoxal(HUG)polycondensation resins,and to use this for bonding plywood.The results show that the glyoxal can well react with HU polyuria via addition and schiff base reaction,and also the HUG resin exhibits excellent bonding strength and water resistance.The shear strength of the plywood bonded with this HUG at 160°C hot press temperature as high as 1.93 MPa,2.16 MPa and 1.61 MPa,respectively,which meets the requirement of the China national standard GB/T 9846-2015(≥0.7 MPa),and can be a good choice as a wood adhesive for industrial application.

Crosslinking Mechanism of Soy Protein-based Adhesives based on Glyoxal and a Compound of Protein Model

The crosslinking mechanism of glyoxal and asparagine was analyzed,and the relationship between the mechanism and practical performances of soy protein-based adhesives was also discussed.It is shown that when pH=1 and 3,glyoxal reacted with asparagine in the form of major cyclic ether compounds.When pH=5,glyoxal reacted with asparagine in two structural forms of sodium glycollate and cyclic ether compounds.However,amidogens of asparagine were easy to develop protonation under acid conditions.Supplemented by the instability of cyclic ether compounds,the reaction activity and reaction degree between glyoxal and asparagine were relatively small.Under alkaline conditions,glyoxal mainly reacted with asparagine in the form of sodium glycollate.With the increase of pH,the polycondensation was more sufficient and the produced polycondensation products were more stable.The reaction mechanism between glyoxal and asparagine had strong correspondence to the practical performances of the adhesives.Glyoxal solution could develop crosslinking reactions with soy protein under both acid and alkaline conditions.Bonding strength and water resistance of the prepared soy protein-based adhesives were increased significantly.When pH>7,glyoxal had relatively high reaction activity and reaction intensity with soy protein,and the prepared adhesives had high crosslinking density and cohesion strength,showing relatively high bonding strength,water resistance and thermal stability.

Study on the Preparation Process Optimization of Plywood Based on a Full Biomass Tannin-Sucrose Wood Adhesive

Biomass adhesive is conducive to decreasing the dependence of the wood adhesive industry on synthetic resin based on fossil resources and improving the market competitiveness of adhesives.It is also a critical breakthrough to realize the goal of carbon peaking and carbon neutrality in the wood industry.In this study,a full biomass wood adhesive composed of tannin and sucrose was developed and applied successfully to the preparation of ply-wood.The preparation technique of plywood was optimized,and the chemical structure,curing performance,crystallization property and thermal performance of the adhesive were investigated.Results showed that:(1)hot-pressing temperature played a decisive role in the performances of tannin-sucrose composite adhesives and it also had a very significant influence on the water resistance of plywood.(2)The preparation of tannin-sucrose composite adhesive was a process in which sucrose was transformed into furan aldehydes and then made cross-linking reaction with tannin.These composite adhesives could only get good bonding performances when the curing temperature was above 210℃.(3)The optimal plywood preparation technique was:hot-pressing tem-perature of 220℃,hot-pressing time of 1.2 min/mm,m(tannin):m(sucrose)of 60:40,and adhesive loading of 160 g/m^(2).The wet bonding strength in boiling water of the prepared plywood was 0.83 MPa,meeting the strength requirements of Type-I plywood in the standard of GB/T 17657-2013.(4)The curing temperature of tannin-sucrose composite adhesive was further decreased by lowering the temperature during the transformation of sucrose into 5-HMF,which was a key in subsequent research.

Comparative Study of Effect of Addition of Calcium Carbonate and Clay on the Performance Properties of Polyvinyl Acetate Wood Glue

Polyvinyl alcohol (PVA) stabilized Polyvinyl acetate (PVAc) dispersions-based wood adhesive has poor water and heat resistance. Recently, the addition of fillers in the wood adhesive is one of the most effective ways to enhance the performance of PVAc wood adhesive. Inorganic fillers have unique characteristics to improve the performance of adhesive, such as small size, high surface energy and surface hardness. Hence, the present work investigates the applicability of calcium carbonate and clay incorporated 3% in situ emulsion polymerization PVAc wood adhesive. Effect on physical, thermal and mechanical properties was studied by viscosity, pH, contact angle measurement, differential scanning calorimetry (DSC) and pencil hardness test of films. Emulsions with 3% calcium carbonate and 3% clay were prepared and the shear strength of the applied adhesive on wood was measured. The viscosity of the adhesives was reduced in the case of the addition of calcium carbonate and increased in the case of clay. The mechanical properties like tensile strength of adhesives with calcium carbonate and clay were measured by a universal tensile machine (UTM). Thermal stability was studied by differential scanning calorimetry (DSC). The tensile shear strength demonstrates that clay can improve bonding strength as compared to calcium carbonate of PVAc adhesive in wet conditions. The hardness of PVAc films was also changed positively by the addition of calcium carbonate and clay. Thermal stability of PVAc was significantly improved as calcium carbonate and clay were added to PVAc. Here, we did a comparative study of the effect of the addition of calcium carbonate and clay filler materials in situ polymerization of PVAc on their different properties.

Lignocellulosic Micro and Nanofibrillated Cellulose Produced by Steam Explosion for Wood Adhesive Formulations

The reinforcing impact of Lignocellulosic micro and nanofibrillated cellulose(L-MNFCs)obtained from Eucalyp-tus Globulus bark in Urea-Formaldehyde UF adhesive was tested.L-MNFCs were prepared by an environmentally friendly,low-cost process using a combination process involving steam explosion followed by refining and ultra-fine grinding.Obtained L-MNFCs showed a web-like morphology with some aggregates and lignin nanodroplets.They present a mixture of residual fibers and fine elements with a width varying between 5 nm to 20μm,respec-tively.The effects of the addition of low amounts of L-MNFCs(1%wt.)on the properties of three different adhe-sives(Urea-Formaldehyde UF,Phenol-Formaldehyde PF,and Tannin-Hexamine TH)were studied by the evolution of the pH,the viscosity,and the mechanical properties.Results showed that the viscosity of PF and UF adhesives increased with the addition of L-MNFCs,unlike TH.Meanwhile,the addition led to better mechan-ical behavior for the three adhesives.Particleboards were then prepared using modified UF with L-MNFCs and tested.Results showed that an amount of 1%wt.of L-MNFCs was sufficient to increase the internal bonding by≈67%,the modulus of elasticity by≈43%,and the modulus of rupture by≈29%.

Study on Camellia Oleifera Protein based Wood Adhesive by Epoxy Resin and Its Crosslinking Mechanism

Epoxy resin (EPR) was used to crosslink with Camellia oleifera Abel.protein to prepare wood adhesive,and the bonding performance and curing characteristics of which were mainly investigated,and the synthesis mechanism was also discussed by using model compounds.The experimental results show that EPR can significantly improve the bonding performance of Camellia oleifera Abel.protein-based adhesive,and the maximum of which reaches 0.72 MPa satisfies the strength requirement of Type II plywood in GB/T 17657-2013.After alkali treatment,the protein can more easily crosslink with EPR at low curing temperature,and the adhesive has high degree of crystallinity of curing products,high degree of crosslinking reaction,and high bonding strength.The reaction mechanism of EPR-modified Camellia oleifera Abel.protein adhesive can be divided into resinification phase and curing phase.

An Eco-Friendly Wood Adhesive from Alfalfa Leaf Protein

According to the preparation method commonly used for soy proteinαbased adhesives,alfalfa leaf protein was used as the raw material to prepare alfalfa leaf protein-based wood adhesive.Differential scanning calorimetry analyzer(DSC),X-ray diffraction(XRD)and Fourier transform infrared spectroscopy(FTαIR)were used to characterize properties of the alfalfa leaf protein-based adhesive in this paper.The results revealed the following:(1)Chemical compositions and chemical structures of the alfalfa leaf protein were basically identical with those of the soy protein,both belonging to spherical proteins with the basis and potential for protein adhesives preparation,and spatial cross-linked network structures would be easily formed.(2)Alfalfa leaf protein and soy protein adhesives had the similar curing behaviors,curing temperature of alfalfa leaf protein-based adhesive was relaαtively lower,and the heating rate had minor influence on curing temperature of alfalfa leaf protein-based adhesive.At different heating rates,change tendencies of curing reaction degrees of both the two adhesives were not totally the same.(3)Activation energy and reaction frequency factor of the alfalfa leaf protein-based adhesive were higher than those of soy protein-based adhesive,indicating that the curing reaction of the alfalfa leaf protein adhesive was more difficult than soy protein-based adhesive,thus the dry shear strength and water resistance of alfalfa protein-based adhesive were lower than those of soy protein-based adhesive.Dynamics models of curing reactions of alfalfa leaf protein-based adhesive and soy protein-based adhesive are dα=dt/1.06×10^(13)e^(-97370/RT)(1-α)^(0.938) and dα/dt=1.09×10^(11)e^(-84260/RT) 1-α)^(0.928) respectively.The results of this study will expand the selection of raw materials for protein-based wood adhesives.

Synthesis, performance and structure characterization of glyoxal-monomethylolurea-melamine (G-MMU-M) co-condensed resin

In order to reduce the formaldehyde emission of formaldehyde-based wood adhesive from the source,it is aimed to develop a novel co-condensed resin of glyoxal-monomethylolurea-melamine(G-MMU-M).A series of G-MMU-M resins with various formulations of raw materials were successfully prepared.The basic properties and bonding performance of the G-MMU-M resins were determined.Furthermore,the structures of resins were characterized by FTIR,^(13)C NMR,XPS,and ESI-MS.The results show that the prepared G-MMU-M resin remains stable for 30 d,meanwhile,the dry and wet bonding strength of the plywoods bonded with the resins,solid content and viscosity are influenced greatly by the addition amount of melamine and MMU/G molar ratio.The G-MMU-M resins with MMU/G molar ratio of 0.9:1.0 and 8% melamine exhibit the highest dry and bonding strength of 1.98 MPa and 1.27 MPa,increased by 34% and 63%,respectively,in comparison with glyoxal-monomethylolurea(G-MMU)resin.In the G-MMU-M resins,there were four main oligomers including M—CH(—^(+)CH-MMU)-O-MMU,M-CH(—CH_(2)OH)-MMU-O-MMU,M—CH(—OH)—^(+)CH-MMU-O-MMU,and M—CH(—^(+)CH-MMU)-MMU-p-G.

The Crosslinking Mechanism of Camellia Oleifera Protein Adhesive with Amine Resins by ^(13)C-NMR and ESI-MS

A new protein wood adhesive was studied with Camellia oleifera protein.Formaldehyde and N-(2)-L-Ala-L-Gln(LAG)were used as the model compounds of amino resins and Camellia oleifera protein,aiming to provide scientific foundations for the improvement and applications of Camellia oleifera protein adhesive by the reaction of model compounds.The experimental results demonstrate that,under alkaline conditions,formaldehyde is easier to react with Camellia oleifera protein by quicker reaction and lower curing temperature.Under acid conditions,amino hydroxymethylated structure of aliphatic series from LAG is difficult to form stable reactive intermediates and further polycondensation.Hydroxymethylation of end acylamino and peptide bond amino from LAG is relatively weak.Under alkaline conditions,the free aliphatic amino and acylamino of LAG both can make hydroxymethylation reaction with formaldehyde.In the polycondensation,hydroxymethyl amide is the initial structure and the reactive intermediate is produced by E1cb reaction of hydroxymethyl amide.Methylene bridge bonds and methylene ether bonds are structures of the polycondensation products,which are competing reactions.The former is mainly formed by the reaction between alkaline reactive intermediate and amino of aliphatic series,and the latter is produced by the reaction of reactive intermediate and amino of hydroxymethyl aliphatic series with hydroxymethyl amide.

Synthesis of Microcrystalline Cellulose—Polyvinyl Alcohol Stabilized Polyvinyl Acetate Emulsion

Polyvinyl alcohol (PVA) colloid stabilized Polyvinyl acetate (PVAc) based wood adhesive has poor performance in highly humid conditions. Currently, the addition of natural fillers in the wood adhesive is one of the most effective ways to enhance the performance of PVAc wood adhesive in highly moist conditions. Microcrystalline cellulose (MCC) are strong renewable, bio-based material and has great potential in a reinforcement of the polymeric matrix. Hence, the present work investigates the applicability of microcrystalline cellulose incorporated 3% and 5% in situ emulsion polymerization PVAc wood adhesives. Effect on physical, thermal and mechanical properties was studied by viscosity, pH, contact angle measurement, differential scanning calorimetry (DSC) and pencil hardness test of films. Emulsions with different proportions of MCC were prepared and the shear strength of the applied adhesive on wood was measured. The viscosity of the adhesives was increased by increasing the concentration of MCC. The mechanical properties like tensile strength of adhesives with MCC were measured by universal tensile machine (UTM). Thermal stability was studied by differential scanning calorimetry (DSC). The tensile shear strength demonstrates that MCC can improve bonding strength as compared to PVAc Homo based adhesive in the wet condition which was validated through a contact angle study. The hardness of PVAc films were also changed positively by the addition of MCC. Here, we studied the effect of the addition of different concentrations of MCC materials in situ polymerization of PVAc on their performance properties.

Enzymatic Hydrolysis Lignin(EHL)and its applications for value-added products,a quick review

Enzymatic hydrolysis lignin(EHL)has a variety of active groups,which endow it with excellent properties and broad application prospects.Research work on EHL will promote better utilization of lignin resources and sustainable development of ecological environment.This paper briefly reviewed the research progress on EHL structures,properties,modifications and applications.Future research and development on EHL were also discussed.