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.

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.

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.

Polyurethane Hybrid-Based Wood Adhesive: Review

Based on commercially available polyvinyl alcohol (PVA) stabilised polyvinyl acetate (PVAc), emulsion adhesives are neither heat nor moisture-resistant and show weak strength at high relative humidity and high temperatures. Pre- or post-crosslinking is another method used to manufacture a conventional vinyl-based homopolymers or copolymers system with improved water resistance. Vinyl neodecanoate (VeoVa), N-methylolacrylamide (NMA), Methacrylamide, methacrylic acid (MAA), and other self-crosslinking comonomers are typically inserted to produce highly water-resistant vinyl based homopolymers or copolymers. Additionally, organic crosslinkers like glyoxal, glutaraldehyde, citric acid, tartaric acid, and the like, as well as inorganic crosslinkers like acidic metal salts like aluminium chloride, aluminium nitrate, boric acid, and the like, can be used to prepare the highly water-resistant vinyl based homopolymers or copolymers. It is also possible to combine the self-crosslinking comonomers with the organic crosslinkers. Recently, a different hybrid chemistry has been developed that improves lap shear strength, has outstanding water resistance, good durability, and doesn’t require any additional crosslinker agents. Two distinct polymers were combined to develop hybrid polymers. They usually involve mixing an organic polymer with a polymer. There are many capping agents that are used for polyurethanes to produce acrylics that are capped with polyurethane and used as an oligomer in PVAc wood glue. Here, in this paper, we reviewed the different hybrid chemistry based on polyurethane chemistry for wood bonding applications.

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.

Polyvinyl Acetate and Vinyl Acetate-Ethylene Hybrid Adhesive: Synthesis, Characterization, and Properties

The goal is to develop a hybrid IPN network of polyvinyl acetate (PVAc) and ethylene-vinyl acetate (VAE). In this research work, the vinyl acetate (VAc)/ VAE hybrid emulsion and polyvinyl acetate emulsion (PVAc) were effectively synthesized. Emulsions with various characteristics have been developed by adjusting the weight ratios between the vinyl acetate monomer and the VAE component. The impacts on the mechanical, thermal, and physical properties of the films were investigated using tests for pencil hardness, tensile shear strength, pH, contact angle measurement, differential scanning calorimetry (DSC), and viscosity. When 5.0 weight percent VAE was added, the tensile shear strength in dry conditions decreased by 18.75% after a 24-hour bonding period, the heat resistance decreased by 26.29% (as per WATT 91) and the tensile shear strength decreased by approximately 36.52% in wet conditions (per EN 204). The pristine sample’s results were also confirmed by the contact angle test. The interpenetrating network (IPN) formation in hybrid PVAc emulsion as primary bonds does not directly attach to PVAc and VAE chains. The addition of VAE reduced the mechanical properties (at dry conditions) and heat resistance as per WATT 91. Contact angle analysis demonstrated that PVAc adhesives containing VAE had increased water resistance when compared to conventional PVA stabilised PVAc homopolymer-based adhesives. When compared to virgin PVAc Homo, the water resistance of the PVAc emulsion polymerization was enhanced by the addition of VAE.

Characterization of Curing and Bonding of Wood with Adhesive Mixtures of Liquefied Wood and Hexamethylenediamine

Various crosslinking agents can be added to the formulations of natural-based adhesives for wood bonding in order to achieve better durability and higher strength of the formed joints.In the present study,the effect of hexamethylenediamine(HMDA)addition on the performance of liquefied wood(LW)adhesive for wood bonding is investigated.Differential scanning calorimetry showed the improved thermal stability and crosslinking of the LW adhesive with HMDA.The intensified presence of amide linkages(C–N bonds)was found in LW+HMDA with attenuated total reflection Fourier transform infrared spectroscopy.Analysis of the bonded joints using an automated bonding evaluation system showed that a higher press temperature resulted in stronger bonds for both types of adhesives.Moreover,the addition of HMDA to LW adhesive improved the bond strength of the joints and accelerated the crosslinking of the adhesive.However,with a tensile shear strength of(6.76±2.16)N×mm^(−2)(for LW)and(6.89±2.10)N×mm^(−2)(for LW+HMDA),both adhesives were found to be unsuitable for interior non-structural use.In addition,the acidity of LW resulted in relatively high wood failure(70%)in the adhesive joints tested.Improved crosslinking of LW with HMDA was reflected in improved resistance of LW+HMDA adhesive joints to water degradation.In conclusion,HMDA is a promising additive for improving the adhesive performance of LW adhesives.

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.

Xanthan Gum—Bio-Based Raw Material for Wood Adhesive

Due to their lower environmental impact, ease of accessibility, low cost, and biodegradability, bio-renewable sources have been used extensively in the last several decades to synthesize adhesives, substituting petrochemical-based adhesive. Vegetable oils (including palm, castor, jatropha, and soybean oils), lactic acid, potato starch, and other bio-renewable sources are all excellent sources for the synthesis of adhesives that are being taken into consideration for the synthesis of “eco-friendly” adhesives. Due to their widespread use, accessibility, affordability, and biodegradability, biobased raw materials like carbohydrates used to synthesize wood and wood composite adhesive have gradually replaced petrochemical-based adhesive. Recently, xanthan gum, a naturally occurring polymer, has drawn the interest of scientists as a potentially petroleum source replacement. It possesses specific rheological characteristics, excellent water solubility, and stability to heat, and can be used as a binder, thickener, suspending agent, and stabilizer. Xanthan gum increases the adhesive strength in addition to increasing the viscosity of water-soluble adhesives. This article discusses xanthan gum as a potential substitute for traditional raw materials derived from petroleum that is used as a raw material for adhesives.

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.

Environmentally Friendly Chitosan-Based Wood/Wood Composite Adhesive: Review

Due to the world’s energy issues and dependency on petroleum resources, focus has switched to finding new, sustainable raw material sources for wood adhesives. Renewable biopolymers would gradually replace petroleum and natural gas as the primary raw materials used in wood adhesives. Chitosan is a biomass substance having a lot of reserves. Chitosan is one of the most fascinating biopolymers in the adhesive sector because of its potential qualities for adhesive applications, such as biodegradability, biocompatibility, and non-toxicity. Chitosan and its derivatives have so garnered considerable interest in a wide range of adhesive applications. However, its adhesive strength is insufficient to glue wood under normal, humid conditions. There has been a lot of study done on how to make chitosan-based adhesives more cohesive and water resistant. In order to effectively use chitosan-based wood glue in wood/wood composite adhesive that gives comparable performance to synthetic adhesives, numerous new ways have been developed. It has been modified by the addition of various cross-linkers, including aldehydes like glyoxal glutaraldehyde etc., epoxy compounds, blended with other polymers, different acids and chitosan grafted onto vinyl acetate. In the production of wood composites, chitosan can also scavenge formaldehyde. This review of chitosan-based adhesives focuses on various cross-linkers for chitosan modification in order to improve the properties of chitosan-based wood adhesives.

Study on the Soy Protein-Based Adhesive Cross-Linked by Glyoxal

Based on the ESI-MS and ^(13)C-NMR analysis of the forms of glyoxal in acidic and alkaline solutions,the soy-based adhesive cross-linked by glyoxal was prepared in this work.The results showed that glyoxal existed in water in different forms at different pH levels.Under alkaline conditions,glyoxal transformed to glycolate through the intramolecular disproportionation reaction.Under acidic conditions,although some of glyoxal transformed to glycolate as what happened under alkaline conditions,most of glyoxal molecules existed in the form of fiveor six-membered cyclic ether structure.No ethylene tetraol or free aldehyde group was actually detected under these conditions.Although glyoxal reacted with soy protein under both acidic and alkaline conditions,alkaline conditions were more favorable for the improvement of mechanical performance and water resistance of soybased adhesives than acid conditions.

Little Secrets for the Successful Industrial Use of Tannin Adhesives:A Review

This brief article reviews a very particular and quite narrowfield,namely what has been done and what is needed to know for tannin adhesives for wood panels to succeed industrially.The present fashionable focus on bioadhe-sives has led to producing chemical adhesive formulations and approaches for tannin adhesives as a subject of academic publications.These,as good and original they might be,are and will still remain a rather empty aca-demic exercise if not put to the test of real industrial trials and industrial use.They will remain so without the“little”secrets and techniques outlined here that show that there is a great gap between developing an adhesive formulation in the laboratory and the hard reality to make it work where it does really count,in its industrial application.It outlines the fact that even more modern and excellent,newly developed bioadhesive formulations might well miserably fail once tried in the industry if the problems that always arise in their upgrading are not identified and solved,and solved well.It also outlines the fact that not only must costs always be taken into account and that a practical and possibly easy-to-handle approach must always be used,but too expensive or complex and unyielding adhesive systems are also often shown to be unusable or unsuitable in industry.

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.

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.

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.

A feasibility study of using two-component polyurethane adhesive in constructing wooden structures

This investigation was conducted to determine the feasibility of using a two-component polyurethane （PUR） adhesive, with special waterproof properties, in constructing wooden structures. We designed and conducted tests to compare the shear strength and adhesion performance of PUR with polyvinyl acetate （PVAc） adhesive on block-shear specimens constructed of oriental beech （Fagus orientalis L.）, fir （Abies alba Mill.）, poplar （Populus deltoides Bartr.）, white oak （Quercus alba L.）, sycamore （Platanus orientalis L.） and white walnut （Juglans cinerea L.）. The values of the percentage of wood failure were also determined in specimens constructed with each adhesive. The highest shear strength values of both adhesives were obtained in specimens constructed of beech, while the lowest shear strength values were obtained in fir and poplar specimens. Average shear strength of the PUR adhesive was 16.5% higher than that of the PVAc adhesive. Specimens constructed of fir, poplar and sycamore were characterised by the highest percentages of wood failure, whereas the lowest average percentages of wood failure were obtained in beech and oak specimens. With the exception of oak specimens, there was no statistically significant difference between percentage of wood failure among the PUR and PVAc adhesives. Generally, the PUR adhesive showed an acceptable adhesion performance on wood materials used in our study.

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.

Starch-Based Adhesives for Wood/Wood Composite Bonding: Review

Increasing global energy crisis and scarcity of petroleum resources has shifted focus of chemical industries to look for alternative raw material resources. The main focus of raw materials in wood adhesives, such as petroleum and natural gas [1] [2], would be gradually replaced by renewable biopolymers. Starch is a relatively inexpensive and renewable product from abundant plants, easy processing and it has been extensively used as binders, sizing materials, glues and pastes [3], but its bonding capacity is not strong enough to glue wood [4]. Extensive research has been carried out on improving the cohesive properties, especially water resistance, of starch-based adhesives. In starch-based wood adhesive many new approaches have come forward for effective use it in wood/wood composite adhesive giving comparable performance as synthetic adhesives. This review of starch-based adhesives is made with the focus on starch modification methods for improving properties of starch-based adhesives.

State of Research and Trends in the Development of Polyvinyl Acetate-Based Wood Adhesive

Synthetic wood adhesives, consisting of urea-formaldehyde resins (UF), phenol-formaldehyde resins (PF), melamine-formaldehyde resins (MF), and polyurethane resins, are widely used. For UF and MF, most investigations are concerned with reducing free formaldehyde content;for PF, most studies focused on finding new alternative chemicals to replace phenol. These adhesives come under the Carcinogenic, Mutagenic, and Reprotoxic chemicals (CMR) category. Due to global energy issues and dependency on petroleum sources, the focus has shifted to look for alternative and renewable raw material sources for wood adhesives. Conventionally available wood adhesives are polyvinyl alcohol (PVA) stabilized, with drawbacks like poor water resistance, poor heat resistance, low-temperature workability, and it’s based on petroleum resources. Polyvinyl acetate (PVAc) is non-resistant to moisture polymer, and if such adhesive joints are exploited in a moist environment, its strength substantially decreases. Sufficiently moisture-resistant adhesive joints are obtained by modifying PVAc dispersion with special compounds like reactive comonomer, Silanes, and modified PVA. To improve the workability at low temperature, Vinyl acetate (VAc) is copolymerized with specific comonomers like butyl acetate without affecting the performance properties. Here, we aim to present an overview of the research trend of PVAc-based adhesives in the wood industry. The review summarizes the current state of research PVAc-based adhesives.