Eco-Friendly Adhesives Based on Tannin and N,N-Bis(2-Hydroxy-Ethyl) Fatty Amides (HEFAs) from Non-Traditional Oils for Wood Bonding

Abstract

Wood adhesives were formulated using tannin and N,N-bis(2-hydroxyethyl) fatty amides (HEFAs). The natural tannin-based adhesives can be used to replace formaldehyde-based adhesive systems and thereby reduce formaldehyde and volatile organic compound (VOC) emissions from adhesives used for plywoods. Performance properties of the adhesively bonded wood joints viz., tensile strength, impact strength and chemical resistance were measured. N,N-bis(2-hydroxyethyl) fatty amides (HEFAs) from non-traditional oils were mixed with a pure tannin-based adhesive as a crosslinker, and this increased the tensile strength, impact strength and chemical resistance of wood joints. The results revealed that a high performance and eco-friendly adhesive system for wood can be successfully formulated using tannin and HEFA.     

Biocompatible Catechol-Functionalized Cellulose-Based Adhesives with Strong Water Resistance

Numerous traditional adhesives have good adhesion in dry environments. However, non-environmental-friendliness and poor water resistance largely limit their practical applications. To prepare biocompatible adhesives with strong water resistance and adhesion strength, in this paper, catechol-functionalized cellulose-based adhesive polymers are synthesized by grafting N-(3,4-dihydroxyphenethyl)methacrylamide and methyl methacrylate onto cellulose chain through atom transfer radical polymerization (ATRP). The successful synthesis of the catechol-functionalized cellulose-based adhesive polymers is confirmed by FTIR and ¹H NMR. The different characteristics of the adhesive polymers, such as thermal stability, swelling ratio, biocompatibility, and adhesion strength are investigated. Strong water resistance on various substrates is realized in underwater environment for the catechol-functionalized cellulose-based adhesive with addition of Fe³⁺. The adhesion strength and thermal stability are enhanced when the catechol content is increased. The adhesive with catechol content of 25.4% shows the adhesion strength of 0.45 MPa for iron substrate in underwater environment. In addition, the adhesive with addition of Fe³⁺ exhibits excellent adhesion in dry environment, with maximum adhesion strength of 3.50 MPa for iron substrate. The cell culture test shows that the adhesive polymers have excellent biocompatibility. The biocompatible adhesives with strong water resistance have potential application in electronic, wood, and building fields.     

Curing behavior and viscoelastic properties of pine and wattle tannin-based adhesives studied by dynamic mechanical thermal analysis and FT-IR-ATR spectroscopy

This study investigated the curing behavior and viscoelastic properties of two types of tannin-based adhesives, wattle and pine, with three hardeners: paraformaldehyde, hexamethylenetetramine and TN (tris(hydroxylmethyl)nitromethane), by FT-IR-ATR spectroscopy and dynamic mechanical thermal analysis (DMTA). Using FT-IR-ATR spectroscopy, the chemical structures of tannin-based adhesives were determined and the degrees of curing as a function of temperature and time were compared with the conversion degrees of the hydroxyl groups. Paraformaldehyde was shown to be more reactive with wattle tannin than the other hardeners, while hexamethylenetetramine was the most reactive with the pine tannin. As the quantity of hardener was increased, the conversion degree also increased. The storage modulus (E′), loss modulus (E′′) and loss factor (tan δ) of each adhesive system were obtained by DMTA. With increasing temperature, as the tannin-based adhesives hardened, the storage modulus (E′) increased in all adhesive systems. The curing behavior results obtained by DMTA showed a similar tendency as seen from the FT-IR-ATR spectroscopy results. The curing behavior of the tannin-based adhesives was successfully determined using FT-IR-ATR spectroscopy in combination with DMTA.     

Reduction of formaldehyde emission from plywood

The aim of this work is to evaluate performances of tannin-based resins designed as adhesive in the plywood production. For this purpose, a part of phenol formaldehyde (PF) and melamine formaldehyde (MF) in the classic adhesive formulation was replaced by tannin. The physical properties of the formulated resins (rheological characterization, etc.) were measured. In order to analyze the mechanical performance of tannin-based resins, plywood panels were produced and the mechanical properties including tensile strength wood failure and three-point bending strength were investigated. The performance of these panels is comparable to those of plywood panels made by commercial PF and MF. The results showed that the plywood panels bonded with tannin–PF (PFT) and tannin–MF (MFT) resins exhibited better mechanical properties in comparison to the plywood panels made of commercials PF and MF. The introduction of small properties of tannin in PF and MF resins contribute to the improvement of the water performance of these adhesives. The formaldehyde emission levels obtained from panels bonded with tannin-based resins were lower than those obtained from panels bonded with control PF and MF. Although there are no actual reaction at all between PF, MF, and tannin, addition of tannin significantly improves the water resistance of PF and MF resins. This is a novel finding that manifests the possibility of replacing a convention PF and MF resins by tannin. Modified adhesive is one of the goals in the plywood production without changing any of their production conditions with improvement to their overall properties.     

Physico-mechanical properties of particleboards bonded with pine and wattle tannin-based adhesives

This study investigated the physical and mechanical properties of particleboards made using two types of tannin-based adhesives, wattle and pine, with three hardeners, paraformaldehyde, hexamethylenetetramine (hexamine) and TN (tris(hydroxyl)nitromethane), by measuring the physical (thickness swelling, linear expansion and water absorption) and mechanical properties (bending strength and internal bond strength). The performance of the particleboards made using tannin-based adhesives was influenced by physical conditions such as press time and temperature as well as by chemical conditions, such as the chemical structure of the tannin and the hardener. Wattle tannin-based adhesive being a thermoset, the wattle tannin-based particleboards were more influenced by physical conditions, while the pine tannin-based particleboards were influenced by the chemical structure of the pine tannin nuclei, which include phloroglucinolic A-rings. The reactivity of the hardener toward the tannin was in the order: paraformaldehyde > hexamine > TN for wattle tannin, while for pine tannin the order was hexamine > paraformaldehyde > TN.     

低温抗结晶型粘钢胶的性能研究

以含环氧基酚基树脂(X)作为通用EP(环氧树脂)胶粘剂的改性剂,制备了低温抗结晶型EP粘钢胶,并着重探讨了X对粘钢胶的基本力学性能、耐温变性能、抗结晶性能和综合性能等影响。结果表明:X改性粘钢胶的基本力学性能随温度或龄期的增加而不断增大;当w(X)=20%或30%时,X改性粘钢胶具有良好的抗结晶性能和力学性能;通过调整配方,可配制出满足GB50367—2006标准(A级)的抗低温结晶型粘钢胶。     

Soy-based,tannin-modified plywood adhesives

In this research, two different types of commercial tannins, namely a hydrolysable tannin (chestnut) and a condensed flavonoid tannin (mimosa), were used to prepare two types of soy-based (soy flour (SF) and soy protein isolate) adhesives for making plywood. Thermogravimetric properties (TGA) and its derivative as function of temperature (DTG) of different soy-based adhesive were measured in the range 40°C–300°C. Thermomechanical analysis (TMA) from 25°C to 250°C was done for the different resin formulations. Duplicate three-ply laboratory plywood panels were prepared by adding 300 g/m² of the adhesives’ total resin solid content composed of SF or isolated soy protein (ISP), urea, chestnut, and mimosa tannin extracts with hexamine as hardener. Based on the results obtained, tannins can improve SF adhesion properties. The TMA showed that chestnut tannin extract appeared to react well with SF, while mimosa tannin extract appeared to react well with ISP. Matrix-assisted laser desorption ionization time of flight (MALDI-TOF) mass spectrometry also showed that among other reactions, the soy protein amino acids reacted with the tannins. Furthermore, delamination and shear strength test results showed the good water resistance of plywood bonded with soy-based tannin modified adhesive.     

Lignin–phenol–formaldehyde resin adhesives prepared with biorefinery technical lignins

In this study, four biorefinery technical lignins were used to synthesize lignin–phenol–formaldehyde (LPF) resin adhesives with a proposed formulation that was designed based on accurate analysis of the active sites in lignin with ³¹P nuclear magnetic resonance (NMR). The properties of the LPF resin adhesives and the plywoods prepared with them were tested. The structural features and curing behavior of the LPF resin adhesives were thoroughly investigated by solution‐ and solid‐state ¹³C NMR. Results indicated that the proposed formulation exhibited favorable adaptability for all four of these technical lignins for synthesis of LPF resin adhesives. High‐performance plywood with low emissions of formaldehyde could be successfully prepared with the synthesized LPF resin adhesives. All the LPF resin adhesives exhibited similar structure and curing behavior with the commercial phenol–formaldehyde (CPF) resin adhesive. However, the LPF resin adhesives showed relatively higher curing temperatures as compared with the CPF resin adhesive. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42493.     

光学用透明胶粘剂的研究进展

介绍了光学用透明胶粘剂的性能特点及分类,重点介绍了合成树脂胶粘剂。合成树脂胶粘剂由于粘接强度高,耐高低温性好,能在振动、辐射等苛刻条件下工作,逐渐成为主要的光学透明胶粘剂。重点介绍了合成树脂胶粘剂中的环氧树脂胶粘剂和光固化胶粘剂。探讨了环境因素对胶粘剂光学性能的影响,并且指出环氧树脂和光固化胶粘剂是未采光学透明胶粘剂的发展方向。     

Soy-based adhesive cross-linked by melamine–glyoxal and epoxy resin

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.     

Plant Polyphenol-Inspired Crosslinking Strategy toward High Bonding Strength and Mildew Resistance for Soy Protein Adhesives

Soybean protein adhesives are environmentally friendly biomass-based aldehyde-free adhesives that have good economic value for the wood industry; however, it remains challenging to produce soybean protein adhesives with excellent water resistance, toughness, and mildew resistance through a simple modification method. In this work, inspired by plant polyphenols, a novel crosslinked soybean meal adhesive (SMPT) is obtained using a facile economic method. Polyamidoamine-epichlorohydrin (PAE) and tannic acid (TA) are combined with a soybean meal matrix to form a tough co-crosslinked network through strong intermolecular forces (covalent bonds, ionic bonds, and hydrogen bonds) in adhesive system. The results show that the wet bonding strength of SMPT adhesives for plywood is 134.1% higher than the unmodified soybean meal adhesive. The adhesion properties met the standard requirements for interior-use plywood. And the compact cross-linking network structure is accelerated the greater energy dissipation, which improves the toughness of adhesive. Moreover, cationic azetidinium groups in PAE and phenol hydroxyl groups in TA synergistically not only exhibit the good antibacterial activities but also improve mildew resistance for SMPT adhesives. This facile strategy provides an economic sustainable method to prepare high-performance environmentally friendly wood adhesives.     

Bond Formation By Wood Surface Reactions Part Iv Analysis of Furfuryl Alcohol,Tannin and Maleic Acid Bridging Agents

Abstract

Solid wood panels (Acer saccharum Marsh.) were bonded with various bridging materials following nitric acid activation. These chemical bridging materials included tannin, furfuryl alcohol and mixtures of the two with and without maleic acid. High shear strengths were achieved with a tannin-furfuryl alcohol-maleic acid mixture (T-F-M) with or without the nitric acid activation.

The curing reactions of the bridging material were examined with differential scanning calorimetry (DSC). Furfuryl alcohol was found to be the most reactive component of the T-F-M. Results from both the bonding work and the DSC analysis showed little effect of open assembly time or pot-life. The furfuryl alcohol appeared to be nitrated by the nitric acid catalyst. The nitrated material apparently degraded at high temperature (180 C) in a violent reaction detected by DSC. While these reactions were not observed with the panels the possibility of violent reactions during pressing must be considered.     

Combination of lignin polyol–tannin adhesives and polyethylenimine for the preparation of green water‐resistant adhesives

In this study, a green adhesive from renewable lignin and tannin was developed with polyethylenimine (PEI) with a method to improve the water resistance of the lignin/tannin adhesive. Lignin polyols were prepared through the liquefaction of oil‐palm empty fruit bunches. The characteristics of the adhesive samples were compared with those of a commercial phenol–formaldehyde resin. Three plywood specimens bonded with the new adhesive showed a very high tensile strength (63.04 MPa) and were very water resistant. The effect of the solid content of the adhesives on the tensile strength and gel time and various weight ratios of PEI on the tensile strength and water resistance of the plywood specimens were evaluated. Thermal stability tests revealed that the lignin polyol–tannin/PEI adhesives had a high heat resistance (360 °C). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43437.     

化学交联法改善氧化淀粉胶粘剂性能的研究

以硼砂、甲苯二异氰酸酯(TDI)、环氧氯丙烷和三聚氰胺-甲醛树脂等分别作为氧化淀粉的交联改性剂,研究了交联改性剂类型对氧化淀粉胶粘剂耐水性、干燥速率等影响。结果表明:经交联改性后,氧化淀粉胶粘剂的耐水性及干燥速率均明显提高;当交联改性剂为三聚氰胺-甲醛树脂时,相应胶粘剂的吸水率(58.9%)相对最低、干燥时间(700 s)相对最短,说明其改性效果相对最好;当交联改性剂为硼砂时,相应胶粘剂的吸水率(144.9%)相对最高、干燥时间相对最长,说明其改性效果相对最差。用三聚氰胺-甲醛树脂交联改性淀粉胶粘剂制成的瓦楞纸板,在常温水中浸泡48 h后不开胶,完全满足包装纸箱用相关标准的耐水性指标要求。     

Evaluation of natural rubber latex-based PSAs containing aliphatic hydrocarbon tackifier dispersions with different softening points—Adhesive properties at different conditions

Natural rubber latex-based water–borne pressure sensitive adhesives (PSAs) have been formulated with three aliphatic hydrocarbon water-based dispersions (varying softening points) at two different resin addition levels (25% and 50%). Time–temperature superposition analysis using WLF approximations for adhesive peel has revealed that the adhesives formulated with 50% resin addition level show good adhesive behavior. It has also been determined from time–temperature superposition analysis that peel force increases systematically with softening point and peel rate. Correlation of viscoelastic behavior with adhesive properties suggests that at least 50% resin addition level is needed to bring the natural rubber-based formulations into PSA criteria as defined by Dahlquist and others. Adhesive property evaluations performed on a high surface energy substrate (stainless steel) and low surface energy substrate (LDPE) suggested that optimum tack, peel and shear properties at room temperature were obtained for a formulation containing a higher softening point dispersion (95 °C) at 50% resin addition level. Adhesive peel and tack tend to follow softening point trends as well. A 25% tackifier dispersion addition level did not provide any significant adhesion. Humid aging (50 °C and 100% relative humidity) evaluations of the water–borne adhesives seem to correlate well with the room temperature adhesive property observations.     

Viscosity and shear strength of natural‐rubber‐based adhesives in the presence of gum rosin and petroresin

The viscosity and shear strength of pressure‐sensitive adhesives based on natural rubber (standard Malaysian rubber grade L) were studied with gum rosin and petroresin as the tackifying resins. Effects of the concentration of the tackifying resin and the molecular weight of rubber on the two properties were systematically investigated. Toluene was used as the solvent throughout the study to prepare the adhesives. The viscosity and shear strength of the adhesives were determined with a rotary viscometer and a texture analyzer, respectively. For the shear test, a hand coater was used to coat the adhesives on the release paper substrate to provide coating thicknesses of 60 and 120 μm. The results indicated that the viscosity increased with the resin loading and molecular weight of rubber increasing. The viscosity of the adhesive prepared from petroresin had a higher value than that of the gum‐rosin‐based adhesive. The shear strength of the adhesives decreased gradually with increasing resin content for both tackifying resins and coating thicknesses, and this observation was attributed to the decrease in the cohesive strength due to the dilution effect of the resins. However, the shear strength passed through a maximum at a molecular weight of rubber of 8.5 × 10⁴ for both resins. The gum‐rosin‐based adhesive consistently showed higher shear strength than that of the petroresin/natural rubber adhesive because of the better cohesiveness and compatibility of the former system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

三聚氰胺改性脲醛树脂胶粘剂的研究进展

三聚氰胺改性脲醛树脂胶粘剂具有比脲醛树脂胶粘剂更好的耐水性、耐热性及稳定性,井能减少游离甲醛的含量,已成为木材加工业的重要用胶。本文主要从发展概况、合成机理、合成工艺和应用等几个方面,介绍了三聚氰胺脲醛树脂胶粘剂的研究进展,并对其发展前景进行了展望。     

Morphologic accessibility of wood adhesives

Accessibility of wood adhesives was determined using a potassium bromide-embedding technique during resin cure. Cured resin was then extracted with water, followed by x-ray analysis of residual potassium bromide retention in the adhesive matrix. Cured urea–formaldehyde (UF), phenol–formaldehyde resol (PF), and phenol–resorcinol formaldehyde (PRF) accommodated large quantities of potassium bromide. However, only PRF adhesive showed crystallization of trapped potassium bromide, suggesting the presence of large pore sizes in the polymer lattices. Both UF and PRF adhesives, after room-temperature soaking, were equally resistant to water access. At higher temperature, water accessibility of UF increased greatly which may be attributed to thermal softening of the adhesive, while the accessibility of water to the PRF adhesive matrix was mainly a surface phenomenon and was not very temperature dependent. PF was highly accessible to water, even at room temperature, as a result of swelling from the presence of sodium hydroxide (catalyst). Accessibility of PRF adhesive was greatly increased by base (NaOH) solutions but not by acid (H₂SO₄) solutions. The UF resin showed slight increase of accessibility with increase in acidity and basicity of the water solution, but the accessibility increase of this adhesive in base solution was substantially less than that of PRF. The acid hydrolysis influence on accessibility increase of UF adhesive was far less severe than that of temperature.     

新型呋喃树脂的制备与改性

以糠醇和糠醛为原料在草酸催化作用下发生缩聚制取新型呋喃树脂。研究表明,当糠醇与糠醛的质量比为7：3,草酸用量为原料质量的0．33％,在回流温度下反应3．5h时,反应制得的呋喃树脂黏度达到78s,且与水玻璃混合良好,采用对苯甲酸作固化剂固化后耐水、耐高温性能优,从而达到改性水玻璃胶泥的目的。采用尿素与甲醛替代所有的糠醛与大部分的糠醇进行缩聚合成出脲醛呋喃树脂。研究表明,当n（尿素）：n（甲醛）：n（糠醇）为3：1：2,在回流温度下反应3．5h,可获得性价比优的改性呋喃树脂。     

Effect of anhydride curing agents,imidazoles, and silver particle sizes on the electrical resistivity and thermal conductivity in the silver adhesives of LED devices

This study investigated the preparation of silver adhesives applied to a light‐emitting diode (LED) device as die‐attach materials consisting of silver particles, on epoxy resin, curing agents, and accelerants for complete curing at 150 °C for 30 min. For the epoxy resin, this study used 3,4‐epoxycyclohexyl‐methyl‐3,4‐epoxycyclohexanecarboxylate mixed with different types of anhydride curing agents such as 4‐methylcyclohexane‐1,2‐dicarboxylic anhydride and hexahydrophthalic anhydride as well as imidazole accelerants such as 2‐ethyl‐4‐methyl‐1H‐imidazole‐1‐propanenitrile, 2‐phenylimidazole, 2‐methylimidazole, 2‐phenyl‐2‐imidazoline, and 1,2‐dimethylimidazole. In addition, different size of silver particles and hybrid silver particles were used for the electrical resistivity and thermal conductivity of silver adhesives. Differential scanning calorimetric (DSC) measured conversion of silver adhesives based on different types and contents of the curing agents and accelerants under heating. The silver particles' distribution of silver adhesive also affected electrical resistance, as proved by scanning electronic microscopy (SEM) and four‐point probe. The obtained results showed that the silver adhesive containing an 100 wt % of epoxy resin mixed with 85 wt % of hexahydrophthalic anhydride, 1.0 wt % (weight of epoxy resin) of 2‐ethyl‐4‐methyl‐1H‐imidazole‐1‐propanenitrile, and 80 wt % (weight of epoxy resin) of hybrid silver particles (40 wt % 15 μm and 40 wt % 1.25 μm) was perfect, having the lowest electrical resistivity at 1.11 × 10^?4 Ω·cm and good thermal conductivity at 3.2 W/m·K. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43587.