Investigation of formaldehyde-free wood adhesives from kraft lignin and a polyaminoamide–epichlorohydrin resin

A formaldehyde-free wood adhesive system consisting of kraft lignin and a polyaminoamide-epichlorohydrin (PAE) resin (a paper wet strength agent) has been investigated in detail. The lignin-PAE adhesives were prepared by mixing an alkaline kraft lignin solution and a PAE solution. Mixing times longer than 20 min had little impact on the shear strength of the wood composites bonded with the lignin-PAE adhesives. The shear strength of the wood composites bonded with the lignin-PAE adhesives increased and then flattened out when the press time and the press temperature increased. The shear strength and water resistance of the wood composites bonded with the lignin-PAE adhesives depended strongly on the lignin/PAE weight ratio. Of the weight ratios studied, the 3:1 lignin/PAE weight ratio resulted in the highest shear strength and the highest water resistance of the resulting wood composites. The wood composites bonded with the lignin-PAE adhesives did not delaminate and retained very high strengths even after they underwent a boiling-water test. The lignin-PAE adhesives could be stored at room temperature for two days without losing their adhesion ability. PAE was the crosslinking agent in this lignin-PAE adhesive. Possible reactions between lignin and PAE are discussed in detail.     

Shear strength and water resistance of modified soy protein adhesives

Soy protein polymers recently have been considered as alternatives to petroleum polymers to ease environmental pollution. The use of soy proteins as adhesives for plywood has been limited because of their low water resistance. The objective of this research was to test the water resistance of adhesives containing modified soy proteins in walnut, maple, poplar, and pine plywood applications. Gluing strength and water resistance of wood were tested by using two ASTM standard methods. Glues with modified soy proteins had stronger bond strength than those containing unmodified soy proteins. Plywood made with glue containing urea-modified proteins had higher water resistance than those bonded with glues containing alkali-modified and heat-treated proteins. After three 48-h cycles of water-soaking, followed by 48 h of air-drying, no delamination was observed for either walnut or pine specimens glued with the urea-modified soy protein adhesives. Gluing strength for wood species with smooth and oriented surface structure was lower than for those with rough, randomly oriented, surface structures. Wood species with greater expansion of dimensions during water-soaking had a higher delamination rate than those showing less expansion.     

Effects of phosphorus-containing additives on soy and cottonseed protein as wood adhesives

Soy and cottonseed proteins appear promising as sustainable and environment-friendly wood adhesives. Because of their higher cost relative to formaldehyde-based adhesives, improvement in the adhesive performance of proteins is needed. In this work, we evaluated the adhesive properties of soy and cottonseed protein formulations that included phosphorus-containing acids and esters. For cottonseed protein isolate, most of these additives improved dry adhesive strength, with methylphosphonic acid, phosphorous acid, and phosphoric acid increasing the dry strength by 47, 44, and 42%, respectively, at their optimal concentrations. For soy protein isolate, these additives did not show significant benefits. The phosphorus-containing additives also improved the hot water resistance of the cottonseed protein formulations but showed either no effect or a negative effect for the of soy protein formulations. Thus, the combination of cottonseed protein with phosphorus additives appears to be attractive as wood adhesives.     

Development of High-Strength Soy Protein Adhesives Modified with Sodium Montmorillonite Clay

This study investigated the high strength of a soy protein adhesive system with good flowability at high protein concentration. Sodium montmorillonite (Na MMT), the most widely used silicate clay, was incorporated into viscous, cohesive soy protein adhesives at concentrations ranging from 1 to 11 % (dry basis, w/w). Hydroxyethyl cellulose was used as a suspension agent to stabilize the soy protein and nano clay to be the dispersion system. The interaction between soy protein and Na MMT was characterized by XRD, FTIR, Zeta potential and DSC. Results indicated that soy protein molecules were adsorbed on the surface of the interlayer of Na MMT through hydrogen bonding and electrostatic interaction. The soy protein/Na MMT adhesives had the intercalation structure with Na MMT contents ranging from 1 to 11 %. Adhesion strength, specifically wet adhesion strength, of soy protein adhesives at isoelectric point (pI) was significantly improved by the addition of Na MMT. It is believed that the physical cross‐linking reactions between soy protein and Na MMT mainly contribute to the improved adhesion performance of soy protein adhesives. Wet adhesion strength increased from 2.9 MPa of control soy protein adhesive to 4.3 MPa at 8 % Na MMT. An increase of pH beyond pI value resulted in decreased adhesion strength due to increased surface charges of soy protein and slightly reduced affinity of soy protein on the nano clay surface.     

Wood adhesive properties of cottonseed protein with denaturant additives

Most commercial wood adhesive use either formaldehyde-based resins or polyurethanes, both of which include potentially toxic chemicals in their formulations. As a result, proteins are being considered as greener and more sustainable wood adhesives. While most of the protein adhesive studies focus on soy proteins, there is also interest in exploring alternatives. In this work, testing of the adhesive performance of cottonseed protein isolate was undertaken in the presence of protein denaturants, i.e. guanidine hydrochloride (GuHCl), sodium dodecyl sulfonate (SDS), urea, and alkali. For comparison, soy protein isolate was also included in the study. At optimal dosage levels, the dry adhesive strength of cottonseed protein isolate could be enhanced by 38, 25, or 47% with SDS, GuHCl, or urea, respectively. The dry adhesive strength and hot water resistance of cottonseed protein isolate was generally superior to that of soy protein isolate, with or without the denaturants. Thus, the combination of cottonseed protein with an optimal concentration of a denaturant may be a potentially promising polymeric system for use as wood adhesives.     

Investigation of soy protein-kymene<Superscript>®</Superscript> adhesive systems for wood composites

This study investigated a new adhesive system, consisting of soy protein isolate (SPI) and Kymene^® 557H (simply called Kymene) (a commercial wet-strength agent for paper), that was prepared by mixing SPI and Kymene. Wood composites bonded with SPI-Kymene adhesive preparations had shear strengths comparable to or higher than those bonded with commercial phenol formaldehyde resins. Wood composites bonded with the new adhesive system had high water resistance and retained relatively high strength even after they had undergone a boiling-water test. The new adhesive system is formaldehyde-free, easy to use, and environmentally friendly. Kymene was proposed to serve as a curing agent in SPI-Kymene adhesives.     

Thermal properties and adhesiveness of soy protein modified with cationic detergent

This research studied the effects of cationic detergents on the adhesiveness and thermal properties of soy protein isolate (SPI). Three cationic detergents, hexadecyltrimethyl ammonium bromide, ethylhexadecyldimethyl ammonium bromide (EDAB), and benzyldimethylhexadecyl ammonium chloride, each at concentrations of 1.3, 2.6, 5.2, and 7.8 mM, were used to modify SPI. The effect of pH at selected EDAB concentrations was also studied. Results showed that both detergent concentration and pH had significant effects on the adhesiveness of modified SPI. SPI modified with detergent at a concentration of 2.6 mM yielded the greatest dry tensile strength and water resistance, which indicated that a moderate protein denaturation might be favorable to the adhesion of SPI. Both modified and unmodified SPI showed greater adhesive strength at their optimal pH values. Modified SPI showed greatest adhesive strength at pH 7, whereas unmodified SPI showed greatest adhesive strength at pH 4.5; the tensile strength of modified SPI was greater than that of unmodified SPI. The protein-denaturation temperature and the enthalpy of modified SPI adhesives were also analyzed by using DSC. Denaturation of the native structure of SPI increased as detergent concentration increased.     

A new environmentally friendly bioadhesive mainly modified by propanetriol

In this paper, a series of new environmentally friendly bioadhesives with improved bonding strength were quickly synthesized via urea, sodium dodecyl sulfate (SDS) and propanetriol are mixed with soy isolate protein. The results showed that the bonding strength of the modified adhesives was changed with the increasing content of propanetriol. The maximum dry shear strength of the plywood bonded with the resultant adhesive was increased to 2.45 MPa when the propanetriol content was 20 ml. While the maximum wet shear strength of the plywood bonded with the resultant adhesive arrived 1.32 MPa, which is acceptable for industrial application in plywood fabrication according to the national standards of the People’s Republic of China (≥0.7 MPa). In addition, the orthogonal experiment suggested that the obtained material with pH of 9 for 5 h mixing at the hot pressing temperature of 120 °C exhibited the best comprehensive performance. Also, the FTIR, SEM and DSC measurements showed that the adhesives had a compact structure with stable thermal property.     

大豆7S与11S球蛋白尿素变性后的粘接性质研究

随着人们对环境保护意识的增加和地球有限资源的缺乏,大豆蛋白在胶粘剂工业中的应用也越来越显示出强大的吸引力,鉴于前人的研究成果,文章研究了大豆7S和11S球蛋白经过尿素变性后在松木、樱桃木和胡桃木上的粘接强度和湿润能力。结果表明在不同的木块上不同胶粘剂有不同的粘接强度和湿润性能。7S大豆蛋白尿素变性后在硬木上有较好的湿润性。1M尿素变性赋予11S蛋白的粘接强度最高,3M尿素变性后,7S蛋白在硬木上的粘接强度大于11S蛋白。蛋白质的二级结构测量表明β-折叠对于3 M尿素变性后的大豆蛋白在硬木上的粘接强度起着重要作用,而无规则卷曲是降低1 M尿素变性7S大豆蛋白粘接强度的主要因素。     

Soy-oil-based waterborne polyurethane improved wet strength of soy protein adhesives on wood

Soy-oil-based waterborne polyurethane (WPU) is used to improve wet strength in shear test of wood bonded with an adhesive of soy protein isolate (SPI) by dispersing WPU into SPI slurry. WPU׳s effects on the physiochemical properties of WPU-SPI adhesives are characterized through Fourier transform infrared spectrum, transmission electron microscopy, thermal analysis, contact angle, and mechanical strength. Wet strength of the WPU-SPI adhesives increases by 65% compared to SPI control. Moreover, the microstructure of WPU has effects on the interactions between WPU and SPI. In this study, smaller and more uniform distributed WPU0002 is easier to interact and form stronger crosslinking network with protein than WPU0500. The stronger interaction between WPU0002 and protein results in increased viscosity and bond strength. The WPU-SPI blended adhesives show significantly improved wet strength, demonstrating their potential as wood adhesives.     

Cottonseed protein-based wood adhesive reinforced with nanocellulose

Although protein-based adhesives are eco-friendly, sustainable, and biodegradable, continued improvement in their adhesive performance is desirable. In this work, the effect of adding nanocellulose particles to cottonseed protein-based wood adhesives was studied. Cellulose nanofibers (CNF) were found to be most beneficial at about a 2% additive level, giving 22% improvement in dry adhesive strength over the cottonseed protein control. Cellulose nanocrystals (CNC) were optimal at about 10% additive level, giving 16% strength improvement relative to cottonseed protein alone. The hot water resistance of cottonseed protein isolate was also improved with CNF addition, but not with CNC addition. For comparison, soy protein isolate was also studied and showed about the same relative dry strength improvements with nanocellulose addition, but improvement of hot water resistance was less apparent. Infrared and thermogravimetric analysis suggested that the protein and the nanocellulose were interacting with each other. Thus, CNF may be a useful additive to cottonseed protein formulations used as wood adhesives.     

Evaluation of block shear properties of selected extreme‐pH structural adhesives by short‐term exposure test

Nine structural adhesives with varying pH were selected to examine the effect of adhesive pH on wood–adhesive bond quality. The adhesives evaluated included four highly alkaline phenol–formaldehyde, one intermediate pH phenol–resorcinol–formaldehyde, two acidic melamine–urea–formaldehyde, and two acidic melamine–formaldehyde resins. Block shear specimens were prepared using Douglas‐fir and black spruce wood. The adhesive performance was evaluated by measuring the shear properties (strength and wood failure) of the specimens tested at the dry and vacuum–pressure–redry (VPD) conditions. Adhesive pH, test condition, and wood species showed significant effects on shear properties. The different adhesives performed differently at the dry and VPD conditions. The high‐pH adhesives (phenol–formaldehyde and phenol–resorcinol–formaldehyde) showed similar high wood failures at both test conditions and performed better than the low‐pH adhesives (melamine–formaldehyde and melamine–urea–formaldehyde), especially after the VPD conditioning. The low‐pH adhesives showed high wood failure at the dry condition, but wood failure decreased significantly after VPD conditioning for both species, indicating that the low‐pH adhesives were less durable than the high‐pH adhesives. High‐pH adhesives did not have a negative impact on the strength of the bonded specimens. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Improvement of the water resistance of soybean protein-based wood adhesive by a thermo-chemical treatment approach

In order to extend the applications of wood composites and products bonded by soybean protein adhesive from interior to exterior fields of application, this study proposes a novel approach for improving the water resistance of soybean protein-based wood adhesives using thermo-chemical treatment of soybean protein. The soybean protein formed stable three-dimensional networks due to repolymerization or self-crosslinking during thermo-chemical treatment, confirmed by both increases in the water-insoluble content of the treated soybean protein and the improved hydrothermal-aged wet bond strength of the resulting soybean protein adhesive. Thermo-chemical treatment in the presence of 1 wt% sodium sulfite (which cleaves disulfide bonds) and 1 wt% sodium dodecyl sulfate (which destroys the hydrophobic interactions of proteins) released active groups buried within the globular structure of soybean protein via unfolding. This release both promoted the repolymerization of the soybean protein molecules and exposed more active sites for effective crosslinking by the post-added crosslinker EMPA. Plywood bonded by the optimal soybean protein adhesive possessed a good hydrothermal-aged bond strength of 1.22 MPa, exceeding the value required for structural use according to the JIS K6806-2003 commercial standard.     

A New Soy Flour-Based Adhesive for Making Interior Type II Plywood

In this study, we developed a formaldehyde-free adhesive from abundant, renewable, and inexpensive soy flour (SF). The main ingredients of this adhesive included SF, polyethylenimine (PEI), and maleic anhydride (MA). The optimum formulation of this adhesive and the optimum hot-press conditions for making plywood were investigated. A three-cycle soak test and a boiling water test (BWT) were employed for evaluating the strength and water-resistance of plywood bonded with this adhesive. Results showed that SF, PEI, MA and sodium hydroxide were all essential components for the adhesive and the SF/PEI/MA weight ratio of 7/1.0/0.32 resulted in the highest water-resistance. When the hot-press temperature was in the range of 140–170 °C, both water-resistance and shear strength of plywood bonded with the adhesive remained statistically the same, except that the dry shear strength of plywood at 170 °C was statistically lower than that at 160 °C. When the hot-press time ranged from 2 to 6 min, the plywood panels at 5 min had the highest boiling water test/wet (BWT/w) shear strength. The plywood panels made at 5 min had a higher dry shear strength than those made at 3 min. Plywood panels bonded with this SF/PEI/MA adhesive exceeded the requirements for interior applications.     

Sequential Fractionation of Cottonseed Meal to Improve Its Wood Adhesive Properties

For better understanding of the adhesive properties of different fractions of cottonseed protein, cottonseed meals from both glanded and glandless cotton varieties were separated into several fractions. Each meal was sequentially extracted with water and 1 M NaCl solution, or with phosphate buffer and NaCl solution. Adhesives were prepared from the recovered fractions and hot-pressed onto maple veneer strips and tested for their properties. The adhesive strength of the water- and buffer-washed solid fractions (i.e., the un-extractable residues of the meals) from the glanded seed ranged from 1.32 to 1.62 MPa and were unchanged or increased compared with the adhesive strength of the original meal that varied from 0.98 and 1.49 MPa. Soaking the wood specimens bonded at 80 °C revealed that the water resistance of these water- and buffer-washed adhesives was significantly improved in that they exhibited no delamination during soaking compared with the meal adhesive that showed some delamination (20–30 % of the samples). Furthermore, the water resistance of these fractions with wet shear strength around 1.5 MPa was comparable to that of cottonseed protein isolate (>90 % protein) when the joints were bonded at 100 °C. The preparations from glandless cottonseed meals showed similar adhesive performances. Additional extraction of the meals with NaCl solution reduced adhesive performance. The results suggest that water- or buffer-washed cottonseed meal fractions can be used as wood adhesives and would be less costly to prepare than cottonseed protein isolates.     

A Formaldehyde-Free Water-Resistant Soy Flour-Based Adhesive for Plywood

The phasing out of the use of urea–formaldehyde adhesive in the fabrication of interior‐used hardwood plywood requires development of environmentally friendly bio‐based wood adhesives. We recently reported that phosphorylation of soy flour (SF) using phosphoryl chloride (POCl₃) greatly improved the moisture resistance of soy flour adhesive. In the present study, we investigated the effects of inorganic oxidizing agents, such as NaClO₂ and Ca(NO₂)₂, to further improve the wet bonding strength of phosphorylated SF (PSF) wood adhesive. We report that addition of 1.8 % (wet weight basis) Ca(NO₂)₂ to phosphorylated SF (PSF) adhesive formulation containing 25 % soy flour solids increased the wet bonding strength to greater than 3 MPa at 140 °C hot‐press temperature. The water resistance testing of the glued three‐ply hardwood plywood panels passed the three‐cycle soak/dry test recommended by the American National Standard for Hardwood and Decorative Plywood/Hardwood Plywood and Veneer Association protocol (ANSI/HPVA HP‐1‐2004). Since the process involves only inorganic chemistry and no petroleum‐based chemicals such as formaldehyde or polyamidoamine–epichlorohydrin are used, the PSF + Ca(NO₂)₂ adhesive is non‐toxic and environmentally safe.     

水性环氧树脂包覆有机蒙脱土制备木材胶粘剂

摘要：水性环氧树脂通常含有水溶性分子或分子链，导致在高温和潮湿条件下作为木材胶粘剂时耐水性及力学性能较差。采用有机改性的纳米蒙脱土改性水性环氧树脂增强水性环氧树脂胶粘剂的耐水性及力学性能。并通过乳液包覆蒙脱土的方法与直接共混的方法对比，研究了不同添加量有机蒙脱土（0%，3%，6%，9%）对胶粘剂性能的影响。胶粘剂的耐水性及力学性能通过测量胶粘剂在干燥及潮湿条件下的剪切强度来表示。通过TGA、SEM、TEM、DSC研究了复合胶粘剂的热稳定性和结构。结果表明，在水性环氧树脂中添加有机改性的纳米蒙脱土，可以有效地提高胶粘剂的粘结强度，此外，采用乳液包有机覆蒙脱土的方法比直接共混的方法制备得到胶粘剂，有机蒙脱土在胶粘剂中分布更均匀，具有更优异的力学性能，说明有机蒙脱土在复合材料中的分散质量是影响复合胶粘剂性能的主要原因。     

Urea-Modified Soy Globulin Proteins (7S and 11S): Effect of Wettability and Secondary Structure on Adhesion

This investigation characterized wettability and adhesive properties of the major soy protein components conglycinin (7S) and glycinin (11S) after urea modification. Modified 7S and 11S soy proteins were evaluated for gluing strength with pine, walnut, and cherry plywood and for wettability using a bubble shape analyzer. The results showed that different adhesives had varying degrees of wettability on the wood specimens. The 7S soy protein modified with urea had better wettability on cherry and walnut. The 11S soy protein modified with 1M urea had better wettability on pine. The 1M urea modification gave 11S soy protein the greatest bonding strength in all the wood specimens. The 3M urea modification gave 7S soy protein stronger adhesion on cherry and walnut than did 11S protein; but with pine, 11S soy protein had greater adhesion strength than 7S soy protein. Measurement of protein secondary structures indicated that the β-sheet played an important role in the adhesion strength of 3M urea-modified soy protein in cherry and walnut, while random coil was the major factor reducing adhesion strength of 7S soy protein modified with 1M urea.     

Adhesive properties of soy proteins modified by sodium dodecyl sulfate and sodium dodecylbenzene sulfonate

A study was conducted on adhesive and water-resistance properties of soy protein isolates modified by sodium dodecyl sulfate (SDS) (0.5, 1, and 3%) and sodium dodecylbenzene sulfonate (SDBS) (0.5, 1, and 3%) and applied on walnut, cherry, and pine plywoods. Soy proteins modified by 0.5 and 1% SDS showed greater shear strengths than did unmodified protein. One percent SDS modification had the highest shear strength within each wood type tested. Soy proteins modified with 0.5 and 1% SDBS also showed greater shear strengths than did the unmodified protein. The 1% SDBS-modified soy protein had the highest shear strength in all wood samples tested. Compared to the unmodified protein, the modified proteins also exhibited higher shear strengths after incubation with two cycles of alternating relative humidity and zero delamination rate and higher remaining shear strengths after three cycles of water soaking and drying. These results indicate that soy proteins modified with SDS and SDBS have enhanced water resistance as well as adhesive strength. Possible mechanisms for the effects of SDS and SDBS also are discussed.     

Physicochemical Properties of Soy Protein Adhesives Obtained by In Situ Sodium Bisulfite Modification During Acid Precipitation

Successful industrial applications of soy protein adhesives require high adhesion strength and low viscosity at high solid protein concentration. This study examined the effects of β-conglycinin (7S) and glycinin (11S) ratios on the physicochemical properties of soy protein adhesives. Soy protein adhesives with various 7S/11S ratios were extracted from soy flour slurry modified with sodium bisulfite using the acid precipitation method, which is based on the different solubilities of 7S and 11S globulins. Seven glycinin-rich soy protein fractions and six β-conglycinin-rich soy protein fractions were obtained. The external morphology of the samples changed from the viscous cohesive phase to the clay-like phase without cohesiveness. The viscous cohesive samples had good flowability and good water resistance with a wet adhesion strength of 2.0–2.8 MPa. They were stable for up to several months without phase separation at room temperature. Based on the results, we suggest that proper protein–protein interaction, hydration capacity (glycinin-rich soy protein fractions), and certain ratios of 7S and 11S (β-conglycinin rich soy protein fractions) in the soy protein sample are crucial to continuous protein phase formation. Hydrogen bonding, electrostatic forces, and hydrophobic interactions are involved in maintaining the protein viscous cohesive network, whereas disulfide bonds do not exert significant effects. This study describes a new way to investigate viscous cohesive soy protein systems with high solid protein content, thus alleviating the disadvantages of traditional methods for studying the adhesive properties of soy protein isolates, which tend to have poor water resistance, low solid contents, and short storage life.