Soy flour dispersibility and performance as wood adhesive

Soy flour adhesives using polyamidoamine-epichlorohydrin (PAE) resin as the curing agent are being used commercially to make bonded wood products. The original studies on the soy-PAE adhesives used purified soy protein isolate, but the much lower cost soy flour is now used commercially. We examined the performance of commercially available soy flours that have their proteins either mainly in their native (90 protein dispersibility index (PDI)) or denatured (70 and 20 PDI) states. We expected that the more native state soy proteins with their better dispersibility would provide better adhesion to wood surfaces and enhanced reaction with PAE resin. Small-scale wood bonding tests showed that neither of these effects was observed without and with a low level of PAE. In these tests, the solids content of the soy formulations had a large influence on adhesive viscosity but little influence on bond strength. Additionally, little difference was observed in any of the adhesive or viscosity properties between the soy flours having either a 0.152 or 0.075?mm (100 or 200 mesh) particle size.     

Improvements and limitation of soy protein-based adhesive: A review

Soy protein is known for its eco-friendly, sustainable, and biodegradable qualities that are likely used as raw material in producing bioadhesive. However, soy protein-based adhesive are lacking in terms of adhesive strength and water-resistance compared to commercial formaldehyde-based adhesives such as phenol and urea-formaldehyde resin. Therefore, continuous research has been done to improve adhesive performance. This can be done via physical or modification methods, including the usage of cross-linking agents, structural modification, enzymatic modification, and the addition of additives. This review will cover these modification methods that give significant enhancement to the water-resistance and adhesive strength of soy protein-based adhesives.     

Soybean meal-based adhesive enhanced by MUF resin

Soybean meal flour, polyethylene glycol (PEG), sodium hydroxide (NaOH), and a melamine-urea-formaldehyde (MUF) resin were used to formulate soybean meal/MUF resin adhesive. Effects of the adhesive components on the water resistance and formaldehyde emission were measured on three-ply plywood. The viscosity and solid content of the different adhesive formulations were measured. The functional groups of the cured adhesives were evaluated. The results showed that the wet shear strength of plywood bonded by soybean meal/NaOH adhesive increased by 33% to 0.61 MPa after adding NaOH into the adhesive formulation. Addition of PEG reduced the viscosity of the soybean meal/NaOH/PEG adhesive by 91% to 34,489 cP. By using the MUF resin, the solid content of the soybean meal/MUF resin adhesive was improved to 39.2%, the viscosity of the adhesive was further reduced by 37% to 21,727 cP, and the wet shear strength of plywood bonded by the adhesive was increased to 0.95 MPa, which met the interior plywood requirements (≥0.7 MPa). The formaldehyde emission of plywood bonded by the soybean meal/MUF resin adhesive was obtained at 0.28 mg/L, which met the strictest requirement of the China National Standard (≤0.5 mg/L). FTIR showed using the MUF resin formed more  CH₂ group in the cured adhesive. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.     

The Effect of Nanoclay on Melamine-Urea-Formaldehyde Wood Adhesives

Abstract

In this work it has been shown that the addition of small percentages of Na⁺-montmorillonite (Na-MMT) and organic modified-montmorillonite (O-MMT) nanoclay to thermosetting melamine-urea-formaldehyde (MUF) resins appeared to improve, considerably, their performance as adhesives for wood particleboard. X-ray diffraction (XRD) studies indicated that Na-MMT when mixed in small proportions, loses the periodic atomic structure during the curing of MUF resins. This can be interpreted as becoming exfoliated under such conditions. Thermomechanical analysis (TMA) on laboratory MUF-bonded particleboard indicated that small percentages of Na-MMT and O-MMT improved the internal bond strength imparted by the MUF adhesive to the panel, when tested dry and also, more importantly, when tested after 2 h of boiling. The increase in water resistance of the MUF-bonded panel was particularly noticeable. Furthermore, the addition of Na-MMT was shown to increase considerably the resistance of the MUF resin to abrasion. This is important from a wood surface finish point of view.     

Soy proteins as plywood adhesives: formulation and characterization

Soybean proteins have great potential as bio-based adhesives. The objectives of our study were to develop and characterize formaldehyde-free soybean wood adhesives with improved water resistance. Second-order response surface regression models were used to determine the effects of soy protein isolate concentration, sodium chloride, and pH on adhesive performance. All three variables affected both dry and wet strengths of bonded wood specimens. The optimum operation zone for preparing adhesives with improved water resistance is at a protein concentration of 28% and pH 5.5. Sodium chloride had negative effects on adhesive performance. Soy adhesives modified with 0.5% sodium chloride had dry strength, wet strength, and boiling strength of bonded specimens comparable to nonmodified soy adhesives. Rheological study indicated that soy adhesives exhibited shear thinning behavior. Adhesives modified with sodium chloride showed significantly lower viscosity and yield stress. Sodium chloride-modified soy adhesives formed small aggregates and had low storage moduli, suggesting reduced protein–protein interactions. These formaldehyde-free soy adhesives showed strong potential as alternatives to commercial formaldehyde-based wood adhesives.     

Chromatographic Analysis of the Reaction of Soy Flour with Formaldehyde and Phenol for Wood Adhesives

The desire to make more biobased and lower-cost bonded wood products has led to an interest in replacing some phenol and formaldehyde in wood adhesives with soybean flour. Improved knowledge of the soy protein properties is needed to relate resin chemistry to resin performance before and after wood bonding. To expose the soy protein’s functional groups, it needs to be disrupted, with minimal hydrolysis, to maximize its incorporation into the final polymerized adhesive lattice. The best conditions for alkali soy protein disruption were to maintain the temperature below 100 °C and react the soy flour with sodium hydroxide at pH 9–12 for about 1 hour. A gel permeation chromatography procedure was optimized to determine conditions for selectively breaking down the high molecular weight soy protein fragments that contribute to high adhesive viscosity. This method and extraction data were used to evaluate the reaction of the disrupted soy flour protein with formaldehyde and phenol to provide a stable adhesive. The results were used to develop more economical adhesives that are ideally suited for the face section of oriented strandboard.     

Adhesion properties of soy protein adhesives enhanced by biomass lignin

Soy protein adhesives have great potential as sustainable eco-friendly adhesives. However, low adhesion under wet conditions hinders its applications. The objective of this research was to enhance the water resistance of soy protein adhesives. The focus of this research was to understand the effect of protein to lignin ratio and lignin particle size i.e. large (35.66 μm), medium (19.13 μm), and small (10.26 μm) on the adhesion performance of soy protein adhesives as well as to characterize its rheological and thermal properties. Results showed that the lignin particle size and the protein to lignin ratio greatly affected the adhesion performance of soy protein adhesives. The addition of lignin slightly increased the viscosity, spreadability, and thermostability of soy protein adhesives. The wet strength of soy protein adhesives increased as lignin particle size decreased. Soy protein mixed with small size lignin at a protein to lignin ratio of 10:2 (w/w) at 12% concentration presented the lowest contact angle and the highest wet adhesion strength of 4.66 MPa., which is 53.3% higher than that of 10% pure soy protein adhesive. The improvements in adhesion performance and physicochemical properties of soy protein adhesives by lignin were ascribed to the interactions between protein and lignin. Lignin with smaller particle size increased the wet shear strength of soy protein adhesives because a larger surface area of lignin was available to interact with the protein.     

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.     

Acetal‐induced strength increases and lower resin content of MUF and other polycondensation adhesives

Acetals such as methylal and ethylal are shown to be particularly effective additives in improving the strength of wood boards bonded with melamine‐ urea‐formaldehyde (MUF) resins, although they show some appreciable but lesser effect on other resins too, particularly phenol‐ formaldehyde resins. They equally allow a considerable decrease in resin loading, and thus, in melamine content, on the bonded wood panel and at parity of performance. Their development as additives is then primarily, but not only, targeted at the MUF adhesive resins. One‐third decreases in MUF adhesives loading at parity of performance or equally internal bond (IB) strength increases approximately up to 50% by addition of methylal are shown to be possible by laboratory particleboard as well as by thermomechanical analysis (TMA). The reasons for methylal and ethylal behavior were studied by a variety of techniques, including liquid‐ and solid‐ phase ¹³C‐NMR and could be mostly ascribed to the increased effectiveness and participation of the melamine to resin crosslinking due to its now preferentially homogeneous rather than heterogeneous reactions, consequences of the increased solubility in water afforded by the acetal cosolvents. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2561–2571, 2002     

皮胶蛋白增量剂对脲醛树脂胶合性能的影响

研究了化学改性皮胶加入脲5醛（UF）树脂对胶合性能的影响,旨在提高普通脲醛树脂应用性能。讨论了pH值、黏度、固化时间、耐水性、拉伸剪切强度等胶黏剂指标。结果表明：改性剂的加入使得改性合成的脲醛树脂在耐水性、胶合强度等方面优于未改性的脲醛树脂。改性皮胶的含量为3％时,改性脲醛树脂胶黏剂的主要的技术性能和指标均已达到国家标准。确定了改性皮胶做为增量剂的加入会使脲醛树脂本身的耐水性能和胶合强度均有提高。     

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。     

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.     

改性三聚氰胺-尿素-甲醛共缩聚树脂胶粘剂的合成

通过三聚氰胺-尿素-甲醛(MUF)共缩聚树脂胶粘剂的合成,探讨了三聚氰胺的用量对该MUF树脂耐水性能的影响及其规律。实验结果表明,当w(三聚氰胺)=43%～65%时,该MUF树脂的湿强度从0.93 MPa增加到2.74 MPa,耐沸水性明显提高;但是,当w(三聚氰胺)>65%时,该MUF树脂的湿强度增长极其缓慢,其耐沸水性提高并不明显;通过引入复合改性剂和适量的水,可使该MUF树脂的游离甲醛含量降低50%、成本降低10%～15%、固含量基本不变、胶合强度和耐沸水性均有所提高且适用期良好。     

Bonding performance of melamine-urea-formaldehyde and phenol-resorcinol-formaldehyde adhesives in interior grade glulam

Wood moisture content (MC) affects the glued laminated beam (glulam) bonding strength. Selected adhesives were Phenol-Resorcinol-Formaldehyde (PRF) and Melamine-Urea-Formaldehyde (MUF) adhesives with 1, 1.5 and 2% (w/w) carboxymethyl cellulose (CMC) formic acid solutions. Douglas fir (pseudotsuga menziesii) from North America was used in the test. The bonding behavior of these adhesives with wood at 12 and 18% MC were investigated. The study focused on the effect of 18% MC on shear strength performance of MUF and PRF adhesives and optimizing the formula of CMC formic acid solution. Compressive shear strength of wood with MUF adhesive with 2% (w/w) formic acid solution at 12 and 18% MC stabilized at 10.6 and 10.0 MPa, respectively, which were 17 and 16% higher than that with PRF adhesive at the same condition. At 12–18% MC, MC had a little effect on bonding strength. However, 18% MC wood with PRF adhesive had 52.2% less initial strength increasing rate than that of 12% MC wood. 18% MC wood with MUF adhesives with 1, 1.5 and 2% (w/w) CMC formic acid solutions had 16.0, 15.5 and 27.0% less initial strength increasing rates than that of 12% MC wood, respectively. MUF adhesive using 2% CMC formic solution required the shortest press time at 12 and 18% MC about 1.6 and 2.7 h, respectively. The strength of PRF adhesive was significantly affected by wood MC and enough press time is essential for the proper bonding strength.     

Use of additives to enhance the properties of cottonseed protein as wood adhesives

Soy protein is currently being used commercially as a “green” wood adhesive. Previous work in this laboratory has shown that cottonseed protein isolate, tested on maple wood veneer, produced higher adhesive strength and hot water resistance relative to soy protein. In the present study, cottonseed protein and soy protein isolates were tested on different wood types, and cottonseed protein again showed better performance relative to soy protein. Furthermore, the effects of several protein modifiers were evaluated, including amino acids, fatty acids, and other organic molecules with cationic or anionic charges. Aspartic acid, glutamic acid, acetic acid, butyric acid, and adipic acid gave improved performance when included with cottonseed protein isolate whereas no significant effect was observed on soy protein isolate. Both dry adhesive strength and hot water resistance were tested. The enhanced performance observed with these additives provides an additional incentive for the use of cottonseed protein in this application.     

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。     

三聚氰胺含量对MUF性能的影响

MUF(三聚氰胺-尿素-甲醛共缩聚树脂)兼具UF(脲醛树脂)和MF(三聚氰胺甲醛树脂)的优点,通过调节m(三聚氰胺)/m(尿素)配比,可得到性价比较高的MUF;然后采用MUF胶粘剂制备刨花板,并考察了三聚氰胺含量对刨花板的内结合强度、耐水性和耐沸水性等影响。结果表明:三聚氰胺的引入,虽能有效提高MUF的性能,但并非加量越多越好;当w(三聚氰胺)=11.0%~14.0%时,MUF的性价比相对最高,相应刨花板的内结合强度、耐水性和耐沸水性俱佳。     

Adhesive properties of soy proteins modified by urea and guanidine hydrochloride

An investigation was conducted on the adhesive and water-resistance properties of soy protein isolates that were modified by varying solutions of urea (1, 3, 5, and 8 M) or guanidine hydrochloride (GH) (0.5, 1, and 3 M) and applied on walnut, cherry, and pine plywoods. Soy proteins modified by 1 and 3 M urea showed greater shear strengths than did unmodified protein. The 3 M urea modification gave soy protein the highest shear strength. Soy proteins modified with 0.5 and 1 M GH gave greater shear strengths than did the unmodified protein. The 1 M GH-modified soy protein gave the highest shear strength. Compared to the unmodified protein, the modified proteins also exhibited higher shear strengths after incubating with two cycles of alternating relative humidity, zero delamination, and higher remaining shear strengths after three cycles water soaking and drying. These results indicate that soy proteins modified with urea and GH enhance water resistance as well as adhesive strength. Secondary structures of globule proteins may enhance adhesion strength, and the exposure of hydrophobic amino acids may enhance water resistance. Proteins modified by 3 M urea or 1 M GH may have higher content of secondary structure and more exposed hydrophobic amino acids, compared with other modifications or unmodified proteins.     

Effects of polyisocyanate on properties and pot life of epoxy resin cross‐linked soybean meal‐based bioadhesive

In this study, polyisocyanate (pMDI) was introduced into epoxy resin modified soybean meal‐based bioadhesive to address the issue of low dry bond strength. Specifically, we investigated the effects of adding pMDI in terms of amount and storage time on dry bond strength, water resistance, and pot life of adhesive. Factors examined included shear strength, apparent viscosity, chemical reaction, crystallinity, and morphology of modified adhesives. Results indicated that the dry bond strength and water resistance of the resultant plywood was respectively improved 29.5% and 39.7% by adding 2% pMDI. In addition, the pot life of modified adhesive reached in 4 h. Results also shown that the cross‐linking reactions between epoxy group and carbonyl as well as isocyano and amino increased the cross‐linking density and formed a denser cross‐linking network structure of cured adhesive. The composite cross‐linked soybean meal‐based adhesive is environmental‐friendly and high‐performance, which will promote the industrial application of the soy protein‐based adhesives. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43362.