Preparation of a New Type of Polyamidoamine and Its Application for Soy Flour-Based Adhesives

The most commonly used curing agents for soy-based adhesives are polyamines, which have the problem of low solid content and/or high viscosity. To overcome this problem, a new type of polyamidoamine (PADA) resin was synthesized and applied to soy flour-based adhesives to improve their water resistance. The PADA solution obtained had a high solid content of 50 wt% and low viscosity of 270 cP. The optimum weight ratio of soy flour/PADA/maleic anhydride to prepare adhesive was 40/7/1.68. The wet strength of plywood prepared at the optimum weight ratio was 0.82 MPa, which meant the plywood could be used as type II plywood according to the Chinese National Standard GB/T 9846.7-2004. The results of water-insoluble solid content measurement and SEM observation demonstrated that cured soy flour–PADA–maleic anhydride adhesive had a 16 % greater water-insoluble solid content than soy flour–NaOH adhesive. The cross-linking network formed by the reactions of PADA and MA would increase the water-insoluble solid contents and improve water resistance of cured soy flour-based adhesives.     

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.     

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.     

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.     

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.     

Soy-based adhesives for wood-bonding – a review

Over recent years, the interest in bio-adhesives, including soy-based adhesives, has increased rapidly. Among natural renewable resources suitable for industrial use, soy is a reasonable choice due to its high production volume and the small use of soy meal-based products for human food consumption. Soy flour can be an ideal raw material for the manufacturing of wood adhesives due to its low cost, high protein content and easy processing. There are also more concentrated forms of soy proteins, i.e. concentrates and isolates, which are also suitable raw materials for adhesive production except that their prices are higher. Extensive research has been carried out on improving the cohesive properties, especially water resistance, of soy-based adhesives. However, there is insufficient experimental data available for understanding the influences of modification methods on the structure of soy proteins and therefore for understanding the influences of structural changes on the adhesion. In this paper, some experimental techniques are proposed to be used for analysing soy-based adhesives to enable better understanding of those factors and improve future development. This review of soy-based adhesives is made with the focus on soy proteins’ chemical composition, soy protein product types (raw materials for adhesive production), modification methods for improving the adhesive properties of soy-based adhesives, and commercial soy-based adhesives.     

Effects of typical soybean meal type on the properties of soybean-based adhesive

In order to effectively apply soybean meal for the preparation of water-resistant soybean-based adhesives for plywood, the effects of three typical soybean meal products, namely, low-temperature soybean meal (LM), high-temperature soybean meal (HM), and physical soybean meal (PM), on the properties of soybean-based adhesive were investigated. The results indicated that the number of reactive groups in the three soybean meals followed the order LM > HM > PM, which in turn led to various crosslinking densities when these soybean meals were crosslinked by epichlorohydrin-modified polyamide (EMPA) during the curing process. The LM soybean adhesive had 6.6% higher soaking bond strength and 16.5% higher boiling-dry-boiling bond strength than the HM soybean adhesive, and 19% higher soaking bond strength and 33% higher boiling-dry-boiling bond strength than the PM soybean adhesive, respectively. These three soybean meals could be used to prepare soybean adhesives for interior-use plywood because all plywood panels bonded with their adhesives passed a water-soaking test at 63 °C for 3 h, but only the LM soybean adhesive achieved the desired water resistance for floor-base plywood. Among the three evaluated soybean meals, LM was the most promising raw material for the preparation of soybean-based adhesive because of a greater number of reactive groups, higher crosslinking density, and superior bond strength. Plywood panel bonded with HM soybean adhesive had a water resistance lower than, but very close to, the standard required value (>0.8 MPa) for floor-base plywood.     

Adhesive qualities of soybean protein-based foamed plywood glues

The potential of soy protein-based plywood glues for foam extrusion was evaluated. Standard glue mixes containing the soy flours Honeysoy 90, ISU-CCUR, Nutrisoy 7B, and defatted Soyafluff, and the soy concentrates Arcon F and Procon 2000 showed excellent foaming and adhesive qualities but did not have the ability to refoam. To improve refoaming capability, the formulations were modified by increasing the quantities of soy flour or concentrate so that they provided 3.48 g protein/100 g of glue mix. This was the amount of protein contributed by animal blood when it was used as the extender in the standard formulation for foamed glue. All the modified glues containing soy flour or concentrate had good refoaming properties and adhesive strengths that were at least equal to that of the control glue. Simple cost analysis also indicated that when soy flour was used, the modified formulations were cheaper to produce than the current blood-based glue.     

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.     

协同交联型大豆胶黏剂的流变与固化性能研究

利用饲料级大豆粉为原料,通过水性聚酰胺和异氰酸酯对其进行协同复合改性制备出具有良好流变行为和固化性能的大豆胶黏剂。采用旋转流变仪研究了复合改性剂用量对大豆胶黏剂流变行为和固化性能的影响,结果表明：改性后的大豆胶黏剂属于假塑性流体,当水性聚酰胺添加量为10%时,所得大豆胶黏剂的流变性能较优,而异氰酸酯添加量对大豆胶黏剂的流变行为几乎没有影响;运用动态温度扫描模式研究大豆胶黏剂的黏弹性能,异氰酸酯添加量对大豆胶黏剂的储能模量和损耗模量影响较大。水性聚酰胺/异氰酸酯协同交联体系可与大豆蛋白分子间发生交联,当10%水性聚酰胺和4%异氰酸酯协同改性时,所得胶合板的胶合强度可达0.74 MPa,满足国家Ⅱ类胶合板使用要求（≥0.70 MPa）。     

High temperature performance of soy-based adhesives

We studied the high temperature performance of soy meal processed to different protein concentrations (flour, concentrate, and isolate), as well as formulated soy-based adhesives, and commercial nonsoy adhesives for comparison. No thermal transitions were seen in phenol-resorcinol-formaldehyde (PRF) or soy-phenol-formaldehyde (SoyPF) or in as-received soy flour adhesive during differential scanning calorimetry scans heating at 10?°C/min between 35 and 235?°C. Heat flow rates decreased in the order soy flour (as received)?>?SoyPF?>?PRF?>?emulsion polymer isocyanate (EPI). In thermogravimetric analysis (TGA) scans from 110 to 300?°C at 2?°C/min, total weight loss decreased in the order soy flour (as-received)>SoyPF?>?PRF?>?casein?>?maple?>?EPI. For bio-based materials, the total weight loss (TGA) decreased in the order soy flour (as-received) > concentrate, casein?>?isolate. Dynamic mechanical analysis from 35 to 235?°C at 5?°C/min of two veneers bonded by cured adhesive showed 30–40% decline in storage modulus for maple compared to 45–55% for the adhesive made from soy flour in water (Soy Flour) and 70–80% for a commercial poly(vinyl acetate) modified for heat resistance. DMA on glass fiber mats showed thermal softening temperatures increasing in the order Soy Flour?<?casein?<?isolate?<?concentrate. We suggest that the low molecular weight carbohydrates plasticize the flour product. When soy-based adhesives were tested in real bondlines in DMA and creep tests in shear, they showed less decrease in storage modulus than the glass fiber-supported specimens. This suggests that interaction with the wood substrate improved the heat resistance property of the adhesive. Average hot shear strengths (ASTM D7247) were 4.6 and 3.1?MPa for SoyPF and Soy Flour compared to 4.7 and 0.8?MPa for PRF and EPI and 4.7 for solid maple. As a whole, these data suggest that despite indications of heat sensitivity when tested neat, soy-based adhesives are likely to pass the heat resistance criterion required for structural adhesives.     

Investigation of epoxy-based wood adhesives

Cold-set epoxy-based wood adhesives were investigated for production of exterior plywood. Effective adhesives were composed of bisphenol A diglycidyl ether (BPADGE), polyamidoamine (PAA), and polyethylenimine (PEI). Three-ply plywood panels were prepared with BPADGE–PAA–PEI adhesives and evaluated for their strengths and water resistance in accordance with a standard for exterior plywood. The effect of BPADGE/(PAA + PEI) weight ratio, PAA/PEI weight ratio, the mixing time for preparing the adhesive, and the pressing time for making plywood panels on the water resistance and the shear strengths of the plywood panels was investigated. The pot life of the adhesive was also measured. Plywood panels made with the BPADGE–PAA–PEI adhesives met the industrial requirements for exterior applications. Adhesion mechanisms are discussed in detail. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47741.     

A new formaldehyde-free wood adhesive from renewable materials

A formaldehyde-free adhesive that consists of soy flour (SF) and a new curing agent (CA) was developed and evaluated for making interior plywood. Three types of plywood panels (seven-ply maple/white fir/pine/white fir/pine/white fir/maple, five-ply yellow poplar, and five-ply aspen) were prepared with the SF–CA adhesives and evaluated for their water resistance. The CA was derived from the reaction of epichlorohydrin (ECH) and ammonium hydroxide in water. Effects of the reaction time, reaction temperature, NaOH usage, heat treatment of CA, addition order of reactants in the preparation of the CA, and storage time of the CA on the water resistance of plywood panels bonded with SF–CA adhesives were investigated. The reaction time required for the completion of the reaction significantly decreased as reaction temperatures increased. The addition of NaOH to the SF–CA adhesive improved the water resistance and dry shear strength of the five-ply aspen panels. All plywood panels met the requirements for interior plywood when the CAs were prepared at 45–60 °C no matter whether the CA was heat-treated or not. Mixing ECH and ammonium hydroxide all at once resulted in better water resistance of the resulting plywood panels than adding either of ECH or ammonium hydroxide to the other dropwise. The viscosity of heat-treated CA was comparable to that of untreated CA when the CA was prepared at 50 °C. Both heat-treated and untreated CAs could be stored at room temperature for at least two months without compromising the water resistance of the resulting plywood panels.     

Using Renewables in Panelboard Resins to Influence Volatile Organic Compound Emissions from Panels

Technical lignin and condensed tannins have been combined with soy flour as model of no-added-formaldehyde adhesive binders for veneer wood products to understand their impacts on volatile organic compounds (VOCs) produced during panel manufacture. VOC emissions captured on manufacturing lauan hardwood plywood at 170?C were dominated by acetaldehyde, hexaldehyde, acetone, and terpenes in both the condensate and gaseous fractions of press emissions. Other aldehydes including formaldehyde, valeraldehyde, and propionaldehyde were produced in relatively lower quantity during panel manufacture. Compared to using soy flour alone, lignin, and tannin reduced the formaldehyde and acetaldehyde contents in press emissions. These reductions in VOCs had a dependency on adhesive resin pH with an alkaline formulation proving to also decrease longer chain aldehydes such as valeraldehyde and hexaldehyde. Chamber testing plywood panels found the composition of VOC emissions initially released from panels to be prominent compounds released in press emissions formed on panel manufacture. Use of soy flour alone as binder produced relatively high acetaldehyde emissions from panels, whereas incorporating lignin and tannin with soy flour as adhesive binders reduced both acetaldehyde and formaldehyde emissions from panelboards post-manufacture.     

Comparison of Canola and Soy Flour with Added Isocyanate as Wood Adhesives

Canola is widely grown in the northern latitudes for its vegetable oil, generating large quantities of residual, low value canola flour used as animal feed. The common wood adhesive poly(diphenylmethylene diisocyanate) (pMDI) should react with the wide variety of functional groups in proteins. Therefore, it would seem that canola flour with added pMDI could be an effective adhesive. Two main questions are addressed in this study: How do the wood adhesive properties of canola flour compare to the better-studied soy flour? How well do proteins, which contain an abundance of functional groups, cure with the very reactive pMDI? These questions were addressed using the small-scale adhesive strength test ASTM D-7998, with various adhesive formulations and bonding conditions for canola flour plus pMDI compared to soy adhesives. The more challenging wet cohesive bond strength was emphasized because the dry strengths were usually very good. Generally, soy adhesives were better than canola ones, as was the polyamidoamine-epichlorohydrin cross-linker compared to pMDI, but these generalizations can be altered by the conditions selected. Three-ply plywood tests supported the small-scale test results.     

Glutaraldehyde-wheat gluten protein adhesives for wood bonding

ABSTRACT

Wheat gluten protein hydrolysate was used as a biomass feedstock to prepare environmentally friendly protein-based adhesives, with hydrolyzed wheat protein as control. Glutaraldehyde was used to modify it to obtain a glutaraldehyde-wheat protein (GP) adhesive. Polyethylenimine (PEI) was also used as a crosslinking agent. Plywood has been prepared and tested, and its performance was used to measure the wheat gluten protein hydrolysate adhesive bonding performance. Differential scanning calorimetry (DSC) and thermomechanical analysis (TMA) were used to analyze the adhesive thermal properties and the microstructures of the cured adhesives by scanning electron microscopy (SEM). The results show that modification by glutaraldehyde can effectively improve the bonding performance of wheat protein adhesives, the plywood bonded strength having been improved by its addition. The effect of PEI as a crosslinking agent became evident. It can greatly improve the bonding properties of glutaraldehyde-modified wheat protein adhesives. TMA analysis indicates that the glutaraldehyde-modified GP adhesive has a higher storage modulus than the unmodified one. The modulus of the adhesive increased after adding the PEI cross-linking agent.     

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     

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.     

A Soy Flour-Based Adhesive Reinforced by Low Addition of MUF Resin

The desire to prepare a lower-cost soy-based adhesive has led to an interest in using the abundant and inexpensive soy flour (SF) as a substitute for expensive soy protein isolates (SPI) in wood adhesives. However, the weakness of this adhesive is poor water-resistance and bonding strength due to a low protein content, which limits its application in the wood industry. The objective of this research was to provide a simple and useful approach for improving the adhesion performance of SF-based adhesive by introducing a small addition of melamine-urea-formaldehyde (MUF) resin into the cured system. The optimum addition level of MUF resin, as well as the adhesion performance and conformation change of SF-based adhesive, were investigated. The analytical results indicated that the co-condensed methylene bridges were formed through the reaction of methylol groups of MUF resin with soy units during the hot-press process. The addition of MUF resin, not only significantly decrease the viscosity of SF-based adhesive but also increase its water-resistance and wet shear strength value. The SF-based adhesive containing 20% MUF resin, is a relatively low-cost adhesive, has a reasonable viscosity, and moreover can pass the Chinese Industrial Standard requirement (0.7 MPa) for interior plywood panels.     

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.