Potential of carbohydrates for exterior-type adhesives

A.W. Christiansen R.H. Gillespie

Abstract New exterior-quality adhesives for wood products need to be available if the cost or supply of phenol-based adhesives should become unfavorable. Carbohydrates represent a large, inexpensive, renewable resource from which to obtain polymerizable materials. Preliminary trials led to exploratory evaluation of a system in which carbohydrates and some urea replace as much as 35 percent of the phenol in a softwood plywood formulation. Carbohydrates included glucose, fructose, sucrose, methyl glucoside, corn syrup, and xylose. Acidcatalyzed dehydration drives the initial reaction. During exposure to acid at high temperature, weight loss from hexose carbohydrates is equivalent to over 4 moles of water per mole of monosaccharide, over 3 moles for a pentose. In the initial synthesis reaction, the carbohydrate is degraded and reacted with urea. The resulting product is neutralized and reacted with phenol and formaldehyde. Finally, alkali is added as the curing catalyst. Adhesive resins synthesized with various molar ratios of the ingredients were used to bond twoply laminated veneer panels, which were tested for bond strength. Promising results were obtained. If the molar ratio of phenol-to-monosaccharide did not fall below 1:1 and that for formaldehyde-to-phenol did not fall below 2:1, then bond strengths were equal to those for phenolic resins, dry, wet, or after 2 hours of boiling. Slightly higher pressing temperatures were needed compared to a phenolic resin. Preliminary 13C nuclear magnetic resonance analysis did not indicate expected furan ring structures in the liquid resin.

Adhesives presently used for exterior-type, woodbased products depend upon petroleum for their starting materials. With the increasing energy needs of an expanding population and the inevitable decline in oil and gas supplies in the long term, the need for alternative adhesive systems from renewable resources is selfevident. The purpose of this investigation was to explore the potential of carbohydrates as constituents in waterresistant adhesives. Many renewable materials have been investigated over past years for constituents usable in adhesives, but none of the systems developed are suitable for exterior exposure. The largest volume of renewable material is from plants. These plants produce lignocellulosic material that becomes partially available as wastes or residues from food or wood processing. Although there is a wide variety of chemicals that are produced by plants,

The authors are, respectively, Chemical Engineer and Supervisory Research Chemist, USDA Forest Serv., Forest Prod. Lab., One Gifford Pinchot Dr., Madison, WI 53705. The authors express their appreciation to the following Forest Prod. Lab. employees for their help in this study: Wesley L. Rork, Physical Science Technician, for synthesizing the resins and evaluating their bond strengths; Martin F. Wesolowski, Chemist, and Lester C. Zank, Chemist, for FTIR and NMR spectroscopic analyses, and Virgil H. Schwandt, Chemist, for the HPLC analyses. This paper was received for publication in April 1985. Forest Products Research Society 1986. Forest Prod. J. 36(7/8):20-28.

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their basic chemical constituents are hemicellulose, cellulose, lignin, and extractives. From among these, we chose the carbohydrates or sugars from the hemicellulose and cellulose portions to evaluate as woodadhesive constituents. Their basic chemical structure is well known, and a wealth of information is available about their reactions and reaction mechanisms. Although carbohydrates contain large numbers of hydroxyl groups that would possibly lend water sensitivity to reaction products, we felt that a polymerization system might be found to overcome this effect.

Background Carbohydrates have been investigated in the past as coreactants with phenolic resins and as the sole ingredient in the adhesive. Meigs (14, 15, 16) carried out some of the earliest work with phenol-carbohydrate combinations. He was searching for a process to produce solid, fusible, thermoset molding compounds. The reactions used both basic and acid catalysis and often included coreactions with aniline or aliphatic amines. In other examples, Chang and Kononenko (3) developed an adhesive system (claimed to be suitable for exterior plywood applications) by coreacting sucrose in a phenolformaldehyde resin preparation under alkaline conditions. More recently, Gibbons and Wondolowski (8) reacted carbohydrates with phenol and urea, or a diamine, in the presence of an acid catalyst. The fusible resin, which was used as a molding compound, was cured to the thermoset stage by heating with hexamethylenetetramine. Later, Gibbons and Wondolowski (9) produced a soluble, liquid resin in which the carbohydrate-ureaphenol reaction poduct was neutralized. reacted further with formaldehyde, and formulated as an alkaline system for potential use as a plywood adhesive. Other investigators have used acidic conditions only. Mudde (17) described a system that depended upon the acidic conversion of starch to 5-hydroxymethyl2-furaldehyde (HMF) for condensing with phenol in a novolac resin. Turner et al. (24) investigated carbohydrates, not involving phenol as a coreactant, and produced a water-resistant adhesive. Turner et al. degraded pentose or hexose sugars by acids, while coreacting with such materials as formaldehyde, furfuryl alcohol, polyvinyl alcohol, or amines to produce an adhesive suitable for particleboard production. As another example, Stofko (21, 22, 23) proposed systems that used a variety of carbohydrate sources and reactions under acidic conditions with different modifiers to yield adhesives that produced water-resistant bondlines. All the adhesives investigated depended upon the degradation of carbohydrates under acid catalysis. Resin formation takes place between the degradation products themselves, or with intermediates formed during the degradation, or between degradation products and other monomers such as phenol and urea. Taking glucose as an example of a carbohydrate which can form a resin, the following mechanism, proposed by Anet (1) and modified by Feather and Harris (6), illustrates the mechanism for its degradation to HMF (structure IV):

Glucose, after intermolecular rearrangement to form the 1,2-enediol (I) loses 3 moles of water successively to finally form the aldehyde-substituted furan ring of HMF (IV). The fact that resins or polymers can be formed from carbohydrates under acidic conditions has been attributed to the formation of HMF (IV) from hexoses, or 2-furaldehyde (furfural) from pentoses. These compounds form resins quite readily under acid conditions through the loss of water by a series of complex reactions which have not been clarified. Consequently, the process of forming resins from sugars involves the loss of large amounts of water. For example, a hexose sugar having a formula weight of 180 grams can lose 4 or 5 moles of water (72-90 g or 40%-50%) during resinification. Materials and methods Experimental approach This was an exploratory investigation of resin systems that might yield durable adhesives from carbohydrates. Thus, there were few replications and no effort to optimize reaction or bonding conditions. The procedures used were selected to evaluate small quantities of starting materials. Consequently, small two-

Glucose exists as a glucopyranose ring structure. The open chain structure is shown here for simplification.

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ply parallel-laminated veneer panels were bonded, and specimen size was reduced to a minimum consistent with the collection of reliable data. Yellow birch was selected for the veneer because of its uniform grain structure and high shear strength relative to that of softwoods. Both 2-hour boil and vacuum-pressure-soak (VPS) exposures were selected to provide a measure of water resistance and an indication of any undercure during bonding. The reactions evaluated involved carbohydrates that included an aldohexose (glucose), a ketohexose (fructose), an aldopentose (xylose), a disaccharide (sucrose), a partially hydrolyzed polysaccharide (corn syrup), and a methyl ether of an aldohexose (methyl glucoside). The number of moles of carbohydrate was calculated from the basic monosaccharide that would be produced by complete hydrolysis of the di- or polysaccharides used. The mole ratios of the reactants of phenol-to-carbohydrate-to-urea-to-formaldehyde (P/C/ U/F) were varied over rather broad limits to explore the range of reactant concentrations that might prove useful. For most experimental adhesives, two-ply panels were prepared using several combinations of bonding time and temperature to estimate pressing conditions that would yield well-bonded panels. Materials The carbohydrates and other chemicals used in the syntheses included a-D-glucose ( 2% -anomer ), Dxylose (approximately 98%), corn syrup (82.8% nonvolatiles), D-fructose (98%), methyl glucoside (a mixture of and -anomers), sucrose (commercially purified granulated sugars), phenol (reagent grade), urea, formaldehyde (37% with 5% methanol), sulfuric acid (5.0 N), and calcium hydroxide. Other materials, used only in the weight loss experiments, were a retail bleached wheat flour, ammonium chloride, ammonium sulfate, ferric chloride hexahydrate, and 85 percent phosphoric acid. The phenol-formaldehyde resin used as a control adhesive was a commercial resin reported by the manufacturer to have 43.1 0.1 percent nonvolatiles, a pH of 12.2 0.3, a viscosity of 0.5 to 0.78 pascal-second (Pa s.) (500-780 cP) at 25C (77F), and a specific gravity of 1.205 0.005 at 25C (77F). The wood adherends were clear, flat-grained, rotary-peeled yellow birch veneer with moisture content (MC) equilibrated at 27C (80F) and 30 percent relative humidity (RH) (about 6% MC on an ovendry basis). The pieces were 3.2 mm (1/8 in.) thick and 150 by 150 mm (6 by 6 in.) in area. Preliminary experiments The reaction mechanism of Scheme I requires extensive dehydration of the carbohydrate. An estimate of the speed and extent of dehydration was obtained for acid-catalyzed carbohydrates. Weight loss and reactivity An indication of how rapidly water can be lost from different carbohydrates at different temperatures was obtained by weighing formulations in wide-mouth

weighing bottles heated for various time periods (Table 1). The carbohydrates included glucose, fructose, xylose, sucrose, and wheat flour. All carbohydrates were evaluated with ammonium chloride as the acid catalyst, while fructose was also evaluated with ammonium sulfate, phosphoric acid, and ferric chloride. These results show that dehydration reactions of acid-catalyzed carbohydrates proceed at temperatures as low as 100C (212F) but only at a slow rate. In fact, at temperatures as high as 170C (388F), weight losses appear to continue for at least 24 hours. As much as 4 to 5 moles of water per mole of carbohydrate seem to be released upon prolonged heating if the weight loss is considered to be all water. Some of the intermediates or products of dehydration may have been partly volatilized or steam distilled to make the weight-loss values higher than for water loss alone. Sucrose, the disaccharide, requires consumption of a mole of water to hydrolyze to glucose and fructose, its two monosaccharides. The experiments did not show that less water was evolved from sucrose upon degradation (Table 1). Enhanced dehydration at the lowest temperature of 100C (212F) was indicated when phosphoric acid or ferric chloride was used. The data for wheat flour was calculated on the assumption that it contained approximately 75 percent carbohydrate hydrolyzable predominantly to hexoses. The importance of dehydration is noted later in the discussion of results on the carbohydrate-phenol-urea-formaldehyde resins.

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after the formulation was spread on the surfaces to be mated. A typical example involved a formulation consisting of 74 percent sucrose, 5 percent concentrated phosphoric acid, and 21 percent water. This was refluxed at a temperature ranging from 105 to 112.5C (221 to 234.5F) with portions removed for bonding after 8, 30, and 40 minutes. The adhesive was spread by brush at a rate of 0.39 kg/m2 (80 pounds per thousand square feet of single glueline (lb./MSGL)) with half on each of the mating surfaces to be bonded. The adherends were then heated in an air-circulating oven at 150C (302F) for 6 minutes. Two-ply panels were pressed at both 5 and 10 minutes at 200C (392F) and 1.03 MPa (150 psi). As a control, a phenolic adhesive (containing 10% walnut shell flour) was spread at a rate of 0.45 kg/m 2 (91 lb./MSGL) and pressed at 200C (392F), 1.03 MPa (150 psi) after 15-minute open assembly time. After pressing, the panels were aged at 27C (80F)/30 percent RH for different periods of time up to 13 days before testing. Because there was no significant difference in the results due to time of pressing or to time of aging after pressing, the results were combined and averaged for presentation in Table 3. The dry strength of the sucrose adhesive was 68 percent of that for the phenolic-bonded panels and the wet strength after a VPS treatment was 74 percent. These results demonstrated that the dehydration products from acid-catalyzed carbohydrates were capable of providing water-resistant bonds with wood. The major problem involves the dehydration reactions and how to optimize and control the conditions necessary to produce the highest water resistance the system can yield. In addition, the control of bondline acidity after cure of the adhesive would have to be established. These problems were solved in the next system, in which two coreactants were added to the acidic reaction mixture, the carbohydrate was strongly dehydrated, and the final wood bonding was performed with an alkaline adhesive. Adhesive formulation and bonding experiments After various adhesive systems described in the literature (21, 22, 24) were evaluated in the survey phase of this investigation, we selected the carbohydrate-phenol-urea-formaldehyde system (9) for more detailed investigation. Methods Resin synthesis procedure. The carbohydrate, phenol, and urea were placed in a 0.5-liter resin kettle fitted with a thermometer, a stirrer, and a side-arm condenser. The mixture was heated to 90C (194F) while stirring, then the sulfuric acid catalyst was added. In most cases, the amount of sulfuric acid used to degrade the carbohydrate was held constant at 40 milliequivalents (meq) per mole of monosaccharide. The temperature was allowed to rise as high as 150C (302F) during 4 hours or until the desired amount of condensate had been collected (e.g., 64 mL of condensate per mole of glucose was often the goal). Heating was discontinued until the temperature fell to 90C (194F) at which time the collected condensate was returned to

Differential scanning calorimetry (DSC) gave additional information about the degradation reactions of these five carbohydrate materials (Table 2). These data show that catalyzed fructose was the most reactive (i. e., had the lowest reaction peak temperatures) under the conditions evaluated. Xylose was next most reactive, then sucrose, followed closely by glucose. Wheat flour was the slowest to start reacting, but at the maximum rate, it behaved much like glucose. Of the four different catalysts used with fructose, ferric chloride started the degradation reaction sooner than did phosphoric acid, which was followed in turn by ammonium sulfate, and then ammonium chloride. The strong acids were more effective than the acidic salts. The peak temperatures, although not so widely separated, followed almost the reverse trend. Bonding experiment with acidified carbohydrate In a preliminary bonding experiment, part of the dehydration was accomplished by prereacting the ingredients in flasks and part by heating the adherends

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the reaction mixture. The pH was raised to near 7 by the addition of 6 meq of finely powdered calcium hydroxide per meq of sulfuric acid. After the temperature had fallen to 70C (158F), the desired amount of formalin was added, and the mixture was again heated with stirring for 1 hour at 80C (176F). After cooling to room temperature, the pH and viscosity were measured. The viscosity was adjusted to a minimum of 0.3 Pas. (300 cP) by further heating at 80C (176F) if necessary. Adhesive formulation. Adhesive formulation consisted of adjusting the pH to between 11 and 12 and the viscosity to between 0.5 and 2.5 Pas. (500 and 2,500 cP). The pH adjustment was made with sodium hydroxide (6.6% of liquid resin weight) and sodium carbonate (2.2% of liquid resin weight). The viscosity adjustment was made by further heating at 80C or by water dilution, whichever need was indicated. Panel preparation. Each adhesive was brushed on each of the mating veneer surfaces at a rate of 0.17 to 0.25 kg/m2 (60-100 lb./MSGL). After a 15-minute open assembly time, the panels were assembled with their grain direction parallel. After a 10-minute closed assembly time, the panels were pressed at 1.21 MPa (175 psi) for either 5 or 10 minutes at a selected temperature between 145and 180C (293 to 356F) At least one two-ply panel was prepared with the phenolic resin as a control during each experiment. Specimen preparation and testing. Each panel yielded 14 specimens 62 mm (2.4 in. ) long in the grain direction and 18 mm (0.71 in.) wide. Prior to cutting out the specimens, saw kerfs were cut to the bondline across both faces of the panels to produce an overlap region 10 mm (0.39 in. ) long in the center of each specimen. This provided a specimen shear test area of 180 mm2 (0.280 in.2). For each bonded panel, specimens were randomly assigned to three conditioning groups of four specimens each, leaving two as possible replacements. One group was conditioned at 27C (80F), 30 percent RH for at

least 16 hours before being tested for shear strength in the dry condition. A second group was conditioned in the same manner and then subjected to a VPS cycle. This consisted of a 1/2-hour submersion in tap water under a vacuum of 740 mm (29 in. ) of mercury followed by 1/2 hour of pressure of 0.41 MPa (60 psi). These specimens were tested for shear strength in the wet condition. The third group was conditioned at 27C (80F) and 30 percent RH before submerging in water, boiling for 2 hours, cooling in water, and testing for shear strength in the wet condition. A substantial increase of strength for this treatment over the VPS treatment would be taken as an indication of undercure during bonding. There were only a few experiments in which replicate panels were pressed and assembled under the same conditions for one resin. From these, several specimens from each panel were tested after conditioning at the various regimes. In general, the panel-topanel variation was larger than the within-panel variation in these few experiments. Therefore, for the great majority of trial resins presented (for which there is no estimate of panel-to-panel variation), statistical tests on the data to verify the impressions of these initial results would not be meaningful. Results and discussion Strength values for the best formulations for the glucose- and xylose-based adhesives showed which press conditions were sufficient to confidently reach the plateau of maximum strength, for dry and wet tests. These conditions were found to be 5 minutes at 155C (311F) for the glucose-based adhesives, and 160 to 170C (320 to 338F) for the xylose-based adhesives. Strength values in Tables 4 to 7 are for panels that were bonded at these sufficient press conditions, where possible. The results of bonding experiments using adhesives from glucose-based resins (as described in the Methods section) are shown in Table 4. These results can be compared with those from panels bonded with the

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commercial phenolic adhesive and which are shown as the mean shear strength from 23 different panels produced at different times. The shear strength results from the glucose-based adhesives varied widely, ranging from values equal to those for the phenolic specimens to no strength at all in the wet condition. As the mole ratio of phenol to carbohydrate (P/C) was reduced from 1/1 to 0.5/1, both dry- and wet-shear strengths fell drastically, although the changes made in other variables obscured the certainty of this effect. The most encouraging results were obtained with P/C/U/F mole ratios of 1.0/1 .0/0.25/3.6 and removal of the volume equivalent of 3.6 moles of water as condensate of reaction (experiment 3); the shear strength results matched those for the phenolic-bonded specimens. Table 5 shows the shear strength results with carbohydrates that yield hexose sugars, such as glucose or fructose, upon hydrolysis. In most cases, these gave high shear strengths often comparable to strengths of the phenolic-bonded specimens. The fructose-based adhesive yielded high dry- and wet-shear values. Methyl glucoside, corn syrup, and sucrose required hydrolysis to monosaccharides prior to reaction with urea and phenol. The hydrolysis required much additional time and energy to carry out, in contrast to the use of simple hexose sugars.

The panels bonded with adhesives based upon xylose (a pentose sugar) also had high dry- and wet-shear strengths (Table 6). The best results were obtained in experiment 16, which involved a P/C/U/F ratio of 1/1/0.5/2.5 with only 2.4 moles of water per mole of fructose eliminated during the dehydration reaction. Experiment 17 demonstrated that the resin could be stored for at least a week following synthesis and still provide shear properties equivalent to those obtained when first formulated. The lower strength values for experiment 17 compared with experiment 16 were attributed to lower formaldehyde use. These bonding experiments demonstrated that a variety of different carbohydrates could be coreacted with phenol, urea, and formaldehyde to produce wood bonds that, when tested wet or dry, were within the range provided by the conventional phenolic adhesive. In general, it appeared that at least two moles of water per mole of monosaccharide needed to be eliminated during the dehydration reaction for high shear strength to develop. The amount of formaldehyde required to produce high shear strength appears to be at least 2.0 moles per mole of phenol. In the tables, the formaldehyde content is shown as based upon the moles of monosaccharide used. When the P/C ratio was 1/1, the F/P ratio was the

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same as the F/C ratio. In the case of experiments 4 to 9 (Table 4), a calculated F/P ratio would in no case be less than 2/1. The effect of formaldehyde-to-phenol ratio with glucose as the carbohydrate is shown in Table 7. The highest wet shear strength values were reached only after the formaldehyde content had been increased to 2.0 moles per mole of phenol. Wood failure was estimated in some cases with both the phenolic and the carbohydrate-based adhesives. But because of the parallel-grain laminated hardwood and the very small area of bond being tested, high variability among specimen replicates characterized the wood failure estimates. The only conclusion that seemed reasonable was that the experimental adhesive could develop wood-tearing bonds similar to those produced by a conventional phenolic adhesive. Savings resulting from phenol replacement are difficult to calculate with precision because of the ever changing formulations used in the industry and the uncertainties about the actual reactions that take place during resin formation and adhesive cure. Assumptions need to be made, such as the elimination of a mole of water for every mole of formaldehyde used, the formation of sodium phenate to the full extent of phenol content, and equivalent spread rates and waste factors. Calculations based upon resin formation according to Redfern (19) and adhesive formulation for Douglas-fir according to Jarvi (12) resulted in a value of 50 pounds of phenol required for 100 pounds of cured adhesive solids in a conventional phenolic resin. An adhesive with a P/C/U/F molar ratio of 1/1/0.5/2.0 would result in a considerable savings of phenol in a softwood plywood application. A PF resin adhesive with carbohydrate and urea used in the above ratio and 4 moles of water eliminated during resin formation and adhesive cure requires 32.2 pounds of phenol to produce 100 pounds of cured adhesive solids. This would be a savings of about 35 percent of the phenol required for softwood plywood production. Part of this savings is due to the fact that a hexose sugar has a molecular weight that is almost twice that of phenol so that a 1/1 molar ratio of P/C is actually a 1/2 ratio by weight. Although adhesive formulations for southern pine (such as reported by Sellers (20)) use extenders as well as fillers with variations in the amounts of ingredients used, a similar savings in phenol would be expected by the addition of carbo-

hydrates and urea as reported here. On the other hand, such formulations might not tolerate the addition of fillers and extenders without loss of shear strength and water resistance. To allow for smooth plant operations, it might be necessary to add fillers and extenders to adjust the theological properties of the adhesive. Reaction mechanisms The reaction mechanisms involved in the formation of the trial resins and these cured-adhesive solids are at best highly speculative. If only the carbohydrate provided the material for resin formation, the mechanism (Scheme I) proposed by Anet (1) would appear to have some applicability. When starting from glucose under acid catalysis, three dehydration steps result in the formation of HMF. But following this, rearrangements and the addition of 2 moles of water could result ultimately in the formation of formic acid (V) and levulinic acid (VI), in a mechanism such as that of Scheme II, adapted from Feather and Harris (6). After reaction has been in progress for awhile, the reaction mixture might easily contain a wide variety of molecular species including glucose, HMF, and levulinic acid. Efforts were made to detect the presence of furan rings in the reaction mixture after various reaction times to obtain evidence in support of the above hypothesis.

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When carbohydrates were coreacted with phenol and urea in acid medium, the same series of reactions just referred to could be expected, plus a wide variety of additional reactions. Any of the dehydration or hydration intermediates mentioned might react with either phenol or urea and, at the same time, monoand/or diglycosyl ureas (VII and VIII in Scheme III) would be expected to form (10). The formation of glycosyl ureides usually requires at least a small amount of water in the reaction mixture (2,18). The conditions used in this study, however, would be expected to force dehydration reactions through the removal of the water of reaction as soon as it was formed. Efforts were made to detect the types of amide linkages that would be expected of glycosyl urea formation. Analytical methods Samples taken during the synthesis were analyzed one of two ways using high performance liquid chromatography (HPLC). Samples containing phenol were analyzed on a Bio-Rad HPX87H + (acid) column, in 0.015 N phosphoric acid, with an ultraviolet absorbance detector. Samples from which phenol had been sublimed away were analyzed on a series of two Bio-Rad HPX87P (lead ion) sugars analysis columns, in distilled water, with a differential refractometer detector. Samples were filtered before injection. A Nicolet 6000 Fourier transform infrared (FTIR) spectrometer recorded the infrared spectra. Samples from reaction mixtures were dispersed in water, spread on KBr crystals, and quickly dried in a vacuum desiccator for 2 hours. Two materials were used to generate reference spectra for spectral subtractions: either a sample from the initial heated reaction mixture just before acid catalyst was added, or the previous sample of a partially reacted mixture. Pure component spectra of the carbohydrates, phenol, urea, HMF, and water (between AgCl crystals) were used to identify individual infrared peak positions of the reaction mixture. 13 C nuclear magnetic resonance (NMR) spectrograms were collected on a Bruker WM-250 FT-NMR spectrometer at 62.89 MHz. The spectra were obtained at ambient temperature with broad band decoupling. The chemical shifts were measured relative to internal DMSO-d 6, the solvent, and converted to values relative to tetramethylsilane.

Results and discussion FTIR spectroscopy. Spectroscopic and chromatographic techniques were used in attempts to identify intermediate products in samples taken from a reaction mixture at various times. Interferences from the reactants prevented identification of the presence of HMF by infrared spectroscopy, even by using spectral subtractions. Not much pure HMF is expected to exist at any time because of its high reactivity under acid catalysis. HMFs strong infrared absorption peak is at 1,680 cm -1, but ureas strongest absorption region covers the range from 1,600 to 1,680 cm-1. One of HMFs two medium strength absorption peaks is at 1,020 cm 1, where glucose also has its strongest absorption. HMFs other medium strength absorption peak is at 1,520 c m- l , near the end of a strong absorption doublet at 1,475-1,510 cm-1. Samples taken only minutes after the acid was added, in experiments 3 or 6 (Table 4 ), show that the mixtures absorb fairly strongly in the whole region from 970 to 1,720 cm -1. Constantly shifting ratios of reactants and products make it difficult to identify or quantify minor components. HPLC. Samples for HPLC taken before acid addition show only peaks for initial ingredients, on either set of columns. After acid addition, samples show new peaks scattered around the glucose peak. These peaks have not been assigned to particular compounds. Only rarely were even minor peaks observed near the retention time found separately for HMF. NMR spectroscopy . HMF is more reactive than either 2-furaldehyde or furfuryl alcohol, both of which form resins by themselves or with phenol under acidic conditions (4). Gibbons and Wondolowski (8,9) postulated that during their synthesis glucose degrades to HMF. Then the aldehyde group of HMF reacts with urea to form disubstituted urea compounds containing furan rings from the HMF. Next, the hydroxymethyl groups attached to the furan rings react with available phenol. However, samples taken from our syntheses using either glucose or xylose showed no 13C NMR signals attributable to furan rings, especially in the 105 to 125 ppm region where the less reactive C3 or C4 carbons of the furan rings produce signals (5,7,10). In the region from 115 to 158 ppm, where the original phenol produces signals, no new signals or shifts arise during the acid-catalyzed step, indicating that phenol essentially acted only as a solvent during this step. New signals do appear in this region after formaldehyde was reacted into the mixture. In the region from 60 to 100 ppm, the signals produced by the carbohydrate decrease as the acidcatalyzed reaction proceeds, while some new peaks arise and then fall in the same region. Near the end of the acid step, there is only a smear of very low intensity signals in the spectrum between 60 and 85 ppm. This indicates that either a multitude of products has been formed, or the carbon atoms are present in new bonds that give less intense signals, or the relaxation time of the carbon species spins has changed significantly (perhaps by being incorporated into polymeric molecules), or all of these.

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For a sample taken from the reaction mixture before the acid catalyst is added, there is only one signal above 158 ppm, that at 160.8 ppm produced by ureas carbonyl group. In samples taken after acid addition, another signal 1.5 ppm below the first, rises and falls with time. This signal is probably due to the carbonyl group of a substituted urea. Monomethyl and dimethyl substitutions of formamide cause such shifts (13). Near the end of the acid step, both signals have disappeared. Summary and conclusions The dehydration products from acid-catalyzed carbohydrate reactions, without addition of coreactants, were capable of providing water-resistant bonds with wood. But this acidic system required the elimination of large amounts of water during a very high-temperature bonding operation. Experiments with a second system have shown that a reaction system using carbohydrates as the major component seems to provide wood-bonding strengths equal to the strength of bonds made with a conventional phenolic resin. Acidcatalyzed dehydration of carbohydrates in the presence of urea occurs in the first stage, Phenol, which remains as an inactive medium in that stage, reacts in the subsequent neutral stage when formaldehyde is added into the reaction mixture. Alkaline catalyst is then added for the bonding reaction. The most waterresistant bonds were formed when the phenol-tocarbohydrate mole ratio was at least 1/1, the urea-tocarbohydrate mole ratio changed from 0.25/1 to 0.5/1, and a formaldehyde-to-phenol mole ratio was at least 2/1, with at least two moles of product water per mole of monosaccharide removed during resin formation. Bonding conditions were not excessive and included a spread rate of about 0.39 kg/m2 (80 lb./MSGL), a 15-minute open assembly time, and a 10-minute closed assembly time with pressing for 5 minutes under 1.21 MPa (175 psi) pressure. Temperatures as low as 155C (311F) were satisfactory with hexose sugars, while 160 to 170C (320 to 338F) was required for an adhesive based upon a pentose sugar. Six carbohydrates glucose, fructose, sucrose, xylose, corn syrup, and methyl glucosideall performed satisfactorily. This indicated that a wide variety of carbohydrate sources would be usable for adhesives if reaction and bonding conditions were optimized. Fourier transform infrared (FTIR), 13C nuclear magnetic resonance (NMR), and high performance liquid chromatography (HPLC) were used in attempts to elucidate reaction mechanisms. These methods were unable to detect any appreciable quantities of 5-hy droxymethyl-2-furaldehyde (HMF), which would be formed upon complete dehydration of hexose sugars. Amide linkages characteristic of glucosyl ureide formation remained undetected because of interference from the other components of the complex mixtures that resulted from the reactions. The mechanism of the reaction remained obscure. Recommendations The carbohydrate-phenol-urea-formaldehyde (P/C/

U/F) system needs further development before it can be considered a definite replacement for phenolic adhesives. Additional studies of the reaction mechanism should be conducted to optimize the adhesive system. Resin reaction conditions and adhesive formulation must be optimized for particular adhesive applications. Assembly and pressing condition tolerances must be established. Finally, larger size softwood panels bonded with this adhesive must be tested after outdoor exposure to assure the long-term durability of this adhesive compared to phenolic resins.

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