Carbohydrate-phenolic-based resins

Carbohydrate-phenolic-based resins have shown promise for partial replacement of phenol and formaldehyde in exterior plywood adhesives (7,2). Such resins are produced in a two-stage reaction sequence. First, the carbohydrate is reacted with phenol, and sometimes urea, under acid catalysis at elevated temperatures (up to 150 °C), to produce an acid-stage resin. The acid-stage resin is then made basic, formaldehyde added, and the reaction continued at lower temperatures to produce a resol-type resin. Adhesives formulated from these resins have curing speeds consistent with present-day plywood production needs in the western United States, veneers are typically dried to 0 to 7% moisture content and the adhesive cured by hot pressing the panels at approximately 140 to 150 °C and 1.2 MPa. 

Carbohydrate-phenolic-based resins can be modified to change their physical and chemical properties, and faster curing adhesives can be made from these modified resins. However, the nature of the research presented here is exploratory, and much remains to be done. In particular, the molecular structure of these resins needs to be defined. 

Gibbons, J. P. Wondolowski, L. Carbohydrate-Phenol Based Condensation Resins Incorporating Nitrogen-Containing Compounds Canadian Patent 1 090 026, 1980. 

Based on these results, it can be concluded that phenol-formaldehyde resins modified with 0.6 to about 1.0-mole of carbohydrate per mole of phenol and cured at neutral conditions can bond wood with acceptable dry- and wet-shear strengths, and wood failures. Also, reducing as well as non-reducing carbohydrates can be used as modifiers for neutral phenol-formaldehyde resins. It was found that the resins formulated under neutral conditions are very light in color and would thus be useful in the preparation of decorative products. Carbohydrate modifiers are incorporated into the resin via ether linkages between the hydroxyls of the carbohydrate and the methylol groups in the resin. Apparently carbohydrates, at least in theory, can participate in a crosslinked network. 

The presence of numerous hydroxyl groups able to react with formaldehyde makes starch-derived products suitable chemicals for formaldehyde-based resins. Research on this subject started many years ago and showed that in a number of applications it is possible to partially replace or extend urea formaldehyde, phenol formaldehyde and melamine formaldehyde resins without significantly affecting the finished product s performance. In many applications, adhesive systems based on formaldehyde resins incorporate a polysaccharide component. More than 4.5 Mio mto of formaldehyde-based resins have been produced in Western Europe alone. The use of carbohydrates allows lower consumption of oil-based resins and, consequently, reduced release of formaldehyde in the environment. 

Few examples have been described of nucleophilic cleavage of carbonate- or carbamate-linked alcohols from insoluble supports. A serine-based linker for phenols releases the phenol upon fluoride-induced intramolecular nucleophilic cleavage of an aryl carbamate (Entry 2, Table 3.36). A linker for oligonucleotides has been described, in which the carbohydrate is bound as a carbonate to resin-bound 2-(2-nitrophen-yl)ethanol, and which is cleaved by base-induced 3-elimination (Entry 3, Table 3.36). Trichloroethyl carbonates, which are susceptible to cleavage by reducing agents such as zinc or phosphines, have been successfully used to link aliphatic alcohols to silica gel (Entry 4, Table 3.36). These carbonates can also be cleaved by acidolysis (Table 3.22). 

Phenol-formaldehyde type polymers had been the only exterior-durable adhesives for wood bonding, until the recent limited use of isocyanates. Both systems are petrochemical-based. Several researchers substituted carbohydrates for part of phenolic adhesives (1-4) > producing solid, fusible novolak resins. Recently, reaction of carbohydrate acid-degradation products with phenol and formaldehyde has produced liquid resols (5). Gibbons and Wondolowski (6,7) replaced a considerable amount of phenol with carbohydrate and urea to pro-... 

There are a few minor wood-based chemical industries. After chestnut blight wiped out the American chestnut, U.S. tannin production essentially ceased. The main natural tannins, watde and quebracho, are now imported. High U.S. labor costs and the advent of synthetic tannins make re-establishment of a U.S. tannin industry unlikely. Tannins are used in oil-weU drilling muds. Tree exudates are a continuing wood-based chemical industry. Tree exudates include mbber, tme carbohydrate gums (eg, acacia gum), kinos (eg, the phenolic exudates from eucalyptus), balsams (eg, Storax from l iquidambar spp.), and many different types of oleoresins (mixtures of a soHd resin and a liquid essential oil). The most important oleoresin stiU collected in the United States is pine gum (rosin plus turpentine). 

The primary chemical classes from which adhesives are made include epoxies, acrylics, phenolics, urethanes, natural and synthetic elastomers, amino resins, silicones, polyesters, polyamides, aromatic polyheterocyclics, and the various natural products such as carbohydrates and their derivatives as well as plant- and animal-based proteins. Chemical class was once a relatively clean differentiator of adhesives, but so many adhesives now are hybrids, designed to take advantage of specific attributes of more than one chemical class or type of material. Hybridization can be accomplished by incorporating into an adhesive a nonreactive resin of a different chemical class adding another type of reactive monomer, oligomer,... 

---