Phenolic resins chemical reactivity

The outstanding performance characteristics of the resins are conveyed by the bisphenol A moiety (toughness, rigidity, and elevated temperature performance), the ether linkages (chemical resistance), and the hydroxyl and epoxy groups (adhesive properties and formulation latitude, or reactivity with a wide variety of chemical curing agents) (see also Phenolic resins). 

By far the most important phenolic resins are those made from phenol and formaldehyde. They exhibit high hardness, good electrical and mechanical properties, and chemical stability. Very often they are used in combination with (reactive) fillers like sawdust, chalk, pigments etc. 

It is becoming apparent that wood components, especially lignin, are chemically modified by solvents during wood dissolution, and that the resulting wood tars or pastes become highly reactive. Attempts have therefore been made to prepare effective adhesives, moldable resins and other products from wood after dissolution in phenols or polyhydric alcohols. This review presents recent progress on wood dissolution, and on the preparation of epoxy and phenol resin adhesives from kraft lignin. 

Phenolic resins are well known for their contribution in improving hardness, gloss, and water and chemical resistance in oleoresinous varnishes. Those based on p-alkyl-substituted phenols and with heat-reactive methylol groups have also been incorporated into alkyd resins. The reaction has not been well smdied. Presumably, the methylol group would react with the unsaturation functionality on the fatty acid chain to form the chroman stmcture, similar to what is believed to have occurred in the varnish. Etherification between the methylol group and free hydroxyl of the alkyd resin, catalyzed by the residual acidity in the resin, would be another possible reaction. 

A second generation of phenolic dispersions, patented by J. S. Fry (33). involved the post dispersion of phenolic resins in a mixture of water and water-miscible solvents. To conform with air pollution regulations, the solvent was held to 20 volume %, or less, of the volatiles. A heat-reactive phenolic resin dispersion (34) and a phenolic-epoxy codispersion have become commercially available based on the above technology. Supplied at 40-45% solids, these products, which have a small particle size (0.75-1.0 ym), are better film formers than the earlier dispersions. Used alone or in blends with other waterborne materials, corrosion-resistant baking coatings may be formulated for coil coating primers, dip primers, spray primer-surfacers, and chemically resistant one-coat systems. Products of this type are also tackifiers for acrylic latexes, and such systems have been employed as contact, heat seal, and laminating adhesives for diverse substrates. 

The main parameter for the application of tannins as adhesives for wood-based panels is the content of reactive polyphenols and the reactivity of these components towards formaldehyde. Tannins can be used as adhesives alone (with a formaldehyde component as crosslinker) or in combination with aminoplastic or phenolic resins. These resins can react chemically with the tannin component in a polycondensation reaction, form only two interpenetrating networks, or both. The simplest adhesive mix formulation consists of the tannin solution and powdered paraformaldehyde as crosslinker [283]. The addition of paraformaldehyde can cause in the short term a relatively high level of formaldehyde emission. Glue mixes using paraformaldehyde for the production of particleboards with low formaldehyde emission are described and used industrially [284]. In the literature a large number of papers describe the combinations of tannins with synthetic resins (Table 14). 

Although these tannins can be reacted with formaldehyde and other aldehydes, the rates of these interactions are low, and they are therefore not favoured for the preparation of resins. They have, however, been used successfully as partial substitutes (up to 50 per cent) of phenol in the manufacture of phenol-formaldehyde resins [9, 10]. Their chemical behaviour towards formaldehyde is analogous to that of simple phenols of low reactivity and their moderate use as phenol substitutes in the above-mentioned resins does not present difficulties. Their lack of macro-molecular stmcture, the low level of phenol substitution they allow, their low nucleophilicity, limited worldwide production and relatively high price, somewhat decrease their chemical and economical interest for resin production. Consequently, their main use is for leather tanning where their performance, especially in terms of clarity of colour and light resistance, is truly excellent. 

Addition of p-cresol formaldehyde (PCF) into phenolic/NBR blends resulted in rednction in the domain size of the dispersed phase and improvement in mechanical properties [244]. PCF resin has an intermediate polarity compared with NBR and resole and can react faster with NBR. Therefore, PCF molecules are likely to be concentrated at the phenolic/NBR interface and act as an external compatibilising agents [245]. Thus compatibility and chemical bonding between NBR and phenolic resin is improved, leading to the enhancement in properties. The other materials used as toughening agents of phenolic resin include elastomers such as natural rubber and nitrile rubber [246, 247], reactive liquid polymers [248] and thermoplastics such as polysulfone, polyamide, polyethylene oxide [249, 250]. 

Phenol has unique chemical properties due to the presence of a hydroxyl group and an aromatic ring, which are complementary in that they facilitate both electrophilic and nucleophilic reactions. The aromatic ring of phenol is highly reactive towards electrophilic snbstitntion, which assists its acid-catalyzed reaction with formaldehyde. Phenol is a weak acid and easily forms sodium phenoxide (NaPh) in a base-catalyzed medinm. In the presence of sodium phenoxide, the nucleophilic addition of the phenolic aromatic ring to the carbonyl group of formaldehyde occurs. Thus, phenol can react with formaldehyde under acidic or basic conditions, leading to either novolac or resole resins (Weber and Weber, 2010). 

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