Phenol-formaldehyde weak-base resins

The use of the anion-exchange resin Duolite A-7 for concentrating organic acids was reported as early as 1965 by Abrams and Breslin (7) and more recently by Leenheer (8). A-7 is a high-surface-area, macro-porous, phenol-formaldehyde, weak-base resin. This resin combines weak-base, secondary-amine functional groups with the relatively hydrophilic phenol-formaldehyde matrix to effectively sorb and elute organic acids. 

Anion exchangers can also be made which have either a strong base or weak base character. The former are usually phenol-formaldehyde or polystyrene resins with extra quarternary ammonium groups. Ionisation occurs in both the salt and hydroxide form, and all kinds of anions are exchanged with reasonable ease ... 

Prior to the development of polystyrene resins, phenol-formaldehyde (P-F) condensates were used as matrices, but they have now been replaced. A few weak-base types still exist (e.g., Duolite ES562 of Rohm and Haas), which are made by adding an amine during polycondensation. These P-F condensates are used for enzyme fixation. 

Weakly acidic cation exchange resins are obtained by copolymerizing divinyl benzene with acrylic esters. The ester groups are then saponified with alkali. Many other types are known besides these types for example, those based on phenol-formaldehyde resins, cellulose, etc. 

Very early hydrocarbon-based membranes tested as electrolytes in PEMECs for Gemini space missions, such as sulfonated phenol-formaldehyde resins, sulfonated poly(styrene-divinylbenzene) copolymers, and grafted polystyrene sulfonic acid membranes, were chemically weak, and therefore PEMFCs using these membranes showed poor performance and had only lifetimes of several hundred hours (LaConti et al. 2003). Nafion , a PESA membrane, was developed in the mid-1960s by DuPont (LaConti et al. 2003). It is based on an aliphatic perfluorocarbon sulfonic acid, and exhibited excellent physical properties and oxidative stability in both wet and dry states. A PEMEC stack using Nafion 120 (250- tm thickness, equivalent weight = 1,200) achieved continuous operation for 60,000 h at 43-82°C (LaConti et al. 2003, 2006). A Nafion -based PEMFC was used for the NASA 30-day Biosatellite space mission (LaConti et al. 2003). 

Positive-Tone Photoresists based on Dissolution Inhibition by Diazonaphthoquinones. The intrinsic limitations of bis-azide—cyclized rubber resist systems led the semiconductor industry to shift to a class of imaging materials based on diazonaphthoquinone (DNQ) photosensitizers. Both the chemistry and the imaging mechanism of these resists (Fig. 10) differ in fundamental ways from those described thus far (23). The DNQ acts as a dissolution inhibitor for the matrix resin, a low molecular weight condensation product of formaldehyde and cresol isomers known as novolac (24). The phenolic structure renders the novolac polymer weakly acidic, and readily soluble in aqueous alkaline solutions. In admixture with an appropriate DNQ the polymer s dissolution rate is sharply decreased. Photolysis causes the DNQ to undergo a multistep reaction sequence, ultimately forming a base-soluble carboxylic acid which does not inhibit film dissolution. Immersion of a pattemwise-exposed film of the resist in an aqueous solution of hydroxide ion leads to rapid dissolution of the exposed areas and only very slow dissolution of unexposed regions. In contrast with crosslinking resists, the film solubility is controlled by chemical and polarity differences rather than molecular size. 

Resins based on para-substituted phenols can be either one-step or two-step, but they cannot cure to a thermoset state. In the manufacture of phenolic resins, smaller quantities of acetaldehyde and furfuraldehyde are used in addition to formaldehyde. Furthermore, resorcinol, bisphenol A, and p-alkylphenols are employed, in addition to phenol, when special properties are desired. Formaldehyde concentrations of 37-50 weight % in aqueous solutions are most commonly employed. The catalysts most frequently used are acids such as oxalic, hydrochloric, sulfuric, p-toluenesul-fonic, and phosphoric and bases such as sodium, calcium, and barium hydroxide. In the weakly acidic range metal carboxylates are employed. Thermoset phenolic resins are employed as structural adhesives for laminating and bonding applications. Para-alkyl-substituted resins are employed as tackifiers in contact adhesives, pressure-sensitive adhesives, and hot-melt adhesives. 

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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