Resoles

Resoles are usually mixtures of a number of methylol phenols, with small amounts of higher condensation products involving methylene and benzylic ether linkages. The kinetics of base-catalyzed phenol-formaldehyde reactions have been extensively researched. At high dilution and at a pH not exceeding 10, the rate equation can be expressed by Eq. (13), where [PhO ] denotes the concentration of phenoxide anion and [F] the concentration of unreacted formaldehyde, determined titrimetrically.  

Second-order kinetics were also established for base-catalyzed formaldehyde reactions with m-cresol and p-cresol. However, Fitzgerald and Martin reported fractional orders for reactions of 2,3,4,5-tetramethylphenol and 2,6-xylenol.  

Zavitsas has found that Eq. (13) is followed only by systems containing low levels of formaldehyde and that the kinetics are influenced strongly by equilibria of the type shown in Eqs. (14) and 

With improved analytical capabilities, several other workers have studied these reactions, especially under more dilute conditions. 

Although still a fair amount of discrepancy exists, all workers are in general agreement that substitution in the ortho position enhances the reactivity at both remaining positions and that para metholylation on the other hand shows little effect on subsequent reactivity. 

Formaldehyde reacts with phenol by electrophilic substitution at the 2-, 4- and 6-positions of phenol and will subsequently condense, forming a densely cross-linked network. This reaction can be catalyzed by acid as well as base catalysts. The nature of the product obtained is largely dependent on the type of phenol, the molar ratio of formaldehyde to phenol (f p) and the catalyst used. Phenolic resins are mainly divided into two broad classes resoles and novolacs. 

---

TEST Phenol Resorcinol 1 Hydro-Catechol 1 quinone e-Cresol m-C resol p-C resol i-Naphthol 2-Naphthol... 

Stopping the polymer at this point requires the ratio of formaldehyde to phenol to be less than unity. Both methylene and ether bridges are known to be present. The reaction is either acid or base catalyzed, and branching is uncommon at this stage. The products are variously known as A stage resins, novolacs, or resole prepolymers. 

Phenolic Resins. Phenohc resins (qv) are formed by the reaction of phenol [108-95-2] C H O, and formaldehyde [50-00-0] CH2O. If basic conditions and an excess of formaldehyde are used, the result is a resole phenohc resin, which will cure by itself Hberating water. If an acid catalyst and an excess of phenol are used, the result is a novolac phenohc resin, which is not self-curing. Novolac phenohc resins are typically formulated to contain a curing agent which is most often a material known as hexamethylenetetraamine [100-97-0] C H22N4. Phenohc resin adhesives are found in film or solution... 

Polyphenols. Another increa singly important example of the chemical stabilization process is the production of phenoHc foams (59—62) by cross-linking polyphenols (resoles and novolacs) (see Phenolic resins). The principal features of phenoHc foams are low flammabiUty, solvent resistance, and excellent dimensional stabiUty over a wide temperature range (59), so that they are good thermal iasulating materials. 

Most phenohc foams are produced from resoles and acid catalyst suitable water-soluble acid catalysts are mineral acids (such as hydrochloric acid or sulfuric acid) and aromatic sulfonic acids (63). Phenohc foams can be produced from novolacs but with more difficulty than from resoles (59). Novolacs are thermoplastic and require a source of methylene group to permit cure. This is usually suppHed by hexamethylenetetramine (64). 

Early phenoHc resins consisted of self-curing, resole-type products made with excess formaldehyde, and novolaks, which are thermoplastic in nature and require a hardener. The early products produced by General BakeHte were used in molded parts, insulating varnishes, laminated sheets, and industrial coatings. These areas stiH remain important appHcations, but have been joined by numerous others such as wood bonding, fiber bonding, and plywood adhesives. The number of producers in the 1990s is approximately 20 in the United States and over 60 worldwide. 

Other Reactants. Other reactants are used in smaller amounts to provide phenoHc resins that have specific properties, especially coatings appHcations. Aniline had been incorporated into both resoles and novolaks but this practice has been generally discontinued because of the toxicity of aromatic amines. Other materials include rosin (abietic acid), dicyclopentadiene, unsaturated oils such as tung oil and linseed oil, and polyvalent cations for cross-linking. 

Alkaline Catalysts, Resoles. Resole-type phenoHc resins are produced with a molar ratio of formaldehyde to phenol of 1.2 1 to 3.0 1. For substituted phenols, the ratio is usually 1.2 1 to 1.8 1. Common alkaline catalysts are NaOH, Ca(OH)2, and Ba(OH)2. Whereas novolak resins and strong acid catalysis result in a limited number of stmctures and properties, resoles cover a much wider spectmm. Resoles may be soHds or Hquids, water-soluble or -insoluble, alkaline or neutral, slowly curing or highly reactive. In the first step, the phenolate anion is formed by delocali2ation of the negative charge to the ortho and para positions. 

Special resoles are obtained with amine catalysts, which affect chemical and physical properties because amine is incorporated into the resin. For example, the reaction of phenol, formaldehyde, and dimethylamine is essentially quantitative (28). 

In practice, ammonia is most frequendy used. With hexa, the initial reaction steps differ, but the final resole resins are identical, provided they contain the same number of nitrogen and CH2 groups. Most nitrogen from ammonia or hexa is incorporated as diben2ylamine with primary, tertiary, and cycHc amine stmctures as minor products. 

The methylene-isomer distributions of NaOH and hexa-cataly2ed resoles are shown in Table 6. The distribution of amine stmctures is ... 

With a bulk process, resole resins, in neat or concentrated form, must be produced in small batches (ca 2—9.5 m ) in order to maintain control of the reaction and obtain a uniform product. On the other hand, if the product contains a large amount of water, such as Hquid plywood adhesives, large reactors (19 m ) can be used. Melt-stable products such as novolaks can be prepared in large batches (19—38 m ) if the exotherms can be controlled. 

Resoles. Like the novolak processes, a typical resole process consists of reaction, dehydration, and finishing. Phenol and formaldehyde solution are added all at once to the reactor at a molar ratio of formaldehyde to phenol of 1.2—3.0 1. Catalyst is added and the pH is checked and adjusted if necessary. The catalyst concentration can range from 1—5% for NaOH, 3—6% for Ba(OH)2, and 6—12% for hexa. A reaction temperature of 80—95°C is used with vacuum-reflux control. The high concentration of water and lower enthalpy compared to novolaks allows better exotherm control. In the reaction phase, the temperature is held at 80—90°C and vacuum-refluxing lasts from 1—3 h as determined in the development phase. SoHd resins and certain hquid resins are dehydrated as quickly as possible to prevent overreacting or gelation. The end point is found by manual determination of a specific hot-plate gel time, which decreases as the polymerization advances. Automation includes on-line viscosity measurement, gc, and gpc. 

In the post-dispersion process, the soHd phenoHc resin is added to a mixture of water, cosolvent, and dispersant at high shear mixing, possibly with heating. The cosolvent, frequently an alcohol or glycol ether, and heat soften the resin and permit small particles to form. On cooling, the resin particles, stabilized by dispersant and perhaps thickener, harden and resist settling and agglomeration. Both resole and novolak resins have been made by this process (25). 

The in situ process is simpler because it requires less material handling (35) however, this process has been used only for resole resins. When phenol is used, the reaction system is initially one-phase alkylated phenols and bisphenol A present special problems. As the reaction with formaldehyde progresses at 80—100°C, the resin becomes water-insoluble and phase separation takes place. Catalysts such as hexa produce an early phase separation, whereas NaOH-based resins retain water solubiUty to a higher molecular weight. If the reaction medium contains a protective coUoid at phase separation, a resin-in-water dispersion forms. Alternatively, the protective coUoid can be added later in the reaction sequence, in which case the reaction mass may temporarily be a water-in-resin dispersion. The protective coUoid serves to assist particle formation and stabUizes the final particles against coalescence. Some examples of protective coUoids are poly(vinyl alcohol), gum arabic, and hydroxyethjlceUulose. 

Resoles. The advancement and cure of resole resins foUow reaction steps similar to those used for resin preparation the pH is 9 or higher and reaction temperature should not exceed 180°C. Methylol groups condense with other methylols to give dibenzyl ethers and react at the ortho and para positions on the phenol to give diphenyknethylenes. In addition, dibenzyl ethers eliminate formaldehyde to give diphenyknethanes. 

In some resole appHcations, such as foam and foundry binders, a rapid cure of a Hquid resin is obtained at RT with strong acid. The reactions proceed in the same manner as those of novolak resin formation. Methylol groups react at ortho and para phenoHc hydrogen to give diphenyknethane units (41). 

Table 9. Chemical Shifts of Methylene Carbons in Liquid Resoles...

Gas chromatography (gc) has been used extensively to analyze phenoHc resins for unreacted phenol monomer as weU as certain two- and three-ring constituents in both novolak and resole resins (61). It is also used in monitoring the production processes of the monomers, eg, when phenol is alkylated with isobutylene to produce butylphenol. Usually, the phenoHc hydroxyl must be derivatized before analysis to provide a more volatile compound. The gc analysis of complex systems, such as resoles, provides distinct resolution of over 20 one- and two-ring compounds having various degrees of methylolation. In some cases, hemiformals may be detected if they have been properly capped (53). 

The combined techniques of gas chromatography/mass spectrometry (gc/ms) are highly effective in identifying the composition of various gc peaks. The individual peaks enter a mass spectrometer in which they are analyzed for parent ion and fragmentation patterns, and the individual components of certain resoles are completely resolved. 

Fig. 3. Programmed dma scan of a resole phenoHc resin heating rate is 5°C/min.

Aqueous dispersions are alternatives to solutions of Hquid and soHd resins. They are usuaUy offered in 50% soHds and may contain thickeners and cosolvents as stabilizers and to promote coalescence. Both heat-reactive (resole) and nonheat-reactive (novolak) systems exist that contain unsubstituted or substituted phenols or mixtures. A related technology produces large, stable particles that can be isolated as discrete particles (44). In aqueous dispersion, the resin stmcture is designed to produce a hydrophobic polymer, which is stabilized in water by an interfacial agent. 

Neoprene—phenohc contact adhesives, known for thein high green strength and peel values, contain a resole-type resin prepared from 4-/-butylphenol. The alkyl group increases compatibiHty and reduces cross-linking. This resin reacts or complexes with the metal oxide, eg, MgO, contained in the formulation, and increases the cohesive strength of the adhesive. In fact, the reactivity with MgO is frequently measured to determine the effectiveness of heat-reactive phenoHcs in the formulation. 

Heat resistance is an important characteristic of the bond. The strength of typical abrasive stmctures is tested at RT and at 300°C. Flexural strengths are between 24.1 and 34.4 MPa (3500—5000 psi). An unmodified phenoHc resin bond loses about one-third of its room temperature strength at 298°C. Novolak phenoHc resins are used almost exclusively because these offer heat resistance and because the moisture given off during the cure of resole resins results in undesirable porosity. Some novolaks modified with epoxy or poly(vinyl butyral) resin are used for softer grinding action. 

---