Novolaks

The initial phenol-formaldehyde reaction products may be of two types, novolaks and resols. 

The novolaks are prepared by reacting phenol with formaldehyde in a molar ratio of approximately 1 0.8 under acidic conditions. Under these conditions there is 

The novolak resins themselves contain no reactive methylol groups and do not form cross-linked structures on heating. If, however, they are mixed with compounds capable of forming methylene bridges, e.g. hexamethylenetetramine or paraformaldehyde, they cross-link on heating to form infusible, thermoset structures. 

In general it is considered essential that the bulk of the phenol used initially should not be substituted, i.e. should be reactive, at the o- and p-positions and is thus trifunctional with respect to the reaction with formaldehyde. 

There are three possible isomers and the proportions in which they are formed will depend on the pH of the reaction medium. Under the acid conditions normally employed in novolak manufacture the 2,4 - and 4,4 -HPM compounds 

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The condensation proceeds somewhat differently with an acid catalyst the product is termed Novolak. 

Hgh nitrile polymers Hgh oleic canola Hgh oleic sunflower Hgh ortho novolaks... 

Novolak photoresist Novolak process Novolak resin... 

In the case of phenoHcs, it is possible to make linear thermoplastic polymers called novolaks, but this is done by reaction of less than one mole of formaldehyde with one mole of phenol the resulting resin has a large excess of free phenol. Usually in appHcation hexamethylene tetramine (HEXA) is added to the novolak. When heated, the HEXA breaks down into ammonia and formaldehyde and enters the reaction to form a light degree of cross-links in the final product. 

Epoxidized phenol novolak and cresol novolak are the most common curing agents. The composition of the resin and hardener system is optimized for each specific appHcation eg, incorporating phenol novolaks in the matrix resin can iacrease cure speed. 

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. 

Strong-Acid Catalysts, Novolak Resins. PhenoHc novolaks are thermoplastic resins having a molecular weight of 500—5000 and a glass-transition temperature, T, of 45—70°C. The phenol—formaldehyde reactions are carried to their energetic completion, allowing isolation of the resin ... 

The typical acid catalysts used for novolak resins are sulfuric acid, sulfonic acid, oxaUc acid, or occasionally phosphoric acid. Hydrochloric acid, although once widely used, has been abandoned because of the possible formation of toxic chloromethyl ether by-products. The type of acid catalyst used and reaction conditions affect resin stmcture and properties. For example, oxaUc acid, used for resins chosen for electrical appHcations, decomposes into volatile by-products at elevated processing temperatures. OxaUc acid-cataly2ed novolaks contain small amounts (1—2% of the original formaldehyde) of ben2odioxanes formed by the cycli2ation and dehydration of the ben2yl alcohol hemiformal intermediates. 

Novolaks produced from these catalysts exhibit a high content of 2,2 -methylene units. The mechanism proposed for the ortho-directing effect involves chelation of the phenoHc unit with the metal ion. 

High ortho novolaks have faster cure rates with hexa. Typical properties of a 2inc acetate-cataly2ed high ortho novolak are also shown in Table 4. The gel time with hexa is one-third of that with a strong acid-cataly2ed novolak. 

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. 

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. 

Novolak Resins. In a conventional novolak process, molten phenol is placed into the reactor, foHowed by a precise amount of acid catalyst. The formaldehyde solution is added at a temperature near 90°C and a formaldehyde-to-phenol molar ratio of 0.75 1 to 0.85 1. For safety reasons, slow continuous or stepwise addition of formaldehyde is preferred over adding the entire charge at once. Reaction enthalpy has been reported to be above 80 kj /mol (19 kcal/mol) (29,30). The heat of reaction is removed by refluxing the water combined with the formaldehyde or by using a small amount of a volatile solvent such as toluene. Toluene and xylene are used for azeotropic distillation. FoHowing decantation, the toluene or xylene is returned to the reactor. 

The reaction is completed after 6—8 h at 95°C volatiles, water, and some free phenol are removed by vacuum stripping up to 140—170°C. For resins requiring phenol in only trace amounts, such as epoxy hardeners, steam distillation or steam stripping may be used. Both water and free phenol affect the cure and final resin properties, which are monitored in routine quaHty control testing by gc. OxaHc acid (1—2 parts per 100 parts phenol) does not require neutralization because it decomposes to CO, CO2, and water furthermore, it produces milder reactions and low color. Sulfuric and sulfonic acids are strong catalysts and require neutralization with lime 0.1 parts of sulfuric acid per 100 parts of phenol are used. A continuous process for novolak resin production has been described (31,32). An alternative process for making novolaks without acid catalysis has also been reported (33), which uses a... 

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). 

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). 

Novolaks. Novolak resins are typically cured with 5—15% hexa as the cross-linking agent. The reaction mechanism and reactive intermediates have been studied by classical chemical techniques (3,4) and the results showed that as much as 75% of nitrogen is chemically bound. More recent studies of resin cure (42—45) have made use of tga, dta, gc, k, and nmr (15). They confirm that the cure begins with the formation of benzoxazine (12), progresses through a benzyl amine intermediate, and finally forms (hydroxy)diphenyknethanes (DPM). 

The cure of novolaks with hexa has been studied with differential scanning calorimetry (dsc) and torsional braid analysis (tba) (46) both a high ortho novolak and a conventional acid-cataly2ed system were included. The dsc showed an exothermic peak indicating a novolak—hexa reaction ca 20°C higher than the gelation peak observed in tba. Activation energies were also calculated. 

Spectroscopy. Infrared spectroscopy (48) permits stmctural definition, eg, it resolves the 2,2 - from the 2,4 -methylene units in novolak resins. However, the broad bands and severely overlapping peaks present problems. For uncured resins, nmr rather than ir spectroscopy has become the technique of choice for microstmctural information. However, Fourier transform infrared (ftir) gives useful information on curing phenoHcs (49). Nevertheless, ir spectroscopy continues to be used as one of the detectors in the analysis of phenoHcs by gpc. 

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). 

Uncured resins are skin sensitizers and contact should be avoided, as weU as breathing the vapor, mist, or dust. Novolak-based pulverized products generally contain hexamethylenetetramine, which may cause rashes and dermatitis. PhenoHc molding compounds and pulverized phenoHc adhesives must be controUed as potentially explosive dusts. In addition, they contain irritating or toxic additives. 

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