Phenol-formaldehyde applications

In 1993, worldwide consumption of phenoHc resins exceeded 3 x 10 t slightly less than half of the total volume was produced in the United States (73). The largest-volume appHcation is in plywood adhesives, an area that accounts for ca 49% of U.S. consumption (Table 11). During the early 1980s, the volume of this apphcation more than doubled as mills converted from urea—formaldehyde (UF) to phenol—formaldehyde adhesives because of the release of formaldehyde from UF products. Other wood bonding applications account for another 15% of the volume. The next largest-volume application is insulation material at 12%. 

Today the phenol-formaldehyde moulding compositions do not have the eminent position they held until about 1950. In some, important applications they have been replaced by other materials, thermosetting and thermoplastic, whilst they have in the past two decades found use in few new outlets. However, the general increase in standards of living for much of this period has increased the sales of many products which use phenolics and consequently the overall use of phenol-formaldehyde moulding powders has been well maintained. 

The term aminoplastics has been coined to cover a range of resinous polymers produced by interaction of amines or amides with aldehydes. Of the various polymers of this type that have been produced there are two of current commercial importance in the field of plastics, the urea-formaldehyde and the melamine-formaldehyde resins. There has in the past also been some commercial interest in aniline-formaldehyde resins and in systems containing thiourea but today these are of little or no importance. Melamine-phenol-formaldehyde resins have also been introduced for use in moulding powders, and benzoguanamine-based resins are used for surface coating applications. 

At one time urea-formaldehyde was used extensively in the manufacture of plywood but the product is today less important than heretofore. For this purpose a resin (typically U-F molar ratio 1 1.8)-hardener mixture is coated on to wood veneers which are plied together and pressed at 95-110°C under pressure at 200-800 Ibf/in (1.38-5.52 MPa). U-F resin-bonded plywood is suitable for indoor application but is generally unsuitable for outdoor work where phenol-formaldehyde, resorcinol-fonnaldehyde or melamine modified resins are more suitable. 

By far the preponderance of the 3400 kt of current worldwide phenolic resin production is in the form of phenol-formaldehyde (PF) reaction products. Phenol and formaldehyde are currently two of the most available monomers on earth. About 6000 kt of phenol and 10,000 kt of formaldehyde (100% basis) were produced in 1998 [55,56]. The organic raw materials for synthesis of phenol and formaldehyde are cumene (derived from benzene and propylene) and methanol, respectively. These materials are, in turn, obtained from petroleum and natural gas at relatively low cost ([57], pp. 10-26 [58], pp. 1-30). Cost is one of the most important advantages of phenolics in most applications. It is critical to the acceptance of phenolics for wood panel manufacture. With the exception of urea-formaldehyde resins, PF resins are the lowest cost thermosetting resins available. In addition to its synthesis from low cost monomers, phenolic resin costs are often further reduced by extension with fillers such as clays, chalk, rags, wood flours, nutshell flours, grain flours, starches, lignins, tannins, and various other low eost materials. Often these fillers and extenders improve the performance of the phenolic for a particular use while reducing cost. 

Phenolics. Phenol-formaldehyde (Bakelite) is one of the oldest synthetic materials available. It is a strong, hard, brittle material with good creep resistance and excellent electrical properties. Unfortunately the material is only available in dark colours and it is susceptible to attack by alkalis and oxidising agents. Typical applications are domestic electrical fittings, saucepan handles, fan blades, smoothing iron handles and pump parts. 

Phenolics are also used in a variety of other applications such as adhesives, paints, laminates for building, automobile parts, and ion exchange resins. Global production of phenol-formaldehyde resins exceeded 5 billion pounds in 1997. 

Phenol-formaldehyde (phenolic) plastics The chemical resistance is affected by the phenol used, cresols giving the best acid resistance whilst xylenols are often used to obtain the best alkali resistance. For chemical-resistant applications the fillers used in moulding powder and reinforcing material in laminates should be inorganic, e.g. asbestos or glass. The resins are usually dark in colour. 

Among the separator varieties described, the phenol-formaldehyde-resorcinol separator (DARAK 2000) [60] as well as the microporous PVC separator [86] have proven effective for this construction. For applications without deep discharges, concessions may be made with the respect to porosity and pore sizes of the separator therefore polyethylene separators or a spe-... 

Phenolic phenol formaldehydes (PFs) are the low-cost workhorse of the electrical industry (particularly in the past) low creep, excellent dimensional stability, good chemical resistance, good weatherability. Molded black or brown opaque handles for cookware are familiar applications. Also used as a caramel colored impregnating plastics for wood or cloth laminates, and (with reinforcement) for brake linings and many under-the-hood automotive electricals. There are different grades of phenolics that range from very low cost (with low performances) to high cost (with superior performances). The first of the thermosets to be injection-molded (1909). 

Unlike phenol-formaldehyde polymers, the amino resins are not themselves deeply coloured, but are of a naturally light appearance. They can be easily pigmented to give a variety of shades, which leads to application in uses where good appearance is highly valued, for example in decorative tableware, laminated resins for furniture, and modem white electrical plugs and sockets. 

From this brief discussion it is clear that crosslinking in phenol-formaldehyde resins is complicated and no individual specimen of these materials can be characterised well at the molecular level. Crosslinking is irregular and variable, though it gives rise to a material having sufficiently acceptable properties that it became the first commercially important plastic material indeed, as mentioned in Chapter 1, these resins continue to retain some commercial importance in certain specialised applications. 

Sulfur cross-links have limited stability at elevated temperatures and can rearrange to form new cross-links. These results in poor permanent set and creep for vulcanizates when exposed for long periods of time at high temperatures. Resin cure systems provide C-C cross-links and heat stability. Alkyl phenol-formaldehyde derivatives are usually employed for tire bladder application. Typical vulcanization system is shown in Table 14.24. The properties are summarized in Tables 14.25 and 14.26. 

Thermosets differ molecularly from thermoplastics in that their individual chains are anchored to one another through crosslinks. The resulting network creates cohesive materials that demonstrate better thermal stability, rigidity, and dimensional stability than thermoplastics. Some examples of traditional thermosets are melamine-formaldehyde resins, which are used to treat fabrics to make them wrinkle-free, and Bakelite (a phenol-formaldehyde resin), a historically important polymer used in many applications, such as costume jewelry, electrical switches, and radio casings. 

In general, the acid-sorbing resins may be classified as high molecular weight polyamines or polyimines. Thus, the original Adams and Holmes material was a polymer of m-phenylenediamine. Cation Exchange materials include synthetic resins, such as sulfonated phenol-formaldehyde or polystyrene types, and sulfonated coal. Some manufacturers have a variety of sub-types which are considered superior for particular applications. 

James Swinburne also discovered phenol-formaldehyde resins at the same time, but he was one day late in his application for patent than Baekeland. 

The polymerization of phenols or aromatic amines is applied in resin manufacture and the removal of phenols from waste water. Polymers produced by HRP-catalyzed coupling of phenols in non-aqueous media are potential substitutes for phenol-formaldehyde resins [123,124], and the polymerized aromatic amines find applications as conductive polymers [112]. Phenols and their resins are pollutants in aqueous effluents derived from coal conversion, paper-making, production of semiconductor chips, and the manufacture of resins and plastics. Their transformation by peroxidase and hydrogen peroxide constitutes a convenient, mild and environmentally acceptable detoxification process [125-127]. 

In the development of a reactive non-chrome post-treatment, a variety of phenolic resins were synthesized and commercial phenolic resins evaluated. It was found that phenol-formaldehyde resins, creso1-forma1dehyd e condensates, ortho-novo 1 ak resins, and phenol-formaldehyde emulsions gave positive results when employed as post-treatments over zinc and iron phosphate conversion coatings. The above materials all possessed drawbacks. The materials in general have poor water solubility at low concentrations used in post-treatment applications and had to be dried and baked in place in order to obtain good performance. The best results were obtained with poly-4-vinylphenol and derivatives thereof as shown in the following structure (8,9,10)... 

The advanced applications for nitrocellulose plastisol propellants require that they be integrally bonded to the motor case. Successful case bonding for the multiyear storage life of a rocket calls for special adhesives and liners which are completely compatible with these highly plasticized propellants. Best results have been obtained with a combination of an impervious rubber liner and a crosslinked adhesive system with a limited affinity for the plasticizers used in the propellants. Examples of effective liners are silica-filled butyl rubber and chlorinated synthetic rubber. Epoxy polyamides, isocyanate-crosslinked cellulose esters, and combinations of crosslinked phenol-formaldehyde and polyvinyl formal varnishes have proved to be effective adhesives between propellant and impervious liners. Pressure curing of the propellants helps... 

Spent resins are generally compatible with the polymer matrix material. Generally, the polymer and the resin do not interact chemically. The immobilization of spent ion-exchange resins in polymers is a common application all over the world. Epoxy resins, polyesters, polyethylene, polystyrene and copolymers, polyurethane, phenol-formaldehyde, and polystyrene are among the polymers used (IAEA, 1988). Inorganic materials are generally not immobilized using polymers because they are more acceptable to other immobilization matrices such as cement. 

Since the days of Bakeland many varieties and applications of phenol-formaldehyde resins have been found (1). In this paper we are concerned only with recent applications of functionally substituted phenol-formaldehyde-Novolak resins as applied to lithographic uses for micro-image fabrication. 

When two polymeric systems are mixed together in a solvent and are spin-coated onto a substrate, phase separation sometimes occurs, as described for the application of poly (2-methyl-1-pentene sulfone) as a dissolution inhibitor for a Novolak resin (4). There are two ways to improve the compatibility of polymer mixtures in addition to using a proper solvent modification of one or both components. The miscibility of poly(olefin sulfones) with Novolak resins is reported to be marginal. To improve miscibility, Fahrenholtz and Kwei prepared several alkyl-substituted phenol-formaldehyde Novolak resins (including 2-n-propylphenol, 2-r-butylphenol, 2-sec-butylphenol, and 2-phenylphenol). They discussed the compatibility in terms of increased specific interactions such as formation of hydrogen bonds between unlike polymers and decreased specific interactions by a bulky substituent, and also in terms of "polarity matches" (18). In these studies, 2-ethoxyethyl acetate was used as a solvent (4,18). Formation of charge transfer complexes between the Novolak resins and the poly (olefin sulfones) is also reported (6). 

Since the introduction of phenol-formaldehyde in 1909, a steady stream of new plastics has been appearing on the scene. Today there must be close to 50 separate families of these materials, not including alloys or other modifications of the basic types. Not all of these have engineering applications, but most do. 

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