Cross-linked formaldehyde resin

As the name implies, these resins are derived from phenol and formaldehyde. The structural formula is shown in Figure 3.7. Phenol-formaldehyde is cross-linked phenolic resin and, in general, has approximately the same basic physical and mechanical properties as other phenolic resins. However, it does not have the impact resistance of the polyesters or epoxies. 

The resin used for pre-coating is a phenolic "novolac", with a formaldehyde/phenol ratio lower than 1. Hexamethylenetetramine is added to the resin as a hardener. Hexa decomposes at 160 C into its 2 basic components formaldehyde and ammonia. When pre-coated sand contacts the heated pattern, the hexamethylenetetramine decomposes and the formaldehyde cross-links the resin binder to form the characteristic strong bond. 

Urea, melamine, phenol or substituted phenols can be modified with formaldehyde to produce corresponding resins. An excess of free formaldehyde must be removed in order to prevent interference with the film-forming properties of the paint. These resins can also be used to cross-link alkyd resins. The curing takes place by heating. Phenol-formaldehyde resins are stable to variations of temperature and have a good resistance to moisture, acids and solvents (Piper 1965 Mathias 1984 Fischer and Adams 1990). 

The use of hydroxyethyl (also hydroxypropyl) methacrylate as a monomer permits the introduction of reactive hydroxyl groups into the copolymers. This offers the possibility for subsequent cross-linking with an HO-reactive difunctional agent (diisocyanate, diepoxide, or melamine-formaldehyde resin). Hydroxyl groups promote adhesion to polar substrates. 

Epoxy novolac resins are produced by glycidation of the low-molecular-weight reaction products of phenol (or cresol) with formaldehyde. Highly cross-linked systems are formed that have superior performance at elevated temperatures. 

One-Stage Resins. The ratio of formaldehyde to phenol is high enough to allow the thermosetting process to take place without the addition of other sources of cross-links. 

Two-Stage Resins. The ratio of formaldehyde to phenol is low enough to prevent the thermosetting reaction from occurring during manufacture of the resin. At this point the resin is termed novolac resin. Subsequently, hexamethylenetetramine is incorporated into the material to act as a source of chemical cross-links during the molding operation (and conversion to the thermoset or cured state). 

Some commercially important cross-linked polymers go virtually without names. These are heavily and randomly cross-linked polymers which are insoluble and infusible and therefore widely used in the manufacture of such molded items as automobile and household appliance parts. These materials are called resins and, at best, are named by specifying the monomers which go into their production. Often even this information is sketchy. Examples of this situation are provided by phenol-formaldehyde and urea-formaldehyde resins, for which typical structures are given by structures [IV] and [V], respectively ... 

Uses. Furfuryl alcohol is widely used as a monomer in manufacturing furfuryl alcohol resins, and as a reactive solvent in a variety of synthetic resins and appHcations. Resins derived from furfuryl alcohol are the most important appHcation for furfuryl alcohol in both utihty and volume. The final cross-linked products display outstanding chemical, thermal, and mechanical properties. They are also heat-stable and remarkably resistant to acids, alkaUes, and solvents. Many commercial resins of various compositions and properties have been prepared by polymerization of furfuryl alcohol and other co-reactants such as furfural, formaldehyde, glyoxal, resorcinol, phenoHc compounds and urea. In 1992, domestic furfuryl alcohol consumption was estimated at 47 million pounds (38). 

Phenol—formaldehyde (PF) was the first of the synthetic adhesives developed. By combining phenol with formaldehyde, which has exceptional cross-linking abiHties with many chemicals and materials, and a small amount of sodium hydroxide, a resin was obtained. The first resins soHdified as they cooled, and it was discovered that if it was ground to a powder with a small amount of additional formaldehyde and the appHcation of more heat, the mixture would Hquify and then convert to a permanently hard material. Upon combination of the powdered resin mixture with a filler material such as wood flour, the result then being placed in a mold and pressed under heat and pressure, a hard, durable, black plastic material was found to result. For many years these resulting products were called BakeHte, the trade name of the inventor. BakeHte products are still produced today, but this use accounts for only a small portion of the PF resins used. 

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. 

Polymers. AH nitro alcohols are sources of formaldehyde for cross-linking in polymers of urea, melamine, phenols, resorcinol, etc (see Amino RESINS AND PLASTICS). Nitrodiols and 2-hydroxymethyl-2-nitro-l,3-propanediol can be used as polyols to form polyester or polyurethane products (see Polyesters Urethane polymers). 2-Methyl-2-nitro-l-propanol is used in tires to promote the adhesion of mbber to tire cord (qv). Nitro alcohols are used as hardening agents in photographic processes, and 2-hydroxymethyl-2-nitro-l,3-propanediol is a cross-linking agent for starch adhesives, polyamides, urea resins, or wool, and in tanning operations (17—25). Wrinkle-resistant fabric with reduced free formaldehyde content is obtained by treatment with... 

In recent years, synthetic polymeric pigments have been promoted as fillers for paper. Pigments that ate based on polystyrene [9003-53-6] latexes and on highly cross-linked urea—formaldehyde resins have been evaluated for this appHcation. These synthetic pigments are less dense than mineral fillers and could be used to produce lightweight grades of paper, but their use has been limited in the United States. 

Tire Cord. Melamine resins are also used to improve the adhesion of mbber to reinforcing cord in tires. Textile cord is normally coated with a latex dip solution composed of a vinylpyridine—styrene—butadiene latex mbber containing resorcinol—formaldehyde resin.. The dip coat is cured prior to use. The dip coat improves the adhesion of the textile cord to mbber. Further improvement in adhesion is provided by adding resorcinol and hexa(methoxymethyl) melamine [3089-11 -0] (HMMM) to the mbber compound which is in contact with the textile cord. The HMMM resin and resorcinol cross-link during mbber vulcanization and cure to form an interpenetrating polymer within the mbber matrix which strengthens or reinforces the mbber and increases adhesion to the textile cord. Brass-coated steel cord is also widely used in tires for reinforcement. Steel belts and bead wire are common apphcations. Again, HMMM resins and resorcinol [108-46-3] are used in the mbber compound which is in contact with the steel cord to reinforce the mbber and increase the adhesion of the mbber to the steel cord. This use of melamine resins is described in the patent Hterature (49). 

Quinone dioximes, alkylphenol disulfides, and phenol—formaldehyde reaction products are used to cross-link halobutyl mbbers. In some cases, nonhalogenated butyl mbber can be cross-linked by these materials if there is some other source of halogen in the formulation. Alkylphenol disulfides are used in halobutyl innerliners for tires. Methylol phenol—formaldehyde resins are used for heat resistance in tire curing bladders. Bisphenols, accelerated by phosphonium salts, are used to cross-link fluorocarbon mbbers. 

Early Gross-Linking Agents. Eormaldehyde, urea—formaldehyde, and melamine—formaldehyde were among the eadiest agents utilized for resin finishes. Concerns about the safety of formaldehyde, the need for lower formaldehyde release values, and the safety of exposure to melamine have reduced the use of these early cross-linking agents by industry substantially. 

Amino Resins. Amino resins (qv) include both urea- and melamine—formaldehyde condensation products. They are thermosets prepared similarly by the reaction of the amino groups in urea [57-13-6] or melamine [108-78-1] with formaldehyde to form the corresponding methylol derivatives, which are soluble in water or ethanol. To form plywood, particle board, and other wood products for adhesive or bonding purposes, a Hquid resin is mixed with some acid catalyst and sprayed on the boards or granules, then cured and cross-linked under heat and pressure. 

Other amino resins besides MF resins are used to a lesser degree in coatings. Urea—formaldehyde resins are used in some coatings for wood furniture because these resins cross-link at lower temperatures than MF resins and the higher water resistance and exterior durabiUty that can be obtained using MF resins are not needed. Ethers of formaldehyde derivatives of 6-phenyl-l,3,5-triazine-2,4-diamine [91-76-9] (benzoguanamine resins) give... 

The thermoplastic or thermoset nature of the resin in the colorant—resin matrix is also important. For thermoplastics, the polymerisation reaction is completed, the materials are processed at or close to their melting points, and scrap may be reground and remolded, eg, polyethylene, propjiene, poly(vinyl chloride), acetal resins (qv), acryhcs, ABS, nylons, ceUulosics, and polystyrene (see Olefin polymers Vinyl polymers Acrylic ester polymers Polyamides Cellulose ESTERS Styrene polymers). In the case of thermoset resins, the chemical reaction is only partially complete when the colorants are added and is concluded when the resin is molded. The result is a nonmeltable cross-linked resin that caimot be reworked, eg, epoxy resins (qv), urea—formaldehyde, melamine—formaldehyde, phenoHcs, and thermoset polyesters (qv) (see Amino resins and plastics Phenolic resins). 

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