Coating formaldehyde

Paraformaldehyde [30525-89-4] is a mixture of polyoxymethylene glycols, H0(CH20) H, with n from 8 to as much as 100. It is commercially available as a powder (95%) and as flake (91%). The remainder is a mixture of water and methanol. Paraformaldehyde is an unstable polymer that easily regenerates formaldehyde in solution. Under alkaline conditions, the chains depolymerize from the ends, whereas in acid solution the chains are randomly cleaved (17). Paraformaldehyde is often used when the presence of a large amount of water should be avoided as in the preparation of alkylated amino resins for coatings. Formaldehyde may also exist in the form of the cycHc trimer trioxane [110-88-3]. This is a fairly stable compound that does not easily release formaldehyde, hence it is not used as a source of formaldehyde for making amino resins. 

Poly (hexamethylenebiguanide) hydrochloride preservative, cut flowers 1,3,5-Trihydroxybenzene preservative, cutting fluids Hexahydro-1,3,5-triethyl-s-triazine Quaternium-15 2-Thiocyanomethylthiobenzothiazole preservative, cutting oils 6-Acetoxy-2,4-dimethyl-m-dioxane Tetrachlorosalicylanilide preservative, defoamers coatings, food-contact Potassium trichlorophenate preservative, defoamers food-contact coatings Formaldehyde p-Naphthol Potassium pentachlorphenate Sodium 2-mercaptobenzothiazole Sodium pentachlorophenate Sodium-2,4,5-trichlorophenate preservative, defoamers food-contact paper/paperboard... 

Although the use of simple diluents and adulterants almost certainly predates recorded history, the use of fillers to modify the properties of a composition can be traced as far back as eady Roman times, when artisans used ground marble in lime plaster, frescoes, and po22olanic mortar. The use of fillers in paper and paper coatings made its appearance in the mid-nineteenth century. Functional fillers, which introduce new properties into a composition rather than modify pre-existing properties, were commercially developed eady in the twentieth century when Goodrich added carbon black to mbber and Baekeland formulated phenol— formaldehyde plastics with wood dour. 

Syntactic Cellular Polymers. Syntactic cellular polymer is produced by dispersing rigid, foamed, microscopic particles in a fluid polymer and then stabilizing the system. The particles are generally spheres or microhalloons of phenoHc resin, urea—formaldehyde resin, glass, or siUca, ranging 30—120 lm dia. Commercial microhalloons have densities of approximately 144 kg/m (9 lbs/fT). The fluid polymers used are the usual coating resins, eg, epoxy resin, polyesters, and urea—formaldehyde resin. 

Fomialdehyde is a basic chemical budding block for the production of a wide range of chemicals finding a wide variety of end uses such as wood products, plastics, and coatings. Table 6 shows the distribution of formaldehyde production in the United States from 1966 through 1989 (115). Production percentages reported in the following discussion are for the United States. 

Urea—formaldehyde resins are also used as mol ding compounds and as wet strength additives for paper products. Melamine—formaldehyde resins find use in decorative laminates, thermoset surface coatings, and mol ding compounds such as dinnerware. 

Polyols. Several important polyhydric alcohols or polyols are made from formaldehyde. The principal ones include pentaerythritol, made from acetaldehyde and formaldehyde trimethylolpropane, made from -butyraldehyde and formaldehyde and neopentyl glycol, made from isobutyraldehyde and formaldehyde. These polyols find use in the alkyd resin (qv) and synthetic lubricants markets. Pentaerythritol [115-77-5] is also used to produce rosin/tall oil esters and explosives (pentaerythritol tetranitrate). Trimethylolpropane [77-99-6] is also used in urethane coatings, polyurethane foams, and multiftmctional monomers. Neopentyl glycol [126-30-7] finds use in plastics produced from unsaturated polyester resins and in coatings based on saturated polyesters. 

A Methylolhydantoins. l,3-Bis(hydroxymethyl)-5,5-dimethyIhydantoia [6440-58-0] is used extensively as a preservative in cosmetic and industrial appHcations, and carries EPA registration for the industrial segment. It is available in soHd and in aqueous solution forms, including low free formaldehyde versions of the latter. A related derivative, l,3-bis(hydroxyethyl)-5,5-dimethyIhydantoia [26850-24-8] is used in the manufacture of high temperature polyesters, polyurethanes, and coatings, offering improved heat resistance, uv stabiUty, flexibiUty, and adhesion. 

Substituted Hydantoins. 5-Methylhydantoin [616-03-5] has been selected from several stmctures as a formaldehyde scavenger for color photosensitive materials and water-thinned inks and coatings (102,103). 

Fig. 2. Curves 1, 2, and 3 show the spectral radiance factor for equivalent coatings of separate toluenesulfonamide—melamine—formaldehyde Day-Glo pigments containing 0.5% of a dye, either Alberta Yellow, Rhodamine F5G, or Rhodamine B Extra. Curve 4 is for a bright nonfluorescent red-orange printing ink. The illuminant was Source C. A magnesium oxide-coated block was used as a comparison white.

Other. 2-Nitro-1-butanol is an excellent solvent for many polyamide resins, cellulose acetate butyrate, and ethylceUulose. It can be utilized in paint removers for epoxy-based coatings. 2-Hydroxymethyl-2-nitro-l,3-propanediol is usebil for control of odors in chemical toilets. Its slow release of formaldehyde ensures prolonged action to control odor, and there is no reodorant problem which sometimes is associated with the use of free formaldehyde. 2-Hydroxymethyl-2-nitro-l,3-propanediol solutions are effective preservative and embalming fluids. The slow Uberation of formaldehyde permits thorough penetration of the tissues before hardening. 

In the late 1800s, when the demand for coated paper for the halftone printing process increased, casein rapidly replaced glue. Casein forms a hard, tough film when dry, and can be waterproofed easily with formaldehyde (qv). The properties of soy protein are similar to those of casein, and soy protein has been substituted for it in many types of coated papers requiring a casein-type binder (see Soybeans and other oilseeds). Casein, a valuable food product, is seldom used as a paper adhesive, in spite of its excellent adhesive properties. 

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. 

The maximum recommended film thickness is 25 p.m. At greater thicknesses, volatiles from the curing reaction, mainly water and some formaldehyde and phenol, can cause defects. These coatings have excellent electrical insulation properties, ie, up to 20 V/p.m, because of low moisture absorption and low conductance. The coatings are hard with low flexibiUty, depending on curing conditions and film thickness. 

The resins should dry quickly and cure weU at low temperatures. They usually are made at a high pH with high ratios of formaldehyde to phenol and held to fairly low molecular weight. Typical viscosities are 15, 000 mPa-s(=cP) at 75% soHds content for a first coat and 1000 mPa-s(=cP) at 50% soHds for the top resin. For dense backing materials, such as fiber disks, a typical resin has a viscosity of 50, 000 mPa-s(=cP) at 80% soHds and is cured at 148°C. 

Different phenoHc resins are used for different types of wood for example, plywood adhesives contain alkaline-catalyzed Hquid resole resins. Extension with a filler reduces cost, minimizes absorption, and increases bond strength. These resins have an alkaline content of 5—7% and are low in free phenol and formaldehyde. Because many resins have a high water content and limited storage stabiHty, they are frequently made at or near the mill producing the plywood product. The plywood veneers are dried, coated with resin, stacked for pressing, and cured at 140—150°C. 

Methylphenol is converted to 6-/ f2 -butyl-2-methylphenol [2219-82-1] by alkylation with isobutylene under aluminum catalysis. A number of phenoHc anti-oxidants used to stabilize mbber and plastics against thermal oxidative degradation are based on this compound. The condensation of 6-/ f2 -butyl-2-methylphenol with formaldehyde yields 4,4 -methylenebis(2-methyl-6-/ f2 butylphenol) [96-65-17, reaction with sulfur dichloride yields 4,4 -thiobis(2-methyl-6-/ f2 butylphenol) [96-66-2] and reaction with methyl acrylate under base catalysis yields the corresponding hydrocinnamate. Transesterification of the hydrocinnamate with triethylene glycol yields triethylene glycol-bis[3-(3-/ f2 -butyl-5-methyl-4-hydroxyphenyl)propionate] [36443-68-2] (39). 2-Methylphenol is also a component of cresyHc acids, blends of phenol, cresols, and xylenols. CresyHc acids are used as solvents in a number of coating appHcations (see Table 3). 

Formaldehyde. Pure formaldehyde, CH2O, is a colorless, pungent smelling reactive gas (see Formaldehyde). The commercial product is handled either as soHd polymer, paraformaldehyde (13), or in aqueous or alcohoHc solutions. Marketed under the trade name Formcel, solutions in methanol, / -butanol, and isobutyl alcohol, made by Hoechst-Celanese, are widely used for making alcohol-modified urea and melamine resins for surface coatings and treating textiles. 

Melamine—Formaldehyde Resins. The most versatile textile-finishing resins are the melamine—formaldehyde resins. They provide wash-and-wear properties to ceUulosic fabrics, and enhance the wash durabiHty of flame-retardant finishes. Butylated melamine —formaldehyde resins of the type used in surface coatings may be used in textile printing-ink formulations. A typical textile melamine resin is the dimethyl ether of trimethylolmelamine [1852-22-8] which can be prepared as follows ... 

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). 

Negatwe P/ate Coatings. The bulk of negative plates have a diazo-based coating. This often comprises an A/-aryl- or alkyl aminobenzenedia zonium salt condensed with formaldehyde (66) or a methylol derivative (67) to form a low molecular weight polymer such as the following ... 

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