Melamine-formaldehyde plastics

Dicyandiamide forms white, non-hygroscopic crystals which melt with decomposition at 209°. Its most important reaction is conversion to melamine (Fig. 8.25) by pyrolysis above the mp under a pressure of NH3 to counteract the tendency to deammonation. Melamine is mainly used for melamine-formaldehyde plastics. Total annual production of both H2NCN and NCNC(NH2)2 is on the 30 000 tonne scale. 

Well-known thermosetting plastics include the phenolics, urea-formaldehyde and melamine-formaldehyde plastics, polyesters and epoxides. 

Amino and Phenolic Resins. The largest use of formaldehyde is in the manufacture of urea—formaldehyde, phenol—formaldehyde, and melamine—formaldehyde resins, accounting for over one-half (51%) of the total demand (115). These resins find use as adhesives for binding wood products that comprise particle board, fiber board, and plywood. Plywood is the largest market for phenol—formaldehyde resins particle board is the largest for urea—formaldehyde resins. Under certain conditions, urea—formaldehyde resins may release formaldehyde that has been alleged to create health or environmental problems (see Amino RESINS AND PLASTICS). 

Daylight fluorescent pigments (qv) are considered to be nontoxic. Since they are combinations of polymers and dyestuffs, the combined effect of the ingredients must be taken into account when considering the net toxic effect of these materials. Table 5 gives results of laboratory animal toxicity tests of standard modified melamine—formaldehyde-type pigments, the Day-Glo A Series, and the products recommended for plastic mol ding, Day-Glo Z-series. 

Amino resins are thermosetting polymers made by combining an aldehyde with a compound containing an amino (—NH2) group. Urea—formaldehyde (U/F) accounts for over 80% of amino resins melamine—formaldehyde accounts for most of the rest. Other aldehydes and other amino compounds are used to a very minor extent. The first commercially important amino resin appeared about 1930, or some 20 years after the introduction of phenol—formaldehyde resins and plastics (see Phenolic resins). 

In the eady 1920s, experimentation with urea—formaldehyde resins [9011-05-6] in Germany (4) and Austria (5,6) led to the discovery that these resins might be cast into beautiful clear transparent sheets, and it was proposed that this new synthetic material might serve as an organic glass (5,6). In fact, an experimental product called PoUopas was introduced, but lack of sufficient water resistance prevented commercialization. Melamine—formaldehyde resin [9003-08-1] does have better water resistance but the market for synthetic glass was taken over by new thermoplastic materials such as polystyrene and poly(methyl methacrylate) (see Methacrylic polya rs Styrene plastics). 

Both urea— and melamine—formaldehyde resins are of low toxicity. In the uncured state, the amino resin contains some free formaldehyde that could be objectionable. However, uncured resins have a very unpleasant taste that would discourage ingestion of more than trace amounts. The molded plastic, or the cured resin on textiles or paper may be considered nontoxic. Combustion or thermal decomposition of the cured resins can evolve toxic gases, such as formaldehyde, hydrogen cyanide, and oxides of nitrogen. 

The decorative plastic laminates widely used for countertops and cabinets are based on melamine—formaldehyde resin (see Laminates). Several layers of phenohc-saturated kraft paper are placed in a press and a sheet of a-ceUulose paper printed with the desired design and impregnated with melamine—formaldehyde resin is placed over them. Then a clear a-ceUulose sheet, similarly impregnated with the resin, is placed on top to form a clear, protective surface over the decorative sheet. The assembly is cured under heat and pressure up to 138°C and 10 MPa (1450 psi). A similar process is used to make wall paneling, but because the surfaces need not be as resistant to abrasion and wear, laminates for wall panels are cured under lower pressure, about 2 MPa (290 psi). 

Additional commercial markets for 1-butanol include plasticizer esters (eg, dibutyl phthalate), butylated melamine—formaldehyde resins, and mono-, di-, and tributylamines. 

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). 

Plastic laminated sheets produced in 1913 led to the formation of the Formica Products Company and the commercial introduction, in 1931, of decorative laminates consisting of a urea—formaldehyde surface on an unrefined (kraft) paper core impregnated with phenoHc resin and compressed and heated between poHshed steel platens (8,10). The decorative surface laminates are usually about 1.6 mm thick and bonded to wood (a natural composite), plywood (another laminate), or particle board (a particulate composite). Since 1937, the surface layer of most decorative laminates has been fabricated with melamine—formaldehyde, which can be prepared with mineral fiUers, thus offering improved heat and moisture resistance and allowing a wide range of decorative effects (10,11). 

The generic thermosets are the epoxies and the polyesters (both widely used as matrix materials for fibre-reinforced polymers) and the formaldehyde-based plastics (widely used for moulding and hard surfacing). Other formaldehyde plastics, which now replace bakelite, are ureaformaldehyde (used for electrical fittings) and melamine-formaldehyde (used for tableware). 

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. 

Mouldings from melamine-formaldehyde powders are superior to the urea-formaldehyde plastics in a number of respects. 

As with the U-F moulding powders the relative importance of M-F moulding powders for other plastics materials and also in other uses for melamine-formaldehyde resins has declined. 

Aminos. There are two basic types of amino plastics - urea formaldehyde and melamine formaldehyde. They are hard, rigid materials with good abrasion resistance and their mechanical characteristics are sufficiently good for continuous use at moderate temperatures (up to 100°C). Urea formaldehyde is relatively inexpensive but moisture absorption can result in poor dimensional stability. It is generally used for bottle caps, electrical switches, plugs, utensil handles and trays. Melamine formaldehyde has lower water absorption and improved temperature and chemical resistance. It is typically used for tableware, laminated worktops and electrical fittings. 

Uses of Urea. The major use of urea is the fertilizer field, which accounts for approximately 80% of its production (about 16.2 billion pounds were produced during 1994 in U.S.). About 10% of urea is used for the production of adhesives and plastics (urea formaldehyde and melamine formaldehyde resins). Animal feed accounts for about 5% of the urea produced. 

This group includes many plastics produced by condensation polymerization. Among the important thermosets are the polyurethanes, epoxy resins, phenolic resins, and urea and melamine formaldehyde resins. 

Important thermosetting plastics include the phenolics, melamine-formaldehyde, epoxides and polyester resins used in glass-reinforced plastics. (See also Sections 14.5 and 14.9.)... 

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