Melamine producers

Since melamine resins are derived from urea, they are more cosdy and are therefore restricted to appHcations requiring superior performance. Essentially ad of the melamine produced is used for making amino resins and plastics. 

Uses. Most of the melamine produced is used ia the form of melamiae—formaldehyde resias (see Amino resins and plastics). Other appHcations (63) iaclude the use of melamine pyrophosphate [15541 -60-3] ia fire retardant textile finishes, chloriaated melamine as a bactericide, and melamine as a tarnish inhibitor in detergent compositions, in papermaking, and manufacture of adhesives. 

Uses of Formaldehyde. Formaldehyde is the simplest and most reactive aldehyde. Condensation polymerization of formaldehyde with phenol, urea, or melamine produces phenol-formaldehyde, urea formaldehyde, and melamine formaldehyde resins, respectively. These are important glues used in producing particle hoard and plywood. 

This plant will use the high-pressure Shortened Liquid Phase (SLP) process developed by DSM. Melamine produced with the SLP process has the same quality as melamine produced in the gas phase (or low pressure) process. The new technology is a result of DSM s further development of a process acquired from MCI (Melamine Chemical Industries) in 1997. The SLP process is expected to increase efficiency by 25%. It is also expected to enable the plant to reach a level of cost-effectiveness similar to a 100,000 tonnes/year production facility. The new process requires only 3 or 4 processing steps, in contrast to the 10 steps in conventional processes115,231. The process employs the same raw materials as the low-pressure urea process, but the final melamine recrystallization step is eliminated. The company may be able to make 99% purity melamine without recrystallization114. 

Between 1997 and 2001 the number of melamine producers in China increased from less than twenty (20) to at least sixty (60). During this time capacity grew from 45,000 tons per year to 197,400 tons per year (Note Another source states that melamine capacity in China in 2001 was 222,500 tonnes per year235). China s melamine consumption is about 60,000 tons per year so most of the melamine enters the export market234. 

Melamine production capacity in Europe is around 360,000 tonnes. DSM had the largest capacity with around 25% in 1999. Agrolinz Melamin, producing in Italy and Austria has expanded from 100,000 tonnes to 130 kt by the end of 2000. This means they have claimed the first spot from DSM. BASF has 65 kt capacity and Atofina around 26,000 tonnes. Most is used for thermoset resins and adhesives, but a significant proportion goes into flame retardants. Further capacity exists in Romania and Poland. 

The major urea-melamine producers and their current and projected capacity are shown in Table I. 

About 95% of the melamine produced is largely used as a feedstock In the production of melamine-formaldehyde thermoset composites In the plastics industry and to produce molding compounds, textile finishes, and paper coatings. Melamine is also used in ieather tanning. 

Uses. The principal use of adiponitrile is for hydrogenation to hexamethylene diamine leading to nylon-6,6. However, as a result of BASE s new adiponitrile-to-caprolactam process, a significant fraction of ADN produced may find its way into nylon-6 production. Adipoquanamine, which is prepared by the reaction of adiponitrile with dicyandiamide [461-58-5] (cyanoguanidine), may have uses in melamine—urea amino resins (qv) (see "Benzonitrile, Uses"). Its typical Hquid nitrile properties suggest its use as an extractant for aromatic hydrocarbons. 

Both melamine—formaldehyde (MF) and resorcinol—formaldehyde (RF) foUowed the eadier developments of phenol—, and urea—formaldehyde. Melamine has a more complex stmcture than urea and is also more expensive. Melamine-base resins requite heat to cure, produce colorless gluelines, and are much more water-resistant than urea resins but stiU are not quite waterproof. Because of melamine s similarity to urea, it is often used in fairly small amounts with urea to produce melamine—urea—formaldehyde (MUF) resins. Thus, the improved characteristics of melamine can be combined with the economy of urea to provide an improved adhesive at a moderate increase in cost. The improvement is roughly proportional to the amount of melamine used the range of addition may be from 5 to 35%, with 5—10% most common. 

Resorcinol is to phenol as melamine is to urea. Resorcinol—formaldehyde (RF) is very expensive, produces dark and waterproof gluelines, but will cure at room temperature. As with melamine and urea, resorcinol is often combined with phenol to produce phenol—resorcinol—formaldehyde (PRF) adhesives, thus producing an exceUent adhesive with some of the economy of phenol. These adhesives are the mainstay of the laminated timber industry which generally requites a room-temperature cure with durable, waterproof gluelines. 

The primary adhesive used ia hardwood plywood is urea—formaldehyde (UF) mixed with wheat flour as an extender to improve spreadabiUty, reduce penetration, and provide dry-out resistance. A catalyst may also be added to UF resias to speed the cure or to cause the UF to cure. Scavengers also may be added to reduce formaldehyde emissions from finished panels. If more water-resistance is requited using a UF bond, small amounts of melamine maybe added, producing a melamine—urea—formaldehyde (MUF) adhesive. 

A small amount of particleboard is made with a fire-retardant treatment for use in locations where codes require this material, as in some offices and elevators. Particleboards receive overlay and finishing treatments with ease. Wood veneers, melamine overlays, printed paper overlays, vinyl overlays, foils, and direct grain printing can all be done quite simply. A small amount of particleboard is also made in the form of shaped, molded articles such as furniture parts, paper roU plugs, bmsh bases, and even toilet seats. There is another small increment of particleboard made by the extmsion process. These products are made in small captive operations owned by furniture manufacturers which consume all of this production in their furniture. The extmsion process differs from conventional flat-pressed particleboard in that the wood furnish is forced between two stationary heated surfaces. The mats are formed from one edge and this edge is alternately formed and pushed between the heated platens, which are maintained at a distance equal to the thickness of board produced. This is an old, slow, small-scale process, but is stiU in use in at least one location. 

THPC—Amide Process. The THPC—amide process is the first practical process based on THPC. It consists of a combination of THPC, TMM, and urea. In this process, there is the potential of polymer formation by THPC, melamine, and urea. There may also be some limited cross-linking between cellulose and the TMM system. The formulation also includes triethanolamine [102-71-6J, an acid scavenger, which slows polymerization at room temperature. Urea and triethanolamine react with the hydrochloric acid produced in the polymerization reaction, thus preventing acid damage to the fabric. This finish with suitable add-on passes the standard vertical flame test after repeated laundering (80). 

Melamine reacts similarly to produce methylol derivatives, which form the familiar melamine—formaldehyde resins on heating (63) (see Aminoresins). 

Formaldehyde—Alcohol Solutions. These solutions are blends of concentrated aqueous formaldehyde, the alcohol, and the hemiacetal. Methanol decreases the average molecular weight of formaldehyde oligomers by formation of lower molecular weight hemiacetals. These solutions are used to produce urea and melamine resins the alcohol can act as the resin solvent and as a reactant. The low water content can improve reactivity and reduce waste disposal and losses. Typical specifications for commercially available products are shown in Table 7 (117). 

In fires, melamine—phenolic laminates ignite slowly at high temperatures and bum slowly producing smoke that has about the same toxicity as wood smoke (17). 

The recovery of fiber from broke (off-specification paper or trim produced in the paper mill) is compHcated by high levels of urea—formaldehyde and melamine—formaldehyde wet-strength resin. The urea resins present a lesser problem than the melamine resins because they cure slower and are not as resistant to hydrolysis. Broke from either resin treatment may be reclaimed by hot acidic repulping. Even the melamine resin is hydrolyzed rapidly under acidic conditions at high temperature. The cellulose is far more resistant and is not harmed if the acid is neutralized as soon as repulping is complete. 

Many large chemical companies produce amino resins and the raw materials needed, ie, formaldehyde, urea, and melamine. Some companies may buy raw materials to produce amino resins for use in their own products, such as plywood, chipboard, paper, textiles, or paints, and may also find it profitable to market these resins to smaller companies. The technology is highly developed and sales must be supported by adequate technical service to select the correct resin and see that it is appHed under the best conditions. 

Ammonia is used in the fibers and plastic industry as the source of nitrogen for the production of caprolactam, the monomer for nylon 6. Oxidation of propylene with ammonia gives acrylonitrile (qv), used for the manufacture of acryHc fibers, resins, and elastomers. Hexamethylenetetramine (HMTA), produced from ammonia and formaldehyde, is used in the manufacture of phenoHc thermosetting resins (see Phenolic resins). Toluene 2,4-cHisocyanate (TDI), employed in the production of polyurethane foam, indirectly consumes ammonia because nitric acid is a raw material in the TDI manufacturing process (see Amines Isocyanates). Urea, which is produced from ammonia, is used in the manufacture of urea—formaldehyde synthetic resins (see Amino resins). Melamine is produced by polymerization of dicyanodiamine and high pressure, high temperature pyrolysis of urea, both in the presence of ammonia (see Cyanamides). 

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). 

Melamine is produced by heating urea under pressure in the presence of a catalyst. The result is a ring stmcture as shown below. The reaction by-products, ammonia and carbon dioxide, can be recycled for urea production. 

Industrial uses make up most of the market for cyanamide. Calcium cyanamide is used directly for steel nitridation (34) and to some extent for desulfurization (36) (see Steel). Cyanamide is used to produce cationic starch (36) and calcium cyanide. Cyanamide is, of course, the raw material for dicyandiamide and melamine. New uses include intermediates for pesticides, detergents (37), medicines such as antihistamines, hypertension, sedatives, contraceptives, etc (38), the photography industry (39), as an additive for fuels and lubricants, as a paper preservative, and as a cement additive. 

Reactions. The reactions of dicyandiamide resemble those of cyanamide. However, cycUzations take place easily and the nitrile group is less reactive. Under pressure and ia the presence of ammonia, dicyandiamide cyclizes to melamine. Considerable toimages of melamine have been made ia this manner however, melamine is produced chiefly by the urea process (43). 

Melamine ia a skin test on rabbits produced neither local irritation nor systemic toxicity. As a 10% solution ia methylceUulose, it caused no irritation ia the eyes of rabbits. Human subjects were given patch tests with melamine. No evidence of either primary irritation or sensitization was found. Such results suggest that melamine crystal may be handled ia ordinary iadustrial use without special hygienic precautions. 

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