Formaldehyde Adhesives Melamines

Urea-formaldehyde and melamine-formaldehyde adhesives are resins in particleboard. 

Figure 1 Methylolation (hydroxymethylation) and subsequent condensation reactions to form melamine-formaldehyde adhesive systems.

A. Pizzi, Melamine-formaldehyde adhesives, in Handbook of Adhesive Technology, 2nd edn, A. Pizzi and K. L. Mittal, Eds., Dekker, New York, 2003. Chap 32. 

Plywood is an assembly of three or more layers of wood (veneers) joined together with an adhesive. Hardwood plywood has an outside layer of decorative wood such as walnut, oak, maple, etc. with interior or support layers of cheaper softwood such as pine. Ordinary plywood is 100% softwood and is used for structural applications only. It is usually made with phenolic resin adhesive to provide good water resistance. Hardwood plywood is made in both outdoor and indoor grades. The water resistant type is made with a melamine-formaldehyde adhesive that will not discolor a light decorative surface veneer. Phenolic resin can be used to provide good water resistance with dark colored veneers. 

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. 

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. 

One type of thick hardwood plywood stiU available is imported from the northern Scandinavian countries and is generally known as Finnish birch. Characteristically, these plywoods are manufactured using multiple layers of veneer of the same thickness, about 1.5 mm (1 /16 in.), and bonded with a urea—formaldehyde or melamine—urea—formaldehyde adhesive. 

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). 

Poly(vinyl alcohol) is employed as a modifier of thermosetting resins used as adhesives in plywood and particle board manufacture (314,315). The polymer is added to urea-formaldehyde or urea—melamine—formaldehyde resins to improve initial grab, to increase viscosity, and, in general, to improve the characteristics of the board. 

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. 

A range of acetoacetylated lesins has been intioduced (68,69). The acetoacetoxy functionahty can be cioss-linked with melamine—formaldehyde resins, isocyanates, polyacrylates, and polyamines. There is particular interest for possible corrosion protection on steel because the acetoacetoxy group can form coordination compounds (qv) with iron, perhaps enhancing the adhesion to steel surfaces (see Chelating agents). 

By far the bulk of amino resins are used in the woodworking industry for the manufacture of chipboard, plywood and as general glues and adhesives. Melamine-formaldehyde is an important component of decorative laminates. The amount of amino resins used for moulding applications is only of the order of 5% of the total. 

Melamine (I,3,5-triamino-2,4,6-triazine) was first prepared by Liebig in 1835. For a hundred years the material remained no more than a laboratory curiosity until Henkel patented the production of resins by condensation with formaldehyde. Today large quantities of melamine-formaldehyde resins are used in the manufacture of moulding compositions, laminates, adhesives, surface coatings and other applications. Although in many respects superior in properties to the urea-based resins they are also significantly more expensive. 

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. 

Developments in glued laminated structures and panel products such as plywood and chipboard raises the question of the durability of adhesives as well as wood. Urea-formaldehyde adhesives are most commonly used for indoor components. For exterior use, resorcinol adhesives are used for assembly work, whilst phenolic, tannin and melamine/urea adhesives are used for manufactured wood products. Urea and casein adhesives can give good outdoor service if protected with well-maintained surface finishes. Assembly failures of adhesives caused by exudates from some timber species can be avoided by freshly sanding the surfaces before glue application. 

A cement slurry additive consisting of methylcellulose, melamine-formaldehyde resin, and trioxane has been proposed for better bonding of cement to the casing string [20]. Bisphenol-A epoxide resins, with amine-based curing agents, sand filler, and a mixture of n-butanol and dimethyl benzene as a diluent, have been proposed as additives to increase adhesion properties of cement [572]. 

Together, antifreeze, PET, and polyester polymers account for about 98% of the ethylene glycol produced in the United States. It is also used sometimes as a deicer for aircraft surfaces. The two hydroxyl groups in the EG molecule also make EG suitable for the manufacture of surfactants and in latex paints. Other applications include hydraulic brake fluid, the manufacture of alkyd resins for surface coatings, and stabilizers for water dispersions of urea-formaldehyde and melamine-formaldehyde The hygroscopic properties (absorbs moisture from the air) make EG useful as a humectant for textile fibers, paper, leather, and adhesives treatment. 

In similar bending-creep tests, both control and acetylated pine particleboards made using melamine-urea-formaldehyde adhesive failed because T. palustris attacked the adhesive in the glueline ( ). Mycelium invaded the inner part of all boards, colonizing in both wood and glueline in control boards but only in the glueline in acetylated boards. 

Urea- and melamine-formaldehyde resins are used as moldings, lacquers, and adhesives (for wood), also as textile additives (increased crease resistance) and paper additives (improved wet strength). 

Another use of urea is for resins, which are used in numerous applications including plastics, adhesives, moldings, laminates, plywood, particleboard, textiles, and coatings. Resins are organic liquid substances exuded from plants that harden on exposure to air. The term now includes numerous synthetically produced resins. Urea resins are thermosetting, which means they harden when heated, often with the aid of a catalyst. The polymerization of urea and formaldehyde produces urea-formaldehyde resins, which is the second most abundant use of urea. Urea is dehydrated to melamine, which, when combined with formaldehyde, produces melamine-formaldehyde resins (Figure 96.2). Melamine resins tend to be harder and more heat-resistant than urea-formaldehyde resins. Melamine received widespread attention as the primary pet food and animal feed contaminant causing numerous cat and dog deaths in early... 

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