Melamine formaldehyde resin

Formaldehyde resins with better water- and temperature-stabilities are obtained if the urea is partly or wholly replaced by melamine (aminoplasts). These condensations are likewise carried out mainly in alkaline medium, again yielding soluble pre-condensates consisting essentially of N-[tris- and hexakis-(hy-droxymethyl)] compounds of melamine. 

These pre-condensates are most stable at pH 8-9 they are transformed by further condensation (essentially by elimination of water from hydroxymethyl groups and free NH groups) into poorly soluble and Anally insoluble, crosslinked products. Chemical modification of the soluble pre-condensate, for example, by esterification or ether formation, is again possible. 

The practical preparation of melamine-formaldehyde resins is done under the same conditions as for urea-formaldehyde resins. Melamine is at first insoluble in the aqueous reaction mixture but dissolves completely as the condensation proceeds. Because of the greater stability of the N-hydroxymethylmel-amines compared with the corresponding urea compounds the reaction can easily be followed by titration of the unconverted formaldehyde with sodium hydrogen sulfite (see Sect. 4.1.4.1). 

Melamine-formaldehyde (MF) resins of a molar ratio F/M = 1.70 were prepared at 95°C by dissolving 505 g melamine in 592 g formalin (34.5 wt% aqueous formaldehyde with a pH of 9.2). The reaction was stopped when the reaction mixture reached the cloud point [75]. At 25°C, the pH of the MF resin was adjusted to 7.5 and 9.5. These resins were spray-dried using a Buchi spray dryer and further dried for half an hour in a vacuum oven at 60° C before each MTDSC experiment. Liquid C-NMR spectra showed that more methylene bridges and ether bridges and fewer residual methylol groups (see section 2.2.1 were present in MF pH 7.5 compared to MF pH 9.5. 

Crosslinking (hardening) of these pre-condensates can be carried out exactly as for the urea-formaldehyde resins, best at a pH value of 3.5-5. Melamine-formaldehyde condensates crosslink most quickly if prepared using a 2.8-3-fold excess of formaldehyde. 

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). 

These resins are quite similar to urea-formaldehyde condensates and, probably, for that reason, find similar applications. Melamine reacts with formaldehyde under slightly alkaline conditions to form mixtures of various methylolmelamines [155]  

7 Step-Growth Polymerization and Step-Growth Polymers 

Further heating causes condensation into resins. The rate of such resinifications is pH-dependent. Melamine-formaldehyde resins are also etherified for solvent solubility. Methanol is often used and hexamethyl ether of hexamethylolmelamine as well as higher homologues are available commercially. The hexamethyl ether can be shown as follows  

The ethers cleave upon acidification and network structures form. For methylolated melamines that are not etherified, acidification is not necessary and heating alone is often adequate for network formation. Melamine-formaldehyde resins have the reputation of being harder and more moisture-resistant than the urea-formaldehyde ones. 

---

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. 

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

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). 

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. 

Paraformaldehyde is used by resin manufacturers seeking low water content or more favorable control of reaction rates. It is often used in making phenol—, urea—, resorcinol—, and melamine—formaldehyde 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). 

N,]S7-bis(methoxymethyl)uron was first isolated and described in 1936 (41), but was commercialized only in 1960. It is manufactured (42) by the reaction of 4 mol of formaldehyde with 1 mol of urea at 60°C under highly alkaline conditions to form tetramethylolurea [2787-01-1]. After concentration under reduced pressure to remove water, excess methanol is charged and the reaction continued under acidic conditions at ambient temperatures to close the ring and methylate the hydroxymethyl groups. After filtration to remove the precipitated salts, the methanolic solution is concentrated to recover excess methanol. The product (75—85% pure) is then mixed with a methylated melamine—formaldehyde resin to reduce fabric strength losses in the presence of chlorine, and diluted with water to 50—75% soHds. Uron resins do not find significant use today due to the greater amounts of formaldehyde released from fabric treated with these resins. 

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 ... 

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. 

Melamine—formaldehyde resins may be used in paper which contacts aqueous and fatty foods according to 21 CFR 121.181.30. However, because a lower PEL has been estabUshed by OSHA, some mills are looking for alternatives. Approaches toward achieving lower formaldehyde levels in the resins have been reported (66,67) the efficacy of these systems needs to be estabUshed. Although alternative resins are available, significant changes in the papermaking operation would be required in order for them to be used effectively. 

W. Lindlaw, The Preparation of Butylated Erea—Formaldehyde and Butylated Melamine Formaldehyde Resins Using Celanese Formcel and Celanese Paraformaldehyde. 

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. 

Some of the chemicals mentioned above and others, such as chlorinated mbber or paraffin, antimony trioxide, calcium carbonate, calcium borate, pentaerythrithol, alumina trihydrate, titanium dioxide, and urea—melamine—formaldehyde resin, may be used to formulate fire retardant coatings. Many of these coatings are formulated in such a way that the films intumesce (expand) when exposed to fire, thus insulating the wood surface from further thermal exposure. Fire retardant coatings are mostly used for existing constmction. 

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). 

Amino resins are lighter in color and have better tensile strength and hardness than phenoHc resins their impact strength and heat and water resistance are less than those of phenoHcs. The melamine—formaldehyde resins are harder and have better heat and moisture resistance than the urea resins, but they are also more expensive. The physical properties of the melamine—formaldehyde laminates are Hsted in Table 1. 

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

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). 

Although phenolic resins are too dark for use in the surface layers of decorative laminates these resins are employed in impregnating the core paper. In the.se cases a melamine-formaldehyde resin is used for impregnating the top decorative layer. Phenolic laminates have also been used in aircraft construction and in chemical plant. 

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. 

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. 

---