Melamine-formaldehyde polymers cross-linking

Polymers. AH nitro alcohols are sources of formaldehyde for cross-linking in polymers of urea, melamine, phenols, resorcinol, etc (see Amino RESINS AND PLASTICS). Nitrodiols and 2-hydroxymethyl-2-nitro-l,3-propanediol can be used as polyols to form polyester or polyurethane products (see Polyesters Urethane polymers). 2-Methyl-2-nitro-l-propanol is used in tires to promote the adhesion of mbber to tire cord (qv). Nitro alcohols are used as hardening agents in photographic processes, and 2-hydroxymethyl-2-nitro-l,3-propanediol is a cross-linking agent for starch adhesives, polyamides, urea resins, or wool, and in tanning operations (17—25). Wrinkle-resistant fabric with reduced free formaldehyde content is obtained by treatment with... 

Urea/formaldehyde (UF) or melamine/formaldehyde (MF) thermoset resins are also formed via the initial addition of HCHO to form methylol derivatives (dimethylol urea and hexamethylol melamine). Curing or cross-linking with acids yields thermoset polymers. 

Melamine-formaldehyde resins were introduced about ten years after the urea-formaldehyde products came on the market. The Henkel Company was granted patents for products based on melamine in 1936 and 1937. The products made with melamine-formaldehyde resin were very similar to those based on urea but with some important superiority. Molded plastics based on melamine-formaldehyde resin had much better water resistance and outdoor weatherability than moldings made with urea-formaldehyde resin. The combination of hardness, water resistance, and unlimited colora-bility made melamine-formaldehyde ideal for molded plastic dinnerware and this remains the major application. The good stability of the symmetrical triazine ring makes the melamine-formaldehyde polymers very resistant to chemical change once the resin has been cured to the insoluble cross-linked state. 

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). 

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). 

The polymers can be categorised as formaldehyde containing and formaldehyde free and as thermoset or thermoplastic resins. Typical formaldehyde containing resins are melamine formaldehyde sulfonamide resins, where the sulfonamide is ortho and para toluenesulfonamide. The sulfonamide, which is a solvent for the dye, undergoes a condensation polymerisation with formaldehyde and melamine, the latter acting as a cross-linking agent. Non-formaldehyde, thermoplastic resins are usually polyamides and polyesters. 

In the early 1930 s, a second type of resin prepared from formaldehyde was introduced to the market—namely, urea-formaldehyde resins. A few years later, melamine-formaldehyde resins also appeared. The same basic process is employed in polymerization of all these resins it consists of the catalyzed reaction of formaldehyde with the second ingredient—phenol, urea, or melamine—to evolve water and produce three-dimensional, cross-linked thermosetting polymers. 

The first synthetic plastics were the phenol-formaldehyde resins introduced by Baekeland in 1907 [1], Melamine and urea also react with formaldehyde to form intermediate methylol compounds which condense to cross-linked polymers much like phenol-formaldehyde resins. Paper, cotton fabric, wood flour or other forms of cellulose have long been used to reinforce these methylol-functional polymers. Methylol groups react with hydroxyl groups of cellulose to form stable ether linkages to bond filler to polymers. Cellulose is so compatible with these resins that no one thought of an interface between them, and the term reinforced composites was not even used to describe these reinforced systems. 

Since both of the hydrogen atoms of the -NH2 group are replaceable, each amino group has a functionality of two. Therefore, an amino compound having only one amino group can form only linear polymers with formaldehyde. Amino compounds such as urea and melamine that have more than one amino group per molecule can form cross-linked three-dimensional polymer networks with formaldehyde. 

Melmac , a highly cross-linked thermosetting polymer of melamine and formaldehyde, is a hard, moisture-resistant material. Because it is colorless, Melmac can be made into materials with pastel colors. It is used to make hghtweight dishes and counter surfaces. 

The principal feature that distinguishes thermosets and conventional elastomers from thermoplastics is the presence of a cross-linked network structure. As we have seen from the above discussion, in the case of elastomers the network structure may be formed by a limited number of covalent bonds (cross-linked rubbers) or may be due to physical links resulting in a domain structure (thermoplastic elastomers). For elastomers, the presence of these cross-links prevents gross mobility of molecules, but local molecular mobility is still possible. Thermosets, on the other hand, have a network structure formed exclusively by covalent bonds. Thermosets have a high density of cross-links and are consequently infusible, insoluble, thermally stable, and dimensionally stable under load. The major commercial thermosets include epoxies, polyesters, and polymers based on formaldehyde. Formaldehyde-based resins, which are the most widely used thermosets, consist essentially of two classes of thermosets. These are the condensation products of formaldehyde with phenol (or resorcinol) (phenoplasts or phenolic resins) or with urea or melamine (aminoplastics or amino resins). 

Alkylated melamine-, urea-, and benzoguanamine-formaldehyde resins are the principal cross-linking agents in many industrially applied baked coatings. They are combined with acrylic, alkyd, epoxy, and polyester resins. The amide, hydroxyl, or carboxyl groups of these backbone polymers are used as functional sites for reaction with the amino resin. 

The results and eflectiveness of Eqs. (7) were checked also for other, quite dilferent polymers, namely the polycondensates of resordnol-formaldehyde, of melamine urea formaldehyde (MUF), of PF, and of quebracho and pine polyflavonoid tannins hardened with formaldehyde. The comparison of the energies of interaction obtained by measures of TMA deflection and the use of this formula compared well with the results already obtained for their energy of adhesion with crystalline cellulose in previous work [16 10]. It appears, then, that the formula works also for entanglement rather than just cross-linked networks. 

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