Thermosets aminos

Thermosetting amino resins produced from urea are built up by condensation polymerization. Urea is reacted with formaldehyde, which results in the formation of addition products such as methylol compounds. Further reaction and the concurrent elimination of water leads to the formation of low-molecular-weight condensates, which are stUl soluble. Higher-molecular-weight products, which are insoluble and infusible, are obtained by further condensing the low-molecular-weight condensates. 

Thermoset Amino Protein Resin Is Said to D rade Naturally, Modem Plastics, May 1996, p. 36. 

The thermosetting amino and phenolic adhesives are by far the predominant adhesives used in making wood composites. These adhesives are described below, but more detailed information is available elsewhere (4,7,16-21) (see Adhesive Compounds). 

The commonly used resins in the manufacture of decorative and industrial laminates ate thermosetting materials. Thermosets ate polymers that form cross-linked networks during processing. These three-dimensional molecules ate of essentially infinite size. Theoretically, the entire cured piece could be one giant molecule. The types of thermosets commonly used in laminates ate phenoHcs, amino resins (melamines), polyesters, and epoxies. 

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). 

The term amino resin is usually appHed to the broad class of materials regardless of appHcation, whereas the term aminoplast or sometimes amino plastic is more commonly appHed to thermosetting molding compounds based on amino resins. Amino plastics and resins have been in use since the 1920s. Compared to other segments of the plastics industry, they are mature products, and their growth rate is only about half of that of the plastics industry as a whole. They account for about 3% of the United States plastics and resins production. 

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). 

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. 

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). 

Other backbone stmctures that have generated a great interest are the polyether ketones. An attempt was made to synthesize amino-terminated arylene ether ketones, which were subsequendy converted into the corresponding maleinhde-terrninated oligomers (26). The aim of this approach was to obtain tough, solvent-resistant, high temperature thermosets. 

Commonly accepted practice restricts the term to plastics that serve engineering purposes and can be processed and reprocessed by injection and extmsion methods. This excludes the so-called specialty plastics, eg, fluorocarbon polymers and infusible film products such as Kapton and Updex polyimide film, and thermosets including phenoHcs, epoxies, urea—formaldehydes, and sdicones, some of which have been termed engineering plastics by other authors (4) (see Elastol rs, synthetic-fluorocarbon elastol rs Eluorine compounds, organic-tdtrafluoroethylenecopolyt rs with ethylene Phenolic resins Epoxy resins Amino resins and plastics). 

Of the various amino-resins that have been prepared, the urea-formaldehyde (U-F) resins are by far the most important commercially. Like the phenolic resins, they are, in the finished product, cross-linked (thermoset) insoluble, infusible materials. For application, a low molecular weight product or resin is first produced and this is then cross-linked only at the end of the fabrication process. 

Although phenolic and amino moulding powders remain by far the most important of the thermosetting moulding compositions a number of new materials have been introduced" over the last 30 years based on polyester, epoxide and silicone resins. 

Amino resins are condensation thermosetting polymers of formaldehyde with either urea or melamine. Melamine is a condensation product of three urea molecules. It is also prepared from cyanamide at high pressures and temperatures ... 

Thermoset Plastics Alkyd, amino resin, thermosetting acrylic resin, casein, epoxy, phenolic, polyester, polyamide, silicone. 

Amino resins are those polymers prepared by reaction of either urea or melamine with formaldehyde. In both cases the product that results from the reaction has a well crosslinked network structure, and hence is a thermoset polymer. The structures of the two parent amino compounds are shown in Figure 1.1. 

Urea-formaldehyde resins are the most prominent examples of the thermosetting resins usually referred to as amino resins, comprising ca. 80% of the amino resins produced worldwide. Melamine-formaldehyde resins constitute most of the remainder of this class of resins, with other minor amounts of resins being produced from the other aldehydes or amino compounds (especially aniline), or both. 

Melamine, having three amino groups and six labile hydrogens, will form thermoset resins with formaldehyde. The chemistry is similar to that for the urea resins. 

Highly cross-linked condensation materials form the basis for a number of important adhesives and bulk materials, especially phenolic and amino plastics. Most of these products have formaldehyde as one of their starting reactants. These materials are thermosets that decompose prior to melting, and are therefore more difficult to recycle than most condensation polymers that are thermoplastics and do melt prior to decomposition. 

Both thermoset and thermoplastic resin systems are employed in the construction of composites (Table 8.3). The most common thermoset resins are polyimides, unsaturated polyesters, epoxys, PFs, and amino-formaldehydes. A wide variety of thermoplastic resins have been developed. 

The most common and widely used thermoset molding compounds are classified as follows (a) alkyd, (b) allylic (diallyl phthalate), (c) amino (melamine and urea), (d) epoxy, (e) phenolic, (f) polyester, and (g) silicone. There may be other specialty thermoset resin materials used on specific applications. 

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