UREA RESIN

Urea is largely used as a fertilizer (ISy ), and as a non-protein feed supplement for sheep and cattle. The most important chemical use, which however accounts for only a small part of urea production, is in the manufacture of urea-formaldehyde resins. U is also used in the manufacture of adhesives, pharmaceuticals, dyes and various other materials. U.S. production 1981 7 0 megatonnes urea resins 1983 6 megatonnes. 

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. 

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... 

Melamine resins were introduced about ten years after the Beetle molding compound. They were very similar to those based on urea but had superior quaHties. Henkel in Germany was issued a patent for a melamine resin in 1936 (7). Melamine resins rapidly supplanted urea resins and were soon used in molding, laminating, and bonding formulations, as well as for textile and paper treatments. The remarkable stabiHty of the symmetrical triazine ring made these products resistant to chemical change once the resin had been cured to the insoluble, cross-linked state. 

Urea resin adhesives, by the use of the proper hardener, may be set either by heat or at room temperature. For room temperature curing, the hardener may be ammonium chloride, together with basic materials like calcium phosphate to neutralize excess acid that might damage the wood. Cold set or room temperature set adhesives are those that set satisfactorily at 20 —30°C, whereas a hot set adhesive generally means one that is set above 99 °C. 

Like methylolureas, cycHc ureas are based on reactions between urea and formaldehyde however, the amino resin is cycHc rather than linear. Many cychc urea resins have been used in textile-finishing processes, particularly to achieve wrinkle resistance and shrinkage control, but the ones described below are the most commercially important. They ate all in use today to greater or lesser extents, depending on specific end requirements (see also Textiles, finishing). 

Propylene Urea Resins. In similat fashion to ethyleneurea, dimethyl-olpropyleneurea [3270-74-4] [l,3-bis(hydroxymethyl)tetrahydro-2-(m)-pyrimidinone] is the basis of propyleneurea—formaldehyde resin [65405-39-2], Its preparation is from urea, 1,3-diaminoptopane [109-76-2] and formaldehyde. 

In 1945, cationic urea resins were introduced and quickly supplanted the anionic resins, since they could be used with any type of pulp (62). Although they have now become commodities, their use in the industry has been steadily declining as the shift towards neutral and alkaline papermaking continues. They are commonly made by the reaction of urea and formaldehyde with one or more polyethylene—polyamines. The stmcture of these resins is very compHcated and has not been deterrnined. Ammonia is evolved during the reaction, probably according to the following ... 

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. 

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. 

During the next 15 years the urea resins were also developed for use as adhesives, as textile finishing agents and in the production of surface coatings and wet-strength paper. Since World War II the development of chipboard has resulted in a large new outlet for urea-based resins which have also found other uses, such as in firelighters and foams. 

Modification of urea resins with certain organic bases, e.g. triethylene-tetramine, will give resins with basic groups which form ionisable salts in the presence of acids ... 

MF/MUF melamine- and melamine-urea-resins MF-resins are only used mixed with UF-resins. 

Melanine-modified urea resin SuperHM-M DMF containing LiBr... 

Compression and injection molding are used with amino resins to produce articles such as radio cabinets, buttons, and cover plates. Because melamine resins have lower water absorption and better chemical and heat resistance than urea resins, they are used to produce dinnerware and laminates used to cover furniture. Almost ah molded objects use fillers such as cellulose, asbestos, glass, wood flour, glass fiber and paper. The 1997 U.S. production of amino resins was 2.6 billion pounds. 

The melamine resins have many more reactable groups and so less are needed for crosslinking (25% of total compared with 50% of total with UF resins), and have greater heat resistance than the urea resins because of the pseudo-aromatic nature of the six membered ring. 

Formox [Formaldehyde by oxidation] A process for oxidizing methanol to formaldehyde, using a ferric molybdate catalyst. Based on the Adkins-Peterson reaction, developed by Reichold Chemicals, and licensed by that company and Perstorp, Sweden. Acquired by Dyno Industries in 1989. The process uses formaldehyde produced in this way to make formaldehyde-urea resin continuously. A plant using this process was to be built in Ghent by 1991, owned jointly by Dyno and AHB-Chemie. Licensed to 35 sites worldwide. Several other companies operate similar processes. 

Propylene production, 24 259 Propylene urea resins, 2 639 n-Propyl formate, physical properties, 6 292t... 

As shown in the infrared absorbance spectrum of the condensation polymer (See Fig. 1), bands characteristic of absorbance of the urea resin at 3,400 cm-1, 3,000 cm-1, 1,680 cm-1, 1,540 cm-1, 1,380 cm-1, 1,100 cm-1, 1,020 cm-1, 780 cm-1, and characteristic absorbance of acrylami demethyl base at 800 cm-1 are present judging from this data, it is considered that N-methylacrylamide is connected with the end group of urea resin main chains and the imino group. The nuclear magnetic resonance (See Fig. 2) spectrum of the oligomer shows a resonance value of 6.48 ppm based on CH2= and a resonance value of 5.74 ppm based on -CH=. 

Uses Stabilizing rubber latex solvent for albumin, casein, shellac, and sulfur neutralizing oils in antifreeze as a corrosion inhibitor emulsifier adhesives textile lubricants fungicides manufacturing chelating agents such as EOT A (ethylenediaminetetraacetic acid) dimethylol-ethylene-urea resins organic synthesis. 

Uses. Intermediate in the manufacture of 2-ethylhexyl acetate, a lacquer solvent solvent for nitrocellulose, urea, resins, enamels, alkyd varnishes, and lacquers used in ceramics, paper coatings, textiles, and latex rubbers... 

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. 

Urea and melamine are tetra- and hexa-functional molecules. However, the formation of a network polymer is prevented by adding alcohols such as w-butanol and by condensing with formaldehyde at low temperatures under basic conditions. While phenol resins have better moisture and weather resistance than urea resins, the latter are preferred for light-colored... 

Among the naturally occurring filler materials are cellulosics such as wood flour, a-cellulose, shell flour, and starch, and proteinaceous fillers such as soybean residues. Approximately 40,000 t of cellulosic fillers are used annually by the U.S. polymer industry. Wood flour, which is produced by the attrition grinding of wood wastes, is used as filler for phenolic resins, urea resins, polyolefins, and PVC. Shell flour, which lacks the fibrous structure of wood flour, has been used as a replacement for wood flour for some applications. 

Unicellular foams are used for insulation, buoyancy, and flotation applications, while multicellular foams are used for upholstery, carpet backing, and laminated textiles. Expanded PS (Styrofoam), which is produced by the extrusion of PS beads containing a volatile liquid, is used to produce low-density moldings such as foamed drinking cups and insulation boards. Foamed products are also produced from PVC, LDPE, urea resins, ABS, and PU. PU foams are versatile materials, which range from hard (rigid) to soft (flexible). These are produced by the reaction of a polyol and a diisocyanate. 

Thermosets A number of thermosets have been used as adhesives. Phenolic resins were used as adhesives by Leo Baekeland in the early 1900s. Phenolic resins are still used to bind together thin sheets of wood to make plywood. Urea resins have been used since 1930 as binders for wood chips in the manufacture of particle board. Unsaturated polyester resins are used for body repair and PUs are used to bond polyester cord to rubber in tires, and vinyl film to particle board, and to function as industrial sealants. Epoxy resins are used in the construction of automobiles and aircraft and as a component of plastic cement. 

Melurac Melamine-urea resins American Cyanamid... 

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