Urea-formaldehyde products

UF solutions are clear water solutions. They contain only very low molecular-weight, water-soluble UF reaction products plus unreacted urea. Various combinations of UF solutions are found. They contain a maximum of 55% unreacted urea with the remainder as one or more of methylolureas, methylolurea ethers, MDU, DMTU, or triazone, a cycHcal oligomer. AAPFCO has defined this class of compounds as urea—formaldehyde products (water- s oluble). 

Various processes can be employed to manufacture urea—formaldehyde products. They are generally categorized into two types, ie, dilute solution processes and concentrated solution processes. Table 3 Hsts select U.S. manufacturers of UF reaction products and their products. 

Hubbard, D. A. (Imper. Chem. Ind.) Process for Producing Expanded Urea-Formaldehyde Products. British Pat. 1,463,063 (1977)... 

Since urea is relatively quickly metabolized, so-called controlled release fertilizers have been developed. Examples are crotonylidene urea (I) (from urea and acetaldehyde) and isobutylidene urea IBDH (II) (from urea and isobutyraldehyde). The most important are, however, the urea-formaldehyde products of which 191 lO-M were produced in the USA in 1993. 

Research on controlled-release nitrogen sources is in two broad categories the synthesis of nitrogen compounds with desired solubility characteristics and the application of protective coatings on soluble nitrogen fertilizers. Examples of synthesized compounds that dissolve slowly are urea-formaldehyde products, isobutylidene diurea, and crotonylidene diurea. However, the relatively high cost of these products tends to limit their consumption to specialty uses. 

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. 

Reactions of urea-formaldehyde products with cellulose yield products with more stable crosslinks than reaction with formaldehyde. Examples of these reactions are... 

Cyclic urea-formaldehyde products that have been of commercial importance as crosslinking reagents are N,iV -bis(hydroxymethyl)-2-imidazolidone (2 jV,AT -dimethylolethyleneurea, DMEU) and N,N -bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolidone (3 7V,iV -dimethyloldihydroxy-ethyleneurea, (DMDHEU). 

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. 

Urea - formaldehyde polymers. Formalin and urea (usually in the molecular proportions of 3 2) condense in the presence of ammonia, pyridine or hexamine to give urea - formaldehyde polymers, known commercially as Bedle or Plaskon, and are widely used as moulding powdens. It is believed that the intermediate products in the condensation are methylol-urea and dimethylol-urea ... 

The reaction of urea with formaldehyde yields the following products, which are used as monomers in the preparation of urea formaldehyde resin. 

Some commercially important cross-linked polymers go virtually without names. These are heavily and randomly cross-linked polymers which are insoluble and infusible and therefore widely used in the manufacture of such molded items as automobile and household appliance parts. These materials are called resins and, at best, are named by specifying the monomers which go into their production. Often even this information is sketchy. Examples of this situation are provided by phenol-formaldehyde and urea-formaldehyde resins, for which typical structures are given by structures [IV] and [V], respectively ... 

Phosphoric Acid-Based Systems for Cellulosics. Semidurable flame-retardant treatments for cotton (qv) or wood (qv) can be attained by phosphorylation of cellulose, preferably in the presence of a nitrogenous compound. Commercial leach-resistant flame-retardant treatments for wood have been developed based on a reaction product of phosphoric acid with urea—formaldehyde and dicyandiamide resins (59,60). 

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. 

Slow-Release Fertilizers. Products containing urea—formaldehyde are used to manufacture slow-release fertilisers. These products can be either soHds, Hquid concentrates, orHquid solutions. This market consumes almost 6% of the formaldehyde produced (115) (see Controlled release TECHNOLOGY, AGRICULTURAL). 

Formaldehyde. Worldwide, the largest amount of formaldehyde (qv) is consumed in the production of urea—formaldehyde resins, the primary end use of which is found in building products such as plywood and particle board (see Amino resins and plastics). The demand for these resins, and consequently methanol, is greatly influenced by housing demand. In the United States, the greatest market share for formaldehyde is again in the constmction industry. However, a fast-growing market for formaldehyde can be found in the production of acetylenic chemicals, which is driven by the demand for 1,4-butanediol and its subsequent downstream product, spandex fibers (see Fibers, elastomeric). 

In 1993, worldwide consumption of phenoHc resins exceeded 3 x 10 t slightly less than half of the total volume was produced in the United States (73). The largest-volume appHcation is in plywood adhesives, an area that accounts for ca 49% of U.S. consumption (Table 11). During the early 1980s, the volume of this apphcation more than doubled as mills converted from urea—formaldehyde (UF) to phenol—formaldehyde adhesives because of the release of formaldehyde from UF products. Other wood bonding applications account for another 15% of the volume. The next largest-volume application is insulation material at 12%. 

Particle board and wood chip products have evolved from efforts to make profitable use of the large volumes of sawdust generated aimually. These products are used for floor undedayment and decorative laminates. Most particle board had been produced with urea—formaldehyde adhesive for interior use resin demand per board is high due to the high surface area requiring bonding. Nevertheless, substantial quantities of phenol—formaldehyde-bonded particle board are produced for water-resistant and low formaldehyde appHcations. 

Spheres. HoUow spherical fillers have become extremely useflil for the plastics industry and others. A wide range of hoUow spherical fillers are currently available, including inorganic hoUow spheres made from glass, carbon, fly ash, alumina, and 2h conia and organic hoUow spheres made from epoxy, polystyrene, urea—formaldehyde, and phenol—formaldehyde. Although phenol—formaldehyde hoUow spheres are not the largest-volume product, they serve in some important appHcations and show potential for future use. 

Formaldehyde Scavenging. The formation of oxazoHdines from alkanolamines and formaldehyde is rapid at room temperature and provides a method for the elimination of excess formaldehyde from products such as urea—formaldehyde resins. AEPD and TRIS AMINO are the products of choice for this purpose because one mole of each will react with two moles of formaldehyde (22). 

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). 

Continuous production of urea—formaldehyde resins has been described in many patents. In a typical example, urea and formaldehyde are combined and the solution pumped through a multistage unit. Temperature and pH are controlled at each stage to achieve the appropriate degree of polymerization. The product is then concentrated in a continuous evaporator to about 60—65% soflds (31). 

Uron Resins. In the textile industry, the term uron resin usually refers to the mixture of a minor amount of melamine resin and so-called uron, which in turn is predorninantly N,]S -bis(methoxymethyl)uron [7388-44-5] plus 15—25% methylated urea—formaldehyde resins, a by-product. 

Formaldehyde may react with the active hydrogens on both the urea and amine groups and therefore the polymer is probably highly branched. The amount of formaldehyde (2—4 mol per 1 mol urea), the amount and kind of polyamine (10—15%), and resin concentration are variable and hundreds of patents have been issued throughout the world. Generally, the urea, formaldehyde, polyamine, and water react at 80—100°C. The reaction may be carried out in two steps with an initial methylolation at alkaline pH, followed by condensation to the desired degree at acidic pH, or the entire reaction may be carried out under acidic conditions (63). The product is generally a symp with 25—35% soHds and is stable for up to three months. 

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). 

Urea—formaldehyde (UF) resias commonly were used ia the past. However, because of the lack of moisture resistance and the potential for the resias to hydroly2e ia the presence of moisture and decompose iato urea and formaldehyde, they are not used as much now. Governmental regulations are under development that eliminate the use of UF resia ia wood products. This would limit the exposure of the pubHc to formaldehyde, a Hsted carciaogen, formed by the decomposition of UF resia. Today most wood products use pheaol—formaldehyde (pheaoHc) resias, but urethane-based resias are becoming more common. 

Plastic laminated sheets produced in 1913 led to the formation of the Formica Products Company and the commercial introduction, in 1931, of decorative laminates consisting of a urea—formaldehyde surface on an unrefined (kraft) paper core impregnated with phenoHc resin and compressed and heated between poHshed steel platens (8,10). The decorative surface laminates are usually about 1.6 mm thick and bonded to wood (a natural composite), plywood (another laminate), or particle board (a particulate composite). Since 1937, the surface layer of most decorative laminates has been fabricated with melamine—formaldehyde, which can be prepared with mineral fiUers, thus offering improved heat and moisture resistance and allowing a wide range of decorative effects (10,11). 

Urea—Formaldehyde Reaction Products. Urea—formaldehyde (UF) reaction products represent one of the older controlled release nitrogen technologies. An early disclosure of the reaction products of urea [57-13-6] and formaldehyde [50-00-0] was made in 1936 (1) (Amino resins and plastics). In 1948, the USDA reported that urea (qv) and formaldehyde (qv) could react to produce a controlled release fertilizer at urea to formaldehyde mole ratios (UF ratio) greater than one (2). 

Urea—formaldehyde reaction products represented the first synthetically produced form of controlled release nitrogen and were commercialized in 1955 under the trade names Uramite (DuPont) and Nitroform (Nitroform Corp.). 

Liquid Compositions. Urea—formaldehyde reaction products also are available commercially as Hquids that can be categorized into two classes, ie, water suspensions and water solutions. 

The nitrogen content of granular urea—formaldehyde reaction products typicahy ranges from 35 to 42% depending on the methylene urea polymer distribution. 

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