Formaldehyde hardener

Formaldehyde hardens proteins and prevents them decaying. Hence, it is used to store biological products, to make mummies and also as a disinfectant as it kills insects and microorganisms. 

SPI hardened with an aldehyde at or near the proteins isoelectric point ("pH 4.5 for soy protein) produces a material that is thermoplastic and absorbs <10% moisture during 24 h of soaking. An aqueous suspension of the formaldehyde-hardened SPI can be used as a laminating material for Kraft paper. Laminating material made from soy plastics has similar properties to the more expensive phenol and urea laminating materials, but is less water-resistant. SPI was discontinued during the early 1950s in favor of modified soybean meals used as modifiers and extenders in PF plastics. 

Isocyanate-based adhesives are being studied as partial or complete replacements for the traditional formaldehyde-hardened adhesives, such as urea-formaldehyde and phenol-formaldehyde resins. These latter adhesives are being used for the production of wood laminates, bonded wood joints, and as binders for composition board. 

Furan resin modified by phenol of a furfuryl alcohol content > 50%, of an increased content of phenol and formaldehyde, hardened by phenylsulphortic acid and sulphuric acid ... 

Protein Fibers. Reaction with formaldehyde hardens proteins, decreases their water solubihty, and increase. their resistance to chemical reagents. The nature of the formaldehyde-protein reactions which produce these results ha.s ahead) been discussed fpages 221-224 . These same reactions are responsible for the modifying action of formaldehyde and reacth e formaldehyde deri at-h es on, protein fillers and related fibers containing amido and amino radicals. 

Urea.—Forma.IdehydeResins. Cellular urea—formaldehyde resins can be prepared in the following manner an aqueous solution containing surfactant and catalyst is made into a low density, fine-celled foam by dispersing air into it mechanically. A second aqueous solution consisting of partially cured urea—formaldehyde resin is then mixed into the foam by mechanical agitation. The catalyst in the initial foam causes the dispersed resin to cure in the cellular state. The resultant hardened foam is dried at elevated temperatures. Densities as low as 8 kg/m can be obtained by this method (117). 

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... 

Other. 2-Nitro-1-butanol is an excellent solvent for many polyamide resins, cellulose acetate butyrate, and ethylceUulose. It can be utilized in paint removers for epoxy-based coatings. 2-Hydroxymethyl-2-nitro-l,3-propanediol is usebil for control of odors in chemical toilets. Its slow release of formaldehyde ensures prolonged action to control odor, and there is no reodorant problem which sometimes is associated with the use of free formaldehyde. 2-Hydroxymethyl-2-nitro-l,3-propanediol solutions are effective preservative and embalming fluids. The slow Uberation of formaldehyde permits thorough penetration of the tissues before hardening. 

Early phenoHc resins consisted of self-curing, resole-type products made with excess formaldehyde, and novolaks, which are thermoplastic in nature and require a hardener. The early products produced by General BakeHte were used in molded parts, insulating varnishes, laminated sheets, and industrial coatings. These areas stiH remain important appHcations, but have been joined by numerous others such as wood bonding, fiber bonding, and plywood adhesives. The number of producers in the 1990s is approximately 20 in the United States and over 60 worldwide. 

Ammonium chloride has a number of iadustrial uses, most importantiy ia the manufacture of dry-ceU batteries, where it serves as an electrolyte. It is also used to make quarryiag explosives, as a hardener for formaldehyde-based adhesives, as a flame suppressant, and ia etching solutions ia the manufacture of ptinted circuit boards. Other appHcations iaclude use as a component of fluxes ia ziac and tin plating, and for electrolytic refining of ziac. 

Nail hardeners have been based on various proteia cross-linking agents. Only formaldehyde is widely used commercially. Contact with skin and inhalation must be avoided to preclude sensiti2ation and other adverse reactions. The popularity of products of this type is decreasiag because the polymers used ia nail elongators can be used to coat nails to iacrease the mechanical strength. 

Other modifications of the polyamines include limited addition of alkylene oxide to yield the corresponding hydroxyalkyl derivatives (225) and cyanoethylation of DETA or TETA, usuaHy by reaction with acrylonitrile [107-13-1/, to give derivatives providing longer pot Hfe and better wetting of glass (226). Also included are ketimines, made by the reaction of EDA with acetone for example. These derivatives can also be hydrogenated, as in the case of the equimolar adducts of DETA and methyl isobutyl ketone [108-10-1] or methyl isoamyl ketone [110-12-3] (221 or used as is to provide moisture cure performance. Mannich bases prepared from a phenol, formaldehyde and a polyamine are also used, such as the hardener prepared from cresol, DETA, and formaldehyde (228). Other modifications of polyamines for use as epoxy hardeners include reaction with aldehydes (229), epoxidized fatty nitriles (230), aromatic monoisocyanates (231), or propylene sulfide [1072-43-1] (232). 

It is likely that the quinone methide and related structures formed at these temperatures account for the dark colour of phenolic compression mouldings. It is to be noted that cast phenol-formaldehyde resins, which are hardened at much... 

The importance of the nature of the catalyst on the hardening reaction must also be stressed. Strong acids will sufficiently catalyse a resol to cure thin films at room temperature, but as the pH rises there will be a reduction in activity which passes through a minimum at about pH 7. Under alkaline conditions the rate of reaction is related to the type of catalyst and to its concentration. The effect of pH value on the gelling time of a casting resin (phenol-formaldehyde ratio 1 2.25) is shown in Figure 23.15. 

Hexa is used almost universally as the hardener. It is made by passing a slight excess of ammonia through a lightly stabilised aqueous solution of formaldehyde, concentrating the liquor formed and crystallising out the hexa (Figure 23.17). 

The resins are hardened by acidic conditions. Phosphoric acid, or more commonly ammonium chloride, an acid donor, is employed. The ammonium chloride functions by reaction with formaldehyde to give hydrochloric acid. Hexamine is also formed during this reaction. 

At one time urea-formaldehyde was used extensively in the manufacture of plywood but the product is today less important than heretofore. For this purpose a resin (typically U-F molar ratio 1 1.8)-hardener mixture is coated on to wood veneers which are plied together and pressed at 95-110°C under pressure at 200-800 Ibf/in (1.38-5.52 MPa). U-F resin-bonded plywood is suitable for indoor application but is generally unsuitable for outdoor work where phenol-formaldehyde, resorcinol-fonnaldehyde or melamine modified resins are more suitable. 

For example, a UF-resin for particleboard at the end of the 1970s would have had a F/U molar ratio of approx. 1.6-1.8. To day a UF-resin for the same application has a molar ratio of between 1.02 and 1.08, but the requirements for the boards, as given in the quality standards, are still the same. The degree of crosslinking of the cured resins as well as the reactivity of the hardening reaction depends on the availability of free formaldehyde in the system. 

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