Hexamethylenetetramine resins

Two-Stage Resins. The ratio of formaldehyde to phenol is low enough to prevent the thermosetting reaction from occurring during manufacture of the resin. At this point the resin is termed novolac resin. Subsequently, hexamethylenetetramine is incorporated into the material to act as a source of chemical cross-links during the molding operation (and conversion to the thermoset or cured state). 

The production of hexamethylenetetramine consumes about 6% of the U.S. formaldehyde supply (115). Its principal use is as a thermosetting catalyst for phenoHc resins. Other significant uses are for the manufacture of RDX (cyclonite) high explosives, in mol ding compounds, and for mbber vulcanisation accelerators. Some hexamethylenetetramine is made as an unisolated intermediate in the manufacture of nitfilotriacetic acid. 

Uncured resins are skin sensitizers and contact should be avoided, as weU as breathing the vapor, mist, or dust. Novolak-based pulverized products generally contain hexamethylenetetramine, which may cause rashes and dermatitis. PhenoHc molding compounds and pulverized phenoHc adhesives must be controUed as potentially explosive dusts. In addition, they contain irritating or toxic additives. 

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). 

Although in the dry state carbon tetrachloride may be stored indefinitely in contact with some metal surfaces, its decomposition upon contact with water or on heating in air makes it desirable, if not always necessary, to add a smaH quantity of stabHizer to the commercial product. A number of compounds have been claimed to be effective stabHizers for carbon tetrachloride, eg, alkyl cyanamides such as diethyl cyanamide (39), 0.34—1% diphenylamine (40), ethyl acetate to protect copper (41), up to 1% ethyl cyanide (42), fatty acid derivatives to protect aluminum (43), hexamethylenetetramine (44), resins and amines (45), thiocarbamide (46), and a ureide, ie, guanidine (47). 

The novolak resins themselves contain no reactive methylol groups and do not form cross-linked structures on heating. If, however, they are mixed with compounds capable of forming methylene bridges, e.g. hexamethylenetetramine or paraformaldehyde, they cross-link on heating to form infusible, thermoset structures. 

Resol resins thermoset on heating and are used for adhesives. Novolacs require a further source of formaldehyde in the form of hexamethylenetetramine to produce molding powders. Phenolic moldings are resistant to heat, chemicals, and moisture with good electrical and heat insulation qualities. Complex phenols from, e.g., cashew-nut shell liquid, are used in making brake... 

This chapter emphasizes the recent mechanistic and kinetic findings on phenolic oligomer syntheses and network formation. The synthesis and characterization of both novolac- and resole-type phenolic resins and dieir resulting networks are described. Three types of networks, novolac-hexamethylenetetramine (HMTA),... 

Normally the reaction Is useful for the conversion of alkyl halides to primary amines without concomitant formation of secondary amines.29 Treatment of polymer 17 with hexamethylenetetramine in a mixture of ethanol/THF afforded an insoluble resin. Using diazabicyclooctane (DABCO), we demonstrated that the reaction could be limited to attack by a single nitrogen in a multifunctional amine, so we did not anticipate crosslinking via bis-quat salt formation. Hydrolysis of 2 with anhydrous HC1 in ethanol generated free amino groups as evidenced by a positive ninhydrin test, but quantitative hydrolysis could not be achieved and the product remained insoluble. One would have expected a simple bis-quat to hydrolyse and open the crosslinked structure. 

An acidic-cure catalyst is added to the urea-formaldehyde resin before it is used as an adhesive. Ammonium chloride and ammonium sulfate are the most widely used catalysts for resins in the forest products industry. A variety of other chemicals can be used as a catalyst, including formic acid, boric acid, phosphoric acid, oxalic acid, and acid salts of hexamethylenetetramine. 

Sand has been treated with oil-soluble organosilicon compounds to form a hydrophobic proppant (77). A double layer resin coating has also been developed. The inner layer coating the sand particle is a cured gamma-aminopropyltriethoxvsilane - hexamethylenetetramine. The outer layer is an uncured mixture of the same two chemicals which cures within the fracture to form a consolidated permeable mass holding the fracture open (78). 

Hexamethylenetetramine (HMTA) has important uses in modifying phenolic resin manufacture and is an intermediate in explosive manufacture. Although it is a complex three-dimensional structure, it is easily made by the condensation of formaldehyde and ammonia. 

Formaldehyde, used in the production of phenolic and amino resins, is produced by the catalytic hot-air oxidation of methanol. In turn, hexamethylenetetramine is produced by the condensation of ammonia and 30% aqueous formaldehyde (formalin). 

A composition is prepared by dissolving the MMBS modified thermoset resin in acetone. To the resulting solution, additives may be added, for example, pigments, flame retardants, lubricants or cure accelerators, e.g., hexamethylenetetramine. 

AN Explosives Containing Nondetonable Sensitizers. Many substances which are not in themselves expls greatly increase the sensitivity of AN when added to it. To these belong powdered metals (such as flaked Al) and combustible org materials (such as rosin, many metallic resinates, hexamethylenetetramine, many org bases, and paraffin oils and waxes). Usually these AN expls are prepd by coating granules of AN, either alone or mixed with NaCl, with a thin layer of sensitizer. If it is desired to make an expl of exceptional safety, there is employed an amt of sensitizer... 

HEXAMINE. CAS 100-97-0], (CH-),N . formula weight 140,19, white crystalline solid, mp 280rC. decomposes at higher temperatures. Alsu known as hexamethylenetetramine, nicihenuiniiie. and urotiopitie. the compound is soluble in H2O and only very slightly soluble in alcohol or ether. Although used to some extent in medicine as an internal antiseptic, the primary use of hexamine is in the manufacture of synthetic resins where the compound is a substitute for formalin (aqueous solution of paraformaldehyde) and its NaOH catalyst. Hexamine also is used as an accelerator for rubber. 

For example, novolacs are phenolic resins obtained by the condensation of phenol (trifunctional monomer) and formaldehyde (bifunctional monomer), using a stoichiometric excess of phenol so that formaldehyde is completely consumed without leading to gelation. In a second step, instead of directly adding the necessary formaldehyde, the polymer network is formed by reaction with hexamethylenetetramine (a condensation product of formaldehyde and ammonia usually called hexa), through a complex set of chemical reactions (Chapter 2). 

We now compare theoretical predictions with experimental results obtained using silica sand coated with a 4% resin consisting of 100 parts by weight of a phenol-formaldehyde novolac and 5, 10, or 15 parts of hexamethylenetetramine (hexa) as hardener (Aranguren et al., 1984). 

Triazaphosphaadamantane forms complexes with phenol, catechol, resorcinol, and hydroquinone. These compounds are similar to those formed by hexamethylenetetramine, and were proposed as intermediates for the preparation of Bakelite-type resins (76MI1). 

It also can be produced directly from natural gas, methane, and other aliphatic hydrocarbons, but this process yields mixtures of various oxygenated materials. Because both gaseous and liquid formaldehyde readily polymerize at room temperature, formaldehyde is not available in pure form. It is sold instead as a 37 percent solution in water, or in the polymeric form as paraformaldehyde [HO(CH20)nH], where n is between 8 and 50, or as trioxane (CH20)3. The greatest end use for formaldehyde is in the field of synthetic resins, either as a homopolymer or as a copolymer with phenol, urea, or melamine. It also is reacted with acetaldehyde to produce pentaerythritol [C(CH2OH)4], which finds use in polyester resins. Two smaller-volume uses are in urea-formaldehyde fertilizers and in hexamethylenetetramine, the latter being formed by condensation with ammonia. 

Application Formaldehyde as a liquid solution of 37-52 wt% is primarily used in the production of polyoxymethylene (POM) and hexamethylenetetramine as well as synthetic resins in the wood industry. 

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