Cotton cellulose reaction with formaldehyde

Cellulosic fibers (cotton, rayon) are crosslinked by reaction of the hydroxyl groups of cellulose with formaldehyde, diepoxides, diisocyanates, and various methylol compounds such as urea-formaldehyde prepolymers, /V, /V -di tnethylol-A(A -dimethy lene urea, and trimethyl-olmelamine [Marsh, 1966]. Crosslinking imparts crease and wrinkle resistance and results in iron-free fabrics. 

Figure 1 shows the repeating glucose units of cellulose with the carbons labeled, including those with the reactive 2, 3, and 6 hydroxyls. Ihe most important reactions of cotton cellulose commercially are esterification and etherification, with the products of etherification ranking first. It is generally agreed today among textile scientists that durable press cellulosic textiles ow their smooth-drying and resilient properties to the reactivity of formaldehyde and its amide derivatives with cellulose to produce crosslinks between adjacent cellulose chains (Figure 2). Hovever, the theory that crosslinking was responsible for increased resiliency developed only after the treatmaits were in wide use.

Although not a measure of cellulose crosslinking, since mono functional agaits are incapable of crosslinking, the response to hydrolysis conditions of cotton fabric treated with N-methyl, N -hydroxymethylethyleieurea offers evidence of cellulose reaction. This response can be seen in Table II. Formaldehyde is released from the... 

Flame-Retardant Finishes on Cellulosic Substrates. The flame retarding of cotton and viscose-rayon fabrics has been the object of a large worldwide effort on phosphorus-containing finishes (217-219). The commercial cotton finishes are based on tetrakis(hydroxymethyl)phosphonium salts, usually the chloride or sulfate (220). These salts are prepared by reaction of formaldehyde with phosphine in the presence of an acid. 

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). 

The most important cotton etherification treatments are those that produce wrinkle resistance in fabrics [331,333,334]. The aldehydes, formaldehydes, and glyoxals, react with the OH groups of two cellulose chains as well as those of one chain. Reaction in which a bond is established between the two cellulose molecules is called cross-linking and is the basis for profound changes in the cotton fiber. Cross-linking produces resiliency in the fiber to give the needed dimensional stabilization, wrinkle resistance, and crease retention for modern durable-press cellulosic fabrics. Cross-links based on etherification reactions traditionally have been used because of their durability to repeated laundering and wear. 

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