Reaction Mechanisms of Glyoxal-Based Durable-Press Resins with Cotton

Abstract

Leaving-group and other effects in acid-catalyzed nucleophilic substitution reactions with a number of 4,5-disubstituted ethyleneureas, 1,3-disubstituted ethyleneureas, and N-substituted methyl carbamates are considered. Acetoxy and secondary alkoxy leaving groups enhance reactivity from formaldehyde-hased (primary carhonium ion formed) systems hut not from glyoxal-based (secondary carhonium ion formed) systems. The 1,3-dimethylol-4,5-dihydroxyethyleneurea (DMDHEU) molecule, for best reaction with cotton or other nucleophiles should be activated by selected leavint; groups on the methylenes in the 1,3-positions, but not necessarily in the 4,5-positions. Reactivity to small nucleophiles of 1,3- and 4,5-positions in DMDHEU systems are equal when leaving groups are hydroxy or methoxy. Ring (4,5-) positions are hindered. Other factors which influence reactivity or carhonium-immonium ion stability in DMDHEU are discussed. Evidence is presented which suggests that anhydroglucose units in cellulose possess groups of different leaving ability which will influence the location and durability of agents reacted with cellulose. Implications of these findings on the finishing of cotton cellulose are discussed.

Keywords

Cotton 4,5-disubstituted ethyleneureas 1,3-disubstituted ethyleneureas N-substituted methyl carbamates glyoxal- based DP resins nucleophiles DMDHEU derivatives reactants. Chemically modified cotton leaving groups. Cotton finishing. Isopropanol methanol D2O water CCl4 CHCl3 nonreactive solvents p-toluenesulfonic acid acid catalyst Reactive sites temperature concentration. Leaving effects nmr spectra reaction rates reactivity steric effects ion stabilities wrinkle resistance acid resistance hydrolysis resistance. Reaction mechanisms. Nucleophilic reactions nmr spectrometry.

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References

Hamada, H. , Isayama, S. , and Yamabe, K. , Urea Resins. XIV. Acid Hydrolysis of N,N'-Bis(sec-butoxymethyl)urea at Room Temperature, Kogyo Kagaku Zasshi 71, 1294-5 (1968) ; C. A. 70, 46792 (1969).

Jung, H.Z. , Benerito, R.R. , Gonzales, E.J. , and Berni, R.J. , Influence of Structure of Cyclic Urea Derivatives on their Reactivities with Cotton, J. Appl. Polym. Sci. 13, 1949-1963 (1969).

Moran, C.M. , Vail, S.L. , and Kullman, R.M.H. (to Secretary of Agriculture), Process of Producing Wrinkle Resistant Cellulosic Fabrics of Relatively High Moisture Regain, U. S. 3,230,030, January 18, 1966.

Petersen, H. , Recent Developments in the Chemistry of Cross-Linking Agents, Texlile Res. J. 40, 335-344 (1970).

Roberts, D.D. and Hendrickson, W. , Neighboring-Group Study in Solvolyses of Cyclopentyl and Cyclohexyl Tosylates, J. Org. Chem. 34, 2415-2417 (1969).

Rowland, S.P. , Stark, S.M. , Cirino , V.O. , and Mason, J.S. , Structural Features of Cotton Treated by Pad-Dry-Cure, Mild Cure, Poly-Set, and Wet-Fix Process, Textile Res. J. 41, 57-64 (1971).

Soignet, D.M. , Boudreaux, G.J. , Berni , R.J. , and Gonzales , E.J. , Nuclear Magnetic Resonance Studies of Substituted Cyclic Ureas, Appl. Speclry. 24, 272-276 (1970).

Vail, S.L. , The Reactivity-Hydrolysis Relationship in Chemical Finishing of Cotton, Textile Res. J. 39, 774-780 (1969).

Vail, S.L. , Kullman, R.M.H. , Reeves, W.A. , and Barker, R.H. , Principles of Reactivity of Nitrogenous Agents with Cotton, Textile Res. J. 40, 355-362 (1970).

10.

Vail, S.L. and Moran, C.M. , N-Methylol, N-Substituted Amides as Cross-Linking Reagents for Cotton , Amer. Dyestuff Reptr. 53, 282-286 (1964).

11.

Vail, S.L. , Verburg, G.B. , and Young, A.H.P. , The 4,5-Dihydroxy-2-Imidazolidinone System for Cross-Linking Cotton, Textile Res. J. 39, 86-93 (1969).