Formation of Cyclic Anhydride Intermediates and Esterification of Cotton Cellulose by Multifunctional Carboxylic Acids: An Infrared Spectroscopy Study

Abstract

Multifunctional polycarboxylic acids have been used as nonformaldehyde cross linking agents for cotton fabrics to replace the traditional N-methylol reagents. Ester ification of cotton cellulose by seventeen aliphatic and aromatic polycarboxylic acids is studied using Fourier transform infrared spectroscopy. Five-membered cyclic an hydride intermediates formed under the curing conditions are identified on cotton fabrics treated with these acids. Only those polycarboxylic acids that form cyclic an hydride intermediates esterify cotton cellulose. Formation of the cyclic anhydride intermediates and esterification of cotton cellulose take place in the same curing tem perature regions. The infrared spectroscopy data also indicate that the second carboxyl group in a bifunctional carboxylic acid is not able to esterify cotton cellulose effectively. Therefore, we can conclude that a polycarboxylic acid esterifies cotton cellulose through the formation of a cyclic anhydride intermediate. The infrared spectroscopy data also reveal that 1,2,3,4-butanetetracarboxylic acid is the most effective crosslinking agent for cotton cellulose among the acids studied.

Get full access to this article

View all access options for this article.

References

Andrews, B.A.K. , Non-Formaldehyde Durable Press Finishing of Cotton with Citric Acid, Textile Chem. Color. 22(9), 63-67 (1990).

Bellamy, L.J. , "The Infrared Spectra of Complex Molecules," 3rd ed., Chapman and Hall, London , 1975, p. 144.

Caulifield, D.F. , Ester Crosslinking to Improve Wet Performance of Paper Using Multifunctional Carboxylic Acids, Butanetetracarboxylic and Citric Acid, TAPPI J. 77, 205-212 (1994).

Ckythup, N.B. , Daly, L.H. , and Wiberley, S.E. , "Introduction to Infrared and Raman Spectroscopy, " ch. 9, Academic Press, San Diego, CA, 1990 , pp. 310-312.

Laemmermann, D. , New Possibilities for Non-Formaldehyde Finishing of Cellulosic Fibers, Melliand Taxtilber 3, 274-279 (1992).

Rowland, S.P. , Welch, C.M. , Brannan , A.F. , and Gallagher , D.M. , Introduction of Ester Cross-links into Cotton Cellulose by a Rapid Curing Process, Textile Res. J. 37,933-941 (1967).

Welch, C.M. , Formaldehyde-Free Durable Press Finishes, Rev. Prog. Color. 22, 32-41 (1992).

Welch, C.M. , Formaldehyde-Free DP Finishing with Polycarboxylic Acids, Am. Dyest. Rep. 83(2), 19-26,132 (1994).

Welch, C.M. , Tetracarboxylic Acids as Formaldehyde-Free Durable Press Finishing Agents , Textile Res. J. 58, 480-486 (1988).

10.

Welch, C.M. , and Andrews, B.A.K. , Cross-links : A Route to High Performance Nonformaldehyde Finishing of Cotton, Textile Chem. Color. 21(2), 13-17 (1989).

11.

Welch, C. M., and Andrews, B. A. K., Catalysts and Processes for Formaldehyde Free Durable Press Finishing of Cotton Textiles with Polycarboxylic Acids, U.S. patent 4,926,865, June 26, 1990.

12.

Yang, C.Q. , Characterizing the Ester Crosslinkages of Cotton Cellulose with FT-IR Photoacoustic Spectroscopy, Textile Res. J. 61, 298-305 (1991).

13.

Yang, C.Q. , and Andrews, B.A.K. , Infrared Spectroscopic Studies of the Nonformaldehyde Durable Press Finishing of Cotton Fabrics by Polycarboxylic Acids, J. Appl. Polym. Sci. 43,1609-1616 (1991).

14.

Yang, C.Q. , FT-IR Spectroscopy Study of the Ester Crosslinking Mechanism of Cotton Cellulose , Textile Res. J. 61, 433-440 (1991).

15.

Yang, C.Q. , Infrared Spectroscopy Studies of the Cyclic Anhydride as the Intermediate for the Ester Crosslinking of Cotton Cellulose by Polycarboxylic Acid, I: Identification of the Cyclic Anhydride Intermediate, J. Polym. Sci. Polym. Chem. Ed. 31, 1187-1193 (1993 ).

16.

Yang, C.Q. , Infrared Spectroscopy Studies of the Effects of the Catalyst on the Ester Crosslinking of Cotton Cdlulose by Poly(carboxylic Acid)s, J. Appl. Polym. Sci. 50, 2047-2053 (1993 ).

17.

Yang, C.Q. , Effect of pH on Nonformaldehyde Durable Press Finishing of Cotton Fabric: FT-IR Spectroscopy Study, Part I: Ester Crosslinking, Textile Res. J. 63, 420-430 (1993).

18.

Yang, C.Q. , Effect of pH on Nonformaldehyde Durable Press Finishing of Cotton Fabrics: FT-IR Spectroscopy Study, Part II: Formation of the Anhydride Intermediate , Textile Res. J. 63, 706-711 ( 1993).