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ARS Home » Southeast Area » New Orleans, Louisiana » Southern Regional Research Center » Cotton Chemistry and Utilization Research » Research » Publications at this Location » Publication #173361
Title: EFFECTS OF CIS-TRANS ISOMERIZATION OF THE PHOTOPOLYMERIZATION BEHAVIOR OF N-VINYL AMIDE MONOMERS

Author
item White, Leslie
item HOYLE, CHARLES - UNIV. OF SOUTHERN MISS.
item JONSSON, SONY - BECKER ACROMA AB
item MATHAIS, LON - BECKER ACROMA AB

Submitted to: Trade Journal Publication
Publication Type: Peer Reviewed Journal
Publication Acceptance Date: 11/1/2004
Publication Date: 2/15/2005
Citation: White, L.A., Hoyle, C.E., Jonsson, S., Mathais, L.J. 2005. Effects of cis-trans isomerization of the photopolymerization behavior of n-vinyl amide monomers. Trade Journal Publication. v. 8(4). p. 297-308.

Interpretive Summary: A series of five N-substituted N-vinyl formamide derivatives was synthesized, and their reactivities to ultraviolet light initiation and atmospheric conditions were studied. Such derivatives are members of a promising class of compounds for textile finishing that can act as oxygen scavengers and polymerize in ambient conditions. It was determined by 13C NMR analysis that the more reactive NVF exists predominantly in the trans conformation but the cyclic commercial monomers and the N-substituted derivatives of NVF exist totally or mostly in the cis conformation. The increased cis isomer content has a deleterious effect on polymerization. The cis amide bond is less reactive due to electronic and steric hindrance, and the predominance of this isomer in the reaction mixture leads to low overall reactivity of some of the derivatives.

Technical Abstract: Photopolymerization behavior of three commercially available N-vinyl amide monomers was compared in air and nitrogen. Additionally, a series of N-substituted N-vinyl formamides was synthesized, and their reactivities under photolytic initiation conditions were studied. Of the five derivatives synthesized, only the benzyl derivative and the N-vinyl formamide/methacrylate derivative showed any reactivity toward free radical bulk photopolymerization. It was determined by 13C NMR analysis that, while the more reactive NVF exists predominantly in the trans conformation with respect to the planar C-N amide bond, the cyclic commercial monomers and the N-substituted derivatives of NVF exist totally or mostly in the cis conformation. The increased cis isomer content has a deleterious effect on polymerization. The cis amide bond is less reactive due to electronic and steric hindrance around the propagating radical center, and the predominance of this isomer leads to low overall reactivity to photolytically catalyzed bulk polymerizations of these monomers.