The use of 1 H NMR and UV–vis measurements for quantitative determination of trans/cis isomerization of a photo‐responsive monomer and its copolymer

• Published in: Journal of applied polymer science 2006-04, Vol.100 (2), p.1103-1112
• Main Authors: Moniruzzaman, M., Talbot, J. D. R., Sabey, C. J., Fernando, G. F.
• Format: Article
• Language: English
• ISSN: 0021-8995; 1097-4628
• DOI: 10.1002/app.23490

Photo‐induced trans–cis isomerization of trans‐4‐methacryloyloxyazobenzene and its copolymer with methylmethacrylate, synthesized in this work, were investigated in a polar protic (CDCl 3 ) and a polar aprotic (DMSO‐ d 6 ) solvent, using 1 H‐NMR . The results were cross‐correlated with trans–cis isomerization calculated from UV–visible spectra. The kinetics of the photoisomerization reaction of the monomer species under UV light irradiation is described by a simple first order exchange between the trans and cis forms of the monomer. The behavior was found to be similar for both solvents. The cis‐to‐trans reversion in the absence of irradiation is about 3% of the back reaction under irradiation. For the polymer in solution, the behavior was more complicated and is described by the sum of two equilibria, each of first order exchange kinetics of the trans form with two different types of cis isomer in the polymer; a first type of isomerization similar in behavior to that of the monomer and the second type much faster in cis / trans exchange rate. This bikinetic behavior is in agreement with that of the azobenzene moiety in PMMA as a solid phase mixture. The relative proportion of the two rates comprising the bikinetic effect is solvent‐dependent. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1103–1112, 2006