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This article reports the synthesis and characterization of a new type of copolymer consisting of acrylamide and trans‐4‐methacroyloxyazobenzene and their gel. Free‐radical polymerization initiated with 2,2′‐azobisisobutyronitrile was used to conduct the synthesis although N,N′‐methylene bisacrylamide was used as a crosslinking agent for the gel synthesis. Despite the insolubility of the different monomers in a single solvent, a certain ratio of water/tetrahydrofuran (THF) enabled the propagating species to stay in the solution and thus to facilitate chain growth. The solubility, Fourier transform infrared spectra, and solid‐state 13C NMR investigations revealed that two monomers in the copolymer were chemically bonded. The compositions of the incorporated acrylamide and azobenzene in the copolymer and the gel were determined by NMR spectroscopy. Because the potential actuating behavior of such materials was due to the volume change involved in reversible solvent uptake, the sorption and evaporation of the gel were also investigated and showed that the gel could absorb about 460% water, which corresponded to a polymer content of the weight gel of 18% and was compatible with thermogravimetric analysis of a saturated gel that revealed about 83 wt % of a swollen gel was lost within 12 h. Finally, photoinduced trans–cis isomerization kinetics of the copolymer was investigated in a 30:70 mixture of water and THF against irradiation time. A photostationary state was reached within 5.5 min with a corresponding conversion of 70% of the trans isomer to the cis form. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2886–2896, 2004

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 (DMSOd 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.