The structures of the water-insoluble complexes of acrylate-based copolymers containing diazosulfonate groups and a fluorinated cationic surfactant (Hoe L-3658-1) were examined by X-ray diffraction, contact angle measurements, differential scanning calorimetry, and spectroscopic methods (IR, UV−vis, fluorescence). The structures of the complexes were shown to be lamellar and determined by using Ruland's interface distribution function procedure. Remarkably low critical surface tensions were found, indicating the formation of ordered layers of fluorocarbon segments at the surfaces of the complexes. Fine-tuning of the complex structures was achieved by varying the composition of the copolymers as well as the pH value present at the time of preparation. The formation of excimers was found to be strongly influenced by the complex structure.

Polymeric complexes were prepared by using acrylate based copolymers, which contained 20, 30, 50, and 100 mol % diazosulfonate groups and a commercially available fluorinated surfactant (Fluorad FC135). The glass transition temperatures of the complexes were determined to be 71 ± 3 °C, this was independent of the amount of diazogroups. All these complexes are stable up to temperatures of about 200 °C. As determined by wide- and small-angle X-ray diffraction, the solid states of the complexes in the bulk material were determined to be smectic A-like structures with long periods of 3.8−4.4 nm. Ultrathin films with thicknesses in the range 4−40 nm were prepared by spin coating. The wetting behavior of the films was found to be independent of their thickness. As determined by automatic drop shape analysis of the contact angle measurements, the surface energies of complex films were in the range 10−14 mN/m.

Abstract-The copolymerization of a methylated-¯-cyclodextrin (m-¯-CD) 1 : 1 host-guest compound of styrene (1a) with various molar ratios of sodium 4-(acrylamido)-phenyldiazosulfonate (2) is described. The copolymerization of complex 1a with 2 was carried out in water with 2,2 0 -azobis-(N,N 0 -dimethyleneisobutyramidine)-dihydrochloride as the free radical initiator at 40 ± C. Depending on the amount of 2 incorporated in the copolymer, water-or DMF-soluble copolymers of high molar mass were obtained. Irradiation of the copolymers with UV light in solution resulted in rapid decomposition of the azo chromophore, and irradiation of the polymers as lms led to crosslinking and thus to insolubility.