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ESR study and copolymer analysis of acrylamide‐methacrylamide solid solutions
Author(s) -
Ramelow Ulku,
Baysal Bahattin M.
Publication year - 1988
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.1988.070350409
Subject(s) - methacrylamide , copolymer , radical , photochemistry , polymer chemistry , chemistry , polymerization , materials science , acrylamide , polymer , organic chemistry
When acrylamide‐methacrylamide mixed crystals are irradiated by ultraviolet (UV) rays, a copolymeric sample is obtained containing both monomeric constituents. For identification and quantitative analysis of these copolymers, a modified form of UV spectroscopy was used. The greatest advantage of UV spectroscopy for copolymer analysis lies in its rapid application. A comparison of the spectrum of the unknown compositions with spectra of known systems by using a calibration curve and the shifts in absorption maxima in different concentrations are valuable aids in establishing the composition. Electron spin resonance (ESR) provides a correlation between the obtained copolymer composition and the shape of the signal of the responsible radical. ESR spectra obtained for UV‐irradiated acrylamide‐methacrylamide mixed crystals reveal that during polymerization both radicals are present. As methacrylamide percentage increases in the mixture, the signal becomes similar to the 9‐line spectrum of pure methacrylamide. When there is 90% methacrylamide present in the original mixture, a 5‐line signal is observed, with even‐numbered peaks in the methacrylamide signal appearing now as shoulders. When the methacrylamide percentage is about 16%, a characteristic 3‐line signal of acrylamide is dominant. As the methacrylamide percentage increases in the original mixture of the copolymers, ESR signals indicate a decrease in the rate constant values for second‐order decay at 60°C. The stability of the formed radicals was studied by admitting oxygen to the copolymeric samples as well as to the homopolymeric systems. Since the peroxidic radicals are more active in the hydrogen abstraction process, they decay more rapidly than the macro radical itself by a bimolecular termination reaction. As the methacrylamide percentage increases in the copolymeric mixtures, the peroxide radical formation becomes more difficult. This indicates that polymethacrylamide brings more stability in copolymerization reactions with acrylamide. The polymerization rate of both monomers and their mixed crystals were enhanced by adding chlorine gas before irradiation. Chlorine acts as an agent for slowing down the radical decay as well as accelerating the radical initiation reactions.