Abstract
The microheterogeneous network formation processes in the free-radical copolymerization of methyl methacrylate (MMA) with ethylene dimethacrylate (EDMA) were pursued Electron spin resonance (ESR)-spectroscopically by using copper tetraphenylporphyrin (CuTPP) and copper methacryloyloxyphenyl triphenylporphyrin (CuMAOTPP) as spin probes. Thus, CuTPP could be a useful tool to evaluate the mobility of low-molecular-weight molecules in the gelled system. In the MMA-EDMA copolymerization containing CuMAOTPP, three types of CuTPP moieties existed in the polymerization solution as immobilized in the densely crosslinked network, incorporated into the loosely crosslinked network, and unreacted monomer; their proportion was estimated by a semi-quantitative spectral simulation. For example, in the MMA-EDMA (70:30)-CuMAOTPP terpolymerization in a dilution of 1/10 in benzene, 30% of CuMAOTPP was immobilized at 76% conversion by the densely crosslinked network or microgel, just like as in a frozen state, while no restricted mobility was observed for unreacted CuMAOTPP in spite of a complete loss of fluidity of the polymerization solution.
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Aota, H., Sanai, Y., Matsumoto, A. et al. Electron Spin Resonance Spectroscopic Pursuit of Network Formation Processes in Free-Radical Crosslinking Polymerizations I. Microscopic Environmental Evaluation around Copper(II) Tetraphenylporphyrin Spin Probe Incorporated into or Excluded from Polymer Network in Methyl Methacrylate-Ethylene Dimethacrylate Copolymerization. Polym J 28, 867–873 (1996). https://doi.org/10.1295/polymj.28.867
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DOI: https://doi.org/10.1295/polymj.28.867