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SYNOPSISDifferential scanning calorimetry together with dynamic mechanical analysis were employed to investigate the crystallinity and the miscibility in poly (ethylene oxide) /crosslinked poly ( methyl methacrylate) semi-IPN ( interpenetrating polymer networks). The crystallinity of poly( ethylene oxide) in the semi-IPN is found to depend on the crosslink density of PMMA as well as the overall content of PEO. Of special interest is that an increase in the crosslink density tends to increase the crystallinity contrary to our expectation, indicating crystallization and phase separation may proceed simultaneously during IPN formation. The investigation of glass transition behaviors with dynamic mechanical analysis suggests phase separation (i.e., there exist two amorphous phases: one PEO-rich phase, the other a PMMA-rich phase). 0 1993 John Wiley & Sons, Inc.

Nitroxide-mediated homopolymerization of styrene (St) and copolymerization of styrene and acrylonitrile (An) were monitored respectively by electron spin resonance and Fourier transform infrared technique in situ, and the polymerization kinetics was investigated in detail. Homopolymerization of St was well controlled in the presence of 4-hydroxyl-2,2,6,6-tetramethyl-l-piperidinyloxy (HTEMPO, N*) at high temperature. The initiation reactions and polymerization rates were changed by varying initiators, such as benzoyl peroxide (BPO), 2,2-azobis-isobutylonitrile (AIBN) and dicyclohexyl dicarbonate peroxide (DCPO) because of the different half-period values of the initiators. For the St system containing the DCPO with longer half-period value, the reaction rate was enhanced and the final conversion was increased because the larger amount of the DCPO residual released continuously the excess radicals to increase growing radical concentration. But the polydispersity of the resulting polymer became somewhat larger. The copolymerization of St and An with AIBN as initiator in the presence of HTEMPO was also tamed in the living fashion of stable free radical polymerization in the range of the total monomer conversion below 40%. The hydrogen-abstracting effect on the pen-