"Living" radical network polymerization: Alkoxyamine-mediated copolymerization of dimethacrylates with styrene

The kinetics of network copolymerization of styrene with dimethacrylates in the presence of alkoxyamines as initiators of "living" radical polymerizat ion (iniferters) was studied. Conclusive evidence that the copolymerization proceeds in the "living" chain mode was obtained with the techniques of pr ecision isothermal calorimetry, ESR, and rheokinetics. This conclusion is b ased on the dramatic shift of the conversion corresponding to the formation of a continuous polymer network to the region of high degrees of polymeriz ation (>10%) as compared to the conventional network polymerization (<1%), as well as on the high concentrations of a nitroxide radical, the inhibitor , during the polymerization process at simultaneously retained fairly high reaction rates.