Effect of the structure of a three-dimensional network of the polymer triethylene glycol dimethylacrylate on the kinetics of its radical polymerization☆

Abstract NMR spectroscopy has been used to measure the spin-lattice relaxation times T 1 of 13 C nuclei of triethylene glycol dimethacrylate during its three-dimensional radical polumerization. It is shown that in the interval of extents of conversion from the start of gelation (∼1%) to the transition of the reaction to the regime of auto-inhibition (∼20%) a structure of the type of a three-dimensional network swollen in the oligomer prevails. The influence of the glassy microheterogeneous formation on the mobility of the oligomer and the chain propagation rate constant is insignificant. The stabilization of the asymmetrical associates of the oligomer by the three-dimensional polymer network may be the cause of gelation for low extents of conversion.