Mechanism of formation of oligo(carbonate methacrylate)s from bis(chloroformate)s of glycols and hydroxyl-containing telogens

Composition of oligo(carbonate methacrylate)s formed by the reaction of diethylene glycol his(chloroformate) with ethylene glycol monomethacrylate depends on the nature of the catalyst, tert-amine or aqueous alkali. The type of catalyst controls the phase state of the reaction mixture and, as a consequence, a set of side reactions. For homogeneous reactions that take place in the presence of pyridine, the hydrolysis of his(chloroformate) leading to the formation of higher oligomer homologs is the only side reaction. In a heterophase organoaqueous medium, alkali-catalyzed hydrolysis of telogen and its transesterification lead to ethylene glycol and the corresponding dimethacrylate. The presence of higher oligomer homologs in the product of the homogeneous reaction is responsible for its higher viscosity and density and the enhanced mechanical properties of the resulting network polymer.