Abstract: | Glass transition temperatures Tg of methyl methacrylate/butyl acrylate copolymers obtained by means of atom‐transfer radical polymerization are measured using differential scanning calorimetry. Due the nature of this polymerization method an increase in molecular weight is produced as the reaction progresses, which gives rise to an increase in Tg. Simultaneously, a composition gradient with the enrichment of butyl acrylate causes a decrease in Tg. These opposite effects almost compensate each other and, therefore, no influence on the molecular weight at M?n < 10000 is found. This fact allows the application of the Johnston's equation and the Mayo‐Lewis terminal model to describe and predict the variation in Tg with copolymer conversion for the copolymers and under the experimental conditions investigated. |