Ladder-like polymer synthesized by template polymerization of poly(2-methacryloyloxyethyl methacrylate): architectural effect of ladder-like polymer on glass transition temperature

Ladder-like polymers with different degrees of ladder were synthesized by copper-mediated atom transfer radical polymerization (ATRP) of poly(2-methacryloyloxyethyl methacrylate) with alpha,alpha'-dibromo-p-xylene, as a bifunctional initiator. The livingness of ATRP was confirmed by kinetic analysis. The size of ladder-like sequence in ladder-like polymer was controlled by the hydrolysis. It was found that the remaining ester group was preferentially hydrolyzed and then the ester group of the ladder unit was hydrolyzed due to the high mobility of the remaining ester groups and high chemical resistance of the ladder-like unit. The products are block copolymers with different content of ladder-like sequences in the range of 18.2-73.5 mol%. All products showed two different glass transition temperatures (Tgs) and their high Tg was owing to the ladder-like sequence. The segregation of cyclic units in the ladder-like polymers was effective in improving the thermal stability of products. Copyright (C) 2008 John Wiley & Sons, Ltd.