By employing anionic techniques, methacrylate containing block systems with controlled compositions, molecular weights and narrow molecular weight was synthesized. Subsequent hydrolysis of the ester functionality to the carboxylic acid or carboxylate group by potassium superoxide or the acid catalyzed hydrolysis of t-butyl methacrylate blocks has a profound effect on solution and bulk mechanical behavior. The synthesis of the t-butyl methacrylate is facilitated by the enhanced t-butyl methacrylate anion stability at room temperature. In addition, the protected nature of the carbonyl group eliminates the necessity to cap the first block in order to prevent carbonyl attack during crossover. The synthesis of various substituted styrenes or diene block copolymers with alkyl methacrylates is discussed.