Syndiotactic Poly(methyl methacrylate) (sPMMA)−Polybutadiene (PBD)−sPMMA Triblock Copolymers: Synthesis, Morphology, and Mechanical Properties

Abstract

A series of syndiotactic poly(methyl methacrylate) (sPMMA)−polybutadiene (PBD)−sPMMA triblock copolymers, or MBM, have been successfully synthesized by using dilithium initiators (DLi's) based on the diadduct of tert-butyllithium (t-BuLi) to either 1,3-bis(1-phenylethenyl)benzene (PEB) or m-diisopropenylbenzene (m-DIB). The efficiency of these DLi's in building up MBM triblock copolymers has been compared under the same experimental conditions, i.e., in a cyclohexane/diethyl ether mixture for the butadiene polymerization at room temperature and in a cyclohexane/THF mixture for the MMA polymerization at −78 °C. Although all the synthesized copolymers show a monomodal, symmetric, and very narrow molecular weight distribution, the MBM copolymers synthesized with the m-DIB/t-BuLi diadduct are pure triblocks and show a high tensile strength, in contrast to copolymers initiated by the PEB/t-BuLi diadducts that are of a lower tensile strength and contaminated by MB diblock copolymers. Solvent cast films of MBM p...