Triblock copolymer based thermoreversible gels. 1. Self-association of sPMMA end-blocks in o-xylene and viscoelasticity of the gels

Syndiotactic poly(methyl methacrylate) (sPMMA)-polybutadiene (PBD)-sPMMA triblock copolymers, or MBM, have been studied in the presence of o-xylene which is a selective solvent for the central PBD block. Syndiotactic PMMA is known to self associate in o-xylene. The central PBD sequence does not prevent the self-association of sPMMA from occurring. Actually, this phenomenon contributes to the stability of the gels formed at room temperature. An endotherm is observed at 35°C, which is responsible for a gel-sol transition. The original solutions have been heated up to 80°C and then rapidly cooled down below 35°C and maintained at 10, 20 and 25°C respectively. The self-association of the sPMMA outer blocks, and thus the liquid-solid transition, have been studied at each of these temperatures. Dependence of the gel viscosity on frequency and temperature effects on viscoelasticity has also been investigated.