Synthesis and characterization of novel octa-arm star-block thermoplastic elastomers consisting of poly (p-chlorostyrene-b-isobutylene) arms radiating from a calix[8]arene core

Abstract

The synthesis and characterization of novel octa-arm star-blocks consisting of poly(p-chlorostyrene-b-isobutylene) (PpClSt-b-PIB) arms radiating from a calix[8]arene (C8) core are described. The synthesis was accomplished by living isobutylene (IB) polymerization induced by a novel octafunctional calix[8]arene derived initiator 1, followed by addition and living polymerization of p-chlorostyrene (pClSt). This sequential block copolymerization method allowed for precise molecular weight control of both polymeric blocks and thus gave rise to star-block thermoplastic elastomers (TPE) with an outstanding combination of mechanical and thermal properties, i.e., high tensile strengths (22 – 27 MPa) and elongations (∼500 %). Differential scanning calorimetry (DSC) indicated microphase separation into glassy PpClSt (T_g= 129°C) and rubbery PIB (T_g=−66°C) domains, and transmission electron microscopy (TEM) indicated that the PpClSt domains are dispersed in the PIB matrix.