Synthesis and self-assembly of copolymers

Abstract

This research outlines the preparation of nanostructured materials by the self­assembly of functional block copolymers in both the bulk phase and in solution. The polymer poly(solketal methacrylate )-block-poly(2-hydroxyethyl methacrylate )-block­poly(allyl methacrylate) [PSMA-b-PHEMA-b-PAMA] was prepared by sequential living anionic polymerization and formed spherical mixed corona micelles in toluene with the PSMA and PAMA blocks sharing the corona of the micelles. Following partial cinnamation of the HEMA block to CEMA, permanent nanospheres were formed by photo­dimerization of the core CEMA moieties. Tellurium mediated living radical polymerization (TERP) was shown to be useful in the controlled polymerization of the homopolymer poly(N-isopropyl acrylamide) (PNIP AM), the random copolymer [P(NIP AM-r-AA)] and the block copolymer PNIPAM­b-PHEA-TMS, where AA denotes acrylic acid and PHEA-TMS denotes poly(2- trimethylsilylethyl acrylate). The PHEA block of the diblock copolymer was fully cinnamated to give [PNIPAM-b-PCEA], with a PNIPAM volume fraction of 29.6%. The bulk phase morphology of the PNIPAM-b-PCEA copolymer revealed that the PNIPAM block formed cylindrical domains within a matrix of PCEA.