Synthesis and characterization of novel ABA-type azobenzene-containing tri-block copolymers from telechelic polystyrene

Abstract

The telechelic polystyrene (tPS) was used as a macro-reversible addition fragmentation chain transfer (RAFT) agent to prepare the ABA-type tri-block copolymers (TBCs), poly{4-[4-(11-acryloyloxyundecyloxy)phenylazo]benzonitrile}-b-polystyrene-b-poly{4-[4-(11-acryloyloxyundecyloxy)phenylazo]benzonitrile} [poly(AUPAB)-b-PS-b-poly(AUPAB)] with 4-[4-(11-acryloyloxyundecyloxy)phenylazo]benzonitrile (AUPAB) as a monomer by the RAFT polymerization process. The poly(AUPAB) was used as a reference to probe the role of polystyrene block in poly(AUPAB)-b-PS-b-poly(AUPAB) macromolecular chain. The TBCs were characterized by spectral techniques, thermal analysis, and polarizing optical microscopic studies and compared the results with individual blocks, poly(AUPAB), and tPS. The TBCs exhibited higher thermal stability and liquid crystal-isotropic phase transition peak temperature (TLC-I), and glass transition temperature (Tg) values compared to the poly(AUPAB). TBC TLC-I value was dependent on the AUPAB wt% in macromolecular chain. Furthermore, the acquired results by optical microscopy suggest that after incorporation of the polystyrene block in acrylate-based pendant azobenzene polymer chain resulted in lower domain size of focal conic texture, which is characteristic of smectic-A liquid crystalline phase compared to the homopolymer. The photophysical properties of the TBCs were similar to those of the poly(AUPAB). Microphase-separated nano-segregation was observed in annealed thin films of TBCs.