Synthesis, characteristics and thermally induced self-assembly of silicon-based thermo/photo-responsive block copolymers prepared from monomer bearing paired side-chain azo mesogens using RAFT process

Novel silicon-based liquid crystalline (LC) monomer (CASPA) and corresponding Poly(MMA)-b-Poly(CASPA) diblock copolymers (DBCs) containing symmetric azobenzene mesogens in the side chain were successfully synthesized by coupling reaction and reversible addition-fragmentation chain transfer (RAFT) polymerization, respectively. Block copolymerization by RAFT proceeded with well-controlled manner in anisole solution involving new CASPA monomer, Poly(MMA)-RAFT macroinitiator and AIBN initiator, yielding Poly(MMA)-b-Poly(CASPA) DBCs with excellent control over molecular weights (Mw/Mn ≤ 1.39) and compositions. Chemical structures and properties of CASPA and Poly(MMA)-b-Poly(CASPA) were extensively studied using 1H NMR, FTIR, GPC, DSC, POM, AFM and GISAXS. The CASPA exhibited enantiotropic liquid crystallinity with nematic four-brush schlieren texture, while DBCs showed monotropic liquid crystallinity with batonnet textures of smectic A phase. All DBC films exhibited photochemical trans-cis isomerization and photoinduced phase transition from mesophase to isotropic phase under UV irradiation. Morphologies of DBC thin films under thermal annealing depended on volume ratio of building LC block relative to Poly(MMA) segment, DBC-2 containing approximately equal block volume fractions self-assembled into lamellar nanostructure with domain-spacing of 34 nm, whereas DBC-3 and DBC-4 possessing higher LC contents (65 wt% and 72 wt%) formed highly ordered hexagonal cylindrical nanostructures with domain-spacing ranging from 37 to 39 nm as evidence by AFM and GI-SAXS, conforming with the self-consistent field theory. Novel AB-type liquid crystalline diblock azo copolymers (DBCs) with good control over their molecular weights, compositions and architectures, were synthesized from macroinitiator Poly(MMA)-RAFT and new silicon-containing acrylate monomer CASPA carrying paired azobenzene mesogens using RAFT polymerization. The DBCs exhibited low polydispersity index, monotropic liquid crystallinity with batonnet textures of smectic A phase, photochemical trans-cis isomerization and photoinduced phase transition from mesophase to isotropic phase upon UV irradiation. In addition, DBCs formed lamellar and hexagonal cylindrical nanostructures. Thus, synthesized DBCs can be deemed as promising candidate for photonics and nanolithography applications. [Display omitted] •Microphase-separated nanostructures in azo-based LCBCs by supramolecular cooperative motion.•Photoinduced phase t