Spontaneous self-assembly of block copolymers or hybrid macromolecules on surfaces or in solutions to form precise microphase segregated structures has been the strategy behind many potential and useful applications of nano-materials such as nanoporous membranes, memory devices, drug-delivery agents, and antireflective coatings to name a few. Designing and synthesizing stimuli-responsive, multi-block polymers by stitching together well-defined and discrete polymer units/blocks having dissimilar properties using a stimuli-responsive linker might lead to new nanostructured materials with enhanced functionality and properties. Herein, we report the design and synthesis of a well-defined photo-sensitive PVDMA-polybutadiene polymer system that has been stitched together by photo-responsive o-nitro-benzyl (NB) alcohol derivatized linkers. In this current work, we further exploit the base sensitivity of the reactive VDMA block to form amphiphilic block polymers, which self-assemble in appropriate solvent systems and have the potential of undergoing complete photo-triggered disassembly.First, a well-defined hydroxyl end-functional polybutadiene (PBd-OH) with low PDI was synthesized via living anionic polymerization of 1,3-butadiene and then end-capped with ethylene oxide. For the controlled synthesis of PVDMA, a new NB-functionalized RAFT agent was synthesized, which was subsequently used to mediate the polymerization of VDMA thereby producing a well-defined NB-end functionalized PVDMA with low PDI.    PBd-OH was reacted further with a di-isocyanato-NB-oligo-urethane to form a polybutadiene based nitrobenzyl isocyanate (PBd-NB-NCO). Subsequently, the PBd-NB-NCO was reacted with the NB-end functional PVDMA thereby generating a PBd-NB-PVDMA multicomponent polymer system. The products obtained in this multi-step synthesis were characterized and confirmed via FTIR, 1H NMR, and 13C NMR spectroscopies, and GPC-MALLS.

Poly(vinyldimethylazlactone)-<i>?block</i>?-polybutadiene: Creating modular photosensitive materials

246th National Meeting (2013)

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Poly(vinyldimethylazlactone)-?block?-polybutadiene: Creating modular photosensitive materials