Abstract
Coil–coil block copolymers rarely self-assemble into flat low-curvature micelles due to the lack of proper interchain association. Here, we report a facile route to prepare disk-like micelles through the self-assembly of amphiphilic polystyrene-b-polybutadiene-b-poly(2-vinylpyridine) triblock copolymers in a mixture of acetone and cyclohexane, which shows distinct selectivity towards the PS, PB and P2VP blocks. Subtle solvation/aggregation of these blocks in this frustrating solvent system provides access to low-curvature micellar structures, and thus favors the formation of uniform disk-like micelles. Further variation of the volume ratio of the mixed solvents also leads to the emergence of other interesting morphologies, including disk arrays, disk clusters and perforated disk-like micelles. This work provides a complementary insight into the solution self-assembly of block copolymers in a view of selective solvents and demonstrates a distinctive pathway to unconventional micellar nanostructures through the use of complex solvent systems.
Highlights
Amphiphilic block copolymers (BCPs) have been demonstrated to be a family of versatile and promising materials to construct a diverse array of nanostructures.[1,2,3] In the past few decades, numerous studies have been focused on the fabrication and characteristics of various micellar morphologies.[1,2,3,4] In solution, these were mainly achieved by adjusting the chemistry and composition of BCPs, solvent selectivity, and external conditions,[2,5] such as temperature,[6,7] pH7,8 and salts.[8,9,10] Besides, complex micellar structures, including toroids,[11,12] janus[4] and multicompartment micelles,[13,14,15] can be realized by more exquisite self-assembly of diblock and triblock copolymers.Among these morphologies, disk-like micelles were relatively rarely observed and so far were generally fabricated by the use of (i) rod–coil BCPs with a conjugated block;[16,17,18] (ii) crystalline–coil BCPs with a crystallization block (through crystallization-driven self-assembly)[19,20,21] and (iii) polypeptide-derived BCPs.[22,23,24] The presence of a rigid core-forming block appeared to be essential for the formation of at (low-curvature) self-assembly nanostructures
We report a facile route to prepare disk-like micelles through the self-assembly of amphiphilic polystyrene-b-polybutadiene-b-poly(2-vinylpyridine) triblock copolymers in a mixture of acetone and cyclohexane, which shows distinct selectivity towards the PS, PB and P2VP blocks
This work provides a complementary insight into the solution self-assembly of block copolymers in a view of selective solvents and demonstrates a distinctive pathway to unconventional micellar nanostructures through the use of complex solvent systems
Summary
Amphiphilic block copolymers (BCPs) have been demonstrated to be a family of versatile and promising materials to construct a diverse array of nanostructures.[1,2,3] In the past few decades, numerous studies have been focused on the fabrication and characteristics of various micellar morphologies.[1,2,3,4] In solution, these were mainly achieved by adjusting the chemistry and composition of BCPs, solvent selectivity, and external conditions,[2,5] such as temperature,[6,7] pH7,8 and salts.[8,9,10] Besides, complex micellar structures, including toroids,[11,12] janus[4] and multicompartment micelles,[13,14,15] can be realized by more exquisite self-assembly of diblock and triblock copolymers.Among these morphologies, disk-like micelles were relatively rarely observed and so far were generally fabricated by the use of (i) rod–coil BCPs with a conjugated block;[16,17,18] (ii) crystalline–coil BCPs with a crystallization block (through crystallization-driven self-assembly)[19,20,21] and (iii) polypeptide-derived BCPs.[22,23,24] The presence of a rigid core-forming block appeared to be essential for the formation of at (low-curvature) self-assembly nanostructures. We report a facile route to prepare disk-like micelles through the self-assembly of amphiphilic polystyrene-b-polybutadiene-b-poly(2-vinylpyridine) triblock copolymers in a mixture of acetone and cyclohexane, which shows distinct selectivity towards the PS, PB and P2VP blocks.
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