화학공학소재연구정보센터
Macromolecules, Vol.52, No.18, 7042-7051, 2019
Aqueous Self-Assembly of Amphiphilic Cyclic Brush Block Copolymers as Asymmetry-Tunable Building Blocks
Cyclic brush (cb) copolymers that are composed of a cyclic core densely grafted with radiating polymer brushes have emerged recently as innovative materials for both fundamental and practical investigations due to the unique polymer topology-generated properties. The self-assembled microstructures of amphiphilic cb block copolymers in solutions are investigated by dissipative particle dynamic simulation. A series of structures, such as rods, plates, vesicles, large compound vesicles, bilayers, and spheres, are obtained from the solutions at various solvophilic/solvophobic side chain lengths, solvophilic/solvophobic backbone lengths, and grafting densities. The structures of the representative aggregates are studied. When it comes to vesicles, we find the cavity size decreases and the membrane thickness increases as the solvophobic side chain length or solvophobic backbone length increases with fixed solvophilic side chain length and solvophilic backbone length, and their vesicle sizes are almost the same. The thickness of the plate becomes larger while its width becomes narrower as solvophobic side chain length or solvophobic backbone length increases with fixed solvophilic side chain length and solvophilic backbone length. As regards spheres, the cb amphiphiles can be approximated as cones with the cone height equivalent to the micelle core radius and the cone base area approximated as the cross-sectional area of the solvophilic brush. This model explains well all kinds of parameters (e.g., number of spheres, average number of chains per sphere, radius of gyration of the sphere and its micellar core, and thickness of the micellar shell) measured in simulations. In general, amphiphilic cb copolymers with higher backbone asymmetry and graft asymmetry (i.e., relatively larger solvophilic components) or larger grafting density are expected to form morphologies with progressively more curved interfaces, leading to a morphological transition from vesicles to plates and finally to spheres. We suppose this work could inspire researchers to design structurally complex functional material with broad applications, such as sensing, bioimaging, drug delivery, nano- or microreactors, and optoelectronics.