title: Self-assembly of cyclic rod-coil diblock copolymers.
abstract: The phase behavior of cyclic rod-coil diblock copolymer melts is investigated by the dissipative particle dynamics simulation. In order to understand the effect of chain topological architecture better, we also study the linear rod-coil system. The comparison of the calculated phase diagrams between the two rod-coil copolymers reveals that the order-disorder transition point (χN)ODT for cyclic rod-coil diblock copolymers is always higher than that of equivalent linear rod-coil diblocks. In addition, the phase diagram for cyclic system is more "symmetrical," due to the topological constraint. Moreover, there are significant differences in the self-assembled overall morphologies and the local molecular arrangements. For example, frod = 0.5, both lamellar structures are formed while rod packing is different greatly in cyclic and linear cases. The lamellae with rods arranged coplanarly into bilayers occurs in cyclic rod-coil diblocks, while the lamellar structure with rods arranged end by end into interdigitated bilayers appears in linear counterpart. In both the lamellar phases, the domain size ratio of cyclic to linear diblocks is ranged from 0.63 to 0.70. This is attributed to that the cyclic architecture with the additional junction increases the contacts between incompatible blocks and prevents the coil chains from expanding as much as the linear cases. As frod = 0.7, the hexagonally packed cylinder is observed for cyclic rod-coil diblocks, while liquid-crystalline smectic A lamellar phase is formed in linear system. As a result, the cyclization of a linear rod-coil block copolymer can induce remarkable differences in the self-assembly behavior and also diversify its physical properties and applications greatly.
authors.affiliation: Department of Physics, Wenzhou University, Wenzhou 325035, People's Republic of China. helinli155@163.com
authors.forename: Linli
authors.initials: L
authors.lastname: He
authors.forename: Zenglei
authors.initials: Z
authors.lastname: Chen
authors.forename: Ruifen
authors.initials: R
authors.lastname: Zhang
authors.forename: Linxi
authors.initials: L
authors.lastname: Zhang
authors.forename: Zhouting
authors.initials: Z
authors.lastname: Jiang
mesh_terms: D056004:Molecular Dynamics Simulation; D011108:Polymers / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D011108:Polymers