Core–Shell Double Gyroid Structure Formed by Linear ABC Terpolymer Thin Films

Abstract

The synthesis and self-assembly in thin-film configuration of linear ABC triblock terpolymer chains consisting of polystyrene (PS), poly(2-vinylpyridine) (P2VP), and polyisoprene (PI) are described. For that purpose, a hydroxyl-terminated PS-b-P2VP (45 kg mol ) building block and a carboxyl-terminated PI (9 kg mol ) are first separately prepared by anionic polymerization, and then are coupled via a Steglich esterification reaction. This quantitative and metal-free catalyst synthesis route reveals to be very interesting since functionalization and purification steps are straightforward, and well-defined terpolymers are produced. A solvent vapor annealing (SVA) process is used to promote the self-assembly of frustrated PS-b-P2VP-b-PI chains into a thin-film core-shell double gyroid (Q , space group: Ia3¯d) structure. As terraces are formed within PS-b-P2VP-b-PI thin films during the SVA process under a CHCl vapor, different plane orientations of the Q structure ((211), (110), (111), and (100)) are observed at the polymer-air interface depending on the film thickness.

Self‐Assembly of Nonfrustrated ABCBA Linear Pentablock Terpolymers

“…[ 23,24 ] More complex microstructures of AB diblock copolymers have been discovered under certain conditions from recent experiments and simulations, including the helical structures [ 25–28 ] and the Frank–Kasper σ phase. [ 29 ] Besides, with the advance in synthetic techniques, adding a third component [ 3–7,30–55 ] and/or modifying the block numbers [ 8–13,16–18,56–68 ] to the linear block chains could be achieved. The more complex block copolymers provide opportunities to obtain diverse morphologies.…”

“…The self‐assembly behaviors of ABC triblock copolymers become more complicated, producing intricate structures, such as the hierarchical structure‐within‐structure morphologies. [ 3–7,30–55 ] According to the relative interactions between the three different blocks, the linear ABC triblock copolymers could be generally classified as frustrated and nonfrustrated. [ 30 ] For the frustrated ABC triblock copolymers, the interaction parameter between the two end blocks is smaller than the others ( χ AC << χ AB , χ BC ), thus the end A and C blocks tend to contact with each other.…”

Core–Shell and Zigzag Nanostructures from a Thin Film Silicon-Containing Conformationally Asymmetric Triblock Terpolymer

“…Linear ABC triblock terpolymers are particularly attractive because they can produce a much wider spectrum of accessible morphologies than diBCPs, − with expanded opportunities for functionalization, , and their cost of synthesis is similar to that of AB or ABA BCPs. By designing combinations of chain architecture, block sequence, degree of polymerization, and volume fraction, the interaction parameters and morphologies can be selected. , Multiphase and core–shell morphologies can be formed analogous to the well-studied diBCPs morphologies (lamellae, perforated lamellae, gyroids, cylinders, and spheres), ,,, and nanoscale patterns can be produced by removing one or two blocks. In particular, the selective removal of the shell and matrix of core–shell structures is expected to yield asymmetric line-space patterns.…”

“…By designing combinations of chain architecture, block sequence, degree of polymerization, and volume fraction, the interaction parameters and morphologies can be selected. 33,34 Multiphase and core−shell morphologies can be formed analogous to the well-studied diBCPs morphologies (lamellae, perforated lamellae, gyroids, cylinders, and spheres), 31,33,35,36 and nanoscale patterns can be produced by removing one or two blocks. In particular, the selective removal of the shell and matrix of core−shell structures is expected to yield asymmetric line-space patterns.…”

Nanoscale Archimedean Tilings Formed by 3‐Miktoarm Star Terpolymer Thin Films

“…Therefore, CO 2 was bubbled through the reactive media at the end of the reaction to achieve the functionalization of the PI homopolymer . The desired terpolymers were subsequently produced via a Steglich esterification between the hydroxy mid‐functionalized PS‐ b ‐P2VP and two different carboxylic acid–terminated PI (PI—COOH) chains with N , N ′‐diisopropylcarbodiimide (DIC) as coupling reagent and N , N ‐dimethyl‐4‐pyridinaminium 4‐methylbenzenesulfonate (DPTS) as catalyst in order to increase the ester reaction yield …”