The Largest Quasicrystalline Tiling with Dodecagonal Symmetry from a Single Pentablock Quarterpolymer of the AB(1)CB(2)D Type

摘要

A quasicrystalline tiling pattern with tile size of ca. 60 nm has been discovered in the bulk state of a four-component pentablock polymer molecule of the AS(1)IS(2)P type, where A, S, I, and P denote poly(4-vinylbenzyldimethylamine), polystyrene, polyisoprene, and poly(2-vinylpyridine), respectively. The polymer samples used were prepared by anionic polymerizations and have narrow molecular weight distribution. The sample films were obtained by an extremely slow solvent-cast process from dilute solutions of tetrahydrofuran for 14 days. It has been found by TEM observation that the quarterpolymer, AS(1)IS(2)P-4 (M-n = 149 kg/mol, phi(A)/phi(S1)/phi(I)/phi(S2)/phi(P) = 0.12/0.27/0.20/0.29/0.13), reveals two final stable structures, i.e., a 3.3.4.3.4 periodic tiling pattern as a minor component and a quasicrystalline (QC) tiling with dodecagonal symmetry as a major component, where the former includes a triangle/square number ratio of 2 and the latter has one of approximately 2.28, which is close enough to the ideal ratio, 4/root 3 (sic) 2.31, for the triangle/square random tiling of the dodecagonal QC tiling (DDQC). Two structures were also clearly proved by SAXS diffraction patterns. Here, it should be noted this QC structure having a tile side length of ca. 60 nm was created with a single block polymer molecule.