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

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, ϕ A /ϕ S1 /ϕ I /ϕ S2 /ϕ 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/ 3 ≑ 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.