Partic. vol. 64 pp. 98-109 (May 2022)
doi: 10.1016/j.partic.2021.09.002

Formation of biomimetic hierarchical nanostructure in homopolymers and block copolymer ternary blend particles

Shu Kikuchi^a, Ryoka Shoji^a, Shinji Kanehashi^a,b, Guanghui Ma^a,b,c, Kenji Ogino^a,b,*

kogino@cc.tuat.ac.jp

Abstract

In order to mimic hierarchical nanostructures in nature, particles of polymer blends consisting of poly(4-butyltriphenylamine) (PBTPA), poly(methyl methacrylate) (PMMA) and PBTPA-block-PMMA were fabricated by a solvent evaporation method. Effects of the molecular weight and the chemical composition of PBTPA-b-PMMA, molecular weights of homopolymers, and the composition of the blend on the morphology were investigated. The polymer blend particle consisting of PBTPA and PMMA homopolymers exhibited thermodynamically favored core-shell structure, in which more hydrophilic PMMA-shell surrounded PBTPA-core. The addition of 10 wt% of PBTPA-b-PMMA caused the morphological transition from core-shell to Janus or inversed core-shell, in which PBTPA-shell surrounded PMMA-core, depending on the molecular weight of PBTPA segment in PBTPA-b-PMMA. When the molecular weight of PMMA segment was higher than that of PMMA homopolymer, watermelon-like particles in which small PBTPA domain less than 80 nm dispersed in the PMMA domain surrounded by PBTPA shell were observed. As the ratio of PBTPA-b-PMMA increased, the interface of the macrophase separation became obscure. At 50 wt% of the PBTPA-b-PMMA, only microphase separation was observed. The measurement of interfacial tension by pendant drop method demonstrated that PBTPA-b-PMMA lower the interfacial tension between PBTPA and the aqueous phase to the value similar to that of PMMA with the aqueous phase.

Graphical abstract

Keywords

Microsphere; Hierarchical structure; Polymer blend; Block copolymer; Solvent evaporation; Phase separation