Formation of biomimetic hierarchical nanostructure in homopolymers and block copolymer ternary blend particles --颗粒学报PARTICUOLOGY

Kikuchi, S., Shoji, R., Kanehashi, S., Ma, G., & Ogino, K. (2022). Formation of biomimetic hierarchical nanostructure in homopolymers and block copolymer ternary blend particles. Particuology, 64, 98-109. https://doi.org/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 *}

a Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Nakacho, Koganei-shi, Tokyo 184-8588, Japan
b Institute of Global Innovation Research, Tokyo University of Agriculture and Technology, 2-24-16 Nakacho, Koganei-shi, Tokyo 184-8588, Japan
c State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100080, China

10.1016/j.partic.2021.09.002

Volume 64, May 2022, Pages 98-109

Received 1 June 2021, Revised 18 August 2021, Accepted 5 September 2021, Available online 16 September 2021, Version of Record 17 December 2021.

E-mail: kogino@cc.tuat.ac.jp

Highlights

• Polymer blend particles with hierarchical nanostructure were fabricated.

• Addition of block copolymer to homopolymer blends changed the morphology.

• Resulting morphologies were dependent on the molecular weight of each segment.

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

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