Issue 10, 2021

Amphiphilic random and random block terpolymers with PEG, octadecyl, and oleyl pendants for controlled crystallization and microphase separation

Abstract

Controlled crystallization and microphase separation of multi-component copolymers are one possibility to construct precise nanostructures in functional polymer materials. In this paper, we report the crystallization and sub-10 nm microphase separation of amphiphilic random and random block terpolymers in the solid state. By using living radical copolymerization, we designed A/B/C random terpolymers and A/C–B/C random block terpolymers, into which a hydrophobic and crystalline octadecyl group (A), a hydrophobic and amorphous oleyl group (B), and hydrophilic poly(ethylene glycol) (C) were randomly and/or site-selectively introduced as side chains. The crystallization and melting temperatures of A/B/C random terpolymers gradually decreased with increasing content of amorphous oleyl units. The random terpolymers with a relatively small amount of oleyl units induced microphase separation of the side chains to form lamellae with hydrophilic and hydrophobic alternating layers in a domain spacing of about 6 nm, while the lamellar structure was gradually disordered by increasing oleyl groups. In contrast, A/C–B/C random block terpolymers efficiently induced crystallization of the octadecyl groups even in the presence of random copolymer segments with amorphous oleyl units. The random block copolymers opened the possibility of controlling microphase separation from the side chains of the random copolymers and the main chains of the block copolymers.

Graphical abstract: Amphiphilic random and random block terpolymers with PEG, octadecyl, and oleyl pendants for controlled crystallization and microphase separation

Supplementary files

Article information

Article type
Paper
Submitted
27 Oct 2020
Accepted
02 Dec 2020
First published
08 Dec 2020

Polym. Chem., 2021,12, 1439-1447

Amphiphilic random and random block terpolymers with PEG, octadecyl, and oleyl pendants for controlled crystallization and microphase separation

S. Imai, Y. Ommura, Y. Watanabe, H. Ogawa, M. Takenaka, M. Ouchi and T. Terashima, Polym. Chem., 2021, 12, 1439 DOI: 10.1039/D0PY01505A

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