Issue 22, 2023

Installation of the adamantyl group in polystyrene-block-poly(methyl methacrylate) via Friedel–Crafts alkylation to modulate the microphase-separated morphology and dimensions

Abstract

Although polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) is the most widely employed template and scaffold for constructing nanoscale patterns, its relatively small Flory–Huggins interaction parameter makes it challenging to realize microphase-separated structures with a periodicity (or domain spacing) of less than 20 nm. The direct post-polymerization modification of PS-b-PMMA can resolve this issue. In this study, we present the PS block post-polymerization modification of commercially available PS-b-PMMA through a metal-free Friedel–Crafts alkylation reaction with adamantanols to modulate its microphase-separated morphology and dimensions. The adamantyl group can be easily installed on the PS benzene ring, which increases the incompatibility with the PMMA block, enabling ordered microphase-separated structures, including lamellar, gyroid and hexagonally close-packed cylindrical structures, from low-molecular-weight PS-b-PMMA. Notably, a periodicity as low as approximately 16 nm was realized with this strategy, which is much lower than the lowest accessible periodicity of pristine PS-b-PMMA. Furthermore, we observed additional benefits from the installation of the adamantyl group, such as increased thermal stability, glass transition temperature and etching contrast.

Graphical abstract: Installation of the adamantyl group in polystyrene-block-poly(methyl methacrylate) via Friedel–Crafts alkylation to modulate the microphase-separated morphology and dimensions

Supplementary files

Article information

Article type
Paper
Submitted
01 feb 2023
Accepted
24 mar 2023
First published
29 mar 2023
This article is Open Access
Creative Commons BY-NC license

Polym. Chem., 2023,14, 2675-2684

Installation of the adamantyl group in polystyrene-block-poly(methyl methacrylate) via Friedel–Crafts alkylation to modulate the microphase-separated morphology and dimensions

T. Isono, E. Baba, S. Tanaka, K. Miyagi, T. Dazai, F. Li, T. Yamamoto, K. Tajima and T. Satoh, Polym. Chem., 2023, 14, 2675 DOI: 10.1039/D3PY00113J

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements