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Deprotection of the tert-butyl ester of poly(n-butyl methacrylate-b-tert-butyl methacrylate) under flow conditions by heterogeneous catalysts leading to acidic diblock copolymers

Polymer Journal volume 57, pages 215–224 (2025)Cite this article

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Abstract

The selective deprotection of tertiary-butyl (tert-Bu) esters in diblock copolymers of polyesters was studied via heterogeneous acid catalysts and flow reactors. Diblock copolymers composed of n-butyl methacrylate (nBMA) as the 1st block and tert-butyl methacrylate (tBMA) as the 2nd block were prepared by group transfer polymerization (GTP) using diisobutyl ketone (DIBK) as the solvent. The selective deprotection of the tert-Bu ester in the poly(nBMA-b-tBMA) under flow conditions was examined. The results show that the selective deprotection of the tert-Bu ester was achieved successfully via an acidic macroreticular polymeric catalyst, Amberlyst 35DRY, packed in a flow reactor. The deprotection process required 15 min of residence at 180 °C to yield acidic poly(nBMA-b-methacrylic acid) with a polydispersity index (Ð) value as low as 1.28. The durability of the catalyst was also examined during a continuous process for 1500 min by an HPLC pump.

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Acknowledgements

We wish to express our appreciation to Tayca Corporation for providing TAYCACURE SAC-6. This work was supported by Grants-in-Aid for Scientific Research from the Japan Society for the Promotion of Science (JSPS) (24K08433 and 19H02722). IR wishes to thank NSTC (112-2113-MA49-013) and the Centre for Emergent Functional Matter Science at NYCU for additional support (112R10194C).

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Authors and Affiliations

  1. Department of Chemistry, Graduate School of Science, Osaka Metropolitan University, 3-3-138 Sugimoto-cho Sumiyoshi-ku, Osaka, Osaka, 558-8585, Japan

    Ryo Takabayashi & Takahide Fukuyama

  2. BYK-Chemie GmbH, Abelstrasse 45, 46483, Wesel, Germany

    Stephan Feser

  3. BYK Japan KK, 3-29 Ichigaya-Honmura-cho, Shinjuku-ku, Tokyo, 162-0845, Japan

    Hiroshi Yonehara

  4. Organization for Research Promotion, Osaka Metropolitan University, 1-1 Gakuen-cho Naka-ku, Sakai, Osaka, 599-8531, Japan

    Mamoru Hyodo & Ilhyong Ryu

  5. Department of Applied Chemistry, National Yang Ming Chiao Tung University (NYCU), Hsinchu, 30010, Taiwan

    Ilhyong Ryu

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  1. Ryo Takabayashi
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Correspondence to Takahide Fukuyama.

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Takabayashi, R., Feser, S., Yonehara, H. et al. Deprotection of the tert-butyl ester of poly(n-butyl methacrylate-b-tert-butyl methacrylate) under flow conditions by heterogeneous catalysts leading to acidic diblock copolymers. Polym J 57, 215–224 (2025). https://doi.org/10.1038/s41428-024-00978-7

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