Synthesis of AB block and A2B2 and A3B3 miktoarm star-shaped copolymers using ω-end-functionalized poly(methyl methacrylate) with a hydroxyl group prepared by organocatalyzed group transfer polymerization

Ofosu-Twum Eric; Yougen Chen; Kenji Takada; Shin-ichiro Sato; Toshifumi Satoh; Toyoji Kakuchi

doi:10.1039/C5PY01112D

Synthesis of AB block and A₂B₂ and A₃B₃ miktoarm star-shaped copolymers using ω-end-functionalized poly(methyl methacrylate) with a hydroxyl group prepared by organocatalyzed group transfer polymerization†

Ofosu-Twum Eric,^a Yougen Chen,^b Kenji Takada,^a Shin-ichiro Sato,^c Toshifumi Satoh^c and Toyoji Kakuchi*^bc

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* Corresponding authors

^a Graduate School of Chemical Sciences and Engineering, and Hokkaido University, Sapporo, Japan

^b Frontier Chemistry Center, Hokkaido University, Sapporo, Japan

^c Division of Applied Chemistry, Faculty of Engineering, Hokkaido University, Sapporo, Japan
E-mail: kakuchi@poly-bm.eng.hokudai.ac.jp

Abstract

The synthesis of miktoarm star-shaped polymers has been studied using various poly(methyl methacrylate)s (PMMAs) functionalized with a hydroxyl group, which were prepared by organocatalyzed group transfer polymerization (GTP) of methyl methacrylate, followed by Mukaiyama aldol-type termination of a silyl ketene acetal (SKA) moiety at the living PMMA end. To further elucidate this method, the effects of the employed catalysts, polymer chain length, and benzaldehyde derivatives on the ω-end-functionalization efficiency (%F) were investigated in detail. The electrophilic termination of the living PMMA end with benzaldehyde as the terminator produced a structurally defect-free ω-end-functionalized PMMA with a hydroxyl group (PMMA-OH). In addition, a two-arm PMMA with two hydroxyl groups (PMMA₂-OH₂) and a three-arm star-shaped PMMA with three hydroxyl groups (PMMA₃-OH₃), whose hydroxyl groups were located at the polymer chain centers, were prepared using terephthalaldehyde and benzene-1,3,5-tricarbaldehyde, respectively. The PMMA-OH, PMMA₂-OH₂, and PMMA₃-OH₃ obtained were then used as macroinitiators for the ring-opening polymerization (ROP) of D-lactide (DLA) to synthesize an AB block copolymer, and A₂B₂ and A₃B₃ type miktoarm copolymers.

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Article information

DOI: https://doi.org/10.1039/C5PY01112D
Article type: Paper
Submitted: 16 Jul 2015
Accepted: 13 Sep 2015
First published: 15 Sep 2015

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Polym. Chem., 2015,6, 7841-7850

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Synthesis of AB block and A₂B₂ and A₃B₃ miktoarm star-shaped copolymers using ω-end-functionalized poly(methyl methacrylate) with a hydroxyl group prepared by organocatalyzed group transfer polymerization

O. Eric, Y. Chen, K. Takada, S. Sato, T. Satoh and T. Kakuchi, Polym. Chem., 2015, 6, 7841 DOI: 10.1039/C5PY01112D

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Polymer Chemistry