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Double-cyclopolymerization using trifunctional incompletely condensed cage silsesquioxane with methacryloyl groups


A tris(methacrylethoxypropyldimethylsiloxy)-heptaisobutyl-substituted corner-opening typed cage silsesquioxane (CO-POSS) monomer (3) was prepared as a pale-yellow liquid by hydrosilylation of trisdimetylsilyl-capped heptaisobutyl-substituted trisilanol (1) with ethylene glycol monoallyl ether and subsequent reaction with methacryloyl chloride. Free-radical and reversible addition-fragmentation chain transfer (RAFT) polymerization was performed using the newly prepared trifunctional CO-POSS monomer (3). Although the free radical polymerization of 3 showed gelation at a monomer concentration of 0.2 M, the RAFT polymerization of 3 afforded a homogeneous solution at the same monomer concentration. The optical transmittances of the cast films for the resulting soluble polymers were over 95% in the visible region. Decreasing the number of dangling chains in the polymer improved the thermal stability and Martens’ hardness. Introducing the CO-POSS unit in the side chain significantly improved the surface hydrophobicity and no surface reorganization occurred even though the film was in contact with water for several days.

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This work was supported by Grant-in-Aid for Scientific Research (No. 19H02764) from the Ministry of Education, Culture, Sports, Science, and Technology, Government of Japan. We thank Prof. Tsuyoshi Kawai, Ms Yoshiko Nishikawa, and Mieko Yamagaki of Nara Institute of Science and Technology for performing MALDI-TOF-MS supported by ARIM Program of the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan.

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Correspondence to Kensuke Naka.

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Nakano, T., Okamoto, K., Imoto, H. et al. Double-cyclopolymerization using trifunctional incompletely condensed cage silsesquioxane with methacryloyl groups. Polym J 55, 193–201 (2023).

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