Abstract
The anionic ring-opening polymerization of 3,3-bis(hydroxymethyl)oxetane (BHO) was carried out using t-BuOK as an initiator in the presence of 18-crown-6-ether (18-C-6) in NMP at 180 °C, affording the corresponding hyperbranched polyethers, poly(BHO)s containing an oxetanyl group and many hydroxyl groups at the ends in 83–98% yields. Since the resulting poly(BHO)s were insoluble in common organic solvents, the poly(BHO)s were treated with acetic anhydride to obtain poly(BHO-Ac)s containing acetyl groups at the ends. The Mns and degree of branching (DB) of poly(BHO-Ac)s were in the range of 2600–4400 estimated by SEC and 0.09–0.55 calculated by 13C NMR spectroscopy, respectively. The cationic copolymerization of poly(BHO-Ac) and 3-ethyl-3-phenoxymethyloxetane (EPO) was examined using BF3OEt2 as an initiator in CHCl3 at 0 °C for 24 h, affording pseudo dendritic polymers, poly[poly(BHO-Ac)/EPO]s with Mn=11000–15000 in 58–65% yields. Furthermore, the obtained poly[poly(BHO-Ac)/EPO] was hydrolyzed with KOH to afford the poly[poly(BHO)/EPO] containing many hydroxyl groups.
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Poly(BHO) was synthesized by the anionic ring-opening polymerization in NMP at 130 °C for 24 h in 41% yield. The resulting poly(BHO) was treated with acetic anhydride to obtain the corresponding poly(BHO-Ac) with Mn = 1500, Mw/Mn = 1.35 in quantitative yield.
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Morita, A., Kudo, H. & Nishikubo, T. Synthesis of Hyperbranched Polymers by the Anionic Ring-Opening Polymerization of 3,3-Bis(hydroxymethyl)oxetane. Polym J 36, 413–421 (2004). https://doi.org/10.1295/polymj.36.413
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DOI: https://doi.org/10.1295/polymj.36.413