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A multivinyl template monomer with 20.4 methacryloyl groups was synthesized with β-cyclodextrin by esterification of hydroxyl groups with methacrylic anhydride. Copper-mediated atom transfer radical polymerization of the template monomer was carried out with methyl 2-bromopropionate, 2,2‘-dipyridyl, and CuBr as an initiator, a ligand, and a catalyst, respectively. The effects of solvent and polymerization temperature on the degree of polymerization in the template monomer were investigated by kinetic analysis of conversion and the molecular weight of methacrylic acid oligomers obtained by hydrolysis of the polymerized products by GPC. Poly(methacrylate) oligomers with 7 and 14 degrees of polymerization were synthesized along the rims of the template monomer-3 by ATRP in a methanol/water mixture (water 10 vol %) at 50 °C. The observed propagation rate constant, k obs, of the methacryloyl group in the methanol/water mixture (water 10 vol %) at 50 °C was 11.3 × 10-5/s.

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Poly(methacrylic acid) (PMAA) oligomers were synthesized by combining template polymerization and copper‐mediated atom transfer polymerization with multivinyl monomer of β‐cyclodextrin (CD) having 20.4 methacryloyl groups on both primary and secondary hydroxyl group sides of CD scaffold, with 1,3‐dibromobutane as an initiator. The initiation and propagation sites of polymerized sequence of β‐CD were connected by postpolymerization of polymerized products with CuBr and tris[(2‐dimethylamino)ethyl]amine (Me6TREN) in a methanol/water mixture of 10 wt % of water. Polymerized and cyclized sequences, PMAA oligomers formed on the primary and the secondary hydroxyl group sides, were detached from β‐CD scaffold by hydrolysis. Molecular weights of PMAA oligomers were measured by GPC and matrix assisted laser desorption ionization time‐of‐flight mass measurement. By 1H NMR measurements, it was found that three types of cyclic PMAA were obtained by postpolymerization. The cyclization preferentially occurred on the secondary hydroxyl group side than on the primary hydroxyl group side. From the structures of cyclic PMAA, two reaction positions were proposed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6262–6271, 2005