Abstract
The radical copolymerization of vinylbenzyl-terminated poly(2-methyl-2-oxazoline) macromonomers (1 Me-n; n (degree of polymerization) = 3, 15, 28, 31) (M1) with vinyl monomers (M2), i.e., methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) was performed using 2, 2′-azobis(isobutyronitrile) (AIBN) as an initiator at 60°C in ethanol (EtOH). CD3OD, or CD3CN. Monomer reactivity ratios r1 and r2 were evaluated based on the terminal model. Copolymerization of 1 Me-3 with MMA gave reactivity ratios as r1=1.86±1.15 and r2=0.07±0.03 in EtOH, and r1=1.25±0.10 and r2=0.18±0.05 in CD3OD, exhibiting remarkably higher reactivity of the Me-3 compared with the comonomers and corresponding small monomer, styrene. In CD3CN, however, copolymerization of 1 Me-3 with MMA gave r1=0.41±0.10 and r2=0.66±0.10, showing rather lower reactivity of the macromonomer compared with MMA. With HEMA, 1 Me-3 showed high reactivity in EtOH, i.e., r1=1.44±0.10, r2=0.04±0.02. The reactivity of HEMA against the macromonomers was found higher than that of MMA, possibly due to affinity to aprotic poly(2-methyl-2-oxazoline) graft chains on growing species. The high reactivity of 1 Me-n in EtOH and CD3OD would be due to the formation of a micelle-like state. The reactivity of macromonomers decreased generally with chain length (n).
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Shimano, Y., Sato, K., Fukui, D. et al. Reactivity in the Radical Copolymerization of Poly(2-oxazoline) Macromonomers with Methacrylate Monomers. Polym J 31, 296–302 (1999). https://doi.org/10.1295/polymj.31.296
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DOI: https://doi.org/10.1295/polymj.31.296