Abstract
Reactivity in radical homopolymerization of vinylbenzyl-ended poly(2-alkyl-2-oxazoline) macromonomers (VB-PROZO-n; n (degree of polymerization) = 3—34) and methacryloyl-ended macromonomers (MA-PROZO-n; n=4—34) was examined at 60°C in CD3CN, CDCl3, or D2O using 2,2′-azobis(isobutyronitrile) (in organic solvents) or 2,2′-azobis(2-amidinopropane) dihydrochloride (in D2O) as initiator. R was Me, Bu, or n-octyl (Oc) group. In CD3CN (R = Me, Bu), macromonomers were polymerized faster with increase in n. Higher Rp was observed for Bu group and MA end group than Me group or VB end group, respectively. In CDCl3, polymerization of VB-ended POcOZO macromonomers showed higher Rp than PBuOZO macromonomers. The rate increased with in n, whereas, polymerization of MA-ended POcOZO macromonomers showed lower Rp than PBuOZO macromonomers of similar n, and rate decreased with increase in n. In D2O, PMeOZO macromonomers were polymerized 9 to 14 times faster than CD3CN. Kinetic orders of monomer concentration were 1.55 to 1.73 in organic solvents, while nearly 1.0 in water, and those of initiator concentration were close to 0.5 in CD3CN. Rp is thus affected by carbon number of acyl side chains in PROZO and by n, and D2O increases enormously Rp of PMeOZO macromonomers by micelle formation.
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Shimano, Y., Sato, K. & Kobayashi, S. Reactivity in Radical Polymerization of Poly(2-oxazoline) Macromonomers. Polym J 31, 219–225 (1999). https://doi.org/10.1295/polymj.31.219
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DOI: https://doi.org/10.1295/polymj.31.219
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