Polymerization of allyl esters of unsaturated acids. IX. Controlled ring closure in the radical cyclopolymerization of allyl methacrylate

Abstract

Abstract Radical cyclopolymerization of allyl methacrylate (AMA) was investigated in detail, especially under the specified conditions; that is, above the ceiling temperature for a head‐to‐tail propagation (Δ G ht ≥ 0) in the polymerization of methacrylate. Thus the structure of the polymer obtained was examined by 1 H‐ and 13 C‐NMR and infrared (IR) spectroscopy; no existence of unreacted pendant methacrylyl groups was observed, which suggests that, as a cyclopolymerization mechanism of AMA, intermolecular propagation of growing radicals, followed by intramolecular cyclization or intermolecular propagation of the resulting uncyclized methacrylyl radical, occurs exclusively with methacrylyl group. Temperature dependency of cyclization constant K c was unusual; K c increased rapidly at elevated temperatures and no linear relationship of ln K c vs. 1/ T was observed. Five‐membered ring formation was favored at an elevated temperature and diluted monomer concentration. These results are discussed thermodynamically in terms of controlled ring closure in cyclopolymerization.