Abstract
The cyclocopolymerizations of o-allylphenyl acrylate (APA) and 2-(o-allylphenoxy)ethyl acrylate (2-AOEA) with a donor monomer, p-chlorostyrene (p-ClS), in the presence of AlEti1.5Cl1.5 have shown that the electron-withdrawing double bonds are consumed in an equal proportion to the electron-releasing double bonds, irrespective of the initial composition of monomer feed. The copolymer composition tended to a limiting value with 50-mol % p-ClS units as the p-CIS mole fraction in the monomer feed increased. The extent of cyclization for the APA and the 2-AOEA units sharply decreased with an increase in the p-ClS unit fraction. The fraction of acrylic double bonds in the consumed double bonds always amounted to about 50-mol % this indicates that the cyclocopolymerizations are composed by alternating participation of the electron-withdrawing and the electron-releasing double bonds. On the other hand, the following values of kp/kc, the ratio of the rate constants for linear propagation and for cyclization, were obtained for APA at 40°C: 0.20 l mol−1 in the presence of AlEti1.5Cl1.5 and 0.045 l mol−1 in the presence of AlEtCl2. These values imply that the intramolecular interaction between the two double bonds plays an important role in the cyclopolymerization. The results have indicated that the mechanism being proposed for the alternating copolymerization would be applicable also to the cyclocopolymerization. The character of cyclocopolymerization was explained by the molecular complex mechanism rather than by the complexed radical mechanism.
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Yokota, K., Kakuchi, T. & Takada, Y. Studies of the Cyclopolymerization in the Presence of Alkylaluminum Chlorides. III. Cyclocopolymerizations of o-Allylphenyl Acrylate and 2-(o-Allylphenoxy)ethyl Acrylate with p-Chlorostyrene. Polym J 10, 19–25 (1978). https://doi.org/10.1295/polymj.10.19
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DOI: https://doi.org/10.1295/polymj.10.19