Abstract
The radical telomerization of vinyl (VMA) and allyl (AMA) methacrylates was carried out using bromotrichloromethane (BTCM) as a telogen at 50, 70, and 90°C. The m[Cl3CBr]:n[Monomer]adducts (m=1, 2, 3; n=1, 2) were fractionated by means of silica gel column chromatography. Compared with VMA, AMA was subject to addition of BTCM and telomerized with a lower average degree of telomerization. The addition of BTCM occurred on both the vinylidene and vinyl groups, but the vinylidene group was much more susceptible to addition of BTCM in preference to the vinyl group. Furthermore, the chain of dimeric adducts was exclusively made up by a vinylidene–vinylidene coupling. The successive addition reaction of BTCM to telomeric molecules increased with temperature, time, and quantity of 2,2′-azobisiso-butyronitrile (AIBN) as an initiator. In the telomerization at 90°C, however, the addition rate of BTCM decreased in response to rapid inactivation of AIBN. The lactonization of dimeric adducts (m=1, n=2) was induced by the catalytic action of silica gel or heating. The lactone yield of the AMA adducts was higher than that of the VMA one. The VMA adduct was preferentially oligomerized by pyrolysis at 150°C.
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Kimura, T., Hamashima, M. Study on Radical Telomerization of Esters of Methacrylic Acid Using Bromotrichloromethane and Characteristics of the Resulting Telomers VI. Difunctional Methacrylates. Polym J 20, 45–53 (1988). https://doi.org/10.1295/polymj.20.45
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DOI: https://doi.org/10.1295/polymj.20.45