Radical polymerization of allyl alcohol and allyl acetate

Monoallyl compounds are not readily homopolymerized by a conventional free-radical mechanism. However, the polymerization of allylbiguanide hydrochloride was reported to proceed in a concentrated solution of hydrochloric or phosphoric acid in the presence of a radical initiator. Here we have studied the polymerization of allyl alcohol by a radical initiator in the presence of a Lewis acid (ZnCl2, CUCl2 or MgCl2) in an organic solvent (toluene, hexane, methanol or isopropanol). Reactions were performed either at room temperature or 50 degrees C under an atmosphere of nitrogen or in a sealed tube. The same polymerization was also carried out in water and in a concentrated acid solution. The polymer product was purified by dialysis in 0.2-3.7% yield and confirmed by elemental analysis, infrared spectroscopy and H-1 NMR. The molecular weight range of poly(allyl alcohol) was 10,000-35,000. The polymerization of allyl acetate by the radical initiator under the above conditions gave poly(allyl acetate) with the molecular weight range of 10,000-13,800 by multi-angle laser light scattering. Copyright (c) 2007 John Wiley & Sons, Ltd.