To develop a radical polyaddition reaction of 2-benzoyloxypentafluoropropene [CF2=C(CF3)OCOC6H5] (BPFP) with tetrahydrofuran (THF), the reactions of bis(alpha-trifluoromethyl-beta-difluorovinyl) terephthalate [CF2=C(CF3)OCOC6H4COOC(CF3)=CF2] (BFP) with THF and of BPFP with 1,4-dioxane were investigated as model reactions to form 1 :1 and 1.2 addition products of BFP with THE This evidenced that THF is monofunctional, and dioxane is bifunctional since the 1:1 and 2:1 addition products of BPFP with dioxane were formed. The polyaddition reaction of BFP with dioxane turned out to produce a white powdery substance which was found to possess a mole ratio of BFP units to dioxane units in the polymers of 1 : 1. The highest molecular weight obtained was (M) over bar(n) = 9.9 x 10(3).