The results on radical self-polyaddition reactivity of two trialkylsilyl perfluoroisopropenyl ethers, triethysilyl perfluoroisopropenyl ether [CF2=C(CF3)OSi(C2H5)3] (FTEE) and dimethylphenylsilyl perfluoroisopropenyl ether [CF2=C(CF3)OSi(CH3)2C6 H5] (DMPE), and two perfluoroisopropenyl carboxylates, 2-butyroxypentafluoropropene [CF2=C(CF3)OCOC3H7] (BuFPP) and 2-(methoxyacetoxy)pentafluoropropene [CF2=C(CF3)OCOCH2OCH3] (MFPP), are described. Radical self-polyaddition of FTEE afforded a polymer as high as 1.87 × 104 in molecular weight in the presence of radical generators such as benzoyl peroxide and di-tert-butyl peroxide. DMPE gave only addition products with initiating radicals. BuFPP and MFPP scarcely yielded even addition products with radical. The mechanism that the self-polyaddition of FTEE was initiated by the addition of radical onto the perfluoroisopropenyl group followed by a 1,5-shift to afford a methyl radical that attacked the perfluoroisopropenyl group of another FTEE molecule is proposed.
|ジャーナル||Journal of Polymer Science, Part A: Polymer Chemistry|
|出版ステータス||出版済み - 9 15 2003|
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