In order to synthesize poly-(fluorinated alkanesulfonamides)a series of model experimentswere carried out:(1)reactions of fluorinated alkanesulfonyl fluorides with amines,(2)reactions offluorinated alkanesulfonyl chloride with amines and(3)reactions of sodium salts of fluorinated alkane-sulfonamides with alkyl iodides of fluorinated alkanesulfonie acid esters.Seventeen new fluorinatedalkanesulfonamides were prepared in good yields,namely:R_FO(CF_2)_2SO_2NR~1R~2(la-h),R~1R~2NSO_2R_F-SO_2NR~1R~2(2a-h)and [CI(CF_2)_4O(CF_2)_2SO_2NH(CH_2)_3]_2(3).Reaction of R_FSO_2NH_2 with equivalentamount of NaOCH_3 and methyl iodide was shown to give both the N-mono- and N,N--di-substitutedamides.Consequently the N-monosubstituted alkanesulfonamides were chosen as monomers forsyntheses of the poly-(fluorinated alkanesulfonamides)and two new polymers were synthesized.Theeffect of the condition of the polycondensation on(?)n of the polymers were discussed and elementalcomposition,~(19)F NMR,IR,(?)n,Tg,tensile strength,thermal and chemical stabilities of the polymerswere measured.Several new perfluoroalkanesulfonyl chlorides ClSO_2R_FSO_2Cl(4a-e)and fluorinated alkanesul-fonic acid esters(6a-d)were synthesized.However,reaction of CFCl_2CF_2O(CF_2)_2SO_2F with AlCl_3was found to give Cl_3CCF_2O(CF_2)_2SO_2F(5)instead of the expected sulfonyl chloride. In order to synthesize poly- (fluorinated alkanesulfonamides) a series of model experimentswere carried out: (1) reactions of fluorinated alkanesulfonyl fluorides with amines, (2) reactions offluorinated alkanesulfonyl chloride with amines and (3) reactions of sodium salts of fluorinated alkane- (2a-2), sulfonamides with alkyl iodides of fluorinated alkanesulfonie acid esters. Seventeen new fluorinated alkanesulfonamides were prepared in good yields, namely: R_FO (CF_2) _2SO_2NR ~ 1R ~ 2 The reaction of R_FSO_2NH_2 with equivalent amount of NaOCH_3 and methyl iodide was shown to give both the N-mono- and N, N-di (h) and [CI (CF_2) _4O (CF_2) _2SO_2NH (CH_2) _3] _2 -substitutedamides. Conferred the N-monosubstituted alkanesulfonamides were chosen as monomers forsyntheses of the poly- (fluorinated alkanesulfonamides) and two new polymers were synthesized. The effect of the conditions of the polycondensation on (?) n of the polymers were discussed and elemental composition, ~ (19) F NMR, IR, (?) N, Tg, te nsile strength, thermal and chemical stabilities of the polymers were measured. Further new perfluoroalkanesulfonyl chlorides ClSO_2R_FSO_2Cl (4a-e) and fluorinated alkanesul- fonic acid esters (6a-d) were synthesized.However, reaction of CFCl_2CF_2O (CF_2) _2SO_2F with AlCl_3was found to give Cl_3CCF_2O (CF_2) _2SO_2F (5) instead of the expected sulfonyl chloride.