Synthesis and radical polymerization of N,N-diethyl-α-fluoroacrylamide

N,N-Diethyl-α-fluoroacrylamide (DEFAA) was prepared by the reaction of ethyl α-fluoroacrylate and dimethylaluminum N,N-diethylamide. DEFAA was easily polymerized with dimethyl 2,2′-azobisisobutyrate (MAIB) to yield poly(DEFAA) as a white solid. Poly(DEFAA) was soluble in many organic solvents but not in aliphatic hydrocarbons. The polymerization of DEFAA with MAIB was kinetically investigated in benzene. The overall activation energy was estimated to be 64 kJ/mol. The polymerization rate (Rp) at 40°C was given by Rp=k[MAIB]1.0[DEFAA]1.0. The high order with respect to initiator might be caused by unimolecular termination. The molecular weight (3–10×104) of poly(DEFAA) decreased with initiator concentration and temperature and increased with monomer concentration. The tacticities were found by 19F-NMR spectroscopy as mm=0.32, mr=0.50 and rr=0.18. The glass transition temperature of poly(DEFAA) was 50°C by differential scanning calorimeter. Copolymerization of DEFAA(M1) and styrene at 50°C in benzene gave the following results: r1=0.15, r2=2.59, Q1=0.18, and e1=+0.18.