N,N-Diethyl-alpha -fluoroacrylamide (DEFAA) was prepared by the reaction of
ethyl alpha -fluoroacrplate and dimethylaluminum N,N-diethylamide. DEFAA w
as easily polymerized with dimethyl 2,2'-azobisisobutyrate (MAIB) to yield
poly(DEFAA) as a white solid. Poly(DEFAA) was soluble in many organic solve
nts but not in aliphatic hydrocarbons. The polymerization of DEFAA with MAI
B was kinetically investigated in benzene. The overall activation energy wa
s estimated to be 64 kJ/mol. The polymerization rate (R-p) at 40 degreesC w
as given by R-p = 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 x 10(4)) of poly(DEFAA) decreased with initiator concentration and t
emperature and increased with monomer concentration. The tacticities were f
ound by F-19-NMR spectroscopy as mm = 0.32, mr = 0.50 and rr = 0.18. The gl
ass transition temperature of poly(DEFAA) was 50 degreesC by differential s
canning calorimeter. Copolymerization of DEFAA(M-1) and styrene at 50 degre
esC in benzene gave the following results: r(1) = 0.15, r(2) = 2.59, Q(1) =
0.18, and e(1) = +0.18. (C) 2000 Elsevier Science Ltd. All rights reserved
.