Polymerization of 1,3‐dienes with functional groups. III. Free‐radical polymerization of N,N‐diethyl‐2‐methylene‐3‐butenamide

Abstract

Free‐radical homo‐ and copolymerization behavior of N,N‐diethyl‐2‐methylene‐3‐butenamide (DEA) was investigated. When the monomer was heated in bulk at 60 °C for 25 h without initiator, rubbery, solid gel was formed by the thermal polymerization. No such reaction was observed when the polymerization was carried out in 2 mol/L of benzene solution with with 1 mol % of azobisisobutyronitrile (AIBN) as an initiator. The polymerization rate (Rp) equation was Rp ∝ [DEA]1.1[AIBN]0.51, and the overall activation energy of polymerization was calculated 84.1 kJ/mol. The microstructure of the resulting polymer was exclusively a 1,4‐structure where both 1,4‐E and 1,4‐Z structures were included. From the product analysis of the telomerization with tert‐butylmercaptan as a telogen, the modes of monomer addition were estimated to be both 1,4‐ and 4,1‐addition. The copolymerizations of this monomer with styrene and/or chloroprene as comonomers were also carried out in benzene solution at 60 °C. In the copolymerization with styrene, the monomer reactivity ratios obtained were r1 = 5.83 and r2 = 0.05, and the Q and e values were Q = 8.4 and e = 0.33, respectively. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 999–1007, 2004

Polymerization of 1,3-Dienes with Functional Groups. 4.

“…The formation of 1,2-linkage in the anionic polymerization provides important information on the reactivity of the active chain-end. As previously reported, almost no 1,2-linkage was formed in the free-radical polymerization of DEA, indicating that 1,2-radicals could not attack other monomers 7) . The observation that a considerable amount of 1,2-structure was contained in the polymer obtained in this study indicates that the amideenolate anion of the 1,2-propagating species has higher nucleophilic reactivity toward other monomer propagation resulting in the formation of 1,2-linkage in the polymer chain.…”

“…As previously reported, 1,4-E and Z linkage, cis-and trans-1,4 structures of the main chain, respectively, were the main structures of polyDEA prepared by free-radical polymerization 7) . The two olefinic signals centered at 5.35 and 5.23 ppm in Figure 5(a) can be assigned to protons in 1,4-E and 1,4-Z linkages, respectively.…”

“…The synthetic procedure of DEA has been described elsewhere 7) . The monomer was stirred for 12 h with calcium hydride, and was distilled under high-vacuum conditions.…”

“…In our previous studies, we have reported the freeradical polymerization of N,N-dialkyl-2-methylene-3-butenamides 6,7) . Although there have been several reports on the anionic polymerization of N,Ndialkylacrylamides [8][9][10] , our reports were the first ones describing the polymerization behavior of their butadiene analogs.…”

Free-radical polymerization of tetraethyl (2,3-dimethylenebutane-1,4-diyl)bis(phosphonate)

“…Though an appropriate methylene spacer was introduced between the functional groups and the polymerizable dienyl function in these cases, it is also possible to introduce functional groups directly onto butadienyl group. Free-radical polymerization of 1,3-butadiene derivatives containing dialkylamide [7][8][9] , triethoxymethyl 10) , and triethoxysilyl 11) groups were reported.…”