SYNTHESIS OF SUBSTITUTED POLYMETHYLENES BY RADICAL POLYMERIZATION OF N,N,N',N'-TETRAALKYLFUMARAMIDES AND THEIR CHARACTERIZATION
Matsumoto, A; Fukushima, K; Otsu, T; ,
Radical polymerization of N,N,N',N'-tetraalkylfumaramides (TRFAm) bearing methyl, ethyl, n-propyl, isopropyl, and isobutyl groups as N-substituents (TMFAm, TEFAm, TnPFAm, TIPFAm, and TIBFAm, respectively) was investigated. In the polymerization of TEFAm initiated with 1,1'-azobiscyclohexane-1-carbonitrile (ACN) in benzene, the polymerization rate (R(p)) was expressed as follows: R(p) = k [ACN]0.28 [TEFAm]1.26, and the overall activation energy was 102.1 kJ/mol. The introduction of a bulky alkyl group into N-substituent of TRFAm decreased the R(p) in the following order: TMFAm > TEFAm > TnPFAm > TIBFAm > TIPFAm approximately 0. The relative reactivities of these monomers were also investigated in radical copolymerization with styrene (St) and methyl methacrylate (MMA). In copolymerization of TRFAm (M2) with St (M1), monomer reactivity ratios were determined to be r1 = 1.07 and r2 = 0.20 for St-TMFAm, and r1 = 1.88 and r2 = 0.11 for St-TEFAm, from which Q2 and e2 values were estimated to be 0.35 and 0.44 for TMFAm, and 0.19 and 0.47 for TEFAm, respectively. The other TRFAm were also copolymerized with St, but copolymerization with MMA gave polymers containing a small amount of TRFAm units. The polymer from TRFAm consists of a less-flexible poly (NN-dialkylaminocarbonylmethylene) structure. The solubility and thermal property of the polymers were also investigated.