ANIONIC-POLYMERIZATION OF NORMAL-BUTYRALDEHYDE AZINE TO CRYSTALLINE TRANS-1,4-POLY(NORMAL-BUTYRALDEHYDE AZINE)

Anionic polymerizability of n-butyraldehyde azine (C3H7CH=N-N=CHC3H7)(BuAz) was investigated by anionic initiators in various solvents. Highly crystalline polymers along with oligomers were obtained by the polymerization of BuAz with CH3MgI in toluene, diethyl ether, benzene, and 1,4-dioxane. The formation of oligomers was explained by the occurrence of a proton transfer from the monomer to propagating anion. The structures of the polymers obtained were investigated by IR, Raman, H-1 NMR, and C-13 NMR spectroscopies, which indicated that these azine polymers are composed of trans-1,4-addition units. The X-ray diffraction patterns of the polymers showed two distinct diffractions which are ascribable to fiber period of the polymer chain and intermolcular regular structure, respectively, indicating that the polymer is highly crystalline. The polymer was thermally stable up to 100-degrees-C, inspite of existence of azo group in the main chain.