POLYMERIZATION OF DIAZABUTADIENE DERIVATI VES - SUBSTITUENT EFFECT ONMACROMOLECULAR STRUCTURE

The polymerizabilities of azine compounds (RCH-N-N=CHR) with various t ypes of anionic initiators were investigated. Only oligomers were obta ined by the polymerizations of alkyl azines (R=CH3, C2H5, n-C3H7), alt hough monomers were quantitatively consumed. This is because a chain t ransfer reaction took place in which the active chain end extracted th e proton on the ct-carbon of the C=N. However, high molecular weight p olymers were obtained by the polymerization by Grignard reagents. Spec troscopic analyses of the obtained polymers showed that the polymers c onsisted of trans-1,4-units. Furthermore, we prepared trifluoroacetald ehyde azine (R = CF3, TFAcAz) to suppress the chain transfer reaction, and studied its polymerizability. In contrast to our expectation, onl y oligomers were obtained by the polymerizations of TFAcAz with BuLi, CH3MgI, CH3OK/18-crown-6, and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) . However, TFAcA2 was polymerized by triethylamine to form an insolubl e polymer. The polymer was found to consist of 1,2-units by several sp ectroscopies. In addition, the polymers obtained in this work were hig hly crystalline and thermodegradable.