Preparation and Polymerization of Benzaldehyde Formaldehyde Azine (1-Phenyl-2,3-diaza-1,3-butadiene)

• Published in: Macromolecules Vol. 33; no. 7; pp. 2397 - 2402
• Main Authors: Hashidzume, Akihito, Tsuchiya, Atsuki, Morishima, Yotaro, Kamachi, Mikiharu
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 04.04.2000
• Subjects: Applied sciences; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; Solvent effect; Molecular structure; Azine derivatives; Cationic polymerization; Experimental study; Solution polymerization; Thermal stability; Structure processing relationship; Free radical polymerization; Anionic polymerization; Monomer; Chemical reactivity; Chemical synthesis
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma991529n

Benzaldehyde formaldehyde azine (BzFAz) was prepared as a new monomer having CN bonds, and its polymerizability was investigated by using several initiators. Polymers were obtained from BzFAz by polymerizations initiated by trifluoroacetic acid (CF3COOH), butyllithium (n-C4H9Li), and methylmagnesium iodide (CH3MgI). The structures of these polymers were investigated by elemental analysis, IR, Raman, and 1H NMR spectroscopies. The polymers obtained by CF3COOH and by n-C4H9Li consisted of 3,4-units, whereas that obtained by CH3MgI consisted of both 1,4- and 3,4-units. In the polymerization initiated by CH3MgI, the content of 1,4-unit increased as an increase in the dielectric constant of the solvent used. Powder X-ray diffraction of the polymers revealed that the polymer obtained by n-C4H9Li was highly crystalline. In addition, the thermogravimetric analyses showed these polymers were fully decomposed below 300 °C.