Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated, ¹⁵N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and Theoretical Calculations

Abstract

Polymerization of benzoxazine resins is indicated by the disappearance of a 960–900 cm –1 band in infrared spectroscopy (IR). Historically, this band was assigned to the C–H out-of-plane bending of the benzene to which the oxazine ring is attached. This study shows that this band is a mixture of the O–C 2 stretching of the oxazine ring and the phenolic ring vibrational modes. Vibrational frequencies of 3-phenyl-3,4-dihydro-2 H -benzo[ e ][1,3]oxazine ( PH-a ) and 3-( tert -butyl)-3,4-dihydro-2 H -benzo[ e ][1,3]oxazine ( PH-t ) are compared with isotope-exchanged and all-substituted compounds. Deuterated benzoxazine monomers, 15 N-isotope exchanged benzoxazine monomers, and all-substituted benzoxazine monomers without aromatic C–H groups are synthesized and studied meticulously. The various isotopic-exchanges involved deuteration around the benzene ring of phenol, selective deuteration of each CH 2 in the O– CH 2 –N (2) and N– CH 2 –Ar (4) positions on the oxazine ring, or simultaneous deuteration of both positions. The chemical structures were confirmed by 1 H nuclear magnetic resonance spectroscopy ( 1 H NMR). The IR and Raman spectra of each compound are compared. Further analysis of 15 N isotope-exchanged PH-a indicates the influence of the nitrogen isotope on the band position, both experimentally and theoretically. This finding is important for polymerization studies of benzoxazines that utilize vibrational spectroscopy.