Isomeric Speciation of Bisbenzoxazine Intermediates by Ion Spectroscopy and Ion Mobility Mass Spectrometry

Author(s)

Ribeiro, Francisco W. M. ; Silva-Oliveira, Danilo ; Cervi, Gustavo ; Koyanagui, Eduardo D. ; Correra, Thiago C.

• Document type: Journal article
• Source: ACS OMEGA; v. 9, n. 39, p. 9-pg., 2024-09-18.

Abstract

Bisbenzoxazines (BisBz) are a relevant model for the diverse bifunctional benzoxazines that are used to increase the polybenzoxazines cross-linking extensions and modulate the final resin properties for various usages. The presence of side products and intermediates during monomer formation can influence the resin characteristics by inducing chain termination and ramifications, affecting the polymerization and cure processes. This work investigated the diverse isomeric intermediates and side products that are present during the BisBz formation from bisphenol A, aniline, and formaldehyde by ion mobility coupled to tandem mass spectrometry (MS/MS) and ion spectroscopy techniques. The species detected in this work suggest that these multifunctional phenols open diverse concurrent reaction pathways based on two main reactive steps: (i) the imine/iminium phenol attack to form a phenylamino intermediate and (ii) the formaldehyde attack followed by dehydration to form the oxazine ring. The species observed also support previous studies of the benzoxazine formation mechanism and showcase the application of advanced analytical techniques in studying complex chemical systems. (AU)

• FAPESP's process: 17/18485-1 - Mechanistic studies of haloamination reactions promoted by metallic and organic catalysts
• Grantee: Francisco Wanderson Moreira Ribeiro
• Support Opportunities: Scholarships in Brazil - Doctorate
• FAPESP's process: 21/06726-0 - Investigation of reactive intermediates in complex chemical and biochemical processes
• Grantee: Thiago Carita Correra
• Support Opportunities: Research Grants - Young Investigators Grants - Phase 2
• FAPESP's process: 22/00498-8 - Multi-user equipment approved in grant 21/06726-0: ion mobility mass spectrometry system (IMS-MS)
• Grantee: Thiago Carita Correra
• Support Opportunities: Multi-user Equipment Program
• FAPESP's process: 23/01180-4 - Developments of advanced methods for the evaluation of isomers by mass spectrometry of chemical and biological systems.
• Grantee: Francisco Wanderson Moreira Ribeiro
• Support Opportunities: Scholarships in Brazil - Technical Training Program - Technical Training
• FAPESP's process: 23/01070-4 - Development of methods for sample analysis in complex matrices by mass spectrometry.
• Grantee: Eduardo Delago Koyanagui
• Support Opportunities: Scholarships in Brazil - Technical Training Program - Technical Training
• FAPESP's process: 15/08539-1 - Multi-User Equipment approved in grant 2014/15962-5: ion trap mass spectrometer modified to perform infrared vibrational spectroscopy (IRMPD)
• Grantee: Thiago Carita Correra
• Support Opportunities: Multi-user Equipment Program
• FAPESP's process: 19/16026-5 - Cyclization reactions promoted by Pd/Cu Catalysts
• Grantee: Francisco Wanderson Moreira Ribeiro
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate