Evaluation of polymerization reactions by differential ion mobility and infrared ion spectroscopy

• Grant number: 25/06785-7
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)
• Start date: June 01, 2025
• End date: May 31, 2029
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Thiago Carita Correra
• Grantee: Pedro Henrique Martins Garcia
• Host Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil
• Associated research grant: 21/06726-0 - Investigation of reactive intermediates in complex chemical and biochemical processes, AP.JP2

Abstract

Synthetic polymerization processes are simultaneously challenging and relevant to be studied on the reactivity context because the polymers and resins are ubiquitously used on the modern economy are dependent on their specific properties and, therefore, on the very initial steps of their formation. MALDI-TOF and other sampling techniques coupled to high resolution MS (HRMS) can be used to determine polymer size distribution and chemical composition but, despite the relative success of these MS techniques, the actual connectivity of the monomers is usually not determined, as the polymers chains formed can be present as different isomers with the same exact mass to charge ratio (m/z). In this context, we propose to use advanced sampling techniques to evaluate the initial polymerization steps by IMS and IRMPD spectroscopy. IMS plays a relevant role by adding an orthogonal dimension of detection to both MS and IRMPD techniques, as the increase of the molecular mass of the oligomer makes the IR spectra of these species too crowded to enable correct isomer identification and their theoretical prediction. Therefore, the use of IMS-MS and IMS-IRMPD-MS could greatly increase the identification power and allow the exact determination of the oligomers identity and, in consequence, the complete characterization of polymerization pathways. The two polymerization reactions that will be initially evaluated are: i) the polybenzoxazine formation and the; ii) aniline electropolymerization. (AU)