Fluoropolymers are widely used due to their high stability and resistance to degradation. It follows that the development of new polymers and their constituent monomers is an ongoing process. Characterization of new materials by high resolution mass spectrometry (HRMS) is common; however, success in the analysis of some fluoromonomers by electrospray ionization (ESI)-HRMS is limited due to their low polarity and lack of basic/acidic sites. The purpose of this work is to develop a method, based on atmospheric pressure chemical ionization (APCI) to determine exact mass of a class of monomer compounds. Ongoing experiments aim to build on this APCI-MS method to determine collision-induced dissociation pathways that can be used to identify structural characteristics of these compounds and differentiate between different synthetic products. While a tentative method has been developed to allow for HRMS characterization, ongoing work aims to optimize ionization conditions by systematically changing source parameters (e.g., flow rate, temperature, etc.) and evaluating the effect of these parameters on the appearance of different types of ions (e.g., molecular ion, protonated analyte, sodiated analyte). The exact mass of a series of ((perflurocyclohex-1-en-1-yl)oxy)phenyl monomers has been successfully measured using the developed method. Good signal was obtained using a methanol-water 3:1 solvent system and a flow rate of 50 µL/min. Acidification was also tested, but there was no clear advantage to using an acidified solution. In the analysis of bis(PFCH-PE-BP), bis(PFCP-AQ-BP), and bis(PFCP-AR-BP), [M+H]<sup>+</sup> mass error was below 5 ppm with some being less than 1 ppm. Bis(PFCP-AR-BP) does not have a ketone and the intensity was one and two order of magnitude less than bis (PFCH-PE-BP) and bis(PFCP-AQ-BP) respectively, illustrating the important relationships between analyte structure and instrument response. While the protonated analyte was the most intense characteristic ion in each case, there was also a minor molecular ion, which was of a higher relative intensity for bis(PFCP-AR-BP), the monomer that does not contain a ketone. Preliminary CID spectra were collected for select monomers. This preliminary data show great promise for diagnostic neutral loss patterns for each structural characteristic we included. Ongoing work aims to improve the intensities of the CID-MS spectra and to expand the coverage to all monomers for which exact mass has been recorded.

Characterization of synthetic monomers by high-resolution mass spectrometry

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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