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Characterizing chain‐end structures formed during initiation reactions of radical polymerization for MMA‐St‐BA terpolymer using pyrolysis ‐ gas chromatography / atmospheric pressure chemical ionization high‐resolution time‐of‐flight mass spectrometry
Author(s) -
Harata Kenji,
Kitagawa Shinya,
Iiguni Yoshinori,
Ohtani Hajime,
Ezaki Tatsuya
Publication year - 2020
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.8691
Subject(s) - chemistry , atmospheric pressure chemical ionization , mass spectrometry , chemical ionization , methyl methacrylate , analytical chemistry (journal) , resolution (logic) , monomer , polymer , copolymer , pyrolysis , styrene , gas chromatography , methyl acrylate , ionization , chromatography , ion , organic chemistry , artificial intelligence , computer science
Rationale Analyzing polymer end groups using pyrolysis (Py) gas chromatography/mass spectrometry (GC/MS) in multi‐component polymer samples is not an easy task because of the insufficient sensitivity, selectivity, and mass resolution of conventional Py‐GC/MS systems. Methods A new Py‐GC/MS system using an atmospheric pressure chemical ionization (APCI) source combined with high‐resolution time‐of‐flight mass spectrometry (TOFMS) was used for end‐group analysis of a methyl methacrylate (MMA)‐styrene (St)‐butyl acrylate (BA) terpolymer (P (MMA‐St‐BA)), which was radically polymerized using 2,2′‐azobis(2‐methylbutyronitrile) (AMBN) as an initiator. Results Five possible pyrolyzates, comprising an AMBN fragment and a monomer unit, formed during the initiation reactions from one of the three types of end groups, were selectively detected and exclusively identified in their respective extracted ion chromatograms for molecule‐related ions, such as M + and [M + H] + , with a narrow mass window of ±2 milli m/z units. Conclusions It was demonstrated that Py‐APCI‐TOFMS is a powerful technique to characterize in detail the complex end groups in multi‐component polymer samples, because of the soft ionization nature of APCI and the high mass resolution of TOFMS.