Complementary Characterization of End Groups in Radically Polymerized Poly(methyl methacrylate) by Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry and Pyrolysis-Gas Chromatography-Mass Spectrometry

Abstract

e end groups in radically polymerized poly(methyl methacrylate) samples with tert-butyl peroxy-2-ethylhexanoate as an aliphatic peroxide initiator and 1-octanethiol as a chain transfer reagent were complementarily characterized by high-resolution matrix assisted laser desorption/ionization (MALDI) spiral time-ofight mass spectrometry (MS) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). e end groups comprised of three types of the initiator fragments and octylthio group originating from the chain transfer agent were con rmed by MALDI-MS measurements. In addition, their quantitative information was obtained by Py-GC-MS. Furthermore, combined with size exclusion chromatographic fractionation, the molar mass dependence of the end groups in the PMMA samples was also examined. It was suggested that the relative content of the octylthio end groups might increase with increase in the molar mass of the fractions. e observed results were interpreted in terms of the polymerization reactions of the PMMA samples.

End group analysis of poly(methylmethacrylate)s using the most abundant peak in electrospray ionization‐ion mobility spectrometry‐tandem mass spectrometry and Fourier transform–based noise filtering

“…Possible end structures for the estimated elemental compositions are shown in Figure 3. The ESI‐IMS‐TOFMS results for lower‐molecular‐weight PMMAs were in agreement with those identified in MALDI‐TOFMS 35 …”

“…The PMMAs analyzed in this section were synthesized using tert-butyl peroxy-2-ethylhexanoate as an initiator, and it was reported that possible initiation end group structures included in the polymer were tert-butoxy (C 4 H 9 O), methyl (CH 3 ), and 1-ethylphentyl (C 7 H 15 ). 35 Figure 3A shows the 2D distribution of the PMMAs in ESI-IMS-TOFMS, and the related extracted mass spectra for monovalent analytes are shown in Figure 3B, with an enlarged spectrum in This study demonstrated the characterization of synthetic polymers using the most abundant peak. The proposed method requires isotope-level separation in MS spectrum.…”

“…Therefore, the proposed method was applied for the analysis of PMMAs synthesized via free radical polymerization with various end groups. The PMMAs analyzed in this section were synthesized using tert ‐butyl peroxy‐2‐ethylhexanoate as an initiator, and it was reported that possible initiation end group structures included in the polymer were tert ‐butoxy (C 4 H 9 O), methyl (CH 3 ), and 1‐ethylphentyl (C 7 H 15 ) 35 …”

End group analysis of styrene-butyl acrylate copolymers initiated with benzoyl peroxide by stepwise chemolysis-pyrolysis gas chromatography

“…Even the end groups in a polymer sample, which are generally difficult to analyze because of their trace concentrations as compared to the polymer main chains, can be characterized qualitatively and quantitatively by Py-GC due to the method's high sensitivity [1]. In general, initiator fragments and chain transfer agents are incorporated into the polymer chains as end groups.…”

Stochastic dynamics mass spectrometric structural analysis of poly(methyl methacrylate)

“…The soft-ionization mass spectrometry has become an important analytical tool in polymer science [1,2], analogously to its application to omics-methods for purposes of biology and medicine [3]. The field of polymeromics deals with determining polymer structure via MS approaches [4].…”