Mass Spectrometry of Synthetic Polymers

Peacock, Patricia M.; McEwen, Charles N.

doi:10.1021/ac0606249

Cited by 83 publications

(66 citation statements)

References 115 publications

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“…This approach showed that, contrary to expectation, pMMA degradation does occur at the (comparatively) low temperature of 95 °C, and does not necessarily proceed via radical intermediates. The use of soft ionisation mass spectrometry for the analysis of synthetic polymers has been discussed in numerous publications and review articles 25–50. Particularly in a primary study which is one of the first of its kind, it is important to use the softest ionisation method possible to eliminate errors in the analysis of polymer degradation mechanisms.…”

Section: Introductionmentioning

confidence: 99%

Degradation of Poly(methyl methacrylate) Model Compounds Under Extreme Environmental Conditions

Bennet

Hart‐Smith

Gruendling

et al. 2010

Macro Chemistry & Physics

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There is a significant knowledge gap in the degradation of poly(methyl methacrylate) (pMMA) under conditions experienced by surface coatings in the harsh Australian environment. In the current study pMMA model compounds were exposed to 95 8C temperatures and high UV radiation (1 kW Á m À2 ), separately as well as in combination. Contrary to the findings of previous studies, degradation proceeds in these conditions via a non-radical cyclic mechanism. The mechanism was further confirmed by synthesis and degradation of ethylene-oxideterminated pMMA, an intermediate product in the cycle. Electrospray ionisation mass spectrometry analysis of thermally degraded samples after 155 weeks shows degradation consistent with the proposed cycle in vinyl-terminated pMMA, while saturated pMMA was shown to be stable after the same period. Saturation delayed the UV-induced degradation, yet these compounds still displayed some slight degradation after 52 weeks, confirming the terminal vinyl bond in pMMA as a weak point. Combined UV and thermal radiation after 56 weeks showed degradation of both pMMA samples, with the vinyl-terminated sample also exhibiting crosslinking. The combination of thermal and UV radiation also caused acceleration of degradation, shown by a comparison of the polymer samples after %60 weeks.

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Section: Introductionmentioning

confidence: 99%

Degradation of Poly(methyl methacrylate) Model Compounds Under Extreme Environmental Conditions

Bennet

Hart‐Smith

Gruendling

et al. 2010

Macro Chemistry & Physics

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show abstract

“…Many attempts of using MS with soft ionization to derive relative or absolute concentrations of functional oligomers of variable chainlength as well as attempts to determine accurate MWD have therefore been made. [36][37][38][39] Unfortunately, the values obtained by direct analysis of the polymer sample are usually biased. This is because the complex chemical and physical processes involved in ion formation, mass spectrometric separation, ion transfer and ion detection all show a functional dependence on the molecular weight/structure of the analyte.…”

Section: Introductionmentioning

confidence: 99%

A Perfect Couple: PLP/SEC/ESI‐MS for the Accurate Determination of Propagation Rate Coefficients in Free Radical Polymerization

Gruendling

Voll

Guilhaus

et al. 2009

Macro Chemistry & Physics

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Pulsed laser polymerization (PLP) in conjunction with online size exclusion chromatography – electrospray ionization mass spectrometry (SEC/ESI‐MS) has successfully been applied for the determination of accurate propagation rate coefficients, kp, in free radical polymerization. SEC/ESI‐MS is used in this context to precisely determine the molecular weight distribution of the polymer produced by the PLP‐experiment. The novel approach allows for a highly accurate internal calibration of the size exclusion system to be obtained from first principles, as the molecular weight of the polymer is determined with ppm accuracy by the mass spectrometer and allows corrections for SEC band broadening effects to be made. Molecular weight measurements can furthermore be performed regardless of the monomer class, as long as the macromolecule is amenable to electrospray ionization. The proposed approach successfully eliminates work‐steps and problems incurred in the analysis of new and poorly characterized monomers, where universal calibration or multi‐detector SEC had to be applied until now and provides an alternative also to PLP/MALDI‐MS. Applicability of the method is demonstrated for the homologous series of methyl‐, ethyl‐ and butyl methacrylate. The experimentally determined kp values were 5–10% higher than the currently available benchmark data. The experimental kp is in agreement with the results of kinetic simulations, assuming a short chain length dependency of kp, in accordance with the empirical model of Smith, Heuts and Russell.magnified image

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“…In the last decade the analysis of polymers has taken advantage from the development of matrix assisted laser desorption ionization-time of flight MS (MALDI-TOF MS), a highly sensitive, nonaveraging technique that allows the direct determination of the individual molecules contained in a polymer sample [8,9]. Applications of MALDI to the study of polymer photo-and thermooxidation are quite recent [10][11][12][13][14][15][16] and involve the collection of MALDI spectra at different irradiation times and/or temperature to observe the structural changes induced by heat or light under an oxidizing atmosphere.…”

Section: Introductionmentioning

confidence: 99%

Comparative investigation of photo- and thermal-oxidation processes in poly(butylene terephthalate)

Carroccio¹,

Rizzarelli²,

Giuseppina³

et al. 2008

Polymer

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Mass Spectrometry of Synthetic Polymers

Cited by 83 publications

References 115 publications

Degradation of Poly(methyl methacrylate) Model Compounds Under Extreme Environmental Conditions

Degradation of Poly(methyl methacrylate) Model Compounds Under Extreme Environmental Conditions

A Perfect Couple: PLP/SEC/ESI‐MS for the Accurate Determination of Propagation Rate Coefficients in Free Radical Polymerization

Comparative investigation of photo- and thermal-oxidation processes in poly(butylene terephthalate)

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