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

Abstract

Polymers such as poly(methyl methacrylate), comprising of all-carbon backbones are regarded as ubiquitous functional materials mainly due to their low cost, unique physical properties, and impressive robustness. The latter properties are results from relative chemical inertness of the polymer backbone carbon–carbon bonds. The highlighted stability crucially challenges not only innovations to plastic recycling polymer materials, but also developments of reliable analytical protocols for determining both quantitatively and structurally polymers. Despite, the fact that there are numerous applications of mass spectrometric methods to polymer science, the analysis involves chiefly annotation of monomers of polymers and additives, owing to the fact that the additives are low molecular weight analytes. The exact structural determining of end-chain groups, particularly highlighting chemically substituted end carbon–carbon bond represents significant challenge even utilizing the superior features of the analytical mass spectrometric instrumentation. This study, in the latter context, illustrates innovative stochastic dynamics approach and model equations capable of not only determining unambiguously substituted carbon–carbon end chain of the entitled polymer but also to predict mass spectra of its derivatives: thus, extending crucially the applicability of the method to many fields of the fundamental scientific and industrial research. The latter claim is argued still at the beginning of the study with the achieved method performances showing |r|=0.99998. The study utilizes experimental and theoretical mass spectrometric data on high resolution electrospray ionization mass spectrometry; high accuracy quantum chemical static methods, molecular dynamics; and chemometrics.