Abstract

Fingerprinting spectra of polymer materials containing information of monomers' molecular weight and detailed structure, constituents, and sequences were obtained by a direct analytical process using arc plasma-based dissociation (APD)-mass spectrometry. The thermal arc plasma generated using a simple arc discharge device induces the dissociation of the polymeric backbone, producing mass spectra with strong regularity within seconds. The molecular weight of the repeating unit was revealed by equal intervals between peak series and protonated monomer ions in the mass spectra. Meanwhile, lots of secondary fragment ions were produced to provide abundant structural information. For polyethers, it is even possible to decipher (read) the "sequence" directly from their spectra. Polymers composed of isomers or only differing in their initiator moieties were easily distinguished with their characteristic APD mass spectra. The spectra were highly reproducible according to the results of similarity calculation. Unlike pyrolysis mass spectrometry, in the APD device, polymers in liquid, solid, powder, and crude samples can be analyzed directly without any pretreatment, and the regular spectra are easier to interpret. Compared with other direct analytical methods, more structural informative spectra can be acquired owing to the high energy, high temperature, and unique chemical reactivity of arc plasma. Thus, this technique is promising to be a valuable tool in rapid elucidation of polymer materials.

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