Characterisation of low molecular weight polymers using matrix assisted laser desorption time-of-flight mass spectrometry

Abstract Matrix assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF MS) is used to mass characterise several low molecular weight, commercially available PS, PMMA and PEG samples. In addition, the utility of the technique for the study of polymer synthesis is demonstrated; different initiation and termination mechanisms leave dead chains with characteristic end groups which, in many cases, can be rapidly identified mass spectrometrically. There is broad agreement between MWDs derived from MALDI spectra and those obtained from conventional GPC analysis, but in some instances the differences are significant. Polydispersities obtained mass spectrometrically are invariably lower than those determined by GPC.