Abstract
Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry is shown to be a new and powerful technique for the analysis of macrocyclic polystyrenes and their linear precursors. The oligomer distributions for samples of different molar masses are obtained and the end groups of the linear precursors are identified. The chemical structure of the cyclization products is determined and it is shown that in the MALDI process the labile benzylic chlorine substituent at the macrocycle is abstracted, to yield a double bond. It is shown that MALDI mass spectrometry alone does not provide full information on the composition of the reaction products. The chemical structure of the macrocycles and the linear byproducts can be determined by chromatographic separation and subsequent MALDI analysis.
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