Macrocyclic polystyrenes prepared by a single-step, pseudo-unimolecular cyclization of a linear R-(diethoxyethyl)-ω-styrenylpolystyrene can effectively be analyzed by liquid chromatography at the critical point of adsorption. Using silica gel as the stationary phase and THF-hexane as the eluent, the macrocyclic oligomers are separated from their linear precursors and other nonfunctional linear oligomers. The quantitative determination of the cyclization yield can be carried out via appropriate detector calibration for the linears and cyclics. Additional information on the chemical structure of the linears and cyclics is obtained by matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. In conclusion, a possible cyclization mechanism is given including an interpretation of the MALDI behavior of the samples.

Carboxy-terminated oligostyrenes, prepared by radical polymerization using a dicarboxy-functional initiator, can efficiently be separated by gradient high performance liquid chromatography (HPLC). On a normal phase chromatographic system, comprising a silica gel stationary phase and a tetrahydrofuran-hexane eluent, elution occurs in the order of increasing polarity of the oligomers and separation into non-, mono-, and dicarboxy oligomer fractions is obtained. The chemical structure of the different functionality fractions is determined by matrix assisted laser desorptiordionization mass spectrometry (MALDI-MS). The results indicate that further functionality fractions in addition to the carboxy oligomers are formed, due to contamination of the initiator or side reactions during the polymerization process.