Analysis of copolymers by laser desorption fourier transform mass spectrometry.

A series of methylmethacylate/butylacrylate, methylmethacrylate/styrene, and poly-(ethylene glycol)/poly(propylene glycol) copolymers were analyzed by laser desorption Fourier transform mass spectrometry. Molecular weight distributions and overall copolymer compositions were determined. Typical spectra arise from a distribution of alkali metal cationized oligomer ions reflecting copolymer composition. Number- and weight-average molecular weights were calculated for each category of copolymer series as well as for overall copolymer mixtures. In addition, mass spectra were analyzed to estimate copolymer monomer contributions; these results were compared with manufacturer free mix ratios as a test of the relative accuracy of the analysis. Although a dual-cell Fourier transform mass spectrometer was used, all copolymer analyses reported were carried out as single (source) cell measurements to ensure that no mass discrimination would occur. A series of Fourier transform mass spectrometry dual-cell experiments also were performed to evaluate the effect of ion transfer time on molecular weight averages and compositions. As expected, mass discrimination occurred when short transfer times and analyzer cell detection were employed. Under these conditions, molecular weight averages varied by more than 50% from values obtained in the single-cell measurements.