Comparison of different methods for the determination of the molar mass and molar mass distribution of poly(ethylmethylsiloxane)

The application of a poly(dimethylsiloxane) (PDMS) calibration curve for si ze exclusion chromatography (SEC) to poly(ethylmethylsiloxane) (PEMS) leads to molar masses, which are 15-40% higher than expected compared to measure ments of the absolute molar mass values. As for the analysis of physical pr operties of PEMS, the exact knowledge of the molar mass is fundamental, the refore PEMS calibration curves for both SEC and viscometry were established . Eleven narrow distributed linear PEMS samples in the range between 4000 a nd 110000 g/mol were synthesised by anionic ring-opening polymerisation of a cyclic monomer. The molar masses of the PEMS samples were determined by m atrix assisted laser desorption ionisation time-of-flight mass spectrometry (MALDI-TOF-MS), light scattering, membrane osmometry, vapour pressure osmo metry, and by viscometry. The polydispersities calculated from MALDI-TOF-MS spectra were lower compared to the SEC results. With the help of universal calibration, a SEC calibration curve for PEMS was established. Small angle neutron scattering (SANS) experiments on a 50%/50% protonated/deuterated P EMS blend match exactly the molar mass obtained from the PEMS calibration c urve for SEC.