The influence of elastic light scattering on the Raman signal of polymer latexes was investigated by varying the sample position relative to the confocal Raman probe. Measurements on polystyrene latexes revealed that the absolute Raman signal is very sensitive to the alignment of the sample. Furthermore, it was shown that for particle sizes below 140 nm and solid weight contents below 20%, changes in the absolute Raman signal can be described fairly well by turbidity laws. For larger particle sizes and higher solid weight contents deviations occur, but a correlation between these variables and the Raman signal still exists. In contrast, the normalized intensities are not influenced by varying the sample alignment in measurements on polymer latexes when using an excitation laser source at 532 nm. The important consequence of this is that the determination of chemical composition is not influenced by the elastic light scattering effects.

ABSTRACT:A new model for estimating reactivity ratios using the integrated copolymerization equation is presented. The model is a general nonlinear least squares method taking the error in both monomer conversion and monomer fraction into account by a relation between these two variables. Simulations show that the model is able to predict reactivity ratios successfully. Special attention is given to experimental design, i.e., at which initial monomer feed ratios the experiments should be performed in order to obtain reliable values for the reactivity ratios.

A new model for estimating reactivity ratios using the integrated copolymerization equation is presented. The model is a general nonlinear least squares method taking the error in both monomer conversion and monomer fraction into account by a relation between these two variables. Simulations show that the model is able to predict reactivity ratios successfully. Special attention is given to experimental design, i.e., at which initial monomer feed ratios the experiments should be performed in order to obtain reliable values for the reactivity ratios. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3793–3803, 1999

The copolymerization of α‐methylene‐γ‐butyrolactone and methyl methacrylate in DMSO was studied by on‐line Raman spectroscopy. Reactivity ratios for this system were estimated from the in situ conversion measurements. The estimates are in good agreement with estimates obtained from low‐conversion experiments where the composition of the copolymer was analyzed by 1H‐NMR. In order to obtain reliable estimates from the Raman data in combination with the integrated copolymerization equation, at least two experiments starting from different initial monomer feed fractions should be conducted. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3804–3816, 1999

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