Emulsion co- and terpolymerization of styrene,methyl methacrylate,and methyl acrylate. I. Experimental determination and model prediction of composition drift and microstructure in batch reactions

In Part I of this series the reactivity ratios of the comonomer pair methyl acrylate-methyl methacrylate were determined with low-conversion bulk polymerizations. It was shown that the binary reactivity ratios of the systems styrene-methyl acrylate, styrene-methyl methacrylate, and methyl acrylate-methyl methacrylate describe composition drift in low-coversion bulk terpolymerizations with these monomers reasonably well. A computer model was developed to simulate the composition drift in emulsion co- and terpolymerizations. The composition drift in two batch emulsion copolymerization systems (styrene-methyl acrylate and methyl acrylate-methyl methacrylate) and one emulsion terpolymerization system (styrene-methyl acrylate-methyl methacrylate) was investigated both experimentally and with the model. Experimental results were compared with model calculations. The copolymer chemical composition distributions (CCD) were determined with gradient polymer elution chromatography (GPEC®). This technique was also used for the first time to obtain information about the extent of composition drift in emulsion terpolymerizations. Cumulative terpolymer compositions were determined with ³H-NMR as a function of conversion and with this information the three-dimensional CCD was obtained. The composition drift was analyzed with respect to free radical copolymerization kinetics (reactivity ratios) and monomer partitioning. It was shown that in most emulsion copolymerizations the composition drift is mainly determined by the reactivity of the monomers and to a lesser extent by monomer partitioning, except in systems where there is a large difference in water solubility. The model predictions for cumulative terpolymer composition as a function of conversion and the three-dimensional terpolymer CCD showed excellent agreement with the experiments. The GPEC® elution chromatogram of the terpolymer was found to be in accordance with the predicted CCD and the experimentally determined CCD. © 1996 John Wiley & Sons, Inc.