Harold A. S. Schoonbrood

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.

Effect of composition drift on emulsion copolymerization rate

Abstract With potassium persulphate as initiator and sodium dodecyl sulphate as emulsifier, the batch emulsion copolymerization rate behaviour of styrene (S) and methyl acrylate (MA) was investigated at 50°C, varying the monomer ratio and the monomer to water ratio. The composition drift occurring during the copolymerization is determined by the reactivity ratios and by the monomer partitioning between the various phases present in the emulsion system. Monomer partitioning studies show that the monomer ratio in the latex particles is equal to the monomer ratio in the droplets, although the total monomer swellability of the (co)polymer latex particles depends upon copolymer composition and monomer droplet composition. In the absence of monomer droplets the equilibrium monomer concentration in the aqueous phase is closer to its saturation value (i.e. water solubility) than the monomer concentration in the latex particles. As a consequence of the composition drift, the kinetic behaviour differs widely from the homopolymerizations depending upon the initial monomer ratio. The copolymerization rate strongly varies during copolymerization resulting in a conversion-time plot differing in shape from the sigmoidal shape usually observed in emulsion homopolymerization. The penultimate effect in S-MA copolymerization has been proved to be responsible for this, as can be seen clearly from the conversion dependence of the copolymerization rate during batch emulsion copolymerizations starting from an MA-rich monomer feed, leading to a strong composition drift.

Emulsion co- and terpolymerization of styrene, methyl methacrylate and methyl acrylate. II. Control of emulsion terpolymer microstructure with optimal addition profiles

An optimal addition profile for the preparation of a chemically homogeneous emulsion terpolymer of styrene, methyl methacrylate, and methyl acrylate was determined using a recently developed model for describing composition drift in emulsion co- and terpolymerizations. TRISEPS, described in Part I of this series. The model uses recently published simplified equations to describe monomer partitioning and the terminal model for describing terpolymer composition. The optimal addition rate profile was determined from the calculated optimal addition profile with a purely empirical and iterative method. With gradient polymer elution chromatography (GPEC®) the homogeneity and/or heterogeneity of the terpolymers prepared in the iterative series of experiments could be determined and compared to the heterogeneity of the corresponding batch terpolymer described in Part I. It was shown that a homogeneous terpolymer could be obtained indicating that the simplified equations for monomer partitioning and the terminal model for terpolymer composition describe the system adequately. It was also shown that GPEC® was useful in the determination of the optimal addition rate profile.