In this work, for a semicontinuous emulsion polymerization reaction, it is shown that using a redox initiation system at 40°C, substantial modifications in copolymer chain composition with conversion can be easily obtained. To test controllable trajectories for comonomer feeding, linear and parabolic profiles were chosen to get different types of chain composition variations for the 50/50 w/w styrene/n-butyl acrylate system. For the “forced composition copolymers,” the molecular weight averages and distribution were obtained by size exclusion chromatography. The composition along conversion was followed by proton nuclear magnetic resonance to determine the weight composition distribution (WCD) of the copolymer chains. Mechanodynamic (dynamic-mechanical analysis), tensile, and hardness tests exhibited consistent results depending on the WCD that outcomes from the respective feeding profile. The results confirm that this methodology is of great potential for industrial applications when looking for synergy in copolymer properties, and low-cost processes.
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