| Abstract: | Products of free‐radical polymerization (FRP) are usually not regulated on the molecular scale, consisting of blocks obtained through the fastest kinetic scheme pathways. The side or kinetically restricted products can be a source of impurities in a complex FRP case, or possess new properties if isolated solely. FRP synthesis of poly(divinyl ether‐alt‐maleic anhydride), known as “DIVEMA”, serves as a polymerization example with such kinetic and thermodynamic complexities. Uncertainty in factors regulating polymer structure is a challenge in advancement “DIVEMA” derivatives toward medical practice. In‐depth investigation via quantum‐chemical and molecular mechanics methods unveils mechanistic aspects of polymer stereoisomerism and confirms possible isolation of thermodynamically or kinetically controlled products on a large data set. Strategies toward regulation of 5‐exo/6‐endo cycloisomerism are theorized and then studied via microkinetic modeling. Thermodynamically controlled products can be isolated utilizing lower monomer concentrations, in range of 10?3 to 10?1 m , and/or application of a complexing agent that is better to realize via solvents, capable of formation π‐ and σ‐radical complexes. Change of electrophilic monomer is proposed as an approach for designing more molecularscale adjustable copolymerization processes. Methodology, obtained results, and conclusions for “DIVEMA” can be valuable to control other FRP processes on the molecular scale, unlocking polymers with improved or new functionalities. |
