Combatting ionic aggregation using dielectric forces—combining modeling/simulation and experimental results to explain end-capping of primary amine functionalized polystyrene

Chain-end functionalization of living poly(styryl)lithium using 1-(3-bromopropyl)-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclo-pentane (BTDP) to generate primary amine end-functionalized polystyrene was investigated using high vacuum anionic polymerization techniques. 13C NMR spectroscopy and Matrix Assisted Laser Desorption Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS) were used to evaluate polymer end-groups and demonstrated that quantitative amine functionalized polymer was attained under appropriate reaction conditions. In general, the polymerization of styrene was conducted in benzene and the end-capping reaction was performed by adding tetrahydrofuran (THF) to the reaction prior to the addition of BTDP in THF at room temperature. Results indicated that approximately 20% THF by volume is required to obtain 100% end-capping free from side reactions. When too little or no THF was present, side reactions such as lithium halogen exchange followed by Wurtz coupling resulted in unfunctionalized head-to-head dimer as well as other byproducts. Modeling and simulation of the solvent effects using hybrid methods (the so-called QM/MM method) suggest that THF effectively dissociated the anionic chain-end aggregation, thereby resulting in the desired primary amine functionalized polymer. Molecular dynamics (MD) simulations were conducted to develop an understanding of the physics of counterions involved in the end-functionalization process.