The influence of monomer ionization and hydrolysis on the radical polymerization kinetics of 2-(dimethylamino)ethyl methacrylate in aqueous solution

Abstract

The aqueous solution radical polymerization of 2-(dimethylamino)ethyl methacrylate (DMAEMA) is investigated using in-situ nuclear magnetic resonance spectroscopy. While fully ionized DMAEMA is stable over the time scale of polymerization, the...

Propagation rate coefficients of 2-(dimethylamino)ethyl methacrylate radical polymerization in bulk, alcohols and alcohol/water solutions determined by PLP-SEC

“…Previous studies show that k p of DMAEMA is significantly higher in water than in bulk. 40 The rate of monomer conversion has also been found to be much higher in water compared to that measured in organic solvent, 10 suggesting that direct synthesis of PDMAEMA in water should be favoured. However, the pH-dependent hydrolysis of DMAEMA in water to form ionized MAA and 2-(dimethylamino)ethanol (DMAE) complicates the polymerization system, with the final polymer product formed a copolymer of DMAEMA and MAA.…”

“…However, the pH-dependent hydrolysis of DMAEMA in water to form ionized MAA and 2-(dimethylamino)ethanol (DMAE) complicates the polymerization system, with the final polymer product formed a copolymer of DMAEMA and MAA. 10 Polymerization in EtOH provides a means to reduce this monomer loss, as the rate of DMAEMA alcoholysis to form ethyl methacrylate (EMA) and DMAE is greatly reduced compared to the rate of monomer hydrolysis in water. 11,12 While degradation is significantly retarded in EtOH, the advantage of a higher polymerization rate is lost, as the PLP-SEC data reported above indicates that the k p of DMAEMA in EtOH is not increased above the bulk value until monomer concentration is greatly reduced.…”

“…While directly reacting DMAEMA in water would simplify polymer synthesis, the polymerization is complicated by pH-dependent DMAEMA ionization and hydrolysis reactions, with the hydrolysis product methacrylic acid (MAA) reacting as an in situ generated comonomer. 10 Although a similar reaction occurs in alcohols, the scant data available suggests that the rate of DMAEMA alcoholysis is greatly reduced compared to its rate of hydrolysis in aqueous solution. 11,12 Thus, we are undertaking a systematic study of DMAEMA radical polymerization kinetics in water and other polar solvents.…”

“…11,12 Thus, we are undertaking a systematic study of DMAEMA radical polymerization kinetics in water and other polar solvents. 10…”

Elucidating the Effect of Amine Charge State on Poly(β-amino ester) Degradation Using Permanently Charged Analogs

“…By furthering our understanding of the phenomena involved in PBAE and PBQAE degradation as well as the role of amine charge state on ester hydrolysis, we hope this work informs future predictive degradation models, a step toward realizing these versatile polymers as sacrificial materials, drug delivery vehicles, and degradable alternatives to single-use plastics. Moreover, these findings may inform the degradation behavior of other emerging hydrolyzable polymers with basic groups, including poly­(α-amino ester)­s, poly­(ester urea)­s, and poly­(2-[dimethylamino]­ethyl acrylate)­s and methacrylates. ,,, …”