Thermal Polymerization of Dimethylaminoethyl Methacrylate

Synthetic and characterization aspects of dimethylaminoethyl methacrylate reversible addition fragmentation chain transfer (RAFT) polymerization

“…P 5 could correspond to the expected chains that have undergone an oxidation of the thiocarbonyl bond (possibly during storage under air). DMAEMA is able to self initiate under thermal conditions as depicted by Shalati and coworkers 41. Although the authors underlined that the corresponding rate of initiation was very low, P 6 could result from chains thermally initiated and under RAFT control.…”

“…This set of two experiments seems to show that no retardation occurs in this system, although several studies including theoretical simulations reported that slow fragmentation of the intermediate radical during the pre‐equilibrium35–37 or termination of the intermediate radical38–40 may be at the origin of such a phenomenon, particularly observed for phenyl based CTA and methacrylate monomers. In the particular case of DMAEMA, the bending ability of the amine group41, 42 could influence the stability of the intermediate radical, the origin of which should be identified by a deeper investigation and sets of experiments well designed to probe this issue. The decrease of polymerization rate when increasing the targeted DP n results from the decrease of the radical flux since the ratio [CPDB]/[AIBN] is kept constant for all the experiments.…”

PDMAEMA from α to ω chain ends: tools for elucidating the structure of poly(2-(dimethylamino)ethyl methacrylate)

“…This value, coinciding with the calculated M n,theo , is an indication of overall good control over the polymerization; possible side reactions have not led to a deviation from the targeted DP. The occurrence of self-initiation (which has been shown to take place at higher polymerization temperature than that selected in this study 44 ) would affect this calculation; however, the absence of self-initiation was confirmed by MALDI TOF-MS analysis.…”

“…Polymer Chemistry take place at higher polymerization temperature than that selected in this study 44 ) would affect this calculation; however, the absence of self-initiation was confirmed by MALDI TOF-MS analysis.…”

“…24,43 Moreover, the amines may participate in nucleophilic substitutions and redox reactions. (2) Thermally induced selfinitiated free radical polymerization of DMAEMA is known to take place, although with a low rate of initiation, as first elucidated by Shalati et al 44 (3) DMAEMA readily undergoes hydrolysis when polymerized in the presence of water, generating methacrylic acid which is then incorporated into the polymer chain, to an extent that can be limited by controlling the pH and quantified. 45 PDMAEMA, on the other hand, is not sensitive to hydrolysis, 46 unlike its acrylate counterpart poly(2-(dimethylamino)ethyl acrylate).…”