Atom Transfer Radical Polymerization of iso‐Butyl Methacrylate in Microemulsion with Cationic and Non‐Ionic Emulsifiers

Abstract

Direct atom transfer radical polymerization (ATRP) of iso‐butyl methacrylate in microemulsion has been performed successfully for the first time. ATRP was performed at 40 °C with different emulsifier systems: i) the cationic emulsifier n‐tetradecyltrimethylammonium bromide (TTAB); and ii) mixed emulsifier systems based on TTAB and the non‐ionic emulsifiers Emulgen 911 or Emulgen 931. All polymerizations proceeded in a controlled/living fashion, and the microemulsions were transparent with particle diameters less than 15 nm. The emulsifier system TTAB/Emulgen 911 exhibited better control than TTAB only. This is proposed to be caused by complex formation between Emulgen 911 in the organic phase and CuBr2 (the deactivator), thus reducing the extent of exit of CuBr2 to the aqueous phase. The more hydrophilic Emulgen 931 did not lead to improved control.magnified image

RAFT Synthesis of Sterically Stabilized Methacrylic Nanolatexes and Vesicles by Aqueous Dispersion Polymerization

“…[9] For example, nitroxide-mediated living radical polymerization has been used by Charleux, [10][11][12][13][14][15] El-Aasser, [16] Okubo, [17] and Georges [18] to mediate the miniemulsion polymerization of n-butyl acrylate and styrene. ATRP has been optimized by Matyjaszewski [19][20][21][22] and Okubo [23][24][25] for the (mini)emulsion polymerization of (meth)acrylic and styrene monomers. Reversible additionfragmentation chain transfer (RAFT) polymerization has been extensively exploited in the context of both emulsion and miniemulsion polymerization by Hawkett, [26][27][28][29] Charleux, [30][31][32][33] El-Aasser, [34] Cunningham, [35] and Zhu.…”

Low Ppm Atom Transfer Radical Polymerization in (Mini)Emulsion Systems

“…Initially, it was thought that the key to success in ARGET ATRP in aqueous dispersed systems is strongly dependent on the ligand, which must be both hydrophobic and highly active [84]. Hydrophobicity prevents the catalyst from diffusing to the aqueous phase [84], while high activity, or K ATRP value, affords well-controlled polymerizations at low catalyst concentration [85]. The breakthrough in the field of ARGET ATRP in aqueous dispersed media was the design and synthesis of bis[2-(4-methoxy-3,5-dimethyl)pyridylmethyl]octadecylamine (BPMODA*) as a highly active ligand.…”

Atom transfer radical polymerization in aqueous dispersed media

“…The same AGET ATRP microemulsion procedure has also been successfully applied for polymerization of nBA. In another report, Okubo et al described a normal ATRP of iso-butyl methacrylate (iBMA) in microemulsion by employing dNbpy as ligand and the cationic emulsifier tetradecyltrimethylammonium bromide (TTAB) at 40°C [111]. The polymerization resulted in a monomodal and relatively narrow MWD (M w /M n = 1.32) and a transparent emulsion with D n ~ 13 nm.…”