Copper(0)-mediated living radical polymerization of styrene

Abstract

The use of zerovalent copper and commercially available ligands enables the control of the polymerisation of styrene at 90 °C in toluene.

Cu(0)-Mediated Living Radical Polymerization: A Versatile Tool for Materials Synthesis

“…187 In addition, relatively small changes in ligand concentration can dramatically affect the end-group fidelity of the polymer chains, highlighting the importance of the ligand in Cu(0)-mediated polymerizations. 84 netriamine (PMDETA), 58,71,79,92,96,134,135,138,150 and tris(2-aminoethyl)amine (Tren) 79,136 have also been utilized as disproportionation in the presence of these ligands is near quantitative and polymerization proceeds with equally high end-group fidelity although a bit slower. 189 Interestingly, although Tren provided a slower polymerization rate when compared with Me 6 -Tren, the high end-group functionality was maintained demonstrating that the commercially available Tren is also an efficient ligand.…”

“…These polymerizations were performed in toluene at 90°C, and PMDETA was found to provide the best control (Đ ∼ 1.2) with good agreement between theoretical and experimental molecular weight, although conversion did not reach quantitative levels. 134 It should be noted that, in a nondisproportionating solvent, such as toluene, Cu I Br/Me 6 -Tren is expected to be relatively stable and thus contribute to the polymerization kinetics after the initial activation by Cu(0). In addition, the copolymerization of styrene with MMA was also 145 have also been polymerized via SET-LRP, demonstrating the versatility of the approach ( Figure 6 and Table 2).…”

Kinetic Studies of Elementary Reactions in SET-LRP / SARA ATRP

“…Thus performing polymerization in the presence of copper(0) in toluene (19,26,27) is a useful model for SET-LRP or SARA ATRP reactions in solvents that favor disproportionation or comproportionation, as equilibration between copper species can be neglected, leading to the simplified mechanism shown in Scheme 3. It is immediately apparent from Scheme 3 that the reaction involves net consumption of copper(0) and generation of dead polymer -indeed it could be summarized as:…”

Cu(0)-mediated living radical polymerisation in dimethyl lactamide (DML); an unusual green solvent with limited environmental impact

“…24,25 The polymerisation of styrene with Fe wire was investigated by Wang et al in DMF. 26 copolymer of styrene and acrylamide was also synthesised with Fe/TMEDA in DML.…”