Copper(0)-mediated radical polymerisation in a self-generating biphasic system

Abstract

ABSTRACT. Herein, we demonstrate the synthesis of well-defined poly(n-alkyl acrylate)s via copper (0)-mediated radical polymerisation in a self-generating biphasic system. During the polymerisation of n-butyl acrylate in DMSO the polymer phase separates to yield a polymer-rich layer without trace of copper salts (XPS analysis). The poly(n-butyl acrylate) has been characterized by a range of techniques, including GPC, NMR and MALDI-TOF, to confirm both the controlled character of the polymerisation and the end group fidelity. Moreover, we have successfully chain extended poly(n-butyl acrylate) in this biphasic system several times with n-butyl acrylate to high conversion without intermediate purification steps. A range of other alkyl acrylates have been investigated and the control over the polymerisation is lost as the hydrophobicity of the polymer increases as the alkyl chain length increases indicating that it is important for the monomer to be soluble in the polar solvent.

Graft modification of methyl acrylate onto chicken feather via surface initiated Cu(0)‐mediated reversible‐deactivation radical polymerization

“…All of three types of vinyl monomers were grafted onto feather successfully. Both narrow distribution and good consistency with theoretical molecular mass were achieved in grafting acrylates (e.g., EA and n ‐BA) onto feather as expected . Besides, the controllability of grafting MMA was limited.…”

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

“…Many groups currently performing SET-LRP choose this method due to its speed and simplicity. 164,205 3.5.2.3. Self-Activating Solvents.…”

Aqueous SET-LRP catalyzed with “in situ” generated Cu(0) demonstrates surface mediated activation and bimolecular termination

“…3 Subsequently, SET-LRP was expanded to acrylates, [4][5][6][7][8][9][10][11][12][13][14][15][16][17] methacrylates, 8,[18][19][20][21][22][23][24][25] acrylamides, [26][27][28][29][30][31] methacrylamide, 32 acrylonitrile, 33,34 and monomers containing more complex water soluble side groups, such as sugars, 35,36 N-(2-hydroxypropyl) methacrylamide, 32 dimethylacrylamide, 26 N-isopropylacrylamide, 26,[37][38][39] oligo(ethylene oxide) methyl ether acrylate, 40 oligo(ethylene oxide) methyl ether methacrylate, 41 hydroxyethyl acrylate, 10 hydroxyethyl methacrylate 23 and acryloyl morpholine. 42 At the same time as these developments, the list of solvents used in SET-LRP was expanded to other solvents that in combination with aliphatic N-donor ligands, such as tris[(2-dimethylaminoethyl)...…”