Alkylation of polyethyleneimine for homogeneous ligands in ATRP

• Published in: Polymer (Guilford) Vol. 52; no. 3; pp. 617 - 621
• Main Authors: Zorvaryan, Artun, Inceoglu, Sebnem, Acar, Metin H.
• Format: Journal Article
• Language: English
• Published: Kidlington Elsevier Ltd 03-02-2011; Elsevier
• Subjects: Alkylation; Applied sciences; Atom transfer radical polymerization (ATRP); Exact sciences and technology; Homogeneous polymerization; Ligands; Organic polymers; Physicochemistry of polymers; Polyethyleneimine; Polyethyleneimine ligand; Polymerization; polymers; Polymethyl methacrylates; Preparation, kinetics, thermodynamics, mechanism and catalysts; Radicals; Rate constants; styrene; Styrenes; Homogeneous polymerization; Atom transfer radical polymerization (ATRP); Polyethyleneimine ligand; Ethyleneimine derivative polymer; Ligand effect; Atom transfer polymerization; Living polymer; Organic ligand; Methyl methacrylate polymer; Copper complex; Complex catalyst; Experimental study; Alkylation; Chemical reaction kinetics; Solution polymerization; Chemical modification; Preparation; Styrene polymer; Rate constant; Catalyst activity; Reaction propagation; Polyethylene imine
• ISSN: 0032-3861; 1873-2291
• DOI: 10.1016/j.polymer.2010.12.041

Ethylated and butylated polyethyleneimine ligands were synthesized and employed in copper catalyzed atom transfer radical polymerization of styrene and methyl methacrylate with suitable initiators in order to obtain homogeneous polymerizations, resulting in well defined polymers with low polydispersities. Linear curves drawn from kinetics and conversion–molecular weight plots indicate that all the polymerizations were successfully controlled. In ATRP reactions of S and MMA, the apparent rate of polymerization,
k
p
app, exhibits a plateau at [Ligand]/[CuBr]
≥
0.5 ratio for both ligands. The apparent rate constant also decreases by increasing the alkyl chain length of the alkylated polyethyleneimine ligand. Ethylated and butylated polyethyleneimine ligands in ATRP of S and MMA were found to be faster than the existing ATRP ligands.
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