Atom transfer radical polymerization of styrene initiated by triphenylmethyl chloride

Triphenylmethyl chloride (TPMCl) was employed for the first time as the initiator of atom transfer radical polymerization (ATRP) of styrene in the presence of CuCl/N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA) as catalyst and cyclohexanone as solvent. The kinetic plot was first-order with respect to monomer. A linear increase of number average molecular weight (Mn) vs. monomer conversion was observed, and the molecular weight distribution (MWD) was relatively narrow (Mw/Mn = 1.2–1.5). 1H NMR spectra revealed the ω-Cl group at the chain end. Another two initiators, benzyl chloride (BzCl) and diphenylmethyl chloride (DPMCl), were also employed in contrast with triphenylmethyl chloride to investigate the influence of phenyl numbers on the polymerization.