The synthesis of (N<SUP>1</SUP>E,N<SUP>4</SUP>E)-N<SUP>1</SUP>,N<SUP>4</SUP>-bis(pyridine-2-YL) ethylene benzene-1,4-diamine and investigation of its efficiency as new binuclear catalyst complex in copper-based ATRP
H Arslan, M. Gurkan Kaptan, Orcun Zirtil, Murat Emre Hanhan, Sadi Sen
article (Uluslararası, Hakemli) | Yazar(lar): H Arslan, M. Gurkan Kaptan, Orcun Zirtil, Murat Emre Hanhan, Sadi Sen | Yıl: 2014 | Dergi/Kurum: POLYMER BULLETIN | İndeks: WOS.SCI | DOI: 10.1007/s00289-014-1110-9 | Anahtar Kelimeler: (N-1 EN4 E)N1, N-4-bis( pyridin-2-yl) ethylene benzene-1, 4-diamine (BPEBD), Cu-based at
((NE)-E-1,(NE)-E-4)-N-1,N-4-bis(pyridin-2-yl) ethylene benzene-1,4-diamine (BPEBD) was synthesized by condensation of 2-acetyl pyridine and 1,4-diaminobenzene and its efficiency as a catalyst in Cu-based atom transfer radical polymerizations (ATRP) of methyl methacrylate (MMA) and styrene (S) was investigated. Linear first-order kinetic plots were obtained. However, there were induction periods. The apparent rate constant values of ATRP of MMA with CuCl/BPEBD catalyst system in toluene were found to be between 2.10 x 10(-5) and 9.83 x 10(-5) s(-1), while they were between 6.67 x 10(-6) and 3.30 x 10(-5) s(-1) in the case of acetonitrile, indicating the presence of a low radical concentration throughout the polymerizations. Low apparent rate constant values denote a good control over ATRP in general. Apparent rate constant vs [ligand]/[catalyst] ratio plots showed a maximum at the [ligand]/[catalyst] ratio of 1. In the ATRP of MMA in toluene, M (n,GPC) values increased linearly with conversion and these molecular weight values were close to M (n,th) in comparison to that of in acetonitrile. In the polymerization of S, the control of molecular weights was not good, although the reactions were first-order kinetics. Cyclic voltammetry measurements confirmed that CuCl/BPEBD complex in acetonitrile gives quasi-reversible redox couples, and copper (I) centers in CuCl/BPEBD binuclear catalyst complexes are readily oxidized and it potentially suits to facile ATRP.