Atom transfer rearrangement radical polymerization of (2,4,6-trihalophenolato) Fe(II) / Ce(III) / Ce(IV) complexes in solid state

Abstract

The synthesis of poly(dihalophenylene oxide)s by thermal decomposition of Fe(II), Ce(III) and Ce(IV) phenolato complexes with pyridine as neutral ligands were achieved at different temperature ranges (140o - 250oC) with different time intervals (3 - 48 hr) via atom transfer rearrangement radical polymerization (ATRRP). The complexes were characterized by FTIR, DSC, UV-Visible, mass spectroscopy, magnetic susceptibility and elemental analyses. Structural analyses of polymers were performed by 1H and 13C-NMR, FTIR spectroscopic analyses, Tg by DSC and the molecular weights by viscometrical method. 1H-NMR spectra of polymers are quite similar in pattern except the relative intensities of two main peaks, all having branched structures. The lowest percent conversion values were observed for polymers synthesized from Fe(III) complexes compared to Ce(III) and Ce(IV) complexes. The glass transition temperature of the polymers were quite high indicating they are rigid polymers (162o to 187 oC).

Poly(dibromophenylene oxide)s Through Atom Transfer Radical Rearrangement Polymerization of Various Transition Metal Complexes

“…This mechanism was modified (4) in 1981 as a result of 13 C-NMR studies. The final proposal provided by Kısakürek et al (11,12) involves a similar mechanism which concludes the reaction to be atom transfer radical rearrangement polymerization.…”

“…Kısakürek et al (4,6,(8)(9)(10)(11)(12) revealed much progress in understanding the mechanism of the reaction.…”