Synthesis of poly(dihalophenylene oxide)s by atom transfer radical rearrangement polymerization via Ce(IV)/Ce(III) complexes in solid state

Authors: Çelik, Güler Bayrakli; Kisakürek, Duygu

Source: Designed Monomers & Polymers, Volume 9, Number 6, 2006 , pp. 663-676(14)

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Abstract:

Poly(dihalophenylene oxide)s by solid-state thermal decomposition of (trihalophenolato) cerium complexes with either N-methyl imidazole or pyridine as neutral ligands were synthesized at different temperatures (80-250°C) and different time intervals (3-48 h) via atom transfer rearrangement radical polymerization. The complexes were characterized by FT-IR, DSC, SEM, mass spectroscopy, magnetic susceptibility and elemental analyses. Structural analyses of polymers were performed by ¹H- and ¹³C-NMR, SEM and FT-IR spectroscopic analyses, T_g by DSC and the molecular weights by viscometry. 2,4,6-Trichlorophenolate displayed a slightly higher selectivity in favor of 1,2-addition, whereas 1,2- and 1,4-additions took place at equal rates in the case of 2,4,6-tribromophenolate. Pyridine complexes decomposed at lower temperatures and had lower polymer yield than the N-methyl imidazole complexes. Among the synthesized polymers in solid state, the highest intrinsic viscosity value of 0.058 dl/g (M_w = 7.15 × 10⁴) was achieved only with Ce(TCP)₃(Py)₂ complexes. All the polymers having high T_g values (178-189°C) were rigid.

Keywords: POLY(DIHALOPHENYLENE OXIDE); SOLID-STATE THERMAL DECOMPOSITION; ATOM TRANSFER RADICAL REARRANGEMENT POLYMERIZATION; CE(IV)/CE(III) COMPLEXES

Document Type: Research article

DOI: http://dx.doi.org/10.1163/156855506778944000

Publication date: 2006-11-01