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Synthesis and characterization of poly(dihalophenylene oxides) by thermal decomposition of copper complexes with tetramethylethylenediamine and ethylenediamine ligands
Date
1989-2
Author
Ünal, H. Ibrahim
Kısakürek, Duygu
Şanlı, Oya
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Thermal polymerization of bis(trihalophenoxo)-N,N,N′,N′-tetramethylethylenediamine copper(ii) and bis(trihalophenoxo)ethylenediamine copper(ii) was achieved in toluene at 70°C. The dependences of intrinsic viscosity and the percentage yield of the polymers on a sequence of increasing decomposition times of copper complexes were investigated. Structural analyses of the polymers were carried out using mainly1H nuclear magnetic resonance spectroscopy and differential scanning calorimetry. 1,4-Catenation was highly favoured over 1,2-addition in 4-bromo-2,6-dichlorophenoxide- and 2,4,6-triiodophenoxide- (with ethylenediamine ligand) and 2,4,6-triiodophenoxide- (with tetramethylethylenediamine ligand) derived polymers. However, polymers synthesized from 2,4,6-trichlorophenoxide with either ligand displayed a selectivity in favour of 1,2-catenation, whereas for 2,4,6-tribromophenoxide with ethylene diamine ligand, 1,4-catenation and ortho substitution took place at roughly equal rates.
Subject Keywords
Organic Chemistry
,
Polymers and Plastics
,
Polymer Science
URI
https://hdl.handle.net/11511/51718
Journal
Polymer
DOI
https://doi.org/10.1016/0032-3861(89)90127-4
Collections
Department of Chemistry, Article
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BASTURKMEN, M; KISAKUREK, D (Elsevier BV, 1993-01-01)
Thermal polymerization of bis(pyridine)bis(trichlorophenoxo)copper(II) was achieved in the solid state for the first time. The time and temperature effect on polymer molecular weight, percentage yield and the structure of polymer was first studied, at constant temperature and then for constant decomposition time. Polymers were characterized by i.r., H-1 n.m.r. and C-13 n.m.r. The molecular weights of the polymers were obtained by viscometric measurements at 30-degrees-C in toluene and glass transition tempe...
POLYMERIZATION OF BIS(TRICHLOROPHENOXO) ETHYLENEDIAMINE COPPER (II) COMPLEX BY ELECTRO-OXIDATION
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Electroinitiated polymerization of bis(trichlorophenoxo) ethylenediamine copper (II) complex was carried out in dimethyl-formamide at various anodic peak potentials of the complex. The oxidation and reduction peak potentials were determined by cyclic voltammetry. These potentials were measured in tetrabutylammonium fluoroborate-dimethylformamide supporting electrolyte-solvent couple at room temperature. Polymerization reactions were carried out under air and nitrogen atmospheres using a constant potential a...
THERMAL POLYMERIZATION OF BIS(TRIHALOPHENOXO)COPPER(II) COMPLEXES IN EXCESS DIMETHYLFORMAMIDE AND DIMETHYL-SULFOXIDE AS LIGANDS
KISAKUREK, D; SANLI, O (1989-08-01)
Thermal decomposition of bis(trihalophenoxo)copper(II) complexes was achieved at 50°C in dimethylformamide or dimethyl sulfoxide. The resulting polymers, poly(oxydihalophenylene)s (2), were characterized by FTIR, 1H NMR and 13C NMR spectroscopy and by differential scanning calorimetry. The molecular weights were determined by the vapour pressure method. Tribrominated phenol derivatives prefer 1,4‐substitution, whereas with trichlorophenol derivatives 1,2‐and 1,4‐substitutions take place at equal rates in ei...
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Electroninitiated polymerization of bis(trichlorophenoxo)‐N,N,N′,N′‐tetramethylethylene diamine copper(II) was achieved in acetonitrile at various peak potentials of the monomer. A constant potential approach was selected in polymerization reactions. Electrolyses were carried out under air, nitrogen, and oxygen atmospheres. Structural analyses of the polymers were done by 1H‐NMR and 13C‐NMR FT–IR spectroscopy. Molecular weights of the polymers were determined by vapor pressure (isopiestic) method.
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Low-molecular-weight atactic poly(propylene oxide) and poly(epichlorohydrin) (PECH) were chlorinated on average up to 4.42 chlorine atoms per repeat unit. A study of the products showed that chlorine substitution preferentially occurred on already chlorinated repeat units, yielding chlorine -rich and chlorine -poor sequences. As the extent of chlorine substitution increased, the glass-transition temperature of the polymers markedly increased, and their solubility in most of the organic solvents drastically ...
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H. I. Ünal, D. Kısakürek, and O. Şanlı, “Synthesis and characterization of poly(dihalophenylene oxides) by thermal decomposition of copper complexes with tetramethylethylenediamine and ethylenediamine ligands,”
Polymer
, pp. 344–347, 1989, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/51718.