Effect of N‐methylimidazole and 3,5‐dimethylpyrazole ligands on the polymerization of di(2,6‐dichlorophenolato) Cu(II)/Co(II) complexes in the solid state

The polymerization of 2,6-dichlorophenol (DCPH) was achieved through the thermal decomposition of copper complexes of DCPH with N-methylimidazole (NMIz) and 3,5-dimethylpyrazole (DMPz) ligands. Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), mass spectrometry, ultraviolet–visible spectroscopy, diffuse reflectance spectroscopy, magnetic susceptibility balance, electron spin resonance, X-ray analysis, and elemental analysis were used to characterize the complexes. The polymerization was achieved either in the solid state or in the melt. The structural analyses were performed with FTIR and NMR spectroscopy analyses. The glass-transition temperatures were determined by DSC, and the intrinsic viscosities were determined by viscosimetry. The effects of the temperature and time on the conversion percentage and viscosity of the polymers were examined. Varying the decomposition temperature during a 3-h scan showed that the DMPz complex of Cu decomposed at lower temperatures than the NMIz complex, whereas the NMIz complex yielded a higher conversion to the polymer. Complexes of DCPH with NMIz and DMPz ligands produced 1,2- and 1,4-addition products, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3797–3805, 2004

[1]  J. Reedijk,et al.  Transition metal compounds of chlorophenols: synthesis, characterization and single-crystal X-ray structures of (N,N,N′,N′-tetramethyl-ethylenediamine)bis(2,4,6-trichlorophenolato)cobalt(II) and bis(N-methylimidazole)bis(2,6-dichlorophenolato)copper(II) , 1998 .

[2]  M. Pulat,et al.  Synthesis of poly(dihalophenylene oxide)s by solid state thermal decomposition of bis(4-chloro-2,6-dibromo phenoxo) ethylenediamine copper (II) complex , 1995 .

[3]  M. F. Richardson,et al.  Coordination of ortho chlorines in nickel and zinc 4-substituted 2,6-dichlorophenolates. Crystal and molecular structures of (N,N,N',N'-tetramethyl-1,2-ethanediamine)bis(2,4,6-trichlorophenolato-O,Cl)nickel(II) and tris(pyridine)bis(2,4,6-trichlorophenolato-O)nickel(II) , 1993 .

[4]  W. Pennington,et al.  Diiron and dicobalt complexes of a phenolate-bridged binucleating ligand with mixed phenolate and pyridine podands , 1993 .

[5]  M. Baştürkmen,et al.  Synthesis and characterization of poly(dichlorophenylene oxide)s through solid state thermal decomposition of bis(pyridine)bis(trichlorophenoxo)copper(II) complexes , 1993 .

[6]  M. Baştürkmen,et al.  Solid state polymerization of bis(trichlorophenoxo) cobalt(ii) complex to give poly(dichlorophenylene oxide) , 1993 .

[7]  M. Ward,et al.  The Co-ordination chemistry of mixed pyridine-phenol and phenanthroline-phenol ligands ; effects of π-stacking interactions and ligand rigidity on complex structures , 1992 .

[8]  M. Ward,et al.  Co-ordination chemistry of mixed pyridine–phenol and phenanthroline–phenol ligands; a variable-temperature electron paramagnetic resonance and magnetic susceptibility study on two binuclear copper(II) complexes with Cu2(µ-O)2(µ-1,3,-O2CMe) cores , 1992 .

[9]  T. N. Sorrell,et al.  Synthesis and dioxygen reactivity of dinuclear copper-phenolate and copper-phenol complexes with pyrazole and pyridine donors , 1990 .

[10]  J. D. Crane,et al.  The crystal structure of a µ-phenolato copper(II) dinuclear complex containing two chemically distinct metal co-ordination environments , 1990 .

[11]  G. Wulfsberg,et al.  A 35Cl NQR study of coordination of chlorines in cobalt(II) 4-substituted-2,6-dichlorophenolates , 1983 .

[12]  J. Reedijk,et al.  Transition metal compounds containing substituted imidazole ligands and substituted phenoles as anions , 1983 .

[13]  A. Shaver,et al.  Comparison of the structures of poly(dibromophenylene oxides) produced by free radical initiation and by decomposition of copper tribromophenoxide , 1982 .

[14]  J. Plowman,et al.  Small molecule analogues for the specific metal-binding site of lactoferrin. Part 2. Phenolato-complexes of copper(II) and the nature of the charge-transfer transition in the visible region , 1981 .

[15]  M. Ladd,et al.  The structures of bis(pyridine)bis(2,4,6-trichlorophenolato)copper(II) and bis(2-methoxy-4-nitrophenolato)bis(γ-picoline)copper(II) , 1980 .

[16]  J. Reedijk,et al.  Transition metal 2,4,6-trichlorophenolates coordinated by imidazole, N-methylimidazole and 1,2-dimethylimidazole , 1980 .

[17]  J. Reedijk,et al.  SPECTROSCOPIC STUDY AND X-RAY STRUCTURE OF TETRA(N-METHYLIMIDAZOLE)PLATINUM(II) HEXACHLOROPLATINATE(IV) , 1980 .

[18]  R. G. Little.  Structure of cis‐bis(1‐methylimidazole)bis‐(o‐nitrophenolato)cobalt(II) , 1979 .

[19]  K. J. Palmer,et al.  The crystal and molecular structure of bis(2,4,6‐trichlorophenolato)diimidazolecopper(II) monohydrate, Cu(C3H4N2)2(C6H6OCl3)2.H2O , 1976 .

[20]  J. Harrod,et al.  Chemistry of phenoxo complexes. III. Preparation and characterization of some bis(chelato)bis(phenoxo)titanium(IV) complexes , 1975 .

[21]  D. Povey,et al.  Substituted phenols as ligands. Part IV. Six- and four-co-ordinate copper(II) complexes with nitrogen bases. X-Ray crystal structure analysis of bis-(2-methoxy-4-nitrophenolato)bis(pyridine)copper(II) , 1974 .

[22]  B. Hathaway.  The correlation of the electronic properties and stereochemistry of mononuclear {CuN4–6} chromophores , 1972 .

[23]  A. Haaland,et al.  Metal Complexes with Mixed Ligands. 5. The Crystal Structure of Diimidazole-copper(II) Dichloride, Cu(C3H4N2)2Cl2. , 1972 .

[24]  S. Svensson,et al.  Metal Complexes with Mixed Ligands. 2. Molecular and Crystal Structure of Catena-di-mu-perchlorato[di-mu-imidazolato-diperchlorato-octa-imidazolo-tricopper(II)]; Cu3(C3H3N2)2(C3H4N2)8(ClO4)4. , 1972 .

[25]  L. H. Vogt,et al.  Autoxidation of some phenols catalyzed by ring-substituted salcomines , 1970 .

[26]  J. Harrod.  Phenoxo complexes of copper(I1) , 1969 .

[27]  H. M. V. Dort,et al.  Poly-p-phenylene oxide , 1968 .

[28]  実男 杉田.  過酸化ニッケルと2,6-二置換フェノール類との反応 , 1966 .

[29]  H. S. Blanchard,et al.  Polymerization by oxidative coupling. IV. Polymerization of 4‐bromo‐ and 4‐chloro‐2,6‐dimethylphenol and preparation and decomposition of the silver and copper salts of certain other phenols , 1962 .

[30]  W. Hunter,et al.  A CATALYTIC DECOMPOSITION OF CERTAIN PHENOL SILVER SALTS. II. THERMAL DECOMPOSITIONS: THE FORMULA OF THE UNPOLYMERIZED RESIDUES. , 1917 .

[31]  W. Hunter,et al.  A CATALYTIC DECOMPOSITION OF CERTAIN PHENOL SILVER SALTS. [FIRST PAPER.1] , 1916 .