Metal-4,4',4",4"'-tetracarboxyphthalocyanine [Metal = Fe(III), Co(II), Mt-taPc] were synthesized by the hydrolysis of metal-4,4 ',4 ",4 "'-tetracarboxamidephthalocyanine (Mt-tamPc). These metal-taPc are soluble in water and in aprotic polar solvents such as N.N '-dimethylformamide. Poly(styrene) bonded Mt-taPc was synthesized by Friedel-Crafts reaction of poly(styrene) with Mt-taPc tetraacid chloride. The polymers contain about 4 mole-% Mt-Pc rings which are covalently bonded to poly(styrene). The decomposition reaction of hydrogen peroxide by catalysis with polystyrene containing Mt-Pc rings was carried out in heterogeneous aqueous media at pH 7,O. The polymer catalysts show a catalase-like activity. The activation energies with the polymer bonded Mt-Pc were found to be about half of those with Mt-taPc.From continuous flow experiments in a column, the polymer attached catalyst was found to be very stable, compared with free Mt-taPc.

The decomposition reaction of hydrogen peroxide was carried out by using Fe(II1)-3,4,3 ',4',3 ",4'~,3"',4"'-octacarboxyphthalocyanine (Fe(II1)-oaPc) as a catalyst, which has previously been reported by Boston et al. Fe(II1)-oaPc is a remarkably effective catalyst for the reaction, compared with hemin, other metal-phthalocyanine compounds, or other iron complexes such as [Fe(III)-(bipy),]X,. The kinetics of this reaction was also investigated in the pH range 5 3 -10,5 by measuring the initial velocity, V,, of the increasing concentration of 0, using a Warburg respirometer. The reaction proceeds according the catalase-like mechanism. On the basis of the results of Sigel et al., the reaction mechanism is discussed.

A novel class of polyimides (14) containing Mt(I1)-phthalocyanine rings has been synthesized by the solution condensation in N-methyl-2-pyrrolidone (NMP) of Mt(I1)-[2,9or10(or2,16or17)bis(3,4-dicarboxybenzoyl)]phthalocyanine dianhydride (Mt(I1)-dahPc; Mt(1I) =Co(II), Ni(I1) and Cu(I1); (2-4)) with aromatic diamines such as 4,4'-methylenebis(aniline), followed by thermal imidization in vacuo at 200 "C. The polyamides obtained were soluble in NMP and hexamethylphosphoric triamide, having inherent viscosities up to 0.7 d1.g-I. The polyimides were stable up to 350 "C, and showed room temperature-dc-resistivities in the range of 10" to 10'fl.cm.

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A novel class of polyimides (6ac) containing Mt(I1)-phthalocyanine rings was synthesized by solution condensation in N-methyl-2-pyrrolidone of Mt(I1)-[2,9, or 10(or 2,16, or 17)bis(3,4-dicarboxybenzoyl)]phthalocyanine dianhydride [Mt(II)-dahPc: Mt(I1) = Co(II),Ni(II), and Cu(II)] with 2,6-diaminopyridine, followed by thermal imidation. The polyimides showed room temperature dc-conductivities in the range of -Q-' .cm-', and, after quaternization of the pyridine group, the conductivities increased by 1 to 3 orders of magnitude.n-' .crn-'.containing metal-phthalocyanines and ion components in the conjugated chain.The present paper is concerned with the synthesis and conductivity of polyimides a) Part 11: 0. Hirabaru, T.