Preparation and reactivity of metal-containing monomers.

The thermal decomposition of Cu^II, Co^II, Ni^II, Mn^II, Fe^III, and Cr^III methacryloylacetonates has been compared with the thermal behavior of the corresponding acetylacetonates and poly (methacryioylacetonates). Dehydration and thermal polymerization of methacryioylacetonates occur at 110–160 °C. The results of the thermolysis conform with the Irving-Williams sequence for the stability of the complexes of bivalent transition metals. Thermal destruction of metallopolymers differs from that of low-molecular analogs. The temperature of complete decomposition of the compounds studied correlates with the number of electrons in the d-orbital of the metal.For part 35 seeRuss. Chem. Bull., 1993,42, 1972.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 43–47, January, 1994.     

Preparation and reactivity of metal-containing monomers

Vinylporphyrins containing one vinyl group at the pyrrole or benzene ring and their complexes with Cu²⁺ and Zn²⁺ have been obtained by the Wittig reaction. Compounds obtained were characterized by physicochemical methods. X-ray diffraction analysis of 5-(4-vinylphenyl)-10,15,20-triphenylporphyrin has been carried out. It is likely that the inclusion of the vinyl group is accompanied by weak electron effects on the macrocycle. No nonequivalence of N-H bonds is observed in initial macrocycles.     

Preparation and reactivity of metal-containing monomers

The stability of chelates of several bivalent metals with poly(methacryloylacetone) was determined by pH titration. Two models in which the fragment of a polymeric molecule in the coordination sphere of a metal was approximated by either a mono- or a bidentate ligand were considered. Different mechanisms of complex formnation were realized depending on the nature of M(II).For part 29 seeIzv. Akad. Nauk, Ser. Khim., 1993, 975 [Russ. Chem. Bull., 1993,42, 937 (Eng.Transl.)].Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1063–1066, June, 1993.     

Thermooxidative degradation of poly(methyl methacrylates) containing β-diketonate fragments

Thermooxidative degradation of poly(methyl methacrylates) containing in the chain cobalt, copper, and nickel 3-allylpentane-2,4-dionate residues was studied. The increase in the initial degradation temperature is associated with a change in the termination mechanism, decrease in the number of double bonds, and increase in the number of branchings. The increase in the final degradation temperature is associated with the formation of anhydride rings and chain branching, and is always proportional of the metal content of the polymer.     

Preparation and reactivity of metal-containing monomers

The stability constants of some bi- and trivalent metal complexes with methyl-, trifluoromethyl-, and phenyl-substituted 6-heptene-1,3-diones have been determined by pH-metric titration at 20 °C and an ionic strength = 0.1. It is proposed that vinyl groups of ligands are involved in complexation.For Part 44 seeIzv. Akad. Nauk, Ser. Khim., 1995, 1827 [Russ. Chem. Bull., 1995,44, 1758 (Engl. Transl.)].Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2404–2408, December, 1995.This work was partially financially supported by the International Science Foundation (Grant No. NJB000).     

Preparation and reactivity of metal-containing monomers. 23. Transition metal complexes of methacryloylacetone

The Cu(II), Ni(II), Co(II), Mn(II), Fe(III), and Cr(III) complexes of methacryloylacetone have been obtained. Magnetochemical, IR, and electronic spectroscopic studies have shown these to contain the copper ion in a square planar configuration, and the other metals in the octahedral configuration. The complexes have similar steric structures both in the crystal and in solution.Institute of Chemical Physics, Russian Academy of Sciences, 142432 Chernogolovka. I. I. Mechnikov Odessa State University. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 694–699, March, 1992.     

Preparation and reactivity of metal-containing monomers

Polymethacryloylacetonates of some transition metals were obtained by free-radical polymerization of the corresponding metal-containing monomers and the main regularities of the process were studied. The complexation with a metal ion decreased the reactivity of the methacryloylacetone towards polymerization in the series Mn^II > Co^II > Ni^II > Cr^III, which is analogous to the electronegativity of these metals. Macrochelates thus obtained contain one equivalent of metal per monomer unit and their molecular weights are within 10000–18200. The structure of the coordination site was shown to be retained in the course of polymerization.For communication 34, see Ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2060–2064, December, 1993.     

Enhancement of the luminescence of europium(III) β-diketonates in the ligand series β-diketones-their unsaturated analogues-copolymers

A change in the luminescence intensity of europium compounds was studied for the series of ligands β-diketones-their unsaturated analogues (monomers)-copolymers with styrene (methyl methacrylate). The optimal ratios of comonomers (1 : 2; 1 : 5) providing the maximum luminescence intensity of europium were determined. Europium (n x 10^-3%) was determined in Ce, Pr, Nd, and Ho oxides, which are strong luminescence quenchers, using copolymers containing trifluoroacetylacetone and benzoylacetone.     

Benzoyl peroxide-cobalt(II) vinyl-β-diketonate systems as initiators of styrene and methyl methacrylate polymerization

New cobalt(II) vinyl-β-diketone-benzoyl peroxide [or azobis(isobutyronitrile)] binary systems were studied as initiators of polymerization of styrene and methyl methacrylate.     

Preparation of Branched Poly(Methyl Methacrylate) Using a Macroinitiator Based on Cobalt(II) 3-Allylpentane-2,4-dionate

Cobalt(II) 2-allylpentane-2,4-dionate, when used as an initiator of methyl methacrylate polymerization, yields a polymer containing metal chelate groups and exhibiting the properties of a macroinitiator capable of initiating secondary polymerization with the formation of branched high-molecular-weight methyl methacrylate polymers with a low polydispersity.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 3, 2005, pp. 479–483.Original Russian Text Copyright © 2005 by Shevchenko, Voloshanovskii, Petrova, Berbat.