Synthesis of polyesters by using divalent metal salts of monohydroxyethyl phthalate: Metal-containing polyesters from such metal salts,anhydride, and epoxide

Synthesis of metal-containing polyesters by reactions of the divalent metal salts of monohydroxyethyl phthalate with phthalic anhydride and epoxide were investigated. It was found that the metal carboxylate groups of these metal salts catalyze the above reactions. These reactions were further studied in model reactions with the use of the Ca salt of monoethyl phthalate. Products obtained were linear metal-containing polyesters containing ionic links in the main chain; they were yellow or slightly yellow glassy materials; yields were generally high. Molecular weights obtained by the end-group analyses were generally low; with increase in content of the metal salts in the feed the molecular weight of the polyesters decreased. Inherent viscosities (in DMF at 30°C) of the metal-containing polyesters were low, ranging from 0.033 to 0.052. Elemental analyses are generally in good agreement with the calculated values. Thermogravimetric analyses of the polyesters were also discussed.     

Synthesis of Polymers by Using Divalent Metal Salts of Mono(hydroxyethyl) Phthalate: Metal-Containing Three-Dimensional Polyesters from Metal Salts,Pyromellitic Dianhydride,and Epoxides

Syntheses of metal-containing three-dimensional polyesters were investigated by the reactions of divalent metal salts of mono(hydroxyethyl) phthalate-pyromellitic dianhydride-epoxide in DMF at 90° C. The metal carboxylate groups of these metal salts catalyzed the reactions. Systems with low metal salt content gelled during reaction. The yield of the products obtained by precipitating or washing with water increased with decreasing metal salt content in the feed. The products were metal-containing, three-dimensional polyesters containing ionic links; they were slightly yellow powdery materials. Hydroxyl values of the products were much higher than the values of acidity. Inherent viscosities (in DMF at 30° C) of the products obtained from the systems which did not gel were low, ranging from 0.031 to 0.083. The thermal stability of the products showed a tendency to increase with decreasing metal salt content in the feed.     

Syntheses and properties of halato-telechelic polyurethane-ureas from divalent metal salts of p-aminobenzoic acid,diamine, dialkylene glycols,and diisocyanate

Halato-telechelic polyurethane-ureas were synthesized from divalent metal salts of p-aminobenzoic acid, 4,4′-diaminodiphenylmethane (4,4′-methylenedianiline, MDA), dialkylene glycols, and 2,4-toluylene diisocyanate (TDI). As the divalent metal, Mg and Ca were used, and diethylene glycol and dipropylene glycol were the glycols used. The halatotelechelic polyurethane-ureas obtained showed better solubilities in dimethylformamide (DMF) and dimethylsulfoxide (DMSO) than previously reported halato-telechelic polyureas from the metal salts, MDA, and TDI. The reduced viscosities of the polyurethane-ureas in DMF and DMSO were very low at very low concentrations but increased as the concentration increased. The increase was higher in DMF having lower dielectric constant, due to lower depression of ionic association. Introducing the metal into the urethane-urea backbone resulted in a considerable decrease in decomposition temperature. In dynamic mechanical property measurements, they exhibited no sharp decrease in relative shear modulus and no peak of tan δ, probably due to aggregation of ionic groups in the polymer main chain.     

Synthesis and properties of new carbazole-containing metallopolymers with transannular polyconjugation in the backbone

New metal-containing polymers, poly(salicylidene azomethines) containing metal atoms (Co, Ni, Cu) in the backbone, were synthesized from aromatic carbazolediamine derivatives. It was found that the polymers with a decyl substituent in the carbazole fragment are soluble in organic solvents (chloroform, methanol, DMSO, DMF) and exhibit film-forming and semiconductor properties. IR and NMR spectroscopy was used to show that the semiconductor properties of the new polymers are associated with the presence in the polymer backbone of transannular polyconjugation zones formed by intramolecular donor?acceptor interactions of the metal and nitrogen valence shells.     

配合物聚合反应研究──Ⅰ.以对氨基苯磺酸盐合成聚酰亚胺

以对氨基苯磺酸的二价金属配合物为原料合成了一系列主链上含金同元素（Ｃａ，Ｃｕ．Ｃｏ，Ｍｉ）的聚酰亚胺．以元素分析、ＩＲ和固体（１３）Ｃ－ＮＭＲ对其组成及结构进行了表征，通过ＴＧ－ＤＴＡ研究了其热性能，并讨论了含金属元素聚酰胺酸溶液的粘度与其中金属元素及其含量的关系     

Metal-containing crosslinked polyester resins by combined polyesterification and polymerization of curable mixtures based on divalent metal salts of mono(hydroxyethyl)phthalate

Preparations of metal-containing crosslinked polyester resins based on divalent metal salts of mono(hydroxyethyl)phthalate were investigated by the cure, by combined polyesterification and polymerization, of curable mixtures prepared from above metal salts, maleic anhydride, glycidyl methacrylate, and methyl methacrylate. The curable mixtures containing Ca showed lower viscosity than those containing Mg. They were subjected to curing reactions in the presence of peroxide and under photoirradiation, respectively. In the cure, polyesterification and polymerization proceeded simultaneously smoothly, giving metal-containing cured resins. Generally, the peroxide-cured resins showed better physical properties than the photo-cured resins. Especially, the former resins with high metal content showed high compressive strength and Rockwell hardness. Further, resistance to chemical attack and boiling water and thermal behavior are also discussed.     

Synthesis of polymers by using divalent metal salts of mono(hydroxyethyl) phthalate: Metal-containing polyurethanes

As difunctional compounds containing an ionic bond in the molecule, divalent metal salts (I) of mono(hydroxyethyl) phthalate were prepared in high purity and high yield. Mg and Ca were selected as divalent metal. Metal-containing polyurethanes containing ionic links in the main chain were synthesized by the polyaddition reaction of I or, I–glycols with diisocyanates. The polyurethane obtained were glassy materials or white powders, depending on the species of diisocyanates and glycols. Close agreement between observed and calculated values of metal content of the polyurethanes were obtained. The viscosities (in dimethyl-formamide) of the polyurethanes decreased markedly with increasing of metal content. Moreover, the decomposition temperatures were lowered by introduction of metals into the polyurethanes. However, the decomposition rates of metal-containing polyurethanes were lower than those of polyurethanes not containing metal.     

Oxidation of Chromium and Molybdenum Arenetricarbonyl Complexes with tert-Butyl Hydroperoxide in Aprotic Solvents and in Methanol

Oxidation of chromium and molybdenum arenetricarbonyl complexes AreneM(CO)₃ with tert-butyl hydroperoxide (ROOH) in aprotic solvents such as heptane, aromatic hydrocarbons, dioxane, and in methanol (R"OH). Kinetic characteristics of the oxidation reaction, its rate, the composition and properties of the metal-containing products, and the yield of CO and CO₂ gases were found to depend on the acidity of the solvent used. The effect of the solvent nature was explained in terms of the proposed mechanism of AreneM(CO)₃ oxidation involving the formation of AreneM(CO)₃ · 2ROOH complexes in aprotic solvents and AreneM(CO)₃(ROH · ROOH) complexes in methanol and their further conversion into the reaction products by one-electron transfer route or through the stage of the metal complex protonation.     

Characterisation of metal-binding biomolecules in the clam Chamelea gallina by bidimensional liquid chromatography with in series UV and ICP-MS detection

The presence of metal-binding biomolecules has been studied in Chamelea gallina, a bioindicator used for environmental contamination monitoring and very popular for human consumption in the Atlantic southwest coast of Spain. This area is affected by metal pollution from mining activities, which can modify biomolecules expression in this bivalve. Total content of elements was determined by ICP-MS and revealed a remarked presence of Fe, Zn, Cu, As and Mn. A metallomics approach has been optimised for this mollusc using size-exclusion chromatography on column Superdex 30?pg HiLoad 26/60 with in series UV and ICP-MS detection. At least four fractions with molecular weight in the range 1540 to 415 Da were observed with UV detection, but the ICP-MS chromatogram showed the presence of metals of interest only in the first two fractions. The apparent molecular weights of these metal-containing fractions were from 1325 to 764 Da. The fractions containing metals compounds were collected and lyophilised for further purification of reconstituted extracts with a second orthogonal chromatographic separation using reverse phase (RP) HPLC with ICP-MS detection. Several peaks were obtained in this second dimension separation which allows the isolation of As-, Cu- and Zn-containing biomolecules.     

Synthesis of polymers by use of divalent metal salts of monohydroxyethyl phthalate: Metal-containing isocyanurate-type crosslinked polyurethanes

Divalent metal salts (I) of monohydroxyethyl phthalate have catalytic activity for polymerization of isocyanate groups. The synthesis of novel metal-containing isocyanurate-type crosslinked polyurethanes were investigated by the crosslinking reaction of I in DMF with diisocyanates or urethane prepolymers, that is, diisocyanate adducts of polyethylene glycol. 2,4-Toluene diisocyanate and diphenylmethane diisocyanate were used as diisocyanates, and DMF was the solvent. The crosslinking reactions were followed by determining the gelation time. Gelation time decreased with increasing temperature. The Ca salt was more effective than the Mg salt in the crosslinking reaction. The yields of resulting metal-containing three-dimensional polymers decreased with increasing metal content in the feed. The Ca salt was more easily introduced into the network polymers than the Mg salt was. Decomposition temperatures decreased on introducing metals into the network polymers. Some physical properties of the metal-containing network polymers are also discussed.     

Synthesis of Polymers by Using Divalent Metal Salts of Mono(hydroxyethyl)phthalate: Metal-Containing Unsaturated Polyesters with Pendent Methacrylate Groups

Syntheses of novel metal-containing unsaturated polyesters having pendent methacrylate groups obtained by use of divalent metal salts of mono(hydroxyethyl)phthalate-maleic anhydride (MA)-glycidyl methacrylate (GMA) reactions were investigated. The yields were generally high. The metal-containing polyesters obtained were slightly yellow-brown solids, and the molecular weights ranged from 1546 to 2174, depending on the mole ratio of feed. Among them, the polyesters obtained at a feed mole ratio of metal salt:MA:GMA of 1:8:8 were miscible with methyl methacrylate (MMA), giving homogeneous solutions suitable for copolymerization, and the polyesters could be easily cross-linked with MMA to give cured resins. The metal-containing cured polyester resins showed excellent physical properties. Resistance of the resins to chemical attack and boiling water and thermal behavior are also discussed.     

The application of the simplified form of the quasiequilibrium theory to the mass spectra of some mononuclear metal carbonyls

The concept of molecular ions and metal-containing fragment ions formed in the mass spectra of the mononuclear metal carbonyls, M(CO)₆ (M = Cr, Mo,W), Fe(CO)₅, Ni(CO)₄, containing the metal in an excited state appears to violate the quasi-equilibrium theory. Calculations, using the simplified form of the theory, show that the high values obtained for the heats of formation of the metal ions determined by mass spectrometry axe consistent with the “excess energies” representing kinetic shifts.     

Membrane-based solvent extraction for selective removal and recovery of metals

A membrane-based solvent extraction process was developed for selective removal and recovery of metals from aqueous solutions. The process utilizes microporous membranes as an interface between an aqueous solution and organic solvents containing liquid ion exchangers. Metal ions are transported from the aqueous solution to the organic phase at the interface created in the pores of membrane. The organic solvent, which is loaded with metal ions in the extraction module, is regenerated in contact with the stripping solution in the stripping module. One important feature of this process is the stability of the membrane system, which results from using an aqueous—organic separator to remove aqueous solution from the organic circulating line. This process was evaluated for enrichment of copper using solvents containing LIX 64N. The process is applicable to selective recovery of metals from ore leachates or metal-containing wastewater.     

(Co)polymerization of metal-containing monomers as a way of MMC synthesis

The principal advances and problems of the synthesis, of poly-, co- and graft- polymerization of metal-containing monomers (MCM) are analysed. The MCMs are classified on the type of the metal bond with the organic part of the molecule, viz. MCM with σ-, nv-, and π-bonds. The effect of a transition metal on both the polymerization and on the properties of the products formed is of special interest. The basic fields of application of metal-containing polymers have been summed up.     

Reactivity of metal-containing monomers 70. Preparation and magnetic properties of metal-containing nanocomposites

Nanocomposites containing magnetically active nanoparticles stabilized by the carbon-containing matrix formed in parallel were obtained by the polymerization—destruction synthesis. The composition, structure, and magnetic properties of nanocomposites synthesized by the thermal decomposition of unsaturated metal carboxylates and transition metal (Co^II, Ni^II, Fe^III) acrylamide complexes were studied by powder X-ray diffraction, scanning and transmission electron microscopy, and Mössbauer spectroscopy. The key macro stages and kinetic features of thermolysis of the metal-containing monomers were identified. The variation of the conditions of thermal transformations allows one to control the magnetic properties of nanocomposites from ferromagnetic to superparamagnetic behavior.

     

Polymers based on divalent metal salts of p-aminobenzoic acid: a review

Divalent metal salts of p-aminobenzoic acid are useful starting materials for syntheses of ionic polymers into which metal is firmly incorporated. This paper is a review of a series of polymers that have been prepared using the metal salts. The salts can react with compounds having functional groups capable of reacting with amino groups. By polyaddition reactions of the salt–aromatic diamine with diisocyanate, and with isocynate-terminated adducts of diisocyanate and dialkylene glycol, halatotelechelic polyureas and polyurethane-ureas are obtained. By amine–epoxy reactions of systems of the salt–diamine–bisepoxide, and addition reactions of systems of the salt–dicarboxylic acid anhydride–bisepoxide, metal-containing cured resins are obtained. In this case, the metal carboxylate groups of the salts have catalytic activities for the curing reactions, and also for etherification of epoxy groups as a side reaction. Therefore, crosslinking of bisepoxide with the salts, and with adducts of the salts and the anhydride, has been investigated by taking advantage of the catalytic activity of the metal carboxylate groups for the etherification of epoxy groups. Interestingly, the metal-containing cured resins obtained by crosslinking by etherification of bisepoxide with the adducts show very high impact strength. © 1997 John Wiley & Sons, Ltd.     

MALDI-TOFMS analysis of coordination and organometallic complexes: a nic(h)e area to work in

A mini-review of the characterisation of metal-containing compounds by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS) is presented. Organometallic and coordination compounds have many varied applications, most notably in industrial catalytic processes and also in the electronics and healthcare sectors. In general, the compounds discussed, be they small or large molecules, have a high percentage metal content, rather than simply containing 'a metal atom'. A brief history of the field is given, but the main scope over the last 5 years is covered in some detail. How MALDI-TOFMS compliments electrospray for metal-containing compounds is highlighted. Perspectives on recent advances, such as solvent-free and air/moisture-sensitive sample preparation, and potential future challenges and developments, such as nanomaterials and metallodrug/metallometabolite imaging, are given.     

Application of a heated electrospray interface for on-line connection of the AAS detector with HPLC for detection of organotin and organolead compounds

A heated electrospray interface that affords high sensitivity and long-term signal stability for AAS detection of metal-containing analytes in organic or organic-water solvents after HPLC separation is described. The vitreous body of the electrospray interface is externally heated above the boiling point of the solvent and quartz furnace AAS is used for detection. Interface working conditions were optimized with a full experimental design for the detection of tin- (tetramethyl-, tetraethyl-, tetrabutyl-, and tetrapentyltin, tributyltin chloride, dibutyltin dichloride, and butyltin trichloride) and lead- (tetraethyl- and tetraphenyllead) containing compounds in the column eluate. The heated electrospray interface enables use of a wide range of flow rates - from 50 to 1000 micro L min(-1). The measurement sensitivity and detection limit achieved were compared with those obtained by use of the thermospray interface and post-column conversion of the organotin compounds to gaseous hydrides. The detection limits for the low-molecular weight species of the homologous series (2.8+/-0.1 ng (140+/-5 ng mL(-1)) for tetramethyltin and 3.1+/-0.2 ng (155+/-10 ng mL(-1)) for tetraethyltin) were obtained approximately one order of magnitude lower than those obtained by use of the thermospray interface. With this HPLC-ES-QFAAS system the tributyltin content of BCR reference material 477, mussel tissue, was analyzed. This system was also applied to analysis of tetraethyllead in gasoline samples.     

Synthesis of Polymers by Using Divalent Metal Salts of Mono(hydroxyethyl)phthalate: Metal-Containing Unsaturated Polyesters

Syntheses of metal-containing unsaturated polyesters based on divalent metal salts (I) of mono (hydroxyethyl)phthalate were investigated by the polycondensation reactions of I-glycols with maleic anhydride (MA)-phthalic anhydride (PA). Among various combinations of components, the systems of MA-PA-diethylene glycol (DEG)-Mg salt, and MA-PA-ethylene glycol (EG)-propylene glycol (PG)-Mg salt gave polyesters soluble in styrene. Viscosities of styrene solutions of the polyesters obtained showed a tendency to increase with increase in metal content in the polyester. The styrene solutions could be cured. The cured polyester resins were evaluated for physical properties. Generally, the polyesters of MA-PA-EG-PG-Mg salt have good physical properties. Further, resistance to chemical attack and boiling water, and thermal behavior are also discussed.     

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.