Metal‐coordinated epoxy polymers with suppressed combustibility. Preparation technology,thermal degradation,and combustibility test of new epoxy‐amine polymers containing the curing agent with chelated copper(II) carbonate

The diethylenetriamine chelate complex of copper(II) carbonate—DETA‐CuCO₃ (a fire retardant hardener of epoxy resins)—and the CuCO₃‐containing epoxy‐amine polymers—DGEBA/DETA‐CuCO₃(6), DGEBA/DETA‐CuCO₃(12), DGEBA/DETA‐CuCO₃(40), and DGEBA/DETA‐CuCO₃(80) with suppressed combustibility—have been obtained in the DETA‐DGEBA‐CuCO₃ system (DETA and DGEBA are diethylenetriamine and bisphenol A diglycidyl ether, respectively). The DETA‐CuCO₃ chelate complex was characterized by X‐ray powder diffraction, infrared spectra, and thermal analysis. The thermal gravimetric analysis results have revealed that thermal destruction of DETA‐CuCO₃ was finished at 400°С, and the maximal temperature of the combustion gases amounted to 520°С. The thermal behavior and combustibility of the CuCO₃‐containing epoxy‐amine polymers were studied using thermal analysis and “Ceramic tube” (CT) method. Thermal gravimetric analysis confirms that incorporation of the DETA‐CuCO₃ into DGEBA appreciably heightens the thermal stability and antiflammability of the CuCO₃‐containing epoxy‐amine polymers. Results of CT measurement reveal that maximal temperature of the combustion gases under burning of the DGEBA/DETA‐CuCO₃(12) sample in comparison with unmodified epoxy‐amine polymer (DGEBA/DETA) is lowered on 219°С and the loss of weight is decreased on 20.5 wt%. According to ASTM 635‐14, ASTM D2863‐13, and ASTM D1929‐16, the flame propagation rate, limiting oxygen index, and temperatures of ignition and self‐ignition have been measured for the elaborated polymer samples.     

Effect of Cu(II) ligands on electroless copper deposition rate in formaldehyde solutions: An EQCM study

The electroless copper deposition rate for 6 Cu^II complexes decreases in the ligand sequence: nitrilotriacetic acid (NTA) > N,N,N′,N′-tetrakis-(2-hydroxypropyl)-ethylenediamine (Quadrol) > glycerol > L(+)-tartrate ~ sucrose > -tartrate. Both Cu^II complex stability and specific ligand effects were found to influence the Cu deposition process. The specific ligand effects are most obvious in the case of Quadrol (high kinetic activity at a high Cu^II complex stability), glycerol and sucrose (additional reaction of Cu₂O formation by interaction of Cu^II with ligand). According to the EQCM data for 11 Cu^II complexes (including data from the former study) the higher kinetic activity is demonstrated by complexes with ligands containing amino groups; this factor is more important for Cu deposition rate than copper complex stability. A potential dependence of the Cu reduction partial current on the electrode potential has been extracted from the EQCM data in the complete electroless plating bath. An increase in Cu^II reduction rate was found to occur in electroless plating solution for Cu^II complexes with NTA and Quadrol compared with that in formaldehyde-free solutions. Possible reasons for the acceleration of the partial Cu^II reduction reaction and the overall process kinetics are discussed using a hypothetical reaction sequence involving intermediate copper oxy-species and active Cu* formation as well as development of the preferred Cu surface structure.     

Preparation,characterization, and adsorption properties of chitosan microspheres crosslinked by formaldehyde for copper (II) from aqueous solution

The chitosan microspheres crosslinked by formaldehyde were prepared by spray drying method and used as an adsorbent for copper (II) from aqueous solution. A batch adsorption system was applied to study the adsorption of copper (II) from aqueous solution by chitosan microspheres. The maximum adsorption capacity of the chitosan microspheres for copper (II) was 144.928 mg/g at pH 6.0. Langmuir adsorption model was found to be applicable in interpreting the adsorption process. To elucidate the adsorption mechanism, the chitosan microspheres before and after copper (II) adsorption were further characterized by Fourier transform infrared spectra, zeta potential analysis, and scanning electron microscope. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of poly(ferrocenylsilane) high polymers

Ring-opening polymerization of strained, ring-tilted cyclic ferrocenylsilanes has recently provided access to the first examples of high molecular weight poly(ferrocenylsilanes) [1], which possess backbones of alternating ferrocenyl groups and silicon atoms. In this paper we provide an overview of the progress to date on the synthesis and properties of these unusual polymers.Presented at the XXVIth Silicon Symposium, Indiana University-Purdue University at Indianapolis, March 26–27, 1993.     

Synthesis,adsorption and selectivity of inverse emulsion Cd(Ⅱ) imprinted polymers

Inverse emulsion polymerization was employed to synthesize inverse emulsion Cd(II) imprinted polymers(IEII P). The morphology and functional groups of IEIIP were characterized by SEM,FTIR and TG. Static adsorption experiments and competitive adsorption test were used to evaluate the adsorption ability of IEIIP. The adsorption capacity of polymers could reach 86.7 mg·g~(-1) under the optimal adsorption conditions. The pseudo second order kinetic model and Langmuir isotherm model could be used to analyze the experimental data well. The adsorption process of IEIIP was chemical adsorption process and monomolecular type. Thermodynamic parameters showed that the adsorption process was endothermic and could occur spontaneously. The selectivity coefficients k of Cd~(2+)/Pb~(2+), Cd~(2+)/Zn~(2+) and Cd~(2+)/Cu~(2+) were 2.4998, 1.2437 and 4.6882, respectively. The proposed method provides a new thought for removing Cd(II) in water samples.     

Synthesis and characterization of coordination polymers of Hg(II) with poly(thiooxamides)

Coordination polymers of Hg(II) with dithiooxamide, poly(ethylene thiooxamide), poly(butane thiooxamide), and poly(hexane thiooxamide) have been synthesized. All coordination polymers are solid compounds insoluble in common organic solvents. Coordination polymers have been characterized by elemental analysis, IR spectra, and thermogravimetric analysis and structures have been proposed leading to coordination of metal through S alone as well as N and S both. Thermal stability of the polymers has also been discussed.     

Synthesis,spectral and structural study of sulfur-containing copper(II) complexes

A series of four new copper(II) complexes [Cu(H₂L)(L¹)] 1, [Cu(H₂L)(PMDT)] 2, [Cu(H₂L)(Dien)] 3 and [Cu(H₂L)(L²)] 4 have been synthesized by template condensation (H₂L=thiodiglycolic acid, L¹=N-[(1)-1-(4-methylphenyl)ethylidene]benzohydrazide, PMDT=N,N,N′,N′,N ^′′-pentamethyldiethylene- triamine, Dien=diethylenetriamine L²=N-[(1)-pyridin-2-ylmethylidene]benzohydrazide). The bonding and stereochemistry of the complexes have been characterized by molar conductance, elemental analysis, magnetic susceptibility, infrared, UV–visible, electron paramagnetic resonance structural studies and electrochemical studies. g-Values were calculated for all complexes in polycrystalline form as well as in DMSO solution. The magnetic and spectral data indicate square pyramidal geometry for 1 and octahedral geometry for 2–4 complexes. Cyclic voltammograms for all the complexes are similar and involve two irreversible redox processes. Their biological properties have also been studied. The thio complexes show more antibacterial activity than the controlled one. The antibacterial activities of the compounds have also been tested against Escherichia coli with different concentrations.     

Discharge behaviour of copper(II) halide cathodes with molten nitrate electrolytes

This paper describes the discharge behaviour between 150 and 220°C of cells using copper(II) halide as the cathode material and molten nitrate as the electrolyte for a reserve battery of high energy density running at medium temperatures. At these temperatures a lithium–aluminium alloy/copper(II) chloride cell can be discharged at a current density of 50mAcm–2. The open-circuit potentials are 3.45V (against 20wt% lithium–aluminium alloy). Discharge results on the combination LiAl/LiNO3–KNO3/CuCl2 cells show a capacity of 1343Cg–1 to zero voltage at a current density of 50mAcm–2 at 230°C. In practice, this is equivalent to a specific energy output of 356Whkg–1 of cathode to a 70% voltage cut-off. The compatibility of copper(II) chloride with nitrate electrolytes has been investigated. Copper(II) chloride appears to be compatible with nitrate up to about 260°C. The performance of the LiAl/NO3/CuF2 cell was very poor giving a capacity of 50Cg–1.     

Electrical properties of Cu(II) and Ni(II): N-salicylidene polymethacrylic acid hydrazide complexes

Different types of chelated polymer complexes have been synthesized to obtain improved electrical properties. Compact discs from powders of the chelated polymers were prepared and heated in a specially designed holder. Electrical conductivity and dielectric constant of Cu(II) and Ni(II): N-salicylidene polymethacrylic acid hydrazide samples were measured at a fixed frequency (1600 Hz) throughout the temperature range 25-150°C. The AC conductivity as well as dielectric measurements showed maxima at 85°C. The water molecules which were trapped in the polymer matrix are believed to play the main role in conduction and dielectric behaviour of the polymeric material. From the AC conductance and dielectric constant measurements, the dielectric losses of these polymeric materials were calculated as a function of temperature.     

Optical and electrochemical properties and sensing application for iron(II) and mercury(II) ions of polyfluorenes with imidazole in the main chain

Polyfluorenes bearing imidazole and triphenylamine moieties in the main chain were synthesized. The imidazole/triphenylamine molar ratios in the polymer backbone were 100/0 (PFIM100), 50/50 (PFIM50) and 25/75 (PFIM25). Cyclic voltammetry revealed reversible oxidation only for polymers containing triphenylamine moieties (PFIM50 and PFIM25) and irreversible reduction for all polymers. Optical properties of the polymers were investigated using UV‐visible and photoluminescence spectroscopies in solution. The sensing properties of PFIM100 were investigated. The polymer showed recognition towards two analytes, Fe²⁺ and Hg²⁺. PFIM100 exhibited selective fluorescence ‘turn‐off’ response to Fe²⁺ cations. Interaction of PFIM100 with I^? anions produced a non‐emissive complex. The PFIM100/I^? complex exhibited excellent ‘turn‐on’ sensing properties for detection of Hg²⁺. © 2019 Society of Chemical Industry     

Combined effects of sucrose and copper(II) ions on the growth and copper(II) bioaccumulation properties of Candida sp

A microbiological process using Candida sp was developed for the removal of copper(II) ions in the presence of molasses as nutrient. The combined effects of sucrose (in molasses) and copper(II) ions on the growth and copper(II) bioaccumulation properties of adapted Candida cells was tested under laboratory conditions as a function of initial pH and single‐sucrose and dual‐sucrose and copper(II) ion concentrations. The optimum pH value for maximum growth and metal ion accumulation was determined as 4.0 for the microorganism. At a constant copper(II) concentration, growth and copper(II) bioaccumulation increased with increasing concentrations of molasses sucrose up to 15 gdm⁻³. Although increased initial copper(II) concentration increased the copper(II) uptake capacity of the microorganism, inhibition by copper(II) ions of the growth of Candida sp was observed at all the concentrations of copper(II) at all the sucrose concentrations studied. The non‐competitive inhibition kinetics (assuming copper(II) ions as the toxic inhibitory component) were used to define the relationship between the specific growth rate and molasses sucrose and copper(II) concentrations and model parameters were determined by using experimental data. © 2000 Society of Chemical Industry     

Mechanical properties,flame retardancy,and smoke suppression of lanthanum organic montmorillonite/poly(vinyl chloride) nanocomposites

A dimethyl dioctadecyl ammonium chloride modified organic montmorillonite (OMMT_‐I.44P)/poly(vinyl chloride) (PVC) nanocomposite and anionic‐surfactant‐modified lanthanum organic montmorillonite (La‐OMMT)/PVC nanocomposites (with three different anionic surfactants for the La‐OMMTs) were prepared via melt‐intercalation technology. The effects of the La‐OMMTs and OMMT_‐I.44P on the mechanical properties, flame retardancy, and smoke suppression of PVC were studied. X‐ray diffraction characterization showed that the La‐OMMTs were exfoliated in the PVC matrix. The mechanical properties of the nanocomposites were enhanced by the incorporation of the La‐OMMTs. Cone calorimetry and gas chromatography–mass spectrometry analyses indicated that the incorporation of the La‐OMMTs enhanced the flame retardancy and smoke suppression of the PVC nanocomposites. Scanning electron microscopy photos further showed that the residual char surfaces of La‐OMMT/PVC were all intact and, thus, provided better barriers to energy and smoke transport. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43951.     

Synthesis and structures of dinuclear copper(II) complex and μ-phenolatotetrazinc(II) complex with 1,3-diphenyl-4-(salicylidene hydrazone)-phenylethylene-pyrazolone-5

Novel dinuclear copper(II) complex and phenoxy-bridged tetranuclear zinc(II) complex with 1,3-diphenyl-4-(salicylidene hydrazone)-phenylethylene-pyrazolone-5 (DPPeP-SAH) have been synthesized and characterized by X-ray crystallography. The X-ray diffraction analyses of the complexes show that two Cu(II) centers are bonded with two tetradentated ligands and the geometries around the central ions are slightly distorted square planar, while in zinc(II) complex central metal ions are held together by four μ-phenoxo bridges that lead to the formation of the tetra-μ-phenolatotetrazinc(II) centers.     

Synthesis of methoxysilanes by the reaction of metallic silicon with methanol using copper(II) acetate as the catalyst

The reaction of methanol with silicon was studied using various copper compounds other than the halides. Copper(II) acetate and copper(I) oxide gave high silicon conversions (82%) though the selectivities for trimethoxysilane were low (<19%). The selectivity was appreciably improved by addition of a small amount of thiophene or propyl chloride to the methanol feed.     

2-取代苯并咪唑与铜（II）配合物的微波合成与表征

采用2-取代基苯并咪唑化合物、氯化铜为原料、丙酮或2-丁酮为溶剂,在微波辐射下合成了2-苄基苯并咪唑(BIm_a)和1-(对甲氧基苄基)-2-(对甲氧基苯基)苯并咪唑(BIm_b)的铜配合物,收率分别为80%和75%.测得BIm_a和BIm_b铜配合物熔点分别为144.7～145.8 ℃和224.5～226.0℃.应用摩尔电导率、XRD、紫外光谱、SEM和热分析测试对目标配合物进行表征,摩尔电导率、紫外和红外光谱解析表明,2-取代苯并咪唑配体与Cu(Ⅱ) 发生了配合反应;XRD和SEM表征证明晶型为单斜晶系;热分析得出BIm_a、BIm_b和氯化铜的配位数分别为1和1/2.     

Diffusion coefficients of Cu(II) complexes with ligands used in alkaline electroless copper plating solutions

The diffusion coefficient values of the Cu(II) complex compounds with EDTA, DTPA, NTA, Quadrol, glycerol, saccharose, (+)- and (±)-tartaric acid, OH^– ions obtained by polarographic measurements in alkaline solutions lie in the range (1.2–5.7) × 10^–6 cm² s^–1 (at 20 C and J = 3) depending on the size of complex species, and are less than those of free (hydrated) Cu(II) ions and methanediol anion (H₂C(OH)O^–) determined under the same conditions which are 7.0 × 10^–6 and 10 × 10^–6 cm² s^–1, respectively. The linear dependence of the polarographically determined diffusion coefficient values on the inverse radius of Cu(II) complex species is observed.     

Polyphosphazene hybridized perovskite copper hydroxystannate microspheres effectively improve the flame retardant and mechanical properties of Poly(vinyl Chloride) Resin

To effectively reduce the fire hazard of flexible polyvinyl chloride (PVC), this study explored the synthesis of perovskite-type copper hydroxystannate (CuSn(OH)₆) microspheres by co-precipitation method. Then an organic–inorganic hybrid microsphere (CuSn(OH)₆@PZS) with core-shell structure was fabricated by in situ coating with poly(cyclotriphosphazene-co-4,4′-sulfonyldiphenol) (PZS). The results showed that CuSn(OH)₆@PZS performs most significantly in reducing the total heat release, while the CuSn(OH)₆ alone achieves the best smoke suppression effect. The limiting oxygen index (LOI) value of the PVC composites is improved from 29.0% to a maximum of 35.3%. During combustion, the peak heat release rate (PHRR) and total smoke production (TSP) decrease by a maximum of 50.8% and 44.9%, respectively. Significantly, the presence of the PZS coating also improves the interfacial compatibility with PVC. The mechanical properties were significantly improved and the elongation at break improving by 40.9%.     

Activity of ruthenium hydrogenation catalysts in copper(II) formate decomposition

Charcoal-, silica-, alumina- and titanium(IV) oxide-supported ruthenium catalysts, prepared by conventional impregnation and incipient wetness methods from a ruthenium(III) oxide precursor were tested in copper(II) formate decomposition in aqueous solution. Such a reaction was found to be an efficient and simple activity test of charcoal-supported catalysts. The application of this reaction for a bimetallic ruthenium–copper catalyst preparation was also suggested. Experimental results were compared with those obtained using commercial catalysts and ruthenium black.     

Synthesis,Characterization and Properties of New Semifluorinated Poly(arylene ether phosphine oxide)s

Bis(4‐fluoro‐3‐trifluoromethylphenyl)phenylphosphine oxide is synthesized and six new poly(arylene ether)s are prepared by nucleophilic displacement of the fluorine atom on the benzene ring by several diphenols under basic conditions. The products show very high glass transition temperatures of up to 252 °C and very good thermal stabilities of up to 490 °C for 5% weight loss. The polymers display very low heat release rates in the microscale combustion calorimeter test, suggesting good flame retardance. All polymers are soluble in a wide range of organic solvents. Transparent thin films cast from dichloromethane exhibit tensile strengths up to 54 MPa, a modulus of elasticity up to 0.97 GPa and elongation at break up to 47% depending on their exact repeating unit structures.