Soapfree emulsion polymerization of methyl methacrylate in the presence of CaSO3

In the soapfree emulsion polymerization of a methyl methacrylate-K₂S₂O₈-CaSO₃-H₂O system, the polymerization rate, average molecular weight of polymer, particle size and particle concentration would vary with the concentration of CaSO₃. It was shown that when the concentration of CaSO₃ was well below the saturation concentration (3 × 10^?4mol/litre H₂O), the polymerization rate was higher than that of the system not containing CaSO₃. On the other hand, when the concentration of CaSO₃ was above the saturation concentration, the polymerization rate at the latter stage was lower than that of the system not containing CaSO₃ within our experimental conditions. The molecular weight of polymer was measured by Gel Permeation Chromatography (GPC). It decreased initially and then increased due to the gel effect over the entire course of polymerization. The size of the polymer particles was measured by both photo correlation spectroscopy (PCS) and transmission electron microscopy (TEM), The reaction mechanism was studied according to the above observation. The mechanical property of poly(methyl methacrylate)-CaSO₃ composite obtained from soapfree emulsion polymerization was tested and compared with that obtained from mechanical blending.     

Butadiene polymerization in the presence of VOCl3–dialkylmagnesium catalytic system

The butadiene polymerization in toluene at 25°C on VOCl₃? (n‐C₄H₉)Mg(iso‐C₈H₁₇) catalytic system was investigated. The kinetic parameters of polymerization and molecular characteristics of polybutadiene were determined. It was shown that substitution of traditional organoaluminum cocatalysts in trans‐regulating vanadium systems does not have an effect on its stereospecificity, but significantly influences on the active centers reaction ability. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 596–600, 2003     

Ethylene/1‐octadecene copolymerization using [η5:η1‐C5Me4‐4‐R1‐6‐R‐C6H2O]TiCl2 catalysts

Copolymerization of ethylene with 1‐octadecene was studied using [η⁵:η¹‐C₅Me₄‐4‐R₁‐6‐R‐C₆H₂O]TiCl₂ [R₁ = ^tBu (1), H (2, 3, 4); R = ^tBu (1, 2), Me (3), Ph (4)] as catalysts in the presence of Al(i‐Bu)₃ and [Ph₃C][B(C₆F₅)₄]. The effect of the concentration of comonomer in the feed and Al/Ti molar ratio on the catalytic activity and molecular weight of the resultant copolymer were investigated. The substituents on the phenyl ring of the ligand affect considerably both the catalytic activity and comonomer incorporation. The 1 /Al(i‐Bu)₃/[Ph₃C][B(C₆F₅)₄] catalyst system exhibits the highest catalytic activity and produces copolymers with the highest molecular weight, while the 2 /Al(i‐Bu)₃/[Ph₃C][B(C₆F₅)₄] catalyst system gives copolymers with the highest comonomer incorporation under similar conditions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polymerization of butadiene with Co(acac)3–(i-Bu)3Al–H2O catalyst

The polymerization of butadiene in toluene using Co(acac)₃–(i-Bu)₃Al–H₂O catalyst system was studied. Presented are the effects of the addition order, aging time, and composition of catalysts on rates, polymer microstructure, and molecular weights. The polymerization was found to be initiated by the Co(acac)₃-hydrolized aluminum alkyl complex. The chain propagation proceeds according to a first-order reaction with respect to monomer and active species and is a strong function of Al/H₂O with an optimum ratio of 1.0, but independent of Al/Co. The nature of polymerization seems to change as Al/H₂O increases from less than 1 to greater than 1. Transfer reaction is significant. From the kinetic data it was found that the termination reaction is most likely to be by combination.     

Polymerization of propylene with TiCl3–AlEt2Cl–trilauryltrithiophosphite catalyst

AlEt₃Cl was modified with TLTTP (trilauryltrithiophosphite) in the catalyst system consisting of TiCl₃ and AlEt₂Cl. The effects of TLTTP on the polymerization of propylene were studied in comparison with those of alkyl homologues of TLTTP. The catalytic behavior of the TiCl₃–AlEt₂Cl-TLTTP catalyst system in the polymerization of propylene was also studied in comparison with that of the TiCl₃–AlEt₂Cl catalyst system. In the study of the effect of various alkylthiophosphites added, it is found that the bulkiness of the alkyl group affects the rate of propylene polymerization and the stereoregularity of the resultant polymers. The TiCl₃–AlEt₂Cl–TLTTP catalyst system gave different catalytic behavior in the propylene polymerization from that of the unmodified conventional catalyst system (TiCl₃–AlEt₂Cl). These effects of TLTTP were considered to be due to the bulkiness of the alkyl groups attached to the phosphorous atom and the higher reactivity to TiCl₃ of the modified AlEt₂Cl than of the unmodified AlEt₂Cl.     

Catalytic reduction of N2O with CH4 and C3H6 over Ag–Rh/Al2O3 bimetallic catalyst in the presence of oxygen

A study of nitrous oxide (N₂O) reduction with methane (CH₄) and propene (C₃H₆) in the presence of oxygen (5%) over Ag/Al₂O₃, Rh/Al₂O₃ and Ag–Rh/Al₂O₃ catalysts, with Ag and Rh loadings of 5 wt% and 0.05 wt% respectively, has been performed. From the results, it was observed that the Ag–Rh bimetallic catalyst was the most active for both nitrous oxide removal (more than 95%) and hydrocarbon oxidation. This high activity seems to be connected with a synergistic effect between Ag and Rh. The findings from X‐ray diffraction and X‐ray photoelectron spectroscopy studies showed also, that there were no strong interactions (eg alloying) between Ag and Rh. Copyright © 2005 Society of Chemical Industry     

Thermal Stability,Optical Transmittance,and Refractive Index Dispersion of La2O3–Nb2O5–Al2O3 Glasses

La₂O₃–Nb₂O₅–Al₂O₃ high‐refractive‐index glasses were fabricated by containerless processing, and the glass‐forming region was determined. The thermal stability, density, optical transmittance, and the refractive index dispersion of these glasses were investigated. All the glasses were colorless and transparent in the visible to near infrared (NIR) region and had high refractive index with low wavelength dispersion. Some of these glasses were found to have significantly high glass‐forming ability. These results indicate that the ternary glasses are suitable for optical applications in the visible to NIR region. The effects of the substitution of Al₂O₃ for Nb₂O₅ on optical properties were discussed on the basis of the Drude–Voigt equation. It was suggested that the substitution of Al₂O₃ for Nb₂O₅ increased the molecular density and suppressed a decrease in the refractive index, even when both the average oscillator strength and inherent absorption wavelength decreased in La₂O₃–Nb₂O₅–Al₂O₃ glasses. These results are helpful for designing new optical glasses controlled to have a higher refractive index and lower wavelength dispersion.     

Ethylene/α‐olefin copolymerization by nonbridged (cyclopentadienyl)(aryloxy)titanium(IV) dichloride/AliBu3/Ph3CB(C6F5)4 catalyst systems

A series of nonbridged (cyclopentadienyl) (aryloxy)titanium(IV) complexes of the type, (η⁵‐Cp′)(OAr)TiCl₂ [OAr = O‐2,4,6‐^tBu₃C₆H₂ and Cp′ = Me₅C₅ ( 1 ), Me₄PhC₅ ( 2 ), and 1,2‐Ph₂‐4‐MeC₅H₂ ( 3 )], were prepared and used for the copolymerization of ethylene with α‐olefins (e.g., 1‐hexene, 1‐octene, and 1‐octadecene) in presence of AlⁱBu₃ and Ph₃CB(C₆F₅)₄ (TIBA/B). The effect of the catalyst structure, comonomer, and reaction conditions on the catalytic activity, comonomer incorporation, and molecular weight of the produced copolymers was examined. The substituents on the cyclopentadienyl group of the ligand in 1 – 3 play an important role in the catalytic activity and comonomer incorporation. The 1 /TIBA/B catalyst system exhibits the highest catalytic activity, while the 3 /TIBA/B catalyst system yields copolymers with the highest comonomer incorporation under the same conditions. The reactivity ratio product values are smaller than those by ordinary metallocene type, which indicates that the copolymerization of ethylene with 1‐hexene, 1‐octene, and 1‐octadecene by the 1–3/ TIBA/B catalyst systems does not proceed in a random manner. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A Catalytic Deprotection of S,S‐, S,O‐ and O,O‐Acetals Using Bi(NO3)3⋅5 H2O under Air

S,S‐Acetals are smoothly deprotected with air in the presence of a catalytic amount of Bi(NO₃)₃⋅5 H₂O (1–50 mol %) under ambient conditions to regenerate the original carbonyl compounds in good to excellent yield. This mild, simple, and environmentally benign system is successfully applied to the deprotection of S,O‐ and O,O‐acetals and is compatible with various functional groups. From the mechanistic study of the reaction, the catalytic cycle is considered to be composed of the following four steps: (1) the nitrososulfonium ion of the S,S‐acetal is formed by attack of nitrosonium ion (NO ⁺) generated from Bi(NO₃)₃⋅5 H₂O through the equilibrium with NO₂, (2) the nitrososulfonium ion is hydrolyzed to afford the hemithioacetal and thionitrite, (3) the hemithioacetal collapses to the original carbonyl compound and thiol, which is oxidized by NO ⁺ to give disulfide and NO via thionitrite, and (4) the NO captures molecular oxygen from air to regenerate NO₂.     

Hydrothermal synthesis,crystal structure and fluorescent properties of a novel 1D polymer: VO2(C7H3O4N)Ag(C10H8N2)·H2O

The hydrothermal synthesis of V₂O₅, AgNO₃, pyridine-2,6-dicarboxylic acid (H₂pdc) and 2,2′-bipyridine (bpy) in water at 160 °C for 4 days yields a novel 1D coordination polymer VO₂(C₇H₃O₄N)Ag(C₁₀H₈N₂)·H₂O (1). Each V center chelates to a tridentate ligand pdc^2? and coordinates to two O atoms, while the square based pyramid conformation of Ag center consists of three O atoms and a bpy molecular. V and Ag polyhedra alternate by either carboxyl or oxo bridges to further form a unique 3d–4d heterometal-based 1D double-chain ribbon.     

Structure of active centers,their stereospecificity distribution,and multiplicity in diene polymerization initiated by NdCl3‐based catalytic systems

On the basis of quantum‐chemical calculations, it was shown that among six types of active centers (ACs) that can form during the polymerization of butadiene with lanthanide‐based catalytic systems, five types (containing electron‐accepting chlorine atoms in the coordination sphere of a lanthanide) exhibit a π‐allyl binding of the terminal unit of a growing polymer chain to a lanthanide atom and function as cis‐regulating. The sixth type of ACs is characterized by a σ‐alkyl structure and shows a trans‐stereospecificity. This results was used to interpret the data on the microstructure of polybutadiene prepared using NdCl₃ · 3TBP‐Al(iso‐C₄H₉)₃, NdCl₃ · 3TBP–Mg(n‐C₄H₉)(iso‐C₈H₁₇) catalytic systems and their combinations (TBP is tributyl phosphate). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 601–603, 2003     

Morphology and deactivation behaviour of Co–Ru/γ‐Al2O3 Fischer–Tropsch synthesis catalyst

Deactivation of Co–Ru/γ‐Al₂O₃ Fischer–Tropsch (FT) synthesis catalyst along the catalytic bed over 850 h of time‐on‐stream (TOS) was investigated. Catalytic bed was divided into four parts and structural changes of the spent catalysts collected from each catalytic bed after FT synthesis were studied using BET, ICP, XRD, TPR, carbon determination, H₂ chemisorption and oxygen titration techniques. Rapid deactivation was observed during first 200 h of FT synthesis. In this case, the deactivation rate was not dependent on the number of the catalyst active sites. It was zero order to CO conversion and independent of the size of active sites. Beyond the TOS of 200 h, the deactivation could be simulated with a power law expression: . The physical properties of the catalyst charged in 1st half of the reactor did not change significantly. Interaction of cobalt with alumina and formation of mixed oxides of the form xCoO·yAl₂O₃ and CoAl₂O₄ was increased along the catalytic bed. Percentage reducibility and dispersion decreased by 2.4–25.5% and 0.5–8.8% for the catalyst in the beds 1 and 4, respectively. Particle diameter increased by 0.8–6.1% for the catalyst in the beds 1 and 4 respectively suggesting higher rate of sintering at last catalytic bed. The amount of coke formation in the 4th catalytic bed was 6 times more than that of in bed 1.     

Ethylene polymerization by phenylenedimethylene‐bridged homobinuclear zirconocene/methylaluminoxane systems

In the presence of methylaluminoxane (MAO), ethylene polymerization was successfully performed with homobinuclear zirconocene complexes {[(C₅H₅)ZrCl₂](C₅H₄CH₂ C₆H₄CH₂C₅H₄)[(C₅H₅)ZrCl₂]; 3o , 4m , and 5p }, which were prepared conveniently by the reaction of disodium(phenylenedimethylene)dicyclopentadienide [C₆H₄(CH₂C₅H₄Na)₂] with 2 equiv of (N⁵‐Cyclopentadienyl)trichlorozirconium dimethoxyethane (CpZrCl₃(DME)) in tetrahydrofuran and characterized by ¹H‐NMR and elemental analysis. The effects of the polymerization parameters, such as the temperature, time, concentration of the catalyst, MAO/catalyst molar ratio, and isomeric difference of the homobinuclear metallocene complexes 3o , 4m , and 5p were studied in detail. The results showed that all three catalytic systems had moderate activities in ethylene polymerization and afforded polyethylene with relatively broad polydispersities. The catalytic activity of 4m was somewhat higher than that of 3o and 5p but lower than that of 4,4′‐bis(methylene)biphenylene‐bridged zirconocene catalysts; this indicated that the distance between the two metal centers was too short in comparison with a 4,4′‐bis(methylene)biphenylene bridge to increase the catalytic activity. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Interaction of transuranium elements with biologically relevant ligands. Synthesis,crystal structure,IR and electronic spectra of neptunium glycolate [NpO2(C2O3H3)(Bipy)] · 2.5H2O

As a result of Np(V) glycolate reaction with 2,2′-bipyridyl, the novel coordination polymer [NpO₂(C₂O₃H₃)(Bipy)] · 2.5H₂O was formed. The structure consists of infinite chains of [NpO₂(C₂O₃H₃)(Bipy)] and water molecules. The crystal structure is confirmed by IR and UV–vis spectroscopic data. This complex is the first example of An glycolate with neutral molecular ligand.     

Synthesis of (C5H5)2Zr(O2C)CH3 and (C5H5)2Zr(O2C)CH2CH3 for olefin polymerization

Summary (C₅H₅)₂Zr(O₂C)CH₃ and (C₅H₅)₂Zr(O₂C)CH₂CH₃ complexes were synthesized, characterized and activated with MAO for ethylene polymerization. The highest catalytic activity was achieved at Al/Zr molar ratio of 3000 for both systems. The effects of the size of the R group in the carboxylate ligands, the Al/Zr molar ratio and reaction temperature on the catalytic activity and polymer properties were studied and discussed.     

Synthesis and nanostructure of [Mo(C6H4O2)3]·2(C4H8N2O) and the synthesis from 1,2-PDA to (C4H8N2O)

Continuing our work on the synthesis of MoO₂L₂ and MoO₃L_AL_B that show excellent anti-cancer activities in vitro, the MoL₃ have been synthesized by the solvothermal reaction of Na₂MoO₄ with catechols and 1,2-DPA in the mixed solvent of MeCN/MeOH. X-ray diffraction revealed that Mo in chiral octahedral geometry coordinate with three catechol ligands formed three five-membered rings, and the [Mo(C₆H₄O₂)₃] are linked by hydrogen bonds Mo(OC₆H₄)O…H–N(C₄H₈O)N–H…O(C₆H₄O)Mo through the by-product (C₄H₈N₂O) that are formed by one 1,2-DPA with one CO₂ on the catalysis of Mo-complex. Also, we have disassembled bulk crystal into nano-aggregates, and under TEM mono-lamella morphology of nanostructures was observed, which agrees well with the previous conclusion that the morphologies of the nano-aggregates are associated with the quantum motifs in their crystal lattices. [Mo(C₆H₄O₂)₃] have also been characterized by UV–vis spectra, cyclic voltammogram and thermogravimetric analysis.     

Synthesis of Fe3O4-nanocatalysts with different morphologies and its promotion on shifting C5+ hydrocarbons for Fischer–Tropsch synthesis

The shape-defined Fe₃O₄ nanocatalysts such as spheres and polyhedrons prepared by a simple solvothermal method without calcination were applied in Fischer–Tropsch synthesis (FTS), which showed excellent catalytic activity and C₅⁺ selectivity compared to the traditional Fe catalyst. Especially, the Fe₃O₄ nanocatalyst with nanospheres (FNS) displayed higher catalytic activity and C₅⁺ selectivity (> 64%) than the Fe₃O₄ nanopolyhedrons (FNP). It was found that FNS was more favorable to the reduction and dispersion of iron species as well as formation of surface carbonaceous species (especially for χ-Fe₅C₂) compared to FNP, which provided more active sites for FTS and facilitated the product distribution shifting towards heavy hydrocarbons.     

The Nature of Active Sites of Co/Al2O3 for the Selective Catalytic Reduction of NO with C2H4

The effects of Co loading and calcination temperatures on the catalytic activity of Co/Al₂O₃ for selective catalytic reduction (SCR) of NO with ethylene in excess oxygen were investigated. Co/Al₂O₃ showed high and low activities when calcined at high (800 °C) and low (350 °C) temperatures, respectively. The formation and dispersion of cobalt species for catalysts calcined at 350 and 800 °C as well as for Al₂O₃ were studied by XRD, UV–vis and FTIR spectra. Combined with DRIFTS results of ad-species and reaction experiments, it allowed us to correlate the catalytic activity with active sites of Co/Al₂O₃, and the catalytic functions of active cobalt species and support were clarified. Co₃O₄ species contributed to the oxidation of NO to various nitrates and of C₂H₄ to reactive formate species, even in the absence of O₂, whereas the side reaction of ethylene combustion occurred simultaneously when excess oxygen was present. Tetrahedral Co²⁺ ions in CoAl₂O₄, which acted as the active sites, were responsible for the reaction between formate and nitrate species to form organic nitro compound.     

Thermal Conductivity of Molten Li2O–B2O3 and K2O–B2O3 Systems

Using the transient hot‐wire method, the thermal conductivity properties of the molten Li₂O–B₂O₃ and K₂O–B₂O₃ systems were measured. The thermal conductivity increases with decreasing the temperature due to the borate structure change. In addition, calculations of the one‐dimensional Debye temperature and the phonon mean free paths as a function of temperature of the alkali borate systems were made. At a fixed temperature of 1273 K, the effect of the alkali oxide concentration on the thermal conductivity was evaluated. Within a range of 10–30 mol% Li₂O (or K₂O), a positive relationship between the thermal conductivity and 4‐coordinate boron was obtained. However, below 10 mol% Li₂O (or K₂O), the change in the intermediate‐range order of the borate structure had a more dominant effect on the thermal conductivity. Finally, the effect of cations on the thermal conductivity in the various molten R₂O–B₂O₃ (R=Li, Na and K) systems was considered. Depending on the type of cation, the change in the ionization potential had an effect on the thermal conductivity and also resulted in a change in the bond strength.     

Study of ClO2 generation reaction via experimental data of aqueous mixed electrolyte solutions: HClO4–NaCLO3–H2O and HCLO4–NaCl–H2O

A new model for mixtures (two and more solutes) of aqueous electrolyte solutions was found to be as accurate as other models, or more accurate, in prediction of new experimental results of the ternary systems HClO₄–NaClO₃–H₂O and HClO₄–NaCl–H₂O. The water activity values are then used to study the mechanism of the chloride–chlorate reaction, generating chlorine dioxide: 2H⁺ + ClO^?₃ + Cl^? → ClO₂ + 1/2Cl₂ + H₂O Spectrophotometric measurements of the production rate of ClO₂ have confirmed that the intermediary species in the proposed equilibrium H⁺(mH₂O) → H⁺(m-n)H₂O + nH₂O Is actually H(H₂0)⁺_m-n. The final kinetic expression for the reaction rate of chlorine dioxide generation, used in pulp bleaching, is then derived to explain the high order with respect to acid concentration.