Synthesis and characterization of propylene‐α‐olefin random copolymers with isotactic propylene sequence. II. Propylene–hexene‐1 random copolymers

A series of novel hexene‐1–propylene random copolymers with isotactic sequence of propylene was synthesized with a MgCl₂‐supported Cr(acac)₃ catalyst. The molecular weight distribution of copolymers and homopolymers was considerably narrower than that of typical polyolefins produced by heterogeneous Ziegler–Natta catalysts. The crystallizability of the copolymers having a propylene‐unit content of more than 50 mol % drastically decreased with decreasing propylene‐unit content, and the copolymers with a propylene content of less than 50 mol % were completely amorphous. In the present novel type of random copolymers with crystallizable and noncrystallizable units, a single glass transition was observed between pure polypropylene and polyhexene‐1, and a major component was found to govern the final morphology and the mechanical characteristics. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2949–2954, 2004     

Novel High‐Temperature Antiferroelectric‐Based Dielectric NaNbO3–NaTaO3 Solid Solutions Processed in Low Oxygen Partial Pressures

The (1?x)NaNbO₃–(x)NaTaO₃ solid solution was investigated for x ≤ 0.4 in terms of new high‐temperature and high‐permittivity dielectric system that is suitable for base metal inner electrode capacitor applications. The addition of Ta significantly enhanced the resistivity of the dielectric, resulting in superior resistivity than the dielectrics‐formulated BaTiO₃ systems that dominate the multilayer ceramic capacitor dielectric devices. The voltage dependence of the permittivity was also superior to BaTiO₃‐based materials, providing higher capacitance at higher temperatures. A transmission electron microscopy study illustrated that the grains had so‐called core‐shell structure. According to the electron diffraction analysis, the core region had an inhomogeneous structure between antiferroelectric and ferroelectric phases, and shell region had an incommensurate ferroelectric‐like structure. The core and shell region had Nb‐ and Ta‐rich composition, respectively, and their interface was compositionally sharp, implying that shell region was formed via a liquid phase during the sintering process with an incongruent Ta dissolution reprecipitation. We anticipate that these or similar materials based on the alkali‐niobate perovskites can be further enhanced to provide capacitor solutions from 150°C to 250°C, which is an important range for a number of new AC–DC invertor and engine control units.     

Absorption and Fluorescence Spectra of Nitrobenzanthrones

To identify nitrobenzanthrones (NBAs) such as 3-nitro-7 H -benz[ de ]anthracene-7-one (3-NBA) on the basis of their electronic spectral data, we have synthesized 1-, 2-, 3-, 9-, and 10-NBAs and measured their absorption and emission spectra. The first strong absorption band of the NBAs appeared in the region 350-440 nm; the band of 10-NBA was red-shifted by about 20 nm. The molar absorptivities of 3- and 9-NBA were about two times as large as those of the others. The fluorescence spectra of the NBAs varied more largely with the position of the nitro group compared to the absorption spectra. The quantum yields of fluorescence were very small, ranging from ～10 m 2 for 2- and 10-NBA to ～10 m 4 for 1- and 3-NBA. 3-NBA exhibited a characteristic spectrum with two broad bands at 450 and 530 nm. On excitation causing an n ~ * transition in the NBAs, their fluorescence intensities increased by a factor of 10. Phosphorescence was observed at 77 K for all compounds though that of 1-NBA was very weak. These results give the promise of characterizing individual isomers of NBAs on the basis of their spectroscopic data.     

Novel Fabrication of High-Quality ZrO2 Ceramic Thin Films from Aqueous Solution

We report on the direct deposition of high-quality ZrO₂ thin films on various kinds of substrates by the liquid phase deposition method. After reaction for 24 h, thin films formed on various kinds of substrates, and the obtained thin film was comprised of densely packed nano-sized particles. The film annealed at 500°C showed a tetragonal phase at room temperature and this phenomenon has been discussed from the viewpoint of crystallite size effect. The result of optical transmittance measurement revealed that high transparency, more than 70% transmittance, has been achieved for the film after annealing at 900°C.     

New kinetic aspects on the mechanism of thermal oxidative degradation of polypropylenes with various tacticities

Thermal oxidative degradation behavior of polypropylene (PP) with different tacticities was studied based on the activation energy (ΔE) data obtained by thermogravimetric analysis (TGA). The ΔE value showed a negative proportion to the content of meso pentad fraction (mmmm) in all of isotactic PP (iPP) samples, and that of syndiotactic PP sample considerably deviated from this negative proportion relationship. Since the value of mmmm was directly related to polymer chain conformation, the ΔE value was thought to have close connection with the concentration of 3₁ helix conformation in the iPPs. The ΔE changes would be caused by the competition between uni- and bimolecular hydroperoxide decomposition, which was controlled by concentration and character of conformations of PPs.     

Effects of Various Preparation and Polymerization Procedures on the Isospecific Nature of TiCl3-Based Polypropylene Catalysts

Summary As one of a series approaches in using two-component and three-component donor-free Ziegler–Natta catalysts, in this preliminary work, the effects of various preparation and polymerization conditions including catalyst preparation by wet- or dry- grinding, the type of cocatalyst, with or without pretreatment of catalyst by cocatalyst before polymerization, Al/Ti molar ratio and polymerization temperature, etc., on the isospecific nature of active sites of the TiCl₃ catalyst were studied through a systematic characterization of the PPs by a combination of GPC, ¹³C-NMR with TREF method. It was demonstrated that the types of Al-alkyl cocatalysts play the most dominant role in determination of isospecificity of activate sites and its distribution. A plausible mechanism (Scheme 1) regarding the formation of isospecific active sites with different stability in terms of Ti–Al bimetallic complexing depending on the type of cocatalyst had been proposed. Except the catalyst grinding method, other factors eg., pretreatment, temperature, and Al/Ti molar ratio, etc. did not show obvious effects on the isospecific nature of active sites.     

Germanium recovery using polyphenol microspheres prepared by horseradish peroxidase reaction

BACKGROUND: The formation of polyphenol microspheres by the polymerization of 3‐methylcatechol was performed in a methanol/phosphate buffer solution using horseradish peroxidase (HRP), without the use of a surfactant or a water/oil interface, to be used for germanium recovery. RESULTS: The polyphenol microspheres were of diameter 1 mm. The functional group density of phenol group in the polymer was approximately 15 mol kg^?1 determined by the Folin‐Denis method. In batchwise experiments, the amount of germanium adsorbed was 0.23 mol kg^?1. CONCLUSION: Because germanium is a rare metal, a system for its recovery is required. Using the proposed system, continuous recovery of germanium can be achieved using multilayered microspheres. Copyright © 2011 Society of Chemical Industry     

Performances of metal fluoride added carbon anodes with pre-electrolysis for electrolytic synthesis of NF3

Metal fluoride added carbon anodes treated by pre-electrolysis were investigated for electrolytic production of nitrogen trifluoride (NF₃) in molten NH₄F·KF·4HF at 100 °C. The conditions for pre-electrolysis were first optimized using a graphite sheet anode as a model anode. The formation of fluorine-graphite intercalation compounds (fluorine-GICs) with semi-covalent C–F bonds, (C_xF)_n, on the MgF₂ and CaF₂ added carbon anode surface was accelerated by pre-electrolysis at potentials less than 4.0 V. Critical current densities (CCD) on the MgF₂ added carbon anodes pre-electrolyzed under various conditions were determined, and the highest CCD was 290 mA cm⁻² obtained for that pre-electrolyzed at 3.5 V for 500 C cm⁻². This anode was successfully used in the electrolysis at 100 mA cm⁻² for 290 h and the maximum NF₃ current efficiency was 55%. From these results, it was concluded that the metal fluoride added carbon anode treated by pre-electrolysis has a high potential for electrolytic production of NF₃ at higher current density.     

Active sites deterioration of MgCl2‐supported catalyst induced by the electron donor extraction by alkylaluminium

To investigate the role of the internal donor in a Ziegler–Natta catalyst, the nature and existing states of the internal donor were intentionally varied by alkylaluminium treatment before polymerization, and the catalytic properties during propene polymerization were accurately evaluated using the stopped‐flow method. A significant decrease in the amount of the remaining internal donor was observed during the initial stage of the extraction. The polymerization results show a gradual decrease in the polymer isotacticity with an increase in the extraction time. These different patterns, as a function of the extraction time, indicate that the amount of the remaining internal donor is not directly related to the isotacticity of the produced polymer. © 2002 Society of Chemical Industry