Miscible blends of modified poly(aryl ether ketones) with aromatic polyimides

The phase behavior of binary blends of poly(ether ether ketone) (PEEK), sulfonated PEEK, and sulfamidated PEEK with aromatic polyimides is reported. PEEK was determined to be immiscible with a poly(amide imide) (TORLON 4000T). Blends of sulfonated and sulfamidated PEEK with this poly(amide imide), however, are reported here to be miscible in all proportions. Blends of sulfonated PEEK and a poly(ether imide) (ULTEM 1000) are also reported to be miscible. Spectroscopic investigations of the intermolecular interactions suggest that formation of electron donoracceptor complexes between the sulfonated/sulfamidated phenylene rings of the PEEKs and the n-phenylene units of the polyimides are responsible for this miscibility. © 1993 John Wiley & Sons, Inc.     

Chemical synthesis and electric properties of the conducting copolymer of aniline and o‐aminophenol

A copolymer, poly(aniline‐co‐o‐aminophenol), was prepared chemically by using ammonium peroxydisulfate as an oxidant. The monomer concentration ratio of o‐aminophenol to aniline strongly influences the copolymerization rate and properties of the copolymer. The optimum composition of a mixture for the chemical copolymerization consisted of 0.3 M aniline, 0.021 M o‐aminophenol, 0.42 M ammonium peroxydisulfate, and 2 M H₂SO₄. The result of cyclic voltammograms in a potential region of ?0.20 to 0.80 V (vs.SCE) indicates that the electrochemical activity of the copolymer prepared under the optimum condition is similar to that of polyaniline in more acid solutions. However, the copolymer still holds the good electrochemical activity until pH 11.0. Therefore, the pH dependence of the electrochemical property of the copolymer is improved, compared with poly(aniline‐co‐o‐aminophenol) prepared electrochemically, and is much better than that of polyaniline. The spectra of IR and ¹H NMR confirm that o‐aminophenol units are included in the copolymer chain, which play a key role in extending the usable pH region of the copolymer. The visible spectra of the copolymers show that a high concentration ratio of o‐aminophenol to aniline in a mixture inhibits the chain growth. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5573–5582, 2007     

Chemical reactivity of hypervalent silicon compounds: The local hard and soft acids and bases principle viewpoint

The silicon atom may increase its coordination number to values greater than four, to form pentacoordinated compounds. It has been observed experimentally that, in general, pentacoordinated compounds show greater reactivity than tetracoordinated compounds. In this work, density functional theory is used to calculate the global softness and the condensed softness of the silicon atom for SiH _n F_4−n and SiH _n F _5−n ¹⁻ . The values obtained show that the global and condensed softness are greater in the pentacoordinated compounds than in the tetracoordinated compounds, a result that explains the enhanced reactivity. If the results are analysed through a local version of the hard and soft acids and bases principle, it is possible to suggest that in nucleophilic substitution reactions, soft nucleophiles preferably react with SiH _n F _5−n ¹⁻ , and hard nucleophiles with SiH _n F_4−n .     

Structure of norbornene-fused 3,1-oxazine double cycloadducts

Pentacyclic isoxazolines were obtained by the cycloaddition of benzonitrile oxide to norbornene-azetidinone-fused 3,1-oxazines. The constitutions of two of the isomers obtained, and the configurations and conformations of all products, were determined by means of ¹H and ¹³C NMR spectroscopy and DNOE experiments.     

Studies on calcium‐containing poly(urethane ether)s

The calcium salt of mono(hydroxyethoxyethyl)phthalate [Ca(HEEP)₂] was synthesized by the reaction of diethylene glycol, phthalic anhydride, and calcium acetate. Calcium‐containing poly(urethane ether)s (PUEs) were synthesized by the reaction of hexamethylene diisocyanate (HMDI) or tolylene 2,4‐diisocyanate (TDI) with a mixture of Ca(HEEP)₂ and poly(ethylene glycol) (PEG₃₀₀ or PEG₄₀₀) with di‐n‐butyltin dilaurate as a catalyst. A series of calcium‐containing PUEs of different compositions were synthesized with Ca(HEEP)₂/PEG₃₀₀ (or PEG₄₀₀)/diisocyanate (HMDI or TDI) molar ratios of 2:2:4, 3:1:4, and 1:3:4 so that the coating properties of the PUEs could be studied. Blank PUEs without calcium‐containing ionic diols were also prepared by the reaction of PEG₃₀₀ or PEG₄₀₀ with HMDI or TDI. The PUEs were well characterized by Fourier transform infrared, ¹H and ¹³C NMR, solid‐state cross‐polarity/magic‐angle‐spinning ¹³C NMR, viscosity, solubility, and X‐ray diffraction studies. The thermal properties of the polymers were also studied with thermogravimetric analysis and differential scanning calorimetry. The PUEs were applied as top coats on acrylic‐coated leather, and their physicomechanical properties were also studied. The coating properties of PUEs, such as the tensile strength, elongation at break, tear strength, water vapor permeability, flexing endurance, cold crack resistance, abrasion resistance, color fastness, and adhesive strength, were better than the standard values. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2865–2878, 2003     

Effects of tributyltin(IV) chloride on the gametes and fertilization of Ascidia malaca (Ascidiacea: Tunicata)

Ascidia malaca gametes before fertilization incubated in 10^?5 or 10^?7 M solutions of tributyltin(IV) chloride, TBTCl, for 3 h appear highly damaged under transmission electron microscopy observation. Also, the fertilization process is affected by the compound: the damaged spermatozoa are present in the vitelline coat and the egg does not cleave. An increase of microbodies, structurally similar to peroxisomes, have been detected in the egg peripheral cytoplasm, probably in relation to their role in alleviating damage to some cellular components. The results have shown that the reproduction of ascidians under unfavourable environmental conditions is prevented. Copyright © 2003 John Wiley & Sons, Ltd.     

Depth profile analysis of polyimide film treated by potassium hydroxide

The structural change in the depth direction of a polyimide (UPILEX‐S) film treated in alkaline solution, which was a representative surface treatment used to form a seed layer for plating and to improve the adhesive strength, was analyzed by means of micro Fourier transform infrared attenuated total reflection (FTIR‐ATR) line analysis with gradient shaving preparation. The polyimide film was treated with KOH. The imide ring opened through the alkaline treatment, and the amide structure and carboxylic acid salt were formed. The attainment depth of this structural change was almost proportional to the treatment time, and it reached about 8 μm after a 30‐min treatment. The degree of structural change through the alkaline treatment was almost constant after it reached a considerably degraded stage, and the chemically changed region penetrated into the inner part of the film from the surface. An intermediate layer before the final degraded stage appeared in the treated layer, and its thickness increased with the treatment time. The region that was changed chemically by the alkaline treatment progressed to the inner part simultaneously and continuously as the treatment time increased. The combined use of gradient shaving preparation and micro FTIR‐ATR line analysis was found to be extremely effective for the depth profiling of organic materials. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2071–2078, 2003     

Physicochemical studies on hydrophobic PEO‐PPO‐PEO triblock copolymer micelles in SDS micellar environment

The shape, size, aggregation, hydration, and correlation times of water insoluble PEO‐PPO‐PEO triblock copolymer micelles with sodium dodecylsulfate (SDS) micelles were investigated using transport studies and dynamic light scattering technique. From the conductance of micellar solutions of the polymer in 25 mM SDS and 5 mM NaCl, the hydration of polymer micelles were determined using the principle of obstruction of electrolyte migration by the polymer. The asymmetry of the micellar particles of polymer and polymer‐SDS mixed micellar systems in 5 mM NaCl and their average axial ratios were calculated using intrinsic viscosity and hydration data obeying Simha–Einstein equation. Hydration number and micellar sizes were variable with temperature. The shape of the polymer micelles has been ellipsoidal rather than spherical. The micellar volume, hydrodynamic radius, radius of gyration, diffusional coefficients as well as translational, rotational and effective correlation times have been calculated from the absolute values of the axes. The partial molal volume of polymer micelles has also been determined and its comparison with the molar volume of pure polymer suggested a volume contraction due to immobilization of the water phase by the hydrophilic head groups of the polymer. The thermodynamic activation parameters for viscous flow favor a more ordered water structure around polymer micelles at higher temperatures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2410–2420, 2007     

ℙmax variations related to slaloms

We prove the iteration lemmata, which are the key lemmata to show that extensions by Pmax variations satisfy absoluteness for Π₂-statements in the structure 〈H (ω ₂), ∈, NS_{ω 1}, R 〉 for some set R of reals in L (ℝ), for the following statements: (1) The cofinality of the null ideal is ℵ₁. (2) There exists a good basis of the strong measure zero ideal. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Supercompactness and measurable limits of strong cardinals II: Applications to level by level equivalence

We construct models for the level by level equivalence between strong compactness and supercompactness in which for κ the least supercompact cardinal and δ ≤ κ any cardinal which is either a strong cardinal or a measurable limit of strong cardinals, 2^δ > δ ⁺ and δ is < 2^δ supercompact. In these models, the structure of the class of supercompact cardinals can be arbitrary, and the size of the power set of κ can essentially be made as large as desired. This extends and generalizes [5, Theorem 2] and [4, Theorem 4]. We also sketch how our techniques can be used to establish a weak indestructibility result. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)