Oxidative aging of thermoplastic polyimide films

Two linear polyimides were subjected to accelerated isothermal aging at temperatures between 300 and 400°C. Losses in toughness correlated well with changes in glass transition temperature (T_g) of the films, but not with weight loss. Both materials have extrapolated lifetimes of 100,000 h near their T_g's. © 1995 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

     

Mowrah (Madhuca latifolia) seed saponin. Toxicological studies

Mowrah seed (Madhuca latifolia) meal

1 Meal refers to solvent extracted material.

contains high levels of saponin (7%) making it unsuitable for incorporation in animal feedstuff formulations. The saponin from mowrah seed meal was isolated and purified by paper chromatography. This was used for in vitro tests as well as pharmacological and acute toxicity studies for a better understanding of its properties and toxicity. The oral, intraperitoneal and intravenous LD₅₀ of mowrah saponins in mice are 1 g, 15–20 mg and 15 mg/kg body weight respectively. Processing of the meal to remove or inactivate the saponin will be essential prior to its incorporation in animal feeds.     

Fracture behavior of coated/uncoated graphite-epoxy composites

The static delamination behavior of graphite/epoxy composite specimens subjected to mode I tensile opening (using UDCB

1 Uniform double cantilever beam.

specimens), and pure mode II shear loading (using ENF

2 End-notched flexural.

specimens) were studied. The graphite epoxy composites for the study were made from commercially treated fibers, with and without an electropolymerized interlayer. The mode I fracture energy (G_IC) was found to be significantly higher (more than 50 percent) for the coated fibers. However, this improvement was accompanied by a high reduction (more than 3 times) in the mode II fracture energy (G_IIC). This effect is apparently related to poor adhesion between the interlayer and the epoxy resin, which may be corrected by use of a “top layer” of appropriate composition to form chemical bonds between the phases. The fracture toughness (K_IC) of composites made with commercially treated fibers was also evaluated, using double side-notched specimens.     

Solvent replacement in the synthesis of persubstituted phosphonitrilic hydroquinone prepolymer materials

A desirable solvent replacement has been effected in the synthesis of persubstituted phosphonitrilic hydroquinone prepolymer materials. The replacement of carbon tetrachloride with cyclohexane has no adverse effect on the composition and quality of the material prepared. The overall yield of the reaction increases from 65 to 70% and the toxicity of the reaction mixture and of the waste generated from the reaction are greatly reduced. The particularly close match of solvent properties between carbon tetrachloride and cyclohexane makes this an excellent solvent replacement. Such changes to less-expensive, less-toxic, and less-environmentally damaging solvents are on the increase. A brief list of some known replacement solvents for use in polymer and coatings applications is presented. © 1994 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

     

Effects of water content on the properties of starch/poly(ethylene–vinyl alcohol) blends

The physical properties of unmodified starch, poly(ethylene vinyl alcohol), glycerol, and water mixtures are reported. Thermal and melt-flow properties of the preprocessed, physically mixed materials were determined along with the tensile properties and morphology of injection-molded microtensile samples. Melt-flow properties were measured by a capillary rheometer, and the water content was varied from 4 to 18%. The morphology, rheology, and tensile properties are all highly related to the percentage of water present. A transition in the tensile properties and morphology of the blends was observed at approximately 11% moisture content. © 1994 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

     

Glass fiber-reinforced epoxy composites

Glass fiber-reinforced epoxy composites were prepared from the matrix resins tetraglycidyl diaminodiphenylmethane

1 Systematic name: N,N,N′,N′-Tetrakis(2,3-epoxypropyl)-4,4′-diaminodiphenylmethane.

(TGDDM) and tetraglycidyl bis(o-toluidino)-methane

2 Systematic name: N,N,N′,N′-Tetrakis(2,3-epoxypropyl)-4,4′-bis(o-toluidino)methane.

(TGMBT) using various amines like 4,4′-diaminodiphenylmethane (DDM), 4,4′-diaminodiphenylsulfone (DDS) and diethylene triamine (DETA) as curing agents. The fabricated laminates were evaluated for their mechanical and dielectrical properties and chemical resistance. The composites prepared using an epoxy fortifier (20 phr) showed significant improvement in the mechanical properties.     

Synthesis of phosphorus-containing wofatit cation exchangers and their affinity toward selected cations

A number of solid Cationits have been prepared derived from Wofatit

1 Trademark, VEB Chemiekombinat Bitterfield.

gel and canal structures: styrene/DVB, chloromethylated ST/DVB, and acrylic acid/DVB copolymers. To functionalize the copolymers, PCl₃/AlCl₃ and dialkyl phosphites or trialkyl phosphites were used. The influence of the polymer matrix structure and the chemical structure of the functional groups of obtained Ionits on their affinity toward 23 metallic cations in acidic media has been investigated using the conductivity method. To obtain comparison data, commercial “Wofatit”–sulfonic and–carboxylic Cationits, have been tested under identical conditions.     

The synthesis and properties of a cation-exchange resin prepared by the pyrolysis of starch in the presence of phytic acid

A black charcoal-like material having cation exchange and adsorption properties was prepared by the controlled pyrolysis of starch in the presence of a commercial phytic acid solution. Resins with binding capacities of 0.7–5.7 meq/g of calcium were prepared by varying the phytic acid to starch ratio, the temperature, or the duration of heating of the reaction mixture. SEM photomicrographs of some of these new materials showed that they are composed of particles similar in size and shape to the starting starch granules. These resins also removed atrazine from aqueous solutions. © 1995 John Wiley & Sons, Inc.

1 This article is a US Government work and , as such, is in the public domain in the United States of America.

     

Dicyclopentadienoxidation. II 5. Katalysierte Flüssigphasenoxidation von Dicyclopentadien

Dicyclopentadiene Oxidation. II. Catalyzed Liquid-Phase Oxidation of Dicyclopentadiene The liquid-phase oxidation of dicyclopentadiene 1 by molecular oxygen was studied in the presence of MoO₂(acac)₂

1 Acac- Acetylacetonat

as a typical epoxidation catalyst. The yield of the mono-epoxides 2 and 3 is increased to 56,4% (uncatalyzed reaction: 43,6%). The ratio of the two mono-epoxides is decreased to 2/3 = 2,6 in relation to the uncatalyzed reaction ( 2/3 = 7,1). The influence of temperature, conversion and solvents is described. The bisepoxide 4 is formed at lower conversions than in the uncatalyzed reaction. But also at higher conversions of 1 not more than 10% of the bisepoxide 4 is formed     

Grafting of methyl methacrylate on isoprene rubber

Methyl methacrylate has been grafted on artificial isoprene rubber (IR) latex, with use of redox initiation. The properties of latices containing up to 40 phr

1 Parts per hundred parts of rubber.

methyl methacrylate (MMA) as well as solid products containing up to 80 phr of this compound were studied. Compared with ungrafted IR latex with the same solids content, the grafted IR latices had a lower viscosity, owing to their particle size being larger. Vulcanised films obtained from the grafted latices showed a considerably higher modulus, particularly at large deformations, than those based on IR or blends of IR with polymethyl methacrylate. by incorporation of certain reinforcing white fillers in the MMA-grafted IR latices, a further increase in the modulus of the latex films was effected.     

The use of volume-averaging techniques to predict temperature transients due to water vapor sorption in hygroscopic porous polymer materials

Volume-averaging techniques developed for modeling drying processes in porous materials offer a convenient framework for analyzing vapor sorption in porous hygroscopic polymeric materials. Because of the large temperature changes associated with water vapor sorption in these materials (from 10° to 20°C), sorption/diffusion processes are best characterized through the coupled differential equations describing both the transport of energy and mass through the porous structure. Experimental and numerical results are compared for a variety of natural and man-made porous polymeric materials (textiles) using the volume-averaging technique. Boundary heat and mass transfer coefficients and assumptions about thermal radiative properties of the experimental apparatus are shown to influence results obtained with the numerical solution method. © 1997 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

J Appl Polym Sci 64: 493–505, 1997     

Thermomechanical properties of blends of pectin and poly(vinyl alcohol)

Blends of citrus pectin and several types of poly(vinyl alcohol) were investigated to determine the effects of compositional variables and polymer type on film properties. Some films were also plasticized with glycerol. Films were cast from water onto Lexan™ plates, dried, and removed. Thermomechanical properties were obtained using a dynamic mechanical analyzer, and thermodynamic transitions were also obtained using a differential scanning calorimeter. Increasing the amount of poly(vinyl alcohol) in the blends reduced the storage and loss modulus of the films above the glass transition temperature (T_g). The T_g values observed decreased as the amount of PVOH in the blend increased. Addition of glycerol depressed the PVOH T_g and merged it into the T_g of the pectin/glycerol blend. Changes in the molecular weight and degree of ester hydrolysis of poly(vinyl alcohol) exerted a rather small effect on the blends. © 1996 John Wiley & Sons, Inc.

1 Reference to a brand or firm name does not constitute an endorsement by the U.S. Department of Agriculture over others of a similar nature.

     

Synthesis and characterization of melt-polymerizable aminophthalocyanine monomers

The strategy, synthesis, and characterization of a soluble amine-functionalized phthalocyanine monomer and two examples of its polymerization into optically transparent glasses are reported. A simple, fast, and versatile method for incorporating metal ions into the metal-free phthalocyanine is demonstrated. Measurements of the nonlinear optical properties associated with a lead-substituted phthalocyanine/urethane copolymer are also reported. © 1995 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

     

Zur übergangsmetallkatalysierten nucleophilen Epoxidringöffnungsreaktion

The Transition Metal Catalyzed Nucleophilic Epoxide Ring Opening Reaction The catalytic influence of MoO₂(acac)₂

1 Acac-Acetylacetonat

, Mo(CO) ₆ , MoCl ₅ , WCl ₆ and TaCl ₅ on the reaction of 1,2-epoxy-octane with ethanol at 100°C in dioxan or chlorobenzene as solvents is proved. Water and hydroperoxides react with a higher rate than alcohols. When changing from primary to secondary and tertiary alcohols a decrease of the reaction rate is observed. 2,3- and 3,4-Epoxyheptane and cis- and trans-4,5-epoxy-octane react more slowly than the corresponding 1,2-epoxides. Epichlorhydrin and methylglycidether react with a lower, cyclohexene oxide, styrene oxide and norbornene oxide react with a higher rate than 1,2-epoxyoctane. The reactivities of the two dicyclopentadiene monoepoxides correspond with the reactivities of the norbornene and cyclopentene oxides. In the molybdenum catalyzed epoxide ring opening reaction an isomer distribution appears in favour of the 1-hydroxy-2-ethoxy-alkane 2 . A mechanism in the coordination sphere of the transition metal complex is proposed.     

The STOBBE Condensation with Dimethyl Homophthalate. Part I

The condensation of methyl 2-thienyl, methyl 2-furyl, and phenyl 2-thienyl ketone with dimethyl homophthalate in the presence of either potassium t-butoxide or sodium hydride as condensing agent, gave predominantly the (z)-half esters

1 The nomenclature of cis/trans isomers follows the IUPAC Tentative rules, Section E, Fundamental Stereochemistry, J. org. Chemistry 35 , 2849 (1970). See also N. R. El-Rayyes, J. prakt. Chem. 315 (2), 300 (1973). (E) = trans-(Heterocyclic ring/CO₂CH₃) (Z) = cis-(Heterocyclic ring/CO₂CH₃)

. The structure and configuration of the products were inferred by chemical and spectroscopic means.     

The hierarchical structure and flexure behavior of woven carbon fiber epoxy composite

The hierarchical structure and flexure behavior of woven carbon fibers epoxy composite were investigated in this work. First, the hierarchical structure of the composite is characterized on three levels: composite, ply, and yarn. Structura imperfections,

1 In this paper, “structural imperfections” is used to describe the inherent structural characteristics of the actual composite, which deviate from the theoretically ideal and perfect composites, control, that are used in composite theories.

such as, ply‐ply misalignment, ply‐ply offset, and resin pockets, are identified and described. Second, a four‐point bending arrangement is used to study the flexure properties of the composite. Additionally, in‐situ traveling microscope and acoustic emission (AE) techniques are utilized to gain insight to the failure proceses during flexure test. AE showed early stages of matrix cracking before visual observation, which makes it a valuable tool for early failure detection.     

Detection of Radicals at the Photolysis of tert-Butyl Hydroperoxide in DMSO and water

The decomposition of tert-butyl hydroperoxide by photochemically induced reactions in DMSO

1 Abbreviations used: DMSO, dimethyl sulfoxide; DMSO-d₆, completely deuterium labelled dimethyl sulfoxide; cw-ESR, continuous-wave Electron Spin Resonance; u. v., ultra violet; DMPO, 5, 5-dimethyl-I-pyrroline N-oxide; TMPO, 3, 3, 5, 5-tetramethyl-l-pyrroline N-oxide.

and water was investigated by cw-e.s.r. spectroscopy. The products tert-butylperoxyl, methyl and sulfur-centered free radicals were identified. The tert-butoxyl free radical is involved in the primary process as shown by time-resolved e.s.r. technique. On the basis of directly identified radical species, a mechanism for the photochemically induced reactions of tert-butyl hydroperoxide in DMSO is proposed. At concentrations below 0.8 mol · l⁻¹ the radical formation from tert-butyl hydroperoxide proceeds by cleavage of the O O bond rather than by hydrogen abstraction.     

Gel permeation chromatography: Physical characterization and chromatographic properties of porasil

Porasil

1 Porasil is the Water Associates registered trademark for a powdered porous silica chromatographic substrate.

porous silica has been characterized by the methods of gas adsorption–desorption isotherms, mercury porosimetry, and electron microscopy. The pore structure has been shown to be quite heterogeneous, particularly at the surface of the particles. From the same sample of Porasil, columns were packed and calibrated in a gel permeation chromatograph. The availability of high molecular weight fractions of polystyrene allowed the exclusion limit of these materials to be determined for the first time. The heterogeneous pore structure did not seem to affect the effectiveness of these materials for macromolecular separation.     

Über die katalysierte Flüssigphasenoxidation von cis- und trans-Oct-4-en

The Catalyzed Liquid-Phase Oxidation of cis- and trans-Oct-4-ene The influences of MoO₂(acac)₂

1 acac-Acetylacetonat.

, MoO ₃ and Co(acac) ₃ on the liquid-phase oxidation of cis- and trans-oct-4-ene at 110°C were studied. In the presence of molybdenum catalysts the yield of epoxides and the stereoselectivity of epoxide formation are increased. The results are in good agreement with the hypothesis that molybdenum compounds effect only the stereospecific reaction of the hydroperoxides formed with the starting olefin yielding the corresponding epoxide. The cobaltic complex increases the rate of autoxidation, but has no remarkable influence on the yield of epoxides. In the presence of Co(acac)₃ more trans-epoxide is formed from cis-oct-4-ene than in the uncatalyzed reaction. This can be explained by an increase of the lifetime of the intermediate peroxyalkyl radical, effected by complex formation of the radical with a cobalt species.