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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 1859-1871 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effect of titanium compounds on thermooxidation stability of stabilized polypropylene was studied. It was found that the presence of titanium compounds shortens the induction period of PP oxidation. This phenomenon is brought about by the thermal reactions of titanium compounds with antioxidants which take place during polymer processing. The first step is the reaction of Ti—Cl with OH groups of phenolic antioxidant, which gives rise to a colored titanate and HCl. Hydrogen chloride functions as a Friedel-Crafts catalyst for degradation and dealkylation of phenolic antioxidants. The products of degradation have a very low stabilization efficiency. Hydrogen chloride acceptors suppress antioxidant degradation and increase the polymer stability even in the presence of small amounts of titanium compounds.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 1895-1897 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Protein was irradiated by gamma rays from a cobalt 60 source. At different times after irradiation, the reactivity decay of the irradiated protein was examined. An empirical equation for the reactivity decay was obtained.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 1899-1908 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Tensile strength data at high and low rates of loading were obtained for a glass-reinforced polyester and a glass-reinforced epoxy. Analysis of the data by a rate method indicated that such a method may be used to predict behavior of polymers from limited test data.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 1909-1919 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A system has been designed and developed to subject a sample of powder on a grounded metal plate to charging by ion bombardment and to measure the charge accepted by the sample. Observation of the charge decay from the sample was also possible. A method of sample preparation was evolved which made it possible to obtain samples of known particle size and number of particles. The sensitivity of measurement and the noise levels were investigated and found to be acceptable. Calibration tests were made to determine the validity of the proposed equation relating the measured voltage, circuit capacitances, and the ratio of probe height to net charge location. It was found that for a wide range of values of the ratio of probe height to particle diameter, the linear equation was a good description of the process and could be used to accurately determine the charge on a sample. Some measurements were made on typical powders to illustrate the feasibility of the method and equipment to characterize variable charging properties.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 1949-1963 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The structure of the cyclic urea influenced the rate of reaction with cotton cellulose and the mechanism by which reaction occurred. Reaction of N, N′-dimethylolethylene-urea (DMEU) and N, N′-dimethylolpropyleneurea (DMPU) with cellulose in presence of inorganic salt catalysts proceeded through methylol hydroxyls and at the same rate; but reaction mechanism differed. With DMEU, N → metal ion coordination occurred and SN2 mechanism prevailed. With DMPU, O → metal ion coordination resulted.Reaction of dihydroxyethylene urea (DHEU), N, N′-dimethyldihydroxyethyleneurea (DMeDHEU), and N, N′-dimethyloldihydroxyethyleneurea (DMDHEU) with cotton cellulose proceeded through ring hydroxyls with the formation of a carbonium ion, indicating an SN1 mechanism. The much faster rate of reaction with DMeDHEU than with DHEU was attributed to the more electronegative environment of its ring hydroxyl, while the much slower rate of reaction of DMDHEU was attributed to hydrogen bonding between its methylol and ring hydroxyls.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 2031-2032 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 2069-2072 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Glass transitions in certain polymer samples were detected as a step change in a DTA trace in the exothermic sense. This anomaly is explained as a manifestation of the volume relaxation shown to occur at the glass transition in internally strained samples.
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  • 8
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 2057-2068 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: It was found that an ion radical complex is formed by the reaction of carbon black with an alkali metal (Li, Na, K) in tetrahydrofuran. The graft copolymerization of styrene with carbon black was carried out using the ion radical complexes as initiator, and free polystyrene and carbon black-polystyrene graft copolymer were obtained. The identification of the graft copolymer with carbon black was carried out by fractionation and thermal degradation. The initiation activity of the alkali metals increased in the order Li 〈 Na 〈 K. The effect of the particle size of the carbon black on the graft copolymerization was studied.
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  • 9
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The products obtained on degradation of poly(m-aminostyrene) in vacuo are described. The effect of molecular weight and pyrolysis temperature are discussed and the behavior of poly(m-aminostyrene) compared with that of polystyrene. Quantitative analytical methods using ultra-violet spectroscopy and gas liquid chromatography are described for m-aminostyrene and m-toluidine. The possible mechanisms of degradation to yield the products are discussed.
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  • 10
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 2073-2084 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The pyrolysis of acrylic fiber up to 400°C in an inert atmosphere at 1° and 6°C/min was studied by means of thermogravimetric and differential thermal analysis. The exothermic reaction occuring at 180-300°C was shown to be due to the reaction of nitrile groups by comparing the extent of exotherm with the number of nitrile groups present, determined by infrared spectroscopy. In addition, results of single-fiber tensile measurements, density, and elemental analysis of the pyrolyzed fibers are interpreted in terms of possible molecular structures. The gases evolved on pyrolysis were analyzed for both ammonia and hydrogen cyanide and the liberation of ammonia was attributed to a termination reaction of the polymerization of nitrile groups. The critical conditions necessary for the production of high strength and modulus carbon fiber are discussed briefly in ralation to the chemical changes occurring on pyrolysis.
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  • 11
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 2119-2127 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The properties of crosslinked thermosetting resins depend markedly on the completeness of the crosslinking process. Determination of the degree of cure of an unsaturated polyester resin has been studied previously by mechanical, spectroscopic and volume resistivity methods. In this respect the effect of cure time and temperature on the ac dielectric constant and dissipation factor at 1 kc/s and 10 kc/s is considered. The dissipation factor appears to be a most useful parameter for detecting changes in the degree of cure in the later stages of reaction.The electrical properties of the cured resin are discussed, and values for the energy of activation for electrical conduction are compared with literature reports on similar materials.
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  • 12
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 2183-2191 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polysulfone, polycarbonate, and phenoxy resins were aged under thermal and ultraviolet light conditions. Thermoxidative processes in polysulfone and polycarbonate are of such minor significance as not to impart noticeable losses in these materials below 125°C. In phenoxy, however, thermal oxidation above 100°C results in rapid deterioration of all physical properties. This probably results from the low glass transition temperature of this polymer. Photo-oxidation rapidly degrades polysulfone. This appears to be a consequence of scission at the sulfone link. In polycarbonate, however, the only serious result of short-term irradiation is discoloration. For phenoxy resin, crosslinking through reactions at the hydroxyl group is the principal result of photo-oxidation. In all processes the bisphenol A portion of the three polymers appears to play only a small role.
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  • 13
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 2209-2221 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The difficulties involved in the measurement of the partition coefficient and diffusion coefficient of NaCl in hydrophilic polymer membranes are examined by the initial rate and late-time analysis of desorption data for three nonionic polymer systems. The late-time analysis, based on the plot of the logarithmic relative desorption versus time, was found to be useful when the diffusion is Fickian and the magnitude of D2/l2 is small. Depending on the magnitude of D2/l2, an accurate measurement of k2 and determination of D2 cannot be achieved without correction for the effect of surface salt solution, impossible with late-time analysis. The initial rate measurement was found more versatile for general non-Fickian diffusion and it gave a means of correction of the errors involved in estimating the partition coefficient. In general, the diffusion of NaCl in hydrophilic polymers is not ideal Fickian and the discrepancy between the two analyses is appreciable.
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  • 14
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 2247-2255 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The reactions of trans-2,5-dimethoxy-4′-aminostilbene with poly(maleic anhydride-co-methylvinyl ether) and trans-2,5-dimethoxy-4′-isocyanatostilbene with poly(oxy-1,4-phenyleneisopropylidene:1,4-phenyleneoxy-2-hydroxytrimethylene) yield polymeric systems which undergo rapid crosslinking upon short exposure to ultraviolet light. The extent of photocrosslinking as a function of exposure time was determined by the decrease of the trans-stilbene ultraviolet absorption at 350 nm.
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  • 15
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    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 2265-2268 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: When protein was irradiated by gamma rays from a cobalt 60 sources, an activated state on the position of the groups in the vicinity of the asymmetric carbon atoms in the protein molecule was caused. An empirical equation for the change in optical rotation was obtained, and the phenomena were explained on the basis of the molecular mechanism. The general equation for the change in optical rotation is given by [α] = (b + a log R) (1 - e-kt), where [α] is the specific rotation of the solution, R is the gamma radiation dose, t is time, and a, b, and k are adjustable constants.
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  • 16
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 2277-2292 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The two constants in the equation log η = A + C′ M̄n1/2 (η is the viscosity of molten alkyd and M̄n the number average molecular weight) were determined at 110°C for two kinds of alkyd resin prepared with the same formulation but with different cooking schedules. It was found that the magnitude of the slope C′ was larger for the alkyd which was prepared by raising the reaction temperature directly up to 230°C, in comparison with that of the alkyd which was prepared by maintaining the temperature at 170°C for an hour and then raising it up to 230°C.Measurements of η and M̄n were carried out until the gelation occurred. Both upward and downward breaks were observed in log η vs. M̄n1/2 plot. Based on these viscometric data, the gel point mechanism was discussed. Disagreements between the molecular weight observed and that calculated from the Flory's theoretical equation became more remarkable as the esterification proceeded. This suggested that a large extent of intraesterification reaction is taking place in alkyd synthesis.
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  • 17
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    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 2333-2340 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The reaction of hydrazine hydrate with manganic hydroxide and its application to the solution polymerization of methyl methacrylate has been studied. The kinetic evidence suggests that the hydrazine and the monomer are both adsorbed on the surface of the manganic hydroxide sol and that the decomposition of the hydrazine and the polymerization of the methyl methacrylate follow zero-order kinetics. The rate of polymerization increases slowly with increasing temperature, the activation energy for the polymerization being 4.9 ± 0.2 kcal/mole.
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  • 18
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    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 2383-2395 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The properties of 4-methyl-pentene-1 polymer (TPX-RT-D30) were altered by blending petroleum jelly (P.J.) with the polymer. The polymer was blended with up to 40% by weight P. J. The plasticization of the polymer by the P. J. apparently allows high molecular weight fractions of the polymer to crystallize and influences the crystalline size and perfection. Tensile properties of the blends showed both a break and yield value in all ratios as compared to only a break value for the pure polymer. Breaking strength ranged from 4000 psi for the polymer to 1000 psi at 40% P. J. The samples had a “necking down” effect at 10% P. J. Modulus decreased from 1.8 × 104 (literature value 2.1 × 105) to 2.3 × 104 at 40% P. J. Brittle point values varied from above room temperature to 5°C at 40% P. J. The Vicat softening point ranged from 181°C for the polymer to 87°C at 40% P. J. Differential thermal analysis (Stone) showed a melting point depression from 235°C to 218°C at 40% P. J.
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  • 19
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    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 2439-2445 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Curing reactions were investigated after the gel point, using infrared transmittance and reflection spectrophotometric techniques. In the system carboxyl-terminated polybutadiene (CTPB)/Epon X801 or Epotuf STF-6, catalyzed with Fe(III)-acetyl-acetonate (FeAA), at an equivalent ratio of carboxyl to epoxide groups, the final extent of reaction of COOH groups was found to be between 64% and 77% for eight CTPB samples. Increasing the ratio of epoxide to carboxyl groups (up to 1.6) resulted in an increase in the conversion, but the complete reaction of COOH groups could not be accomplished. The final extent of reaction also depends upon the functionality of the crosslinking agent. The lower the functionality of the epoxide, the higher the conversion of COOH groups. The use of chromium naphthenate as a catalyst for epoxide-COOH reactions gave higher conversions than FeAA. This result is related to side reactions catalyzed by the chromium naphthenate. The change in mechanical properties and the change in extent of reaction were followed simultaneously; it was found that no further development of mechanical properties occurred when the curing reaction between COOH and epoxide groups had ceased.
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  • 20
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    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 133-140 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In the ceric ammonium nitrate-initiated graft polymerization of acrylonitrile (AN) with starch, grafting frequencies and molecular weights of grafted polyacrylonitrile changed from 600 anhydroglucose units (AGU)/graft and 120000 to 280 AGU/graft and 36000 when concentrations of starch and AN were varied from 0.27 and 1.20 to 0.023 and 0.235 moles/l. of water, respectively. The influence of variety of starch, size of the starch granules, and reaction time was studied, and possible reasons for the influence of reactant concentration on the composition of the copolymer are considered.
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  • 21
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    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 141-148 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An automated collagen solubilizing apparatus that maintains constant electrolytic conditions during solubilization is described. It was used in solubilization of 6.95% of a calfskin corium as monomeric collagen in citrate buffer at pH 3.44 and ionic strength of 0.44 and a temperature of 8°C. It is shown that this is the limit of solubilization for undenatured collagen in this buffer.
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  • 22
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    Journal of Applied Polymer Science 13 (1969), S. 117-131 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The viscosities of moderately concentrated solutions of low-density polyethylenes in ethane, propane, and ethylene have been measured at low shear rate in the temperature range of 150-250°C and in the pressure range of about 15000-30000 psi. Within the precision of the measurements, the relative viscosity is independent of pressure over the range investigated but increases as the solvent is changed from propane through ethane to ethylene. The activation energy for the relative viscosity in ethane varies from about 0.5 to 2.5 kcal/mole as the concentration changes from 5 to 15 g/dl. Effects of polymer concentration and molecular weight on solution viscosity in ethane at 150°C have been determined, and all of the data can be represented by a single straight-line plot of the logarithm of relative viscosity versus the intrinsic viscosity (in p-xylene at 105°C) times concentration. This simple relation is valid over wide ranges of polymer concentration and molecular weight and over more than two orders of magnitude of relative viscosity. The solution viscosities of the polyethylenes in the three supercritical fluid solvents used appear surprisingly low at first sight. This behavior is partly a result of the low solvent viscosities but also might mean that the polymer has an abnormally low segmental friction factor compared to that in solutions under more familiar conditions.
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  • 23
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    Journal of Applied Polymer Science 13 (1969), S. 2643-2648 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Rates and extents of crystallization of nylon 11 and nylon 6/11 copolymers have been measured by dilatometry. As the amount of copolymerization increased there was a decrease in the extent of crystallization and in the rates of crystallization for any degree of supercooling below the melt.
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  • 24
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    Journal of Applied Polymer Science 13 (1969), S. 2649-2656 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Acrylonitrile was grafted onto cellulose with the use of ceric salt as initiator and the grafting was found to be maximum at 0.6N acid concentration. The effect of monomer and initiator concentration on the extent of grafting was studied. A new method for quantitative estimation of extent of grafting on cellulose was developed and its validity was established. The grafted samples with 20% increase in weight were found to be highly resistant to microorganisms.
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  • 25
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    Journal of Applied Polymer Science 13 (1969), S. 2657-2663 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In order to prepare porous, macroscopically homogeneous filters without a separate packing process, ethylene was polymerized by radiation in glass tubes. The bulk density of the polyethylene is approximately proportional to ρ(ƒM)2I0.9t2, where ρM is average ethylene density, ƒM is average ethylene fugacity, I is radiation dose rate, and t is reaction time. The effect of the bulk density on “treatment capacity” was investigated by experiments where air samples containing 0.1 wt-% iodine vapor were filtered. Treatment capacity is difined as that amount of air per gram of polyethylene which passes through a filter until the polyethylene reaches the break point. The treatment capacity is approximately constant at 9 × 102 cm3/g over the bulk density range from 0.03 to 0.07 g/cm3, and it is lower at the outside of this range. The pressure drop due to the polyethylene filters varies with the 2.7th power of the bulk density when the bulk density is more than 0.03 g/cm3; below 0.03 g/cm3 this exponent increases with decreasing bulk density. Because of both the necessity of high Treatment capacity and that of low pressure drop, the optimum bulk density of polyethylene in the filter is about 0.03 g/cm3.
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  • 26
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    Journal of Applied Polymer Science 13 (1969), S. 2721-2733 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The influence of hydrogen bonding on the flow behavior of polymer melts at high shear rate has been investigated using a capillary extrusion rheometer. The systems studied were copolymers of ethylene and acrylic or methacrylic acid. Hydrogen bonding was found to substantially enhance both flow activation energy and viscosity level, as well as the degree of dependence of viscosity on rate of shear. It was also found that hydrogen bonding does not influence the critical shear stress for onset of “melt fracture.” The data support the view that hydrogen bonds act effectively as temporary (quasi-) crosslinks during the short time scales of deformation involved in flow at high shear rates.
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  • 27
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    Journal of Applied Polymer Science 13 (1969), S. 2699-2703 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Adhesives data are presented at -320° to +400°F for adhesion to aluminum or stainles steel to indicate that poly-2-oxazolidone-type adhesives give poor results when conpared to epoxy amine, polyurethane prepolymer amine, or a mixture of the latter two resins.
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  • 28
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    Journal of Applied Polymer Science 13 (1969), S. 337-340 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Mounting media for examining rubber reinforced copolymers using the phase microscope are described. The mounting media are based on cinnamaldehyde as the basic solvent with suitable adjustments made depending upon the copolymer under examination.
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  • 29
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    Journal of Applied Polymer Science 13 (1969), S. 437-443 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effect of varying the nature of crosslinks in phenolic resins has bee studied with the use of resins made from phenol, p-cresol, and bisphenol A. Thermal analysis showed that the methylene bridge was stronger under nonoxidative conditions than the isopropylidene linkage. The result is somewhat affected by the degree of crosslinking.
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  • 30
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: An infrared method has been developed for the determination of the isotacticity of polypropylene in the 90-100% range. The method requires the annealing of thin films at 165-167°C. for 3 hr. in an inert atmosphere, followed by slow cooling to room temperature. For approximate answers the ratio of the intensity of the 10.00 μ band to that of the 10.27 μ band can be reported as the fraction of isotactic material. Better results are obtained, however, by using Figure 2 as a calibration curve and reading the values from it.
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  • 31
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    Journal of Applied Polymer Science 13 (1969), S. 445-458 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The relationship is shown between the flex life and long-termtensile strength of flexible composite material. The long-term strength is interpreted in terms of a kinetic theory of failure. However, it is not posible to predict the flex life from tensile strength or even long-term strength data unless the stiffness or modulus is considered along with the thickness of the sample. With these factors it becomes possible to predict the flex life of a material and to compare various flex-testing instruments utilizing a new concept, which material and to compare various flex-testing instruments utilizing a new concept, which we call “effective force.” The usefulness of the concept of effective force is explained.
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  • 32
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    Journal of Applied Polymer Science 13 (1969), S. 459-462 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Corresponding flexural stress and strain data for polycarbonate failure (at yield or break when brittle), at various temperatures are reported. It is shown that a specific failure locus is obtained at each temperature examined and that the results provide a means of construction of an appropriate locus for any temperature within the range 77-373°K investigated.
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  • 33
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    Journal of Applied Polymer Science 13 (1969), S. 463-476 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Diallyl 2-substituted succinates, obtainable via the addition of alkenes or alkylaromatics to maleic anhydride, undergo intramolecular cyclization during polymerization to low molecular weight prepolymers. The amount of this cyclization and the properties of the cured prepolymers are profoundly affected by the structure of these 2-substituents. Thus, the degree of cyclization decreases with these substituents in the order: aralkyl and isobutyl 〉 unhindered alkenyl 〉 alkyl 〉 hindered alkenyl. Properties of thermosetting molding compounds based on these prepolymers are inferior to those of poly-(diallyl phthalate) molding compounds.
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  • 34
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    Journal of Applied Polymer Science 13 (1969), S. 477-486 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A mathematical model for the kinetics of polycondensation reactions was developed. Reaction rates were expressed in terms of reactive functional groups where the reactivity of each functional group was assumed to be independent of the size of the polymer molecule. A method of testing the validity of the model with batch reactor data is demonstrated. The model is then employed to derive expressions for the equilibrium constant and molecular weight distributions. Continuous reactor yields and molecular weight distributions are then predicted from the batch reactor data. The reactions considered include chain growth, scission, and ester exchange reactions.
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  • 35
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    Journal of Applied Polymer Science 13 (1969), S. 577-598 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In view of the intensifying interest in the application of polymeric membranes in mixture separation processes, the permeation and permselective properties of polypropylene films toward several candidate organic liquids and vapors were investigated. Polymer films were subjected to solvent and thermal treatments, and the effects of these treatments on film morphology and transport properties were studied. Structure-property relationships for membrane permeation were then developed. Polypropylene films were found to be selective toward toluene, relative to isooctane, and p-xylene relative to o-xylene. Liquid flux rates were found to depend primarily upon the solubility of the permeants in the films and the absolute difference in the solubility parameters of the polymer-liquid pair provided a good basis for correlation of this effect. Considering liquids of closely similar solubility parameters, fluxes were found to be dependent upon the apparent molecular cross sections of the permeants. Films annealed in various organic solvents at temperatures of 60-100°C exhibited enhanced permeability, with up to fifteenfold increase relative to untreated membranes, but with reduced selectivity towards the permeants. A mechanism to account for these effects through consideration of the influence of treating solvent type on polymer morphology is proposed. It postulates the formation of more open or coarser spherulitic structures as a result of recrystallization in the presence of solvent during annealing. The enhanced flux rates in the treated films are attributed to the changes in the spherulite textures and to diminished intercrystalline tie chain constrainment within the spherulitic substructure.
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  • 36
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    Journal of Applied Polymer Science 13 (1969), S. 629-636 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A range of block copolymers of styrene and methacrylic acid has been prepared by the suspension method involving migration of a growing radical across a phase boundary. The way in which copolymer composition varies with change in the amount of the two monomers in the reaction mixture has been studied, and explanations are suggested to account for these variations. Two methods, involving calculation from solubility data and thermogravimetric analysis respectively, have been used to give an estimate of the length and composition of the blocks.
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  • 37
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    Notes: Sulfhydryl groups have been introduced into cotton and into diethylaminoethyl (DEAE)-cotton by reaction with neat 1-chloro-2,3-epithiopropane or alcoholic solutions of the thiirane. Reactions at room temperature have been compared with those at higher temperatures, and fabric properties obtained with various S/Cl ratios have been compared. The effects of additional external base catalysis on these reactions have been studied. Fabric properties resulting from cotton-1-chloro-2,3-epithiopropane or DEAE-cotton-1-chloro-2,3-epithiopropane reactions have been compared with properties obtained with the corresponding reactions of cotton or DEAE-cotton with epichlorohydrin. Sulfhydryl groups have also been introduced into cotton and DEAE-cotton by the in situ formation of 1-chloro-2,3-epithiopropane in the fabric as a result of the reaction of the oxygen analog with a thiourea or a thiocyanate. These in situ reactions have been carried out in the absence and presence of solvent and external base catalysts. Attempts to vary the wet and conditioned (dry) recovery angles by oxidation of sulfhydryl groups and by reduction of disulfide groups met with little success. Smaller improvement in wrinkle recovery properties imparted by the thiirane than by epichlorohydrin at a given add-on has been explained on the basis of greater tendency of the thiirane to open abnormally in neutral or slightly acidic conditions and thus the greater tendency of the thiirane to form polymers rather than to crosslink cotton. Tendency of the oxirane to open normally and therefore act difunctionally results in finished fabrics with low chlorine contents, a high degree of crosslinking, and little polymer formation.
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  • 38
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    Journal of Applied Polymer Science 13 (1969), S. 659-668 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The dichroic behavior of PET film dyed at 70°C with Disperse Red 17 or Disperse Yellow 7 was investigated in the temperature range 20-200°C with a view to studying the changes in amorphous region of PET at high temperatures. The dichroic orientation factor D versus temperature plot is expressed by a straight line with negative slope; two breaks appear at 80 (Tg) and 120°C. So long as the amorphous structure does not change irreversibly, the values of D change reversibly with the temperature. Hence, if a change in D after heating is observed at room temperature, it is evidence that an irreversible change occurred in the amorphous structure during the heating. The break at 120°C is a new amorphous transition point of PET existing along with Tg, although the Tg can hardly be observed after the cold crystallization; some phenomena reported in the literature are proposed as evidence.
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  • 39
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    Journal of Applied Polymer Science 13 (1969), S. 637-657 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Experimental data support the hypothesis that the surface layer of the asymmetric Loeb-Sourirajan type porous cellulose acetate membranes has a heterogeneous microporous structure. A general method is proposed for improving the performance of the above membranes in reverse osmosis, by which product rates are increased without decreasing solute separation. The method consists in pumping pure water past the back side of the membrane under just enough pressure for a sufficiently prolonged period of time; after such pretreatment, the membrane is used in the reverse osmosis experiments in the normal manner with the surface layer facing the feed solution. Back-pressure treatment at 400 psig for 85 hr on preshrunk and normally pressure-treated membranes increases the product rate by over 20% without decreasing solute separation in reverse osmosis experiments at 600 psig with the use of 0.5 wt-% NaCl-H2O feed solutions; with a different sequence of back-pressure treatment, similar results have been obtained in reverse osmosis experiments at 1500 psig also. The compaction effect of a normal membrane and that of a back pressure treated membrane are the same during continuous reverse osmosis operation under 600 psig; the effects of back-pressure treatment on a normal membrane and a compacted membrane are also the same. The pure water permeability data obtained in cyclic experiments show that the smaller pores on the surface layer are opened more than the bigger ones during the back side operation. The probable structural changes taking place in the film during back-pressure treatment are discussed.
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  • 40
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The permeabilities of nitrogen, oxygen, and carbon dioxide through polyethylene-styrene graft copolymer films were measured by means of a gas permeability apparatus based on a modification of Barrer's high vacuum technique. Polyethylene-styrene grafts were prepared by mutual γ-ray irradiation of low-density polyethylene films in styrene-methanol solution. Densities and thicknesses of the graft copolymer films were determined. It was observed that the gas permeability constants decreased with increasing grafting to minimum values at 20-30% styrene grafting and increased again above 30% grafting. These results are explained in terms of a decrease in the free volume of the amorphous regions of the polyethylene by a “filling in” effect of the grafted polystyrene chains. Above 30% grafting, disruption of the crystallites may occur resulting in increased gas permeation. Activation energies for gas permeation through polyethylene-styrene graft copolymer films were calculated and found to decrease with increasing per cent styrene grafting. For nitrogen permeation, the activation energy decreased from 11.7 kcal/mole for unirradiated polyethylene to 9.5 kcal/mole for a 50.5% graft. Corresponding values for oxygen and carbon dioxide were 10.2-8.2 kcal/mole for a 48.7% graft and 8.4-6.5 kcal/mole for a 50.5% graft.
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  • 41
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    Journal of Applied Polymer Science 13 (1969), S. 765-774 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Literature data on the non-Newtonian flow of bulk polymer and of polymer solutions are correlated on the basis of a four-parameter equation, η = η∞ + (η0 - η∞)/[1 + (τD)m], η being the viscosity at shear rate D, and η0 and η∞ limiting values at D = 0 and D = ∞, respectively. The parameters η0, η∞, and τ all show dependence on molecular weight, and in general there is good correlation between τ and η0. There is evidence that τ is related to a molecular weight higher than the weight-average. The exponent m shows dependence on molecular weight distribution and approaches an upper limit of unity for a monodisperse linear polymer. For linear unblended polymers it may be expressed empirically by m = (M̄n/M̄w)1/5.
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  • 42
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    Journal of Applied Polymer Science 13 (1969), S. 871-881 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A method is proposed for predicting the density of a linear, amorphous polymer. The method is based on the additivity of group increments for the molar volume of a polymer unit. It is analogous to the published methods for predicting the molar volume of organic liquids. The method may be improved as additional experimental values on polymer densities become available.
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  • 43
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    Journal of Applied Polymer Science 13 (1969), S. 883-897 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Interfaces of evaporated viterous selenium and various organic polymeric resins of both the thermosetting and thermoplastic type have been studied by ultra-thin sectioning and transmission electron microscopy techniques. Epoxy, phenoxy, polyamide, butadien-styrene copolymer, vinyl-toluene-butadiene copolymer, resins as well as polyethylene are among those organic polymers studied. Interfaces prepared by vaccum evaporation of selenium onto the various substrates and under varying processing conditions were examined. Intermixing and interdiffusion of the inorganic and organic polymers in the interfacial region were observed in certain cases when selenium was evaporated onto incompletely curved epoxy or lower viscosity polymers. These occurrences were found to contribute significantly to the mechanical strength of the assembly. Electrical properties of certain specific systems have also been investigated.
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    Journal of Applied Polymer Science 13 (1969), S. 899-909 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Amorphous unoriented poly(ethylene terephthalate) was crystallized at 25°C by various organic liquids. The crystalliznity induced in the amorphous polymer was measured by differential scanning calorimetry and infrared spectroscopy. The ability of liquids to interact with and induced crystallinity in the amorphous polymer was classified on the basis of their solubility parameters. Measurements of the density of liquid-crystallized 0.8-mil films of poly(ethylene terephthalate) indicated the presence of extensive internal voids in the semicrystalline polymer matrix. Comparison of differential scanning calorimetric thermograms and infared spectra of heat-crystalized and liquid-crystallized polymer indicated significant differences in the polymer morphologies induced by the two crystallization processes.
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  • 45
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    Journal of Applied Polymer Science 13 (1969), S. 1159-1167 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polyacrylonitrile can be compression-molded with conventional equipment if the inherent polymer particle structure is modified. With normal polymerization methods, a circumferential orientation in the polymer particle is obtained. This structure can be changed under the effects of shear to yield highly ordered, laminar particles with planar orientations. In this form, PAN can be compression-molded into tough, clear, chemically resistant articles with retention of the laminar structure. The polymer has been characterized by its x-ray diffraction and infrared spectrum which, in combination, distinguish it from previously observed forms of PAN.
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  • 46
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    Journal of Applied Polymer Science 13 (1969), S. 1169-1173 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A rapid quantitative method has been developed for the determination of small amounts of water present in plasticizer-pigment and epoxy resin-pigment dispersion used in polyurethane formulations. Specific dispersions examined have been the systems diisooctyl phthalate-titanium dioxide and titanium dioxide-epichlorhydrin-Bisphenol A. The samples examined contained 50-70% titanium dioxide.
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  • 47
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    Journal of Applied Polymer Science 13 (1969), S. 1129-1157 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The objective of the work reported in this paper is to explain theoretically the observations made in an earlier study that castings of an epoxide resin reinforced by electrically conductive inserts, after having been postcured by inductive heating, had strength properties superior to those achieved by a purely thermal postcure. A search of the literature on adhesion suggested that among the theories presented, those dealing with electrical double layer formation, interdiffusion, and mixed polymer grafting on the insert-polymer interface deserve to be considered. Experiments were then planned in such a manner as to permit a choice between these theories. Epoxide resin specimens reinforced with various metals (pure silver, silver with an oxide layer, pure copper, copper with an oxide layer, aluminum, and stainless steel) were prepared. They were then either postcured in a heated oven, or postcured in an induction furnace for various lengths of time. Bonding strength was determined by a knife-edge method, and the exposed insert and resin surfaces were tested for electrical potential and surface wettability (angle-of-contact). Most strikingly, the curves obtained with increasing induction heating times for bonding strength, electrical potential, and wettability were all sinusoidal in shape, and their maxima and minima generally were found to coincide. For oven-postcured specimens, bonding between different metal inserts and an epoxide resin is explained by double electrical layer formation (insert positive, resin negative), with bonding strength increasing as the stability of the oxide forming the surface layer of the metal decreases. Metals with no oxide surface layer thus have the highest bonding strengths. For inductively postcured specimens, bonding is effected by both electrical double layer formation and mixed polymer grafting through the oxygen atoms in the metal surfaces, with the more stable metal oxide giving the stronger bonding in grafting. Where the insert does not carry an oxygen surface layer, bonding takes place through electrical forces only. Alternating build-up and internal discharge of electrical double layers are the direct cause of the sinusoidal shape of the electrical potential curves and the indirect cause of the comparable shape of the wettability curves. Their combination results in the observed periodicity of the breaking load curves.
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  • 48
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    Journal of Applied Polymer Science 13 (1969), S. 1191-1199 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Rate constants for intermolecular bond breaking (k1) and bond re-formation (k2) were calculated from contraction measurements. Variation of ΔH
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  • 49
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    Journal of Applied Polymer Science 13 (1969), S. 1175-1189 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Studies have been made of the γ-induced emulsion polymerization of styrene and comparisons made with chemically initiated emulsion polymerization. The polymerization proceeded smoothly to high conversions at 0 and 60°C, the reaction showing a high G (monomer) value. Complete conversions were obtained with total doses of less than 0.05 Mrad. In accordance with the behavior expected of systems having a constant rate of initiation, the molecular weight was found to decrease with decreasing temperature. The molecular weight and particle size distributions were narrower than those obtained in chemically initiated emulsion polymerizations at the same temperature. The radiation-induced emulsion polymerization of vinyl acetate proceeded smoothly at temperatures in the range 0-50°C to give polymers of much higher molecular weight than these obtained from chemically initiated polymerizations at the same temperature. Complete conversion was attained after a dose of 0.02 Mrad for latices approaching 50% solids. The elimination of ionic endgroups in the poly(vinyl acetate) radicals tends to drive the polymerization from the aqueous phase, resulting in faster rates and higher molecular weights than are obtained from chemically initiated systems. Rates of polymerization were found to be independent of temperature and the molecular weight of the polymer to be independent of dose rate. Latices of poly(vinyl acetate) of high solids content were evaluated for latex and film properties and found to have improvements over commercially available samples in both areas, especially in clarity of film and scrub resistance. A number of acrylate and maleate esters were copolymerized with vinyl acetate in a radiation-initiated emulsion system. High molecular weight copolymers were produced after low dose.
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  • 50
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    Journal of Applied Polymer Science 13 (1969), S. 1201-1214 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The thiol-disulfide exchange reaction is shown to be applicable to cleavage of disulfide crosslinks in accelerated sulfur vulcanizates of natural rubber. The reaction, in conjunction with the previously reported selective cleavage of polysulfide crosslinks, is used to determine the distribution of crosslink types for several accelerated sulfur vulcanization systems as a function of cure time. Discrepancies between the results and published results obtained using the reagent sodium di-n-butyl phosphite for disulfide crosslink cleavage are discussed.
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    Journal of Applied Polymer Science 13 (1969), S. 1309-1318 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Compressive stress softening (Mullins effect) in black-filled vulcanizates of the blended system natural : nitrile : brominated butyl rubber has been investigated. The results are expressed in terms of parameters derived from successive stress-strain cycles. The ratio of the work done on loading in the first and second cycles is called the load work ration, Rw. A similar quantity, Rh, is defined for the loss or hysteresis work. Both load and loss work ratios show a compositional dependence similar to other properties of blends. The variation of Rw and Rh with composition agrees with the recent thesis of Mullins, Harwood, Payne and others that the Mullins effect is a property of the elastomer. Sudden variation of Rh with elongation has been interpreted in light of recent results of R. W. Smith as indicative of vacuole formation.
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  • 52
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    Journal of Applied Polymer Science 13 (1969), S. 1327-1327 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 53
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    Journal of Applied Polymer Science 13 (1969), S. 1326-1326 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 54
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    Journal of Applied Polymer Science 13 (1969), S. 1329-1335 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effects of a number of sulfur compounds on the melt stability of polypropylene milled at 165°C have been studied. Dilaurylthiodipropionate (DLTP), Mercaptobenzimidazole (MBI), and Mercaptobenzthiazole (MBT) are all antioxidiants in a polymer lightly stabilized with a phenolic antioxidant although the last two are initially pro-oxidants. 2,2′-Dibenzoylaminodiphenyldisulfide (22BDD) is a pro-oxidant under the Conditions studied.In the absence of a phenolic antioxidant the effectiveness of DLTP is reduced in the early stages of oxidation, with increasing concentration although its over all antioxidant activity increases. The results are consistent with the view that both radical and non-radical processes occur concomitantly.
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  • 55
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    Journal of Applied Polymer Science 13 (1969), S. 1337-1351 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The preparation of the acetaldehyde polymers (PACH) having a poly(vinyl alcohol)-type structure and the thermal degradation of PACH have been reported previously. This paper will describe detailed aspects of several reactions of PACH. Copolymerization of PACH with toluene diisocyanate (TDI) was performed both thermally and catalytically. When piperidine was used as catalyst, the rate of reaction between PACH and TDI was found to depend on the concentration of both the active hydrogen of PACH and the isocynante group TDI. Acid and alkali treatment of PACH were carried out. On treatment with sulfuric acid, white polymers with good spinnability were obtained. The copolymerization of acetaldehyde with n-butylaldehyde were performed in the presence of sodium amalgam as catalyst. The reaction products were colorless, viscous liquids and assumed from the infrared and NMR spectra, elemental analyses, molecular weight and solubility tests to be aldol condensation-type copolymers.
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  • 56
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    Journal of Applied Polymer Science 13 (1969), S. 1373-1380 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Depending on heating rate, differences as large as 15°C in polymer transition temperatures may be observed in DCS measurements. A heat transfer analysis of the method shows that this rate dependence is a result of a lag in the heat path to the test sample and lag in heat transfer within the sample. Experiments confirmed the analysis. Methods for obtaining the correct values of transition temperatures are given.
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  • 57
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    Journal of Applied Polymer Science 13 (1969), S. 1353-1371 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A novel technique for the control of continuous synthesis of addition polymers with precisely controlled average molecular weight and minimum polydispersity has been developed. A control system adjusts the concentration of chain-transfer agent in the reactor feed to compensate for all other upsets, in the reactor inputs: initiator and monomer concentrations, temperature and feed rate. The technique has been evaluated quantitatively on a digital computer using a kinetic model of homogeneous, free-radical solution polymerization. In computational tests, the modeled control system generally held the instantaneous number-average chain length within 1%, and quickly returned it to the desired value in response to a wide variety of upsets. By generalizing the Schulz distributions to include termination by disproportionation, combination and chain-transfer, it is shown that changes in the molecular-weight distribution resulting from the action of the control system are minor.
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  • 58
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    Journal of Applied Polymer Science 13 (1969), S. 1381-1419 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A new-method of interpreting GPC chromatograms which accounts for skewing and symmetrical axial dispersion has been developed. General relationships for a symmetrical axial dispersion correction and for a skewing correction are derived.The method has been verified experimentally for unimodal chromatograms and linear calibration curves over a wide range of GPC operating conditions, polymer molecular weights and polydispersities. Measurements of h and skewing factors were obtained by a once-through technique. The need for performing reverse flow experiments has been eliminated. Artificial oscillations in the corrected chromatogram due to step size (Method of Pierce-Armonas), and to number of terms in a polynomial expansion (Method of Tung and Method of Smith) are eliminated.The method has yet to be evaluated for nonlinear calibration curves and multi-modal distributions. However, suggestions for its application in these circumstances are presented.
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  • 59
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    Journal of Applied Polymer Science 13 (1969), S. 1447-1458 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Fractional crystallization was used to separate a commercial, predominatly isotactice, unstabilized polypropylene into fractions of relatively low and relatively high atacticity, but of similar molecular weight. IR spectroscopy was used to follow the photo-oxidations of films formed from these fractions during irradiation in air with light of wavelengths greater than 3000 À. The major oxidation products included hydrogenbond hydroperoxides and carbonyl compounds. Films of constant tacticity, but varying morphology were prepared by quenching from the melt. No distinct correlation was found between sample photostability and morphology, as indicated by film density. Films of low atactic content were found to undergo faster photo-oxidation than films of high atactic content, irradiated under identical conditions. This effect is believed to be due to the occurrence of a stereo-dependent step (or steps) in the oxidative chain, and not due to differences in sample morphology. The possible nature of the stereo-dependent steps is considered in terms of well-established oxidative chain processes. The effects of polypropylene polymorphism on oxygen permeability are briefly considered.
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  • 60
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The concentration dependence of the selectivity in fractionation experiments with polyethylene terephthalate has been investigated. The values obtained with 0.25% solutions showed close approximation to the SCHULZ-FLORY distribution. Lowering the concentration resulted in an essential increase of efficiency. Almost quantitative fractionation was achieved with various model blends of polyethylene terephthalate samples having different molecular weight.
    Notes: Es wurde die Konzentrationsabhängigkeit der Selektivität der Fraktionierung von Polyäthylenterephthalat untersucht. Die Fraktionierung aus 0,25-proz. Ausgangslösung ergab nahezu Kongruenz zwischen Experimentalkurve und SCHULZFLORY-Kurve. Durch die Konzentrationserniedrigung konnte die Rationalität wesentlich verbessert werden. Verschiedene Modellmischungen von Polyäthylenterephthalaten unterschiedlicher Molmasse konnten nahezu quantitativ getrennt werden.
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  • 61
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The reduction of atactic poly(vinyl chloride), PVC, with lithium aluminum hydride in tetrahydrofuran is a random process; in polymers containing long syndiotactic chain segments the latter withstand reduction longest. The reduced polymers contain CH3-groups, the amount of which can be determined by i. r. spectroscopic compensation against polymethylene. Furthermore, the i. r. spectra indicate the existence of trans-vinylene groups; depending upon the conditions of polymerization, both these groups are found to be present in amounts of 5 to 15 per 1000 carbon atoms.The experimental results of thermal degradation of PVC samples reduced to different extents are in agreement with the assumption that dehydrochlorination is primarily caused by carbon double bonds within the PVC chains.
    Notes: Die Reduktion von ataktischem Polyvinylchlorid (PVC) mit Lithiumaluminiumhydrid in Tetrahydrofuran erfolgt statistisch; bei Polymeren mit längeren syndiotaktischen Sequenzen widerstehen die syndiotaktischen Kettenabschnitte der Reduktion am längsten. Die reduzierten Polymeren enthalten CH3-Gruppen, deren Anteil durch IR-spektroskopische Kompensation gegen Polymethylen bestimmt werden kann. Außerdem zeigen die IR-Spektren trans-Vinylengruppen an; je nach den Polymerisationsbedingungen findet man von beiden Gruppierungen zwischen 5 und 15 je 1000 Kohlenstoffatome.Die Ergebnisse beim thermischen Abbau von verschieden weit reduziertem PVC stehen mit der Annahme in Einklang, daß die für die Dehydrochlorierung wesentliehsten Stellen im PVC-Molekel kettenständige Kohlenstoff-Doppelbindungen sind.
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  • 62
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    Angewandte Makromolekulare Chemie 7 (1969), S. 134-146 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Copolymers of ethylene and vinyl acetate of different composition were investigated by differential thermal and x-ray analysis in the temperature range of -80 to 140°C. Compounds with more than 60 weight-% of vinyl acetate are amorphous. In the partially crystalline copolymers with lower contents of vinyl acetate the glass transition temperature is independent of composition and lies below that in amorphous copolymers. The melting points of the partially crystalline compounds increase with ethylene contents and can be described with the aid of a modified FLORY equation. The increase of the degree of crystallinity with ethylene content is demonstrated. The influence of thermal pre-treatment on the melting behaviour is discussed.
    Notes: Äthylen-Vinylacetat-Copolymere (ÄVAc) unterschiedlicher Zusammensetzung wurden im Temperaturbereich von -80 bis 140°C durch Differential-Thermoanalyse und röntgenographisch untersucht. Substanzen mit mehr als 60 Gew.-% VAc sind amorph. Bei den teilkristallinen Copolymeren mit geringen VAc-Anteilen ist die Glastemperatur unabhängig von der Zusammensetzung und liegt niedriger als bei amorphen Substanzen. Die Schmelzpunkte der teilkristallinen Stoffe nehmen mit dem Äthylengehalt zu und können mit einer modifizierten FLORYschen Gleichung erfaßt werden. Die Zunahme des Kristallinitätsgrades mit dem Äthylengehlat wird dargestellt. Der Einfluß der thermischen Vorbehandlung auf den Schmelzverlauf wird diskutiert.
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  • 63
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    Angewandte Makromolekulare Chemie 7 (1969), S. 147-180 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: With the assumption of additivity of the specific refractivities of monomer units in a polymer and of solvent and solute theoretical expressions for the specific refractive index increments of homo-, co-, ter- and higher multipolymers are derived. They give the specific refractive index increments as functions of the refractive index of solvents, of the specific refractivity of the polymers, of the compositions of multipolymers, of the wave length and of the partial specific volumes of the polymers in infinitely dilute solutions.The theory is confirmed by experimental results obtained with solutions of methacrylate/styrene-, methacrylate/benzylacrylate- and ethylacrylate/methylmethacrylate-copolymers and of the corresponding homopolymers. It is shown that the formulas derived can be used for accurate determinations of the compositions of co- and other multipolymers from measurements of their specific refractive index increments.
    Notes: Unter der Annahme der Additivität der spezifischen Refraktionen der Monomereinheiten in einer Polymermolekel und von Lösungsmittel und Gelöstem werden theoretische Ausdrücke für das spezifische Brechungsinkrement für Homo-, Co-, Ter- und höhere Multipolymere abgeleitet. Sie geben das spezifische Brechungs inkrement als Funktion des Brechungsindexes des Lösungsmittels, der spezifischen Refraktion des Polymeren, der Zusammensetzung des Multipolymeren, der Lichtwellenlänge und des partiellen spezifischen Volumens des Polymeren in unendlich verdünter Lösung an.Die Theorie wird durch experimentelle Ergebnisse an hochverdünnten Lösungen von Methylacrylat/Styrol-, Methylacrylat/Benzylacrylat- und äthylacrylat/Methylmethacrylat-Copolymeren und den entsprechenden Homopolymeren bestätigt. Es wird gezeigt, daß die abgeleiteten Gleichungen ür genaue Bestimmungen der Zusammensetzung von Co- und höheren Multipolymeren aus Messungen ihrer spezifischen Brechungsinkremente verwandt werden können.
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  • 64
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    Angewandte Makromolekulare Chemie 7 (1969), S. 198-200 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 65
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    Angewandte Makromolekulare Chemie 7 (1969), S. 194-197 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The separation of NO3-, NO2-, N2O22- and N2O32- has been studied by elutionchromatography on the strong basic anion-exchange resin Wofatit SBW. The solutions proper for elution-chromatography have been chosen on basis of measured anion-affinities. Quantitative separations were obtained with the mixtures of N2O22-, NO2- and NO3- as well as of N2O32-, NO2- and NO3- with a solution of Na2SO4. Both separation methods can be applied to prepare solutions of hyponitrite and nitrohydroxylaminate which are free of nitrate and nitrite.
    Notes: Mit Hilfe der Elutionschromatographie wurden Trennversuche von Nitrat, Nitrit, Hyponitrit und Nitrohydroxylaminat am stark basischen Anionenaustauscher Wofatit SBW durchgeführt. Die Auswahl der Elutionsmittel erfolgte mit Hilfe der gemessenen Affnitätsreihen. Eine quantitative Trennung wurde bei den Gemischen Hyponitrit-Nitrit-Nitrat und Nitrohydroxylaminat-Nitrit-Nitrat mit Natrium-sulfatlösung erzielt. Beide Trennungen können zur Herstellung von Hyponitrit- und Nitrohydroxylaminat-Lösungen, die frei von Nitrit und Nitrat sind, verwendet werden.
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  • 66
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    Angewandte Makromolekulare Chemie 7 (1969), S. 201-202 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 67
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    Angewandte Makromolekulare Chemie 7 (1969), S. 181-193 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The thermal conductivity of the following homopolymers was measured or extrapolated from measurements on copolymers in the temperature range from - 180 to + 150°C: Polymethylmethacrylate, polyethylmethacrylate, poly-n-butyl-methacrylate, polymethylacrylate, polyethylacrylate, poly-n-butylacrylate, polystyrene, polyacrylonitrile.In all cases a flat maximum at the glass transition temperature was found, if the thermal conductivity was plotted over the temperature. The thermal conductivity of polyacrylonitrile, extrapolated from measurements on copolymers of methylmethacrylate and acrylonitrile, is greater than those of the other polymers as a consequence of hydrogene bonds.If the thermal conductivity of polymethacrylates and polyacrylates is plotted over the temperature difference T  -  TE, a decrease of the thermal conductivity with increasing length of the side chain will be found. Also increasing substitution of H-atoms in the polyethylene chain by Cl-atoms leads to a decrease in thermal conductivity at room temperature.By measurements on copolymers of methylmethacrylate and styrene, methylmethacrylate and methylacrylate, methylmethacrylate and acrylonitrile the thermal conductivity, plotted over the molar concentration, changes monotoneously between the values of the homopolymers of the two components. Only with copolymers of methylmethacrylate and styrene this change is linear.It may be generally concluded, that the thermal conductivity of a linear polymer, plotted over T  -  TE, will decrease, if units of the chain will be substituted by units of a greater mass (e. g. with longer side-chains etc.) without change of the intermolecular forces.
    Notes: Im Temperaturbereich von - 180 bis + 150°C wurde die Wärmeleitfähigkeit folgender Homopolymerer gemessen oder durch Extrapolation aus Messungen an Copolymeren ermittelt: Polymethylmethacrylat, Polyäthylmethacrylat, Poly-n-butylmethacrylat, Polymethylacrylat, Polyäthylacrylat, Poly-n-butylacrylat, Polystyrol, Polyacrylnitril.In allen Fällen findet man bei der Einfriertemperatur TE ein flaches Maximum der über der Temperatur T aufgetragenen Wärmeleitfähigkeit. Die durch Extrapolation aus der Wärmeleitfähigkeit von Methylmethacrylat-Acrylnitril-Copolymerren ermittelte Wärmeleitfähigkeit des Polyacrylnitrils liegt als Folge von Wasserstoffbrücken wesentlich höher als die der übrigen Polymeren.Trägt man die Wärmeleitfähigkeit der Polymethacrylate und Polyacrylate über der Temperaturdifferenz T  -  TE auf, so findet man durchweg einen Abfall der Wärmeleitfähigkeit mit zunehmender Seitenkettenlänge. Auch der zunehmende Einbau von Chloratomen an Stelle von Wasserstoff in der Polyäthylenkette führt zu einem Absinken der bei Zimmertemperatur gemessenen Wärmeleitfähigkeit.Bei Messungen an Methylmethacrylat-Styrol-, Methylmethacrylat-Methylacrylat und Methylmethacrylat-Acrylnitril-Copolymeren wurde gefunden, daß die über den molaren Anteilen der beiden Komponenten aufgetragene Wärmeleitfähigkeit monoton zwischen den Wärmeleitfähigkeiten der beiden Homopolymeren verläft. Nur bei Methylmethacrylat-Styrol-Copolymeren ist dieser Verlauf linear.Man kann allgemein folgern, daß die über T  -  TE aufgetragene Wärmeleitfähigkeit eines Linearpolymeren sinkt, wenn man Kettenbausteine durch solche mit größere Masse (z. B. mit längeren Seitengruppen o. ä.) ersetzt, ohne dabei die zwischenmolekularen Kräfte wesentlich zu verändern.
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  • 68
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The redoxreaction H2O2-rongalite was investigated in the presence of catalytic amounts of iron. Radicals responsible for initiation of polymerization are produced only when at least traces of heavy metals are available. For the above reaction iron is the most effective one. Reaction rates for the consumption of H2O2 and rongalite with respect to complexbound and free iron, without and with the addition of acrylonitrile, are provided. A scheme of reactions is being presented which helps to unterstand the reaction rates, reaction products aldehyde bisulphite and sulphate, as well as the mode and degree of polymerization.
    Notes: Die Redoxreaktion H2O2/Rongalit läuft nur dann über Radikale ab, die die Polymerisation starten, wenn Schwermetalle zumindest in Spuren vorhanden sind. Am wirksamsten ist Eisen. Die Zeitgestze für den Umsatz von H2O2 und Rongalit in Abhängigkeit von komplexgebundenem und freiem Eisen ohne und mit Zusatz von Acrylnitril werden ermittelt. Ein Reaktionsschema wird angegeben, das die Zeitgesetze, die Umsetzungsprodukte Aldehydbisulfit und Sulfat, sowie Ablauf und Grad der Polymerisation verstehen läßt.
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  • 69
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    Angewandte Makromolekulare Chemie 8 (1969), S. 61-72 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The polymerization-depolymerization equilibrium of α-methyl styrene can be shifted by high pressures towards the polymerization step. The equilibrium concentrations of the α-methyl styrene monomer were calculated at different pressures and temperatures from already known data for ΔH and ΔS°. The equilibrium concentrations are reported for temperatures from 40 to 100°C and for pressures from 1-5000 kg/cm2. The data show for example, that at 70°C and atmospheric pressure the polymerization of α-methyl styrene is not possible because the required equilibrium concentration (9,6 mole/liter) is greater than the highest possible monomer concentration (7,3 mole/liter). However, at the same temperature and a pressure of 3000 kg/cm2, the polymerization should take place up to the monomer concentration of 1,1 mole/liter. Experiments demonstrate, that under these conditions polymeric α-methyl styrene of high molecular weight is obtained by free radical polymerization. Analogous experiments were carried out with anionic initiation of the polymerization by naphthalene-sodium.
    Notes: Das Polymerisations-Depolymerisations-Gleichgewicht von α-Methylstyrol läßt sich durch die Anwendung hoher Drucke in Richtung der Polymerisation verschieben. Auf Grund bekannter Daten für die Reaktionsenthalpie ΔH und die Reaktionsentropie ΔS° läßt sich die Abhängigkeit der Gleichgewichts-Monomeren-Konzentration des α-Methylstryrols vom Druck für verschiedene Temperaturen berechnen. Die Gleichgewichtskonzentrationen zwischen 40 und 100°C und zwischen Normaldruck und 5000 atü werden angegeben. Während z. B. bei 70°C und Normaldruck eine Polymerisation des α-Methylstyrols nicht mehr möglich ist, weil die Gleichgewichtsmonomerenkonzentration ([M]g1 = 9,6 mol/1) höher liegt als die höchstmögliche Monomerenkonzentration (7,3 mol/1), ist bei 70°C und 3000 atü eine Polymerisation bis zu einer Monomerenkozentration von [M]gl = 1,1 mol/l möglich. Experimente zeigen, daß man unter diesen Bedingungen durch Radikalpolymerisation hochmolekulares Poly-α-methylstyrol erhält. Analoge Versuche wurden auch mit anionischer Initiierung der Polymerisation durch Naphthalin-Natrium ausgeführt.
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  • 70
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Mechanical properties and melt flow behaviour have been measured on thermal polystyrenes in order to study the effect of different molecular weight and different molecular weight distribution. The mechanical properties (impact strength, tensile strength and flexural strength) were found to depend upon a critical molecular weight Mw = 1.5 × 105, where the polystyrenes reached ultimate strength. An influence of molecular weight distribution only can be observed when the average molecular weight is near the critical molecular weight limit. The broader the distribution, the poorer are mechanical properties. Injection molded specimens with different molecular weight distribution but equal average molecular weight showed different molecular orientation and different anisotropic mechanical properties. On the basis of equal orientation the narrow distributed specimens showed higher mechanical strength in direction of orientation. The broader the distribution, the higher the elastic properties of melt. An optimum of physical properties and ease of fabrication will be obtained with narrow molecular weight distributed polystyrenes with an average molecular weight slightly above the critical molecular weight limit.
    Notes: Die vom molekularen Aufbau thermisch hergestellter Polystyrole abhängigen Eigenschaftskennfunktionen lassen erkennen, daß das durch die angegebenen Prüf- und Verarbeitungsvrfahren definierte Eigenschaftsverhalten bei einem mittleren Molgewicht von etwa 150000 und hoher Polymereinheitlichkeit ein Optimum erreicht. Ausreichend hohe mechanische Festigkeit und geringe Orientierungsneigung stehen hier in einem ausgewogenen Verhältnis zur thermoplastischen Verarbeitbarkeit.
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  • 71
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    Angewandte Makromolekulare Chemie 8 (1969), S. 87-98 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: K.-H. ILLERS has recently shown that the mechanical properties of PVC foils can be considerably influenced by annealing the material at a temperature some-what below the glass transition. This effect ist due to the fact that, in general, at the glass temperature a relative high hole concentration is frozen in which can be diminished by annealing the polymer glass. The variation of the hole concentration during the annealing process was measured by ILLERS with the aid of a new calorimetric method.The purpose of the investigation presented here was to continue ILLERS' measurements and in particular to complete them with regard to the mechanical properties. For this reason tensile tests in the speed range between 10-3 and 1 cm/s and biaxial impact penetration tests were carried out, using specimens cut from a sheet of PVC without plasticizer and annealed for differently long times.It was found that the position of the brittle-tough transition between times until fracture from 10 to 1000 s, caused by a certain molecular relaxation mechanism, is not influenced perceptibly by the hole concentration.If the time until fracture ist shorter than the transition time, or with other words, if the strain rate is sufficiently high, the extensibility of the specimens does not depend very much on the hole concentration. On the other hand the fracture stress, i. e. the strength of the sheet, distinctly increases in this region if the hole concentration decreases.Above the transition, i. e. at long times or low strain rates, the fracture stress is nearly independent of the hole concentration whereas the extensibility strongly decreases with decreasing hole concentration.This means that the sheet material, when being annealed, is improved (reinforced) in the brittle region and deteriorated (brittled) in the tough region.The above-mentioned experimental results were interpreted qualitatively. Furthermore their technical consequences were pointed out with regard to the investigated material as well as to other thermoplastic materials.
    Notes: Wie K.-H. ILLERS kürzlich gezeigt hat, werden die mechanischen Eigenschaften einer PVC-Folie durch Temperung unterhalb der Glastemperature erheblich beeinflußt. Dieser Effekt beruht darauf, daß die hohe Leerstellenkonzentration der Schmelze, die bei der Glastemperatur eingefroren wird, durch Tempern des glasig erstarrten Materials erniedrigt werden kann. Die Änderung der Leerstellenkonzentration wurde dabei nach einem von ILLERS entwickelten Verfahren kalorimetrisch bestimmt.In der vorliegenden Arbeit werden diese Untersuchungen fortgeführt und besonders in bezug auf die mechanischen Eigenschaften ergäzt. Dazu wurden Zugversuche im Geschwindigkeitsberich zwischen 10-3 und 1 cm/s und biaxiale Durchstoßversuche an verschieden lange getemperten Proben aus einer weich-macherfreien PVC-Folie durchgeführt.Es zeigte sich, daß die Lage des durch molekulare Relaxationsmechanismen verursachten spröde-zäh-Überganges bei Bruchzeiten zwischen 10 und 1000 s nicht merklich durch die Leerstellenkonzentration beeinflußt wird.Bei Bruchzeiten unterhalb dieses Überganges, d. h. bei hohen Beanspruchungsgeschwindigkeiten, ändert sich die Dehnbarkeit der Folie nur weing mit der Leerstellenkonzentration. Die Bruchspannung, also die Festigkeit der Folie, steigt dagegen in diesem Bereich deutlich mit abnehmender Leerstellenkonzentration an.Im Gegensatz dazu bleibt die Bruchspannung oberhalb dieses Überganges, d. h. bei niedrigen Beanspruchungsgeschwindigkeiten, nahezu unverändert, während die Bruchdehnung erheblich geringer wird, wenn die Leerstellenkonzentration abnimmt.Die Folie wird also durch Tempern im spröden (Kurzzeit-)Bereich verbessert (verstärkt), im zähen (Langzeit-) Bereich dagegen verschlechtert (versprödet).Diese experimentellen Ergebnisse werden qualitativ gedeutet. Außerdem werden ihre technischen Konsequenzen auch in bezung auf andere thermoplastische Materialien angegeben.
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  • 72
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    Angewandte Makromolekulare Chemie 8 (1969), S. 133-142 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: To prepare very narrow distributed polystyrene samples, a two step procedure of polymerization is proposed, which includes a change of solvent. The first solvent, used for the initiation step, has to be characterized by a high value of vst/vp, while the second one, used for the propagation step, should guarantee a good control of temperature during the polymerization reaction. In our case, tetrahydrofuran and benzene were chosen and n-Li-butyl has been used for the initiation.The polymerization products have been characterized by MW-averages and MW-distribution. Finally a preparative fractionation has been carried out to separate the low and high MW tail of the distribution thus leading to samples whose values for M̄w/M̄n can be shown to be about 1,01.
    Notes: Zur Herstellung hocheinheitlicher Polystyrole wird ein Verfahren angegeben, das auf einer zweistufigen Lösungspolymerisation mit Austausch des Lösungsmittel beruht. Die Lösungsmittel müssen so gewählt werden, daß bei der Vorpolymerisation die Startgeschwindigkeit wesentlich größer ist als die Wachstumsgeschwindigkeit, für die weitere Polymerisation jedoch die Reaktion thermisch gut kontrolliert werden kann; in dem beschriebenen Verfahren wurden Tetrahydrofuran und Benzol verwenigte Polymere entstehen sollten.Die Polymerisationsprodukte wurden durch ihr mittleres Molekulargewicht und ihre Molekulargewichts-Verteilungskurve charakterisiert. Nach einer Spitzenfraktionierung zur Abtrennung der hoch- und niedermolekularen Ausläufer liegt die erreichte Einheitlichkeit bei einem Wert M̄w/M̄n ≈ 1,01.
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  • 73
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    Angewandte Makromolekulare Chemie 8 (1969), S. 143-152 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß von Chlorwasserstoff auf die Zersetzung von Polyvinylchlorid (PVC) wurde untersucht. Aufgrund der Ergebnisse wurde eine Hypothese über den Mechanismus der Autokatalyse entwickelt. Das bei Dissoziation des Chlorwasserstoffs entstehende Chlorid-Ion wirkt im betreffenden Reaktionsmedium wie eine starke Base und bildet somit das aktive Element. Die Beschleunigung der Zersetzung des PVC läßt sich daher vermeiden, wenn man entweder die freie Säure mit Hilfe eines Säure-Acceptors aus dem System entfernt oder einen Komplexbildner zusetzt, wie z. B. Ferrichlorid.
    Notes: The effect of hydrogen chloride on the decomposition of poly(vinyl chloride) (PVC) has been studied and a mechanism for the autocatalysis is given. The chloride ion formed upon dissociation of the hydrogen chloride is a strong base in the medium of the reaction, and hence constitutes the active species. Therefore, the acceleration of the decomposition of PVC can be prevented by either removing the free acid from the system with the aid of an acid acceptor or adding a complexing agent such as ferric chloride.
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  • 74
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    Angewandte Makromolekulare Chemie 8 (1969), S. 153-166 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The reactivity of vinyl monomers V-XIV and cellulose (beach sulfit pulp, filter paper) shows an optimum depending on the use of peroxide (I-IV) or ionic type catalysts (TiCl4, Fe3+, Ce4+) and their concentrations. The swelling degree in various systems of inclusion agents (H2O/NaOH, LiOH, KOH/CH3OH/CH3COCH3/C6H6) which must be properly chosen with respect to the used monomer, or in the monomers, in their mixtures and mixtures of monomers with solvents is of dicisive importance for a positive course of the reaction, for its yield and velocity.The obtained grafted products have modified properties in comparison with non grafted cellulose and, according to the type of the grafting monomers and the reaction conditions, they form a wide series from brash, brittle, hard, water repellent products to adsorbent, weldable and strong cracking resistent materials.
    Notes: Die Reaktionsbereitschaft der Vinylmonomeren V-XIV mit Cellulose (Buchensulfitzellstoff, Filterpapier) zeigt ein Optimum in Abhängigkeit von peroxidischen (I-IV) oder ionischen Katalystoren (TiCl4, Fe3+, Ce4+) und deren Konzentrationen. Von entscheidender Bedeutung für den positiven Verlauf der Pfropfreaktion sowie deren Ausbeute und Geschwindigkeit ist der Quellungsgrad in verschiedenen Inclusionssystemen (H2O/NaOH, LiOH, KOH/CH3OH/CH3COCH3/C6H6), die spezifisch auf das Monomere abgestimmt sein müssen, oder in den Monomeren, Monomergemischen oder Monomer-Lösungsmittel-Gemischen.Die erhaltenen Pfropfprodukte zeigen gegenüber der ungepfropften Cellulose modifizierte Eigenschaften, die je nach Art des Pfropfmonomeren und der Reaktionsbedingugen variierbar sind von brüchig, spröde, hat, hydrophob bis stark saugfähig, schweißbar und reißfest.
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The influence of coupling agents in E-glass cellulose acetate composites was investigated by stereoscan photographs, that have been taken from the surfaces of broken test bars, and correlated with mechanical properties of the systems. Furthermore some stereoscan photographs show the different types of adhesion in glass reinforced nylon-6, poly(ethyleneterephthalate) and polyester resin.
    Notes: Der Einfluß der Schlichte von E-Glasfasern auf die Haftung bei Celluloseacetat wurde mit Hilfe von Stereoscan-Aufnahmen der Bruchflächen gespritzter Normkleinstäbe sichtbar gemacht und mit den mechanischen Eigenschaften der Systeme korreliert. Weiterhin zeigen Bruchflächenaufnahmen von glasfaserverstärktem 6-Polyamid, Polyäthylenglykolterephthalat und Polyester verschiedene Formen der Benetzung der geschlichteten Glasfaser durch das Polymere.
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  • 76
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wird gezeigt, daß die Eigenschaften dichter, aus Celluloseacetat (Eastman Chemical Products E-398-3) hergestellter Membranen von der Verdampfungsgeschwindigkeit und von der Reinheit des Lösungsmittels (Aceton) abhängen.Das Kochen dieser Membranen in 80°C warmem Wasser vermindert ihren Wassergehalt und ihre Permeabilität für Wasser und für NaCl. Ihre Widerstandsfahigkeit gegen Hydrolyse wird dadurch erhöht. Bei Membranen, welche durch langsame Verdampfung des Lösungsmittels hergestellt wurden, ist die Verminderung des Wassergehaltes und der Permeabilitäten am schwächsten.Der mittels direkter Osmose gemessene Permeationskoeffizient für NaCl erreicht einen gemeinsamen Wert für Membranen, welche unter schneller Verdampfung des Lösungsmittels hergestellt und danach in Wasser gekocht wurden, und für Membranen welche unter langsamer Verdampfung des Lösungsmittels gewonnen wurden. Dieser Wert liegt zwischen 3 · 10-11 und 4 · 10-11 cm2/sek. Bei der Gegenosmose unter 100 bar (∼ 99 atm.) Druck ist dieser Wert mit 3 bis 4 zu multiplizieren.Um diese Ergebnisse zu erklären, nehmen wir an, daß zwei verschiedene Transportmechanismen den Durchgang von Wasser und NaCl durch die Membranen bestimmen, nämlich die FICKsche Diffusion durch das Gel und die POISEUILLE-Strömung durch die Poren.
    Notes: On montre que les propriétés des membranes denses en acetate de cellulose (Eastman Chemical Products E-398-3) dépendent de la vitesse d'évaporation et de la pureté du solvant (acétone).Le traitement thermique de ces membranes dans l'eau portée à 80°C diminue leur teneur en eau ainsi que leurs perméabilités à l'eau et au ClNa et augmente leur résistance à l'hydrolyse dans les expériences d'osmose inverse. La diminution de la teneur en eau et des perméabilités est la plus faible pour les membranes préparées dans des conditions d'évaporation lente.Le coefficient de perméabilité au ClNa mesuré en osmose directe tend vers une valeur commune aux membranes préparées dans des conditions d'évaporation rapide et traités thermiquement et aux membranes préparées dans des conditions d'évaporation lente. Cette valeur est comprise entre 3 · 1011 et 4 · 10-11 cm2/sec. En osmose inverse, sous une pression de 100 bars, cette valeur est multipliée par un facteur compris entre 3 et 4.Nous interprétons ces résultats en supposant que l'eau et le ClNa traversent la membrane selon un double mécanisme: diffusion dans le gel et écoulement visqueux au travers de pores.
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  • 77
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    Angewandte Makromolekulare Chemie 7 (1969), S. 79-84 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Some new araliphatic polyesteramides were prepared from oligomers. The starting materials were an aromatic oligoester of the ethylene glycol terephthalattype in the form of a bishydroxy acid and aliphatic oligoamides of the Nylon-type in the form of a bis-ω-amino acid. The resulting polymers are tuff and have relatively low melting points. They show a weak fibre-forming ability. The values of the inherent viscosity are not too high. These properties can be explained through the fact that the polycondensation was not complete as was seen from the thin-layer chromatogramms.
    Notes: Eine Anzahl neuer Polyesteramide wurde aus araliphatischen Bausteinen auf der Basis von aromatischen Oligoestern vom Äthylenglykolterephthalat-Typ und aliphatischen Oligoamiden vom Nylon-Typ aufgebaut. Es bildeten sich spröde, schlecht fadenziehende Harze. Die Produkte haben ziemlich niedrige Schmelzpunkte und inhärente Viskositäten. Wie man aus Dünnschicht-Chromatogrammen ersieht, ist die Polykondensation vermutlich nicht vollständig verlaufen.
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  • 78
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    Angewandte Makromolekulare Chemie 7 (1969), S. 57-66 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Supercontraction and DTA-measurements of Corriedale-wool in solutions of anion- and kation-active detergents were carried out at various pH. The temperature Ts and the amount of the fibre shrinkage were lowered at pH 7 by the detergents especially in dodecylamine-hydrochlorid (Dah) solutions. The DTA peak in Dah-solutions at pH 7 is broadened to high extent and the heat of transition is decreased drastically.At low pH-values - e. g. 2,5 - the DTA peak in Dah-solutions is unchanged in respective to that in pure water. In contrast the peak in acid solutions of sodium dodecylsulphate (Nds) has disappeared completely because the transition process has lost its cooparative character. This behaviour can be explained by the adsorption of the anion-active detergent caused by the protonated basic groups and the splitting of salt-bridges in the acid medium. In this way the hydrophobic interactions stabilizing the fibre structure are weakened and therefore the order-disorder transition begins already at low temperatures and takes place in a wide range.
    Notes: Es wurde die Superkontraktion sowie das differentialkalorimetrische Verhalten von Corriedale-Wolle in anion- und kationaktiven Tensidlösungen untersucht. Dabei ergab sich, daß bei pH 7 die Temperatur des Kontraktionsbeginnes und der Betrag der Faserschrumpfung durch die Tenside gegenüber Wasser herabgesetzt wird. Besonders wirksam ist in dieser Hinsicht das kationaktive Dodecylaminhydrochlorid. Bei den differentialkalorimetrischen Messungen zeigte sich in Dodecylaminhydrochlorid-Lösungen eine sehr starke Verbreiterung des Peaks und eine erhebliche Abnahme der Umwandlungswärme. Die Unterschiede in der Temperaturlage zwischen Superkontraktion und kalorischen Messungen sind durch die verschiedenen Aufheizbedingungen zu erklären.In sauren Dodecylaminhydrochlorid-Lösungen (pH 2,5) ist im Gegensatz zum neutralen Milieu der Umwandlungspeak gegenüber dem in dest. Wasser nahezu unverändert, während er in sauren Natriumdodecylsulfat (Nds)-Lösungen vollständig verschwindet, da die Umwandlung hier zu unschaf ist. Dieses Verhalten wird so gedeutet, daß eine starke Sorption des anionaktiven Tensids an den protonierten basischen Gruppen stattfindet und durch die in die Faser eingelagerten Tensidmicellen wahrscheinlich eine Schwächung der hydrophoben Wechselwirkungen eintritt.
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    Angewandte Makromolekulare Chemie 7 (1969), S. 101-109 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurde eine neue Methode entwickelt zur Bestimmung kleiner Mengen Ozon in Luft durch Kettenspaltung von Polymerfilmen.Die vorgeschlagene Methode hat für hochmolekulares Polystyrol (M̄v = 1,8 × 106) eine Empfindlichkeitsgrenze von 2 ppm Ozon in Luft. Dagegen hat Butylkautschuk (M̄v = 5,62 × 105, 1,75 Gew.-% Isoprenbausteine) eine niedrigere Empfindlichkeitsgrenze von 0,02 ppm ± 20% bei 35°C und 24 Stdn. Reaktionszeit. Die Grenze kann durch höhere Temperaturen wesentlich herabgesetzt werden. Eine noch höhere Empfindlichkeit läßt sich prinzipiell erreichen mit höhermolekularem Butylkautschuk mit größerem Isoprengehalt.
    Notes: A novel method has been elaborated for the determination of small amounts of ozone in air by chain scissioning of polymer films due to the high reactivity of ozone.The proposed method has a sensitivity limit for high molecular weight of polystyrene (M̄v = 1.8 × 106) of 2 p.p.m. of ozone in air. However, a butyl rubber (M̄v = 5.62 × 105, 1.75% by weight of isoprene) has a lower sensitivity limit of 0.02 p.p.m. ± 20% at 35°C and 24 hours reaction time. The latter can be decreased considerably if higher temperatures are used. Still lower sensitivity limits could be in principle attained with butyl rubber of longer chain length and higher isoprene content.
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  • 80
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    Angewandte Makromolekulare Chemie 7 (1969), S. 85-100 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polyester- und Polyamid-Garn wurden in Gegenwart von Chemikalien wie Ammoniak, Chlor, Methylmethacrylat, Vinylacetat und Acrylnitril mit kontrollierten Dosen von γ-Strahlen bestrahlt. Die physikochemischen sowie mechanischen Eigenschaften der bestrahlten Garne wurden untersucht. Die Ergebnisse zeigen, daß durch Bestrahlung in Gegenwart dieser Chemikalien merkliche Verbesserungen einiger wünschenswerter Fasereigenschaften möglich sind.
    Notes: Polyester and polyamide yarns have been irradiated under controlled doses of γ-rays in presence of chemicals like gaseous ammonia and chlorine as also methyl methacrylate, vinyl acetate, and acrylonitrile monomers. The irradiated monomers have been tested for some of the more important physico-chemical and mechanical properties. The results indicate that the improvements obtained in various desirable properties are of much higher order when irradiation is carried out in presence of the chemicals employed.
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  • 81
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    Angewandte Makromolekulare Chemie 6 (1969), S. 1-23 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The adsorbed layer of polar molecules like carbon acids on solid surfaces of oxides were found to be not completely desorbable. Using compounds able to copolymerize or to initiate a polymerization the adsorbed layer can copolymerize with a boundaring phase of vinyl compounds or initiate a polymerization. The formed polymers are fixed on the solid surface.
    Notes: Die Adsorption von polaren organischen Verbindungen wie Carbonsäuren an oxidische Feststoffoberflächen führt zu Adsorptionsschichten, die nicht vollständig desorbierbar sind. Bestehen die irreversibel adsorbierten Schichten aus copolymerisationfähigen oder polymerisationsinitiierenden Verbindungen, so können die Adsorptionsschichten mit einer an sie grenzenden copolymerisationsfähigen Phase copolymerisieren oder eine Polymerisation auslösen. Auf diese Weise können Polymere hergestellt werden, die eine große Haftfestigkeit auf der Feststoffoberfläche besitzen.
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    Angewandte Makromolekulare Chemie 7 (1969), S. 1-14 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Two celluloses, which were different in composition and structure (sulphite and sulphate cellulose), were grafted with side chains of polyacrylonitrile. It was found that with increase of the degree of grafting, and with decrease of the degree of polymerization of the side chains, under constant amount of grafted polyacrylonitrile the capacity of acetylation grows for both types of cellulose, especially for the sulphite cellulose. The grafting raises the amorphous part in the modified triacetyl celluloses being accompanied by an increase of their solubility in dimethyl formamide. Investigations on the structure formation in diluted solutions of grafted triacetyl celluloses in dimethyl formamide and in mixtures of dimethyl formamide and water were made by viscosimetric measurements.
    Notes: Auf zwei nach Zusammensetzung und Struktur unterschiedliche Zellstoffe - gebleichte Sulfit-und viskose Sulfatvorhydrolysecellulose - wurden Polyacrylnitrilseitenzweige aufgepfropft. Dabei wurde festgestellt, daß mit Steigerung des Pfropfungsgrades bei Herabsetzung des mittleren Polymerisationsgrades der Pfröpflinge und konstanter Polyacrylnitrilmenge das Acetyliervermögen für beide Cellulosearten steigt und zwar besonders bei der Sulfitzellulose. Das Pfropfen erhöht den amorphen Anteil in den modifizierten Triacetylcellulosen, was mit einer Erhöhung ihrer Löslichkeit in Dimethylformamid einhergeht. Es wurden viskosimetrische Prüfungen über die Strukturbildung in verdünnten Lösungen von gepfropften Triacetylcellulosen in Dimethylformamid und in binären Gemischen von Dimethylformamid/Wasser durchgeführt.
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    Angewandte Makromolekulare Chemie 7 (1969), S. 15-28 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Poly(2,6-dimethyl-1,4-phenylene ether), prepared by oxidative coupling of purified 2,6-dimethylphenol, was chlorinated with FeCl3 or AlCl3 as catalysts (I) and under UV -radiation (II). By (I) polymers with up to a maximum content of 36% Cl (disubstituted structural units) and by (II) polymers with up to a maximum 55% Cl (tetrasubstituted structural units) were obtained. During the chlorination a strong chain degradation takes place, which is recognizable by decrease in viscosity number [η] and by loss of mechanical strength and tenacity of the material. The proof of the degradation was furnished by dechlorination with LiAlH4, which caused no increase in [η] and by molecular weight determination via sedimentation (Dr. E. Schuch, BASF). The degree of polymerization decreased from P̄ = 620 to P̄ = 89 by the 30% chlorinated polymer and to P̄ = 62 by the 51% chlorinated product. It was shown that the scission of the poly(phenylene ether) chains is not caused by HCl but by chlorine.
    Notes: Poly-2,6-dimethyl-1,4-phenylenäUther, dargestellt durch oxidative Kupplung von gereinigtem 2,6-Dimethylphenol, wurde unter kernchlorierenden und unter seitengruppenchlorierenden Bedingungen nach verschiedenen Methoden chloriert. Bei Kernchlorierung (FeCl3 oder AlCl3 als Katalysator) läßt sich der für das Dichlorderivat zu erwartende Chlorgehalt von 37,6% nahezu erreichen. Bei Seitenkettenchlorierung unter UV-Bestrahlung werden Präparate mit maximal 55% Chlorenem Tetrachlorderivat entsprechend - erhalten.Die Chlorierung ist stets von einem starken Kettenabbau begleitet. Der Abbau äußert sich in einer mit der Chlorierung einhergehenden Abnahme der Viskositätszahl und einem Verlust der mechanischen Festigkeit.Daß die Viskositätsabnahme durch einen Kettenabbau verursacht wird, wurde durch teilweise Entfernung des Chlors durch LiAlH4 und durch Sedimentations messungen in der Ultrazentrifuge (Untersuchungen von Dr. E. SCHUCH, BASF) bewiesen. Die Sedimentationsmessungen ergaben einen Abbau von P̄ = 620 auf P̄ = 62 bei einer Chlorierung bis 51 Gew.-% Cl. Die Spaltung der Polyphenylenätherkette wird nicht durch HCl, sondern durch Chlor bewirkt.
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    Angewandte Makromolekulare Chemie 7 (1969), S. 29-38 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Chlorwasserstoffabspaltung am Polyvinylchlorid wurde in phenolischen Lösungsmitteln unter Stickstoffatmosphäre im Bereich von 137° bis 206°C untersucht. Phenol, o-Cresol, Methyl-, Äthyl-, Amyl- und Phenylsalizylat wurden als Lösungsmittel verwendet. In Phenol war die Reaktion schnell und in Amylsalizylat langsam. Mit zunehmender Größe des Alkylrestes im Salizylat nahm die Geschwindigkeit der Abspaltung des Chlorwasserstoffs ab. In Amylsalizylat war die Aktivierunsenergie niedriger (26 Kcal/mol) als in o-Cresol (29 Kcal/mol) bei den anderen Lösungsmitteln lagen die Werte dazwischen. Die Ergebnisse lassen sich durch die unterschiedliche Aktivität des phenolischen Wasserstoffs und die sterische Hinderung der verschiedenen Lsöungsmittel erklären.
    Notes: The thermal degradation of polyvinyl chloride in phenolic solvents has been investigated in an atmosphere of nitrogen in the temperature range 137-206°C. The solvents used were phenol, o-cresol, methyl, ethyl, amyl, and phenyl salicylates. The reaction was fast in phenol and slow in amyl salicylate. The rate of dehydrochlorination decreased with increasing size of the alkyl side chain in salicylates. The activation energy was low in amyl salicylate (26 kcal/mole) and high in o-cresol (29 kcal/mole), and for other solvents it was in between these two values. The results have been explained as being due to the variation in the reactivity of phenolic hydrogen and to steric factors of the various substituents.
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  • 85
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    Angewandte Makromolekulare Chemie 7 (1969), S. 67-78 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Infrarotspektroskopie wird als Methode zur Charakterisierung und zur qualitativen Bestimmung der beiden Gruppen von Gerbstoffen vorgeschlagen. Gallussäure, Gerbsäure und Chebulinsäure wurden als Modellverbindungen für die hydrolysierbaren und Catechin für die kondensierten Gerbstoffe genommen. Die erstgenannte Gruppe ist durch starke Absorptionsmaxima bei 1710 - 35 cm-1 gekennzeichnet. Beide Gruppen zeigen charakteristische Absorptionen, die zur Erkennung des Gerbstofftyps dienen können.
    Notes: Infrared spectroscopy is suggested as a diagnostic method for the characterisation and qualitative estimation of the two classes of tannins. Gallic acid, tannic acid and chebulinic acid have been taken as model compounds for the hydrolysable and catechin for the condensed tannins. The former class is marked by the presence of strong absorption maxima at 1710 - 35 cm-1. The two classes have characteristic pattern of absorption, from which it is possible to characterise the particular type of tannin.
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  • 86
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Styrene-maleic acid-butylester-copolymers (SMB-polymers) with a variable number of maleic acid-monobutylester-units in the polymer chain are suitable model polymers for systematical studies of the deposition-mechanism of paints for electrodeposition.By the addition of organic solvents the amine salts of these polymers give water thinnable solutions. The viscosity and the conductivity of these solutions is similar to that of other polyelectrolyte solutions. The nature and the quantity of the added organic solvent is important for the electric resistance of the deposited film. The relation between the added solvent and the film resistance is discussed.The deposition behaviour of the polymers is characterised by voltage-time-diagramms, which are available from the experiments with constant current density during deposition.The influence of the degree of esterfication and neutralisation of the SMB-polymers, the current density, the bath temperature, stirring of the solution and electrode geometrie on the specific film resistance was studied.Characteristic changes in the voltage-time-curve indicate the occurence of surface disturbances of the deposited film. They are caused by the anodic formation of oxygen. The attainable thickness of depositions without surface disturbances depends on the quantity of salt groups in the polymer chain.
    Notes: Alternierende Styrol-Maleinsäurebutylester-Copolymere (SMB-Polymere) mit definiert variierbaren Anteilen von Maleinsäuremonobutylester-Struktureinheiten erwiesen sich als geeignete Modellbindemittel für eine systematische Untersuchung der Abscheidungsvorgänge bei der Elektrotauchlackierung. Unter Zusatz organischer Lösungsmittel erhält man mit Wasser verdünnbare Lösungen von Aminsalzen dieser Polymeren, die in bezug auf Viskosität und Leitfähigkeit das bekannte Verhalten von Polyelektrolyten zeigen. Durch Art und Menge der zugesetzten organischen Lösungsmittel wird der spezifische Widerstand der abgeschiedenen Filme in charakteristischer Weise beeinflußt. Der Zusammenhang zwischen Lösungsmittel-eigenschaften und Filmwiderstand wird diskutiert.Das Abscheidungsverhalten der Copolymeren wurde durch Spannungs-Zeit-Kurven charakterisiert, die bei automatisch konstant gehaltener Stromdichte aufgenommen wurden, und die daher bei konstant bleibendem spezifischem Filmwiderstand Geraden sind. Im einzelnen wurde der Einfluß folgender Parameter auf den spezifischen Filmwiderstand untersucht: Art und Konzentration organischer Lösungsmittel, Veresterungsgrad und Neutralisationsgrad der SMB-Polymeren sowie Stromdichte, Badtemperatur, Badumwälzung und Elektrodengeometrie.Maxima oder Plateaus der Spannungs-Zeit-Kurven zeigen das Auftreten von Filmstörungen durch lokales Aufreißen des Films infolge der anodischen Sauerstoffentwicklung an. Die bis zum Auftreten dieser Filmstörungen erreichbare maximale Schichtdicke ist eine Funktion des Salzgruppengehaltes der Polymeren.
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  • 87
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    Angewandte Makromolekulare Chemie 9 (1969), S. 122-128 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The equilibrium coefficients and relative affinities of 10 monovalent anions on the strongly basic anion-exchanger resin Wofatit SBK were determined in batches by the conductivity method in water-miscible solvents (H2O: org. solvent = 20:80) methanol, ethanol, 2-propanol, acetone, dimethylsulfoxide and acetonitrile. The measured values are investigated with respect to their practical applicability and are discussed in relation to values measured in pure aqueous medium.
    Notes: Die Gleichgewichtskoeffizenten und relativen Affinitäten von 10 einwertigen Anionen zum stark basischen Anionenaustauscher Wofatit SBK wurden nach der batch-Methode in den mit Wasser mischbaren Lösungsmitteln Methanol, Äthanol, Propanol-(2), Aceton, Dimethylsulfoxid und Acetonitril (Mischungsverhältnis H2O: org. Lösungsmittel = 20:80) bestimmt. Die mit Hilfe von Leitfähigkeitsmessungen ermittelten Werte wurdern qualitativ auf ihre praktische Anwendbarkeit untersucht und in Bezug zu den in rein wäßriger Lösung gefundenen Werten diskutiert.
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  • 88
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    Angewandte Makromolekulare Chemie 9 (1969), S. 129-135 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Reaktionsgeschwindigkeit einer Reihe von Phosphiten mit Cyclohexenyl-hydroperoxid und mit Peroxy-Radikalen des Cyclohexens wurde untersucht. Die Ergebnisse wurden mit der Stabilisierungswirksamkeit derselben Verbindungen an isotaktischem Polypropylen bei 120°C und 160°C und während der atmosphärischen Alterung verglichen. Es wurde festgestellt, daß die Stabilisierungs-wirksamkeit den Reaktionskonstanten der Phosphite mit den Hydroperoxiden umgekehrt proportional ist. Die wichtigste Stabilisationsreaktion der Phosphitstabilisatoren ist die Reaktion der Phosphite bzw. der aus ihnen entstehenden Stoffe mit den Radikalen. Die Möglichkeit der Bildung von freien Phenolen als Folge der Reaktion der Phosphite mit Hydroperoxidgruppen wurde überprüft.
    Notes: The rate of the reaction of a series of phosphites with cyclohexene hydroperoxide and cyclohexene peroxy radicals was studied. The results of the measurements were compared with the stabilization efficiency of the same compounds in isotactic and in atactic polypropylene at 160°C and 120°C respectively and during the course of atmospheric ageing. It was found the reverse relation between the stabilization efficiency and the reaction constants of the reaction of phosphites with hydroperoxides. The main stabilization reaction of the phosphorous stabilizers seems to be the reaction of phosphites or of their decomposition products with radicals. The possibility of splitting off of free phenol from phosphites as a result of the reaction of the esters with hydroperoxide groups was checked.
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  • 89
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    Angewandte Makromolekulare Chemie 9 (1969), S. 151-164 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Two new procedures are described that allow an exact determination of the equilibrium conditions for phase separation of dilute polymer solutions. Their development has been necessary, because the procedures known to date are generally neither considering the kinetic delay of gel formation nor the finite exceeding of the equilibrium requisite for observing the new phase. Contrary to the procedures so far, several gel formation procedures are performed on each polymer solution; the equilibrium conditions are then determined by extrapolation. The system polystyrene-butylacetate-propanole was used to demonstrate the new procedures.
    Notes: Es werden zwei neue Verfahren beschrieben, die eine exakte Bestimmung der Gleichgewichtszustände verdünnter Polymerlösungen ermöglichen. Mit ihnen lassen sich die grundsätzlichen Fehler vermeiden, die den bisher bekannten Verfahren anhaften, da diese im allgemeinen weder der kinetischen Verzögerung des Gelbildungsprozesses noch der zur Beobachtung der neuen Phase notwendigen endlichen Überschreitung des Gleichgewichtes Rechnung tragen. Bei den neuen Verfahren werden für jede Polymerlösung mehrere Gelbildungsprozesse durchgeführt, aus denen dann durch eine Extrapolation der gesuchte Gleichgewichtszustand gewonnen wird. Die Verfahren sind am Beispiel des Systems Polystyrol-Butylacetat-n-Propanol angewandt worden.
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  • 90
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    Angewandte Makromolekulare Chemie 9 (1969), S. 182-185 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 91
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    Angewandte Makromolekulare Chemie 6 (1969), S. 24-38 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In this work various methods concerning the determination of compatibility of polymers are discussed. The conclusion is, that the earlier proposed “kinetical” method, besides the method of phase separation in common solution, is one of the surest methods of compatibility determination for polymers. However, over the latter, the kinetical method offers the advantage of rapidity and the possibility to predict the thermostability, the interactions of functional groups and the formation of solution in the solide state. While the interaction of functional groups may be established also by IR-spectroscopy, the other methods permit no conclusions of this kind. Generally it is very difficult to make statements on the formation of solution in the solid state on the basis of other methods of compatibility investigation. Quite useless, at least for our polymer mixtures, are the measurements of viscosity in concentrated as well as in dilute polymer solutions.
    Notes: In vorliegender Arbeit werden verschiedene Methoden für Verträglichkeitsbestimmungen von Polymeren vergleichend besprochen, wobei sich die früher vorgeschlagene kinetische Methode, neben der Phasentrennung in gemeinsamer Lösung, als eine der sichersten erweist. Gegen letztgenannte Methode bietet sie aber den Vorteil, daß sie viel schneller ist und auch Aussagen über Thermostabilität, Wechselwirkung von funktionellen Gruppen und Lösungsbildung im festen Zustand ermöglicht. Wenn die Wechselwirkung von funktionellen Gruppen auch IR-spektroskopisch eindeutig festgelegt werden kann, so erlauben andere Methoden diesbezüglich keine Schlüsse, und am schwersten ist es im allgemeinen, Aussagen über Lösungsbildung im festen Zustand auf Grund der Ergebnisse anderer Untersuchungsmethoden zu machen. Ganz unbrauchbar, zumindest in den von uns untersuchten Fällen, erweisen sich Viskositätsmessungen sowohl in konzentrierten als auch in verdünnten Polymerlösungen.
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  • 92
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    Angewandte Makromolekulare Chemie 6 (1969), S. 39-45 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Ketovinylester Vinyl-4-benzoylbutyrat, Vinyl-4-(p-toluoyl)-butyrat, und Vinyl-4-(m-nitrobenzoyl)-butyrat wurden hergestellt ; ihre Struktur wurde durch NMR-Spektren belegt. Die Substanzpolymerisation der neuen Monomeren wurde unter-sucht, und die Molekulargewichte und Glastemperaturen der Polymerisate wurdenbestimmt. Das Nitroderivat war erwartungsgemäß nicht polymerisierbar. Vinyl-4-benzoylbutyrat ergab infolge von Übertragungsreaktionen eine Verzögerung der Polymerisation.
    Notes: Vinyl 4-benzoyl butyrate, vinyl 4-(p-toluoyl) butyrate and vinyl 4-(m-nitro-benzoyl) butyrate were prepared by vinyl interchange with vinyl acetate. Theoptimum conditions for the preparation of these monomers have been studied.Their structures were established by NMR spectroscopy. The polymers of thesemono em were synthesised by free radical polymerization, their molecular weightsand glass temperatures determined. Vinyl 4-(m-nitrobenzoyl) butyrate was not-polymerizable. Vinyl 4-benzoyl butyrate showed degradcttive transfer reaction on polymerization due to the presence of active methylene groups.
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  • 93
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    Angewandte Makromolekulare Chemie 6 (1969), S. 60-69 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Vibration grinding of high-molecular pectic acid results in preparations of nearly constant composition and decreased average molecular weight in dependence of grinding time. By using this favourable procedure it is generally possible to produce standardized pectic acid preparations with better and more reproducible solubility properties. Such preparations are required, e.g., for comparative enzymatic investigations. For evaluating polygalacturonase activity it is proposed to use pectic acid preparations with the following properties: viscosity number [η] (intrinsic viscosity) in the range of 50-100 ml/g, mineral content lower than 1 %, and anhydrogalacturonic acid content in the ash-free dry substance minimum 80 %.
    Notes: Durch Schwingmahlung hochmolekularer Pektinsäure von unterschiedlicher Dauer gelangt man zu Präparaten weitgehend konstanter Zusammensetzung und vermindertem Durchschnitts-Molekulargewicht. Diese vorteilhafte Methode ermöglicht generell die Herstellung von standardisierten Pektinsäurepräparaten mit verbessertem und reproduzierbarem Lösungsverhalten, wie sie beispielsweise als Substrate für vergleichende enzymatische Untersuchungen benötigt werden. In diesem Zusammenhang wird zur Ermittlung der Polygalakturonase-Aktivität empfohlen, Pektinsäurepräparate mit einer Viskositätszahl [η] im Bereich von 50 bis 100 ml/g und einem unter 1% liegenden Aschegehalt sowie mit einem Mindestanteil von 80% Anhydrogalakturonsäure in der aschefreien Trockensubstanz zu verwenden.
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  • 94
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    Angewandte Makromolekulare Chemie 6 (1969), S. 70-78 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Probably due to the bulky fluorine substituents perfluorocyclohexadiene-1,3 (PFC) is not able to form homopolymers; likewise the copolymerization behavior is essentially influenced by this fact. Experiments in CCl3 solutions with azobisisobutyronitrile as the initiator have shown, that α-methylstyrene does not yield copolymers; in the relatively low molecular products (Pn≈10) resulting from PFC and N-vinylpyrrolidone (NVP) and PFC and indene, two successive PFC units are separated by at least two or three comonomer units, respectively. The insertion of this minimum number of seperating links is a slow process compared with the monomer addition to the sterically unhindered radicals. This is borne out by the decrease of the overall rate of polymerization Vbr with increasing PFC concentration and by the increase of Vbr with increasing concentration of the chain transfer agent. The reactivity ratios at 50°C are rnvp = 0,54 and rindene = 3,O. This results in Qpfc 〈 0,02 and epfc 〉 1.The “dead end” of the reaction and the variation of the mean polymer compo-sition with conversion are calculated on the basis of the experimentally obtained kinetic equations. A discussion of the copolymerization behavior of PFC and butadiene-l,3 is given.
    Notes: Perfluorcyclohexadien-1,3 (PFC) bildet wahrscheinlich infolge der großen Raumbeanspruchung der F-Atome keine Hompolymeren; auch das Copolymerisationsverhalten wird dadurch wesentlich beeinflußt. Versuche in CHCl3-Lösung mit Azobisisobutyronitril als Starter haben ergeben, daß PFC mit α-Methylstyrol keine Copolymeren bildet; in den mit N-vinylpyrrolidon (NVP) bzw. Inden entstehenden niedrigmolekularen Produkten (P ≈ 10) sind zwei aufeinanderfolgende PFC-Einheiten durch mindestens zwei bzw. drei Comonomereinheiten getrennt.Der Einbau dieser Mindestanzahl von Zwischengliedern erfolgt langsam, verglichen mit der Monomeraddition an die sterisch nicht behinderten Radikale, wie die Abnahme der Bruttopolymerisationsgeschwindigkeit vBr mit zunehmender PFC-Konzentration und die Zunahme von vBr bei Erhöhung der Überträgerkonzentration zeigen.Die Copolymerisationsparameter bei 50°C sind rnvp=0,54 und pindn=3,0. Daraus ergibt sich Qpfc 〈 0,02 und epfc 〉 1.Aus den erhaltenen kinetischen Gleichungen werden die Umsatzgrenzen (“dead end”) und die Änderung der mittleren Polymerzusammensetzung mit dem Umstaz berechnet.Das Copolymerisationsverhalten von PFC und Butadien-1,3 wird diskutiert.
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  • 95
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    Angewandte Makromolekulare Chemie 6 (1969), S. 79-88 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The influence of polymer structure on the incompatibility in solution was investigated with combinations of 15 polyacrylates and polymethacrylates with different ester chain length. Small changes in polymer structure already cause an incompatibility in solution. In general it was found that the higher the difference in the carbon number the higher is the incompatibility. Furthermore there exists a dependence on the molecular weight of the polymer and on the nature of the solvent.Finally it was found that in contradiction to published data polyvinylacetate and polymethylacrylate are incompatible both, in dissolved and in solid state.
    Notes: Anhand von 15 Polyacrylaten und Polymethacrylaten, die sich vor allem in der Art der Alkoholkomponente voneinander unterscheiden, wurde der Einfluß der Polymerstruktur auf den Grad der Unverträglichkeit in Lösung von Zweierkombinationen der Polymeren untersucht.Zwei Polymere sind im allgemeinen um so unverträglicher, je größer die Differenz der Gesamtzahl der C-Atome in beiden Komponenten ist. Die Erscheinungen hängen in der früher von uns angegebenen Weise vom Molekulargewicht und von der Natur des Lösungsmittels ab.Bereits geringe Unterschiede in der Struktur können eine relativ starke Unverträglichkeit in Lösung bedingen.Schließlich wird gezeigt, daß Polyvinylacetat und Polymethylacrylat sowohl in Lösung als auch im festen Zustand miteinander unverträglich sind.
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  • 96
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Polymerisation von Methylmethacrylat wurde in Anwesenheit von Nylon-6-Fasern und Wasser durchgeführt. Es ergab sich, daß der Umsatz bei der Polymerisation in Abwesenheit von Wasser wie bei der thennischen Polymerisation, dagegen in Anwesenheit von Wasser viel höher war. Ist Methylmethacrylat sowie Wasser in genügender Menge im Polymerisationssystem vorhanden, so gehorcht die Polymerisationsgeschwindigkeit (Rp) folgender Gleichung: \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm R}_{\rm p} = {\rm k}\left( {{\rm Nylon}} \right)^{1,0} \left( {{\rm MMA}} \right)^0 \left( {{\rm Wasser}} \right)^0 . $\end{document} Die Bruttoaktivierungsenergie der Polymerisation wurde zu 13 kcal/mol gefunden. Die Polymerisation von Styrol, Acrylnitril, Vinylacetat und Methylacrylat konnte durch das System Nylon und Wasser nicht ausgelöst werden. Der scheinbare Pfropfungswirkungsgrad von Polymethylmethacrylat an die Nylonfaser wurde aus der mit Aceton nicht extrahierten Polymerenmenge berechnet. Der Wirkungsgrad ist unabhängig von der Reaktionszeit sowie von der Wassermenge und nimmt mit der Nylonmenge zu, während er mit der Methylmethacrylatmenge und mit der Reaktionstemperatur abnimmt. Aus der Tatsache, daß der Hauptteil des Polymethylmethacrylats nicht extrahiert werden konnte, wurde gefolgert, daß die Polymerisation von Methylmetharcylat in Anwesenheit von Nylon und Wasser vornehmlich im Innern der Faser verläuft. Der Polymerisationsgrad des im Innern der Nylonfaser gebildeten Polymethylmethacrylats war beträchtlich höher als derjenige vom außerhalb der Faser gebildeten Homopolymethylmethacrylat. Es wurde qualitativ geschlossen, daß das innerhalb der Nylonfaser gebildete Poly-methylmethacrylat hauptsächlich als Homopolymeres vorlag und nicht auf die Nylonfaser gepfropft war.
    Notes: The polymerization of methyl methacrylate in the presence of nylon-6 fibers and water was carried out. It was found that the conversion in the absence of water was the same as that of thermal polymerization, but in the presence of water the conversion was much higher. When methyl methacrylate and water existed sufficiently in the polymerization system, the rate of polymerization (Rp) was given by the following equation; Rp = k (Nylon)1,0 (Methyl methacrylate)0 (Water)0. The over-all activation energy of the polymerization was found to be 13 kcal/mole. The polymerization of styrene, acrylonitrile, vinyl acetate, and methyl acrylate could not be initiated by the system of nylon and water. Apparent grafting efficiency of polymethyl methacrylate onto nylon was calculated from the amount of polymer which was not extracted with acetone. The efficiency was independent on the reaction time and the amount of water, and increased with the amount of nylon, while it decreased with the amount of methyl methacrylate and with reaction temperature. From the fact that a major part of the polymethyl methacrylate could not be extracted, it was concluded that the polymerization of methyl methacrylate in the presence of nylon and water occured predominantly inside the fiber. The degree of the polymerization of polymethyl methacrylate formed inside the nylon fiber was considerably higher than that of homopolymethyl methacrylate formed outside the fiber. It was qualitatively recognized that the major part of the polymethyl methacrylate generated in the fiber was not grafted onto nylon, but existed as homopolymer.
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  • 97
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    Angewandte Makromolekulare Chemie 6 (1969), S. 89-100 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: This publication relates to examples of the application of redox resins in organic chemistry. These redox resins contain various quinone/hydroquinone systems. p-Benzoquinone was reduced to hydroquinone and some hydrogenated aromatic and heterocyclic compounds were dehydrogenated to the corresponding aromatic and heterocyclic parent compounds by redox resins. Following the STRECKER degradation α-aminocarboxylic acids were degraded to the corresponding aldehydes having one C-atom less than the α-aminocarboxylic acid. Redox resins can be used as antioxydants as has been shown in the synthesis of 3-acetoindole.
    Notes: Es wird über Anwendungsbeispiele für Redoxharze in der organischen Chemie berichtet, die als Redoxsysteme verschiedene Chinon-Hydrochinon-Systeme enthalten. p-Benzochinon läßt sich zu Hydrochinon reduzieren. Hydroaromaten und Hydroheterocyclen können durch Redoxharze zu den entsprechenden Aromaten bzw. Heterocyclen dehydriert werden. Entsprechend dem STRECKERschen Abbau lassen sich α-Aminocarbonsäuren durch Redoxharze zu dem um ein C-Atom ärmeren Aldehyd abbauen. Anhand der 3-Acetylindoldarstellung wird gezeigt, daß ein Redoxharz als Antioxydans eingestzt werden kann.
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  • 98
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    Angewandte Makromolekulare Chemie 6 (1969), S. 101-108 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The specific heats of polyvinylbutyral (Mowital®) with and without 28% by weight plasticizer (triethylene glycol-di-(2-ethylbutyrate)) and of pure plasticizer were determined by means of an adiabatic calorimeter in the temperature range from - 50°C to + 120°C. The glass transition temperatures derived from the heat capacity temperature relationships are -0.5°C and 59.3°C respectively for the polyvinylbutyral resin with and without plasticizer. Specific volume measurements yielded the same transition temperatures within the limits of error. The heat capacity of the plasticized PVB (in the liquid state) deviates significantly from the value obtained from the pure components by the simple mixing rule. This indicates a non zero value of the heat of mixing for the system polymer / plasticizer.
    Notes: Die spezifischen Wärmen des Polyvinylbutyrals (Mowital®) ohne und mit 28 Gew.-% Weichmacher (Triäthylenglykoldi-2-äthylbutyrat), sowie die des reinen Weichmachers wurden im Temperaturbereich von - 50 bis + 120°C mit einem adiabatischen Kalorimeter gemessen. Die aus dem Temperaturverlauf der spezifischen Wärmen bestimmten Einfriertemperaturen betragen 59,3°C für das weichmacherfreie und --0,5°C für das weichgemachte Polyvinylbutyral. Zum Vergleich ausgeführte Untersuchungen der spezifischen Volumina ergaben innerhalb der Meßgenauigkeit die gleichen Werte für die Einfriertemperaturen. Die spezifische Wärme des weichgemachten Polyvinylbutyrals läßt sich (im flüssigen Zustand) nicht aus der der Komponenten berechnen, was auf das Auftreten einer Mischungswärme hindeutet.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 99
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 6 (1969), S. 109-115 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The equilibrium coefficients and relative affinities of 28 anions on the strongly basic anion-exchanger resin Wofatit SBW has been determined in batches by the conductive method. The practical application of the measured values are qualitatively discussed.
    Notes: Es wurden die Gleichgewichtskoeffizienten und relativen Affinitäten von 28 Anionen zum stark basischen Anionenaustauscher Wofatit SBW nach der batch-Methode bestimmt. Die mit Hilfe von Leitfähigkeitsmessungen gefundenen Werte wurden qualitativ auf ihre praktische Anwendbarkeit untersucht und diskutiert.
    Additional Material: 1 Tab.
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  • 100
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 6 (1969), S. 127-135 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurde die Einwirkung von γ-Strahlen auf Polyester- und Polyamid-Garn in verschiedenen Dosen in Gegenwart sowie unter Ausschluß von Luft untersucht. Die Veränderung in den Fasereigenschaften wie Schmelzpunkt, relative Viscosität, Festigkeit und Farbstoffaufnahme wurde ermittelt. Die in dieser Arbeit gefundenen Ergebnisse zeigen, daß - obwohl mit höheren Strahlungsdosen die Faserstoffe beschädigt wurden - es mit kontrollierter Bestrahlung jedoch möglich ist, einige Fasereigenschaften ohne wesentlichen Faserabbau zu verbessern.
    Notes: Polyester and polyamide yarns have been exposed to γ-rays with varying doses of irradiation, both in vacuum and in the presence of air. The changes in such properties of the polymers as melting point, relative viscosity, tensile strength, and dye absorption have been investigated. The results of the present study indicate that, though with higher doses there is degradation of the polymer, under controlled conditions certain desirable properties of the fibre are greatly improved without affecting the mechanical strength.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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