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  • 1
    Electronic Resource
    Electronic Resource
    Water-containing resin based on unsaturated polyester (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 13-21 
    Details
    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: Unsaturated polyester resins containing water were prepared through two steps: formation of a stable W/O emulsion of polyester prepolymer and subsequent polymerization of the emulsion. In this paper, conditions for formation of the resins from the W/O type emulsion and the heat-protection properties of the resulting water-containing resins are reported. The stability of the emulsions was measured, and the results are discussed in relation to the gelation time, since the polymerization of the emulsions is required to proceed faster than their disintegration. It was found that with increasing viscosity of the emulsions their stability increases and the gelation time shortens. The above requirement is fulfilled at almost all regions of emulsifier concentration where stable W/O emulsions are formed. Water-containing unsaturated polyester resins exhibit a remarkable heat-protection effect at elevated temperatures (500 and 2500°C.) in comparison with polyester resins not containing water.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1968.070120103
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  • 2
    Electronic Resource
    Electronic Resource
    Determination of true flow curves from capillary rheometer data (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 123-129 
    Details
    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 evaluation of polymer melt viscosity versus shear rate has been customarily done by a time-consuming graphical method, which corrects for non-Newtonian behavior and pressure losses at flow transitions. It is shown by mathematical analysis that the flow data in terms of applied pressure and apparent shear rate can be treated by a semigraphical method, in which calculation of the true flow curve can be done with a computer. Moreover, it is possible in some cases to program the data treatment entirely for computer calculation. Results obtained by the proposed method are in excellent agreement with those obtained by the older graphical method.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1968.070120111
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  • 3
    Electronic Resource
    Electronic Resource
    Epoxy resins from dinaphthols (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 699-709 
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    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: Epoxy resins were prepared from di-α-naphthol(4,4′-dihydroxy-1,1′-dinaphthyl) and di-β-naphthol(2,2′-dihydroxy-1,1′-dinaphthyl). The resins consisted mainly of the reaction product of 1 mole of dinaphthol with 2 moles of epichlorhydrin. They contained chlorine, however, and were correspondingly deficient in diepoxide functionality. The resins from di-α-naphthol were crystalline, had m.p. 200°C., and were not miscible with conventional curing agents. Di-β-naphthol gave resins with softening points in the range 50-70°C., which cured with diethylenetriamine or the anhydrides of dibasic acids, giving hard but brittle products. The brittleness was not removed by curing with plasticizing curing agents, such as tetrapropenyl succinic anhydride. The cured di-β-naphthol-based resins had thermal stabilities similar to analogous epoxy resins based on bisphenol A.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1968.070120408
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  • 4
    Electronic Resource
    Electronic Resource
    Determination of degree of nitration of nitrocellulose by refractometry (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1865-1871 
    Details
    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: Nitrocellulose (NC) films, when dried on a rigid substrate, tend to be biaxial and thus exhibit two refractive indices. The absolute difference between these indices has been found to provide an accurate measure of the degree of nitration of NC. A film of NC is cast from a 1% solution in butyl acetate to provide a film about 0.5 mil thick. The dry film, when placed in an Abbé-3L refractometer, gives two white lines which go to extinction alternately upon rotation of a cap analyzer through the east-west (EW) and north-south (NS) directions. Refractive index measurements are made using the line visible in each direction of the analyzer. The absolute difference between the two indices is related to the degree of nitration through standard curves for various grades of NC. The standard deviation for the proposed method was found to be ±0.01% N.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1968.070120808
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  • 5
    Electronic Resource
    Electronic Resource
    Some properties of low molecular weight polybutadiene and polytetrahydrofuran (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1889-1899 
    Details
    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 proposition, that low molecular weight polymer fractions in good solvents behave as if they were under ⊖ conditions, has been examined experimentally. Series of monodisperse hydroxy-terminated polytetrahydrofuran (PTHF), 82% 1,4-polybutadiene (PBD), and 30% 1,4-PBD were prepared, and values of M̄n obtained by vapor-pressure osmometry and endgroup analysis. The Mark-Houwink viscosity parameters K and ν were determined in a number of solvents. The general conclusion is that the proposition is invalid for these systems notwithstanding the fact that ν = 0.50 for one of them [82% 1,4-PBD in methyl ethyl ketone (MEK) at 25°C]. For this particular case, the following evidence suggests that these are actually ⊖ conditions so that the apparent fulfilment of the proposition is fortuitous. (1) Cloud-point precipitation yields ⊖ = 26 ± 3°C in MEK. (2) The value of K is close to that of K⊖ found elsewhere for PBD in a different solvent at a similar temperature. (3) Application of the Kurata-Stockmayer iterative procedure for estimating K⊖ from data in good and bad solvents yields a reasonably small discrepancy (10%) between the K⊖ values from data in toluene and MEK at 25°C for this polymer and only a 3% difference in the unperturbed dimensions (〈r02〉/M)1/2 derived from them. Measured melting points Tm of PTHF (M̄n = 1000-13000), plotted as a function of chain length Z, viz., 1/Tm = 1/Tm0 + 2R/ZΔHf, yield 43 ± 3°C and 1.6 kcal/submole, respectively, for the limiting melting point Tm0 and the heat of fusion ΔHf. The former is in good agreement with the value obtained dilatometrically for high molecular weight polymer, while the latter indicates a degree of crystallinity of ca. 54%.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1968.070120810
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  • 6
    Electronic Resource
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    Novel thermally stable and chemically resistant epoxy polymers derived from phenylene oxides (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 607-618 
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    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: Thermogravimetric and differential thermal analysis data are presented for three novel bisepoxy monomers and formulated coatings derived therefrom. The coatings were insensitive to impact in liquid oxygen and showed excellent resistance to liquid nitrogen tetroxide, concentrated nitric acid, and a variety of organic solvents. All coatings showed excellent adhesion to metals and oxidation resistance superior to any known commercial epoxy polymer. Thermal resistance was excellent at 500°F. for periods of at least 500 hr. in air. Other data on these novel epoxy polymers are also presented.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1968.070120401
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  • 7
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    The mechanism of oxidative degradation of ABS resin. Part II. The mechanism of photooxidative degradation (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 671-682 
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    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 mechanism of oxidative degradation of ABS resin under ultraviolet irradiation, especially with respect to the wavelength dependencies of the photooxidative rate, has been examined by a spectroweather tester and infrared spectroscopy. The irradiation wave region was 290-800 mμ, and the region was divided into six parts. The changes in each part were examined by infrared spectroscopy. The absorption bands belonging to nitrile and phenyl groups showed no changes, but bands belonging to carbonyl and hydroxyl groups changed markedly, much as in the thermooxidative degradation described in a previous paper. There was a distinct gap between the third and fourth regions, which corresponded to 350 mμ. The graph of the normalized absorbance ratio and the logarithm of the wavelength gave a straight line, and it indicated that the rate of oxidation is proportional to the light intensity and the logarithm of the wavenumber.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1968.070120406
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  • 8
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    The effect of strain rate on the stress-strain curve of oriented polymers. I. Presentation of experimental results (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 731-738 
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    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 stress-strain curves of viscose, nylon 6.6, poly(ethylene terephthalate), polyacrylonitrile, and polypropylene have been determined at a large number of different strain rates between 10-4 and 330 sec.-1. The shape of these stress-strain curves and its change with strain rate is shown to depend upon whether the material is tested above or below its glass temperature. The stress-strain curves of materials tested below their glass temperature consists of an initial straight portion followed by a yield point at a few per cent strain. The breaking strain is only slightly affected by strain rate, and the energy to rupture increases with increasing rate. For materials tested above their glass temperature the initial portion of the stress-strain curves in nonlinear, and the yield strain is much higher than for the other materials. There is a small range of strain rate, in which the breaking strain falls sharply to the yield strain with increasing rate, and the energy to rupture also decreases. Outside this range the energy to rupture increases with increasing rate.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1968.070120411
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  • 9
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    Electronic Resource
    Adiabatic compressibility of polyelectrolytes in aqueous solutions: Poly(methacrylic acid)Communication No. 1105 from the National Chemical Laboratory, Poona, India (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 751-760 
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    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 adiabatic compressibility of dilute aqueous solutions of methacrylic acid, poly-(methacrylic acid), and three poly(sodium methacrylates) obtained by neutralizing the polyacid with sodium hydroxide to different extents were determined from soundvelocity and density data. The ultrasonic velocity at 25°C. was measured by employing a precision ultrasonic interferometer, and the density was measured with Ostwald-type pycnometers. The plots of the decrease of compressibility per unit concentration, (β1 - β)/c versus c shows that there is a marked difference between the curves of monomer and of polymer solutions. In case of the monomer there is a proportional decrease with increase in concentration, whereas in polymer in the dilute region (0.1-0.5g./dl.) the curve rises sharply, then shows down, and finally approaches a constant value at comparatively higher concentrations. The nature and number of the free counterions and the shape and the concentration of the polymer molecules are responsible for the compressibility of polymer solutions. However, the contribution of the size and shape and concentration of the polymer seem to be less than that of the nature and number of the counterions. The apparent molal volume ΦV2 and apparent molal compressibility ΦK2 for polymer repeat units show a sharp decrease with increase in concentration and finally attain a constant value at higher concentrations; this has been explained by the fact that in the dilute region the polymer, being extended by coulombic repulsion between similar charges situated on the side chain, enhances the formation of water clusters around it, and the free counterions are solvated, leading to a decrease to these values. The number of free counterions proportionately increases with concentration, causing a proportional decrease of the ΦV2 and ΦK2 values, until the concentration reaches a definite stage, above which the so-called condensation of ions occurs, and the number of free counterions does not increase further at higher concentrations.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1968.070120413
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  • 10
    Electronic Resource
    Electronic Resource
    Capillary extrudate puff-up of PVC and other structural melts (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 218-219 
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    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
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1968.070120120
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  • 11
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    Anomalous freezing point depression of swollen gelsPaper presented to American Chemical Society and Chemical Institute of Canada, Divisions of Rubber Chemistry, Montreal, May 1967. (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 223-247 
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    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 anomalous freezing point depression, ΔT, of benzene-swollen vulcanizates has previously been attributed to the limitation of (benzene) crystallite size by the polymer network. This study was initiated to determine the benzene crystallite size in a number of rubber and benzene systems. A special low-temperature specimen holder was designed and constructed in the Cambridge Laboratories for running diffraction patterns at temperatures near -30°C. X-ray line broadening techniques were used to study a series of filled and unfilled vulcanizates of varying crosslink density. The results indicate that crystallite size is not depressed to the degree predicted by freezing-point measurements. Benzene crystallite sizes were similar in all rubber benzene systems, regardless of degree of crosslinking or benzene fraction, although carbon black loading appears to increase crystallite size. This effect may be attributed to lesser depth of penetration of the x-rays due to greater density as carbon black loading increases. Additional studies measuring the ΔT for solutions and similar vulcanizates of NR and SBR over a wide range of rubber concentrations showed that at the same rubber in benzene fraction, crosslinking increases ΔT but the addition of carbon black reduces ΔT. An explanation for the observed phenomena is advanced.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1968.070120201
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  • 12
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    Electronic Resource
    Polymer news (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 381-382 
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    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
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1968.070120213
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  • 13
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    Diffusion during the coagulation step of wet-spinning (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 383-402 
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    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 coagulation of viscous polymer solutions by diffusional interchange with a liquid bath is the key step to fiber formation by wet-spinning. Model experiments were performed on gelled solutions of an acrylic polymer in dimethylacetamide, to determine the mass-transfer rates of solvent and nonsolvent (water) during coagulation, the rate of movement of a boundary associated with coagulation, and the final equilibrium between the coagulated phase and the bath. Each is given as a function of bath composition and temperature. The data are analyzed by means of various diffusion models, one of them giving quite good agreement. The data and the models are used in conjunction with each other for the elucidation of the mechanism of the processes involved in coagulation.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1968.070120301
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  • 14
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    The alcoholysis of cellulose (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 455-465 
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    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 alcoholysis of cellulose in solutions of sulfuric acid in ethanol and n-butanol is described; emphasis is placed on the reactions of a cellulose that is 97% disordered, as measured by an infrared-deuteration technique, but the reactions of several partially ordered celluloses are also investigated. Alcoholysis produces only very slight increases in hydrogen-bond order, and the rate of reaction is roughly related to the degree of hydrogen-bond disorder in the starting material. The reactivity of the 97% disordered cellulose is dependent upon the method of freeing the film from the non-aqueous media used in its preparation. This variable reactivity is not associated with differences in hydrogen-bond order or in the surface area of internal voids, capillaries, etc., as measured by nitrogen sorption and a nonswelling oxidation technique, but could be due to the existence of a very fine pore structure in some of the films.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120306
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  • 15
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    Elution column fractionation of branched polyethylene (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 509-525 
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    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 a systematic study of the elution column fractionation of a well characterized branched polyethylene sample it was found that one of the most important factors contributing to the efficiency was the composition selected for the p-xylene-butyl cellosolve eluting mixture. With a mixture representing the critical solvent composition at 126°C., as determined by cloud point measurements, and deposition to an amorphous phase on a fine sand support, viscosity-distribution curves were obtained which were highly reproducible and completely free of any reversal. No further improvement was gained by using an elution temperature other than 126°C. or by the substitution of tetralin or mesitylene for p-xylene. Precipitation down a temperature gradient to produce a physical separation of species provided enhanced fractionation but is of doubtful practical interest. Fractionation was readily scaled up from 2g. to 4 or 6g., merely by increasing the mixing vessel size from 500 cc. to 1000 cc. There was no loss of efficiency, and fractions with M̄w = 8 × 106, more than twentyfold higher than the sample value, were obtained despite eluted polymer concentrations exceeding 0.2%. There is evidence that many of the expected differences in the fractionation behavior of linear and branched polyethylene are erased when a solvent mixture is used which has been adjusted to the appropriate critical composition.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120310
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  • 16
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    Examination of the temperature coefficient of polystyrene. Effect of solvent, temperature, and molecular weight (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 581-591 
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    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 temperature coefficient of polystyrene was examined in three θ solvents by several different methods. Four homogeneous samples were employed, having molecular weights of 51,000, 97,200, 160,000, and 392,000. It was found that the linear expansion factor α and the temperature coefficient were dependent upon the solvent, temperature range and molecular weight of the polymer.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120316
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  • 17
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    Dynamic mechanical properties of some polymeric acid zinc salts (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1041-1051 
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    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: Mechanical properties, shear modulus, and damping of a series of polyacid divalent metal salts have been correlated with the degree of salt formation. The salts were prepared in situ by molding mixed powders of 94/6 acrylic acid-2-ethylhexyl acrylate and zinc oxide at temperatures of 200-300°C. and pressures of 5,000-10,000 psi. Zinc oxide consumption was followed by x-ray techniques. Compositions contained 25-200% of theory metal oxide as charged. Excesses, over theory, of metal oxide were shown to lead to the formation of substantial amounts of pendent half-salts which are high damping and have temperature-sensitive shear moduli. Only complete reaction as the di-salt, at 300°C. and 10,000 psi, leads to low damping products with temperature-insensitive high modulus. The modulus increase due to ionic bonding as the di-salt, over that expected from classical filler action alone, ranged from 40 to 80%, depending upon the theory chosen to calculate filler action. The pendent half-salt gives much smaller moduli increases and unreacted metal oxide appears to act as classical filler in an intertangled complex polyelectrolyte salt matrix. The modulus of the di-salt was found to be 6-7 times higher than moduli for normal organic rigid polymers.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120506
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  • 18
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    Flammability and thermal stability of isocyanate-based polymers (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1053-1074 
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    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 series of model polyurethanes and polyureas, a polyamide, and a polyimide were prepared by reacting 4,4′-diphenylmethane diisocyanate or polyisocyanates having similar polybenzyl structures with aliphatic or aromatic coreactants. Thermogravimetric analyses indicated that the flammability of the polymers was related to the formation of volatile flammable products during early stages of decomposition. Determinations of the heat evolved during differential thermal analyses and of the thermodynamic heats of combustion suggested that the extent and rate of reaction were among the important factors governing flame propagation. Flame-resistant polymers were prepared by use of structural elements which were thermally stable and nonvolatile or which formed nonflammable decomposition products.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120507
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  • 19
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    Reactions of carbon black. Part I. Nonthixotropic carbon black compositions (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1109-1118 
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    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 solution polymerization of butyl acrylate in the presence of a furnace black was found to produce a stable dispersion of carbon black which showed Newtonian flow, while the mixture prepared by mixing the same carbon black into a solution of poly(butyl acrylate) homopolymer had a large degree of thixotropy. A marked change in the viscosity of the reaction mixture was also observed at an early stage of polymerization when the initial mixture which was a moist mass with no fluidity, turned to a fluid easily stirred. The change in viscosity and the transition in flow behavior were carefully followed with a rotary cylinder type viscometer. The non-Newtonian initial mixture was found to turn to a Newtonian fluid at low conversion of the monomer. Beside the adsorption of the homopolymer onto the surface of carbon black particles, which would occur also in mechanical mixing, the change in the flow behavior was estimated to be caused by the change in the shape and the size of the dispersed carbon black particles due to the change in the condition of the surface of the particles by which growing polymer radicals, as well as initiator radicals, were captured.
    Additional Material: 9 Ill.
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    Melting points of cellulose nitrates (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 761-769 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Fresh determinations and estimations of the melting temperatures of cellulose nitrates have been found to be much lower than previously reported and to be in line with those of other cellulose derivatives, varying from 200°C. for the dinitrate to 280°C. for a sample approaching the trinitrate in composition. The heat of fusion of at least 3000 cal./unit is also similar to values of other cellulose derivatives. The paper contains some observations on the applicability of Flory's theory of the effect of diluents on the crystalline melting temperature of polymers.
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    Aromatic imide polymers for high-temperature adhesives (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 805-829 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: During the past decade the aerospace industry has sought materials for bonding stainless-steel and titanium alloys that have a high degree of thermal and oxidative stability. The Air Force Materials Laboratory has anticipated these requirements and sponsored many development programs aimed at achieving these goals. This paper describes the results of one such program devoted to development of high-temperature adhesives from aromatic imide polymers. The family of polymeric materials known as aromatic polyimides possess excellent thermal and oxidative resistance at temperatures up to 650°F. Mechanical and electrical properties of glass-fiber-reinforced laminates prepared with these polymers have been reported. This work has been extended to the development of structural adhesives that will withstand long-time exposure in air at 600°F. Stainless steel and titanium have been successfully bonded with adhesives made from aromatic imide and benzimidazole imide polymers. Bonds made with stainless steel have retained approximately 80% of their original strength at 600°F. after 1000 hr. of aging at 600°F. Adhesives made with benzimidazole imide polymers are the prepared materials for bonding titanium. Initial bond strengths of 1300 psi have been measured at 600°F. After 1000 hr. at 600°F. the bond strengths drop to 800 psi. The processing conditions for making a bond are quite moderate, except that a high temperature is required. The preparation and processing conditions associated with these adhesives are described. A large number of aromatic imide and amide-imide polymers have been prepared and adhesives formulated. By comparing the bond strengths obtained with these adhesives it is possible to deduce the effect of molecular weight and various molecular components on bond strength.
    Additional Material: 9 Ill.
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    Epoxy polymers. II. Macrostructure (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1263-1278 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: A variety of measurements indicate that thermosetting epoxy polymers contain closely packed floccules and an interstitial liquid similar to the starting materials. The fioccules are thought to be of colloidal origin and appear to be ordered with respect to each other in a three-dimensional array.
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    Fracture behavior of rubber-modified thermoplastics after aging (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1311-1320 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Experiments show that the effects of outdoor aging on rubber-modified thermoplastics can be reproduced by laminating a layer of a glassy polymer onto the surface of unaged specimens. This technique is used to study the effects of fracture temperature, specimen geometry, and polymer composition on the impact strength of aged HIPS and ABS. Aging reduces the energy of crack initiation, so that the impact strength is determined by the crack-propagation energy, which is in turn governed by the nature and concentration of the rubber and by the fracture temperature.
    Additional Material: 9 Ill.
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    Study of a heat-resistant plastic laminate from the standpoint of a mechanical-chemical equation of state (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1365-1372 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: The object of this study was to analyze the complex degradation history of a heat-resistant epoxy resin laminate using the mechanical-chemical equation of state. A further object was to determine if weight-loss measurements at elevated temperatures could be used to predict long-term rupture strength. Master rupture curves drawn by using a second-order parametric form of the equation of state largely clarified the anomalous behavior of the laminate. It was not found possible to predict the longterm mechanical properties from weight-loss data although there was evidence of some correlation.
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    Variation of refractive index of polystyrene with molecular weight: Effect on the determination of molecular weight distributions (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1373-1377 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Sensitive refractive index measurements on solutions have indicated that the narrow molecular weight polystyrene samples prepared by the Mellon Institute method exhibit a small systematic molecular weight-refractive index dependence up to 300,000 and higher. This upper limit is higher than had previously been suggested. Sensible consistency is generally assumed above a few thousand molecular weight. The effect on this molecular weight-refractive index dependence on gel permeation chromatography and light-scattering molecular weight measurements on polystyrene standards is illustrated.
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    Equation of consumption rate of free-radical vinyl polymerization. II (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1379-1384 
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    Notes: The vinyl polymerization reaction is a two-molecule reaction. However, it is more convenient to use a specially defined rate constant than to use the general constant, because a new radical is formed instantaneously in the same radical compound when one monomer combines with an existing radical in a living polymer or an initiator radical. This special rate constant is named the propagation constant and is proportional to the concentration of monomer when the polymer is formed from a unit mole concentration of the initiator radical. The specific propagation constant is related to the concentration of monomers which react in unit time and unit concentration of monomer and radical. Arnett's experiments are discussed in terms of the equation formulated. The value of Δ[M]/([M]0·t) is found not to be a reaction rate but a value of ln [M]0/[M] when [M]0 - [M] is very small. Autoacceleration of the polymerization is found with high concentrations of monomer which yield an increase in the velocity of propagation and also at low concentrations of initiator, which cause prolongation of the propagation stage. When the concentration of initiator is high, this phenomenon does not take place until enough initiator is consumed and the necessary low initiator level is reached. The time required is called the induction period. The larger the polymer molecule is, the higher the viscosity becomes.
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    Acrylate monomers from olefins via tertiary butyl hypochlorite (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1449-1458 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: A variety of olefins were readily converted to acrylate monomers by combining them with t-butyl hypochlorite and acrylic or methacrylic acid at 25-65°C. The predominate product was the vicinal acyloxychloro derivative formed by addition at the olefinic double bond. By-products were the vicinal butoxychloro derivative and the still unsaturated chlorinated olefin. The main reaction was shown to occur by an ionic mechanism. 2-Chloro-1-methyl propyl methacrylate was isolated and identified as the main product of the reaction of 2-butene, methacrylic acid, and t-butyl hypochlorite. The crude olefin products readily homopolymerized and copolymerized with other vinyl monomers by incorporating free-radical initiators.
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    Photopolymerization of hydroxypropyl acrylate and tetraethylene glycol dimethacrylate initiated by uranyl ion (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1471-1475 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Uranyl nitrate, acetate, sulfate, and dibutyl phosphate were used in solution for the photoinitiation of homopolymerization and copolymerization of hydroxypropyl acrylate and tetraethylene glycol dimethacrylate. Solvents used included water, water-ethylene glycol mixtures, and dimethylformamide. Polymer yields in excess of 90% can readily be obtained by exposing solutions containing 0.014M UO22+ to light from a tungsten bulb for 1 hr. The rigidity of the polymers varied directly, the affinity for water in-versely, with the concentration of tetraethylene glycol dimethacrylate in the monomer mixture. Poly(hydroxypropy1 acrylate) contained 52% water and poly(tetraethy1ene glycol dimethacrylate) 34% water, a t equilibrium.
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    Effects of dissolved monomers in the methyl methacrylate-α-methyl styrene copolymer system (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1480-1483 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Additional Material: 3 Ill.
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    Time-dependent capillary flow of polyethylene melt (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1505-1513 
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    Notes: The variation of output rate with extrusion time is examined experimentally for capillary flow of high density polyethylene melt. The increase in output rate is divided into two parts. One of these is due to the decrease in the amount of the material in the reservoir and is well interpreted from the consideration of the so-called reservoir effect. The other part is mainly attributed to the disentanglement or orientation of polymer chain during flow in the reservoir.
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    Cleavage behavior of bonds made with adherends capable of plastic yield (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1487-1503 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: The failure behavior of adhesive joints under cleavage stresses depends upon the thickness of the adherend. With thick, rigid adherends failure occurs by rapidly propagated adhesive rupture. Thinner adherends can exhibit plastic flexural yield, the subsequent adhesive failure then being progressive and strain-limited, and occurring only in the region of bond directly adjacent to the yielding adherend. A fairly sharp discontinuity between these two types of behavior occurs over a small range of adherend thickness T. Work to rupture can differ by more than an order of magnitude, for otherwise identical joints having T above or below the transitional range (around Tc). For T 〉 Tc the applied load P causing rupture is proportional to T1.5 while the moment arm remains constant, as predicted by Yurenka. For T 〈 Tc the turning moment during failure is proportional to T2 and is substantially independent of the nature of the adhesive. Empirically, the radius of the yielded adherend after failure is proportional to T. The manner of interaction of various adhesive mechanical properties in defining P in the two ranges and, thereby, Tc, are related to this and other empirical correlations. The initial free moment arm in the joint, L, determines the stability of peel at initiation of adhesive rupture. Reducing L leads ultimately to instability. The change of controlling factors as L → 0 is discussed.
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    Irradiation of poly(vinyl chlorides). Part II. Effect of dynamic mechanical propertiesSee footnote, p. 1543 (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1551-1556 
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    Notes: The dynamic Young moduli of purified PVC and PVC derivatives were measured at room temperature during the course of irradiation by ultraviolet light at 2537 A. wave-length. The PVC derivatives with copper salicylate, ferrocene, or copper phthalocyanine were prepared by Friedel-Crafts reaction as described in the previous paper. The loss tangent decreased monotonically with irradiation time, while the dynamic modulus appeared to pass through a maximum. More pronounced variations in both E and tan 6 were observed for the PVC derivatives than for the purified PVC, owing to enhanced crosslinking and scission in the presence of the substituents. The gel permeation chromatograms of irradiated PVC samples have been observed to skew to the left, where low molecular weight material occurs. The decrease in E after long exposure was discussed in terms of molecular polydispersity of the soluble fractions of PVC.
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    Ultraviolet irradiation of poly(vinyl chlorides). Part I. Effect of substituents on radiation parametersThe Editors have been informed by Professor Kryszewski that reference to prior work of Mn. Kwei-Ping Shen Kei and Mr. J. P. Luongo was unintentionally omitted from a communication by M. Kryssewski and M. Mucha that appeared in J. Polymer Sci. B, 5, 1093 (1967) and reported studies similar to those described here. The work of Kwei and Luongo evidently has priority since it was presented a t the ACS Meeting in Miami Reach in April 1967 and was further disseminated through Polymer Preprints, 8, 588 (1967). (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1543-1550 
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    Notes: The crosslinking and main-chain scission of PVC and its derivatives by ultraviolet radiation at 2537 A. were investigated. Examination of the relationship between gel fraction and radiation dose showed that the number of crosslinks formed in pure PVC per 100 e.v., Gc., was 0.29 and did not vary greatly from pure PVC to commercial PVC. However, the efficiency of scission was lowest (Gs = 0.06) for purified PVC, increased to 0.23-0.26 for commercial PVC, and increased further when chelates were substituted on PVC at C1 atoms. Gs for PVC with opper thalocyanine was 0.62, with copper salicylate was 1.38, and was 6.20 with ferrocene. Gc values also increased in the same order, from 0.40 to 3.10. The ratio of main-chain fractures to number of crosslinks formed (β/α) increased again in this order from 0.1 for purified PVC to 1.0 for PVC-ferrocene. For purified PVC, β/α increased after 36 hr. of ultraviolet irradiations. In the presence of copper salicylate and ferrocene, ion-radical reactions probably contribute towards the high β/α ratio. Ability of the aromatic substituents to enter chain-transfer reactions with polymeric radicals followed by coupling reactions may contribute partly towards crosslinking in PVC.
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    Characterization of branched polyethylene fractions from the elution columnThis paper is assigned No. TP432 in the series of papers approved for publication by the U.S. Army Natick Laboratories. (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1567-1587 
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    Notes: Fractions from several elution column runs on samples of up to 6 g. of a well-characterized high-pressure polyethylene were analyzed by absolute molecular weight methods and several other techniques. The Mn and Mw integral distribution curves are free from any reversal, as was the viscosity distribution curve. Fractions with Mw as high as 8 × 106 were recovered, more than 20 times higher than the original sample's Mw. The polydispersity of the fractions increases from Mw/Mn = 1.5 or less in the low molecular weight fractions to a nearly constant value of 4.5-5.0 in fractions above 60% cumulative sample weight. Nonetheless, refractionation on the elution column shows that the fractions are narrowly distributed in terms of solubility, while GPC analysis reveals that the fractions have an extremely narrow size distribution. It is concluded from the combined results that long-chain branching plays an important role in determining the equilibrium solubility and, further, that long-chain branching increases the polymer solubility. Sample calculations are provided, which illustrate the effect of fraction polydispersity on calculated original sample molecular weights and the fit of the fractionation results to several model distribution functions.
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    The solubility parameter of polypropylene (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1621-1624 
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    Notes: Solubility parameter values for polypropylene as reported in the literature cover a rather broad span, ranging from 7.9 to 9.4 (cal./cm.3)1/2. This communication suggests the approximate value 8.2. This value is based on the swelling and dissolution characteristics of polypropylene films in various organic liquids. A calculated value of 8.1, obtained by Small's method, compares well with the experimentally determined value.
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    Cerium-initiated grafting of acrylonitrile onto cellulosic materials (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1625-1647 
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    Notes: Grafting of acrylonitrile onto native cotton, swollen cotton, viscose, ramie, and hydrocellulose was studied with tetravalent cerium as initiator. The effect of temperature on the graft yields is examined. With ceric ammonium nitrate the grafting yields are found to be higher at 20 and 40 than at 60°C. Ceric ammonium sulfate, on the other hand, produces more grafting at 60 than at 20 and 40°C. The consumption of ceric ions is less, whereas the per cent graft yields are higher for the swollen cottons and viscose than for native cotton. Graft yields are shown to be related to substrate accessibility if the grafting reaction is carried out under conditions that suppress homopolymerization. Oxidation of these celluloses with CeIV has also been studied. It is found that more CeIV is consumed during grafting than during oxidation of cellulose under identical reaction conditions. Excess CeIV consumed in the grafting reaction has been shown to be directly related to extent of homopolymerization, which accompanies grafting. Some data on the storage stability of the free-radical activity produced by oxidation of cellulose with CeIV are also reported. It is observed that the cerium-oxidized samples can initiate graft poly merization even after 4-5 hr. if stored in nitrogen.
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    Studies of the fractionation of polyoxymethylene (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1661-1669 
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    Notes: The precipitation of polyoxymethylene in p-chlorophenol solution and the molecular weight fractionation of the polymer by mechanical agitation were investigated. The agitation of the solution was carried out in a glass vessel with a stirrer, usually at 60°C. After agitation for several minutes a fibrous polymer precipitated. High molecular weight polymer precipitated around the stirrer in an early stage, and therefore the method might be applied to the fractionation of polyoxymethylene. The method was applied to the fractionation of polyoxymethylene prepared in a solid-state and in a solution polymerization of trioxane, catalyzed by BF3.OEt2. It was found that the polymer from the solid state contained a small amount of extremely high molecular weight fraction, and that obtained from the solution had a relatively narrow distribution of molecular weight.
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    The polymerization and copolymerization of nitroalkyl acrylates and nitroalkyl methacrylates (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1683-1695 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Nitroalkyl acrylates and methacrylates involving some new compounds were prepared. The homopolymerization of these monomers in toluene and their copolymerization with styrene in acetone were carried out with azobisisobutyronitrile as initiator. The rate of polymerization of the nitroalkyl acrylates showed a correlation with the number of nitro groups situated on the ester side chain. The apparent activation energies of the polymerization were found to be 22.0-27.5 kcal./mole for the nitroalkyl acrylates and about 11.5-13.0 kcal./mole for the nitroalkyl methacrylates. From the reactivity ratios and Q-e values of the copolymerization the following information was obtained. The copolymerization behavior of nitroalkyl acrylates and methacrylates showed an alternating tendency, and these monomers belong to the conjugative monomer groups. On the reactivities of these monomers, the polarity of vinyl group was affected a little by nitro group of ester bond side, and the resonance affected little. These monomers were crosslinked with 2-methyl-2-nitro-1,3-propylene diacrylate. Some of the polymers showed marked improvement in the physical properties of elastomers.
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    Chlorination of polyestersPaper presented at the 154th National Meeting of the American Chemical Society, Chicago, Illinois, September 10-15, 1967. (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1713-1733 
    Details
    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: By photochemical chlorination chlorine was substituted on the gem-dimethyl groups of the polyterephthalate and polycarbonate of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, the polyterephthalate of 2,2-dimethyl-1,3-propanediol, and the polycarbonate of 4,4′-isopropylidenediphenol (bisphenol A). The factors affecting polyester degradation, the efficiency of chlorination, and the degree of chlorination were investigated, and the effects of chlorine content on the solubility, flammability, density, hydrolytic stability, thermal stability, tensile properties, electrical properties, and heat-distortion temperatures of cast films were determined. The chlorinated polyesters of particular interest, because of their properties, are the polycarbonates of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and bisphenol A.
    Additional Material: 7 Tab.
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    Oxidative aging of natural rubber vulcanizates. Part III. Crosslink scission in monosulfidic networks (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 295-307 
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    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 natural rubber vulcanizate containing almost entirely monosulfidic crosslinks was oxidized in oxygen and with tert-butyl hydroperoxide. The changes in physical properties due to oxidation were followed by stress-strain measurements, and the changes in chemical structure were investigated with chemical probes, and by spectroscopic methods. The results show that when the oxidized vulcanizates are heated at 75°C., the monosulfidic crosslinks are broken, that crosslinks containing two sulfur atoms are formed, and that conjugated diene and triene structures are introduced into the main polyisoprene chains.
    Additional Material: 1 Ill.
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    Studies of the water-soluble polymers. XVI. Azo dyes of poly-N-vinylimidazole (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 325-332 
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    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: Homopolymer of 2-methyl-N-vinylimidazole and copolymer of the monomer with acrylamide were coupled with some aromatic diazonium compounds to give polymeric azo dyes. The dyestuff prepared from the homopolymer was soluble in water only when it was coupled with diazonium component containing sulfonic acid group, but the dyestuffs prepared from the copolymer were soluble. The reactivity, chemical structure, color, and dyeability of the polymeric dyes are discussed by comparing them with those of the corresponding monomeric dyes. The color fastness of the polymeric dyes was found to be in a high class; the rubbing and dry-cleaning fastness were especially excellent.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120208
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  • 42
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    Fine structure of cellophane-acrylamide graft copolymer by the ceric ion method (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 337-351 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The relationship between the grafting yield and the structure of graft copolymer is studied by measuring the branched chain lengths, the number of branches, the crystallinities, and the diffraction intensities of the (101) and (101) + (002) planes determined by x-ray diffraction, and the distribution of branched polymers, observed by interferometry. Over a relatively wide range of grafting yield the number of initiating sites is almost constant and about 1-2 per 2 moles of cellulose chain. Therefore, the increase of grafting yield seems to be due mainly to the propagation of branched polymers. Branched polymers are assumed to be formed in cellulose crystallites both on the normal (101) planes and in the amorphous regions of cellulose. It is found that branched polymers grow from the outer layer into the inner part of the film as the grafting yield increases. At more than 250% of grafting yield, however, branched polymers are uniformly formed throughout the layer of film in which the crystalline regions of cellulose are gradually destroyed. This result agrees with the dimensional change of gel film during the reaction. The temperature dependence of tensile strength and elongation and the wet strength of graft copolymer are also investigated. At higher grafting yields, such as 250%, the crystalline structure of cellulose is disturbed by the formation of branched polymer, and no improvement in waterproofness can be expected from grafting; the secondary bonding between branched polymers may be presumed to be same as those among cellulose. In addition, the fine cracking of the film in the burst state is found to appear more easily as the grafting yield increases, in which the aggregating state of cellulose is recognized to be changed by the formation of branched polymer.
    Additional Material: 14 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120210
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    Thermal conductivity measurements with the differential scanning calorimeter (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1800-1802 
    Details
    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
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120731
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  • 44
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    Some effects of ionizing radiation on a polyhydroxyether (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1807-1813 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The behavior of the polyhydroxyether derived from bisphenol A and epichlorohydrin on exposure to electron irradiation (0-500 Mrads) in vacuum has been investigated. The polymer underwent chain scission, G = 0.20 (scission per 100 e. v.), with no evidence of crosslinking. Degradation was accompanied by the loss of H2 together with smaller quantities of CO, CO2, and CH4. Spectroscopic studies are reported, and a mechanism of degradation is proposed. The tensile yield stress and fracture energy of molded specimens were also examined, and changes in these properties as functions of radiation dose and molecular weight are discussed.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120801
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    Mechanism of photostabilization of polypropylene by nickel oxime chelates (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1825-1833 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Recent work has shown that certain nickel oxime chelates act as effective light stabilizers for polypropylene. The mechanism of their protective action was examined by spectrophosphorimetry and flash photolysis. Examination of the phosphorescence from the commercial polymer shows that it is due to aldehydic carbonyl groups. From flash photolysis observations of the triplet quenching action of a range of nickel chelates it is suggested that stabilization by the oxime chelates is achieved by a mechanism of efficient energy transfer from the photoreactive carbonyl group to the chelate, where the energy is harmlessly dissipated. The efficiency of this quenching action is primarily dependent on the spatial configuration of the ligand around the central metal atom in the chelate.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120803
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    Cohesive energy density of polytetrahydrofuran (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 473-485 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Measurements have been conducted on radiation-crosslinked polytetrahydrofuran (PTHF) of stress-strain and of swelling coefficients in simple esters. For the linear polymer, measurements have been made of density and intrinsic viscosities in the esters. [η] was also determined under the θ conditions of 33.5°C. in diethyl malonate. The results have been incorporated into several (sometimes interdependent) approaches towards the evaluation of the solubility parameter δp of PTHF. The mean of the nine values obtained is 8.55 (cal./cc.)1/2, whence the cohesive energy density is 5.17 kcal./mole. Seventeen experimental values of the Flory interaction parameter χ are also reported.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120308
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    Mechanism of reinforcement in rubber-modified polystyrene systems studied by use of a miniature dart drop test (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 533-546 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: A miniature dart drop test was used in a study of the mechanism of reinforcement in impact resistant rubber-modified polystyrene. A typical SBR-polystyrene system was diluted with varying amounts of polystyrene, and thin compression moldings were made from each blend. The impact-whitened areas were observed directly under the microscope and photomicrographs are presented. The whitening is caused by scattering of light from interfacial separation of portions of many rubber particles from polystyrene and by formation of a multitude of microcracks and/or crazes, starting at the partially separated particles. The absorption of energy by this mechanism can be very large. The driving force for the initial separation appears to be the triaxial tension under which the rubber particles exist, and this results from the higher volume shrinkage rate of rubber compared to that of polystyrene. Included also are photomicrographs taken of specimens after tensile stretching, and the mechanism derived from the impact case is extended to explain the increased elongation and corresponding whitening.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120312
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    Effects of molecular weight and strain rate on the flexural properties of polycarbonate (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 557-569 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The effects of changes in molecular weight (7000 to 22,000) and strain rate (0.0001 to 4 min.-1) on the flexural properties of polycarbonate have been examined in detail with the use of speciments of different molecular weight prepared by high-energy electron irradiation. The results have been plotted as surfaces which show the dependence of both stress and strain on molecular weight and strain rate, and these surfaces have been described in terms of brittle, transitional, and ductile regions. The relationships between stress or strain and molecular weight in the brittle region have been shown to be hyperbolic. A single failure locus has been found to include all the corresponding stress and strain data obtained at the various molecular weights and strain rates. In the low strength region this locus exhibits a proportionality between stress and strain, while at high strength values, strain becomes a logarithmic function of stress. Stress-molecular weight data obtained at the various rates have been superimposed to form a single composite curve, and the corresponding crossplots of stress-log rate have been treated similarly. It is concluded from these superpositions that an equivalence exists between changes in both molecular weight and strain rate such that a tenfold change in strain rate corresponds approximately to a change of 1000 in molecular weight. Strain-strain rate data obtained at the various molecular weights have also been superimposed in a similar manner. Modulus is shown to increase slowly with decrease in molecular weight and appears to be relatively insensitive to changes in strain rate.
    Additional Material: 14 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120314
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    Relation between nylon fiber mechanical properties and dye diffusion behavior (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 627-638 
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    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 mobility of polymer chain segments is shown to play a major role in the diffusion of dyes in nylon 66. The rate of dye diffusion has been related to the time-dependent mechanical properties, such as creep and stress relaxation, which are controlled by the mobility of the chain segments. The theoretical relations derived by Fujita et al. relating the diffusion of small molecules in amorphous polymers to other properties are shown to be applicable for the dyeing of semicrystalline nylon. Data showing the effects of surface area, temperature, and the amount of dye absorbed at saturation on the dyeing rate are presented and discussed.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120403
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    Effects of thermal history on isotactic polypropylene (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1901-1919 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The effect of past thermal history on the melting behavior of isotactic polypropylene is investigated in some detail. It is shown that a series of stepwise annealing treatments at steadily increasing temperatures will raise the final melting point and will result in a double endothermic peak if the final anneal temperature is at or close to 160°C. It is also shown that a series of stepwise annealing treatments at steadily decreasing temperature will lead to multiple DSC peaks. The number of such separate peaks is equal to or greater than the number of annealing steps. Even low-temperature anneals (100-130°C) affect the melting endotherm, while high-temperature anneals have a marked effect on both the degree of crystallinity of the sample and the final melting temperature. For a 3-min anneal, the highest degree of crystallinity is produced by an anneal temperature of 155°C. The highest melting temperature (∼182°C) is produced by a 30-min, or longer, anneal at about 160°C. The implications of these results in terms of crystal thickening and perfection are discussed.
    Additional Material: 11 Ill.
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    Molding of polyacrylonitrile (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1939-1946 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: A method has been devised whereby clear, chemically resistant, compression-molded articles of polyacrylonitrile are prepared within minutes. The molding powder consists of preformed polyacrylonitrile, acrylonitrile, and initiator. The effects of process variables on the physical properties are discussed.
    Additional Material: 7 Ill.
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    Investigation of ionic copolymers by thermal volatilization analysis (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1981-1982 
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    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
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120817
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    Relationships between surface wettability and glass temperatures of high polymersPaper presented in part at the 52nd Annual Meeting of the Association of Pulp and Paper Industry, February 1967 and to the Organic Coatings and Plastics Chemistry Division, 154th American Chemical Society Meeting, Chicago, September 1967. (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 719-730 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The adhesion between a polymer and a solid substrate may be considered to be one type of complex liquid-solid interaction. Relationships between surface wettability and bulk properties of liquidlike polymers are discussed. A new and direct empirical relationship between the glass temperature (Tg) and critical surface tension of a polymer (γc) is established: \documentclass{article}\pagestyle{empty}\begin{document}$ \gamma _c^{0.86} = \left( {0.03RT_g - 1.5} \right)\left( {{{n\Phi ^2 } \mathord{\left/ {\vphantom {{n\Phi ^2 } {V_m^{0.71} }}} \right. \kern-\nulldelimiterspace} {V_m^{0.71} }}} \right) $\end{document} where n = degree of freedom, defined by Hayes, Vm = molar volume, and Φ = interaction parameter, or the ratio between reversible work of adhesion and geometrical mean of the work of cohesion. The effect of polarity and hydrogen bonding on this relationship is also discussed. The calculated γc's are much closer to the observed values than those calculated on the basis of parachor. With this new wettability relationship the wettability of polymers, especially of those forming no hydrogen bonds, can be related to thermal, rheological, mechanical, and relaxational properties.
    Additional Material: 2 Ill.
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    Novel substrates or preparing free films from paints or polymers (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1983-1984 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1968.070120818
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    Pressure-volume-temperature behavior of polyisobutylene (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1986-1991 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120820
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    Thermal transitions in reduced wool fibers (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1992-1996 
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    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
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120821
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    Physical chemistry of filled polymers. (Russian). Yu. S. Lipatov. Naukova Dumka, Kiev, 1967. 233 pp. Rubles 1.25. ($1.37) (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 1997-1998 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1968.070120823
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    Gel-water relationships in hydrophilic polymers: Thermodynamics of sorption of water vapor (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 2023-2032 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: A thermodynamic study was conducted of water vapor adsorption on four hydrophilic polymers (agar, carboxymethyl cellulose, gelatin, and maize starch) at 12 and 25°C. Monolayer coverage amounted, after correction for crystallinity, respectively, to 0.93, 1.46, 0.51, and 0.77 mol water/mol monomer. Evidence is adduced from the Bradley equation and thermodynamic data to indicate that at least during coverage with the second layer of water, the energy of adsorption is greater than that due to condensation alone. Differences in the amount of sorption and in the trend of values of ΔS̄° and ΔH̄° with the amount of sorbed water are related with differences in the strength of intermolecular association as affected by steric hindrances.
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    Molecular weight changes during polyolefin autoxidation (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 2033-2038 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Expressions were derived relating changes of intrinsic viscosity to reaction time, based on a scheme previously presented for the uncatalyzed, uninhibited thermal oxidation of polyolefins. A value of the kinetic parameter A may be obtained from these expressions by using an iterative type of procedure and employing data presented by other workers for the oxidation of atactic polybutene-1. This value of A was compared with the corresponding value obtained by the authors from rate of carbonyl formation studies in oxidation of atactic polybutene-1 by means of infrared absorption spectroscopy methods. The good agreement between the values of A obtained from the two different experimental techniques employed lends further support to the validity of the scheme used and the expressions derived therefrom.
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    Characterization of nylon 66 structure from x-ray diffraction (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 2067-2078 
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    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: A description of methods available for the determination of structural parameters in nylon 66 is given for both wide- and small-angle x-ray diffraction. The methods are applied to a series of drawn nylon 66 fibers, and the results indicate that the drawing process is one of crystal slip. It is concluded that the methods of characterization give a great deal of information about the structure along the fiber axis but that methods for examining the structure perpendicular to the fiber axis give less quantitative information and new methods are desirable.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120909
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    Physical properties of some vinyl tetrahydroabietate and vinyl maleopimarate acid anhydride copolymers (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 2079-2082 
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    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 stress-strain and torsional characteristics of some experimental copolymers of vinyl tetrahydroabietate and vinyl maleopimarate acid anhydride with vinyl chloride and vinyl acetate have been determined. Similar studies were also undertaken on peroxide-cured compositions of a vinyl chloride-vinyl tetrahydroabietate copolymer. Elastie moduli for the uncured copolymers range from 80,200 to 338,000 psi. Cured compositions of vinyl chloride-vinyl tetrahydroabietate copolymer exhibited both lower and higher moduli than that of the uncured copolymer. Some of the cured compositions appear to have an improved impact resistance over that of the uncured polymers.
    Additional Material: 3 Tab.
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    GPC data interpretation (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 2111-2116 
    Details
    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 rigorous procedure for reducing gel permeation chromatography elution data to differential molecular weight distribution curves is discussed and demonstrated by two sample calculations. The errors introduced by failure to correct the ordinates of the elution curve by means of a differential calibration curve are identified, and a simple graphical conversion procedure is illustrated.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120914
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    Permeation of ethane-butane mixtures through polyethylene (1968)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 12 (1968), S. 2083-2095 
    Details
    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: Permeation of ethane-butane mixtures a t atmospheric pressure through polyethylene was investigated in the temperature interval of 30-60°C. The integral permeation constant P̄ and the integral diffusion coefficient D̄ of both ethane and butane were satisfactorily correlated by using an exponential and also a linear function of butane concentration. This was attributed to the plasticizing of the film by butane, whose solubility constant is approximately ten times that of ethane in the temperature interval investigated. The separation factor Gi, j defined as the ratio of the permeation constant of butane to the permeation constant of ethane over the range of mixture compositions and temperatures investigated, remained nearly constant at values in the range of 2.8-3.2. The insignificant change in Gi, j is due to the proximity of the activation energies of permeation of ethane and butane (10.95 and 10.75 kcal/mol, respectively) and the similar magnitude of change in the permeation constants with increasing butane concentration. Experiments were run in which the film was initially in equilibrium with the same partial pressure of butane as in the mixture to be studied. It can be shown that the diffusion coefficient of ethane in this case is related to the following function of film position: D = D(o)(β0 + β1x)δ. The time lag of diffusion of ethane in these experiments decreased with inrreasing butane concentration.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/app.1968.070120911
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    Zur oligomerenbildung bei der thermischen polymerisation von styrolHerrn Prof. Dr. Dr. h. c. A. STEINHOFER zum 60. Geburtstag gewidmet (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 2 (1968), S. 39-50 
    Details
    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: It is shown that in thermal polymerization of styrene four dimers and six trimers are formed by parallel occurring oligomerization reactions. With increasing temperature the rate of oligomerization increases more rapidly than the rate of polymerization. The relativ yields of the different oligomers depend on temperature, too.
    Notes: Die mit der thermischen Polymerisation von Styrol einhergehende Oligomerisierung führt zu vier Dimeren und sechs Trimeren. Mit zunehmender Temperatur wird das Verhältnis von Oligomerisierung zu Polymerisation zugunsten der Oligomerisierung verschoben. Auch die Mengenanteile der Oligomeren untereinander sind von der Temperatur abhängig.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1968.050020103
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    Untersuchung über die agglomeration von polymerisatlaticesHerrn Prof. Dr. Dr. h. c. A. STEINHOFER zum 60. Geburtstag gewidmet (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 2 (1968), S. 1-25 
    Details
    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: Different polymer latices are often incompatible, even when the emulsifying agent is the same in each. If one polymer has a proportion of hydrophilic groups (type „A“ latex) and the other does not (type „S“ latex), a mixture of the two latices may coagulate within seconds of mixing. Quite small proportions of type „A“ will cause agglomeration of the particles of a type „S“ latex. If 1% of a latex prepared from ethyl acrylate and acrylic acid (95:5) is added to a poly(butylacrylate) latex, D̄w, = 800 Å, and the pH is adjusted to 8-9, the resulting latex is characterized by D̄n, = 6300 Å, D̄w, = 7300 Å; addition of any given type „S“ latex increases the average particle size still more.The mechanisms involved were studied by observing changes in particle size distribution, by the use of polymerizable dyes as markers, and by electron microscopy. The results of these investigations are : The latices are protected only in some respect by the emulsifier. The protective ionic doublelayer formed by the emulsifier around a type „S“ particle repels other particles, but not type „A“ particles.If a collision occours between particles of type „A“ und type „S“ they stick together; this process is repeated as often as a type „S“ particle hits the surface of „A“. All the type „S“ particles of the associate combine to one big particle in such a way that the „A“ particle stays at the surface and remains active for further agglomeration.
    Notes: Polymerisatdispersionen sind selbst dann, wenn sie mit demselben Emulgator hergestellt worden sind, nicht immer miteinander verträglich. Enthält das Polymerisat der einen Dispersion hydrophile Gruppen, etwa durch Mitverwendung kleiner Mengen wasserlöslicher Monomerer bei der Emulsionspolymerisation (Typ „A“), und enthält das andere keine derartigen Gruppen (Typ „S“), so koaguliert eine Mischung der beiden Dispersionen oft schon wenige Sekunden nach ihrer Herstellung. Ein Zusatz von wenigen Prozent des Typs „A“ vermag indessen eine Agglomeration der Teilchen einer Dispersion „S“ herbeizuführen. Mischt man beispielsweise eine Polybutylacrylatdispersion, deren Teilchen im Durchschnitt einen Durchmesser D̄w von 800 Å haben, mit 1 Gewichtsprozent der Dispersion eines Copolymerisates aus 95% Äthylacrylat und 5% Acrylsäure und stellt den pH-Wert auf 8-9 ein, so resultiert ein Latex mit folgenden Kenndaten: D̄n = 6300 Å; D̄w = 7300 Å. Das Wachstum der Teilchen setzt sich fort bei weiterer Zugabe einer beliebigen Dispersion des Typs „S“.An Hand von Verteilungsfunktionen der Teilchendurchmesser und mit Hilfe von Latices, die mit polymerisierbaren Farbstoffen indiziert waren, sowie unter Verwendung von elektronenmikroskopischen Aufnahmen mit spezieller Präpariertechnik wurden Vorstellungen über den Agglomerationsmechanismus entwickelt. Danach sind die Latexteilchen durch ihre Emulgatorhülle nur bedingt gegen Assoziat-(Koagulat-)bildung geschützt. Treffen Latexteilchen des Typs „S“ nur auf ihresgleichen, so bildet die durch den Emulgator aufgebaute elektrische Doppel-schicht ausreichenden Schutz gegen Koagulation. Treffen Teilchen des Typs „S“ auf solche vom Typ „A“, so erfolgt irreversible Assoziation. Jedeszufälligaufdie Ober-fläche von Teilchen „A“ auftreffende Teilchen „S“ wird festgehalten und verschmilzt mit anderen Teilchen „S“ zum Sekundärteilchen, auf dessen Oberfläche das hydrophile Teilchen „A“ „schwimmt“. Es bleibt dort praktisch unbegrenztwirksam und nimmt jederzeit neu hinzugefügte Teilchen des Typs „S“ auf.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1968.050020101
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    Oberflächenstruktur von beschichteten kunststoff-folienHerrn Professor Dr. Dr. h. c. A. STEINHOFER zum 60. Geburtstag gewidmet (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 2 (1968), S. 26-38 
    Details
    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: Plastic foils are increasingly used for packing. In order to make the foils gas- and steamproof, they are coated by machine with an adhesive layer and then with a top coat mainly of vinylidenchlorid copolymers. Some time these coated foils look spotted owing to the fact that some regions are more, others less transparent. The microscopic and the electron microscopic investigation of these foils showed that the surface, in sharply defined regions, has a small difference of level between 500 and 1000 Å, same depending on the kind of dispersion. When rolling up the foil the surface structure of the uncoated back is imprinted on the higher regions of the top coat while the lower regions of the top coat are not touched and thus remain smooth. Owing to the different scattering of the transmitted light on the structured and the smooth surface the regions are showing a different transparency. Foils without a surface structure of their own have an equal constant transparency after the coating although the top coat shows the same differences of level.Apart from this kind of structured top coating also a surface structure is to be stated which is due to slightly crystallized or harder polymer particles. This surface structure is demonstrated by means of two examples.
    Notes: Um die in steigendem Maß als Verpackungsmaterial eingesetzten Kunststoff-Folien gas- und wasserdampfdicht zu machen, werden diese maschinell mit einem haftvermittelnden Grundstrich und dann mit einem Decketrich, vorwiegend aus Vinylidenchlorid-Copolymerisaten, beschichtet. Gelegentlich haben so beschichtete Folien durch Bereiche höherer und geringerer Transparenz ein fleckiges Aussehen. Die licht- und elektronenmikroskopische Untersuchung von solchen beschichteten Folien ergab, daß die Oberfläche in scharf abgegrenzten Bereichen einen je nach Art der verwendeten Dispersion geringen Niveauunterschied zwischen 500 und 1000 Å hat. Beim Aufwickeln der Folie wird die Reliefstruktur der unbeschichteten Folienrückseite in die höherliegenden Oberflächenbereiche der Deckschicht eingeprägt, während die etwas tieferliegenden Oberflächenbereiche der Deckschicht nicht davon berührt werden und glatt bleiben. Durch die unterschiedliche Streuung des durchfallenden Lichtes an der strukturierten und der glatten Oberfläche haben die Bereiche eine verschiedene Transparenz. Folien ohne eigene Oberflächenstruktur sind nach der Beschichtung bei gleichen auftretenden Höhenunterschieden der Oberflächen der Deckschicht durchgehend gleich transparent.Außer dieser Art von Strukturierung der Deckschichtoberflächen tritt bei leichter kristallisierenden oder härteren Polymerisatteilchen auch noch eine Oberflächenstruktur in der Dimension der Polymerisatteilchen selbst auf, die an zwei Beispielen beschrieben wird.
    Additional Material: 12 Ill.
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    Ein automatisches dilatometer für versuche zur polymerisationskinetikHerrn Prof. Dr. Dr. h. c. A. STEINHOFER zum 60. Geburtstag gewidmet (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 2 (1968), S. 64-70 
    Details
    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: A dilatometer is described which does automatically the following work essential in kinetic investigations of polymerizations: Registering and plotting of the volume contraction of the sample (proportional to conversion) as a function of time, differentiation of the conversion-time curve and logarithmic plotting of the resulting rate of polymerization against time. Some examples are given to demonstrate the efficiency of the experimental set-up.
    Notes: Die bei polymerisationskinetischen Untersuchungen stets wiederkehrenden Arbeiten: Messung der Volumenkontraktion des Ansatzes (proportional dem Umsatz) und Auftragung als Funktion der Zeit, Differentiation der Umsatz-Zeit-Kurve und logarithmische Auftragung der so gefundenen Polymerisationsgeschwindigkeit gegen die Zeit werden von einem entsprechend ausgerüsteten Dilatometer auto-matisch durchgeführt. Aufbau und Wirkungsweise des Gerätes werden beschrieben und die Leistungsfähigkeit der Versuchsanordnung wird an einigen Beispielen gezeigt.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1968.050020105
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    Die anwendung von redoxharzen in der anorganischen chemieHerrn Prof. Dr. Dr. h. c. A. STEINHOFER zum 60. Geburtstag gewidmet (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 2 (1968), S. 86-98 
    Details
    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: Ag, Cu, Te and Se were precipitated from aqueous solutions by a redox resin containing the system anthraquinone/anthrahydroquinone. Ag, Cu and Te were dissolved in 1 N nitric acid. Se was dissolved in a solution of KCN. This resin was able to alter the valences of variable-valence ions (UO22+ → U4+; VO2-2 → V3+). It was possible to produce H2O2 solutions up to a concentration of 1.3 N in a continuous process with a resin made by condensation of hydroquinone and phenol with formaldehyde.
    Notes: Ein das Anthrachinon-Anthrahydrochinon-System enthaltendes Redoxharz wurde zur Abscheidung von Ag, Cu, Te und Se aus wäßriger Lösung eingesetzt. Ag, Cu und Te wurden in 1 n HNO3 und Se in KCN-Lösung gelöst. Mit diesem Harz wurden auch Ionenumladungen (UO2+2 → V4+ und VO-2 → V3+) vorgenommen. Mit einem Kondensationsharz aus Hydrochinon, Phenol und Formaldehyd konnten in einem kontinuierlichen Verfahren bis zu 1,3 n H2O2-Lösungen hergestellt werden.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1968.050020107
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    Zum mechanismus der thermischen abspaltung von chlorwasserstoff aus polyvinylchlorid. 5. Mitt.vorhergehende Mitteilungen s.1, 2, 3, 4.: Über die verteilung der polyensequenzlängen in thermisch abgebauten technischen polyvinylchloriden und in anwesenheit stabilisierend wirkender substanzenHerrn Prof. Dr. Dr. h. c. A. STEINHOFER zum 60. Geburtstag gewidmet (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 2 (1968), S. 71-85 
    Details
    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 rates of dehydrochlorination of commercial poly (vinyl chlorides) and the distribution of the lengths of the resulting polyene sequences may vary widely depending on the origin of the polymer. - In the presence of diphenyllead dichloride the rate of dehydrochlorination is increased, while the resulting discoloration is less intense compared to that of pure poly (vinyl chloride) because of a shift of the polyene sequence lengths distribution. Genuine stabilizers, on the other hand, effect retardation in dehydrochlorination as well as a shift of the sequence lengths distribution towards shorter polyene sequences. The causes for this behavior of admixed stabilizers using lead and cadmium octoate as examples as well as of internally stabilized PVC are discussed.
    Notes: Technische Polyvinylchloride verschiedener Herkunft unterscheiden sich teilweise stark in der Goschwindigkeit der thermischen Chlorwasserstoffabspaltung und in der Verteilung der dabei entstehenden Polyensequenzlängen. In Gegenwart von Diphenylbleidichlorid wird die Dehydrochlorierung von Polyvinylchlorid beschleunigt, wobei jedoch infolge Verschiebung der Polyensequenzlängenverteilung eine weniger starke Verfärbung als bei reinem Polyvinylchlorid auftritt. Dagegen bewirken echte Stabilisatoren sowohl eine Verzögerung der Chlorwasserstoffabspaltung als auch eine Verschiebung der Sequenzlängenverteilung nach kürezeren Polyensequenzen. Die Ursachen hierfür werden am Beispiel von Blei- und Cadmiumoctoat als zugemischten Stabilisatoren und für innerlich stablisiertes Polyvinylchlorid diskutiert.
    Additional Material: 10 Ill.
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    Elektrochemisch initiierte polymerisation von acrylnitrilHerrn Professor Dr. Dr. h. c. A. STEINHOFER zum 60. Geburtstag gewidmet (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 2 (1968), S. 51-63 
    Details
    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 aid of an electrochemical initiated reaction of pure acrylonitrile in the presence of 0,1-1% water and of small concentrations of quaternary ammonium salts, an oligomeric, yellow, in acetone soluble compound was obtained with a molecular weight of 1000-3000. The high current-yield - up to 100 g/Ah, this means that per electrontransfer up to two polymeric molecules were obtained -, the low molecular weight, the independence of molecular weight of current density, the insensitivity to oxygen, and experiments of copolymerization with styrene indicate that the oligomer is formed at the cathode by an anionic mechanism. The influence of electrolyte structure, of cathode material, of current density, of water concentration, of convection, and of temperature on the formation of the oligomer has been investigated. A proposal of the structure of the oligomeric acrylonitrile has been made.
    Notes: Durch eine elektrolytisch gestartete Reaktion von reinem Acrylnitril in Gegenwart von 0,1 bis 1% Wasser und in Anwesenheit geringer Mengen eines quartären Ammoniumsalzes wurde ein oligomeres, acetonlösliches, gelbgefärbtes Produkt erhalten, dessen Molgewicht zwischen 1000 und 3000 liegt. Die hohe Stromausbeute - sie erreichte 100g/Ah, d. h. es wurden pro Elektronentransfer bis zu 2 Polymermoleküle gebildet -, das niedere Molgewicht, die Unabhängigkeit des Molgewichts von der Stromdichte, die Unempfindlichkeit gegen Sauerstoff sowie Co-polymerisationsversuche mit Styrol lassen darauf schließen, daß das Oligomere an der Kathode durch einen anionischen Mechanismus entstehen muß. Der Einfluß der Art des Leitsalzes, der Kathode, der Stromdichte, der Wasserkonzentration, der Konvektion und der Temperatu auf die Oligomerenbildung wurden untersucht. Ein Strukturvorschlag wird zur Diskussion gestellt.
    Additional Material: 6 Ill.
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    Permeation von flüssigem wasser bei eingetauchten, gefüllten polymerfilmenHerrn Prof. Dr. Dr. h. c. A. STEINHOFER zum 60. Geburtstag gewidmet (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 2 (1968), S. 99-113 
    Details
    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 permeation rate of water in fully immersed, filled polymer films considerably exceeded that in films, of which one side adjoined water-saturated air or liquid water and the other dry air. This result may be explained by a preferential permeation in water-filled interspaces between the filler and the polymer matrix.In case of immersed alkyd resin films the permeation rate at first increased with rising pigment concentration and then tended to decrease at higher concentrations. On the other hand with different water concentration adjoining both sides of the film, the permeation rate steadily decreased with rising pigment concentration. There is some evidence that under these conditions a dry boundary layer exists at the downstream side in which no interspaces may be formed at the inner phase boundaries. This layer therefore acts as the main barrier against water permeation.
    Notes: Die Permeationsgeschwindigkeit von Wasser ist bei eingetauchten, gefüllten Polymerfilmen erheblich größer, als wenn auf der einen Seite wassergesättigte Luft bzw. flüssiges Wasser, auf der anderen wasserfreie Luft angrenzt. Dieses Ergebnis läßt sich durch eine bevorzugte Permeation in wassergefüllten Zwischenrämen zwischen Füllstoff und Polymermatrix erklären.Bei eingetauchten Alkydharzfilmen nahm die Permeationsgeschwindigkeit mit steigender Pigmentkonzentration zuerst deutlich zu und zeigte bei höherer Konzentration wieder eine abfallende Tendenz. Bei angrenzender unterschiedlicher Wasserkonzentration verringerte sich dagegen die Permeationsgeschwindigkeit stetig. Offenbar liegt unter diesen Versuchsbedingungen an der trockenen Ausströmseite des Films eine Grenzschicht vor, in der sich solche Zwischenräume an den inneren Phasengrenzen nicht bilden können. Diese Grenzschicht wirkt als Hauptsperre gegen die Wasserpermeation.
    Additional Material: 6 Ill.
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    Über anionische pfropfcopolymerisationen. 9. Mitt.8. Mitteilung : G. Greber, J. Tölle und W. Burchard, Makromolekulare Chem. 71 (1964) 47.. Herstellung von pfropfcopolymeren mit hilfe von makromolekularen natriumorganischen verbindungenHerrn Prof. Dr. Dr. h. c. A. STEINHOFER zum 60. Geburtstag gewidmet (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 2 (1968), S. 133-145 
    Details
    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-p-chlorostyrene or poly-p-dimethylchloromethylsilylstyrene or the copolymers of p-chlorostyrene and p-dimethylchlorosilylstyrene with styrene were metalated with the equivalent amounts of sodiumnaphthalene in tetrahydrofuran. By addition of methylmethacrylate, 2-vinylpyridine or acrylonitrile graft copolymers were obtained free from homopolymers. By termination of the „living“ end groups of the branches with functional chlorosilanes, one can introduce reactive terminal groups. Addition of another monomer instead of the functional chlorosilanes yields graft copolymers the branches of which are block copolymers.
    Notes: Poly-p-chlorstyrol und Poly-p-dimethylchlormethylsilylstyrol sowie Copolymere aus p-Chlorstyrol oder p-Dimethylchlormethylsilylstyrol und Styrol werden mit stöchiometrischen Mengen Natrium-Naphthalin quantitativ in natriumorganische Verbindungen übergeführt. Gibt man hierzu Vinylmonomere (z. B. Methylmethacrylat, 2-Vinylpyridin oder Acrylnitril), dann erhält man reine Pfropfcopolymere, die nicht durch unumgesetzte Ausgangspolymere oder Homopolymere der aufgepfropften Monomeren verunreinigt sind. Durch Abbruch der „lebenden“ Endgruppen der Seitenäste mit funktionellen Chlorsilanen können reaktive Endgruppen eingeührt werden. Fügt man anstelle funktioneller Chlorsilane ein anderes Vinylmonomeres hinzu, dann entstehen Pfropfcopolymere, deren Seitenäste aus Blockcopolymeren aufgebaut sind.
    Additional Material: 4 Ill.
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    Versuche zur darstellung von poly-2,6-dimethylphenylenäther mit suspendiertem katalysatorHerrn Prof. Dr. Dr. h.c. A. STEINHOFER zum 60. Geburtstag gewidmet (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 2 (1968), S. 114-132 
    Details
    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: Experiments to prepare poly-2,6-dimethyl-1,4-phenylenether (DMPPO) by oxydative coupling of 2,6-dimethylphenol have shown that it is also possible to get DMPPO with high molecular weights if the catalyst which is a Cu-pyridin-complex - PynCuClX (X = OH, OCH3, O1/2) - is suspended e. g. in a mixture from xylene and pyridine. Although the catalyst is so slightly soluble in such mixtures (up to 20 vol % pyridine) that the filtrate does not give polymers with dimethyl- phenol and oxygen and the catalyst can be recovered after the polycondensation, the reaction is homogeneous. In the first step of the synthesis a part of the catalyst is dissolved by a reaction with the monomer (formation of a Cu-phenolate-pyridine-complex). This complex can catalyse the polycondensation. When the monomer concentration decreases the catalyst precipitates from the solution.The kinetics of the reaction were investigated to find out the optimal conditions of preparation.The dependence of the induction periode and the maximum reaction rate on various parameters are discussed.Experiments with a series of backmix-reactors showed that the continuous preparation of the polymer with suspended catalysts is possible.When the catalyst was fixed on acid ion exchange resins, it was not possible to prepare polymers.
    Notes: Versuche zur Darstellung von Poly-2,6-dimethyl-1,4-phenylenäther (DMPPO) durch oxydative Kupplung von 2,6-Dimethylphenol zeigten, daß die Reaktion auch dann zu DMPPO mit hohen Molekulargewichten führt, wenn der als Katalysator verwendete Cu-Pyridin-Komplex Pyn CuClX (X = OH, OCH3 oder O1/2) in suspendierter Form vorliegt, z. B. in einer Mischung von Xylol und Pyridin. Obwohl der Katalysator in solchen Mischungen (bis zu 20 Vol.-% Pyridin) so wenig löslich ist, daß das Filtrat mit Dimethylphenol und O2 kein Polymeres liefert, und der Katalysatorkomplex nach der Reaktion in unveränderter Form wiedergewonnen werden kann, verläuft die Polykondensation als homogene Reaktion. Wie die Versuche zeigten, wird zu Beginn der Synthese ein Teil des Katalysators durch Reaktion mit dem Monomeren gelöst (Bildung eines Cu-Phenolat-Pyridin-Komplexes) und katalysiert die weitere Reaktion. Wenn die Monomerkonzentration immer geringer wird, scheidet sich der ursprüngliche Komplex wieder aus.Die Kinetik der Reaktion wurde zur Ermittlung der optimalen Reaktionsbedingungen untersucht. Die Abhängigkeit der Anlaufzeit und der maximalen Reaktionsgeschwindigkeit von verschiedenen Reaktionsparametern wird diskutiert.Versuche mit einer Rührkesselkaskade zeigten, daß die kontinuierliche Darstellung des Polymeren mit suspendiertem Katalysator möglich ist.Bei Fixierung des Katalysators an saure Ionenaustauscherharze wurden bislang keine Polymeren erhalten.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1968.050020109
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    Zur unverträglichkeit von polymergemischen. 1. Lichtstreuungsmessungen am system polystyrol/polymethylmethacrylat/benzolHerrn Prof. Dr. Dr. h. c. A. STEINHOFER zum 60. Geburtstag gewidmet (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 2 (1968), S. 146-156 
    Details
    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: A polystyrene (PS) with M̄w = 9,7 · 104 was investigated by means of light scattering in the isorefractive polymer/solvens-mixture polymethylmethacrylate (PMMA)/benzene. It was found, that the second osmotic virial coefficient A2 of PS was strongly dependent on the average viscosimetric molecular weight M̄v and on the concentration of PMMA, but scarcely on the temperature in the range of 20°C to 60°C. The θ-Point, where A2 is zero, was independent of the temperature within experimental error.By defining the PMMA concentration at the θ-Point as cθ, and by reducing the measured PMMA concentration c to c/cθ, an unequivocal relation was obtained between A2 and c/cθ, which is independent of molecular weight and molecular weight distribution of PMMA.PS shows a high second virial coefficient in dimer and trimer MMA as well as in non-hydrogenated and hydrogenated MMA. The investigated PS constitutes a θ-System in PMMA of a degree of polymerisation of P̄w, ∼ 17without the use of benzene.
    Notes: Ein Polystyrol (PS) mit M̄w = 97000 wurde im isorefraktiven Polymer/Lö-sungsmittelgemisch Polymethylmethacrylat (PMMA)/Benzol mittels Lichtstreuung untersucht. Es zeigte sich, daß der zweite osmotische Virialkoeffizient A2 des PS stark vom mittleren viskosimetrischen Molekulargewicht M̄v und der Konzentration des PMMA abhängt, dagegen zwischen 20°C und 60 °C innerhalb der Meßgenauigkeit kaum von der Temperatur. Der θ-Punkt, bei dem A2 gleich Null ist, erwies sich als praktisch temperaturunabhängig.Bezeichnet man die PMMA-Konzentration am θ-Punkt mit Cθ, und normiert man die vermessene PMMA-Konzentration c auf c/cθ, so erhält man eine eindeutige Beziehung zwischen A2 und c/cθ, die unabhangig vom Molekulargewicht und der Molekulargewichtsverteilung des verwendeten PMMA ist.Im hydrierten und nicht hydrierten MMA sowie im dimeren und trimeren MMA zeigt PS große positive zweite Virialkoeffizienten. Das untersuchte PS bildet in PMMA mit einem Polymerisationsgrad von P̄w ∼ 17 ohne Benzolzusatz ein θ-System.
    Additional Material: 6 Ill.
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    Zur unverträglichkeit von polymergemischen. 2. Trübungsmessungen am system polystyrol/polymethylmethacrylat/benzolHerrn Prof. Dr. J. W. BREITENBACH zum 60. Geburtstag gewidmet1. Mitt.: R. Kuhn, H.-J. Cantow und W. Burchard, Angew. Makromolekulare Chem. 2 (1968) 146. (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 2 (1968), S. 157-164 
    Details
    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 first visual points of turbidity were determined in the ternary system polystyrene/polymethylmethacrylate/benzene. Mathematical equations are given for the dependence of the turbidity points on molecular weight and concentration. It is possible to extrapolate these equations to solid polymers. If the molecular weight of one of the polymers is known, the compatibility in the solid state of the polymers can be calculated. Test measurements on films show, that the method of extrapolation is a valid approximation.
    Notes: Die ersten visuellen Trübungspunkte im ternären System Polystyrol/Polymethyl-methacrylat/Benzol wurden bestimmt. Die Molekulargewichts- und Konzentrationsabhüngigkeiten dieser Trübungspunkte wurden in mathematische Gleichungen gefaßt. Diese lassen Extrapolation auf den Festzustand der Polymeren zu. Gibt man das Molekulargewicht eines der Polymeren vor, so kann man die Verträglichkeitagrenzen der Polymeren im Festzustand berechnen. Testmessungen an Folien bestätigen die näherungsweise Anwendbarkeit der Extrapolationsmethode.
    Additional Material: 3 Ill.
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    Änderungen des fließvermögens von geschmolzenem polypropylen durch geringe zusätze von niedermolekularen organischen stoffen (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 2 (1968), S. 165-179 
    Details
    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 extreme changes in the flow properties of polypropylene melts under the influence of small amounts (less than 1 % by weight) of low-molecular organic compounds are thoroughly investigated. The flow properties of the polymer melts are envisaged as functions of the type and amount of low-molecular additive, of the shear stress at which the polymer flows out, of the temperature of the melt, and of the molecular wight of the polymer. The observed phenomena are in accord with the proposed conception of intermolecular and interstructural distribution of the organic compounds within the melt.
    Notes: Die unter dem Einfluß geringer Mengen (unter 1 Gew.-%) von niedermolekularen organischen Zusätzen auftretenden extremen Änderungen des Fließvermögens von Polypropylenschmelzen werden eingehend untersucht. Das Fließvermögen der Polymerenschmelze wird angesehen als eine Funktion der Art und Menge der niedermolekularen Zusätze, der Scherspannung, bei der das Polymere herausfließt, der Temperatur der Schmelze und des Molekulargewichts des Polymeren. Die beobachteten Erscheinungen stehen in Einklang mit der vorgeschlagenen Vorstellung von der zwischenmolekularen und zwischenstrukturellen Verteilung der organischen Substanzen in der Schmelze.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1968.050020113
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    Über den einfluß geringer mengen pulverförmiger stoffe auf das fließvermögen von polymerschmelzen (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 2 (1968), S. 180-189 
    Details
    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: Investigations of the effect of small amounts of silicagel and carbon black on the flow properties of low-pressure polyethylene as well as the effect of a titanium white on the flow properties of poly (vinyl chloride) showed that the polymer melts exhibit a maximum flow if the amount of powdery compounds is 0.2 to 0.7 % by weight. The increased flow is due to the lessened number of molecular aggregates and to the extent in which they occur in the melt as individual kinetic units. The results were as expected on the basis of the explanation given by us earlier for the viscosity changes of polymer melts under the influence of small amounts of organic compounds.
    Notes: Die Untersuchung des Einflusses geringer Mengen von Silicagel und Ruß auf das Fließvermögen von Niederdruck- Polyäthylen und von Titanweiß auf dasjenige von Polyvinylchlorid ergab, daß die Polymerschmelzen ein maximales Fließvermögen aufweisen, wenn der Anteil an pulverförmigen Stoffen 0,2 bis 0.7 Gew.-% beträgt. Für das gesteigerte Fließvermögen sind verantwortlich die verminderte Anzahl der Molekülaggregate und das Ausmaß, in dem sie in der Polymerschmelze als selbständige kinetische Einheiten auftreten. Die Ergebnisse stimmen mit denjenigen überein, die anhand der bereits früher von uns vorgeschlagenen Erklärung für die Viskositätsänderung der Polymerenschmelzen unter der Einwirkung geringer Mengen organischer Stoffe zu erwarten waren.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1968.050020114
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    Studies in a modified cadoxen solvent (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 2 (1968), S. 190-203 
    Details
    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: Ein modifiziertes Cadmium-Äthylendiamin-Lösungsmittel, Cadoxen, mit der Zusammensetzung 0.5 m Natriumhydroxid, 5% Cadmium und 28-30% Äthylendiamin löst auch Baumwolle mit hohem Polymerisationsgrad bei den in Indien üblichen Temperaturen. Die Beständigkeit von Zelluloselösungen in Cadoxen ist groß genug, um Viscositätsmessungen ohne Luftausschluß durchzuführen. Grenzviskositäten einer großen Anzahl von Zellulosen wurden bestimmt. Die Untersuchung der Abbaukinetik der Zellulose-Lösung in Cadoxen lieferte Werte für die Geschwindigkeitskonstanten in Stickstoff sowie für die Aktivierungsenergie, die im Vergleich mit der in anderen alkalischen Lösungsmitteln verhältnismäßig hoch sind. Danach ist also der Abbau in Cadoxen nicht hauptsächlich als oxidativ anzusehen.
    Notes: A cadmium ethylenediamine solvent (cadoxen) of modified composition containing 0.5 M sodium hydroxide, 5% cadmium, and 28-30 % ethylenediamine was found to dissolve high molecular cotton materials even under higher ambient temperature conditions as in India. The stability of cellulose solutions in this solvent was still high enough to enable viscosity measurements without exclusion of air. Intrinsic Viscosity values were determined for a large number of cellulosic materials. A study of the kinetics of degradation of cellulosic solutions in cadoxen gave comparatively higher rate constants in nitrogen atmosphere and a higher energy of activation as compared to other alkaline solvents indicating that degradation in cadoxen cannot be considered primarily oxidative in nature.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1968.050020115
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    Einfluß von zusatzstoffen auf die wärmestabilität von auf PVC basierenden systemen (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 3 (1968), S. 38-68 
    Details
    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 instability of systems on PVC basis may be attributed to physical and chemical phenomena. The stability of the system is basically influenced by the oxidation stability of the plasticizers. The volatility loss in plasticizer is only partially due to physical processes. During ageing, oxidation and degradation processes take place to a minor or major degree, or exclusively, depending on the structure of the plasticizer. These processes may be affected in their order of magnitude by the stabilizers and fillers present in the system.
    Notes: Die Instabilität von Systemen auf PVC-Basis kann auf physikalische und chemische Erscheinungen zurückgeführt werden. Die Stabilität des Systems wird grundsätzlich von der Oxydationsstabilität der Weichmacher beeinflußt. Der Flüchtigkeitsverlust an Weichmacher ist nur teilweise das Ergebnis physikalischer Erscheinungen. Je nach der Struktur des Weichmachers treten auch Oxydations- und Degradationsvorgänge, im kleineren, größeren oder überwiegenden Maße, während der Alterung auf, de von anwesenden Stabilisatoren und Füllstoffen in ihrer Größenordnung beeinflußt werden können.
    Additional Material: 27 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1968.050030103
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    Über das verhalten von pektin gegenüber farbadsorbern vom Typ „Wofatit EZ“ (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 3 (1968), S. 28-37 
    Details
    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 percolating aqueous apple pectin solutions on the colour adsorber „Wofatit EZ“, especially the fractions with low molecular weight are adsorbed. Contrarily to galacturonic acid as well as to high-molecular pectin these fractions cannot be regained by washing with water. The lower the weight-average molecular weight of the tested pectins, the higher is the adsorption effect. Moreover the percolates show a decreased content in substances reducing 3,5-dinitrosalicylic acid. They contain pectins of a slightly increased degree of esterification. Therefore, preparative separation of degraded fractions from high-molecular pectin preparations by means of highly porous discolouring resins seems to be possible. However, during regeneration of Wofatit EZ by alkali and acid the adsorbed pectin fractions are desorbed to a great extent.
    Notes: Bei der Perkolation von wäßrigen Apfelpektinlösungen über den Farbadsorber „Wofatit EZ“ werden vorwiegend Fraktionen von niederem Molekulargewicht adsorptiv gebunden, die sich im Gegensatz zur Galakturonsäure und zum hochmolekularen Pektin durch Waschen mit Wasser nicht zurückgewinnen lassen. Dieser Adsorptionseffekt ist um so stärker ausgeprägt, je niedriger das Gewichtsdurchschnitts-Molekulargewicht der Testpektine liegt. Die Perkolate weisen außerdem einen geringeren Gehalt an 3,5-Dinitrosalicylsäure-reduzierenden Substanzen auf, und sie enthalten Pektine mit schwach erhöhtem Veresterungsgrad. Dadurch erscheint eine präparative Abtrennung von abgebauten Fraktionen aus hochmolekularen Pektinpräparaten mit Hilfe hochporöser Entfärbungsharze möglich. Im Prozeß der Regenerierug von Wofatit EZ mittels Lauge und Säre werden die adsorptiv gebundenen Pektinfraktionen hingegen wieder weitgehend desorbiert.
    Additional Material: 2 Ill.
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    Zur kinetik der polymerisation von vinylchlorid mit modifizierten ziegler-katalysatoren (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 3 (1968), S. 69-78 
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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 polymerization of vinylchloride in methylcyclohexane with the catalyst system TiCl4-(C2H5)2Al(OC2H5)-p-dioxane has been investigated kinetically. The dependence of the rate of polymerization on the concentration of the catalyst and the monomer followed the equation VBr=[Kat]0,53[M]. The overall activation energy was 8,3 kcal/mol. The monomer reactivity ratio of the copolymerization of vinylchloride with styrene coincides with that of a radical mechanism.
    Notes: Es wurde die Polymerisation des Vinylchlorids in Methylcyclohexan mit dem Katalysatorsystem TiCl4-(C2H5)2Al(OC2H5)-Dioxan kinetisch untersucht. Die Abhängigkeit der Bruttopolymerisationsgeschwindigkeit von der Katalysator- und Monomerkonzentration folgte der Beziehung VBr=[Kat]0,53[M]. Die Gesamtaktivierungsenergie betrug 8,3 kcal/Mol. Die Parameter der Copolymerisation von Vinylchlorid mit Styrol stimmen mit denen des radikalischen Mechanismus überein.
    Additional Material: 9 Ill.
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    Schlagfestes polystyrol auf acrylesterbasis, ein beitrag zur struktur schlagfester polystyroleDie Arbeiten, über die hier zusammenfassend berichtet wird, wurden in den Jahren 1954 bis 1962 in der Badischen Anilin- & Soda-Fabrik AG, Ludwigshafen am Rhein, durchgeführt. Ein erster Bericht erschien 1960 in der „Festschrift Carl Wurster“ der Badischen Anilin- & Soda-Fabrik AG. (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 3 (1968), S. 1-27 
    Details
    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: Impact resistant polystyrene is insufficiently resistant to aging because of the olefinic nature of its butadiene polymer components. All attempts to obtain impact resistant polystyrene in the usual manner by employing saturated elastomers failed.Experiments are reported which were conducted to obtain impact resistant polystyrene on polyacrylate basis by joining the polystyrene chains with polyacrylate chains, which was achieved by incorporating into the polymeric components the necessary functional groups via copolymerization with small amounts of acrylic acid and butanediol monoacrylate, respectively. The crosslinked graft co-polymers obtained in this way become thermoplastic upon mechanical degradation and then exhibit high impact strength as well as improved resistance to aging.Because of the incompatability of the different polymer components (polystyrene and rubber) the presence of graft copolymers obtained from these components is necessary to impart a certain minimum of compatability which is apparently essential to obtain the desired impact strength. By synthesis of pure, homopolymer-free graft copolymers transparent, impact resistant polystyrene can be prepared.
    Notes: Wegen des Olefincharakters der Butadienpolymeren ist die Alterungsbeständigkeit von schlagfestem Polystyrol unbefriedigend. Alle Versuche, schlagfeste Polystyrole mit gesättigten Elastomeren auf die übliche Art herzustellen, führten nicht zum Ziel.Es wird über Versuche zur Darstellung von schlagfestem Polystyrol auf Polyacrylesterbasis durch Verbindung der Polystyrolketten mit den Polyacrylesterketten durch Carbonsäureamid- oder Esterbindungen berichtet, wobei die zur Verknüpfung der Polymerketten notwendigen funktionellen Gruppen durch Copolymerisation mit geringen Mengen von Acrylsäure einerseits und Butandiolmonoacrylat andererseits in die Polymerketten eingebaut werden. Die so erhaltenen, zunächst noch vernetzten Pfropfcopolymeren werden durch mechanischen Abbau thermoplastisch und haben dann hohe Schlag- und Kerbschlagzähigkeit sowie erheblich verbesserte Alterungsbeständigkeit.Wegen der Unverträglichkeit der verschiedenartigen Polymerkomponenten (Polystyrol und Kautschuk) ist die Anwesenheit von Pfropfcopolymeren, die aus diesen Komponenten gebildet sind, notwending, um ein für das Auftreten von Schlagzähigkeit offensichtlich erforderliches Minimum an Verträglichkeit zu vermitteln. Durch Synthese von reinen, homopolymerfreien Pfropfcopolymeren lassen sich molekular-homogene, klar transparente, schlagfeste Polystyrole herstellen.
    Additional Material: 11 Ill.
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    Beitrag zum elektronenmikroskopischen studium der morphologischen veränderungen bei der quellung makroporöser kationenaustauscher auf styrolbasis (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 3 (1968), S. 149-159 
    Details
    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 cation exchangers on styrene basis swell in 2-hydroxyethylmethacrylate, and the swollen state can be fixed by polymerization: If the mentioned monomer is used as embedding material for the preparation of ultra-thin cuttings, the structural changes which are caused in the macroporous cation exchanger by swelling can be observed with an electron microscope. In the samples with high divinylbenzene content a partial decay of the microgel agglomerates was observed, while in the region of low divinylbenzene content the formation of a macroporous structure resulted in the samples with indicated heterogenity.
    Notes: Die Kationenaustauscher auf Styrolbasis quellen in 2-Hydroxyäthylmethacrylat, und der gequollene Zustand kann durch Polymerisation fixiert werden: Wird das genannte Monomere als Einbettungsmittel zur Herstellung von Ultradünnschnitten verwendet, so können die Strukturveränderungen, die in den makroporösen Kationenaustauschern durch die Quellung bewirkt wurden, mit dem Elektronenmikroskop beobachtet werden. Bei den Proben mit höherem Divinylbenzolgehalt wurde ein teilweiser Zerfall der Mikrogel-Agglomerate beobachtet und im Gebiet niedrigerer Divinylbenzolgehalte war bei den Proben mit angedeuteter Heterogenität die Bildung einer makroporösen Struktur festzustellen.
    Additional Material: 5 Ill.
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    Kinetics of accelerated vulcanization. Sulfur vulcanization accelerated with 2-mercaptobenzothiazole and its zinc salt in presence of zinc oxide and zinc oxide and stearic acid (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 3 (1968), S. 79-121 
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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: Die mit 2-Mercaptobenzthiazol und Zinkoxid mit und ohne Stearinsäre beschleunigte Vulkanisation von Naturkautschuk und Styrol-Butadienkautschuk wurde untersucht; die Ergebnisse wurden mit den Untersuchungen verglichen, in denen anstelle des Thiazols dessen Zinksalz verwendet wurde. Für die Geschwindigkeit der Vulkanisation, die aus der Abnahme an freiem Schwefel oder aus der Vernetzung bestimmt wurde, ergab sich eine Reaktionsordnug von 1, während in Bezug auf die Beschleunigerkonzentration eine Ordnung kleiner 1 gefunden wurde.Ohne Zusatz von Stearinsaure ist das Zinksalz wesentlich weniger wirksam fur die Beschleunigung der Vulkanisation als das Thiazol und das Thiazol merklich wirksamer mit Zinkoxid als ohne. Der Zusatz von Stearinsiiure hebt nicht nur die Wirksamkeit beider Systeme auf das gleiche Niveau, sondern bewirkt auch eine Erhohung der Vulkanisationsgeschwindigkeit und des Vernetzungsgrades sowie die Vermeidung einer Reversion und fuhrt zu erheblich verbesserten mechanischen Eigenschaften des Vulkanisats. Es wurde versucht, die Ergebnisse uber die Annahme einer Komplexbildung zwischen dem Zinksalz des Thiazols und Zinkstearat zu deuten.
    Notes: Sulfur vulcanization of natural rubber (NR) and styrene-butadiene rubber (SBR) accelerated with 2-mercaptobenzothiazole and zinc oxide with or without stearic acid has been studied and the results compared with those obtained by replacing the thiazole with its zinc salt. The order of the rate of vulcanization as measured from free sulfur decrease or crosslink formation is observed to be unity with respect to time and less than one with respect to accelerator concentration. In absence of stearic acid, the zinc salt is much less efficient than the thiazole in promoting vulcanization, and the efficiency of the latter shows a noticeable improvement over what is attained in absence of zinc oxide. Addition of stearic acid not only raises the efficiency of both the systems to the same level but also leads to a faster rate of vulcanization, a much higher degree of crosslinking, avoidance of reversion, and production of vulcanizates with considerably improved mechanical properties. The formation of zinc sulfide also reveals interesting variation. Attempts have been made to interprete these results in terms of complex formation between zinc salt of thiazole and zinc stearate.
    Additional Material: 33 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1968.050030105
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    Properties of chlorinated polyvinyl chlorideShort communication presented at the International Conference “Chemical Transformation of Polymers”, June 1968, Bratislava, Czechoslovakia. (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 3 (1968), S. 141-148 
    Details
    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: Durch Chlorierung von Polyvinylchlorid in wässeriger Suspension wurde eine Reihe von Proben des chlorierten Polyvinylchlorids von verschiedenem Chlorgehalt hergestellt. Von diesen Proben wurden die Dichte, die Temperaturabhängigkeit des dynamischen Moduls G' und des Verlustfaktors tg δ, sowie einige mechanische Eigenschaften gemessen. Die Struktur des chlorierten PVC wird diskutiert und die Annahme ausgesprochen, daß das Nebenmaximum bei -10°C den Bewegungen der kurzen Kettensegmente aus Poly- 1,2-Dichloräthan entspricht. Die Zug- und Biegefestigkeit steigt linear mit dem Chlorgehalt. Die Schlagfestigkeit nimmt ab 65% Cl stark ab. Durch sein Verhalten nähert sich das chlorierte Polyvinylchlorid einem statistischen Copolymeren aus Vinylchlorid und 1,2-Dichloräthan.
    Notes: By chlorination of polyvinyl chloride in a water suspension, a number of samples of chlorinated polyvinyl chloride of varied chlorine content were prepared. The density, the temperature dependence of the dynamic modulus G' and the loss factor tg δ, as well as some mechanical properties of these samples were measured. The structure of the chlorinated PVC is discussed and the assumption expressed that the secondary maximum at - 10°C corresponds to the movements of the short chain interceptions of poly (1,2-dichloroethylene). The tensile strength and flexural strength is growing linearly with the chlorine content. The impact strength from 65% Cl on is violently decreasing. By its behaviour, chlorinated polyvinyl chloride resembles a random copolymer of vinyl chloride and 1,2-dichloroethylene.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1968.050030107
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    Verhalten metallorganischer mischkatalysatoren gegenüber sterisch gehinderten monomeren (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 3 (1968), S. 122-140 
    Details
    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 behavior of ZIEGLER-type coordination catalysts from triethyl and triisobutyl aluminium and titanium trichloride, titanium tetrachloride, vanadium trichloride, and vanadium oxytrichloride towards trimethylallylmethane, styrene, trimethylvinylmethane, and triphenylallymethane is investigated; the steric hinderance of these monomers increases in the above order.In the presence of sterically hindered monomers, all catalysts investigated, each of which contains triethyl aluminium as a component, tend to split off ethylene at temperatures as low as 40°C as the result of a displacement reaction; the displaced ethylene is either copolymerized with the monomer at hand, or it is homopoly-merized if the respective catalyst is too weak to polymerize the monomer. In the latter case, polyethylenes of different degrees of methyl branching are formed. When using triisobutyl aluminium instead of triethyl aluminium, this side reaction is avoided. Trimethylvinylmethane can only be polymerized with the most active of the mentioned catalysts and only if ethylene from the catalyst is available for copolymerization. At 150°C some of the less active catalysts effect isomerization copolymerization with ethylene to a small degree. Triphenylallylmethane cannot be polymerized even with the most active of the catalysts.The reaction product from tributylboron and titanium tetrachloride does not constitute a heterogeneous catalyst system and is incapable of polymerizing styrene stereoregularly.
    Notes: Das Verhalten metallorganischer Mischkatalysatoren aus Triäthyl- und Triisobutylaluminium und Titantrichlorid, Titantetrachlorid, Vanadiumtrichlorid und Vanadiumoxytrichlorid gegenüber Trimethylallylmethan, Styrol, Trimethylvinylmethan und Triphenylallylmethan wurde untersucht; die sterische Behinderung dieser Monomeren steigt in der angegebenen Reihenfolge.Alle untersuchten Katalysatorsysteme, deren eine Komponente Triäthylaluminium ist, neigen unabhängig von der Natur des Übergangsmetallhalogenides in Anwesenheit eines sterisch gehinderten Monomeren schon bei etwa 40°C zur Abspaltung von Äthylen infolge einer Verdrängungsreaktion; das verdrängte Äthylen wird entweder mit den zu untersuchenden Monomeren copolymerisiert oder, wennder betreffende Katalysator zur Polymerisation des Monomeren zu schwach ist, homopolymerisiert, wobei Polyäthylene mit verschiedenem Methylverzweigungsgrad entstehen. Mit Triisobutylaluminium an Stelle von Triäthylaluminium läßt sich diese Nebenreaktion vermeiden. Trimethylvinylmethan ist nur mit dem aktivsten der hier verwendeten Katalysatoren polymerisierbar und auch nur dann, wenn Äthylen aus dem Katalysator zur Copolymerisation zur Verfügung steht. Mit einigen weniger aktiven Katalysatoren erfolgt bei 150°C in geringem Umfang Isomerisierungscopolymerisation mit Äthylen. Triphenylallylmethan ist selbst mit dem aktivsten Katalysator nicht polymerisierbar.Das Reaktionsprodukt aus Tributylbor und Titantetrachlorid stellt keinen heterogenen Katalysator dar und kann Styrol nicht stereoregulär polymerisieren.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1968.050030106
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    Umsetzungen an polymeren (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 4 (1968), S. 1-25 
    Details
    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: There are different aims for studying reactions with high polymers: syntheses of new polymers or modification of properties of known polymers; elucidation of the structure of polymers or analytical problems; investigations of chemical resistance or aging; introduction of specific functional groups and the study of their reactivity; kinetics of the reactions with polymers.Selected examples of the following topics are discussed: ring closing reactions of polymers; ring opening reactions of polymers; polymers with metal organic substituents; polymers with odd electrons in the side chains; photochemical reactions of polymers.
    Notes: Umsetzungen an Polymeren können mit verschiedenen Zielen ausgeführt werden: Darstellung neuer Polymerer oder Modifizierung der Eigenschaften bekannter Polymerer; Strukturaufklärung und Analytik bei Polymeren; Untersuchung chemischer Beständigkeit und Alterungsprozesse; Einführung spezifischer funktioneller Gruppen und Untersuchung ihrer Reaktivität; Reaktionskinetik bei Polymeren.Folgende Themen werden an ausgewählten Beispielen behandelt: Ringschlußreaktionen bei Polymeren; Ringöffnungsreaktionen bei Polymeren; Polymere mit metallorganischen Seitengruppen; Polymere mit ungepaarten Elektronen in den Seitengruppen; photochemische Reaktionen mit Polymeren.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1968.050040101
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    Synthese und anwendung polymerer redoxsysteme (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 4 (1968), S. 26-64 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In dieser Übersicht werden die Synthesemöglichkeiten für Polymere, die reversible organische Redoxsysteme enthalten, beschrieben. An ausgewählten Beispielen werden ihre Eigenschaften erlätert. Zur Deutung des elektrochemischen Verhaltens werden molekulareinheitliche niedermolekulare Modellverbindungen herangezogen. Die polymeren Redoxsysteme lassen sich als unlösliche regenerierbare Reduktions- bzw. Oxydationsmittel einsetzen.This review describes various possibilities of synthesizing polymers having incorporated reversible organic redox systems. The properties of these polymers are discussed for selected examples. Low and uniform molecular weight model compounds were synthesized in order to study the electrochemical properties. The redox resins can be employed as insoluble regenerative oxidation and reduction agents.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1968.050040102
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    Zur frage der gegenseitigen durchdringung von polymerknäueln in konzentrierten lösungen (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 3 (1968), S. 182-189 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The entanglement (mutual toothing) of random coils in concentrated polymer solutions was tested by crosslinking-reaction of two polybutylacrylate-copolymers Ax and AY. AX is a copolymer of butylacrylate (BA) with the monoacrylic ester of butanediole (1-20 mole- % OH-groups) and AY is a copolymer of BA with isocyanatoethylacrylate (1-20 mole- % —N = C = O). The maximum conversion U of this reaction, which can be realized, depends on the polymer content of the solution and on the content [X] of functional groups X or Y in the copolymer chains. By extrapolation of the experimental curves U = f([X]) to [X] = 0 the extent of the entanglement for non crosslinked random coils could be determined. It was found, that the toothing-zone increases with the polymer content of the solution from 0 (at 5 g polymer in 100 g solution) to about 20 % of the total volume of the swollen coils at 30 g polymer in 100 g solution, that is only a relatively small border zone of the coils.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1968.050030110
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    Zur kenntnis der kathodisch angeregten polymerisation von acrylnitrilWähringerstr. 42, A - 1090 Wien. (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 3 (1968), S. 160-181 
    Details
    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 in water content to less than approximately 1 · 10-3 m has a marked influence on the polymerization of acrylonitrile initiated by electrolysis at the cathode, although the anionic mechanism is retained and no living polymers are formed. Polymer yields and viscosity numbers are heavily increased in comparison to systems which have been dried less extensively. A purely white polymer is formed instead of the yellow polymer otherwise obtained at the cathode. There are great variations in polymer yields and polymer viscosity numbers when different organic quaternary ammonium and phosphonium salts are applied as supporting electrolytes. This is attributed to the influence of the counter ion on the rate of propagation and termination. The addition of small amounts of water practically causes these differences to disappear, water playing the role of an efficient, and strongly retarding chain transfer agent. The mechanism of polymerization is discussed.
    Notes: Die Herabsetzung des Wassergehalts auf weniger als etwa 1 · 10-3 m hat eine tiefgreifenden Einfluß auf die durch Elektrolyse kathodisch angeregte Polymerisation von Acrylnitril, obgleich der anionische Mechanismus erhalten bleibt und keine lebenden Ketten gebildet werden. Polymerausbeuten und Viskositätszahlen der Polymeren werden gegenüber nicht exterm getrockneten Systemen stark erhöht; anstelle des sonst elektrolytisch an der Kathode erhaltenen gelben Polymeren wirdein rein weißes Polymeres gebildet. Eine Reihe verschiedener organischer quaternärer Ammonium- und Phosphoniumsalze, die als Leitsalze verwendet wurden, liefern stark unterschiedliche Polymerisationsausbeuten und Polymerviskositätszahlen. Dies wird auf den Einfluß der Gegenionen auf die Geschwindigkeit der Wachstums- und Abbruchreaktion zurückgeführt. Durch Wasserzusatz werden diese Unterschiede weitgehend zum Verschwinden gebracht; dem Wasser kommt hierei die Rolle eines Kettenüberträgers mit starker Verzögerungswirkung zu. Eine Diskussion des Polymerisationsmechanismus wird gegeben.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1968.050030109
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    Direct substitution of polyolefins (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 4 (1968), S. 81-90 
    Details
    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 Umsetzung von Äthylen-Propylen-Copolymeren mit Spendern von Carboniumionen, wie zum Beispiel Isopropylbenzol, führt in Gegenwart von sauren Katalysatoren zur Einführung von aromatischen und hydroxylischen Gruppen in das Polymerengerüst. Gasfömige Hauptprodukte sind Isobutan und Propan. Die Reaktion ist von Kettenspaltung begleitet.
    Notes: Reaction of solutions of ethylene-propylene copolymer with carbonium ion sources, such as isopropylbenzene, in the presence of acid catalysts leads to the introduction of the aromatic and hydroxylic moieties onto the copolymer backbone. Major gaseous products are isobutane and propane. Chain scission accompanies the reaction.
    Additional Material: 4 Tab.
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    URL: http://dx.doi.org/10.1002/apmc.1968.050040104
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    Über die vernetzung eines ungesättigten äthylen-propylen-terpolymer-kautschuks (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 4 (1968), S. 65-80 
    Details
    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 various aspects of the sulfur vulcanization chemistry and mechanism of „Nordel“ hydrocarbon rubber, an ethylene-propylene terpolymer, are discussed. The chemical nature of the reactions undergone by the accelerators has been found to be analogous to those observed for natural rubber and SBR. During vulcanization approximately 50% of the double bonds are saturated, and approximately one crosslink is formed for each two double bonds initially present. The type of crosslink formed has been examined and the vulcanization kinetics studied with the aid of a Monsanto rheometer.
    Notes: Der Verlauf sowie der Mechanismus der Schwefelvulkanisation von „Nordel“ Kohlenwasserstoffkautschuk, einem ungesättigten Äthylen-Propylen-Terpolymer-Kautschuk, wird von verschiedenen Standpunkten aus behandelt. Die chemischen Veränderungen der Beschleuniger während der Vulkanisation sind denen analog, die man bei Natur- und Styrol-Butadienkautschuk beobachtet. Während der Vulkanisation werden ungefähr 50% der Doppelbindungen abgesättigt, und für je zwei ursprünglich vorhandene Doppelbindungen wird eine Vernetzungsstelle gebildet. Die Art der Vernetzungsstelle wurde untersucht und die Kinetik der Vulkanisation mit Hilfe des Monsanto-Rheometers studiert.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1968.050040103
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    Abspaltungsreaktionen an hochpolymeren (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 4 (1968), S. 91-115 
    Details
    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: Elimination reactions of macromolecular compounds can be initiated by various forms of energy (such as heat and radiation) or by chemical attack. In the elimination reactions to be dealt with in this context either polymers or low-molecular reaction products with olefine structures are formed. Condensation reactions between neighboring monomer units under formation of cyclic units in the polymer chains will, however, not be considered here.The following classes of polymers are surveyed regarding their most important elimination reactions investigated to date, including the resulting structures of the polymers: Polymeric alcohols and ethers, polymeric esters, halogen-containing polymers. Furthermore, several conversions on polymers (Wittig reactions, dehydrochlorination, dehydration) are dealt with, some of which, however, are not completely clarified as yet.
    Notes: Abspaltungsreaktionen an makromolekularen Stoffen können durch physikalische Kräfte (Wärme, Strahlungsenergie) oder durch chemischen Angriff ausgelöst werden. Hierzu gehören alle Eliminierungsreaktionen, bei denen entweder Polymere oder niedermolekulare Spaltprodukte mit olefinischen Strukturen entstehen. Nicht berücksichtigt werden dagegen kondensierende Reaktionen zwischen benachbarten Grundbausteinen unter Bildung von cyclischen Einheiten in den Polymerketten.Es wird über die wichtigsten bisher untersuchten Abspaltungsreaktionen bei folgenden Klassen von makromolekularen Stoffen und über die Struktur der dabei entstehenden Polymeren berichtet: Polymere Alkohole und äther, polymere Ester, halogenhaltige Polymere. Ferner werden verschiedene, z. T. noch nicht völlig geklärte Umsetzungen an Polymeren (Wittig-Reaktionen, Enthalogenierungen, Dehydrierungen) behandelt.
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    URL: http://dx.doi.org/10.1002/apmc.1968.050040105
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    Reaktive klebstoffe (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 4 (1968), S. 116-141 
    Details
    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: Adhesives based on polychloroprene, natural rubber or polyurethanes are frequently used in practice with an addition of polyisocyanates as „reactive adhesives“ in order to improve the strength and durability of the bonds.It is investigated wether the polyisocyanate increases the cohesion of the high polymer adhesive base by a network formed by a polyisocyanate-humidity reaction product, i. e. mere mechanically or by real chemical bonds.It is stated that chemical bonds are formed. The increase of cohesion is strongly influenced by the type of polyisocyanate added. The adhesion to rubber materials is also promoted by chemical reactions at the interface.
    Notes: Klebstoffe aus Polychloropren, Naturkautschuk oder Polyurethan werden in der Praxis vielfach mit Polyisocyanaten als „reaktive Klebstoffe“ angewandt, um Klebungen höherer Festigkeit und Widerstandsfähigkeit zu erhalten. Es wurde untersucht, ob durch das Polyisocyanat die Kohäsion des hochpolymeren Klebstoff-Bindemittels durch eine Gerüstbildung der mit Feuchtigkeit reagierenden Polyisocyanate rein mechanisch erhöht wird oder durch eine chemische Bindung mit den Hochpolymeren.Der Nachweis einer chemischen Bindung wurde erbracht. Die Kohäsionserhöhung wird sehr stark von der Art des Polyisocyanats beeinflußt.Auch die Adhäsion dieses Klebstoffes an Gummiwerkstoffen wird durch chemische Wechselwirkungen in der Grenzfläche erhöht.
    Additional Material: 11 Ill.
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    Reaktive polyacrylate für den oberflächenschutz (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 4 (1968), S. 142-167 
    Details
    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: Acrylic polymers find increasing application as binders for protective coatings. The monomeric acrylic compounds easily copolymerize with each other and with many other monomers, thus permitting the synthesis of polymeric substances with very different properties. By introduction of suitable functional groups into the copolymers the synthesis of reactive polymers is possible. These products are well soluble and easily processable and can be crosslinked by the application of heat to give products of excellent chemical and mechanical resistance. The reactive groups may be introduced either by use of reactive monomers or by reaction with a suitable prepolymer. Especially acrylic polymers with hydroxyl-, amide-, N-methylolamide-, epoxy-, and active CH-groups in the molecule have received considerable attention for protective coatings. The most important types of these polymers and their crosslinking reactions are discussed with special consideration of polymers with methylolamide functions. Finally examples of important fields of application for reactive acrylic coatings are given.
    Notes: Unter den synthetischen Hochpolymeren, die als Bindemittel für Beschichtungsmassen verwendet werden, gewinnen die Polyacrylate steigende Bedeutung. Die monomeren Acrylverbindungen sind gut miteinander und mit wichtigen anderen Monomeren copolymerisierbar und erlauben die Herstellung einer Palette von Produkten mit recht verschiedenen Eigenschaften.Durch Einbau geeigneter funktioneller Gruppen in die Copolymerisate kann man reaktive Polymerisate herstellen, die gut löslich und gut verarbeitbar sind, die abernach der Applikation z. B. durch Wärmeeinwirkung zu unlöslichen, chemikalienfesten und mechanisch stabilen Produkten vernetzt werden können. Die reaktiven Gruppen können entweder durch Verwendung von geeigneten Comonomeren oder durch Umsetzung an einem geeigneten Vorpolymerisat eingeführt werden. Für den Oberflächenschutz haben besonders Polymerisate, die Hydroxyl-, Amid-, Methylolamid-, Epoxid-, Carboxyl- oder aktivierte CH-Gruppen im Molekül enthalten, Bedeutung erlangt. Die wichtigsten dieser Produkte und ihre Vernetzungsreaktionen werden diskutiert. Insbesondere wird anhand von Modell- und Vergleichsversuchen auf die Methylolamidfunktionen enthaltenden Polymerisate eingegangen. Zum Schluß werden die wichtigsten Einsatzgebiete für reaktive Polyacrylatlacke kurz diskutiert.
    Additional Material: 11 Ill.
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    Polyacetale mit reaktiven gruppen (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 4 (1968), S. 168-184 
    Details
    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 introduction of reactive groups into polyacetals is possible via three different routes: 1Reaction of the OH-endgroups with suitable reagents,2Chain transfer during polymerization,3Copolymerization of trioxane or formaldehyde with functional comonomers.The copolymerization of trioxane with monomers containing additional functional groups is described in detail. Polyacetals containing aldehyde-, ester-, carboxylate-, nitro- and aminefunctions are easily prepared when using glycidoxyphenyl- compounds as comonomers. These reactive polyacetals can be further modified by subsequent chemical reactions. Finally, there are indicated some applicational aspects of polyacetals with reactive groups like improvement of adhesion and clue properties, incorporation of stabilizers or dyestuffs and modification of flow properties.
    Notes: Zur Einführung reaktiver Gruppen in Polyacetale kommen im wesentlichen drei Wege in Frage: 1Umsetzung der OH-Endgruppen mit geeigneten Reagenzien,2Einbau durch eine Übertragungsreaktion während der Polymerisation,3Copolymerisation von Trioxan oder von Formaldehyd mit Monomeren mit funktionellen Gruppen.Die Copolymerisation von Trioxan mit Monomeren, die eine zusätzliche reaktive Gruppe besitzen, wird ausführlich besprochen; hier haben sich substituierte Phenylglycidyläther als Comonomere gut bewährt. Auf diese Weise lassen sich Polyacetale mit freien Aldehyd-, Ester-, Carboxylat-, Nitro- und Aminogruppen herstellen. Anhand ausgewählter Beispiele werden Möglichkeiten aufgezeigt, diese Reaktiv-Polyacetale durch nachträgliche chemische Umsetzungen weiter zu modifizieren. Schließlich werden noch einige anwendungstechnisch interessante Aspekte der Polyacetale mit reaktiven Gruppen behandelt, wie die Verbesserung der Haftfähigkeit und der Verklebbarkeit, der Einbau von Stabilisatoren und von Farbstoffen sowie die Beeinflussung der Fließfähigkeit.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1968.050040108
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    Ionenaustauscher als beispiel für reaktionsfähige hochpolymere (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 4 (1968), S. 185-211 
    Details
    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 resin-based ion exchange materials used nowadays are insoluble polyelectrolytes. Synthetic processes allow a large variety of modifications of the ion exchange substance itself as well as of the functional groups. It is thus possible to offer tailormade special resins for many different uses. Beside resins which are resistant at elevated temperatures or in oxidizing media, the introduction of the macroporous matrix has proved to be a special success. It leads to more resistant products and makes it possible to use appropriately designed ion exchange resins for general adsorption purposes as well, similar to activated carbon.The range of application of ion exchange resins is rapidly increasing as new resins are being offered and improved process engineering is being developed. The most important fields are water conditioning, detoxification of waste waters, recovery of valuable inorganic and organic substances, as well as use in chemical processes. These versatile products will in future be used in these fields to a greater extent and new applications will certainly be found.
    Notes: Die heute verwendeten Ionenaustauscher auf Kunstharzbasis sind unlösliche Polyelektrolyte. Durch geeignete Syntheseverfahren hat man gelernt, eine große Zahl von Abwandlungen der Grundsubstanz und der austauschaktiven Gruppen herzustellen. Damit ist man in der Lage, für viele Anwendungsgebiete Spezialharze anzubieten, welche auf die ihnen zugedachte Arbeit zugeschnitten sind. Neben Harzen, die beständig sind bei erhöhter Temperatur oder in oxydierenden Medien, hat sich die Einführung der makroporösen Matrix besonders bewährt. Sie führt zu resistenteren Produkten und ermöglicht es, entsprechend aufgebaute Ionenaustauschharze auch zur Allgemeinadsorption ähnlich wie Aktivkohle einzusetzen.Der Anwendungsbereich für Ionenaustauscher vergrößert sich rasch mit dem Angebot neuer Harze und der Entwicklung einer verbesserten Verfahrenstechnik. Die wichtigsten Gebiete sind die Wasseraufbereitung, die Entgiftung von Abwasser, die Gewinnung von wertvollen Stoffen aus dem anorganischen und organischen Bereich sowie der Einsatz in chemischen Prozessen. Für die Zukunft ist mit vermehrter Anwendung auf diesen Gebieten und mit dem Auffinden neuer Nutzungsmöglichkeiten für diese vielseitigen Produkte zu rechnen.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1968.050040109
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  • 98
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    Gelchromatographie, die möglichkeiten verschiedener trennmaterialienHerrn Prof. Dr. J. W. Breitenbach zum 60. Geburtstag gewidmet (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 4 (1968), S. 268-278 
    Details
    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: Organic and inorganic materials are applicable to gel chromatography. In this paper the widely used highly crosslinked Styragel serves as a standard to test the separating power of porous glasses, silica, and aluminum compounds.Very high molecular polymers require gels with large pore sizes as separating materials. For this purpose inorganic gels are especially suited because of their strong mechanical stability.Polymers of low molecular weight can be separated by organic and inorganic gels with roughly the same efficiency. For these polymers one can select the gel material according to its chemical inertness. Then a reasonably pure physical separation process is possible.
    Notes: Zur Gelchromatographie lassen sich organische und anorganische Trennmaterialien verwenden. Das repräsentative hochvernetzte Styragel wird benutzt, um vergleichende Untersuchungen mit porösen und Stoffen auf der Basis von Silicium und Aluminium auszuführen.Für die Trennung sehr hochmolekularer Substanzen, die Gele großer Porenweite erfordern, sind die anorganischen Gele wegen ihrer hohen mechanischen Stabilität besonders geeignet.Für Substanzen mit niedrigem Molekulargewicht sind organische und anorganische Trennstoffe häfig etwa gleich gut verwendbar, so daß man den Geltyp wählen kann, der möglichst nur hydrodynamische und keine chemische Wechselwirkung mit der Substanz zeigt.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1968.050040112
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  • 99
    Electronic Resource
    Electronic Resource
    The chemical modification of polymers for analytical purposes (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 4 (1968), S. 279-309 
    Details
    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: Derivate von Polymeren, die durch quantitative Umwandlung entstanden sind, können in gewissen Fällen dazu benutzt werden, die Eigenschaften des Ausgangspolymeren zu untersuchen. Das Polymerderivat kann auch als Bezugssubstanz bei der Entwicklung von Methoden zur Charakterisierung von Polymeren dienen. In dieser Arbeit wird über die Anwendung derartiger Methoden für Untersuchungen über die Verzweigung und Stereogularität von Homopolymeren und die Sequenzverteilung von Copolymeren berichtet. Es werden verschiedene Reaktionen beschrieben, darunter Hydrolyse, Ammonolyse, Alkoholyse, Veresterung, Umesterung und die Hydrierung von Polyhalogenkohlenwasserstoffen und ungesättigten Polykohlenwasserstoffen. Weiterhin wird ein Überblick über neuere Ringschlußreaktionen an Polymeren gegeben. Derartige Reaktionen können für Untersuchungen der Sequenzverteilung von Copolymeren von Wichtigkeit sein.
    Notes: When it is possible to convert one polymer quantitatively into another, the derived polymer can sometimes be studied to obtain information about the original polymer. In other instances, the derived polymer can serve as a reference material for use in the development of polymer characterization procedures. This paper reviews the use of such techniques in studies on branching and stereoregularity in homopolymers and in studies on sequence distribution in copolymers. The reactions covered include hydrolysis, ammonolysis, alcoholysis, esterification, transesterification and the hydrogenation of polyhalocarbons and unsaturated polyhydrocarbons. In addition, recent studies on cyclization reactions in polymers are surveyed. Such studies can provide information about sequence distribution in copolymers.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1968.050040113
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  • 100
    Electronic Resource
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    Oxydation mehrfach ungesättigter polymerer mit organischen hydroperoxiden (1968)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 4 (1968), S. 255-267 
    Details
    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: A series of results is known about oxidation of low molecular weight olefins with alkyl hydroperoxides in the presence of derivates of transition metals. Depending on the catalyst the reaction products mainly have epoxide or alkenyl alkyl peroxide groups.The reactions of polymers with a high degree of unsaturation - mainly performed with tertiary butyl hydroperoxide - gave on catalysis with molybdenum compounds almost exclusively polymers containing epoxide groups. With vanadium derivates polymers having mainly epoxide groups were obtained. Application of derivates of manganese, cobalt, and copper resulted in a selective formation of polyfunctional peroxides. The reaction is inhibited by water. No cross-linking was observed when the reaction was performed in solution.Explanations are given for the formation of epoxides or peroxides in the presence of transition metal compounds as catalysts. Reaction mechanisms for the epoxidation or peroxidation are proposed.On epoxidation of liquid polybutadienes with tertiary butyl hydroperoxide the presence of molybdenyl bisacetylacetonate curable liquid epoxidized poly-butadienes are obtained. In the presence of acetylacetonates of copper, manganese, and cobalt polyfunctional polybutadienyl tertiary butyl peroxides with a “critical temperature” of about 120°C are obtained which are useful for the initiation the polymerization of styrene.
    Notes: Über die Oxydation von niedermolekularen Olefinen mit organischen Hydroperoxiden in Gegenwart von Verbindungen der Übergangsmetalle als Katalysatoren ist eine Reihe von Einzelergebnissen bekannt. Je nach der Art des Katalysators erhält man als Reaktionsprodukte überwiegend Epoxide oder Alkenyl-alkylperoxide.Die Reaktion an mehrfach ungesättigten Polymeren, die bevorzugt mit tert.-Butylhydroperoxid durchgeführt wurde, ergab bei der Katalyse mit Molybdänverbindungen nahezu ausschließlich und mit Vanadiumverbindungen vornehmlich Epoxidgruppen enthaltende Polymere. Mangan-, Kobalt- und Kupferverbindungen bedingten die selektive Bildung polyfunktioneller Peroxide. Durch Anwesenheit von Wasser wird die Reaktion inhibiert. Vernetzungen wurden bei der in Benzol als Lösungsmittel durchgeführten Umsetzung nicht beobachtet.Für die Bildung von Epoxiden einerseits und Peroxiden andererseits bei Verwendung verschiedener Nebengruppenmetalle als Katalysatoren wird eine Begründung gegeben. Reaktionsmechanismen für die Epoxydierung und Peroxydierung werden vorgeschlagen.Durch Epoxydierung von flüssigen Polybutadienen mit tert.-Butylhydroperoxid in Gegenwart von Molybdänyl-acetylacetonat erhält man härtbare, flüssige Polybutadienepoxide. In Gegenwart von Kupfer-, Mangan- und Kobaltacetylacetonaten werden polyfunktionelle Polybutadienyl-tert. -butylperoxide gebildet, die eine „Anspringtemperatur“ von etwa 120°C besitzen und zur Initiierung der Polymerisation von Styrol verwendet werden können.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1968.050040111
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