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  • Polymer and Materials Science  (19)
  • 1960-1964  (19)
  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. S51 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 1731-1741 
    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: Morphological changes effected in the two-phase high impact polystyrene system by several methods of securing high surface gloss of extruded sheet were studied microscopically. In the glazing process changes occur in refractive index of the copolymer particles and in the matrix. Excessive glazing may result in oxidative damage. The effects of temperature and oxidation and temperature alone on the copolymer particles have been investigated.
    Additional Material: 11 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 50 (1961), S. 227-243 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The application of the sand columm extraction, fractional coacervation, and coacervate extraction methods to the molecular weight fractionation of polypropylene is described. Extremely reproducible results are given by the sand column method, and ten fractions taken by this method are adequate for characterization of the usual polypropylene distribution. The variation between the molecular weight distributions derived from six fractionations of a test polypropylene by the three methods was small and indicates that fraction polydispersity probably contributes negligibly to any deviation of the experimental distributions from the true distribution. Polypropylenes made with aluminum triethyl-transition metal trichloride catalysts contain relatively large amounts of low molecular weight polymer and have broad distributions similar to that of low-pressure polyethylene. All such polypropylene samples had distributions which were described well by a logarithmic normal equation with a constant standard deviation. The distribution was not altered when the aluminum triethyl in the catalysts was replaced by aluminum triisobutyl. Catalysts containing vanadium as the transition metal, however, produced polypropylenes with distributions distinctively different from those made with titanium trichloride.
    Additional Material: 8 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 56 (1962), S. 485-499 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular weight distributions of polypropylene samples subjected to various degrees of thermal degradation were experimentally determined and compared with those expected theoretically for random scission of the polymer chains. The comparison demonstrated that the chain breakage is predominately random and also indicates that current methods of determining molecular weight distributions are adequate for use in evaluating hypothesized degradation mechanisms. In terms of the free radical depolymerization theory, intermolecular transfer of the radical is the dominant process. A curve relating the degree of degradation to the intrinsic viscosity was obtained from calculations based upon a random degradation. With this curve, intrinsic viscosities measured as a function of degradation time could be used to obtain the time dependence of the degree of degradation. The observed degradation rates could not be described by a simple process in which the rate of bond rupture was proportional to the number of bonds present. Neither a similar process involving two bond types nor a dependence of the free radical diffusion rate upon the degree of degradation was by itself a satisfactory basis for interpreting the kinetics. The activation energy estimated for the polypropylene degradation at 250-300°C. was not significantly different from that determined by volatilization measurements at higher temperatures.
    Additional Material: 7 Ill.
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  • 5
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 66 (1963), S. 196-204 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 2,4-Toluoldiisocyanat kann ein Dimeres (TDID) und cin Trimeres (TDIT) bilden. Bei der Polymerisation in Substanz im Temperaturbereich von 40 bis 100°C gilt für die Anfangsgeschwindigkeiten Bei jeder Temperatur blieb die Trimerisierungsgeschwindigkeit im untersuchten Umsetzungsbereich im großen und ganzen konstant, während die Dimerisierungsgeschwindigkeit allmahlich auf Null absank. Die Gleichgewichtskonzentrationen von TDID bei 78 und 100°C waren 8,5 bzw. 7,1%. Unter den Versuchsbedingungen kamen 1. nur die sich von der Isocyanatgruppe in 4-Stellung ergebenden Oligomere bei der Di- und Trimerisation in Betracht, und 2. war die Trimerisierungs- von der Dimerisierungsreaktion unabhängig. Nimmt man für die Kinetik der Dimerisation den Vorgang an, so erhält man für Nach den Ergebnissen spielt die Di- und Trimerisierung von 2,4-TDI bei der Herstellung der Polyurethane keine groß Rolle. Indessen konnen sich bei langer Lagerung und erhohter Temperatur merkbare Mengen an TDID und TDIT bilden, so daß es wichtig ist, die Reinheit des Isocyanats unmittelbar vor Gebrauch zu bestimmen.
    Notes: 2,4 tolylene di-isocyanate can form a dimer (TDID) and a trimer (TDIT). For bulk polymerisation at temperatures in the range 40°C. to 100°C. the initial rates of these processes are given by the expressions, At each temperature the rate of trimerisation remained essentially constant over the conversion range examined, but the rate of dimerisation decreased gradually to zero. The equilibrium concentrations of TDID at 78°C. and 100°C. were 8.5 per cent and 7.1 per cent respectively.Experimental evidence indicated that under the conditions examined (i) only oligomers resulting from interaction between isocyanate groups in the 4-position were important in dimerisation and trimerisation, and (ii) the trimerisation process was independent of the dimerisation process.Assuming the kinetics of dimerisation to be represented by This investigation shows that the dimerisation and trimerisation of 2,4-TDI are not important competing processes in the cure of a polyurethane. However as appreciable amounts of TDID and TDIT can be formed as a result of prolonged storage at elevated temperatures it is important that the purity of the isocyanate is determined immediately before use.
    Additional Material: 3 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 77 (1964), S. 185-190 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Anfangsgeschwindigkeit der durch Eisenacetylacetonat (FeAA) katalysierten Dimerisierung und Trimerisierung von 2,4-Tolylendiisocyanat wird durch folgende Gleichungen wiedergegeben: \documentclass{article}\pagestyle{empty}\begin{document}$$\frac{{\rm {d[TDID]}}} {{\rm {dt}}} = 3.8 \cdot 10^8 \rm{ }[\rm {FeAA] exp }\frac{{\rm { - 19,500}}} {{\rm {RT}}}\rm {moles ml}^{\rm { - 1}} \sec ^{ - 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\frac{{\rm {d[TDIT]}}} {{\rm {dt}}} = 1.23 \cdot 10^3 \rm{ }[\rm {FeAA] exp }\frac{{\rm{ - 10,500}}} {{\rm {RT}}}\rm {moles ml}^{\rm { - 1}} \sec ^{ - 1} $$\end{document}Verglichen mit der durch FeAA katalysierten Urethanbildung sind die Dimerisierung und Trimerisierung unwesentliche Reaktionen. Zu dem gleichen Ergebnis waren wir bei der Untersuchung der unkatalysierten Polyurethanbildung gelangt.Es ist sehr wahrscheinlich, daß bei den verwendeten Temperaturen (25 bis 78°C) als Folge des thermischen Abbaus von FeAA der katalytische Effekt reduziert wird. Der Stabilität von FeAA kommt daher eine wichtige Rolle bei der Polyurethanbildung zu.
    Notes: The initial rates of dimerisation and trimerisation of 2,4-tolylene diisocyanate (TDI), catalysed by ferric acetyl acetonate (FeAA), are given by the expressions \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{\rm {d[TDID]}}} {{\rm {dt}}} = 3.8 \cdot 10^8 \rm{ }[\rm {FeAA] exp }\frac{{\rm { - 19,500}}} {{\rm {RT}}}\rm {moles ml}^{\rm { - 1}} \sec ^{ - 1} $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$\frac{{\rm {d[TDIT]}}} {{\rm {dt}}} = 1.23 \cdot 10^3 \rm{ }[\rm {FeAA] exp }\frac{{\rm{ - 10,500}}} {{\rm {RT}}}\rm {moles ml}^{\rm { - 1}} \sec ^{ - 1} $$\end{document} Compared to the FeAA catalysed urethane reaction the processes of dimerisation and trimerisation are unimportant, a conclusion similar to that arrived at for the uncatalysed cure of a polyurethane.There is strong evidence that at the temperatures employed (25 to 78°C.), the catalytic effect is reduced as a result of thermal decomposition of FeAA. It would appear therefore that stability of FeAA is likely to be an important factor in the cure of a polyurethane.
    Additional Material: 4 Ill.
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  • 8
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Messungen der Viskositätszahl eines thermisch im Vakuum abgebauten Polycarbonates zeigen, daß das Polymere eine statistische Kettenspaltung erleidet, im Einklang mit der Gleichung \documentclass{article}\pagestyle{empty}\begin{document}$$\log [\eta ] = - \alpha \log ({\rm t} + {\rm t}_0 ) + {\rm C}$$\end{document} Der Wert für α aus den in Methylenchlorid erhaltenen Viskositätswerten stimmt mit dem veröffentlichten, auf osmotischem Wege bestimmten Wert von 0,83 als Exponent der Kuhn-Houwink-Gleichung überein.Die Analyse der Molekulargewichtsveränderungen im Verlauf des Abbaues bei verschiedenen Temperaturen zeigt, daß der Prozeß der Kettenspaltung der ersten Ordnung gehorcht und durch die Geschwindigkeitsgleichung k = 4,8·107·e-39500/RT ausgedrückt werden kann.
    Notes: Measurements of the intrinsic viscosity of a polycarbonate degraded thermally in vacuum show that the polymer undergoes random chain scission according to the equation \documentclass{article}\pagestyle{empty}\begin{document}$$\log [\eta ] = - \alpha \log ({\rm t} + {\rm t}_0 ) + {\rm C}$$\end{document} The viscosity results obtained in methylene chloride yield a value of α, the exponent of the Kuhn-Houwink equation in agreement with the published value (0.83) obtained by osmometry.Analysis of the molecular weight changes occurring during degradation at various temperatures shows that the chain scission process obeys first order kinetics and can be expressed by the rate equation k = 4.8·107·e-39,500/RT.
    Additional Material: 4 Ill.
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  • 9
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Monomer reactivity ratios for the copolymerization of styrene (M1)with p-methylstyrene (M2)using labeled styrene and an ionization chamber assay technique gave values of r1 = 0.83 and r2 = 0.96. These values are believed to be more reliable than those obtained by direct counting techniques (r1 = 0.99 and 0.94). There is a possibly significant difference between these values and those for this monomer pair in the aluminumtrialkyl-titanium chloride-initiated copolymerization (r1 ∼ r2 ∼ 1.0), which requires further evaluation.
    Additional Material: 1 Ill.
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  • 10
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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