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  • Articles  (49)
  • Chemistry  (49)
  • Analytical Chemistry and Spectroscopy
  • Atomic, Molecular and Optical Physics
  • Industrial Chemistry
  • 1965-1969
  • 1960-1964
  • 1955-1959
  • 1950-1954  (49)
  • 1954  (49)
  • Physics  (49)
  • Biology
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  • Articles  (49)
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  • 1965-1969
  • 1960-1964
  • 1955-1959
  • 1950-1954  (49)
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  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 12 (1954), S. 469-480 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In a radical polymerization in which initiation is solely by the addition of an initiator fragment to a monomer molecule, there must be in the polymer one combined initiator fragment for each kinetic chain; analysis of the polymer therefore can lead to a determination of the kinetic chain length. The rate of initiation is equal to the over-all rate of polymerization divided by the kinetic chain length, and so it can be calculated. This new method for calculating rates of initiation is not subject to the uncertainties associated with older methods. Analysis for initiator fragments can be performed accurately if the initiator is labeled with a radioactive isotope; in the work described here C14-α,α′-azo-bis-isobutyronitrile was used. An essential requirement is that the polymer molecules of low molecular weight must not be lost during precipitation of the polymer. Tests are described showing that loss of low molecular weight materials is negligible in most cases and that even when the average molecular weight of the polymer is low and there is an appreciable loss a correction can be made. A correction can also be made for the consumption of initiator during the reaction. The results presented in this paper refer to the copolymerization of butyl acrylate and styrene in benzene solution at 60°. It is shown that for a given monomer mixture the rate of initiation is proportional to the concentration of initiator, and that for each initiator molecule decomposed approximately one reaction chain is started.
    Additional Material: 3 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 14 (1954), S. 169-179 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When a solution of natural rubber hydrocarbon is cold vulcanized with sulfur monochloride, a gel is formed. The rate of gel formation is used to characterize the rate of reaction between rubber and sulfur monochloride and a preliminary kinetic investigation is described. It is shown that the reaction is accelerated by compounds normally used for speeding up sulfur (hot) vulcanization, and it is suggested that these function by virtue of their possessing an active hydrogen atom. Several series of simple compounds, containing the groups —SH, —OH, and —NH2, are shown to function as effective accelerators and their activity is attributed to the presence of a labile hydrogen atom in the molecule R—X—H, where R = organic radical and X = S, O, or N. The absence of a direct relationship between accelerating power and basic or acidic strength suggests a free radical mechanism of accelerator action, based upon the process ${\rm R} - {\rm X} - {\rm H } \to {\rm R} - \mathop {{\rm X }}\limits^ * {\rm + }\mathop {{\rm H }}\limits^ * $.
    Additional Material: 4 Ill.
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  • 3
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study of the dilution effect of four hydrocarbons (biallyl, hexane, 3-methyl-1-butene, and isopentane) on the rate of polymerization of butadiene and on the characteristics of the resulting polymer has shown that chain transfer of the following type is an unimportant reaction in butadiene polymerization: The above result is consistent with the kinetic treatment of crosslinking as developed by Flory. The results of a comparison of the emulsion polymerization of 2,2′-azobisisobutyronitrile- and of persulfate-catalyzed butadiene are adequately accounted for without considering the effect of the catalysts on branching or crosslinking. As previously suggested, the differences noted between 2,2′-azobisisobutyronitrile- and persulfate-catalyzed polybutadienes are probably due to a different molecular-weight distribution. This difference in molecular-weight distribution is partly produced by a large difference in r values for the two systems. The unmodified emulsion polymerization of butadiene with 2,2,-azobisisobutyronitrile in an oxygen-and peroxide-free system produces a highly crosslinked polymer.
    Additional Material: 16 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 13 (1954), S. 329-353 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: As a step toward the better understanding of acrylonitrile polymerization a kinetic study was made in bulk with azo and peroxy catalysts over the range 30 to 60°C. Rates were followed gravimetrically in most cases, and molecular weights were estimated from viscosity measurements. Electron micrographs and nitrogen sorption data were obtained. Following a short induction period (which could not be eliminated) polymer separated as a fine suspension, coagulated to form curds at a few tenths percent polymerization and formed a hard, porous mass at about 60% reaction. Product at 5 to 50% polymerization was in the form of dense particles about 0.5 micron across; these appeared to be aggregates of 400 A. particles. The rate of polymerization accelerated up to 1-3% conversion and was then nearly constant to about 50%, beyond which it could not be measured. Rate increased with the 0.8 power of catalyst concentration and showed an over-all activation energy of 35 to 37 kcal./mole. Molecular weight varied inversely with the 0.2 power of the catalyst concentration, was nearly constant from 5 to 50% conversion and went through a slight maximum with temperature. To account for these observations a kinetic scheme is proposed that involves the possibility of unimolecular chain termination by a process of “burial.” This process is conceived of as a mechanism by which a growing chain may become shielded from further growth by coiling or embedding itself in the solid phase. Equations derived for rate and degree of polymerization fit the data adequately. Consideration is given to the simultaneous effects at high conversion of a small loss in initiator by thermal decomposition, of enrichment of the solution by shrinking liquid volume and of depletion of monomer.
    Additional Material: 10 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
    Notes: The hydrodynamic properties of native and urea-denatured fibrinogen have been investigated, primarily to examine further the suggestion, based on a consideration of data for horse serum albumin, that urea denaturation may involve swelling instead of increased asymmetry. A sedimentation-diffusion and also a light scattering molecular weight determination at the isoelectric point indicate that 6 M urea causes neither splitting nor aggregation of the native protein in the denaturation process. The observed increase in the intrinsic viscosity and frictional coefficient upon denaturation can be interpreted in terms of an equivalent hydrodynamic ellipsoid of approximately the same shape but of a volume which is approximately 1.7 times that for the native protein. The effective volume appears to be slightly dependent on pH with a minimum at the isoelectric point. It thus appears that the urea denaturation of bovine fibrinogen, like that of horse serum albumin, may involve swelling. There is no indication in the case of either protein that increased asymmetry is involved in accounting for the frictional behavior of the denatured substances.
    Additional Material: 7 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 14 (1954), S. 110-114 
    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: Les auteurs ont étudié la dépendance de la viscosité de solutions de polyméthacrylates de méthyle (Mw 〉 106) en fonction du gradient de vitesse. Les measures ont été effectuées aux viscosimètres de Couette et d'Ostwald entre des gradients de 0,246 et 1700 sec-1 et sur des solution dans le chloroforme, le dianxe et l'acétone.
    Notes: Es wird über die Abhängigkeit der Viskosität von Polymethylmethacrylaten in Lösung (Mw 〉 106) vom Geschwindigkeitsgradienten berichtet. Die Messungen wurden im Couette- und im Ostwaldviskosimeter bei Gradienten zwischen 0,246 und 1700 sec-1 in Chloroform, Dioxan und Aceton ausgeführt.
    Additional Material: 2 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 14 (1954), S. 503-504 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Tab.
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  • 8
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 12 (1954), S. 543-546 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experiments are described made with the object of measuring the alleged catalytic effect of HCl on PVC decomposition. The conclusion is that this effect does not exist.
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  • 9
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 12 (1954), S. 209-219 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The sedimentation constants and diffusion coefficients of sodium polymethacrylate and of polymethacrylic acid have been determined at various concentrations of polymer and of added electrolyte and the nature of the charge effects is considered. A ratio y = (molarity of added electrolyte)/(grundmolarity of polymer) is used to obtain S20 at y = ∞ when the polyelectrolyte is assumed to be uncharged. The variation of the effective radius with y is considered not to be due to asymmetry but to the open network nature of the polyelectrolyte coil.The sedimentation constant of unionized polymethacrylic acid is determined and also the variation of sedimentation constant with degree of ionization.
    Additional Material: 10 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 12 (1954), S. 237-252 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The salts of carboxymethylcellulose (CMC) are used in large quantities to improve the dirt-suspending power of synthetic detergents and soaps. Hardly any attention has been given to the question as to which properties they should have to obtain the greatest suspending power. They exert their specific influence because they are adsorbed by cellulose fibers from their solutions in water. Theoretical considerations are given, showing that: (1) The degree of substitution (DS) should probably be about 0.5. (2) The substitution should be as uniform as possible. (3) The cellulose chains should be neither too short nor too long. Normally only the average degree of substitution, DS, is determined. The fiber contents, FC, i.e., the percentage of insoluble and partly swollen fibers in 1/20 N NaOH can be taken as a measure of the uniformity of the substitution. Technical products differ greatly in pH and salt contents; therefore the viscosity of solutions of the technical products containing 1% of the cellulose ether, to which 2.5% Na2CO3 and 2.5% NaHCO3 have been added, is taken as a measure of the length of the cellulose chains. The easiest way to obtain uniformly substituted products is by dispersing cellulose and reagents in a suspending liquid, e.g., an alcohol or a hydrocarbon. FC's smaller than 2 to 4% are obtained. Then the dirt-suspending power was greatest with a DS between 0.48 and 0.53; and a viscosity measured as above with a Hoeppler standard viscometer between 11 and 29 c.p.s. The substitution in general is much less uniform when CMC is prepared according to the customary method by mixing cellulose, NaOH, and ClCH2COONa or ClCH2COOH and a little water. Then the results were best with an average DS between 0.51 and 0.60, and an FC between 6 and 16%, said viscosity being 20 to 30 c.p.s.
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