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  • Polymer and Materials Science  (28)
  • 1955-1959  (28)
  • 1955  (28)
  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 17 (1955), S. 159-177 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal structure of nylon 6 (—NH (CH2)5CO—)p has been determined by interpretation of the x-ray diffraction patterns given by drawn, rolled fibers. The determination was part of a program to investigate the relation between structure and physical properties, in particular melting point. Nylon 6 melts 50°C. lower than its isomer nylon 66 (—NH (CH2)6NH·CO (CH2)4CO—)p; it had been suggested that this was due to deficient hydrogen-bond formation in nylon 6 crystallites. The unit cell contains eight chemical units (—NH (CH2)5CO—) and is monoclinic with a = 9.56 A., b = 17.24 A., c = 8.01 A., and β = 671/2°. Calculated density = 1.23. Observed density for a drawn monofilament = 1.16. The structure consists of planar chains of CH2 groups and amide groups tilted 7° from the (001) plane. Alternate chains in this plane are oppositely directed, an arrangement which allows all hydrogen bonds to be made perfectly. The hydrogen-bonded sheets of atoms are packed in an “up-and-down” staggered configuration along the c-axis. Distances between atoms in neighboring molecules are all normal van der Waals contact distances. It appears, from a general survey of polyamide melting points published elsewhere, that the determining factor is the number of CH2 groups between the amide “anchor points” - polymers with odd numbers of CH2 groups melt lower than those with even numbers. The present work shows that the odd number of CH2 groups in this polymer does not lead to deficient hydrogenbond formation, and that the lower melting point of nylon 6 as compared with nylon 66 must be ascribed to some other cause, possibly connected with the propagation of vibrations along odd-numbered chain segments.
    Additional Material: 10 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 15 (1955), S. 51-67 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Infrared absorption spectra were used to study the structural changes resulting from oxidation in a number of unvulcanized, purified polymers under a variety of experimental conditions. The results showed that as oxidation progressed, the structural changes which were detected were qualitatively the same for all of the polymers under all of these experimental conditions. Correlation of volumetric measurements with spectral data indicated that considerably more oxygen was absorbed by the polymer samples before structural changes could be detected than the minimum amount required for the initial detection of the hydroxyl and carbonyl structures. From the interpretation of information from the absorption spectrum, it is believed that the structural evidence is in substantial agreement with current theories on autoxidation. Although the initial hydroperoxide formation is not observed in the spectrum, it is quite probable that this reaction takes place with almost immediate decomposition which results in a net hydroperoxide concentration so low as to make infrared methods insensitive for its detection. Correlation of physical properties with structural studies indicate that little change in these properties take place until the hydroxyl and carbonyl structures become evident in the infrared spectrum.
    Additional Material: 17 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 17 (1955), S. 133-135 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 4
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Acrylate esters of seven n-1,1-dihydroperfluoroalkanols have been synthesized. The esters are: 1,1-dihydroperfluoroethyl-; 1,1-dihydroperfluoropropyl-; 1,1-dihydroperfluorobutyl-; 1,1-dihydroperfluoropentyl-; 1,1-dihydroperfluorohexyl-; 1,1-dihydroperfluorooctyl-; and 1,1-dihydroperfluorodecyl acrylates. Since these alcohols were difficult to esterify using conventional procedures, acrylyl chloride or acrylic acid plus perfluoroacetic anhydride have been empolyed in this work.
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  • 5
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 15 (1955), S. 157-166 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Recently the depolymerization of addition polymers has been treated in terms of four elementary reactions: initiation, propagation, transfer, and termination; analogous to those reactions which operate in the polymerization process. It is the transfer process which, according to its relative importance, gives rise to differences in polymers in the monomer yield, in the rate vs. conversion behavior, and in the molecular weight vs. conversion behavior. The transfer process is assumed to operate through the abstraction of a hydrogen from the polymer chain by a radical. By substituting a deuterium for the hydrogen at selected points in the polymer chain, the amount of the transfer process should be decreased due to an isotope effect. Two deuterated polymers were made from α- and β-deuterated styrenes and their depolymerization behavior studied. In the case of the α-deuterostyrene polymer the results are compatible with a ½ decrease in the rate of the transfer process and also an increase in the rate of the propagation. The results with the β-polymer imply an increase in both the transfer and propagation rates. The data obtained indicate that in polystyrene the intermolecular transfer process is mainly responsible for the fall in molecular weight of the polymer residue during depolymerization.
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  • 6
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A detailed study has been made of the intrinsic viscosity-molecular weight relationship for a polybutadiene prepared at 50°C. and one prepared at 5°C. Original fractions were at least twice refractionated from very dilute solutions in an attempt to obtain fairly sharp distributions. Fox-Flory K constants are observed to decrease with increasing molecular weight in each case, and the intrinsic viscosity-molecular weight plots show a curvature. This is interpreted to be a result of branching. A method of plotting the data is proposed which simultaneously yields the K for unbranched material and an estimate of the degree of branching. It is estimated that, in polybutadiene prepared at 50°C., one out of 6500 monomer units is involved in a branch, and that in 5°C. polybutadiene, one out of 10,000.
    Additional Material: 5 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 15 (1955), S. 405-411 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of the thermal diffusion constant of polystyrene in toluene and butyl acetate solutions have been made. Direct observation of a moving boundary was used. There is a small change of thermal diffusion constant with molecular weight, but it is doubtful that it could be used for analytical purposes. The results for polystyrene in toluene have been compared with those obtained by Debye and Bueche with a convection-type column.
    Additional Material: 3 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 16 (1955), S. 131-142 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Essential features of the crystallization of unoriented high polymers from the molten and supercooled liquid conditions are outlined to provide a background for a proposed structure and mechanism of growth of spherulites. Homogeneous and heterogeneous nucleation mechanisms of crystallite growth are discussed. Spherulites are recognized as crudely oriented spheroidal aggregates of crystallites and their attached amorphous regions. It is proposed that a spherulite originates from a single nucleus and that growth proceeds thence in a statistically radical fashion until all crystallizable domains are utilized or until growth is arrested due to increasing viscosity of the medium. It is assumed that crystallite growth occurs by lateral accretion of suitable oriented molecular segments and that nucleation proceeds from one crystallite to another by means of fine streamers of crystalline order (protofibrils) which may grow either by longitudinal extension along fringes or by lateral aggregation of very short segments. The predominant shapes of the crystallites are believed to determine the structure and optical properties of the spherulite. A roughly conical arrangement of crystallites around a spherulite radius is preferred to a helical one.
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  • 9
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 17 (1955), S. 154-156 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 17 (1955), S. 391-401 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A polymethyl methacrylate polymer, prepared by the emulsion technique, was fractionated three times to obtain essentially homogeneous fractions. The intrinsic viscosities and weight average molecular weights were determined in an ideal solvent at 23°C. and in nonideal solvents at 25°C. The constants K and a in the conventional modified equation [η] = KMa were determined. The intrinsic viscosity in an ideal solvent was found to fit closely over the molecular range studied with the relation [η]θ = KM1/2. Light scattering measurements giving root-mean-square distance between ends of a polymer chain were carried out. It was shown that these results support both Kuhn's relation (r̄2)1/2 ≍ M0.50 and Flory's relation (r̄2)3/2 = M[η]/2.1 × 1021 in an ideal solvent. In a nonideal solvent only Flory's relation was found to be in agreement with the experimental results. The values of volume expansion factor α3 ratios A2Mw2/(r̄2)3/2 and A2Mw/[η] in a nonideal solvent and the value of the ratio [η]/M1/2 in an ideal solvent showed that the polymer molecules were expanded beyond their random flight dimensions in a nonideal solvent.
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