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  • 1
    Electronic Resource
    Electronic Resource
    Evidence for ionic clusters in butadiene-methacrylic acid copolymers neutralized with various salts (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 115-130 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Effects of neutralization on butadiene-methacrylic acid copolymers have been studied. In Hycar CTB with 2% acid groups, small-angle x-ray scattering gives evidence of some cation clustering and leads to a value of the mean radius of 5.6 Å for the clusters and a value of the distance between them of 70 Å. When the concentration of salt is increased there is no appreciable change in the distance between clusters or in their size, but their number increases. The structure of clusters has been studied by electron paramagnetic resonance in copolymers neutralized with copper salts. The appearance of a line as in the monohydrated acetate salt permits one to define the structure of clusters consisting of two Cu2+ and four RCOO- ions with two H2O or RCOOH molecules. When the temperature is increased, the signal corresponding to Cu2+-Cu2+ pairs disappears. In high molecular weight butadiene methacrylic acid copolymers with 9% acid groups, we have found the ion pair clusters gathered into larger clusters. In dynamic mechanical properties, a relaxation peak appears at 340°K. We interpret this as due to breaking and possible re-forming of dipolar associations.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.180120110
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  • 2
    Electronic Resource
    Electronic Resource
    Vinylhydroquinone. III. Copolymerization of vinylhydroquinone and vinyl monomers by tri-n-butylboraneDedicated to Professor Yoshio Iwakura on the occasion of his 60th birthday. (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2801-2808 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymerization of vinylhydroquinone (VHQ) and vinyl monomers, e.g., methyl methacrylate (MMA), 4-vinyl-pyridine (4VP), acrylamide (AA), and vinyl acetate (VAc), by tri-n-butylborane (TBB) was investigated in cyclohexanone at 30°C under nitrogen. VHQ is assumed to copolymerize with MMA, 4VP, and AA by vinyl polymerization. The following monomer reactivity ratios were obtained (VHQ = M2): for MMA/VHQ/TBB, r1 = 0.62, r2 = 0.17; for 4VP/VHQ/TBB, r1 = 0.57, r2 = 0.05; for AA/VHQ/TBB, r1 = 0.35, r2 = 0.08. The Q and e values of VHQ were estimated on the basis of these reactivity ratios as Q = 1.4 and e = -;1.1, which are similar to those of styrene. This suggests that VHQ behaves like styrene rather than as an inhibitor in the TBB-initiated copolymerization. No homopolymerization was observed either under nitrogen or in the presence of oxygen. The reaction mechanism is discussed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121209
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  • 3
    Electronic Resource
    Electronic Resource
    Mechanism of vinyl chloride polymerization (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2821-2843 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An overall mechanistic scheme for the suspension polymerization of vinyl chloride is presented. The process can be resolved into five discrete stages, each of which presents a unique environment for the interaction of the systems parameters. It is shown that the surface area of the polymer formed during the reaction is not a major factor in autoacceleration and that the increase of kinetic chain length with conversion is due to a radical dilution effect. The latter is a direct result of the difference in rates between polymerization and radical formation, the former being greater. The increase of the initial polymerization rate and the reduction of autoacceleration brought about by chain transfer agents can be explained by the lower diffusion rate and greater bulkiness of the chain transfer agent radical relative to that of the monomer radical. The chaintransfer agent CBr4 is preferentially absorbed by PVC from solution in vinyl chloride. With lauryl peroxide as initiator it is shown that the “hot spot” is the result of a build-up of initiator in the monomer caused by its exclusion from the polymer phase. Vinyl chloride was found to dissolve 0.03% PVC at ambient temperature and to have no effect on the decomposition rate of lauryl peroxide.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121211
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  • 4
    Electronic Resource
    Electronic Resource
    Radiation-induced crosslinking of cellulose with acroleinPaper presented at IUPAC meeting in Macromolecular Chemistry, Budapest, August 26, 1969. (1971)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 9 (1971), S. 1013-1025 
    Details
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The process of radiation-induced crosslinking of cellulose is found to be highly influenced by radiation dosage and dose as well as by the solvents used and their concentration. The best crease resistance has been obtained in cases when cellulose is crosslinked with acrolein in the vapor phase. Moreover, the process is entirely radiation-induced and practically no homopolymer is formed. Chemical analysis and investigations of infrared spectra indicate that crosslinking proceeds on vinyl as well as on aldehyde groups of acrolein.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1971.150090416
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  • 5
    Electronic Resource
    Electronic Resource
    Conformational characteristics of polymorphous optically active macromolecules: A statistical zigzag model (1970)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 177-190 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformational properties of optically active macromolecules are considered. A statistical zigzag model is used for the calculation of averaged physical properties. The macromolecule is considered to consist of segments of two different types with a statistical distribution of lengths. The expressions for the mean square of the end-to-end vector h2 and the dipole moment μ2 and also of the mean optical anisotropy ΔA and the anisotropy of the optical rotation tensor ΔG were obtained in the cases of freely jointed and freely rotating segments. The equations obtained were applied to the problem of the helix-coil transition. In the case of poly-α-olefins the values of h2, μ2, and ΔA, are larger than corresponding values for typical optically inactive macromolecules. The anisotropies ΔA and ΔG of two poly-α-olefins of similar structures were calculated. The polarizability theory of optical activity was used for the calculations of ΔG. The values obtained for ΔA are similar, but the values of ΔG differ markedly. The possibility of obtaining valuable information about the structure of optically active macromolecules in solution by a study of anisotropy of the optical rotation tensor is considered.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1970.160080201
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  • 6
    Electronic Resource
    Electronic Resource
    Vibrational spectra of thiuram sulfides: Normal coordinate analysis of tetramethylthiuram mono-, di-, and tetrasulfides (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 1001-1013 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The normal coordinate analyses of tetramethylthiuram mono-, di-, and tetrasulfides have been carried out by utilizing vibrational energies obtained from infrared and Raman spectroscopic data reported here. The C=S vibration is demonstrated to be highly coupled and to contribute to frequencies in the 850-1000 cm-1 region, but can be identified based on the strong Raman intensity. The results are useful in interpreting the spectra of these complex vulcanizing agents.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.180120511
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  • 7
    Electronic Resource
    Electronic Resource
    Structure of poly(N-methyl laurolactam) (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 223-238 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure of poly(N-methyl laurolactam) has been studied in the solid state and in solution. In oriented, annealed monofilaments, the chain exhibits a distorted extended planar zigzag conformation. Upon orientation, an increase in crystallinity and a slight shift of the large d spacing in the diffraction pattern to a higher value is observed. In the crystalline regions of the polymer, the amide groups are proposed to have the anti conformation, whereas the amorphous regions may consist of both the syn and anti forms. Differential scanning calorimetry and thermal mechanical analysis showed multiple melting endotherms which probably result from partial melting and reorganization of small, imperfect crystallites. In solution, nuclear magnetic resonance spectroscopy showed the presence of a conformational equilibrium of the syn and anti amide groups in the polymer chains. The effect of thermal and mechanical treatments on certain infrared group frequencies of the amide moieties was studied and correlated with other pertinent analytical data.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.180120201
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  • 8
    Electronic Resource
    Electronic Resource
    Normal coordinate analysis of cis-1,4-polybutadiene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 445-454 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The fundamental vibrational frequencies of an isolated chain of cis-1,4-polybutadiene have been calculated. Infrared and polarized Raman data are used in the force constant refinement routine. The assignments of the vibrational frequencies are discussed in terms of the potential energy distribution.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.180120301
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  • 9
    Electronic Resource
    Electronic Resource
    Spherulite size effects in linear polyethylene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 12 (1974), S. 819-821 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.180120416
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  • 10
    Electronic Resource
    Electronic Resource
    Kinetics of radiation-induced bulk polymerization of vinyl chloride in the temperature range of -50 to 90°c (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 411-432 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetic investigations on the bulk polymerization of vinyl chloride initiated by exposure to 60Co γ-rays were carried out in the temperature range of -50 to 90°C at dose rates varying from 0.15 to 50 rad/c. Some polymerization runs were also carried out in a centrifugal field. As generally reported for this polymerization system, in which the polymer is insoluble in the monomer, the polymerization rate was found to change as a function of the amount of the polymer formed in a special fashion. This particular function has been shown to be greatly influenced by the polymerization temperature and to be independent of the rate of initiation, or, more rigorously, of the dose rate. Thus, at any given temperature the equation of the polymerization conversion rate could be written in the form of the product of two separate functions, one for the polymerization conversion and the other for the dose rate. While for the latter the results gave an essentially square-root dependence on dose rate as is normally found for homogeneous polymerization, the former has been discussed in the terms of recently advanced kinetic schemes, based on a two-phase polymerization model. The kinetic parameters found in this work are in agreement with previous authors' data.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120213
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