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  • Articles: DFG German National Licenses  (496)
  • 2020-2022
  • 1965-1969  (496)
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  • 1968  (496)
  • Physics  (496)
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  • ZIB Catalog
  • Articles: DFG German National Licenses  (496)
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  • 2020-2022
  • 1965-1969  (496)
  • 1890-1899
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  • 101
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1527-1533 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Drawn, nylon 66 yarns have been annealed in oil under relaxed conditions. Shrinkage and tensile modulus were measured and the yarns were examined by wide- and small- angle x-ray diffraction. The results are similar to those obtained by Dismore and Statton, but there are significant differences. The data indicate a model for a drawn nylon 66 fiber in which substantial amounts of folds remain.
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  • 102
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure of the crystalline complex of poly(ethylene oxide) with mercuric chloride, whose composition is (CH2CH2O)4 · HgCl2, has been determined by x-ray diffraction. The unit cell is orthorhombic with the dimensions of a = 13.55 Å, b = 8.58 Å, and c (fiber axis) = 11.75 Å, and the unit cell contains 4 HgCl2 molecules and 16 CH2CH2O units. Four chains pass through the lattice and four monomeric units are contained in the fiber identity period. The space group is Ccmm-D2h17, Ccm21-C2v12, Cc2m-C2v16 or C2221-D25. The positions of Hg and Cl atoms have been determined by the Patterson function synthesized by the use of intensity data of the fiber sample, and the molecular conformation of poly(ethylene oxide) has been determined by examining the space not occupied by mercuric chloride molecules in the crystal lattice. The conformation of polyethylene oxide in the complex has been found to be the form of T5GT5G; that is, where G and G mean the right- and left-handed gauche forms, respectively. This molecular structure has been confirmed further by the results of the Fourier syntheses by using the more accurate data refined by the intensity measurements with a diffractometer on the powder sample. The bond length between Hg and Cl in the complex (2.30 Å) is a little longer than that of HgCl2 in the crystal (2.25 Å). This is consistent with the fact that the infrared absorption band associated with the antisymmetric stretching vibration of HgCl2 shifts to 353 cm-1 in the complex from 367 cm-1 in the crystal. It was also found that another type of complex, giving a different infrared spectrum and x-ray diffraction pattern, was obtained when the original complex was soaked much longer in a saturated ether solution of HgCl2.
    Additional Material: 9 Ill.
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  • 103
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1579-1591 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: GPC appearance volumes have been determined for a series of linear polyethylene, polystyrene, and polybutadiene fractions (Mw/Mn 〈 1.1) in trichlorobenzene at 130°C. and for the latter two series in tetrahydrofuran at 23°C. A polymer-type independent relationship between appearance volumes and the equivalent hydrodynamic radii of the polymer molecules has been demonstrated. The equivalent hydrodynamic radius is calculated from intrinsic viscosity data. It is proposed that this relationship can be used to construct a universal GPC calibration curve for polymers that assume a spherical conformation in solution. Methods for applying the universal curve to the determination of molecular weight averages and molecular weight distribution are described. In addition, a method is outlined by which the universal calibration curve can be empolyed for determining number-average Mark-Houwink constants from polydisperse samples.
    Additional Material: 4 Ill.
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  • 104
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 2051-2066 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dilute solution viscosity and osmotic pressure measurements were performed on polystyrene (PS), polybutadiene (PB), polystyrene-polybutadiene (SB) diblock and polystyrene-polybutadiene (SBS) triblock copolymers. Anionic polymerization was used in such a way that the molecular weight of the PS block was kept constant (ca. 10 000), while the molecular weight of the PB block varied from 18000 to 450000. The measurements were carried out at a fixed temperature of 34.20°C in three solvents, namely toluene, a good solvent for PS as well as for PB, dioxane, which is a good solvent for PS and almost a theta solvent for PB, and cyclohexane, which is nearly a theta solvent for PS and a good solvent for PB. The compositions of SB and SBS, as derived from kinetic data agree with ultraviolet measurements in CHCl3 solutions. The viscosity and osmotic pressure results indicate that the properties of SB and SBS are similar. Their intrinsic viscosities and second virial coefficients can be calculated from their chemical compositions, molecular weight, properties of parent polymers, and values of the interaction parameter \documentclass{article}\pagestyle{empty}\begin{document}$\bar \beta _{{\rm SB}}$\end{document} between styrene and butadiene units, for molecular weights not exceeding approximately 105. The magnitude of \documentclass{article}\pagestyle{empty}\begin{document}$\bar \beta _{{\rm SB}} $\end{document} varies with the solvent. The results suggest that the domains of the PS and PB blocks overlap to a great extent.
    Additional Material: 4 Ill.
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  • 105
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1241-1253 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of conductivity, permittivity, and dissipation factor on polystyrene, low-density polyethylene, poly(ethylene terephthalate), and polytetrafluoroethylene under irradiation with x-rays at exposure rates from 0.004 to 400 r/sec. are presented. The radiation-induced anomalous conductivity as well as the induced dielectric loss are interpreted by Maxwell-Wagner polarization due to radiation imbalance in surface layers of the specimen. The nature of radiation-induced steady-state conductivity is also discussed.
    Additional Material: 10 Ill.
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  • 106
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1747-1758 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Rayleigh-Gans theory of light scattering by a homogeneous cylinder has been applied to the case of scattering by a pad of fibers immersed in a liquid. The theory enables one to locate precisely the matching wavelength at which the mean refractive index of a sample of optically heterogeneous fibers coincides with that of an immersion medium. Thereby it offers a method of determining the mean refractive index. Besides, it facilitates a quantitative estimation of the variability of refractive index. The new technique has been used to study the birefringence of untreated cotton and ramie. The results are presented and discussed.
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  • 107
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1783-1789 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using the criterion that a coupling entanglement in a polymer network is trapped if all four strands radiating from it terminate in chemical cross-links (an approximation to a more rigorous treatment of Langley), an equation is derived relating the equilibrium modulus to the magnitude of the compliance in the frequency region where all coupling entanglements, whether trapped or not, contribute to the elasticity. The latter value is estimated from the storage compliance at the frequency where the storage compliance of the uncross-linked polymer corresponds to the entanglement compliance derived from integration over the loss compliance. The theory agrees rather well with data on vulcanizates of natural rubber. For 1,4-polybutadiene and styrene-butadiene rubbers, the agreement is somewhat less satisfactory, but the results support the hypothesis that the low-frequency losses observed in lightly cross-linked rubbers are due to relaxation of untrapped entanglements.
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  • 108
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1817-1833 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements have been made of the anisotropy of viscoelastic behavior in specially oriented sheets of low-density polyethylene. The results for the cold-drawn sheets show a β relaxation process of very characteristic anisotropy. The annealed sheets show two relaxations in this region of temperature. The lower relaxation (about -10°C) is identified as an interlamellar shear process. The higher relaxation (about 70°C) has a very similar anisotropy to the β relaxation in cold-drawn samples. Isotropic sheets of low-density polyethylene have been also investigated. Two β relaxations are found in these materials.
    Additional Material: 13 Ill.
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  • 109
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1887-1902 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The steady-flow behavior of five samples of branched poly(vinyl acetate) has been studied with the Weissenberg rheogoniometer. The branching densities and molecular weight distributions were known from an analysis of the polymerization kinetics. Measurements were made on concentrated diethyl phthalate solutions (0.170 and 0.225 g/ml) at temperatures of 30 and 70°C. The viscosities of all solutions at zero shear rate were less than of solutions of linear poly(vinyl acetate) with the same weight-average molecular weight. The amount of decrease was in excellent agreement with Bueche's theory of melt viscosity in branched systems. The viscosity versus shear rate curves were surprisingly independent of molecular weight distribution, the data from all samples being superimposable on the same master curve. Relaxation times derived independently from the viscosity behavior and the normal stress data were of similar magnitude and always close to the Rouse relaxation time of each solution.
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  • 110
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1935-1937 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 111
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1944-1944 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 112
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 2021-2041 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A modus operandi is developed for characterizing, in quantitative morphological terms, the structural changes occurring during the preparation (spinning, drawing, and heat setting) and testing (tensile modulus) of isotactic polypropylene fiber. This involves the application of the following eight different physical techniques: wide-angle x-ray diffraction, birefringence, density, sonic modulus, small-angle x-ray diffraction, dark-field microscopy, small-angle light scattering, and tensile modulus. Structural changes on several organizational levels, the spherulitic, the interlamellar, and the molecular, are determined in this manner and related to the processes involved.
    Additional Material: 15 Ill.
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  • 113
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1481-1492 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rapid cracking of lightly stressed rubbery block polymers of styrene and isoprene in certain liquids and vapors has been examined experimentally, by using model test pieces containing a single crack. Solvents which preferentially dissolve the rigid molecular end blocks rather than the rubbery center blocks are efficient cracking agents. The stress required for crack growth to occur is shown to be in accord with a simple energy criterion: the stored elastic energy must be sufficient to provide a characteristic energy for the newly formed surface. This characteristic energy ranges from values close to the surface energy of simple liquids up to about 100 times this value for thicker test pieces or slowly diffusing vapors, when some tearing of an incompletely swollen core is inferred. “Induction times,” before the initial crack starts to grow, are shown to be due to a progressive increase in stored energy under a constant stress as the material absorbs solvent and softens until the critical energy criterion is met. Thus, a timedependent fracture process is shown to be in accord with a constant energy criterion. Above the critical condition the rate of crack growth depends strongly upon stress, like tearing of amorphous elastomers, and the crack then accelerates rapidly.
    Additional Material: 7 Ill.
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  • 114
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1551-1554 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 115
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 111-127 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method has been developed for determining the molecular weight distribution of a polymer sample from the sedimentation-diffusion equilibrium data for a solution under pseudo-ideal conditions. From some theoretical examples it appears that the method works well and that the molecular weight distribution can be determined with a reasonable degree of resolution. From three polymer samples (polyethylene, polystyrene, and polycaprolactam) the molecular weight distribution was determined in this way. The average molecular weights, M̄n, M̄w, M̄z, and Mz+1, calculated from these distribution functions agree well with those calculated directly from the equilibrium data.
    Additional Material: 10 Ill.
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  • 116
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 141-154 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Flow birefringence data for dilute solutions of various linear and branched polymers of different degrees of polydispersity are discussed. The polymers considered are polystyrene, polypropylene, and polyethylene. By making use of a well-known stress-optical relation, reduced elastic normal stresses, which can also be interpreted as coil expansions, are plotted against reduced shear stresses. As elastic normal stresses are rather sensitive to the shape of the molecular weight distribution at high molecular weight, a characteristic, p, related to the skewness of the distribution, is obtained. Experimental values of p are compared with theoretical ones based on special types of distribution functions. Attention is paid to the method of extrapolating experimental results to zero shear stress and concentration.
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  • 117
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 155-163 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A commercial elastomeric block copolymer of butadiene (B) with styrene (A) is studied. A single chain of the material has the formula A-B-A. Differential thermal analysis studies show the presence of two transitions. The lower transformation temperature corresponds to the Tg of the butadiene chain segments, and the upper transformation temperature corresponds to the Tg of the styrene chain segments. The upper transition of the material is also studied by following the variation of the torsional modulus with temperature. This transition is found to be quite unusual. Our experiments show that the upper transformation of unstressed block copolymer samples is broad. The transition sharpens for samples which, prior to the modulus-temperature experiments, are stress-relaxed at high elongations. These observations (and those of the literature) suggest that the styrene and butadiene chain segments in the block copolymer aggregate in the solid state and give rise to two distinct transition phenomena. Our studies of the upper transformation suggest that stretching of the bulk material enhances the aggregation of the styrene chain segments. Pure polystyrene (A) blocks of the material are recovered by selective cleavage and fractionation experiments. The Tg of the pure polystyrene blocks is found to be similar to the value of the upper transition temperature of the copolymer. The ABA blocks copolymer is found also to undergo a stress-softening phenomenon analogous to that of reinforced rubber.
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  • 118
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 181-196 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Studies of the crystallization kinetics of natural rubber networks held in simple extension are reported. In these experiments the length of the specimen was held constant, and the crystallization process was followed by the decay in stress that occurred. A wide range of extension ratios and crystallization temperatures was encompassed by these experiments. From an analysis of the shapes of the crystallization isotherms, it can be concluded that major changes take place in the nucleation and growth processes as the extension ratio is increased. This conclusion is in accord with reports in the literature of changes in the crystallite morphology with extension ratio. Analysis of the temperature coefficient of crystallization, by means of nucleation theory, indicates a substantial increase in apparent interfacial free energies with increased deformation. This latter observation is interpreted to indicate a departure from a correlated crystallization process to one where isolated crystallites are formed.
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  • 119
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dimensional stability of regenerated cellulose film on swelling with water is discussed in relation to the biaxial orientation of the two kinds of structural units, cellulose II crystallites and noncrystalline chain segments, and their anisotropic swelling (anisotropic absorption of water). Considerable dimensional stability in the plane of the film but enormous instability of thickness on swelling in water of some commercial cellophanes is qualitatively interpreted in terms of the planar orientation of crystal (101) planes along the film surface and the orientation of the noncrystalline chain segments parallel to the film surface. The dimensional changes on swelling from the completely dry state to 10% moisture regain were further interpreted quantitatively in terms of the degrees of biaxial orientation of the two kinds of structural units and their degrees of anisotropic swelling by modifying the Hermans monophase model for crystalline and noncrystalline biphase structures. The following degrees of anisotropic swelling of the structural units were thus obtained: qc, [101] = 0.40%, qc, [101] = -0.33%, and qa = 2.42%.
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  • 120
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 259-263 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The stress relaxation properties of poly(ethyl acrylate) and polydimethylsiloxane were investigated under conditions where oxidative degradation was minimized. The relaxation observed is thought to result from the continued approach to equilibrium of the network chains with cooperative thermal motion. These elastomers, representing two new classes of polymer, and two new types of crosslinking, were found to behave surprisingly like natural rubber and butadiene-styrene copolymer. Relaxation was found to obey a power law in time, with a negative exponent of 0.22 for both polymers.
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  • 121
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 305-323 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymers are complex mixtures that may have widely different compositions even if they contain only components having the same chemical constitution. The effect of the chain length distribution on the phase behavior of polymer solutions in a single solvent is described qualitatively. To obtain a quantitative understanding of these phenomena a numerical calculation method is developed which is based on the Flory-Huggins relation for the free energy of mixing. Some examples are presented, and the accuracy and the reliability of the results are discussed.
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  • 122
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 367-381 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular weight distributions of the fractions in the two liquid phases which, in preparative fractionation, form upon a change in temperature, have been calculated for various initial concentrations and model distributions differing widely in shape and width. It was found that the normally recommended conditions do not always lead to the result desired, i.e., to a fraction with a narrow distribution. Under these conditions (dilute solution; large phase-volume ratio; small fraction, i.e., little polymer in the concentrated phase) it may even happen that the fraction has a relatively wider distribution than the parent polymer. Treatment of a single-peaked distribution will then be liable to yield a two-peak fraction distribution. These unwanted phenomena do not occur in Staverman and Overbeek's variant of the extraction fractionation method. Here, the bulk of the polymer goes into the concentrated phase, and the macromolecules left in the dilute phase constitute the fraction to be isolated. In this way, relatively narrow distributions can be obtained in one step, even at high concentrations. Moreover, the method is very well suited for use in large-scale fractionation. Fraction distribution wider than the initial distribution were found experimentally in the systems polyethylene-diphenyl ether and polystyrene-cyclohexane.
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  • 123
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 529-558 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is argued on the basis of a simple model for a polymer chain that characteristics of conformation can be determined from the analysis of the frequency distribution of backbone vibrations. In a chain with one degree of freedom per repeat unit, a fold tends to uncouple the motions on each side of the fold. This transfers highest and lowest modes towards the mean value. Conversely, a local unfolding of a random chain enhances the coupling and produces out-of-band modes. From the ordering of these modes, statistical aftereffects can be detected. The Green's function method allows a calculation of the single localized mode as a function of angular parameters. The dynamical matrix elements of the Kirkwood-Pitzer model are calculated for a folded polyethylene backbone chain. The eigenvalue distribution is determined with the Givens-Sturm procedure. It indicates a one-to-one correspondence between modes in the vicinity of 670 cm.-1 in the stretch-bend gap and chain folds, for low concentration of folds. We conclude that conformations should have two characteristic parameters distinctively reflected in the frequency distribution, namely the range of allowed dihedral angles and the ordering of configurations along the chain. The frequency distribution for a given conformation depends however on the force constant ratios when the degree of freedom is greater than one. Interpretation of the frequency spectrum is then made by adjustment of dynamical and geometrical parameters. These are seen to be dependent variables with respect to the spectrum.
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  • 124
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 607-620 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The stress-system curves have been measured for isotropic and oriented specimens of poly(ethylene terephthalate) in extension, shear, and compression. It was found that for all these types of deformations there was an intrinsic yield drop, i.e., a fall in true stress. It is concluded therefore that the stress for initiation is greater than the stress for propagation of yielding.
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  • 125
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 639-651 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When the first asymptotic probability function of smallest values was applied to analyze the distribution of tensile strength data for rubbers, good agreement between observed values and theory did not always result. In order to improve the agreement, use of another distribution function, the third asymptotic probability function, was proposed. Experiments verified that this function yielded good agreement with theory for the distribution of tensile strengths of rubbers, especially for SBR vulcanizates loaded with light calcium carbonate. The third asymptotic probability function contains three parameters: the characteristic value V, the lower limit ε, and the shape parameter k which is dimensionless. Analysis is made by use of a logarithmic extremal probability paper on which the probability function plots as a straight line if ε = 0. There appears to be a lower limit for the distribution of tensile strengths but not for the distribution of elongations. This suggests that the tensile properties follow the third asymptotic distribution function, with the breaking elongations following the simplified form of the Weibull distribution.
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  • 126
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 675-685 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Diffusivities and solubilities in the system n-pentane-polystyrene were measured for low penetrant concentrations at several temperatures above the glass transition temperature. The relatively sharp changes in the activation energy of diffusion and the heat of solution near 150°C. are interpreted tentatively as indicating that a second-order transition exists in atactic polystyrene above the glass transition temperature. Evidence indicating the existence of this transition has been obtained by other techniques and the effects observed in this study should also be present in the diffusion of other penetrants in polystyrene. Correlation of these and other available data for diffusion in polystyrene as a function of the molecular size of the penetrant indicates that specific thermodynamic interactions between polymer and penetrant have little influence on the diffusion process.
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  • 127
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 695-706 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Data already existing in the literature for the overall crystallization kinetics of a variety of polymers have been analyzed according to different possible nucleation mechanisms. The conclusions reached are similar to those previously deduced from an examination of ata for spherulite growth rates. It is demonstrated that, if allowed a reasonable choice for the equilibrium melting temperature, no unbiased selection of a unique nucleation process can be made. Moreover, a set of universal parameters exists for each of the nucleation and growth processes considered which allows the data for all polymers to be represented by a single straight line. The only quantities that are unique to a given polymer are the equilibriun melting temperature and the activation energy for transport.
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  • 128
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 713-721 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(methyl acrylate) (PMA) and 1:1 poly(styrene-co-methyl acrylate) (PSMA) were prepared by solution and bulk polymerization, respectively. The copolymer was analyzed with NMR to ascertain its composition and microstructure. The solution properties of unfractionated PMA and fractionated PSMA in ethyl acetate were investigated by light-scattering and viscosity techniques at 35°C. Narrow composition heterogeneity as revealed from the light-scattering measurements in different solvents justified the use of a single solvent for the copolymer characterization. The equations relating the limiting viscosity number to molecular weight, the molecular dimension to molecular weight, etc., were found for homopolymer and copolymers in ethyl acetate at 35°C. In the evaluation of the Flory constant K for the unperturbed state by methods based on Flory-Fox-Schaefgen, Kurata-Stockmayer, and Stockmayer-Fixman expressions, only the first method gave a value for PMA in ethyl acetate, consistent with that obtained in other solvents, whereas similar values of K were obtained by the three methods for PSMA in ethyl acetate. The studies indicate reduced thermodynamic interaction for PSMA-ethyl acetate compared to PMA-ethyl acetate, but increased steric effect in the copolymer compared with the homopolymer.
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  • 129
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 783-786 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Light scattering from polymer films containing ringed spherulites may show multiple-order intensity maxima directly related to the period of the banded structure. Calculations based on spherulite models where the angle of twist of lamellae ω varies linearly with radial distance predict only first-order peaks. If the variation of ω is nonlinear, even though the ring spacing remains constant, higher-order intensity maxima will result. Other sources of multiple-order scattering are considered. It is concluded that for polyethylene the presence of multiple-order scattering is due to non-uniform twisting of the lamellae.
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  • 130
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 795-800 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 131
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 801-811 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Six oligoethylene glycols were crosslinked with triphenylmethane triisocyanate, and polymers with systematically changing network chain lengths were obtained and investigated. The 10-sec. torsion moduli versus temperature, glass transition temperatures, and cohesive energy densities of the polymers were determined and studied. The 10-sec. torsion modulus versus temperature plots show that all six polymers have a glassy transition and rubbery region of rheological behavior. The front factor calculated from the equation for the torsion modulus in the rubbery region when measured values of the modulus were used was compared with the front factor computed from equations that take into consideration molecular structures of the rubbery networks. With the exception of the case of crosslinked diethylene glycol the agreement in all the other cases between the values obtained for the front factor in both ways was good. In the investigated range of temperatures the polymers have below the glass transition temperature another transition point. The solubility parameters of the polymers, calculated from swelling experiments, were with the exception of the first member in the series almost identical.
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  • 132
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 861-869 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two crystalline forms (α and β) of poly(vinylidene fluoride) were studied by infrared spectroscopy. The spectral differences permitted the study of the transformation and the ratio of the two forms. The ordinary \documentclass{article}\pagestyle{empty}\begin{document}$ \vec G,\vec F $\end{document} matrix method was used to calculate the fundamental mode with a Urey-Bradley type potential field, and a preferred set of the force constants was obtained.
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  • 133
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 885-894 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: As an extension of earlier work on the crystallization kinetics of isotactic polystyrene, the spherulite growth rate in mixtures of isotactic polystyrene and benzophenone has been measured over a concentration range extending from pure polymer to a mixture containing about 30% benzophenone. The glass transition temperature has been measured over the entire range from pure polymer to pure benzophenone. For the mixtures the dependence of the growth rate on temperature is similar to that of the undiluted polymer. The addition of benzophenone causes a shift of the crystallization range to lower temperatures. For mixtures containing up to about 20% benzophenone, the maximum in the growth rate increases with increasing content of benzophenone. On addition of more benzophenone, the maximum rate is depressed. Taking into account the glass transition temperature of the mixtures, the influence of benzophenone on the melting point of isotactic polystyrene, and the volume fraction of polymer, we can describe the influence of benzophenone on the growth rate in a semiquantitative way.
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  • 134
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 961-965 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular motion of low molecular weight polychlorotrifluroethylene of different molecular weights between 500 and 1300 was investigated by means of broad-line nuclear magnetic resonance measurements. The line width and second moment of the resonant absorption lines were obtained at temperatures from 77 to 300°K. The line narrowing for low molecular weight samples takes place in one step. In samples higher than 900 in molecular weight, however, there appears to be a glass transition process, and the line narrowing tends to occur in three steps. The line narrowing due to local molecular motion becomes observable with increasing molecular weight.
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  • 135
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 947-952 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The intramolecular structure of oligomeric polyethylene (PE) in solvent mixtures of α-chloronaphthalene and carbon tetrachloride, α-chloronaphthalene and deuterated octane, and α-chloronaphthalene and deuterated hexadecane was studied at 35°C. by a high-resolution nuclear magnetic resonance technique. It was clearly shown that the n-alkanes show no detectable selective solvent absorption in these systems. The conformational structure (Pp), which was formed in “bulky” aromatic solvents when the chain length was greater than 16, was significantly destroyed by the presence of carbon tetrachloride, octane, or hexadecane in the above-mentioned solvent mixtures. Therefore, the “bulky” aromatic solvents, such as α-chloronaphthalene and 9-chloroanthracene, can be classified as Pp-structure-promoting solvents, in which the PE remains in the Pp conformation. In contrast, carbon tetrachloride and linear alkanes are Pm-structure-promoting solvents, in which the PE does not exhibit any Pp structure but is in the disordered Pm conformation. It is speculated that the Pp structure is caused by a “chain-fold” mechanism.
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  • 136
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 981-993 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A nylon 66 composed of uniformly sized spherulites approximately 50 μ in diameter was examined before and after cold drawing by light and electron microscopy of thin sections and by low-angle x-ray diffraction. Spherulites retained their identity through drawing, but the spherulites elongated less than the bulk specimen indicating that relative motion of spherulities must have occurred. The observation of dilations (0.3 μ long) at interspherulitic boundaries support this contention. The thin-section electron micrographs indicated that the spherulites were composed of radiating lamellae approximately 95 A. thick. After drawing, the lamellae were preferentially oriented both parallel and perpendicular to the draw direction. Lamellae parallel to draw had thinned to approximately 70 A. While lamellae perpendicular to the draw had apparently thickened to 150 A. Three low-angle x-ray diffraction patterns yielded quantitative agreement with the electron-micrograph data. The pattern form the undrawn nylon was a diffuse ring corresponding to a 95 A. spacing. On the drawn specimen, with the beam parallel to draw, a ring corresponding to the 150 A. spacing was obtained, while with the beam perpendicular to draw two arcs were recorded at spacings of 70 and 150 A. The drawing was done at room temperature and proceeded by neck formation and propagation, yielding a 4:1 draw ratio.
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  • 137
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1035-1040 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 138
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1041-1050 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theoretical analysis of the thermoelastic behavior of polymeric networks in swelling equilibrium with excess diluent, using both the kinetic theory of elasticity and the Flory-Huggins theory of mixing, is presented. Our calculations are restricted to the special case of diluents composed of a single constituent. The results are used to obtain the ratio of the energy component of the force fe to the total force f of rubber networks swollen in excess n-decane, and we find fe/f to be 0.17, which compares favorably with the value 0.18 reported for the unswollen network. Furthermore, fe/f is independent of elongation, in accordance with theory. The kinetic theory of elasticity is reasonably well obeyed in this highly swollen system although there remains a small contribution to the force from the C2 term of the Mooney-Rivlin phenomenological elasticity equation. It is not believed that this has an appreciable effect on fe/f.
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  • 139
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1065-1081 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Conformations of a series of poly(γ-alkyl L-glutamates) (ethyl, n-propyl, n-butyl, isobutyl, and isoamyl) were studied by ORD and infrared absorption methods. All except the n-propyl ester were found to be in helical form in nonpolar non-aromatic solvents such as ethyl acetate, chloroform, ethylene dichloride, methylene chloride, carbon tetrachloride, 2-chloroethanol, dimethylformamide, and dioxane. In such cases, the Cotton effects due to the n-π* transition of peptide bonds occurred near 234 mμ and were of a magnitude similar to those found for poly(γ-benzyl L-glutamate) and poly-L-methionine in nonpolar non-aromatic organic solvents. These four polypeptides in aromatic nonpolar solvents, such as benzene, benzyl alcohol, pyridine, and m-cresol, were also found to be in helical form, although the ORD parameters differed considerably from the values in non-aromatic solvents. An essential cause seems to be the interaction of π electrons on peptide bonds with π electrons in the solvents. Helix-coil transitions of these esters in chloroform-dichloroacetic acid mixtures (dichloroacetic acid seems to be a random coil-forming solvent) were expressed by the Shechter-Blout formulation. This was not true, however, for helix-coil transitions in benzyl alcohol-dichloroacetic acid mixtures. The dependence of the helical stability of these polypeptides in chloroform solution upon the side-chain length and upon temperature is discussed.
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  • 140
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1101-1139 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The submicroscopic morphology of uniaxially deformed isotactic polypropylene films has been examined by small-angle light scattering (SALS), electron microscopy, optical microscopy, small-angle x-ray scattering (SAXS), wide-angle x-ray diffraction, birefringence, sonic modulus, and density methods. Several new interpretations and extensions of existing theories are developed and verified experimentally as follows. (1) The Vv SALS pattern is shown to be a new tool for the identification of the sign of the birefringence of spherulites too small to be seen in the optical microscope. The theoretical dependence of the Vv SALS pattern is developed and verified experimentally with patterns from isotactic polypropylene, polyethylene, Penton, nylon 6,6, poly(ethylene terephthalate), and nylon 6,10. (2) Intraspherulitic lamellar behavior during deformation can be identified from the SAXS pattern. This includes quantitative evaluation of the long spacing between lamellae and their average orientation. (3) The two-phase sonic modulus theory is valid over the wide range of deformations, crystallinities, processing temperatures, and molecular weights used in this study. The deformation of isotactic polypropylene films drawn at 110 and 135°C. has been characterized quantitatively in terms of an integrated picture of mass movement on all morphological levels: the molecular, the interlamellar, and the spherulitic. At both temperatures, the spherulites deform affinely with extension, whereas the deformation mechanisms within the spherulite depend on the location of the radii with respect to the applied load. During spherulite deformation, lamellar orientation and separation processes predominate, whereas at high extensions, fibrillation occurs and crystal cleavage processes predominate. The noncrystalline region orients throughout the draw region. At 135°C. non-orienting relaxation processes appear in the noncrystalline region which retard the rate of molecular orientation with extension.
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  • 141
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 517-527 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The stochastic theory of chromatography developed by Giddings and Eyring and by McQuarrie is applied to gel permeation chromatography (GPC) by first recasting their assumptions to fit the GPC process and secondly by making specific assumptions about the molecular size dependence of the rate constants λ1 and λ2 for entrapment and elution of a polymer molecule, respectively. The model assumes that: (1) a monodisperse sample is injected; (2) molecules behave independently within the column; (3) no molecular diffusion occurs; (4) the polymer molecules are unperturbed random coils; (5) entrapment sites in the bed are identical; (6) λ1 is proportional to the probability Pe that the square of the polymer end-to-end distance is less than the square of the average pore radius in the bed; (7) λ2 is constant. The calculated difference in retention times, tR-to (where tR is the retention time for a molecule of arbitrary molecular size and to is the retention time for a molecule whose size totally precludes entrance into the pores of the bed), is shown to be proportional to Pe. The model as thus applied is based on only one parameter. The theory is tested by examining the ratio Pe/(tR - to)exp, predicted to be constant, for narrow polystyrene fractions in the molecular weight range 1.1 × 104 - 8.9 × 105. Chromatographs were obtained by Moore and Arrington by using a θ solvent and a single column packed with a porous glass bed having a sharp distribution of pore sizes. Ratio values ranged from 0.046 to 0.073 with an average value of 0.058 ± 0.009. This relative constancy demonstrates semiquantitative utility of the model for gaining insight into the GPC process.
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 621-638 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A torsional creep and recovery apparatus has been designed and constructed to measure extremely wide ranges of recoverable creep compliance (10-10 to 10-2 cm.2/dyne) and viscosity (10-1 to 1016 poises) within the temperature range -60 to 220°C. Friction is avoided by supporting the moving element, the rotor, in a magnetic field, inducing the required torque with a drag cup motor, and monitoring the angular displacement with a light lever and a light following recorder. Measurements of recoverable compliance can be made further into the region of time scale which is dominated by viscous deformation than has been heretofore possible. In situ sample manipulation of viscoelastic liquids is utilized. Measurement is made on liquid cylinders between circular stainless steel platens. Results which have been obtained on a 1.22 × 105 molecular weight polystyrene are presented to illustrate the range of possible measurements and to indicate the value of such results covering up to six logarithmic decades of time scale.
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  • 143
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 657-663 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray diffraction patterns have been taken as a function of time and temperature on a sample of polypropylene held under high pressure (4.14 kbar) for 180 hr. at a temperature of 248°C. and subsequently cooled to room temperature. The molded sample initially crystallizes in the triclinic γ-phase but transforms to the γ-phase at elevated temperatures. The rate of conversion from γ to α is a function of time and temperature and tends to approach a constant value with increasing time. The nature of the thermal changes occurring in the sample was also studied by differential scanning calorimetry. It appears that at low scan speeds, there is a solid-solid transformation from the α-phase to the γ-phase, but at high scan speeds, the γ-phase melts without conversion to the α-phase.
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  • 144
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1627-1637 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fibrous crystals of polyethylene are produced by crystallization from agitated solutions in xylene. If crystallization temperature is maintained between 97°C and 108°C these fibers are free from overgrowth effects and are seen to consist of flat, striated ribbons. This material was treated with fuming nitric acid, and the molecular weight distribution of the degradation product was analyzed by gel permeation chromatography. This distribution was found to consist of a low molecular weight peak and an exceptionally resistant high molecular weight tail over a wide range of degradation times in quantitative agreement with the serrations developed during the nitric acid attack. This is consistent with the fibers possessing a composite folded and extended chain structure. The lateral pulling out of smooth fibrils from the original fibers in the course of certain electron microscope sample preparation methods is consistent with the presence of chain-folded material and might account for the structureless fibrils reported in the literature. Partially successful attempts to obtain the extended chain portion in pure form by selective dissolution are mentioned together with some low-angle x-ray results.
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1683-1685 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1673-1681 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To learn more about the out-of-plane deformation of polymer lamellae during drawing, we have measured the resistance to shear along various planes in uniaxially oriented polyethylene and polypropylene. Fissures parallel to the orientation axis in oriented materials always cause too small an experimental value for the resistance of crystal glide parallel to the chain axes, but a rough estimate for the resistance to crystal glide is obtained using the elastic anisotropy. Also, the results suggest that kinking can be easier than glide when glide is inhibited by tie molecules.
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  • 147
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1705-1722 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We studied the high-temperature mechanical behavior of unplasticized poly(vinyl chloride) by stress relaxation experiments covering a temperature range of 100-180°C and a time interval of 0.01-3600 sec at an elongation of 40%. The polymer was observed to respond elastomerically within these set temperature limits. The molecular basis for this behavior is linked to the partial crystalline nature of this material. The crystalline phase is postulated to be the seat of the relaxation process taking place in the rubbery response region, and evidence is presented supporting this point of view. A comparison is made between free volume variations arising from thermal expansion and those originating instead from uniaxial straining. It is also pointed out that, following linear viscoelastic theory, the viscosity is a time-dependent quantity, and it is shown that for this polymer its variation with temperature at short times is ninefold less than the corresponding variations in its limiting value. Finally it is noted that the measured high-temperature tensile strength corresponds to a chain bond strength approximately 1/300 of the theoretical value.
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  • 148
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1773-1781 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Either of the two endothermic melting peaks found by differential thermal analysis of nylon 66 may be converted to the other by appropriate choice of annealing conditions. The two peaks are considered due to the melting of two morphological species, forms I and II. Form I is relatively fixed in melting temperature, while the form II melting temperature varies with annealing conditions and can be either above or below form I. The two forms can be distinguished by whether or not the conversion I → II takes place; if the sample is in form II no change in the thermogram is observed under suitable conversion conditions. The conversion of form I to form II also takes place during cold drawing. It has been previously shown that form I results from rapid cooling from the melt, and form II results from slow cooling. Form I appears to be kinetically favored, while form II is thermodynamically preferred. The variability in the form II melting point is attributed to variable crystal size and/or perfection.
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  • 149
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1803-1809 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1835-1851 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of various thermal pretreatments on the nucleation of isotactic polystyrene has been studied quantitatively by dilatometry. A distinction can be made between nuclei still present above the melting point (“resistant” nuclei) and nuclei created by severe supercooling (“induced” nuclei). The number of spherulites formed has been determined for different combinations of supercooling and crystallization temperatures. The results are interpreted in a satisfactory manner by assuming that in severe supercooling induced nuclei are created, which may grow into effective nuclei at higher temperatures. The crystallization of a severely supercooled polymer is completely governed by these induced nuclei, because they outnumber the resistant nuclei by some orders of magnitude. The number of induced nuclei can be decreased by purifying the polymer (removing catalyst residues). When cooled polymer is heated to temperatures just above the melting point, the induced nuclei are destroyed (“reversible melting”), so that only the resistant nuclei, which are few in number, remain. These resistant nuclei govern the crystallization behavior of a polymer which has not previously been cooled. Their number decreases on heating to temperatures far above the melting point.
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1919-1932 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theory of Cahn and Hilliard is used to derive an equation for the interfacial tension (free energy) between some demixed polymer solutions, applying a simple solution model treated by Debye in his theory of light scattering near the critical solution temperature. For a (symmetrical) system containing two polymers in a common solvent it is found that the interfacial tension is given by σ = (l/12½)Ωϕp 2σr, where l is the Debye l parameter for the range of molecular interaction - here equal to (2S2)½, where (S2)½ is the radius of gyration of both polymers, Ω is a heat of mixing parameter for polymer-polymer interaction, ϕp is the total volume fraction of polymer and σr is a function of the ratio of temperature and critical solution temperature. The equation is in qualitative agreement with experiments of Langhammer and Nestler.
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  • 152
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1903-1917 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Peak spreading in gel permeation chromatography has been studied with a range of gels including those whose permeation limit corresponded to about 103, 106, 108, and 109 molecular weight polystyrene. Peak spreading conformed to the equation YV2 = YM2 + YA2 + YI2 + YD2 + YS2, where YV is the peak width of a normal chromatogram, YM is the contribution due to the true molecular weight of the sample, YA is due to peak spreading in the apparatus, YI is spreading in the interstitial volume, YD is diffusional spreading due to time spent in the gel, and YS is due to sorption. Evaluating the appropriate parts of the equation leads to measures of the true molecular weight distribution and the contribution due to diffusion into and out of the gel. The data also allowed estimates as to the diffusional spreading with small molecules. With polystyrene having 100 000 molecular weight, diffusional spreading accounts for 80% of YV,2 but with small molecules the contribution due to diffusion was not detected.
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  • 153
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1943-1944 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 154
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1987-1997 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of thermal treatment in the 70-90°C. region on polybutene-1 crystals, prepared by precipitation from dilute pentyl acetate solutions and with lath, hexagonal, and square morphologies, have been studied by using electron microscopy. The stability of polybutene-1 crystals to thermal treatment increases in the order: lath 〈 hexagonal 〈 square. Elucidation of the crystallographic directions in unheated lath crystals with respect to the overall morphology was carried out; evidence for restricted folding in these crystals is discussed.
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  • 155
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of flow birefringence of cellulose tricarbanilates were carried out on nine fractions (0.27 × 105 〈 M ≤ 12 × 105) in a temperature range of 55-110°C, with benzophenone as a matching solvent (dn/dc = 0). The ratio of Maxwell constant to intrinsic viscosity, which has been found to be independent of molecular weight for the limiting case of Gaussian molecules, is successfully interpreted as a function of molecular weight in terms of the recent theory of Gotlib and Svetlov (based on the wormlike chain model of Kratky and Porod). From the measurements at 55°C a number of 36.6 monomer units per random link is deduced. This is in accord with results of small-angle x-ray scattering. For the extinction angle curves a clear transition is observed from rodlike to statistical molecules when the molecular weight is increased. At high molecular weights the master curves obtained for anionic polystyrenes and cellulose tricarbanilates coincide. Implications of this observation on the kinetic stiffness of the cellulose tricarbanilate chain are discussed. The intrinsic viscosity-molecular weight relationship is considered. From a comparison with the results of the theory of Eizner and Ptitsyn it is concluded that the cellulose tricarbanilate chain must be highly solvated in benzophenone.
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  • 156
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 2043-2049 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymer melt viscosity was determined as a function of hydrostatic pressure in an extrusion rheometer. An extrusion rheometer consisting of a barrel and a capillary can be looked upon as two capillaries in series. The barrel itself was used as the main viscometer and several different capillaries having length/diameter ratios of 3.5-100 were used as pressure boosters. For a Phillips type polyethylene of 0.95 g/cc density and 0.4 melt index, the apparent viscosity at 190°C and 7.12 sec-1 was increased nearly fourfold as the average pressure in the barrel was raised from atmospheric to 24000 psi. With colored layers of polyethylene as tracers the flow pattern in the barrel was examined. The velocity profiles in the barrel were well developed and parabolic, and thus indicated regular laminar flow under these conditions.
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  • 157
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1791-1801 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The spherulitic growth rate of isotactic polystyrene has been measured in a wide range of temperature by means of a polarizing microscope provided with a hot stage. It was possible to fit the experimental data to theory by choosing a value of 75 for the constant C2 of the WLF equation. The growth rate parameters were compared with those of polyethylene and polychlorotrifluoroethylene. The slowness of crystallization of isotactic polystyrene is mainly a consequence of the lower mobility of the molecules caused by the bulky phenyl groups.
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  • 158
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1813-1816 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 159
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1863-1886 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fickian and non-Fickian diffusion into polymer-solvent systems were simulated on both analog and digital computers. Methods were evaluated to solve the descriptive nonlinear ordinary and partial differential equations. Analog methods published previously have been expanded. It was shown that discrete time solutions are superior to discrete distance solutions for partial differential equations, as hardware requirements are small. Also, accuracy problems on some of the smaller installations can be reduced by reverse time integration. For highly nonlinear equations, analog methods are superior to digital in stability and effort required. Digital solutions can be require extensive preliminary work to define computation parameters. However, the errors introduced by the finite difference equations are small in moderately nonlinear equations and much more accurate solutions are possible. Generalized solutions for polymer-solvent diffusion with exponential concentration dependence are presented for the Fickian cases. Also, typical solutions are demonstrated for all known types of non-Fickian diffusion.
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  • 160
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1943-1943 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 161
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1975-1985 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The polarization of fluorescence from a polymer characterizes two segment orientation functions, fs(2) and fs(4). These may be calculated as a function of elongation using the kinetic theory of rubber elasticity. Three cases are considered: (a) the transition moment direction lies parallel to the segment axis and does not change its orientation during the lifetime of the excited state, (b) the transition moment direction lies at an angle γ to the segment axis, and (c) the transition moment changes its orientation during the lifetime of the excited state.
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  • 162
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1297-1315 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric properties and the d. c. conductivity of poly(vinyl chloride), poly(vinyl acetate), polychlorotrifluoroethylene, and poly(ethylene terephthalate) were measured at temperatures above and below the glass transition temperature and at various pressures up to 3000 atm. The α relaxation associated with the micro-Brownian motion of amorphous chain segments depends strongly upon temperatures and pressure, while the β relaxation due to local-mode motion of the frozen main chain shows weak dependence on temperature and pressure. It is found that the free volume concept is valid for description of the temperature and the pressure dependence of the relaxation time for the α process. Activation energy and volume for both relaxation processes are determined from the experimental data. A simple relation between activation energy and volume for the α relaxation and pressure dependence of the glass transition temperature are derived. Temperature and pressure dependence of the d. c. conductivity in the rubbery state are notably different from those in the glassy state. Ionic conduction appears to be dominant in these polymers.
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  • 163
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1357-1369 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A novel procedure is presented for calibrating a gel permeation chromatograph by using broad polymer fractions. The limit in accuracy is set by the accuracy of number-average and weight-average molecular weight measurements and the reproducibility of the chromatograph. In the particular calibration for linear polyethylene described here, low molecular weight fractions were prepared by nitric acid oxidation of annealed single crystals. The calibration is then of particular value in morphological studies of polyethylene. The influence in the calibration of polar endgroups on the polymer, as produced in these oxidized samples is discussed.
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  • 164
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of operational variables on calibration of GPC are reported. Variables examined include (1) temperature and solvent changes, (2) sample concentration, (3) injection time, and (4) flow rate. Each of these variables significantly affected molecular weight averages calculated from GPC data. The causes and methods of minimizing the effects produced by the individual variables are discussed.
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  • 165
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1613-1619 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper describes the application of gel permeation chromatography to the morphology of polymer single crystals. Various types of single crystals of polyethylene were etched with fuming nitric acid, and the molecular weight distributions of the degraded fragments determined. The crystal preparations studied were monolayer crystals grown from xylene solution at 85°C and multilayer crystals grown at 84°C and 70°C. In all cases peaks in the molecular weight distribution were observed corresponding to single and double transverses of the molecular chains through the lamellae. By using the chromatograph calibration described in a previous paper, the position of these peaks were compared and correlated with previous estimates of lamellar thickness from low-angle x-ray measurements. The relative positions of the peaks provide information regarding the nature of the fold surface. The results are found to be consistent with a model in which the majority of the molecules are tightly folded.
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  • 166
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1621-1625 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Preliminary results are reported on the use of gel permeation chromatography in morphological studies of bulk polymers and fibres. Several samples of bulk isotropic and drawn polyethylene were analyzed by gel permeation chromatography following nitric acid oxidation. In all cases suitable samples showed two peaks in the molecular weight distribution, suggesting a qualitative similarity with results for single crystals. It is concluded that the present data are consistent with chain folding in bulk polymers, both in the isotropic and oriented states, with a less degree of regularity than exists in single crystals.
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  • 167
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1659-1672 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Conventional extrapolation procedures for the calculation of intrinsic viscosities and the Huggins constant k′ have been critically examined. A condition which must be satisfied by the basic equation for viscosity-concentration relations of dilute solutions of nonelectrolytic polymers has been clarified. On the basis of the comparison of the curvatures for empirical equations and for the basic equation, it is proposed to use arithmetic averages of the values calculated from a Huggins plot and those from a Martin plot for good-solvent systems, and to employ the averages of values from the former and those from a Schulz-Blaschke plot for poor-solvent systems as approximations to the correct values. Failure to confine approximations in the usual statistical treatment of experimental points to the given range of the variables as well as neglect of the fact that curvatures for the empirical and basic equations do not necessarily coincide are the usual sources of error in the conventional extrapolation procedures.
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  • 168
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1723-1732 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple theoretical development is proposed to explain the variation of birefringence with degree of crystallization for crosslinked, stretched polymer networks. The model adopted for the calculations is one proposed by Flory in order to calculate the thermodynamic properties of such systems and hence is restricted to the special case of network orientation prior to the onset of crystallization. Our findings are briefly discussed and possible applications of the results are considered.
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  • 169
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 1-12 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,1,3,3-Tetramethyl-1,3-disilacyclobutane (I) was polymerized under the following conditions with H2PtCl6·6H2O as catalyst: (a) addition of I dropwise to a large excess of catalyst at room temperature, producing [(CH3)3SiCH2(CH3)2Si]2O in 90% yield; (b) polymerization at room temperature in the presence of 10% water with 23 ppm Pt, yielding 9% conversion to low molecular weight polymer after 4 weeks; (c) polymerization in an open vessel (25°C., 7 ppm Pt, M̄n = 1.2 × 105), a closed vessel (100°C., 28 ppm Pt, M̄n = 1.7 × 105), in a closed tube after twice freezing and evacuating (25°C., 23 ppm Pt, M̄n = 2.9 × 105); (d) polymerization in an oxygen atmosphere (25°C., 17 ppm Pt, M̄n = 2.7 × 105). The molecular weight distributions of the polymers with M̄n = 1.2 × 105 and 1.7 × 105 was studied by gel-permeation chromatography. Ratios of M̄w/M̄n are 3.1 and 2.7, respectively. In both cases a long tail of high molecular weight polymer is evident. Interpretation of the molecular weight distributions is qualitatively discussed on the basis of a postulated seven-step mechanism. Water is shown to be a source of chain termination. Evidence is presented for the existance of ≡SiOSi≡ and ≡SiOH in the silmethylene polymers. Negligible cyclization occurs. Orders of thermal stability measured by DTA and TGA for polydimethylsilmethylene (A), polydimethylsiloxane (B), and polysiobutylene (C) are: in He, A 〉 B 〉 C; in air, in air, B 〉 C ≅ A. A fractionally precipitated polydimethylsilmethylene had a weight loss of less than 5% by 600°C. by TGA analysis at 10°C./min. in He.
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  • 170
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 13-20 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Styrene (St) and methyl methacrylate (MMA) were polymerized by azobisisobutyronitrile at 50°C. in the presence of silanes such as tetramethylsilane, trimethylcholorosilane, dimethyldichlorosilane, methyltrichlorosilane, and tetrachlorosilane. The polymerization rates of both St and MMA in the presence of silanes were nearly equal to those in the absence of silanes. On the other hand, the molecular weights decreased gradually as the concentration of chlorosilane increased. The chain transfer constants of all the silanes in the polymerization of St and MMA at 50°C. were calculated by Mayo's equation. The chain transfer constants of Me4Si, Me3SiCl, Me2SiCl, MeSiCl3, and SiCl4 were 0.31 × 10-3, 1.25 × 10-3, 1.78 × 10-3, 1.92 × 10-3, and 2.0 × 10-3, for St and 0.13 × 10-3, 0.22 × 10-3, 0.245 × 10-3, 0.27 × 10-3, and 0.30 × 10-3, for MMA, respectively. From these results, it was found that the Si—Cl bond was radically cleaved. The Qtr values of the silanes, in the same order as above, were found to be 1.03 × 10-4, 2.33 × 10-4, 2.83 × 10-4, 3.10 × 10-4, and 3.35 × 10-4, respectively and the etr values were +0.58, +1.30, +1.50, +1.48, and +1.43, respectively.
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  • 171
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 375-379 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyethylene hydroperoxide (PEH) was prepared by low-temperature autoxidation initiated by AIBN. Over 85% of the total hydroperoxyl groups decompose by a rapid process, the remainder dissociate at about one-tenth of that rate. The results are the same whether PEH is decomposed in solution or in the solid state. Large amounts of scavenger have no effect on these decompositions; there is no radical-induced processes. The results suggest mechanisms of decomposition involving neighboring group assistance.
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  • 172
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 459-465 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetic studies were carried out on the polymerization of tetrahydrofuran with catalyst systems of aluminum alkyl-epichlorohydrin. As aluminium alkyl species AlEt3, AlEt3-H2O (1:0.1 to 1:1.0), and “oxyaluminum ethyl” were employed. The polymerizations with these catalysts are characterized by a mechanism of stepwise addition without chain transfer or termination, which is expressed by the kinetic relation Rp = Kp[P*] ([M]-[M]e), where [M] and [M]e are the instantaneous and equilibrium concentrations of monomer and [P*] is the concentration of propagating species calculated from the amount and molecular weight of the product polymer. The determination of the rate constant kp for these catalysts has shown that the polymerization rate varied considerably with the change of aluminum alkyl species, i.e., with the water-to-aluminum ratio, but the propagation rate constant itself varied very little. The variation of polymerization rate was, therefore, attributed primarily to the differences in concentration of the propagating species, i.e. the efficiency of the catalyst in forming propagating species. The catalyst efficiency was closely related to the acid strength of the aluminum alkyl species, which was estimated from the magnitude of shift of the xanthone carbonyl band in the infrared spectrum of its coordination complex with aluminum alkyl. The maximal catalyst efficiency was attained at about [H2O]/[AlEt3] = 0.75.
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  • 173
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 513-526 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three new, optically active, methyl-substituted 2-oxohexamethyleneimines were prepared by cyclization of the respective optically active C-methylated 6-aminohexanoic acids. The active forms of the amino acids used for the preparation of (-)-3-methyl-2-oxohexamethyleneimine and (-)-7-methyl-2-oxohexamethyleneimine were obtained by resolution of their diastereomeric quinine salts. s-(+)-5-methyl-2-oxohexamethyleneimine was synthesized without racemization from optically pure 2-isopropylidene-5-methyleyclohexanone (pulegone).
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  • 174
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 537-546 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solubility of cellulose triacetate in a range of solvents was measured, and the results for tetrachloroethane, chloroform, and acetic acid were compared with those from initial phase separation in solvent-nonsolvent mixtures and viscosity-concentration studies. The correlation found between solubilities, precipitation values, and values of the Huggins viscosity constant is discussed with reference to the type of polymer-solvent interaction proposed previously to explain fractionation behavior. A qualitative comparison of solubility-swelling behaviour was also made for a very low molecular weight cellulose triacetate sample in a wide range of solvents. Results are compared with those for higher molecular weight samples and discussed with regard to the cohesiveenergy densities of solvent and polymer. Some attempt has been made to predict suitable solvents for cellulose triacetate, based on consideration of their molecular structures.
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  • 175
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 589-593 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study was carried to determine experimentally the crosslinking of irradiated polypropylene by ultraviolet rays in vacuo. Three methods of detecting crosslinking were used: measuring the degree of swelling in decalin at room temperature, measuring the gel fraction in a tetrachloroethylene solution of the irradiated sample, and comparing the infrared spectra before and after irradiation. It was found that as the time of irradiation increases, the degree of swelling decreases, whereas the gel fraction in tetrachloroethylene solution increases. This shows that the crosslinking reaction proceeds with time. On the other hand, the infrared spectra of the irradiated sample remained almost unchanged, which shows that different bond species can hardly be formed by irradiation in vacuo. From these facts it may be concluded that the measurements amply confirm the hypothesis. Furthermore, it is demonstrated that ash residue in polypropylene plays an important role in photocrosslinking; that is, the photochemical primary process of the reaction is the absorption of light by the ash residue.
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  • 176
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 623-641 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The most important assumptions underlying the Smith-Ewart theory are that the locus of chain propagation is the monomer-swollen latex particle, polymeric chains are initiated by radicals entering from the water phase into the particles, chain termination is an instantaneous reaction between two radicals within one particle, and particles are nucleated by radicals absorbed into monomer-swollen soap micelles. Right or wrong, these and other assumptions used by Smith and Ewart are retained in this paper. The newly derived and experimentally verifiable equations contain only such parameters which can be determined by experiments not involving emulsion polymerization. The proportionality constant between the particle number and the appropriate powers of soap and initiator concentrations is defined in terms of these independent parameters. Absolute rate equations are presented for the intervals before and after the completion of particle nucleation. To calculate these rates it is not necessary to have prior knowledge of the experimental particle number. The conversion at which particle nucleation is complete is calculated. The molecular weight is defined in terms of independent parameters. Predictions are made for the particle size distribution. It is shown that the validity of the theory is confined to specifiable intervals of conversion, to a certain range of monomer/water ratio, and to soap concentrations whose upper and lower limits are given.
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  • 177
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 687-710 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A large body of data shows that the time dependence of conversion fits the equation P = At2 + Bt in the interval where, according to the Smith-Ewart model, the relationship should be linear. For latexes of very small particle size the Smith-Ewart linear relationship (P = Bt) is often observed, and for latexes of very large particle size the conversion was found to be proportional to t2. The experimental value of parameter B was in good agreement with independent theoretical predictions. From A and B the ratio between termination and propagation constants was calculated and was in the 5-200 range. Independent estimates of this ratio give the same order of magnitude. These independent estimates are from the literature and are obtained from the increase in conversion rate at catalyst post-addition during emulsion polymerization or from emulsion polymerization initiated by intermittent irradiation or from homogeneous polymerization in the presence of inert polymers of high viscosity. The conversion-time curves describing the whole conversion process generally have sigmoid shape. The molecular weight is often found to pass through a maximum as the conversion increases. In one experiment this maximum coincided with the calculated maximum in the average number of radicals per particle Q. The variation of experimental molecular weights with conversion accurately followed the theoretical predictions. The deviation from the Smith-Ewart model was often significant. The value of Q was not 0.5, as the Smith-Ewart model requires it to be, but often reached values much larger, as large as 10. The particle size distribution broadened with increasing conversion and became increasingly skew. Numerous data taken from the literature are in good quantitative or qualitative agreement with the theory proposed in Part III and for these data the observed deviations from the Smith-Ewart theory are readily explainable. The new data obtained with styrene, n-butyl methacrylate, and methyl methacrylate are also in quantitative agreement with the new theory. One experiment involving methyl methacrylate is analyzed in great detail. The variation of time, of Q, of molecular weight, of average particle size, and of particle size distribution with conversion are reported. The molecular weight distribution is also calculated from the conversion dependence of molecular weight.
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  • 178
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 755-762 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of ethylene with ball-milled titanium dichloride leads to a completely linear polymer with terminal unsaturation corresponding to approximately one carbon-carbon double bond per molecule. Polymerization rate is first-order in both monomer and catalyst concentration at 140°C. Due to a thermal deactivation of the catalyst, the polymerization rate falls sharply with temperature above 180°C. Propylene and butene-1 will copolymerization with ethylene in this system, propylene more efficiently than butene-1. Evidence for copolymerization of trans-2-butene, but not of the cis-isomer or of isobutene, in trace concentrations is presented. Propylene is homopolymerized to a product low in isotactic content. The significance of the structural and (limited) kinetic data in terms of the mechanism of polymerization are discussed.
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  • 179
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 243-246 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 180
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 269-289 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The action of aluminium halides upon polystyrene was studied as a function of the nature of the reaction medium and of the concentration of catalyst. It was demonstrated that polystyrene undergoes crosslinking, the extent of which is particularly important in chlorinated aliphatic solvents and at high catalyst concentrations. In additions, phenyl rings of the polymer are alkylated and halogenated by the solvent or catalyst. Infrared spectroscopic investigation of the structure of the products indicated that in most cases crosslinking was connected with the formation of 1,4-disubstituted, and eventually 1,2,4-trisubstituted benzenes. In carbon tetrachloride medium, meta substitution was also detected. In products obtained when polystyrene was treated with high amounts of the Lewis acid in CCl4 medium degrees of substitution even higher than three were probable.
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  • 181
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 353-361 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A comparison of the x-ray diffraction from twisted nylon 66 and poly(ethyleneterephthalate) monofilaments is made with the scatter predicated by a model assuming an affine deformation of the fiber. The x-ray diffraction of the model is characterized by an approximately constant intensity over the entire range of the azimuthal dispersion. With twisted nylon 66 fibers the (010) reflection is split into a bimodal intensity distribution about the equator, while the (100) reflection maintains a distinct maximum on the equator. It is proposed that this difference is due primarily to the fact that a plastic deformation involving rotation of crystal planes occurs more readily when the shear stress acts in [010] direction than in the case when it acts in the [100] direction. A similar behavior is found with poly(ethylene terephthalate) fiber.
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  • 182
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A cationic polymerization of formaldehyde which gave a high molecular weight polymer was studied in liquid carbon dioxide at 20-50°C. In the polymerization without any catalyst both the rate of polymerization and the molecular weight of the resulting polymer increased rapidly with a decrease in the loading density of the monomer solution to the reaction vessel, and also increased with an increase in the initial monomer concentration. From these results it was concluded that the initiating species could be ascribed to an impurity contained in the monomer solution. Both the rate of polymerization and the degree of polymerization of the polymer also increased with rising temperature. The carboxylic acid added acted as a catalyst in the polymerization because of increase in the polymer yield, the molecular weight of polymer formed, and the number of moles of polymer chain with increasing dissociation constant of acid used. It was concluded that the polymerization in liquid carbon dioxide proceeded by a cationic mechanism. Methyl formate had no influence on the polymerization, but methanol and water acted as a chain-transfer agent.
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  • 183
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetic behavior on the polymerization of formaldehyde with and without acidic catalyst, in liquid carbon dioxide, in the temperature range of 30 to 50°C. was investigated. In the polymerization without catalyst both the polymer yield and the degree of polymerization increased with reaction time and also with rising temperature. With acidic catalyst, such as acetic acid and dichloroacetic acid, both the polymer yield and the degree of polymerization increased more than that in the polymerization without catalyst. The overall rate of polymerization with and without acidic catalyst was expressed by the first-order rate equation with respect to monomer concentration. From the results it was concluded that the polymerizations belonged to a type of successive polymerization with rapid initiation and no termination. The rate constant and the activation energy of each elementary process of polymerization were estimated on the basis of the results.
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  • 184
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 475-484 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of crystallinity on water sorption behavior by poly(vinyl alcohol) (PVA) was studied by using a PVA of low crystallinity (15% crystalline by x-ray analysis) and an annealed sample there from (46%) crystalline. With the increase of crystallinity, the sigmoid shape (which is a characteristic for the sorption isotherm of the low crystalline polymer) diminishes. The B.E.T. plots of the isotherms are linear between the relative vapor pressures of 0.1 and 0.4 as usual, and deviate from straight lines in the higher pressure range in the direction of a larger sorbed quantity than that predicted by the B.E.T. theory. This tendency is regarded as a kind of dissolution, and the Flory-Huggins interaction parameter χ1 was calculated. In both polymers, the χ1 versus pressure relation has a maximum, while overall χ1 values are smaller in the polymer of low crystallinity. The maximum point (which lies in the higher pressure region in case of the less crystalline sample) is considered to be a transition point from a phenomenon controlled mainly by an adsorption mechanism to a phenomenon controlled mainly by a dissolution mechanism. Accordingly, the separation of the isotherm into adsorption and a dissolution components was made, and the polymer fraction which contributes to the dissolution mechanism versus pressure relation was calculated. The result indicates that the crystalline region observed by x-ray analysis may partly contribute to the dissolution process at room temperature.
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  • 185
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 1281-1291 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The vinyl ester of dehydrogenated abietic acid has been homopolymerized, copolymerized with vinyl chloride, vinyl acetate, and butadiene and terpolymerized with styrene and acrylonitrile. Both in the homopolymerization and the copolymerization, the vinyl ester of dehydroabietic acid has given lower molecular weight polymers than were obtained with the vinyl ester of tetrahydroabietic acid. Polymers containing the vinyl ester of dehydroabietic acid can be readily crosslinked with peroxide.
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  • 186
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 1315-1323 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The action of dicumyl peroxide on poly(n-butyl methacrylate) and poly(n-nonyl methacrylate) produces degradation and crosslinking reactions in both polymers. Crosslinking and degradation of poly(n-alkyl methacrylates) are influenced also by the initial molecular weight of the polymer as well as by the type of alkyl group. The ratio of degradation to crosslinking p/q determined on the basis of the equation of Charlesby and Pinner, S + S0.5 = (p/q) + (1/qPn) is for poly(n-butyl methacrylate) of viscosity molecular weight 0.923 × 106 and 2.16 × 106 of 0.78 and 0.60, respectively; for poly(n-nonyl methacrylate) of weight average molecular weight 3.83 × 105, p/q is 0.16. Crosslinking efficiencies (moles of crosslinks per mole of decomposed dicumyl peroxide) of the above polymers are relatively very low: 0.014, 0.005, and 0.039, respectively. The critical concentration of dicumyl peroxide necessary for the formation of gel, provided it undergoes complete decomposition, is for the above polymers 1.82, 1.65, and 0.98 wt.-%, respectively. Under the critical concentration of dicumyl peroxide the limiting viscosity number of poly(n-butyl methacrylate) increases with increasing concentration of dicumyl peroxide. An initial decrease of the value of the limiting viscosity number, which is characteristic for polymers undergoing simultaneous degradation and crosslinking, was not observed.
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  • 187
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 1341-1349 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-(4-phenyl-1-butene) was prepared by using a titanium tetrachloride-triethyl-aluminum catalyst. The crystalline polymer melts at 158°C. Double orientation could not be obtained but all the reflections on the x-ray fiber diagram can be indexed on the basis of an hexagonal cell (a = 20.8 A., c (fiber repeat) = 6.61 A.). However the crystal structure proposed does not belong to an hexagonal space group but to the monoclinic (pseudo-orthorhombic) space group Pa (a = 10.4 A., b = 18.0 A., c = 6.61 A.). The 31 helix, common to systems of this type, is consistent with an isotactic (not syndiotactic) configuration for the polymer chain.
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  • 188
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Under different conditions two products, one green and one brown, were obtained by the air oxidation of chromium(II) diphenylphosphinate. Air oxidation of an aqueous suspension of the phosphinate apparently yields a mixture in which the green form predominates. As initially isolated, the green form is a low molecular weight polymer corresponding to {Cr(H2O)(OH)[OP(C6H5)2O]2}n, with n approximately 11. It spontaneously polymerizes further in organic solvents to high molecular weight polymers of the same composition, with n in the range 150-200. This polymerization reaction in volves the elimination of water and is probably a reaction between endgroups resulting in a basically linear polymer. The brown product, corresponding to low molecular weight {Cr2(H2O)(OH)2[OP(C6H5)2O]4}p, also polymerizes spontaneously but at a faster rate and to a gel. The polymer so produced is less soluble than that produced from the low molecular weight green product and is probably crosslinked.
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  • 189
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 1381-1396 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A vinyl monomer that has the nitrile or carbonyl group conjugated to the C=C double bond, such as acrylonitrile, methyl acrylate, and methyl methacrylate, forms a complex with an alkylaluminum halide, and the complex reacts spontaneously with a hydrocarbon monomer such as styrene, propylene, or ethylene, giving a high molecular weight copolymer. The copolymers always contain the two monomer units in 1:1 ratio. Thus styrene, copolymerized with methyl acrylate or methyl methacrylate in the presence of ethylaluminum sesquichloride in homogeneous toluene solution, gives such an equimolar copolymer regardless of the initial monomer compositions. The NMR spectra of these copolymers are distinctly different from those of the equimolar copolymers obtained with azobisisobutyronitrile as initiator and have simpler and well separated patterns. The copolymers and the corresponding radical copolymers appear to be amorphous, judged by their x-ray diffraction patterns and their differential thermal analyses. Their infrared spectra resemble each other very closely. Hence, the difference in the NMR spectra may be ascribed to the matter of the sequence distribution. The infrared spectrum of ethylene-methyl acrylate copolymer shows no absorption near 720 cm.-1 due to the methylene sequence arising from ethylene-ethylene linkage. These experimental data lead to the inference that the equimolar copolymers obtained in this work may have an alternating sequence.
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  • 190
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 1367-1379 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study was made of the gamma-ray-induced copolymerization of tetrafluoroethylene and 3,3,3-trifluoropropene. Copolymerizations were carried out at 100°C. and 5000 atm. pressure and at 21°C. and various pressures up to 8000 atm. The reactivity ratios calculated from the composition data indicate that the propagation rate constants favor addition of trifluoropropylene by a factor of 3-7; individual values depended little on the polymerization pressure and temperature. Polymerization rates changed little with monomer composition between 0 and 75% tetrafluoroethylene; between 75 and 95% tetrafluoroethylene they increased by a factor of 10. As many as 850,000 molecules were polymerized per 100 e.v. absorbed. The copolymers are soluble in hexafluorobenzene at 29.6°C. if they contain less than 70% tetrafluoroethylene. Intrinsic viscosities range from 0.1 to about 10 dl./g. From various considerations it appears likely that the degree of polymerization is about equal to the kinetic chain length in high-pressure polymerizations at 21°C.; at autogenous pressure or at 5000 atm and 100°C., monomer transfer reduces the value considerably.
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  • 191
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 1431-1440 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By irradiation with gamma rays styrene was grafted onto hydrochloric acid lignin. When the graft polymers were subjected to nitrobenzene oxidation, the vanillin yields indicated two kinds of reaction occurring in the grafting. Polystyrene branches were separated from the graft polymers, and their M̄n were determined osmometrically. At grafting ratios of up to 100 the vanillin yields diminished proportionately with increasing grafting, and the M̄n of the branches, 5000, was unchanged. At grafting ratios of more than 100 the vanillin yields were constant, independent of the ratios, but the M̄n values of the branches increased with grafting. Paper chromatography of the aromatic acids obtained by oxidation of methylated lignin and the graft polymer indicated that isohemipic and metahemipic acids were more abundant in the acid fraction of the graft polymer than in the lignin itself. A qualitative mass analysis of the gaseous products evolving from the irradiated lignin showed the presence of hydrogen molecules only. Gamma-ray radiation brought about no change in the yields of vanillin. It was therefore concluded that radiation grafting on lignin at grafting ratios of less than 100 proceeded through the addition of the styrene polymer radicals to the aromatic nuclei of the lignin and that then branches propagated from the aliphatic part of the lignin, where C—H bond scission had been caused by the irradiation. The grafting sites of lignin would be C-5 and C-6 of the guaiacyl nucleus and, probably the β and γ carbon atoms of the aliphatic side chain of the lignin.
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  • 192
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 1625-1632 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of five different polymers containing sugar residues on side chain is described. 1-O-Methacryloyltetra-O-acetyl-D-glucose, 1-O-methacryloyltetra-O-acetyl-D-galactose, and 6-O-methacryloyltetra-O-acetyl-D-glucose were prepared and polymerized. The polymethacrylates obtained were converted into water-soluble polymers by removing the acetyl protective group with sodium methoxide. 6-O-Methacryloyldiisopropylidene-D-galactose was also prepared and polymerized. The isopropylidene protective group was removed by acid hydrolysis. Poly (N-methacryloylglucosamine) was prepared directly by the polymerization of N-methacryloyl-D-glucosamine without the use of any protective group.
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  • 193
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 1655-1660 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The NMR spectra of stereoblock poly(methyl methacrylate) in several solvents were measured. It is concluded from the following experimental results that the solute-solvent complexes are formed in benzene solution: the chemical shifts measured in C6H6 go to a lower field than do those in CDCl3, except those of the ester methyl group, which splits into three resonances, and the shifts in the aromatic solvents are so different from those in the aliphatic solvents that Buckingham's theory cannot be applied to the results. The analysis of the temperature dependence of the chemical shifts of PMMA in benzene solution gave the heat of formation of the complex: ΔH = 2.8 ± 0.5 kcal./mole.
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  • 194
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fractional precipitation and gel permeation chromatography yield comparable information on the molecular weight distribution of various cellulose esters. The GPC technique applied to samples obtained by fractional precipitation gives a much more definitive analytical tool than either method used independently. One practical application of this work showed the same molecular weight distribution of two cellulose acetates prepared by different methods.
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  • 195
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 1643-1653 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic approach to the polymer reaction, with KOH as catalyst, between ethanol and poly(p-vinylphenyldimethylsilane) containing silicon-hydrogen as a functional group on the side chain was carried out. The rate equation was obtained by measuring the initial rate of the model reaction as v = k[KOH] [SiH] [EtOH] in benzene and v = k[KOH] [SiH] in methyl ethyl ketone. It was observed that the rate of reaction was affected by the polarity of the solvents. In the polymer reaction the rate constant decreased markedly with increasing ethanol concentration. A change of viscosity of the polymer in various solvents was observed to have a good correlation with the decrease in reaction rate in corresponding solvents. In mixed solvents, consisting of both good and poor solvents for the polymers, the reaction rate depended upon two factors, the entanglement of the polymer chain and the polarity of the solvents. The equivalent globular model of the polymer chain is suggested for study of the polymer reaction. A schematic local-distribution curve of the reaction species is proposed.
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  • 196
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 1058-1060 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 197
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 1071-1071 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 198
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and polymerization of a series of perhaloalkyl allyl and vinyl ethers derived from perhaloketones is described. Data on the critical surface tension of wetting (γc) for high molecular weight polymers of heptafluoroisopropyl vinyl ether and low molecular weight poly(heptafluoroisopropyl allyl ether) is also presented. Preparation of the allyl ethers is a one-step, high-yield displacement reaction between the potassium fluoride-perhaloacetone adduct and an allyl halide, such as allyl bromide. The vinyl ethersare prepared by a two-step process which involves displacement of halide from a 1,2-dihaloethane with a KF-perhaloacetone adduct and dehydrohalogenation of the 1-halo-2-perhaloalkoxyethane to a vinyl ether. Low molecular weight polymers were obtained with heptafluoroisopropyl allyl ether by using a high concentration of a free-radical initiator. The low molecular weight poly(heptafluoroisopropyl allyl ether) had a γc of 21 dyne/cm. No polymer was obtained with tributylborane-oxygen or with VCl3-AIR3, with gamma radiation, or by exposure to ultraviolet light. High molecular weight polymers were obtained from heptafluoroisopropyl vinyl either by using either lauryl peroxide or ultraviolet light but not by exposure to BF3-etherate. The γc for poly(heptafluoroisopropyl vinyl ether) ranged from 14.2 to 14.6 dyne/cm., and the significance of this value is discussed in relation to the γc for poly(heptafluoroisopropyl acrylate).
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  • 199
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 2051-2058 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of conventional novolacs with polyfunctional materials is known to yield crosslinked infusible products. Surprisingly, high proportions of polyfunctional phosphorus derivatives can be esterfied with o,o′-linked novolacs without encountering gelation. Soluble, fusible resins of high phosphate content, which possess improved flame retardance, are conveniently obtained. We attribute this result to the formation of cyclic esters in preference to crosslinking, as evidenced by the formation, in good yield, of the eight-membered heterocyclic compound C27H31O4P from o,o′-methylenebis(p-tert-butylphenol) and phenyl phosphorodichloridate. Relatively large amounts of polyfunctional derivatives of boron and silicon can also be reacted with o,o′-linked novolacs, presumably in a similar manner. Novolacs partially reacted with phosphorus, boron, or silicon derivatives and retaining some phenolic hydroxyl cure readily with hexamethylenetetramine, yielding products exceptionally low in volatile loss at 400°C.
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  • 200
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    Journal of Polymer Science Part A-1: Polymer Chemistry 6 (1968), S. 2079-2083 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Free-radical copolymerization of methyl acrylate, ethyl acrylate, butyl acrylate, and methyl methacrylate with 9-vinylanthracene was studied, and the reactivity ratios r1 and r2 were calculated. In the light of earlier data on copolymerization of 9-vinylanthracene with styrene results show that the difference in polarity of the monomers participating in the copolymerization has an insignificant influence compared with that of the steric factors involved in the reaction.
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