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  • Physics  (492)
  • 1995-1999
  • 1980-1984
  • 1975-1979  (492)
  • 1976  (492)
  • 1
    Electronic Resource
    Electronic Resource
    Degradation of polymer mixtures. VIII. Blends of poly(vinyl acetate) with poly(methyl methacrylate) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1839-1856 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The degradation of blends of PVA and PMMA in the form of films cast from a common solution of the polymers has been studied by TVA, TG, and EGA (evolved gas analysis) for acetic acid. Volatile degradation products have been characterized by spectroscopic and GLC techniques. Molecular weight, spectral and thermal stability changes in PMMA extracted from partially degraded blends have been examined. These blends behave in a closely analogous manner to PVC-PMMA blends already investigated. The results suggest that the PMMA component of the heterogeneous blends is modified in two ways: (1) in a destabilization reaction series initiated by attack of acetate radicals generated in the PVA phase which migrate into the PMMA phase, and (2) in a stabilization reaction involving conversion of ester side groups to acid and subsequently to anhydride ring structures which act as blocking points for depolymerization. The rate of acetic acid production in the blend is less than in PVA degraded alone. The mechanism of degradation of PVA is reconsidered in the light of these results.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140804
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  • 2
    Electronic Resource
    Electronic Resource
    Effect of pH on the reactivity ratios in aqueous solution copolymerization of acrylic acid and N-vinylpyrrolidone (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1987-1992 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acrylic acid (AA) and N-vinylpyrrolidone (NVP) were copolymerized in aqueous solution at 30°C in the pH range 4-9 and the monomer reactivity ratios (r1 for AA and r2 for NVP) were determined as a function of pH from the high conversion data by using both the differential (YBR) and the integrated copolymerization equations. The value of r1 decreased from 5.2 at pH 4 to a minimum of 1.3 at pH 5 and then increased to 8.1, 6.6, and 7.2 at pH 7, 8, and 9, respectively. Addition of 1M NaCl at pH 6.5 restored the r1 nearly to that at pH 4, the predominantly un-ionized acid. The r2 values for NVP were nearly zero at all pH values except at pH 5. The variation of the reactivity ratios with pH was examined in terms of the electrostatic interactions between the ionized monomer molecules, the rate of homopolymerization of acrylic acid, and the cation binding to the poly(acrylic acid) molecules. The r2 values for NVP compared favorably with the literature values reported in bulk and organic solvent systems, although r1 values are much higher.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140815
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  • 3
    Electronic Resource
    Electronic Resource
    Polymerization of coordinated monomers. XII. Alternating copolymerization of γ-crotonolactone with styrene with the use of stannic chloride (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1993-2007 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: γ-Crotonolactone and styrene copolymerize alternately in the presence of stannic chloride at -10°C under photoirradiation. The intrinsic viscosity of the resulting copolymer is in the range of 0.6-0.8 dl/g at 30°C in chloroform. The equilibrium constants for the complex formation between stannic chloride and γ-crotonolactone were determined in 1,2-dichloroethane-toluene solution at 0 and -20°C by use of absorption band at 350 nm. Continuous variation plots based on the 1H-chemical shift show a 1:1 interaction between styrene and the γ-crotonolactone coordinated to stannic chloride. The equilibrium constants for the ternary molecular complex formation between the coordinated γ-crotonolactone and styrene were determined in 1,2-dichloroethane in the temperature range from -20 to 0°C. The equilibrium constants, derived independently from the measurements of the nonequivalent protons in γ-crotonolactone, are equal to each other within the experimental error. The mechanism of the alternating copolymerization of γ-crotonolactone and styrene in the presence of stannic chloride is discussed in terms of the homopolymerization of the ternary molecular complex.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140816
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  • 4
    Electronic Resource
    Electronic Resource
    Oligomeric polyaromatic ether-ketone-sulfones with acetylenic end groups. IX. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2033-2042 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two oligomeric polyaryl ether-ketone-sulfones with acetylenic end groups have been prepared. These materials which are low melting and readily soluble in organic solvents on heating undergo reactions which are presumably trimerizations of the terminal acetylenic groups to give cured polymers which do not soften until about 200°C and which are stable in circulating air at 300°C with less than 10% weight loss in 10 days.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140819
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  • 5
    Electronic Resource
    Electronic Resource
    Polymerization of coordinated monomers. XIII. Binding in the ternary molecular complex composed of γ-crotonolactone, styrene, and stannic chloride (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2009-2022 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The time-averaged orientation of the styrene molecule in the ternary molecular complex composed of stannic chloride, γ-crotonolactone, and styrene is determined by use of 1H-chemical shifts of the nonequivalent protons of the γ-crotonolactone. The chemical shift change for each of the various protons of the γ-crotonolactone on the ternary molecular complex formation can be represented by the anisotropic shielding effect of the benzene ring of one oriented styrene molecule. This fact indicates that the ternary molecular complex has a definite time-averaged conformation, though the “complexing” styrene molecule exchanges between in the oriented state and in the free state more rapidly than the time scale of the 1H-NMR spectrometry. The magnitudes of the Coulomb, induction, dispersion, charge-transfer, and exchange-repulsion energies between the γ-crotonolactone and the styrene in the ternary molecular complex are estimated by use of the result of the extended Hückel calculation and that of absorption spectrometry. The Coulomb and dispersion forces between the carboryl group of the coordinated γ-crotonolactone and the benzene ring of the styrene function mainly in the ternary molecular complex formation. Both the induction force and the charge-transfer force make a small contribution to the ternary molecular complex formation.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140817
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  • 6
    Electronic Resource
    Electronic Resource
    Conductance studies of salt solutions in the presence of poly(vinylbenzo crown ethers) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2023-2031 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conductance of acetone and methyl ethyl ketone solutions of tetraphenylborate salts in the presence of homopolymers and styrene copolymers of vinylbenzo-15-crown-5 and vinylbenzo-18-crown-6 was studied, and the results compared with data obtained for crown ethers. Polycations are formed on binding cations to the poly(crown ethers), and the conductance behavior of the polyelectrolytes depends on the nature of the cation-crown complex and the spacing between crown moieties which in turn determines the charge density on the polymer chain. The compositions of the crown-cation complexes were determined for crown ethers. The complex formation constants of sodium and potassium cations to poly(vinylbenzo-18-crown-6) were found to change as more cations bind to the chain. This is not the case for the copolymers where the crown ligands are spaced farther apart. A mixture of poly(vinylbenzo-15-crown-5) and 10-3M potassium tetraphenylborate in methyl ethyl ketone or acetone has a minimum conductance at a crown to cation ratio of 3.0, but the conductance rapidly increases on addition of crown ether. This was used to qualitatively determine the binding efficiency of a series of crown ethers since the rate of increase in the conductance is a measure of the binding ability of the crown ether to the cation.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140818
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  • 7
    Electronic Resource
    Electronic Resource
    Liquid crystal polymers. I. Preparation and properties of p-hydroxybenzoic acid copolyestersPaper presented in part at the Society of the Plastics Industry Annual Technical Conference, Washington, D.C., February 4-8, 1975. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2043-2058 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High molecular weight copolyesters were prepared by the acidolysis of poly(ethylene terephthalate) with p-acetoxybenzoic acid and polycondensation through the acetate and carboxyl groups. The mechanical properties of the injection-molded copolyesters containing 40-90 mole-% p-hydroxybenzoic acid (PHB) were highly anisotropic and dependent upon the PHB content, polyester molecular weight, injection-molding temperature, and specimen thickness. As the injection-molding temperature increased and the specimen thickness decreased, the tensile strength, stiffness, and Izod impact strength increased when measured along the direction of flow of the polymer melt, and the coefficient of thermal expansion was zero. In some compositions these properties were superior to those of commercial glass fiber reinforced polyesters. Maximum tensile strengths, flexural moduli, notched Izod impact strengths, and minimum melt viscosities were obtained with polyesters containing 60-70 mole-% PHB. Higher oxygen indicies (39-40) and heat deflection temperatures (150-220°C) were obtained with 80-90 mole-% PHB.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140820
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  • 8
    Electronic Resource
    Electronic Resource
    Kinetics of two-phase bulk polymerization. II. The influence of dissolved polymer (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2121-2134 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of dissolved polybutadiene on the initial rate of polymerization of styrene was investigated by using high-precision dilatometric techniques. The dissolved polymer reduced the rate of polymerization by amounts greater than can be accounted for by a reduction in monomer concentration. Rate reductions increased with the amount of dissolved polybutadiene and with its molecular weight and were greater for benzoyl peroxide initiator than for equal concentrations of azobisisobutyronitrile. Surprisingly, analogous rate reductions were observed when polystyrene were substituted for the polybutadienes, except that at high polystyrene concentrations, the expected autoacceleration was observed. These rate reductions showed no correlation with the viscosity of the reaction mass, nor did the dissolved polymer affect initiator efficiency. At a given level of a particular dissolved polybutadiene, rate reductions were diminished by increasing levels of each initiator, and by adding a chain-transfer agent. Good quantitative agreement was obtained with the number-average length of the growing polymer chains, whether varied by using different initiators, changing initiator level, or adding chain-transfer agent. These results are inconsistent with a chemical mechanism, but they are explained by a proposal originated by North and Reed whereby the dissolved polymer makes the reaction mass a “poorer” solvent for the growing polymer chains, reducing their overall coil dimensions and enhancing their rate of diffusion together for termination.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140903
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  • 9
    Electronic Resource
    Electronic Resource
    Acidic dehydration as an analytical method for evaluating ethylene oxide-propylene oxide copolymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2135-2145 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acidic dehydration by p-toluenesulfonic acid at 250°C converts poly(alkylene oxides) into dioxane derivatives which can be separated by gas-liquid chromatography. This procedure has been developed as an analytical technique for characterizing some aspects of the molecular structure of polymers of ethylene and propylene oxides. Experimental data on homopolymers, their blends, and some model copolymers have shown that the method is capable of distinguishing between copolymers of different structures, giving correct overall comonomer contents and also ranking copolymers according to their degrees of blockiness.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140904
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  • 10
    Electronic Resource
    Electronic Resource
    Study of radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. IX. Preirradiation polymerization of styrene-silica gel system (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2193-2205 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preirradiation polymerization of the styrene-silica gel system was studied in detail. Both graft polymers and homopolymers have bimodal GPC spectra. High molecular weight peaks were formed in a radical mechanism and the low molecular weight peaks were formed in a cationic mechanism as same as those in the simultaneous irradiation polymerization. The rate of formation of the low molecular weight peaks was very high compared with that of the high molecular weight peaks. Monomer conversion and percent grafting leveled off at about 1-2 Mrad. Radiation dose dependence of the four peaks were different from each other. Monomer conversion and percent grafting decreased as the preheating temperature of silica gel increased. The amount of the low molecular weight peaks of graft polymers depended on the number of silanol groups, as in the case of the simultaneous irradiation polymerization. A reaction mechanism for the preirradiation polymerization is proposed based on the results obtained.
    Additional Material: 18 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140910
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  • 11
    Electronic Resource
    Electronic Resource
    Reaction of poly(vinyl alcohol) with pentavalent vanadium ion (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2251-2261 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of poly(vinyl alcohol) (PVAL) with V(V), i.e., pentavalent vanadium ion, was studied in aqueous H2SO4 medium. The viscosity change of reaction mixture with time showed a peculiar feature owing to formation of labile complex between V(V) and PVAL and the subsequent decomposition of the complex. On the other hand, the change of viscosity disappeared when NaOH was added during the reaction to neutralize H2SO4 in the reaction mixture. Under a suitable condition, the reaction mixture set to a gel as a result of complex formation. It appeared that reactive sites in PVAL responsive to complexing with V(V) were 1,2-glycol unit and 1,2-ketoalcohol unit resulting from the oxidation of 1,2-glycol by V(V). The rate of oxidation was increased with increasing H2SO4 concentration. The main-chain scission of PVAL took place to an insignificant extent, unless the reaction condition was severe. Based on the results obtained a reaction mechanism has been proposed.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140915
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  • 12
    Electronic Resource
    Electronic Resource
    Radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene. VI. Effects of pressure and temperature (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2307-2318 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In a radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene, the effects of pressure and temperature were investigated in the range of 0-40 kg/cm2 and 7-53°C at emulsifier concentration of 0.5 and 2.0%. Both the polymerization rate and the molecular weight of copolymer increase with increasing pressure and decreasing temperature. These facts are mainly due to an increase of the monomer concentration in the polymer particles. The rate of polymer chain formation was found to be independent of pressure and temperature. The initiation reaction is due mainly to the entry of radicals generated in the aqueous phase into the polymer particles. The apparent activation energy is -2.0 to -3.8 kcal/mole for the polymerization in the presence of 0.5% emulsifier, but is nearly zero at an emulsifier concentration of 2.0%. This difference in apparent activation energies at emulsifier concentrations of 0.5 and 2.0% is explained in terms of the termination mechanisms.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140919
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  • 13
    Electronic Resource
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    A note on linear calibration curve for gel-permeation chromatography developed from a single standard (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2321-2321 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140921
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  • 14
    Electronic Resource
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    Polymerization of methyl methacrylate in the presence of graphite (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2327-2328 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140923
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  • 15
    Electronic Resource
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    Cure of unsaturated novolacs by addition polymerization (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2323-2325 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140922
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  • 16
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    Poly-D-glutamate esters with aromatic side chains: Syntheses by ester interchange reactions and their kinetics (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2329-2334 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140924
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  • 17
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    Polymerization of phenylacetylene by tungsten hexachloride catalysts (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2335-2337 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140925
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  • 18
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    Characterization of novolac resins based on p-tert-butylphenol by PMR spectroscopy (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2341-2349 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The direct silylation of tert-butylphenol formaldehyde resins with N,O-bis(trimethylsily)acetamide (BSA) has allowed a more complete analysis of these resins to be made with proton magnetic resonance (PMR) spectrometry. A quantitative determination of mixtures of the monomer, dimer, trimer, and tetramer may be carried out at 100 MHz.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141001
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  • 19
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    Preparation and heat of polymerization of 3-methyl-3-butyl-2-azetidinone (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2357-2363 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of 3-methyl-3-butyl-2-azetidinone, which forms a polymer which is soluble in a number of common solvents including toluene, chloroform, and carbon tetrachloride, is described. Anionic polymerization, carried out in toluene solution in a calorimetric vessel, yielded for the heat of polymerization of a four-membered lactam -19.1 kcal/mole at 25°C.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141003
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  • 20
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    Formation of free radicals in photoirradiated cellulose and related compounds (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2513-2525 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Free-radical formation in various modifications of celluloses, namely, wood cellulose I, II, III, and IV, rayon cellulose, amorphous cellulose, cotton linters, and absorbent cotton, irradiated with ultraviolet light, has been studied by means of ESR spectroscopy at 77°K. Various types of free radicals were generated from these samples. The line shapes and the signal intensities of the ESR spectra depended greatly upon the degree of crystallinity, the lattice type, and the arrangement of molecules in cellulose. The effect of degree of crystallinity and the amount of sensitizer (Fe3+) absorbed revealed that photochemical reactions in cellulose occurred exclusively in the amorphous regions of the polymer. Free radicals formed in these samples behaved distinctively upon a warm-up process. Phenomena of radical migration and formation of new radicals were observed from the sensitized samples of rayon cellulose and amorphous cellulose.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170141016
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  • 21
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    Investigation of structural changes in wool fibers due to annealing (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2535-2544 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Structural changes in wool fibers after annealing, i.e., storage at 45°C and 80% RH, have been investigated by using the method of laser Raman spectroscopy and by measuring birefringence and density of wool. The results show that CH2 groups in wool give parallel Raman dichroism which increases very significantly after annealing. No increase in birefringence and density occurred after annealing. A hypothesis has been put forward which states that for minimum energy considerations in wool fibers the existence of intrahelix crosslinks other than hydrogen bonds is important. It is highly probable that a large number of electrovalent intrahelix crosslinkages exist between the suitable side groups on the main polypeptide chain in the α-helix of annealed wool.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141018
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  • 22
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    Preparation of block copolymers from occluded vinyl acetate macroradicals (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2545-2552 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stable vinyl acetate macroradicals were produced by polymerization in a nonviscous poor solvent, a viscous good solvent and a viscous poor solvent. These macroradicals were then allowed to react with a second vinyl monomer to produce block copolymers. The formation of block copolymers was monitored for rate and yield data. The block copolymers produced were poly(vinyl acetate-b-methyl methacrylate), poly(vinyl acetate-b-acrylic acid), poly(vinyl acetate-b-vinylpyrrolidone), poly(vinyl acetate-b-acrylonitrile), poly(vinyl acetate-b-styrene), and poly(vinyl acetate-b-methyl acrylate). The block copolymers were characterized by yield, precipitation in selected solvents, pyrolysis gas chromatography, and differential scanning calorimetry.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141019
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  • 23
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    Copolymerization characteristics of N-(2,4,6-tribromophenyl)maleimide and N-(2,3,4,5,6-pentachlorophenyl)-maleimide with butadiene and styrene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2587-2588 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141023
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    Electronic Resource
    Electronic Resource
    Polymerization of propylene with TiCl3-AlEt2Cl-polymeric electron donor catalyst (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2565-2574 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymeric donors having ether or carbonyl groups were added to the TiCI3-AlEt2CI catalyst system as the third component, and the effects on the polymerization of propylene were investigated in comparison with the effect of the electron donors with low molecular weight. The polymeric donors were effective in making the catalyst more active, but the donors of low molecular weight depressed the catalyst activity. In the case of poly(propylene glycol dimethyl ether) (PPG-DME), PPG-DME with a number of propylene oxide units (n) of more than 6.7 was effective in enhancing the catalyst activity. These effects were considered to be due to the different reactivities between TiCI3 and AlEt2CI-polymeric donor complexes having various chain lengths.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141021
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  • 25
    Electronic Resource
    Electronic Resource
    Radiation-induced polymerization of sodium allylsulfonate at high pressure (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2575-2585 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Irradiation of sodium allylsulfonate in aqueous solution at high pressure (up to 9000 kg/cm2) gave a deliquescent white powder which is insoluble in organic solvent. The product was addition polymer of allylsulfonate from the high-resolution NMR and infrared spectra. The rate of polymerization was proportional to the third and second powers of monomer concentration in the initial and later stages, respectively. From the high dependence of the rate on monomer concentration, the reaction was deduced to proceed in an associated monomer or micelle. The rate of polymerization was increased by addition of sodium chloride. The G value for monomer consumption was about 104 at high pressure, which suggests that the degradative chain transfer is not important in the polymerization. Overall activation volumes were -7 and -5 ml/mole in the initial and later stages, respectively.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170141022
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  • 26
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    220-MHz NMR spectra of acrylic monomer-2-substituted 1,3-diolefin alternating copolymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2553-2563 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An investigation by 220-MHz NMR spectroscopy was carried out on the alternating copolymers of acrylic monomer with 2-substituted 1,3-diolefin. The chain structures were determined. The acrylic monomers used were methyl methacrylate (MMA), acrylonitrile (AN), and methacrylonitrile (MAN); isoprene (IP) and chloroprene (CLP) were the 1,3-diolefins. In the MAN-IP alternating copolymer, the 1-position methylene protons of IP showed an AB quartet peak, confirming the α-1 linkage structure. Similarly, in the MMA-CLP and AN-CLP copolymers, the 1-position methylene protons of CLP showed and AB quartet and an ABX pattern, respectively, confirming the α-1 linkage structure in both these cases also. The α-1 linkage structure was also revealed by the decoupling technique in the MAN-CLP alternating copolymer. The AN-IP and MMA-IP alternating copolymers also possess a bond between the α-position of the acrylic monomer and the 1-position of IP. The monomeric units in the alternating copolymers of acrylic monomers with 2-substituted 1,3-diolefins were generally linked at the α-position of acrylic monomer and the 1-position of 1,3-diolefin. On the other hand, in the Diels-Alder adducts of acrylic monomer with 2-substituted 1,3-diolefin, the reaction takes place between the α-position of acrylic monomer and the 4-position of 1,3-diolefin.The regioselectivity of the alternating copolymers and the Diels-Alder adducts is quite compatible with the expectations from molecular orbital theory.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141020
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  • 27
    Electronic Resource
    Electronic Resource
    Kinetics of bulk polymerization of styrene-acrylonitrile copolymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2589-2593 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170141024
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  • 28
    Electronic Resource
    Electronic Resource
    The nature of active centers of a polymeric catalase analog (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2595-2605 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition of hydrogen peroxide by a polymer complex of Fe3+ and poly(acrylic acid) partially amidated by diethylenetriamine has been studied. The molecular mechanism of catalysis is discussed. The rate constant of the reaction is k = 6.9 × 107 exp {-2.300/RT}. Decomposition of hydrogen peroxide proceeds via activation by the diethylenetriamine which is a cofactor.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170141101
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  • 29
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    Studies on propagating species in cationic polymerization of styrene derivatives by acetyl perchlorate or iodine. II. Salt effect on the relative reactivity in the cationic copolymerization of styrene derivatives with 2-chloroethyl vinyl ether initiated by iodine (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2621-2629 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To determine the effect of the dissociation of propagating species on the relative reactivity of monomers, 2-chloroethyl vinyl ether was copolymerized with p-methoxystyrene or with p-methylstyrene by using iodine in various solvents at 0°C. A common-ion salt (tetra-n-butylammonium iodide or tetra-n-butylammonium triiodide) was added to these copolymerization systems in a polar solvent to depress the dissociation of the propagating species. The addition of a common-ion salt increased the vinyl ether content in the copolymer. The more the dissociation of propagating species was depressed, the more the vinyl ether content in the copolymer increased. This effect of common-ion salt was in agreement with that of decreasing solvent polarity which yielded vinyl ether-rich copolymer as well. Therefore, the change of the monomer reactivity ratio by the solvent polarity, which used to be explained in terms of a selective solvation, must be reconsidered from the viewpoint of varying degrees of the dissociation of propagating species.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141103
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  • 30
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    Synthesis of oligoesters from oxalic acid and glycerol (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2631-2638 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new synthesis for the polycondensation of oxalic acid and glycerol was used. Polycondensation was carried out in the presence of compounds that do not dissolve oxalic acid and glycerol, but form an azeotropic mixture with water below 100°C. Anhydrous oxalic acid and oxalic acid dihydrate was used for the synthesis of oligoesters. The decarboxylation proceeds parallel with polycondensation of oxalic acid and glycerol was investigated. Decarboxylation of carboxyl groups of glycerol monooxalate was found to be accelerated by the arrangement of primary and secondary hydroxyl groups in the glycerol molecule in the 1,2 position.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141104
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    Alternating copolymerization of the styrene-methyl methacrylate system complexed with diethylaluminum chloride (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2639-2647 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate and molecular weight profiles were obtained for the spontaneous alternating copolymerizations conducted with diethylaluminum chloride. The rate formally fitted an expression, R = kp[MMA][Sty], and the rate constant was established by two distinct methods: (1) from the yield versus time data and (2) from initial rate over a range of initial concentrations; it was determined as 5.4 × 10-6 l./mole-sec with Ea = 4.2 kcal/mole. Molecular weights were determined by gel-permeation chromatography. No increase in molecular weight was observed with increased reaction time. Thus living centers or diradicals are not involved in the process. The M̄n shows a steady decrease with increase in monomer-diethylaluminum chloride concentration but the rate is maximum at equimolar monomer concentrations. The data are interpreted on a chain-transfer mechanism and show close agreement to a model in which the excess complexed acceptor monomer is the transfer agent. The chain-transfer constant of 7.1 × 10-4 l./mole-sec is several orders of magnitude greater than for uncomplexed systems.
    Additional Material: 7 Ill.
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  • 32
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    Electronic Resource
    Chloroaromatic ether amines (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2649-2657 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new and useful class of aromatic amines, based on multichlorinated benzenes and polyphenyls, has been developed. The amines are prepared by reacting the alkali metal salt of p-aminophenol with the chloroaromatics under nucleophilic substitution reaction conditions. Oligomeric amines can be obtained by condensing, e.g., the dialkali salt of bisphenol A and the alkali metal salt of p-aminophenol with the chloroaromatics. The products are mixtures of mono-, di-, and triamines, as a result of the complex functionalities of the chloroaromatics employed. Unique features of the amines include: (1) flame-retarding characteristics; (2) markedly reduced amine reactivity (compared with aniline); (3) thermal stability; (4) good solubility in the usual organic solvents.
    Additional Material: 4 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141106
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  • 33
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    Polycondensation of pyridine-2,6-dicarboxylic acid with some di- and tetraamino compounds (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2659-2664 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyridine-2,6-dicarboxylic acid phenyl ester was condensed with 3,3′-diaminobenzidine and 3,3′,4,4′-tetraaminodiphenyl ether. Polyamides were also synthesized by condensation of the above ester with p-phenylenediamine, benzidine, 4,4′-diaminodiphenyl sulfide and 4,4′-diaminodiphenyl sulfone. These amides had higher inherent viscosities and greater thermal stability than was reported before. Model compounds of imidazoles were prepared by condensation of the same ester with o-phenylenediamine and 2,3-diaminopyridine and of polyamides by condensation with aniline and 2-aminopyridine. In the case of the polyimidazole, the completely closed ring of imidazole did not form. The ultraviolet spectra of model compounds were compared with those of the polymers. The thermogravimetric curves show that the polymers are stable up to more than 400°C under argon atmosphere. All polymers were insoluble in most organic and inorganic solvents. They dissolved only partially in DMSO and DMF. Inherent viscosity was measured for the soluble polymer fraction.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141107
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    Synthesis of polyamides from active 1-benzotriazolyl diesters and diamines under mild conditions (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2665-2673 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of the solvent on the inherent viscosity of polyamides was investigated in the polycondensation of new active 1-benzotriazolyl diesters, such as 1,1′-(adipolydioxy)bisbenzotriazole and 1,1′-(isophthaloyldioxy)bisbenzotriazole, with diamines. The preferred polymerization media were polar aprotic solvents, including N-methyl-2-pyrrolidone and hexamethylphosphoramide. The solution polycondensation at room temperature afforded a series of polyamides having inherent viscosities as high as 1.8 from both aliphatic and aromatic diamines. The 1-benzotriazolyl diesters were more reactive than di(2,4-dinitrophenyl) isophthalate toward diamines. Prior to polymer synthesis, the aminolysis of some active monoesters was carried out as a model compound study.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141108
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    Polymerization of allyl phenyl ether (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2689-2694 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Allyl phenyl ether polymerized rapidly and quantitatively to a resin with a structure similar to a phenolic thermoset in the presence of boron trifluoride etherate at 50°C. The structure and properties of this polyphenol were studied. A reaction mechanism involving rearrangement was discussed.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141110
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    Syntheses and properties of phosphorus-containing copolyamides (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2675-2687 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Caprolactam was copolymerized with 1,5-dioxo-1-methyl-4-azaphosphepane or methylphosphacaprolactam. The molecular weight of the resulting copolymers decreased with increasing concentration of the thermally labile phosphorus moieties. Copolymers based on ≥40% caprolactam were shown to be crystalline by differential scanning calorimetry and x-ray techniques. As the concentration of the phosphorus structures in the copolymers increased, the glass transition and crystallization temperatures increased while the melting temperatures, crystallinities, and thermal stabilities decreased. Melt blends of nylon 6 and polymethylphosphacaprolactam were shown by differential scanning calorimetry, a selective extraction technique, and elemental analysis to contain appreciable amounts of block copolyamides, and no crystalline random structures were detected. The thermal stabilities of the melt blends were similar to those of random copolymers having comparable concentrations of the phosphorus-containing sequences.
    Additional Material: 8 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141109
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    Vinyl polymerization. CCCXXXIX. Effect of chain length of nylon 3 on the polymerization of methyl methacrylate initiated with the system of nylon 3, copper(II) ion, and water (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2695-2702 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It was found recently that the system of nylon 3, copper(II) ion, and water could initiate a radical polymerization of methyl methacrylate(MMA). In the present paper, the effect of average chain length of the molecules of nylon 3 on the rate of polymerization of MMA was studied. The rate increased with the chain length of nylon 3. This result was explained well by the fact that the shorter nylon 3 forms a complex with copper (II) ion more easily than longer nylon 3. It was assumed that the shorter nylon 3 fills three or four coordination sites of copper(II) ion and loses the ability to initiate the polymerization. The efficiency of grafting of MMA and the degree of polymerization of MMA homopolymer were independent of the chain length of nylon 3.
    Additional Material: 2 Ill.
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    ESR and NMR study of the γ-ray-induced postpolymerization of vinyl monomers adsorbed on zeolite (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2703-2724 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The γ-ray-induced postpolymerization of acrylonitrile and methyl methacrylate adsorbed on Linde zeolite 13X irradiated at 77°K has been studied between 303 and 343°K as a function of the amount of adsorbed monomer and of the irradiation dose. The change in the nature and the concentration of free radical with temperature and duration of the postpolymerization was followed by the ESR method, whereas the formation of polymer was monitored continuously by the decay of the 1H-NMR absorption line of the monomer under high-resolution conditions. It was found that the overall postpolymerization kinetics may be accounted for by assuming an exponential decay of radical propagation and recombination reactions with chain length. The tacticity of the polymer recovered by destroying the matrix in hydrofluoric acid was determined by 13C-NMR. The probability of isotactic addition of AN and MMA is larger than in the radical polymerization in solution owing likely to the association of adsorbed monomer molecules in pairs preforming an isotactic diad.
    Additional Material: 11 Ill.
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    Solvent effects on the radiation-induced graft polymerization of styrene onto poly(isobutylene oxide) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2773-2783 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The graft polymerization of styrene onto preirradiated poly(isobutylene oxide) (PIBO) with methanol and benzene was studied. The order of grafting yield and of the number-average molecular weight of graft chains decrease in the order; undiluted styrene 〉 styrene-methanol (1:1) solution 〉 styrene-benzene (1:1) solution. A kinetic treatment to calculate rate constants from the rate of grafting and the molecular weight of the graft chain was proposed. The propagation rate constant kp was 0.2-0.3 l./mole-sec and the termination rate constant kt was 1.0-16.0 l./mole-sec. The ratio kp/kt in this heterogeneous system was larger than that in homogeneous system by a factor of about 104-105.
    Additional Material: 9 Ill.
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    Photochemistry of fiber-forming polymers. II. Ketone-containing poly(ethylene terephthalates) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2791-2796 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(ethylene terephthalate) copolymers were prepared containing minor amounts of comonomers containing backbone and side-chain ketone groups. The photochemistry of these polymers was studied at 313 nm, both in film and fiber form. It was demonstrated that only the comonomer, dimethyl-γ-ketopimelate (DMKP), gave a copolymer with enhanced sensitivity to ultraviolet degradation in air. Since this sensitivity is reduced in a nitrogen atmosphere, it is suggested that the mechanism involves main-chain scission to form two free radicals by the Norrish type I mechanism, and that recombination of these radicals is reduced by reaction with oxygen. The use of copolymers of this type provides a method for the controlled photodegradation of polyester fibers.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141118
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    Synthesis of polypyridazinophthalazinediones from dibenzoylphthalic acids and aromatic dihydrazines (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2797-2805 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel class of polypyridazinophthalazinediones has been synthesized by the solution cyclopolycondensation in m-cresol of dibenzoylphthalic acids with aromatic dihydrazines such as bis(4-hydrazinophenyl)methane and bis(4-hydrazinophenyl) sulfone. The polyheterocycles derived from 4,6-dibenzoylisophthalic acid, which had inherent viscosities of up to 0.5, were soluble in m-cresol and hot dichloroacetic acid, whereas the polymers from 2,5-dibenzoylterephthalic acid were practically insoluble in organic solvents. Thermogravimetric analyses showed that all the polymers underwent weight losses of 10% at 490-520°C in both air and nitrogen.
    Additional Material: 2 Ill.
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    Homogeneous polyblend of poly(vinyl chloride) with α-methylstyrene-methacrylonitrile-ethyl acrylate terpolymer (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 123-127 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Blends of poly(vinyl chloride) (PVC) and α-methylstyrene-methacrylonitrile-ethyl acrylate (AMS-MAN-EA) terpolymer have been prepared and properties studied. The polyblends are unusual inasmuch as they are transparent and possess a single glass transition; therefore, they are homogeneous. The single Tg suggests a single-phase system. The polyblends exhibit rarely observed polymer-polymer compatibility.
    Additional Material: 4 Ill.
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    Copolymerization of trioxane with cyclic acetals. Effect of catalyst on polymerization and monomer reactivity (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 143-151 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymerization of trioxane with cyclic acetals, viz., 1,3-dioxolane, m-dioxane, and 4-methyl-m-dioxane, have been investigated. Three types of catalyst have been employed: a metal chelate, MoO2(AcAc)2; a Lewis acid, BF3·Bu2O; and an ion-pair, It has been ascertained that, in agreement with the previous results on copolymerization of trioxane and ethylene oxide,1 both the polymerization kinetics and the monomer reactivity have been found to be influenced by the catalyst employed. In copolymerization with 1,3-dioxolane, both BF3·Bu2O and have been found to give high molecular weight copolymers with high incorporation of 1,3-dioxolane. However, contrary to the results obtained in copolymerization with ethylene oxide, higher rate and yield have been obtained with BF3·Bu2O, making it a superior catalyst. In copolymerization with m-dioxane, has been found to be a superior catalyst to the others yielding high molecular weight copolymers with high incorporation of m-dioxane. In copolymerization with 4-methyl-m-dioxane, MoO2(AcAc)2 has been found to be an overall superior catalyst to the others. Higher rate, yield, and comonomer incorporation have been obtained using MoO2(AcAc)2 as catalyst, although somewhat higher molecular weight copolymers have been obtained with
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140114
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    Poly(vinyl chloride-g-butyl rubber) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 153-157 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of poly(vinyl chloride-g-butyl rubber) and some of its physical properties are described. The key to the synthesis involves copolymerization initiation of an isobutylene-isoprene charge by a PVC/Et2AlCl initiator system with 1,2-dichloroethane as solvent. The graft is a thermoplastic; cast films are flexible and optically clear. Proof of grafting is the crosslinking with S2Cl2 of the pentane-extracted product in THF solution. Crosslinking the butyl rubber moiety in the graft reduces overall stress properties.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140115
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    PolyimidothioethersPaper presented in part at the 164th Meeting, American Chemical Society, New York, August 1972. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 159-182 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The condensation of maleimide compounds with hydrogen sulfide and bisthiols was studied in several model systems. Bismaleimide compounds undergo rapid, exothermic polymerization with thiol-containing compounds in dipolar and basic solvents to give crosslinked polymidothioethers. Effective supression of the crosslinking reaction was achieved by carrying out the polymerization in the presence of a proton donor to inhibit anionic polymerization. A number of linear polyimidothioether homopolymers and copolymers were prepared and a study was made of their properties.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140116
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    Use of model compounds to determine equilibrium melting points of polymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2845-2852 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Evidence is given for the relationship \documentclass{article}\pagestyle{empty}\begin{document}$ T_m = T_m^ \circ \left[ {1 - 2RT_m \ln {{{\rm (}n)} \mathord{\left/ {\vphantom {{{\rm (}n)} n}} \right. \kern-\nulldelimiterspace} n}\Delta h} \right] $\end{document} describing the approximate dependence of the observed melting points Tm of oligomers on their degree of polymerization n, and its use in determining the equilibrium melting point T°m of the extended chain crystal and the heat of fusion Δh. Polyethylene and the n-alkanes, poly(ethylene oxide) and poly(methylene oxide), polyphenylene and other systems are considered.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141201
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  • 47
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    Relaxation processes in mixtures of polymers with linear amides (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2867-2873 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Results of dynamic measurements of mixtures of polymer with linear low molecular amides are presented. New secondary relaxation processes that were revealed were elucidated by conformation motions of the amide group of low molecular compounds. The effect of water and similar substances on the character of low-temperature relaxation processes is also discussed.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170141203
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    Alternating copolymerization of styrene and methyl α-chloroacrylate with diethylaluminum chloride (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 45-55 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The alternating copolymerization of styrene and methyl α-chloroacrylate (MCA) with diethylaluminum chloride (Et2AlCl) in benzene at 0°C has been investigated. The copolymer has an equimolar composition irrespective of the feed monomer composition, the copolymer yield and the amount of Et2AlCl used. The copolymerization proceeds first very rapidly and then rather slowly after attaining a certain yield which varies proportionally to the amount of Et2AlCl used. A maximum copolymer yield is observed at about 60% MCA feed composition. The 1H-NMR analyses of dyad, triad, and pentad of the alternating deuterated α-d-St-MCA copolymer indicate that the configuration of this copolymer can be explained by a single parameter, coisotacticity σ(σ = 0.69). A favorable mechanism of the alternating propagation as well as of the stereoregularity control is discussed.
    Additional Material: 6 Ill.
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    Determination of coisotacticities of some alternating styrene-acrylic copolymers by NMR spectra (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 57-71 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Coisotacticities σ for some alternating copolymers were determined through the analyses of their CH3O, CH3 and CH2 proton NMR spectra; styrene-methyl methacrylate (σ = 0.56), styrene-methyl acrylate (σ = 0.53), styrene-methyl α-chloroacrylate (σ = 0.69), styrene-methacrylonitrile (σ = 0.19), styrene-methacrylamide (σ = 0.16), α-methylstyrene-methyl methacrylate (σ = 0.21), and α-methylstyrene-methyl acrylate (σ = 0.53) were studied. It was found that a terminal model or Bernoullian trial prevails in these complexed copolymerizations with diethylaluminum chloride. The influence of monomer structure on σ values is discussed.
    Additional Material: 7 Ill.
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  • 50
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    Sequence distribution of 1,4 and 3,4 units in polyisoprenes (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 73-81 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 13C-NMR spectra of hydrogenated polyisoprenes were investigated. Polyisoprenes containing various ratios of 1,4 and 3,4 units were prepared with n-BuLi/Et2O and were hydrogenated by using p-toluenesulfonylhydrazide. 13C-NMR signals of the hydrogenated polymers were assigned for the triad sequences arising respectively from the 1, 4 and 3, 4 units of polyisoprenes. On the basis of these assignments it was confirmed that 1,4 and 3,4 units were randomly distributed in the polyisoprenes prepared with n-BuLi and that these polymers did not contain appreciable amounts of head-to-head or tail-to-tail 1,4 linkages.
    Additional Material: 4 Ill.
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    Mechanism of oxidation at a copper-polyethylene interface. II. Penetration of copper ions in the polyethylene matrix (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 93-104 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two surface analysis techniques (Rutherford backscattering and surface composition by analysis of neutral and ion impact radiation) have been applied to the study of interfacial copper transport in the oxidation of polyethylene films over copper surfaces. Analysis of films oxidized several thousand hours at 40, 57, and 87°C shows maximum concentrations of copper species in the polymer matrix of ∼0.1M extending to depths of several thousand angstroms. These results, together with previous infrared spectroscopic studies, allow some significant conclusions and hypotheses to be drawn as regards the roles of heterogeneous and homogeneous catalytic processes which occur in the thermal-oxidative degradation of polyethylene-copper systems.
    Additional Material: 8 Ill.
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    Monomer sequence distribution in α-methylstyrene-methacrylonitrile copolymer (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 113-121 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The sequence distributions of α-methylstyrene-methacrylonitrile copolymers have been determined quantitatively as a function of monomer feed composition and conversion at 60°C by use of the run-number concept. The azeotropic copolymer was found to be highly alternating. For this copolymer the data showed that 83% of the diad placements took the form of an AMS unit followed by a MAN unit, or vice versa. The triad sequence in which an AMS unit is centered between two MAN units was 92%. It was found that the AMS-AMS diad sequence is only 2%, and there were no AMS-AMS-AMS triad sequences in the copolymer. The sequence distributions were correlated with Izod impact strength and heat-deflection temperature properties.
    Additional Material: 5 Tab.
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    Effect of gegen ion in cationic polymerization and copolymerization of trioxane (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 129-142 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: p-Chlorophenyldiazonium hexafluorophosphate has been reported to be a superior catalyst for cationic polymerization and copolymerization of trioxane as compared to boron trifluoride dibutyl etherate (BF3·Bu2O)1. In the present investigation the effect of anions derived from elements in Group VA, AsF6- and SbF6-, has been ascertained. It has been concluded that p-chlorophenyldiazonium hexafluoroarsenate is also a superior catalyst to boron trifluoride dibutyletherate (BF3·Bu2O), while p-chlorophenyl-diazonium hexafluoroantimonate is inferior.Copolymers with the highest polymer yield (〉95%) and molecular weight (intrinsic viscosity = 4 to 5) were obtained with Simple dependences on catalyst concentration have been observed to hold for a wide catalyst concentration range ([M]/[C]) = (1 to 20) × 105: \documentclass{article}\pagestyle{empty}\begin{document}$ \begin{array}{*{20}c} {{\rm polymer yield}} & \prop & {\left[ {{\rm catalyst}} \right]^0 } \\ {{\rm molecular weight}} & \prop & {\left[ {{\rm catalyst}} \right]^{ - 0.5} } \\ {\frac{{\left[ {{\rm chain transfer}} \right]}}{{{\rm catalyst}}}} & \prop & {\left[ {{\rm catalyst}} \right]^{ - 0.5} } \\ \end{array} $\end{document} For the same relationships hold. However, the polymer yield (75%) and molecular weights (intrinsic viscosity ≃1) are considerably lower while the extent of chain transfer is higher. Furthermore, the polymerization proceeds with explosive violence.The quantitative aspects resulting from polymerization, for the most part, can be interpreted in terms of the extent of dissociation of the propagating ions.
    Additional Material: 5 Ill.
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    Polyimide structure-property relationships. I. Polymers from fluorene-derived diaminesPresented in part at Southeast-Southwest Regional meeting of the American Chemical Society, New Orleans, La., December 5, 1970. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 225-235 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of fluorene and fluorenone diamines were polymerized with two aromatic dianhydrides, and the resulting polyamic acids were cyclodehydrated to aromatic polyimides. A study of the mechanical properties of the polyimide films disclosed they are among the stiffest reported to date, with an excellent retention of rigidity at elevated temperatures. Comparisons of the tensile properties and glass transition temperatures of the fluorene-derived polymer films with those from the corresponding open-chain polyimide films established that the unusual rigidity, especially at elevated temperatures, was in large part due to the contribution of the bulky, tricyclic fluorene (one) moieties in the polymer structures.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140119
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    1H-NMR spectra of complexes between methacrylic monomer and ethylaluminium dichloride in toluene and methylene chloride (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 237-255 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1H-NMR spectra of mixtures of a methacrylic monomer such as methacrylonitrile or methyl methacrylate and ethylaluminium dichloride at various molar ratios were measured in toluene or methylene chloride at various temperatures. It was found that only one kind of binary complex is detectable in the methacrylonitrile-ethylaluminum dichloride equimolar mixture, while in nonequimolar systems there are several kinds of binary complexes, depending on the molar ratio at low temperature in these solvents. Moreover, the chemical shifts of the protons of methacrylonitrile due to complex formation with ethylaluminum dichloride show a remarkable temperature dependence in toluene, but not in methylene chloride. This fact can be interpreted by an assumption of the formation of a ternary complex of methacrylonitrile, ethylaluminum dichloride, and aromatic donor molecules, mainly due to the dipole interaction between the nitrile group complexed with ethylaluminum dichloride and aromatic donor. The orientation of toluene molecules in the ternary complex of methacrylonitrile or methyl methacrylate is discussed.
    Additional Material: 12 Ill.
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    Polymerization of coordinated monomers. IX. Charge-transfer spectrum of the system composed of metal halide, polar vinyl monomer, and electron-donating monomer (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 183-194 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 1:2 stannic chloride-methyl methacrylate complex, the 1:2 stannic chloride-acrylonitrile complex, the ethylaluminum dichloride-methyl methacrylate complex, and the ethylaluminum dichloride-acrylonitrile complex exhibit charge-transfer absorption bands in the wavelength region longer than 300 nm with electron-donating compounds such as mesitylene, styrene, toluene, and butadiene. The absorption spectrum of the mixture of either methyl methacrylate or acrylonitrile with the electron-donating compound is, however, a superpostion of the spectra of the components without any additional absorption. Methyl isobutylate, 3-butenyl methyl ketone, and propionitrile show no charge-transfer absorption bands with the electron-donating compound, even in the presence of a metal halide. Both the presence of the C-C double bond conjugating with the polar group and the coordination of the polar group to a metal halide are essential for an electron-accepting monomer to exhibit a charge-transfer absorption with the electron-donating compound. Continuous variation plots with the use of the charge-transfer band definitely show a 1:1 interaction between the methyl methacrylate coordinated to stannic chloride and styrene, resulting in the determination of the equilibrium constants for the charge-transfer complex formation in methylene chloride: 0.21 l./mole at 25°C and 0.67 l./mole at -50°C. The charge-transfer absorption is attributed to a ternary molecular complex composed of a metal halide, a polar vinyl monomer, and an electron-donating monomer.
    Additional Material: 15 Ill.
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    Physical properties of some low polymer content radiation-grafted wool copolymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 257-264 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Wool copolymers with low polymer content (6-18%) have been prepared by radiation grafting techniques. Supercontraction, density, and formic acid vapor sorption measurements have been used to assess changes in the keratin structure produced by the grafting processes. Kinetic studies of the contractile forces developed in the first (reversible) stage of the supercontraction of wool in lithium bromide showed that grafting with poly(N-methylol acrylamide) or polyacrylonitrile has a “repairing” action which offsets changes in the wool structure produced by the small radiation dose (2 Mrad) used for the grafting process. By contrast, grafting with poly(vinyl acetate) had no repairing effect. The bonds formed by grafting of poly(N-methylol acrylamide) or polyacrylonitrile to keratin do not reduce swelling of the wool by formic acid, which is a measure of effective crosslink density. Grafting with poly(vinyl acetate) led to increased swelling by formic acid, indicating some disruption of the keratin structure during polymerization. It is suggested that the role of the grafted polymer is mainly to stabilize the hydrogen-bonded secondary network by interaction between the polypeptide and polymer chains.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140121
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    Study of radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. V. Effects of p-benzoquinone and dose rate on methyl methacrylate-silica gel system (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 275-286 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to elucidate the mechanism of radiation-induced polymerization of methyl methacrylate adsorbed on silica gel, the effects of p-benzoquinone addition and dose rate were studied in detail. Most of the polymerization is inhibited by p-benzoquinone at levels above 10-2 mole/l. The GPC spectra of both graft polymers and homopolymers show two peaks. The high molecular weight material appears to have been formed by polymerization by a radical mechanism, because these peaks decrease as p-benzoquinone concentration increases; on the other hand, their low molecular weight polymers seem to be products of an ionic polymerization mechanism because those peaks are almost not affected by p-benzoquinone. The four GPC peaks differ in dose rate dependences of their polymerization rate. The dose-rate exponents of polymerization rate were obtained for the four GPC peaks. The behavior of the low molecular weight peaks of graft polymers and homopolymers were quite different, suggesting that the polymers differ considerably in formation mechanism.
    Additional Material: 18 Ill.
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    Photopolymerization via the Paterno-Büchi reaction. I. Reaction of aromatic diketones with tetramethylallene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 319-330 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aromatic diketones of the benzophenone type undergo photopolymerization on irradiation at 350 nm with tetramethylallene in benzene solution. The polymers produced contain oxetane units in the main chain, and spectroscopic analysis demonstrates that the distribution of structural units parallels that found in the reaction between benzophenone and tetramethylallene. The polymers are rapidly degraded thermally and by mineral acids.
    Additional Material: 4 Ill.
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    Photopolymerization via the Paterno-Büchi reaction. II. Reaction of aromatic diketones with furans (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 331-341 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Attempts to photopolymerize 1:1 mixtures of furan and aromatic diketones of the benzophenone type by irradiation of benzene solutions at 350 nm were unsuccessful. An alternative route via furan-diketone 2:1 adducts was more successful but was complicated by the intervention of hydrogen abstraction reactions in competition with oxetane formation, leading to crosslinking and insolubilization in some cases.
    Additional Material: 1 Ill.
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    Degradation of polymer mixtures. VI. Blends of poly(vinyl chloride) with polystyrene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 353-364 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The degradation of films containing both PS and PVC has been examined by TVA and TG. Stabilization of both polymers, more notably PS, is observed, but the degradation products are the same as when the polymers are degraded alone. Molecular weight measurements indicate a more rapid decrease in the molecular weight of PS when PVC is present. The possibility of grafting or other processes leading to chlorine incorporation in PS has been excluded by the results of experiments using 36Cl-labeled PVC. The mechanisms of possible interactions between the degrading polymers are discussed. Processes involving reaction of chlorine radicals with PS at lower temperatures and reaction of PS radicals with the residue of PVC dehydrochlorination or its decomposition products at higher temperatures appear probable.
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    Effects of diethylzinc in alkyllithium-initiated polymerizations (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 379-386 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In an alkyllithium-initiated polymerization of butadiene or styrene, dialkylzinc complexed with the initiator and effectively increased the initiation rate. This is particularly true with initiator of low solubility due to its very high state of aggregation. Dialkylzinc also complexes with the aggregated polymer-lithium molecules to give a lower apparent solution viscosity. In the presence of a base such as tetrahydrofuran, diethylzinc served as chain-transfer agent.
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    Structure of chlorinated poly(vinyl chloride). III. Preparation of poly(vinyl chloride)-β,β-d2 as a model for the study of the mechanism of chlorination and of the chlorinated poly(vinyl chloride) structure (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 403-408 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method for the preparation of poly(vinyl chloride)-β,β-d2 (PVC-β,β-d 2) as a model for the investigation of the mechanism of chlorination and of the CPVC structure has been suggested. The conditions of preparation of deuterated intermediates of a multistage synthesis of vinyl chloride-β,β-d2 and of suspension-polymerized PVC-β,β-d2 have been described including the mass balance. Malonic acid was used as the starting compound. Tacticity values of a sample of PVC-β,β-d2 and its infrared and NMR spectra are presented and compared with data already published.
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    Ferric oxide-catalyzed polymerization of methyl methacrylate (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 433-440 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of methyl methacrylate was carried out in water at various concentrations of sodium bisulfite, ferric oxide, and methyl methacrylate at 30, 40, and 50°C. The effect of ferric oxide on the rate of polymerization was studied at 50°C. Rates of polymerization increased in the presence of ferric oxide. For example, the rate of polymerization increased from 3.4 × 10-5 mole/l.-sec to 11.8 × 10-5 mole/l.-sec when the ferric oxide concentration was varied from 0 to 15 g/l. water. The molecular weight of the polymer decreased from an average of 1.4 × 106 in the absence of ferric oxide to 2.8 × 105 when the ferric oxide was present. The variation of molecular weight of the polymers with temperature and conversion was studied. At a fixed conversion of 80%, the average molecular weight decreased from 3.4 × 105 at 30°C to 2.2 × 105 at 50°C. The average molecular weight was also found to increase with increasing monomer and initiator concentrations. It increased from 8.1 × 104 to 5.3 × 105 and from 3.4 × 105 to 8.9 × 105 as the initiator and monomer concentrations increased from 0.01 to 0.05 mole/l. and from 0.235 to 0.705 mole/l., respectively. The apparent energy of activation for the polymerization was found to be 15.6 and 9.7 kcal/mole in absence and in presence of ferric oxide, respectively.
    Additional Material: 5 Ill.
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    Diffusion control in radiation graft polymerization with varying dependence of rate on monomer concentration (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 3045-3066 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The quantitative effect of diffusion control on the rate of radiation-initiated graft polymerization has been studied theoretically for systems in which the diffusion-free reaction may show various dependencies of rate on monomer concentration other than the usual first-order dependence. The study is also very general in that it can be applied to systems involving a variety of different modes of initiation and termination. Whether the grafting process is diffusion-free or diffusion-controlled has been analyzed in terms of the interaction of the initiation rate Ri, the propagation and termination rate constants kp and kt, the equilibrium solubility M of the monomer in the polymer, the polymer film thickness L, the diffusivity D of the monomer in the polymer, and the diffusion-free kinetic order of dependence v of the grafting rate on monomer concentration. The dependence of the grafting rate for both the diffusion-free and diffusion-controlled reactions on these parameters is expressed both by mathematical experssions and graphically. Diffusion control is shown to occur at a critical value of the parameter A which is proportional to L(kpRiw/ktzD)1/2M(ε-1)/2 where w, z, and v have different values depending on the specific modes of initiation, propagation and termination in a particular grafting system. The grafting rate is shown to vary with the value of A according to specific mathematical expressions. In comparing diffusion-free to diffusion-controlled reaction, it is shown that the former is independent of L and D while the latter is directly dependent on L and inversely on D1/2. Further, the change from diffusion-free to diffusion-controlled reaction involves a change in the dependence of rate on monomer from v-order to [(v - 1)/2]-order. The nonsteady-state as well as the steady-state reaction rates have been analyzed.
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    Anionic polymerization. IV. Effect of crown ethers on alkylsodium initiator (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 583-589 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of butadiene and copolymerization of butadiene-styrene with alkylsodium catalyst modified by crown ethers in hydrocarbon solvent has been investigated. This catalyst system produced polybutadiene of high viscosity (2.0-5.0) and high vinyl content (80%) in high conversion (75-95%). These results are in contrast to those obtained with aliphatic ether-modified alkylsodium polymerization which typically gives products of low molecular weight and at low conversion. The copolymerization of butadiene-styrene with alkylsodium catalyst modified by crown ethers gave a copolymer which did not contain block styrene. Although the copolymer did not contain block styrene, there was an unusually high level of incorporation of styrene in the copolymer at low conversion. This behavior is quite different from either modified organolithium or unmodified organosodium initiators, in which the styrene is uniformly and randomly incorporated along the chain.
    Additional Material: 3 Ill.
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    Degradation of polymer mixtures. VII. Blends of poly(vinyl acetate) with polystyrene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 603-608 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The degradation of films containing both PVA and PS has been investigated for comparison with the behavior already reported for PVC/PS blends. The presence of PS had little, if any, effect on the behavior of PVA, but PVA had an effect similar to that of PVC on the degradation of PS. Styrene production was retarded in the blend, compared to PS alone, and an increase in the rate of chain scission was observed for a high molecular weight sample. The molecular weight effect, however, was much smaller than in corresponding experiments with PVC/PS blends. Interference with intermolecular transfer in PS is again advanced as the probable explanation of the stabilization of PS.
    Additional Material: 3 Ill.
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    Effect of evolved hydrogen fluoride on radiation-induced crosslinking and dehydrofluorination of poly(vinylidene fluoride) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 617-625 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(vinylidene fluoride) (PVdF) was irradiated by 60Co γ-rays with and without potassium hydroxide (KOH) under vacum. KOH tablets were added to absorb completely hydrogen fluoride (HF) which is the main volatile product of radiolysis of PVdF in the irradiation cell. In the presence of HF, the rates of radiation-induced crosslinking and dehydrofluorination of PVdF were lower than those in the absence of HF. The experimental results are discussed from the standpoint of stabilization of alkyl free radicals in PVdF by reaction with hydrogen fluoride.
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    Free radicals in γ-irradiated poly-α-methylstyrene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 671-675 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electron spin resonance (ESR) spectra were observed at -160°C and at room temperature for γ-irradiated poly-α-methylstyrene. The spectrum observed at room temperature has been attributed to the radical species while that at -160°C results from the same radical and superposition of the spectrum due to the radical ĊH2-C(CH3)(C6H5)-. The radicals which are stable at room temperature could be used to graft vinyl acetate.
    Additional Material: 3 Ill.
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    Effect of nonpolar field formed by polymer ligand on the oxidation of 2,6-xylenol catalyzed by Cu complexes (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 825-832 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidative polymerization catalyzed by Cu(II)-poly(vinylpyridine) derivatives and the effect of the nonpolar field formed by the polymer ligand on the catalysis was studied in dimethyl sulfoxide (DMSO) solvent. The catalytic activity of the Cu complex increases in the following order; Cu-(styrene-vinylpyridine copolymer) (St·VP) complex 〉 Cu-partially quarternized (by benzyl chloride) poly(vinylpyridine)(BCQP) complex 〉 Cu-poly(vinylpyridine) (PVP) complex 〉 Cu-pyridine (Py) complex 〉 Cu-partially quarternized (by ethyl bromide) poly(vinylpyridine) (EBQP) complex. This order is the same as that of the reoxidation rate constant of the catalyst. Acceleration of ko process in Cu-St〉VP and Cu-BCQP systems, where the active site is in the nonpolar field formed by the polymer ligand, is explained by an increase in strength of the coordination bonds.
    Additional Material: 4 Ill.
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    Radical polymerization of butadiene-1-carboxylic acid (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 693-700 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The homopolymerization and copolymerization of butadiene-1-carboxylic acid (Bu-1-Acid) (M1) were studied in tetrahydrofuran at 50°C with azobisisobutyronitrile as an initiator. The initial rate of polymerization was proportional to [AIBN]1/2 and [Bu-1-Acid]1. The overall activation energy for the polymerization was 22.87 kcal/mole. For copolymerization with styrene (M2) and acrylonitrile (M2), the monomer reactivity ratios r1, r2 were determined by the Fineman-Ross method, as follows; r1 = 5.55, r2 = 0.08 (M2 = styrene); r1 = 11.0, r2 = 0.03 (M2 = acrylonitrile). Alfrey-Price Q-e values calculated from these values were 6.0 and +0.11, respectively. The Bu-1-Acid unit in the copolymer as well as the homopolymer was found from infrared and NMR spectral analyses to be composed of a trans-1,4 bond. The hydrogen-transfer polymerization of Bu-1-Acid leading to polyester was attempted with triphenylphosphine as initiator, but did not occur.
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    Effects of molecular weight distribution in drag reduction and shear degradation (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 713-727 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A reduction of frictional drag in turbulent flow was obtained in benzene by using three monodisperse polystyrene samples having weight-average molecular weights of 1.8, 4.1 and 7.1 × 106. By testing these polymers individually and in mixtures, data were obtained for samples with known molecular weight distributions. The drag reduction of these samples was studied as a function of polymer concentration and flow rate so that a generalized picture of the effects of polydispersity could be obtained. These results are used to help explain much of the behavior that was observed for polystyrene and other polymers. This includes the fact that the polystyrene samples exhibit a remarkably high resistance to the loss of drag reduction via degradation in turbulent flow. Such experiments indicate that drag reduction and degradation depend strongly on molecular weight distribution. Thus a molecular level interpretation of experimental results cannot be made unless the effects of the distribution are considered.
    Additional Material: 7 Ill.
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    Short branching in poly(vinyl alcohol). II. NMR spectroscopy of model polymers of short-branched poly(vinyl alcohol) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 759-766 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to develop a method of measuring the amounts of short branches in PVA, an NMR study was made of a model poly(vinyl alcohol) having short branches, one or two monomer units in length. Detection and estimation of the short branches were shown to be possible by using the 13C-NMR spectra of PVA and the 1H-NMR of acetylated PVA. In the 19F-NMR spectra of trifluoroacetylated model PVA, the resonance peaks of primary and tertiary alcohols in the branching structure were not well resolved from that of secondary alcohol of the main chain.
    Additional Material: 6 Ill.
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    Gel formation through interpolymer interaction of poly(methacrylic acid)-poly(vinylbenzyltrimethylammonium chloride) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 767-771 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140324
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    Active polycondensation of diethyl 2,3,4,5-tetrahydroxyadipate with diamines (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 783-792 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polycondensation of diethyl 2,3,4,5-tetrahydroxyadipate with various diamines was carried out in solutions under mild conditions. The polycondensation reaction occurred rapidly even at room temperature in polar solvents such as alcohols, and in aqueous solution a cyclic product was obtained instead of linear polymers although the reaction with diamines was completed within several minutes. Polymers obtained from diethyl 2,3,4,5-tetrahydroxyadipate were a linear polyamide having pendant hydroxyl groups, which decomposed on heating at around 200°C. A solid-phase polycondensation of the precursor polyamide yielded a high molecular weight polyamide.
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    ESR study of linear aliphatic oligoesters under γ-irradiation. I. Paramagnetic species produced in the material by irradiation at 77°K (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 813-824 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Paramagnetic species produced in a series of linear aliphatic oligoesters $ [\bond;{\rm O}\bond;({\rm CH}_{\rm 2} {\rm )}_m\bond;{\rm O}\bond;{\rm CO}\bond;({\rm CH}_{\rm 2} {\rm )}_n\bond;{\rm CO\rlap{--} ]}_P $ by γ-irradiation at 77°K was investigated by an ESR method. A predominant doublet observed immediately after γ-irradiation, which has hyperfine splitting of 20-23 gauss, is attributed to a radical anion III. Slight decay of this radical anion is observed by illuminating the sample with visible light at 77°K. A small amount of the radical anion is converted to double triplet, which is assigned to —(ES)—CH—CH2— (where ES denotes the ester group), from the result of heat treatment. The conformational angles for the two β-protons in the (6,2) oligoester are determined to be θ1 = θ2 = 30°.
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    Graft copolymerization of styrene on rubber containing halogen by chromous acetate (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 961-971 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Graft copolymerization of styrene on rubber containing chlorine, e.g., chloroprene rubber (CR) and chlorosulfonated polyethylene (Hypalon), with chromous acetate (Cr2+) was carried out in DMF-THF mixed solvent at 50°C. From the kinetic study, the normal kinetic orders with respect to the concentration of initiator and monomer were obtained at low concentrations of CR, but the deviation from conventional first-order to second-order kinetics with respect to the monomer concentration was observed at high CR concentrations: Rp ∝ [CR]1/2 [Cr2+]1/2[styrene]1 (at low CR concentration); Rp ∝ [CR]1/2 [Cr2+]1/2[styrene]1 (at high CR concentration). This result was explained in terms of the high viscosity of the reaction medium due to the rubber contained in solution. An initiation site along the polymer chain was assumed from the graft copolymerization with three kinds of CR having different microstructures. The results of fractionation of obtained polymer showed that the graft efficiency was high but a large amount of gel was formed.
    Additional Material: 8 Ill.
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    Effect of structure on properties of aromatic-aliphatic polybenzimidazoles (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 973-980 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Homopolymers and copolymers containing the polybenzimidazoles ring were prepared from terephthalic acid (T), fumaric acid (F), and 3,3′-diaminobenzidine tetrachloride (DAB) in polyphosphoric acid. The polymers were characterized by viscometry, infrared spectroscopy, and nitrogen analyses. The effect of copolymer composition on the ultraviolet and visible spectra, solubility in various solvents, and density was also investigated. The relative thermal stability of the various polybenzimidazoles was investigated by using dynamic thermogravimetry in air. Polybenzimidazole derived from terephthalic acid was most stable, and the introduction of aliphatic residues resulted in a decrease in thermal stability. However, the homopolymer of fumaric acid was more stable than the copolymers of fumaric acid and terephthalic acid.
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    Photopolymerization of methyl methacrylate and some other vinyl monomers with the use of a pyridine-bromine charge-transfer complex as photoinitiator (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 981-991 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of MMA was carried out under visible light (440 nm) with the use of pyridine-bromine (Py-Br2) charge-transfer (CT) complex as the photoinitiator. Initiator exponent and intensity exponent were 0.5 and 0.43, respectively, and the monomer exponent was found to be dependent on the nature of the solvent or diluent used. The Polymerization was inhibited in the presence of hydroquinone, but oxygen had very little inhibitory effect. An average value of kp2/kt for this polymerization system was 1.19 × 10-2, and the activation energy of photopolymerization was 4.95 kcal/mole. Kinetic data and other evidence indicate that the overall polymerization takes place by a radical mechanism. With Py-Br2 complex as the photoinitiator, the order of polymerizability at 40°C was found to be MMA, EMA ≫ Sty, MA.
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    Photopolymerization of methyl methacrylate and other vinyl monomers with the use of N-bromosuccinimide as photoinitiator (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 993-1004 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of MMA was done in the presence of visible light (440 nm) with the use of N-bromosuccinimide (NBS) as the photoinitiator. The initiator exponent and intensity exponent were 0.5, and the monomer exponent was found to be unity. The polymerization was inhibited in the presence of hydroquinone. The average kp2/kt for this photopolymerization system was found to be 0.296 × 10-2 and the activation energy of photopolymerization was 4.67 kcal/mole. Kinetic and other evidence indicate that the overall polymerization takes place by a radical mechanism. With NBS as the photoinitiator, the order of polymerizability at 40°C was MMA, EMA ≫ MA ≃ VA, and styrene could not be polymerized under similar conditions.
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    Aspects of plastics scintillators. I. Behavior of fluorescent molecules in polymerizing medium (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1005-1013 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction between a number of organic fluors and vinyltoluene during thermally induced polymerization has been investigated by using kinetic and fluorescence techniques. It has been confirmed that 2,5-diphenyloxazole, bis-2(5-phenyloxazoyl)benzene and p-terphenyl do not react in the polymerizing medium and are present in the final product as solute in a solid solution. However, 1,1′4,4′-tetraphenyl-1,3-butadiene and 9-methylanthrancene do react, via chain-transfer steps. The diene is concentrated in the low molecular weight tail of a polymer of broad molecular weight distribution and can be removed by further fractionation. The anthrancene species undergoes structural rearrangement with accompanying loss of fluorescence activity during reaction with the growing polymer chains.
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    Étude des irregularités observées dans la polymérisation du (-) sulfure de propylene amorcée par le triethylaluminium et ses derivésDédié à Monsieur le Professeur G. Champetier à l'occasion de son 70e anniversaire. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1015-1029 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of propylene sulfide by use of triethylaluminum derivatives as initiators leads to low molecular weight polymers with irregularities in the chain, e.g. head-to-head units and disulfide bonds. Abnormal chiroptical properties due to the presence of these linkages were observed on polymerizing a levorotatory enantiomer. The formation of irregularities may be explained by the simultaneous presence of anionic and cationic mechanism and gives polymers without irregularities.
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    Radiation copolymerization of vinylene carbonate with isobutyl vinyl ether (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1045-1049 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radiation-induced copolymerization of vinylene carbonate (M1) with isobutyl vinyl ether (M2) has been investigated over the temperature range of 40-80°C. The monomer reactivity ratios r1 and r2 were determined to be 0.118 and 0.148, respectively, and an activation energy of 7.6 kcal/mole (31.8 kJ/mole) was calculated for the copolymerization process.
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    Radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. VI. Temperature dependence and effects of additives on methyl methacrylate-silica gel system (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1031-1041 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To elucidate the reaction mechanism of radiation-induced polymerization of methyl methacrylate adsorbed on silica gel, the temperature dependence and effects of acetone and pyridine were investigated. It was found that even at -78°C the polymerization rate was quite fast. The amounts of high molecular weight GPC peaks of both graft polymers and homopolymers increased with increasing irradiation temperature. The activation energy of the adsorbed state polymerization was low compared with that of bulk polymerization. The low molecular weight peaks of homopolymers decreased with acetone addition but were almost unaffected by pyridine. The low molecular weight peaks of homopolymers were thus polymerized by an anionic mechanism. In the methyl methacrylate-silica gel system both radical and anionic polymerization take place at the same time in formation of graft polymers and homopolymers. A reaction mechanism for the methyl methacrylate-silica gel system was proposed based on the results obtained to date.
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    Effect of valence state of vanadium on stereoblock polymerization of methyl methacrylate with VOCl3-AlEt2Br catalyst system (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1397-1402 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of methyl methacrylate with the VOCL3-ALEt2Br catalyst system in n-hexane has been studied. The first-order dependence of rate of polymerization on catalyst and monomer concentrations, activation energy of 6.67 kcal/mole, and NMR spectra of polymer lend support to a coordinate anionic mechanism of polymerization. It has been shown that the vanadium in V+2 oxidation state is less active than V+3 oxidation state of active complex.
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    Hydrogen-transfer polymerization of methyl-substituted acrylamides (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1347-1361 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Base-catalyzed hydrogen-transfer polymerization and copolymerization of acrylamide and its methyl-substituted derivatives were studied in pyridine at 110°C. n-Butyllithium was used as an initiator. The observed rates of these homopolymerizations were found to decrease in the following order: acrylamide 〉 crotonamide 〉 methacrylamide 〉 N-methylacrylamide 〉 N-methylcrotonamide 〉 tiglinamide 〉 N-methylmethacrylamide ≫ α-chlorocrotonamide ≃ α-cyanocrotonamide = 0. Acrylamide gave the polymer with the highest degree of polymerization among the monomers examined. It was found that the number and the position of the methyl substituent in acrylamide affected significantly both the rate of polymerization and the molecular weight of the polymer. Although all polymers obtained, except the N-methyl derivatives, contained both methanol-soluble and methanol-insoluble fractions, a polyamide structure with unsaturated terminal monomer unit was confirmed by both infrared and NMR determinations. From the NMR determination of the saturated and terminal unsaturated units, the degree of polymerization of the resulting polyamides were also obtained. The monomers were also found to copolymerize by a hydrogen-transfer mechanism. However, the main chain of the resulting copolymers was composed of the more reactive monomer unit, and the less reactive monomer was incorporated only as a terminal unit when a less reactive monomer was copolymerized with a more reactive one. From these results, it was concluded that these polymerizations proceeded via an intermolecular hydrogen-transfer mechanism (i.e., stepwise mechanism).
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140605
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    Solution properties of phosphonitrilic fluoroelastomersPaper was presented, in part, at the Technology Assessment and Planning Conference-Phosphazene and Phosphazene High Polymers, Army Materials and Mechanics Research Center, Watertown, Mass., May 20-22, 1975. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1379-1395 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of phosphonitrilic fluoroelastomers which have excellent solvent resistance and low temperature flexibility, and which perform well under a broad range of service conditions, have been developed. The solution properties of one of these polymers were studied more extensively in order to develop suitable quality control procedures and to gain a better understanding of the polymer structure. Solvents for these procedures were established, fractionation procedures were developed, and intrinsic viscosity, osmotic pressure, and light-scattering measurements were conducted. We found this polymer to have a very broad molecular weight distribution. And, although fractionation by molecular weight was effected, the fractions retained a broad molecular weight distribution. Our data do not indicate significant branching for this polymer. As a result of our studies, we have theorized that a supermolecular structure may be present in this polymer.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140607
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  • 88
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    Amide-exchange reactions in mixtures of N-alkyl amides and in polyamide melt blends (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1403-1417 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The amide-exchange reactions which cause copolymer formation in polyamide melt blends were studied with mixtures of N-ethylcaproamide and N-hexylacetamide containing small concentrations of caproic acid and hexylamine as a model system for melt blends of aliphatic polyamides. Amide exchange was found to involve acidolysis and aminolysis reactions with no detectable contribution of direct reaction between amide groups. Kinetics data are consistent with formation of an anhydride intermediate in amide acidolysis. Rate constants over the range 200-275°C and activation energies for amide acidolysis and aminolysis reactions are given. Equations are given for calculating amide exchange rates in polyamide melt blends and for relating degree of amide exchange to block copolymer composition.
    Additional Material: 20 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140609
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  • 89
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    Modification of poly(ethylene terephthalate) and nylon 66 surfaces by using organometallic polymerization catalysts (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1429-1446 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Zirconium hydrocarbyl catalysts react with nylon and poly(ethylene terephthalate) (PET) fibers to produce a supported species which may be used to polymerize a sheath of polyethylene around the fiber. Very high catalyst activities have been achieved over very short reaction periods on PET spinning threadlines. It is also possible to use these reagents to produce strongly adhered oxide and sulfide surface coatings. Infrared evidence is given for a mechanism in the case of reaction between catalyst and PET.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140611
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  • 90
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    Effect of isotopic composition on free-radical reactions in polyolefins (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1419-1427 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On substitution of hydrogen by deuterium the radiation yield of free radicals in polyolefins decreases ca. 2-fold. Under ultraviolet illumination (γ 〈 300 nm) in deuterated polyethylene (DPE), allyl radicals are converted into alkyl radicals (hfs constants aDα = 3.2 Oe, aDβ = 4.4 Oe); in deuterated polypropylene (DPP), allyl and peroxide radicals are converted into alkyl radicals (aDβ = 3.7 Oe). At 77°K under ultraviolet light in γ-irradiated polyethylene (PE) and DPE, triene, tetraene, dienyl, trienyl, and tetraenyl radicals are formed. Deuterium substitution has no effect on absorption spectra of polyenyl radicals and polyenes. In polyolefins the quantum yields of photochemical reactions of allyl and peroxide radicals are 0.1-1.0. Photochemical reactions of peroxide radicals result in a radical concentration increase of ca. 3-fold. In reactions of peroxide radicals in the dark, a kinetic isotope effect has been observed. Activation energies of substitution reactions of peroxide radicals are in PE, 9.3 ± 0.3 kcal/mole; in DPE, 10.2 ± 0.3 kcal/mole; in PP, 12.7 ± 0.4 kcal/mole; in DPP, 14 ± 0.5 kcal/mole. Possible mechanisms of the effect of polyolefin isotope composition on radical formation by high energy irradiation as well as on photochemical and dark reactions of free radicals are discussed. The effect of the energy released from phototransformations and radiationless deactivation of macroradicals on the migration of free valence is also considered.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140610
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  • 91
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    Studies on the photooxidation mechanism of polymers. IV. Effect of ultraviolet light (2537 Å) on solid PVC particles suspended in different liquids (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1447-1462 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of virgin PVC powder suspended in water, methanol, n-hexane, aqueous NH4OH (30 wt-%), and 0.1 wt-% iodine in methanol and also as dry powder was studied. The mechanism of photolysis of PVC powder has been investigated by using ESR spectroscopy, conductivity titration, gel-permeation chromatography (GPC), and absorption spectroscopy. Photolysis of PVC has been found to occur by a free-radical mechanism. ESR spectroscopy permits a partial identification of several different types of free radicals in PVC such as alkyl, polyenyl, and peroxy radicals. An interpretation is proposed of the mechanism of formation of conjugated polyene structures, and also a new explanation of the crosslinking mechanism, in which transfer of unpaired electrons to double bonds occurs, is suggested. It has also been found that conjugated double bonds can photosensitize free-radical formation as a result of increased ultraviolet absorption due to polyene structures.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140612
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  • 92
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    Studies on the photooxidation mechanism of polymers. V. Oxidation of polybutadienes by singlet oxygen from microwave discharge and in dye-photosensitized reactionsPresented in part at International Symposium on Ultraviolet Light-Induced Reactions in Polymers, American Chemical Society, Philadelphia, April 6-11, 1975. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1463-1473 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The singlet oxygen oxidation of cis- and trans- 1,4-polybutadienes was studied by using singlet oxygen generated in a microwave generator and in dye-photosensitized reactions of these polymers in the solid state and in solution. It was shown that the reactions of singlet oxygen result in formation of hydroperoxide groups, whereas ultraviolet oxidation by molecular oxygen in addition leads to formation of carbonyl groups. During dye-photosensitized oxidation of polydienes in benzene solution, a very rapid decrease in the molecular weight was observed.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140613
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  • 93
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    Effect of comonomer sorption on radiation-induced copolymer grafting onto polyethylene and EVA films in the vapor phase (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1175-1182 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radiation-induced copolymer grafting of acenaphthylene and maleic anhydride onto polyethylene or EVA film in the vapor phase was carried out and the effect of comonomer sorption on the grafting was studied. When polyethylene film was used as a backbone polymer, the sorption of the binary monomers during the grafting increased linearly as the grafting reaction proceeded. The marked increase was probably caused by the formation of a grafted layer. Particularly, the sorption of maleic anhydride was brought about by the existence of a grafted layer. In grafting onto EVA film, the content of maleic anhddride in the grafted copolymer increased with the increasing content of vinyl acetate in EVA. Continuous measurements of sorption of the comonomers onto EVA and grafted EVA films were carried out by use of an electrobalance. The distinctive feature of the sorption was that the equilibrium sorption of acenaphthylene or maleic anhydride onto the grafted EVA film increased and the diffusion constants for both comonomers decreased markedly with increasing percentage of graft. The copolymer grafting was explained from these results by assuming that the monomer molecules are supplied to the propagating chain ends mostly through a sorbed state on the polymer film.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140515
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  • 94
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    Effect of solvent in radical polymerization of butadiene 1-carboxylic acid (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1183-1193 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radical polymerization and copolymerization of butadiene 1-carboxylic acid (Bu-1-Acid) were studied in a variety of the electron-donor solvents such as dimethylformamide (DMF), tetrahydrofuran (THF), methyl ethyl ketone (MEK), acetonitrile (ACN), and benzene (BZ) using AIBN as an initiator at 50°C. Under these conditions, the polymerization rate of Bu-1-Acid increased in the order, DMF 〈 THF 〈 MEK 〈 ACN 〈 BZ in the various solvents. In copolymerization with styrene [M2] and acrylonitrile [M2], the monomer reactivity ratio r1 increased and r2 decreased in the same order. Moreover, it was found that Alfrey-Price Q-e value of Bu-1-Acid increased depending on solvent in the order DMF 〈 THF 〈 MEK 〈 ACN 〈 BZ. These variations were correlated to the electron-donating power (Δvcm-) of the solvents used and are discussed on the basis of the solvation of Bu-1-Acid into the solvent. Also, it was found that the microstructures of these polymers were always trans-1,4 and did not change with the solvent used.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140516
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  • 95
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    Morphology of organosilicon ladder polymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1205-1212 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The morphology of organosilicon ladder polymers was studied by various methods, including x-ray techniques, diffraction of monochromatic polarized light, and electron microscopy. The morphology is discussed as a function of the chemical composition, the molecular weight, and the method of preparation.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140518
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  • 96
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    Effect of pH on radical polymerization of butadiene 1-carboxylic acid in aqueous solutions (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1195-1203 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical polymerization of butadiene 1-carboxylic acid (Bu-1-Acid) was carried out in aqueous solutions at 50°C with ammonium persulfate (APS) as an initiator. Kinetic studies led to the rate equation, Rp = k[APS]1/2 [Bu-1-Acid]1 at pH 6.8. The overall activation energy for the polymerization was 16.0 kcal/mole. The polymerization rate Rp of Bu-1-Acid decreased with an increase of pH in the range 2.4-6.8 and increased with an increase of pH in the range 6.8-8.4. Moreover, in the pH range 8.4-13, the rate of polymerization was not affected by the pH of the system. In copolymerization with acrylonitrile, the trends of changes in the monomer reactivity ratios r1, r2 and Q-e values caused by changes in pH were similar to trends found in homopolymerization described above. In addition, it was observed that the resultant polymer was extended in alkaline solution and contracted in acidic solution.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140517
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  • 97
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    Effect of chemical structure and thermal history on the β transition of polystyrene and some substituted polystyrenes (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1627-1636 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: DTA (differential thermal analysis) traces for various kinds of polystyrene and substituted polystyrenes, including bulk-polymerized, monodisperse, and isotactic samples, have been recorded below the glass temperature. It has been shown that the β transition is dependent upon polymer structural modification, traces of water or solvent, and sample thermal history. The experimental data presented here support the conclusion that the β transition is due to conformational changes involving backbone motions and phenyl ring reorientation.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140706
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  • 98
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    ESR study on photodecomposition mechanism of oxidized poly(vinyl alcohol) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1617-1625 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photolysis behavior of oxidized poly(vinyl alcohol) (PVA) in which carbonyl groups were introduced by oxidation with sodium hypochlorite and periodic acid was investigated by using ESR spectrometry. Increased formation of PVA radicals was observed in the sample with low degree of oxidation, which showed an emphasized formation of triplet component radical. On the other hand, the formation of radicals tended to be depressed in the highly oxidized sample, and a singlet component was dominant in the ESR spectrum. By examining infrared and ultraviolet spectra of the oxidized sample, the sample was found to contain two structures, a saturated ketone group and an α,β-unsaturated group; the latter structure was intensified with increasing degree of oxidation. Based on ESR studies of the photoirradiated acetone and mesityl oxide, the models of saturated and α,β-unsaturated ketone structures in the oxidized PVA, respectively a photodecomposition mechanism of oxidized PVA was proposed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140705
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    Aromatic polyethers, polysulfones, and polyketones as laminating resins. VIII. Aryl disulfide units as crosslinking agentsFor Part VII, see Chang and Marvel.1 (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1637-1644 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxidation of 1,4-phenylenedimercaptan has given a cyclic trimeric disulfide. Oxidation of 1,3-phenylenedimercaptan has yielded a similar product. These monomers have been incorporated in the chains of aromatic polyether, sulfone, ketone polymers and serve as crosslinking sites on heating these polymers.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140707
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  • 100
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    Multiblock copolymers of styrene and isoprene. I. Synthesis and characterization (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1645-1659 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An anionic polymerization procedure for preparing multiblock copolymers of styrene and isoprene is described. The process is based on the initial specific incorporation of isoprene when mixtures of styrene and isoprene are polymerized with butyllithium in hydrocarbon solution. As examples, linear (AB)3 block copolymers have been prepared by interrupting styrene polymerization by step additions of isoprene at times programmed according to the reactivity ratios and the rate constants for styrene and isoprene propagations. The products were characterized by means of osmometry, light scattering, gel-permeation chromatography, and density-gradient ultracentrifugation. The analyses showed that the multiblock copolymers are free from polymeric impurities and reasonably homogeneous in molecular weight and composition. The polystyrene segment lengths were analyzed by means of GPC after the oxidative degradation of the polyisoprene moieties in the copolymers. The results suggest that the polyisoprene blocks contain a nonnegligible amount of styrene but that this monomer is incorporated as very short segments. On the other hand the polystyrene blocks produced at the end of the copolymerizations appear to have narrow molecular weight distributions.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140708
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