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  • 1
    Electronic Resource
    Electronic Resource
    Decomposition of polypropylene hydroperoxide by hindered aminesIssued as NRCC No. 19889. (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 575-582 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hindered amine-induced decomposition of polypropylene hydroperoxide was studied in the solid state and in the presence of a liquid solvent and the polymer was compared with model hydroperoxides. The high reactivity of the macrohydroperoxides appears to be related to the adjacent, hydrogen-bonded hydroperoxide groups that occur in the polymer. The hindered amines are converted to nitroxides in the reaction via hydroxylamine intermediates. Amine-induced decomposition of polypropylene hydroperoxide is faster in the absence of a liquid solvent for the amine than in the presence of the solvent, probably because of the strong amine-hydroperoxide association that occurs in the solid state. The decomposition process in the solid state is sufficiently rapid for the reaction to contribute to the effectiveness of hindered amines in the light stabilization of polymers.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200231
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  • 2
    Electronic Resource
    Electronic Resource
    Spectroscopic study of rigid-rod polymers. II. Protonation effect (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 509-521 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The protonation of a heterocyclic rigid-rod polymer poly(p-phenylene benzbisthiazole) and its model compound has been studied by UV-visible and Raman spectroscopy. Because of the two nitrogens on the heterocyclic ring, spectroscopic features of unprotonated, half-protonated, and fully protonated structures have been identified. For the fully protonated molecule, there is also an increase in conjugation between the phenyl ring and the heterocyclic ring.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.180200312
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  • 3
    Electronic Resource
    Electronic Resource
    Investigation of molecular order in liquid-crystalline solutions of cellulose triacetate using PMR spectroscopy (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1019-1028 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Liquid-crystalline solutions of cellulose triacetate (CTA) in trifluoroacetic acid (TFA)-CH2Cl2, TFA-1.2-dichloroethane (1,2-DCE) solvent mixtures were examined by means of PMR spectroscopy. CTA forms both cholesteric and nematic phases in these solvents depending on the CTA concentration. In cholesteric solutions the CH2Cl2 signal is initially a singlet and then splits into a doublet. The time dependence of the splitting and the effect of CTA concentration are reported. The results suggest that the cholesteric phase slowly changes into a nematic phase in the magnetic field. The splitting of the CH2Cl2 proton signal into a doublet and the 1,2-DCE signal into a quartet are due to direct magnetic dipole-dipole interactions. Rotation of the sample in the magnetic field results in the disappearance of the doublet or quartet and suggests that the solvent molecules are originally oriented in the direction of the magnetic field. In the biphasic region, immediate splitting of the CH2Cl2 proton signal suggests that the anisotropic phase is nematic.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.180200610
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  • 4
    Electronic Resource
    Electronic Resource
    Microphase separation in sulfonated polystyrene ionomers (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1503-1509 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Small- and wide-angle x-ray scattering results for a series of un-neutralized and neutralized sulfonated polystyrenes are presented for the range of sulfonation from 0 to 7.26 mol %. From the small-angle scattering it is shown that above the 3 mol % level for both the zinc and sodium salts, a Bragg spacing (37 Å) and diameter (6.9-8.4 Å) of the scattering unit can be calculated. When the concentration of salt is increased, there is no appreciable change in the latter two measurements. The wide-angle data indicate that the cations do not influence to any large extent the basic intramolecular and intermolecular structure of polystyrene. All the data are consistent with the onset of clustering above a critical ion concentration.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.180200815
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  • 5
    Electronic Resource
    Electronic Resource
    Radiation-induced graft copolymerization of mixtures of styrene and acrylamide onto cellulose acetate. I. Effect of solvents (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 939-950 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The grafting of styrene and acrylamide, from both their binary and unitary systems, on cellulose acetate film was studied by means of the cobalt-60 postirradiation grafting technique. The extent of grafting was found to be dependent on preirradiation dose, reaction time, and temperature, and the optimum conditions were evaluated. The effect of solvents, e.g., water, methanol, ethanol, isopropanol, and t-butanol were studied. The composition of the binary mixture as well as the nature of the alcohol used as the solvent were found to have a strong influence in modifying the course of grafting. Each component of the binary monomer mixture was found to sensitize the grafting of the other, when the former is present in relatively large concentration. The observed results are discussed in detail in terms of relative molecular reactivity and reactivity ratios.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200404
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  • 6
    Electronic Resource
    Electronic Resource
    Diffusion-controlled vinyl polymerization. III. Free volume parameters and diffusion-controlled propagation (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1331-1344 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The values of the parameters that are necessary to compute the free volume changes accompanying polymerization were determined from viscosity data of concentrated polymer solutions. Relationships applicable above and below the glass transition temperature of the polymer were quantified. A general treatment of the variation of the propagation rate constant with free volume was postulated, based on the variation of the monomeric diffusivity with free volume. This, in turn, was related to the friction coefficient of a polymer chain segment, the values of which are readily available. A discussion of the reaction behavior in the last stage of polymerization and the occurrence of limiting conversion is also presented.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200515
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  • 7
    Electronic Resource
    Electronic Resource
    Amylose-polyester block copolymers (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 997-1009 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of amylose-polyester block copolymers is described. 2,3,6-Tri-0-allyl amylose was synthesized by amylose alkoxide and allyl bromide and hydrolyzed by hydronium ions to give an hydroxyl-terminated allyl amylose oligomer (HTAA). The allyl groups were isomerized with t-BuoK to yield the prop-1-enyl isomer (HTPA). The HTPA was capped with a diisocyanate. The HTPA prepolymer was reacted with hydroxy-terminated poly(ethylene-co-propylene adipate) and poly-(ethylene terephthalate) to form block terpolymers. Block terpolymer formation was demonstrated by intrinsic viscosity increases, gel permeation chromatographic results, and infrared (IR) and PMR spectroscopy. The products were depropenylated by HgCl2 to yield amylose block terpolymers. These polymers were readily degraded by α-amylase.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200409
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  • 8
    Electronic Resource
    Electronic Resource
    Complex formation between poly(ethylene oxide) and alkali picrates (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1389-1400 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of poly(ethylene oxide) with alkali picrates in tetrahydrofuran and dioxane was studied by optical and NMR spectroscopy and conductance measurements. Evidence was found of the formation of two kinds of solvation complex, differing in the nature of the ion pairs involved. A strong anion effect on cation binding to the polyether was demonstrated.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200602
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  • 9
    Electronic Resource
    Electronic Resource
    Complexes of polyacids with poly(vinylbenzocrown ether)s and polyvinylbenzoglymes in water (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1629-1638 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Insoluble complexes are formed in acidic aqueous media when poly(acrylic acid) (PAA) and poly-(vinylbenzo-18-crown-6) (P18C6) or polyvinylbenzoglymes are mixed. Complex formation results from hydrogen bonding between carboxyl groups and crown ether- or glyme-oxygen atoms as well as from hydrophobic interactions. The precipitation is pH dependent and was determined as a function of the ratio PAA to P18C6 or to polyglyme at different HCl concentrations in 10-4M solutions of polycrown or polyglyme. Precipitation is nearly quantitative in 0.01N HCl. The compositions of PAA/P18C6 precipitates were determined as a function of the initial PAA/P18C6 ratio in solution. The complexes with P18C6 can be solubilized in acidic media when crown-complexable cations (K+, Cs+, Ba2+) are added, but the charged P18C6 reprecipitates in basic solution as a polysalt complex with the PAA-polyanion. More stable PAA-P18C6 complexes in the form of fibers can be obtained by interfacial complex formation. Poly(methacrylic acid) is less effective as a complex former.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200623
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  • 10
    Electronic Resource
    Electronic Resource
    Acrylonitrile-4-vinylpyridine copolymers effect of comonomer sequence distribution on properties (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1653-1667 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acrylonitrile-,4-vinylpyridine copolymers were prepared in chloroform solution at 60°C with AIBN as initiator. Copolymer compositions were determined from their 15.01-MHz 13C-NMR spectra. Reactivity ratios of rAN = 0.093 and r4VP = 0.32 were calculated by the Kelen and Tudos method. The run number, number-average sequence lengths, and monomer sequence distributions were also calculated. The Tg values of the copolymers, their dye uptake, and degree of alkaline hydrolysis were influenced by the overall copolymer composition but particularly by the monomer sequence distribution in the copolymers.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170200701
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