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  • Physics  (27)
  • Organic Chemistry
  • 1980-1984  (33)
  • 1965-1969
  • 1940-1944
  • 1981  (33)
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 19 (1981), S. 1577-1591 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A set of isothermally melt-crystallized polyethylene samples was examined using small-angle x-ray scattering (SAXS). Time and temperature of crystallization were the variable parameters used to create the set of samples. Following background subtraction, desmearing, and application of the Lorentz factor to the raw SAXS data it is possible to see many orders of reflection. This suggests that much higher degrees of order are present in isothermally melt-crystallized samples than had previously been thought possible. A combination of SAXS and DSC data indicates that there is no evidence for isothermal thickening in these samples. This study, coupled with data obtained from PE single crystals, produced information concerning the extrapolation of single-crystal data to fit bulk systems. In addition, the equilibrium melting point T0m determined is somewhat lower than previously claimed. This study also suggests that the surface energy of the mature crystals is always lower than that of the nucleated state and/or the nucleation factor Kσen increases with decreasing supercooling.
    Additional Material: 11 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 19 (1981), S. 487-497 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The width at half-height of SAXS discrete diffraction peaks has been used to compute the number of polyethylene lamellae in a stack. The dependence of this width on diffraction order reflects the nature and magnitude of lattice fluctuations. Within the literature there have been conflicting reports on this order dependence and hence on the nature of the lattice fluctuations. Previous studies have neglected the effects of instrumental broadening. These present studies show that instrumental effects can account for some 40% of the observed first-order peak width and drastically change the ratio of peak widths as a function of order. These studies, carried out on isothermally grown polyethylene single-crystal mats, also demonstrate the importance of the functions chosen to represent the various broadening factors. A mat was made up consisting of randomly stacked lamella with two distinct fold periods. The scattering from this mixed mat could not be described by either of the prevailing theories.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 64 (1981), S. 1058-1062 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates of proton transfer from 2, 4-hexadiene, 1, 3-cycloheptadiene, cyclopentadiene and acetone to t-butoxide have been measured in the gas phase using pulsed-ion-cyclotron-resonance spectroscopy. The rate constants are (units of 10-10 cm3 molecule-1 s-1): 2.7 ± 0.4, 3.8 ± 0.4, 6.1 ± 0.7 and 10.8 ± 1.5, respectively. These results are analyzed in terms of the properties of the encounter complex and reaction transition states. The reaction profile for t-butoxide + cyclopentadiene is modeled using RRKM theory and an estimate for the central barrier height is obtained.
    Additional Material: 1 Ill.
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  • 4
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Tasmanine, a New Indole Alkaloid from Aristotelia peduncularis (LABILL.) HOOK. F.The new indole alkaloid tasmanine (3) was isolated from Aristotelia peduncularis. Its relative configuration was elucidated on the basis of spectroscopic data (mainly NMR. spectra). It is closely related to the other known alkaloids from Aristotelia with double substitution at the indole nucleus. A biosynthetic pathway to these related natural compounds is proposed; also a biogenetic numbering system is suggested.
    Notes: No Abstract.Another representative of this group of alkaloids, aristoteline (2), was also isolated from A. peduncularis. This natural compound has previously been isolated from A. serrata and A. chilensis.
    Additional Material: 1 Tab.
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  • 5
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4,2-Chloronitrobenzenediazonium ions in aqueous buffer solutions between pH 2.9 and 7.9 do not hydrolyze by dediazoniation as previous authors have assumed, but by denitration. The isomeric 2,4-compound reacts by denitration (ca. 70%) and dechlorination (ca. 30%). The reactions are general base catalyzed. The products and kinetics are consistent with an SNAr-mechanism in which the general base-catalyzed addition of a hydroxyl group at the reacting C-atom is rate-limiting. The rate maxima at or near the pH-values corresponding to (pK1 + pK2)/2 of the diazonium ⇄ cis-diazotate equilibria can be rationalized on the assumption that the diazonium ion is the only equilibrium form of the diazo compound which enters the substitution proper, and the superposition of the rate term B∑kB[B] of all nucleophiles involved (H2O, OH- and buffer bases).
    Additional Material: 3 Ill.
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  • 6
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Untersuchungen an Azoverbindungen. V. Polarographisches Verhalten einiger kondensierter Phenylringe enthaltender 1-Hydroxyazoverbindungen
    Additional Material: 4 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2869-2880 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chemical reaction in aqueous medium of polyacrylonitrile and acrylonitrile-vinyl acetate co-polymer using asymmetrical diamines of H2N—(CH2)m—NR2 (m = 2,3) structure was studied. It was found that the nitrile group is modified to an dialkylaminoalkylacrylamide group; also determined were the reaction conditions required to obtain the highest degree of chemical transformation of the nitrile groups. All modified compounds were characterized by analytical spectroscopy (IR and 1H NMR) and by rheological methods. It was also established that glutaronitrile can be used as a low-molecular-weight model to study the chemical transformation of nitrile groups in polyacrylonitrile and related polymers.
    Additional Material: 4 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2881-2894 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction kinetics of halogenated compounds with tertiary amine groups attached at an acrylic macromolecular chain have ben studied. Three acrylic polymers were used. Two of them have mainly a structural unit of N, N-dimethylaminopropylacrylamide and the third is poly(N,N-dimethylaminoethylmethacrylate). Dimethylformamide, dimethylacetamide, and dimethylsulfoxide (DMSO) were used as dipolar aprotic solvents. Benzyl chloride and allyl chloride were considered as halogenated compounds with increased reactivity. The reaction kinetics depend on the polymer and halogenated-compound structures as well as the nature of the solvent. In the most of the cases the reactions carried out on polymers are accompanied by self-accelerating processes, with the exception of DMSO, which obviously has normal second-order kinetics. The reaction of polymers containing units of N,N-dimethylaminopropylacrylamide are compared with one having a low molecular weight, for instance N,N′-bis(3-dimethylaminopropyl)glutaramide.
    Additional Material: 10 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 879-889 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and the molecular weight distribution in the radical polymerization of methyl methacrylate in the presence of a cobalt complex of hematoporphyrin tetramethyl ether is investigated. The whole complex of experimental data indicates the new kinetic phenomenon - catalyzed chain transfer to monomer. The possible mechanism of the chain transfer and the chain transfer agent regeneration acts is suggested.
    Additional Material: 5 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1495-1508 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Qualitative and quantitative free radical transformations between polypropylene alkyl radicals, oxygen, and brominated flame retardants in the molten and gaseous phases of thermally treated samples are described. By ESR technique it has been proved that, depending on the applied pressure during pyrolysis, highly reactive peroxy radicals or less reactive radicals of the retardant are formed. For flame-retarded samples, compared with polypropylene without additives, the concentration of the primary alkyl radicals transferred from the molten to the gaseous phase is reduced by two orders of magnitude (from 7 × 1014 to 7 × 1012 spins/0.02 g), whereas the limiting oxygen index [LOI] is raised from 17-18% to 25-26%. The great variety of physical and chemical processes proceeding in molten polymer in the preflame zone and burning gaseous phase calls for use of different retardant types with a programmed release of Br and HBr with the temperature increase. The chain oxidation of the “fuel,” a product of the endothermic decomposition of polymer, determines the temperature of self-ignition according to the number of initiating alkyl and allyl radicals formed per unit time; the [LOI] index depends more on the length of the kinetic chain of propagation reactions in the stationary process of oxidation at a given pressure.
    Additional Material: 6 Ill.
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