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  • Articles  (554)
  • Physics  (554)
  • Wiley-Blackwell  (554)
  • American Chemical Society
  • Blackwell Publishing Ltd
  • 1980-1984  (554)
  • 1984  (554)
  • Chemistry and Pharmacology  (554)
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  • Articles  (554)
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  • Wiley-Blackwell  (554)
  • American Chemical Society
  • Blackwell Publishing Ltd
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  • 1980-1984  (554)
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  • Chemistry and Pharmacology  (554)
  • Physics  (185)
  • 1
    Electronic Resource
    Electronic Resource
    Fire-resistant polyimides and copolyimides based on 1-[(dialkoxyphosphinyl)methyl]-2,4- and -2,6-diaminobenzenes (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1065-1076 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Various phosphorus-containing polyimides were prepared by the reaction of 1-[(dialkoxyphosphinyl)methyl]-2,4- and -2,6-diaminobenzenes (1) with a tetracarboxylic dianhydride like pyromellitic dianhydride (PMDA) and benzophenone tetracarboxylic dianhydride (BTDA). In addition, copolyimides that contained approximately 3% phosphorus were prepared by the reaction of 1 and m-phenylenediamine (MPD) with the aforementioned tetracarboxylic dianhydrides. Elemental analysis, inherent viscosity, infrared (IR) spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) studies were performed to characterize the polymers. Their thermal properties were compared with those of the corresponding common polyimides. It was shown that the molecular weight and thermal stability of the polymers were reduced as the concentration of the phosphorus moieties increased. The fire-resistance of the copolyimides was evaluated by determining their limiting oxygen index (LOI) value. Copolyimides that contained about 3% phosphorus showed an LOI value approximately 30% higher, than the value of the corresponding common polyimides. In addition, a model diamic acid and diimide was synthesized by the reaction of 1-[di(2-chloroethoxyphosphinyl)methyl]-2,4- and - 2,6-diaminobenzene (DCEPD) with phthalic anhydride and characterized by elemental analysis, IR, proton nuclear magnetic (1H-NMR) spectroscopy, DSC, and TGA. The pyrolysis behavior of the model compounds was investigated by gas chromatography-mass spectrometry (GC-MS). A direct cleavage of the P—C bond and a possible rearrangement to diisocyanates occurred during their pyrolysis.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220507
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  • 2
    Electronic Resource
    Electronic Resource
    Plasma polymerization of trifluoromethyl substituted aromatic compounds (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1123-1130 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thin film coatings were prepared by polymerizing trifluoromethyl-substituted aromatic compounds in a glow discharge with low power levels and medium pressures. Smooth, continuous films which are adherent and insoluble in conventional solvents were produced. A significant amount of the fluorine content from the monomer was retained in the polymer. The trifluoromethyl group was not removed by the plasma conditions and appeared in the film as trifluoromethyl and difluoromethylene groups. The films were slightly less wettable than those of the unfluorinated films.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220512
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  • 3
    Electronic Resource
    Electronic Resource
    Synthesis and conformation of asymmetric rigid polyamides (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1153-1177 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Asymmetric polyamides from the reaction of either optically active trans-1,2-cyclopropanedicarboxylic acid (C3) or trans-1,2-cyclohexanedicarboxylic acid (C6) with 2,7-diazaspiro[4,4]nonane(DSN) were synthesized. The possible conformations of these polymers and their model compounds in 2,2,2-trifluoroethanol (TFE), water, methanesulfonic acid (MSA), and sulfuric acid were examined by circular dichroism (CD), NMR, viscosity, and dipole moment measurements. The racemic polyamides (±)C3·(±)DSN and (±)C6·(±)DSN exist in extended forms. No intrinsic viscosity changes were observed for these two polymers in TFE and MSA. Certain viscosity and spectral changes have been observed for the optically active polyamides, although no specific ordered conformations can be assigned. The optically active diacid units incorporated into the polymer give a conformation unique from the totally extended chain. CD studies seem to evidence some conformational differences among the polyamide derived from (+)C6 diacid and the optically active DSN. By changing the solvent from TFE to MSA a blue shift of the trough was observed for (+)C6·(±)DSN, a red shift for (+)C6·(-)DSN, and an inversion of the CD spectrum for (+)C6·(+)DSN polyamides. The results of the work with (+)C6·(-)DSN in dilute acid solution suggest that the rotation around the C-N bond is a relatively low-energy process. The spectral and intrinsic viscosity data are consistent with this suggestion. No drastic spectral changes have been observed for the C3·DSN polyamides by changing the solvent from TFE to MSA. The amide group in the C3·DSN polyamide and the corresponding model compound prefer a similar conformation with the carbonyl group bisecting the cyclopropane ring. The C3·DSN polyamide seems to exist in an extended form.
    Additional Material: 17 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220515
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  • 4
    Electronic Resource
    Electronic Resource
    Cationic grafting from carbon black. II. Polymerization of styrene initiated by CO+ClO-4 group on the surface of carbon black (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1515-1524 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cationic grafting of polystyrene initiated by carbon black containing the CO+ClO-4 group was investigated. The introduction of CO+ClO-4 groups onto a carbon black surface was achieved by the reaction of AgClO4 with carbon black that contained a COCI group. The latter was introduced by the reaction of carboxyl groups with SOCl2. It was found that polystyrene chains could be grown from CO+ClO-4 groups on the surface of carbon black. Moreover, polystyrene was effectively grafted from carbon black: the grafting ratio at 20°C increased to 58% as conversion increased. Furthermore, the grafting ratio and molecular weight of ungrafted polystyrene decreased with an increase in polymerization temperature. These results were explained by the fact that the increasing temperature of the polymerization caused an increase in the rate of chain transfer reaction of the growing polymer chain to the monomer. The carbon black obtained from the reaction produced a stable colloidal dispersion in a good solvent for polystyrene.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220630
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  • 5
    Electronic Resource
    Electronic Resource
    Polymerization of alkyl allyl oxalates in the evolution of carbon dioxide at elevated temperatures (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1541-1550 
    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 several alkyl allyl oxalates, including methyl allyl oxalate (MAO), ethyl allyl oxalate, propyl allyl oxalate, butyl allyl oxalate, and octyl allyl oxalate, was conducted in the evolution of carbon dioxide at elevated temperatures, and was compared with the anomalous polymerization behavior of diallyl oxalate (DAO) discussed in our earlier articleA. Matsumoto, I. Tamura, M. Yamawaki, and M. Oiwa, J. Polym. Sci. Polym. Chem. Ed., 17, 1419 (1979).. The kinetic equations for the polymerization of alkyl allyl oxalate were derived following the kinetic treatment of the DAO polymerization by further consideration of the absence of cyclization of the growing polymer radical and the effective reinitiation by alkyl radical, and were then satisfactorily applied to the polymerization of MAO, as a representative alkyl allyl oxalate. The evolution of carbon dioxide in the polymerization of alkyl allyl oxalates was enhanced with the increase of bulkiness of the alkyl substituent, as a result of steric suppression of the propagation of the growing polymer radical.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220702
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  • 6
    Electronic Resource
    Electronic Resource
    Plasma polymerization. XI. A comparison of the plasma polymerization of the isomeric perfluorinated diazines (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 17-28 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Plasma polymers synthesized by inductively coupled RF techniques have been investigated as a function of operating parameters for the isomeric perfluorinated diazines (pyrazine, pyrimidine, and pyridazine). A combination of ESCA and microanalytical studies shows that plasma polymers are produced by rearrangement mechanisms: the C/F and C/N stoichiometric ratios are similar to those of the starting monomers over a range of operating parameters. A comparison of rates of formation of plasma polymer films reveals distinctive differences between the isomeric diazines that suggest that equilibration of valence isomers occurs on a substantially slower time scale than for isomeric fluorinated benzenes5-9 which, in general, polymerize at essentially the same rates. In contrast to the remarkably low critical surface tension of plasma polymers based on perfluorobenzenes (ca. 20 dynes cm-2), the plasma polymer films from the perfluorinated diazines which are initially hydrophobic become hydrophilic in contact with water droplets. This is attributed to the hydrolytic instability of films associated with the labilizing influence of nitrogen on nucleophilic displacement of fluoride which is a feature of the chemistry of monomers.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220102
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  • 7
    Electronic Resource
    Electronic Resource
    Water-soluble copolymers. VII. Cerium (IV) induced graft copolymerization of acrylamide and sodium-2-acrylamido-2-methylpropane sulfonate onto dextran (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 49-60 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies were conducted on grafting of acrylamide (AM) and sodium-2-acrylamido-2-methylpropane sulfonate (NaAMPS) comonomers onto dextran utilizing Ce(IV) induced initiation. The effects of reaction temperature, the Ce(IV)/dextran ratio, and the AM/NaAMPS ratio on grafting yield were investigated. The graft copolymerization behavior can be explained by exchange of the AMPS anion with one of the ligands on the Ce(IV) initiator. Oxidative modification of the dextran substrate improved the yield of graft copolymer. The dextran-g-poly(acrylamido-co-sodium-2-acrylamido-2-methylpropane sulfonate) samples prepared by this method were characterized as to copolymer composition and molecular weight utilizing elemental analysis, dilute solution viscometry, and aqueous size exclusion chromatography. Relationships of molecular weight and charge density to kinematic viscosity and salt sensitivity are discussed.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220105
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  • 8
    Electronic Resource
    Electronic Resource
    Photoinitiation of cationic polymerization. III. Photosensitization of diphenyliodonium and triphenylsulfonium saltsFor Part II, see ref. 1. (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 77-84 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photoinitiated cationic polymerization by photosensitization of diphenyliodonium and triphenylsulfonium salts is shown to proceed by two distinct electron transfer process: (1) direct electron transfer from excited-state photosensitizers and (2) indirect electron transfer from photogenerated radicals. The efficiency of the former process is attributed to the instability of the reduction products (from diphenyliodonium and triphenylsulfonium salts), which dissociate in competition with undergoing energy-wastage reverse electron transfer. Amplification of photons in the production of protons (or other reactive cations) is postulated to account for the high quantum yields observed in the latter process. Potential advantages of utilizing the indirect redox process in the design of UV curable hybrid systems, which contain functionality for both radical and cationic polymerization, are noted. The results also provide evidence against the importance of triplet states of the onium salts in photoinitiator activity.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220108
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  • 9
    Electronic Resource
    Electronic Resource
    Attempted polymerization of substituted pipecolic acid NCA's: Dimerization and mechanism (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 107-120 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Racemic and optically active N-carboxyanhydrides (NCA)s of 2-methyl- and cis-6-methylpipecolic acid, when subjected to polymerization conditions in solution or in bulk whether with “weak” or “strong” base initiators, resisted polymerization under all conditions tried. Instead, the NCA of 2-methylpipecolic acid gave the corresponding cyclic dipeptide and the NCA of cis-6-methylpipecolic acid formed the cyclic dipeptide derived from trans-6-methylpipecolic acid. The mechanism of dimerization of these NCA's was investigated. Evidence was provided for the proposed mechanism in which the active moiety is not a carbamate ion but an amino group. Methyl 2-methylpipecolate underwent an intermolecular SN2-type reaction upon heating, yielding equimolar quantities of methyl N-methyl-2-methylpipecolate and 2-methylpipecolic acid.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220111
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  • 10
    Electronic Resource
    Electronic Resource
    The effect of organic nitriles on the radiation induced polymerization of styrene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 135-144 
    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 a range of 10 organic nitriles on the radiation-induced polymerization of styrene was studied. A dose rate of 4.4 rad s-1 was used. A rate of polymerization of styrene (1.744 mol L-1 of toluene solution) of 5.0 × 10-7 mol L-1 s-1 was found. With organic nitriles present (styrene:nitrile ratio of 1:0.28) the rate of polymerization increased. Rates in the range of 5.5 × 10-7 -5.2 × 10-6 mol L-1 s-1, depending on the nitrile present, were obtained. The polymers were partially characterized and evidence of involvement of each of the nitriles in the polymer chains was revealed. The increase in rate of polymerization has been attributed to the part played by nitrile radicals in the initiation of styrene polymerization. Radical yield values [as G(nitrile radical)] were derived from the relevant rate expressions. Values ranged from 2.7 to 49.5, depending on the particular nitrile. Corresponding values of G(nitrile radical) in the range of 5.1-129.4 were obtained by the manipulation of number-average molar mass data. Values of kpkt of approximately 2 × 10-5 L mol-1 s-1 were found. Trommsdorff types of effect are absent from these systems.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220114
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