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  • 1960-1964  (3)
  • Polymer and Materials Science  (3)
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  • 1
    Electronic Resource
    Electronic Resource
    Recent developments in polymerization by an alternating intra-intermolecular mechanism (1960)
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 48 (1960), S. 279-289 
    Details
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Recent developments in polymerization by an alternating intra-intermolecular mechanism are summarized and discussed briefly. The methods used to prove the structure of typical polymers, which in turn established the mechanism of polymerization, are reviewed. A study of larger ring formation by Marvel and Garrison is also summarized. Ring of sizes from 7 to 21 members were formed from α-diolefins in yields of from 4 to 25%. A study of certain unsymmetrical dienes has shown that cyclization occurs in yields up to 60%, but that gelation eventually occurs because of the difference in relative reactivities of the two olefinic double bonds. Copolymerization of certain 1,4-dienes with certain olefins to produce linear copolymers containing six-membered rings is discussed. In an effort to explain the strong driving force to close a six-membered ring during polymerization of 1,6-diolefins, a pronounced interaction between the double bonds, which can be represented by several resonance forms of the molecule, is proposed.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1960.1204815026
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    Paper (German National Licenses)
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  • 2
    Electronic Resource
    Electronic Resource
    Proton magnetic resonance studies of the microstructure of polymethacrylic anhydride (1961)
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 54 (1961), S. 329-342 
    Details
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Methacrylic anhydride was polymerized, in high yields, at temperatures ranging from 1 to 80°, in benzene solution, to linear, soluble polymers. The polymethacrylic anhydride so prepared was hydrolyzed to the corresponding polymethacrylic acid and this poly(acid) esterified by reaction with diazomethane to yield polymethyl methacrylate. The result is given of an x-ray diffraction study of an unstretched film of polymethyl methacrylate prepared in a similar manner. The determination of the fraction of the polymer present in each of the three possible stereoconfigurations, isotactic, syndiotactic, and heterotactic, was made from a nuclear magnetic resonance investigation of the derived polymethyl methacrylate. The results indicate that the stereoconfiguration is influenced by the cyclic polymerization mechanism. The results also indicate that there is a bias toward increasing isotactic character in the polymers with an increase in polymerization temperature. Two possible explanations are offered: one in terms of a kinetic control of the steric placements and the other in terms of a balance between equilibrium and kinetic considerations.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1961.1205416006
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    Paper (German National Licenses)
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  • 3
    Electronic Resource
    Electronic Resource
    ω-Cyanothiaalkyl polyacrylates: A new class of synthetic rubbers (1964)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A: General Papers 2 (1964), S. 1941-1953 
    Details
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The synthesis and polymerization of a series of ω-cyanothiaalkyl acrylates, CH2=CHCO2(CH2)mS(CH2)nCN, are described. The length of the side chain and the position of the sulfur atom are varied. Microgelation is found to occur during polymerization, as indicated by viscosity and molecular weight measurements (for 5-cyano-3-thiapentyl polyacrylate at 90% conversion: [η], 0.37 in acetone; M̄w, 600 million). Possible mechanisms of gelation are considered. Glass transition temperatures and solvent swellings are reported as follows: 4-cyano-3-thiabutyl polyacrylate, Tg -24°C., 14% volume swell in benzene; 5-cyano-3-thiapentyl polyacrylate, -50°C., 20% 6-cyano-3-thiahexyl polyacrylate, -58°C., 38% 6-cyano-4-thiahexyl polyacrylate, -58°C., 42% 8-cyano-7-thiaoctyl polyacrylate, -59°C., 120%. The relation between these properties and the structure of the polymers is discussed. The swelling of 5-cyano-3-thiapentyl polyacrylate in eighteen other fluids is given; an estimate (between 10 and 12.5) is made of the solubility parameter of this polymer. Bulk properties are reported for the vulcanizate of 5-cyano-3-thiapentyl polyacrylate.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1964.100020434
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    Paper (German National Licenses)
    Fulltext
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