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  • Physics  (3)
  • 1970-1974  (3)
  • 1970  (3)
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  • 1970-1974  (3)
Year
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 8 (1970), S. 3155-3162 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: trans-Cinnamonitrile (M1) was copolymerized with several of its ring-substituted derivatives (M2) in toluene at 25°C, calcium zinc tetraethyl being used as catalyst. The ring substituents investigated include H, p-CH3O, m-CH3O, p-CH3, m-CH3, p-Cl, and m-Cl. It was found that the values of log (1/r1) are linearly correlated with Hammett's σ constants with the reaction constant σ ρ 0.7. The effects of coordination between monomer and catalyst sites upon the Hammett relation are discussed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 8 (1970), S. 1147-1163 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Butadiene-1,3 and acrylonitrile were copolymerized by alkylaluminum halides alone or, more effectively, by the alkylaluminum halide/vanadium compound systems, into an alternating copolymer in which the butadiene units are linked predominantly in the trans-1,4 configuration. The efficiency of the aluminum components in the latter catalyst systems appear to decrease in the following order: AlEtCl2 〉 Al2Et3Cl3 ≫ AlEt2Cl(≫AlCl3). The alkylaluminum halides could also be used effectually in the form of the complex with acrylonitrile. The catalytic activity was markedly affected by the order of mixing of the catalyst components and the monomers. Effective catalysts could be prepared only when the catalyst components were mixed in the presence of acrylonitrile. The catalyst activity was also found to depend upon the Al/V ratio, reaching its maximum when the ratio was about 20 in the AlEtCl2·AN/VO(Ot-Bu)3 system. Other combinations of conjugated diene with conjugated polar vinyl monomer were similarly copolymerized by these catalysts. It was found that different feed ratios between the diene and the vinyl monomer which were varied over a wide range always resulted in the formation of a 1:1 copolymer. The butadiene-acrylonitrile copolymer thus formed gave an NMR spectrum in which there was only one peak assignable to the methylene protons (7.72 τ) of the butadiene unit. On the basis of these findings, it may be suggested that alternating copolymerization prevails in the polymerization systems here investigated.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 8 (1970), S. 2979-2987 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: cis- and trans-cinnamonitriles were polymerized in the presence of various anionic catalysts such as Grignard reagent, alkali metal naphthalenes, and calcium zinc tetraethyl. It was found that both monomers undergo concurrent geometrical isomerization as well as polymerization. Investigation on the calcium zinc tetraethyl catalyst showed that the trans-nitrile had polymerizability noticeably greater than that of the cis isomer. Polymers resulting from these isomeric monomers had different microstructures. These results seem to be interpretable in terms of the four-centered coordination model of the transition state.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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