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  • 1
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 217-223 
    ISSN: 0887-624X
    Schlagwort(e): aromatic polyacetylene ; Rh complex catalyst ; cis-transoid ; pressure ; isomerization ; solitons ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: This study reports that stereospecific polymerization of aromatic acetylenes, e.g., p-methoxyphenylacetylene (pMOPA) and p-ethoxyphenylacetylene (pEOPA)was successfully performed to give polyacetylene selectively bearing cis-transoid forms in high yield when a Rh complex catalyst, [Rh(norbornadiene)Cl]2 was used in the presence of triethylamine as the polymerization solvent together with a detailed characterization of the resulting polymers, before and after compression. Compression of these polymers induced a cis-trans isomerization at room temperature under vacuum even in the solid state. Based on data collected before and after compression it is estimated that the trans conjugated length, (C=C)n, produced as a result of the compression is n = 26 for PpMOPA and n = 40 for PpEOPA polymers, respectively. We further found that g values in the ESR spectra of the pristine polymer were shifted to higher magnetic field by compression, indicating that unpaired electrons called solitons are stabilized in the trans conjugation length as mobile electrons, although in the pristine polymers the unpaired electrons are stabilized in the less conjugated chain, showing large g value, suggesting a magnetic interaction between oxygen in the alkoxy group of phenyl moiety and unpaired electrons in the cis form. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 217-223, 1998
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2457-2461 
    ISSN: 0887-624X
    Schlagwort(e): polyalkylpropiolate ; Rh complex catalyst ; isomerization ; ESR ; soliton ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Alkylpropiolate having n-hexadecyl moiety in the ester group was stereospecifically polymerized with a [Rh(norbornadiene)Cl]2 complex catalyst in alcohol to give rise to cis-transoid polyacetylenes in high yields. The unusually facile cis to trans isomerization for the polymer was found to be induced when the polymer was warmed to even less than ca. 57°C. Under these conditions ESR spectra bearing hyperfine structures due to the radicals generated by the rotational scission in the cis-π bond were observed. This isomerization induced a large g value shift in the ESR spectra together with an increase of the radical concentration during the isomerization, indicating formation of planar conjugated trans sequences that stabilize mobile unpaired electrons as solitons. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2457-2461, 1998
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 3
    ISSN: 1022-1352
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The stereospecific polymerization of o- and p-methoxyphenylacetylenes (MOPAs) with [Rh(norbornadiene)Cl]2 as a catalyst in the presence of an organic base (triethylamine) at 30°C is reported, together with the detailed characterization using resonance Raman, diffuse reflection UV, and ESR spectroscopic methods. The resulting polymers were shown to selectively have a cis-transoid form. It was found, interestingly, that the resultant aromatic polyacetylenes in the cis form are easily isomerized to those in the trans form when a pressure of ca. 100∼200 kg/cm2 was exerted on the solid polymers at room temperature.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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