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  • 1
    ISSN: 0025-116X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The polymerization mechanism of 1,6-anhydro-2,3,4-tri-O-benzyl-β-D-glucopyranose (1) was investigated in order to synthesize 2,3,4-tri-O-benzyl-[1→6]-α-D-glucopyranan (2a) and [1→6]-α-D-glucopyranan (2b) (dextran) with high molecular weight. It was found that the optimum polymerization time to obtain high molecular weights was 40min when the monomer was polymerized in methylene chloride at -60°C. Stereoregular 2a with a \documentclass{article}\pagestyle{empty}\begin{document}$ \overline {DP} _{\rm n} $ of 1800 (M̄n = 777000), which was about twice as high as the highest \documentclass{article}\pagestyle{empty}\begin{document}$ \overline {DP} _{\rm n} $ previously reported, was obtained in 77% yield by polymerizing the monomer with 0.8 mole-% PF5 as catalyst applying a monomer-to-solvent weight/volume ratio of 50%. 2a with a high molecular weight was debenzylated to give 2b with a \documentclass{article}\pagestyle{empty}\begin{document}$ \overline {DP} _{\rm n} $ of 446 (M̄n = 72300). The α-stereospecificity and the solid state of the synthetic dextran were investigated by means of optical rotation, NMR spectroscopy, and X-ray diffraction pattern.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2313-2329 
    ISSN: 0360-6376
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Cationic graft copolymerizations of bicyclic acetals, 1,6-anhydro-2,3,4-tri-O-benzyl-β-D-glucopyranose (LGTBE) and 1,6-anhydro-2,3,4-tri-O-methyl-β-D-glucopyranose (LGTME), were investigated with macromolecular carbenium ions formed from polymers that contain reactive halogens. Macromolecular complex catalysts formed from chlorosulfonated polyethylene or poly(isoprene-co-chloromethylstyrene) by the action of phosphorus pentafluoride yielded graft copolymers with low proportions (0.6-16%) of poly(LGTBE) or poly(LGTBE-co-epichlorohydrin) branchings. It was found that macromolecular complex catalysts formed from poly(styrene-co-fluoromethylstyrene) or poly(methyl methacrylate-co-fluoromethylstyrene) by the action of boron trifluoride etherate give graft copolymers with high proportions (up to 80%) of poly(LGTBE) or poly(LGTME) branchings. In addition, the model reactions for the graft copolymerization of LGTBE were examined with organic halide-PF5, organic halide-AgPF6, and organic fluoride-BF3·OEt2 catalytic systems, of which the last two indicate that the polymerization is effected by a carbenium ion mechanism.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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