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  • Chemistry  (4)
  • Anaerobiosis
  • Nuclear Reactions
  • 1990-1994  (4)
  • 1
    Digitale Medien
    Digitale Medien
    Effects of procatalyst composition on the stereospecificity of a Ziegler-Natta catalyst systemRevised manuscript of December 20, 1991. (1992)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 193 (1992), S. 1463-1468 
    Details
    ISSN: 0025-116X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: In propylene polymerization with MgCl2/TiCl4/phthalate ester catalysts, using 2,2,6,6-tetramethylpiperidine as external donor, it has been found that the fraction of atactic polymer formed increased with decreasing ester content in the catalyst. At the same time, however, the stereoregularity of the isotactic polymer fraction, as measured by 13C NMR, increased. Polymerization in the absence of the external donor led to lower polymer yield and a lower stereoregularity of the isotactic fraction. The results indicate that the external donor is actively involved in the generation of isospecific sites, particularly in catalysts having relatively low ester contents.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/macp.1992.021930622
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    Hydrogen activation in propene polymerization with MgCl2-supported Ziegler-Natta catalysts: the effect of the external donor (1994)
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 195 (1994), S. 167-172 
    Details
    ISSN: 1022-1352
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: 13C NMR analysis of relatively low-molecular-weight polypropylenes prepared using the catalyst system MgCl2/TiCl4/phthalate ester-AlEt3-external Lewis base has revealed the presence of up to around 20% butyl (n-Bu) chain ends, indicative of regioirregular (2,1-) monomer insertion followed by chain transfer with hydrogen. The effect of hydrogen on catalyst activity depends on the nature of the external donor, and the results indicate that at least part of the observed increase in catalyst activity in the presence of hydrogen can be ascribed to the regeneration of active species via chain transfer at dormant (2,1-inserted) sites.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/macp.1994.021950114
    Standort Signatur Erwartet Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    Application of conservation law to NMR measurements of poly(propylene) stereoregularity (1993)
    Basel : Wiley-Blackwell
    Die Makromolekulare Chemie, Theory and Simulations 2 (1993), S. 385-398 
    Details
    ISSN: 1018-5054
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A new method is presented for data reconciliation in the 13C NMR determination of the pentad distribution in regioregular poly(propylene). Deviations of experimentally measured data from mathematically derived conservation laws are corrected by a maximum-likelihood method. In this method some assumptions are made about the structure of the erros to obtain better estimates of the correct data. The validity of this procedure was demonstrated with Monte Carlo simulation, after which the method has been applied to real 13C NMR data to show what corrections may be obtained. Conservation laws for hexads and heptads are derived as well, for possible future use.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/mats.1993.040020309
    Standort Signatur Erwartet Verfügbarkeit
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  • 4
    Digitale Medien
    Digitale Medien
    Probabilistic multi-site modelling of propene polymerization using markov models (1993)
    Basel : Wiley-Blackwell
    Die Makromolekulare Chemie, Theory and Simulations 2 (1993), S. 399-420 
    Details
    ISSN: 1018-5054
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Possible propagation mechanisms in propene polymerization using heterogeneous catalysts are described by combinations of Bernoulli and first- or even second-order Markov models. Both NMR-measured pentad fractions and GPC Gel permeation chromatography.-measured molecular weight distributions are directly taken into account to fit an appropriate propagation model for a specific catalyst. The analytical data so obtained have been used for an examination of the applicability of multi-site propagation models and for estimation of the main parameters in each model. The propagation and termination probabilities are estimated, as are “mix” parameters giving the fraction of the polymer population stemming from each kind of propagation mechanism. In this way the subpopulation produced by each site is characterized in terms of tacticity and molecular weight distribution. A three-site model is required to explain the measured data properly.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/mats.1993.040020310
    Standort Signatur Erwartet Verfügbarkeit
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