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  • Polymer and Materials Science  (7)
  • Anaerobiosis
  • Nuclear Reactions
  • 1995-1999  (7)
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  • 1
    Digitale Medien
    Digitale Medien
    Propylene polymerization with catalysts containing divalent titanium (1997)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2645-2652 
    Details
    ISSN: 0887-624X
    Schlagwort(e): propylene polymerization ; titanium oxidation state ; hydrogen activation ; catalyst decay ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The behavior in propylene polymerization of divalent titanium compounds of type [η6-areneTiAl2Cl8], both as such and supported on activated MgCl2, has been studied and compared to that of the simple catalyst MgCl2/TiCl4. Triethylaluminium was used as cocatalyst. The Ti-arene complexes were active both in the presence and in the absence of hydrogen, in contrast to earlier reports that divalent titanium species are active for ethylene but not for propylene polymerization. 13C-NMR analysis of low molecular weight polymer fractions indicated that the hydrogen activation effect observed for the MgCl2-supported catalysts should be ascribed to reactivation of 2,1-inserted (“dormant”) sites via chain transfer, rather than to (re)generation of active trivalent Ti via oxidative addition of hydrogen to divalent species. Decay in activity during polymerization was observed with both catalysts, indicating that for MgCl2/TiCl4 catalysts decay is not necessarily due to overreduction of Ti to the divalent state during polymerization. In ethylene polymerization both catalysts exhibited an acceleration rather than a decay profile. It is suggested that the observed decay in activity during propylene polymerization may be due to the formation of clustered species that are too hindered for propylene but that allow ethylene polymerization. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2645-2652, 1997
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    Regio- and stereospecificity in propene polymerization with MgCl2-supported Ziegler-Natta catalysts: effects of hydrogen and the external donor (1995)
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 196 (1995), S. 1431-1437 
    Details
    ISSN: 1022-1352
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Investigation of the effects of hydrogen and different external donors on the stereoregularity and chain-end distribution of polypropylene prepared using MgCl2/TiCl4/phthalate ester-AlEt3-alkoxysilane catalyst systems has not only confirmed the importance of regiospecificity in relation to hydrogen activation but has also indicated a significant effect of stereospecificity. Alkoxysilanes giving high isospecificity also give high molecular weight polypropylene. Polymer stereoregularity also increases with increasing hydrogen concentration in polymerization. These effects indicate that not only regioirregular but also stereoiregular insertion slows down chain propagation. In each case the probability of chain transfer with hydrogen is higher than that following a stereoregular insertion, and in each case chain transfer with hydrogen leads to the regeneration of isospecific propagation.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/macp.1995.021960506
    Standort Signatur Erwartet Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    Isotactic 1-butene polymerization promoted by C2-symmetric metallocene catalysts (1997)
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 198 (1997), S. 1257-1270 
    Details
    ISSN: 1022-1352
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: 1-Butene polyinsertion promoted by two typical C2-symmetric zirconocene catalysts (i.e. rac-ethylenebis(1-indenyl)ZrCl2 (1) and rac-dimethylsilylbis(1-indenyl)ZrCl2) (2) was investigated under both hydrooligomerization and polymerization conditions and compared with that of propene. It was found that, in spite of a similar regiospecificity for the two monomers, the fraction of “dormant” sites is higher in 1-butene polymerization, as a result of a (much) lower reactivity of a 2,1 last-inserted unit. Accordingly, in the investigated cases, 2,1 units of 1-butene were not incorporated in the growing chains but either isomerized to 4,1 units or remained at the chain end until they underwent chain transfer via β-hydrogen elimination. Experimental evidence is also presented of an epimerization reaction of the growing poly(1-butene) chain with a 1,2 last-inserted unit, leading to a decrease of polymer stereoregularity with decreasing monomer concentration.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/macp.1997.021980427
    Standort Signatur Erwartet Verfügbarkeit
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  • 4
    Digitale Medien
    Digitale Medien
    Polymerization of 3-methyl-1-butene promoted by metallocene catalysts (1996)
    Weinheim : Wiley-Blackwell
    Macromolecular Rapid Communications 17 (1996), S. 589-597 
    Details
    ISSN: 1022-1336
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: 3-Methyl-1-butene was polymerized in the presence of a number of homogeneous metallocene catalysts (co-catalyst methylalumoxane). Contrary to literature reports, it was found that even the simplest C2-symmetric metallocenes promote the isotactic polymerization of this monomer with reasonable productivities. Quite surprisingly, a prevailingly isotactic polymer was also obtained in the presence of Cs-symmetric metallocenes, which are instead syndiotactic-specific in propene polymerization.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/marc.1996.030170813
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  • 5
    Digitale Medien
    Digitale Medien
    Aspects of hydrogen activation in propene polymerization using MgCl2/TiCl4/diether catalysts (1996)
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 197 (1996), S. 2501-2510 
    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 the chain-end distribution of poly(propylenes) prepared using the highly active catalyst system MgCl2/TiCl4/diether - AlEt3 has revealed particularly high proportions of butyl chain-ends in polymers prepared at relatively low hydrogen pressures. This indicates that the high sensitivity of this type of catalyst to hydrogen, both with respect to catalyst activity and polymer molecular weight, can largely be ascribed to chain transfer following regioirregular (2,1-) insertion, such an insertion leading to a species having low activity in chain propagation. Isotactic stereoregularity increases with increasing hydrogen pressure, indicating that a stereoirregular insertion may also slow down the chain propagation, again leading to chain transfer and resulting in the conversion of a potential chain defect into an isobutyl chain-end. Analysis of highly isotactic polymer fractions isolated via temperature rising elution fractionation revealed the presence of both butyl and isobutyl chain-ends, indicating that even the most highly stereo-specific sites in MgCl2-supported catalysts are not totally regiospecific.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/macp.1996.021970814
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  • 6
    Digitale Medien
    Digitale Medien
    Propene polymerization with MgCl2-supported catalysts: effects of using a diether as external donor (1997)
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 198 (1997), S. 1181-1188 
    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 poly(propylene) fractions of different tacticity, obtained using a catalyst system of type MgCl2/TiCl4/diisobutyl phthalate - AlEt3 - diether, has provided further evidence that the active species in this system are similar to those in which the ether is used as “internal” rather than “external” donor. Chain-end analysis of relatively low molecular weight polymer fractions indicated, for polymers of similar molecular weight, similar proportions of butyl-terminated chain-ends, indicative of chain transfer with hydrogen following regioirregular (2,1-) insertion. The relatively high hydrogen response of diether-containing catalyst systems can therefore be largely ascribed to this phenomenon, irrespective of whether the diether is used as internal or external donor. At relatively low hydrogen concentrations, chain transfer to hydrogen takes place predominantly after the occasional secondary insertion, while the additional presence of vinylidene chain-ends in certain xylene-soluble fractions indicates that chain transfer via β-H transfer takes place mainly after primary insertion.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/macp.1997.021980419
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  • 7
    Digitale Medien
    Digitale Medien
    Effect of polymerization temperature on the microtacticity of isotactic poly(propylene) prepared using heterogeneous (MgCl2-supported) Ziegler-Natta catalysts (1998)
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 199 (1998), S. 1873-1878 
    Details
    ISSN: 1022-1352
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A study of the effect of polymerization temperature on the microtacticity of poly(propylene) prepared using various MgCl2-supported catalysts has shown that, in almost all cases, an increase in temperature leads not only to higher proportions of isotactic polymer but also to increased stereoregularity of the isotactic fraction. The results indicate a greater relative increase in productivity, with increasing temperature, for highly isospecific as opposed to moderately isospecific centres. It is suggested that easier propagation after the occasional regioirregular (2,1-) insertion may contribute to this effect.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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