Tantalum- and titanium-based catalytic systems for the synthesis of hyperbranched polyethene

Shahid Murtuza, Seth B. Harkins, Gregory S. Long, Ayusman Sen

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

Hyperbranched polyethene was synthesized using a novel TaCl5/alkylaluminum halide catalyst system. The polymers were viscous oils with a ratio of methyl hydrogens/total alkyl hydrogens of 0.25-0.40 and weight-average molecular weights of 600-4000 daltons. Both branching and molecular weight can be varied by changing reaction conditions and catalyst composition. The system can also be modified to synthesize 1-alkenes (principally, 1-hexene). A second system, involving TiCl4/alkylaluminum halide, also gave hyperbranched polyethene, with a ratio of methyl hydrogens/total alkyl hydrogens of 0.10-0.25. Weight-average molecular weights varied from 900 to 1800 daltons. Higher selectivity to liquid product was achieved through the addition of dihydrogen. The mechanism of the formation of branched polyethene appears to involve, for the most part, oligomerization of ethene to 1-alkenes (principally 1-hexene) by a transition metal alkyl species followed by cationic oligomerization of the 1-alkenes by Lewis acidic species. The addition of tetraalkylammonium chloride to the TaCl5/Et3Al system resulted in a change in product selectivity from all polyethene to > 65% 1-hexene. The highly selective trimerization of ethene by the tantalum system is unusual.

Original languageEnglish (US)
Pages (from-to)1867-1872
Number of pages6
JournalJournal of the American Chemical Society
Volume122
Issue number9
DOIs
StatePublished - Mar 8 2000

Fingerprint

Tantalum
Titanium
Hydrogen
Alkenes
Olefins
Oligomerization
Molecular Weight
Molecular weight
Weights and Measures
Catalysts
Transition metals
Chlorides
Polymers
Oils
Metals
Liquids
Chemical analysis
1-hexene
ethylene

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Murtuza, Shahid ; Harkins, Seth B. ; Long, Gregory S. ; Sen, Ayusman. / Tantalum- and titanium-based catalytic systems for the synthesis of hyperbranched polyethene. In: Journal of the American Chemical Society. 2000 ; Vol. 122, No. 9. pp. 1867-1872.
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abstract = "Hyperbranched polyethene was synthesized using a novel TaCl5/alkylaluminum halide catalyst system. The polymers were viscous oils with a ratio of methyl hydrogens/total alkyl hydrogens of 0.25-0.40 and weight-average molecular weights of 600-4000 daltons. Both branching and molecular weight can be varied by changing reaction conditions and catalyst composition. The system can also be modified to synthesize 1-alkenes (principally, 1-hexene). A second system, involving TiCl4/alkylaluminum halide, also gave hyperbranched polyethene, with a ratio of methyl hydrogens/total alkyl hydrogens of 0.10-0.25. Weight-average molecular weights varied from 900 to 1800 daltons. Higher selectivity to liquid product was achieved through the addition of dihydrogen. The mechanism of the formation of branched polyethene appears to involve, for the most part, oligomerization of ethene to 1-alkenes (principally 1-hexene) by a transition metal alkyl species followed by cationic oligomerization of the 1-alkenes by Lewis acidic species. The addition of tetraalkylammonium chloride to the TaCl5/Et3Al system resulted in a change in product selectivity from all polyethene to > 65{\%} 1-hexene. The highly selective trimerization of ethene by the tantalum system is unusual.",
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Tantalum- and titanium-based catalytic systems for the synthesis of hyperbranched polyethene. / Murtuza, Shahid; Harkins, Seth B.; Long, Gregory S.; Sen, Ayusman.

In: Journal of the American Chemical Society, Vol. 122, No. 9, 08.03.2000, p. 1867-1872.

Research output: Contribution to journalArticle

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