Living carbocationic polymerization - XXIX. The synthesis of telechelic polyisobutylenes by the trans-2,5-diacetoxy-2,5-dimethyl-3-hexene/BCl3 initiating system in 1,2-dichloroethane in the -30 to 21°C range

M. Zsuga, R. Faust, J. P. Kennedy

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11 Citations (Scopus)

Abstract

The living polymerization of isobutylene (IB) by the trans-2,5-diacetoxy-2,5-dimethyl-3-hexene (DiOAcDMH6=)/BCl3 initiating system in 1,2-dichloroethane (DCE) in the -30 to +21°C range has been investigated. Well-defined tert-chlorine terminated polyisobutylenes ( {Mathematical expression}) have been obtained at suitably low IB and DiOAcDMH6= concentrations in the -30° to 0°C range. Theoretical {Mathematical expression} end functionality -Fn ∼2.0 ±0.1 was demonstrated by dechlorination with sodium biphenyl coupled with titration using a chloride ion selective electrode, and by1H NMR spectroscopy. The {Mathematical expression} was quantitatively dehydrochlorinated to ∼CH2C(CH3) =CH2 capped PIBs which in turn were quantitatively converted by hydroboration/peroxidation to ∼CH2CH(CH3)CH2OH ended PIBs. The internal ∼C(CH3)2CH=CHC(CH3)2∼ initiator fragment in the polymer remains unchanged during end group functionalizations due to steric protection by the gem-dimethyl groups and the polymer chain.

Original languageEnglish
Pages (from-to)273-280
Number of pages8
JournalPolymer Bulletin
Volume21
Issue number3
DOIs
Publication statusPublished - Mar 1989

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hexenes
Living polymerization
Polymers
polymerization
butenes
Gems
Ion selective electrodes
Dechlorination
Chlorine
synthesis
Titration
hydroboration
Nuclear magnetic resonance spectroscopy
ion selective electrodes
Chlorides
Sodium
polymers
initiators
titration
chlorine

ASJC Scopus subject areas

  • Polymers and Plastics
  • Materials Chemistry

Cite this

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title = "Living carbocationic polymerization - XXIX. The synthesis of telechelic polyisobutylenes by the trans-2,5-diacetoxy-2,5-dimethyl-3-hexene/BCl3 initiating system in 1,2-dichloroethane in the -30 to 21°C range",
abstract = "The living polymerization of isobutylene (IB) by the trans-2,5-diacetoxy-2,5-dimethyl-3-hexene (DiOAcDMH6=)/BCl3 initiating system in 1,2-dichloroethane (DCE) in the -30 to +21°C range has been investigated. Well-defined tert-chlorine terminated polyisobutylenes ( {Mathematical expression}) have been obtained at suitably low IB and DiOAcDMH6= concentrations in the -30° to 0°C range. Theoretical {Mathematical expression} end functionality -Fn ∼2.0 ±0.1 was demonstrated by dechlorination with sodium biphenyl coupled with titration using a chloride ion selective electrode, and by1H NMR spectroscopy. The {Mathematical expression} was quantitatively dehydrochlorinated to ∼CH2C(CH3) =CH2 capped PIBs which in turn were quantitatively converted by hydroboration/peroxidation to ∼CH2CH(CH3)CH2OH ended PIBs. The internal ∼C(CH3)2CH=CHC(CH3)2∼ initiator fragment in the polymer remains unchanged during end group functionalizations due to steric protection by the gem-dimethyl groups and the polymer chain.",
author = "M. Zsuga and R. Faust and Kennedy, {J. P.}",
year = "1989",
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AU - Zsuga, M.

AU - Faust, R.

AU - Kennedy, J. P.

PY - 1989/3

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N2 - The living polymerization of isobutylene (IB) by the trans-2,5-diacetoxy-2,5-dimethyl-3-hexene (DiOAcDMH6=)/BCl3 initiating system in 1,2-dichloroethane (DCE) in the -30 to +21°C range has been investigated. Well-defined tert-chlorine terminated polyisobutylenes ( {Mathematical expression}) have been obtained at suitably low IB and DiOAcDMH6= concentrations in the -30° to 0°C range. Theoretical {Mathematical expression} end functionality -Fn ∼2.0 ±0.1 was demonstrated by dechlorination with sodium biphenyl coupled with titration using a chloride ion selective electrode, and by1H NMR spectroscopy. The {Mathematical expression} was quantitatively dehydrochlorinated to ∼CH2C(CH3) =CH2 capped PIBs which in turn were quantitatively converted by hydroboration/peroxidation to ∼CH2CH(CH3)CH2OH ended PIBs. The internal ∼C(CH3)2CH=CHC(CH3)2∼ initiator fragment in the polymer remains unchanged during end group functionalizations due to steric protection by the gem-dimethyl groups and the polymer chain.

AB - The living polymerization of isobutylene (IB) by the trans-2,5-diacetoxy-2,5-dimethyl-3-hexene (DiOAcDMH6=)/BCl3 initiating system in 1,2-dichloroethane (DCE) in the -30 to +21°C range has been investigated. Well-defined tert-chlorine terminated polyisobutylenes ( {Mathematical expression}) have been obtained at suitably low IB and DiOAcDMH6= concentrations in the -30° to 0°C range. Theoretical {Mathematical expression} end functionality -Fn ∼2.0 ±0.1 was demonstrated by dechlorination with sodium biphenyl coupled with titration using a chloride ion selective electrode, and by1H NMR spectroscopy. The {Mathematical expression} was quantitatively dehydrochlorinated to ∼CH2C(CH3) =CH2 capped PIBs which in turn were quantitatively converted by hydroboration/peroxidation to ∼CH2CH(CH3)CH2OH ended PIBs. The internal ∼C(CH3)2CH=CHC(CH3)2∼ initiator fragment in the polymer remains unchanged during end group functionalizations due to steric protection by the gem-dimethyl groups and the polymer chain.

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