Living carbocationic polymerization - XXVIII. Telechelic polyisobutylenes by bifunctional tert-dichloroacetate initiator

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

Research output: Article

9 Citations (Scopus)

Abstract

The synthesis of α,ω-di-tert-chloropolyisobutylenes {Mathematical expression}with up to Mn ∼25,000 has been accomplished by the living polymerization of isobutylene (IB) using aliphatic di-tert-dichloroacetate initiators in conjunction with BCl3 coinitiator in CH3Cl and C2H5Cl solvents at -30°C. In comparison with the corresponding di-tert-diacetates, both rates and initiator efficiencies (Ieff) are greatly increased. Thus polymerizations are rapid and give 50-75 and 100% Ieffs with 2,5-dichloroacetoxy-2,5-dimethylhexane (D(Cl2AcO)DMeH6) and trans-2,5-dichloroacetoxy-2,5-dimethyl-3-hexene (D(Cl2AcO)DMeH6=), respectively. With 2,5-dichloroacetoxy-2,5-dimethyl-3-hexyne (D(Cl2AcO)DMeH6) the rates are relatively slower but the Ieffs are ∼100%. The number average end functionalities -Fn were found to be 2.0 ± 0.1 by 1H NMR spectroscopy.

Original languageEnglish
Pages (from-to)125-131
Number of pages7
JournalPolymer Bulletin
Volume21
Issue number2
DOIs
Publication statusPublished - febr. 1989

Fingerprint

Living polymerization
initiators
Nuclear magnetic resonance spectroscopy
polymerization
Polymerization
hexenes
butenes
nuclear magnetic resonance
synthesis
spectroscopy
isobutylene
1-hexene
2,5-dimethylhexane

ASJC Scopus subject areas

  • Polymers and Plastics
  • Materials Chemistry

Cite this

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title = "Living carbocationic polymerization - XXVIII. Telechelic polyisobutylenes by bifunctional tert-dichloroacetate initiator",
abstract = "The synthesis of α,ω-di-tert-chloropolyisobutylenes {Mathematical expression}with up to Mn ∼25,000 has been accomplished by the living polymerization of isobutylene (IB) using aliphatic di-tert-dichloroacetate initiators in conjunction with BCl3 coinitiator in CH3Cl and C2H5Cl solvents at -30°C. In comparison with the corresponding di-tert-diacetates, both rates and initiator efficiencies (Ieff) are greatly increased. Thus polymerizations are rapid and give 50-75 and 100{\%} Ieffs with 2,5-dichloroacetoxy-2,5-dimethylhexane (D(Cl2AcO)DMeH6) and trans-2,5-dichloroacetoxy-2,5-dimethyl-3-hexene (D(Cl2AcO)DMeH6=), respectively. With 2,5-dichloroacetoxy-2,5-dimethyl-3-hexyne (D(Cl2AcO)DMeH6≡) the rates are relatively slower but the Ieffs are ∼100{\%}. The number average end functionalities -Fn were found to be 2.0 ± 0.1 by 1H NMR spectroscopy.",
author = "R. Faust and M. Zsuga and Kennedy, {J. P.}",
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AU - Zsuga, M.

AU - Kennedy, J. P.

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N2 - The synthesis of α,ω-di-tert-chloropolyisobutylenes {Mathematical expression}with up to Mn ∼25,000 has been accomplished by the living polymerization of isobutylene (IB) using aliphatic di-tert-dichloroacetate initiators in conjunction with BCl3 coinitiator in CH3Cl and C2H5Cl solvents at -30°C. In comparison with the corresponding di-tert-diacetates, both rates and initiator efficiencies (Ieff) are greatly increased. Thus polymerizations are rapid and give 50-75 and 100% Ieffs with 2,5-dichloroacetoxy-2,5-dimethylhexane (D(Cl2AcO)DMeH6) and trans-2,5-dichloroacetoxy-2,5-dimethyl-3-hexene (D(Cl2AcO)DMeH6=), respectively. With 2,5-dichloroacetoxy-2,5-dimethyl-3-hexyne (D(Cl2AcO)DMeH6≡) the rates are relatively slower but the Ieffs are ∼100%. The number average end functionalities -Fn were found to be 2.0 ± 0.1 by 1H NMR spectroscopy.

AB - The synthesis of α,ω-di-tert-chloropolyisobutylenes {Mathematical expression}with up to Mn ∼25,000 has been accomplished by the living polymerization of isobutylene (IB) using aliphatic di-tert-dichloroacetate initiators in conjunction with BCl3 coinitiator in CH3Cl and C2H5Cl solvents at -30°C. In comparison with the corresponding di-tert-diacetates, both rates and initiator efficiencies (Ieff) are greatly increased. Thus polymerizations are rapid and give 50-75 and 100% Ieffs with 2,5-dichloroacetoxy-2,5-dimethylhexane (D(Cl2AcO)DMeH6) and trans-2,5-dichloroacetoxy-2,5-dimethyl-3-hexene (D(Cl2AcO)DMeH6=), respectively. With 2,5-dichloroacetoxy-2,5-dimethyl-3-hexyne (D(Cl2AcO)DMeH6≡) the rates are relatively slower but the Ieffs are ∼100%. The number average end functionalities -Fn were found to be 2.0 ± 0.1 by 1H NMR spectroscopy.

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