Electron donors in carbocationic polymerization - IV. Preparation of narrow-dispersity tert.-chlorine-capped polyisobutylene by the trans-2,5-diacetoxy-2,5-dimethyl-3-hexene/BCl3/dimethyl sulfoxide system

M. Zsuga, J. P. Kennedy

Research output: Article

32 Citations (Scopus)

Abstract

Low molecular weight (-Mn ∼900-5000) narrow molecular weight distribution (MWD; -Mw/Mn = 1.1-1.2)tert.-chlorine telechelic polyisobutylenes (PIBs) have been synthesized by the use of the trans-2,5-dimethyl-2,5-diacetoxy-3-hexene (DiOAcDMeH6)/BCl3 initiating system in the presence of the electron donor (ED) dimethyl sulfoxide (DMSO) in methyl chloride diluent at -30°C. The living character of the polymerization was demonstrated by linear Mn versus Wp (weight of polymer) plots starting at the origin with the slope of 1/[Io] (where [Io] = initiator concentration). DMSO reduces the overall rate of polymerization, however, it increases the initiator efficiency (Ieff) to ∼100%. The number average tert.-chlorine end functionality is -Fn=1.97±0.04, by1H NMR spectroscopy. Polymerization mechanistic details are discussed. This is the first time narrow MWD tert.-chlorine telechelic PIB has been prepared close to the reflux temperature of methyl chloride.

Original languageEnglish
Pages (from-to)5-12
Number of pages8
JournalPolymer Bulletin
Volume21
Issue number1
DOIs
Publication statusPublished - jan. 1989

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polyisobutylene
hexenes
Dimethyl sulfoxide
Chlorine
Dimethyl Sulfoxide
Methyl Chloride
chlorine
methyl chloride
Io
polymerization
Polymerization
initiators
preparation
Electrons
electrons
diluents
low molecular weights
Molecular weight distribution
Nuclear magnetic resonance spectroscopy
molecular weight

ASJC Scopus subject areas

  • Polymers and Plastics
  • Materials Chemistry

Cite this

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title = "Electron donors in carbocationic polymerization - IV. Preparation of narrow-dispersity tert.-chlorine-capped polyisobutylene by the trans-2,5-diacetoxy-2,5-dimethyl-3-hexene/BCl3/dimethyl sulfoxide system",
abstract = "Low molecular weight (-Mn ∼900-5000) narrow molecular weight distribution (MWD; -Mw/Mn = 1.1-1.2)tert.-chlorine telechelic polyisobutylenes (PIBs) have been synthesized by the use of the trans-2,5-dimethyl-2,5-diacetoxy-3-hexene (DiOAcDMeH6)/BCl3 initiating system in the presence of the electron donor (ED) dimethyl sulfoxide (DMSO) in methyl chloride diluent at -30°C. The living character of the polymerization was demonstrated by linear Mn versus Wp (weight of polymer) plots starting at the origin with the slope of 1/[Io] (where [Io] = initiator concentration). DMSO reduces the overall rate of polymerization, however, it increases the initiator efficiency (Ieff) to ∼100{\%}. The number average tert.-chlorine end functionality is -Fn=1.97±0.04, by1H NMR spectroscopy. Polymerization mechanistic details are discussed. This is the first time narrow MWD tert.-chlorine telechelic PIB has been prepared close to the reflux temperature of methyl chloride.",
author = "M. Zsuga and Kennedy, {J. P.}",
year = "1989",
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T1 - Electron donors in carbocationic polymerization - IV. Preparation of narrow-dispersity tert.-chlorine-capped polyisobutylene by the trans-2,5-diacetoxy-2,5-dimethyl-3-hexene/BCl3/dimethyl sulfoxide system

AU - Zsuga, M.

AU - Kennedy, J. P.

PY - 1989/1

Y1 - 1989/1

N2 - Low molecular weight (-Mn ∼900-5000) narrow molecular weight distribution (MWD; -Mw/Mn = 1.1-1.2)tert.-chlorine telechelic polyisobutylenes (PIBs) have been synthesized by the use of the trans-2,5-dimethyl-2,5-diacetoxy-3-hexene (DiOAcDMeH6)/BCl3 initiating system in the presence of the electron donor (ED) dimethyl sulfoxide (DMSO) in methyl chloride diluent at -30°C. The living character of the polymerization was demonstrated by linear Mn versus Wp (weight of polymer) plots starting at the origin with the slope of 1/[Io] (where [Io] = initiator concentration). DMSO reduces the overall rate of polymerization, however, it increases the initiator efficiency (Ieff) to ∼100%. The number average tert.-chlorine end functionality is -Fn=1.97±0.04, by1H NMR spectroscopy. Polymerization mechanistic details are discussed. This is the first time narrow MWD tert.-chlorine telechelic PIB has been prepared close to the reflux temperature of methyl chloride.

AB - Low molecular weight (-Mn ∼900-5000) narrow molecular weight distribution (MWD; -Mw/Mn = 1.1-1.2)tert.-chlorine telechelic polyisobutylenes (PIBs) have been synthesized by the use of the trans-2,5-dimethyl-2,5-diacetoxy-3-hexene (DiOAcDMeH6)/BCl3 initiating system in the presence of the electron donor (ED) dimethyl sulfoxide (DMSO) in methyl chloride diluent at -30°C. The living character of the polymerization was demonstrated by linear Mn versus Wp (weight of polymer) plots starting at the origin with the slope of 1/[Io] (where [Io] = initiator concentration). DMSO reduces the overall rate of polymerization, however, it increases the initiator efficiency (Ieff) to ∼100%. The number average tert.-chlorine end functionality is -Fn=1.97±0.04, by1H NMR spectroscopy. Polymerization mechanistic details are discussed. This is the first time narrow MWD tert.-chlorine telechelic PIB has been prepared close to the reflux temperature of methyl chloride.

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