Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Journal of Polymer Science Part A: Polymer Chemistry

Special Issue: Dedicated to the Memory of Professor Michael Szwarc

1 July 2002

Volume 40, Issue 13

Pages 2099–2214

  1. Miscellaneous

    1. Top of page
    2. Miscellaneous
    3. Articles
    4. Article
    5. Articles
    1. You have free access to this content
      Michael Szwarc, 1909–2000 (pages 2099–2100)

      Joseph Jagur-Grodzinski and Johannes Smid

      Version of Record online: 29 MAY 2002 | DOI: 10.1002/pola.10292

  2. Articles

    1. Top of page
    2. Miscellaneous
    3. Articles
    4. Article
    5. Articles
    1. New bifunctional initiator for use in anionic polymerizations (pages 2108–2115)

      Kurt A. Alberty, Rong Chen and Thieo E. Hogen-Esch

      Version of Record online: 29 MAY 2002 | DOI: 10.1002/pola.10290

      Thumbnail image of graphical abstract

      The synthesis is described of 2,7-dimethyl-3,6-diphenyl-octane dianion (DDO2−) by electron transfer from lithium or potassium metal to 3-methyl-2-phenyl-1-butene in tetrahydrofuran (THF) at temperatures between −78 and −100 °C. The 2,7-dimethyl-3,6-diphenyl-octane structure was demonstrated by 1H and 13C NMR as well as gas chromatography/mass spectrometry. The initiation of styrene by DDO2− led to narrow molecular weight polymers.

  3. Article

    1. Top of page
    2. Miscellaneous
    3. Articles
    4. Article
    5. Articles
    1. Functional polymers by living anionic polymerization (pages 2116–2133)

      Joseph Jagur-Grodzinski

      Version of Record online: 29 MAY 2002 | DOI: 10.1002/pola.10291

      Thumbnail image of graphical abstract

      The application of living anionic polymerization for the functionalization of polymers and block copolymers is reviewed. The attachment of functional groups to polymeric chains of predetermined lengths and narrow molecular weight distributions is described. General methods based on the use of substituted haloalkanes or diphenylethylenes substituted with functional groups are discussed. The living anionic polymerization of monomers with protected functional groups is discussed. The combination of living anionic polymerization and controlled radical and living cationic polymerizations is described.

  4. Articles

    1. Top of page
    2. Miscellaneous
    3. Articles
    4. Article
    5. Articles
    1. Relation between the reactivities of vinyl monomers in ionic polymerizations and their 1H NMR spectra (pages 2134–2147)

      Koichi Hatada, Tatsuki Kitayama, Takafumi Nishiura and Wataru Shibuya

      Version of Record online: 29 MAY 2002 | DOI: 10.1002/pola.10296

      Thumbnail image of graphical abstract

      The 1H NMR chemical shifts of the protons in the vinyl groups of monomers are a practical measure of the reactivity of monomers in ionic polymerizations and also a tool for understanding the mechanism of polymerization. Plots of the relative reactivity [log (1/r1)] in the copolymerization of styrene with substituted styrenes at 40 °C with TiCl3–Al(C2H5)3 against the chemical shift of H1H1) give linear relations with negative slopes; the reactivity increases with increasing π-electron density on the β-carbon. This indicates that the coordination of monomers to Ti or Al in the catalyst is the rate-determining step and also is a clear indication that the vinyl groups of monomers are bound to the catalyst complex at its β-position in the coordination step.

    2. Dual influence of lithium chloride on the anionic propagation of polystyryllithium in ethereal solvents (pages 2148–2157)

      Hilde Verheyden, Paul Van Lierde, Michael Szwarc, Galina Litvinenko and Marcel Van Beylen

      Version of Record online: 29 MAY 2002 | DOI: 10.1002/pola.10287

      Thumbnail image of graphical abstract

      The addition of lithium chloride (LiCl) to a solution of polystyryllithium (PStLi) in tetrahydropyran (THP) reduces the rate of propagation of PStLi at a low concentration of the latter but accelerates it at higher concentrations of PStLi. Moreover, the addition of LiCl, which is dimeric in ethereal solutions, increases the conductance of PStLi solutions in tetrahydrofuran and THP to a much greater extent than expected from the separate conductances of PStLi and LiCl. These phenomena are attributed to the ionic dissociation of (LiCl)2 into Li+ and LiClLi ions on the one hand and to its Li+-ion scavenging properties on the other hand.

    3. Single-electron and two-electron transfer in the anionic polymerization of vinyl monomers and the ring-opening polymerization of lactones (pages 2158–2165)

      Zbigniew Jedliński

      Version of Record online: 29 MAY 2002 | DOI: 10.1002/pola.10293

      Thumbnail image of graphical abstract

      Single-electron-transfer and two-electron-transfer reactions at the initiation steps of the anionic polymerizations of styrene and lactones were investigated. Naphthalene sodium and potassium, able to transfer single electrons, were used as active catalysts in the polymerization of styrene, for example, as were several alkali-metal supramolecular complexes capable of two-electron transfer.

    4. Synthesis of model linear tetrablock quaterpolymers and pentablock quintopolymers of ethylene oxide (pages 2166–2170)

      Nikos Ekizoglou and Nikos Hadjichristidis

      Version of Record online: 29 MAY 2002 | DOI: 10.1002/pola.10288

      Thumbnail image of graphical abstract

      Multiblock copolymers of ethylene oxide, with four and five different blocks, were synthesized by the sequential anionic polymerization of styrene, isoprene, 2-vinyl pyridine, t-butyl methacrylate, and ethylene oxide with benzyl potassium as an initiator. The monomer sequence was based on the relative nucleophilicity of the active centers. Characterization of the multiblock copolymers by size exclusion chromatography (with refractive-index and UV detectors), membrane osmometry, and NMR spectroscopy confirmed that benzyl potassium is an efficient initiator for the synthesis of well-defined multicomponent copolymers of ethylene oxide.

    5. Living cationic polymerization route to poly(oligooxyethylene carbonate) vinyl ethers (pages 2171–2183)

      Ben-Ami Feit and Baruch Halak

      Version of Record online: 29 MAY 2002 | DOI: 10.1002/pola.10294

      Thumbnail image of graphical abstract

      The conductivities of solutions of lithium salts in lithium batteries increased significantly in the presence of di(oligooxyethylene) carbonates such as RO([BOND]CH2CH2O[BOND])nC([DOUBLE BOND]O)O([BOND]CH2CH2O[BOND])nR (R = Et, n = 1, 2, or 3). Related comb-shaped polymers with narrow molecular weight distributions of the type [BOND]CH2CH2(OR)[BOND] were prepared [R = ([BOND]OCH2CH2[BOND])nOC([DOUBLE BOND]O)O([BOND]CH2CH2O[BOND])mR′; (a) n = 2 or 3, m = 0, R′ = Et; (b) n = 2 or 3, m = 3, R′ = Me]. Prepolymers were prepared first by a living cationic polymerization of CH2[DOUBLE BOND]CHO([BOND]CH2CH2O[BOND])nAc (n = 2 or 3). The reaction of the hydrolyzed prepolymers with each of several chloroformates of the type ClC([DOUBLE BOND]O)O([BOND]CH2CH2O[BOND])mR′ (R′ = Me or Et) resulted in the target comb-shaped polymers.

    6. β-Butyrolactone polymerization initiated with tetrabutylammonium carboxylates: A novel approach to biomimetic polyester synthesis (pages 2184–2189)

      Piotr Kurcok, Monika Śmiga and Zbigniew Jedliński

      Version of Record online: 29 MAY 2002 | DOI: 10.1002/pola.10285

      Thumbnail image of graphical abstract

      The anionic polymerizations of (R,S)-β-butyrolactone and (S)-β-butyrolactone in the presence of tetrabutylammonium salts of carboxylic acids as initiators were investigated. The end groups and structures of the resulting polymers were defined with electrospray ionization/mass spectrometry and NMR techniques.

    7. Controlled ring-opening polymerization of cyclic carbonates and lactones by an activated monomer mechanism (pages 2190–2198)

      Takeshi Endo, Yuji Shibasaki and Fumio Sanda

      Version of Record online: 29 MAY 2002 | DOI: 10.1002/pola.10289

      Thumbnail image of graphical abstract

      This article reviews recent topics in the controlled synthesis of polycarbonates and polylactones with small polydispersity indices by activated monomer cationic ring-opening polymerizations, especially with new initiator systems, such as alcohol/protonic acid and boron alkoxide/protonic acid.

    8. Synthesis of block copolymers by the transformation of cationic polymerization into reversible atom transfer radical polymerization (pages 2199–2208)

      Ioan Cianga, Yesim Hepuzer, Ersin Serhatli and Yusuf Yagci

      Version of Record online: 29 MAY 2002 | DOI: 10.1002/pola.10295

      Thumbnail image of graphical abstract

      Azo-containing polytetrahydrofuran obtained by cationic polymerization was used as a macroinitiator in the reverse atom transfer radical polymerization of styrene and methyl acrylate in conjunction with CuCl2/2,2′-bipyridine as a catalyst to yield corresponding block copolymers.

    9. Competitive complexation in the cationic polymerization of isobutylene in a nonpolar medium (pages 2209–2214)

      Yixian Wu and Guanying Wu

      Version of Record online: 29 MAY 2002 | DOI: 10.1002/pola.10307

      Thumbnail image of graphical abstract

      Cationic polymerizations of isobutylene by the H2O/Al(i-Bu)Cl2 system in the presence of methyl acrylate (MA) and/or dimethyl sulfoxide (DMSO) led to polymers with high molecular weights and narrow molecular weight distributions. There existed competitive complexation of H2O, MA, or DMSO with Al(i-Bu)Cl2. The roles of MA or DMSO were to take part in the initiation step by competitive complexation and to modify the reactivity of growing chain ends in the propagation step by mediation and/or solvation.

SEARCH

SEARCH BY CITATION