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Living Anionic Polymerization of 1,4-Diisopropenylbenzene.

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Title: Living Anionic Polymerization of 1,4-Diisopropenylbenzene.
Authors: Raita Goseki1, Suguru Onuki1, Shunsuke Tanaka1, Takashi Ishizone1, Akira Hirao1
Source: Macromolecules. May2015, Vol. 48 Issue 10, p3230-3238. 9p.
Subjects: Alpha-methylstyrol, Addition polymerization, Uniform polymers, Nucleophilic reactions, Isopropenyl compounds
Abstract: Theanionic polymerization of diisopropenylbenzene (DIPB) derivativeswas conducted in THF at −78 °C with a specially designedinitiator system prepared from oligo(α-methylstyryl)lithiumand an excess potassium tert-butoxide (KOBut) (2.7–5.0 equiv to the Li salt). Among the ortho-, meta-, and para-isomers of DIPBderivatives, it was found that the para-isomer (p-DIPB) successfully underwent the living polymerizationin a selective manner through one of the two isopropenyl groups underthe above stated conditions. With this living polymerization system,soluble polymers with controllable Mnvaluesranging from 7620 to 31 500 g/mol and near monodisperse distributions(Mw/Mn≤1.03) were obtained for the first time. The obtained living polymerswere stable at −78 °C even after 168 h and at −40°C after 6 h, in which the intermolecular addition reaction ofthe chain-end anion to the pendant isopropenyl group could be completelysuppressed. In contrast, the living polymerization of either the ortho- or meta-isomer was not successfulunder the same conditions. The block copolymerization of p-DIPB with either styrene (S), 2-vinylpyridine (2VP), or tert-butyl methacrylate (tBMA) by the sequentialaddition of such monomers was conducted. Four new PS-block-P(p-DIPB), P2VP-block-P(p-DIPB), P(p-DIPB)-block-P2VP, and P(p-DIPB)-block-PtBMA containing reactive P(p-DIPB) segmentswere synthesized. On the basis of the block copolymerization results,it is understood that p-DIPB is comparable to 2VPand located between S and tBMA in monomer reactivity. Thereactivity increases as follows: S < 2VP ∼ p-DIPB < tBMA, while the nucleophilicity of the livingchain-end anion decreases in the following order: PS–> P2VP–∼ P(p-DIPB) –> P(tBMA) –. [ABSTRACT FROM AUTHOR]
Copyright of Macromolecules is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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DbLabel: Engineering Source
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  Data: Living Anionic Polymerization of 1,4-Diisopropenylbenzene.
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  Data: &lt;searchLink fieldCode=&quot;JN&quot; term=&quot;%22Macromolecules%22&quot;&gt;Macromolecules&lt;/searchLink&gt;. May2015, Vol. 48 Issue 10, p3230-3238. 9p.
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  Data: Theanionic polymerization of diisopropenylbenzene (DIPB) derivativeswas conducted in THF at −78 &#176;C with a specially designedinitiator system prepared from oligo(α-methylstyryl)lithiumand an excess potassium tert-butoxide (KOBut) (2.7–5.0 equiv to the Li salt). Among the ortho-, meta-, and para-isomers of DIPBderivatives, it was found that the para-isomer (p-DIPB) successfully underwent the living polymerizationin a selective manner through one of the two isopropenyl groups underthe above stated conditions. With this living polymerization system,soluble polymers with controllable Mnvaluesranging from 7620 to 31 500 g/mol and near monodisperse distributions(Mw/Mn≤1.03) were obtained for the first time. The obtained living polymerswere stable at −78 &#176;C even after 168 h and at −40&#176;C after 6 h, in which the intermolecular addition reaction ofthe chain-end anion to the pendant isopropenyl group could be completelysuppressed. In contrast, the living polymerization of either the ortho- or meta-isomer was not successfulunder the same conditions. The block copolymerization of p-DIPB with either styrene (S), 2-vinylpyridine (2VP), or tert-butyl methacrylate (tBMA) by the sequentialaddition of such monomers was conducted. Four new PS-block-P(p-DIPB), P2VP-block-P(p-DIPB), P(p-DIPB)-block-P2VP, and P(p-DIPB)-block-PtBMA containing reactive P(p-DIPB) segmentswere synthesized. On the basis of the block copolymerization results,it is understood that p-DIPB is comparable to 2VPand located between S and tBMA in monomer reactivity. Thereactivity increases as follows: S &lt; 2VP ∼ p-DIPB &lt; tBMA, while the nucleophilicity of the livingchain-end anion decreases in the following order: PS–&gt; P2VP–∼ P(p-DIPB) –&gt; P(tBMA) –. [ABSTRACT FROM AUTHOR]
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  Data: &lt;i&gt;Copyright of Macromolecules is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder&#39;s express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.&lt;/i&gt; (Copyright applies to all Abstracts.)
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RecordInfo BibRecord:
  BibEntity:
    Identifiers:
      – Type: doi
        Value: 10.1021/acs.macromol.5b00575
    Languages:
      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 9
        StartPage: 3230
    Subjects:
      – SubjectFull: Alpha-methylstyrol
        Type: general
      – SubjectFull: Addition polymerization
        Type: general
      – SubjectFull: Uniform polymers
        Type: general
      – SubjectFull: Nucleophilic reactions
        Type: general
      – SubjectFull: Isopropenyl compounds
        Type: general
    Titles:
      – TitleFull: Living Anionic Polymerization of 1,4-Diisopropenylbenzene.
        Type: main
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      – PersonEntity:
          Name:
            NameFull: Raita Goseki
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          Name:
            NameFull: Suguru Onuki
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            NameFull: Shunsuke Tanaka
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            NameFull: Takashi Ishizone
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          Name:
            NameFull: Akira Hirao
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          Dates:
            – D: 26
              M: 05
              Text: May2015
              Type: published
              Y: 2015
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              Value: 00249297
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              Value: 48
            – Type: issue
              Value: 10
          Titles:
            – TitleFull: Macromolecules
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