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Entropy-driven material separation method: Size exclusion chromatography using pores in crystals

Research Project

Project/Area Number 19K03772
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 13040:Biophysics, chemical physics and soft matter physics-related
Research InstitutionKeio University

Principal Investigator

Chiba Ayano  慶應義塾大学, 理工学部(矢上), 講師 (20424195)

Co-Investigator(Kenkyū-buntansha) 秋山 良  九州大学, 理学研究院, 准教授 (60363347)
勝本 之晶  福岡大学, 理学部, 教授 (90351741)
Project Period (FY) 2019-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2021: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2020: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2019: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Keywords結晶性高分子 / 分子吸蔵 / 液体分離 / 枯渇相互作用 / アルカン / ホスト-ゲスト構造 / ポリオレフィン / 高分子結晶
Outline of Research at the Start

液体クロマトグラフィーは、液体中の分子を種類ごとに分ける手法であり、広い分野の基盤技術の一つである。一般に、高分子のクロマトグラフィーにおいては、親水性・疎水性による種別分離の他に、分子の体積で分離する手法が確立されている。一方、低分子のクロマトグラフィーにおいては、これまで分子体積で液体を分離する手法は確立していない。本研究では、低分子にも、分子の体積による液体分離がありうることを実験的に示す。

Outline of Final Research Achievements

The film of the semi-crystalline polymer P4MP1 (isotactic poly (4-methyl-1-pentene))is found to absorb alkane molecules. It is also found that the film preferentially absorbs a long chain alkane when immersed in a mixture liquid of long and short alkanes. We also proposed that the concept of depletion interaction explains this preferential absorption.
The P4MP1 film has an interesting property that the density of the crystal is slightly smaller than the density of the amorphous. However we found that the solvent molecules are preferentially absorbed in the amorphous region. As an result, an x-ray diffraction peak was found to appear at 0.16 nm -1 (lamellar long-spacing peak) with the absorption of the solvent. This peak disappears with the desorption of the solvent.

Academic Significance and Societal Importance of the Research Achievements

通常、ヘキサンとペンタンなど炭素数の近いアルカン同士を分離することは難しく、沸点の違いを利用する。しかしP4MP1膜は、炭素数の多い方のアルカンを優先吸蔵することを我々は見出し、このような長鎖アルカン優先吸蔵現象を枯渇相互作用によって説明できることを提唱した。枯渇相互作用を利用した液体分離法はこれまで研究されたことがないと考えられ、新しい液体分離法としての可能性を有すると考えている。

Report

(4 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Research-status Report
  • 2019 Research-status Report
  • Research Products

    (26 results)

All 2022 2021 2020 2019

All Journal Article (5 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 5 results,  Open Access: 1 results) Presentation (20 results) (of which Int'l Joint Research: 7 results,  Invited: 11 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] 高分子 P4MP1 膜への低分子混合溶液からの選択的分子吸蔵2021

    • Author(s)
      千葉文野, 秋山良
    • Journal Title

      高圧力の科学と技術

      Volume: 31 Pages: 82-89

    • NAID

      130008111011

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Streak Patterns Observed in Small Angle X-Ray Scattering from Highly Oriented Pyrolytic Graphite (HOPG)2020

    • Author(s)
      Ohmasa Yoshinori、Chiba Ayano
    • Journal Title

      Zeitschrift fur Physikalische Chemie

      Volume: 235 Issue: 1-2 Pages: 37-57

    • DOI

      10.1515/zpch-2020-1617

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Confined Space Enables Spontaneous Liquid Separation by Molecular Size: Selective Absorption of Alkanes into a Polyolefin Cast Film2019

    • Author(s)
      Chiba Ayano、Oshima Akio、Akiyama Ryo
    • Journal Title

      Langmuir

      Volume: 35 Issue: 52 Pages: 17177-17184

    • DOI

      10.1021/acs.langmuir.9b02509

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Diffuse + Bragg double scattering and specular reflection observed in the small-angle X-ray scattering from highly oriented pyrolytic graphite2019

    • Author(s)
      Ohmasa Yoshinori、Chiba Ayano
    • Journal Title

      Journal of Applied Crystallography

      Volume: 52 Issue: 3 Pages: 652-664

    • DOI

      10.1107/s1600576719005648

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Structural studies on fluid sulfur at high temperatures and high pressures: I. Atomic dynamics investigated by inelastic x-ray scattering2019

    • Author(s)
      Inui M.、Kajihara Y.、Chiba A.、Matsuda K.、Tsutsui S.、Baron A.Q.R.
    • Journal Title

      Journal of Non-Crystalline Solids

      Volume: 522 Pages: 119571-119571

    • DOI

      10.1016/j.jnoncrysol.2019.119571

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] Structural changes of isotactic poly(4-methyl-1-pentene) with alkane absorption2022

    • Author(s)
      Ayano Chiba
    • Organizer
      POLYSOLVAT-14
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Selective absorption of longer alkanes from alkane binary mixtures in the isotactic poly(4-methyl-1-pentene) film2021

    • Author(s)
      Ayano Chiba
    • Organizer
      POLYSOLVAT-13
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Selective absorption of longer alkane from alkane mixtures into a crystalline polyolefin as-cast film2021

    • Author(s)
      Ayano Chiba
    • Organizer
      11th LIQUID MATTER CONFERENCE 2020/2021
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 細孔のあるポリオレフィン膜に対するアルカン混合液体からの長鎖アルカンの選択的吸蔵現象2021

    • Author(s)
      Ayano Chiba
    • Organizer
      Mini-Symposium on Liquids 2021 (MSL2021)
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] 高分子融体構造と相変化2021

    • Author(s)
      千葉 文野
    • Organizer
      第88回マテリアルズ・テーラリング研究会
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] 高分子溶融構造と相変化2021

    • Author(s)
      千葉文野
    • Organizer
      第88回マテリアルズ・テーラリング研究会
    • Related Report
      2020 Research-status Report
    • Invited
  • [Presentation] Selective absorption of longer alkanes from alkane mixtures to polyolefin P4MP1 film2021

    • Author(s)
      Ayano Chiba
    • Organizer
      13th International IUPAC Conference on Polymer-solvent Complexes and Intercalates (POLYSOLVAT-13)
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] はじめに(領域12・11合同シンポジウム「粒子間近距離斥力の活用形」の開催にあたって)2020

    • Author(s)
      千葉文野
    • Organizer
      日本物理学会2020年秋季大会
    • Related Report
      2020 Research-status Report
  • [Presentation] 高分子膜による選択的吸蔵現象と枯渇相互作用2020

    • Author(s)
      千葉 文野
    • Organizer
      第9回 次世代の物質科学・ナノサイエンスを探る
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] 液体中における空隙: 多孔性液体としての液体・溶融体2020

    • Author(s)
      千葉 文野
    • Organizer
      第85回マテリアルズテーラリング研究会
    • Related Report
      2019 Research-status Report
  • [Presentation] Depletion Interaction : Polyolefin P4MP1 as a Host for Selective Absorption of Long-Chain Alkanes2020

    • Author(s)
      Ayano CHIBA, Akio OSHIMA, Kenzaburo OKUBO, Ryo AKIYAMA
    • Organizer
      13th International IUPAC Conference on Polymer-solvent Complexes and Intercalates (POLYSOLVAT-13)
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Selective absorption of alkanes by pores in the crystal of polymer P4MP1 and its causes2020

    • Author(s)
      Ayano Chiba, Akio Oshima, Ryo Akiyama
    • Organizer
      第69回高分子学会年次大会
    • Related Report
      2019 Research-status Report
  • [Presentation] 枯渇相互作用による高分子結晶空隙へのアルカンの選択的吸蔵現象2020

    • Author(s)
      千葉文野, 大島章生, 秋山良
    • Organizer
      凝縮系の理論化学2020
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] 高分子結晶膜中の主鎖間空隙への選択的分子吸蔵2020

    • Author(s)
      千葉文野, 大島章生, 秋山良
    • Organizer
      日本物理学会 第75回年次大会(2020年)
    • Related Report
      2019 Research-status Report
  • [Presentation] ポリオレフィン膜を用いた 新しい液体分離法と分離膜の薬品耐性への課題2020

    • Author(s)
      千葉文野, 大島章生, 秋山良
    • Organizer
      2019年度 不規則系物質先端科学研究会
    • Related Report
      2019 Research-status Report
  • [Presentation] 高分子結晶の空隙へのアルカン溶液からの選択的吸収2019

    • Author(s)
      千葉文野、 大島章生、 折戸朗子、 秋山良
    • Organizer
      第42回溶液化学シンポジウム
    • Related Report
      2019 Research-status Report
  • [Presentation] 多孔性ポリマーへの選択的吸蔵におけるvan der Waals 描像2019

    • Author(s)
      大久保堅三郎, 大島章生, 千葉文野, 秋山良
    • Organizer
      第42回溶液化学シンポジウム
    • Related Report
      2019 Research-status Report
  • [Presentation] 2成分流体中の管状空間への大粒子選択的吸蔵2019

    • Author(s)
      千葉文野, 大島章生, 秋山良
    • Organizer
      日本物理学会2019年秋季大会
    • Related Report
      2019 Research-status Report
  • [Presentation] Separation of inert solvent mixtures accentuated by confined spaces2019

    • Author(s)
      Ayano CHIBA, Akio OSHIMA, Kenzaburo OKUBO, Ryo AKIYAMA
    • Organizer
      6th Japan-Korea International Symposium on Materials Science and Technology 2019 (JKMST2019)
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Polystyrene Crystals as Porous Materials: Selective Absorption of Solvents2019

    • Author(s)
      Ayano CHIBA, Akio OSHIMA, Kenzaburo OKUBO, Ryo AKIYAMA
    • Organizer
      6th Japan-Korea International Symposium on Materials Science and Technology 2019 (JKMST2019)
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Patent(Industrial Property Rights)] ポリオレフィン系重合体並びにそれを用いた有機化合物の吸着、吸蔵、及び分離2020

    • Inventor(s)
      千葉 文野
    • Industrial Property Rights Holder
      学校法人慶應義塾
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2020-056735
    • Filing Date
      2020
    • Related Report
      2019 Research-status Report

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Published: 2019-04-18   Modified: 2023-01-30  

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