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WO2002075324A1 - Procede de fabrication d'un corps structurel a micro-canaux et film de polymere a haute fonctionnalite - Google Patents

Procede de fabrication d'un corps structurel a micro-canaux et film de polymere a haute fonctionnalite Download PDF

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Publication number
WO2002075324A1
WO2002075324A1 PCT/JP2002/002475 JP0202475W WO02075324A1 WO 2002075324 A1 WO2002075324 A1 WO 2002075324A1 JP 0202475 W JP0202475 W JP 0202475W WO 02075324 A1 WO02075324 A1 WO 02075324A1
Authority
WO
WIPO (PCT)
Prior art keywords
microchannel
polymer film
functional polymer
micro
diaphragm
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2002/002475
Other languages
English (en)
Japanese (ja)
Inventor
Takehiko Kitamori
Manabu Tokeshi
Hideaki Hisamoto
Akihide Hibara
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kanagawa Academy of Science and Technology
Original Assignee
Kanagawa Academy of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kanagawa Academy of Science and Technology filed Critical Kanagawa Academy of Science and Technology
Priority to JP2002573682A priority Critical patent/JPWO2002075324A1/ja
Publication of WO2002075324A1 publication Critical patent/WO2002075324A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions

Definitions

  • the invention of this application relates to a method for producing a microchannel structure and a functional polymer film. More specifically, the invention of this application is provided with a microchannel having a functional polymer membrane capable of separating a trace substance in a minute space, etc., and enables high-speed separation and separation of a trace substance.
  • the present invention relates to a microstructure to be used and a method for producing a functional polymer film. Background art
  • the inventors of the present application have been studying the technology for integrating chemical reactions in a micro space, and have been working on devices (micro chips) with micro channels (micro reaction spaces) in channels.
  • a photothermal conversion absorption spectroscopy method using the thermal lens effect generated by light absorption of a liquid sample has been established, and the path to practical use has been opened.
  • the invention of this application is a new technology necessary for realizing a new reaction device (microchip) that can greatly expand the range of use of chemical reactions in a minute space. It is an object of the present invention to provide a new structure having a functional polymer film capable of expressing a specific function in a minute space as a release membrane or the like, and a new method capable of manufacturing the same. Disclosure of the invention
  • a functional polymer film is disposed as a diaphragm in a microchannel in which a micro waveguide on a microchip is in a confluence area.
  • a functional polymer film is disposed as a diaphragm between a plurality of layers in a confluence area where a multi-layer flow is formed.
  • a microchannel structure is provided.
  • the present invention provides a microchannel structure characterized in that the functional polymer membrane is a selective separation membrane.
  • the functional polymer membrane is provided with a microchannel structure according to any one of claims 1 to 3, characterized in that the functional polymer film is surface-modified. 5.
  • the microchannel structure according to any one of claims 1 to 4 wherein the microchannel structure has an enzyme reaction function.
  • the invention of this application is directed to a method for producing a functional polymer film in a microchannel in which a micro-waveguide on a microchip is in a confluence area, comprising: An aqueous solution and an organic solution of another raw material are supplied to different micro-waveguides and merged in a microchannel, and a functional polymer film is formed as a diaphragm in the confluence area microchannel by a liquid-liquid interface reaction.
  • the present invention provides a method for producing a functional polymer film in a microchannel characterized by the following.
  • the invention of this application is directed to a function in a microchannel, characterized in that the functional polymer membrane formed as a diaphragm by the above method is surface-modified with a modifier introduced through a microscopic waveguide.
  • FIG. 1 is a plan view illustrating a microchip for carrying out the method for producing a polymer film of the present invention.
  • FIGS. 2A and 2B are schematic diagrams showing a process of synthesizing a functional polymer membrane by merging a raw material A aqueous solution and a raw material B organic solution in a microchannel.
  • FIG. 3 (A) is a schematic diagram of a functional polymer film formed in a microchannel, and (B) is a schematic diagram of a polymer film formed by polymerization of raw materials A and B. is there.
  • FIG. 4 is a schematic diagram showing an example of a selective separation membrane for ionic components and gas components in a liquid.
  • FIG. 5 is a diagram illustrating selective separation by a polymer membrane having a molecular recognition site.
  • Figure 6 is a photograph showing an example in which a 6,6 nylon membrane was formed in a microchannel using 1,6-diaminohexane and adipic acid chloride as raw materials.
  • FIGS. 7 (A) to (D) are continuous photographs when bubbles are passed through the nylon membrane-formed microchannel shown in FIG.
  • the invention of this application is implemented, for example, in a microchip (10) as shown in a plan view in FIG.
  • the microchip (10) illustrated in FIG. 1 is made of a transparent cell substrate made of, for example, glass, silicon, plastic, or the like, and the surface of the substrate is also covered with a transparent cover.
  • the size of the chip has been reduced to a length and width of several centimeters.
  • micro liquid passages (20a) and (20b) are formed, and a part of these merges to form a microchannel (30).
  • the solutions dropped in the micro passages (20a) and (20b) flow in the directions of the arrows in the figure, respectively, and merge in the microchannel (30).
  • not only liquids but also gases can be passed through the micro passages (20a) and (20b) and the microchannels (30).
  • Each of 20 a) and 20 b) has two liquid inlets (2 1a) (2 2a) and (2 1b) (2 2b). Liquids can be passed in combination with each other. Or
  • micro-liquid passages (20a) (20b) and micro-channels (30) are formed by etching or other fine processing means, and their width and depth are about 1 to 500m. It is.
  • the length of the microchannel (30) can be freely adjusted to about 300 mm.
  • an aqueous solution of the raw material A is supplied to the fine liquid passage (20a) of the micro-mouth chip having the above-described configuration, and the solution is supplied to the minute liquid passage (20b).
  • Supply the organic solution of raw material B is supplied.
  • Raw materials A and B are compounds capable of synthesizing a polymer film by a polymerization reaction.
  • the aqueous solution of raw material A and the organic solution of raw material B are incompatible or hardly compatible, and can form a liquid-liquid interface. Shall be.
  • the polymerization reaction shall occur at this liquid-liquid interface.
  • a 6,6 nylon membrane is synthesized by a combination of 1,6-diaminohexane and adipic acid chloride as shown in Examples.
  • the polymer film formed by such a combination may be of various types. That is, the raw materials A and B may be any of these compounds, as long as a polymer film having a characteristic function can be synthesized.
  • Raw material A aqueous solution is prepared by mixing raw material A with water
  • raw material B organic solution is prepared by mixing raw material B with an organic solvent. Further, the concentrations of the raw materials A and B, the type of the organic solvent to be used, the reaction strength, and the like can be appropriately set according to the type, the function expected of the polymer film to be synthesized, and the like.
  • the raw material A aqueous solution and the raw material B organic solution prepared in this way flow through the microchannels (20a) and (20b), respectively, they merge in the microchannel (30), and 2
  • the organic solution ( A liquid-liquid interface (50) is formed between 40B) and the aqueous solution (40A), and the respective raw materials A and B undergo interfacial polymerization at the liquid-liquid interface (50), as shown in Fig. 2 (B).
  • the polymer film (60) is synthesized.
  • Fig. 3 (A) shows the state of the polymer film (60) synthesized in the microchannel (30)
  • Fig. 3 (B) schematically shows the state of polymerization of raw materials A and B. It is.
  • the microchannel (30) is provided with the functional high molecular film (60). A structure is obtained.
  • FIG. 3 (A) shows an example in which the functional polymer membrane (60) is formed as a diaphragm across the entire flow direction of the microchannel (30) in the junction area.
  • the diaphragm may be partially provided depending on the intended function.
  • the functional polymer membrane (60) as the formed diaphragm may have various functions and purposes.
  • the components of the solution or gas flowing through the micro-flow passages (20a) and / or (20b) are separated by the functional high molecular membrane (60), or the separated components are separated by the microchannel (3). It can be used for various purposes, such as analysis within 0).
  • a polymer membrane (60) is provided as a diaphragm in a microchannel having a width of up to about 500 m, and the ionic and gas components in the liquid are selectively separated.
  • a function to transmit harmful ions may be provided.
  • a polymer membrane as a diaphragm at the interface of a two-layer flow such as the case of an organic phase and an aqueous phase
  • the invention of this application is not limited to such a two-layer flow. It may be a multilayer flow, and a polymer film as a diaphragm may be formed and disposed at each of a plurality of interfaces formed in the multilayer flow or at some of the interfaces.
  • a functional polymer film as a diaphragm may be formed at two interfaces of a three-layer flow of organic phase Z aqueous phase Z organic phase.
  • the polymer membrane formed as a diaphragm may be subjected to surface modification to impart chemical or biological activity such as enzymatic activity.
  • a microchip (10) whose schematic diagram is shown in Fig. 1 was fabricated using a glass substrate and a glass cover. On the surface of the glass substrate, micro-flow channels (20a) (20b) and micro-channels (30) were formed by wet etching.
  • the microchannel (30) was 250 m wide, 100 m deep, and 1.0 mm long.
  • the inner wall of the microchannel (30) was surface-modified with 3-aminopropyltriethoxysilane.
  • a 1,6-diaminohexane-NaOH aqueous solution (0.01 M) is passed through the microfluidic channel (20 a), and adipic acid chloride dichloride solution (0.01 M) is passed finely.
  • the liquid flowed into the liquid channel (20b) and merged in the microchannel (30).
  • Each raw material solution was flowed at 101 / min.
  • a 6,6 nylon film (61) having a thickness of about 30 / zm was formed so as to divide the inside of the microchannel (30).
  • the aqueous phase (hexamethylene diamine-NaOH aqueous solution (0.01 M)) was passed through the central inlet of the microfluidic passage having a three-branched inlet, and the channels from both sides
  • An organic phase (chloride dichloroethane adipate solution (0.01 M) was introduced into the confluence zone to form a three-layer flow, and at a constant flow rate, the same as in Example 1 at each of the two interfaces.
  • a nylon film was formed along the two liquid-liquid interfaces formed in the junction channel, and a multi-layer 6,6-nylon film was successfully produced.
  • a 5 m microchannel was formed on a glass chip, and a 6,6-nylon film was formed by an interfacial polymerization method in the same manner as in Example 1.
  • An aqueous solution of an enzyme (peroxidase) was introduced into one of the channels partitioned by the membrane, and the enzyme was immobilized on the membrane surface by the dartalaldehyde method.
  • a substrate that produces a dye by enzymatic reaction with hydrogen peroxide (4-1A
  • the invention of this application provides a microchannel structure having a functional polymer film in a microchannel.
  • a microchannel structure having a functional polymer film in a microchannel.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

L'invention concerne un corps structurel à micro-canaux présentant un film polymère à haute fonctionnalité, dans un micro-canal. L'invention traite aussi d'un procédé de fabrication de ce corps. Ce procédé comprend les étapes consistant à former une solution d'un matériau A et une solution organique d'un matériau B avec les matériaux A et B du film polymère à haute fonctionnalité, à assurer l'écoulement de ces solutions dans les deux passages d'écoulement de fluide (20a , 20b) et permettre à ces solutions de fusionner dans un micro-canal (30) pour fabriquer le film polymère à haute fonctionnalité (60) par polymérisation d'interface liquide.
PCT/JP2002/002475 2001-03-15 2002-03-15 Procede de fabrication d'un corps structurel a micro-canaux et film de polymere a haute fonctionnalite Ceased WO2002075324A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2002573682A JPWO2002075324A1 (ja) 2001-03-15 2002-03-15 マイクロチャネル構造体と機能性高分子膜の作製方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001-075087 2001-03-15
JP2001075087 2001-03-15

Publications (1)

Publication Number Publication Date
WO2002075324A1 true WO2002075324A1 (fr) 2002-09-26

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JP (1) JPWO2002075324A1 (fr)
WO (1) WO2002075324A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005007352A (ja) * 2003-06-20 2005-01-13 Sharp Corp 粒子の分離方法及び分離装置並びに検出装置
WO2007099932A1 (fr) * 2006-03-02 2007-09-07 Inter-University Research Institute Corporation National Institutes Of Natural Sciences Reacteur a microcanal
JP2014030382A (ja) * 2012-08-03 2014-02-20 Univ Of Tokyo マイクロ流体デバイス及び脂質二重膜の形成方法
CN110694563A (zh) * 2019-10-31 2020-01-17 重庆大学 具有无支撑体的自形成尼龙膜的微通道反应器及制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4960789A (fr) * 1972-08-23 1974-06-12
JPH08502534A (ja) * 1992-10-21 1996-03-19 コーネル リサーチ ファウンデーション、インコーポレーテッド 多孔物質の細孔サイズ選択的修飾法
JPH10507406A (ja) * 1994-10-22 1998-07-21 セントラル リサーチ ラボラトリーズ リミティド 不混和性流体間の拡散移動のための方法及び装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4960789A (fr) * 1972-08-23 1974-06-12
JPH08502534A (ja) * 1992-10-21 1996-03-19 コーネル リサーチ ファウンデーション、インコーポレーテッド 多孔物質の細孔サイズ選択的修飾法
JPH10507406A (ja) * 1994-10-22 1998-07-21 セントラル リサーチ ラボラトリーズ リミティド 不混和性流体間の拡散移動のための方法及び装置

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
SHIMIZU YUKI ET AL.: "Micro channel ni okeru kobunshi kakumaku no sakusei", KAGAKU TO MICRO SYSTEM KENKYUKAI KOEN YOKOSHU, vol. 3, 16 May 2001 (2001-05-16), pages 11, XP002955848 *
SHIMIZU YUKI ET AL.: "Micro chip o mochiita ekiso bisho kukan kagaku no kenkyu (9) micro channel-nai no kaimen jugo ni yoru kobunshi kakumaku no sakusei", CSJ: THE CHEMICAL SOCIETY OF JAPAN, KOEN JOKOSHU, vol. 79, 15 March 2001 (2001-03-15), pages 3, XP002955847 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005007352A (ja) * 2003-06-20 2005-01-13 Sharp Corp 粒子の分離方法及び分離装置並びに検出装置
WO2007099932A1 (fr) * 2006-03-02 2007-09-07 Inter-University Research Institute Corporation National Institutes Of Natural Sciences Reacteur a microcanal
JP5162758B2 (ja) * 2006-03-02 2013-03-13 大学共同利用機関法人自然科学研究機構 マイクロチャンネルリアクター
JP2014030382A (ja) * 2012-08-03 2014-02-20 Univ Of Tokyo マイクロ流体デバイス及び脂質二重膜の形成方法
CN110694563A (zh) * 2019-10-31 2020-01-17 重庆大学 具有无支撑体的自形成尼龙膜的微通道反应器及制备方法

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