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WO2014116053A1 - Procédé pour modifier le caractère hydrophile superficiel du ptfe - Google Patents

Procédé pour modifier le caractère hydrophile superficiel du ptfe Download PDF

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Publication number
WO2014116053A1
WO2014116053A1 PCT/KR2014/000703 KR2014000703W WO2014116053A1 WO 2014116053 A1 WO2014116053 A1 WO 2014116053A1 KR 2014000703 W KR2014000703 W KR 2014000703W WO 2014116053 A1 WO2014116053 A1 WO 2014116053A1
Authority
WO
WIPO (PCT)
Prior art keywords
ptfe
plasma
supply amount
gas
acetylene
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/KR2014/000703
Other languages
English (en)
Korean (ko)
Inventor
정용호
석동찬
정현영
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.)
Korea Basic Science Institute KBSI
Original Assignee
Korea Basic Science Institute KBSI
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 Korea Basic Science Institute KBSI filed Critical Korea Basic Science Institute KBSI
Priority to CN201480006282.4A priority Critical patent/CN104955884B/zh
Priority to JP2015555105A priority patent/JP6091659B2/ja
Publication of WO2014116053A1 publication Critical patent/WO2014116053A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene

Definitions

  • the present invention relates to a method of hydrophilic modification of PTFE surfaces. Specifically, the present invention relates to a method for modifying PTFE surface hydrophilicity by plasma treatment. More specifically, the present invention relates to a method of hydrophilic modification of a PTFE surface by generating a plasma with a mixed gas of a hydrocarbon-based gas and a carbon compound and exposing it to the PTFE surface. More particularly, it relates to a method of hydrophilic modification of PTFE surface under atmospheric pressure.
  • PTFE Polytetrafluoroethylene
  • the PTFE has a heat resistance and low temperature durability of -270 to 300 degrees due to the combination of very strong C, -F, and is well known as a material having excellent chemical resistance and insulation.
  • it has excellent non-tackiness due to strong hydrophobicity and low surface energy by -F atoms, and has a very low coefficient of friction due to repulsive force between -F atoms.
  • PTFE with this feature is a semicrystalline polymer discovered by accident by Roy Plunkett in 1938 and patented by DuPont in 1941 and named Teflon. Since it was first commercialized for military and industrial purposes in 1946, and since 1960, it has been widely applied to electric, electronic, medical, and energy materials as well as filter applications.
  • PTFE has a lack of hydrophilicity due to strong hydrophobicity and low surface energy and difficulty in attaching to other materials, thus making it difficult to process and form for use in various industrial fields.
  • US Pat. No. 5,300,300 discloses a method using PTFE resin for water treatment membrane applications, which discloses fluorine-containing units and hydrophilic pores within the membrane to impart hydrophilicity to the PTFE membrane. It is known to add hydrophilicity by coating with a hydrophilic fluorine containing polymer comprising a non-fluorinated vinyl monomeric unit.
  • Korean Patent Application No. 1994-0026594 (method for producing modified polytetrafluoroethylene and its use), including polymerization of a monomer in an aqueous medium by a suspension polymerization method using a permanganate initiator at a temperature of 60 ° C. or lower, A method for producing a polymer of tetrafluoroethylene containing perfluorine having 1 to 4 carbon atoms in the fluoroalkyl chain is disclosed.
  • the method of modifying the surface of a polymer material such as PTFE using plasma is aimed at reducing the contact angle of water to the surface of the polymer material to have hydrophilicity. For example, if the contact angle is less than 90 °, the water droplets may lose their shape and hydrophilicity may appear that wets the surface of PTFE. If the contact angle is greater than 90 °, the water droplet may not wet the surface of PTFE while maintaining the shape of the sphere. And hydrophobicity, which is a unique feature of PTFE, which flows easily according to external forces.
  • a method of using a plasma for modifying the surface of a polymer material such as PTFE to change the contact angle a method such as a high voltage corona discharge and a direct current plasma discharge may be used.
  • the high voltage corona discharge fills the reactor with atmospheric pressure in a vacuum chamber, ionizes the reactor by electrons emitted from the electrode, and forms a plasma that has the same positive and negative charge as the electrons. It refers to a method of reacting on a surface and depositing on a surface or modifying a surface.
  • Japanese Laid-Open Patent Publication No. 1985-13823 is a conventional technique for modifying the surface of a polymer material such as PTFE using such a high voltage corona discharge.
  • This patent discloses a case where the surface of vinyl chloride is treated with chlorine gas at atmospheric pressure.
  • the DC plasma discharge is similar to the high voltage corona discharge, but fills the reactor in the vacuum chamber with an amount of 0.01 to 5 torr, using the plasma generated through the glow discharge, that is, the ionized reactor.
  • the present invention is to recognize the above problems and needs, and to provide a simple method for overcoming the above problems. That is, the present invention provides a method for modifying the surface of PTFE by a simple plasma treatment using a hydrocarbon gas and a carbon compound gas at atmospheric pressure.
  • the present invention comprises the steps of generating a plasma with a mixed gas of a hydrocarbon gas and a carbon compound; It provides a method of hydrophilic modification of the surface of PTFE, comprising exposing the PTFE to the generated plasma.
  • the hydrocarbon gas is preferably acetylene
  • the carbon compound gas is preferably carbon dioxide.
  • the present invention is characterized in that the amount of carbon dioxide supplied is greater than the amount of acetylene supplied.
  • the present invention is characterized in that the acetylene supply amount is a maximum of 0.08, based on the supply amount of the carbon dioxide 1. Excessive acetylene feed would rather reduce the hydrophilicity of the surface of the PTFE and cause discoloration.
  • the acetylene supply amount has a threshold value up to 0.08, based on the supply amount of carbon dioxide 1, but the supply of excess acetylene discolors PTFE.
  • the maximum supply amount of acetylene gas which is free from discoloration of PTFE and provides the maximum hydrophilicity value (lowest contact angle), is 0.03, based on the supply amount 1 of the carbon compound gas.
  • the present invention is characterized in that the plasma treatment is performed under atmospheric pressure.
  • the PTFE material may be in various forms, for example powder, sheet and block.
  • FIG. 1 is a schematic diagram illustrating a DBD type plasma generating apparatus of the present invention.
  • Fig. 4 is a photograph of the surface of PTFE after plasma treatment when the gas supply ratio of carbon dioxide and acetylene gas is 1: 0.02.
  • Figure 5 is a micrograph of the powder of the hydrophilized PTFE surface of the powder using the tubular plasma module of the present inventors Korean Application No. 10-2012-0078234 using the gas combination used in the first experiment.
  • a DBD-type plasma generator operating under atmospheric pressure was prepared. It will be apparent to those skilled in the art that various types of DBD types may be used. Examples of various types of DBD type devices are shown in FIG. 1. As a gas generating plasma, a mixture of nitrogen, carbon dioxide, and acetylene gas was supplied to the plasma generating region, and high frequency power of 30 kH and 1 kW was applied to the high voltage electrode 210.
  • the gas feed rate was 250 lpm for nitrogen, acetylene for 0.1 lpm, and carbon dioxide for 0.01 to 1 lpm.
  • the PTFE sheet was moved to the plasma generating region in the plasma generator at a rate of 10 mm / second.
  • the gap between the sheet and the DBD module was 4 mm.
  • the hydrophilic modification of the plasma treated PTFE was confirmed by a contact angle measuring method (Goniometer, KRUSS DSA100) according to the water droplet contact angle measuring method.
  • Figure 5 is a micrograph of the powder of the hydrophilized PTFE surface of the powder using the tubular plasma module of the present inventors Korean Application No. 10-2012-0078234 using the gas combination used in the first experiment.
  • the gas feed rate was 250 lpm for nitrogen, 1 lpm for carbon dioxide, and acetylene for 0.02 to 0.1. The result is shown in FIG.
  • the surface hydrophilicity of PTFE is improved as the supply amount of acetylene increases with respect to the carbon dioxide supply amount 1, but it can be seen that the surface hydrophilicity of PTFE is lowered from the supply amount of 0.08 or more with respect to the carbon dioxide supply amount 1.
  • FIG. 4 is a photograph of the surface of PTFE after plasma treatment when the gas supply ratio of carbon dioxide and acetylene gas is 1: 0.02 in the above experiment. Through the second experiment, it was confirmed that when the excess acetylene gas was supplied, the PTFE surface was discolored. 5 shows this.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

Cette invention concerne un procédé pour modifier le caractère hydrophile superficiel du PTFE. Plus spécifiquement, cette invention concerne un procédé pour modifier le caractère hydrophile superficiel du PTFE au moyen d'un traitement par plasma. Plus spécifiquement encore, cette invention concerne un procédé pour modifier le caractère hydrophile superficiel du PTFE par génération d'un plasma au moyen d'un gaz hydrocarboné et d'un mélange de gaz constitué de composés carbonés, puis exposition du plasma sur la surface du PTFE. Un procédé pour modifier le caractère hydrophile superficiel du PTFE dans des conditions de pression atmosphérique est en outre décrit.
PCT/KR2014/000703 2013-01-28 2014-01-24 Procédé pour modifier le caractère hydrophile superficiel du ptfe Ceased WO2014116053A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201480006282.4A CN104955884B (zh) 2013-01-28 2014-01-24 聚四氟乙烯表面亲水性改性方法
JP2015555105A JP6091659B2 (ja) 2013-01-28 2014-01-24 Ｐｔｆｅ表面の親水性改質方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20130009131A KR101480094B1 (ko) 2013-01-28 2013-01-28 Ｐｔｆｅ 표면의 친수성 개질 방법
KR10-2013-0009131 2013-01-28

Publications (1)

Publication Number Publication Date
WO2014116053A1 true WO2014116053A1 (fr) 2014-07-31

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PCT/KR2014/000703 Ceased WO2014116053A1 (fr) 2013-01-28 2014-01-24 Procédé pour modifier le caractère hydrophile superficiel du ptfe

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JP (1) JP6091659B2 (fr)
KR (1) KR101480094B1 (fr)
CN (1) CN104955884B (fr)
WO (1) WO2014116053A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101725367B1 (ko) 2015-04-24 2017-04-11 (주)씨맥스와이어리스 분산형 무선 기지국에서의 업링크 전송에 대한 harq 처리 방법
CN108456317B (zh) * 2018-03-30 2021-03-30 南京腾逸新材料科技有限公司 一种低温等离子体制备极性聚合物粉体的方法
KR20220155311A (ko) * 2020-03-19 2022-11-22 에이지씨 가부시키가이샤 표면 개질된 테트라플루오로에틸렌계 폴리머의 제조 방법, 개질 파우더의 제조 방법, 액상 조성물, 개질 성형물의 제조 방법, 및 개질 성형물
CN115066080B (zh) * 2022-07-14 2025-08-01 佛山大学 一种基于二氧化碳气氛的低温常压等离子体表面亲水改性装置及方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0127149A2 (fr) * 1983-05-31 1984-12-05 Idemitsu Petrochemical Co. Ltd. Procédé pour le traitement d'une matière thermoplastique
JPH06107828A (ja) * 1992-03-19 1994-04-19 Toray Ind Inc フッ素フイルムの表面改質方法
US20060165975A1 (en) * 2002-12-17 2006-07-27 Moser Eva M Substrate comprising a polar plasma-polymerised coating

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2911610B1 (fr) * 2007-01-24 2012-09-21 Air Liquide Procede de traitement de surface de substrats polymeres, substrats ainsi obtenus et leur utilisation pour la realisation de materiaux multicouches.
CN101979429B (zh) * 2010-10-14 2012-08-29 中国科学院宁波材料技术与工程研究所 一种聚四氟乙烯制品表面改性的方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0127149A2 (fr) * 1983-05-31 1984-12-05 Idemitsu Petrochemical Co. Ltd. Procédé pour le traitement d'une matière thermoplastique
JPH06107828A (ja) * 1992-03-19 1994-04-19 Toray Ind Inc フッ素フイルムの表面改質方法
US20060165975A1 (en) * 2002-12-17 2006-07-27 Moser Eva M Substrate comprising a polar plasma-polymerised coating

Also Published As

Publication number Publication date
JP2016504480A (ja) 2016-02-12
KR101480094B1 (ko) 2015-01-07
KR20140096526A (ko) 2014-08-06
CN104955884B (zh) 2018-01-09
JP6091659B2 (ja) 2017-03-08
CN104955884A (zh) 2015-09-30

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