WO1999007781A1 - Fluoropolymer articles having improved impermeability to fluids - Google Patents

Fluoropolymer articles having improved impermeability to fluids Download PDF

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Publication number
WO1999007781A1
WO1999007781A1 PCT/US1998/016296 US9816296W WO9907781A1 WO 1999007781 A1 WO1999007781 A1 WO 1999007781A1 US 9816296 W US9816296 W US 9816296W WO 9907781 A1 WO9907781 A1 WO 9907781A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluoropolymer
article
molded
examples
filler
Prior art date
Application number
PCT/US1998/016296
Other languages
English (en)
French (fr)
Inventor
Daniel N. Levy
Original Assignee
E.I. Du Pont De Nemours And Company
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 E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to EP98938389A priority Critical patent/EP1002010A1/en
Priority to JP2000506272A priority patent/JP2001512768A/ja
Publication of WO1999007781A1 publication Critical patent/WO1999007781A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/016Additives defined by their aspect ratio

Definitions

  • the present invention relates to impermeable fluoropolymer articles used to contain and transport fluids such as liquids and gases.
  • Metals such as carbon steel are materials of choice to store or transport fluids because they are relatively cheap and strong and are therefore widely used in such fields. For certain applications metals are often not suitable because of either their high weight or corrosion problems.
  • plastics either alone as materials for components and structures, or in conjunction with other materials such as metals, helps minimize the problems with metals.
  • Plastics also have limitations: they are not compatible with all chemical substances, they are resistant to temperatures that are in general lower than the temperatures metals are resistant to, and plastics are, to various degrees, permeable to fluids. Of all types of plastics, fluoropolymers are the best suited for these applications where it is desirable to have compatibility with chemical substances, resistance to temperatures and impermeability to fluids, such as applications for fuel and harsh chemical storage and transport.
  • Fluoropolymers such as polytetrafluoroethylene (PTFE), perfluoroalkoxy (PFA) and fluorinated ethylene- propylene (FEP) are resistant to attack from most of the known chemical substances under normal use, can withstand relatively high temperatures of up to 260 C continuous and have one of the lowest permeation rates of all plastics. Permeation can be a problem with plastics because gases or liquids permeating the plastic may pollute or create safety hazards in their environment, or, in the case of permeants such as acids, may corrode metal supports. liners, may cause the liner to collapse.
  • PTFE polytetrafluoroethylene
  • PFA perfluoroalkoxy
  • FEP fluorinated ethylene- propylene
  • PTFE fluoropolymer is an exception because it is formed or extruded into these type of articles by a powder process which does not involve melting during the forming process, but only afterwards. Molded and extruded articles of fluoropolymers are usually thicker than 0.3 mm.
  • the present invention relates to a molded or extruded article made from a composition comprising a fluoropolymer and a platelet filler having a particle size between 1 and 500 micrometers and an aspect ratio of from 10 to 10,000.
  • molded or extruded articles exhibit reduced permeation of fluids therethrough.
  • the articles may be used as stand alone or may be extruded or molded in combination with other materials such as metal backings and supports.
  • the present invention relates to a molded or extruded article made from a composition comprising a fluoropolymer and a platelet filler.
  • the molded and extruded articles of this invention include molded or extruded article which is used to transport or contain a fluid such as a liquid or a gas.
  • a fluid such as a liquid or a gas.
  • these articles include those used in the transportation of fuels, such as fuel hoses for automobiles, as well as tubes and other parts that come in which is used in the transport of a fluid where impermeability is an important criterion, including heat exchanger tubes, hoses, tubes and vessels used to transport or hold chemicals.
  • the term "article” means objects having a thickness of greater than 0.3 mm, and includes extruded or molded films.
  • fluoropolymer is well known in the art, and includes fluoropolymers such as polytetrafluoroethylene (PTFE), perfluoroalkoxy (PFA), fluorinated ethylene -propylene (FEP), polyvinylidene fluoride (PVDF), ethylene- tetrafluoroethylene (ETFE) and ethylene-chlorotrifluoroethylene (ECTFE).
  • the composition also includes a platy filler, sometimes referred to in the art as a platelet filler.
  • Platy fillers represent a special class of fillers which, because of their structure, may be delaminated into very thin flakes that are characterized by a high ratio of their average diameter to their thickness. This ratio is known as the Aspect Ratio.
  • the planar structure of the platy fillers yields a very flat and regular surface, such that the average thickness is quite uniform.
  • the term "platy filler” is intended to mean ultra thin particles having a high Aspect Ratio.
  • the best results in lowering permeation are obtained when the average particle size of the platy filler is between 1 and 500 micrometers, or microns, preferably between 5 and 100 microns, and the Aspect Ratio of the platy filler is between 10 and 10,000, preferably between 10 and 2000.
  • platy fillers examples include mica, glass flakes, talc, silicon carbide flakes, alumina flakes, graphite flakes, vermiculite, or mixtures thereof.
  • the fluoropolymer is present in the composition in an amount of between 50 and 99.5 weight percent, preferably between 75 and 99.5 weight percent, based upon the total weight of the fluoropolymer and filler only.
  • the platy filler is present in the composition in an amount of between 0.5 and 50 weight percent, preferably between 0.5 and 25 weight percent, based upon the total weight of the fluoropolymer and filler only. While to 50 weight percent of the filler may be used, when greater than 25 weight percent filler is used the apparent viscosity of invention.
  • a molded sheet was made by first preparing a molding composition of a fluoropolymer and a filler and then molding the composition into a flat sheet.
  • the fluoropolymer used was perfluoroalkoxy fluoropolymer (PFA) type 5026A, available from DuPont.
  • the fillers used were Iriodin 120 mica filler available from Merck and A125 ceramic powder available from Baikowski Chimie.
  • the mica filler had a particle size of 5-20 micrometers and an Aspect ratio of 10 to 200.
  • the ceramic powder had a round particle morphology of average diameter (D 50 ) of 5 micrometers.
  • the molding composition was molded into a flat sheet having a nominal thickness of 0.3 mm.
  • the flat sheets were tested for the oxygen transmission rate using air according to ASTM method F 1307-90. The results are summarized in Table 1 below.
  • Table 1 show that the molded sheets made from the compositions which included a mica filler had a dramatic increase in the oxygen permeation rate compared to the fluoropolymer alone. Further, the use of ceramic powder actually increased the oxygen transmission rate in the molded sheets. Molded sheets were made as in the previous Examples, except that the nominal thickness of the molded sheets was 0.4 mm. The types of fillers used are indicated below.
  • the larger thicknesses in these examples represent thicknesses commonly found in fluoropolymer liners used to protect other materials from harsh chemicals.
  • pure oxygen instead of the air used in the previous examples, was used at a temperature of 90C.
  • a Siemens DiffuPerm analytical instrument was used to measure the oxygen permeability.
  • EXAMPLE 23 In this example a molded plaque was made by transfer molding from a composition of 93 weight percent PFA fluoropolymer type 350, available from DuPont with 5% by weight mica type Iriodin 504, available from Merck, with an average particle size of 10 to 60 micrometers and an average Aspect ratio of 20 to 600, and 2% by weight talc type Micro-Talc IT Extra, available from Norwegian Talc, with an average particle size of approximately 5 micrometers and an average aspect ratio of approximately 50.
  • the molded plaque, having a nominal thickness of 3mm was subjected to a steam/cold water cycle according to ASTM test method F-423. No blistering, delamination or any other defect was present in the molded plaque after the test.
  • EXAMPLE 24 A composition of PTFE fluoropolymer, type 669-N, available from
  • PTFE paste extrusion was extruded by a process known in the art as PTFE paste extrusion to make a tube having a nominal outside diameter of 80mm and a nominal wall thickness of 2mm. These are common dimensions for fluoropolymer liners used in the chemical industry. An appropriate sample was cut from this liner and was subjected to the steam/cold water cycling test ASTM F- 423. No blistering, delamination or any defect was present in the tube sample.
  • COMPARATIVE EXAMPLE 25 A tube was made as in Example 24, except that it was 100 weight percent PTFE, type 669-N. The tube was subjected tot the steam/cold water cycling test ASTM F-423. Small blisters and light signs of delamination were present.
  • COMPARATIVE EXAMPLE 26 AND EXAMPLES 27-28 Fluoropolymer molded sheets are produced in the same manner as in Examples 5 and 6. Sheets that are 0.4 mm thick are tested with a carbon steel backing in an Atlas cell with dilute hydrochloric acid (0.05M) in deionized water at 98C. In Examples 27 and 28, the sheets are laid freely against the backing. In Example 28, the sheet is melt bonded in a hot press so that the sheet is strongly secured against the steel plate.
  • Examples 26-27 show that molded sheets that are produced in accordance with this invention protect a metal backing from corrosion and blistering. This occurs whether the molded sheet is laid freely against the backing or is adhered to the backing. Another beneficial aspect is that the improved permeability of the molded sheet prevents deterioration of the bonding structure or bonding agent that secures the molded sheet to the backing, and therefore there is a greatly decreased likelihood that the molded sheet will separate from the backing. to the present invention exhibit improved permeability and resistance to blistering and delamination.
  • additives known in the art may be added to the inventive composition.
  • additives include pigments, thermally and/or conductive fillers such as carbon, reinforcements such as glass or carbon fibers, light transmittance blockers such as titanium dioxide, or mixtures thereof.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/US1998/016296 1997-08-07 1998-08-06 Fluoropolymer articles having improved impermeability to fluids WO1999007781A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP98938389A EP1002010A1 (en) 1997-08-07 1998-08-06 Fluoropolymer articles having improved impermeability to fluids
JP2000506272A JP2001512768A (ja) 1997-08-07 1998-08-06 改良された流体不透過性を有するフルオロ重合体物品

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US90827097A 1997-08-07 1997-08-07
US08/908,270 1997-08-07

Publications (1)

Publication Number Publication Date
WO1999007781A1 true WO1999007781A1 (en) 1999-02-18

Family

ID=25425486

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/016296 WO1999007781A1 (en) 1997-08-07 1998-08-06 Fluoropolymer articles having improved impermeability to fluids

Country Status (3)

Country Link
EP (1) EP1002010A1 (ja)
JP (1) JP2001512768A (ja)
WO (1) WO1999007781A1 (ja)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1384750A1 (en) * 2002-06-04 2004-01-28 Solvay Solexis S.p.A. Fluoropolymer compositions containing inorganic nanometric particles
US20150330538A1 (en) * 2014-05-16 2015-11-19 Eaton Corporation Aerospace hose having epdm rubber layer
CN111793309A (zh) * 2019-04-05 2020-10-20 哈金森公司 橡胶组合物,其制备方法,结合它的燃料胶管和燃料供给回路

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050098945A (ko) * 2003-02-19 2005-10-12 듀폰-미쯔이 플루오로케미칼 가부시끼가이샤 불소 수지 복합체 조성물

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5925833A (ja) * 1982-08-04 1984-02-09 Du Pont Mitsui Fluorochem Co Ltd 溶融加工性含フツ素樹脂成形用組成物
JPS62148532A (ja) * 1985-12-23 1987-07-02 Sumitomo Bakelite Co Ltd ガスバリア性透明プラスチツクフイルム及びその製造方法
JPS63301245A (ja) * 1987-05-29 1988-12-08 Kuraray Co Ltd ゴム組成物
JPH0341149A (ja) * 1989-07-10 1991-02-21 Mitsubishi Rayon Co Ltd 絹雲母含有ポリエステル組成物及びその製造法
JPH05186606A (ja) * 1992-01-08 1993-07-27 Tokai Rubber Ind Ltd 自動車用ホース

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5925833A (ja) * 1982-08-04 1984-02-09 Du Pont Mitsui Fluorochem Co Ltd 溶融加工性含フツ素樹脂成形用組成物
JPS62148532A (ja) * 1985-12-23 1987-07-02 Sumitomo Bakelite Co Ltd ガスバリア性透明プラスチツクフイルム及びその製造方法
JPS63301245A (ja) * 1987-05-29 1988-12-08 Kuraray Co Ltd ゴム組成物
JPH0341149A (ja) * 1989-07-10 1991-02-21 Mitsubishi Rayon Co Ltd 絹雲母含有ポリエステル組成物及びその製造法
JPH05186606A (ja) * 1992-01-08 1993-07-27 Tokai Rubber Ind Ltd 自動車用ホース

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8412, Derwent World Patents Index; Class A14, AN 84-071652, XP002080323 *
DATABASE WPI Section Ch Week 8732, Derwent World Patents Index; Class A60, AN 87-224381, XP002080319 *
DATABASE WPI Section Ch Week 8904, Derwent World Patents Index; Class A12, AN 89-027831, XP002080322 *
DATABASE WPI Section Ch Week 9114, Derwent World Patents Index; Class A23, AN 91-097785, XP002080321 *
DATABASE WPI Section Ch Week 9334, Derwent World Patents Index; Class A14, AN 93-269879, XP002080320 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1384750A1 (en) * 2002-06-04 2004-01-28 Solvay Solexis S.p.A. Fluoropolymer compositions containing inorganic nanometric particles
US7745513B2 (en) 2002-06-04 2010-06-29 Solvay Solexis S.P.A. Fluoropolymer compositions and inorganic nanometric particles
US20150330538A1 (en) * 2014-05-16 2015-11-19 Eaton Corporation Aerospace hose having epdm rubber layer
CN111793309A (zh) * 2019-04-05 2020-10-20 哈金森公司 橡胶组合物,其制备方法,结合它的燃料胶管和燃料供给回路
US11932755B2 (en) 2019-04-05 2024-03-19 Hutchinson Rubber composition, method for preparing same, fuel hose and fuel feed circuit incorporating same
CN111793309B (zh) * 2019-04-05 2024-03-19 哈金森公司 橡胶组合物,其制备方法,结合它的燃料胶管和燃料供给回路

Also Published As

Publication number Publication date
EP1002010A1 (en) 2000-05-24
JP2001512768A (ja) 2001-08-28

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