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WO1996026980A1 - Compositions de resines fluorees thermoplastiques et articles moules produits avec ces resines - Google Patents

Compositions de resines fluorees thermoplastiques et articles moules produits avec ces resines Download PDF

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Publication number
WO1996026980A1
WO1996026980A1 PCT/EP1996/000845 EP9600845W WO9626980A1 WO 1996026980 A1 WO1996026980 A1 WO 1996026980A1 EP 9600845 W EP9600845 W EP 9600845W WO 9626980 A1 WO9626980 A1 WO 9626980A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
fluoro resin
moulded articles
copolymer
thermoplastic fluoro
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/EP1996/000845
Other languages
English (en)
Inventor
Takatoshi Kuratsuji
Yoshiyuki Miyaki
Kazuyoshi Ohashi
Jérôme MAILLET
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.)
Arkema France SA
Original Assignee
Elf Atochem SA
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 Elf Atochem SA filed Critical Elf Atochem SA
Priority to AU48317/96A priority Critical patent/AU4831796A/en
Publication of WO1996026980A1 publication Critical patent/WO1996026980A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
    • 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
    • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • thermoplastic fluoro resin compositions and moulded articles produced therefrom in particular to thermoplastic fluoro resin compositions and moulded articles improved in melt-mouldability which permit high-speed extrusion and high-shear molding.
  • Thermoplastic fluoro resin possessing high weather- and chemical resistance is utilized in many fields such as paint, electrical or electronics parts, steel pipe liner, materials for chemical plant and stain- and weather-resistant film.
  • This resin is difficult to combine with other material due to its poor adhesiveness and its improvement is limited. Fibres of this resin are difficult to stretch due to their viscosity and crystallinity and their knot strength is low.
  • the use of a polymer possessing a high degree of polymerization which is indispensable to guarantee the desired properties of moulded articles, results in increasing its viscosity, so that such polymer cannot be extruded at high speed or through a small orifice of narrow cross-section.
  • the melt temperature is raised so as to lower the viscosity, the polymer decomposes in dead spaces of the extruder, resulting in defects in the moulded articles.
  • thermoplastic fluoro resin composition comprising (A) polyvinylidene fluoride and (B) vinylidene fluoride copolymer containing, as comonomers, 5 to 50 parts by weight of tetrafluoroethylene and 0 to 30 parts by weight of third monomers, the total proportion of the comonomers being 5 to 50 % by weight, the ratio of (A/B) being 95/5 to 40/60, preferably the logarithmic viscosity number (inherent viscosity: ⁇ inh) of polyvinylidene fluoride (A) being 0.6 to 1.8 dl/g and the logarithmic viscosity number of vinylidene fluoride VF2 copolymer (B) being 0.3 to 1.5 dl/g, the logarithmic viscosity number of PVDF (A) being higher than the
  • polyvinylidene fluoride (A) (hereinafter, polyvinylidene fluoride is expressed by PVDF) comprises mainly units or sequences of vinylidene fluoride VF2 but includes copolymer containing less than 3 % by weight of other comonomers such as trifluoroethylene (VF3), chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), hexafluoropropylene (HFP) and perfluoroalkyl vinyl ethers.
  • VF3 trifluoroethylene
  • CTFE chlorotrifluoroethylene
  • VF vinyl fluoride
  • HFP hexafluoropropylene
  • perfluoroalkyl vinyl ethers perfluoroalkyl vinyl ethers
  • the vinylidene fluoride copolymer (B) also called “copolymer VF2 (B)” is a copolymer of VF2 and tetrafluoroethylene (TFE), the proportion of TFE being 5 to 50 % by weight, preferably 10 to 40 % by weight.
  • the copolymer VF2 (B) may contain other comonomers.
  • the proportion of other comonomers is 0 to 30 % by weight, preferably 0 to 25 % by weight and the total proportion of comonomers (TFE and third monomer(s)) is 5 to 50 % by weight, preferably higher than 20 % by weight but lower than to 45 % by weight.
  • the comonomers may be VF3, CTFE, VF, HFP, perfluoroalkyl vinyl ether and/or ethylene.
  • TFE is an indispensable component in the copolymer.
  • high ⁇ speed moulding or high-shear moulding which is another object of the present invention, cannot be improved by an other comonomer such as HFP and CFE alone
  • HFP and CFE alone
  • thermal stability is assured if TFE is incorporated in the copolymer when the third comonomer(s) is (are) incorporated so as to lower the melting point.
  • the weight ratio of (A/B) is 95/5 to 40/60, preferably 95/5 to 60/40. and depends on application.
  • the degrees of polymerization according to the present invention are such that the logarithmic viscosity number of PVDF (A) is 0.6 to 1.8 dl/g and the logarithmic viscosity number of copolymer VF2 (B) is 0.3 to 1.5 dl/g.
  • the logarithmic viscosity number ( ⁇ inh) is measured in N.N'-dimethylformamide solution at a polymer concentration of 0.4 g/dl.
  • the composition according to the present invention can be extruded directly from a dry blend of components or from two separate components.
  • Kneading and extrusion can be done by any known technique such as a Banbury mixer, rubber rolls and a single- or twin-screw extruder.
  • the resin composition is melt-kneaded at 100 to 300 °C, preferably 150 to 260 °C.
  • composition according to the present invention may contain known additives such as antioxidants, antipyrolysis agents, UV absorbents, antihydrolysis agents, colorants (dyes, pigments), antistatic agents, electrically conductive agents, crystal nucleating or improving agents, plasticizers, slip agents, lubricants, mould release agents, flame retardants, reinforcements, fillers, adhesives and tackifiers.
  • additives such as antioxidants, antipyrolysis agents, UV absorbents, antihydrolysis agents, colorants (dyes, pigments), antistatic agents, electrically conductive agents, crystal nucleating or improving agents, plasticizers, slip agents, lubricants, mould release agents, flame retardants, reinforcements, fillers, adhesives and tackifiers.
  • the articles moulded from the composition according to the present invention are not limited to special products but include those produced by injection, moulding, extrusion, rotational moulding and compression moulding, such as films, sheets, tubes and pipes.
  • the composition according to the present invention is not limited to injection and extrusion moulding in which the composition is subjected to high shear but is also useful as material for rotational moulding or for paint or coating.
  • Thermal decomposition of the composition according to the present invention does not occur under high shear even if the composition is heated for a long time, so that the products moulded therefrom possess improved heat-resistance and flexibility.
  • PVDF-A2 100 % PVDF homopolymer
  • ⁇ inh 0.8 PVDF-B0 100 % PVDF homopolymer
  • ⁇ inh 0.3 copolymer VF2-B1 : copolymer of VF2 and TFE (30 %)
  • ⁇ inh 0.6 copolymer VF2-B2: copolymer of VF2, TFE (20 %) and HFP (15 %)
  • ⁇ inh 0.6 copolymer VF2-C2: copolymer of VF2 and CTFE (30 %)
  • ⁇ inh 0.7
  • PVDF-A1 and copolymer VF2-B2 were blended in a proportion of 80/20 an the resulting blend was extruded from an extruder equipped with a flat die having slit of 500 ⁇ m and a width of 100 mm to produce a sheet.
  • the resin temperature wa 280 °C and the shear rate was about 1 ,000/s and the head pressure was 4 MPa
  • the resulting sheet showed good appearance. The same sheet was obtaine continuously even if the screw rotation speed was increased so that the hea pressure was raised to 7 MPa. Comparative Example 6
  • PVDF-A2 and copolymer VF2-B2 were blended in a proportion of 90/10.
  • a test sample 80 x 10 x 4 mm was produced from the resulting material by injection moulding.
  • the flexural modulus of this sample was measured according to ISO 178 and was 1 ,000 MPa.
  • compositions according to the present invention show neither decomposition nor fluctuation in high-shear and high-speed melt moulding and the moulded articles obtained therefrom show improved heat resistance and flexibility.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)

Abstract

La présente invention a pour objet une composition de résine fluorée thermoplastique dont l'aptitude au moulage à l'état fondu, avec un effort de cisaillement important et à une vitesse élevée, est améliorée, de même que sa flexibilité et sa résistance à la chaleur. L'invention porte aussi sur des articles moulés obtenus avec ces résines. La composition de résine fluorée thermoplastique comprend (A) du fluorure de polyvinylidène et (B) un copolymère de fluorure de vinylidène comportant, comme comonomères, de 5 à 50 parties en poids de tétrafluoréthylène et de 0 à 30 parties en poids de troisièmes monomères. La proportion totale de comonomères est de 5 à 50 % en poids, le rapport pondéral de (A/B) est de 95/5 à 40/60. L'invention concerne aussi des articles moulés obtenus avec ces résines.
PCT/EP1996/000845 1995-03-01 1996-02-28 Compositions de resines fluorees thermoplastiques et articles moules produits avec ces resines Ceased WO1996026980A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU48317/96A AU4831796A (en) 1995-03-01 1996-02-28 Thermoplastic fluoro resin compositions and moulded articles produced therefrom

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP4176695A JPH08239537A (ja) 1995-03-01 1995-03-01 熱可塑性フッ素系樹脂組成物、及びそれから製造された成形品
JP7/41766 1995-03-01

Publications (1)

Publication Number Publication Date
WO1996026980A1 true WO1996026980A1 (fr) 1996-09-06

Family

ID=12617532

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/000845 Ceased WO1996026980A1 (fr) 1995-03-01 1996-02-28 Compositions de resines fluorees thermoplastiques et articles moules produits avec ces resines

Country Status (3)

Country Link
JP (1) JPH08239537A (fr)
AU (1) AU4831796A (fr)
WO (1) WO1996026980A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1342752A1 (fr) * 2002-03-07 2003-09-10 Atofina Compositions à base de polyfluorure de vinylidène
FR2877009A1 (fr) * 2004-10-21 2006-04-28 Solvay Composition polymere a base de pvdf homopolymere et de copolymere thermoplastique fluore
EP1715087A1 (fr) * 2005-04-20 2006-10-25 Kureha Corporation Monofilament en polyfluorure de vinylidène et procédé pour sa fabrication
EP1454954A4 (fr) * 2001-10-15 2006-11-15 Kureha Corp Composition polymere de revetement de fils de fer
US8252398B2 (en) 2007-12-27 2012-08-28 Kureha Corporation Adhesive vinylidene fluoride resin sheet
WO2013128142A1 (fr) * 2012-03-01 2013-09-06 Arkema France Composition de polyfluorure de vinylidène
FR2999590A1 (fr) * 2012-12-13 2014-06-20 Arkema France Formulation d'une membrane fluoree poreuse mise en œuvre par un procede d'etirage
US20150041118A1 (en) * 2012-03-01 2015-02-12 Alain Chalumeau Method for Installing a self-supporting tower for Extracting Hydrocarbons
CN107922702A (zh) * 2015-07-09 2018-04-17 阿科玛股份有限公司 用于制备高光泽涂料的基于半结晶氟化聚合物和成核剂的组合物

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11152366A (ja) * 1997-11-19 1999-06-08 Asahi Chem Ind Co Ltd フッ化ビニリデン系樹脂製多孔膜
JP6090683B1 (ja) * 2016-11-09 2017-03-08 株式会社デュエル ポリフッ化ビニリデン系モノフィラメント及びポリフッ化ビニリデン系モノフィラメントの製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4302556A (en) * 1978-08-24 1981-11-24 Kureha Kagaku Kogyo Kabushiki Kaisha Polyvinylidene fluoride filaments
JPS616307A (ja) * 1984-06-18 1986-01-13 Unitika Ltd ポリ弗化ビニリデン系モノフイラメント
EP0282243A2 (fr) * 1987-03-06 1988-09-14 Kureha Kagaku Kogyo Kabushiki Kaisha Filaments abrasifs et leur procédé de fabrication
JPH01201516A (ja) * 1988-02-05 1989-08-14 Central Glass Co Ltd ポリフッ化ビニリデン系樹脂モノフィラメント

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4302556A (en) * 1978-08-24 1981-11-24 Kureha Kagaku Kogyo Kabushiki Kaisha Polyvinylidene fluoride filaments
JPS616307A (ja) * 1984-06-18 1986-01-13 Unitika Ltd ポリ弗化ビニリデン系モノフイラメント
EP0282243A2 (fr) * 1987-03-06 1988-09-14 Kureha Kagaku Kogyo Kabushiki Kaisha Filaments abrasifs et leur procédé de fabrication
JPH01201516A (ja) * 1988-02-05 1989-08-14 Central Glass Co Ltd ポリフッ化ビニリデン系樹脂モノフィラメント

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 112, no. 10, 5 March 1990, Columbus, Ohio, US; abstract no. 79310, XP002003549 *
DATABASE WPI Section Ch Week 8608, Derwent World Patents Index; Class A14, AN 86-052457, XP002003550 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1454954A4 (fr) * 2001-10-15 2006-11-15 Kureha Corp Composition polymere de revetement de fils de fer
EP1342752A1 (fr) * 2002-03-07 2003-09-10 Atofina Compositions à base de polyfluorure de vinylidène
RU2249021C2 (ru) * 2002-03-07 2005-03-27 Атофина Композиции на основе поливинилиденфторида
FR2877009A1 (fr) * 2004-10-21 2006-04-28 Solvay Composition polymere a base de pvdf homopolymere et de copolymere thermoplastique fluore
WO2006045753A1 (fr) * 2004-10-21 2006-05-04 Solvay (Societe Anonyme) Composition polymere a base d'un homopolymere pvdf et d'un fluorocopolymere thermoplastique
US8609756B2 (en) 2004-10-21 2013-12-17 Solvay (Societe Anonyme) Polymeric composition based on a PVDF homopolymer and a thermoplastic fluorocopolymer
EP1715087A1 (fr) * 2005-04-20 2006-10-25 Kureha Corporation Monofilament en polyfluorure de vinylidène et procédé pour sa fabrication
US8252398B2 (en) 2007-12-27 2012-08-28 Kureha Corporation Adhesive vinylidene fluoride resin sheet
FR2987624A1 (fr) * 2012-03-01 2013-09-06 Arkema France Composition polymerique fluoree
WO2013128142A1 (fr) * 2012-03-01 2013-09-06 Arkema France Composition de polyfluorure de vinylidène
CN104144980A (zh) * 2012-03-01 2014-11-12 阿克马法国公司 聚偏氟乙烯组合物
US20150041118A1 (en) * 2012-03-01 2015-02-12 Alain Chalumeau Method for Installing a self-supporting tower for Extracting Hydrocarbons
US10301462B2 (en) 2012-03-01 2019-05-28 Arkema France Polyvinylidene fluoride composition
US11199057B2 (en) * 2012-03-01 2021-12-14 Technip France High-strength flexible tubular structure for oil exploitation
FR2999590A1 (fr) * 2012-12-13 2014-06-20 Arkema France Formulation d'une membrane fluoree poreuse mise en œuvre par un procede d'etirage
CN107922702A (zh) * 2015-07-09 2018-04-17 阿科玛股份有限公司 用于制备高光泽涂料的基于半结晶氟化聚合物和成核剂的组合物

Also Published As

Publication number Publication date
AU4831796A (en) 1996-09-18
JPH08239537A (ja) 1996-09-17

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