[go: up one dir, main page]

EP2160444A1 - Verbundmaterial mit in einer fluorinierten polymermatrix dispergierten nanoröhrchen - Google Patents

Verbundmaterial mit in einer fluorinierten polymermatrix dispergierten nanoröhrchen

Info

Publication number
EP2160444A1
EP2160444A1 EP08806113A EP08806113A EP2160444A1 EP 2160444 A1 EP2160444 A1 EP 2160444A1 EP 08806113 A EP08806113 A EP 08806113A EP 08806113 A EP08806113 A EP 08806113A EP 2160444 A1 EP2160444 A1 EP 2160444A1
Authority
EP
European Patent Office
Prior art keywords
nanotubes
copolymer
material according
fluorinated
homo
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
EP08806113A
Other languages
English (en)
French (fr)
Inventor
Gilles Hochstetter
Michael Werth
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
Arkema France 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 Arkema France SA filed Critical Arkema France SA
Publication of EP2160444A1 publication Critical patent/EP2160444A1/de
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/06—Hoses, i.e. flexible pipes made of rubber or flexible plastics with homogeneous wall
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article

Definitions

  • Composite material comprising nanotubes dispersed in a fluorinated polymeric matrix
  • the present invention relates to a composite material comprising nanotubes of at least one chemical element chosen from the elements of columns IHa, IVa and Va of the periodic table, dispersed in a polymer matrix comprising (a) at least one fluorinated homo- or copolymer and (b) at least one fluorinated homo- or copolymer grafted with at least one caiboxylic polar function.
  • this composite material also relates to the uses of this composite material, as well as the use of at least one fluorinated homo- or copolymer grafted with at least one polar carboxylic function to increase the tensile strength of a composite material comprising the aforementioned nanotubes dispersed in a fluorinated polymeric matrix.
  • fluoropolymer-based monomers such as polyvinylidene fluoride. These materials, however, do not always provide sufficient life at high temperatures, especially when subjected to stress.
  • fluoropolymers have compatibility problems with the carbon nanotubes used to strengthen them.
  • the interfaces between the fluoropolymer and the nanotubes therefore lack cohesion, which leads to the appearance of weak points at the microscopic scale when the matrix polyme ⁇ que is subject to a solicitation.
  • dispersion of the nanotubes in the fluoropolymer is not always satisfactory, which can lead to the formation of agglomerates detrimental to the desired properties po ⁇ r the final composite.
  • the subject of the present invention is thus a composite material comprising nanotubes of at least one chemical element chosen from the elements of columns IHa, IVa and Va of the periodic table, dispersed in a polyme ⁇ que matrix comprising (a) at least one homo- or fluorinated copolymer and (b) at least one fluorinated homo- or copolymer grafted with at least one polar carboxylic function.
  • It also relates to the use of at least one fluorinated homo- or copolymer grafted with at least one polar carboxylic function to increase the tensile strength of a composite material comprising ranotubes of at least one chemical element choiSx among the elements of columns IHa, IVa and Va of. periodic table, dispersed in a fluorinated polymeric matrix.
  • the composite material according to the invention comprises as first component a polymeric matrix containing at least one homo- or fluorinated copolymer, hereinafter referred to as "fluoropolymer”.
  • this fluorinated polymer comprises at least 50 mol%, and advantageously consists of monomers of formula (I):
  • X and X 1 independently denote a hydrogen or halogen atom (in particular fluorine or chlorine) or a perhalogenated alkyl radical (in particular perfluorinated).
  • X F and
  • fluoropolymers examples include:
  • PVDF poly (vinylidene fluoride)
  • TFE perfluoromethylvinyl ether
  • PMVE perfluoromethylvinyl ether
  • CFE chlorotrifluoroethylene
  • HFP hexafluoropropylene
  • the fluoropolymer is polyvinylidene fluoride (PVDF).
  • the polymeric matrix of the composite material according to the invention contains at least one fluorinated homo- or copolymer grafted with at least one polar function carbexylic, hereinafter referred to as "grafted fluoropolymer".
  • This fluorinated graft polymer is capable of being obtained by grafting at least one polar monomer carboxylic acid bearing for example at least one carboxylic acid or anhydride function on a fluorinated polymer.
  • this grafted fluoropolymer can be prepared according to a process comprising: (a) mixing, preferably in the molten state, for example by means of an extruder or a kneader, a fluoropolymer with a polar monomer bearing a carboxylic acid or anhydride function, (b) the possible transformation of this mixture into granules, powder, film or plate, (c) the irradiation of this mixture, optionally in the absence of oxygen (and, for example, in bags of polyethylene) in a dose ranging from 1 to 15 Mrad of photon or electron irradiation, to carry out the grafting of the polar monomer on the fluoropolymer, and (d) optionally the removal of the residual polar monomer not having reacted with the fluoropolymer.
  • a preparation process of this type is described in particular in application EP-I 484 346.
  • the fluorinated polymer from which the grafted fluoropolymer may be obtained may be any of the fluorinated polymers described above and in particular polyvinylidene fluoride (PVDF) or the copolymers of VDF and HFP containing preferably at least 50% by weight of VDF units.
  • PVDF polyvinylidene fluoride
  • unsaturated mono- and di-carboxylic acids having from 2 to 20 carbon atoms, and in particular from 4 to 10 carbon atoms, such as acrylic, methacrylic acids, maleic, fumaric, itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1,2-dicarboxylic, 4-methyl-cyclohex-4-ene-1,2-dicarboxylic, bicyclo (2,2,1) hept-5- ene-2,3-dicarboxylic, x-methylbicyclo (2,2,1) hept-5-ene-2,3-dicarboxylic and undecylenic, and their anhydrides.
  • the grafted fluoropolymer is therefore capable of being obtained from at least one of these monomers. It is preferred that this fluoropolymer is grafted with maleic anhydride.
  • Such a grafted fluoropolymer is especially available from Arkema under the trade name Kynar ° ADX 710, 711, 720 or 721.
  • the weight proportion of the fluoropolymer to the polar monomer used in the manufacture of the grafted fluoropolymer is usually 90:10 to 99.9: 0.1.
  • the grafted fluoropolymer may represent from 5 to 99% by weight and preferably from 10 to 50% by weight, relative to the weight of the polymer matrix.
  • the fluoropolymer and the grafted fluoropolymer may be mixed either in powder form or by compounding followed by granulation and grinding of the granules.
  • the polymer matrix used according to the invention may also contain various adjuvants, such as plasticizers, anti-oxygen stabilizers, light stabilizers, colorants, agents and the like. anti-shock, antistatic agents, flame retardants, lubricants, and mixtures thereof.
  • the composite material according to the invention contains nanotubes of at least one chemical element chosen from the elements of the columns IHa, IVa and Va of the periodic table.
  • These nanotubes may be based on carbon, boron, phosphorus and / or nitrogen (borides, nitrides, carbides, phosphides) and for example consisting of carbon nitride, boron nitride, boron carbide, phosphide boron, phosphorus nitride and carbon boronitride.
  • CNTs C ⁇ rbono nanotubes
  • the nanotubes that can be used according to the invention can be single-walled, double-walled or multi-walled.
  • the double-walled nanotubes can in particular be prepared as described by FLAHAUT et al in Chem. Corn. (2003), 1442.
  • the multi-walled nanotubes may themselves be prepared as described in WO 03/02456.
  • the nanotubes usually have a mean diameter ranging from 0.1 to 200 nm, preferably from 0.1 to 100 nm, more preferably from 0.4 to 50 nm and better still from 1 to 30 nm and advantageously a length of from 0 to 100 nm. , 1 to 10 ⁇ m. Their length / diameter ratio is advantageously greater than 10 and most often greater than 100. Specific surface area is for example between 100 and 300 m 2 / g and their apparent density may especially be between 0.05 and 0.5 g / cm 3 and more preferably between 0.1 and 0.2 g / cm J.
  • the Muitiparois nanotubes may for example comprise from 5 to 15 sheets and more preferably from 7 to 10 sheets.
  • crude carbon nanotubes is especially commercially available from Arkema under the trade name Graphistrength® ® C100.
  • nanotubes can be purified and / or treated (for example oxidized) and / or milled and / or functionalized before being used in the process according to the invention.
  • the grinding of the nanotubes may in particular be elfecluted cold or hot and be carried out according to known techniques used in devices such as ball mills, hammers, grinders, knives, gas jet or any other grinding system likely to reduce the size of the entangled network of nanotubes. It is preferred that this grinding step is performed according to a gas jet grinding technique and in particular in an air jet mill.
  • the purification of the crude or milled nanotubes can be carried out by washing with a sulfuric acid solution, so as to rid them of any residual mineral and metallic impurities originating from their preparation process.
  • the weight ratio of nanotubes to sulfuric acid may especially be between 1: 2 and 1: 3.
  • the purification operation may also be carried out at a temperature ranging from 90 to 120 ° C., for example for a period of 5 to 10 hours. This operation may advantageously be followed by rinsing steps with water and drying the purified nanotubes.
  • the oxidation of the nanotubes is advantageously carried out by putting them in contact with a solution of sodium hypochlorite containing from 0.5 to 15% by weight of NaOCl and preferably from 1 to 10% by weight of NaOCl, for example in a weight ratio of nanotubes to sodium hypochlorite ranging from 1: 0.1 to 1: 1.
  • the oxidation is advantageously carried out at a temperature of less than 60 ° C. and preferably at ambient temperature, for a duration ranging from a few minutes to 24 hours. This oxidation operation can advantageously be followed by filtration and / or centrifugation steps, washing and drying of the oxidized nanotubes.
  • the functionalization of the nanotubes can be carried out by grafting reactive units such as vinyl monomers on the surface of the nanotubes.
  • the constituent material of the nanotubes is used as a radical polymerization initiator after having been subjected to a heat treatment at more than 900 0 C, in an anhydrous medium and oxygen-free, which is intended to eliminate the oxygenated groups from its surface. It is thus possible to polymerize methyl methacrylate or hydroxyethyl methacrylate on the surface of carbon nanotubes in order, in particular, to facilitate their dispersion in the polymer matrix.
  • Crude nanotubes, optionally milled, that is to say nanotubes that are not oxidized, purified or functionalized and have undergone no other chemical treatment, are preferably used in the present invention.
  • the nanotubes may represent from 0.5 to 30%, preferably from 0.5 to 10 and even more preferably from 1 to 5% of the total weight of the fluoropolymer and grafted fluoropolymer mixture.
  • the nanotubes and the polymer matrix are compounded by conventional devices such as twin-screw extruders or co-kneaders.
  • polymer granules (s) are typically melt blended with the nanotubes.
  • the nanotubes may be dispersed by any suitable means in the polymeric matrix in solution in a solvent.
  • the dispersion can be improved, according to an advantageous embodiment of the present invention, by the use of particular dispersing systems or dispersing agents.
  • the method of manufacturing the composite material according to the invention may comprise a step of dispersing the nanotubes in the polymer matrix by means of ultrasound or a rotor-stator system.
  • a rotor-stator system is sold by the company SILVERSON under the trademark Silverson * L4RT.
  • Another type of rotor-stator system is marketed by the company IKA-WERKE under the name Corrrectciale Ultra-Turrax *.
  • rotor-stator systems still consist of coil mills, deflocculating turbines and high-shear mixers of the rotor-stator type, such as devices sold by the company IKA-WERKE or the company ADMIX.
  • the dispersing agents may in particular be chosen from plasticizers which may themselves be chosen from the group consisting of alkyl esters of phosphates and of hydroxybenzoic acid (the alkyl group of which, preferably linear, contains from 1 to 20 carbon atoms) of lau ⁇ que acid, azelaic acid or pelargonic acid, phthalates, in particular dialkyl or alkylaryl, in particular alkylbenzyl, linear or branched alkyl groups, independently containing from 1 to 12 carbon atoms, adipates, in particular dialkyls, sebacates, in particular dialkyls and in particular dioctyls, in particular in the case where the polymeric matrix contains a fluoropolymer, benzoates, glycols or glycerol, dibenzyl ethers, ⁇ -chloroparaffins, propylene oxide, and sulfonamides, in particular in the case where the Polyme ⁇ q ⁇ Patrice contains a polyamide, and in particular
  • the dispersing agent may be a copolymer comprising at least one hydrophilic anionic monomer and at least one monomer including at least one aromatic ring, such as the copolymers described in document FR-2 766 106, the weight ratio of the In this case, the dispersing agent with nanotubes preferably ranges from 0.6: 1 to 1.9: 1.
  • the dispersing agent may be a vinylpyrrolidone homo- or copolymer, the ratio by weight of the nanotubes to the dispersing agent preferably ranging from 0.1 to less than 2.
  • the dispersion of the nanotubes in the polymer matrix can be improved by putting them in contact with at least one compound A which can be chosen from among various polymers, monomers, plasticizers, emulsifiers, coupling agents and / or carboxylic acids, the two components (nanotubes and compound A) being mixed in the solid state or the mixture being in pulverulent form, optionally after removal of one or more solvents.
  • the composite material as described above is of interest in various applications.
  • the present invention also relates to the use of this composite material for making hollow parts such as tubes, sheaths or connectors intended in particular for containing or transporting hot fluids and possibly under pressure and / or corrosive, and in particular pipes transporting hydrocarbons such as offshore hose sheaths; fluid transport pipes produced or used in the chemical industry; or injected fittings of pressurized pipelines.
  • the pipes and hollow parts above can for example be manufactured by extrusion or injection of the composite according to the invention.
  • the composite material according to the invention can constitute the inner layer of a multilayer pipe, in contact with the fluid to be contained or transported, the other layers, external and possibly intermediate, being constituted by other materials such as polyolefin or polyamide.
  • the composite material according to the invention preferably comprises, as fluoropolymer, a fluoropolymer having a melting point of between 14 ° C. and 17 ° C., preferably between 160 ° C. and 17O 0 C, and for example around 165 0 C, to obtain a good resistance to hot creep and blistering in the event of rapid decompression due to production stoppage,
  • D3835 advantageously of extrusion grade, preferably plasticized and impact-reinforced by core-shells systems to obtain in particular good cold strength (impact resistance, fatigue resistance).
  • a hot fluid typically 90 ° C.
  • a fluoropolymer of VDF preferably extrusion grade (viscous) for the manufacture of tubes or injection grade (fluid) for the manufacture of fittings.
  • FIG. 1 illustrates the tensile strength (stress-dependent deformation) of specimens of composite materials containing or not a grafted fluoropolymer
  • FIG. 2 illustrates the resistance to hot creep of these same test pieces.
  • a homopolymer of VDF was mixed (Rynar 3710 supplied by Arkema) in solution in DMF (dimethylformamide) with a fluoropolymer (Kynar 710 v) grafted with maleic anhydride, in a weight proportion of the PVDF fluoropolymer grafted 75:25.
  • Carbon nanotubes (CNTs) (Graphistrength '3 ClOO) were then added to this mixture in a proportion of 2.5% by weight based on the weight of the polymer blend.
  • test piece was made from this compression mixture of powders obtained after evaporation of the solvent and subjected to a tensile test at 23 ° C according to ISO 527 under the following conditions: IBA; 25 mm / min.
  • the test consists of imposing a constant tensile force on the tested material and measuring the evolution of the resulting deformation over time. For a given force, the greater the creep resistance of the material, the lower the deformation over time. This force is expressed in stress, by bringing the force back to the initial section of the specimen, so as to overcome the effect of the geometry of the specimen used.
  • This specimen is typically an ISO 529 type tensile specimen.
  • Deformation is measured by means of a displacement sensor (typically of the LVDT type) attached to the barrel of the tensile specimen and the recording of the deformation over time. is done by computer acquisition, at a typically logarithmic frequency to account for the slowdown of the process over time and not to unnecessarily saturate the acquisition system.
  • the test machine used may be a dynamometer such as those used for standard tensile tests, provided that it is possible to enslave correctly the moving system of the moving crosshead of the machine to which the test specimen is hung in order to be able to work by imposing a constant force over time. This imposes a continuous and regular movement of the traverse of the machine, in order to compensate for the elongation of the specimen.
  • Another, simpler system may be used, which is to load the specimen with a dead weight.
  • the CNTs greatly increase the creep resistance of the fluorinated polymer matrix 130 n C. Incorporation of a grafted fluoropolymer does not alter the effectiveness hot CNTs.
  • the addition of the grafted fluoropolymer makes it possible to preserve or even improve the mechanical properties of the fluoropolymer at ambient temperature, without losing the advantageous properties imparted by the nanotubes to the fluoropolymer when hot.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP08806113A 2007-06-27 2008-06-27 Verbundmaterial mit in einer fluorinierten polymermatrix dispergierten nanoröhrchen Ceased EP2160444A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0704618A FR2918067B1 (fr) 2007-06-27 2007-06-27 Materiau composite comprenant des nanotubes disperses dans une matrice polymerique fluroree.
PCT/FR2008/051185 WO2009007615A1 (fr) 2007-06-27 2008-06-27 Matériau composite comprenant des nanotubes dispersés dans une matrice polymérique fluorée

Publications (1)

Publication Number Publication Date
EP2160444A1 true EP2160444A1 (de) 2010-03-10

Family

ID=39032308

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08806113A Ceased EP2160444A1 (de) 2007-06-27 2008-06-27 Verbundmaterial mit in einer fluorinierten polymermatrix dispergierten nanoröhrchen

Country Status (8)

Country Link
US (1) US20100189946A1 (de)
EP (1) EP2160444A1 (de)
JP (1) JP2010531380A (de)
KR (1) KR20100036267A (de)
CN (1) CN101688039B (de)
BR (1) BRPI0812976A2 (de)
FR (1) FR2918067B1 (de)
WO (1) WO2009007615A1 (de)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2918082B1 (fr) * 2007-06-27 2011-07-01 Arkema France Procede d'impregnation de fibres continues par une matrice polymerique composite renfermant un polymere fluore greffe.
FR2956183B1 (fr) * 2010-02-09 2012-03-16 Technip France Conduite flexible sous-marine comprenant une couche comprenant une resine polymere comprenant des nanoparticules de titane modifiees en surface
FR2968060B1 (fr) * 2010-11-25 2013-06-21 Technip France Conduite flexible sous marine comprenant une couche comprenant une resine polymere comprenant des nanotubes alumino- ou magnesiosilicate
GB201122296D0 (en) 2011-12-23 2012-02-01 Cytec Tech Corp Composite materials
KR101598250B1 (ko) 2012-06-01 2016-02-26 주식회사 엘지화학 중합체, 그의 제조방법, 이를 포함하는 조성물 및 막
CN103509298B (zh) * 2012-06-20 2015-11-25 中国科学院合肥物质科学研究院 氟塑料基微纳复合吸波材料及其制备方法
GB201322093D0 (en) 2013-12-13 2014-01-29 Cytec Ind Inc Compositive materials with electrically conductive and delamination resistant properties
GB201402264D0 (en) * 2014-02-10 2014-03-26 Wellstream Int Ltd Composite
JP6517068B2 (ja) * 2015-04-03 2019-05-22 株式会社クレハ フッ化ビニリデン系樹脂組成物および成形物ならびにそれらの製造方法
WO2019013934A1 (en) 2017-07-14 2019-01-17 Arkema Inc. HIGH STRENGTH POLYVINYLIDENE FLUORIDE REINFORCED COMPOUNDS
CN110892018B (zh) * 2017-07-14 2023-10-27 阿科玛股份有限公司 高强度聚偏二氟乙烯复合材料
KR102244303B1 (ko) * 2019-05-22 2021-04-26 연세대학교 산학협력단 마찰재 및 그 제조방법
CN112852077B (zh) * 2021-01-13 2023-10-27 业成科技（成都）有限公司 压电复合材料薄膜及其制造方法及压电式扬声器
CN115716895A (zh) * 2022-11-14 2023-02-28 上海森桓新材料科技有限公司 含氟聚合物的合成方法、含氟橡胶及其制备方法

Family Cites Families (57)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3561493A (en) * 1965-04-21 1971-02-09 Paul Maillard Composite tubes and method of manufacturing same
US4129617A (en) * 1975-06-09 1978-12-12 Japan Atomic Energy Research Institute Fluoro carbon graft copolymer and process for the production thereof
DE2559260C3 (de) * 1975-12-31 1982-04-01 Dynamit Nobel Ag, 5210 Troisdorf Verfahren zur Modifizierung von Polyvinylidenfluorid
US5093427A (en) * 1990-05-10 1992-03-03 Atochem North America, Inc. Copolymers of vinylidene fluoride and hexafluoropropylene and process for preparing the same
US5759329A (en) * 1992-01-06 1998-06-02 Pilot Industries, Inc. Fluoropolymer composite tube and method of preparation
JPH085167B2 (ja) * 1992-01-06 1996-01-24 パイロット インダストリーズ、インコーポレイテッド フルオロポリマー複合材料製チューブおよびその製造方法
US5743304A (en) * 1992-04-14 1998-04-28 Itt Corporation Multi-layer fuel and vapor tube
US5296318A (en) * 1993-03-05 1994-03-22 Bell Communications Research, Inc. Rechargeable lithium intercalation battery with hybrid polymeric electrolyte
EP0637509B1 (de) * 1993-08-03 2002-10-23 Nitta Moore Company Kraftstofftransportschlauch
EP0650987B1 (de) * 1993-10-28 2010-04-28 Asahi Glass Company Ltd. Fluorid-enthaltender Polymerklebstoff und diesen gebrauchendes Laminat
US5576106A (en) * 1994-07-28 1996-11-19 E. I. Du Pont De Nemours And Company Grafted fluoropolymer powders
US5656121A (en) * 1994-08-19 1997-08-12 Minnesota Mining And Manufacturing Company Method of making multi-layer composites having a fluoropolymer layer
US5566720A (en) * 1995-01-10 1996-10-22 Itt Corporation Elongated fuel and vapor tube having multiple layers and method of making the same
FR2731497B1 (fr) * 1995-03-10 1997-04-30 Atochem Elf Sa Tube pour transport d'eau potable
US6476125B1 (en) * 1995-08-24 2002-11-05 Asahi Glass Company Ltd. Fluorine-containing polymer alloy, and method for its preparation and method for its molding
FR2742445B1 (fr) * 1995-12-19 1998-01-16 Atochem Elf Sa Compositions antistatiques et adherentes a base de polyamide
US6176268B1 (en) * 1996-01-29 2001-01-23 Hybritech Polymers Multi-layer assembly for fluid and vapor handling and containment systems
US6263920B1 (en) * 1996-01-29 2001-07-24 Hybritech Polymers Multi-layer assembly for fluid and vapor handling and containment systems
WO1997029153A1 (fr) * 1996-02-09 1997-08-14 The Yokohama Rubber Co., Ltd. Composition thermoplastique elastomere, procede pour sa fabrication, tuyau realise avec cette composition et procede pour le fabriquer
US5993922A (en) * 1996-03-29 1999-11-30 Cryovac, Inc. Compositions and methods for selectively crosslinking films and improved film articles resulting therefrom
JPH10144571A (ja) * 1996-09-13 1998-05-29 Tdk Corp 固体型電気二重層キャパシタ
US6743876B2 (en) * 1997-02-28 2004-06-01 Atofina Chemicals, Inc. Copolymers of vinylidene fluoride and hexafluoropropylene having reduced extractable content and improved solution clarity
JPH10334948A (ja) * 1997-05-30 1998-12-18 Tdk Corp 電極、この電極を用いたリチウム２次電池および電気２重層キャパシタ
DE69835649T2 (de) * 1997-10-15 2007-09-13 E.I. Dupont De Nemours And Co., Wilmington Copolymere aus Maleinsäure oder dessen Anhydrid und fluorierten Olefinen
FR2776228B1 (fr) * 1998-03-20 2000-05-19 Solvay Corps creux multicouche en matiere thermoplastique
US6645590B1 (en) * 1998-06-28 2003-11-11 E. I. Du Pont De Nemours And Company Articles of functional fluoropolymer
JP3608406B2 (ja) * 1998-11-25 2005-01-12 日立電線株式会社 改質ふっ素樹脂成形体の製造方法
AU7448000A (en) * 1999-09-30 2001-04-30 Asahi Glass Company Limited Fuel hose
DE60010910T3 (de) * 1999-09-30 2013-02-28 Asahi Glass Co., Ltd. Kraftstoffschlauch
EP1144469B1 (de) * 1999-11-03 2010-12-22 Arkema Inc. Verfahren zur herstellung von copolymeren aus vinylidenfluorid und hexafluorpropen mit geringer kristallinität
JP4055344B2 (ja) * 1999-11-16 2008-03-05 東海ゴム工業株式会社 燃料系ホース
US6470691B1 (en) * 2000-06-13 2002-10-29 Atofina Chemicals, Inc. Fluid transport
TW592960B (en) * 2001-01-22 2004-06-21 Atofina Thermoforming multilayer film for protecting substrates, and objects obtained
US20030106602A1 (en) * 2001-12-07 2003-06-12 Hsich Henry S. Multi-layer assembly for fluid handling and containment systems
US7423084B2 (en) * 2002-02-15 2008-09-09 Dsm Ip Assets B.V. Method of producing high strength elongated products containing nanotubes
US6849314B2 (en) * 2002-04-18 2005-02-01 3M Innovative Properties Company Fluoropolymer blends and multilayer articles
EP1362870A1 (de) * 2002-05-16 2003-11-19 Atofina Mehrschichtiger Aufbau mit einem Bindemittel auf Basis eines mit einem Acrylatmonomer gepfropften Polyolefins
JP2004075848A (ja) * 2002-08-19 2004-03-11 Asahi Glass Co Ltd 導電性含フッ素共重合体組成物及びそれを用いた積層体
KR100827861B1 (ko) * 2003-05-22 2008-05-07 지벡스 퍼포먼스 머티리얼즈, 엘엘씨 나노복합물 및 이의 제조 방법
US7956108B2 (en) * 2003-05-30 2011-06-07 The Provost, Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth, Near Dublin Product
US7241817B2 (en) * 2003-06-06 2007-07-10 Arkema France Process for grafting a fluoropolymer and multilayer structures comprising this grafted polymer
ATE382469T1 (de) * 2003-12-01 2008-01-15 Arkema France Verwendung eines rohres aus gepfropftem fluorpolymer, hergestellt durch bestrahlung, für den kraftstofftransport
EP1541343B1 (de) * 2003-12-02 2008-04-30 Arkema France Verwendung einer Struktur auf Basis eines gepfropften Fluorpolymeren für die Aufbewahrung und den Transport von chemischen Produkten.
FR2864542B1 (fr) * 2003-12-29 2007-02-23 Arkema Procede de greffage de polymere fluore et structures multicouches comprenant ce polymere greffe
US7557154B2 (en) * 2004-12-23 2009-07-07 Sabic Innovative Plastics Ip B.V. Polymer compositions, method of manufacture, and articles formed therefrom
FR2870251B1 (fr) * 2004-05-11 2010-09-17 Arkema Materiaux composites a base de nanotubes de carbone et matrices polymeres et leurs procedes d'obtention
WO2006045636A1 (en) * 2004-10-19 2006-05-04 Arkema France Tube based on a vulcanized elastomer and a modified fluoropolymer
FR2876626B1 (fr) * 2004-10-19 2007-01-05 Arkema Sa Utilisation d'un polymere fluore pour proteger la surface d' un materiau inorganique contre la corrosion
WO2006129029A2 (fr) * 2005-06-02 2006-12-07 Arkema France Tube multicouche pour le transport d'eau ou de gaz
FR2886708B1 (fr) * 2005-06-02 2007-08-17 Arkema Sa Utilisation de polymere fluore modifie pour le transport d'eau ou de gaz
FR2892171B1 (fr) * 2005-10-13 2008-04-18 Arkema Sa Tube multicouche a base de polymere fluore modifie
FR2892172B1 (fr) * 2005-10-13 2007-12-14 Arkema Sa Tube multicouche a base de polymere fluore modifie
FR2893696B1 (fr) * 2005-11-24 2009-03-06 Arkema Sa Tube multicouche pour le transport d'eau ou de gaz
FR2896445B1 (fr) * 2006-01-25 2010-08-20 Arkema Film flexible a base de polymere fluore
US8585753B2 (en) * 2006-03-04 2013-11-19 John James Scanlon Fibrillated biodegradable prosthesis
CN101472741A (zh) * 2006-04-21 2009-07-01 阿肯马法国公司 具有接枝聚偏二氟乙烯共混物层的多层结构
FR2908075B1 (fr) * 2006-11-07 2012-03-16 Arkema France Structure multicouche a base d'un polymere barriere eventuellement renforce a l'impact

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009007615A1 *

Also Published As

Publication number Publication date
BRPI0812976A2 (pt) 2014-12-16
FR2918067B1 (fr) 2011-07-01
FR2918067A1 (fr) 2009-01-02
WO2009007615A1 (fr) 2009-01-15
JP2010531380A (ja) 2010-09-24
KR20100036267A (ko) 2010-04-07
CN101688039B (zh) 2014-05-07
US20100189946A1 (en) 2010-07-29
CN101688039A (zh) 2010-03-31

Similar Documents

Publication Publication Date Title
EP2160444A1 (de) Verbundmaterial mit in einer fluorinierten polymermatrix dispergierten nanoröhrchen
EP2160275B1 (de) Verfahren zur imprägnierung durchgehender fasern mit einer verbundpolymermatrix mit einem gepfropften und fluorinierten polymer
US8231974B2 (en) Fluoropolymer molding method and molded article
US20110251331A1 (en) Use of nanotubes, especially carbon nanotubes, to improve the high temperature mechanical properties of a polymeric matrix
EP2158256A2 (de) Verfahren zur imprägnierung durchgehender fasern mit einer verbundpolymermatrix mit einem thermoplastischen polymer
WO2015028761A1 (fr) Composition de polymeres fluores thermoplastiques pour les tubes off-shore
FR2946176A1 (fr) Fibre conductrice multicouche et son procede d'obtention par co-extrusion.
FR3010082A1 (fr) Procede de preparation d'une composition de polymeres fluores reticules
EP1995274A1 (de) Vorbereitungsverfahren von Vorverbundstoffen auf der Basis von Nanokanälen, insbesondere aus Kohlenstoff
FR2594380A1 (fr) Materiau composite flexible renforce de fibres de verre utilisant une resine fluoree souple
BE1004682A3 (fr) Compositions a base de polyamides et objets faconnes a partir de ces compositions.
FR2935706A1 (fr) Composition fluoree pour tuyau offshore
EP0554931B1 (de) Plastikmaterialien aus heterogenen Vinylidene-Fluoride-Copolymeren und Chlortrifluorethylen
WO2018224583A1 (fr) Fibre multicouche de polymeres fluores
EP1279685B1 (de) Vinylidenfluoridpolymer mit nicht übertragenem Kettenteil und Verfahren zu seiner Herstellung
FR2893696A1 (fr) Tube multicouche pour le transport d'eau ou de gaz
EP3328630A1 (de) Fluorierte polymerzusammensetzung
FR3067364A1 (fr) Fibre multicouche de polymeres fluores
FR2886707A1 (fr) Utilisation d'un tube a base de polymere fluore greffe par irradiation pour le transport de fluides sous pression
FR2893944A1 (fr) Copolymere greffe par du polyamide, materiau le contenant, procede de fabrication et utilisations
FR3052167A1 (fr) Composition a base de polymere fluore greffe et son utilisation pour limiter la proliferation batcterienne

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20091207

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

17Q First examination report despatched

Effective date: 20100326

DAX Request for extension of the european patent (deleted)
REG Reference to a national code

Ref country code: DE

Ref legal event code: R003

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20130505