EP3728431A1 - Couche barrière pour tuyau flexible - Google Patents

Couche barrière pour tuyau flexible

Info

Publication number
EP3728431A1
EP3728431A1 EP18792870.0A EP18792870A EP3728431A1 EP 3728431 A1 EP3728431 A1 EP 3728431A1 EP 18792870 A EP18792870 A EP 18792870A EP 3728431 A1 EP3728431 A1 EP 3728431A1
Authority
EP
European Patent Office
Prior art keywords
carbon
layer
hose
fluororubber
mixture
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.)
Pending
Application number
EP18792870.0A
Other languages
German (de)
English (en)
Inventor
Wolfram Herrmann
Dieter Borvitz
Steffen Wietzke
Frank Jungrichter
Hartmut Bangert
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.)
ContiTech Schlauch GmbH
Original Assignee
ContiTech Schlauch GmbH
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 ContiTech Schlauch GmbH filed Critical ContiTech Schlauch GmbH
Publication of EP3728431A1 publication Critical patent/EP3728431A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/02—Small extruding apparatus, e.g. handheld, toy or laboratory extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
    • B29C48/151—Coating hollow articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/02—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D23/00—Producing tubular articles
    • B29D23/001—Pipes; Pipe joints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a general shape other than plane
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/02—Layered products comprising a layer of natural or synthetic rubber with fibres or particles being present as additives in the layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/042—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/10—Layered products comprising a layer of natural or synthetic rubber next to a fibrous or filamentary layer
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    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
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    • B32—LAYERED PRODUCTS
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    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/16—Layered products comprising a layer of natural or synthetic rubber comprising polydienes homopolymers or poly-halodienes homopolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/026—Knitted fabric
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/044—Carbon nanohorns or nanobells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C08L15/02—Rubber derivatives containing halogen
    • 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
    • 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
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B32B2262/0269—Aromatic polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • B32B2262/0284—Polyethylene terephthalate [PET] or polybutylene terephthalate [PBT]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/107—Ceramic
    • B32B2264/108—Carbon, e.g. graphite particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2597/00—Tubular articles, e.g. hoses, pipes
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/30—Applications used for thermoforming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • F16L2011/047—Hoses, i.e. flexible pipes made of rubber or flexible plastics with a diffusion barrier layer

Definitions

  • the invention relates to hoses with a barrier layer and a barrier layer and a
  • FKM blends also referred to as FPM blends
  • FPM blends can be used with polyols and quaternary ones
  • a tube comprising at least one barrier layer as inner layer and one outer layer, wherein the barrier layer is obtainable by extrusion of a mixture comprising a) at least one thermoplastic fluoropolymer,
  • this object has surprisingly been achieved by a tube which comprises at least one barrier layer as inner layer and one outer layer, wherein the barrier layer is obtainable by extrusion of a mixture comprising a) at least one thermoplastic fluoropolymer,
  • the hoses according to the invention according to the first and second embodiments show both a good dynamic and crack resistance and a high
  • thermoplastic elastomer is used, melting of the thermoplastic can not be observed in the DMA of the carbon-filled barrier layer of the present invention.
  • the unfilled material shows a tan delta> 1 (G "> G ') while the filled material has a Tan delta of 0.7.
  • the loss modulus is very small compared to the memory module. Viscoelastic materials have both a measurable storage modulus and a measurable loss modulus. If the storage modulus is greater than the loss modulus, it is called solids, otherwise liquids.
  • the carbon filler in the thermoplastic will cause or promote cross-linking.
  • the barrier layer as the end product preferably no thermoplastic elastomer is present, but probably a crosslinked thermoplastic.
  • the barrier layer produced according to the invention is no longer fusible.
  • Additional advantages are a further reduced permeation and a reduction of the shear forces in the processing.
  • the latter leads to a reduced polymer degradation of the fluoropolymers, so that stress corrosion cracking is avoided. It is particularly advantageous to use electron beam-modified PTFE powder.
  • the vulcanization is carried out at 150 ° C to 200 ° C.
  • the vulcanization takes place at the hose construction formed, comprising at least the barrier layer as the inner layer and the outer layer.
  • the hose according to the invention comprises at least one barrier layer as the inner layer and an outer layer.
  • the barrier layer is obtainable by extrusion of a mixture as defined above. The following information applies to the first and the second
  • the blend used for the extrusion comprises at least one thermoplastic fluoropolymer.
  • One, two or more thermoplastic fluoropolymers can be used.
  • Thermoplastic fluoropolymers are generally semicrystalline, meltable and melt-processible fluoropolymers.
  • the thermoplastic fluoropolymer may be any thermoplastic fluoropolymer except for irradiated PTFE.
  • Irradiated PTFE may be included in the mixture as an optional additional component in the first embodiment.
  • irradiated PTFE is included as a compulsory additional component in the mixture.
  • thermoplastic fluoropolymers are poly (chlorotrifluoroethylene-co-vinylidene fluoride) (CTFE / VDF), polyethylene-co-chlorotrifluoroethylene (ECTFE), poly (ethylene-co-tetrafluoroethylene) (ETFE), polychlorotrifluoroethylene (PCTFE), poly (tetrafluoroethylene -co-perfluoroalkylvinylether) (PFA or TFA), polyvinylidene fluoride (PVDF), polyvinylfluoride (PVF), poly (tetrafluoroethylene-co-hexafluoropropylene) (FEP) or poly (tetrafluoroethylene-co-hexafluoropropylene-co-vinylidene fluoride) (TFB), wherein FEP is preferred, since it is characterized by particularly good processing behavior and high elasticity with high barrier effect against fuel diffusion.
  • FEP is preferred, since it is characterized by particularly good processing
  • the mixture used for the extrusion further comprises at least one fluororubber and a crosslinking agent and / or at least one fluororubber elastomer.
  • One, two or more fluororubbers or fluororubber elastomers can be used.
  • the mixture contains at least one fluororubber and a crosslinking agent for the crosslinking of the fluororubber.
  • Vulcanization of the fluororubber which usually occurs during the formation of the barrier layer, forms a fluororubber elastomer.
  • the crosslinked fluororubber i. the fluororubber elastomer.
  • the crosslinking of the fluororubber occurs partially or completely already before the extrusion.
  • the mixture already contains fluororubber elastomer, either without or in admixture with fluororubber and crosslinking agent.
  • fluororubber all conventional fluororubbers can be used. Often, fluorororubbers contain vinylidene fluoride (VDF) as a comonomer.
  • VDF vinylidene fluoride
  • suitable fluororubbers are poly (vinylidene fluoride-co-hexafluoropropylene) (VDF / HFP),
  • VDF / TFE / PMVE Poly (vinylidene fluoride-co-tetrafluoroethylene-co-perfluoromethylvinyl ether)
  • TFE / P poly (tetrafluoroethylene-co-propylene)
  • VDF / CTFE poly (vinylidene fluoride-co-chlorotrifluoroethylene)
  • the fluororubber used in the mixture is preferably a co-polymer or ter-polymer.
  • thermoplastic fluoropolymer in the mixture may be, for example, in the range of 60 to 90% by weight, preferably 70 to 80% by weight.
  • the proportion of fluororubber and / or fluororubber elastomer in the mixture may be, for example, in the range from 10 to 40% by weight, preferably from 20 to 30% by weight.
  • the total amount of thermoplastic fluoropolymer and fluororubber and / or fluororubber elastomer in the mixture may be, for example, in the range of 80 to 99.8% by weight, preferably 90 to 98% by weight.
  • Crosslinking agents are commercially available as FTPV, e.g. Dai-EL Fluoro TPV SV-1020, Dai-EL Fluoro TPV SV-1030, Dai-EL Fluoro TPV SV-1032 from Daikin.
  • the mixture according to the first or second embodiment contains as component c) at least one carbon filler and / or irradiated PTFE.
  • the mixture further comprises, as component c), at least one carbon filler selected from carbon black, in particular conductive carbon black, graphene, carbon nano-fillers, in particular carbon nanotubes, or a combination thereof, the mixture being 0.05% by weight. to 20 wt .-%, preferably 0.2 wt .-% to 10 wt .-%, more preferably 0.2 wt .-% to 9 wt .-%, of the carbon filler or contains.
  • the carbon black content in the mixture should be as low as possible.
  • only one or more carbon blacks, in particular conductive carbon black, are used as the carbon filler.
  • the carbon black is preferably a conductivity black.
  • the mixture preferably contains from 1 to 20% by weight, more preferably from 2 to 10% by weight, particularly preferably from 3 to 9% by weight, of carbon black, in particular conductive carbon.
  • the carbon filler in a second variant, graphene, carbon nanofillers, in particular carbon nanotubes, or a combination thereof are selected as the carbon filler, with carbon nanotubes being preferred.
  • the mixture preferably contains 0.05 to 10 wt%, preferably 0, 2 to 5 wt .-%, of the carbon or the fillers.
  • Carbon nanotubes is particularly preferred.
  • the proportion of carbon black can be significantly reduced, whereby a better dynamic behavior of the barrier layer is achieved.
  • the at least one carbon filler is a combination of carbon black, in particular conductive carbon black, and at least one selected from graphene, carbon nanofillers, in particular carbon nanotubes, or a combination thereof, wherein a combination of carbon black, in particular conductive carbon black, and carbon nanotubes more preferably, the mixture preferably contains from 0.2% to 7% by weight, more preferably from 1% to 5% by weight, of the carbon fillers.
  • the weight ratio of carbon black in particular
  • Conductivity soot to the total amount of graphene and carbon nanofillers, especially carbon nanotubes (preferably the weight ratio of carbon black, especially conductivity soot, to carbon nanotubes) in the mixture e.g. in the range of 7: 3 to 3: 0.05, preferably 4: 3 to 3: 0.5.
  • the carbon black in particular the conductivity carbon black, preferably has an oil absorption number (OAN) according to ASTM D 2414-16 of greater than 140 ml / 100 g to 600 ml / 100 g, more preferably from 250 ml / 100 g to 550 ml / 100 g, and / or a specific surface area according to the BET method according to ASTM D6556-04 of 150 to 1400 m 2 / g, preferably from 600 to 1200 m 2 / g.
  • OAN oil absorption number
  • the carbon black is preferably a conductivity black or conductive black. Particularly suitable are highly conductive carbon blacks. Such are commercially available, such as the conductivity blacks of the Ketjenblack EC-600 and EC-300J series from Akzo-Nobel, Ensaco 250G, 260G and 350G from Imerys, Printex XE2-B, L6, XPB538 from Orion Engineered Carbons, Vulcan XC 72 from Cabot, CL-08, EH-02 from Continental Carbon India Limited or N472 conductive carbon black from various manufacturers.
  • Graphene are formed from two-dimensional layers of covalently linked carbon atoms, which correspond approximately to a single graphite layer.
  • Graphene production processes are based, for example, on comminution of graphite, for example by mechanical or chemical exfoliation, or on chemical vapor deposition (CVD).
  • the graphene can be chemically modified.
  • Graphenes have high electrical conductivity and excellent mechanical properties.
  • carbon nanofillers are e.g. Carbon nanofibres (CNF), carbon nanohy- namic (CNH) and carbon nanotubes (CNT), with CNT being particularly preferred.
  • CNF Carbon nanofibres
  • CNH carbon nanohy- namic
  • CNT carbon nanotubes
  • Carbon nanotubes are in particular carbon tubes with a diameter of about 0.5 to 100 nm. The length can be a multiple of the diameter. These tubes may be formed of one or more ordered carbon atoms of substantially graphitic or graphene structure. Common structures of this CNT are of the cylinder type. In the case of the cylindrical structures, a distinction is made between the single-wall, double-walled carbon nanotubes and multi-walled cylindrical CNTs. Common methods for their preparation are for. Arc discharge, laser ablation, chemical vapor deposition, and catalytic chemical vapor deposition. The CNTs can be chemically modified. CNTs are lightweight, tensile and piping
  • the at least one carbon filler is preferably carbon black, in particular
  • PTFE Polytetrafluoroethylene
  • thermoplastic elastomer is present in the resulting barrier layer as end product.
  • the inventively produced barrier layer is at the first
  • Embodiment preferably no longer meltable.
  • the mixture as component c) does not comprise a carbon filler according to the first embodiment, but irradiated Polytetrafluoroethylene (PTFE), the mixture preferably containing from 1% to 30%, more preferably from 1% to 12%, by weight of irradiated PTFE.
  • PTFE Polytetrafluoroethylene
  • Irradiated PTFE is PTFE which has been exposed by irradiation, e.g. by electron or gamma irradiation. Irradiated PTFE contains long-lived radicals, which can be detected by ESR measurements, which allow chemical binding of the irradiated PTFE to polymer chains in the mixture, e.g.
  • irradiated PTFE e.g. with an absorbed dose in the range of 10 to 3000 kGy.
  • the irradiation can be carried out in an inert gas.
  • the barrier layer obtained contains at least three polymer phases: for example, an FKM elastomer phase, a FKM fluorothermoplastic blend phase, a
  • optional additives are fillers other than the carbon fillers listed above, and / or
  • Processing aids may in particular be carnauba waxes, pentaerythrityl tetrastearates, soaps, fatty acid esters, phosphoric acid esters, boric acid esters, acid amides, aliphatic and olefinic waxes and aliphatic and olefinic amines or mixtures thereof.
  • Loss modulus G can be measured, for example, according to the method described in the examples.
  • the hose according to the invention comprises at least one barrier layer as the inner layer and an outer layer.
  • the inner layer with barrier function is the inner layer of the tube which in use is in contact with the medium to be transported.
  • the hose is a two-leg hose without embedded
  • Reinforcements so formed exclusively of an inner layer and an outer layer.
  • a strength element consisting of at least one reinforcement layer, which is arranged in one or more layers between the inner layer and the outer layer.
  • At least one intermediate layer is arranged in the tube according to the invention between the barrier layer or inner layer and outer layer.
  • a strength carrier is arranged in the tube according to the invention between the outer layer and the barrier layer or between the outer layer and the optionally present intermediate layer.
  • FKM fluororubber
  • ACM acrylate rubber
  • AEM ethylene-acrylate rubber
  • CM chlorinated polyethylene rubber
  • ECO ethylene oxide-epichlorohydrin rubber
  • EPM Ethylene-propylene rubber
  • the outer layer is preferably formed from a crosslinked rubber compound or an elastomer.
  • the rubber component of the rubber composition for the outer layer is preferably FKM, ACM, AEM, CM, EPM, ECO, EPDM, HNBR or VMQ or a blend of the aforementioned rubber components, optionally with at least one further rubber component, eg an AEM / EPDM blend. In most cases, however, waste-free rubber mixtures are used. Particularly preferred is the
  • Rubber compound for the outer layer ECO, AEM, ACM, CM or HNBR Rubber compound for the outer layer ECO, AEM, ACM, CM or HNBR. Although the outer layer is subjected to heavy loads, e.g. FKM
  • Rubber mixtures based on ACM and / or AEM are preferably diaminically crosslinked.
  • the intermediate layer if present, is preferably made of a vulcanizate of
  • NBR Acrylonitrile-butadiene rubber
  • ECO ethylene oxide-epichlorohydrin rubber
  • FKM bisphenol-crosslinked fluororubber
  • AEM ethylene-acrylate rubber
  • ACM acrylate Rubber
  • CM chlorinated polyethylene rubber
  • HNBR hydrogenated acrylonitrile-butadiene rubber
  • the intermediate layer can also serve as an adhesive layer between the inner layer and the outer layer and / or the reinforcement.
  • the reinforcement if present, is formed in particular from a woven, knitted or knitted fabric, in particular based on a textile material.
  • Suitable materials for this purpose may be polyamide (PA), polyimide (PI), aramid, in particular para-aramid or meta-aramid, polyvinyl acetal (PVA), polyetheretherketone (PEEK), polyester, in particular polyethylene terephthalate (PET) or polyethylene 2,6-naphthalate (PEN), polysulfone (PSU), polyoxadiazole (POD), polyphenylene or polyphenylene derivative, in particular
  • Polyphenylene sulfide PPS
  • glass fibers Particularly preferred are p-aramid, m-aramid, polyphenylene sulfide (PPS) and / or polyethylene terephthalate (PET). Also
  • Hybrid concepts ie mixed forms of the mentioned, can be used, for example in the form of a mixed intermediate of m- and p-aramid or of PPS and PA.
  • the PPS as High-performance material contributes to a high strength
  • the PA contributes in addition to the strength carrier contribution on its Haft2011ieriana to improved adhesion to the surrounding elastomeric material.
  • Outer layer preferably an elastomeric outer layer containing ethylene oxide-epichlorohydrin rubber (ECO), ethylene-acrylate rubber (AEM), acrylate rubber (ACM), chlorinated polyethylene rubber (CM) and / or hydrogenated acrylonitrile-butadiene rubber (HNBR) , at least one elastomeric intermediate layer, preferably containing ethylene oxide-epichlorohydrin rubber (ECO), ethylene-acrylate rubber (AEM), acrylate rubber (ACM), chlorinated polyethylene rubber (CM) and / or hydrogenated acrylonitrile-butadiene rubber (HNBR ), wherein between the at least one elastomeric
  • Intermediate layer and the outer layer is a strength carrier, preferably containing p-aramid, m-aramid, polyphenylene sulfide (PPS) and / or polyethylene terephthalate (PET), is arranged.
  • a strength carrier preferably containing p-aramid, m-aramid, polyphenylene sulfide (PPS) and / or polyethylene terephthalate (PET).
  • PPS polyphenylene sulfide
  • PET polyethylene terephthalate
  • the tube has five layers.
  • the barrier layer and the outer layer there are two elastomeric intermediate layers, wherein a strength carrier is arranged between the two elastomeric intermediate layers and the outer layer, wherein the barrier layer preferably contains fluorothermoplastic vulcanizates (FTPV), wherein an inner elastomeric
  • Intermediate layer preferably contains fluororubber (FKM), wherein an outer elastomeric intermediate layer preferably contains ethylene oxide-epichlorohydrin rubber (ECO), wherein the reinforcement preferably contains m-aramid, and wherein the outer layer preferably contains acrylate rubber (ACM).
  • FKM fluororubber
  • an outer elastomeric intermediate layer preferably contains ethylene oxide-epichlorohydrin rubber (ECO)
  • ECO ethylene oxide-epichlorohydrin rubber
  • the reinforcement preferably contains m-aramid
  • ACM acrylate rubber
  • each elastomeric layer has one
  • each elastomeric layer is electrically conductive.
  • the hose according to the invention is suitable e.g. for air-carrying hoses, e.g.
  • the hose according to the invention has a high fuel, diesel and oil resistance.
  • the invention also relates to a method for producing an inventive
  • a tube comprising at least one barrier layer as an inner layer and an outer layer, the method comprising:
  • thermoplastic fluoropolymer a thermoplastic fluoropolymer
  • the mixture is preferably extruded to form the barrier layer at a temperature in the range of 170 ° C to 300 ° C, preferably 240 to 270 ° C.
  • the vulcanization is carried out at 150 ° C to 200 ° C.
  • the mixture Prior to extrusion to form the barrier layer, the mixture is preferably compounded by premixing the individual components a), b) and c), wherein the components a) and b), ie thermoplastic fluoropolymer and fluororubber / crosslinking agent and / or fluororubber elastomer, as already prefabricated compound can be used, for example in the form of the types 1020 or 1030 from Daikin.
  • the premixing of components a), b) and c), for example a premix of components a) and b) with component c), for example carbon black, in particular conductive carbon black, can be effected, for example, by means of an extruder, for example a twin-screw extruder.
  • the compounding can be done, for example, at a temperature in the range of 245 to 300 ° C. It is then the compounded mixture, eg as granules obtained. This is extrudable and can be used for extrusion to form the barrier layer.
  • the outer layer can be applied in a conventional manner over the inner layer, e.g. by extruding.
  • Intermediate layer and / or a strength member are applied to the barrier layer.
  • the intermediate layer can be extruded onto the barrier layer.
  • the strength member may be applied in a conventional manner to the barrier layer or the
  • FIG. 1 shows a hose according to the invention, which additionally has an optional intermediate layer and an optional strength member.
  • Fig. 3 recording a melt test on a reference.
  • DMA dynamic mechanical analysis
  • Fig. 1 shows a hose according to the invention with the following example
  • the barrier layer or inner layer 1 was obtained by extrusion of a mixture containing Daikin FTPV SV-1020, a mixture of thermoplastic fluoropolymers and fluororubbers including crosslinking agent, and 7 wt .-%, based on the
  • the barrier layer or inner layer 1 is bounded by the intermediate layer 2.
  • Interlayer 2 is formed by a vulcanizate of ethylene oxide-epichlorohydrin rubber (ECO) and also serves as an adhesive layer between the inner layer 1 and the
  • the reinforcing member 3 is formed of m-aramid and is bounded by the outer layer 4.
  • the outer layer 4 contains acrylate rubber (ACM).
  • a melt test was carried out on the barrier layer or inner layer after the extrusion and before the vulcanization.
  • the barrier layer or inner layer, after extrusion and before vulcanization, was not meltable even at 280 ° C. (FIG. 2).
  • the reference used was granules of Daikin FTPV SV-1020 without carbon filler. This reference was melted at 280 ° C ( Figure 3).
  • DMA dynamic mechanical analysis
  • FIG. 4 depicts the measurement profile of the barrier layer or inner layer according to the invention after extrusion and before vulcanization.
  • the upper section shows the course of the memory module G 'and the loss module G ", each for a duplicate.
  • the bottom shows the course of the memory module G 'and the loss module G ", each for a duplicate.
  • the section for each of the two samples shows the corresponding course of tan delta.
  • the value for tan delta remains below 1.0 even at temperatures above 220 ° C. 5 shows the course for two corresponding samples, only without carbon filler. At temperatures above 220 ° C., a value for tan delta greater than 1.0 is achieved. 6 shows the measurement curves for different barrier layers according to the invention or
  • thermoplastic vulcanizate TPV
  • thermoplastic elastomer a thermoplastic vulcanizate
  • the reference fuses a liquid / melt while the filled material is a solid.

Abstract

L'invention concerne un tuyau flexible présentant au moins une couche barrière comme couche interne et une couche externe, la couche barrière pouvant être obtenue par extrusion d'un mélange qui comprend a) au moins un polymère fluoré thermoplastique, b) au moins un caoutchouc fluoré et un réticulant et/ou au moins un élastomère de caoutchouc fluoré et c) au moins une charge carbonée choisie parmi la suie, en particulier la suie conductible, le graphène, les nanocharges carbonées, en particulier les nanotubes de carbone, les nanocornets de carbone ou une combinaison de ceux-ci, en une quantité de 0,05 % en poids à 20 % en poids du ou des charges carbonées, ou du PTFE irradié et par vulcanisation. Le tuyau flexible présent une résistance élevée au carburant, au diesel et à l'huile et une efficacité dynamique.
EP18792870.0A 2017-12-21 2018-10-15 Couche barrière pour tuyau flexible Pending EP3728431A1 (fr)

Applications Claiming Priority (2)

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DE102017223546.2A DE102017223546A1 (de) 2017-12-21 2017-12-21 Barriereschicht für Schläuche
PCT/EP2018/078013 WO2019120677A1 (fr) 2017-12-21 2018-10-15 Couche barrière pour tuyau flexible

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EP3728431A1 true EP3728431A1 (fr) 2020-10-28

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EP (1) EP3728431A1 (fr)
CN (1) CN111511822A (fr)
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WO (1) WO2019120677A1 (fr)

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US20210080035A1 (en) 2021-03-18
US11719364B2 (en) 2023-08-08
WO2019120677A1 (fr) 2019-06-27
DE102017223546A1 (de) 2019-06-27

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