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WO2002016111A1 - Procede de preparation d'un article multicouche presentant une couche de plastique fluore et une couche d'elastomere - Google Patents

Procede de preparation d'un article multicouche presentant une couche de plastique fluore et une couche d'elastomere Download PDF

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Publication number
WO2002016111A1
WO2002016111A1 PCT/US2000/034718 US0034718W WO0216111A1 WO 2002016111 A1 WO2002016111 A1 WO 2002016111A1 US 0034718 W US0034718 W US 0034718W WO 0216111 A1 WO0216111 A1 WO 0216111A1
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WO
WIPO (PCT)
Prior art keywords
layer
fluoroplastic
process according
article
elastomer
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/US2000/034718
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English (en)
Inventor
Tatsuo Fukushi
Robert E. Kolb
Craig R. Hoff
Steven J. Wellner
Attila A. Molnar
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Dyneon LLC
Original Assignee
Dyneon LLC
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Filing date
Publication date
Application filed by Dyneon LLC filed Critical Dyneon LLC
Priority to AU2001225857A priority Critical patent/AU2001225857A1/en
Publication of WO2002016111A1 publication Critical patent/WO2002016111A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • 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
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0013—Extrusion moulding in several steps, i.e. components merging outside the die
    • B29C48/0015—Extrusion moulding in several steps, i.e. components merging outside the die producing hollow articles having components brought in contact outside the extrusion die
    • B29C48/0016—Extrusion moulding in several steps, i.e. components merging outside the die producing hollow articles having components brought in contact outside the extrusion die using a plurality of extrusion dies
    • 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
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • 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
    • B29C48/06—Rod-shaped
    • 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
    • B29C48/154—Coating solid articles, i.e. non-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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/304—Extrusion nozzles or dies specially adapted for bringing together components, e.g. melts within the die
    • 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 non-planar shape
    • 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
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • B29K2027/18—PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
    • 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

  • This invention relates to preparing multi-layer articles having a fluoroplastic layer and an elastomer layer.
  • Fluorine-containing polymers are a commercially useful class of materials. Fluoropolymers include, for example, crosslinked fluoroelastomers and semi-crystalline or glassy fluoroplastics. Fluoroplastics are generally of high thermal stability and are particularly useful at high temperatures. They may also exhibit extreme toughness and flexibility at very low temperatures. Many of these fluoroplastics are almost totally insoluble in a wide variety of solvents and are generally chemically resistant. Some have extremely low dielectric loss and high dielectric strength, and may have unique non-adhesive and low friction properties. See, e.g., F.W. Billmeyer, Textbook of Polymer Science, 3d ed., pp. 398-403, John Wiley & Sons, New York (1984).
  • Fluoroelastomers particularly the copolymers of vinylidene fluoride with other ethylenically unsaturated halogenated monomers such as hexafluoropropylene, have particular utility in high temperature applications such as seals, gaskets, and linings. See, e.g., R. A. Brullo, "Fluoroelastomer Rubber for Automotive Applications,” Automotive Elastomer & Design, June 1985; “Fluoroelastomer Seal Up Automotive Future,” Materials Engineering, October 1988; and W.M. Grootaert et al., "Fluorocarbon Elastomers,” Kirk-Othmer, Encyclopedia of Chemical Technology, vol. 8, pp.
  • Multi-layer constructions containing a fluoropolymer enjoy wide industrial application. Such constructions find utility, for example, in fuel line hoses and related containers and hoses or gaskets in the chemical processing field. Increased concerns with evaporative fuel standards give rise to a need for fuel system components that have increased barrier properties to minimize the permeation of fuel or fuel vapors through automotive components such as fuel filler lines, fuel supply lines, fuel tanks, and other components of the engine's fuel or vapor recovery systems. Various types of tubing have been proposed to address these concerns.
  • Adhesion between the layers of a multi-layered article may need to meet various performance standards depending on the use of the finished article. However, it is often difficult to establish high bond strengths when one of the layers is a fluoropolymer.
  • One approach is to use an adhesive layer or tie layer between the fluoropolymer layer and the second polymer layer.
  • Surface treatments for the fluoropolymer layer including solvent etching and corona discharge, have also been employed to enhance adhesion.
  • a dehydrofluorinating agent such as a base
  • polyamine reagents applied to the fluoropolymer surface or incorporated within the fluoropolymer itself.
  • the invention relates to a method for enhancing the bond strength between a fluoroplastic layer and an elastomer layer of a multi-layer article.
  • the elastomer may be a fluoroelastomer or a non-fluorinated elastomer.
  • a fluoroplastic composition that includes interpolymerized units derived from vinylidene fluoride (VDF) is applied to the surface of a precursor article that includes a curable elastomer layer, preferably by extrusion coating the composition in molten form through a crosshead die, to form a fluoroplastic layer.
  • VDF vinylidene fluoride
  • the composition is applied directly to the surface of the elastomer layer.
  • the curable elastomer layer Prior to application of the fluoroplastic composition, the curable elastomer layer is thermally insulated to prevent it from undergoing substantial heating.
  • thermal insulation is achieved by equipping the die with a sleeve located at least partially within the upstream end of the die that receives and thermally insulates the curable elastomer layer prior to application of the fluoroplastic composition.
  • the fluoroplastic layer is heated and the curable elastomer layer is cured (preferably thermally cured).
  • the elastomer cure occurs separately from and subsequent to heating of the fluoroplastic layer.
  • the combination of thermally insulating the curable elastomer layer prior to application of the fluoroplastic composition and heating the fluoroplastic layer following application of the fluoroplastic composition results in formation of a strong bond between the fluoroplastic and elastomer layers upon cure, even in the absence of adhesion aids such as surface treatments, separate adhesive layers, and the like. For example, bond strengths of at least 15 N/cm, can be achieved.
  • Multi-layer articles prepared according to this method can be provided in a wide variety of shapes, including sheets, films, containers, hoses, tubes, and the like.
  • the articles are especially useful wherever chemical resistance and/or barrier properties are necessary. Examples of specific uses for the articles include their use in rigid and flexible retroreflective sheets, adhesive articles such as adhesive tapes, paint replacement films, drag reduction films, fuel line and filler neck hoses, exhaust handling hoses, fuel tanks, and the like.
  • the articles are also useful in chemical handling and processing applications, and as wire and cable coatings or jackets.
  • FIG. 1 is a schematic drawing of a process for making a multi-layered article according to the invention.
  • FIG. 1 there is shown one embodiment of a process for preparing a multi-layer article featuring a fluoroplastic layer bonded to an elastomer layer.
  • An extruder 20 extrudes a curable elastomer composition through a die 21 to form a length of tubing 22 having a curable elastomer layer.
  • a second extruder 23 located downstream of extruder 20 and equipped with a crosshead die 25 coats a layer of molten fluoroplastic onto the surface of the curable elastomer layer.
  • the absence of substantial heating prior to application of the fluoroplastic contributes to the development, upon cure, of a strong bond between the fluoroplastic and elastomer layers.
  • the resulting multi-layer article 27 Following extrusion coating, the resulting multi-layer article 27, featuring a fluoroplastic layer deposited on a curable elastomer layer, enters a tubular heater 28 that heats the fluoroplastic layer.
  • a useful tubular heater is a radiant heater.
  • heat is transferred from heater 28 to the fluoroplastic layer, and then transferred inwardly from the fluoroplastic layer to the curable elastomer layer. It is believed that this heating step contributes to the development, upon cure, of a strong bond between the fluoroplastic and elastomer layers.
  • the multi-layer article may be cooled, e.g., by immersion in a cooling bath 29.
  • the elastomer layer may be cured either in heater 28, or, more preferably, in a separate step under pressure and higher temperature either before or after immersion in cooling bath 29.
  • it may be desirable to cool the article in bath 29, cut it into appropriately sized pieces, and then heat the individual pieces under pressure, e.g., in an autoclave, to cure the curable elastomer layer.
  • the fluoroplastic preferably is a material that is capable of being extrusion coated. Such fluoropolastics typically have melting temperatures ranging from about 100 to about 330°C, more preferably from about 150 to about 270°C.
  • the fluoroplastic includes interpolymerized units derived from VDF and may further include interpolymerized units derived from other fluorine-containing monomers, non-fluorine-containing monomers, or a combination thereof.
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • CTFE chlorotrifluoroethylene
  • 3- chloropentafluoropropene examples include tetrafluoroethylene (TFE), hexafluoropropylene (
  • VDF-containing fluoroplastics examples include olefin monomers such as ethylene, propylene, and the like.
  • the VDF-containing fluoroplastics may be prepared using emulsion polymerization techniques as described, e.g., in Sulzbach et al., U.S. 4,338,237, hereby incorporated by reference.
  • Useful commercially available VDF-containing fluoroplastics include, for example, THV 200, THV 400, THV 500G, THV 610X fluoropolymers (available from Dyneon LLC, St.
  • a particularly useful fluoroplastic includes interpolymerized units derived from at least TFE and VDF in which the amount of VDF is at least 0.1% by weight, but less than 20% by weight.
  • the amount of VDF ranges from 3-15% by weight, more preferably from 10-15% by weight.
  • the curable elastomer may be a fluoroelastomer or a non-fluorinated elastomer.
  • suitable fluoroelastomers include VDF-HFP copolymers, VDF-HFP-TFE terpolymers, TFE-propylene copolymers, and the like.
  • non- fluorinated elastomers examples include acrylonitrile butadiene (NBR), butadiene rubber, chlorinated and chlorosulfonated polyethylene, chloroprene, ethylene-propylene monomer (EPM) rubber, ethylene-propylene-diene monomer (EPDM) rubber, epichlorohydrin (ECO) rubber, polyisobutylene, polyisoprene, polysulfide, polyurethane, silicone rubber, blends of polyvinyl chloride and NBR, styrene butadiene (SBR) rubber, ethylene-acrylate copolymer rubber, and ethylene-vinyl acetate rubber.
  • NBR acrylonitrile butadiene
  • EPM ethylene-propylene monomer
  • EPDM ethylene-propylene-diene monomer
  • ECO epichlorohydrin
  • SBR styrene butadiene
  • SBR styrene butadiene
  • elastomers include NipolTM 1052 NBR (Zeon Chemical, Louisville, KY), HydrinTM C2000 epichlorohydrin-ethylene oxide rubber (Zeon Chemical, Louisville, KY), HypalonTM 48 chlorosulfonated polyethylene rubber (E.I. DuPont de Nemours & Co., Wilmington, DE), NordelTM EPDM (R.T. Vanderbilt Co., Inc., Norwalk, CT), VamacTM ethylene-acrylate elastomer (E.I. DuPont de Nemours & Co.
  • a curing agent is preferably blended with the curable elastomer to facilitate cure.
  • useful curing agents include imidazolines, diamines, internal salts of diamines, thioureas, and polyphenol curing agents as discussed in U.S. 4,287,322 (Worm), incorporated herein by reference. Such agents are particularly useful for epichlorohydrin compositions.
  • Other examples, particularly useful in the curing of nitrile rubber- containing compositions include peroxide compounds and sulfur-containing compounds.
  • examples of useful curing agents include polyols in combination with organo-onium salts (e.g., organo-ammonium, organo- phosphonium, and organo-sulfonium salts). Specific examples are described, e.g., in Fukushi, U.S. 5,658,671, "Fluoroelastomer Coating Composition," hereby incorporated by reference. Diamines and peroxides are also useful.
  • the multi-layer article may contain additional polymer layers as well.
  • suitable polymer layers include non-fluorinated polymers such as polyamides, polyimides, polyurethanes, polyolefins, polystyrenes, polyesters, polycarbonates, polyketones, polyureas, polyacrylates, and polymethylmethacrylates.
  • non-fluorinated polymers such as polyamides, polyimides, polyurethanes, polyolefins, polystyrenes, polyesters, polycarbonates, polyketones, polyureas, polyacrylates, and polymethylmethacrylates.
  • a particularly useful construction for fuel applications features a relatively thin layer of the fluoroplastic that acts as a barrier layer bonded on one face to a relatively thick layer of non-fluorinated polymer that acts as a coverstock, and on the opposite face to a relatively thin elastomer layer (e.g., a fluoroelastomer or a non-fluorinated elastomer) that performs a sealing function.
  • the coverstock provides the article with structural integrity.
  • reinforcing aids such as fibers, mesh, and/or a wire screen may be incorporated in the multi-layer article, e.g., as separate layers or as part of an existing layer.
  • any or all of the individual layers of the multi-layer article may further include one or more additives.
  • useful additives include pigments, plasticizers, tackifiers, fillers, electrically conductive materials (e.g., of the type described in U.S. 5,552,199), electrically insulating materials, stabilizers, antioxidants, lubricants, processing aids, impact modifiers, viscosity modifiers, and combinations thereof.
  • electrically conductive materials e.g., of the type described in U.S. 5,552,199
  • electrically insulating materials e.g., of the type described in U.S. 5,552,199
  • stabilizers e.g., antioxidants, lubricants
  • processing aids e.g., impact modifiers, viscosity modifiers, and combinations thereof.
  • impact modifiers e.g., viscosity modifiers, and combinations thereof.
  • viscosity modifiers e.g., viscosity modifiers, and combinations thereof.
  • the article may be subjected to additional heat, pressure, or both, following cure.
  • Another way of increasing the bond strength between the layers is to treat the surface of one or more of the layers prior to forming the multi-layered articles.
  • Such surface treatments may consist of a solution treatment using a solvent. If the solvent contains a base, e.g., l,8-diaza[5.4.0]bicyclo undec-7-ene (DBU), treatment of the fluoropolymer will result in some degree of dehydrofluorination. Such dehydrofluorination may be beneficial to promote adhesion to subsequently applied materials. This is particularly true when the subsequently applied material contains any agent that is reactive to sites of unsaturation.
  • DBU l,8-diaza[5.4.0]bicyclo undec-7-ene
  • surface treatments include charged atmosphere treatments such as corona discharge treatment or plasma treatment. Electron beam treatment is also useful.
  • Interlayer adhesion may also be enhanced using an agent such as an aliphatic di- or polyamine.
  • the amine can be of any molecular weight that, when used, will result in an improvement in the adhesive bond strength between the layers of the multi-layer article.
  • a particularly useful polyamine is polyallylamine having a molecular weight greater than about 1,000, as measured by gel permeation chromatography.
  • An example of a useful commercially available polyamine is polyallyl amine having a molecular weight of about 3,000 available from Nitto Boseki Co., Ltd.
  • the amine may be incorporated into one or more of the layers of the multi-layer article prior to forming the article using conventional means such as melt-mixing.
  • the amine may be applied to a surface of one or more of the layers using conventional coating methods such as spray coating, curtain coating, immersion coating, dip coating, and the like.
  • the elastomer was a fluoroelastomer prepared by combining the following ingredients: 100 parts Dyneon FE-5830Q fluoroelastomer (commercially available from Dyneon LLC, St. Paul, MN); 13 parts N-762 carbon black (commercially available from Cabot Corp.,
  • a cross-head die equipped with a polytetrafluoroethylene (PTFE) sleeve was used to coat a molten fluoroplastic composition onto the surface of the fluoroelastomer tube.
  • the fluoroplastic was a TFE-HFP-VDF terpolymer featuring 76 wt.% TFE, 11 wt.% HFP, and 13 wt.% VDF.
  • the fluoroplastic had a melt flow index of 7 and a melting point of
  • the PTFE sleeve prevented heating of the fluoroelastomer surface prior to application of the fluoroplastic.
  • the resulting multi-layer article was passed through a 15.2 cm long tubular heater set at 220°C (the surface temperature of the fluoroplastic was 140°C) to heat the article prior to cooling. Once cooled, the article was cut into smaller samples that were then placed on a steel mandrel and thermally cured at a temperature of 160°C and a pressure of 0.4 MPa for 60 minutes using steam in an autoclave. Following cure, the samples were removed from the autoclave and cooled to room temperature.
  • the peel adhesion of the cured samples was evaluated by making a cut in each sample to separate a 7 mm wide strip of the fluoroplastic outer layer from the fluoroelastomer core in order to provide a tab for adhesion testing.
  • the thickness of the fluoroplastic layer was 0.3 mm.
  • An Instron® Model 1125 tester, available from Instron Corp., set at a 100 mm/min. crosshead speed was used as the test device. Peel strength between the fluoroplastic and fluoroelastomer layers was measured in accordance with ASTM D 1876 (T-Peel Test) with the exception that the peel angle was 90 degrees. The results of two samples were averaged. The average value is reported in Table 1.
  • Example 2 The procedure of Example 1 was followed except that the fluoroplastic was a TFE-
  • Example 1 The procedure of Example 1 was followed except that the PTFE sleeve was not used. The results of the peel adhesion test are reported in Table 1.
  • Example 1 The procedure of Example 1 was followed except that the heater was not used. The results of the peel adhesion test are reported in Table 1.
  • Example 1 The procedure of Example 1 was followed except that neither the PTFE sleeve nor the heater was used. The results of the peel adhesion test are reported in Table 1.
  • Fig. 1 illustrates the preparation of a multi-layer article in the form of a tube
  • Fig. 1 illustrates the use of extruders to prepare the curable elastomer layer and fluoroplastic layers
  • other polymer processing techniques may be used.
  • the curable elastomer and fluoroplastic compositions can be prepared in the form of sheets and then laminated together, so long as measures are taken to thermally insulate the curable elastomer prior to application of the fluoroplastic.
  • Fig. 1 illustrates the use of a tubular heater for radiantly heating the fluoroplastic layer
  • other heating methods could be used.
  • fluoroplastic layers containing, e.g., metal particles induction heating could be used.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un procédé destiné à renforcer la résistance d'adhésion entre une couche de plastique fluoré contenant du VDF et une couche d'élastomère d'un article multicouche. Une composition de plastique fluoré contenant du VDF est appliquée sur la surface d'un article précurseur qui comprend une couche d'élastomère durcissable afin de former une couche de plastique fluoré. Avant l'application de ladite composition de plastique fluoré, la couche d'élastomère durcissable est isolée thermiquement afin d'éviter qu'elle ne subisse un réchauffement sensible. Suite à ladite application, la couche de plastique fluoré est chauffée et la couche d'élastomère durcissable est durcie (par exemple, thermiquement). De préférence, le durcissement de l'élastomère et le chauffage de la couche de plastique fluoré ont lieu séparément, en commençant par ce dernier. En isolant thermiquement la couche d'élastomère durcissable avant d'appliquer la composition de plastique fluoré tout en chauffant la couche de plastique fluoré après l'application de la composition de plastique fluoré, on obtient une liaison résistante entre les couches de plastique fluoré et d'élastomère suite après durcissement.
PCT/US2000/034718 2000-08-23 2000-12-20 Procede de preparation d'un article multicouche presentant une couche de plastique fluore et une couche d'elastomere Ceased WO2002016111A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001225857A AU2001225857A1 (en) 2000-08-23 2000-12-20 Process for preparing a multi-layer article having a fluoroplastic layer and an elastomer layer

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US64473100A 2000-08-23 2000-08-23
US09/644,731 2000-08-23

Publications (1)

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WO2002016111A1 true WO2002016111A1 (fr) 2002-02-28

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PCT/US2000/034718 Ceased WO2002016111A1 (fr) 2000-08-23 2000-12-20 Procede de preparation d'un article multicouche presentant une couche de plastique fluore et une couche d'elastomere
PCT/US2001/024867 Ceased WO2002016112A1 (fr) 2000-08-23 2001-08-08 Procede de preparation d'un article multicouches possedant une couche de plastique fluore et une couche d'elastomere

Family Applications After (1)

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PCT/US2001/024867 Ceased WO2002016112A1 (fr) 2000-08-23 2001-08-08 Procede de preparation d'un article multicouches possedant une couche de plastique fluore et une couche d'elastomere

Country Status (8)

Country Link
EP (1) EP1311381A1 (fr)
JP (1) JP2004506548A (fr)
KR (1) KR100773306B1 (fr)
CN (1) CN1220578C (fr)
AU (2) AU2001225857A1 (fr)
CA (1) CA2418110A1 (fr)
RU (1) RU2286878C2 (fr)
WO (2) WO2002016111A1 (fr)

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WO2002098657A3 (fr) * 2001-06-04 2003-04-24 Saint Gobain Performance Plast Article polymerique multicouche pourvu de couches polymeriques inter-reticulees et son procede de production
WO2003089239A1 (fr) * 2002-04-18 2003-10-30 3M Innovative Properties Company Collage et assemblage d'articles multicouches contenant une couche fluoropolymere
WO2003089231A1 (fr) * 2002-04-18 2003-10-30 3M Innovative Properties Company Stratifie fluoropolymere-perfluoropolymere
WO2003089232A1 (fr) * 2002-04-18 2003-10-30 3M Innovative Properties Company Articles de fluoropolymere
US6849314B2 (en) 2002-04-18 2005-02-01 3M Innovative Properties Company Fluoropolymer blends and multilayer articles
US6921565B2 (en) 2003-07-30 2005-07-26 The Goodyear Tire & Rubber Company Hose construction containing thermoplastic quadpolymers
US7192646B2 (en) 2003-06-04 2007-03-20 The Goodyear Tire & Rubber Company Hose construction containing fluoroelastomer composition and fluoroplastic barrier
US7598302B2 (en) 2006-08-30 2009-10-06 Veyance Technologies, Inc Adhesion promoter for bonding fluoropolymer layers in a multi-layered article
US7776446B2 (en) 2001-06-04 2010-08-17 Saint-Gobain Performance Plastics Corporation Multi-layer release films
US7776428B2 (en) 2006-02-13 2010-08-17 Saint-Gobain Performance Plastics Corporation Multi-layer release films

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GB2471322B (en) * 2009-06-26 2012-12-12 Tyco Electronics Ltd Uk High performance, high temperature lightweight insulating film, tape or sheath
MX355651B (es) * 2010-09-28 2018-04-26 Saint Gobain Performance Plastics Corp Star Pelicula de fluoropolimero moldeada para cojinetes.
CN103244764A (zh) * 2013-05-10 2013-08-14 苏州嘉目工程有限公司 一种使用寿命长的消防水带
KR102213323B1 (ko) * 2016-03-04 2021-02-05 미쓰이 가가쿠 가부시키가이샤 적층체 및 그의 용도
CN109291391B (zh) * 2018-09-21 2020-10-02 荆州亮诚科技股份有限公司 一种带信息导线的硅芯管生产工艺

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US6998007B2 (en) 2001-06-04 2006-02-14 Saint-Gobain Performance Plastics Corporation Multilayer structure with intercrosslinked polymer layers
US6652943B2 (en) 2001-06-04 2003-11-25 Saint-Gobain Performance Plastics Corporation Multilayer polymeric article with intercrosslinked polymer layers and method of making same
US7776446B2 (en) 2001-06-04 2010-08-17 Saint-Gobain Performance Plastics Corporation Multi-layer release films
WO2002098657A3 (fr) * 2001-06-04 2003-04-24 Saint Gobain Performance Plast Article polymerique multicouche pourvu de couches polymeriques inter-reticulees et son procede de production
CN1302917C (zh) * 2002-04-18 2007-03-07 3M创新有限公司 氟聚合物制品
US6759129B2 (en) 2002-04-18 2004-07-06 3M Innovative Properties Company Adhesion and bonding of multi-layer articles including a fluoropolymer layer
WO2003089239A1 (fr) * 2002-04-18 2003-10-30 3M Innovative Properties Company Collage et assemblage d'articles multicouches contenant une couche fluoropolymere
US6849314B2 (en) 2002-04-18 2005-02-01 3M Innovative Properties Company Fluoropolymer blends and multilayer articles
WO2003089232A1 (fr) * 2002-04-18 2003-10-30 3M Innovative Properties Company Articles de fluoropolymere
US7569275B2 (en) 2002-04-18 2009-08-04 3M Innovative Properties Company Fluoropolymer articles
WO2003089231A1 (fr) * 2002-04-18 2003-10-30 3M Innovative Properties Company Stratifie fluoropolymere-perfluoropolymere
KR101079547B1 (ko) 2002-04-18 2011-11-02 쓰리엠 이노베이티브 프로퍼티즈 캄파니 불소중합체 물품
US7192646B2 (en) 2003-06-04 2007-03-20 The Goodyear Tire & Rubber Company Hose construction containing fluoroelastomer composition and fluoroplastic barrier
US6921565B2 (en) 2003-07-30 2005-07-26 The Goodyear Tire & Rubber Company Hose construction containing thermoplastic quadpolymers
US7776428B2 (en) 2006-02-13 2010-08-17 Saint-Gobain Performance Plastics Corporation Multi-layer release films
US7598302B2 (en) 2006-08-30 2009-10-06 Veyance Technologies, Inc Adhesion promoter for bonding fluoropolymer layers in a multi-layered article

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Publication number Publication date
AU2001281188A1 (en) 2002-03-04
CA2418110A1 (fr) 2002-02-28
JP2004506548A (ja) 2004-03-04
EP1311381A1 (fr) 2003-05-21
KR100773306B1 (ko) 2007-11-06
AU2001225857A1 (en) 2002-03-04
CN1220578C (zh) 2005-09-28
CN1447743A (zh) 2003-10-08
KR20030027057A (ko) 2003-04-03
WO2002016112A1 (fr) 2002-02-28
RU2286878C2 (ru) 2006-11-10

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