EP0822012B1 - Revêtement de surfaces métalliques son application aux tubes et aux câbles - Google Patents

Revêtement de surfaces métalliques son application aux tubes et aux câbles Download PDF

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Publication number
EP0822012B1
EP0822012B1 EP97401839A EP97401839A EP0822012B1 EP 0822012 B1 EP0822012 B1 EP 0822012B1 EP 97401839 A EP97401839 A EP 97401839A EP 97401839 A EP97401839 A EP 97401839A EP 0822012 B1 EP0822012 B1 EP 0822012B1
Authority
EP
European Patent Office
Prior art keywords
polyurethane
cables
layer
metal surface
polyol
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.)
Expired - Lifetime
Application number
EP97401839A
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German (de)
English (en)
French (fr)
Other versions
EP0822012A1 (fr
Inventor
Maxime Deroch
Evelyne Bonnet
Jean-Jacques Flat
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.)
Freyssinet International STUP SA
Original Assignee
Atofina SA
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Publication date
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Publication of EP0822012A1 publication Critical patent/EP0822012A1/fr
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Classifications

    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/16—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics
    • D07B1/162—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics characterised by a plastic or rubber enveloping sheathing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01D—CONSTRUCTION OF BRIDGES, ELEVATED ROADWAYS OR VIADUCTS; ASSEMBLY OF BRIDGES
    • E01D19/00—Structural or constructional details of bridges
    • E01D19/16—Suspension cables; Cable clamps for suspension cables ; Pre- or post-stressed cables
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2083—Jackets or coverings
    • D07B2201/2087—Jackets or coverings being of the coated type
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2083—Jackets or coverings
    • D07B2201/2088—Jackets or coverings having multiple layers
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2205/00—Rope or cable materials
    • D07B2205/20—Organic high polymers
    • D07B2205/2003—Thermoplastics
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2205/00—Rope or cable materials
    • D07B2205/20—Organic high polymers
    • D07B2205/2064—Polyurethane resins
    • 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
    • Y10T428/1393—Multilayer [continuous layer]
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2938—Coating on discrete and individual rods, strands or filaments
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2973—Particular cross section
    • Y10T428/2975—Tubular or cellular
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31562—Next to polyamide [nylon, etc.]
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
    • Y10T428/31576—Ester monomer type [polyvinylacetate, etc.]
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
    • Y10T428/31587—Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31605—Next to free metal

Definitions

  • the present invention relates to a metal surface coating and its application to tubes and cables, it relates more particularly to a coating successively comprising, starting from the metal, a layer of polyurethane and a layer of thermoplastic polymer, an adhesion binder can be placed between the polyurethane and the thermoplastic polymer.
  • the present invention is useful for example for coating the surface outside of pipes, to coat electrical or telephone cables or metal cables such as guy wires.
  • DE 3,422,920 describes coatings for steel pipes successively comprising a layer of epoxy resin, a layer of grafted polypropylene and finally an outer layer of a mixture of polypropylene and a polypropylene / polyethylene block copolymer.
  • the glass transition temperature (T g ) of the epoxy resin is between 80 and 94 ° C. These coatings are suitable for hot water at 90 ° C.
  • Re 30 006 describes coatings of steel pipes comprising successively an epoxy resin and a polyethylene modified by grafting or copolymerization with maleic anhydride.
  • Epoxy resins are not flexible enough and are not perfect for protection against humidity.
  • EP 185,058 describes telecommunication cables coated by polyurethanes for protection against humidity, but these cables have no thermoplastic coating.
  • the coatings of the invention thanks to this shear strength have a very high cohesion, thus for an electric cable which must resist the efforts of its own weight or support the weight of boxes of connection or other instruments, it is necessary that the forces transmitted by through the thermoplastic polymer layer can be spread throughout the cable including the metallic core. It also helps that when connection of two electric cables, the connection box can lean on the external coverings of the two cables to be connected without that this results in a decohesion inside the cable and thus the forces such as the tensile forces on the cables can be transmitted. It is then possible make the connection by stripping the cable only to the minimum. Cables must also withstand winding, which is why it is important that the coating according to the present invention has good flexibility.
  • the invention is useful for strands that are individually protected from suspended civil engineering works.
  • the protective material used in these individually protected strands of the prior art is generally constituted by wax or fat, so these individually protected strands cannot effectively transmit significant axial forces from their outer sheath towards their twisted steel wires.
  • the prior art FR 2739113 has proposed coating the strand and filling the spaces between the metal wires with polybutadiene then coat the strand a polyethylene sheath by placing a grafted polyethylene to reinforce the bond between polybutadiene and the polyethylene sheath.
  • the axial forces are effectively transmitted from the outer sheath of the strand to its twisted steel wires, both by surface adhesion and shape adhesion of polybutadiene to the sheath exterior and on twisted steel wires, and by resistance of polybutadiene to shear.
  • polybutadiene must be vulcanized to present good resistance to aging and keep an elastomeric character to avoid penetration of water into the strands while continuing to provide the connection mechanical with polyethylene sheath.
  • the present invention also relates to the device comprising these bundles of strands or strands of coated steel forming a cable and surrounded by a metal collar made of two substantially hemicylindrical shells which are tightened around the cable at the by means of bolts, said collar is provided with at least one hook.
  • the present invention is therefore a coated metal surface comprising successively starting from the metal at least one layer of polyurethane, and at least a single layer of polymer thermoplastic, a binder that can be placed between the polyurethane and the thermoplastic polymer, said polyurethane resulting from the reaction of at least one polyol with at least one polyisocyanate and optionally at least a chain extender, said polyol being chosen from polydienepolyols.
  • the metal surface can for example be an electric cable, telephone, the outside surface of a pipe, or a guy wire.
  • the metal part can be of circular section or be a set of cables with circular cross-section as usual in cables cables or guy lines.
  • shroud metallic cables used for their tensile strength and generally formed of several cross-section elements which are twisted. Their diameter can be from a few millimeters to several centimeters. Several cables formed of twisted elements can themselves be brought together to form a single shroud.
  • the metal can be steel, copper, aluminum, zinc, stainless steel or their alloys or even galvanized steel.
  • the surface can therefore be either a simple surface like the surface outside of a pipe either the result of several twisted elements or the assembly of cables formed themselves from several twisted elements. This surface is therefore covered with at least one layer of polyurethane.
  • the polyurethane is placed so as to cover the whole surface or surfaces of the different elements and that we obtain essentially a cylinder whose outer surface is polyurethane.
  • the advantage of polyurethane is that it covers metals well and that in the case complex surfaces like twisted elements, it penetrates the heart of cable or guy line.
  • Hydrophobic polyurethanes are preferably used. These polyurethanes are resistant to aqueous acidic, basic or saline and hydrolysis. They have good electrical insulation, adhere to metals and retain a certain flexibility between - 65 ° C and + 100 ° C. polyurethanes result from the reaction of at least one polyol with at least one polyisocyanate and possibly a chain extender.
  • the polyols which can be used according to the present invention can be chosen among the polyester polyols, the polyether polyols, the polythioether polyols, the polyacetals-polyols, polycarbonates-polyols, polyestamides-polyols, polyamide polyols, polydien polyols and the mixture of at least two of the aforementioned polyols.
  • polyesters bearing hydroxy groups By way of polyesters bearing hydroxy groups, mention will be made of the products reaction of polyvalent alcohols, preferably divalent, accompanied optionally trivalent alcohols, and polyvalent carboxylic acids, and preferably divalent. Instead of free polycarboxylic acids, one can also use in the preparation of polyesters the acid anhydrides corresponding polycarboxylic acids or esters of polycarboxylic acids and corresponding lower alcohols or mixtures thereof. Acids polycarboxylics can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic and optionally substituted, for example by halogen atoms, and / or saturated.
  • carboxylic acids and derivatives By way of illustration of such carboxylic acids and derivatives, mention will be made of: succinic, adipic, suberic, azelaic, sebacic, phthalic acids, trimellitic, phthalic, tetrahydrophthalic, hexahydrophthalic anhydrides, tetrachtorophthalic, endomethylene-tetrahydrophthalic, glutaric, acid maleic, maleic anhydride, fumaric acid, unsaturated fatty acids dimerized and trimerized optionally as a mixture with fatty acids unsaturated monomers such as oleic acid; dimethyl terephthalate and bis-glycol terephthalate.
  • polyvalent alcohols there may be mentioned, for example, 1,2-ethanediol, 1,2-and1,3-propanediol, 1,4-and 2,3-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bis-hydroxymethylcyclohexane, 2-methyl-1,3-propanediol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, 1,2,4-butane-triol, trimethylolethane, pentaerythritol, quinitol, mannitol, sorbitol, formitol, methylglucoside, and also diethylene glycol, triethylene glycol, tetra-ethylene glycol and higher polyethylene glycols, dipropylene glycol and higher propylene glycols and dibutylene glycol and higher polybutylene glycol and higher
  • the polyether polyols which can be used according to the invention carrying at least 2, in general 2 to 8, preferably 2 to 3 hydroxy groups are those of the type known per se which are obtained for example by polymerization of epoxides such as oxide ethylene, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin on themselves, for example in the presence of Lewis catalysts such as BF 3 , or by addition of these epoxides, preferably ethylene oxide and propylene oxide, optionally as a mixture or successively, on starting components carrying reactive hydrogen atoms such as water, alcohols, ammonia or amines, for example 1,2-ethanediol, 1,3 or 1,2 propaneediol, trimethylolpropane, glycerol, sorbitol, 4,4'-dihydroxydiphenylpropane, aniline, ethanolamine or ethylene- diamine.
  • epoxides such as oxide
  • Polyethers of sucrose or polyethers condensed on formitol or on formose can also be used in accordance with the invention.
  • polyethers containing preponderant proportions (up to 90% by weight, relative to all the OH groups present in the polyether) of primary OH groups are preferred.
  • polythioters-polyols By way of polythioters-polyols, mention will be made in particular of the products of condensation of thiodiglycol on itself and / or on other glycols, acids dicarboxylics, formaldehyde, and aminocarboxylic acids or amino alcohols. Depending on the nature of the second component, the products obtained are for example mixed polythioethers, polythioether esters or polythioether ester amides.
  • polyacetal polyols By way of illustration of polyacetal polyols, mention will be made, for example, of those which can be prepared from glycols such as diethylene glycol, triethylene glycol, 4,4'-dihydroxyethoxydiphenyldimethylmethane, hexane-diol and formaldehyde. Polyacetals can also be used in the invention obtained by polymerization of cylindrical halves such as, for example, trioxane.
  • polycarbonates carrying hydroxy groups we cite those of known type which are obtained for example by reaction of diols such as propane-diol-1,3, butane-diol-1,4 and / or hexane-diol-1,6, diethylene glycol, triethylene glycol, tetraethylene glycol or thiodiglycol, with diaryl carbonates, for example diphenyl carbonate, or phosgene;
  • diols such as propane-diol-1,3, butane-diol-1,4 and / or hexane-diol-1,6, diethylene glycol, triethylene glycol, tetraethylene glycol or thiodiglycol
  • diaryl carbonates for example diphenyl carbonate, or phosgene
  • polyesteramides-polyols and polyamides-polyols we cite for example the mainly linear condensates obtained from saturated or unsaturated polyvalent carboxylic acids and their anhydrides and saturated or unsaturated polyvalent amino alcohols, diamines, polyamines and their mixtures.
  • polydien-polyols which can be used according to the present invention
  • hydroxytelechelic conjugated diene oligomers which can be obtained by different processes such as polymerization conjugated diene radical having 4 to 20 carbon atoms in the presence a polymerization initiator such as hydrogen peroxide or a compound azo such as azobis-2,2 '[methyl-2, N- (hydroxy-2ethyl) propionamide] or anionic polymerization of conjugated diene having 4 to 20 carbon atoms in the presence of a catalyst such as naphthalene dilithium.
  • the conjugated diene of the polydiene-polyol is chosen from the group comprising butadiene, isoprene, chloroprene, 1,3-pentadiene, cyclopentadiene.
  • the number-average molar mass of polyols which can be used can vary from 500 to 15,000 and preferably from 1000 to 3000.
  • a polydiene polyol based on butadiene is preferably used.
  • the polydiene glycol comprises 70 to 85% by mole, preferably 80% of units and 15 to 30% preferably 20% of patterns
  • copolymers of conjugated dienes and vinyl and acrylic monomers such as styrene, acrylonitrile.
  • the polydien-polyols can have number average molecular weights at most equal to 7000 and preferably between 1000 and 3000.
  • the OH index expressed in mlq / g is between 0.5 and 5, their viscosity is between 1000 and 10 000 M.Pa.s.
  • polystyrene-polyols By way of illustration of polydien-polyols, mention will be made of polybutadienes with hydroxylated terminations marketed by the company ELF ATOCHEM S.A. under the names Poly Bd®R45 HT and Poly Bd®R20 LM.
  • Mixtures of the above-mentioned compounds can be used such as, for example, mixtures of polyether polyols and of polydienes polyols.
  • chain extender we currently designate compounds bearing at least two reactive functions with the isocyanate functions.
  • the chain extender can be chosen from polyols. Their molecular mass can be between 62 and 500.
  • Polyamines can also be used as chain extenders. Their molecular mass can be between 60 and 500.
  • At least part by weight of one or more extenders of aforementioned chain for 100 parts by weight of polyol used and, from preferably 5 to 30 parts by weight.
  • a catalyst which can be chosen from the group including tertiary amines, imidazoles and compounds organometallics.
  • DABCO 1,4-diaza bicyclo [2.2.2] octane
  • organometallic compounds By way of illustration of organometallic compounds, mention may be made of tin dibutyldilaurate, tin dibutyldiacetate.
  • the amounts of catalyst can be between 0.01 and 5 parts by weight per 100 parts by weight of polyol.
  • composition according to the invention may also contain fillers inert and various additives such as antioxidants, anti U-V.
  • the polyisocyanate used can be a aromatic, aliphatic or cycloaliphatic polyisocyanate having at least two isocyanate functions in its molecule.
  • MDI 4,4'-diphenyl-methane diisocyanate
  • TDI liquid modified MDI
  • XDI xylylene diisocyanate
  • TMXDI triphenylmethane triisocyanate
  • PPDI paraphenylene diisacyanate
  • NDI naphthalene diisocyanate
  • the invention relates to preferably 4,4'-diphenylmethane diisocyanate and especially MDI modified liquids.
  • HMDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • CHDI cyclohexyl diisocyanate
  • isocyanate prepolymers obtained by reaction of a mentioned polyisocyanate previously with a polyol such as in particular polyether-polyol, polyester-polyol and polydiene-polyol or with a polyamine.
  • a polyol such as in particular polyether-polyol, polyester-polyol and polydiene-polyol or with a polyamine.
  • the isocyanates are used in such amounts that the NCO / OH molar ratio is between 0.3 and 2 and, preferably, between 0.5 and 1.2.
  • the NCO / OH molar ratio must be calculated taking into account the presence of reactive functions with isocyanate functions, such as hydroxyl and / or amine functions, of the chain extender.
  • adhesion promoters such as functional silanes. ie products having a trialcoxysilane end and an organic function such as amine, epoxy or vinyl, coupling agents such as acids or unsaturated carboxylic acid anhydrides and mineral fillers such as calcium carbonate, anti-bubble agents, anti U.V., sieves molecules, anti-corrosion pigments and flame retardants.
  • the possible binder is any product which makes it possible to adhere the layer of polyurethane and the thermoplastic polymer layer while giving a cohesion to the whole as explained above unless the polymer has good adhesion to polyurethane.
  • Polyolefins grafted with anhydride are advantageously used maleic.
  • the thickness of this binder layer can be between 15 and 500 ⁇ m.
  • thermoplastic polymer it may be by example of a polyamide, a polyolefin, a fluoropolymer, a resin styrenic or polyester.
  • the polyamide can be PA-6, PA-6.6, PA-11, PA-12.
  • the polyolefin can be a polyethylene, a copolymer of ethylene and of an alpha olefin, a homo or copolymer polypropylene, a copolymer of ethylene and a vinyl ester of saturated carboxylic acid.
  • the fluoropolymer can be PVDF.
  • the styrenic resin can be polystyrene.
  • the polyester can be PET or PBT.
  • high density and medium polyethylenes are used density.
  • thermoplastic polymer may also contain a product which facilitates adhesion to polyurethane.
  • This product can be the thermoplastic polymer grafted or the binder mentioned above.
  • thermoplastic polymer is a function of desired properties, they can be between 1 and 30 mm.
  • the present invention also relates to a method for manufacturing these coated surfaces in which the polyurethane is deposited, before the end of the polymerization, on the metal surface then the polymerization is completed optionally by heating, the outer surface of the layer of polyurethane then we cover it with the thermoplastic polymer and then we cools.
  • the deposition of the polyurethane layer depends on the nature of the metal surface. If this is the outside surface of a steel pipe, we will advantageously proceed to a degreasing then a sandblasting unless the surface is not already galvanized. The same is true for cables such as wire.
  • Polyurethane is in the form of at least two parts liquids which are mixed at the time of application on the metal surface.
  • One part contains the polyol, the other isocyanate, the third possibly the catalyst.
  • the other ingredients are divided between parts, depending on their responsiveness and compatibility. We operate advantageously at room temperature for example between 10 and 50 ° C. But we would not get out of the framework of the invention if one operated at 60 or 80 ° C. Generally, the reaction between polyol, polyisocyanate and chain extender takes place between 50 and 80 ° C in a few minutes. It would not go beyond the scope of the invention to use a monocomponent polyurethane powder system with thermal activation.
  • the polyurethane for the outer surface of a pipe, we deposit the polyurethane (before polymerization) by coating or rolling, or by a flat die producing a continuous ribbon which is wrapped around the tube by the rotation of the tube on himself.
  • a flat die For an electric cable or a shroud, one can proceed by a annular die which deposits the mixture of the two parts around the cable or the guy. If it is several twisted elements, we proceed in the same way making sure to fill all the gaps between the different elements.
  • Layer polyurethane being deposited and polymerized we then proceed to deposit the optional layer of binder and thermoplastic polymer.
  • the binder and the polymer are deposited thermoplastic, either by coextrusion in annular dies for small tube diameters or for cables and shrouds either by flat dies producing ribbons that are rolled up. Then cooling is carried out. the water.
  • Example 1 the following polyurethane formulation is prepared.
  • the first part is homogenized and degassed under vacuum (1 hour, 80 ° C at 1,360 Pa absolute pressure). Then we mix the two solutions and the mixture is placed at room temperature (20 ° C) on the exterior surface a galvanized steel pipe with an outside diameter of 115, a thickness of 6.5 mm, length. 3 m.
  • the thickness of the polyurethane layer is 0.5 to 1 mm.
  • the tube thus coated is heated polyurethane at 180 ° C-190 ° C then covered with a layer of binder (OREVAC 1) 200 to 300 ⁇ m thick then a layer of 2.50 to 3 mm of HDPE.
  • the binder and HDPE are each deposited by a flat die producing a ribbon continuous that is wrapped around the tube by the rotation of the tube on itself.
  • the tube coated is then cooled with water for 5 minutes.

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  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Ropes Or Cables (AREA)
  • Paints Or Removers (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Organic Insulating Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP97401839A 1996-07-30 1997-07-23 Revêtement de surfaces métalliques son application aux tubes et aux câbles Expired - Lifetime EP0822012B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9609559 1996-07-30
FR9609559 1996-07-30

Publications (2)

Publication Number Publication Date
EP0822012A1 EP0822012A1 (fr) 1998-02-04
EP0822012B1 true EP0822012B1 (fr) 2003-12-03

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EP97401839A Expired - Lifetime EP0822012B1 (fr) 1996-07-30 1997-07-23 Revêtement de surfaces métalliques son application aux tubes et aux câbles

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US (2) US5993924A (pt)
EP (1) EP0822012B1 (pt)
JP (1) JP2934217B2 (pt)
KR (1) KR100297042B1 (pt)
AT (1) ATE255471T1 (pt)
AU (1) AU719791B2 (pt)
BR (1) BR9704137A (pt)
CA (1) CA2210844C (pt)
DE (1) DE69726502T2 (pt)
DK (1) DK0822012T3 (pt)
ES (1) ES2212061T3 (pt)
NO (1) NO973469L (pt)
PT (1) PT822012E (pt)

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JP4043856B2 (ja) * 2002-06-11 2008-02-06 矢崎化工株式会社 摺動性等の機械的強度に優れた樹脂被覆鋼管
GB2399305B (en) * 2003-06-09 2006-02-22 Wood Ltd E Pipe renovating method
GB0313275D0 (en) * 2003-06-09 2003-07-16 Wood Ltd E Renovating water pipelines
US7868903B2 (en) 2004-10-14 2011-01-11 Daktronics, Inc. Flexible pixel element fabrication and sealing method
US8344410B2 (en) * 2004-10-14 2013-01-01 Daktronics, Inc. Flexible pixel element and signal distribution means
US7893948B1 (en) 2004-10-14 2011-02-22 Daktronics, Inc. Flexible pixel hardware and method
WO2009086029A1 (en) * 2007-12-20 2009-07-09 E. I. Du Pont De Nemours And Company Process for producing a multilayer coating
EP2222762B2 (en) * 2007-12-20 2023-08-23 Coatings Foreign IP Co. LLC Process for producing a multilayer coating
JP5202048B2 (ja) * 2008-03-13 2013-06-05 富士フイルム株式会社 インクジェット記録方法
US20100282400A1 (en) * 2009-05-05 2010-11-11 Chandra Sekar Methods for manufacturing a paint roller and component parts thereof
US8142599B2 (en) * 2009-01-08 2012-03-27 Chandra Sekar Methods for manufacturing a paint roller and component parts thereof
JP5830025B2 (ja) * 2009-12-01 2015-12-09 ナムローゼ・フェンノートシャップ・ベーカート・ソシエテ・アノニムＮ Ｖ Ｂｅｋａｅｒｔ Ｓｏｃｉｅｔｅ Ａｎｏｎｙｍｅ 強化ポリマー複合物
US8795832B2 (en) * 2010-07-30 2014-08-05 Fyfe Co., Llc Systems and methods for protecting a cable or cable bundle
KR101273931B1 (ko) * 2011-01-21 2013-06-11 이영술 천공홀 코팅 금속판 및 그 제조방법
EP3031862B1 (de) 2014-12-11 2018-08-29 Ems-Patent Ag Mehrschichtstruktur mit mindestens einer metallschicht und mindestens einer polyamidschicht
WO2016182254A1 (ko) * 2015-05-11 2016-11-17 엘에스전선 주식회사 전력 케이블
JP6549247B2 (ja) 2015-05-11 2019-07-24 エルエス ケーブル アンド システム リミテッド． 電力ケーブル
KR102787677B1 (ko) * 2020-06-10 2025-03-26 엘에스전선 주식회사 내열성 및 유연성이 우수한 운송수단용 케이블
CN112725711B (zh) * 2020-12-21 2022-02-18 山东大学 一种提高高强铝合金疲劳性能的方法
CN114164984B (zh) * 2021-12-09 2023-03-10 广州市亚丹柜业有限公司 一种由复合板材组成的墙面板及其制备方法

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Also Published As

Publication number Publication date
BR9704137A (pt) 1998-12-15
PT822012E (pt) 2004-04-30
JP2934217B2 (ja) 1999-08-16
EP0822012A1 (fr) 1998-02-04
ATE255471T1 (de) 2003-12-15
NO973469D0 (no) 1997-07-28
AU719791B2 (en) 2000-05-18
AU3237297A (en) 1998-02-05
US5993924A (en) 1999-11-30
JPH10114015A (ja) 1998-05-06
KR980009520A (ko) 1998-04-30
ES2212061T3 (es) 2004-07-16
US6291024B1 (en) 2001-09-18
DE69726502T2 (de) 2004-12-30
CA2210844A1 (fr) 1998-01-30
DK0822012T3 (da) 2004-04-13
NO973469L (no) 1998-02-02
KR100297042B1 (ko) 2002-11-18
CA2210844C (fr) 2001-04-17
DE69726502D1 (de) 2004-01-15

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