EP0822012B1 - Coating on metallic surfaces and use on tubes and cables - Google Patents
Coating on metallic surfaces and use on tubes and cables Download PDFInfo
- 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
Links
Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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]
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- 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
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- 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
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- 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
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- 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.]
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- 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.]
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- 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
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- 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.]
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- 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.]
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- 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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Abstract
Description
La présente invention concerne un revêtement de surface métallique et son application aux tubes et aux câbles, elle concerne plus particulièrement un revêtement comprenant successivement en partant du métal, une couche de polyuréthane et une couche de polymère thermoplastique, un liant d'adhésion pouvant être disposé entre le polyuréthane et le polymère thermoplastique.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.
Le but de l'invention est un revêtement :
- qui présente une bonne adhérence, qu'on peut traduire par exemple par la force de pelage,
- qui présente une bonne résistance au cisaillement (c'est-à-dire aux efforts axiaux),
- qui présente une bonne flexibilité et une bonne élasticité,
- qui résiste à la corrosion.
- which has good adhesion, which can be translated for example by the peel strength,
- which has good resistance to shear (that is to say to axial forces),
- which has good flexibility and good elasticity,
- which resists corrosion.
La présente invention est utile par exemple pour revêtir la surface extérieure de tuyaux, pour enrober des câbles électriques ou téléphoniques ou des câbles métalliques tels que des haubans.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 décrit des revêtements de tuyaux en acier comprenant successivement une couche de résine epoxy, une couche de polypropylène greffé et finalement une couche extérieure d'un mélange de polypropylène et d'un copolymère bloc polypropylène/polyéthylène. La température de transition vitreuse (Tg) de la résine epoxy est comprise entre 80 et 94° C. Ces revêtements conviennent pour l'eau chaude à 90° C.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 décrit des revêtements de tuyaux en acier comprenant successivement une résine epoxy et un polyéthylène modifié par greffage ou copolymérisation avec l'anhydride maléique.Re 30 006 describes coatings of steel pipes comprising successively an epoxy resin and a polyethylene modified by grafting or copolymerization with maleic anhydride.
Les résines epoxy ne sont pas assez flexibles et ne sont pas parfaites pour la protection contre l'humidité.Epoxy resins are not flexible enough and are not perfect for protection against humidity.
EP 185 058 décrit des câbles de télécommunication revêtus par des polyuréthanes pour la protection contre l'humidité, mais ces câbles n'ont pas de revêtement thermoplastique.EP 185,058 describes telecommunication cables coated by polyurethanes for protection against humidity, but these cables have no thermoplastic coating.
Les revêtements de l'invention grâce à cette résistance au cisaillement présentent une très grande cohésion, ainsi pour un câble électrique qui doit résister aux efforts de son propre poids ou supporter le poids de boítes de connexion ou d'autres instruments, il est nécessaire que les efforts transmis par l'intermédiaire de la couche de polymère thermoplastique puissent être répartis dans tout le câble y compris dans l'âme métallique. Il utile aussi que lors du raccordement de deux câbles électriques, la boíte de raccordement puisse prendre appui sur les revêtements extérieurs des deux câbles à raccorder sans qu'il en résulte une décohésion à l'intérieur du câble et qu'ainsi les efforts tels que les forces de traction sur les câbles puissent être transmises. Il est alors possible de faire le raccordement en ne dénudant le câble qu'au minimum. Les câbles électriques doivent aussi supporter l'enroulement, c'est pourquoi il est important que le revêtement selon la présente invention présente une bonne flexibilité.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.
Il en est de même pour les câbles métalliques qui peuvent transmettre les efforts par leur revêtement.The same is true for metallic cables which can transmit efforts by their coating.
L'invention est utile pour les torons individuellement protégés des ouvrages de génie civil suspendus.The invention is useful for strands that are individually protected from suspended civil engineering works.
On connaít des torons individuellement protégés comportant plusieurs fils d'acier torsadés entourés par une gaine extérieure en matière plastique flexible, les fils d'aciers torsadés laissant à l'intérieur de cette gaine des espaces interstitiels qui sont comblés par un matériau protecteur.We know of individually protected strands comprising several wires of twisted steel surrounded by an outer sheath of flexible plastic, the twisted steel wires leaving spaces inside this sheath interstitials that are filled with a protective material.
Ces torons individuellement protégés sont habituellement utilisés pour réaliser des haubans de pont, et ils se sont révélés particulièrement efficaces pour protéger ces haubans contre la corrosion.These individually protected strands are usually used for make deck stays, and they have proven to be particularly effective to protect these shrouds against corrosion.
Le matériau protecteur utilisé dans ces torons individuellement protégés de l'art antérieur est généralement constitué par de la cire ou de la graisse, de sorte que ces torons individuellement protégés ne peuvent pas efficacement transmettre des efforts axiaux importants depuis leur gaine extérieure vers leurs fils d'acier torsadés.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.
C'est la raison pour laquelle de tels torons individuellement protégés ne peuvent pas être utilisés pour réaliser les câbles porteurs des ponts suspendus, de couvertures suspendues, ou d'autres ouvrages suspendus, car de tels câbles porteurs doivent reprendre par frottement des efforts dirigés parallèlement à leur axe, efforts qui sont transmis par des colliers de serrage auxquels une structure de génie civil est suspendue par l'intermédiaire de suspentes.This is the reason why such individually protected strands do not cannot be used to make the supporting cables for suspension bridges, of hanging blankets, or other suspended works, because such cables wearers must resume frictionally directed efforts parallel to their axis, forces which are transmitted by cable ties to which a structure of civil engineering is suspended by lines.
Dans les ponts suspendus ou couvertures suspendues, on a donc recours à des câbles porteurs formés par des faisceaux de brins ou de torons d'acier nus. Ces câbles porteurs sont entourés d'une couche protectrice extérieure qui peut être constituée par de la peinture, du bitume ou une gaine tubulaire, mais cette couche protectrice est interrompue au niveau des colliers, serrés directement sur l'acier.In suspension bridges or suspended roofs, we therefore have recourse to load-bearing cables formed by bundles of bare strands or strands of steel. These carrying cables are surrounded by an outer protective layer which can be made up of paint, bitumen or a tubular sheath, but this protective layer is interrupted at the level of the collars, tightened directly on steel.
Cette configuration présente les inconvénients graves suivants :
- les colliers doivent être très fortement serrés sur les câbles porteurs, d'une part compte tenu de la médiocrité du coefficient de frottement acier sur acier et, d'autre part pour limiter les mouvements relatifs entre les brins d'acier, générateurs d'usure et de fatigue par "fretting corrosion" (également appelée "fatigue induite par petits débattements" ou "usure induite par petits débattements") : ce serrage intense nécessite des colliers très longs (par exemple jusqu'à 2 mètres) et massifs, serrés par de nombreux boulons,
- les phénomènes de fatigue par "fretting corrosion" ne sont jamais complètement évités, ce qui entraíne à la fois un desserrage des colliers et la rupture des brins constitutifs du câble porteur,
- et les phénomènes de corrosion chimique sont extrêmement fréquents.
- the collars must be tightened very tightly on the supporting cables, on the one hand taking into account the poor coefficient of friction steel on steel and, on the other hand to limit the relative movements between the steel strands, generators of wear and fatigue by "fretting corrosion" (also called "fatigue induced by small deflections" or "wear induced by small deflections"): this intense tightening requires very long collars (for example up to 2 meters) and massive, tightened by many bolts,
- the phenomena of fatigue by "fretting corrosion" are never completely avoided, which leads to both loosening of the collars and the breaking of the strands constituting the carrying cable,
- and chemical corrosion phenomena are extremely frequent.
L'art antérieur FR 2739113 a proposé de revêtir le toron et de combler les espaces entre les fils métalliques avec du polybutadiène puis de revêtir le toron d'une gaine de polyéthylène en disposant un polyéthylène greffé pour renforcer la liaison entre le polybutadiène et la gaine de polyéthylène.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.
Grâce à cette disposition on transmet de façon efficace les efforts axiaux depuis la gaine extérieure du toron jusqu'à ses fils d'acier torsadés, à la fois par adhérence de surface et adhérence de forme du polybutadiène sur la gaine extérieure et sur les fils d'acier torsadés, et par résistance du polybutadiène au cisaillement.Thanks to this arrangement, 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.
De plus, lorsqu'on utilise de tels torons individuellement protégés pour constituer les câbles porteurs d'un pont ou autre ouvrage suspendu, il n'est plus nécessaire de serrer les colliers de suspentes de façon aussi intense que dans l'art antérieur, du fait que des gaines des torons individuellement protégés présentent un bon coefficient de frottement.In addition, when using such individually protected strands for constitute the carrying cables of a bridge or other suspended structure, it is no longer necessary to tighten the line collars as hard as in the prior art, due to the fact that the sheaths of the individually protected strands have a good coefficient of friction.
En outre, les phénomènes de fatigue par "fretting corrosion" sont évités puisqu'il n'y a plus de contact direct entre les fils d'acier d'un toron à l'autre.In addition, the phenomena of fatigue by "fretting corrosion" are avoided since there is no longer direct contact between the steel wires from one strand to another.
Enfin, un câble porteur constitué de torons selon l'invention résiste parfaitement à la corrosion chimique.Finally, a carrying cable made up of strands according to the invention resists perfectly to chemical corrosion.
Cependant le polybutadiène doit être vulcanisé pour présenter une bonne résistance au vieillissement et garder un caractère élastomérique pour éviter la pénétration de l'eau dans les torons tout en continuant d'assurer la liaison mécanique avec la gaine en polyéthylène.However, 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.
Le polybutadiène une fois vulcanisé n'est plus thermoplastique, il faut donc le vulcaniser après avoir revêtu le toron ce qui est très compliqué. Le revêtement de la présente invention est beaucoup plus simple, le polyuréthane se forme pendant le revêtement de la surface métallique, il adhère mieux à la surface métallique, est parfaitement hydrophobe et remplit parfaitement tout l'espace entre les faisceaux de brins ou de torons d'acier nus. La présente invention concerne aussi le dispositif comprenant ces faisceaux de brins ou de torons d'acier revêtus formant un câble et entourés d'un collier métallique constitué de deux coques sensiblement hemicylindriques qui sont serrées autour du câble au moyen de boulons, ledit collier est muni d'au moins un crochet.Once vulcanized polybutadiene is no longer thermoplastic, it is necessary so vulcanize it after having coated the strand which is very complicated. The coating of the present invention is much simpler, the polyurethane forms during coating of the metal surface, it adheres better to the surface metallic, is perfectly hydrophobic and fills the entire space perfectly between the bundles of bare strands or strands of steel. 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.
La présente invention est donc une surface métallique revêtue comprenant successivement en partant du métal au moins une couche de polyuréthane, et au moins unie couche de polymère thermoplastique, un liant pouvant être disposé entre le polyuréthane et le polymère thermoplastique, ledit polyuréthane résultant de la réaction d'au moins un polyol avec au moins un polyisocyanate et éventuellement au moins un allongeur de chaíne, ledit polyol étant choisi parmi les polydiènes-polyols.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.
La surface métallique peut être par exemple un câble électrique, téléphonique, la surface extérieure d'un tuyau, ou un hauban. S'agissant des câbles ou des haubans la partie métallique peut être à section circulaire ou être un ensemble de câbles à section circulaire ainsi qu'il est habituel dans les câbles électriques ou les haubans.The metal surface can for example be an electric cable, telephone, the outside surface of a pipe, or a guy wire. Regarding cables or shrouds 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.
On entend par hauban des câbles métalliques utilisés pour leur résistance à la traction et formés en général de plusieurs éléments à section circulaire qui sont torsadés. Leur diamètre peut être de quelques millimètres à plusieurs centimètres. Plusieurs câbles formés d'éléments torsadés peuvent eux-mêmes être réunis pour former un seul hauban.By shroud is meant 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.
Le métal peut être l'acier, le cuivre, l'aluminium, le zinc, l'inox ou leurs alliages ou même l'acier galvanisé.The metal can be steel, copper, aluminum, zinc, stainless steel or their alloys or even galvanized steel.
La surface peut donc être soit une surface simple comme la surface extérieure d'un tuyau soit le résultat de plusieurs éléments torsadés soit la réunion de câbles formés eux-mêmes de plusieurs éléments torsadés. Cette surface est donc recouverte d'au moins une couche de polyuréthane.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.
Avantageusement, on dispose le polyuréthane de manière à recouvrir toute la surface ou les surfaces des différents éléments et qu'on obtienne essentiellement un cylindre dont la surface extérieure est du polyuréthane. L'avantage du polyuréthane est qu'il recouvre bien les métaux et que dans le cas de surfaces complexes comme les éléments torsadés, il pénètre au coeur du câble ou du hauban. On utilise de préférence des polyuréthanes hydrophobes. Ces polyuréthanes sont résistants aux solutions aqueuses acides, basiques ou salines et à l'hydrolyse. Ils présentent une bonne isolation électrique, adhèrent aux métaux et conservent une certaine flexibilité entre - 65° C et + 100° C. Les polyuréthanes résultent de la réaction d'au moins un polyol avec au moins un polyisocyanate et éventuellement un allongeur de chaíne.Advantageously, 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.
Les polyols utilisables selon la présente invention peuvent être choisis parmi les polyesters-polyols, les polyéthers-polyols, les polythioéthers-polyols, les polyacétals-polyols, les polycarbonates-polyols, les polyestéramides-polyols, les polyamides-polyols, les polydiènes-polyols et le mélange d'au moins deux des polyols précités.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.
A titre de polyesters portant des groupes hydroxy, on citera les produits de réaction d'alcools polyvalents, de préférence divalents, accompagnés éventuellement d'alcools trivalents, et d'acides carboxyliques polyvalents, et de préférence divalents. A la place des acides polycarboxyliques libres, on peut également utiliser à la préparation des polyesters les anhydrides d'acides polycarboxyliques correspondants ou esters d'acides polycarboxyliques et d'alcools inférieurs correspondants ou leurs mélanges. Les acides polycarboxyliques peuvent être de nature aliphatique, cycloaliphatique, aromatique et/ou hétérocyclique et éventuellement substitués, par exemple par des atomes d'halogène, et/ou saturés.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.
A titre d'illustration de tels acides carboxyliques et dérivés, on citera : les acides succinique, adipique, subérique, azélaïque, sébacique, phtalique, triméllitique, les anhydrides phtalique, tétrahydrophtalique, hexahydrophtalique, tétrachtorophtalique, endométhylène-tétrahydrophtalique, glutarique, l'acide maléique, l'anhydride maléique, l'acide fumarique, les acides gras insaturés dimérisés et trimérisés éventuellement en mélange avec des acides gras insaturés monomères comme l'acide oléique ; le téréphtalate de diméthyle et le téréphtalate de bis-glycol.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.
Parmi les alcools polyvalents, on citera par exemple le 1,2-éthanédiol, le 1,2-et1,3-propanediol, le 1,4-et 2,3-butanediol, le 1,6-hexanediol, le 1,8-octanediol, le glycol néopentylique, le 1,4-bis-hydroxyméthylcyclohexane, le 2-méthyl-1,3-propanediol, le glycérol, le triméthylolpropane, le 1,2,6-hexanetriol, le 1,2,4-butane-triol, le triméthyloléthane, le pentaérythritol, le quinitol, le mannitol, le sorbitol, le formitol, le méthylglucoside, et également le diéthylène-glycol, le triéthylène-glycol, le tétra-éthylène-glycol et les polyéthylène-glycols supérieurs, le dipropylène-glycol et les propylènes-glycols supérieurs et le dibutylène-glycol et les polybutylène-glycols supérieurs. Les polyesters peuvent porter des groupes carboxyle dans certaines positions terminales. On peut également utiliser des polyesters de lactones, par exemple de l'epsilon-caprolactone, ou d'acides hydroxycarboxyliques, par exemple de l'acide oméga-hydroxycaproïque.Among the 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 glycols. Polyesters can carry groups carboxyl in certain terminal positions. You can also use polyesters of lactones, for example epsilon-caprolactone, or acids hydroxycarboxylic, for example omega-hydroxycaproic acid.
Les polyethers-polyols utilisables selon l'invention portant au moins 2, en général 2 à 8, de préférence 2 à 3 groupes hydroxy, sont ceux du type connu en soi qu'on obtient par exemple par polymérisation d'époxydes comme l'oxyde d'éthylène, l'oxyde de propylène, l'oxyde de butylène, le tétrahydrofuranne, l'oxyde de styrène ou l'épichlorhydrine sur eux-mêmes, par exemple en présence de catalyseurs de Lewis tels que BF3, ou par addition de ces époxydes de préférence de l'oxyde d'éthylène et de l'oxyde de propylène, éventuellement en mélange ou successivement, sur des composants de départ portant des atomes d'hydrogène réactif comme l'eau, les alcools, l'ammoniaque ou des amines, par exemple le 1,2-éthanediol, le 1,3 ou 1,2 propanédiol, le triméthylolpropane, le glycérol, le sorbitol, le 4,4'-dihydroxydiphénylpropane, l'aniline, l'éthanolamine ou l'éthylène-diamine. On peut également utiliser conformément à l'invention des polyéthers de saccharose ou des polyéthers condensés sur formitol ou sur formose. Dans de nombreux cas, on préfère les polyéthers contenant des proportions prépondérantes (jusqu'à 90 % en poids, par rapport à tous les groupes OH présents dans le polyéther) de groupes OH primaires.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. Polyethers of sucrose or polyethers condensed on formitol or on formose can also be used in accordance with the invention. In many cases, 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.
A titre de polythioters-polyols, on citera en particulier les produits de condensation du thiodiglycol sur lui-même et/ou sur d'autres glycols, des acides dicarboxyliques, du formaldéhyde, et des acides aminocarboxyliques ou des aminoalcools. Selon la nature du second composant, les produits obtenus sont par exemple des polythioéthers mélangés, des polythioéther-esters ou des polythioéther-ester-amides.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.
A titre d'illustration de polyacétals-polyols, on citera par exemple ceux qu'on peut préparer à partir de glycols comme le diéthylène-glycol, le triéthylène-glycol, le 4,4'-dihydroxyéthoxydiphényldiméthylméthane, l'hexane-diol et le formaldéhyde. On peut également utiliser dans l'invention des polyacétals obtenus par polymérisation d'écétals cyliques comme par exemple le trioxanne.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.
A titre d'illustration de polycarbonates portant des groupes hydroxy, on citera ceux de type connu en soi qu'on obtient par exemple par réaction de diols comme le propane-diol-1,3, le butane-diol-1,4 et/ou l'hexane-diol-1,6, le diéthylène-glycol, le triéthylène-glycol, le tétraéthylène-glycol ou le thiodiglycol, avec des carbonates de diaryle, par exemple le carbonate de diphényle, ou le phosgène;By way of illustration of 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;
A titre d'illustration de polyesteramides-polyols et polyamides-polyols, on citera par exemple les condensats principalement linéaires obtenus à partir d'acides carboxyliques polyvalents saturés ou insaturés et de leurs anhydrides et d'aminoalcools polyvalents saturés ou insaturés, diamines, polyamines et leurs mélanges.By way of illustration of 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.
On peut également utiliser des polyols contenant déjà des groupes uréthane ou urée, ainsi que des polyols naturels éventuellement modifiés comme l'huile de ricin.It is also possible to use polyols already containing groups urethane or urea, as well as possibly modified natural polyols such as Castor oil.
A titre d'illustration de polydiènes-polyols utilisables selon la présente invention, on citera les oligomères de diène conjugué hydroxytélechélique qui peuvent être obtenus par différents procédés tels que la polymérisation radicalaire de diène conjugué ayant de 4 à 20 atomes de carbone en présence d'un amorceur de polymérisation tel que le peroxyde d'hydrogène ou un composé azoïque tel que l'azobis-2,2'[méthyl-2, N-(hydroxy-2éthyl)propionamide] ou la polymérisation anionique de diène conjugué ayant de 4 à 20 atomes de carbone en présence d'un catalyseur tel que le naphtalène dilithium.By way of illustration of polydien-polyols which can be used according to the present invention, mention will be made of the 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.
Selon la présente invention, le diène conjugué du polydiène-polyol est choisi dans le groupe comprenant le butadiène, l'isoprène, le chloroprène, le pentadiène-1,3, le cyclopentadiène. La masse molaire moyenne en nombre des polyols utilisables peut varier de 500 à 15 000 et de préférence de 1000 à 3000.According to the present invention, 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.
Selon la présente invention, on utilisera de préférence un polydiène-polyol à base de butadiène. Avantageusement, le polydiène glycol comprend 70 à 85 % en mole de préférence 80 % de motifs et 15 à 30 % de préférence 20 % de motifs According to the present invention, a polydiene polyol based on butadiene is preferably used. Advantageously, the polydiene glycol comprises 70 to 85% by mole, preferably 80% of units and 15 to 30% preferably 20% of patterns
Conviennent également les copolymères de diènes conjugués et de monomères vinylique et acrylique tels que le styrène, l'acrylonitrile.Also suitable are copolymers of conjugated dienes and vinyl and acrylic monomers such as styrene, acrylonitrile.
On ne sortirait pas de l'invention si on utilisait des oligomères hydroxytélécheliques de butadiène époxydés sur la chaíne ou bien encore des oligomères hydrogénés hydroxytélecheliques de diènes conjugués.We would not go outside the invention if we used oligomers epoxidized butadiene hydroxytelechelics on the chain or even hydroxytelechelic hydrogenated oligomers of conjugated dienes.
Selon la présente invention, les polydiènes-polyols peuvent avoir des masses moléculaires moyennes en nombre au plus égale à 7000 et de préférence comprise entre 1000 et 3000.According to the present invention, the polydien-polyols can have number average molecular weights at most equal to 7000 and preferably between 1000 and 3000.
L'indice d'OH exprimé en mlq/g est compris entre 0,5 et 5, leur viscosité est comprise entre 1000 et 10 000 M.Pa.s.The OH index expressed in mlq / g is between 0.5 and 5, their viscosity is between 1000 and 10 000 M.Pa.s.
A titre d'illustration de polydiènes-polyols, on citera les polybutadiènes à terminaisons hydroxylées commercialisés par la Société ELF ATOCHEM S.A. sous les dénominations Poly Bd®R45 HT et Poly Bd®R20 LM.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.
On peut utiliser des mélanges des composés précédemment mentionnés tels que par exemple des mélanges de polyéthers-polyols et de polydiènes-polyols. Mixtures of the above-mentioned compounds can be used such as, for example, mixtures of polyether polyols and of polydienes polyols.
On ne sortirait pas du cadre de l'invention si on utilisait des composés
polyaminés ayant une masse moléculaire moyenne en nombre
A titre d'illustration de tels composés, on citera les polyoxypropylènes terminés par des fonctions NH2, les polyoxytétraméthylènes et les polybutadiènes terminés par des fonctions NH2, les copolymères butadiène/styrène et butadiène/acrylonitrile terminés par des fonctions NH2.By way of illustration of such compounds, mention will be made of polyoxypropylenes terminated by NH2 functions, polyoxytetramethylenes and polybutadienes terminated by NH 2 functions, the butadiene / styrene copolymers and butadiene / acrylonitrile terminated by NH2 functions.
Par allongeur de chaíne, on désigne présentement des composés portant au moins deux fonctions réactives avec les fonctions isocyanates.By chain extender, we currently designate compounds bearing at least two reactive functions with the isocyanate functions.
Comme exemples de telles fonctions réactives, on citera les fonctions hydroxyle et les fonctions amine.As examples of such reactive functions, mention will be made of the functions hydroxyl and amine functions.
Selon l'invention, l'allongeur de chaíne peut être choisi parmi les polyols. Leur masse moléculaire peut être comprise entre 62 et 500.According to the invention, the chain extender can be chosen from polyols. Their molecular mass can be between 62 and 500.
A titre d'illustration de tels composés, on citera l'éthylène glycol, le propylène glycol, le diéthylène glycol, le dipropylène glycol, le 1,4-butanediol, le 1,6-hexanediol, le 2-éthyl-1,3-hexanediol, le N,N bis(hydroxy-2 propyl)aniline, le 3-méthyl-1,5-pentanediol et le mélange d'au moins deux des composés précités.By way of illustration of such compounds, mention will be made of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, N, N bis (2-hydroxypropyl) aniline, 3-methyl-1,5-pentanediol and the mixture of at least two of the above-mentioned compounds.
On peut également utiliser comme allongeurs de chaíne des polyamines. Leur masse moléculaire peut être comprise entre 60 et 500.Polyamines can also be used as chain extenders. Their molecular mass can be between 60 and 500.
A titre d'illustration de telles polyamines, on citera l'éthylène diamine, la diphényl méthane diamine, l'isophoronediamine, l'hexaméthylenediamine, la diéthyltoluènediamine.By way of illustration of such polyamines, mention will be made of ethylene diamine, diphenyl methane diamine, isophoronediamine, hexamethylenediamine, diethyltoluenediamine.
On utilisera au moins une partie en poids d'un ou plusieurs allongeurs de chaíne précités pour 100 parties en poids de polyol mis en oeuvre et, de préférence 5 à 30 parties en poids.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.
On peut ajouter un catalyseur qui peut être choisi dans le groupe comprenant des amines tertiaires, des imidazoles et des composés organométalliques.We can add a catalyst which can be chosen from the group including tertiary amines, imidazoles and compounds organometallics.
A titre d'illustration d'amines tertiaires, on peut citer le diaza-1,4 bicyclo [2.2.2]octane (DABCO).By way of illustration of tertiary amines, mention may be made of 1,4-diaza bicyclo [2.2.2] octane (DABCO).
A titre d'illustration de composés organométalliques, on peut citer le dibutyldilaurate d'étain, le dibutyldiacétate d'étain.By way of illustration of organometallic compounds, mention may be made of tin dibutyldilaurate, tin dibutyldiacetate.
Les quantités de catalyseur peuvent être comprises entre 0,01 et 5 parties en poids pour 100 parties en poids de polyol.The amounts of catalyst can be between 0.01 and 5 parts by weight per 100 parts by weight of polyol.
La composition selon l'invention peut contenir en outre des charges inertes et divers additifs tels que des anti-oxydants, des anti U-V. The composition according to the invention may also contain fillers inert and various additives such as antioxidants, anti U-V.
Selon la présente invention, le polyisocyanate utilisé peut être un polyisocyanate aromatique, aliphatique ou cycloaliphatique ayant au moins deux fonctions isocyanate dans sa molécule.According to the present invention, the polyisocyanate used can be a aromatic, aliphatic or cycloaliphatic polyisocyanate having at least two isocyanate functions in its molecule.
A titre d'illustration de polyisocyanate aromatique, on citera le 4,4'-diphényl-méthane diisocyanate (MDI), les MDI modifiés liquides, les MDI polymériques, le 2,4- et le 2,6-toluylène diisocyanate (TDI) ainsi que leur mélange, le xylylène diisocyanate (XDI), le triphénylméthane triisocyanate, le tétraméthylxylylène diisocyanate (TMXDI), le paraphénylène diisacyanate (PPDI), le naphtalène diisocyanate (NDI).By way of illustration of an aromatic polyisocyanate, mention will be made of 4,4'-diphenyl-methane diisocyanate (MDI), liquid modified MDI, MDI 2,4- and 2,6-toluylene diisocyanate (TDI) and their mixture, xylylene diisocyanate (XDI), triphenylmethane triisocyanate, tetramethylxylylene diisocyanate (TMXDI), paraphenylene diisacyanate (PPDI), naphthalene diisocyanate (NDI).
Parmi les polyisocyanates aromatiques, l'invention concerne de préférence le 4,4'-diphenylméthane diisocyanate et tout particulièrement les MDI modifiés liquides.Among the aromatic polyisocyanates, the invention relates to preferably 4,4'-diphenylmethane diisocyanate and especially MDI modified liquids.
A titre d'illustration de polyisocyanate aliphatique on citera l'hexaméthylène diisocyanate (HMDI) et ses dérivés, le triméthylhéxaméthylène diisocyanate.By way of illustration of an aliphatic polyisocyanate, mention will be made hexamethylene diisocyanate (HMDI) and its derivatives, trimethylhexamethylene diisocyanate.
A titre d'illustration de polyisocyanate cycloaliphatique on citera l'isophorone diisocyanate (IPDI) et ses dérivés, le 4,4'-dicyclohexylméthanediisocyanate et le cyclohexyl diisocyanate (CHDI).As an illustration of cycloaliphatic polyisocyanate, mention will be made isophorone diisocyanate (IPDI) and its derivatives, 4,4'-dicyclohexylmethanediisocyanate and cyclohexyl diisocyanate (CHDI).
On ne sortirait pas du cadre de l'invention si l'on utilisait des prépolymères d'isocyanates obtenus par réaction d'un polyisocyanate mentionné précédemment avec un polyol tel que notamment polyéther-polyol, polyester-polyol et polydiène-polyol ou avec une polyamine.We would not go beyond the scope of the invention if we used 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.
Avantageusement les isocyanates sont utilisés en des quantités telles que le rapport molaire NCO/OH est compris entre 0,3 et 2 et, de préférence, compris entre 0,5 et 1,2.Advantageously, 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.
Le rapport molaire NCO/OH doit être calculé en tenant compte de la présence des fonctions réactives avec les fonctions isocyanates, telles que les fonctions hydroxyles et/ou amines, de l'allongeur de chaíne.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.
On peut aussi ajouter dans la formulation du polyuréthane, c'est-à-dire dans le mélange des différents ingrédients avant ou au cours de la polymérisation, des promoteurs d'adhésion tels que des silanes.fonctionnels c'est à dire des produits ayant une extrémité trialcoxysilane et une fonction organique telle qu'amine, époxy ou vinyl, des agents de couplage tels que des acides ou anhydrides d'acides carboxyliques insaturés et des charges minérales telles que du carbonate de calcium, des agents antibullants, anti U.V., des tamis moléculaires, des pigments anticorrosion et des ignifugeants.One can also add in the formulation of polyurethane, that is to say in the mixture of different ingredients before or during the polymerization, 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.
Le liant éventuel est tout produit qui permet de faire adhérer la couche de polyuréthane et la couche de polymère thermoplastique tout en donnant une cohésion à l'ensemble ainsi qu'il a été expliqué plus haut à moins que le polymère ait une bonne adhérence sur le polyuréthane.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.
On utilise avantageusement des polyoléfines fonctionnalisées.Advantageously, functionalized polyolefins are used.
A titre d'exemple de liant, on peut citer :
- le polyéthylène, le polypropylène, les copolymères de l'éthylène et d'au moins une alpha oléfine, des mélanges de ces polymères, tous ces polymères étant greffés par des anhydrides d'acides carboxyliques insaturés tels que par exemple, l'anhydride maléique. On peut aussi utiliser des mélanges de ces polymères greffés et de ces polymères non greffés.
- les copolymères de l'éthylène avec au moins un produit choisi parmi (i) les acides carboxyliques insaturés, leurs sels, leurs esters, (ii) les esters vinyliques d'acides carboxyliques saturés, (iii) les acides dicarboxyliques insaturés, leurs sels, leurs esters, leurs hemiesters, leurs anhydrides, éventuellement les epoxydes insaturés à condition que le copolymère ne contienne pas de fonction acide ; ces copolymères pouvant être greffés ou copolymérisés.
- polyethylene, polypropylene, copolymers of ethylene and at least one alpha olefin, mixtures of these polymers, all of these polymers being grafted with anhydrides of unsaturated carboxylic acids such as, for example, maleic anhydride. It is also possible to use mixtures of these grafted polymers and of these non-grafted polymers.
- copolymers of ethylene with at least one product chosen from (i) unsaturated carboxylic acids, their salts, their esters, (ii) vinyl esters of saturated carboxylic acids, (iii) unsaturated dicarboxylic acids, their salts, their esters, their hemiesters, their anhydrides, possibly the unsaturated epoxides provided that the copolymer does not contain an acid function; these copolymers can be grafted or copolymerized.
On utilise avantageusement les polyoléfines greffées par l'anhydride maléique.Polyolefins grafted with anhydride are advantageously used maleic.
A titre d'illustration de tels copolymères, on peut citer les copolymères éthylène / (méth)acrylate d'alkyle / anhydride maléique ou acide acrylique.
- éthylène / (méth)acrylate d'alkyle / epoxyde insaturé tel que le (méth)acrylate de glycidyle ;
- éthylène / acétate de vinyle / anhydride maléique ou acide acrylique ;
- éthylène / acétate de vinyle / epoxyde insaturé tel que le (méth)acrylate de glycidyle ;
- (éthylène / acétate de vinyle) greffé par l'anhydride maléique, l'acide acrylique ou un epoxyde insaturé ;
- (éthylène / (méth)acrylate d'alkyle) greffé par l'anhydride maléique, l'acide acrylique ou un epoxyde insaturé.
- ethylene / alkyl (meth) acrylate / unsaturated epoxide such as glycidyl (meth) acrylate;
- ethylene / vinyl acetate / maleic anhydride or acrylic acid;
- ethylene / vinyl acetate / unsaturated epoxide such as glycidyl (meth) acrylate;
- (ethylene / vinyl acetate) grafted with maleic anhydride, acrylic acid or an unsaturated epoxide;
- (ethylene / (meth) acrylate) grafted with maleic anhydride, acrylic acid or an unsaturated epoxide.
L'épaisseur de cette couche de liant peut être comprise entre 15 et 500 µm.The thickness of this binder layer can be between 15 and 500 µm.
Quant à la couche de polymère thermoplastique, il peut s'agir par exemple d'un polyamide, d'une polyoléfine, d'un polymère fluoré, d'une résine styrénique ou d'un polyester.As for the layer of thermoplastic polymer, it may be by example of a polyamide, a polyolefin, a fluoropolymer, a resin styrenic or polyester.
Le polyamide peut être le PA-6, le PA-6,6, le PA-11, le PA-12.The polyamide can be PA-6, PA-6.6, PA-11, PA-12.
La polyoléfine peut être un polyéthylène, un copolymère de l'éthylène et d'une alpha oléfine, un polypropylène homo ou copolymère, un copolymère de l'éthylène et d'un ester vinylique d'acide carboxylique saturé. 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.
Le polymère fluoré peut être le PVDF.The fluoropolymer can be PVDF.
La résine styrénique peut être le polystyrène.The styrenic resin can be polystyrene.
Le polyester peut être le PET ou le PBT.The polyester can be PET or PBT.
On utilise avantageusement les polyéthylènes haute densité et moyenne densité.Advantageously, high density and medium polyethylenes are used density.
Le polymère thermoplastique peut aussi contenir une produit facilitant l'adhésion sur le polyuréthane. Ce produit peut être le polymère thermoplastique greffé ou le liant cité ci-dessus.The 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.
L'épaisseur de cette couche de polymère thermoplastique est fonction des propriétés recherchées, elles peut être comprise entre 1 et 30 mm.The thickness of this layer of thermoplastic polymer is a function of desired properties, they can be between 1 and 30 mm.
La présente invention concerne aussi un procédé de fabrication de ces surfaces revêtues dans lequel on dépose le polyuréthane, avant la fin de la polymérisation, sur la surface métallique puis on acheve la polymérisation éventuellement par chauffage, on chauffe la surface extérieure de la couche de polyuréthane puis on la recouvre avec le polymère thermoplastique et ensuite on refroidit. Le dépôt de la couche de polyuréthane est fonction de la nature de la surface métallique. Si il s'agit de la surface extérieure d'un tuyau en acier, on procédera avantageusement à un dégraissage puis un sablage à moins que la surface ne soit déjà galvanisée. Il en est de même pour les câbles tels que les haubans. Le polyuréthane se présente sous forme d'au moins deux parties liquides qu'on mélange au moment de l'application sur la surface métallique. L'une des parties contient le polyol, l'autre l'isocyanate, la troisième éventuellement le catalyseur. Les autres ingrédients sont répartis entre les parties, selon leur réactivité et leur compatibilité. On opère avantageusement à température ambiante par exemple entre 10 et 50° C. Mais on ne sortirait pas du cadre de l'invention si on opérait à 60 ou 80° C. Généralement, la réaction entre le polyol, le polyisocyanate et l'allongeur de chaíne a lieu entre 50 et 80° C en quelques minutes. On ne sortirait pas du cadre de l'invention en utilisant un système polyuréthane monocomposant en poudre à activation thermique.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.
On procède donc au revêtement de la surface métallique avec le polyurethane puis quand la surface est bien revêtue, on chauffe pour polymériser. Par exemple, pour la surface extérieure d'un tuyau, on dépose le polyuréthane (avant polymérisation) par couchage ou laminage, ou par une filière plate produisant un ruban continu qu'on enroule autour du tube par la rotation du tube sur lui-même. Pour un câble électrique ou un hauban, on peut procéder par une filière annulaire qui dépose le mélange des deux parties autour du câble ou du hauban. Si il s'agit de plusieurs éléments torsadés, on procède de même en veillant à bien remplir tous les interstices entre les différents éléments. La couche de polyuréthane étant déposée et polymérisée, on procède ensuite au dépôt de la couche éventuelle de liant et du polymère thermoplastique. Avantageusement, après le polyuréthane soit complètement polymérisé, c'est-à-dire qu'on ait atteint le temps dit "hors collant", on chauffe sa surface extérieure par exemple par un tunnel chauffant ou par induction à une température d'environ 30 ou 40° C inférieure à celle d'extrusion du liant puis on dépose le liant et le polymère thermoplastique , soit par coextrusion dans des filières annulaires pour les petits diamètres de tubes ou pour les câbles et haubans soit par des filières plates produisant des rubans qu'on enroule. On effectue ensuite un refroidissement à l'eau.We therefore proceed to coating the metal surface with the polyurethane then when the surface is well coated, it is heated to polymerize. For example, 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. 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. advantageously, after the polyurethane is completely polymerized, that is to say that we have reached the so-called "sticky" time, we heat its outer surface for example by a heating or induction tunnel at a temperature of around 30 or 40 ° C lower than that of extrusion of the binder then 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.
On utilise les produits suivants :
- PolyBd®R45 HT polybutadiène hydroxylé de
Mn égale à 2800 (déterminée par chromatographie d'exclusion stérique), présentant un indice d'hydroxyle IOH exprimé en milliéquivalent par gramme (meq/g) égal à environ 0,83, une viscosité en m.Pa.s (cp) à 30°C égale à 5000 et une densité égale à 0,90 ;
- OREVAC 1 :
- désigne un mélange de copolymère de copolymères éthylène alphaloléfine greffés par de l'anhydride maléique de MFi.1 à 190° C 2,16 kg et contenant 0,5 % en poids d'anhydride maléique.
- PEHD :
- est un polyéthylène haute densité (TUB 71 de SOLVAY).
- PolyBd ® R45 HT hydroxylated polybutadiene of
mn equal to 2800 (determined by size exclusion chromatography), having a hydroxyl index I OH expressed in milliequivalents per gram (meq / g) equal to approximately 0.83, a viscosity in m.Pa.s (cp) at 30 ° C equal to 5000 and a density equal to 0.90;
- OREVAC 1:
- denotes a mixture of copolymer of ethylene alphalolefin copolymers grafted with maleic anhydride of MFi.1 at 190 ° C. 2.16 kg and containing 0.5% by weight of maleic anhydride.
- HDPE:
- is a high density polyethylene (TUB 71 from SOLVAY).
- Polyol : PolyBd®R45 HT 100 gPolyol: PolyBd®R45 HT 100 g
- Anhydride maléique 1 gMaleic anhydride 1 g
- Allongeur de chaíne (polyol court) : Voranol RA 100 17.5 gChain extender (short polyol): Voranol RA 100 17.5 g
- Charge: carbonate de calcium : Omnya 90 T 100 gFiller: calcium carbonate: Omnya 90 T 100 g
- promoteur d'adhésion : epoxy silane : Silane A 187 1.1 gadhesion promoter: epoxy silane: Silane A 187 1.1 g
- Isonate 143 M (NCO/OH = 1.05) 36 gIsonate 143 M (NCO / OH = 1.05) 36 g
Elle est obtenue par mélange d'une première partie contenant le polyol, l'allongeur de chaíne, le carbonate le silane et le MAH et d'une deuxième partie contenant l'isocyanate.It is obtained by mixing a first part containing the polyol, the chain extender, the carbonate the silane and the MAH and of a second part containing isocyanate.
La première partie est homogénéisée et dégazée sous vide (1 heure, 80 °C sous 1 360 Pa de pression absolue). Puis on mélange les deux solutions et on dépose à la température ambiante (20° C) le mélange sur la surface extérieure d'un tuyau en acier galvanisé de diamètre extérieur.115, d'épaisseur.6,5mm, longueur.3 m.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.
Puis on laisse réticuler.Then let it crosslink.
L'épaisseur de la couche de polyuréthane est 0,5 à 1 mm.The thickness of the polyurethane layer is 0.5 to 1 mm.
A l'aide d'un four à induction, on chauffe le tube ainsi revêtu de polyuréthane à 180°C-190°C puis on recouvre par une couche de liant (OREVAC 1) de 200 à 300 µm d'épaisseur puis une couche de 2,50 à 3 mm de PEHD. Le liant et le PEHD sont déposés chacune par une filière plate produisant un ruban continu qu'on enroule autour du tube par la rotation du tube sur lui-même. Le tube revêtu est ensuite refroidi à l'eau pendant 5 minutes.Using an induction furnace, the tube thus coated is heated polyurethane at 180 ° C-190 ° C then covered with a layer of binder (OREVAC 1) 200 to 300 µm 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.
Des tests de pelage à la température de 23° C selon la norme.DIN 30670 ont été réalisés. Sur un échantillon extrait d'un tube en acier galvanisé revêtu et dont la température de chauffage avant revêtement par le liant et le PEHD par induction était aux alentours de 190° C (± 5° C), nous avons obtenu une force de pelage moyenne de 175 N/cm. La rupture est cohésive dans le polyuréthane.Peel tests at a temperature of 23 ° C according to the standard DIN 30670 were realized. On a sample extracted from a coated galvanized steel tube and whose heating temperature before coating by the binder and HDPE by induction was around 190 ° C (± 5 ° C), we obtained a force of average coat of 175 N / cm. The rupture is cohesive in polyurethane.
Claims (7)
- Coated metal surface including successively, starting at the metal, at least one layer of polyurethane and at least one layer of thermoplastic polymer, it being possible for a binder to 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 with at least one chain extender, said polyol being chosen from polydienes-polyols.
- Coated metal surface according to claim 1, chosen from the external surface of pipes, cables or assemblies of twisted cables of stay wires, electrical cables and telecommunications cables.
- Coated metal surface according to claim 2, in which said polyol is a polybutadiene with hydroxyl ends.
- Coated metal surface according to any one of claims 1 to 3, in which the binder is a polyolefin grafted with maleic anhydride.
- Coated metal surface according to any one of claims 1 to 4, in which the layer of thermoplastic polymer is chosen from polyamides, polyolefins, fluoropolymers, styrene-based resins and polyesters.
- Process for the manufacture of the coated surface of any one of claims 1 to 5, in which the polyurethane is deposited before the end of the polymerization on the metal surface and the polymerization is then finished optionally by heating, the external surface of the layer of polyurethane is heated and is then covered optionally with the binder and then the thermoplastic polymer and subsequently cooling is carried out.
- Device including bundles of wires or of steel strands which have a coating according to one of claims 1 to 5 and which form a cable and are surrounded by a metal clamp consisting of two substantially hemicylindrical shells which are tightened around the cable by means of bolts, the said clamp being provided with at least one hook.
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 |
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EP0822012A1 EP0822012A1 (en) | 1998-02-04 |
EP0822012B1 true EP0822012B1 (en) | 2003-12-03 |
Family
ID=9494617
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97401839A Expired - Lifetime EP0822012B1 (en) | 1996-07-30 | 1997-07-23 | Coating on metallic surfaces and use on tubes and cables |
Country Status (13)
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US (2) | US5993924A (en) |
EP (1) | EP0822012B1 (en) |
JP (1) | JP2934217B2 (en) |
KR (1) | KR100297042B1 (en) |
AT (1) | ATE255471T1 (en) |
AU (1) | AU719791B2 (en) |
BR (1) | BR9704137A (en) |
CA (1) | CA2210844C (en) |
DE (1) | DE69726502T2 (en) |
DK (1) | DK0822012T3 (en) |
ES (1) | ES2212061T3 (en) |
NO (1) | NO973469L (en) |
PT (1) | PT822012E (en) |
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JP3846757B2 (en) * | 1997-08-06 | 2006-11-15 | 古河電気工業株式会社 | cable |
US7874404B1 (en) | 1998-09-29 | 2011-01-25 | Otis Elevator Company | Elevator system having drive motor located between elevator car and hoistway sidewall |
EP1280958B1 (en) * | 2000-05-08 | 2005-05-04 | N.V. Bekaert S.A. | Zinc-coated steel cord with improved fatigue resistance |
JP4043856B2 (en) * | 2002-06-11 | 2008-02-06 | 矢崎化工株式会社 | Resin-coated steel pipe with excellent mechanical strength such as slidability |
GB0313275D0 (en) * | 2003-06-09 | 2003-07-16 | Wood Ltd E | Renovating water pipelines |
GB2399305B (en) * | 2003-06-09 | 2006-02-22 | Wood Ltd E | Pipe renovating method |
US7893948B1 (en) | 2004-10-14 | 2011-02-22 | Daktronics, Inc. | Flexible pixel hardware and method |
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 |
WO2009086034A1 (en) | 2007-12-20 | 2009-07-09 | E. I. Du Pont De Nemours And Company | Process for producing a multilayer coating |
CA2708101A1 (en) * | 2007-12-20 | 2009-07-09 | E. I. Dupont De Nemours And Company | Process for producing a multilayer coating |
JP5202048B2 (en) * | 2008-03-13 | 2013-06-05 | 富士フイルム株式会社 | Inkjet recording method |
US8142599B2 (en) * | 2009-01-08 | 2012-03-27 | Chandra Sekar | Methods for manufacturing a paint roller and component parts thereof |
US20100282400A1 (en) * | 2009-05-05 | 2010-11-11 | Chandra Sekar | Methods for manufacturing a paint roller and component parts thereof |
CN102667025B (en) * | 2009-12-01 | 2014-12-31 | 贝卡尔特公司 | A reinforced polymer composite |
US8795832B2 (en) * | 2010-07-30 | 2014-08-05 | Fyfe Co., Llc | Systems and methods for protecting a cable or cable bundle |
KR101273931B1 (en) | 2011-01-21 | 2013-06-11 | 이영술 | Perforated metal plate lamination and manufacturing method thereof |
EP3031862B1 (en) | 2014-12-11 | 2018-08-29 | Ems-Patent Ag | Multilayer structure having at least one metal layer and at least one polyamide layer |
WO2016182254A1 (en) * | 2015-05-11 | 2016-11-17 | 엘에스전선 주식회사 | Power cable |
JP6549247B2 (en) | 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. | Power cable |
CN112725711B (en) * | 2020-12-21 | 2022-02-18 | 山东大学 | Method for improving fatigue performance of high-strength aluminum alloy |
CN114164984B (en) * | 2021-12-09 | 2023-03-10 | 广州市亚丹柜业有限公司 | Wall panel composed of composite boards and preparation method thereof |
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US30006A (en) * | 1860-09-11 | Safety-gtjakd fob | ||
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AT320718B (en) * | 1969-07-30 | 1975-02-25 | Unitecta Oberflaechenschutz | Process for the production of cables and device for this |
JPS528253B1 (en) * | 1970-05-15 | 1977-03-08 | ||
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DE3046263C2 (en) * | 1980-12-09 | 1982-12-09 | Basf Farben + Fasern Ag, 2000 Hamburg | Method for sheathing a metal pipe |
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US4734545A (en) * | 1986-11-26 | 1988-03-29 | The Furukawa Electric Co., Ltd. | Insulated conductor for a wire harness |
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FR2739113B1 (en) * | 1995-09-26 | 1997-12-05 | Freyssinet Int Stup | INDIVIDUALLY PROTECTED STRAND FOR SUSPENDED CIVIL ENGINEERING STRUCTURE, STRUCTURE INCLUDING SUCH STRANDS, AND METHOD OF MANUFACTURE |
-
1997
- 1997-07-23 DK DK97401839T patent/DK0822012T3/en active
- 1997-07-23 ES ES97401839T patent/ES2212061T3/en not_active Expired - Lifetime
- 1997-07-23 EP EP97401839A patent/EP0822012B1/en not_active Expired - Lifetime
- 1997-07-23 DE DE69726502T patent/DE69726502T2/en not_active Expired - Lifetime
- 1997-07-23 PT PT97401839T patent/PT822012E/en unknown
- 1997-07-23 AT AT97401839T patent/ATE255471T1/en not_active IP Right Cessation
- 1997-07-28 US US08/901,412 patent/US5993924A/en not_active Expired - Lifetime
- 1997-07-28 NO NO973469A patent/NO973469L/en not_active Application Discontinuation
- 1997-07-29 AU AU32372/97A patent/AU719791B2/en not_active Expired
- 1997-07-29 CA CA002210844A patent/CA2210844C/en not_active Expired - Fee Related
- 1997-07-30 JP JP9219224A patent/JP2934217B2/en not_active Expired - Lifetime
- 1997-07-30 KR KR1019970036205A patent/KR100297042B1/en not_active IP Right Cessation
- 1997-07-30 BR BR9704137A patent/BR9704137A/en not_active Application Discontinuation
-
1999
- 1999-09-02 US US09/389,087 patent/US6291024B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
CA2210844A1 (en) | 1998-01-30 |
JPH10114015A (en) | 1998-05-06 |
KR980009520A (en) | 1998-04-30 |
US5993924A (en) | 1999-11-30 |
AU3237297A (en) | 1998-02-05 |
NO973469L (en) | 1998-02-02 |
JP2934217B2 (en) | 1999-08-16 |
AU719791B2 (en) | 2000-05-18 |
CA2210844C (en) | 2001-04-17 |
DE69726502D1 (en) | 2004-01-15 |
PT822012E (en) | 2004-04-30 |
US6291024B1 (en) | 2001-09-18 |
EP0822012A1 (en) | 1998-02-04 |
KR100297042B1 (en) | 2002-11-18 |
DE69726502T2 (en) | 2004-12-30 |
ATE255471T1 (en) | 2003-12-15 |
DK0822012T3 (en) | 2004-04-13 |
ES2212061T3 (en) | 2004-07-16 |
NO973469D0 (en) | 1997-07-28 |
BR9704137A (en) | 1998-12-15 |
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