WO2014125219A1 - Structure thermoplastique pour le transport de fluide frigorigene - Google Patents
Structure thermoplastique pour le transport de fluide frigorigene Download PDFInfo
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- WO2014125219A1 WO2014125219A1 PCT/FR2014/050291 FR2014050291W WO2014125219A1 WO 2014125219 A1 WO2014125219 A1 WO 2014125219A1 FR 2014050291 W FR2014050291 W FR 2014050291W WO 2014125219 A1 WO2014125219 A1 WO 2014125219A1
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- heat transfer
- composition
- copolyamide
- structure according
- transfer fluid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- 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
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
- B05D1/265—Extrusion coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B13/00—Compression machines, plants or systems, with reversible cycle
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B41/00—Fluid-circulation arrangements
- F25B41/40—Fluid line arrangements
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/06—Constructions of heat-exchange apparatus characterised by the selection of particular materials of plastics material
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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
- B05D2254/00—Tubes
- B05D2254/02—Applying the material on the exterior of the tube
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/126—Unsaturated fluorinated hydrocarbons
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B2400/00—General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
- F25B2400/12—Inflammable refrigerants
- F25B2400/121—Inflammable refrigerants using R1234
Definitions
- the present invention relates to a thermoplastic structure comprising at least one layer consisting of a composition based on semi-aromatic copolyamide.
- the thermoplastic structure is particularly suitable for carrying heat transfer fluid transport (such as R-1234yf), in particular in the field of automotive air conditioning.
- the fluids transported may be at a high temperature, and that the temperature of the environment may also be high (in particular in car air conditioning, relevant parts which can be arranged in the vicinity of the engine).
- the fluid R-1234yf (2,3,3,3-tetrafluoropropene), usable in particular in automotive air conditioning, is more chemically reactive than the fluids of the previous generation, such as R-134a (1, 1, 1 , 2-tetrafluoroethane).
- R-134a (1, 1, 1 , 2-tetrafluoroethane
- the chemical resistance and the barrier properties of the elements of the vapor compression circuits are therefore all the more critical.
- the difficulty of meeting certain constraints is further aggravated by the fact that certain lubricants used in admixture with the refrigerants (such as polyalkylene glycols or PAGs) also tend to be aggressive for these circuit elements.
- tubing for transporting refrigerants in automotive air conditioning includes rigid metal portions (usually aluminum) and flexible portions of multilayer tubing.
- Some of these multilayer tubes are known under the English name of "veneer” tubes; they comprise successively, from the outside to the inside, a first rubber-type elastomer layer, a reinforcing braid, a second layer of rubber-type elastomer and a polyamide (or PA) -based inner layer.
- the polyamide-based inner layer may be, for example, a PA 6 (polycaprolactam) formulated (with or without a plasticizer, with or without an impact modifier, with or without a stabilizer), a copolyamide PA 6 / 6.6 formulated (with or without plasticizer, with or without impact modifier, with or without stabilizer), or an alloy of PA 6 or PA 6.6 (polyhexamethylene adipamide) with polyolefins and functionalized polyolefins (product marketed under the trade name Orgalloy®) .
- the document US 2007/0048475 describes a variant of these multilayer tubes, according to which the inner coating is based on PA 9.T (polymer of 1, 9-nonandiamine or 2-methyl-1, 8-ottandiamine and terephthalic acid), optionally mixed with another polyamide resin.
- PA 9.T polymer of 1, 9-nonandiamine or 2-methyl-1, 8-ottandiamine and terephthalic acid
- the inner layer is a composition comprising a polyamide, a shock modifier, a phenolic antioxidant, a plasticizer and a copper-based thermal stabilizer.
- the polyamide may be chosen from a list of polymers, in which, in particular, PA 6 / 6.T (copolymer comprising segments of PA 6 and segments of PA 6.T, that is to say of polymer of hexamethylenediamine and terephthalic acid).
- PA 6 / 6.T copolymer comprising segments of PA 6 and segments of PA 6.T, that is to say of polymer of hexamethylenediamine and terephthalic acid.
- PA 6 / 6.T copolymer comprising segments of PA 6 and segments of PA 6.T, that is to say of polymer of hexamethylenediamine and terephthalic acid.
- PA 6 / 6.T copolymer comprising segments of PA 6 and segments of PA 6.T, that is to say of polymer of hexamethylenediamine and terephthal
- US 201 1/0136957 discloses a resin for an inner layer of a vapor compression circuit, the resin being said to be chemically resistant to R-1234yf.
- the resin is chosen from a long list of polymers, in which polyamides, and in particular semi-aromatic polyamides, are mentioned.
- the resins used are based on PTFE (polytetrafluoroethylene) or polyimide.
- the document US 201 1/0183095 describes tubes for transporting heat transfer fluids in automobile air conditioning, comprising an inner layer based on PA 6.10 (polyhexamethylene sebacamide) and an outer layer based on a polyamide such as a polyphthalamide.
- PA 6.10 polyhexamethylene sebacamide
- PA 9.T T for terephthalic
- US 201 1/0239674 discloses steam compression circuit gaskets made from these same materials.
- US 2012/0018995 also discloses assemblies of tubes and seals made from the same materials.
- WO 2010/061289 and US 201 1/0277492 still describe steam compression circuit elements made from these same materials.
- US 201 1/0155359 relates to tubes especially for the transport of R-1234yf, made from a semiaromatic polyamide-based resin.
- the semi-aromatic copolyamide used in the examples is PA 6.6 / 6.T (copolymer of PA 6.6 and PA 6.T).
- EP 1505099 discloses compositions intended to replace rubbers or metals, or to be used as electrical cable materials, or for the manufacture of tanks, pipes and containers. These compositions comprise copolyamides of the general formula PA X / Y.Ar (with Ar meaning aromatic), among which is PA 1 1 / 10.T, which results from the condensation of the aminoundecanoic acid, the 1, 10- decanediamine and terephthalic acid.
- WO 2006/037615 discloses compositions based on semi-crystalline polyamides for the manufacture of flexible tubes for the transport of various fluids such as fuels (gasoline or diesel), hydraulic brake fluid, and others.
- PA 6.10, PA 6.12 and PA 10.10 are exemplified.
- EP 1717022 relates to multilayer pipes for various applications, and more particularly for the transport of fuel in vehicles, from the tank to the engine.
- These tubes comprise an intermediate layer of polyamide, for example PA 6.10 (polyhexamethylene sebacamide) or PA 6.12 (polyhexamethylene dodecanamide).
- compositions based on semi-aromatic copolyamide of general formula A / 10.T for the manufacture of various objects, such as everyday consumer goods such as electrical and electronic equipment. or automobiles, surgical equipment, packaging or sporting goods.
- the document WO 201 1/077032 seeks to provide a semi-aromatic polyamide that can be used generally in the manufacture of various objects, such as electronic components intended for electrical or electronic equipment in the field of road transport, road traffic or in aeronautics, audio-video, video games and also in the industrial sector.
- This semi-aromatic polyamide can be, among others, of formula 10 / 10.T, 1 1 / 10.T, 12 / 10.T, etc.
- US 201 1/0123749 discloses a copolyamide corresponding to the condensation of 1,6-hexanediamine, 1,10-decanediamine, terephthalic acid and at least one other monomer selected from the group of dicarboxylic acids comprising 8 to 18 carbon atoms, laurolactam, aminolauric acid and combinations thereof.
- the intended uses are containers and pipes in the automotive sector, for example fuel, oil, coolant or urea lines.
- thermoplastic structure comprising at least one layer consisting of a composition comprising a copolyamide of formula X / 10.T7Y, in which:
- X represents either the residues of an aliphatic amino acid comprising from 8 to 18 carbon atoms, or the X1X2 unit representing the residues resulting from the condensation of an aliphatic diamine comprising from 6 to 18 carbon atoms and a (cyclo) aliphatic diacid comprising from 6 to 18 carbon atoms;
- Y represents the residues of the condensation of an aliphatic diamine comprising from 9 to 14 carbon atoms and an aromatic diacid
- the copolyamide of formula X / 10.T7Y is a copolyamide of formula X / 10.T.
- X represents either the residues of an aliphatic amino acid comprising from 10 to 12 carbon atoms, or the X1X2 motif representing the residues resulting from the condensation of a diamine.
- aliphatic composition comprising from 6 to 12 carbon atoms and an aliphatic diacid comprising from 6 to 12 carbon atoms.
- Y represents a pattern 10.1, 9.T, 12.T or
- the copolyamide of formula X / 10.T / Y is chosen from copolyamides of formulas 1 1 / 10.T, 12 / 10.T, 6.10 / 10.T, 6.12 / 10.T, 10.6 /10.T, 10.10 / 10.T, 10.12 / 10.T, 12.12 / 10.T and 10.14 / 10.T and more preferably is a copolyamide of formula 1 1 / 10.T.
- the proportion of X units in the copolyamide is 0.5 to 0.7 moles per one mole of 10.T and Y.
- the X / 10.T / Y copolyamide is present in the composition in a mass proportion of 30 to 99%, preferably 40 to 95%, more preferably 50 to 85%; and / or the composition further comprises:
- one or more functionalized or non-functionalized polyolefins preferably in a mass proportion of 5 to 40%, more particularly preferably of 12 to 36%; optionally, one or more plasticizers, preferably in a mass proportion of 1 to 10%, more preferably 2 to 7%;
- additives selected from processing aids, fillers, thermal stabilizers, UV stabilizers, nucleating agents, dyes, pigments, release agents, flame retardants, agents surfactants, optical brighteners, antioxidants and mixtures thereof.
- thermoplastic structure is a vapor compression circuit element, comprising a light, said element being adapted to contain or transport a heat transfer fluid, said vapor compression circuit element preferably being a connecting element or pipe.
- light refers to the interior of the compression circuit element, particularly the inside of the connection element or the inside of the pipe.
- the heat transfer fluid is chosen from hydrocarbon compounds, hydrofluorocarbons (HFO), ethers, hydrofluoroethers or fluoroolefins, in particular from fluoropropenes, fluoropropanes and fluoroethanes; preferably from 1, 3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, 1,1,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, 2,3,3-trifluoropropene, 1,1,2,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, pentafluoroethane, difluoromethane, 1,1,1,2-tetrafluoroethane, difluoroethane, 1,1,1,2,3,3,3-heptafluoropropane, 1,1,1-trifluoropropan
- the heat transfer fluid is supplemented with a lubricant, preferably chosen from mineral oils, silicone oils, paraffins of natural origin, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha olefins, polyalkylene glycols, polyol esters and / or polyvinyl ethers; the lubricant is more preferably a polyalkylene glycol or a polyol ester.
- the lubricant content in the coolant + lubricant mixture is, for example, from 0.05% to 10%, preferably from 1% to 5% by weight.
- the vapor compression circuit is integrated in a device chosen from mobile or stationary air conditioning devices, refrigeration devices, freezing devices, heat pump heating devices and Rankine cycles. ; and preferably is integrated in a car air conditioning device.
- integrated means that the vapor compression circuit belongs to the device and therefore the vapor compression circuit element, which belongs to the vapor compression circuit, also belongs to the device, as well as the structure thermoplastic which is a vapor compression circuit element,
- the device consists of a vapor compression circuit comprising one or more vapor compression circuit elements.
- thermoplastic structure is a monolayer structure comprising a single layer consisting of the composition comprising the copolyamide of formula ⁇ / 10. ⁇ 7 ⁇ .
- the structure is a multilayer structure, and preferably: a bilayer structure comprising a composition layer comprising the copolyamide of formula X / 10.T / Y superimposed on a layer of a polyamide composition; or
- a three-layer structure comprising two layers of compositions comprising the copolyamide of formula X / 10.T / Y on either side of a layer of a polyamide composition.
- the layer of a polyamide X / 10.T / Y composition of a two-layer or three-layer structure is a layer of composition comprising polyamide PA 6.10 or PA 6.12.
- the thermoplastic structure comprises a composition layer comprising the copolyamide of formula X / 10.T7Y on an inner surface towards a light of the structure; and / or comprises a composition layer comprising the copolyamide of formula X / 10.T / Y on an external surface opposite the light of the structure.
- thermoplastic structure is an extruded object; and / or a reinforcing textile is provided in association with one or more of the layers of the structure.
- the invention also relates to a heat transfer device comprising a vapor compression circuit which comprises at least one thermoplastic structure as described above, and preferably a plurality of such structures.
- the heat transfer device is chosen from mobile or stationary air conditioning devices, refrigeration devices, freezing devices, heat pump heating devices and Rankine cycles; said device preferably being an automotive air conditioning device.
- the vapor compression circuit contains a heat transfer fluid chosen from hydrocarbon, hydrofluorocarbon or HFO compounds, ethers, hydrofluoroethers or fluoroolefins, in particular from fluoropropenes, fluoropropanes and fluoroethanes, preferably from 1, 3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, 1,1,3,3-tetrafluoropropene, 3.3, 3-trifluoropropene, 2,3,3-trifluoropropene, 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, pentafluoroethane, difluoromethane, 1,1-difluoroethane, , 1, 1, 2,3,3,3-heptafluoropropane, 1,1,1-trifluoropropane, 1,1,1,
- the heat transfer fluid is supplemented with a lubricant, preferably chosen from mineral oils, silicone oils, paraffins of natural origin, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha olefins, polyalkylene glycols, polyol esters and / or polyvinyl ethers; the lubricant is more preferably a polyalkylene glycol or a polyol ester.
- a lubricant preferably chosen from mineral oils, silicone oils, paraffins of natural origin, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha olefins, polyalkylene glycols, polyol esters and / or polyvinyl ethers; the lubricant is more preferably a polyalkylene glycol or a polyol ester.
- the invention also relates to the use of a thermoplastic structure as described above for transporting a heat transfer fluid in a vapor compression circuit.
- the heat transfer fluid is as described above.
- the invention also relates to a method for heating or cooling a fluid or a body by means of a vapor compression circuit containing a heat transfer fluid, said method comprising successively evaporation of the fluid heat transfer, compression of the heat transfer fluid, condensation of the heat medium and expansion of the heat transfer fluid, wherein the vapor compression circuit comprises a thermoplastic structure as described above.
- the heating or cooling method is a heating, air conditioning, refrigeration or freezing process, and preferably is an air conditioning method in a motor vehicle.
- the heat transfer fluid is as described above.
- the invention also relates to a method of manufacturing the thermoplastic structure as described above, comprising a step of depositing a layer of a composition comprising a copolyamide of formula X / 10.T7Y.
- the deposition of this layer is carried out by injection, extrusion, extrusion blow molding, coextrusion or multi-injection.
- the thermoplastic structure is a multilayer tube, and the method of manufacturing said structure comprises an extrusion step with an extruder equipped with a coextrusion head.
- the present invention overcomes the disadvantages of the state of the art. It provides more particularly a composition based on semi-aromatic copolyamide that can provide thermoplastic structures with a good compromise between their sealing properties to the heat transfer fluid, water and oxygen, their chemical resistance the heat transfer fluid, water and oxygen, their mechanical strength, flexibility and thermal resistance; and this especially in the field of automotive air conditioning, and especially when the heat transfer fluid is R-1234yf, added with a lubricant such as a PAG or POE oil.
- compositions of the invention exhibit, in particular, improved properties. allowing their use as a layer with improved properties:
- compositions of the invention exhibit, in particular, improved properties:
- thermoplastic structures compared to traditional rubber structures with an inner layer of polyamide, connected to aluminum structures, simplifies connections and limit the risk of leakage. It also allows a reduction of weight of the structures and a reduction of cost.
- thermoplastic structure denotes a structure (or part) consisting of materials of a polymeric nature whose glass transition temperature T g is greater than a temperature of 20 ° C. in the dry state (c). that is, with a quantity of water in the material of less than 0.05%).
- the T g is conventionally measured by DSC (differential scanning calorimetry). It is determined here by the temperature of the point of inflection of the heat flow as a function of the temperature during a temperature ramp of 20 ° C / min.
- the thermoplastic structure may comprise one or more thermoplastic polymers, organized in one or more layers. It may also comprise various additives and fillers mixed therewith (and especially one or more elastomeric polymers mixed with the thermoplastic polymers and not affecting the thermoplastic nature of the compositions concerned). It may also include fibers or even a reinforcing textile. But it is in any case devoid of any layer of elastomeric material such as rubber or the like.
- the invention is based on a thermoplastic multilayer structure comprising a layer of a semi-aromatic copolyamide of the general formula X / 10.T / Y, it being understood that this formula covers either the X / 10.T copolymers (comprising X and X units). .T only), ie terpolymers X / 10. ⁇ / ⁇ (having X, 10.T and Y motifs).
- copolyamide X / 10.T / Y is called "copolyamide of the invention”
- composition of the invention the composition containing this copolyamide
- structure of the invention the thermoplastic structure comprising a layer of this composition
- X represents either the residues of an aliphatic amino acid comprising from 8 to 18 carbon atoms, or the X1X2 unit representing the residues resulting from the condensation of a diamine comprising from 6 to 18 carbon atoms and from a (cyclo) aliphatic diacid comprising from 6 to 18 carbon atoms;
- 10.T represents the remains of the condensation of a decanediamine and terephthalic acid, in stoichiometric proportions;
- Y represents the residues of the condensation of an aliphatic diamine comprising from 9 to 14 carbon atoms and an aromatic diacid (Y is different from the 10.T unit, this being already present in the copolyamide elsewhere) .
- the decanediamine condensed with terephthalic acid (10.T unit) can be linear or branched, or a mixture of several decanediamines. Preferably, it is 1, 10-decanediamine (linear), which is less sensitive to water.
- the diamine may be linear or branched, preferably linear, and may have 9, or 10, or 1 1, or 12, or 13, or 14 carbon atoms.
- the aromatic diacid may in particular be terephthalic acid or isophthalic acid.
- the length of the diamine chain is important for the copolyamide resistance to water.
- Y may especially represent the units 9.T, 12.T, 14.T or 10.1 (I referring to isophthalic acid).
- the molar proportion of Y units with respect to all the units 10.T and Y is 0 to 30%, preferably 0 to 20%, and more preferably 0 to 10%.
- the proportion of X units is from 0.4 to 0.8 moles for one mole of semi-aromatic units (that is to say per mole of all the units 10.sub.T and optionally Y), preferably of 0.5 to 0.7 for one mole of aromatic units.
- the copolyamide X / 10.T7Y is devoid of Y patterns.
- X may be chosen from a unit obtained from an amino acid, a unit obtained from a lactam and an X1.X2 unit corresponding to the formula (aliphatic diamine Ca).
- the copolyamide of the invention advantageously has a polymolecularity index, denoted Ip less than or equal to 3.5.
- the polymolecularity index of said copolyamide is between 2.0 and 3.0 (inclusive).
- the polymolecularity index of the copolyamides of the invention is measured by gel permeation chromatography. More particularly, it is measured in a suitable solvent for the copolyamide, such as a fluorinated solvent such as hexafluoroisopropanol, at a temperature between 20 ° C and 50 ° C, preferably at 40 ° C.
- a suitable solvent for the copolyamide such as a fluorinated solvent such as hexafluoroisopropanol
- X represents an amino acid
- copolyamides formed then comprise three, four, ... or more, patterns, respectively.
- X represents a lactam
- X denotes a unit obtained from a monomer chosen from 10-aminoundecanoic acid (denoted 1 1), amino-1 1-undecanoic acid (denoted 1 1), amino-12- dodecanoic (noted 12) and lauryllactam (noted L12).
- copolyamides are of particular interest: they are copolyamides corresponding to one of the formulas chosen from 1 1 / 10.T and 12 / 10.T.
- the unit (aliphatic diamine in Ca) is chosen from linear or branched diamines.
- the diamine is linear, of formula H 2 N- (CH 2) a -NH 2
- the diamine When the diamine is branched, it may have one or more methyl or ethyl substituents on the main chain.
- the monomer (Ca-diamine) may advantageously be chosen from 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2-methyl- 1,5-pentanediamine, 2-methyl-1,8-octanediamine.
- the diacid when it is cycloaliphatic, it may comprise the following carbon skeletons: norbornylmethane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di (methylcyclohexyl) propane.
- copolyamides X / 10.T in which X is a unit (aliphatic diamine Ca).
- (Cb) di (cyclic) aliphatic diacid the copolyamides corresponding to one of the formulas chosen from 6.10 / 10.T, 6.12 / 10.T, 10.6 / 10.T, 10.10 / 10.T, 10.12. /10.T, 12.12 / 10.T and 10.14 / 10.T.
- the C18 dicarboxylic acid may be octadecanedioic acid, which is saturated, or octadecenedioic acid, which, for its part, exhibits unsaturation.
- the copolyamide of the invention may comprise monomers derived from resources derived from renewable raw materials, that is to say containing organic carbon derived from biomass and determined according to the ASTM D6866 standard. These monomers derived from renewable raw materials may be 1, 10-decanediamine or, when present, especially 11-aminoundecanoic acid, diamines and diacids aliphatic and linear as defined above.
- copolyamides of the invention may be prepared by polycondensation of the comonomers defined above, for example in the presence of hypophosphorous acid or at least one of its salts.
- the polycondensation process comprises the single reaction step between the amino acid X (or the diacids and diamines in Ca and Cb) and the stoichiometric combination of decanediamine and terephthalic acid. (and optionally isophthalic acid), in the presence of sodium hypophosphite, water and possibly other additives.
- the conditions of time, temperature and pressure are described in more detail in WO 2010/015786.
- the polycondensation process comprises two steps.
- the first step leads to the production of a diacid oligomer, which will polycondense during the second stage with decanediamine, according to the following sequence: first reaction step between terephthalic acid (and optionally isophthalic acid) with amino acid X, in the presence of a hypophosphite salt; and second reaction step of the diacid oligomer thus formed in the previous step with decanediamine.
- first reaction step between terephthalic acid (and optionally isophthalic acid) with amino acid X in the presence of a hypophosphite salt
- second reaction step of the diacid oligomer thus formed in the previous step with decanediamine The conditions of time, temperature and pressure are described in more detail in the document WO 2010/015786.
- X is a mixture (aliphatic diamine Ca).
- the polycondensation process comprises two steps: first step of reaction of amino acid X with terephthalic acid (and optionally isophthalic acid), and with from 10 to 90% by weight of decanediamine in the presence of a hypophosphite salt; and second step of reacting the oligomer produced from the first step with the balance of the decanediamine in one or more times.
- first step of reaction of amino acid X with terephthalic acid (and optionally isophthalic acid), and with from 10 to 90% by weight of decanediamine in the presence of a hypophosphite salt and second step of reacting the oligomer produced from the first step with the balance of the decanediamine in one or more times.
- the conditions of time, temperature and pressure are described in more detail in WO 2010/015786.
- X is a mixture (aliphatic diamine Ca).
- the polycondensation process comprises two steps: first step of reaction of the amino acid X with terephthalic acid (and optionally isophthalic acid) and all the diamine, in the presence of a hypophosphite salt; an oligomer is obtained by emptying the reactor under pressure of steam and crystallization of said oligomer; second step of post-polymerization at atmospheric pressure or under vacuum of the oligomer produced in the first step.
- first step of reaction of the amino acid X with terephthalic acid (and optionally isophthalic acid) and all the diamine, in the presence of a hypophosphite salt an oligomer is obtained by emptying the reactor under pressure of steam and crystallization of said oligomer
- second step of post-polymerization at atmospheric pressure or under vacuum of the oligomer produced in the first step The conditions of time, temperature and pressure are described in more detail in WO 2010/015786.
- the processes according to the present invention can be carried out in any reactor conventionally used in polymerization, such as anchor or ribbon stirrer reactors. Continuous polymerization processes are also possible.
- the method comprises a second step, as defined above, it can also be implemented in a horizontal reactor or finisher, more commonly known by those skilled in the art "finisher".
- the finishers can be equipped with a vacuum device, introducing reagent (diamine addition), which can be staged or not, and can operate in a wide range of temperature.
- reagent diamine addition
- the copolyamide additives of the invention are present in an amount of 1 to 70%, preferably 5 to 60%, or 15 to 50%, by weight based on the weight of the composition.
- the copolyamide of the invention preferably has an amine end content of greater than or equal to 20 ⁇ g / g, an acid chain end content of less than or equal to 100 ⁇ g / g, and a non-reactive end chain content. greater than or equal to 20 peq / g.
- the amine chain end content is between
- the acid chain end content is between 2 and 80 ⁇ g / g, and preferably between 15 and 50 ⁇ g / g.
- the non-reactive chain end content is advantageously greater than or equal to 30 ⁇ g / g, and preferably between 35 and 200 ⁇ g / g.
- chain terminating agents that is compounds capable of reacting with the amine and / or carboxylic acid terminal functions of the polyamides, stopping thus the reactivity of the end of the macromolecule, and thus the polycondensation.
- Suitable chain terminators for reacting with the terminal amine function may be monocarboxylic acids, anhydrides, such as phthalic anhydride, monohalogen acids, monoesters or monoisocyanates.
- the monocarboxylic acids are used.
- aliphatic monocarboxylic acids such as acetic acid, propionic acid, lactic acid, valeric acid, caproic acid, capric acid, uric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid, pivalic acid and isobutyric acid; alicyclic acids, such as cyclohexanecarboxylic acid; aromatic monocarboxylic acids such as toluic acid, ⁇ -naphthalenecarboxylic acid, ⁇ -naphthalenecarboxylic acid, acid methylnaphthalene carboxylic acid, phenylacetic acid; and their mixtures.
- aliphatic monocarboxylic acids such as acetic acid, propionic acid, lactic acid, valeric acid, caproic acid, capric acid, uric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid, pivalic acid and isobutyric acid
- the preferred compounds are aliphatic acids, in particular acetic acid, propionic acid, lactic acid, valeric acid, caproic acid, capric acid, lauric acid and tridecyl acid. myristic acid, palmitic acid and stearic acid.
- monoamines monoalcohols, monoisocyanates
- the monoamines are used. They can be chosen from aliphatic monoamines, such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, laurylamine, stearylamine, dimethylamine, diethylamine and dipropylamine.
- dibutylamine dibutylamine; alicyclic amines, such as cyclohexylamine and dicyclohexylamine; aromatic monoamines, such as aniline, toluidine, diphenylamine and naphthylamine; and their mixtures.
- the preferred compounds are butylamine, hexylamine, octylamine, decylamine, laurylamine, stearylamine, cyclohexylamine and aniline.
- the chain terminators may be introduced during the first and / or second stage, in the case of the two-step manufacturing processes described above. Reference is made here for more details to WO 2010/015785.
- the composition of the invention comprises a single X / 10.T / Y copolyamide as described above (and no other polyamide).
- the composition of the invention comprises two or a plurality of different X / ⁇ cop copolyamides as described above.
- the composition of the invention comprises, in addition to the X / 10.T / Y copolyamide (s) as described above, one or more additional polyamides (see below). Polvoléfines
- the composition of the invention optionally and advantageously comprises from 5 to 40%, and preferably from 12 to 36% by weight of at least one polyolefin.
- the function of the polyolefins is, in particular, to soften the composition and / or to give it resistance to shocks and / or to increase its dimensional stability with respect to water (because of their hydrophobic nature).
- the polyolefins used may be chosen from crosslinked polyolefins, functionalized polyolefins, and mixtures thereof, and optionally other polyolefins.
- functionalized polyolefins are present in the composition.
- a crosslinked polyolefin may be a dispersed phase in the matrix formed by the polyamide (s).
- This cross-linked polyolefin is derived from the reaction of two or at least two products having reactive groups with one another.
- the crosslinked polyolefin is obtained from at least one product (A) comprising an unsaturated epoxide and at least one product (B) comprising an unsaturated carboxylic acid anhydride.
- the product (A) is advantageously a polymer comprising an unsaturated epoxide, this unsaturated epoxide being introduced into said polymer, either by grafting or by copolymerization.
- the unsaturated epoxide may especially be chosen from the following epoxides:
- aliphatic glycidyl esters and ethers such as glycidyl allyl glycidyl ether, vinyl glycidyl ether, maleate and itaconate, glycidyl acrylate and methacrylate, and
- alicyclic glycidyl esters and ethers such as 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidyl carboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2-glycidyl carboxylate and endo-cis-bicyclo (2,2,1) -5-heptene-2,3-diglycidyl dicarboxylate.
- the product (A) is a polyolefin grafted with an unsaturated epoxide.
- polyolefin is meant a homopolymer or copolymer comprising one or more olefin units such as ethylene, propylene, butene-1 or any other alpha-olefin units.
- olefin units such as ethylene, propylene, butene-1 or any other alpha-olefin units.
- LDPE low density polyethylene
- HDPE high density polyethylene
- LLDPE linear low density polyethylene
- VLDPE very low density polyethylene
- polypropylene ethylene / propylene copolymers
- polyolefins elastomers as ethylene-propylene (EPR or EPM) or ethylene-propylene-diene monomer (EPDM); or the metallocene polyethylenes obtained by monosite catalysis;
- SEBS styrene / ethylene-butene / styrene block copolymers
- SBS styrene / butadiene / styrene block copolymers
- SIS styrene / isoprene / styrene block copolymers
- the polyolefin may in particular be a copolymer of ethylene and alkyl (meth) acrylate or a copolymer of ethylene and vinyl acetate.
- the product (A) is a copolymer of alpha-olefin and an unsaturated epoxide and, advantageously, a copolymer of ethylene and an unsaturated epoxide.
- the amount of unsaturated epoxide can represent up to 15% by weight of the copolymer (A), the amount of ethylene representing in turn at least 50% by weight of the copolymer (A).
- the alkyl of the (meth) acrylate comprises from 2 to 10 carbon atoms.
- alkyl acrylates or methacrylates which may be used include methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate and acrylate. 2-ethylhexyl.
- the product (A) is a copolymer of ethylene, methyl acrylate and glycidyl methacrylate or a copolymer of ethylene, n-butyl acrylate and glycidyl methacrylate.
- Use may in particular the product marketed by Arkema under the name LOTADER® ® AX8900.
- the product (A) is a product having two epoxide functions, such as, for example, the diglycidyl ether of bisphenol A (DGEBA).
- DGEBA diglycidyl ether of bisphenol A
- the product (B) is advantageously a polymer comprising an unsaturated carboxylic acid anhydride, this carboxylic acid anhydride unsaturated being introduced into said polymer, either by grafting or by copolymerization.
- Examples of unsaturated dicarboxylic acid anhydrides usable as constituents of the product (B) include maleic anhydride, itaconic anhydride, citraconic anhydride and tetrahydrophthalic anhydride.
- the product (B) is a polyolefin grafted with an unsaturated carboxylic acid anhydride.
- a polyolefin is a homopolymer or copolymer comprising one or more olefin units such as ethylene, propylene, butene-1 or any other alpha-olefin units.
- This polyolefin may in particular be chosen from the examples of polyolefins listed above for the product (A), when the latter is a polyolefin grafted with an unsaturated epoxide.
- the product (B) is an alpha-olefin copolymer and an unsaturated carboxylic acid anhydride and, advantageously, a copolymer of ethylene and an unsaturated carboxylic acid anhydride.
- the amount of unsaturated carboxylic acid anhydride may represent up to 15% by weight of the copolymer (B), the amount of ethylene representing in turn at least 50% by weight of the copolymer (B).
- alkyl and an unsaturated carboxylic acid anhydride Preferably, the alkyl of the (meth) acrylate comprises from 2 to 10 carbon atoms.
- the acrylate or the alkyl methacrylate may be chosen from those mentioned above for the product (A).
- the product (B) is a copolymer of ethylene, an alkyl (meth) acrylate and an unsaturated carboxylic anhydride.
- the product (B) is a copolymer of ethylene, ethyl acrylate and maleic anhydride or a copolymer of ethylene, butyl acrylate and maleic anhydride. It will be possible to use the products marketed by Arkema under the names LOTADER ® 4700 and LOTADER ® 3410.
- the weight contents of product (A) and product (B), which are respectively noted [A] and [B] may be such that the ratio [B] / [A] is from 3 to 14 and advantageously from 4 to 9.
- the crosslinked polyolefin may also be obtained from the products (A), (B) as described above and from at least one product (C), this product (C) comprising a unsaturated carboxylic acid or an alpha-omega-aminocarboxylic acid.
- the product (C) is advantageously a polymer comprising an unsaturated carboxylic acid or an alpha-omega-aminocarboxylic acid, one or the other of these acids being introduced into said polymer by copolymerization.
- unsaturated carboxylic acids which may be used as constituents of the product (C) are, in particular, acrylic acid, methacrylic acid, the carboxylic acid anhydrides mentioned above as constituents of the product (B), these anhydrides being completely hydrolysed.
- alpha-omega-aminocarboxylic acids which can be used as constituents of the product (C) are in particular 6-aminohexanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
- the product (C) may be a copolymer of alpha-olefin and an unsaturated carboxylic acid and, advantageously, a copolymer of ethylene and an unsaturated carboxylic acid.
- the fully hydrolysed copolymers of the product (B) may be mentioned.
- the product (C) is a copolymer of ethylene and (meth) acrylic acid or a copolymer of ethylene, an alkyl (meth) acrylate and (meth) acrylic acid.
- the amount of (meth) acrylic acid may be up to 10% by weight and preferably from 0.5 to 5% by weight of the copolymer (C).
- the amount of alkyl (meth) acrylate is generally between 5 and 40% by weight of the copolymer (C).
- the product (C) is a copolymer of ethylene, butyl acrylate and acrylic acid.
- Use may in particular the product marketed by BASF under the name ® LUCALENE October 31.
- the weight contents of product (A), product (B), product (C) which are respectively noted [A], [B] and [C] can be such as the ratio [B] / ([A] + [C]) is between 1, 5 and 8, the weight contents of products (A) and (B) being such that [C] ⁇ [A].
- the ratio [B] / ([A] + [C]) can be between 2 and 7.
- the dispersed phase of crosslinked polyolefin can of course come from the reaction of one or more products (A) with one or more products (B) and, where appropriate, with one or more products (C).
- Catalysts can be used to accelerate the reaction between the reactive functions of the products (A) and (B).
- the polyolefin when it is a crosslinked polyolefin, it is present in the composition in a content of between 13 and 40% by weight relative to the total weight of the composition.
- composition of the invention may comprise at least one functionalized polyolefin (D).
- the term "functionalized polyolefin” (D) means the following polymers.
- the functionalized polyolefin (D) may be an alpha-olefin polymer having reactive units: functionalities. Such reactive units are the carboxylic acid, anhydride or epoxy functional groups.
- homopolymers or copolymers of alpha olefins or of diolefins such as, for example, ethylene, propylene, butene-1, octene-1, butadiene, and more particularly:
- LDPE low density polyethylene
- HDPE high density polyethylene
- LLDPE linear low density polyethylene
- VLDPE very low density polyethylene
- metallocene polyethylene metallocene polyethylene
- ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (ethylene-propylene rubber) and EPDM (terpolymer based on ethylene / propylene / diene),
- SEBS styrene / ethylene-butene / styrene block copolymers
- SBS styrene / butadiene / styrene
- SIS isoprene / styrene
- SEPS styrene / ethylene-propylene / styrene
- unsaturated carboxylic acid salts or esters such as alkyl (meth) acrylate (for example methyl acrylate), or vinyl esters of carboxylic acids Saturated such as vinyl acetate (EVA), the proportion of comonomer up to 40% by weight.
- polyolefins described above may be grafted, copolymerized or terpolymerized by reactive units (functionalities), such as carboxylic acid, anhydride or epoxy functions.
- these polyolefins are grafted or co-polymerized with unsaturated epoxides such as glycidyl (meth) acrylate, or with carboxylic acids or the corresponding salts or esters such as (meth) acrylic acid (the it can be totally or partially neutralized by metal salts such as Zn, etc.) or by anhydrides of carboxylic acids such as maleic anhydride.
- unsaturated epoxides such as glycidyl (meth) acrylate
- carboxylic acids or the corresponding salts or esters such as (meth) acrylic acid (the it can be totally or partially neutralized by metal salts such as Zn, etc.) or by anhydrides of carboxylic acids such as maleic anhydride.
- the functionalized polyolefin (D) may be chosen from the following (co) polymers, grafted with maleic anhydride or glycidyl methacrylate, in which the degree of grafting is, for example, from 0.01 to 5% by weight:
- PE polyethylene
- PP polypropylene
- ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR and EPDM,
- EVA and alkyl (meth) acrylate copolymers containing up to 40% by weight of comonomers EVA and alkyl (meth) acrylate copolymers containing up to 40% by weight of comonomers.
- a functionalized polyolefin is for example a PE / EPR mixture, the weight ratio of which can vary widely, for example between 40/60 and 90/10, said mixture being co-grafted with an anhydride, in particular maleic anhydride, according to a grafting rate of, for example, 0.01 to 5% by weight.
- the functionalized polyolefin (D) may also be chosen from ethylene / propylene predominantly propylene copolymers grafted with maleic anhydride and then condensed with monoamino polyamide (or a polyamide oligomer) (products described in EP-A-0342066). .
- the functionalized polyolefin (D) may also be a co- or terpolymer of at least one of the following:
- anhydride such as maleic anhydride or (meth) acrylic acid or epoxy such as glycidyl (meth) acrylate.
- the (meth) acrylic acid may be salified with a Zn or Li salt.
- alkyl (meth) acrylate in (D) refers to methacrylates and C 1 -C 6 alkyl acrylates, and may be selected from methyl acrylate, ethyl acrylate, acrylate and the like. n-butyl acrylate, iso-butyl acrylate, ethyl-2-hexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.
- the aforementioned polyolefins (D) can also be crosslinked by any suitable method or agent (diepoxy, diacid, peroxide, etc.); the term "functionalized polyolefin” also includes mixtures of the aforementioned polyolefins with a difunctional reagent such as diacid, dianhydride, diepoxy, etc. capable of reacting with them or mixtures of at least two functionalized polyolefins that can react with one another.
- the copolymers mentioned above (D) can be copolymerized randomly or sequentially and have a linear or branched structure.
- the molecular weight, the MFI index, the density of these polyolefins can also vary to a large extent, which the skilled person will appreciate.
- the MFI index is the melt flow index. It is measured according to ASTM 1238.
- the functionalized polyolefins (D) are chosen from any polymer comprising alpha olefinic units and units carrying polar reactive functional groups such as the epoxy, carboxylic acid or carboxylic acid anhydride functions.
- examples of such polymers include terpolymers of ethylene, alkyl acrylate and maleic anhydride or glycidyl methacrylate such as Lotader® of the Applicant or polyolefins grafted with maleic anhydride such as the Orevac® of the Applicant as well as terpolymers of ethylene, alkyl acrylate and (meth) acrylic acid.
- the functionalized polyolefins (D) are:
- the polyolefin when it is a functionalized polyolefin (D), then it is present in a content of between 10 and 40% by weight, preferably between 15 and 30% by weight relative to the total weight of the composition.
- the composition of the invention may comprise, in addition to a crosslinked and / or functionalized polyolefin, at least one non-functionalized polyolefin (E).
- a non-functionalized polyolefin (E) is conventionally a homopolymer or copolymer of alpha olefins or diolefins, such as, for example, ethylene, propylene, butene-1, octene-1, butadiene.
- alpha olefins or diolefins such as, for example, ethylene, propylene, butene-1, octene-1, butadiene.
- LDPE low density polyethylene
- HDPE high density polyethylene
- LLDPE linear low density polyethylene
- VLDPE very low density polyethylene or very low density polyethylene
- metallocene polyethylene metallocene polyethylene
- ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR and EPDM,
- the abovementioned copolymers (E) can be copolymerized randomly or sequentially and have a linear or branched structure.
- the non-functionalized polyolefins (E) are chosen from homopolymers or copolymers of polypropylene and any homopolymer of ethylene or copolymer of ethylene and of a higher olefinic alpha-comonomer such as butene or hexene. octene or 4-methyl-1-pentene.
- polypropylenes high density polyethylenes, medium density polyethylenes, linear low density polyethylenes, low density polyethylenes, and very low density polyethylenes.
- polyethylenes are known to those skilled in the art as being produced according to a radical process, according to a Ziegler type of catalysis or, more recently, according to a so-called metallocene catalysis. Also preferred are copolymers of ethylene and EVA, such as those marketed under the trade name EVATANE by the Applicant.
- the composition of the invention comprises a non-functionalized polyolefin, then it is preferably present in a content of between 5 and 30% by weight, preferably between 10 and 20% by weight relative to the total weight of the composition. .
- the composition of the invention advantageously comprises a plasticizer.
- the proportion by weight of plasticizer is from 1 to 10%, more preferably from 2 to 7%.
- a plasticizer which has good thermal stability so that smoke does not form during the mixing steps of the various polymers and transformation of the composition obtained.
- this plasticizer can be chosen from:
- benzene sulphonamide derivatives such as n-butyl benzene sulphonamide (BBSA), the ortho and para isomers of ethyl toluene sulphonamide (ETSA), N-cyclohexyl toluene sulphonamide and N- (2-hydroxypropyl) benzene sulphonamide; (HP-BSA)
- esters of hydroxybenzoic acids such as 2-ethylhexyl para-hydroxybenzoate (EHPB) and decyl-2-hexyl paraben-2-hydroxybenzoate (HDPB),
- esters or ethers of tetrahydrofurfurylalcohol such as oligoethyleneoxy-tetrahydrofurfurylalcohol
- esters of citric acid or of hydroxymalonic acid such as oligoethyleneoxymalonate.
- a preferred plasticizer because commonly used, is n-butyl benzene sulfonamide (BBSA).
- Another more preferred plasticizer is N- (2-hydroxypropyl) benzene sulfonamide (HP-BSA).
- HP-BSA N- (2-hydroxypropyl) benzene sulfonamide
- composition of the invention advantageously comprises at least one thermal stabilizer.
- the thermal stabilizer may be present in an amount of 0 to 4%, especially 0.01 to 2% or 0.1 to 0.3% by weight relative to the total weight of the composition. It may be a copper thermal stabilizer
- it may be a copper salt or a copper salt derivative, for example copper iodide, copper bromide, copper halides, derivatives or mixtures thereof. -this.
- the copper salts I are preferred. Examples are copper iodide, copper bromide, copper chloride, copper fluoride, copper thiocyanate, copper nitrate, copper acetate, copper naphthenate, copper caprate, copper laurate, copper stearate, copper acetylacetonate, copper oxide. Copper iodide, copper bromide, copper chloride, copper fluoride are preferred.
- thermal stabilizer a metal halide salt in combination with Lil, NaI, Kl, Mgl 2 , KBr or Ca. K1 and KBr are preferred.
- the copper thermal stabilizer is a mixture of potassium iodide and copper iodide (KI / CaI).
- the mixture of potassium iodide and copper iodide useful in the invention is in a ratio of 90/10 to 70/30.
- the composition of the invention comprises from 0.10 to 0.25% by weight of copper thermal stabilizer.
- composition of the invention is devoid of such hindered phenolic antioxidants.
- HALS sterically hindered amine UV stabilizers
- composition of the invention may consist only of these four families of compounds, namely at least one polyolefin, optionally a plasticizer, at least one thermal stabilizer (especially copper) and semi-aromatic copolyamide. However, the composition may also include other compounds besides those just mentioned.
- the composition of the invention may in particular comprise at least one additive and / or at least one additional polymer.
- the additional additives may especially be selected from processing aids, or fillers, fillers, stabilizers other than that defined above, dyes, mold release agents, flameproofing agents, surfactants, optical brighteners and mixtures thereof.
- the dyes mention may in particular be made of carbon black.
- the dyes or pigments (for the purpose of coloring the composition) may be present, for example, in an amount of 0.1 to 0.2% by weight.
- the adjuvants assisting the transformation include stearates, such as calcium or zinc stearates, natural waxes, polymers comprising tetrafluoroethylene (TFE).
- stearates such as calcium or zinc stearates, natural waxes, polymers comprising tetrafluoroethylene (TFE).
- TFE tetrafluoroethylene
- processing aids is conventionally between 0.01 and 0.3% by weight, advantageously between 0.02 and 0.1% by weight, relative to the total weight of the composition.
- fillers mention may be made of silica, graphite, expanded graphite, carbon black, glass beads, kaolin, magnesia, slag, talc, nanofillers (carbon nanotubes), metal oxides ( titanium oxide), metals, fibers (aramids, glass, carbon, vegetable fibers), short or long.
- the amount of these can represent up to 50% by weight, advantageously up to 30% by weight, of the total weight of the composition, and for example from 5 to 30% by weight. 20 to 30% by weight.
- Expenses such as expanded graphite may make it possible to increase the thermal conductivity of the material (for example in order to promote a heat exchange between a light of a tube comprising a composition layer of the invention and the outside, or between two lumens of a tube comprising a composition layer of the invention).
- fibers for example glass fibers, especially short fibers, in an amount of 10 to 60% by weight, preferably 20 to 40% by weight, may make it possible to reinforce the layer formed from the composition question (the presence of fibers may for example be useful at one end of the thermoplastic structure according to the invention, near a connection to another room).
- the fibers can for example have a length of 0.05 to 1 mm, and in particular of 0.1 to 0.5 mm. Their average diameter may be from 5 to 20 ⁇ , preferably from 6 to 14 ⁇ .
- composition of the invention may further comprise one or more additional polymers, and in particular at least one third polymer, such a polymer being distinct from the semi-aromatic copolyamide (s) and from the polyolefin (s) mentioned above.
- additional polymers such as polyethylene glycol dimethacrylate (s)
- third polymer such as polyethylene glycol dimethacrylate (s)
- the composition of the invention may be devoid of such additional polymer.
- the additional polymer may especially be chosen from a polyamide other than that defined above, a polyamide-block-ether, a polyetheramide, a polyesteramide, a phenylene polysulfide (PPS), a polyphenylene oxide (PPO), a fluorinated polymer, and their mixtures.
- the additional polymer is chosen from aliphatic polyamides and polyamide-block-ethers.
- aliphatic polyamides there may be mentioned long-chain polyamides such as PA 1 1, PA 12, PA 6.10, PA 6.12, PA 6.14, PA 10.10, PA 10.12 and PA 12.12.
- the composition may thus contain up to 20% by weight, relative to the total weight of the composition, of at least one additional polymer.
- composition No. 1 having the following mass formulation:
- polyamide PA 1 1 / 10.T (0.7 mole of 11-aminocarboxylic acid per mole of 1,10-decanediamine and terephthalic acid): 55.8%;
- thermal stabilizer composed of 80% of Kl, 10% of Cul and 10% of calcium stearate: 0.7%;
- antioxidant 4,4'-bis- (alpha, alpha-dimethylbenzyl) diphenylamine:
- composition No. 2 having the following mass formulation:
- polyamide PA 1 1 / 10.T 0.5 mole of 11-aminocarboxylic acid per mole of 1,10-decanediamine and terephthalic acid: 68.25%;
- ethylene / ethyl acrylate / maleic anhydride copolymer (mass ratio 69/30/1): 24%; ethylene / methyl acrylate / glycidyl methacrylate copolymer (68/24/8 ratio): 4%;
- thermal stabilizer composed of 80% of Kl, 10% of Cul and 10% of calcium stearate: 0.25%;
- antioxidant 4,4'-bis- (alpha, alpha-dimethylbenzyl) diphenylamine:
- composition No. 3 having the following mass formulation:
- polyamide PA 1 1 / 10.T (0.7 mole of 11-aminocarboxylic acid per mole of 1,10-decanediamine and terephthalic acid): 68.25%;
- composition No. 4 having the following mass formulation:
- polyamide PA 1 1 / 10.T (0.7 mole of 11-aminocarboxylic acid per mole of 1,10-decanediamine and terephthalic acid): 85.9%;
- thermal stabilizer composed of 80% of Kl, 10% of Cul and 10% of calcium stearate: 0.7%;
- antioxidant 4,4'-bis- (alpha, alpha-dimethylbenzyl) diphenylamine:
- composition object of the invention described above is used as a layer in a thermoplastic structure.
- This thermoplastic structure may in particular be a tube or a pipe, or a connection piece or connection between tubes, or between a tube and a device (such as a compressor, a condenser, a heat exchanger for example).
- a device such as a compressor, a condenser, a heat exchanger for example.
- thermoplastic structure may be formed of a single layer constituted by the composition described above.
- the thermoplastic structure may be formed of a plurality of layers, namely at least one layer consisting of the above composition, and at least one other layer.
- Several layers can be provided consisting of the same composition above or several different compositions as described above. It is also possible to provide the presence of one or more layers consisting of other thermoplastic materials, and for example constituted by other compositions based on polyamides.
- thermoplastic structure may be a bilayer structure having a copolyamide composition layer of the general formula ⁇ / 10. ⁇ 7 ⁇ and a layer of another polyamide composition.
- the copolyamide composition layer of general formula X / 10.T / Y may be disposed on the inner face (on the tube light side) or on the outer face (the opposite side to the tube light).
- the thermoplastic structure may also be a trilayer structure, comprising for example two layers of copolyamide composition of general formula X / 10.T7Y (identical or not) surrounding a layer of another composition based on polyamide.
- a layer of copolyamide composition of general formula X / 10.T / Y is disposed both on the inner face (on the side of the tube light) and on the outer side (on the side opposite to the tube light).
- thermoplastic structure is a trilayer structure, comprising a copolyamide composition layer of the general formula ⁇ / 10. ⁇ 7 ⁇ interposed between two respective layers of other polyamide-based compositions, and in contact with these layers.
- the total thickness of the structure of all the layers may for example range from 1 mm to 5 mm, preferably from 1.5 mm to 3 mm.
- Such multilayer structures make it possible to combine the barrier and thermal and chemical resistance properties conferred by the X / 10.T / Y copolyamide layer (s) with advantageous mechanical properties conferred by the layer (s) of other compositions based on polyamide (for example a higher flexural modulus, which is particularly useful when the pressure stresses are important given the intended application).
- compositions based on polyamide it is possible to use polyamide-based compositions of the type PA W.Z, with W being 4 to 12 and Z being 6 to 12.
- PA 6.6, PA 6.10 and PA 6.12 are preferred polyamides. These polyamides can be formulated in compositions of the same type as those described above in relation to PA X / 10.T / Y. It is therefore expressly referred to the whole of the foregoing description with regard to the other possible ingredients of these compositions and the contents of the respective ingredients (polyolefins, plasticizers, etc.).
- the polyolefin content is limited to 20% maximum in these compositions, in order to maintain a sufficient hot pressure resistance.
- thermoplastic structures are:
- the bilayer tubular structures comprising an inner layer of composition based on PA 1 1 / 10.T and an outer layer of composition based on PA 6.6, PA 6.10 or PA 6.12;
- the bilayer tubular structures comprising an inner layer of composition based on PA 6.6, PA 6.10 or PA 6.12 and an outer layer of composition based on PA 1 1 / 10.T;
- the three-layer structures comprising an inner layer of composition based on PA 1 1 / 10.T, an intermediate layer of composition based on PA 6.6, PA 6.10 or PA 6.12 and an outer layer of composition based on PA 1 1 / 10.T.
- composition based on PA 1 1 10.T may be in particular a composition comprising from 10 to 25% (for example from 15 to 21%) of functionalized polyolefins, for increased resistance to high pressures.
- compositions based on PA 6 and PA 6.6 it may be necessary to use an interlayer binder.
- the binders in question are compositions comprising at least one polyamide noted A having an average number of carbon atoms per nitrogen atom noted CA between 4 and 8.5, preferably between 4 and 7; at least one polyamide noted B having a melting point greater than or equal to 180 ° C and an average number of carbon atoms per nitrogen atom noted CB between 7 and 10, preferably between 7.5 and 9.5; and at least one polyamide noted C having an average number of carbon atoms per nitrogen atom noted Ce between 9 and 18, advantageously between 10 and 18; at least 50% by weight of said composition being formed of one or more polyamides chosen from polyamides A, B and C, the mass-weighted average of the melting enthalpies of these polyamides within said composition being greater than 25 J / g (measured by DSC), and the average number of carbon atoms per nitrogen atom of the polyamides A, B and C also satisfying the following strict inequality: CA ⁇ CB ⁇ Ce-
- the difference between the average numbers of carbon atoms per nitrogen atom (CB-CA) and / or (CC-CB) is advantageously between 1 and 4, and preferably between 2 and 3.
- Each of the polyamides A, B and C preferably has a melting enthalpy greater than 25 J / g (measured by DSC).
- the binder comprises from 34 to 84% by weight of polyamide B relative to the total weight of the polyamides present in said composition, and preferably between 50 and 76%.
- the melting temperature of polyamide A is advantageously greater than or equal to 210 ° C. and the melting temperature of polyamide C is advantageously less than 200 ° C.
- the polyamide A may for example be chosen from PA6, PA 4.6 and PA 6.6; the polyamide B may for example be chosen from PA 6.10 and PA 6.12, preferably PA 6.10; and the polyamide C can for example be selected from PA 10.10, PA 1 1, PA 12, PA 10.12, PA 12 / 10.T and PA 6.18.
- this binder composition may also be used to form a layer of "other polyamide composition" as described above, as such.
- One or more of all the layers described above may be associated with a reinforcing fabric (or reinforcing braid), which may be formed by braiding, knitting, spiraling, or helically knitting fibers.
- the fibers may be, for example, glass, cotton, steel, polyester or aramid fibers, or combinations thereof.
- the reinforcing braid ensuring a pressure resistance, reduces the thickness of the structure.
- the thickness of all the layers may be less than 3 mm.
- thermoplastic structures according to the invention makes it possible to simplify the design of circuits by allowing easy connection by welding (for example rotational welding, ultrasonic welding, laser welding or induction welding).
- a vapor compression circuit includes at least one evaporator, a compressor, a condenser and an expander, and heat transfer fluid transport lines between these elements.
- the evaporator and the condenser comprise a heat exchanger for heat exchange between a heat transfer fluid circulating in the circuit and another fluid or body.
- the facility may include a turbine to generate electricity (Rankine cycle).
- the vapor compression circuit may be integrated in an installation which may also optionally include at least one coolant circuit used to transmit heat (with or without a change of state) between the heat transfer fluid circuit and the fluid. or body to be heated or cooled.
- the compression circuit therefore belongs to the installation.
- the installation may also optionally include two or more vapor compression circuits containing identical or different heat transfer fluids.
- the vapor compression circuits may be coupled together.
- the vapor compression circuit operates in a conventional vapor compression cycle.
- the cycle comprises changing the state of the heat transfer fluid from a liquid phase (or two-phase liquid / vapor) to a vapor phase at a relatively low pressure, and then compressing the fluid in the vapor phase to a relatively high pressure. high, the change of state (condensation) of the heat transfer fluid from the vapor phase to the liquid phase at a relatively high pressure, and the reduction of the pressure to restart the cycle.
- Cooling processes include air conditioning processes (with mobile installations, for example in vehicles, or stationary), refrigeration (with mobile installations for example in containers, or stationary) and freezing or cryogenics.
- heat is transferred (directly or indirectly via a heat transfer fluid) from the heat transfer fluid, during the condensation thereof, to the fluid or to the body that is heating, and this at a relatively high temperature compared to the environment.
- heat pump The installation for implementing the heat transfer is called in this case "heat pump”.
- thermoplastic structure according to the invention can be used as a "vapor compression circuit element", i.e. as part of such a circuit having.
- a part comprises a light adapted to contain or transport the heat transfer fluid.
- the term "light” refers to the interior of said part of said circuit.
- the vapor compression circuit element in question is preferably a pipe or tubing (or a hose). Alternatively, it may be a connection or connector between tubings, or between tubing and compressor, or condenser, or heat exchanger or a part of a buffer capacity or a heat exchanger.
- the vapor compression circuit element may also be a heat exchanger as such (in which case it comprises at least two lumens for the circulation of two identical or different fluids, one to yield heat to the other).
- the term “light” therefore refers in particular to the interior of the pipe or tubing or the interior of the connector or connector.
- the heat transfer fluid may be contained or transported in gaseous, liquid or two-phase form in the above circuit element.
- composition of the invention (just like the other compositions based on polyamides optionally used in the invention) can be prepared by any method which makes it possible to obtain a homogeneous mixture such as extrusion with molten state, compacting or roller mixing.
- composition of the invention may be prepared by melt blending the semi-aromatic polyamide (s), the plasticizer (s) and the products (A), ( B) and optionally (C) to obtain the (or) polyolefin (s) crosslinked (s).
- any additional additives and / or polymers may, in turn, be introduced, at the same time as the semi-aromatic polyamide (s), plasticizer (s) and products (A), (B) and if necessary (C) or in a subsequent step.
- the composition can be obtained in the form of granules by compounding, in particular by means of a twin-screw extruder, a co-kneader or an internal mixer.
- twin-screw extruder feeding without intermediate granulation, an injection molding machine or an extruder, in particular for producing tubes, films and / or molded articles.
- the articles or articles according to the invention can be obtained from the above composition by a known transformation process such as injection, extrusion, extrusion blow molding, coextrusion or multi-injection. .
- heat transfer compound or “heat transfer fluid” (or refrigerant, or refrigerant) is meant a compound, respectively a fluid, capable of absorbing heat by evaporating at low temperature and low pressure and provide heat by condensing at high temperature and high pressure, in a vapor compression circuit.
- a heat transfer fluid may comprise one, two, three or more than three heat transfer compounds.
- the heat transfer fluid may optionally include one or more additives that are not heat transfer compounds for the intended application.
- the heat transfer compounds may be hydrocarbon compounds, ethers, hydrofluoroethers, hydrofluorocarbons or fluoroolefins or HFOs. Hydrofluorocarbons and fluoroolefins are preferred, and more particularly fluoroolefins. Fluoropropenes, fluoropropanes and fluoroethans are preferred.
- Examples of preferred heat transfer compounds are 1,3,3,3-tetrafluoropropene (R-1234ze), 2,3,3,3-tetrafluoropropene (R-1234yf), 1,2,3,3,3-pentafluoropropene (R-1225ye), 1,1,3,3-tetrafluoropropene (R-1234zc), 3,3,3-trifluoropropene (R-1243zf), 2, 3,3-trifluoropropene (R-1243yf), 1,1,1,2-tetrafluoroethane (R-134a), 1,1,2,2-tetrafluoroethane (R-134), pentafluoroethane (R-125) , difluoromethane (R-32), 1,1-difluoroethane (R-152a), 1,1,1,2,3,3,3-heptafluoropropane (R-227ea), 1,1,1- trifluoropropane (R-2
- the above compounds can also be used in admixture with ammonia or carbon dioxide.
- the heat transfer fluid is R-134a, or R-1234yf, the latter being particularly preferred.
- R-1234yf and ammonia, and R-1234yf and carbon dioxide are also preferred, especially for stationary air conditioning.
- the additives may especially be chosen from lubricants, nanoparticles, stabilizers, surfactants, tracer agents, fluorescent agents, odorants and solubilizing agents.
- the stabilizer (s), when present, preferably represent at most 5% by weight in the heat transfer composition.
- nitromethane such as ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, phenol compounds such as tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-tert-butyl-4-methylphenol, epoxides (optionally fluorinated or perfluorinated alkyl or alkenyl or aromatic) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether, phosphites, phosphonates, thiols and lactones.
- nitromethane such ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, phenol compounds such as tocopherol, hydroquinone, t-butyl hydroquinone
- Lubricants that may be used include oils of mineral origin, silicone oils, paraffins of natural origin, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha olefins, polyalkylene glycols (PAG), polyol esters and / or polyvinyl ethers.
- the heat transfer fluid circulating in the vapor compression circuit comprises a PAG lubricant or a POE lubricant.
- the heat transfer fluid is R-1234yf supplemented with PAG lubricant (and optionally additional additives).
- lubricants PAG it is possible to use those described in US 2010/0282999, which is expressly referred to herein.
- These lubricants correspond to the formula R 1 - (OR 3) n - R 2, in which R 1 and R 2 are identical or different and represent a hydrogen atom, a C 1 -C 5 alkyl group or a C 2 -C 5 acyl group, R 3 represents a C2-C4 alkylene group, and the molar proportion of C2 alkylene groups in the R3 units is at most 30%.
- the hydroxyl value is preferably at most 100 mgKOH / g, or 50, 30 or 10 mgKOH / g.
- the number-average molecular weight of the PAG is preferably 500 to 3000, or 600 to 2000 or 600 to 1500.
- R 1 represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, a hydrocarbon group having 2 to 6 bond sites and 1 to 10 carbon atoms or a hydrocarbon group containing an atom of oxygen having 1 to 10 carbon atoms
- F3 ⁇ 4 represents an alkylene group having 2 to 4 carbon atoms
- R3 represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, carbon atoms, or a hydrocarbon group containing an oxygen atom having 1 to 10 carbon atoms
- n represents an integer of 1 to 6 and m is a number such that the average value mxn is from 6 to
- PAGs are polypropylene glycol dimethyl ether, the copolymer of polyethylene-polypropylene glycol dimethyl ether, the copolymer of polyethylene-polypropylene glycol methyl butyl ether and the polypropylene glycol diacetate.
- the hydroxyl value is preferably 5 mgKOH / g or less, or 3 mgKOH / g or less, or 1 mgKOH / g or less.
- the number-average molecular weight of the PAG is preferably 500 to 3000, or 600 to 2500.
- PAG lubricants it is also possible to use those described in WO 2010/075046, which is expressly referred to herein.
- These lubricants have the formula RX (R a O) x (R b O) y R c, wherein R is selected from alkyl groups having from 1 to 10 carbon atoms, aliphatic hydrocarbon groups having 2 to 6 valencies, and the substituents comprising a heterocycle in which the heteroatom (s) are oxygen, X is selected from O and S, R a is a C2 alkylene group, R b is a C3 alkylene group, R c is the same as R or represents H, x and y are 0 or an integer less than or equal to 100, independently.
- the sum x + y is an integer of 5 to 100.
- the aliphatic hydrocarbon groups include, in particular, alkanes, alkenes, alkynes, and in particular methyl, butyl and propyl groups.
- the lubricant can be a homopolymer of oxypropylene, linear. Alkoxy and especially methoxy termini are preferred.
- the kinematic viscosity is preferably at least 30 cSt, or 20 cSt, or 10 cSt at 40 ° C, or a viscosity number of at least 150, or 120 or 100.
- the total acid value is preferably less than 0.03, or 0.02, or 0.01 mgKOH / g.
- nanoparticles it is possible to use, in particular, nanoparticles of carbon, metal oxides (copper, aluminum), ⁇ 2, Al2O3, M0S2, etc.
- tracer agents (which can be detected) mention may be made of deuterated or non-deuterated hydrofluorocarbons, deuterated hydrocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, nitrous oxide and combinations thereof.
- the tracer agent is different from the one or more heat transfer compounds composing the heat transfer fluid.
- solubilizing agents mention may be made of hydrocarbons, dimethyl ether, polyoxyalkylene ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and magnesium compounds. 1-trifluoroalkanes.
- the solubilizing agent is different from the one or more heat transfer compounds composing the heat transfer fluid.
- fluorescent agents mention may be made of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanhthenes, fluoresceins and derivatives and combinations thereof.
- alkyl acrylates As odorants, mention may be made of alkyl acrylates, allyl acrylates, acrylic acids, acrylresters, alkyl ethers, alkyl esters, alkynes, aldehydes, thiols, thioethers, disulfides, allyl isothiocyanates and alkanoic acids. , amines, norbornenes, norbornene derivatives, cyclohexene, heterocyclic aromatic compounds, ascaridole, o-methoxy (methyl) phenol and combinations thereof.
- Example 1 general evaluation of the properties of the inner layers according to the invention
- fluorinated refrigerant barrier property a fluorinated refrigerant permeation measurement (see Example 2) demonstrated that the family of polyamides and semi-aromatic copolyamides was significantly better barrier than the family of PA6 and Orgalloy®.
- the heat resistance data show that the aromatic polyamides or copolyamides have a heat resistance greater than the family of PA 6 and Orgalloy®.
- the permeation data show that the aromatic polyamides or copolyamides have an R-134a barrier performance superior to the PA 6 and Orgalloy® family.
- the heat resistance data show that the aromatic polyamides or copolyamides have a thermal behavior greater than the family of PA 6 and Orgalloy®.
- the permeation data show that the aromatic polyamides or copolyamides have an R-1234yf barrier performance superior to the PA 6 and Orgalloy® family.
- the heat resistance data show that the aromatic polyamides or copolyamides have a higher heat resistance than the PA 6 and Orgalloy® family.
- the tensile modulus data show that the aromatic Orgalloy® and copolyamide of the invention are more flexible and therefore lead, at iso-thickness, to more flexible tubes.
- the elastomer adhesion is all the more difficult as the melting temperature of the inner layer is high (see Example 4).
- the permeability to fluorinated refrigerants (R-1234yf and R-134a) of a composition layer is compared.
- a copolyamide of formula X / 10.T (according to the invention) with that of layers consisting of known compositions, namely:
- Flux measurements were performed with a permeation cell, Lyssy GPM500 / GC coupling at a temperature of 23 ° C and 0% relative humidity.
- the upper face of the cell is swept by the test gas, and the flux diffusing through the film in the lower part is measured by gas chromatography.
- Helium is used as the carrier gas sweeping the lower part.
- the results are shown in Tables 2a and 2b below.
- the thicknesses are expressed in ⁇ (average thickness and standard deviation), the refrigerant streams are expressed in cm 3 .25 m / m 2 / 24h / atm.
- the density of the vapor phase of R-134a is 4.24 kg / m 3 and the density of the vapor phase of R-1234yf is 37.6 kg / m 3 .
- the water permeability of a layer consisting of a composition comprising a semi-aromatic copolyamide of formula X / 10.T is compared with that of layers formed.
- composition No. 2 a composition based on PA 1 1 (product Besno TL), a composition based on PA 12 (product Aesno TL), an Orgalloy® composition (R60ES) and a composition of PA 6 stabilized.
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Abstract
Description
Claims
Priority Applications (6)
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KR1020157025533A KR20150121083A (ko) | 2013-02-18 | 2014-02-13 | 냉매 유체를 이동시키기 위한 열가소성 구조 |
JP2015557501A JP6480348B2 (ja) | 2013-02-18 | 2014-02-13 | 冷媒流体を輸送するための熱可塑性構造体 |
KR1020217009620A KR20210038726A (ko) | 2013-02-18 | 2014-02-13 | 냉매 유체를 이동시키기 위한 열가소성 구조 |
CN201480009129.7A CN105073417A (zh) | 2013-02-18 | 2014-02-13 | 用于传输制冷剂流体的热塑性结构体 |
US14/767,549 US10023695B2 (en) | 2013-02-18 | 2014-02-13 | Thermoplastic structure for transporting refrigerant fluid |
EP14708630.0A EP2956301B1 (fr) | 2013-02-18 | 2014-02-13 | Structure thermoplastique pour le transport de fluide frigorigene |
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FR1351371A FR3002233B1 (fr) | 2013-02-18 | 2013-02-18 | Structure thermoplastique pour le transport de fluide frigorigene |
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EP (1) | EP2956301B1 (fr) |
JP (3) | JP6480348B2 (fr) |
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JP2019501797A (ja) * | 2015-12-15 | 2019-01-24 | アルケマ フランス | 伝熱流体用の連続繊維を含む多層構造体 |
FR3089147A1 (fr) | 2018-12-04 | 2020-06-05 | Arkema France | Structure tubulaire multicouche destinee au transport d’un fluide de climatisation |
WO2023170367A1 (fr) | 2022-03-09 | 2023-09-14 | Arkema France | Structure tubulaire multicouche destinee au transport d'un fluide de transfert de chaleur |
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FR3002180B1 (fr) * | 2013-02-18 | 2017-12-29 | Arkema France | Utilisation de copolyamide semi-aromatique pour le transport de fluide frigorigene |
US10450491B2 (en) | 2016-08-08 | 2019-10-22 | Ticona Llc | Thermally conductive polymer composition for a heat sink |
WO2018221520A1 (fr) * | 2017-06-02 | 2018-12-06 | Agc株式会社 | Composition d'éther fluoré destinée à un dépôt en phase vapeur, et article comprenant un film déposé en phase vapeur et procédé de production dudit article |
JP2020070942A (ja) * | 2018-10-29 | 2020-05-07 | 株式会社富士通ゼネラル | 冷凍サイクル装置 |
CN110878194B (zh) * | 2019-10-16 | 2020-11-17 | 珠海格力电器股份有限公司 | 一种含r13i1的环保混合制冷剂及换热系统 |
EP3838988A1 (fr) | 2019-12-20 | 2021-06-23 | Hutchinson | Composition thermoplastique pour tube monocouche, circuit de conditionnement d'air et procédé de préparation de la composition |
CN112226074A (zh) * | 2020-10-30 | 2021-01-15 | 郭勇 | 一种短玻纤增强pa10t共聚物复合材料及制备方法 |
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FR3029923A1 (fr) * | 2014-12-12 | 2016-06-17 | Arkema France | Procede de preparation d'un polyamide semi-aromatique |
KR20170097031A (ko) * | 2014-12-12 | 2017-08-25 | 아르끄마 프랑스 | 반-방향족 폴리아미드 제조 방법 |
CN107108882A (zh) * | 2014-12-12 | 2017-08-29 | 阿科玛法国公司 | 半芳族聚酰胺制备方法 |
WO2016092209A1 (fr) * | 2014-12-12 | 2016-06-16 | Arkema France | Procede de preparation d'un polyamide semi-aromatique |
JP2019501797A (ja) * | 2015-12-15 | 2019-01-24 | アルケマ フランス | 伝熱流体用の連続繊維を含む多層構造体 |
US11485105B2 (en) | 2015-12-15 | 2022-11-01 | Arkema France | Multilayer structure for transporting heat transfer fluid |
US10471677B2 (en) | 2015-12-15 | 2019-11-12 | Arkema France | Multilayer structure comprising continuous fibers for transporting heat transfer fluid |
FR3089147A1 (fr) | 2018-12-04 | 2020-06-05 | Arkema France | Structure tubulaire multicouche destinee au transport d’un fluide de climatisation |
EP3663081A1 (fr) | 2018-12-04 | 2020-06-10 | Arkema France | Structure tubulaire multicouche destinee au transport d'un fluide de climatisation |
WO2020115420A1 (fr) | 2018-12-04 | 2020-06-11 | Arkema France | Structure tubulaire multicouche destinee au transport d'un fluide de climatisation |
CN113165305A (zh) * | 2018-12-04 | 2021-07-23 | 阿科玛法国公司 | 用于运输空调用流体的多层管状结构体 |
US11338541B2 (en) | 2018-12-04 | 2022-05-24 | Arkema France | Multilayer tubular structure intended for transporting an air-conditioning fluid |
CN113165305B (zh) * | 2018-12-04 | 2023-06-27 | 阿科玛法国公司 | 用于运输空调用流体的多层管状结构体 |
WO2023170367A1 (fr) | 2022-03-09 | 2023-09-14 | Arkema France | Structure tubulaire multicouche destinee au transport d'un fluide de transfert de chaleur |
FR3133337A1 (fr) | 2022-03-09 | 2023-09-15 | Arkema France | Structure tubulaire multicouche destinee au transport d’un fluide de transfert de chaleur |
Also Published As
Publication number | Publication date |
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EP2956301A1 (fr) | 2015-12-23 |
JP2019090029A (ja) | 2019-06-13 |
KR20210038726A (ko) | 2021-04-07 |
JP7220568B2 (ja) | 2023-02-10 |
JP2021130820A (ja) | 2021-09-09 |
KR20150121083A (ko) | 2015-10-28 |
US20150376335A1 (en) | 2015-12-31 |
CN105073417A (zh) | 2015-11-18 |
JP2016516834A (ja) | 2016-06-09 |
EP2956301B1 (fr) | 2021-03-24 |
FR3002233B1 (fr) | 2016-01-22 |
JP6480348B2 (ja) | 2019-03-06 |
CN109849478A (zh) | 2019-06-07 |
US10023695B2 (en) | 2018-07-17 |
FR3002233A1 (fr) | 2014-08-22 |
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