High-pressure hose for conveying hydrogen or gasoline

Abstract

The invention relates to hoses having a burst pressure of at least 5.5 bar wherein the hose has a layered structure with an inner barrier layer of a blend of an ethylene vinyl alcohol copolymer and an aliphatic polyketone, at least one reinforcement layer and optionally an outer layer formed of a polymeric material. Such high-pressure hoses are characterized by a very advantageous profile of characteristics for use with hydrogen at high pressure. The invention further relates to a method for producing such a hose, to a tank filling device equipped with such a hose, and to the use of a corresponding high-pressure hose for transferring hydrogen from a storage container to a tank.

Description

Technical Field

[0001] The invention relates to a reinforced hose having a burst pressure of at least 5.5 bar, the hose having a layered structure comprising a barrier layer of a blend of ethylene vinyl alcohol copolymer and aliphatic polyketone, at least one strength-bearing layer and optionally an outer layer of a polymer material. The invention further relates to a method for producing such a hose, a tank filling device equipped with such a hose and the use of a corresponding reinforced hose for transferring hydrogen or other gases from a storage container into a tank. Background Art

[0002] In recent years, the development of fuel cell vehicles has experienced rapid progress. However, hydrogen as a fuel places considerable demands on the materials used to store and transport hydrogen, which are caused by the small molecular size of hydrogen. One aspect of this is the development of hoses through which fuel cell vehicles, etc. can be filled with hydrogen from dispensers installed at hydrogen stations. In order to increase the driving range of fuel cell vehicles, the fuel tank must be filled with hydrogen under high pressure. Therefore, such hoses for filling hydrogen must withstand high internal pressures of, for example, 70 MPa or more over a relatively wide temperature window (-40°C to about 85°C on the vehicle side).

[0003] The material for the inner layer of such hoses must meet a number of requirements such as in particular a low permeability to hydrogen, but also a certain flexibility so that the hose can be connected to a motor vehicle by the user, and of course sufficient strength properties. Barrier materials for the inner layer of the tube that have been described so far include nylon (for example in the form of nylon 6, nylon 66 or nylon 11), polyacetal or ethylene vinyl alcohol copolymers, PEEK or NBR (nitrile rubber).

[0004] For example, EP 3 627 026 A1 describes a hydrogen fuel hose having an inner layer and an outer layer and three or more reinforcement layers with precisely defined braid angles of 53.5° to 55.5°. In one embodiment of EP 3 627 026 A1, the inner layer is formed of nylon and the outer layer is formed of polyester.

[0005] JP 2017-106553 A describes hydrogen hoses with high burst resistance, which, in addition to an inner layer and an outer layer, also have reinforcement layers of polyparaphenylene benzobisoxazole fibers, through which an operating pressure of 70 MPa can be achieved.

[0006] Elaflex sells a hydrogen hose for mobile applications that has an inner NBR layer modified to impart conductivity, multiple layers of low-stretch textile braid, and an outer layer of neoprene (see https: / / elaflex.de / dokumente / download / ElaflexInformation / ELAFLEX_Information_1.20.pdf).

[0007] In addition, hoses for high pressure applications in the context of oil and gas production have been described, which are subjected to strong pressure differences and tensions when used below the surface of the water. For example, US2001 / 021426 A1 discloses a non-bonded hose having a fluid-impermeable barrier layer, a reinforcing layer and an outer layer. As the innermost layer, these hoses have a flexible metal cylinder intended to provide the required mechanical strength and flexibility. The hoses are therefore designed for applications where high pressure acts on the hose from the outside.

[0008] Since barrier materials in hoses for the passage of hydrogen at high pressures must meet various requirements, there is a problem of providing materials with a favorable overall property profile. For example, ethylene vinyl alcohol copolymers (EVOH) have very low permeability to hydrogen, but do not have satisfactory mechanical and strength properties (such as tensile strength, elongation at break or notched impact strength). In particular, ethylene vinyl alcohol copolymers tend to have a high flexural modulus, which makes it difficult to bend the material and also exhibit high stiffness, resulting in low elongation at break. Although the flexibility of ethylene vinyl alcohol copolymers can be increased by increasing the ethylene content (i.e., reducing the alcohol content) or by including a plasticizer, this is achieved at the tradeoff of higher gas permeability.

[0009] An additional difficulty with EVOH is that it exhibits a higher loss in permeation resistance with increasing temperature above ambient than other polymers (e.g., 120 times loss compared to 10 times loss for polyketones with increasing temperature from 30°C to 85°C). This effect is most significant when the temperature approaches the glass transition temperature, which is between 50°C-65°C for EVOH. This temperature is within the operating temperature range of multilayer hydrogen distribution hoses.

[0010] Other polymer materials that have been used as hydrogen barrier materials include polyamides (such as nylon 6 or nylon 11), which are however not completely satisfactory because these polyamides have a relatively low tensile strength and an unsatisfactory permeability to hydrogen, especially at high temperatures such as +85° C. Further barrier materials such as PEEK (=polyetheretherketone) have very favorable mechanical properties and in particular a very high tensile strength, but can only be processed at very high temperatures of more than 340° C. In addition, PEEK has an unsatisfactory hydrogen permeability.

[0011] Against the background of this state of the art, there is a need for a barrier material which has a low permeability to hydrogen and which at the same time imparts advantageous flexibility and mechanical properties and which can be processed at lower temperatures than, for example, PEEK. Furthermore, such a material should preferably allow the incorporation of additives for imparting electrical conductivity without significantly impairing the mechanical and permeability properties of the material. Furthermore, the material should preferably provide good temperature resistance at the operating temperatures of the hydrogen filling hose and improved adhesion to the outer layers of the hose construction.

[0012] The present invention addresses this need. Summary of the invention

[0013] In the research that forms the basis of the present invention, the inventors have surprisingly found that blending ethylene vinyl alcohol copolymers with aliphatic polyketones provides a highly favorable property profile with suitable flexibility and mechanical properties, low hydrogen permeability, and good temperature resistance in the operating temperature range of hydrogen high pressure hoses. In addition, the blend is processable via extrusion and allows the inclusion of additives for imparting conductivity and has better adhesion properties than ethylene vinyl alcohol copolymer alone. Blends with ethylene vinyl alcohol copolymers provide improved flexibility and gas barrier properties relative to the use of aliphatic polyketones alone in the barrier layer.

[0014] Thus, according to a first aspect, the present invention relates to a reinforced hose having a burst pressure of at least 5.5 bar, wherein the hose has a layered structure comprising an inner barrier layer, at least one strength-bearing layer and optionally an outer layer formed of a polymeric material, and wherein the barrier layer is formed of a blend of ethylene vinyl alcohol copolymer and an aliphatic polyketone having the formula

[0015] [[-CHR1 CH2(C=O)-] n [-CHR2 CH2(C=O)-] m ] p

[0016] wherein R1 and R2 are different from each other and independently represent hydrogen or C1-C 12alkyl, n+m=1, and p is an integer, and wherein the two comonomers are randomly distributed or present as blocks. The above formula indicates that the polymer comprises [-CHR1 CH2(C=O)-] and [-CHR2 CH2(C=O)-] units, wherein "n" and "m" are corresponding indicators of the ratio of the units in the polymer. The above formula should not be interpreted as defining a specific order of the units, as indicated, these units can be present in the polyketone "randomly distributed or as blocks".

[0017] The term "formed from..." in the above context is to be understood as the blend being the main component of the barrier layer, while the presence of additional components is possible. Frequently, the barrier layer will contain the blend in an amount of at least 50 wt.-%, preferably in an amount of 60 to 95 wt.-% and more preferably in an amount of 70 to 90 wt.-%. DETAILED DESCRIPTION

[0018] The ethylene vinyl alcohol copolymer in the above blend preferably contains units derived from ethylene in an amount of 23 to 48 mol%, more preferably 23 to 35 mol% and even more preferably 24 to 30 mol%. Such copolymers provide advantageous barrier and mechanical properties. In addition, it is preferred that the ethylene vinyl alcohol copolymer contains at most trace amounts of monomers other than ethylene and vinyl alcohol. Such monomers are most notably vinyl acetate from the ethylene vinyl acetate precursor of the ethylene vinyl alcohol copolymer. Therefore, it is preferred that the content of such other monomers is at most 1 mol%, more preferably at most 0.5 mol% and even more preferably at most 0.2 mol%.

[0019] In the indicated aliphatic polyketone, when R1 and / or R2 represent C1-C 12 When the alkyl group is C1-C 12 The alkyl group is preferably selected from methyl, ethyl, propyl, pentyl or heptyl.

[0020] In a particularly preferred embodiment, R1 is methyl and R2 is H.

[0021] When R1 is C1-C 12 When R1 is alkyl, "n" is preferably less than 0.5, in particular less than 0.15 and particularly preferably between 0.02 and 0.14; for such values ​​of n, it is preferred when R1 is methyl and R2 is H. In another embodiment, n=0 and R2 is H, in which case the aliphatic polyketone is present as poly(ethylene ketone).

[0022] "p" is preferably an integer between 500 and 5,000.

[0023] In one embodiment of the present invention, the aliphatic polyketone is semi-crystalline. The local crystallinity can be detected by DSC measurement of the polymer.

[0024] In a preferred embodiment of the invention, the aliphatic polyketone polymer contains at least 80% by weight, in particular at least 90% by weight and particularly preferably at least 95% by weight of the structural units indicated in the above formula. Other structural units that may be present in addition include, most notably, products from the insertion of two olefin units without the intermediate CO.

[0025] Alternatively or in addition, the aliphatic polyketone has a melting temperature between 180° C. and 250° C., preferably 109° C. to 220° C. Furthermore, in the context of the present invention, when the aliphatic polyketone has a weight average molecular weight M of at least 40,000 g / mol and in particular at least 60,000 g / mol w In a particularly preferred embodiment of the present invention, the aliphatic polyketone has a molecular weight of at least 200,000 g / mol.

[0026] In the present invention, it is further preferred that the aliphatic polyketone has a weight average molecular weight M of 140000 g / mol to 410000 g / mol. w , more preferably a weight average molecular weight of 1500000 g / mol to 210000 g / mol or 290000 g / mol to 400000 g / mol and most preferably a weight average molecular weight of 1600000 g / mol to 200000 g / mol or 300000 g / mol to 390000 g / mol. w This will be determined by GPC using suitable standards (eg polystyrene).

[0027] A commercially available aliphatic polyketone which can be used for producing the barrier layer of the reinforced hose according to the invention is the product sold by Hyosung under the trade name POKETONE.

[0028] In a particularly preferred embodiment, the blend forming the barrier layer has a thickness of 1000 mm*cm 3 *m -2 *d -1 -bar -1 or smaller, especially 800mm*cm 3 *m -2 *d -1 -bar -1 or less and particularly preferably 500 mm*cm 3 *m -2 *d -1 -bar -1 An overall gas permeability to hydrogen (H2) of 100 Å or less (determined in accordance with DIN 53880 (2006) at 30°C and 30 bar, 0% relative humidity).

[0029] For example, aliphatic polyketones can be processed by extrusion.

[0030] The ratio of ethylene vinyl alcohol copolymer to aliphatic polyketone is not subject to any relevant restrictions as long as the blend provides the desired effects in terms of barrier properties and mechanical strength. In a preferred embodiment, the ratio of ethylene vinyl alcohol copolymer to aliphatic polyketone is adjusted within the range of 10:90 to 60:40, with adjustment within the range of 10:80 to 45:55 being more highly preferred.

[0031] In addition to the ethylene vinyl alcohol copolymer and the aliphatic polyketone, the blend may include a compatibilizer that improves the formation of a stable blend between the ethylene vinyl alcohol copolymer and the aliphatic polyketone. Suitable compatibilizers include, for example, polymers and preferably copolymers with non-polar monomers (such as olefins) and polar monomers (such as acidic monomers). In such copolymers, often, the non-polar monomer is present in an excess of at least 2:1 relative to the polar monomer to provide suitable polarity characteristics for mixing with the less polar polyketone.

[0032] Particularly suitable compatibilizers are for example ethylene acrylic acid copolymers, preferably wherein the acrylic acid content is in the range of 2 to 20 mol% and more preferably 7 to 15 mol%.Another particularly suitable compatibilizer is a maleic anhydride based compatibilizer, such as maleic anhydride grafted polyolefin.

[0033] The compatibilizer is often used in a deficient amount relative to the polymers of the blend, the mixing of the blend being improved by the compatibilizer. That is, in a preferred embodiment, the compatibilizer is used in an amount of 2 to 25 wt.-% and more preferably 4 to 10 wt.-% of the combined weight of the ethylene vinyl alcohol copolymer, the aliphatic polyketone and the compatibilizer.

[0034] In addition to the polymer components described above, the blend may further contain one or more additives selected from one or more of the following: antioxidants, heat stabilizers, UV absorbers, light stabilizers, slip agents, inorganic fillers, antistatic agents, flame retardants, crystal modifiers such as crystallization promoters or crystallization inhibitors, chain modification additives such as chain extenders (e.g. to improve extrusion behavior), chain breakers (e.g. to adjust processability) or chain branching agents, plasticizers, dyes, impact enhancers, etc.

[0035] The barrier layer has a thickness suitable for achieving the desired gas permeability. Preferably, the barrier layer has a thickness of at least 0.2 mm and less than 2.0 mm, wherein a thickness in the range of 0.5 to 1.5 mm is preferred. If the hose of the present invention is a hydrogen hose, the inner diameter of the barrier layer is preferably at least 6 mm and more preferably in the range of 7 mm to 12 mm. On the other hand, if the hose of the present invention is a gasoline hose, the hose preferably has an inner diameter of the barrier layer of preferably at least 4 mm and not more than 25 mm.

[0036] To impart conductivity, the barrier layer may contain conductive additives or fillers.

[0037] Suitable conductive additives or fillers are all fillers which can impart conductive properties to the blend of ethylene vinyl alcohol copolymer and aliphatic polyketone, for example particulate, flake-like or fibrous fillers.

[0038] Examples of suitable particulate fillers are carbon black and graphite. Examples of flaky fillers that can be suitably used include aluminum flakes, nickel flakes, and nickel-coated mica. Examples of fibrous fillers include carbon fibers, carbon nanotubes, carbon-coated ceramic fibers, carbon whiskers, and metal fibers such as aluminum fibers, copper fibers, brass fibers, and stainless steel fibers. Among them, carbon black and a mixture of carbon black and carbon nanotubes are most preferred as conductive mediating fillers.

[0039] The carbon black that can be used in the present invention includes any carbon black that is commonly used to impart conductivity. Preferred examples of carbon black include, but are not limited to, acetylene black obtained by complete combustion of acetylene gas, Ketjen black produced by furnace-type incomplete combustion starting from crude oil, oil black, naphthalene black, thermal black, lamp black, channel black, drum black, and pan black. Among them, acetylene soot and furnace soot (Ketjen soot) are more preferred.

[0040] As for carbon black, various carbon powders are produced, which differ in characteristics such as particle size, surface area, DBP absorption and ash content. The carbon black that can be used in the present invention is not particularly limited in terms of these characteristics, but high structured carbon black and carbon black with a large aggregation density are preferred. In terms of impact strength, carbon black is preferably not mixed in a large amount. In order to obtain excellent conductivity in a smaller amount, the average particle size of the carbon black is preferably 500nm or less, more preferably 5 to 100nm and even more preferably 10 to 70nm, and the surface area (by the BET method) is preferably 10m 2 / g or more, more preferably 300m 2 / g or more and even more preferably 500 to 1,500 m 2 / g, and the DBP (dibutyl phthalate) absorption is preferably 50 ml / 100 g or more, further preferably 100 ml / 100 g or more and still further preferably 300 ml / 100 g or more. The ash content of the carbon black is preferably 0.5% or less, and further preferably 0.3% or less. As used herein, the DBP absorption refers to a value measured according to the method specified in ASTM-D2414. Carbon black having a volatile matter content of less than 1.0% by weight is more preferred.

[0041] The conductive filler may be surface treated with a surface treatment agent such as a titanate, aluminum or silane type surface treatment agent. In addition, the conductive filler may be particulate to improve processability when melt-kneading the blend of the ethylene vinyl alcohol copolymer and the aliphatic polyketone.

[0042] When using carbon black as a conductive filler, it has been unexpectedly found that this additive does not make the blend more permeable and unsatisfactorily brittle, but it appears to act as a nucleating agent on the polymer molecules, thereby increasing the crystallinity and contributing to the permeation barrier properties, which become better with higher crystallinity due to the dense packing of the macromolecules in the crystalline domains, which equates to less free volume for permeation.

[0043] The amount of the conductive filler blended varies depending on the type of filler and cannot be specified independently, but in terms of the balance of conductivity, melt flowability and mechanical strength, a conductive filler proportion of 3 to 25 wt.-% and preferably 6 to 20 wt.-% of the barrier layer can be specified as favorable.

[0044] For the hose of the present invention, it is further preferred that the inner barrier layer meets the requirements of the following inequality (see standard 7.18.4 of ISO 19880-5):

[0045]

[0046] Where V B is the dielectric breakdown voltage of the inner barrier material (kV / mm),

[0047] T is the thickness of the inner barrier tube of the hose in millimeters, and

[0048] R V is the volume resistivity of the inner barrier material.

[0049] Here, the thickness of the liner T is a design parameter of the hose geometry that affects the validity of this inequality. That is, if the dielectric breakdown voltage V B Too low and / or volume resistivity R V Too high, and the liner must be thicker. On the other hand, a thicker liner may affect the mechanical properties of the hose, for example in terms of flexibility.

[0050] The barrier layer of the blend of ethylene vinyl alcohol copolymer and aliphatic polyketone usually forms the innermost layer of the reinforced hose, but in individual cases another polymer material can form the innermost layer and the barrier layer of aliphatic polyketone can be placed thereon. In this case, the other material usually has a higher permeability to hydrogen than the barrier layer of the blend. Due to the negative effect of hydrogen on metals and in particular steel at high pressures, the innermost layer of the high-pressure hose according to the invention is not a metal layer and in particular not a steel layer.

[0051] Furthermore, the reinforced hose according to the present invention may have an additional polymer layer between the inner barrier layer and the reinforcement layer, between the reinforcement layers, or between the outermost reinforcement layer and the outer layer formed of a polymer material.

[0052] In addition to the barrier layer made of a blend of ethylene vinyl alcohol copolymer and aliphatic polyketone, the reinforced hose according to the invention additionally contains at least one reinforcing layer, whereby several reinforcing layers, i.e., for example, two, three, four, five or six reinforcing layers are preferred. For preferred designs of the reinforcing layers and their arrangement, reference can be made, for example, to the corresponding explanations in this regard in EP 3 627 026 A1.

[0053] As indicated above, the reinforced hose of the present invention has a burst pressure of at least 5.5 bar, in which case only less reinforcement is required. In a preferred embodiment, the hose has a burst pressure of at least 17 bar, more preferably at least 50 bar, even more preferably at least 130 bar, even more preferably at least 1700 bar and most preferably at least 3500 bar. As a reasonable upper limit, the burst pressure of the hose preferably does not exceed 5000 bar. For such hoses, it is obvious to the skilled person that the reinforcement must be suitable to provide the required burst pressure.

[0054] The burst pressure limit is associated with the fluid being transferred with the hose. For example, if the fluid is a liquid (such as gasoline) at ambient conditions, the burst pressure requirement of the hose may be required to be lower, and it may be sufficient if the burst pressure is at least 5.5 bar, at least 17 bar, or at least 50 bar. On the other hand, if the hose is a hose for transferring hydrogen, which is a gas at ambient conditions, the burst pressure must be higher to ensure safe operation.

[0055] The burst pressure conditions for hydrogen hoses are provided, for example, by DIN ISO 19880-5, which also provides other requirements for hydrogen hoses, such as electrical conductivity. In DIN ISO 19880-5, several "qualities" of hydrogen hoses are described, which are named H11, H25, H35, H50 and H70. The pressure classification "H70" according to DIN ISO 19880-5, for example, means that the hose has an operating pressure of about 700 bar and a corresponding burst pressure of five times the operating pressure, i.e. 3500 bar. Similarly, the pressure classification "H35" according to DIN ISO 19880-5 means that the hose has an operating pressure of about 350 bar and a corresponding burst pressure of 1750 bar. Since the barrier layer of the invention provides particularly advantageous barrier properties for hydrogen, in a preferred embodiment, the hose of the invention is at least an H11 hydrogen hose (burst pressure 550 bar), more preferably at least an H25 hydrogen hose (burst pressure 1250 bar), even more preferably at least an H35 hydrogen hose (burst pressure 1750 bar), more preferably at least an H50 hydrogen hose (burst pressure 2500 bar) and most preferably an H70 hose (burst pressure 3500 bar). Particularly preferably, the hose meets all requirements according to DIN ISO 19880-5 according to the corresponding "H" class (e.g. "H70").

[0056] In one embodiment, one or more reinforcing layers are formed by woven, knitted or braided fiber materials, whereby these fibers are sufficiently stable and have strength suitable for absorbing high internal pressures. It is preferred here to have a fiber with a tensile strength of at least 2GPa determined according to DIN EN ISO 2062 (2010). The fiber can be formed by an organic polymer, such as polyamide, polyester or polyethylene with a higher molecular weight, such as polyethylene (UHMWPE) with a molecular weight exceeding 3,000,000. In one embodiment, the fiber is based on polyparaphenylene benzobisoxazole or UHMWPE. Advantageously, one or more strength members can also be formed as a soft wire or strip with unidirectional orientation of the material, particularly when the strength member is formed by UHMWPE.

[0057] Alternatively or additionally, one or more strength-bearing layers can be formed by metal wires or metal strips, in particular metal wires and metal strips of steel, copper or copper alloys (according to JIS H 3260), aluminum or aluminum alloys (according to JIS H 4040), magnesium alloys (according to JIS H 4203), titanium or titanium alloys (according to JIS H 4670) can be used.

[0058] The reinforced hose of the present invention preferably further comprises an outer layer formed of a polymer material. The polymer material is not subject to any relevant restrictions, provided that the material should be sufficiently flexible and stable at the operating temperature of the hose. Preferred polymer materials here are, for example, rubbers such as chlorinated polyethylene rubber, epichlorohydrin rubber, chloroprene rubber, chloroprene acrylate rubber, butyl rubber, ethylene propylene rubber, chlorosulfonated polyethylene rubber, or thermoplastic polyurethane elastomers and thermoplastic materials such as polyurethane, polyamide (e.g. polyamide 12) or polyester.

[0059] The outer layer will suitably have a thickness in the range of at least 0.2 mm to 1.5 mm or less, with a thickness in the range of at least 0.5 mm to 1.0 mm or less being preferred. The outer diameter of the outer layer is not subject to any relevant restrictions, but will typically be at least 12 mm to 18 mm or less.

[0060] The outer layer may be continuous. Alternatively, the outer layer may have perforations through which gas, in particular in the form of hydrogen, can escape from the interior of the hose to the outside in order to prevent the formation of bubbles or delamination.

[0061] In one embodiment, one or more layers of the hose are "bonded", i.e., the layers are prevented from sliding relative to each other in the longitudinal direction of the hose by bonding. In a hose according to the invention, for example, a barrier layer may be bonded to an adjacent reinforcement layer, or an outermost reinforcement layer may be bonded to an outer layer formed of a polymer material. Furthermore, all layers in the hose (possibly with the exception of the reinforcement layers) may also be connected to each other.

[0062] In another aspect, the present invention relates to a method for manufacturing a reinforced hose as described above, the method comprising the steps of:

[0063] - applying a layer of a blend of ethylene vinyl alcohol copolymer and aliphatic polyketone onto a mandrel or mandrel-less to form a barrier tube;

[0064] - applying one or more reinforcement layers to the barrier tube;

[0065] - Optionally, an outer layer of polymer material is applied to the one or more reinforcement layers.

[0066] The blend of ethylene vinyl alcohol copolymer and aliphatic polyketone is typically applied from the melt, such as by extrusion, onto a mandrel or without a mandrel.

[0067] In addition to the reinforcement layers, the hose may further include one or more "friction" layers for mediating friction between different reinforcement layers, between a reinforcement layer and a barrier layer, or between a reinforcement layer and an outer layer. Such friction layers may also help strengthen the hose or provide other functions besides mediating friction.

[0068] In another aspect, the invention relates to a device for filling a tank, the device comprising a reinforced hose as described above. In addition to the hose, the device for filling a tank suitably comprises distribution means for the fuel passing through the device and closure means for connecting the distribution means in a pressure-tight manner to a container into which the fuel, i.e. in particular hydrogen, is to be introduced.

[0069] In another aspect, the invention relates to a reinforced hose as described above for use in conveying hydrogen or other gases (such as oxygen, helium, nitrogen or halocarbon coolants such as The reinforced hose can also be used to transfer low permeation gasoline fuels (including gasoline or gasoline blends with ethanol or methanol), ethanol, methanol, diesel fuel, biodiesel (and blends with diesel fuel) from a storage container to a tank. Alternatively, the reinforced hose can also be used to transfer low permeation gasoline fuels (including gasoline or gasoline blends with ethanol or methanol), ethanol, methanol, diesel fuel, biodiesel (and blends with diesel fuel) in automotive, aviation (jet fuel or kerosene) and industries including curb pump dispensing hoses. The tank is particularly preferably a tank of an aircraft, a ship or a vehicle (such as a bus, a truck or a rail vehicle).

[0070] In another aspect, the present invention relates to the use of a blend of ethylene vinyl alcohol copolymer and an aliphatic polyketone having the formula as a barrier material in a hose for transporting fluids or compressed gases

[0071] [[-CHR1 CH2(C=O)-] n [-CHR2 CH2(C=O)-] m ] p

[0072] wherein R1 and R2 are different from each other and independently represent hydrogen or C1-C 12 alkyl, n+m=1, and p is an integer, and wherein the two comonomers are randomly distributed or blocky, these compressed gases such as having at least 24 kg / m 3 And preferably between 35 and 45 kg / m 3 In another embodiment of this aspect, a blend of ethylene vinyl alcohol copolymer and aliphatic polyketone is used as a lining material in a tank for storing the corresponding gas, wherein the tank has a coating of the corresponding blend on its inner surface.

[0073] For the foregoing, even if not explicitly stated, the embodiment or configuration described as preferred or useful in one aspect of the present invention is intended to be also preferred or useful in all other aspects described. In addition, all preferred embodiments are considered to be disclosed in the form of combinations of corresponding embodiments.

Claims

1. A reinforced hose having a burst pressure of at least 5.5 bar, wherein the reinforced hose has a layered structure comprising an inner barrier layer, at least one strength bearing layer and an optional outer layer formed of a polymer material, and wherein the inner barrier layer is formed of a blend of ethylene vinyl alcohol copolymer and an aliphatic polyketone having the formula [[-CHR1 CH2(C=O)-] n [-CHR2 CH2(C=O)-] m ] p wherein R1 and R2 are different from each other and independently represent hydrogen or C1-C 12 Alkyl, n+m=1, and p is an integer, and wherein the two comonomers are randomly distributed or present as blocks.

2. The reinforced hose according to claim 1, wherein: The ethylene vinyl alcohol copolymer comprises units derived from ethylene in an amount of 23 to 35 mol.-% and preferably 24 to 30 mol.-%.

3. The reinforced hose according to claim 1 or 2, wherein: The ratio of ethylene vinyl alcohol copolymer to aliphatic polyketone is 10:90 to 60:40 and preferably 20:80 to 45:

55.

4. The reinforced hose according to at least one of claims 1 to 3, wherein: The blend of ethylene vinyl alcohol copolymer and aliphatic polyketone further comprises a compatibilizer, preferably in the form of ethylene acrylic acid copolymer, wherein more preferably the compatibilizer constitutes 2 to 25 wt.-% and especially 4 to 10 wt.-% of the combined weight of ethylene vinyl alcohol copolymer, aliphatic polyketone and compatibilizer.

5. A reinforced hose according to any one of the preceding claims, wherein: The barrier layer is formed as an inner layer having a layer thickness of at least 0.2 mm and less than 2.0 mm and preferably in the range of 0.5 to 1.5 mm.

6. A reinforced hose according to any one of the preceding claims, wherein: The barrier layer contains a conductive mediating filler, which is preferably selected from one or more of the following: carbon black, carbon fibers, carbon nanotubes, carbon-coated ceramic fibers, carbon whiskers and metal fibers, such as aluminum fibers, copper fibers, brass fibers and stainless steel fibers, preferably in the form of carbon black or a combination of carbon black and carbon nanotubes, wherein more preferably the filler constitutes 3 to 25 wt.-% and even more preferably 6 to 20 wt.-% of the barrier layer.

7. A reinforced hose according to any one of the preceding claims, wherein: The blend forming the barrier layer has a thickness of 1000 mm*cm 3 *m -2 *d -1 -bar -1 or smaller, especially 800mm*cm 3 *m -2 *d -1 -bar -1 or smaller, and preferably 500mm*cm 3 *m -2 *d -1 -bar -1 or less gas permeability to hydrogen (H2) (determined according to DIN 53880 (2006) at 30°C and 30 bar, 0% relative humidity).

8. A reinforced hose according to any one of the preceding claims, wherein: The hose comprises at least one strength-bearing layer formed from high-strength organic fibers, wherein the fibers have a tensile strength of at least 2 GPa determined in accordance with DIN EN ISO 2062; or a strength-bearing layer formed from metal wires, which are preferably formed from steel, copper or copper alloys (according to JIS H3260), aluminum or aluminum alloys (according to JIS H 4040), magnesium alloys (according to JIS H4203), titanium or titanium alloys (according to JIS H4670).

9. A reinforced hose according to any one of the preceding claims, wherein: The hose has an outer layer formed of a polymer material selected from rubber and / or thermoplastic materials, wherein the rubber or thermoplastic material is preferably selected from chlorinated polyethylene rubber, epichlorohydrin rubber, chloroprene rubber, chloroprene acrylate rubber, butyl rubber, ethylene propylene rubber, chlorosulfonated polyethylene rubber, polyurethane, polyamide and polyester.

10. A hose according to any one of the preceding claims, wherein The outer layer formed of a polymer material has perforations.

11. A reinforced hose according to any one of the preceding claims, wherein The hose has an inner diameter of at least 6 mm and preferably 7 to 12 mm.

12. A method of manufacturing a reinforced hose according to any one of the preceding claims, the method comprising: - applying a layer of a blend of ethylene vinyl alcohol copolymer and aliphatic polyketone onto a mandrel or without a mandrel to form a barrier tube; - applying one or more reinforcement layers to the barrier tube; - optionally applying one or more friction layers, and - optionally applying an outer layer of polymer material onto the one or more reinforcement layers.

13. A device for filling a tank, the device comprising a reinforced hose according to any one of claims 1 to 11.

14. Use of a reinforced hose according to at least one of claims 1 to 11 for transferring hydrogen from a storage container to a tank, preferably a tank of a vehicle or an aircraft or a ship.

15. Use of a blend of an ethylene vinyl alcohol copolymer and an aliphatic polyketone having the formula [[-CHR1 CH2(C=O)-] n [-CHR2 CH2(C=O)-] m ] p wherein R1 and R2 are different from each other and independently represent hydrogen or C1-C 12 alkyl, n+m=1, and p is an integer, and wherein the two comonomers are randomly distributed or blocky, the compressed gases preferably have a mass fraction of at least 24 kg / m 3 And especially at 35 to 45 kg / m 3 The density of hydrogen gas is in the range of

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