Low extraction HNBR materials with adhesive to polyamide

Abstract

A low permeability barrier and plywood multilayer fuel and air conditioning hose is provided that includes an HNBR rubber layer directly bonded to a polyamide layer. A low extraction, peroxide cured HNBR thermoset rubber formulation is provided that binds directly to a polyamide thermoplastic during the vulcanization step without the need for external adhesive application.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application was filed as a PCT international application on June 7, 2023, and claims priority and benefits to U.S. Provisional Application No. 63 / 350,100 filed on June 8, 2022, the entire contents of which are incorporated herein by reference. background

[0002] In many multi-layer hose designs that include a barrier or veneer layer, an external epoxy or acrylic glue is applied during the manufacturing process to adhere the layers together. These glues or adhesives may have sporadic coverage in these applications, constitute a messy process, and may contain Substances of Very High Concern (SVHC) ingredients such as Bisphenol A.

[0003] Improved processes and hose designs are desired that eliminate the hazards associated with adhesives, eliminate cumbersome process steps, and significantly improve the quality of the bond line and overall hose performance. Summary of the invention

[0004] The present disclosure relates to a novel rubber formulation specifically designed for fluid delivery fuel and air conditioning hoses, particularly the design of implementing a thermoplastic barrier or plywood layer. This thermoset rubber is based on hydrogenated nitrile rubber (HNBR) with a specific peroxide cure system that promotes strong covalent bonding with polyamide thermoplastics without an intermediate adhesive layer. The inventive technology enables the finished composite material to have very low permeation.

[0005] A hydrogenated nitrile rubber (HNBR) formulation is provided that is peroxide cured and produces strong and consistent adhesion to polyamide thermoplastics without the need for adhesives during the vulcanization process. The HNBR formulation is designed to have very low volatile components to help avoid any residual extraction that may foul downstream components in application. The HNBR formulation can be used to prepare a tube layer or backing layer in a fuel hose or a refrigerant hose.

[0006] Hydrogenated nitrile rubber (HNBR) is a synthetic compound prepared by hydrogenation of nitrile rubber (NBR). The hydrogenation process allows for enhanced thermal stability up to about 150° C. HNBR can also improve fluid compatibility over NBR.

[0007] In some examples, a 99% saturated hydrogenated nitrile rubber (HNBR) peroxide cured composition (comprising components containing maleic anhydride and maleimide functional groups) is provided to produce robust covalent linkages with the N-terminal amine and / or carbon backbone of a polyamide thermoplastic resin. The HNBR composition contains very low extractable content (wax and plasticizer) to limit the available residues that can be extracted and subsequently cause blockages in the case of valves or other downstream components. Applications of the invention include barrier or plywood fuel or air conditioning hoses using materials such as polyamide as a gas or fluid permeation barrier.

[0008] A hose is provided, the hose comprising a plurality of layers comprising a hydrogenated nitrile (HNBR) rubber layer directly bonded to a polyamide (PA) barrier layer, wherein the HNBR rubber layer is prepared by a first composition comprising HNBR rubber, phenylenedimaleimide and a maleated compound. The first composition may further comprise a peroxide. The first composition may further comprise one or more fillers. The first composition may further comprise a high molecular weight plasticizer. The first composition may further comprise an antioxidant. During vulcanization, the HNBR layer of the hose may be covalently bonded to the polyamide layer without an intermediate adhesive layer.

[0009] The HNBR rubber can be at least partially saturated, having residual double bonds of no more than 6%, no more than 4%, no more than 2% or no more than 1% by infrared (IR) spectroscopy. The first composition can be included in the HNBR rubber in the range of 20-60wt%, 30-55wt%, or 35-45wt% compared to the gross weight of the first composition.

[0010] In some examples, the first composition comprises phenylene bismaleimide, which is N,N'-1,3-phenylene bismaleimide. The first composition can comprise the phenylene bismaleimide in a range of 0.1-5.0 wt%, 0.5-4.0 wt%, 0.8-3.0 wt%, or 1-2 wt% compared to the total weight of the first composition.

[0011] In some examples, the first composition comprises a maleated compound which is a maleated polybutadiene compound. The first composition may comprise the maleated compound in an amount ranging from 1-7 wt%, 2-6 wt%, 3-5 wt%, or 3.5-4.5 wt% compared to the total weight of the first composition.

[0012] The first composition may further comprise a plasticizer, optionally wherein the plasticizer is a high molecular weight plasticizer (>500 g / mol). The high molecular weight plasticizer may have low volatility. The plasticizer may be tri-C18-11-trimellitate. 6-12Alkyl esters. The first composition may comprise the plasticizer in the range of 0-25 wt%, 0.1-20 wt%, 3-15 wr%, 5-15 wt%, or 7-10 wt% compared to the total wt of the first composition.

[0013] The first composition may include one or more fillers. In some examples, the one or more fillers may be selected from the group consisting of carbon black, silicon dioxide, silicates, talc, aluminum silicate, calcium carbonate, zinc oxide, titanium dioxide, and stearic acid. The first composition may include the one or more fillers in a total amount in the range of 30-60wt%, 35-55wt%, or 35-45wt% compared to the total weight of the first composition.

[0014] The first composition may include a peroxide. The peroxide may be selected from the group consisting of dicumyl peroxide, di-tert-butyl peroxide, and tert-butylcumyl peroxide.

[0015] The present disclosure provides a hose including an innermost HNBR tube layer. A hose is provided, which includes in a radial direction: an inner HNBR tube layer made of an HNBR rubber composition; a polyamide barrier layer; a rubber backing layer; and a braided reinforcement cover layer.

[0016] The present disclosure provides a hose comprising an HNBR backing layer. A hose is provided, comprising the following layers in a radial direction: an inner polyamide plywood; an HNBR rubber backing layer prepared from the first composition; a braided reinforcement layer; and an outer rubber covering layer.

[0017] The polyamide layer may comprise a polyamide selected from the group consisting of PA 6,6, PA 6,6, PA 12, PA11, or blends thereof.

[0018] In some hose configurations, the rubber backing layer can be an EPDM rubber backing layer prepared from a second composition comprising low ethylene EPDM rubber, phenylenedimaleimide and a maleated compound. The second composition can include one or more fillers, paraffin plasticizers and peroxides. After vulcanization, the EPDM rubber backing layer can be covalently bonded to the polyamide barrier layer without an intermediate adhesive layer. The braided reinforcement layer can include polyester, aramid, polypropylene, glass, nylon, cotton, rayon yarn or a blend thereof.

[0019] The vulcanized hose according to the present disclosure may exhibit one or more, or two or more of the following characteristics: an operating temperature range of -40°F to +301°F; a maximum operating pressure of at least 500 psi; a burst rating of at least 4:1 under SAE J1527 burst test conditions; a fuel loss of no more than 15 g or less per square meter of internal surface area in 24 hours with CE fuel at 23°C as specified in SAE J1527-B1 - 15 g / m 2 / 24h - penetration rating; not to exceed 15g or less fuel loss / square meter of internal surface area in 24 hours with E85 fuel at 40°C as specified in SAE 30R9 - 15g / m 2 / 24h——Penetration rating; not exceeding 15g or less fuel loss / square meter of internal surface area in 24 hours at 40°C with fuel C as specified in SAE30R9——15g / m 2 / 24h--penetration rating; in the case of E85 fuel, it exhibits no more than 5g / m 2 / 24h penetration rate; in the case of fuel C, it exhibits no more than 4g / m 2 / 24h penetration rate; meets SAE J30R9 requirements for fuel injection hoses; and meets SAE J1527 requirements for marine fuel hoses.

[0020] A method for making a hose is provided, the method comprising: blending HNBR rubber, phenylene bismaleimide and a maleated compound to prepare a first composition; extruding the first composition onto a mandrel to form an HNBR inner tube layer; extruding a polyamide composition on the HNBR inner tube layer to form a barrier layer; blending a second composition comprising ethylene propylene diene monomer rubber (EPDM), phenylene bismaleimide and a maleated compound; extruding the second composition on top of the polyamide barrier layer to form an EPDM rubber backing layer; applying a textile braid reinforcement layer on the EPDM rubber backing layer to form a green hose; vulcanizing the green hose; and driving the hose off the mandrel. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 A cross-sectional view of an exemplary barrier hose configuration is shown.

[0022] Figure 2 A cross-sectional view of an exemplary plywood hose construction is shown.

[0023] Figure 3 A schematic diagram of an extrusion system for manufacturing a tube layer according to an embodiment is shown. DETAILED DESCRIPTION

[0024] Current multi-layer hose production processes typically employ a step of applying acrylic or epoxy based adhesives directly to the layers for adhesion. This is particularly true for hoses that include barrier or plywood layers. The adhesive application step is cumbersome and messy, and results in some adhesive coverage of the product. Additionally, due to the use of these adhesives, there are EHS implications based on the release of SVHCs such as bisphenol A fumes during processing.

[0025] The present disclosure provides improved multi-layer hoses and methods of manufacture that do not require the application of acrylic or epoxy based adhesives directly to the layers for adhesion.

[0026] A low-extractable, peroxide-cured HNBR thermoset rubber formulation is provided that bonds directly to polyamide thermoplastics during the vulcanization step without the need for external adhesive application. This can be applied to barrier or plywood-type fuel or air conditioning hoses that use materials such as polyamide as a gas or fluid permeation barrier.

[0027] definition

[0028] As used herein, the terms "a" and "an" are defined as being in the singular or plural.

[0029] A "barrier hose" is a multi-layer hose having an inner barrier layer to prevent leakage of fluid (e.g., refrigerant) through its wall. The barrier layer may comprise, for example, polyamide. The barrier layer is not the innermost layer.

[0030] A "plywood hose" is a multi-layer hose comprising an innermost plywood to prevent leakage of a fluid (e.g., refrigerant) through its wall. The innermost plywood may comprise, for example, polyamide. The plywood may comprise one or more, or two or more, plywood layers.

[0031] As used herein, the term "about" means within ten percent (10%) of a given value, ten percent more than a given amount, or ten percent less than a given amount, or both.

[0032] As used herein, the term "composition" refers to one or more of a composite, a mixture, a blend, an alloy, a polymer, and / or a copolymer.

[0033] The term "permeation rating" refers to the amount of fuel that will pass through the hose wall when filled with fuel. In some embodiments, a fuel hose is provided that does not exceed 15 g or less fuel loss per square meter of internal surface area in 24 hours with CE fuel at 23°C as specified in SAE J1527-B1 for marine fuel hoses - 15 g / m 2In some embodiments, a fuel hose is provided that does not exceed 15 g or less of fuel loss per square meter of internal surface area in 24 hours as specified in SAE J309 for 104°F (40°C) fuel injection hose for gasoline, ethanol extended gasoline, diesel fuel, biodiesel (B5, B10, B20), lubricating oils - 15 g / m 2 / 24h - the permeation rating. Fuel C is the test fuel used to determine the permeation and resistance characteristics. Fuel C contains about 50% isooctane and about 50% toluene. E85 gas is a combination of ethanol and gasoline, the combination containing about 51%-83% ethanol blended with gasoline.

[0034] The term "FBU" hose refers to a flexible hose with a NR / BR tube, a textile wrapped reinforcement, and a CR fire resistant cover. The FBU hose can have a temperature range of -40°C to +70°C.

[0035] The term "safety factor" or "burst rating" may refer to the minimum burst pressure of a hose divided by the maximum working pressure. For example, a hose with a 4:1 safety factor may have a burst pressure of 4 times the maximum working pressure. Burst testing may be performed under SAE J1527 burst test conditions.

[0036] As provided herein, ranges are intended to include at least the numbers defining the limits of the range.Terms such as "first" or "second" or other numerical terms do not imply a sequence or order unless expressly specified.

[0037] One advantage of the HNBR formulations of the present invention over other elastomers is the ability to bond directly to polyamide plastics during the vulcanization process without the use of adhesive glues. This helps to give the hoses of the present invention significantly lower E85 and Fuel C permeation than any known competitor. For example, compared to 5.7 to 18.4 g / m for E85 2 / day permeation values ​​for competitive hoses. The hoses of the present invention exhibited a permeation of 4.5 g / m2 for E85. 2 / day of low penetration.

[0038] Figure 1 An exemplary barrier hose construction 100 according to the present disclosure is shown. Thermoset rubber inner tube layer 102 can be made from an HNBR composition according to the present disclosure. Barrier tube layer 104 can be made from a polyamide composition. Rubber backing layer 106 can be made from an EPDM composition. Textile braid outer cover (reinforcement) layer 108 can be made from polyester yarn.

[0039] The inner HNBR rubber tube layer 102 can be directly bonded to the polyamide barrier layer 104 without an intermediate adhesive layer. The HNBR tube layer 102 can be prepared from an elastomeric HNBR composition comprising a blend of hydrogenated nitrile rubber (HNBR), N,N'-meta-phenylene dimaleimide (HVA-2) and a maleated compound. The maleated compound can be maleated polybutadiene. The phenylene dimaleimide can be N,N'-meta-phenylene dimaleimide.

[0040] HNBR obtained by hydrogenating nitrile copolymers has been developed to withstand continuous temperatures up to 302 ° F (150 ° C) while maintaining resistance to petroleum. HNBR is selected to be used as the base rubber for the inner tube layer 102 for preparing the hose to be compatible with fuel C, E85, biodiesel, methanol, hot water, glycols, coolants such as R134a. HNBR should be suitable for peroxide crosslinking. In some embodiments, HNBR should be at least partially saturated, with no more than 6%, or no more than 4% residual double bonds by IR spectroscopy. In some embodiments, HNBR should be fully saturated, with no more than 1% residual double bonds by IR spectroscopy. HNBR rubber can be 99% saturated HNBR. HNBR can have an acrylonitrile content of about 34wt% by ISO 24698-1. HNBR is commercially available, for example as THERBAN from Arlanxeo Deutschland GmbH, such as THERBAN 3407. The HNBR rubber composition may include a total amount of HNBR in a range of 20-60 wt%, 30-55 wt%, or 35-45 wt% compared to the total weight of the HNBR rubber composition.

[0041] The elastomeric HNBR composition allows direct bonding to polyamides without an intermediate adhesive layer upon vulcanization.

[0042] The rubber tube layer 102 and / or the rubber backing layer 206 may be prepared from a composition comprising HNBR, phenylene dimaleimide, a maleated compound, and one or more of a plasticizer, a filler, a vulcanizer, a peroxide, and / or an antioxidant.

[0043] The rubber tube layer 102 can be made of an elastomeric composition that does not contain EPDM. In some examples, the rubber tube layer 102 and / or the rubber backing layer 206 can be made of an elastomeric composition that does not contain polyvinyl butyral (PVB). The rubber barrier tube 102 and / or the rubber backing layer 206 can be made of an elastomeric composition that does not contain polypropylene. The rubber tube layer 102 and / or the rubber backing layer 206 can be made of an elastomeric composition that does not contain polyamide.

[0044] As used herein, the term "maleated compound" refers to a compound having one or more, or two or more maleic anhydride substituents. In some embodiments, the maleated compound is maleated polybutadiene. Maleated polybutadiene can be a commercially available product, such as Ricobond TM ,For example 1756HS (powdered maleated polybutadiene with maleic anhydride addition, in the form of a dispersion on amorphous silica, Cray Valley USA). Anhydrides can be combined with amino groups, while vinyl functional groups are peroxide curable. Maleimide can react via three main pathways: free radical addition to vinyl compounds, Michael addition with compounds having active hydrogen, and Diels-Alder reaction with dienes. For example, the maleic anhydride of the maleated compound can form a covalent bond (CN bond) with the polyamide N-terminal amine group of the polyamide barrier layer 104, while the HVA-2 in the rubber tube layer 102 can form a covalent bond (CC bond) with the carbon skeleton. The HNBR rubber composition can contain a maleated compound in the range of 1-7wt%, 2-6wt%, 3-5wt%, or 3.5-4.5wt% compared to the total weight of the HNBR rubber composition.

[0045] The phenylenedimaleimide may be N,N'-meta-phenylenedimaleimide. In some embodiments, the phenylenedimaleimide is N,N'-meta-phenylenedimaleimide (CAS RN: 3006-93-7; N,N'-1,3-phenylenedimaleimide; HVA-2 curing agent, DuPont Chemical Co.). The HNBR rubber composition may include phenylenedimaleimide in an amount ranging from 0.1-5.0 wt%, 0.5-4.0 wt%, 0.8-3.0 wt%, or 1-2 wt% relative to the total weight of the HNBR rubber composition.

[0046] In certain embodiments, inner tube layer 102 is prepared by a rubber composition comprising hydrogenated nitrile rubber (HNBR), and the rubber composition further comprises a filler or other additive added to the HNBR rubber. The HNBR rubber composition may further comprise one or more fillers. For example, one or more fillers may be selected from carbon black, silicon dioxide, silicate, talcum, aluminum silicate, calcium carbonate, zinc oxide, titanium dioxide and stearic acid. In certain embodiments, the HNBR rubber composition is included in one or more fillers of a total amount in the range of 30-60wt%, 35-55wt% or 35-45wt% compared to the gross weight of the HNBR rubber composition.

[0047] Examples of fillers used in some embodiments include, for example: zinc oxide, for example; calcium carbonate, for example Hubercarb Q325 TM (ground calcium carbonate, Akrochem; Akron, Ohio); talc, e.g. vapor R (hydrated magnesium silicate, Imerys Talc); silicon dioxide, such as HiSil 243LD TM (precipitated amorphous silica from PPG Industries; Monroeville, PA); Kadox 930 TM (zinc oxide, Zinc Corporation of America; Monaca, Pennsylvania); carbon black, such as Continex TM N650 carbon black (Carbon black, Continental Carbon; Houston, Texas), XC72R (powdered carbon black, Cabot Corp.; Billerica, Mass.), and optionally silicates, aluminum silicate, titanium dioxide, and stearic acid.

[0048] The HNBR rubber composition may further include one or more plasticizers. The plasticizer may be a high molecular weight (>500 g / ml) plasticizer with low volatility. For example, the HNBR composition may include a commercially available high molecular weight (>500 g / mol) plasticizer with low volatility. For example, the plasticizer may be a trialkyl trimellitate. The plasticizer may be a trialkyl C 6-12 Ester. Trialkyl C trimellitate 6-12 The ester may be, for example, tri(2-ethylhexyl) trimellitate, trioctyl trimellitate, isodecyl diisooctyl mellitic acid, triisooctyl trimellitate, triheptyl trimellitate, trinonyl trimellitate, trinonyl trimellitate, tridecyl trimellitate, or 1,2,4-benzenetricarboxylic acid branched isodecyl diisooctyl ester, and the like.

[0049] High molecular weight (> 500g / mol) plasticizer can be, for example, tris(2-ethylhexyl) trimellitate (trioctyl trimellitate, TOTM) (MW 546.8g / mol) with low volatility. TOTM is commercially available from, for example, Eastman Chemical Company. The HNBR rubber composition can further include one or more plasticizers in a total amount in the range of 0-25wt%, 0.1-20wt%, 3-15wr%, 5-15wt%, or 7-10wt% compared to the total wt of the HNBR composition.

[0050] The HNBR rubber inner tube 102 is prepared from a composition comprising one or more antioxidants. The antioxidant may be, for example, a hydroquinoline antioxidant, such as Agerite MA TM (2,2,4-trimethyl-1,2-dihydroquinoline polymer). The antioxidant may be, for example, a phenol-phosphite antioxidant, such as 168 (tris(2,4-di-tert-butylphenyl)phosphite, Ciba). When present, the HNBR rubber composition may contain an antioxidant in the range of 0.1 to 1.0 wt%, or 0.2 to 0.6 wt%.

[0051] The HNBR rubber inner tube 102 is prepared from a composition comprising one or more organic peroxides. Examples of peroxides used in some embodiments include, for example, dicumyl peroxide, di-tert-butyl peroxide, and tert-butyl cumyl peroxide, as well as commercial products such as Luperox TM DC40P-SP2 (Dicumyl peroxide spread on calcium carbonate and silica, Arkema) or DCP-99 (bis(1-methyl-1-phenylethyl) peroxide, RT Vanderbilt). In some embodiments, the composition comprises dicumyl peroxide or tert-butyl cumyl peroxide. In some embodiments, the composition comprises dicumyl peroxide. In some embodiments, the peroxide is present at about 0.1 wt % to about 5 wt %; about 1 wt % to about 4 wt %; about 2 wt % to about 3 wt %, based on the total weight of the filled HNBR composition.

[0052] The HNBR rubber composition may have a Mooney viscosity in the range of 20 to about 40, about 25 to about 35, or about 30-32 MS (1+4) at 100° C. by ISO 289 / ASTM 1646.

[0053] The HNBR rubber compositions according to the present disclosure may exhibit a T5 of at least 10 minutes, or at least about 12 minutes.

[0054] Cured HNBR rubber compositions according to the present disclosure may exhibit an elongation percentage of at least 150%, or at least 175%.

[0055] The cured HNBR rubber composition according to the present disclosure may exhibit a viscosity not exceeding 0.1 g / m 2 , not more than 0.05g / m 2 , or not more than 0.03g / m 2 The cured HNBR rubber composition according to the present disclosure can exhibit a hardness in the range of 70-90 Shore A.

[0056] The cured HNBR rubber compositions according to the present disclosure may exhibit a Modulus C tear strength of at least 170, at least 180, or at least 190 lbf / in.

[0057] The cured HNBR rubber composition according to the present disclosure may exhibit a tensile strength of at least 2000 psi, or at least 2100 psi, or at least 2200 psi.The cured HNBR rubber composition according to the present disclosure may exhibit a 100% modulus of at least 1200 psi, at least 1400 psi, or at least 1500 psi.

[0058] Upon cure, the HNBR rubber hose layer 102 is strongly covalently bonded to the polyamide barrier layer 104. Strip adhesion test samples of the HNBR rubber hose layer bonded to the polyamide barrier layer exhibited adhesion between 30 lbf / in and 85 lbf / in; however, this value relates more to rubber tear strength since the two layers never actually separated.

[0059] The polyamide barrier layer 104 comprises a polyamide molding component containing an amide-CO-NH-bond in its main chain and an additive. In some embodiments, a heat-stable polyamide resin is suitable. Examples of suitable nylon polyamides may include PA 6 (polyamide 6; nylon 6), PA 6,6 (polyamide 6,6; nylon 6,6), PA 11 (polyamide 11; nylon 11), PA 12 (polyamide 12; nylon 12), PA 612 (polyamide 612; nylon 6,12), PA 46 (polyamide 46; nylon 46), and PA 610 (polyamide 610; nylon 6,10). In some embodiments, suitable nylon polyamides include PA 6, PA 6,6, PA 12, and PA 11. In still other embodiments, suitable nylon polyamides include PA 6 and PA 6,6. In yet other embodiments, suitable nylon polyamides include PA 6,6. In some embodiments, the polyamide layer 104 is made of commercially available products such as DuPont 45HSB PA 6,6. In some embodiments, the polyamide layer is a continuous layer. In some embodiments, the polyamide barrier layer 104 is made of a polyamide composition, which further comprises additives such as reinforcing agents, fire retardants, stabilizers, processing aids, foaming agents, metal fibers, carbon black, graphite and metal foils, titanium dioxide, color pigments and zinc sulfide.

[0060] In some embodiments, the hose includes multiple layers including a HNBR rubber tube layer 102 directly bonded to a continuous polyamide barrier layer 104 without an intermediate adhesive layer. The HNBR rubber tube layer 102 may be covalently bonded to the continuous polyamide barrier layer 104 without an intermediate adhesive layer.

[0061] The rubber backing layer 106 can be directly bonded to the polyamide barrier layer 104 without an intermediate adhesive layer. The rubber backing layer 106 can be prepared from a rubber backing composition comprising EPDM rubber, phenylene dimaleimide and a maleated compound. The EPDM rubber backing layer 106 can be prepared from an EPDM rubber composition according to the method of US9,841,125 (which is incorporated herein by reference). The maleated compound can be a maleated polybutadiene.

[0062] EPDM is selected for making the rubber backing layer 106 of the hose to help maintain heat resistance to at least 150°C while maintaining low temperature sealing capability (-40°C). The EPDM rubber may be a low ethylene EPDM having no more than about 60 wt% ethylene passing ASTM D3900A.

[0063] With respect to backings or insulation layers comprising EPDM, the EPDM ethylene content is the primary factor affecting compression set. As the ethylene content increases, a low level of crystallinity is formed above 55%-65%. If the ethylene / propylene ratio is approximately equal and the distribution of the two monomers in the polymer chain is random, the EPDM is amorphous. Polymers with ethylene contents above 60% tend to show high compression set, while amorphous (less than 60% ethylene) materials provide reduced deformation values ​​at low temperatures. The EPDM composition according to Table 3 contains a low ethylene EPDM having an ethylene content of no more than 60% ethylene.

[0064] Low ethylene EPDM can exhibit improved low temperature capabilities. In some embodiments, the backing layer 106 comprises a peroxide cured EPDM made with a low ethylene content. In some embodiments, there is no adhesive between the EPDM backing layer 106 and the polyamide reinforcement layer 106. In some embodiments, there is no adhesive between the EPDM backing layer 106 and the reinforcement layer 108. The EPDM rubber can be present in the EPDM rubber composition in a range of about 25wt%-45wt%, 30-40wt%, or 33-37wt% compared to the total weight of the filled EPDM rubber backing composition.

[0065] The maleating compound may be present in the EPDM rubber composition in the following ranges compared to the total weight of the filled EPDM rubber backing composition: from about 0.1 wt % to about 15 wt %; 0.5 wt %-10 wt %; or 3 wt %-7 wt %.

[0066] The phenylene bismaleimide may be present in the EPDM rubber composition at about 0.1 wt% to 5 wt%; 0.5 wt% to 3 wt%; or 1.00 wt% to 1.75 wt% relative to the total weight of the filled EPDM rubber backing composition.

[0067] The EPDM rubber composition may include a plasticizer. The plasticizer may be a paraffin process oil silica blend plasticizer. The plasticizer may be present in an amount of 2-20 wt%, 5-15 wt%, or 8-12 wt% compared to the total weight of the filled EPDM rubber backing composition.

[0068] The EPDM rubber composition may further include an antioxidant. The antioxidant may be, for example, a hydroquinoline antioxidant, such as Agerite MA TM (2,2,4-trimethyl-1,2-dihydroquinoline polymer). The antioxidant may be, for example, a phenol-phosphite antioxidant, such as 168 (tris(2,4-di-tert-butylphenyl)phosphite, Ciba Corporation). When present, the EPDM rubber composition may contain an antioxidant in the range of 0.1 to 1.0 wt%, or 0.2 to 0.6 wt%.

[0069] The EPDM rubber backing layer can be prepared from a rubber backing composition that further comprises one or more fillers. In some embodiments, the rubber backing composition comprises one or more fillers selected from the group consisting of carbon black, silicon dioxide, silicates, talc, aluminum silicates, calcium carbonate, zinc oxide, titanium dioxide, and stearic acid. In some embodiments, the rubber backing composition comprises a filler in an amount of about 30-60wt%, 40-60wt%, or 45-60wt% relative to the gross weight of the rubber backing composition.

[0070] In some embodiments, a hose is provided that includes an HNBR tube layer 102, a rubber backing layer 106, and a polyamide layer 104, wherein the rubber backing layer 106 is covalently bonded directly to the polyamide layer 104 without an adhesive. In some embodiments, the rubber backing layer as provided herein exhibits adhesion to the polyamide layer of greater than 10 lbf / in2 when tested according to ASTM D 413.

[0071] In some embodiments, the rubber backing composition does not contain polyamide. In some embodiments, the rubber backing composition does not contain polyvinyl butyral.

[0072] In some embodiments, the rubber backing composition comprises an organic peroxide.The rubber backing layer 106 may be prepared from a rubber backing composition comprising an organic peroxide selected from dicumyl peroxide and t-butylcumyl peroxide.

[0073] The hose according to the present disclosure may include a textile braided reinforcement cover 108. The reinforcement layer can be prepared by braiding, circling, knitting, or spiral knitting the yarn. The yarn can be selected from polyester, aramid, polypropylene, glass, nylon, cotton, rayon yarn, or a blend thereof. In some embodiments, the polyester yarn can be, for example, polyethylene terephthalate or polyethylene naphthalate. The polyester yarn can be a high tenacity continuous filament polyester yarn. The yarn can contain nylon resin to increase wear resistance. The nylon resin can be present in the polyester yarn as 3%-5% liquid nylon.

[0074] In some embodiments, a hose is provided that includes an HNBR rubber tube layer 102 directly bonded to a polyamide barrier layer 104. The hose may include at least four layers arranged in the radial direction of the hose from the inside to the outside in the following order: an inner HNBR tube layer 102; a polyamide barrier layer 104; an EPDM rubber backing layer 106; and a braided cover reinforcement layer 108.

[0075] In some embodiments, the hose includes multiple layers wherein a continuous polyamide plastic layer 104 is directly bonded to an EPDM rubber backing layer 106 without an intermediate adhesive layer. The polyamide plastic layer 104 may be covalently bonded to the EPDM rubber backing layer 106 without an intermediate adhesive layer.

[0076] The hoses provided herein (including an HNBR inner tube layer directly bonded to a continuous polyamide plastic layer without an intermediate adhesive layer) exhibit unexpectedly improved properties, including one or more of the following: a working pressure of 500 psi (34.5 bar); a 4:1 burst rating; an operating temperature range of 140°F to 301°F (-40°C to +150°C); a low permeation rating of <15 kg / m2 / yr; no odor; kink resistance; improved flexibility over FBU hoses; a tighter bend radius over competitive hoses; compatibility with gasoline, E85, diesel, biodiesel, and hot water; and an acceptable crimp and reusable fitting.

[0077] Figure 2 2 is a diagram of an exemplary plywood hose of the present disclosure, wherein the embodiment includes a hose 200 having multiple layers. In this example, the layers include a resistant layer 202, a polyamide layer 204, an HNBR rubber backing layer 206, a reinforcing layer 208, and a cover layer 210. The rubber backing layer 206 can be prepared from a rubber backing composition comprising HNBR, phenylene dimaleimide, and a maleated compound as described in the present disclosure. The HNBR rubber backing composition allows direct bonding to polyamide without an intermediate adhesive layer during vulcanization. In some embodiments, the rubber backing layer 206 is prepared from a composition comprising HNBR, phenylene dimaleimide, a maleated compound, and one or more of a filler, a plasticizer, a vulcanizing agent, a peroxide, and / or an antioxidant as described in the present disclosure.

[0078] Figure 2The hose includes an inner resistant layer 202 for resisting moisture ingress and oil. In some embodiments, the resistant layer 202 is made of a composition comprising polyamide. In a specific embodiment, the resistant layer 202 is made of a composition comprising PA 6, PA 6,6, PA 6,12, PA 11 or PA 12. In some embodiments, PA 6 or PA 6,12 is used to prepare the resistant layer 202 because it can be directly bonded to PA 6,6. In some embodiments, the resistant layer is a commercially available material, such as DuPont FN727. In other embodiments, the resistant layer 202 is made of a fluorinated polymer. In some embodiments, the fluorinated polymer is, for example, polyvinylidene fluoride (PVDF). In some embodiments, the resistant layer 202 is used as an oil barrier. In some embodiments, the resistant layer 202 is about 0.006" to about 0.01" thick; about 0.007" to about 0.008" thick; about 0.007" to about 0.009" thick; or about 0.0065" to about 0.0085" thick.

[0079] In some embodiments, the resistant layer 202 and the polyamide layer 204 are formed by co-extruding PA6 and PA6,6 to form a plastic plywood.

[0080] exist Figure 2 In the hose, the polyamide layer 204 and the HNBR rubber backing layer 206 are chemically and covalently bonded together without the use of an adhesive. In one embodiment, the rubber backing layer 206 made from a composition comprising HNBR, phenylene dimaleimide, and a maleated compound is directly bonded to the polyamide layer 204 comprising nylon 6,6 when cured.

[0081] Although the exact bonding mechanism between the layers is unclear, possible bonding mechanisms that occur through, for example, conventional press curing or extrusion processing methods utilize two different mechanisms. First: MA can bond to the amine end of nylon 6,6 through a Diels-Alder chemistry reaction to form a CN bond. Second: The ring carbon on the maleimide group can form a covalent CC interaction with the nylon 6,6 backbone using a free radical mechanism through an Alder-ene reaction. In one embodiment, the polyamide layer 104 and the rubber backing layer 106 are sheared and vulcanized at a temperature of about 300°F-350°F.

[0082] The reinforcement layer 208 comprises a textile braid. The textile braid can be made of polyester, nylon, cotton, aramid or rayon yarn. In some embodiments, the reinforcement layer 208 is a discontinuous layer. In some embodiments, the reinforcement layer 208 is a discontinuous layer comprising a polyester braid, aramid, nylon, cotton or rayon. In some embodiments, the cover layer 210 and the rubber backing layer 206 migrate through the gaps of the textile in the reinforcement layer 208 and are vulcanized together.

[0083] The cover layer 210 has the largest outer diameter of the layers. In some embodiments, the cover layer 210 comprises a rubber, such as EPDM. In some embodiments, the cover layer is prepared from a composition comprising an EPDM compound capable of maintaining a seal at low temperatures. In some embodiments, the EPDM is made with low ethylene so it has low temperature capabilities. In some embodiments, the cover layer 210 comprises a peroxide cured EPDM made with low ethylene content. In some embodiments, there is no adhesive between the reinforcement layer 208 and the cover layer 210. In some embodiments, the hose includes five layers.

[0084] Figure 3 A schematic diagram of an extrusion system 300 that can be used to manufacture the tube layer 102 according to an embodiment is shown. HNBR rubber pellets 304, maleated compound 302, and phenylene dimaleimide 306 can be moved to a hopper 312 via a conveyor 310 and blended. The blend is moved from the hopper 312 to an extruder and heated with a heating system 318. A control system 316 is used to communicate between the conveyor 310 and the extruder 314. The heated blend is moved through a crosshead 320 and extruded onto a mandrel to form the HNBR tube 102.

[0085] A method for making a barrier hose is provided, the method comprising blending a first composition comprising HNBR rubber, phenylene bismaleimide and a maleated compound; extruding the first composition onto a mandrel to form an HNBR inner tube layer; extruding a polyamide composition on the inner tube layer to form a barrier layer; blending a second composition comprising ethylene propylene diene monomer (EPDM), phenylene bismaleimide and a maleated compound; extruding the second composition on the polyamide barrier layer to form an EPDM rubber backing layer; applying a textile braid reinforcement layer on the EPDM rubber backing layer to form a green hose; vulcanizing the green hose; and removing the hose from the mandrel. The HNBR rubber is at least partially saturated, having no more than 6%, or no more than 4%, residual double bonds by IR spectroscopy. In some embodiments, the HNBR should be fully saturated, having no more than 1% residual double bonds by IR spectroscopy. The first composition may further comprise a high molecular weight plasticizer. The first composition may further comprise one or more fillers. The first composition may be peroxide curable. The polyamide composition may comprise PA 6,6, PA 6, PA 12, PA 11 or a blend thereof. The EPDM composition may comprise low ethylene EPDM. The textile braid may be formed from a yarn selected from polyester, aramid, polypropylene, nylon, cotton, rayon yarn, or any combination thereof.

[0086] Barrier hoses according to the present disclosure may exhibit an operating temperature range of -40°F to +301°F (-40°C to +150°C). Hoses according to the present disclosure may exhibit the following operating pressures: 400psi or higher; 450psi or higher; or 500psi or higher. Hoses according to the present disclosure may exhibit the following permeation ratings for E85: no more than 5.0g / m2 / day; or no more than 4.5g / m2 / day. Hoses according to the present disclosure may exhibit the following permeation ratings for Fuel C: no more than 4.0g / m2 / day; or no more than 3.6g / m2 / day. Fuel permeation testing may be conducted according to the SAE J1527 permeation test with a maximum 24-hour weight loss (in grams) during the test period. Hoses according to the present disclosure may meet or exceed the SAE J30R9 rating requirements. Hoses according to the present disclosure may meet or exceed the SAE J1527 rating requirements. In some embodiments, a low permeation fuel hose is provided that is CARB approved and compliant with parts of SAE J1527 and SAE J30 R9 specifications.

[0087] A method for making a plywood hose is provided, the method comprising extruding two polyamides (e.g., PA6 and PA6,6) onto a mandrel to make plywood; extruding an HNBR backing layer onto the plywood; braiding a reinforcement layer onto the backing layer; and extruding a cover layer onto the braid to form a green hose; vulcanizing the green hose; and driving the vulcanized hose off the mandrel.

[0088] Test Method

[0089] The rubber may be subjected to Shore A hardness testing. Hardness may be tested using a calibrated Instron automatic durometer tester in accordance with ASTM D 2240-95.

[0090] Compression set (C Set) is one of the main characteristics of a rubber compound that indicates low temperature sealing ability. Compression set can be tested according to ASTM D 395-89. The sample can be prepared as follows. First, EPDM rubber is cured at 320°F for 60 minutes and formed into a 0.49" thick x 1.14" diameter button. The button is then compressed 25% into a C Set fixture. After curing, the sample is exposed to -40°C for 24 hours, and the sample is removed and measured at specified time increments. Time versus compression percentage can be plotted on a graph. The overall compression set can be evaluated on samples that are allowed to run for a full 24 hours and then rebounded at room temperature outside the C Set fixture before the final measurement.

[0091] Strip adhesion test can be carried out according to ASTM D 413-81. For example, this test measures the adhesion strength between each embodiment of HNBR rubber tube layer and the embodiment of polyamide layer. Sample type B-uses 90 ° peeling. Use 4 "long, 1 "wide and 0.075 "thick polyamide 6,6 injection molded sample to prepare the sample. PA 6,6 sample is placed on the rubber sample of 4 "long, 1 "wide and 0.09 "thickness on the standard press cured product. The sample is vulcanized at 320 ° F for 45 minutes. Twenty-four hours after vulcanization, the sample is tested at a rate of 2 " / min using a 5KN (1,125lbf) load cell on a calibrated Instron 5965 (according to ASTM D413 type B (90 ° C peeling)).

[0092] Tensile strength and percent elongation can be tested according to ASTM D 412. Standard ASTM specimens can be tested on a calibrated Instron 5965 test system using a 5KN load cell at a rate of 20" / min. The elastic modulus is the force at a specific elongation value (e.g., at 100% elongation). It is expressed in pounds per square inch (psi) or megapascals (MPa).

[0093] The Die C Tear Strength test can be performed according to ASTM D 624. This test measures the resistance to tear initiation.

[0094] Scorch time (T5) is the time interval (measured from the time the rotor is started) corresponding to the viscosity increase of 5 Mooney units relative to MV measured at the time of rotor startup. The T5 value indicates the pre-vulcanization tendency of the compound. Generally, the greater the T5 value, the lower the pre-vulcanization tendency, and therefore the compound can be processed more reliably on the extruder. T5 can be measured by ASTM D 1646 or ASTM D 2084.

[0095] Rubber extraction tests can be performed with the aid of ISO 1407: 2011. Method A measures the mass of the solvent extract after evaporation of the solvent relative to the mass of the original test portion. Method B measures the difference in mass of the test portion before and after extraction.

[0096] The Green Rubber Shelf Life Test evaluates how the measurements change over time. Samples were cured at intervals (45" at 320°F) over a 3 month period from a standard uncured stock. Those samples were tested according to ASTM 412, ASTM D 2084-95, and ASTM D 413-81.

[0097] Refrigerant permeation of the test hose and the comparative product hose may be tested in accordance with SAE J2064. The samples are stabilized at 23°C ± 2°C for 24 hours prior to testing and inspected to ensure the specified charge and identify charge loss. Examples

[0098] Example 1. HNBR rubber composition

[0099] A direct bonded low extraction rubber composition was developed to bond directly to a barrier or plywood polyamide layer without a separate adhesive layer. HNBR was selected for use as a base rubber to be compatible with Fuel C, E85, biodiesel, methanol, hot water, glycols, and refrigerants such as R134a. The HNBR rubber composition was developed for use in making an inner tube layer (e.g., in a barrier hose), or for use in making a backing layer (e.g., in a plywood hose).

[0100] The HNBR composition of Example 1 below was prepared according to the above protocol. The HNBR composition comprised HNBR which was 99% saturated HNBR (Arlanxo Therban A3407), phenylene bismaleimide and maleated polybutadiene.

[0101] Table 1. Rubber HNBR composition A

[0102] HNBR Composition A exhibited desirable characteristics when cured, as shown in Table 2.

[0103] Using a moving die rheometer at 157°C, 0.5 radian, 100 cpm and 30 minutes, the rubber tube layer exhibited a T5 of 12.47 min; a Mooney viscosity of 31.62 MS (1+4); a tensile strength of 2281.68 psi; an elongation of 180.74%; a 10% modulus of 374.7%; a 100% modulus of 1591.46 psi; a hardness of 82.4 pts A; a die C tear strength of 199.99 lbf / in; and an extraction test result of 0.02 g / m2.

[0104] Table 2. HNBR rubber test results

[0105] The tube layer prepared from HNBR composition A exhibited the desired direct bonding to the polyamide 6,6 barrier layer, as well as multi-refrigerant / oil compatibility. When tested according to ASTM D413, the strip adhesion test samples of the HNBR rubber tube layer bonded to the polyamide barrier layer exhibited adhesion between 40 lbf / in2 and 70 lbf / in2; however, this value is more related to the rubber tear strength because the two layers never actually separated. Example 2. EPDM rubber composition

[0106] A rubber composition that is directly bonded is desired to bond directly to the polyamide layer without a separate adhesive layer. An EPDM rubber composition is prepared according to US 9,841,125 (which is incorporated herein by reference). An EPDM composition is employed to bond directly to a polyamide layer.

[0107] Table 3. Rubber Backing EPDM Composition B

[0108] EPDM composition B exhibits desirable characteristics when cured. Using a moving die rheometer at 157°C, 0.5 radians, 100 cpm, and 30 minutes, the rubber backing layer of Table 3 has a T5 of 5 min; a Mooney viscosity of 41 MU; adhesion to polyamide in the strip adhesion test of greater than 10 lbf / in when tested according to ASTM D413; a tensile strength of 1,472 psi; and an elongation of 148%. In addition, the backing layer prepared from composition B exhibits desirable direct bonding to polyamide 6,6 plywood, as well as multi-refrigerant / oil compatibility. Example 3. Hose Construction and Testing

[0109] A hose according to the present disclosure includes an HNBR inner tube layer 102; a polyamide barrier layer 104; an EPDM backing layer 106; and a textile braid reinforcement cover layer 108. When the hose is vulcanized, the HNBR tube layer 102 is directly bonded to the polyamide barrier layer 104, and the EPDM cover layer is directly bonded to the polyamide barrier layer 104.

[0110] A hose according to the present disclosure can be prepared by blending a first composition comprising HNBR rubber, phenylenedimaleimide, and a maleated compound according to Table 1; extruding the first composition onto a mandrel to form an HNBR inner tube layer; extruding a polyamide composition on the inner tube layer to form a barrier layer; blending a second composition comprising ethylene propylene diene monomer (EPDM), phenylenedimaleimide, and a maleated compound according to Table 3; extruding the second composition on top of the polyamide barrier layer to form an EPDM rubber backing layer; applying a textile braid reinforcement layer on the EPDM rubber backing layer to form a green hose; vulcanizing the green hose; and driving the hose off the mandrel.

[0111] According to ASTM D 3182-07, Banbury TMMixer (Farrel Corporation) is used to mix different rubber formulations as shown in Table 1. First, the polymer is first added to the mixer within a 30-second crushing cycle at 150°C. Secondly, fillers and plasticizers are added within a 120-second mixing cycle at 200°C. Then, processing aids such as vulcanizing agents are added within a 120-second mixing cycle at 220°C. Fourth, the composition undergoes a fourth mixing cycle at 220°C for 90 seconds. The masterbatch rubber is then placed in a mixer with a curing agent and mixed for 120 seconds at 180°C, followed by a final mixing of 120 seconds at 180°C.

[0112] After the rubber drips from the mixer, the rubber is manually applied to a two-roll mill and sheeted to a thickness of 0.75" - 1.25" according to ASTM B 947-06. The two-roll mill stage sheets and cools the mixed formulation.

[0113] The curing kinetics of the rubber formulations can be evaluated according to ASTM D 2084-95 (Cure Studies). Rheometry can be measured using a Monsanto RPA2000 at 160°C for 45 minutes.

[0114] The sheeted material was subjected to a curing press for vulcanization. Based on the T90 values ​​from the curing studies, the sheeted material from the two-roll mill can be placed into a curing press and vulcanized at 320°F for 45 minutes. Example 4. Characteristics of the Inventive and Comparative Hoses

[0115] The barrier hose of the present invention comprises an HNBR tube; a PA66 barrier layer; an EPDM backing layer; and a Tensa filament polyester braid (reinforcement) cover layer having an inner diameter (ID) of 0.43 in and an outer diameter (OD) of 0.66 in, exhibiting an operating temperature range of -40°F to 301°F, an operating pressure of 500 psi, and a permeation rating of E85: 4.5 g / m 2 / day; fuel C: 3.6g / m 2 / day; 2.50in minimum bend radius, 3.7lbs bend force, 0.09lbs / ft weight per foot; and is approved for use with fuels (including E85, methanol, biodiesel) and hot water.

[0116] Table 4 shows the inventive hose characteristics as well as comparative hose characteristics for: Comparative Hose A (Earl's Pro-Lite); Comparative Hose B (Russel Pro-Classic); Comparative Hose C (Fragola EX Street); and Comparative Hose D (Gates Barricade).

[0117] Table 4. Characteristics of the barrier hose of the present invention and the comparative hose

[0118] The inventive hose exhibited an operating temperature range as wide as Comparative Hose A and Comparative Hose B (-40°F to 301°F). The inventive hose exhibited an operating temperature range wider than Comparative Hose C (-29°F to 275°F) and Comparative Hose D (-40°F to 257°F). The inventive hose exhibited a significantly higher operating pressure (500 psi) when compared to Comparative Hose A (350 psi), Comparative Hose B (350 psi), Comparative Hose C (175 psi), and Comparative Hose D (225 psi). The inventive hose exhibited improved permeation ratings for E85 and Fuel C (E85: 4.5 g / m 2 / day; fuel C: 3.6g / m 2 / day), compared to the control hose D (E85: 5.7g / m 2 / day; fuel C: 4.1g / m 2 / day). The inventive hose exhibited significantly improved permeation ratings for E85 and Fuel C compared to Comparative Hose A (E85: 14.4 g / m 2 / day; fuel C: 12.7g / m 2 / day), comparative hose B (E85: 18.4 g / m 2 / day; fuel C: 16.8g / m 2 / day) and control hose C (E85: 13.8 g / m 2 / day; fuel C: 11.6g / m 2 / sky).

[0119] The inventive hose exhibits greater flexibility than comparative hoses A, B, C, and D. The inventive hose exhibits a smaller bend radius (2.50 in) and a smaller bend force (3.7 lbs) than comparative hose A, comparative hose B, comparative hose C, and comparative hose D.

[0120] The inventive hose weighs less (0.09 lbs / ft) than Comparative Hose A (0.13 lbs / ft), Comparative Hose B (0.13 lbs / ft), Comparative Hose C (0.26 vbs / ft), or Comparative Hose D (0.19 lbs / ft).

[0121] The hose of the present invention meets the SAE J30R9 requirements for fuel injection hoses. The hose of the present invention meets the SAE J1527 requirements for marine fuel hoses.

Claims

1. A hose comprising a plurality of layers, the layers comprising: A layer of hydrogenated nitrile (HNBR) rubber directly bonded to a polyamide (PA) barrier layer, The HNBR rubber layer is prepared from a first composition comprising HNBR rubber, phenylene dimaleimide and a maleated compound.

2. The hose according to claim 1, wherein The HNBR layer is covalently bonded to the PA barrier layer without an intermediate adhesive layer.

3. The hose according to claim 1, wherein: The HNBR rubber is at least partially saturated, having no more than 6%, no more than 4%, no more than 2%, or no more than 1% residual double bonds by infrared (IR) spectroscopy.

4. The hose according to claim 3, wherein: The first composition comprises the HNBR rubber in a range of 20-60 wt%, 30-55 wt%, or 35-45 wt% compared to the total weight of the first composition.

5. The hose according to claim 1, wherein The phenylene dimaleimide is N,N'-1,3-phenylene dimaleimide.

6. The hose according to claim 5, wherein: The first composition includes the phenylene bismaleimide in a range of 0.1-5.0 wt%, 0.5-4.0 wt%, 0.8-3.0 wt%, or 1-2 wt% compared to the total weight of the first composition.

7. The hose according to claim 1, wherein: The maleated compound is a maleated polybutadiene compound.

8. The hose according to claim 1, wherein: The first composition comprises the maleated compound in a range of 1-7 wt%, 2-6 wt%, 3-5 wt%, or 3.5-4.5 wt% compared to the total weight of the first composition.

9. The hose according to claim 1, wherein: The first composition further comprises a plasticizer, optionally wherein the plasticizer is a high molecular weight plasticizer (>500 g / mol).

10. The hose according to claim 9, wherein The plasticizer is tri-C trimellitic acid 6-12 Alkyl esters.

11. The hose according to claim 9 or 10, wherein: The first composition comprises the plasticizer in the range of 0-25 wt%, 0.1-20 wt%, 3-15 wr%, 5-15 wt%, or 7-10 wt% compared to the total wt of the first composition.

12. The hose according to claim 1, wherein The first composition comprises one or more fillers, optionally wherein the one or more fillers are selected from the group consisting of carbon black, silica, silicates, talc, aluminum silicate, calcium carbonate, zinc oxide, titanium dioxide, and stearic acid.

13. The hose according to claim 12, wherein: The first composition comprises the one or more fillers in a total amount ranging from 30-60 wt%, 35-55 wt%, or 35-45 wt% compared to the total weight of the first composition.

14. The hose according to claim 1, wherein The first composition comprises a peroxide, optionally wherein the peroxide is selected from the group consisting of dicumyl peroxide, di-tert-butyl peroxide, and tert-butylcumyl peroxide.

15. The hose according to claim 1, wherein The first composition comprises an antioxidant.

16. The hose according to any one of claims 1 to 15, wherein This HNBR layer is the inner HNBR tube layer.

17. The hose according to any one of claims 1 to 16, wherein: The HNBR layer is a HNBR backing layer.

18. A hose as claimed in any one of claims 1 to 17, comprising the following layers in radial direction: an inner HNBR tube layer prepared from the first composition; Polyamide barrier layer; a rubber backing layer; and Braided reinforcement cover.

19. A hose as claimed in any one of claims 1 to 17, comprising the following layers in radial direction: Internal polyamide plywood; an HNBR rubber backing layer prepared from the first composition; Braided reinforcement; and External rubber covering.

20. The hose according to any one of claims 1 to 19, wherein The polyamide layer comprises a polyamide selected from the group consisting of PA6,6, PA6,6, PA 12, PA 11, or blends thereof.

21. The hose of claim 18, wherein: The rubber backing layer is an EPDM rubber backing layer prepared from a second composition comprising a low-ethylene EPDM rubber, phenylene bismaleimide and a maleated compound.

22. The hose of claim 21, wherein The second composition comprises one or more fillers, a wax plasticizer, and a peroxide.

23. The hose according to claim 21 or 22, wherein: The EPDM rubber backing layer is covalently bonded to the polyamide barrier layer without an intermediate adhesive layer.

24. A hose as claimed in any one of claims 18 to 23, wherein The braided reinforcing cover layer comprises polyester, aramid, polypropylene, glass, nylon, cotton, rayon yarn, or blends thereof.

25. The hose according to any one of claims 1 to 24, wherein Vulcanized hoses exhibit one or more of the following: -40°F to +301°F operating temperature range; A maximum working pressure of at least 500 psi; At least 4:1 burst rating under SAE J1527 burst test conditions; Not exceeding 15 g or less fuel loss / m2 of internal surface area in 24 hours with CE fuel at 23°C as specified in SAE J1527-B1 - 15 g / m 2 / 24h——penetration rating; Not exceeding 15 g or less fuel loss / m2 of internal surface area in 24 hours at 40°C with E85 fuel as specified in SAE 30R9 - 15 g / m 2 / 24h——penetration rating; Not exceeding 15 g or less fuel loss / m2 of internal surface area in 24 hours at 40°C with fuel C as specified in SAE 30R9 - 15 g / m 2 / 24h——penetration rating; In the case of E85 fuel, it does not exceed 5g / m 2 / 24h penetration rate; In the case of fuel C, it exhibits no more than 4 g / m 2 / 24h penetration rate; Meets SAE J30R9 requirements for fuel injection hoses; and Meets SAE J1527 requirements for marine fuel hoses.

26. A method of manufacturing a hose as claimed in any one of claims 1 to 18 or 20 to 25, the method comprising: blending HNBR rubber, phenylene dimaleimide, and a maleated compound to prepare a first composition; extruding the first composition onto a mandrel to form an HNBR inner tube layer; extruding a polyamide composition on the HNBR inner tube layer to form a barrier layer; blending a second composition comprising ethylene propylene diene monomer rubber (EPDM), phenylene bismaleimide, and a maleated compound; extruding the second composition over the polyamide barrier layer to form an EPDM rubber backing layer; applying a textile braid reinforcement layer onto the EPDM rubber backing layer to form a green hose; vulcanizing the green hose; as well as The hose is driven off the mandrel.

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