Low-extracting hnbr material having adhesion to polyamide

Abstract

Low permeation barrier and plywood style multilayer fuel and air conditioning hoses are provided that include an HNBR layer directly bonded to a polyamide layer. Low extraction, peroxide cured HNBR thermoset rubber formulations are provided that are directly bonded to polyamide thermoplastics during a vulcanization step without the need for external adhesive application.

Description

Technical Field

[0001] This disclosure relates to a novel rubber compound specifically designed for fluid delivery fuel and air conditioning hoses, particularly with the implementation of a thermoplastic barrier layer or plywood layer. Background Technology

[0002] In many multi-layer hose designs that include barrier or veneer layers, an external epoxy or acrylic adhesive is applied during manufacturing to bond the individual layers together. These adhesives or bonding agents may have sporadic coverage in these applications, creating a messy process, and may contain substances of very high concern (SVHC) such as bisphenol A.

[0003] The desired improvements are in the process and hose design, which eliminate adhesive-related hazards, remove cumbersome process steps, and significantly improve the quality of the adhesive layer and overall hose performance. Summary of the Invention

[0004] The thermosetting rubber of this invention is based on hydrogenated nitrile butadiene rubber (HNBR) with a specific peroxide curing system, which promotes strong covalent bonding with polyamide thermoplastics without an intermediate adhesive layer. This invention enables the finished composite material to have very low permeability.

[0005] A hydrogenated nitrile butadiene rubber (HNBR) formulation is provided, which is peroxide-cured and produces strong and consistent adhesion to polyamide thermoplastics during the vulcanization process without the need for adhesives. This HNBR formulation is designed to have very low volatile components to help avoid any residual extraction that could contaminate downstream components during application. This HNBR formulation can be used to prepare the tubing or backing layer in fuel hoses or refrigerant hoses.

[0006] Hydrogenated nitrile butadiene rubber (HNBR) is a synthetic compound prepared by hydrogenation of nitrile butadiene rubber (NBR). This hydrogenation process allows for enhanced thermal stability up to approximately 150°C. HNBR also exhibits superior fluid compatibility compared to NBR.

[0007] In some instances, a 99% saturated hydrogenated nitrile butadiene rubber (HNBR) peroxide-cured composition (containing components with maleic anhydride and maleimide functional groups) is provided to generate robust covalent bonds with the N-terminal amines and / or carbon skeleton of the polyamide thermoplastic resin. This HNBR composition contains very low extractable contents (waxes and plasticizers) to limit the available residues that can be extracted and subsequently cause blockages in valves or other downstream components. Applications of this invention include the use of materials such as polyamides as barrier layers for gas or fluid permeation, or plywood-type fuel or air conditioning hoses.

[0008] A hose is provided comprising multiple layers, including a hydrogenated nitrile butadiene rubber (HNBR) layer directly bonded to a polyamide (PA) barrier layer, wherein the HNBR layer is prepared from a first composition comprising HNBR, phenylene dimaleimide, and a maleic acid 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 can be covalently bonded to the polyamide layer without an intermediate adhesive layer.

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

[0010] In some instances, the first composition comprises phenylene dimaleimide, which is N,N'-1,3-phenylene dimaleimide. The first composition may contain the phenylene dimaleimide in the range of 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 first composition.

[0011] In some instances, the first composition comprises a maleic acid compound, which is a maleic acid-modified polybutadiene compound. The first composition may contain the maleic acid compound in the range of 1-7 wt%, 2-6 wt%, 3-5 wt%, or 3.5-4.5 wt% relative 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 trimethyltrimethacrylate (TMC). 6-12 Alkyl ester. The first composition may contain the plasticizer in the range of 0-25 wt%, 0.1-20 wt%, 3-15 wt%, 5-15 wt%, or 7-10 wt% relative to the total weight of the first composition.

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

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

[0015] This disclosure provides a hose comprising an innermost HNBR tube layer. A hose is provided that, in the radial direction, comprises: an inner HNBR tube layer prepared from an HNBR composition; a polyamide barrier layer; a rubber backing layer; and a braided reinforcing cover layer.

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

[0017] The polyamide layer may contain polyamides selected from the group consisting of PA6, PA6,6, PA12, 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, phenylene dimaleimide, and a maleic acid compound. This second composition may contain one or more fillers, paraffinic 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 reinforcing layer may comprise polyester, aromatic polyamide, polypropylene, glass, nylon, cotton, rayon yarn, or blends thereof.

[0019] Vulcanized hoses according to this disclosure may exhibit one or more, or two or more, of the following characteristics: an operating temperature range of –40℉ to +301℉; a maximum operating pressure of at least 500 psi; a burst rating of at least 4:1 under SAE J1527 burst test conditions; and an internal surface area loss of no more than 15 g / m² over 24 hours in the case of CE fuel at 23°C as specified in SAE J1527-B1. 2• 24h) — Permeability rating; in the case of E85 fuel at 40°C as specified in SAE 30R9, not exceeding 15 g or less of fuel loss per square meter of internal surface area over 24 hours — 15 g / (m 2 • 24h) — Permeability rating; in the case of fuel C at 40°C as specified in SAE 30R9, not exceeding 15 g or less of fuel loss per square meter of internal surface area in 24 hours — 15 g / (m 2 The permeability rating is 24h; exhibiting no more than 5 g / (m³) in the case of E85 fuel. 2 The permeation rate was 24 h; under fuel C, it exhibited a permeation rate not exceeding 4 g / (m³). 2 The permeation rate is 24h; it meets the SAE J30R9 requirements for fuel injection hoses; and it meets the SAE J1527 requirements for marine fuel hoses.

[0020] A method for manufacturing a hose is provided, the method comprising: blending HNBR, phenylene dimaleimide, and a maleic acid compound to prepare a first composition; extruding the first composition onto a mandrel to form an HNBR inner tube layer; extruding a polyamide composition onto the HNBR inner tube layer to form a barrier layer; blending a second composition comprising ethylene propylene diene monomer (EPDM) rubber, phenylene dimaleimide, and a maleic acid compound; extruding the second composition over the polyamide barrier layer to form an EPDM rubber backing layer; applying a textile braided reinforcement layer onto the EPDM rubber backing layer to form a green hose; vulcanizing the green hose; and removing the hose from the mandrel. Attached Figure Description

[0021] Figure 1 A cross-sectional view of an exemplary blocking hose construction 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 tube layers according to an embodiment is shown. Detailed Implementation

[0024] Current multilayer hose manufacturing processes typically involve applying acrylic or epoxy-based adhesives directly to the layers for adhesion. This is especially true for hoses that include barrier layers or plywood layers. The adhesive application process is cumbersome and messy, and results in some adhesive coverage on the product. Furthermore, due to the use of these adhesives, there are EHS (Environmental Health and Safety) effects during processing, such as SVHC (Sterile Continuous Hazardous Content) emissions based on bisphenol A (BPA) fumes.

[0025] This disclosure provides an improved method for manufacturing multilayer hoses that does not involve directly applying an acrylic or epoxy-based adhesive to the layers for adhesion.

[0026] Low-extraction, peroxide-cured HNBR thermosetting rubber formulations are provided, which bond directly to polyamide thermoplastics during the vulcanization step without the need for external adhesive application. This can be applied to barrier or plywood fuel or air conditioning hoses that use materials such as polyamides as gas or fluid permeation barrier layers.

[0027] definition

[0028] As used herein, the term "a / kind" is defined as either singular or plural.

[0029] A "barrier hose" is a multi-layered hose with an internal barrier layer to prevent fluids (e.g., refrigerant) from leaking through its walls. The barrier layer may contain, for example, polyamide. The barrier layer is not the innermost layer.

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

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

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

[0033] The term "permeability rating" refers to the amount of fuel that will permeate through the hose wall when filled with fuel. In some embodiments, a fuel hose is provided that, as specified in SAE J1527-B1 for marine fuel hoses, has a fuel loss of no more than 15 g / m² of internal surface area over 24 hours in the case of CE fuel at 23°C. 2 • 24h) – Permeability rating. In some embodiments, a fuel hose is provided that, as specified in SAE J309 for fuel injection hoses for gasoline, ethanol-extended gasoline, diesel fuel, biodiesel (B5, B10, B20), and lubricating oil at 104℉ (40°C), has a fuel loss of no more than 15 g / m² of internal surface area over 24 hours – 15 g / (m²) 2The permeability rating is 24h. Fuel C is a test fuel used to determine permeability and tolerance properties. Fuel C contains approximately 50% isooctane and approximately 50% toluene. E85 fuel is a combination of ethanol and gasoline, containing approximately 51%–83% ethanol blended with gasoline.

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

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

[0036] As provided herein, the scope is intended to include at least the numbers that define the scope boundaries. Unless explicitly stated otherwise, terms such as “first” or “second” or other numerical terms do not imply order or sequence.

[0037] One advantage of the HNBR formulation of this invention compared to other elastomers is its ability to bond directly to the polyamide plastic during the vulcanization process without the use of adhesives. This contributes to the fact that the hoses of this invention have significantly lower E85 and fuel C permeability compared to any known competitor. For example, compared to 5.7 to 18.4 g / (m³) for E85. 2 Compared to competing hoses (with a permeability value of 4.5 g / (m²) for E85), the hose of this invention exhibits a permeability value of 4.5 g / (m²) for E85. 2 Low permeability (days).

[0038] Figure 1 An exemplary barrier hose construction 100 according to this disclosure is shown. The thermosetting rubber inner tube layer 102 may be prepared from an HNBR composition according to this disclosure. The barrier tube layer 104 may be prepared from a polyamide composition. The rubber backing layer 106 may be prepared from an EPDM composition. The textile woven outer covering (reinforcing) layer 108 may be prepared from polyester yarn.

[0039] The inner HNBR 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 elastomer HNBR composition comprising a blend of hydrogenated nitrile butadiene rubber (HNBR), N,N'-m-phenylene dimaleimide (HVA-2), and a maleic acid compound. The maleic acid compound can be maleic acid-modified polybutadiene. The phenylene dimaleimide can be N,N'-m-phenylene dimaleimide.

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

[0041] The elastomer HNBR composition allows direct bonding to the polyamide during vulcanization without an intermediate adhesive layer.

[0042] The rubber tube layer 102 and / or the rubber backing layer 206 can be prepared from a composition comprising HNBR, phenylene dimaleimide, maleic acid compound, and one or more of plasticizers, fillers, vulcanizing agents, peroxides, and / or antioxidants.

[0043] The rubber tube layer 102 can be prepared from 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 prepared from an elastomeric composition that does not contain polyvinyl butyral (PVB). The rubber tube layer 102 and / or the rubber backing layer 206 can be prepared from an elastomeric composition that does not contain polypropylene. The rubber tube layer 102 and / or the rubber backing layer 206 can be prepared from an elastomeric composition that does not contain polyamide.

[0044] As used herein, the term "maleic acid compound" refers to a compound having one or more, or two or more, maleic anhydride substituents. In some embodiments, the maleic acid compound is maleic acid-modified polybutadiene. Maleic acid-modified polybutadiene may be a commercially available product such as Ricobond™, for example, Ricobond® 1756 HS (powdered maleic acid-modified polybutadiene with maleic anhydride addition, as a dispersion on amorphous silica, Cray Valley USA). The anhydride may be combined with an amino group, while the vinyl functional group is peroxide-curable. Maleimide can be reacted via three main pathways: 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 maleic acid compound can form a covalent bond (CN bond) with the N-terminal amine group of the polyamide in the polyamide barrier layer 104, while HVA-2 in the rubber tube layer 102 can form a covalent bond (CC bond) with the carbon skeleton. The HNBR composition may contain the maleic acid compound in the range of 1-7 wt%, 2-6 wt%, 3-5 wt%, or 3.5-4.5 wt% relative to the total weight of the HNBR composition.

[0045] The phenylene dimaleimide can be N,N'-m-phenylene dimaleimide. In some embodiments, the phenylene dimaleimide is N,N'-m-phenylene dimaleimide (CAS RN: 3006-93-7; N,N'-1,3-phenylene dimaleimide; HVA-2 curing agent, DuPont Chemical Co.). The HNBR composition may contain phenylene dimaleimide in a total 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 composition.

[0046] In some embodiments, the inner tube layer 102 is prepared from a rubber composition comprising hydrogenated nitrile butadiene rubber (HNBR), the rubber composition further comprising fillers or other additives added to the HNBR. The HNBR composition may further comprise one or more fillers. For example, one or more fillers may be selected from carbon black, silica, silicates, talc, aluminum silicate, calcium carbonate, zinc oxide, titanium dioxide, and stearic acid. In some embodiments, the HNBR composition comprises one or more fillers in a total amount ranging from 30-60 wt%, 35-55 wt%, or 35-45 wt% relative to the total weight of the HNBR composition.

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

[0048] The HNBR composition may further comprise one or more plasticizers. The plasticizer may be a high molecular weight (> 500 g / mol) plasticizer with low volatility. For example, the HNBR composition may comprise a commercially available high molecular weight (> 500 g / mol) plasticizer with low volatility. For example, the plasticizer may be trialkyl trimellitate. The plasticizer may be trialkyl trimellitate. 6-12 Alkyl esters. Trimethylbenzenetriformate (TMC) 6-12 Alkyl esters can be, for example, tri(2-ethylhexyl) trimellitate, trioctyl trimellitate, isodeyl diisooctyl trimellitate, triisooctyl trimellitate, triheptyl trimellitate, trinonyl trimellitate, tridecyl trimellitate, or branched isodeyl diisooctyl ester of 1,2,4-benzenetricarboxylate, etc.

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

[0050] The HNBR 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™ (2,2,4-trimethyl-1,2-dihydroquinoline polymer). The antioxidant may also be, for example, a phenol-phosphite antioxidant, such as Irgafos® 168 (tris(2,4-di-tert-butylphenyl) phosphite, Ciba). When present, the HNBR composition may contain antioxidants in the range of 0.1 to 1.0 wt%, or 0.2 to 0.6 wt%.

[0051] The HNBR 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-butylcumyl peroxide, as well as commercial products such as Luperox™ DC40P-SP2 (dicumyl peroxide spread on calcium carbonate and silica, Arkema) or Varox® DCP-99 (bis(1-methyl-1-phenylethyl) peroxide, R.T. Vanderbilt). In some embodiments, the composition comprises dicumyl peroxide or tert-butylcumyl peroxide. In some embodiments, the composition comprises dicumyl peroxide. In some embodiments, the peroxide is present, by weight of the total HNBR composition filled, in the following quantities: about 0.1 wt% to about 5 wt%; about 1 wt% to about 4 wt%; about 2 wt% to about 3 wt%.

[0052] HNBR compositions may have Mooney viscosities in the range of 20 to 40, 25 to 35, or 30 to 32 MS (1+4) according to ISO 289 / ASTM 1646 at 100°C.

[0053] The HNBR composition disclosed herein can exhibit a T5 of at least 10 minutes, or at least about 12 minutes.

[0054] The cured HNBR composition according to this disclosure can exhibit an elongation percentage of at least 150% or at least 175%.

[0055] The cured HNBR composition disclosed herein can exhibit a concentration of no more than 0.1 g / m³. 2 Not exceeding 0.05 g / m 2 or not exceeding 0.03 g / m 2 The low extraction test results show that the cured HNBR composition disclosed herein can exhibit a hardness in the range of 70-90 Shore A.

[0056] The cured HNBR composition according to this disclosure can exhibit a molded C tear strength of at least 170, at least 180, or at least 190 lbf / in.

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

[0058] During vulcanization, the HNBR tube layer 102 is firmly covalently bonded to the polyamide barrier layer 104. Strip adhesion test samples of the HNBR tube layer bonded to the polyamide barrier layer showed adhesion between 30 lbf / in and 85 lbf / in; however, this value relates more to the rubber tear strength, as the two layers never actually separated.

[0059] The polyamide barrier layer 104 comprises a polyamide molding component containing amide-CO-NH- bonds in its main chain, as well as additives. In some embodiments, a heat-stable polyamide resin is suitable. Examples of suitable nylon polyamides may include PA6 (polyamide 6; nylon 6), PA6,6 (polyamide 6,6; nylon 6,6), PA11 (polyamide 11; nylon 11), PA12 (polyamide 12; nylon 12), PA6,12 (polyamide 6,12; nylon 6,12), PA46 (polyamide 46; nylon 46), and PA6,10 (polyamide 6,10; nylon 6,10). In some embodiments, suitable nylon polyamides include PA6, PA6,6, PA12, and PA11. In other embodiments, suitable nylon polyamides include PA6 and PA6,6. In still other embodiments, suitable nylon polyamides include PA6,6. In some embodiments, the polyamide layer 104 is prepared from a commercially available product such as DuPont Zytel® 45HSB PA6,6. In some embodiments, the polyamide layer is a continuous layer. In some embodiments, the polyamide barrier layer 104 is prepared from a polyamide composition that further comprises additives such as reinforcing agents, flame retardants, stabilizers, processing aids, foaming agents, metal fibers, carbon black, graphite and metal foil, titanium dioxide, colored pigments, and zinc sulfide.

[0060] In some embodiments, the hose includes multiple layers, including an HNBR tube layer 102 directly bonded to the continuous polyamide barrier layer 104 without an intermediate adhesive layer. The HNBR 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 maleic acid compound. The EPDM rubber backing layer 106 can be prepared from the EPDM rubber composition according to the method described in US 9,841,125 (which is incorporated herein by reference). The maleic acid compound can be maleic acid-modified polybutadiene.

[0062] EPDM was selected for use in the rubber backing layer 106 of the hose to help maintain heat resistance of at least 150°C while maintaining low-temperature sealing capability (-40°C). The EPDM rubber can be low-ethylene EPDM with no more than about 60 wt% ethylene as per ASTM D3900A.

[0063] Regarding EPDM-containing backing or insulating layers, the ethylene content of the EPDM is the primary factor affecting compression set. With increasing ethylene content, a low level of crystallinity is formed above 55%-65%. EPDM is amorphous if the ethylene / propylene ratio is approximately equal and the distribution of both monomers in the polymer chain is random. Polymers with an ethylene content higher than 60% tend to exhibit high compression set, while amorphous materials (less than 60% ethylene) provide reduced deformation values ​​at low temperatures. The EPDM compositions according to Table 3 contain low-ethylene EPDM with an ethylene content not exceeding 60%.

[0064] Low-ethylene EPDM can exhibit improved low-temperature performance. In some embodiments, the backing layer 106 comprises 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 reinforcing layer 108. In some embodiments, there is no adhesive between the EPDM backing layer 106 and the reinforcing layer 108. EPDM rubber may be present in the EPDM rubber composition in the range of about 25 wt%-45 wt%, 30-40 wt%, or 33-37 wt% relative to the total weight of the filled EPDM rubber backing composition.

[0065] Maleate compounds may be present in the EPDM rubber composition in the following ranges relative to the total weight of the filled EPDM rubber backing composition: about 0.1 wt% to about 15 wt%; 0.5 wt% to 10 wt%; or 3 wt% to 7 wt%.

[0066] Phenylidene dimaleimide may be present in the EPDM rubber composition in the following amounts relative to the total weight of the filled EPDM rubber backing composition: about 0.1 wt%-5 wt%; 0.5 wt%-3 wt%; or 1.00 wt%-1.75 wt%.

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

[0068] The EPDM rubber composition may further comprise an antioxidant. The antioxidant may be, for example, a hydrogenated quinoline antioxidant, such as Agerite MA™ (2,2,4-trimethyl-1,2-dihydroquinoline polymer). The antioxidant may also be, for example, a phenol-phosphite antioxidant, such as Irgafos® 168 (tris(2,4-di-tert-butylphenyl)phosphite, Ciba). When present, the EPDM rubber composition may contain antioxidants 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, which 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, silica, silicates, talc, aluminum silicate, calcium carbonate, zinc oxide, titanium dioxide, and stearic acid. In some embodiments, the rubber backing composition comprises filler in an amount of about 30-60 wt%, 40-60 wt%, or 45-60 wt% of the total weight of the rubber backing composition.

[0070] In some embodiments, a hose is provided comprising an HNBR tube layer 102, a rubber backing layer 106, and a polyamide layer 104, wherein the rubber backing layer 106 is directly covalently bonded to the polyamide layer 104 without an adhesive. In some embodiments, the rubber backing layer as described herein exhibits a strength greater than 10 lbf / in when tested according to ASTM D 413. 2 The adhesion of the polyamide layer.

[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 tert-butylcumyl peroxide.

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

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

[0075] In some embodiments, the hose comprises 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 also be covalently bonded to the EPDM rubber backing layer 106 without an intermediate adhesive layer.

[0076] The hoses described in this article (including the 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; a working temperature range of 140℉ to 301℉ (-40℃ to +150℃); < 15 kg / (m²) 2 Low permeability rating (years); odorless; kink-resistant; improved flexibility superior to FBU hoses; tighter bend radius than competing hoses; compatibility with gasoline, E85, diesel, biodiesel and hot water; and qualified coiled and reusable fittings.

[0077] Figure 2This is an illustration of an exemplary plywood hose of this disclosure, wherein this embodiment includes a hose 200 having multiple layers. In this example, these layers include a durable layer 202, a polyamide layer 204, an HNBR backing layer 206, a reinforcing layer 208, and a cover layer 210. The rubber backing layer 206 may be prepared from a rubber backing composition comprising HNBR, phenylene dimaleimide, and a maleic acid compound, as described in this disclosure. The HNBR backing composition allows direct bonding to the polyamide during vulcanization without an intermediate adhesive layer. In some embodiments, the rubber backing layer 206 is prepared from a composition comprising HNBR, phenylene dimaleimide, a maleic acid compound, and one or more of fillers, plasticizers, vulcanizing agents, peroxides, and / or antioxidants, as described in this disclosure.

[0078] Figure 2 The hose includes an internal protective layer 202 for preventing moisture ingress and oil. In some embodiments, the protective layer 202 is prepared from a composition comprising polyamide. In a specific embodiment, the protective layer 202 is prepared from a composition comprising PA6, PA6,6, PA6,12, PA11, or PA12. In some embodiments, PA6 or PA6,12 is used to prepare the protective layer 202 because it can directly bond to PA6,6. In some embodiments, the protective layer is a commercially available material, such as DuPont Zytel® FN727. In other embodiments, the protective layer 202 is prepared from a fluorinated polymer. In some embodiments, the fluorinated polymer is, for example, polyvinylidene fluoride (PVDF). In some embodiments, the protective layer 202 serves as an oil barrier. In some embodiments, the protective 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 backing layer 206 are chemically covalently bonded together without the use of an adhesive. In one embodiment, the rubber backing layer 206, prepared from a composition comprising HNBR, phenylene dimaleimide, and a maleic acid compound, is directly bonded to the polyamide layer 204 comprising nylon 6,6 upon curing.

[0081] Although the exact bonding mechanism between the layers is unclear, two different mechanisms are utilized in possible bonding processes, such as conventional compression curing or extrusion processing. First, the maleimide (MA) can bond to the amine terminus of nylon 6,6 via a Diels-Alder chemical reaction, forming a C–N bond. Second, the cyclic carbon on the maleimide group can form a covalent C-C interaction with the nylon 6,6 backbone via an Alder-ene reaction using a radical mechanism. In one embodiment, the polyamide layer 104 and the rubber backing layer 106 undergo shearing and vulcanization at a temperature of approximately 300℉–350℉.

[0082] The reinforcing layer 208 comprises a textile braid. The textile braid may be made of polyester, nylon, cotton, aramid, or rayon yarns. In some embodiments, the reinforcing layer 208 is a discontinuous layer. In some embodiments, the reinforcing 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 in the textile within the reinforcing layer 208 and vulcanize together.

[0083] Cover layer 210 has the largest outer diameter among these layers. In some embodiments, cover layer 210 comprises 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 content, thus possessing low-temperature capability. In some embodiments, cover layer 210 comprises peroxide-cured EPDM made with low ethylene content. In some embodiments, there is no adhesive between reinforcing layer 208 and cover layer 210. In some embodiments, the hose comprises five layers.

[0084] Figure 3 A schematic diagram of an extrusion system 300, according to an embodiment, for manufacturing tube layer 102 is shown. HNBR pellets 304, maleic acid compound 302, and phenylene dimaleimide 306 can be moved via conveyor 310 into hopper 312 and blended. The blend is moved from hopper 312 into an extruder and heated by heating system 318. Control system 316 is used for communication between conveyor 310 and extruder 314. The heated blend is moved through crosshead 320 and extruded onto a mandrel to form HNBR tube layer 102.

[0085] A method for manufacturing a barrier hose is provided, the method comprising: blending a first composition comprising HNBR, phenylene dimaleimide, and a maleic acid compound; extruding the first composition onto a mandrel to form an HNBR inner tube layer; extruding a polyamide composition onto the inner tube layer to form a barrier layer; blending a second composition comprising ethylene propylene diene monomer (EPDM), phenylene dimaleimide, and a maleic acid compound; extruding the second composition over the polyamide barrier layer to form an EPDM rubber backing layer; applying a textile braided reinforcement layer onto the EPDM rubber backing layer to form a green hose; vulcanizing the green hose; and removing the hose from the mandrel. The HNBR is at least partially saturated and has no more than 6% or 4% residual double bonds as determined by IR spectroscopy. In some embodiments, the HNBR is fully saturated and has no more than 1% residual double bonds as determined 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 contain PA6,6, PA6, PA12, PA11, or blends thereof. The EPDM composition may contain low-ethylene EPDM. The textile fabric may be formed from yarns selected from polyester, aramid, polypropylene, nylon, cotton, rayon yarns, or any combination thereof.

[0086] The blocking hoses disclosed herein exhibit an operating temperature range of -40℉ to +301℉ (-40℃ to +150℃). The hoses disclosed herein exhibit the following operating pressures: 400 psi or higher; 450 psi or higher; or 500 psi or higher. The hoses disclosed herein exhibit the following permeation ratings for E85: not exceeding 5.0 g / (m³). 2 • day); or not exceeding 4.5 g / (m 2 • Days). The hoses disclosed herein exhibit the following permeability ratings for fuel C: not exceeding 4.0 g / (m²). 2 • day); or not exceeding 3.6 g / (m 2 • Days). Fuel permeation testing can be performed according to SAE J1527 permeation testing with a maximum weight loss (in grams) of 24 hours during the test period. The hoses according to this disclosure meet or exceed the SAE J30R9 rating requirements. The hoses according to this disclosure meet or exceed the SAE J1527 rating requirements. In some embodiments, a low-permeation fuel hose is provided, which is CARB approved and partially conforms to the SAE J1527 and SAE J30 R9 specifications.

[0087] A method for manufacturing a plywood hose is provided, the method comprising: extruding two polyamides (e.g., PA6 and PA6,6) onto a mandrel to form plywood; extruding an HNBR backing layer onto the plywood; weaving a reinforcing layer onto the backing layer; and extruding a cover layer onto the weave to form a green hose; vulcanizing the green hose; and removing the vulcanized hose from the mandrel.

[0088] Test methods

[0089] This allows rubber to undergo Shore A hardness testing. According to ASTM D 2240-95, the hardness can be tested using a calibrated Instron automatic hardness tester.

[0090] Compression set (C Set) is one of the key characteristics of a rubber compound indicating its cryogenic sealing ability. Compression set can be tested according to ASTM D 395-89. Samples can be prepared as follows: First, vulcanize EPDM rubber at 320℉ for 60 minutes to form a 0.49” thick × 1.14” diameter snap-fit. Then compress the snap-fit ​​by 25% into the C Set fastener. After curing, expose the sample to -40°C for 24 hours, and then remove the sample and measure at specified time increments. The time versus percentage compression can be plotted on a graph. The total compression set can be evaluated on samples that are allowed to run for the full 24 hours and then spring back to room temperature outside the C Set fastener before the final measurement.

[0091] Adhesion tests can be performed according to ASTM D 413-81. For example, this test measures the adhesion strength between embodiments of the HNBR pipe layer and embodiments of the polyamide layer. Specimen type B uses a 90° peel. Samples are prepared using a 4” long, 1” wide, and 0.075” thick polyamide 6,6 injection-molded specimen. The PA6,6 specimen is placed on top of a 4” long, 1” wide, and 0.09” thick rubber specimen on a standard pressed-cured material. The specimen is vulcanized at 320℉ for 45 minutes. Twenty-four hours after vulcanization, the specimen is tested at a rate of 2” / min using a calibrated Instron 5965 (according to ASTM D413 type B (90° peel)) load cell with a 5 kN (1,125 lbf) load cell.

[0092] Tensile strength and percentage elongation can be tested according to ASTM D 412. Standard ASTM samples can be tested on a calibrated Instron 5965 testing system using a 5 kN load cell at a rate of 20” / min. The modulus of elasticity 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 C-type tear strength test can be performed according to ASTM D 624. This test measures the tear initiation resistance.

[0094] Scorch time (T5) corresponds to the time interval of viscosity increase relative to 5 Mooney units of MV measured at rotor start-up. The T5 value indicates the pre-vulcanization tendency of the compound. Generally, a higher T5 value indicates a lower pre-vulcanization tendency, and therefore the compound can be processed more reliably on the extruder. T5 can be measured according to ASTM D 1646 or ASTM D 2084.

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

[0096] The shelf life test for green rubber assesses how measured values ​​change over time. Samples were cured from standard uncured raw materials at 3-month intervals (at 320℉ for 45°C). Those samples underwent testing according to ASTM 412, ASTM D 2084-95, and ASTM D 413-81.

[0097] Refrigerant permeation of the test hose and the control product hose can be tested according to SAE J2064. The samples should be stabilized at 23°C ± 2°C for 24 hours prior to testing, and checked to ensure the specified charge and identify charge loss.

[0098] Example

[0099] Example 1. HNBR composition

[0100] Develop direct-bonding, low-extraction rubber compositions for direct bonding to barrier or plywood polyamide layers without a separate adhesive layer. Select HNBR as the base rubber for compatibility with fuels C, E85, biodiesel, methanol, hot water, glycols, and refrigerants such as R134a. Develop HNBR compositions for use in preparing inner tubing layers (e.g., in barrier hoses) or backing layers (e.g., in plywood hoses).

[0101] The HNBR composition of Example 1 was prepared according to the above scheme. The HNBR composition comprises HNBR (Arlanxo Therban A3407) saturated with 99%, phenylene dimaleimide, and maleicized polybutadiene.

[0102] Table 1. HNBR Composition A for Rubber Tubes

[0103] Material Element PHR Wt% content Calcium carbonate Hubercarb Q325 15 5.94 talc MISTRON VAPOR R 10 3.96 Amorphous silicon dioxide HI-SIL 243 LD 20 7.92 Zinc oxide KADOX 930 (ZNO) 5 1.98 carbon black N650 BLACK 60 23.76 antioxidants AGERITE MA 1 0.40 Phenylidene dimaleimide T(MPBM)D-70 (HVA-2) 3 1.19 Maleated polybutadiene RICOBOND 1756 HS 10 3.96 Dicumyl peroxide LUPEROX DCP-40P-SP2 6.5 2.57 HNBR THERBAN A3407 100 39.60 High molecular weight plasticizers Trioctyl trimellitate (TOTM) 22.00 8.71 total: 252.50 100

[0104] HNBR composition A exhibits the desired characteristics upon curing, as shown in Table 2.

[0105] Using a moving die rheometer at 157°C, 0.5 radians, 100 cpm, and 30 minutes, the rubber tubing 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 psi; a 100% modulus of 1591.46 psi; a hardness of 82.4 pts A; a die tear strength of 199.99 lbf / in; and a tensile strength of 0.02 g / m². 2 The extraction test results.

[0106] Table 2. HNBR Test Results

[0107] test unit result Mooney MS(1+4) 31.62 T5 Min 12.47 Tensile strength psi 2281.68 elongation % 180.74 10% modulus psi 374.7 100% Modulus psi 1591.46 hardness pts A 82.4 Mold C tear strength lbf / in 199.99 Extraction test <![CDATA[g / m 2 ]]> 0.02

[0108] The tubing prepared from HNBR composition A exhibited the desired direct bonding with 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 tubing bonded to the polyamide barrier layer showed a value of 40 lbf / in. 2 Up to 70 lbf / in 2 The adhesion between them; however, this value relates more to the rubber's tear strength, since the two layers never actually separate.

[0109] Example 2. EPDM rubber composition

[0110] A rubber composition is desired for direct bonding to a 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). The EPDM composition is used for direct bonding to a polyamide layer.

[0111] Table 3. Rubber-backed EPDM composition B

[0112] Material Element PPH Wt% content gram EPDM rubber Vistalon 2504 100.00 34.42 499.14 Calcium carbonate Hubercarb Q325 15.00 5.16 74.87 talc MISTRON VAPOR R 10.00 3.44 49.91 Amorphous silicon dioxide HI-SIL 243 LD 20.00 6.88 99.83 Paraffin Processing Oil Silica Blend Plasticizer LUBSPAR 2280 (SUNPAR 2280) 30.00 10.33 149.74 Zinc oxide KADOX 930 5.00 1.72 24.96 antioxidants AGERITE MA 1.00 0.34 4.99 Phenylidene dimaleimide T(MPBM)D-70 (HVA-2) 3.00 1.03 14.97 Maleated polybutadiene RICOBOND 1756 HS 10.00 3.44 49.91 carbon black N650 BLACK 90.00 30.98 449.23 Dicumyl peroxide LUPEROX DCP-40P-SP2 6.50 2.24 32.44 total: 290.5 100 1450

[0113] EPDM composition B exhibited the desired characteristics upon curing. Using a moving die rheometer at 157°C, 0.5 radians, 100 cpm, and 30 minutes, the rubber backing layer in Table 3 showed a T5 of 5 min; a Mooney viscosity of 41 MU; adhesion to polyamide greater than 10 lbf / in in strip adhesion tests according to ASTM D413; a tensile strength of 1,472 psi; and an elongation of 148%. Furthermore, the backing layer prepared from composition B exhibited the desired direct bonding with polyamide 6,6 plywood, as well as multi-refrigerant / oil compatibility.

[0114] Example 3. Hose Construction and Testing

[0115] According to this disclosure, the hose includes an HNBR inner tube layer 102; a polyamide barrier layer 104; an EPDM backing layer 106; and a textile braided reinforcing cover layer 108. During hose vulcanization, the HNBR inner 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.

[0116] The hose disclosed herein can be prepared by: blending a first composition according to Table 1 comprising HNBR, phenylene dimaleimide, and maleic acid compound; extruding the first composition onto a mandrel to form an HNBR inner tube layer; extruding a polyamide composition onto the inner tube layer to form a barrier layer; blending a second composition according to Table 3 comprising ethylene propylene diene monomer (EPDM), phenylene dimaleimide, and maleic acid compound; extruding the second composition onto the polyamide barrier layer to form an EPDM rubber backing layer; applying a textile braided reinforcement layer onto the EPDM rubber backing layer to form a green hose; vulcanizing the green hose; and removing the hose from the mandrel.

[0117] According to ASTM D 3182-07, the Banbury™ mixer (Farrel Corporation) can be used to mix the different rubber formulations shown in Table 1. First, the polymer is added to the mixer in a 30-second pulverizing cycle at 150°C. Second, fillers and plasticizers are added in a 120-second mixing cycle at 200°C. Then, processing aids, such as vulcanizing agents, are added in 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 at 180°C for 120 seconds, followed by a final mixing at 180°C for 120 seconds.

[0118] According to ASTM B 947-06, after the rubber drips from the mixer, it is manually applied to a two-roll mill and sheeted until a thickness of 0.75”–1.25” is achieved. The two-roll milling stage is used to sheet and cool the mixed formulation.

[0119] The curing kinetics of rubber compounds can be evaluated according to ASTM D 2084-95 (Cure Study). Rheological measurements can be performed using a Monsanto RPA2000 at 160°C for 45 minutes.

[0120] The flaked material is subjected to curing pressing for vulcanization. Based on the T90 value from curing studies, the flaked material from a twin-roll mill can be placed in a curing press and vulcanized at 320℉ for 45 minutes.

[0121] Example 4. Characteristics of the Invention and Comparative Hose

[0122] The barrier hose of this invention comprises an HNBR tube; a PA6,6 barrier layer; an EPDM backing layer; and a Tensa filament polyester braided (reinforced) overlay 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℉ to 301℉, an operating pressure of 500 psi, and a permeation rating of E85: 4.5 g / (m³). 2 • Day); Fuel C: 3.6g / (m 2 • (day); minimum bending radius of 2.50 in, bending force of 3.7 lbs, weight per foot of 0.09 lbs / ft; and approved for use in fuels (including E85, methanol, biodiesel) and hot water.

[0123] Table 4 shows the features of the hose of the present invention and the features of the comparative hoses for the following: 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).

[0124] Table 4. Features of the blocking hose of the present invention and the comparative hose

[0125] hose General Construction Nominal ID / Maximum OD Operating temperature range Work pressure <![CDATA[Permeation rate (g / (m 2 ·day))]]> Bending radius Bending force Wt. / Ft. Approved fuel SAE ratings The hose of the present invention HNBR tubing; PA6,6 barrier; EPDM backing; Tensa knitting 0.43in / 0.66in -40℉ to 301℉ 500psi <![CDATA[E85:4.5 g / (m 2 • Day); Fuel C: 3.6 g / (m 2 ·day)]]> 2.50 in 3.7 lbs 0.09 lbs / ft E85, methanol and biodiesel, hot water Refer to J1527J30R9 Comparison with hose A CPE pipe; Nylon braided fabric 0.44in / 0.64in -40℉ to 301℉ 350psi <![CDATA[E85:14.4 g / (m 2 • Day); Fuel C: 12.7 g / (m 2 ·day)]]> 3.00 in 5.6 lbs 0.13 lbs / ft Fuel, oil, coolant N / A Comparison with hose B CPE pipe; Nylon braided fabric 0.44in / 0.68in -40℉ to 301℉ 350psi <![CDATA[E85:18.4 g / (m 2 • Day); Fuel C: 16.8 g / (m 2 ·day)]]> 3.00 in 4.4 lbs 0.13 lbs / ft Fuel, oil, antifreeze N / A Comparison of hose C Nitrile tubing; aramid braided fabric; rubber coverings 0.50in / 0.74in -29℉ to 275℉ 175psi <![CDATA[E85:13.8 g / (m 2 • Day); Fuel C: 11.6 g / (m 2 ·day)]]> 3.00 in 5.5 lbs 0.26 lbs / ft E85, E98, methanol and biodiesel 30R9 Comparison of hose D HNBR pipes; thermoplastic barriers; aramid braided fabrics; CPE coverings 0.50in / 0.75in -40℉ to 257℉ 225psi <![CDATA[E85:5.7 g / (m 2 • Day); Fuel C: 4.1 g / (m 2 ·day)]]> 2.95 in 5.8 lbs 0.19 lbs / ft E85, methanol and biodiesel, hot water 30R14T2

[0126] The hose of the present invention exhibits the same wide operating temperature range (-40℉ to 301℉) as comparative hoses A and B. The hose of the present invention exhibits a wider operating temperature range than comparative hoses C (-29℉ to 275℉) and D (-40℉ to 257℉). When compared to comparative hoses A (350 psi), B (350 psi), C (175 psi), and D (225 psi), the hose of the present invention exhibits a significantly higher operating pressure (500 psi). The hose of the present invention exhibits improved permeability ratings for E85 and fuel C (E85: 4.5 g / (m³)). 2 • Day); Fuel C: 3.6g / (m 2 ·day), compared to the control tube D (E85: 5.7 g / (m) 2 • Day); Fuel C: 4.1 g / (m 2 • (days). The hose of the present invention exhibits a significantly improved permeability rating for E85 and fuel C compared to: Comparison hose A (E85: 14.4 g / (m)). 2 • Day); Fuel C: 12.7 g / (m 2 ·day), and comparison tube B (E85: 18.4 g / (m) 2 • Day); Fuel C: 16.8 g / (m 2 ·day) and comparison tubing C (E85: 13.8 g / (m 2 • Day); Fuel C: 11.6 g / (m 2 ·sky)).

[0127] The hose of the present invention exhibits greater flexibility than comparative hoses A, B, C, and D. Compared with comparative hoses A, B, C, and D, the hose of the present invention exhibits a smaller bending radius (2.50 in) and a smaller bending force (3.7 lbs).

[0128] Compared with comparative hose A (0.13 lbs / ft), comparative hose B (0.13 lbs / ft), comparative hose C (0.26 lbs / ft), or comparative hose D (0.19 lbs / ft), the hose of the present invention is lighter (0.09 lbs / ft).

[0129] The hose of this invention conforms to SAE J30R9 requirements for fuel injection hoses. The hose of this invention conforms to SAE J1527 requirements for marine fuel hoses.

[0130] Cross-reference to related applications

[0131] This application was filed on June 7, 2023 as a PCT international application and claims priority and benefit to U.S. Provisional Application No. 63 / 350,100, filed on June 8, 2022, the entire contents of which are incorporated herein by reference.

Claims

1. A flexible hose comprising a plurality of layers, the layers including a hydrogenated nitrile butadiene rubber layer directly bonded to a polyamide barrier layer, the hydrogenated nitrile butadiene rubber layer being prepared from a first composition comprising hydrogenated nitrile butadiene rubber, phenylene dimaleimide, and a maleic acid compound. in, The hydrogenated nitrile rubber layer is covalently bonded to the polyamide barrier layer, without an intermediate adhesive layer; The phenylene dimaleimide is N,N'-1,3-phenylene dimaleimide, and the maleic acidified compound is a maleic acidified polybutadiene compound.

2. The hose as claimed in claim 1, wherein, The hydrogenated nitrile rubber is at least partially saturated and has no more than 6% residual double bonds as determined by infrared spectroscopy.

3. The hose as claimed in claim 1, wherein, The hydrogenated nitrile rubber is at least partially saturated and has no more than 4% residual double bonds as determined by infrared spectroscopy.

4. The hose as claimed in claim 1, wherein, The hydrogenated nitrile rubber is at least partially saturated and has no more than 2% residual double bonds as determined by infrared spectroscopy.

5. The hose as claimed in claim 1, wherein, The hydrogenated nitrile rubber is at least partially saturated and has no more than 1% residual double bonds as determined by infrared spectroscopy.

6. The hose as claimed in claim 2, wherein, The first composition comprises hydrogenated nitrile butadiene rubber in the range of 20-60 wt% relative to the total weight of the first composition.

7. The hose as claimed in claim 2, wherein, The first composition comprises hydrogenated nitrile butadiene rubber in the range of 30-55 wt% relative to the total weight of the first composition.

8. The hose as claimed in claim 2, wherein, The first composition comprises hydrogenated nitrile butadiene rubber in the range of 35-45 wt% relative to the total weight of the first composition.

9. The hose as claimed in claim 1, wherein, The first composition contains phenylene dimaleimide in the range of 0.1-5.0 wt% relative to the total weight of the first composition.

10. The hose as claimed in claim 1, wherein, The first composition contains phenylene dimaleimide in the range of 0.5-4.0 wt% relative to the total weight of the first composition.

11. The hose as claimed in claim 1, wherein, The first composition contains phenylene dimaleimide in the range of 0.8-3.0 wt% relative to the total weight of the first composition.

12. The hose as claimed in claim 1, wherein, The first composition contains phenylene dimaleimide in the range of 1-2 wt% relative to the total weight of the first composition.

13. The hose as claimed in claim 1, wherein, The first composition contains the maleic acid compound in the range of 1-7 wt% relative to the total weight of the first composition.

14. The hose as claimed in claim 1, wherein, The first composition contains the maleic acid compound in the range of 2-6 wt% relative to the total weight of the first composition.

15. The hose as claimed in claim 1, wherein, The first composition contains the maleic acid compound in the range of 3-5 wt% relative to the total weight of the first composition.

16. The hose as claimed in claim 1, wherein, The first composition contains the maleic acid compound in the range of 3.5-4.5 wt% relative to the total weight of the first composition.

17. The hose as claimed in claim 1, wherein, The first composition further comprises a plasticizer.

18. The hose of claim 17, wherein, The plasticizer is a high molecular weight plasticizer with a molar mass > 500 g / mol.

19. The hose of claim 17, wherein, The plasticizer is trimethyltrimethacrylate (TTRIC). 6-12 Alkyl esters.

20. The hose of claim 17, wherein, The first composition contains the plasticizer in an amount not exceeding 25 wt% of the total weight of the first composition.

21. The hose of claim 17, wherein, The first composition contains the plasticizer in the range of 0.1-20 wt% relative to the total weight of the first composition.

22. The hose of claim 17, wherein, The first composition contains the plasticizer in the range of 3-15 wt% relative to the total weight of the first composition.

23. The hose of claim 17, wherein, The first composition contains the plasticizer in the range of 5-15 wt% relative to the total weight of the first composition.

24. The hose of claim 17, wherein, The first composition contains the plasticizer in the range of 7-10 wt% relative to the total weight of the first composition.

25. The hose as claimed in claim 1, wherein, The first composition contains one or more fillers.

26. The hose of claim 25, wherein, The filler or one filler is selected from the group consisting of: carbon black, silica, silicates, talc, calcium carbonate, zinc oxide, titanium dioxide, and stearic acid.

27. The hose of claim 26, wherein, This silicate includes aluminum silicate.

28. The hose as claimed in claim 25, wherein, The first composition includes one or more fillers in the range of 30-60 wt% relative to the total weight of the first composition.

29. The hose as claimed in claim 25, wherein, The first composition includes one or more fillers in the range of 35-55 wt% relative to the total weight of the first composition.

30. The hose as claimed in claim 25, wherein, The first composition includes one or more fillers in the range of 35-45 wt% relative to the total weight of the first composition.

31. The hose as claimed in claim 1, wherein, The first composition contains peroxide.

32. The hose as claimed in claim 31, wherein, The peroxide is selected from the group consisting of: dicumyl peroxide, di-tert-butyl peroxide, and tert-butylcumyl peroxide.

33. The hose as claimed in claim 1, wherein, The first composition contains an antioxidant.

34. The hose as claimed in any one of claims 1 to 33, wherein, The hydrogenated nitrile rubber layer is the inner hydrogenated nitrile tubing layer.

35. The hose as claimed in any one of claims 1 to 33, wherein, The hydrogenated nitrile rubber layer is a hydrogenated nitrile backing layer.

36. The hose as claimed in any one of claims 1 to 33, comprising the following layers in the radial direction: The internal hydrogenated nitrile butadiene tube layer prepared from the first composition; Polyamide barrier layer; Rubber backing layer; and Woven reinforced cover layer.

37. The hose as claimed in any one of claims 1 to 33, comprising the following layers in the radial direction: Internal polyamide plywood; Hydrogenated nitrile butadiene rubber backing layer prepared from the first composition; Woven reinforcing layer; and External rubber covering layer.

38. The hose as claimed in any one of claims 1 to 33, wherein, The polyamide barrier layer comprises polyamides selected from the group consisting of PA6, PA6,6, PA12, PA11, or blends thereof.

39. The hose as claimed in claim 36, wherein, The rubber backing layer is an EPDM rubber backing layer prepared from a second composition comprising low-ethylene EPDM rubber, phenyl dimaleimide and maleic acid compounds.

40. The hose as claimed in claim 39, wherein, The second composition comprises a paraffinic plasticizer, a peroxide, and one or more fillers.

41. The hose as claimed in claim 39 or 40, wherein, The EPDM rubber backing layer is covalently bonded to the polyamide barrier layer, without an intermediate adhesive layer.

42. The hose as claimed in claim 36, wherein, The woven reinforcing cover layer comprises polyester, aramid, polypropylene, glass, nylon, cotton, rayon yarn, or blends thereof.

43. The hose as claimed in any one of claims 1 to 33, wherein, Vulcanized hoses exhibit one or more of the following: Operating temperature range: -40℉ to +301℉; Maximum operating pressure of at least 500 psi; At least a burst rating of 4:1 under SAE J1527 burst test conditions; In the case of CE fuel at 23°C as specified in SAE J1527-B1, the content shall not exceed 15 g / (m²). 2 • Permeability rating (24h); In the case of E85 fuel at 40°C as specified in SAE 30R9, the content shall not exceed 15 g / (m³). 2 • Permeability rating (24h); Under conditions specified in SAE 30R9 at 40°C and with fuel C, the concentration shall not exceed 15 g / (m³). 2 • Permeability rating (24h); It exhibits no more than 5 g / (m) in the case of E85 fuel. 2 The permeation rate (24h); In the case of fuel C, it exhibits a value of no more than 4 g / (m 2 The permeation rate (24h); Complies with SAE J30R9 requirements for fuel injection hoses; and It meets the requirements of SAE J1527 for marine fuel hoses.

44. A method of manufacturing a hose as claimed in any one of claims 1 to 36 or 38 to 43, the method comprising: The first composition was prepared by blending hydrogenated nitrile rubber, phenylene dimaleimide and maleic acid compound. The first composition is extruded onto a mandrel to form a hydrogenated nitrile butadiene inner tube layer; A polyamide composition is extruded onto the hydrogenated nitrile butadiene inner tube layer to form a barrier layer; The second composition comprising ethylene propylene diene monomer rubber, phenylene dimaleimide and maleic acid compound is blended. The second composition is extruded over the polyamide barrier layer to form an ethylene propylene diene monomer rubber backing layer; A textile braided reinforcement layer is applied to the ethylene propylene diene monomer rubber backing layer to form a green hose; Vulcanizing the green hose; and Remove the tubing from the mandrel.

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