WO2023174734A1 - Couche interne de tuyau de climatisation de véhicule - Google Patents

Couche interne de tuyau de climatisation de véhicule Download PDF

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Publication number
WO2023174734A1
WO2023174734A1 PCT/EP2023/055632 EP2023055632W WO2023174734A1 WO 2023174734 A1 WO2023174734 A1 WO 2023174734A1 EP 2023055632 W EP2023055632 W EP 2023055632W WO 2023174734 A1 WO2023174734 A1 WO 2023174734A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
innermost tube
refrigerant hose
hose according
rubber
Prior art date
Application number
PCT/EP2023/055632
Other languages
English (en)
Inventor
Lorraine Vander Wielen Sabo
Bradley James Haines
Original Assignee
Contitech Techno-Chemie Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Contitech Techno-Chemie Gmbh filed Critical Contitech Techno-Chemie Gmbh
Publication of WO2023174734A1 publication Critical patent/WO2023174734A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a general shape other than plane
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/042—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/10—Layered products comprising a layer of natural or synthetic rubber next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/045—Hoses, i.e. flexible pipes made of rubber or flexible plastics with four or more layers without reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/08—Reinforcements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2597/00—Tubular articles, e.g. hoses, pipes

Definitions

  • the field to which the disclosure generally relates is a hose suitable for use in refrigerant systems such as vehicle, industrial, and residential refrigerant systems, such as automotive air conditioning systems.
  • the hose has an inner layer with improved properties used in air conditioning systems.
  • Hoses are used for transporting refrigerants in vehicle air conditioning (AC) systems, as well as industrial and residential refrigerant systems. Such hoses serve the purpose of joining the principal operating components of the refrigerating device.
  • the hoses are typically designed to have good flexibility, high strength, the ability to bend to small radii without kinking, and to maintain impermeability to the fluids resident therein.
  • the quantity of elemental sulfur can be reduced or eliminated and sulfur containing accelerators can be used. While the number of sulfur atoms within crosslinks will be reduced as compared to rubber conventionally cured with elemental sulfur, any sulfur-to-sulfur bonds will have more susceptibility to bond breakage than carbon-to-carbon bonds when exposed to heat or stress. Any unreacted portions of sulfur accelerators or sulfur donors will also be available to corrode easily corroded AC compressor components such as nickel. Typically, the need to avoid sulfur or the demand for increased service temperatures will drive material selection towards a peroxide cured elastomer, which presents issues described above.
  • a refrigerant hose which includes an innermost tube defining a lumen therein, the innermost tube having an elastomeric material comprising a high temperature resistant polyepichlorohydrin (HT-ECO) rubber which is cured with a bis-phenol-S based curing system.
  • the refrigerant hose may further, and optionally, include a permeation inhibiting layer which surrounds the innermost tube, and, optionally, an elastomeric tie layer.
  • the refrigerant hose also includes a reinforcing layer disposed outwardly from the innermost tube and the optional permeation inhibiting layer, when used, as well as a cover layer disposed outwardly from the reinforcing layer.
  • the innermost tube in some cases, has a volume swell percentage of 10% or less when exposed to polyolester oil or polyalkylene glycol oil for 168 hourrs @ 150°C. Further, the innermost tube is devoid of peroxide, devoid of added reactive sulfur including elemental sulfur, and/or sulfur donors. In some aspects, the lumen contains molecules of 2,3,3,3-tetrafluoropropene refrigerant therein. In some cases, the bis-phenol-S based curing system includes sodium carbonate, bis-phenol-S and organo-onium.
  • the refrigerant hose further includes a tie layer disposed between a permeation inhibiting layer and the reinforcing layer when a permeation barrier layer is incorporated into the refrigerant hose.
  • the cover layer is based on one or more of butyl (HR), halobutyl (CIIR/BIIR), high temperature resistant polyepichlorohydrin (HT-ECO) rubber which is cured with a bis- phenol-S based curing system, brominated isobutylene paramethyl-styrene (BIMS) and ethylene-propylene-diene monomer rubber (EPDM).
  • the reinforcement layer may be a woven polyester fabric, such as a woven polyethylene terephthalate fabric, glass fibers, cotton fibers, polyester fibers, polyaramid fibers, and/or aramid fibers.
  • the reinforcing layer is a spiral reinforcing layer
  • the refrigerant hose further includes a second tie layer surrounding the spiral reinforcing layer, and a second spiral reinforcing layer disposed between the cover layer and the second tie layer.
  • FIG. 1 illustrates a barrier braided hose in a cut away perspective view, in accordance with the disclosure
  • FIG. 2 depicts an all rubber braided hose in a cut away perspective view, in accordance with the disclosure
  • FIG 3 illustrates a spiral barrier hose in a cut away perspective view, in accordance with the disclosure
  • FIG. 4 depicts a cross-section of a hose with refrigerant and oil contained therein.
  • any references to "one embodiment” or “an embodiment” means that a particular element, feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment.
  • the appearances of the phrase “in one embodiment” in various places in the specification are not necessarily referring to the same embodiment.
  • Hose embodiments according to the disclosure generally include a rubber hose having an innermost tube, at least one reinforcement layer, and an outer cover.
  • the hose embodiments also include barrier style hose which generally includes a barrier layer, at least one reinforcement layer, optional reinforcement layer or layers, optional tie layer or layers, an outer cover, and an innermost tube.
  • the innermost tube is formed from an elastomeric material including a high temperature resistant polyepichlorohydrin (HT- ECO) rubber which is cured with a bis-phenol-S based curing system.
  • HT- ECO high temperature resistant polyepichlorohydrin
  • Other suitable additives may also be included in a mixture forming the elastomeric material, such as, but not limited to, one or more carbon blacks, processing aids, antiozonants, retardants to prevent an unduly quick cure, curing aids, antioxidants, other reinforcing agents and fillers, such as silica, coupling agents, dispersants, adhesion promotors, and the like.
  • the innermost tube After curing, the innermost tube has a volume swell percentage of 10% or less, a volume swell percentage in the range of 10% to 1 %, or even a volume swell percentage in the range of 7% to 1 %, when exposed to polyolester oil or polyalkylene glycol oil for 168 hours @ 150°C.
  • a volume swell percentage of 10% or less, a volume swell percentage in the range of 10% to 1 %, or even a volume swell percentage in the range of 7% to 1 %, when exposed to polyolester oil or polyalkylene glycol oil for 168 hours @ 150°C.
  • Such properties provide lower volume swelling when in contact with polyolester oil as compared to typical air conditioning hose compounds.
  • HT-ECO high temperature resistant polyepichlorohydrin
  • HT-ECO high temperature resistant polyepichlorohydrin
  • HT-ECO high temperature resistant polyepichlorohydrin
  • HT-ECO high temperature resistant polyepichlorohydrin
  • Any suitable bis-phenol-S, bisphenol AF or bis-penol Scoring system may be used for cuing the high temperature resistant polyepichlorohydrin (HT-ECO) rubber.
  • Some nonlimiting examples include the DynamarTM bis-phenol-SS based curing system available from Dyneon LLC of Oakdale, Minn.
  • DynamarTM system includes a combination of DynamarTM RC5251 Q sodium carbonate cure activator, DynamarTM FC5157 bis-phenol-S-S, and DynamarTM FX5166 organo-onium.
  • any suitable material when used, any suitable material may be used to form the layer when constructing a barrier style hose.
  • a barrier layer is not used in the all rubber construction.
  • barrier materials includes polyamides such as PA11 , PA46, PA6, PA66, PA6,66, PA66,6, PA69, PA610, PA612, PA1010, PA1212, PA4T, PA6T, PA9T, and PA10T; thermoplastic polyester elastomers based upon polyether-ester block copolymers, such as those supplied under tradename Hytrel®; or thermoplastic elastomers comprised of polyamide and polyether backbone blocks, such as those supplied under tradename Pebax®.
  • tie layer(s) is typically comprised of any suitable thermoset materials including, but not limited to, polybutadiene (BR), copolymers of butadiene and acrylonitrile (NBR), butyl rubber (HR), chlorobutyl rubber (CIIR), bromobutyl rubber (BUR), copolymers of butadiene and styrene (SBR), polychloroprene (CR), ethylene propylene rubber (EPM), or ethylene propene diene (EPDM) or blends of such materials such as, but not limited to, a BIIR/EPDM blend.
  • the base stock material for the layer is EPDM.
  • the reinforcing layer may be based on a material formed by braiding, spiraling, knitting, or helical knitting of yarn.
  • the reinforcing layer may be based on a material which is woven or non-woven.
  • the material may be selected from conventional hose reinforcing yams, such as glass, cotton, polyester, or aramid fibers, or a blend of any of these fibers.
  • the reinforcing layer in the hose is a polyester or aramid fabric, or even a blend of polyethylene terephthalate yam and polyethylene naphthalate yam to form the fabric.
  • any suitable rubber may be used for the cover layer employed in embodiments of this disclosure.
  • the rubber is selected from, but not limited to, ethylene propylene diene rubber (EPDM), ethylene propylene rubber (EPR), butyl rubber (HR), chlorobutyl rubber (CIIR), bromobutyl rubber (BUR), chloroprene rubber (CR), nitrile rubber (NBR), chlorosulfonated polyethylene rubber (CSM), epichlorohydrine rubber (ECO), high temperature resistance polyepichlorohydrine rubber (HT-ECO), acrylic rubber (ACM), chloroprene rubber (CR), ethylene-acrylic elastomer (AEM), or chlorinated polyethylene (CPE), and blends or copolymers thereof, and the like.
  • the base stock for the cover layer is EPDM.
  • the various material components utilized in the hose embodiments of this disclosure can be cured with conventional curatives including, but not limited to, peroxide, sulfur, sulfur donor curatives, amine curatives, resin cure system, metal oxide curatives, and the like.
  • peroxides such as dicumyl peroxide, a-a-bis(t- butylperoxide)diisopropylbenzene, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 1 , 1 -bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(t- butylperoxy)hexane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, and n-butyl 4,4- bis(t-butylperoxy)valerate can be employed in curing the rubber components of the hose.
  • peroxides such as dicumyl peroxide, a-a-bis(t- butylperoxide)diisopropylbenzene, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 1 , 1 -
  • peroxides are preferred as the curative since they are less sensitive to premature crosslinking (scorch). Sulfur/sulfur donor curatives are also commonly used.
  • sulfur containing accelerators and sulfur donors available for rubber cure systems include tetramethyl thiuram disulfide, 4,4’- dithiodimorpholine, dipentamethylene thiuram tetrasulfide, thiocarbamyl sulfenamide, mercaptobenzothiazole, zinc dimethyl carbamate, dibenzothiazole disulfide, and N- cyclohexyl-2-benzothiazole sulfonamide.
  • the other rubber components employed in the hose of this invention can also contain various additives in conventional or suitable amounts.
  • additives may include, and are not limited to retardants to prevent an unduly quick cure, antioxidants, processing aids, reinforcing agents and fillers, such as carbon black, silica, coupling agents, dispersants, adhesion promotors and the like.
  • FIG. 1 illustrates a barrier braided hose 100, in a cut away perspective view.
  • Hose 100 includes an innermost tube 102, formed from an elastomeric material including a high temperature resistant polyepichlorohydrin (HT-ECO) rubber which is cured with a bis-phenol-SS based curing system, and which is surrounded by a permeation inhibiting layer 104.
  • HT-ECO high temperature resistant polyepichlorohydrin
  • Disposed adjacent permeation inhibiting layer 104 is a tie layer 106 which has a reinforcing layer 108 disposed outwardly therefrom.
  • Cover layer 110 is the outermost layer of hose 100.
  • hose 200 includes an innermost layer 202, formed from an elastomeric material including a high temperature resistant polyepichlorohydrin (HT-ECO) rubber which is cured with a bis-phenol-S based curing system, and which surrounded by a reinforcing layer 208, and cover layer 210 is the outermost layer of hose 200.
  • HT-ECO high temperature resistant polyepichlorohydrin
  • Hose 300 includes an innermost elastomer tube 302, formed from an elastomeric material including a high temperature resistant polyepichlorohydrin (HT-ECO) rubber which is cured with a bis-phenol-S based curing system, and which is surrounded by a permeation inhibiting layer 304.
  • Adjacent to permeation inhibiting layer 304 is a tie layer 306 which has a spiral reinforcing layer 308 disposed outwardly therefrom.
  • Surrounding the spiral reinforcing layer 308 is a second tie layer 312 which has second spiral reinforcing layer 314 disposed thereupon.
  • Cover layer 310 is the outermost layer of hose 300.
  • Hose 400 includes an innermost tube 402, formed from an elastomeric material including a high temperature resistant polyepichlorohydrin (HT-ECO) rubber which is cured with a bis- phenol-S based curing system, and which, in some aspects, is surrounded by an optional permeation inhibiting layer 404, and disposed adjacent permeation inhibiting layer 404 is an optional tie layer 406.
  • HT-ECO high temperature resistant polyepichlorohydrin
  • Cover layer 410 is the outermost layer of hose 400. Resident within a lumen 412 defined within innermost tube 402 are molecules 420 of 2, 3,3,3- tetrafluoropropene refrigerant and POE oil droplets 422.
  • innermost tube 402 is formed from an elastomeric material including a high temperature resistant polyepichlorohydrin (HT-ECO) rubber which is cured with a bis-phenol-S based curing system, the 2,3,3,3-tetrafluoropropene refrigerant is stabilized, swelling due to contact of the inner wall of innermost tube 402 with POE oil is minimized, or essentially eliminated, and formation of polymerized 2,3,3,3-tetrafluoropropene molecules 424 is avoided.
  • innermost tube 402 is devoid of peroxide, as well as devoid of any added sulfur or sulfur containing materials, and lumen 412 is devoid of polymerized 2,3,3,3-tetrafluoropropene molecules 424.
  • the cured rubber inner layer was determined to have the physical properties provided in Table 2.
  • first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms may be only used to distinguish one element, component, region, layer or section from another region, layer or section. Terms such as “first,” “second,” and other numerical terms when used herein do not imply a sequence or order unless clearly indicated by the context. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the example embodiments.
  • Spatially relative terms such as “inner”, “adjacent”, “outer,” “beneath,” “below,” “lower,” “above,” “upper,” and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. Spatially relative terms may be intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” the other elements or features. Thus, the example term “below” can encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.

Abstract

Un tuyau de fluide frigorigène comprend un tube le plus à l'intérieur définissant une lumière à l'intérieur de celui-ci, et le tube le plus à l'intérieur est formé dans un matériau élastomère comprenant un caoutchouc de polyépichlorohydrine résistant à de hautes températures (HT-ECO) qui est durci avec un système de durcissement à base de bisphénol S. Le tuyau de fluide frigorigène peut en outre comprendre une couche optionnelle d'inhibition de perméation qui entoure le tube le plus à l'intérieur lorsqu'elle est incorporée, une couche de renforcement disposée vers l'extérieur à partir du tube le plus à l'intérieur et de la couche optionnelle d'inhibition de perméation lorsque cette couche est utilisée, et une couche de recouvrement disposée vers l'extérieur à partir de la couche de renforcement. Le tube le plus à l'intérieur a un pourcentage de gonflement en volume de 10 % ou moins lorsqu'il est exposé à de l'huile polyolester ou de l'huile de polyalkylène glycol pendant 168 heures à 150 °C. En outre, le tube le plus à l'intérieur est dépourvu de peroxyde et peut également être dépourvu de soufre élémentaire ajouté, et/ou de donneurs de soufre.
PCT/EP2023/055632 2022-03-14 2023-03-06 Couche interne de tuyau de climatisation de véhicule WO2023174734A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202263319417P 2022-03-14 2022-03-14
US63/319,417 2022-03-14

Publications (1)

Publication Number Publication Date
WO2023174734A1 true WO2023174734A1 (fr) 2023-09-21

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090131006A (ko) * 2008-06-17 2009-12-28 주식회사 엘지화학 황동 코팅 강선과의 접착력이 강화된 고압호스용 고무 조성물 및 이로부터 제조된 고압호스
US20170067581A1 (en) * 2014-06-30 2017-03-09 Sumitomo Riko Company Limited Fuel hose
WO2020214881A1 (fr) * 2019-04-18 2020-10-22 Contitech Usa, Inc. Tout caoutchouc à faible teneur en soufre et tuyau d'extraction

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090131006A (ko) * 2008-06-17 2009-12-28 주식회사 엘지화학 황동 코팅 강선과의 접착력이 강화된 고압호스용 고무 조성물 및 이로부터 제조된 고압호스
US20170067581A1 (en) * 2014-06-30 2017-03-09 Sumitomo Riko Company Limited Fuel hose
WO2020214881A1 (fr) * 2019-04-18 2020-10-22 Contitech Usa, Inc. Tout caoutchouc à faible teneur en soufre et tuyau d'extraction

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