WO2014002009A2 - Tuyau multicouche - Google Patents

Tuyau multicouche Download PDF

Info

Publication number
WO2014002009A2
WO2014002009A2 PCT/IB2013/055210 IB2013055210W WO2014002009A2 WO 2014002009 A2 WO2014002009 A2 WO 2014002009A2 IB 2013055210 W IB2013055210 W IB 2013055210W WO 2014002009 A2 WO2014002009 A2 WO 2014002009A2
Authority
WO
WIPO (PCT)
Prior art keywords
units
acrylic
layer
hose
elastomer
Prior art date
Application number
PCT/IB2013/055210
Other languages
English (en)
Other versions
WO2014002009A3 (fr
Inventor
Gül UNAL
Original Assignee
Teklas Kaucuk Sanayi Ve Ticaret Anonim Sirketi
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 Teklas Kaucuk Sanayi Ve Ticaret Anonim Sirketi filed Critical Teklas Kaucuk Sanayi Ve Ticaret Anonim Sirketi
Publication of WO2014002009A2 publication Critical patent/WO2014002009A2/fr
Publication of WO2014002009A3 publication Critical patent/WO2014002009A3/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 non-planar shape
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
    • F16L11/081—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more layers of a helically wound cord or wire
    • 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
    • F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
    • F16L11/085—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more braided layers
    • 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
    • F16L11/12—Hoses, i.e. flexible pipes made of rubber or flexible plastics with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting
    • F16L11/125—Hoses, i.e. flexible pipes made of rubber or flexible plastics with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting non-inflammable or heat-resistant hoses

Definitions

  • This invention is about a multi-layer hose with an internal layer resistant to high temperatures and oil and an outer layer resistant to low temperatures.
  • the invention relates more specifically to a multi-layer hose that will meet the heat resistance requirements in fluid lines, especially in charge-air lines of motor vehicles.
  • Prior ArtRubber hoses used in the charge-air lines of motor vehicles are expected to be resistant to the high temperature air conveyed, which is also generally contaminated by aggressive chemicals like engine oil.
  • Rubber blends used in the layers of these hoses are mainly based on ethylene acrylic acid elastomer (AEM) (trade name Vamac®), which is known to be resistant to high temperatures and oil.
  • AEM elastomer is a copolymer of ethylene, methyl acrylate with a cure site monomer containing carboxylic acid groups.
  • grades of AEM elastomer can be derived by controlling the monomer selection- ratio and distribution of molecular weight during the production, available grades are divided into two groups, elastomers in dipolymer form which are cured using a peroxide-based vulcanization system, and elastomers in terpolymer form which are cured using a diamine-based vulcanization system.
  • Inner layer of a charge air hose should meet high heat-resistance and oil- resistance requirements. However, for the outer layer oil resistance is not necessary and heat resistance requirement is considerably low. Therefore, instead of using an AEM based blend on the outer layer, utilizing a peroxide- cured rubber blend based on EP(D)M elastomer ensures a more cost-effective hose structure. The major concern hindering this point is the adherence of polar AEM inner layer to apolar EPDM outer layer.
  • EP1546595 B1 discloses a multilayer hose with an AEM based inner layer, an EPDM based outer layer and a bonding layer interposed between the inner and outer layers, which is based on a peroxide cured blend of AEM dipolymer and EP(D)M elastomer.
  • the rubber blend used in the intermediate layer comprises peroxide- curable AEM dipolymer, and as specified before, this cannot ensure desired dynamic specifications and permanent deformation values.
  • patent application no. WO2011012374 discloses a multilayer hose with an outer layer comprising EP(D)M elastomer and an inner layer comprising terpolymer AEM elastomer wherein the intermediate bonding layer is based on EP(D)M elastomer which is only curable by peroxide vulcanization system.
  • the intermediate bonding layer is based on EP(D)M elastomer which is only curable by peroxide vulcanization system.
  • the operating temperature that the intermediate layer exposed is 160 ° C or higher depending on the wall thickness of the inner layer.
  • EP(D)M elastomer is not able to endure an operating temperature above 160 ° C.
  • the second crucial issue is the fact that the desired interlayer adhesion cannot be attained with such a hose construction as the polarities of EPDM and AEM do not match.
  • the present invention discloses a multi-layer hose with improved dynamic properties, interlayer adhesion and high heat and oil resistance, wherein the hose has an inner layer of AEM elastomer, an outer layer of EP(D)M elastomer and a bonding intermediate layer made of a blend of AEM terpolymer and EPDM and/or EPM elastomers.
  • an inner layer (10) comprising amine-curable AEM terpolymer
  • an outer layer (16) comprising peroxide-curable EPDM and/or EPM
  • the intermediate layer (12) comprising the blend of AEM terpolymer and EPDM and/or EPM adheres to both the inner and outer layers (10, 16) during vulcanization and bonds them together.
  • the blend used in the intermediate layer (12) comprises EPDM and/or EPM elastomer as well as AEM elastomer in terpolymer form; and it is vulcanized by a (amine + peroxide) vulcanization system. It is not possible to cure the intermediate layer blend only with peroxide system.
  • Intermediate layer (12) of the invention comprises the following for each 100 weight units of EPDM and / or EPM;
  • the blend of the intermediate layer (12) comprises the following for each 100 units of EPDM and/or EPM;
  • Ethylene acrylic elastomer used in the blend is in terpolymer form and it can be cross-linked with amine vulcanization agent. Dipolymer-based ethylene acrylic elastomers can be cross-linked with peroxide vulcanization agents, but not amine vulcanization agents. Crosslinking bond energy generated by AEM elastomers in terpolymer form is higher than the AEM elastomers in dipolymer form. Therefore, higher heat resistance is attained with blends comprising AEM elastomers in terpolymer form. Increase in the crosslinking bond energy affects the heat resistance and aging qualities of elastomers drastically.
  • AEM elastomers in terpolymer form comprising higher crosslinking bond energy show better thermal and dynamic properties compared to the AEM elastomers in dipolymer form with lowcrosslinking bond energy. Furthermore, higher crosslinking bond energy show lower permanent deformation values at higher temperatures.
  • Filling material used in the blend is preferably carbon black; however, it can also be furnace black, lamp black or thermal black.
  • Plasticizer may be mineral-based and/or ether-/ester-based or preferably a blend of both.
  • Organic peroxide vulcanization agent to be used in the blend can be diacyl, peroxiester, peroxiketal and dialcyl-type peroxide. Preferred peroxide type is dicumyl peroxide.
  • Amine-based vulcanization agents used in the rubber blend can be hexamethylene diamine (HMD) and/or hexamethylene diamine carbamate (HMDC), while the vulcanization agents to be used as accelerator may be DOTG (di-o-tolyl guanidine) and / or DBU (1.8-Diazabicyclo-(5.4.0)-undec-7- ene) and/or DPG (diphenyl guanidine). DOTG is not used in the rubber blend due to carcinogenic and toxic effects.
  • EPDM or EPM used in both intermediate layer (12) and outer layer (16) can be maleicized.
  • These ethylene propylene-based elastomers may be used together or separately in various ratios.
  • amine-curable polyacrylic elastomer may be used in the inner layer (10) and/or in the intermediate layer (12) instead of ethylene acrylic acid (AEM) terpolymer elastomer.
  • ACM can be used by blending with AEM terpolymer.
  • Different elastomer groups are subjected to cross-linking process with different vulcanization agents in the intermediate layer (12) rubber blend of the present invention.
  • Cross-linking depends on the type, amount, activity and reaction time of the vulcanization agents.
  • vulcanization kinetics should be adjusted according to the elastomer groups.
  • the acrylic-based elastomer used in the intermediate layer (12) rubber blend of the disclosed invention is polar, and ethylene propylene-based elastomer is apolar.
  • a special blending technique has been employed.
  • Step 2 Firstly, filling material and oil, then 0-60 seconds later- ethylene propylene-based elastomer are fed into the internal mixer and mixed. Mixing stops as the maximum temperature of the blend reaches 120°C, which provides the 2 nd blend composition.
  • Step 3 1 st and 2nd blend compositions are mixed together, and intermediate layer (12) blend composition within the scope of the invention is obtained.
  • the hose may also contain one or more reinforcing layers (14) between inner and outer layers (10, 16).
  • Reinforcing layer (14) may be in the form of braid, spiral, wound or any other type known in the art, produced from yarns made of preferably aramide as well as polyester, rayon, cotton, nylon or similar materials.
  • Anti -static agents, filling materials, pigments, vulcanizer and other rubber additives known in the state of the art can be used in the blends of the inner, intermediate and outer layers (10, 12, 16).
  • the hose of the present invention may comprise additional layers as long as it includes the disclosed inner, intermediate and outer layers (10, 12, 16).
  • the hose of the present invention can be produced by conventional manufacturing methods like coextrusion or calendering.
  • bonding promoters can be added to the blends of the inner, intermediate and outer layers (10, 12, 16), or an adhesive solution can be applied between the layers.
  • the multi-layer hose of the invention is preferably produced through the following stages: a) extrusion of the inner layer (10)
  • Knitting a reinforcement layer (14) between stage b and c is also possible.
  • the production stages may also include a step where the adhesive solution is applied.

Landscapes

  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un tuyau multicouche comprenant une couche intérieure contenant un élastomère à base d'acrylique pouvant être durci à l'amine, une couche extérieure contenant un EP(D)M pouvant être durci au peroxyde, et une couche intermédiaire de liaison pouvant être durcie à l'amine et au peroxyde et contenant un mélange d'un élastomère à base d'acrylique et d'un EP(D)M, ledit tuyau répondant aux exigences croissantes en matière de résistance thermique, en particulier pour des circuits de suralimentation.
PCT/IB2013/055210 2012-06-26 2013-06-25 Tuyau multicouche WO2014002009A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR201207422 2012-06-26
TR2012/07422 2012-06-26

Publications (2)

Publication Number Publication Date
WO2014002009A2 true WO2014002009A2 (fr) 2014-01-03
WO2014002009A3 WO2014002009A3 (fr) 2014-04-10

Family

ID=49709760

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2013/055210 WO2014002009A2 (fr) 2012-06-26 2013-06-25 Tuyau multicouche

Country Status (1)

Country Link
WO (1) WO2014002009A2 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105179830A (zh) * 2015-09-15 2015-12-23 绍兴上虞宏晟技术转让服务有限公司 一种耐高温、耐腐蚀橡胶管及其制备方法
CN105179826A (zh) * 2015-09-15 2015-12-23 绍兴上虞宏晟技术转让服务有限公司 一种输送腐蚀液的软管及其制备方法
KR20200123192A (ko) * 2018-03-14 2020-10-28 미쓰이 가가쿠 가부시키가이샤 적층체 및 그의 용도
CN115230266A (zh) * 2021-04-23 2022-10-25 中国科学院大连化学物理研究所 多层结构宽温域耐油密封制品及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1546595B1 (fr) 2002-09-25 2008-07-09 Hutchinson Tuyau, en particulier pour un circuit d'admission d'air dans un moteur de vehicule automobile
WO2011012374A1 (fr) 2009-07-27 2011-02-03 Contitech Mgw Gmbh Tuyau flexible comportant une couche intérieure résistant aux fluides, son utilisation, et procédé pour sa fabrication

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1546595B1 (fr) 2002-09-25 2008-07-09 Hutchinson Tuyau, en particulier pour un circuit d'admission d'air dans un moteur de vehicule automobile
WO2011012374A1 (fr) 2009-07-27 2011-02-03 Contitech Mgw Gmbh Tuyau flexible comportant une couche intérieure résistant aux fluides, son utilisation, et procédé pour sa fabrication

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105179830A (zh) * 2015-09-15 2015-12-23 绍兴上虞宏晟技术转让服务有限公司 一种耐高温、耐腐蚀橡胶管及其制备方法
CN105179826A (zh) * 2015-09-15 2015-12-23 绍兴上虞宏晟技术转让服务有限公司 一种输送腐蚀液的软管及其制备方法
KR20200123192A (ko) * 2018-03-14 2020-10-28 미쓰이 가가쿠 가부시키가이샤 적층체 및 그의 용도
CN111867829A (zh) * 2018-03-14 2020-10-30 三井化学株式会社 层叠体及其用途
KR102480534B1 (ko) * 2018-03-14 2022-12-22 미쓰이 가가쿠 가부시키가이샤 적층체 및 그의 용도
CN115230266A (zh) * 2021-04-23 2022-10-25 中国科学院大连化学物理研究所 多层结构宽温域耐油密封制品及其制备方法和应用
CN115230266B (zh) * 2021-04-23 2023-11-17 中国科学院大连化学物理研究所 多层结构宽温域耐油密封制品及其制备方法和应用

Also Published As

Publication number Publication date
WO2014002009A3 (fr) 2014-04-10

Similar Documents

Publication Publication Date Title
CN1253310C (zh) 热塑性的多层复合材料
KR101474059B1 (ko) 저투과성 플렉시블 연료 호스
JP4175942B2 (ja) 積層構造体
KR101138533B1 (ko) 충격 보강된 폴리아미드 중공체
JP5657651B2 (ja) 媒体抵抗性内側層を有するホース、その用途および製造方法
EP2512793B1 (fr) Structures multicouches comprenant une couche barriere et leur utilisation pour le transport de fluides
JP4989814B2 (ja) ポリマー接着剤および多数のポリマー層を含む構造、その製法並びに使用
EP2762306B1 (fr) Corps stratifié, produit réticulé et élément moulé
JP2005199720A (ja) ポリアミドとｅｖｏｈのバリヤー層を有する加硫エラストマーのチューブ
WO2014002009A2 (fr) Tuyau multicouche
EP3539766B1 (fr) Stratifié de caoutchouc et tuyau flexible utilisant un tel stratifié de caoutchouc
CN1483956A (zh) 用于压缩空气的聚酰胺软管
JP5753897B2 (ja) 低透過性の可撓性燃料ホース
JP4626624B2 (ja) 耐熱エアホース
JP2001200961A (ja) 複合フレキシブルホース
JP2006247883A (ja) オイルホース
EP1559538B1 (fr) Tuyau pour le transport d'air résistant à la chaleur
EP2581223B1 (fr) Corps stratifié et vulcanisat correspondant
WO2003025059A1 (fr) Composition de caoutchouc acrylique et tuyau resistant a la chaleur
JP3166382B2 (ja) 自動車燃料配管用ホース
JP3951651B2 (ja) 自動車用ホース
JP2005199564A (ja) ゴム積層体およびオイルホース
JP3013747B2 (ja) エピクロロヒドリン系ゴムとフッ素含有共重合体樹脂との積層体
JP2003278957A (ja) ホース構造体およびその製法
JP2000273241A (ja) ゴム組成物、ゴム積層体、ホース及びその製造方法

Legal Events

Date Code Title Description
122 Ep: pct app. not ent. europ. phase

Ref document number: 13799362

Country of ref document: EP

Kind code of ref document: A2