CN1107865A - 卤代聚合物对尼龙的粘着 - Google Patents

卤代聚合物对尼龙的粘着 Download PDF

Info

Publication number
CN1107865A
CN1107865A CN94116203A CN94116203A CN1107865A CN 1107865 A CN1107865 A CN 1107865A CN 94116203 A CN94116203 A CN 94116203A CN 94116203 A CN94116203 A CN 94116203A CN 1107865 A CN1107865 A CN 1107865A
Authority
CN
China
Prior art keywords
parts
halopolymer
flexible pipe
carbon black
composition
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
CN94116203A
Other languages
English (en)
Other versions
CN1063464C (zh
Inventor
T·P·索普
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Goodyear Tire and Rubber Co
Original Assignee
Goodyear Tire and Rubber Co
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 Goodyear Tire and Rubber Co filed Critical Goodyear Tire and Rubber Co
Publication of CN1107865A publication Critical patent/CN1107865A/zh
Application granted granted Critical
Publication of CN1063464C publication Critical patent/CN1063464C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43—Compounds containing sulfur bound to nitrogen
    • C08K5/44—Sulfenamides
    • 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
    • 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
    • B32B25/18—Layered products comprising a layer of natural or synthetic rubber comprising butyl or halobutyl 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • 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
    • B32B2305/72—Cured, e.g. vulcanised, cross-linked
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Landscapes

  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polyamides (AREA)

Abstract

本发明涉及一种新的在硫化后对聚酰胺呈现出 优良粘接力的可硫化的化合而成的卤代聚合物。由 于炭黑相对于滑石达到了平衡，这种可硫化的卤代聚 合物获得了更好的粘附力，而当促进剂为环己基苯并 噻唑亚磺酰胺或相应的苯并噻唑亚磺酰胺时效果更 好。
本发明技术在制造专用软管和皮带方面特别有 用。

Description

本发明涉及处理卤代聚合物使其对聚酰胺具有改进的粘连的方法，同时涉及这样制成的层合制品。本发明尤其是涉及在聚酰胺层上粘连着卤代聚合物的成型层合制品的生产，所成型的层合制品在粘着性和抗化学品质性方面均得到了改善。具体地说，本发明涉及改良制品如皮带和软管的制备，本发明还涉及本身具有粘连键的所述，其在硫化的卤代聚合物和聚酰胺之间的粘合力至少为每平方英寸6磅，最好为7磅或更高。
对于冷藏和诸如汽车空调器的空气调节***所用的软管来说，都需要具有柔韧性、高强度，并能耐受较高的温度。对于碳氟化合物类致冷剂，会面临软管材料爆裂而释放出致冷剂方面的困难。因此，不同橡胶的层合制品虽已广泛地得到应用，但是这种层合制品仍然存在许多问题，由于迭层之间粘附力差会引起层离，由于一些金属盐如卤代聚合物中的卤素和硫化剂中的碱和碱土金属氧化物形成的金属盐的存在会引起橡胶的开裂。到目前为止，一直需要在卤代聚合物层和聚酰胺芯层间使用粘合胶以使其互相粘合良好。
层合制品如皮带或软管包括聚酰胺芯层，在核心层上最好直接粘合着卤代聚合物层，其粘合力要达到每平方英寸5磅，最好达到6磅或6磅以上。这种粘合是通过卤代聚合物和双二烯亲和交联剂，用来中和所形成卤酸的碱或碱土金属氧化物、过氧化物或硫化处理剂通过化合得到的，通常应用中还加入约25至70份最好是约35至55份的碳黑和约8至70份最好是约30至55份的滑石。我们惊异地发现，在化合卤代聚合物时通过调节炭黑和滑石的使用量，所产生的硫化卤代聚合物就具有足够强的粘接力，在形成卤代聚合物-聚酰胺层合制品时就无需使用粘合胶。
附图是本发明实施例的软管结构透视图，可见各分割部分的情况。根据该图我们可看到组合软管10的情况。这种软管10具有芯层20，它由诸如商品名为尼龙-6、尼龙-66、尼龙-8、尼龙-10、尼龙-11、尼龙-12、尼龙-666、尼龙-610和有关的或同类的聚酰胺类物质或聚酰胺-聚醚共聚物组成。一般这种聚酰胺均被制成中空的管子。
数字30指在聚酰胺核心层上覆盖的化合的卤代聚合物。最好这种化合的卤代聚合物挤出成型覆盖于芯层上，以便两层粘合在一起。这里要指出的是本发明并不象常规那样当用聚酰胺制成层合制品时需使用粘合剂或粘接胶。这样，这种卤代聚合物被化合和处理的方式使得这种这样处理化合的聚卤代化合物具有足够的粘合力，从而与聚酰胺一起形成令人满意的层压制品。
如需要，用常规软管加固方法将加固材料40如纤维丝用在或包在化合的卤代聚合物层外面。在加固层包裹住化合的卤代聚合物后，可以再在软管上挤出成型上一层化合的卤代聚合物的附加层。也可根据所起的作用和生产的经济性使用其它橡胶覆盖材料如EPDM。
Pilrington等在美国专利4633912中描述了制造这些软管的常规方法，但是需要使用粘合剂或粘接胶来得到满意的粘接效果以防止聚酰胺和囟代聚合物间的层离。在此一并收到参考文献中的美国专利公开463392提供了多种化合的组分及其用量的情况。
用表1所示的成分及用量化合氯丁基橡胶混合物。表1所示的促进剂是N-环己基-2-苯并噻唑亚磺酰胺。
化合的氯丁基橡胶片被施加到尼龙片上并在155℃熟化40分钟。然后对熟化后的层合片进行粘合，粘合力如表中所示。已观察并发现到当滑石占30至35份左右、炭黑占40至45份左右，粘合的效果最好。
Figure 941162036_IMG2
这种直接键合的化合物在与尼龙紧密接触时无需传统的原地粘合剂，在橡胶硫化时能形成粘合键。这种结果对于本领域技术人员来说并不熟悉，与先有技术并不一样。
用溴丁基橡胶也可获得类似的结果。本发明的这种可硫化的化合的卤代聚合物可很好地用于使用或需要聚酰胺层的皮带的制造上。例如，皮带可用表面覆有织物的橡胶和表面覆有可硫化的化合的卤代聚合物片迭成，这种可硫化的化合的卤代聚合物一面可粘接到聚酰胺层或尼龙层上，另一面可和皮带的其它部分如为处理不同具体材料而设的皮带表面层粘接。
为说明本发明的性况，本文已披露了一些有代表性的实施方案及其细节，因此，显然对于本领域技术人员来说，在没有背离本发明的精神或范围情况下，可从中饰以各种变化和修改。

Claims (9)

1、一种可硫化的卤代聚合物组合物，在硫化后能展示出对聚酰胺的改善的粘附力，其中包括100份和作为交联剂的双二烯新和物、碱/或碱土金属氧化物、过氧化物或硫化剂，25至70份左右的炭黑和8至70分左右的滑石。
2、权利要求1的组合物，其中硫化剂是N-环己基-2-苯并噻唑亚磺酰胺。
3、权利要求1的组合物，其中卤代聚合物是氯丁基橡胶。
4、权利要求1的组合物，其中有35至55份左右的炭黑和30至55份左右的滑石。
5、由核心为聚酰胺、外覆有硫化的卤代聚合物层构成的软管，这种硫化的卤代聚合物包括双二烯亲和物、选自碱和碱土金属氧化物和它们的混合物的卤酸中和剂、过氧化物或硫化剂和填充剂、填充剂的用量为对应于100份的卤代聚合物，用约25至70份的炭黑和约8至70份的滑石。
6、权利要求5的软管，其中在卤代聚合物层外覆盖加固物或加固层和另一橡胶覆盖层。
7、权利要求5的软管，其中硫化的卤代聚合物是溴丁基橡胶。
8、作为皮带组成部分的权利要求1的可硫化的组合物。
9、权利要求5的软管，其中炭黑为约35至55份，滑石为约30至55份。
CN94116203A 1993-09-09 1994-09-08 卤代聚合物对尼龙的粘着 Expired - Fee Related CN1063464C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/118,344 US5462091A (en) 1993-09-09 1993-09-09 Adhesion of halopolymers to nylon
US118,344 1993-09-09

Publications (2)

Publication Number Publication Date
CN1107865A true CN1107865A (zh) 1995-09-06
CN1063464C CN1063464C (zh) 2001-03-21

Family

ID=22378002

Family Applications (1)

Application Number Title Priority Date Filing Date
CN94116203A Expired - Fee Related CN1063464C (zh) 1993-09-09 1994-09-08 卤代聚合物对尼龙的粘着

Country Status (9)

Country Link
US (1) US5462091A (zh)
EP (1) EP0643095B1 (zh)
JP (1) JP3547490B2 (zh)
KR (1) KR100307697B1 (zh)
CN (1) CN1063464C (zh)
BR (1) BR9403470A (zh)
CA (1) CA2112623C (zh)
DE (1) DE69416063T2 (zh)
ES (1) ES2128474T3 (zh)

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6155305A (en) * 1994-08-29 2000-12-05 Sumner; Glen R. Offshore pipeline with waterproof thermal insulation
EP0881419B1 (en) * 1996-02-20 2003-01-29 Kabushiki Kaisha Meiji Gomu Kasei Refrigerant conveying hose
DE19837497A1 (de) 1998-08-13 2000-02-24 Trinova Aeroquip Gmbh Flexibler strangförmiger Hohlkörper
DE19837494A1 (de) 1998-08-13 2000-02-24 Trinova Aeroquip Gmbh Flexibler strangförmiger Hohlkörper
DE59901631D1 (de) 1998-08-13 2002-07-11 Trinova Aeroquip Gmbh Flexibler strangförmiger hohlkörper
DE19837498A1 (de) 1998-08-13 2000-02-24 Trinova Aeroquip Gmbh Flexibler strangförmiger Hohlkörper
US5957164A (en) * 1998-09-10 1999-09-28 Aeroquip Corporation Refrigerant hose
US6170532B1 (en) 1999-01-26 2001-01-09 Aeroquip Corporation Flexible hose
JP2001049063A (ja) 1999-08-06 2001-02-20 Tokai Rubber Ind Ltd ゴム組成物、ゴム−樹脂積層体及び不透過性ホース
US6585047B2 (en) 2000-02-15 2003-07-01 Mcclung, Iii Guy L. System for heat exchange with earth loops
US6896054B2 (en) * 2000-02-15 2005-05-24 Mcclung, Iii Guy L. Microorganism enhancement with earth loop heat exchange systems
US6267172B1 (en) 2000-02-15 2001-07-31 Mcclung, Iii Guy L. Heat exchange systems
EP1148283A3 (en) * 2000-04-21 2003-04-02 Bridgestone Corporation Refrigerant transporting rubber hose
JP2002005346A (ja) * 2000-04-21 2002-01-09 Bridgestone Corp 冷媒輸送用ゴムホース
US7063181B1 (en) * 2000-04-27 2006-06-20 Dana Corporation Fluid-borne noise suppression in an automotive power steering system
JP4761416B2 (ja) * 2000-09-27 2011-08-31 株式会社ブリヂストン 冷媒輸送用ゴムホース
EP2202058B1 (en) * 2001-01-15 2014-09-10 Daicel-Evonik Ltd. Composite material and method for preparation thereof
JP2003056761A (ja) * 2001-08-09 2003-02-26 Tokai Rubber Ind Ltd 振動吸収性ゴムホース
GB2398357B (en) * 2003-02-12 2006-09-20 Luk Lamellen & Kupplungsbau Hydraulic system
BRPI0402583A (pt) * 2003-07-11 2005-05-31 Goodyear Tire & Rubber Mangueira para refrigerante
GB201122436D0 (en) * 2011-12-29 2012-02-08 Wellstream Int Ltd Flexible pipe body and method of manufacture
CN102585733B (zh) * 2012-02-14 2013-09-25 贵州轮胎股份有限公司 一种轮胎硫化胶囊的修补胶及其制备方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3062795A (en) * 1958-04-01 1962-11-06 Exxon Research Engineering Co Process for preparing halogenated copolymers
US3931090A (en) * 1974-04-26 1976-01-06 Xerox Corporation Rubber composition for flexible belts
DE2536674C3 (de) * 1975-08-18 1979-09-27 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt Vernetzbare Mischungen auf Basis von Kautschuk, Organosilanen und silikatischen Füllstoffen
US4087343A (en) * 1977-02-23 1978-05-02 The Goodyear Tire & Rubber Company Flexible cover of a platy-filled composition for an electrolytic cell
US4569382A (en) * 1981-05-11 1986-02-11 The Goodyear Tire & Rubber Company Composite of rubber and metal reinforcement therefor
US4633912A (en) * 1985-05-31 1987-01-06 The Goodyear Tire & Rubber Company Hose construction
JPH064267B2 (ja) * 1985-06-27 1994-01-19 横浜ゴム株式会社 ポリアミド樹脂製薄肉内管を備えたホ−スの製造方法
US4721756A (en) * 1986-09-25 1988-01-26 The West Company Molded rubber products
JPH0615914B2 (ja) * 1988-10-18 1994-03-02 東海ゴム工業株式会社 冷媒輸送用ホース
JPH0733878B2 (ja) * 1989-05-29 1995-04-12 東海ゴム工業株式会社 冷媒輸送用ホース
US5200469A (en) * 1990-04-18 1993-04-06 Exxon Chemical Patents Inc. Crosslinked elastomeric polymers and process for producing the same
US5246778A (en) * 1990-05-14 1993-09-21 Exxon Chemical Patents Inc. Hose composition

Also Published As

Publication number Publication date
EP0643095A1 (en) 1995-03-15
KR950008595A (ko) 1995-04-19
CN1063464C (zh) 2001-03-21
CA2112623A1 (en) 1995-03-10
JPH07173349A (ja) 1995-07-11
EP0643095B1 (en) 1999-01-20
CA2112623C (en) 2004-03-30
KR100307697B1 (ko) 2001-12-01
US5462091A (en) 1995-10-31
JP3547490B2 (ja) 2004-07-28
DE69416063T2 (de) 1999-07-15
ES2128474T3 (es) 1999-05-16
DE69416063D1 (de) 1999-03-04
BR9403470A (pt) 1995-05-16

Similar Documents

Publication Publication Date Title
CN1063464C (zh) 卤代聚合物对尼龙的粘着
US5637407A (en) Blends of thermoplastic and rubber which are adherent to thermoplastics
CN101846213B (zh) 硫化橡胶组合物及用其制造的制品
GB2246976A (en) Process of producing a rubber-extruded article
US5405690A (en) Rubber-rubber bonded composite structure
Vijayaram A technical review on rubber
US20070135010A1 (en) Polychloprene composite having adhesive with copolymer of polychloroprene and dichlorobutadiene
US6099972A (en) Fabric-free belt
JPH1182739A (ja) 空気バネ用ゴム組成物
JP2011235520A (ja) ゴム組成物−ポリアミド積層体及びこれを用いた車輌用フレキシブルホース
JPH05170935A (ja) 熱可塑性エラストマーとゴムとの接着複合体の製造方法
JPH01141292A (ja) ホース
JPH0720680B2 (ja) 伝動ベルト
JP2514971B2 (ja) ゴム組成物
CN220484359U (zh) 覆皮传输带
JP3116246B2 (ja) ゴム・ゴム接着複合体
JP2816905B2 (ja) ゴムとゴムとの接着複合体の製造方法
KR100371602B1 (ko) 클로로플렌 합포물
KR200222966Y1 (ko) 클로로플렌 합포물
JP3116247B2 (ja) ゴム・ゴム接着複合体
JP2000094583A (ja) ゴム製品およびゴム製品の製造方法
JPS61125818A (ja) ゴムホースの製造方法
JPH02294380A (ja) 接着用組成物
TW202043037A (zh) 橡膠貼條及其製備方法
JPS59230040A (ja) 耐油性ゴム組成物およびこれを用いた積層体

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee