CN1411980A - 低沉淀物的聚酰胺基管 - Google Patents
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Abstract
低沉淀物的聚酰胺管用于输送流体如汽车燃料。
Description
技术领域
本发明涉及归类为化学领域如聚酰胺，尤其是聚酰胺11和12的制品的组成，涉及用于输送流体领域的制造制品，所述流体例如是溶剂、极性流体和用于诸如内燃机，尤其是机动车辆所用发动机的燃料软管或管用途的燃料，还涉及所述制造制品和所述制品组成的方法。
背景技术
用于内燃机的燃料系统和燃料蒸气污染控制的挠性软管是众所周知的。这种软管由聚酰胺和其它合成聚合物的单层(单壁软管)制成，在过去业已证实其在汽车和其它车辆以及固定用途的内燃机的应用中是令人满意的。这些长度可以大至几米的单壁软管一旦安装好，在其使用寿命的时间内就必须不发生由于随热或冷或在使用过程中施加的任何其它应力而收缩、伸长所致的材料带电或破裂。
近年来有所改变、更为严厉的环境条例要求这些燃料供应软管，尤其是用于汽车的软管是较不透燃料蒸气的，并且由于在燃料的配制过程中需要诸如氧化剂(oxygenates)之类的极性组分，所以要求与燃料接触的软管的材料能抗会沉淀到燃料中或者可能堵塞具有非常小的孔的燃料过滤器、燃料注射器等，并因此降低燃料中颗粒的容许量的材料从软管中提取出(extraction)。
曾有一种解决渗透问题的方法是共挤出具有至少一层不透烃蒸气或其它挥发性燃料组分的层(通常称为“阻挡层”)的多层(多壁(multiwall))管或软管。
为了避免与组分从聚酰胺中提取出而造成的沉淀物有关的问题，在这种软管的设计中，宜避免使用聚酰胺单层管或具有聚酰胺内层的多层管。
典型的这种多层结构是那些在美国专利5,419,374；5,996,642；5,510,160和5,554,426以及在这些专利中引用的参考文献中描述的结构。为什么不希望聚酰胺与燃料接触的详细原因具体在美国专利5,996,642中有说明。在这些专利的结构中，聚酰胺的机械性能与各种含氟聚合物的渗透性阻挡性能相结合，所述含氟聚合物本身对用于汽车制造来说是太昂贵或者缺乏使聚酰胺12或11成为制造燃料软管的较好聚合物的聚酰胺的一种或多种机械性能。由于聚酰胺和许多含氟聚合物没有机械连接或在它们之间没有粘结层的情况下不会很好地粘合在一起，所以上面引用的参考文献也提出了多种解决这个问题的方法，例如使用粘结层或使用丙烯酸类改性的含氟聚合物阻挡层。
本文所用的术语“低沉淀物的聚酰胺”是指对聚酰胺进行洗涤或萃取，以降低诸如低聚物(低分子量聚酰胺)、在与输送的流体接触后以其它方式被聚酰胺释放出来和/或沉淀到流体中的固体或半固体等组分的量。
发明内容
在组成方面，本发明提供用于输送流体的改进的管(或软管)，它由低沉淀物的聚酰胺(较好是聚酰胺12或11)组成，是单层管的形式(较好是用于输送燃料)，和作为多层管的两种管，多层管至少由与流体接触的聚酰胺内层和阻挡层(较好是含氟聚合物如聚偏氟乙烯，它是未改性或改性的，采用诸如聚戊二酰亚胺或丙烯酸酯共聚物等材料提高粘合性)组成。可以采用下述方式将阻挡层粘结到聚酰胺层上，通过粘结层(例如在美国专利5,242,976中所述)，通过粘合剂粘结(例如在美国专利5,419,374和5,510,160中所述)或通过使用本身能粘合到聚酰胺上的丙烯酸类改性的阻挡层(例如在美国专利5,554,426中所述)。一种用于输送燃料的机动车辆所用的较好结构至少包含与燃料接触的聚酰胺内层、粘结到内层外表面上的中间粘结层和粘结到中间粘结层外表面上的聚偏氟乙烯层，改进之处包括使用低沉淀物的聚酰胺作为内层。用于此用途的其它较好结构包括由低沉淀物的聚酰胺内层、改性聚偏氟乙烯中间层和聚酰胺外层组成的多层管，以及由第一层，即能导电以放出静电的低沉淀物的聚酰胺内层，第二层，即聚酰胺层，第三层，即改性的聚偏氟乙烯层，和第四层，即聚酰胺外层组成的多层管。
本发明改进组成方面的实际实施方案具有固有的应用特征，即它适用于输送用于内燃机，尤其是用于汽车用途的流体如烃基燃料和其蒸气以及那些包含氧化添加剂的烃燃料如尤其是醇或醚，同时不会将往往会阻塞所述燃料通过燃料过滤器、燃料泵、化油器量孔或燃料注射喷嘴等的通道的污染物加到所述燃料中。
特别要提到的是本发明组成方面的实施方案，即其中的最内层不具有静电放电能力的实施方案，以及其中的最内层具有静电放电能力的实施方案；具有与软管的纵轴垂直、平行或成某一角度的波纹(例如在美国专利5,996,642中所述)的实施方案；具有一层或多层粘结到阻挡层外表面上的附加层的实施方案；和这样一些实施方案，即其中当与流体接触的最内层具有静电放电能力时，所述静电放电能力不均匀地分布在整个所述最内层中，较好是至少较大部分的静电放电能力集中在表面直接与流体接触的所述最内层的最内表面的附近。
具体实施方式
业已发现甲醇特别可用于制备低沉淀物的聚酰胺(较好是聚酰胺11或12)。用甲醇洗涤聚酰胺的实际技术并非特别关键，因为聚合物仅需要采用任何便利的技术和设备就可以进行洗涤，只要洗涤显示出可提取(extractable)的组分有明显的减少。若需要的话，可以用与聚酰胺低聚物具有相似溶解度能力的溶剂来代替甲醇。洗涤可以在制备软管/管的任何阶段进行。就是说，可以对合成获得的新鲜树脂进行洗涤，可以对与合适的增塑剂如N-正丁基苯磺酰胺和任何其它所需添加剂配混的树脂进行洗涤，或者在制备完整的多层软管后，可以对内部聚酰胺树脂层进行洗涤。
对于多层结构，其它可用于阻挡层的材料包括其它的含氟聚合物如PTFE(聚四氟乙烯)、ETFE(聚乙烯-四氟乙烯)、FEP(氟化乙烯丙烯)、CTFE(聚三氟氯乙烯)和ECTFE(聚乙烯-四氟氯乙烯)以及LCP(液晶聚合物)，和EVOH(乙基乙烯醇)。所有这些聚合物以及上述聚偏氟乙烯聚合物可以购自全世界许多制造公司。
将多层结构共挤出和粘结的技术在已有技术中是皆知的，对实施本发明米说并非是关键性的，它们在上述参考文献中有记载，在此不对它们作较详细的说明。
使用多层结构能使渗透降至最小并能使用薄的聚酰胺内层，这样就使成本和由于输送流体会提取出的材料的量降至最小。对于燃料输送管线的应用，聚酰胺单壁的厚度一般为0.05-0.125英寸，在多层结构的情况下，聚酰胺内壁的厚度更一般地为0.005-0.06英寸。
聚酰胺11是将11-氨基十一烷酸经缩聚反应制得的聚合物。它可以以RILSAN注册商标购自ATOFINA Chemicals，Inc.，U.S.和其在全世界的相关公司。聚酰胺12是12-氨基十二烷酸的内酰胺经缩聚反应制得的聚合物，它在全世界范围内可购自多种来源。
在使用粘结层的结构中，较好的材料是购自美国的ATOFINA Chemicals，Inc.和其在全世界的分支公司的Adheflon ASP720。Adheflon ASP720是一种聚偏氟乙烯与赋予聚酰胺11和12以粘合性的各种添加剂配混的混合物。美国专利5,242,976、6,040,025和6,143,415指出如何制造用于配制本发明所述多层软管的这类的合适材料。
如上所述，可以采用标准方法来制造多层或多壁管，例如除了将聚酰胺和聚偏氟乙烯内外层的位置颠倒过来和甲醇洗涤与美国专利5,419,374中所述聚酰胺树脂品级相类似品级的聚酰胺11或12树脂来代替所述品级的聚酰胺外，可以制备与上述专利中所述相类似的管。
当然，本领域的技术熟练者应明白，如果附加层本来不粘附到聚偏氟乙烯上或者它们相互不粘附，则在所有具有合适粘合层的多层结构中，可以将附加层粘结到阻挡层的外面，并且具有这种附加外层的这些软管或管被认为是本发明的完全等同物。同样也被认为是本发明的完全等同物的是这样的管结构，其中与燃料接触的低沉淀物的聚酰胺层是导电的，以放出在其整个厚度内积累的静电，从横截面上看，所述聚酰胺层具有粘结到其内表面上的洗涤过的聚酰胺的单独导电层或具有碳或其它加入的能静电放电材料的梯度浓度。
用甲醇洗涤聚酰胺11来说明甲醇洗涤对沉淀物量的影响的一个例子，结果可提取组分含量的重量百分数从未洗涤材料中的1.72％降至洗涤过的材料中的0.66％。在另一个例子中，燃料对甲醇洗涤过的聚酰胺11进行的试验表明没有明显的燃料不溶性沉淀物提取出来。
由发明人认为是其发明的主题具体在下述权利要求书中指出和清楚地列出。
Claims (11)
1.用于输送流体的改进的多层管，它至少包含与流体接触的聚酰胺内层和阻挡层，改进之处包括使用低沉淀物的聚酰胺作为内层。
2.如权利要求1所述的管，其中粘结层将聚酰胺内层连接到阻挡层上。
3.如权利要求1所述的管，其中阻挡层是含氟聚合物。
4.如权利要求3所述的管，其中含氟聚合物是聚偏氟乙烯。
5.如权利要求4所述的管，其中聚偏氟乙烯经改性，以改进粘合性。
6.如权利要求1所述的管，其中有(A)至少一层聚酰胺层和(B)与所述层(A)相邻的包含聚偏氟乙烯和聚戊二酰亚胺的混合物的至少一层，其中层(A)和层(B)相互用粘合剂粘结在一起。
7.如权利要求1所述的管，它至少包含(A)聚酰胺层和(B)与所述层(A)相邻的包含聚偏氟乙烯和丙烯酸酯共聚物的混合物的层，各层相互粘合在一起。
8.一种用于输送燃料的机动车辆所用的改进的层状管，它至少包含与燃料接触的聚酰胺内层、粘结到内层外表面上的中间粘结层和粘结到粘结层外表面上的聚偏氟乙烯层，改进之处包括使用低沉淀物的聚酰胺作为内层。
9.如权利要求8所述的管，其中聚酰胺内层包含聚酰胺12或聚酰胺11。
10.用于输送燃料的单层管，它包含低沉淀物的聚酰胺。
11.如权利要求10所述的管，其中聚酰胺选自聚酰胺12或聚酰胺11。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/976,807 US6467508B1 (en) | 2001-10-12 | 2001-10-12 | Low precipitate polyamide based tubing |
| US09/976,807 | 2001-10-12 |
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| CN1411980A true CN1411980A (zh) | 2003-04-23 |
| CN1260059C CN1260059C (zh) | 2006-06-21 |
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| US (1) | US6467508B1 (zh) |
| EP (1) | EP1302308B1 (zh) |
| JP (1) | JP2003154586A (zh) |
| KR (1) | KR20030030969A (zh) |
| CN (1) | CN1260059C (zh) |
| BR (1) | BR0204081B1 (zh) |
| CA (1) | CA2399745C (zh) |
| MX (1) | MXPA02010084A (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100355559C (zh) * | 2004-10-25 | 2007-12-19 | 三樱工业株式会社 | 树脂管 |
| CN100422620C (zh) * | 2004-03-19 | 2008-10-01 | 三樱工业株式会社 | 燃料配管用树脂管 |
| CN101636262B (zh) * | 2006-12-27 | 2012-12-19 | 贝扬斯技术公司 | 为了在高压力以及从低到高的体膨胀的环境下运作的动力转向软管设计 |
| CN104797425A (zh) * | 2012-11-16 | 2015-07-22 | 雷奥两合股份公司 | 具有多层壁的柔性软管 |
| CN108730638A (zh) * | 2017-04-19 | 2018-11-02 | Ti汽车富尔达布吕克有限公司 | 用于储箱，特别是汽车燃料箱的内部管道 |
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|---|---|---|---|---|
| BR0301971A (pt) * | 2002-06-06 | 2005-03-15 | Goodyear Tire & Rubber | Mangueira de célula de combustìvel com propriedades de barreira |
| DE10322026B4 (de) * | 2003-05-16 | 2009-01-22 | Veritas Ag | Mehrschichtiger Schlauch |
| US8541082B2 (en) * | 2003-06-17 | 2013-09-24 | Daikin Industries, Ltd. | Laminated resin formed body, method for producing laminated resin formed body, and multilayer article |
| BRPI0518682B1 (pt) * | 2004-11-30 | 2021-10-13 | Arkema Inc | Estrutura em multicamadas para transporte e/ou armazenamento de fluido |
| US20070036926A1 (en) * | 2005-08-12 | 2007-02-15 | Fish Robert B Jr | Multilayered pipes |
| US20070244244A1 (en) * | 2006-04-13 | 2007-10-18 | Franck Bertoux | Low oligomer conductive polyamide |
| JP4697089B2 (ja) * | 2006-08-10 | 2011-06-08 | 横浜ゴム株式会社 | 水道配管およびその製造方法 |
| US20080145584A1 (en) * | 2006-12-15 | 2008-06-19 | Fish Robert B | Multilayered composite articles |
| KR20120043214A (ko) | 2010-10-26 | 2012-05-04 | 삼성전자주식회사 | 세탁기 |
| US20170074427A1 (en) * | 2015-09-16 | 2017-03-16 | Cooper-Standard Automotive, Inc. | Fuel tube for a gasoline engine |
| FR3045639B1 (fr) * | 2015-12-18 | 2020-08-14 | Arkema France | Structure barriere a base de copolyamide mxdt/xt de haute tg |
| FR3045640B1 (fr) * | 2015-12-18 | 2020-08-28 | Arkema France | Structure barriere a base de copolyamide mpmdt/xt de haute tg |
| DE202016008382U1 (de) | 2016-09-21 | 2017-09-25 | Evonik Degussa Gmbh | Mehrschichtiger Hohlkörper mit hoher Auswaschbeständigkeit |
| EP3299165B1 (de) | 2016-09-21 | 2020-08-12 | Evonik Operations GmbH | Mehrschichtiger hohlkörper mit hoher auswaschbeständigkeit |
| EP3640280A1 (de) | 2018-10-19 | 2020-04-22 | Evonik Operations GmbH | Leitfähige formmassen |
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| JPH03197034A (ja) * | 1989-12-26 | 1991-08-28 | Yokohama Rubber Co Ltd:The | 低抽出性ホース |
| FR2659085B1 (fr) | 1990-03-02 | 1992-05-15 | Atochem | Composition coextrudable avec le polyfluorure de vinylidene permettant l'adhesion de ce dernier avec une resine polymerique non compatible - composite obtenu avec cette composition. |
| FR2687619B1 (fr) | 1992-02-25 | 1994-04-08 | Elf Atochem Sa | Tube pour transport d'essence. |
| US5524673A (en) | 1992-04-14 | 1996-06-11 | Itt Corporation | Multi-layer tubing having electrostatic dissipation for handling hydrocarbon fluids |
| US6041826A (en) * | 1993-06-03 | 2000-03-28 | Elf Atochem S.A. | Petrol supply tube |
| DE4326130A1 (de) | 1993-08-04 | 1995-02-09 | Huels Chemische Werke Ag | Thermoplastische Mehrschichtverbunde |
| FR2711665B1 (fr) | 1993-10-25 | 1995-12-08 | Atochem Elf Sa | Liant d'adhésion du PVDF, son application comme matériau barrière et matériaux obtenus à partir de celui-ci. |
| MX9603600A (es) * | 1994-03-04 | 1997-05-31 | Aeroquip Corp | Cuerpo compuesto y capa de acoplamiento para el mismo. |
| DE4410148A1 (de) | 1994-03-24 | 1995-09-28 | Huels Chemische Werke Ag | Mehrschichtiges Kunststoffrohr |
| US6040025A (en) | 1994-04-28 | 2000-03-21 | Elf Atochem S.A. | Adhesion binder containing glutarimide moieties |
| DE69602048T2 (de) * | 1995-03-09 | 1999-11-11 | Elf Atochem S.A., Puteaux | Auf Polyamid basierende Schläuche zum Kraftstofftransport |
| JPH10158393A (ja) * | 1996-12-04 | 1998-06-16 | Toray Ind Inc | 燃料ホース用樹脂 |
-
2001
- 2001-10-12 US US09/976,807 patent/US6467508B1/en not_active Expired - Lifetime
-
2002
- 2002-08-27 CA CA002399745A patent/CA2399745C/en not_active Expired - Fee Related
- 2002-09-17 EP EP02292273.6A patent/EP1302308B1/en not_active Expired - Lifetime
- 2002-10-02 JP JP2002289760A patent/JP2003154586A/ja active Pending
- 2002-10-04 BR BRPI0204081-6A patent/BR0204081B1/pt active IP Right Grant
- 2002-10-11 MX MXPA02010084A patent/MXPA02010084A/es active IP Right Grant
- 2002-10-11 KR KR1020020062012A patent/KR20030030969A/ko not_active Application Discontinuation
- 2002-10-11 CN CNB021475423A patent/CN1260059C/zh not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422620C (zh) * | 2004-03-19 | 2008-10-01 | 三樱工业株式会社 | 燃料配管用树脂管 |
| CN100355559C (zh) * | 2004-10-25 | 2007-12-19 | 三樱工业株式会社 | 树脂管 |
| CN101636262B (zh) * | 2006-12-27 | 2012-12-19 | 贝扬斯技术公司 | 为了在高压力以及从低到高的体膨胀的环境下运作的动力转向软管设计 |
| CN104797425A (zh) * | 2012-11-16 | 2015-07-22 | 雷奥两合股份公司 | 具有多层壁的柔性软管 |
| CN104797425B (zh) * | 2012-11-16 | 2018-01-19 | 雷奥两合股份公司 | 具有多层壁的柔性软管 |
| CN108730638A (zh) * | 2017-04-19 | 2018-11-02 | Ti汽车富尔达布吕克有限公司 | 用于储箱，特别是汽车燃料箱的内部管道 |
Also Published As
| Publication number | Publication date |
|---|---|
| BR0204081A (pt) | 2003-09-16 |
| US6467508B1 (en) | 2002-10-22 |
| EP1302308B1 (en) | 2017-04-19 |
| JP2003154586A (ja) | 2003-05-27 |
| MXPA02010084A (es) | 2005-08-16 |
| CA2399745A1 (en) | 2003-04-12 |
| EP1302308A1 (en) | 2003-04-16 |
| BR0204081B1 (pt) | 2011-02-08 |
| KR20030030969A (ko) | 2003-04-18 |
| CN1260059C (zh) | 2006-06-21 |
| CA2399745C (en) | 2009-08-04 |
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