CN1708557A - 聚合物管子和衬层以及由含氟聚合物和聚酰胺的共混物制造的燃料管线 - Google Patents
聚合物管子和衬层以及由含氟聚合物和聚酰胺的共混物制造的燃料管线 Download PDFInfo
- Publication number
- CN1708557A CN1708557A CNA200380102662XA CN200380102662A CN1708557A CN 1708557 A CN1708557 A CN 1708557A CN A200380102662X A CNA200380102662X A CN A200380102662XA CN 200380102662 A CN200380102662 A CN 200380102662A CN 1708557 A CN1708557 A CN 1708557A
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- Prior art keywords
- lining
- pipe
- fluoropolymer
- polymeric amide
- grafted
- Prior art date
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Classifications
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- C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
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Abstract
用于石油和天然气工业中的管子或者衬层,其包括聚酰胺和具有极性官能团的接枝含氟聚合物的熔融混合的共混物,其中具有极性官能团的接枝含氟聚合物以分散在聚酰胺基质中的不连续相存在。所述管子或者衬层具有相对于聚乙烯而言提高的对烃类渗透的耐受性。另一个实施方案是燃料管线,其包括聚酰胺和具有极性官能团的接枝含氟聚合物的熔融混合的共混物。
Description
技术领域
本发明涉及用于石油和天然气工业的管道和衬层。更具体地,本发明涉及包含熔融混合的聚酰胺和具有极性官能团的接枝含氟聚合物的共混物的这类管子和衬层,其提供提高的对烃类渗透的阻隔性。本发明还涉及燃料管线,其包含聚酰胺和具有极性官能团的接枝含氟聚合物的熔融混合的共混物。
背景技术
石油和天然气工业的本质决定了各种物质,包括固体、液体和气体,需要在各种条件下经由不同的类型的管道输送。所有这些管道共有的一个特征是它们必须由这样的材料制造,该材料对于被输送的物质是不可渗透的和具有耐受性的。这样的物质不仅可能包括烃类,而且可能包括水和盐水。
例如,钻探的油井通常用钢套管衬层。然而,钢对侵蚀和腐蚀敏感,因此在陆地和海上管道两者中,这些管道已经用塑料衬衬层。套管衬层必须能够承受通常在石油和天然气井中遇到的温度和压力,并且必须具有压缩和记忆性能,这允许其缩小尺寸,以便插入套管中,并且随后容许其扩大,靠着套管形成不透液体的密封。聚乙烯管被认为是优选的用于制造套管的材料。除了其良好的压缩和记忆性能之外,聚乙烯管是耐磨损的,这使其能够承受井下工具的通过,并且是耐盐水和某些化学腐蚀的。此外,聚乙烯管可以被成型为不包含接头的长的连续的管子。其重要性在于,许多套管泄漏发生在套管的一段和另一个之间的连接处或者附近。然而,对于高温和侵蚀性的化学环境,通常使用尼龙11。性能得到了大的改进,但是其成本使得尼龙11只在具有高要求的应用中考虑。
Vloedman的美国专利5,454,419公开了为了腐蚀保护目的的用于在钻井操作中使用的钢套管上加衬的方法,该方法优选使用聚乙烯。其中描述了一个过程,包括降低连续一列的聚乙烯管的直径,然后以这样的方式将其插入套管-衬层的钻孔,使得聚乙烯管保持在缩径的状态中,直到聚乙烯管伸到一个预先选择的深度。在聚乙烯管达到预定深度之后,允许缩径管回弹,由此与套管形成不透水的密封,从而有效地密封套管中的任何裂口。
虽然美国专利5,454,419中公开的方法成功地满足了对以有效的和效率高的方式修复套管中的裂口的需要,但是仍然遇到了几种低效的情况,尤其是当仅仅需要修复选择的一段套管时更是如此。例如,如果仅仅相对短的、大约100到2000英尺的套管部分需要修复,并且这部分位于地表以下几千英尺的位置,如果能够不必须从地表到相关的部分全部进行衬层,则是更加成本有效的,同样属于Vloedman的美国专利6,283,211公开了修复部分管道的方法。
在其它已知的衬层系统中,衬层与主体管道在沿着主体管道的长度上具有紧密的容许间隙,形成稳定的复合系统。安装的衬层可以是松动-配合的或者压缩-配合的。在低压以外的所有应用中,由来自衬层内部的流体压力诱导的应力被传输到围绕的主体管中,并且主体管抵抗这些传输的应力。当烃类流体渗透通过衬层时,在环隙(衬层和主体管道内表面之间的空间)中存在所产生的压力增大,这可能直接导致腐蚀、渗漏和/或衬层陷缩,如果管道内的压力降低到低于环隙中的压力。这些都是较大的缺陷。当衬层外表面保持有效程度的与内主体壁的接触时,则有有效程度的密封。因此,环形横截面积被减小到这样的程度,即沿着该系统仅仅存在极其曲折的路径,供环形间隙流体朝着任何放空途径迁移。
美国专利6,220,079(Taylor)公开了通过降低环隙中压力的不利影响以解决这一问题的方法,该方法对衬层构型进行改进,从通常的均匀圆筒状形状改为在衬层和主体管之间引入许多的导管。这些导管提供了相对廉价的用于放空压力的手段,其有助于防止衬层陷缩,并且容许引入用于进行测量的仪器。
对衬层陷缩的出现有影响的其它因素包括衬层的机械性能、输送的流体的性质、压力、温度和流体渗透的有效速度。本发明公开了通过显著地降低经由衬层的流体渗透速率来解决衬层陷缩的方法。
美国专利6,127,478(Spohn)公开了熔融混合的共混物,其包含良好地分散在不相容的聚酰胺中的极性接枝的含氟聚合物的共混物。该技术要求高剪切和高水平混合,以得到良好分散的共混物。
本发明的一个目的是提供具有良好的烃类渗透耐受性的管道和衬层。本发明的特征是在形成管子和衬层的方法中熔融共混至少一种聚酰胺和至少一种具有极性官能团的接枝含氟聚合物。本发明的优点是提供包含聚合物材料的管子和衬层,其相对于聚酰胺具有提高的阻隔性能。本发明的进一步优点是提供燃料管线,其具有改进的对烃类渗透的耐性。本发明的这些和其他目的、特征和优点,通过参考本文对本发明的详细说明,将被较好地理解。
发明内容
本文公开和要求保护管道和衬层,其适用于输送石油和天然气应用中的物质,该衬层包括以下组分的熔融混合的共混物:
(a)至少一种聚酰胺,和;
(b)至少一种具有极性官能团的接枝含氟聚合物,其中所述含氟聚合物与所述至少一种聚酰胺(a)不相容;
其中,所述聚酰胺(a)在连续的基质相中,和所述含氟聚合物(b)以不连续的分布相存在,其具有包埋在连续相中的大量的薄的、基本上平行的和重叠的物质的层的形式。
发明详述
在此,术语“管道”指空心的、长的、通常圆筒状的管道,其通常用于在输送期间容纳物质,所述物质可以包括流体、烃类流出物、细微颗粒固体或者气体。“石油和天然气应用”是指在石油和天然气工业中的应用,其涉及从地层中开采化石燃料例如原油和天然气以及随后的输送和精炼。这样的应用包括,但是不局限于,管子、套管、虹吸管柱、线管和装置管路。术语“衬层”在此用于指在钢或者其它金属管子内部使用的第二个层,其用于防护的目的,如此产生“衬层管”,其通常为多件管道结构。术语“线管”不同于“衬层管”,并且是在井口、容器、泵、贮藏设备和/或加工设备之间的流送管。术语“管子”在石油和天然气工业中用于指用于各种应用的圆形的管子,包括但不限于导管、套管、虹吸管柱、线管和装置管路。
在此,当提到聚合物时,术语“粒子”指本体聚合物的物理形式,并且可以是粒料、方粒料、薄片、粉末或者本领域技术人员已知的其它形式。
对于本发明的目的,“不相容的聚合物”指在熔融形式中基本上不具有相互溶混性的聚合物材料。
在此,当以措词“大约”修饰数值范围时,其适用于修饰下限和上限两者。
本发明的管子或者衬层包含聚合物组合物,该聚合物组合物包含至少一种聚酰胺和至少一种具有极性官能团的接枝含氟聚合物(在此还称为“接枝含氟聚合物”)的熔融混合的共混物,使得接枝含氟聚合物部分存在于分布在聚酰胺连续相中的不连续相中。不连续的接枝含氟聚合物相以层状的构型存在,意味着其包括大量的相,所述相是薄的、基本上平行的和重叠的物质层的形式,它们包埋在连续的聚酰胺相中。由于存在这些相,产生了延长的曲径,如果烃类或者其它物质渗透或者扩散通过管子或者衬层的壁,则它们必须通过所述曲径,因此改进了未改性聚酰胺的阻隔性能。所述组合物通过将聚合物粒子混合、将混合物加热产生物质的非均相熔体,并且以导致拉伸熔体的方式将熔体成型以产生延伸的不连续相。
存在不连续的接枝含氟聚合物相的层状构型,意味着与从均匀共混物获得的耐渗透性相比,达到给定程度的耐渗透性需要较小量的接枝含氟聚合物。均匀的良好混合的共混物仅仅是部分有效的,除非存在大量的(例如>50%)的含氟聚合物,这对于这些应用而言是成本过高的。衬层的共挤出结构等等将要求用于每种聚合物的附加的挤出机的附加投资。本发明通过以允许显著地减少接枝含氟聚合物量的方式使用单一步骤挤出,避免了这些传统的和更加昂贵的过程。
本发明的管子和衬层相对于聚烯烃管子和衬层具有降低的烃类渗透性。使用本发明的衬层将用于石油和天然气工业中的金属管子加衬层的优点是,由于衬层陷缩而造成系统故障的可能性被降低。这种陷缩最通常地是由于流体在环隙中累积,所述流体已经从用管子输送或者储存的材料渗透或者扩散通过所述衬层。这样的流体,取决于环隙中的条件,可以存在于气相或者液相中。在很大程度上,平衡是有效的;管子内的流体压力通常大于或等于环隙压力。然而,在正常操作的过程中,管子中的压力可能降低到实质上低于环隙中的流体压力,例如在意外的停机时。当压力趋向均衡时,产生的压力差可能允许环隙流体发生膨胀。如果衬层自身不能承受外部应力,则可能导致径向皱缩。
在一个实施方案中,未熔融形式的聚合物粒子被充分地混合,以便提供统计学上的均匀分布,并且在聚合物已经被加热成熔体之后,必须小心避免实质上的额外的混合。在另一个实施方案中,聚合物粒子可以以软化或者熔融形式混合,只要聚合物的混合物保持非均相特征。在一定的温度下混合聚合物,使得聚酰胺或者接枝含氟聚合物之一不被软化或者熔融,然后将混合物加热,也可以制备所述共混物。优选的是,不相容聚合物的熔融非均相共混物应被制造成,当例如借助于挤出力将熔体拉伸时,聚酰胺呈连续的基质相的形式,而接枝含氟聚合物为不连续的分布相的形式。所述不连续相以包埋在连续相中的大量的薄的、基本上平行的和重叠的层的形式存在。
虽然不是要求的,但是优选的是,如所描述的,用于实施本发明的聚酰胺是颗粒形式;并且希望的是聚酰胺和接枝含氟聚合物两者应该作为粒子被混合。通常,粒子将具有这样的尺寸,使得不相容聚合物的熔融共混物,当引入某些熔体拉伸设备时,例如挤出模唇,具有对于实施本发明而言优选的非均相性。当粒子、特别是接枝含氟聚合物粒子的尺寸太小时,熔融共混物,即使没有被过度地混合,也倾向于具有均相组合物的功能,因为构成不连续聚合物相的物质的相太小。当粒子、特别是接枝含氟聚合物的粒子具有太大的尺寸时,熔融共混物倾向于形成具有大理石花纹结构的管子和衬层,而不是层状结构,构成不连续相的材料的大的相延伸到管子或者衬层的相对的边界,并且引起构成连续相的材料的中断。所述粒子优选具有一般规则的形状,例如立方体的或者球形的等等。然而,所述粒子可以是不规则的;并且它们可以具有实质上地大于另一个尺寸的一个尺寸,例如当使用物质的薄片时的情况。当不相容聚合物的每一种作为单个颗粒存在时,所述粒子一般具有大致相同的尺寸,虽然这不是要求的。
不连续相中物质的层的厚度是粒子大小连同成型步骤中拉伸度的函数。接枝含氟聚合物的粒子尺寸一般被选择成,在拉伸后,导致重叠的层,其可以为大约0.5到50微米厚,并且也许有时稍微更厚一些。
本发明的非均相的熔融混合共混物优选通过在低剪切下将成分熔融共混来制备。正如本领域技术人员将理解的,可以首先以希望的比例将成分混合,并且在干燥状态中互相共混,例如借助于在转鼓中桶混,或者借助于使用共混器或者其它混合器,或者可以通过同时或者单独地计量一种或多种所述组分的进料到熔融共混装置中而进行混合。
一旦混合,将不相容的聚合物加热到高于最高熔点聚合物组分的熔点。应当注意,进行所述加热是为了拉伸所述软化的或者熔融的共混物。在不具有明确的熔融温度的不相容聚合物的情况下,在此使用的“熔融温度”指至少足够高的温度,在该温度下聚合物已经被软化到将共混物中每一种聚合物拉伸所需要的程度。这样的加热导致形成软化的或者熔融的非均相材料共混物,并且所述加热必须以这样的方式进行,使得能够避免对不相容聚合物的实质上的附加的混合,因为这样的混合可能导致均化和熔融粒子的结合,并且可能导致具有均匀的、非分层的组成的熔体和管子或者衬层。加热可以借助于本领域技术人员众所周知的几种设备的任何一种来进行,并且通常在挤出机中进行。已经知道,在本发明的加热和成型步骤之间,可以使用为物质输送而不是为物质混合而设计的类型的单螺杆挤出机,而不会引起两相不相容聚合物组合物的均相化。通常用于聚氯乙烯、丙烯腈或者聚偏二氯乙烯的类型的低剪切和低混合挤出机可用于实施本发明,如果它们以软化和输送物质并且最小化组分的混合的方式使用。通常用于尼龙和聚乙烯的类型的高剪切和高混合挤出机对于实施本发明而言是较不希望的。可以使用很多其它低剪切熔融共混装置,正如本领域技术人员已知的,而不背离本发明精神。在所述组合物保持非均相性特征的程度上可以实施和获得本发明的方法和产品。
本发明形成管子和衬层的方法要求拉伸熔融的共混物,然后冷却。拉伸是两相熔体的伸长,导致不连续相的相尺寸的实质变化。拉伸可以借助于几种设备的任何一种或者借助于多于一种这样的设备的组合来完成。例如,所述熔体可以在模唇之间挤出或者共挤出。拉伸可以借助于在挤出或者共挤出非均相熔体的共混物之后轻微地拉伸来完成。
拉伸可以在一个方向中或者在垂直的方向中进行。无论拉伸是在一个方向中进行还是在两个方向中进行,在至少一个方向中伸长率应该为大约100到500%;并且大约100到300%的伸长率是优选的。虽然在此给出的上限不是关键的,但是下限是关键的,因为不足的拉伸不能产生本发明所特有的改进的流体渗透阻隔性。避免过度的拉伸是重要的,这仅仅是因为熔体的过度伸长可能导致制品的弱化或者破裂。
拉伸之后进行冷却,达到低于最低熔点组分的熔点的温度,以使挤出部件固化。冷却可以借助于任何希望的设备和以任何方便的速度进行。
用于本发明中的组合物的一种或多种聚酰胺以大约60到95或者优选大约70到90重量百分数存在,基于组合物中聚酰胺和接枝含氟聚合物的总量。用于本发明中的组合物的一种或多种接枝含氟聚合物以大约5到60或者优选大约10到30重量百分数存在,基于组合物中聚酰胺和接枝含氟聚合物的总量。
所述组分的任何一种可用于将惰性填料引入组合物,条件只是所述填料的种类或者量不妨碍多层结构的形成或者所述组合物的希望的或者要求的性能。可以在此使用通常用于结构聚合物材料中的增塑剂、遮光剂、着色剂、润滑剂、热稳定剂、氧化稳定剂等等的量。这类填料的量不包括在不相容聚合物和相容剂的量的计算中。
当在此使用时,术语“聚酰胺”指均聚物和共聚物两者。聚酰胺是众所周知的,并且通过羧酸或者其反应性的等效物与伯胺和/或内酰胺在众所周知的条件下反应来产生。内酰胺和氨基酸也可以反应而生成聚酰胺。用于聚酰胺制备的羧酸的实例是己二酸、辛二酸、癸二酸、壬二酸、丙二酸、戊二酸、庚二酸、间苯二甲酸、对苯二甲酸等等。伯二胺的实例是四亚甲基二胺、五亚甲基二胺、1,6-己二胺、八亚甲基二胺等等。示例性的聚酰胺包括聚(己二酰戊二胺)、聚(己二酰己二胺)、聚(癸二酰己二胺);从内酰胺例如己内酰胺和从氨基酸例如11-氨基十一酸获得的聚酰胺,等等。共聚酰胺也是适合的。优选的聚酰胺和共聚酰胺各自具有在170℃到270℃范围内、并且甚至更优选地在180℃到240℃范围内的熔点,并且包括以下聚合物,例如,聚己内酰胺、聚(11-氨基十一烷酰胺)、聚十二烷酰胺、聚(癸二酰己二胺)、聚(十二烷酰己二胺)和聚(己二酰己二胺)与聚己内酰胺的共聚物。同样优选的是无定形聚酰胺共聚物,其没有明显的熔点,但是部分地衍生自芳族单体例如间苯二甲酸。
用于本发明中的组合物的聚酰胺应该是可熔融挤出的,并且优选具有至少5000的数均分子量。聚酰胺的实例包括通过等摩尔量的至少一种包含4到14个碳原子的饱和二羧酸与至少一种包含4到14个碳原子的二胺缩合而生产的那些。然而,可以使用过量的二胺,以在聚酰胺中提供相对于羧基端基过量的胺末端基团。特定的实例包括聚己二酰己二胺(66尼龙)、聚壬二酰己二胺(69尼龙)、聚癸二酰己二胺(610尼龙)、聚十二烷二酰己二胺(612尼龙)、聚己内酰胺(6尼龙)以及其共聚物。熔融可挤出的半芳族聚酰胺同样可用于本发明的熔融混合的共混物。
用于本发明的组合物中的具有极性官能团的接枝含氟聚合物是可熔融挤出的,并且通过用包含双键和极性基团的化合物接枝含氟聚合物形成。优选的含氟聚合物是乙烯与全卤代单体例如四氟乙烯(TFE)或者三氟氯乙烯(CTFE)的共聚物,这类共聚物通常被分别称为ETFE和ECTFE。在ETFE情况下,通常使用较小量的附加的单体,以提高性能,例如降低的高温脆性。全氟代(丙基乙烯基醚)(PPVE)、全氟代(乙基乙烯基醚)(PEVE)、全氟丁基乙烯(PFBE)和六氟异丁烯(HFIB)是优选的附加共聚单体。ECTFE还可以具有附加的改性共聚单体。可以使用的其它含氟聚合物包括偏二氟乙烯(VF2)聚合物,其包括均聚物和与其它全氟烯烃、尤其是六氟丙烯(HFP)和任选地TFE的共聚物。
含氟聚合物通过具有在其上接枝的烯属不饱和化合物而被官能化,该烯属不饱和化合物为含氟聚合物提供了极性官能团,所述极性官能团作为烯属不饱和化合物的一部分存在。更特别地,用于本发明的熔融混合的共混物中的接枝含氟聚合物优选是粉末的形式,该粉末具有接枝到粉末颗粒表面的接枝化合物。因此,接枝含氟聚合物是表面-接枝合氟聚合物粉末,或者表面-接枝含氟聚合物。通过接枝提供的极性官能团的实例包括酸类,包括羧酸、磺酸和膦酸,和其酯和盐,以及环氧化物。
甲基丙烯酸缩水甘油酯是提供环氧官能团的接枝化合物的一个实例。在用于接枝到和由此变成接枝含氟聚合物的一部分的化合物当中,马来酸、富马酸和马来酸酐是优选的。接枝到含氟聚合物的化合物以这样的量存在,即在熔融混合时能够有效地导致在共混物中产生接枝含氟聚合物的分散的小片状体。通常,接枝化合物的量基于得到的接枝含氟聚合物的总重量为0.1重量百分数到5重量百分数。优选,接枝极性-官能化合物的量是0.2-3重量百分数和更优选0.3-2重量百分数。接枝含氟聚合物在与聚酰胺熔融共混之前制备。
接枝含氟聚合物形成用于本发明中的熔融混合的共混物的分散相。熔融混合导致接枝含氟聚合物作为分散在聚酰胺基质中的许多的层存在。
用于制备用烯属不饱和化合物接枝的含氟聚合物的方法描述于美国专利5,576,106,其在此引入作为参考。
优选的是接枝含氟聚合物和聚酰胺,如果存在,在本发明的管子和衬层被成型的温度下,具有与聚烯烃相比较高的熔体粘度。
接枝含氟聚合物的许多的层导致多相熔融混合的共混物,其具有良好的机械性能;令人惊奇地低的化学品例如烃类和具有高蒸气压的烃基燃料的渗透性;以及良好的耐化学腐蚀性。这些性能使共混物适合用作各种化学品和烃类的阻隔材料。
因为本发明的熔融混合的共混物还直接粘合到未改性的含氟聚合物和未改性的聚酰胺上,因此包含所述共混物的管子和衬层可以是还包含附加的含氟聚合物和/或聚酰胺层的复合结构。这些复合结构具有良好的完整性,而不要求使用粘合剂结合层,并且含氟聚合物或者聚酰胺不需要包含相容剂。这类复合结构可以通过共挤出形成。当熔融混合的共混物与含氟聚合物层结合使用时,共混物中的接枝含氟聚合物优选以这样的量存在,即其能够有效地引起所述共混物粘合到含氟聚合物层。该量将随含氟聚合物层中的含氟聚合物性质和/或接枝到共混物的含氟聚合物组分上的极性官能化合物的量而变化。
其它聚酰胺或者含氟聚合物层对用于本发明中的熔融混合的共混物的粘合性可能取决于层压条件以及附加层的组成。条件能够包括温度、压出速度、拉伸比、拉伸比平衡、界面压力、冷却速率、冷却条件等等,并且可能受设备选择例如心轴长度、模头设计特征包括成型段长度的影响。
用于本发明中的共混物还可以用于制造用于汽车应用的燃料管线,例如汽车和卡车或者其它交通工具例如飞机中的燃料管线。这类燃料管线是用来将气油或者柴油燃料从车载贮槽输送到发动机的管子,并且优选具有低的烃类渗透性。燃料管线可以包括用于本发明中的聚酰胺与具有极性官能团的接枝含氟聚合物的熔融混合的共混物的单层。它们还可以包括层压或者复合结构,其可以通过共挤出形成。除了所述熔融混合的共混物之外,这种层压制品可以包括一个或多个聚酰胺和/或含氟聚合物的附加层。
本发明的管子和衬层具有包括以下的、但是不局限于以下的石油和天然气工业应用:线管、软管、井下套管、井下套管衬层、分配管、吸入管棒、虹吸管柱、水平管、水平管衬层、水力软管、软管和增压软管。
Claims (18)
1.一种适用于在石油和天然气应用中输送物质的管子或者衬层,其包含以下组分的熔融混合的共混物:
(a)至少一种聚酰胺,和
(b)至少一种具有极性官能团的接枝含氟聚合物,其中所述含氟聚合物与所述至少一种聚酰胺(a)不相容;
其中,所述聚酰胺(a)在连续的基质相中,和所述含氟聚合物(b)以不连续的分布相存在,其具有包埋在连续相中的大量薄的、基本上平行的和重叠的物质的层的形式。
2.权利要求1的管子或者衬层,其中所述至少一种具有极性官能团的接枝含氟聚合物存在于具有大于大约0.5微米和小于大约50微米厚度的物质层中。
3.权利要求1的管子或者衬层,其中所述至少一种聚酰胺选自聚己内酰胺、聚(11-氨基十一烷酰胺)、聚十二烷酰胺、聚(癸二酰己二胺)、聚(十二烷酰己二胺)和聚(己二酰己二胺)与聚己内酰胺的共聚物。
4.权利要求1的管子或者衬层,其中所述至少一种聚酰胺包括部分地衍生自芳族单体的无定形聚酰胺共聚物。
5.权利要求1的管子或者衬层,其中熔融混合共混物还包含至少一种增塑剂。
6.权利要求1的管子或者衬层,其中熔融混合共混物还包含至少一种润滑剂。
7.权利要求1的管子或者衬层,其中熔融混合共混物还包含至少一种稳定剂。
8.权利要求1的管子或者衬层,其中所述至少一种聚酰胺各自具有大约170到270℃的熔点。
9.权利要求1的管子或者衬层,其中所述至少一种聚酰胺各自具有大约180到240℃的熔点。
10.权利要求1的管子或者衬层,其中所述至少一种聚酰胺以大约70到95重量百分数的量存在,并且所述至少一种具有极性官能团的接枝含氟聚合物以大约5到30重量百分数的量存在,其中所有重量百分数是基于聚酰胺和具有极性官能团的接枝含氟聚合物的总量。
11.权利要求1的管子或者衬层,其中所述至少一种具有极性官能团的接枝含氟聚合物选自具有接枝到其上的羧基部分的含氟聚合物,所述羧基部分既可以在含氟聚合物主链本身上,也可以在侧链上。
12.权利要求1的管子或者衬层,其中所述至少一种具有极性官能团的接枝含氟聚合物选自具有接枝到其上的环氧化物的含氟聚合物,所述环氧化物既可以在含氟聚合物主链本身上,也可以在侧链上。
13.权利要求1的管子或者衬层,其为软管的形式。
14.权利要求1的管子或者衬层,其为线管的形式。
15.权利要求1的衬层,其为井下套管衬层的形式。
16.权利要求1管子或者衬层,其还包含至少一个附加的包含聚酰胺和/或含氟聚合物的共挤出层。
17.一种燃料管线,其包含以下组分的熔融混合的共混物:
(a)至少一种聚酰胺,和
(b)至少一种具有极性官能团的接枝含氟聚合物,其中所述含氟聚合物与所述至少一种聚酰胺(a)不相容;
其中,所述聚酰胺(a)在连续的基质相中,和所述含氟聚合物(b)以不连续的分布相存在,其具有包埋在连续相中的大量的薄的、基本上平行的和重叠的物质的层的形式。
18.权利要求17的燃料管线,其还包括至少一个附加的包含聚酰胺和/或含氟聚合物的共挤出层。
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EP (1) | EP1556442A1 (zh) |
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US20060185750A1 (en) * | 2002-10-31 | 2006-08-24 | Mestemacher Steven A | Polymeric pipes and liners suitable for transporting oil and gas materials and made from blends of polyolefins and polyamides |
US20040118468A1 (en) * | 2002-10-31 | 2004-06-24 | Mestemacher Steven A. | Polymeric pipes and liners suitable for transporting oil and gas materials and made from blends of polyolefins and polyamides |
US20070036926A1 (en) * | 2005-08-12 | 2007-02-15 | Fish Robert B Jr | Multilayered pipes |
WO2007082924A1 (en) * | 2006-01-23 | 2007-07-26 | Solvay (Société Anonyme) | Laminates with fluoropolymeric and bonding layers |
EP1811219A1 (en) * | 2006-01-23 | 2007-07-25 | SOLVAY (Société Anonyme) | Laminates with fluoropolymeric and bonding layers |
EP2035522A1 (fr) * | 2006-06-26 | 2009-03-18 | SOLVAY (Société Anonyme) | Compositions polymeriques presentant des proprietes adhesives |
US20100028583A1 (en) * | 2006-10-27 | 2010-02-04 | E.I. Du Pont De Nemours And Company | Pipes containing nanoclays and method for their manufacture |
US20080145584A1 (en) * | 2006-12-15 | 2008-06-19 | Fish Robert B | Multilayered composite articles |
DE102008001678A1 (de) * | 2007-10-17 | 2009-04-23 | Evonik Degussa Gmbh | Verwendung einer Polyamidformmasse zur Auskleidung von Rohrleitungen |
DE202008000821U1 (de) * | 2008-01-18 | 2009-05-28 | Rehau Ag + Co | Kunststoffrohr zur Sanierung von Abwasserleitungen |
US20110020573A1 (en) | 2009-07-22 | 2011-01-27 | E.I. Du Pont De Nemours And Company | Polyamide composition containing ionomer |
US8906479B2 (en) | 2011-12-30 | 2014-12-09 | E I Du Pont De Nemours And Company | Compositions of polyamide and ionomer |
US20130171394A1 (en) | 2011-12-30 | 2013-07-04 | E. I. Du Pont De Nemours And Company | Polyamide Composition Containing Ionomer |
WO2014143489A1 (en) | 2013-03-11 | 2014-09-18 | Exxonmobil Upstream Research Company | Pipeline liner monitoring system |
EP3110888A1 (en) | 2014-02-24 | 2017-01-04 | E. I. du Pont de Nemours and Company | Plasticized polyamide compositions |
RU2744215C1 (ru) | 2017-04-19 | 2021-03-03 | Тойота Босоку Кабусики Кайся | Композиция термопластической смолы, формованный предмет и способы их получения |
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US4444817A (en) * | 1981-03-04 | 1984-04-24 | E. I. Du Pont De Nemours And Company | Laminar articles of polyolefin and a condensation polymer |
US5209958A (en) * | 1992-06-02 | 1993-05-11 | E. I. Du Pont De Nemours And Company | Multilayer laminates from blow moldable thermoplastic polyamide and polyvinyl alcohol resins |
ES2131705T3 (es) * | 1993-09-28 | 1999-08-01 | Inventa Ag | Tuberia de polimero multicapa. |
CN1157001A (zh) * | 1994-06-17 | 1997-08-13 | 联合讯号公司 | 含有挤出的聚酰胺-低密度聚乙烯接枝共混物的制品 |
US5576106A (en) * | 1994-07-28 | 1996-11-19 | E. I. Du Pont De Nemours And Company | Grafted fluoropolymer powders |
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WO1998005493A1 (en) * | 1996-08-05 | 1998-02-12 | E.I. Du Pont De Nemours And Company | Coextruded laminate |
DE19641946A1 (de) * | 1996-10-11 | 1998-04-16 | Huels Chemische Werke Ag | Mehrschichtiges Kunststoffrohr mit segmentierter Sperrschicht |
US6482482B1 (en) * | 1997-07-25 | 2002-11-19 | E. I. Du Pont De Nemours And Company | Hydrocarbon fluid containment for motorized transportation vehicles |
US6127478A (en) * | 1997-07-25 | 2000-10-03 | E. I. Du Pont De Nemours And Company | Blends of grafted fluoropolymer and polyamide |
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JP4619624B2 (ja) * | 2003-03-31 | 2011-01-26 | 旭硝子株式会社 | 積層ホース |
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