CN102821938A - 具有扩散阻隔的柔性管 - Google Patents
具有扩散阻隔的柔性管 Download PDFInfo
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- CN102821938A CN102821938A CN2011800185676A CN201180018567A CN102821938A CN 102821938 A CN102821938 A CN 102821938A CN 2011800185676 A CN2011800185676 A CN 2011800185676A CN 201180018567 A CN201180018567 A CN 201180018567A CN 102821938 A CN102821938 A CN 102821938A
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- Prior art keywords
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- polyamide
- flexible pipe
- acid
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- 230000004888 barrier function Effects 0.000 title description 5
- 238000009792 diffusion process Methods 0.000 title description 4
- -1 ether ketone Chemical class 0.000 claims abstract description 48
- 229920002647 polyamide Polymers 0.000 claims abstract description 45
- 239000004952 Polyamide Substances 0.000 claims abstract description 44
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- 239000002033 PVDF binder Substances 0.000 claims abstract description 21
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 21
- 239000004734 Polyphenylene sulfide Substances 0.000 claims abstract description 20
- 229920000069 polyphenylene sulfide Polymers 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
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- 239000012778 molding material Substances 0.000 claims description 18
- 210000003953 foreskin Anatomy 0.000 claims description 5
- 238000010276 construction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
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- 239000008186 active pharmaceutical agent Substances 0.000 description 3
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Classifications
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- 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
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- 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
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- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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- 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
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B2307/732—Dimensional properties
-
- 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
- F16L2011/047—Hoses, i.e. flexible pipes made of rubber or flexible plastics with a diffusion barrier layer
Landscapes
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Abstract
在具有未粘合的层的多层结构的柔性管中,其中该管具有包括以下层的内衬:a)至少一个其材料选自聚烯烃成型物料、聚酰胺成型物料和聚偏二氟乙烯成型物料的层,以及b)至少一个其材料由基于选自聚亚芳基醚酮、聚苯硫、聚亚芳基醚酮/聚苯硫共混物、聚苯砜和聚萘二甲酸亚烷基二醇酯的聚合物的成型物料组成的层,外部增强层对归因于从输送的介质向外扩散的腐蚀性成分的腐蚀具有特别有效的保护作用。该管因此特别适合于油气输送中的海上应用。
Description
本发明涉及一种具有未粘合层的多层结构的柔性管。为简单起见,以下称作未粘合的柔性管(Unbonded
Flexible Pipe)。这种管对来自输送流体的气体扩散具有高抵抗性,因此可以特别有利地用于输送原油、天然气、甲醇、CO2等。
未粘合的柔性管本身是现有技术。这种管包括作为对抗输送流体逸出的阻隔的通常为塑料管形式的内衬,以及在所述内衬的外侧上的一个或多个增强层(Armierungsschicht)。未粘合的柔性管可以包括附加层,实例为内衬内侧上的一个或多个增强层,以便防止内衬在高外部压力下塌陷。这种内部增强层通常称作帘布层(Karkasse)。此外可以存在外部包皮(Umhüllung),以便为来自外部环境的液体渗入增强层或其它内部聚合物或金属功能层提供阻隔。
典型的未粘合的柔性管例如在WO 01/61232,US 6
123 114和US 6 085 799中描述;它们还更详细地在API Recommended Practice 17B,“Recommended Practice for Flexible Pipe”,第3版,2002年3月,以及API
Specification 17J,“Specification
for Unbonded Flexible Pipe”,第2版,1999年11月中描述。
本上下文中,术语“未粘合的”表示至少两个层(包括增强层(Armierungsschicht)和塑料层)并未在结构上彼此粘合。在实践中,该管包括至少两个增强层,在沿着整个管长度上,其既没有直接也没有间接(即通过其它层)彼此粘合。这使得管可弯曲和足够柔软,可以为了运输目的而卷起。
这类未粘合的柔性管的各种实施方案为用于海上应用,以及各种陆上应用,用于运输液体、气体和悬浮液。作为实例,它们可以用于运输流体,在其中在沿着整个管长度上存在极高或极不同的水压力,例如从海底向上流动直至海面处或海面附近的设备的上升管道,或另外通常作为用于在各种设备之间运输液体或气体的管,或以大的深度铺设在海底的管,或在近海面的设备之间的管。
在常规的柔性管中,一个或多个增强层主要由螺旋形排列的钢丝、型钢或钢带组成,并且单独的层可以相对于管的轴心具有各种卷绕角度。除此之外,还有多种实施方案,其中至少一个增强层或所有增强层由通常包埋在聚合物基质中的例如纤维束或纤维织物形式的纤维,例如玻璃纤维组成。
在现有技术中,内衬通常由还可以是交联的聚烯烃,例如聚乙烯,或者由聚酰胺,例如PA11或PA12,或者由聚偏二氟乙烯(PVDF)组成。
聚乙烯具有与原油或天然气接触显著溶胀,然后发生蠕变的缺点。输送的非极性介质还经过聚乙烯壁强烈向外渗透。聚乙烯因此通常并不用于与产品流直接接触的管道,而是代之以主要用于所谓的注水管道。
聚酰胺,例如PA11或PA12,作为内衬材料具有极好的适用性,这是因为它们具有极好的机械性能,对烃类具有优异的耐受性,仅显示轻微的溶胀。聚酰胺的特殊适用性已经在出版物OTC
5231“Improved Thermoplastic Materials for
Offshore Flexible Pipes”中详细描述。但是,它们仅可以在至多约70℃使用,因为原油或天然气中存在的工艺用水在较高温度下越来越多地发生水解。所述水解如此严重地降低聚酰胺的分子量,以至导致机械性能显著削弱和管最终失效。针对PA11,API 17TR2描述了一种详细的测试方法,用于测定其水解性能,并且该方法可以同样应用于PA12。
PVDF在至多130℃使用。改性之后,其即使在直至约130℃的较高温度下也是刚性的,伴随着低的压缩可变形性。但是,在高于130℃的温度,随着内部压力降低,还预计会出现起泡和起微泡沫。PVDF特别是在超临界CO2中发生严重的溶胀,达约25%的程度;随着压力下降出现的气泡由良好的渗透阻隔产生,这同时意味着扩散不良。在层内发生局部气体解吸,于是超过材料的内聚强度。
通常的问题是当此类未粘合的柔性管用于输送原油或天然气或用于运输其它腐蚀性介质时,运输的介质的不希望有的和腐蚀性的成分扩散穿过内衬并腐蚀增强系统的线或型材。这一问题特别是随着硫化氢的由内向外渗透而产生。
使用高合金钢用于外部增强层可能是有帮助的。但是其不仅昂贵,而且还增加了管的重量,因为高合金钢往往比低合金钢强度更低,因此需要更厚的尺寸以在最终产品中获得类似的强度。现有技术因此具有各种措施来帮助解决所述问题。
WO
00/17479描述一种解决方案,其中可以吹洗内衬和外部包皮之间的间隙,以去除穿过内衬扩散进入间隙的不希望有的气体和液体。但是,这种解决方案是复杂的,并且并不能在所有情况下实施。
WO
02/31394建议在海上应用中,允许海水与外部增强层接触,其中冲去扩散穿过内衬的气体和液体。但是,海水本身是腐蚀性的。
US 6
006 788描述一种具有内部气密波纹金属管的柔性管。但是该管较硬,因为波纹金属管必须具有最小厚度,以便机械稳定。此外,金属管本身必须耐受输送的腐蚀性介质。此类管因此仅具有有限的应用。
本发明的目的在于提供一种内衬,其如此有效地防止输送的介质的腐蚀性成分穿透(Durchtritt),以至显著降低外部增强层的腐蚀。
意外地,可以通过对于硫化氢和其它腐蚀性化合物提供阻隔层来解决所述问题。
WO
2005/028198已经要求保护了一种此类构思。该文献中的内衬由对于选自甲烷、硫化氢、CO2和水的流体具有阻隔性的较厚的聚合物层和较薄的薄膜组成。对于较厚的聚合物层和薄膜的材料给出两个相同的列表;薄膜此外可以由金属组成。后一个实施方案在实施例中论证。WO
2005/028198因此并未包含关于将聚合物材料加以组合以形成对于硫化氢特别有效的阻隔的任何教导,其中这种阻隔即使在所需环境条件(高压差和高温)下工作期间仍长久保持。
本发明提供一种未粘合的柔性管,其中管具有包括以下层的内衬:
a) 至少一个其材料选自聚烯烃成型物料、聚酰胺成型物料和聚偏二氟乙烯(PVDF)成型物料的层,以及
b) 至少一个其材料由基于选自聚亚芳基醚酮、聚苯硫、聚亚芳基醚酮/聚苯硫共混物、聚苯砜和聚萘二甲酸亚烷基二醇酯的聚合物的成型物料组成的层。
根据b)的层可以设置在内衬的外侧;但是,其优选已经朝向内侧设置。
如果必须满足特殊功能,除根据a)和b)的层之外,还可以包含更进一步的层。
各层可以经粘合促进剂彼此粘合;合适的粘合促进剂是本领域技术人员已知的。一定程度的初期粘合有助于生产未粘合的柔性管;但是,层粘合性对于该工作并不是强制性需要的。在工作期间气体会在未粘合的层之间累积的情况下,这些可以通过合适的结构手段来逸出。但是,在根据b)的层在内侧设置的优选实施方案中,气体的累积可以显著减少。
在一个可能的实施方案中,有帘布层位于内衬的内侧。此类帘布层及其实施是现有技术。在另一个可能的实施方案中,未粘合的柔性管不包括帘布层,特别是当其并非设计用于在高外部压力下工作时。
未粘合的柔性管此外包括内衬的外侧上的一个或多个增强层,其通常由螺旋形排列的钢丝、钢型材或钢带组成。所述增强层的实施是现有技术。至少一个所述增强层的结构优选使得该层经受得起内部压力,以及至少一个其它所述增强层的结构使得该层经受得起拉伸力。邻接一个或多个增强层可以为外部包皮,其通常为由热塑性成型物料或弹性体制成的管或软管。
用于根据a)的层的聚烯烃首先可以为聚乙烯,特别是高密度聚乙烯(HDPE),或全同立构或间同立构聚丙烯。聚乙烯优选是交联的,通常通过与自由基引发剂反应或通过其上接枝的甲硅烷基的湿气引发交联进行。聚丙烯可以为均聚物或共聚物,例如使用乙烯或1-丁烯作为共聚单体;这里可以使用无规共聚物以及嵌段共聚物。聚丙烯此外也可以例如根据现有技术,通过使用乙丙橡胶(EPM)或EPDM加以冲击改性。
聚偏二氟乙烯(PVDF)是本领域技术人员已知的,并且可以多种等级商购。其通常以均聚物的形式使用。但是,根据本发明,聚偏二氟乙烯也可以包括基于偏二氟乙烯的具有至多40重量%的其它单体的共聚物。可以提及的这些另外的单体的实例为:三氟乙烯、三氟氯乙烯、乙烯、丙烯和六氟丙烯。
聚烯烃成型物料或PVDF成型物料可以包括常见的助剂和添加剂。PVDF或聚烯烃的比例为至少50 重量%,优选为至少60 重量%,特别优选为至少70 重量%,特别优选为至少80 重量%和极特别优选为至少90 重量%。
根据a)的层的聚酰胺可以由二胺和二羧酸的组合,ω-氨基羧酸或相应的内酰胺制备。原则上,可以使用任何聚酰胺,例如PA6,PA66,或基于它们的具有来源于对苯二甲酸和/或间苯二甲酸(通常称作PPA)的单元的共聚酰胺,以及PA9T和PA10T和这些与其它聚酰胺的共混物。在一个优选的实施方案中,聚酰胺的单体单元平均包括至少8,至少9,或至少10个碳原子。在内酰胺混合物的情况下,这里考虑算术平均值。在二胺和二羧酸组合的情况下,该优选实施方案中二胺和二羧酸的碳原子数的算术平均值必须至少为8、至少为9或至少为10。合适的聚酰胺的实例为:PA610 (可以由己二胺[6个碳原子]和癸二酸[10个碳原子]制备,单体单元中的平均碳原子数因此为8),PA88 (可以由八亚甲基二胺和1,8-辛二酸制备),PA8 (可以由辛内酰胺制备),PA612,PA810,PA108,PA9,PA613,PA614,PA812,PA128,PA1010,PA10,PA814,PA148,PA1012,PA11,PA1014,PA1212和PA12。聚酰胺的生产是现有技术。当然也可以使用基于这些材料的共聚酰胺,也任选可以伴随使用例如己内酰胺的单体。
聚酰胺也可以为聚醚酰胺。聚醚酰胺原则上例如由DE-OS 30 06 961已知。它们包括聚醚二胺作为共聚单体。合适的聚醚二胺可通过将相应的聚醚二醇还原胺化或偶合至丙烯腈,随后氢化来转化获得(例如EP-A-0 434 244;EP-A-0
296 852)。这些的数均摩尔质量通常为230至4000;基于聚醚酰胺,它们的比例优选为5至50 重量%。
衍生自丙二醇的市售聚醚二胺可以JEFFAMIN® D级商购自Huntsman。原则上,衍生自1,4-丁二醇或1,3-丁二醇的聚醚二胺也具有正如例如具有衍生自二醇的单元无规或嵌段分布的混合-结构的聚醚二胺那样的良好适用性。
同样可以使用各种聚酰胺的混合物,前提是相容性充分。相容的聚酰胺组合是本领域技术人员已知的;这里可以提及以下组合作为实例:PA12/PA1012,PA12/PA1212,PA612/PA12,PA613/PA12,PA1014/PA12和PA610/PA12,以及与PA11的相应组合。在拿不准的情况下,可以使用例行实验确定相容的组合。
在一个可能实施方案中,使用30至99 重量%,优选40至98 重量%和特别优选50至96 重量%的狭义上的聚酰胺与1至70 重量%,优选2至60 重量%和特别优选4至50 重量%的聚醚酰胺的混合物。
除了聚酰胺之外,成型物料可以包括其它组分,例如抗冲改性剂、其它热塑性塑料、增塑剂和其它常规添加剂。唯一要求是聚酰胺形成成型物料的基质。
合适的抗冲改性剂的实例为乙烯/α-烯烃共聚物,优选选自
a) 乙烯/C3-C12-α-烯烃共聚物,具有20至96重量%,优选25至85 重量%的乙烯。使用的C3-C12-α-烯烃的实例为丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯、1-癸烯或1-十二碳烯。这里典型实例为乙丙橡胶,以及LLDPE和VLDPE。
乙烯/C3-C12-α-烯烃/非共轭二烯三聚物,具有20至96重量%,优选25至85重量%的乙烯和直至至多约10 重量%的非共轭二烯,例如双环[2.2.1]庚二烯、1.4-己二烯、二环戊二烯或5-亚乙基降冰片烯。合适的C3-C12-α-烯烃也例如为丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯、1-癸烯或1-十二碳烯。
这些共聚物或三聚物例如借助于齐格勒-纳塔催化剂的制造是现有技术。
其它合适的抗冲改性剂为苯乙烯-乙烯/丁烯嵌段共聚物。这里,优选使用苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物(SEBS),其可通过苯乙烯-丁二烯-苯乙烯嵌段共聚物氢化获得。但是,也可以使用二嵌段体系(SEB)或多嵌段体系。这种嵌段共聚物是现有技术。
这些抗冲改性剂优选包括酸酐基团,其中这些通过主链聚合物与浓度足以良好地键合至聚酰胺的不饱和二羧酸酐、不饱和二羧酸或不饱和二羧酸单烷基酯的热或自由基反应以已知的方式引入。合适的反应物的实例为马来酸、马来酸酐、马来酸单丁酯、富马酸、柠康酸酐、乌头酸或衣康酸酐。优选的是通过这一方法已经将0.1至4 重量%的不饱和酸酐接枝到抗冲改性剂上。根据现有技术,不饱和二羧酸酐或其前体也可以与另一种不饱和单体,例如苯乙烯、α-甲基苯乙烯或茚一起接枝。
其它合适的抗冲改性剂为含有以下单体单元的共聚物:
a) 20至94.5 重量%的一种或多种具有2至12个碳原子的α-烯烃,
b) 5至79.5 重量%的一种或多种丙烯酸类化合物,选自以下
-丙烯酸、甲基丙烯酸及其盐,
-丙烯酸或甲基丙烯酸与C1-C12醇的酯,其中这些可以任选带有游离羟基或环氧官能团,
-丙烯腈或甲基丙烯腈,
-丙烯酰胺或甲基丙烯酰胺,
c) 0.5至50 重量%的烯属不饱和环氧化物、羧酸酐、碳酰亚胺、噁唑啉或噁嗪酮。
所述共聚物例如由以下单体组成,其中该列表并非穷举:
a) α-烯烃,例如乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯、1-癸烯或1-十二碳烯;
b) 丙烯酸,甲基丙烯酸,或其例如具有Na⊕或Zn2 ⊕作为平衡离子的盐;丙烯酸甲酯,丙烯酸乙酯,丙烯酸正丙酯,丙烯酸正丁酯,丙烯酸异丁酯,丙烯酸正己酯,丙烯酸正辛酯,丙烯酸2-乙基己酯,丙烯酸异壬酯,丙烯酸十二烷基酯,甲基丙烯酸甲酯,甲基丙烯酸乙酯,甲基丙烯酸正丙酯,甲基丙烯酸正丁酯,甲基丙烯酸异丁酯,甲基丙烯酸2-乙基己酯,丙烯酸羟乙酯,甲基丙烯酸4-羟丁酯,丙烯酸缩水甘油酯,甲基丙烯酸缩水甘油酯,丙烯腈,甲基丙烯腈,丙烯酰胺,N-甲基丙烯酰胺,N,N-二甲基丙烯酰胺,N-乙基丙烯酰胺,N-羟乙基丙烯酰胺,N-丙基丙烯酰胺,N-丁基丙烯酰胺,N-(2-乙基己基)丙烯酰胺,甲基丙烯酰胺,N-甲基甲基丙烯酰胺,N,N-二甲基甲基丙烯酰胺,N-乙基甲基丙烯酰胺,N-羟乙基甲基丙烯酰胺,N-丙基甲基丙烯酰胺,N-丁基甲基丙烯酰胺,N,N-二丁基甲基丙烯酰胺,N-(2-乙基己基)甲基丙烯酰胺;
c) 乙烯基环氧乙烷,烯丙基环氧乙烷,丙烯酸缩水甘油酯,甲基丙烯酸缩水甘油酯,马来酸酐,乌头酸酐,衣康酸酐,还有由这些酸酐通过与水反应产生的二羧酸;马来酰亚胺,N-甲基马来酰亚胺,N-乙基马来酰亚胺,N-丁基马来酰亚胺,N-苯基马来酰亚胺,乌头酰亚胺,N-甲基乌头酰亚胺,N-苯基乌头酰亚胺,衣康酰亚胺,N-甲基衣康酰亚胺,N-苯基衣康酰亚胺,N-丙烯酰基己内酰胺,N-甲基丙烯酰基己内酰胺,N-丙烯酰基月桂内酰胺,N-甲基丙烯酰基月桂内酰胺,乙烯基噁唑啉,异丙烯基噁唑啉,烯丙基噁唑啉,乙烯基噁嗪酮或异丙烯基噁嗪酮。
如果使用丙烯酸缩水甘油酯或甲基丙烯酸缩水甘油酯,该化合物也同时用作丙烯酸类化合物b),因此在(甲基)丙烯酸缩水甘油酯的量充足的情况下不需要存在任何其它丙烯酸类化合物。在该特殊实施方案中,共聚物包含以下单体单元:
a) 20至94.5 重量%的一种或多种具有2至12个碳原子的α-烯烃,
b) 0至79.5 重量%的一种或多种丙烯酸类化合物,选自以下
- 丙烯酸、甲基丙烯酸及其盐,
- 丙烯酸或甲基丙烯酸与C1-C12醇的酯,
- 丙烯腈或甲基丙烯腈,
- 丙烯酰胺或甲基丙烯酰胺,
c) 0.5至80 重量%的丙烯酸或甲基丙烯酸的酯,其中该酯包含环氧基,
其中b)和c)的总和为至少5.5 重量%。
共聚物可以包含少量其它共聚合单体,只要这些不显著损害性能,其实例为马来酸二甲酯、富马酸二丁酯、衣康酸二乙酯或苯乙烯。
这类共聚物的生产是现有技术。多种这些共聚物可商购,例如LOTADER® (Arkema;乙烯/丙烯酸酯/第三组分或乙烯/甲基丙烯酸缩水甘油酯)。
在一个优选实施方案中,聚酰胺成型物料包括以下组分:
1. 60至96.5重量份的聚酰胺,
2. 3至39.5重量份的含有酸酐基团的抗冲改性组分,其中抗冲击改性组分选自乙烯/α-烯烃共聚物和苯乙烯-乙烯/丁烯嵌段共聚物
3. 0.5至20重量份的包含以下单体单元的共聚物:
a) 20至94.5 重量%的一种或多种具有2至12个碳原子的α-烯烃,
b) 5至79.5 重量%的一种或多种丙烯酸类化合物,选自以下
- 丙烯酸、甲基丙烯酸及其盐,
- 丙烯酸或甲基丙烯酸与C1-C12醇的酯,其中这些可以任选带有游离羟基或环氧官能团,
- 丙烯腈或甲基丙烯腈,
- 丙烯酰胺或甲基丙烯酰胺,
c) 0.5至50 重量%的烯属不饱和环氧化物、羧酸酐、碳酰亚胺、噁唑啉或噁嗪酮,
其中根据1.、2.和3.的组分的重量份合计为100。
在另一个优选实施方案中,该成型物料包括:
1. 65至90重量份和特别优选70至85重量份的聚酰胺,
2. 5至30重量份,特别优选6至25重量份和特别优选7至20重量份的抗冲击改性组分,
3. 0.6至15重量份和特别优选0.7至10重量份的共聚物,其优选含有以下单体单元:
a) 30至80 重量%的一种或多种α-烯烃,
b) 7至70 重量%和特别优选10至60 重量%的一种或多种丙烯酸类化合物,
c) 1至40 重量%和特别优选5至30 重量%的烯属不饱和环氧化物、羧酸酐、碳酰亚胺、噁唑啉或噁嗪酮。
作为抗冲击组分也可以使用丁腈橡胶(NBR)或氢化丁腈橡胶(H-NBR),其中这些任选含有官能团。US2003/0220449A1描述了相应的成型物料。
可以存在于聚酰胺成型物料中的其它热塑性塑料主要是聚烯烃。在一个实施方案中,如以上较早部分关于抗冲改性剂所述的,它们可以含有酸酐基团,然后任选与未官能化抗冲改性剂一起存在。在另一个实施方案中,这些是未官能化的并且与官能化抗冲改性剂或与官能化聚烯烃一起组合存在于成型物料中。术语“官能化”表示聚合物根据现有技术提供有可以与聚酰胺的端基反应的基团,例如酸酐基团、羧基、环氧基或噁唑啉基团。这里优选以下组成:
1. 50至95重量份的聚酰胺,
2. 1至49重量份的官能化或未官能化聚烯烃,
以及
3. 1至49重量份的官能化或未官能化抗冲改性剂,
其中根据1.、2.和3.的组分的重量份合计为100。
聚烯烃例如为聚乙烯或聚丙烯。原则上,可以使用任何市售等级。可以使用的的那些实例因此为:高-、中-或低密度线型聚乙烯、LDPE、乙烯-丙烯酸酯共聚物、乙烯-醋酸乙烯酯共聚物、全同立构或无规立构均聚丙烯、丙烯与乙烯和/或1-丁烯的无规共聚物、乙烯-丙烯嵌段共聚物等。聚烯烃可以由任何已知的方法制造,例如齐格勒-纳塔法、Phillips法,或借助于茂金属,或自由基途径。在这种情况下,聚酰胺也可以例如为PA6和/或PA66。
在一个可能的实施方案中,成型物料包括1至25 重量%,特别优选2至20 重量%,和特别优选3至15 重量%的增塑剂。
增塑剂及其在聚酰胺中的使用是已知的。适用于聚酰胺的增塑剂的一般综述可以在Gächter/Müller,Kunststoffadditive
[塑料添加剂],C.Hanser
Verlag,第2版,296页中找到。
适合作为增塑剂的常规化合物的实例为在醇组分中具有2至20个碳原子的对羟基苯甲酸的酯,或在胺组分中具有2至12个碳原子的芳基磺酸的酰胺,优选苯磺酸的酰胺。可以使用的增塑剂特别为对羟基苯甲酸乙酯、对羟基苯甲酸辛酯、对羟基苯甲酸异十六烷基酯、N-正辛基甲苯磺酰胺(Toluolsulfonsäure-n-octylamid)、N-正丁基苯磺酰胺(Benzolsulfonsäure-n-butylamid),或N-2-乙基己基苯磺酰胺(Benzolsulfonsäure-2-ethylhexylamid)。
成型物料另外也可以包括为了产生某些性能所需的常规量的添加剂。为此的实例为颜料或填料,例如炭黑、二氧化钛、硫化锌、增强纤维,例如玻璃纤维,加工助剂,例如蜡、硬脂酸锌或硬脂酸钙,抗氧剂,UV稳定剂,以及赋予产品抗静电性的添加剂,例如碳纤维、石墨原纤、不锈钢纤维或导电炭黑。
聚酰胺在该成型物料中的比例为至少50 重量%,优选为至少60 重量%,特别优选为至少70 重量%,特别优选为至少80 重量%和极特别优选为至少90 重量%。
根据b)的层的聚亚芳基醚酮包括下式的单元
(-Ar-X-) 和 (-Ar’-Y-),
其中Ar和Ar'为二价芳族残基,优选为1,4-亚苯基、4,4'-亚联苯基,以及1,4-、1,5-或2,6-亚萘基。X为吸电子基团,优选为羰基或硫酰基,而Y为另外的基团,例如O、S、CH2、异亚丙基等。这里,至少50%,优选至少70%和特别优选至少80%的X基团为羰基,而至少50%,优选至少70%和特别优选至少80%的Y基团由氧组成。
在优选实施方案中,100%的X基团由羰基组成,100%的Y基团由氧组成。在所述实施方案中,聚亚芳基醚酮可以例如为聚醚醚酮(PEEK;式I),聚醚酮(PEK;式II),聚醚酮酮(PEKK;式III)或聚醚醚酮酮(PEEKK;式IV),但是羰基和氧基团的其它排列当然也是可能的。
聚亚芳基醚酮是部分结晶的,这可例如在DSC分析中通过晶粒熔点Tm的出现体现,该Tm在大多数情况下数量级为300℃或更高。
聚苯硫包括下式的单元
(-C6H4-S-);
其优选由至少50 重量%,至少70 重量%或至少90 重量%的所述单元组成。对于聚亚芳基醚酮的情况,剩余的单元可以为上述的那些,或三-或四官能支化剂单元,其中这些由例如合成期间伴随使用三氯苯或四氯苯产生。聚苯硫以多种类型或以成型物料市售可得。
在聚亚芳基醚酮/聚苯硫共混物的情况下,两种组分可以以任何可想到的混合比率存在,因此从纯的聚亚芳基醚酮扩展至纯的聚苯硫,覆盖组合物的全部范围。该共混物通常分别包括至少0.01 重量%的聚亚芳基醚酮和至少0.01 重量%的聚苯硫。在一个优选实施方案中,该共混物包括至少50 重量%的聚亚芳基醚酮。
聚苯砜(PPSU)由单体4,4'-二羟基联苯和4,4'-二氯二苯砜工业生产。其可例如以RADEL R®商购。
聚萘二甲酸亚烷基二醇酯衍生自具有2至8个碳原子的脂族或脂环族二醇以及萘二甲酸。合适的二醇的实例为乙二醇,1,3-丙二醇,1,4-丁二醇,1,5-戊二醇,1,6-己二醇,1,8-辛二醇,新戊二醇和1,4-环己烷二甲醇。合适的萘二甲酸的实例为1,4-、1,5-、2,6-和2,7-萘二甲酸。优选的聚萘二甲酸亚烷基二醇酯特别为聚-2,6-萘二甲酸亚乙酯,聚-2,6-萘二甲酸亚丙酯,聚-2,6-萘二甲酸亚丁酯和聚-2,6-萘二甲酸亚己酯。
根据b)的层的成型物料可以包括常规助剂和添加剂,以及任选的其它聚合物,在聚亚芳基醚酮的情况下,实例为氟聚合物,例如PFA (四氟乙烯和全氟化乙烯基甲基醚的共聚物),聚酰亚胺,聚醚酰亚胺,LCP,例如液晶聚酯,聚砜,聚醚砜,聚苯砜,聚苯并咪唑(PBI)或其它耐高温聚合物,以及在聚苯硫的情况下,实例分别为乙烯与极性共聚单体的共聚物和三聚物。聚亚芳基醚酮,聚苯硫,聚亚芳基醚酮/聚苯硫共混物,聚苯砜或聚萘二甲酸亚烷基二醇酯的比例为至少50 重量%,优选为至少60 重量%,特别优选为至少70 重量%,特别优选为至少80 重量%,和极特别优选为至少90 重量%。
在各情况下从外向里,可能的层排列的实例为:
聚酰胺/聚亚芳基醚酮
聚酰胺/PPS
聚酰胺/PPS/聚酰胺
聚酰胺/聚萘二甲酸亚烷基二醇酯/聚酰胺
聚酰胺/聚萘二甲酸亚烷基二醇酯/聚酰胺/氟聚合物
聚酰胺/聚萘二甲酸亚烷基二醇酯/聚丙烯
聚酰胺/聚萘二甲酸亚烷基二醇酯/聚丙烯/氟聚合物
聚酰胺/聚萘二甲酸亚烷基二醇酯/HDPE
聚酰胺/聚萘二甲酸亚烷基二醇酯/间同立构聚苯乙烯/氟聚合物
聚亚芳基醚酮/聚酰胺
聚亚芳基醚酮/聚酰胺/聚亚芳基醚酮
PPS/聚酰胺
HDPE或PP/聚亚芳基醚酮
HDPE或PP/PPS
HDPE或PP/PPS/HDPE或PP
HDPE或PP/聚苯砜/HDPE或PP
PVDF/聚亚芳基醚酮
PVDF/聚亚芳基醚酮/PVDF
PVDF/PPS
PVDF/PPS/其它氟聚合物
PVDF/聚苯砜/PVDF
PVDF/聚苯砜/PP。
这里,HDPE可以是未交联的或优选交联的。
内衬的内径通常为至少30 mm,至少40 mm,至少50 mm或至少60 mm,以及至多900 mm,至多800 mm,至多700 mm或至多620 mm;但是,在个别情况下其也可以比那些值更大或更小。内衬的总体壁厚通常为至少2 mm,至少2.5 mm,至少3 mm,至少4 mm或至少5 mm,以及为至多50 mm,至多40 mm,至多30 mm,至多25 mm,至多20 mm或至多16 mm;同样,在个别情况下,其也可以比那些值更大或更小。由阻隔层材料制成的根据b)的层的厚度为总体壁厚的0.5至50%,优选为1至40%和特别优选为2至30%。这里,根据b)的层的厚度优选为至多10 mm。
内衬根据现有技术,通过各个层的共挤出、螺旋挤出(Wickelextrusion),或任选通过带的缠绕来制造。
根据本发明的层的组合可以有效地抑制腐蚀性成分,例如H2S的穿透。这样显著地降低了外部增强层情况下的腐蚀风险。因此使用更强的较低合金钢代替高合金钢成为可能。这样使得能够在保持相同的强度值情况下实现更轻的结构。这里,整体影响为导管结构重量可以减少,以及因此可以开辟更大的海底深度。
在本发明另一个有利实施方案中,外部包皮也使用对例如硫化氢等腐蚀性组分具有高渗透值的材料。合适的材料的实例为LDPE、LLDPE,以及弹性体,例如Santoprene™。该方法防止尽管有所有预防措施仍有少量上述物质渗透穿过内衬在内衬和外部包皮之间的间隙中累积。腐蚀风险因此得到更进一步降低。
Claims (4)
1. 具有未粘合的层的多层结构的柔性管,其中该管具有包括以下层的内衬:
a) 至少一个其材料选自聚烯烃成型物料、聚酰胺成型物料和聚偏二氟乙烯成型物料的层,以及
b) 至少一个其材料由基于选自聚亚芳基醚酮、聚苯硫、聚亚芳基醚酮/聚苯硫共混物、聚苯砜和聚萘二甲酸亚烷基二醇酯的聚合物的成型物料组成的层。
2. 根据权利要求1的柔性管,
特征在于,
所述内衬为管。
3. 根据权利要求1或2的柔性管,
特征在于,
从根据a)的层观察,根据b)的层朝向内侧设置。
4. 根据权利要求1至3任一项的柔性管,
特征在于,
除了所述内衬之外,其还包含一个或多个选自以下的层
- 内置帘布层,
- 一个或多个外置增强层,以及
- 外部包皮。
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BR112012015987B1 (pt) * | 2009-12-28 | 2020-11-10 | National Oilwell Varco Denmark I/S | tubo flexível não ligado |
WO2012155910A1 (en) * | 2011-05-13 | 2012-11-22 | National Oilwell Varco Denmark I/S | A flexible unbonded pipe |
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2010
- 2010-04-13 DE DE102010003917A patent/DE102010003917A1/de not_active Withdrawn
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2011
- 2011-03-25 BR BR112012025999-7A patent/BR112012025999B1/pt active IP Right Grant
- 2011-03-25 WO PCT/EP2011/054578 patent/WO2011128197A1/de active Application Filing
- 2011-03-25 JP JP2013504193A patent/JP2013524131A/ja active Pending
- 2011-03-25 EP EP11711515.4A patent/EP2558285B1/de active Active
- 2011-03-25 RU RU2012147901/05A patent/RU2012147901A/ru not_active Application Discontinuation
- 2011-03-25 US US13/640,586 patent/US20130032240A1/en not_active Abandoned
- 2011-03-25 CA CA2793403A patent/CA2793403C/en active Active
- 2011-03-25 NO NO11711515A patent/NO2558285T3/no unknown
- 2011-03-25 ES ES11711515.4T patent/ES2642634T3/es active Active
- 2011-03-25 CN CN201180018567.6A patent/CN102821938B/zh active Active
- 2011-04-13 AR ARP110101250A patent/AR080890A1/es not_active Application Discontinuation
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CN115461220A (zh) * | 2020-04-29 | 2022-12-09 | 半径-克利特基础设施股份有限公司 | 柔性聚合物多层增强管 |
CN115461220B (zh) * | 2020-04-29 | 2024-07-05 | Rk因福有限公司 | 柔性聚合物多层增强管 |
Also Published As
Publication number | Publication date |
---|---|
CN102821938B (zh) | 2016-05-11 |
RU2012147901A (ru) | 2014-05-20 |
DE102010003917A1 (de) | 2011-10-13 |
AR080890A1 (es) | 2012-05-16 |
EP2558285A1 (de) | 2013-02-20 |
BR112012025999B1 (pt) | 2021-01-19 |
US20130032240A1 (en) | 2013-02-07 |
ES2642634T3 (es) | 2017-11-17 |
NO2558285T3 (zh) | 2018-01-13 |
CA2793403C (en) | 2018-02-13 |
JP2013524131A (ja) | 2013-06-17 |
CA2793403A1 (en) | 2011-10-20 |
BR112012025999A2 (pt) | 2020-08-18 |
WO2011128197A1 (de) | 2011-10-20 |
EP2558285B1 (de) | 2017-08-16 |
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Address after: Essen, Germany Patentee after: Evonik Operations Limited Address before: Essen, Germany Patentee before: EVONIK DEGUSSA GmbH |