CN102821939A - 具有较高耐温性的柔性管 - Google Patents
具有较高耐温性的柔性管 Download PDFInfo
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- CN102821939A CN102821939A CN2011800187760A CN201180018776A CN102821939A CN 102821939 A CN102821939 A CN 102821939A CN 2011800187760 A CN2011800187760 A CN 2011800187760A CN 201180018776 A CN201180018776 A CN 201180018776A CN 102821939 A CN102821939 A CN 102821939A
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- flexible pipe
- polyphenylene sulfide
- ether ketone
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- -1 ether ketone Chemical class 0.000 claims abstract description 28
- 239000004734 Polyphenylene sulfide Substances 0.000 claims abstract description 20
- 229920000069 polyphenylene sulfide Polymers 0.000 claims abstract description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920000412 polyarylene Polymers 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 229920000491 Polyphenylsulfone Polymers 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 238000010276 construction Methods 0.000 claims abstract description 3
- 239000000206 moulding compound Substances 0.000 claims description 9
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229920002313 fluoropolymer Polymers 0.000 abstract description 4
- 239000004811 fluoropolymer Substances 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 238000000465 moulding Methods 0.000 abstract 2
- 238000005253 cladding Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 63
- 239000004696 Poly ether ether ketone Substances 0.000 description 9
- 229920002530 polyetherether ketone Polymers 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000004952 Polyamide Substances 0.000 description 7
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 7
- 229920002647 polyamide Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920000265 Polyparaphenylene Polymers 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 3
- 239000013047 polymeric layer Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
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- 238000005336 cracking Methods 0.000 description 2
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- 239000000835 fiber Substances 0.000 description 2
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- 150000003951 lactams Chemical class 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 229920002480 polybenzimidazole Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- AUVLKYVTAAKSDM-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenylsulfanyl)ethene Chemical compound FC(F)=C(F)SC(F)=C(F)F AUVLKYVTAAKSDM-UHFFFAOYSA-N 0.000 description 1
- GBDZXPJXOMHESU-UHFFFAOYSA-N 1,2,3,4-tetrachlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1Cl GBDZXPJXOMHESU-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000393 Nylon 6/6T Polymers 0.000 description 1
- 229920006154 PA11T Polymers 0.000 description 1
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920003295 Radel® Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 229920006129 ethylene fluorinated ethylene propylene Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229920006119 nylon 10T Polymers 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920006115 poly(dodecamethylene terephthalamide) Polymers 0.000 description 1
- 229920001657 poly(etheretherketoneketone) Polymers 0.000 description 1
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- B32B27/06—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
-
- 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
- B32B27/28—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
-
- 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
- B32B27/28—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
- B32B27/288—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 polyketones
-
- 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
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
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- 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
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
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- 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
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
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- 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
- B32B2270/00—Resin or rubber layer containing a blend of at least two different 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/51—Elastic
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Abstract
具有无粘结层的多层结构的柔性管能够在高于130℃的温度下作业，其具有包含下列层的内衬：a）至少一层由基于选自下列的聚合物的模塑料构成其材料的层：聚亚芳基醚酮，聚苯砜，聚亚苯基硫醚，聚亚芳基醚酮/聚亚苯基硫醚共混物和半芳族聚酰胺，其5-100mol%的二元羧酸比例源自具有8-22个C-原子的芳族二元羧酸且其具有至少260℃的微晶熔点Tm；b）至少一层由含氟聚合物-模塑料构成其材料的层。该管道尤其适合石油或天然气开采中的海上应用。
Description
本发明提供具有无粘合层的多层结构柔性管。为简单起见和根据英语用法，其在下文中被称作无粘合柔性管。这种管以高阻力阻碍气体从传送的流体中扩散出来并因此可特别有利地用于传送原油、天然气、甲醇、CO2等。
无粘合柔性管本身是现有技术。这种管含有作为屏障防止传送的流体逸出的通常为塑料管形式的内衬，以及在这种内衬外的一个或多个增强层。该无粘合柔性管可含有附加层，例如在内衬的内侧的一个或多个增强层以防止内衬在高的外部压力下崩塌。这种内部增强通常被称作帘布层（Karkasse）。此外，可以包含外部套管以提供屏障防止液体从外部环境渗入到增强层或其它位于内部的聚合物功能层或金属功能层中。
例如在WO 01/61232、US 6
123 114和US 6 085 799中描述了典型的无粘合柔性管；此外，它们在API Recommended Practice 17B,
"Recommended Practice for Flexible Pipe", 第3版, 2002年3月中以及在API
Specification 17J, "Specification for Unbonded Flexible Pipe ", 第2版, 1999年11月中被详细表征。
表述“无粘合”在本文中是指至少两个层，包括增强层和塑料层，没有构造性相互连接。在实践中，该管道包含沿管道长度既不直接也不间接（即通过其它层）相互连接的至少两个增强层。以这样的方式管道变得可弯曲并足够柔韧以用于运输。
这种无粘合柔性管以各种设计在海上用途和各种陆上用途中用于输送液体、气体和浆料。例如可以将它们用于输送在沿管道（例如以从海底延伸至位于或接近于海面的装置的上升管形式）长度存在极高或极不同的水压的那里的流体，以及通常用作在不同装置之间输送液体或气体的管道、用作以极大深度铺设在海底的管道或用作在接近海面的装置之间的管道。
在常规柔性管中，一层或多层增强层大多由螺旋状布置的钢丝、钢型材或钢带构成，其中各层可以相对于管轴以不同的缠绕角度来形成。另外还有这样的实施方式，在其中至少一个增强层或所有增强层由通常嵌入聚合基质中的纤维，例如由玻璃纤维（例如以纤维束或纤维织物形式）构成。
在现有技术中，内衬通常由聚烯烃如聚乙烯（也可以将其交联）、由聚酰胺如PA11或PA12、或由聚偏二氟乙烯（PVDF）构成。
聚乙烯具有在与原油或天然气接触时显著溶胀并随后蠕变的缺点。此外，传送的非极性介质通过聚乙烯壁向外强烈渗出。因此，聚乙烯通常不用于直接接触产品流的管道，而是主要用于注水管。
聚酰胺，如PA11或PA12由于它们极好的机械性质、优异的耐烃性和仅仅小的溶胀而非常好地适合作为内衬的材料。在出版物OTC
5231 "Improved Thermoplastic Materials for Offshore Flexible Pipes"中已详细描述聚酰胺的特别适用性。但是，它们仅能在最多大约70℃下使用，因为在更高的温度下由于包含在原油或天然气中的工艺水出现越来越多的水解。由于这种水解令聚酰胺的分子量如此强烈地减小，使得机械性质显著变差且最终管道破坏。在API
17TR2 中描述了用于PA11的测定水解性能的详细检验程序并可同样用于PA12。
PVDF在最多130℃下使用。取决于改性，甚至在最高约130℃的较高温度下其也是刚性的，具有小的压缩变形。然而在130℃以上的温度下，在内部压力下降时，则被预计会起泡和微发泡。PVDF尤其在超临界CO2中强烈溶胀至大约25%；在压降时出现的起泡由良好的渗透屏障（这等同于差的扩散）造成。在这种情况下，在该层内发生局部气体解吸，其中超过了该材料的内聚强度。
在许多情况中，从源头出来的原油或天然气具有明显高于130℃的温度。为了通过柔性管开发这种资源，需要一步前置的用于冷却介质的工艺步骤。因此希望提供在较高温度下也可以使用的无粘合的柔性管，以便能够精简该工艺步骤。
在WO 2008/125807中描述了用于在管道（Umbilical）中输送例如热甲醇的柔性管，其包含PEEK或聚亚苯基硫醚的内层。该管的内径在4-500 mm的范围，而PEEK的层厚为0.7-5 mm。但是，因为在无粘结柔性管的情况下，要求至少2 mm和典型的3-20
mm的层厚，以便确保安装和操作所需的层的机械稳定性，所以这里由已知PEEK的高刚性将产生这样的管道，其没有足够的柔性，以便能够以可接受的半径被缠绕在卷筒上。
另一个具有PEEK内管的柔性多层管的实施方式描述于WO 99/67561中。该管由聚合物层和织物层组成，它们沿管道长度构造性地相互连接；所述内管的典型壁厚为6-12 mm。
在WO 2006/047774中描述了一种带有一层由半芳族聚酰胺构成的层的多层管。
US 5
876 548描述了一种柔性金属管，其中在帘布层上施加了一层弹性体层和在其上施加了一层可收缩聚合物的层；除了大量其它可能性而外，为此也提及了PEEK。
在WO 2005/028198中描述了无粘结柔性管，其中该管由一层较厚的聚合物层和一层较薄的具有屏障功能的膜组成。用于该较厚的聚合物层和所述膜的材料由两个广泛一致的清单给出；所述膜此外可以由金属构成。在两个清单中均提及了PEEK、PEKK和聚亚苯基硫醚（PPS）。
US 5
934 335的管道包含一层可由PFA构成的层。但是，PFA在较高温度下强烈蠕变并且根据压力方向填充帘布层的铰链区域或向外相邻的增强层之间的间隙，这显著减小了管道的柔性。此外，在变形的区域中形成了可导致内增强层毁坏的应力开裂。因此，US 5
934 335建议用弹性体填充帘布层的间隙。
本发明的目的在于，提供在较高的例如高于130℃温度下稳定的内衬，并且此外，管道的柔性未过多减少。
该目的通过具有包含下述层的内衬的柔性管得以实现：
a）至少一层由模塑料构成其材料的层，所述模塑料基于选自下列的聚合物：
- 聚亚芳基醚酮，
- 聚苯砜
- 聚亚苯基硫醚
- 聚亚芳基醚酮/聚亚苯基硫醚共混物和
- 半芳族聚酰胺，其5-100 mol%的二元羧酸比例源自具有8-22个C-原子的芳族二元羧酸且其具有至少260℃，优选至少270℃和特别优选至少280℃的微晶熔点Tm，该微晶熔点根据ISO
11357在第二次加热时测定；
b）至少一层由含氟聚合物-模塑料构成其材料的层。
在最简单的情况中，该内衬是双层的，但优选是具有层顺序a/b/a的三层的。但此外，其也可以还包含另外的层。
在包含帘布层的无粘结柔性管的情况中，内衬的最内层优选是根据a）的层；然后向外接着是根据b）的层和随后任选还是根据a）的层。
在不包含帘布层的无粘结柔性管的情况中，内衬的最内层可以是根据b）的层；然后向外紧邻的是根据a）的层。但这里优选在层b）的两侧分别具有一层根据a）的层，因为借此保护了根据b）的层的材料不受所输送的介质的损害。以此有效地预防了例如起泡。
在所述三层的夹心结构的情况下，两层根据a）的层可以由不同的材料构成。例如，外面的根据a）的层由较便宜的聚酰胺或聚亚苯基硫醚构成，而里面的根据a）的层由聚亚芳基醚酮、聚亚苯基硫醚或一种聚亚芳基醚酮/聚亚苯基硫醚-共混物构成。
可以将所述各层通过增粘剂彼此粘接；合适的增粘剂是本领域技术人员已知的。一定的初始粘附使无粘合柔性管的制造变得容易；但是，对运行而言，层的粘附不是绝对必须的。如果在运行过程中气体要聚集在无粘合层之间，可将它们借助于合适的构造措施导出。但是，在该优选的实施方式中，如果将根据b）的层布置在内侧，则可以显著减少气体的聚集。
在一个可能的实施方式中，在内衬的内侧上具有帘布层。这种帘布层及其设计是现有技术。在另一个可能的实施方式中，该无粘结柔性管不包含帘布层，特别是它不应在高的外部压力下运行时。
此外，该无粘合柔性管在内衬的外侧上包含一个或多个通常由螺旋状布置的钢丝、钢型材或钢带构成的增强层。这些增强层的设计是现有技术。优选如此构造这些增强层的至少一个，使得其耐受内压，并如此构造这些增强层中的至少另一个增强层，以使其耐受拉伸力。在所述一个或多个增强层上可连接一个通常以热塑性模塑料或弹性体的管道或软管形式的外部套管。
根据a）的层的聚亚芳基醚酮包含下式的单元
(-Ar-X-)和(-Ar’-Y-),
其中Ar 和 Ar’是二价的芳族残基，优选1,4-亚苯基、4,4’-亚联苯基以及1,4-、1,5-或2,6-亚萘基。X是吸电子基团，优选羰基或磺酰基，而Y是另外的基团如O、S、CH2、异亚丙基等。这里，基团X的至少50%, 优选至少70%和特别优选至少80%是羰基，而基团Y的至少50%, 优选至少70%和特别优选至少80%由氧构成。
在一个优选的实施方式中，基团X 100%由羰基构成，且基团Y
100%由氧构成。在该实施方式中，所述聚亚芳基醚酮例如可以是聚醚醚酮（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），但是羰基和氧基的其它排布当然也是可能的。
所述聚亚芳基醚酮是半晶质的，这例如在DSC分析中由找到微晶熔点Tm表现出来，该熔点在大多数情况下位于数量级300℃或以上。
聚亚苯基硫醚（PPSU）例如以商品名Radel® 由Solvay
Advanced Polymers生产。它可以由4,4’-二羟基联苯和4,4’-二氯二苯砜通过亲核取代来制备。
所述聚亚苯基硫醚包含下式的单元
(-C6H4-S-);
其优选至少50重量%，至少70重量%或至少90重量%由该单元构成。剩余的单元可以是如其在上述聚亚芳基醚酮的情况中给出的那些，或者是三-或四官能的分支单元，所述分支单元由合成时伴随使用例如三氯苯或四氯苯产生。聚亚苯基硫醚以多种类型或模塑料商购可得。
在聚亚芳基醚酮/聚亚苯基硫醚-共混物的情况中，两种组分可以以任意可能的混合比例存在，因此该组成完整地覆盖了从纯聚亚芳基醚酮到纯聚亚苯基硫醚的范围。通常，该共混物包含至少0.01重量%聚亚芳基醚酮和至少0.01重量%聚亚苯基硫醚。在一个优选的实施方案中，该共混物包含至少50重量%聚亚芳基醚酮。
所述聚酰胺可由二胺和二元羧酸的组合，任选使用ω-氨基羧酸或相应的内酰胺来制备。合适的类型例如是PA66/6T、PA6/6T、PA6T/MPMDT (MPMD表示 2-甲基戊亚甲基二胺)、PA9T、PA10T、PA11T、PA12T、PA14T以及这些后面的类型与脂族二胺和脂族二元羧酸或者与ω-氨基羧酸或内酰胺的共缩聚物。
根据a）的层的模塑料可以包含常规的助剂和添加剂以及任选另外的聚合物，在聚亚芳基醚酮的情况中例如包含含氟聚合物如PFA（四氟乙烯和全氟乙烯基甲基醚的共聚物）、聚亚胺、聚醚亚胺，LCP例如液晶聚酯、聚砜、聚醚砜、聚苯砜、聚苯并咪唑(PBI)或其它耐高温的聚合物，在聚亚苯基硫醚的情况中例如包含乙烯与极性共聚单体的共聚物或三元聚合物，和在半芳族聚酰胺的情况中包含脂族聚酰胺和/或冲击改性剂。聚酰胺模塑料例如也可以包含水解稳定剂。在该模塑料中聚亚芳基醚酮、聚亚苯基硫醚、聚亚芳基醚酮/聚亚苯基硫醚-共混物或半芳族聚酰胺所占比例为至少50重量%，优选至少60重量%，特别优选至少70重量%，尤其优选至少80重量%和最特别优选至少90重量%。
根据b)的层的含氟聚合物可以例如是聚偏二氟乙烯（PVDF）、乙烯-四氟乙烯共聚物（ETFE），借助于一种第三组分（Terkomponente）例如丙烯、六氟丙烯、氟乙烯或偏二氟乙烯改性的ETFE（例如EFEP）、乙烯-氯三氟乙烯共聚物（E-CTFE）、聚氯三氟乙烯（PCTFE）、氯三氟乙烯-全氟烷基乙烯基醚-四氟乙烯共聚物（CPT）、四氟乙烯-六氟丙烯-偏二氟乙烯共聚物（THV）、四氟乙烯-六氟丙烯共聚物（FEP）或四氟乙烯-全氟烷基乙烯基醚共聚物（PFA）。基于偏二氟乙烯的共聚物也是合适的，该共聚物具有最高40重量%的另外的单体例如三氟乙烯、氯三氟乙烯、乙烯、丙烯和六氟丙烯。
根据b)的层的模塑料可包含常规助剂和添加剂。含氟聚合物的比例为至少50重量%，优选至少60重量%，特别优选至少70重量%，尤其优选至少80重量%，和最特别优选至少90重量%。
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，以及最大900 mm，最大800 mm，最大700 mm或最大620 mm；但是在某些情况下，其也可以更高或更低。内衬的总壁厚度通常为至少2 mm，至少2.5 mm，至少3 mm，至少4 mm或至少5 mm，以及最大50 mm，最大40 mm，最大30 mm，最大25 mm，最大20 mm或最大16 mm；在某些情况下，其也可以更高或更低。根据a）的层的厚度为0.1-10
mm和优选0.2-8 mm。
根据现有技术，通过共挤出、通过各层的缠绕挤出，或任选通过带的缠绕来制造内衬。
这种无粘结柔性管可以有利地在高于130℃至约200℃和可能更高的范围作业。通过使用根据a）的层减小了内衬材料蠕变进帘布层的铰链区域或向外紧邻的增强层的危险。因此保持了管道的柔性；在变形区域中没有出现会导致内衬毁坏的应力开裂的形成。
Claims (5)
1. 具有无粘结层的多层结构的柔性管，其具有包含下列层的内衬：
a）至少一层由基于选自下列的聚合物的模塑料构成其材料的层
- 聚亚芳基醚酮，
- 聚苯砜，
- 聚亚苯基硫醚，
- 聚亚芳基醚酮/聚亚苯基硫醚共混物和
- 半芳族聚酰胺，其5-100 mol%的二元羧酸比例源自具有8-22个C-原子的芳族二元羧酸且其具有至少260℃的微晶熔点Tm，该微晶熔点根据ISO 11357在第二次加热时测定；
b）至少一层由含氟聚合物-模塑料构成其材料的层。
2. 根据权利要求1所述的柔性管，
其特征在于，
所述内衬是双层的。
3. 根据权利要求1所述的柔性管，
其特征在于，
所述内衬是具有层顺序a/b/a的三层的。
4. 根据前述权利要求之一所述的柔性管，
其特征在于，
所述内衬是管道。
5. 根据前述权利要求之一所述的柔性管，
其特征在于，
除内衬而外，其包含一个或多个层，它们选自
- 内置的帘布层，
- 一个或多个外置的增强层和
- 外部套管。
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| PCT/EP2011/054773 WO2011128201A1 (de) | 2010-04-13 | 2011-03-29 | Flexibles rohr mit höherer temperaturbeständigkeit |
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| DE102007040683A1 (de) | 2007-08-29 | 2009-03-05 | Evonik Degussa Gmbh | Umhüllte Rohrleitung |
| DE102008001678A1 (de) | 2007-10-17 | 2009-04-23 | Evonik Degussa Gmbh | Verwendung einer Polyamidformmasse zur Auskleidung von Rohrleitungen |
| DE102008044225A1 (de) | 2008-12-01 | 2010-06-02 | Evonik Degussa Gmbh | Verfahren zur Herstellung einer Formmasse oder eines Formteils mit erhöhter Schmelzesteifigkeit |
| DE102008044224A1 (de) | 2008-12-01 | 2010-06-02 | Evonik Degussa Gmbh | Verwendung einer Zusammensetzung für den Kontakt mit überkritischen Medien |
| US8476354B2 (en) * | 2008-12-23 | 2013-07-02 | E I Du Pont De Nemours And Company | Low sink marks and excellent surface appearance reinforced polyamide compositions |
| DE102009001001A1 (de) | 2009-02-19 | 2010-09-02 | Evonik Degussa Gmbh | Verwendung eines Leitungsrohrs zur Herstellung einer im Wasser verlegten Rohrleitung |
| DE102009045882A1 (de) | 2009-10-21 | 2011-04-28 | Evonik Degussa Gmbh | Erdwärmesonde für eine geotherme Wärmepumpe |
| DE102011017811A1 (de) | 2011-04-29 | 2012-10-31 | Evonik Degussa Gmbh | Temperierbare Rohrleitung für Offshoreanwendungen |
| DE102011075383A1 (de) | 2011-05-06 | 2012-11-08 | Evonik Degussa Gmbh | Temperierbare Rohrleitung für Offshoreanwendungen |
| DE102011090092A1 (de) | 2011-12-29 | 2013-07-04 | Evonik Degussa Gmbh | Verfahren zur Herstellung eines Formteils aus einer Polyamidformmasse mit verbesserter Hydrolysebeständigkeit |
-
2010
- 2010-04-13 DE DE102010003920A patent/DE102010003920A1/de not_active Ceased
-
2011
- 2011-03-29 CN CN201180018776.0A patent/CN102821939B/zh active Active
- 2011-03-29 WO PCT/EP2011/054773 patent/WO2011128201A1/de active Application Filing
- 2011-03-29 JP JP2013504194A patent/JP6095566B2/ja active Active
- 2011-03-29 BR BR112012026129-0A patent/BR112012026129B1/pt active IP Right Grant
- 2011-03-29 ES ES11713997.2T patent/ES2544634T3/es active Active
- 2011-03-29 US US13/639,765 patent/US11504939B2/en active Active
- 2011-03-29 EP EP11713997.2A patent/EP2558286B1/de active Active
- 2011-03-29 RU RU2012147900/05A patent/RU2012147900A/ru not_active Application Discontinuation
- 2011-03-29 CA CA2793593A patent/CA2793593C/en active Active
- 2011-04-13 AR ARP110101251A patent/AR081453A1/es not_active Application Discontinuation
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| WO1999067560A1 (en) * | 1998-06-22 | 1999-12-29 | Nkt Cables A/S | Unbonded flexible pipes and method for the production thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104595593A (zh) * | 2015-01-30 | 2015-05-06 | 柳州市二和汽车零部件有限公司 | 耐热耐腐蚀橡胶管 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102010003920A1 (de) | 2011-10-13 |
| BR112012026129B1 (pt) | 2020-01-07 |
| US20130025734A1 (en) | 2013-01-31 |
| US11504939B2 (en) | 2022-11-22 |
| WO2011128201A1 (de) | 2011-10-20 |
| CN102821939B (zh) | 2015-10-14 |
| RU2012147900A (ru) | 2014-05-20 |
| EP2558286A1 (de) | 2013-02-20 |
| JP2013524132A (ja) | 2013-06-17 |
| JP6095566B2 (ja) | 2017-03-15 |
| CA2793593A1 (en) | 2011-10-20 |
| ES2544634T3 (es) | 2015-09-02 |
| CA2793593C (en) | 2018-11-13 |
| BR112012026129A2 (pt) | 2016-06-28 |
| AR081453A1 (es) | 2012-09-05 |
| EP2558286B1 (de) | 2015-05-06 |
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Address after: Essen, Germany Patentee after: Evonik Operations Limited Address before: Essen, Germany Patentee before: EVONIK DEGUSSA GmbH |