AU2009248601B2 - Method of manufacturing a flexible tubular structure - Google Patents
Method of manufacturing a flexible tubular structure Download PDFInfo
- Publication number
- AU2009248601B2 AU2009248601B2 AU2009248601A AU2009248601A AU2009248601B2 AU 2009248601 B2 AU2009248601 B2 AU 2009248601B2 AU 2009248601 A AU2009248601 A AU 2009248601A AU 2009248601 A AU2009248601 A AU 2009248601A AU 2009248601 B2 AU2009248601 B2 AU 2009248601B2
- Authority
- AU
- Australia
- Prior art keywords
- polymer
- sheath
- thermoplastic
- thermoplastic elastomer
- tubular structure
- 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.)
- Active
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 81
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 51
- 239000004743 Polypropylene Substances 0.000 claims abstract description 28
- 239000000806 elastomer Substances 0.000 claims abstract description 28
- -1 polypropylene Polymers 0.000 claims abstract description 28
- 229920001155 polypropylene Polymers 0.000 claims abstract description 28
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 28
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 27
- 229920001971 elastomer Polymers 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims description 51
- 239000003795 chemical substances by application Substances 0.000 claims description 42
- 239000002667 nucleating agent Substances 0.000 claims description 35
- 230000003014 reinforcing effect Effects 0.000 claims description 22
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 20
- 238000001125 extrusion Methods 0.000 claims description 18
- 238000007789 sealing Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 229920001897 terpolymer Polymers 0.000 claims description 13
- 238000001192 hot extrusion Methods 0.000 claims description 11
- 229920000098 polyolefin Polymers 0.000 claims description 7
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims description 4
- BJRMDQLATQGMCQ-UHFFFAOYSA-N C=C.C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 Chemical compound C=C.C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 BJRMDQLATQGMCQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004073 vulcanization Methods 0.000 claims description 2
- 238000009472 formulation Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 9
- 239000012530 fluid Substances 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000009434 installation Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- KYQRDNYMKKJUTH-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,4-dicarboxylic acid Chemical group C1CC2(C(O)=O)C(C(=O)O)CC1C2 KYQRDNYMKKJUTH-UHFFFAOYSA-N 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920003031 santoprene Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical class C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000013020 final formulation Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
Classifications
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- 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
- F16L11/08—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
- F16L11/083—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 three or more layers
-
- 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
- F16L11/14—Hoses, i.e. flexible pipes made of rigid material, e.g. metal or hard plastics
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/13—Articles with a cross-section varying in the longitudinal direction, e.g. corrugated pipes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
- B29C48/34—Cross-head annular extrusion nozzles, i.e. for simultaneously receiving moulding material and the preform to be coated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2023/00—Tubular articles
- B29L2023/22—Tubes or pipes, i.e. rigid
-
- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
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- B32B2262/0269—Aromatic polyamide fibres
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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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/103—Metal fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2274/00—Thermoplastic elastomer material
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- 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
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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
- B32B2597/00—Tubular articles, e.g. hoses, pipes
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to a flexible tubular pipe (10) intended for offshore oil production and to its method of manufacture, said pipe comprising an impermeable internal duct and at least one sheet (20) made of a thermoplastic elastomer polymer of defined thickness around said internal duct (18). According to the invention said thermoplastic elastomer polymer comprises a polypropylene-based thermoplastic polymer and an elastomer based on an ethylene-propylene-diene terpolymer and it further includes a compatibilizer for increasing the miscibility between said polypropylene-based thermoplastic polymer and said elastomer based on an ethylene-propylene-diene terpolymer.
Description
WO 2009/141538 PCT/FR2009/000552 Method of Manufacturing a Flexible Tubular Structure The present invention relates to a method of manufacturing a flexible tubular structure of great 5 length intended to transport fluids for offshore oil production, and to the structure obtained according to said method. It more particularly concerns certain sheaths of the 10 structure, which are made of polymer material. In the present application, the term "flexible tubular structure" refers both to flexible subsea pipes and subsea umbilicals, as well as flexible tubular 15 structures combining the functions of flexible pipes and subsea umbilicals. Flexible subsea pipes are essentially used to transport the oil or gas extracted from an offshore deposit. They 20 can also be used to transport pressurized seawater intended to be injected into the deposit in order to increase the production of hydrocarbons. These flexible pipes are formed by a set of different 25 layers, each intended to allow the pipe to withstand the stresses of offshore service or installation. These layers comprise in particular polymeric sheaths and reinforcing layers formed by windings of shaped metal wires, hoops or filaments made of composite material. 30 The flexible tubular pipes generally comprise, from the inside outward, at least one internal sealing tube intended to convey the transported fluid, reinforcing layers around the internal tube and an external 35 polymeric protective sheath around the reinforcing layers. The internal sealing tube generally consists of a polymeric material, and in this case it may equally be referred to by the term "internal sealing sheath" or "pressure sheath". There are, however, flexible subsea WO 2009/141538 - 2 - PCT/FR2009/000552 pipes in which the internal sealing tube is a thin walled corrugated metal tube, such as those described in the document W098/25063. In certain cases, an intermediate polymeric sheath is also provided between 5 the internal sealing tube and the external protective sheath, for example between two reinforcing layers. The flexible pipe may furthermore comprise a thermal insulation layer arranged between the reinforcing 10 layers and the external protective sheath. This thermal insulation layer is generally made by helicoid winding of syntactic foam strips. Such flexible pipes are described in the 15 standardization documents published by the American Petroleum Institute (API), API 17J "Specification for Unbonded Flexible Pipe" and API RP 17B "Recommended Practice for Flexible Pipe". 20 Subsea umbilicals are mainly used to transport fluids, power and signals to subsea equipment, for example valves, wellheads, collectors, pumps or separators, with a view to supplying power and monitoring and remote controlling the actuators of these items of 25 equipment. The fluids transported for these applications are generally hydraulic control oils. Subsea umbilicals may also be used to transport various fluids intended to be injected into a main hydrocarbon transport pipe, with a view either to facilitating the 30 flow of said hydrocarbon, for example by injecting chemical agents aiming to prevent the formation of hydrate plugs, or methane so as to make it easier for the oil to rise to the surface ("gas lift" method), or to ensure maintenance of said main pipe, for example by 35 injecting corrosion inhibitors. A subsea umbilical consists of an assembly of one or more internal sealing tubes, and optionally electrical WO 2009/141538 - 3 - PCT/FR2009/000552 cables and/or fiber-optic cables, said assembly being made by helicoid or S/Z winding of said tubes and cables so that the umbilical is flexible; said assembly may be surrounded by reinforcing layers and an external 5 polymeric protective sheath. These internal sealing tubes, the function of which is to transport the aforementioned fluids, generally have a diameter very much less than the external diameter of the umbilical. An internal sealing tube of an umbilical generally 10 consists of either a metal sealing tube or an impermeable polymeric tube surrounded by one or more reinforcing layers. Such subsea umbilicals are described in the 15 standardization documents published by the American Petroleum Institute (API), API 17E "Specification for Subsea Umbilicals". The document US6102077 discloses a flexible tubular 20 structure combining the functions of a flexible subsea pipe and a subsea umbilical. At its center, the structure comprises a flexible pipe with a large diameter used to transport hydrocarbons, said central flexible pipe being surrounded by a plurality of 25 peripheral tubes with a small diameter assembled helicoidally or in S/Z fashion around the central flexible pipe, said peripheral tubes being used for functions similar to those of umbilicals, in particular hydraulic control or injection of fluids. Such flexible 30 tubular structures are known to the person skilled in the art by the names "Integrated Subsea Umbilical" and "Integrated Production Bundle". These structures with a large diameter are generally surrounded by an external polymeric sheath. 35 In the present application, the term "internal sealing tube" covers equally the internal polymeric sheath or the pressure sheath of a flexible subsea pipe or the WO 2009/141538 - 4 - PCT/FR2009/000552 metal or polymeric fluid transport tubes of a subsea umbilical. The term "impermeable internal pipe" in turn refers to a part of the flexible tubular structure assembly, said part comprising at least one internal 5 sealing tube. These definitions also apply to flexible tubular structures combining the functions of a flexible subsea pipe and a subsea umbilical. The document W003083344 in the name of the Applicant 10 teaches the use of a thermoplastic elastomer polymer (TEP) for producing the external sheath or the intermediate sheath of flexible subsea pipes. Specifically, these polymers are well suited to such applications while being less expensive than the 15 polyamides used in the past. These polymers are also naturally adapted for the production of external or intermediate polymeric sheaths of subsea umbilicals, or flexible tubular structures combining the functions of a flexible subsea pipe and a subsea umbilical. 20 The methods for producing these tubular pipes are well known; in the case of the aforementioned sheaths made of polymer material, and more precisely the outer sheath for the intermediate sheath, they are extruded 25 directly around the reinforcing layers of the pipe. Thus, the first step is to surround the internal pressure sheath with at least one traction-resistant layer and most often with at least one other pressure resistant layer. The next step is to hot-extrude a 30 softened layer of a thermoplastic elastomer polymer, including an olefin polymer mixed with an elastomer, and finally said layer is cooled in order to obtain at least one second polymeric sheath with a determined thickness around the reinforcing layers. The extrusion 35 is carried out by means of an extruder equipped with a crosshead.
WO 2009/141538 - 5 - PCT/FR2009/000552 Until now, these polymeric sheaths have had a relatively small thickness, typically less than 10 mm, and the method of using the aforementioned thermoplastic elastomer polymer has in fact made it 5 possible to obtain economical sheaths offering good mechanical strength. However, owing to the increase in water depths and the outer diameter of the flexible tubular structure, as well as thermal insulation requirements, attempts are quite naturally being made 10 to increase in particular the thickness of the thermoplastic elastomer polymer sheaths. Unfortunately, it has been found that, overall, the mechanical properties of the thermoplastic elastomer sheaths then obtained with a large thickness are unsatisfactory. In 15 particular, the elongation at break of the thermoplastic elastomer sheaths produced according to the previous method tends to decrease greatly when the thickness of the sheath is more than 15 mm, which has the drawback of increasing the minimum radius with 20 which the flexible pipe can be bent without the risk of tearing said thick sheaths. The document EP1619218 teaches a solution aiming to solve this problem. This solution consists principally 25 in adding a nucleating agent to the thermoplastic elastomer polymer, and furthermore in taking care of the extruded sheath so that it does not have too great a hardness. However, the only test results presented on page 9 of this document relate to samples of extruded 30 strips with a thickness of 2 mm, that is to say a small thickness, and therefore pertain to cases not representative of those in which the aforementioned problem arises. Furthermore, the author deduces from these nonrepresentative tests that this solution would 35 make it possible to solve the fragility problem of external sheaths with a thickness of more than 5 mm, or 10 mm or even 15 mm. However, the Applicant has carried out full-scale tests on this solution and found that H:\txb\lnterwoven\NRPortb\DCC\TXB\5138872_ .doc - 13/5/13 -6 the elongations at break of the thick external sheaths produced in this way remain insufficient, so that the risk of said sheaths rupturing has not been overcome. Also, a technical problem which then arises, and which the 5 present invention aims to solve, is to provide a flexible tubular structure and a method for producing such a pipe, in which at least the external protective sheath or an intermediate sheath, made of thermoplastic elastomer polymer, withstands the working stresses of the structure 10 even though the thickness of the sheath is increased in comparison with the thickness of the sheaths produced according to the prior art. To this end, and according to a first aspect, the present invention provides a method of manufacturing a flexible 15 tubular structure intended for offshore oil production, said method being: an impermeable internal pipe and a thermoplastic elastomer polymer are first provided; a softened layer of said thermoplastic elastomer polymer is then formed by hot extrusion around said impermeable 20 internal pipe; next, said softened layer is cooled in order to obtain at least one polymeric sheath with a determined thickness around said impermeable internal pipe; furthermore, according to the invention said thermoplastic elastomer polymer comprises a thermoplastic polymer based 25 on polypropylene (PP) and an elastomer based on a terpolymer of ethylene-propylene-diene monomers (EPDM) and a compatibilizing agent is added to said thermoplastic elastomer polymer before said hot extrusion to increase the miscibility of said thermoplastic polymer and elastomer 30 during the extrusion, by which the WO 2009/141538 - 7 - PCT/FR2009/000552 elongation at break of said polymeric sheath is increased. Thus, one characteristic of the invention resides in 5 the use of a compatibilizing agent adapted to increase the stability of the thermoplastic polymer and the elastomer in one another during the extrusion, one being based on polypropylene (PP) and the other based on a terpolymer of ethylene-propylene-diene monomers 10 (EPDM) . In this way, it is found that the mechanical properties of the sheath are more homogeneous throughout its thickness. Also, such a sheath is less susceptible to tearing and more generally is stronger despite the more severe working conditions. 15 It has not previously been possible to observe such a benefit of the compatibilizing agent because the sheaths with a small thickness obtained according to the previous methods have had homogeneous mechanical 20 properties throughout their thickness. In fact, the use of a sheath with a large thickness, for example more than 15 mm, has brought to light a technical problem which did not arise in the past. Specifically, it has been discovered that the mechanical characteristics of 25 the thermoplastic elastomer polymer depend greatly on its cooling conditions after extrusion. Thus, the outermost sheath portions and consequently those which are cooled most rapidly, in air or in water after the formation of the softened layer of thermoplastic 30 elastomer polymer around the impermeable internal pipe, have superior mechanical characteristics compared with the sheath portions lying in the vicinity of said impermeable internal pipe. The latter sheath portions are quite clearly cooled more slowly. A correlation has 35 therefore been established between the cooling rate of the softened polymer and the mechanical properties obtained after cooling. Now, there is no economically viable industrial means of cooling the softened layer WO 2009/141538 - 8 - PCT/FR2009/000552 after extrusion homogeneously in its entire thickness. Since optical analysis shows the formation of large crystallites in the outer skin and small crystallites in the inner skin, an attempt was first made to 5 incorporate a nucleating agent in order to homogenize the crystalline structure. Against all expectation, however, this solution (moreover taught by the document EP1619218) has not made it possible to increase the mechanical properties of the sheath sufficiently, 10 despite homogenization of the crystalline structure. Also, and this is one of the advantages of the invention, it was then envisaged for the compatibilizing agent which allows better cohesion between the phases of the two types of polymer, and 15 consequently better mechanical strength of the cooled material, to be incorporated into the thermoplastic elastomer polymer before extrusion. This result is surprising because in the absence of the nucleating agent the extruded sheath has strong crystalline 20 heterogeneities, in particular when the thickness of said sheath is more than 10 mm, and these heterogeneities seem to be affected little by the presence of the compatibilizing agent. Furthermore, according to the prior art and in particular that 25 disclosed in EP1619218, it was thought that the fragility problem of these thick sheaths was essentially linked with too low a cooling rate after extrusion, this overly slow cooling causing excessive growth of the crystallites. The natural solution for 30 solving what was thought to be the main problem was therefore to add a nucleating agent. However, it was discovered after tests that this problem of crystallite size and heterogeneity is in fact secondary, and that another technical effect associated with another main 35 problem conditions the quality of the sheath, and that adding a compatibilizing agent makes it possible to solve this other main problem. This other main problem seems to be linked with the large thermal gradient in WO 2009/141538 - 9 - PCT/FR2009/000552 the thickness of the sheath during its cooling just after extrusion. This is because the cooling of the sheath at the extrusion output takes place mainly through the exterior, the heat essentially being 5 removed by the air of the workshop and by the water of the cooling tanks through which the pipe passes after it emerges from the extrusion head. In the case of a sheath with a large thickness, the thermal gradient resulting from this phenomenon has a large amplitude, 10 the external face of the sheath being cooled much more rapidly than its internal face. The molten polymer solidifies rapidly in the vicinity of the external face of the sheath, then the solidification front progresses toward the internal face with an increasingly slow 15 speed. In the mixture constituting the polymer of the sheath, the elastomer is in the state of solid nodules dispersed in a thermoplastic matrix of polypropylene, said matrix being in the molten state during the extrusion then solidifying progressively in the course 20 of cooling. During the radial progression of the solidification front, the solid EPDM nodules tend to be displaced radially in the sheath and become concentrated in the vicinity of the internal face of the sheath, that is to say the zone which solidifies 25 last. The reason for this displacement is not known, but it seems to be linked with the combination of the strong thermal gradient and the low cooling rate in the vicinity of the internal face. The result observed within the prior art solutions is a significant 30 difference in composition of the thermoplastic elastomer between the zones lying in the vicinity of the internal and external faces. In the case of a thick sheath according to the prior art, for example, respective polypropylene and EPDM concentrations by 35 mass of 70% and 5% have been observed in the vicinity of the external face, and 65% and 10% in the vicinity of the internal face, the polypropylene concentration dropping radially by 5% and the EPDM concentration WO 2009/141538 - 10 - PCT/FR2009/000552 increasing radially by the same order of magnitude. These chemical composition gradients do not of course on their own explain the reason for the problem, but they seem to constitute an indicator revealing another 5 underlying problem probably linked with the morphology and the structure of the polymer. Furthermore, it has been observed that adding a compatibilizing agent of the SEBS or polyolefin type makes it possible to significantly reduce this chemical composition gradient 10 in the thickness of the sheath, and that this reduction in the chemical composition gradient is accompanied by an improvement in the mechanical properties of the sheath, in particular its elongation at break. It seems that the presence of this compatibilizing agent has had 15 the effect of reducing the mobility of the EPDM nodules during the solidification phase, with the compatibilizing agent performing an anchoring role between the polypropylene molecules and the EPDM nodules. 20 Advantageously, a polymer selected from polymers based on polyolefin or styrene-ethylene-butadiene-styrene (SEBS) is provided as the compatibilizing agent. In this way, such a polymer, which has on the one hand 25 chemical functions or groups with an affinity for the elastomer and on the other hand chemical functions or groups with an affinity for the thermoplastic polymer, allows greater miscibility of the two types of polymer with one another when they are hot-extruded. 30 Advantageously, the selected styrene-ethylene butadiene-styrene is furthermore a nongrafted linear triblock polymer. Moreover, a nucleating agent is furthermore 35 advantageously provided and said nucleating agent, said compatibilizing agent, said thermoplastic polymer based on polypropylene and said elastomer based on a terpolymer of ethylene-propylene-diene monomers are WO 2009/141538 - 11 - PCT/FR2009/000552 mixed together before said hot extrusion in order to increase the crystallization rate of said polymers and subsequently homogenize the crystalline structure in the thickness of said softened layer, then the sheath. 5 The nucleating agents make it possible to initiate the crystallization reactions of the polymers by promoting the formation of the crystallites as soon as the polymer is softened, at a temperature lying above its glass transition temperature. It will be noted that the 10 cooling conditions of the thermoplastic elastomer polymer after extrusion directly influence the size and the density of the crystallized zones. However, the nucleating agent initiating the formation of the crystallites very quickly makes it possible to obtain a 15 relatively homogeneous distribution of these crystallized zones both in the thickness of the sheath and furthermore over the circumference of said sheath. It has also been observed that whenever there has been a compatibilizing agent, the addition of a nucleating 20 agent makes it possible to further increase the elongation at break performance even though the same nucleating agent, without the presence of a compatibilizing agent, leads to no improvement in the mechanical characteristics and in particular the 25 elongation at break. To our knowledge, this is the first time that this compatibilizing agent/nucleating agent synergy has been observed in the field of thick sheaths. 30 According to a particularly advantageous embodiment of the invention, a nucleating agent comprising a phosphate salt and/or a dicarboxylate salt is provided so as to obtain an even better distribution of the crystallized zones in the thickness of the sheath. 35 According to a preferred embodiment of the invention, a thermoplastic elastomer polymer comprising between 40% and 70% by weight of said thermoplastic polymer based WO 2009/141538 - 12 - PCT/FR2009/000552 on polypropylene, between 10% and 20% by weight of said elastomer based on a terpolymer of ethylene-propylene diene monomers, and between 1% and 20% by. weight of said compatibilizing agent, is provided. In this way, a 5 sheath is obtained whose mechanical properties, in particular the elongation at break, make it possible to avoid the risks of the sheath tearing. Specifically, as will be explained in more detail below, the material of the sheath obtained according to the aforementioned 10 method has an elongation at break of more than 200% irrespective of its position in the thickness of the sheath and irrespective of the value of this thickness, while the material of the sheaths obtained according to the prior art, and in the vicinity of the impermeable 15 internal pipe when the sheath has a thickness of between 15 and 20 mm, has an elongation at break of between 7% and 50% depending on its surface condition at the interface with the internal pipe. According to the prior art, under these conditions, when the 20 internal face of the sheath has a good surface condition, the elongation at break is of the order of 50%. Conversely, in the zones where the internal face of the sheath has indentations linked with the geometry of the underlying layer, the elongation at break may be 25 degraded and may drop to around 7%. However, when the flexible tubular structure is bent to its allowed minimum radius, the external polymeric sheath may experience an elongation of the order of 5% to 7% along the most greatly stretched generatrix. Thus, the 30 invention makes it possible to significantly increase the elongation at break and therefore move away from the risk zone. Furthermore, a thermoplastic elastomer polymer 35 comprising between 0.1% and 1% by weight of said nucleating agent is provided in order to initiate the crystallization reactions of the polymers when working with the polymer.
H:\txb\lnterwoven\NRPorth\DCC\TXB\5138872_ Idoc - 13/5/13 - 13 Advantageously, a softened layer of said thermoplastic elastomer polymer is formed by hot extrusion around said impermeable internal pipe so as to obtain a polymeric sheath with a thickness of more than 10 mm around said 5 impermeable internal pipe. By virtue of the compatibilizing agent as well as the nucleating agent, such a sheath has homogeneous mechanical characteristics in the thickness of the sheath obtained, even though the cooling rates of the extruded polymer layer are different. 10 According to a second aspect, the invention relates to a flexible tubular structure intended for offshore oil production, said flexible tubular structure comprising an impermeable internal pipe and at least one polymeric sheath with a determined thickness around said impermeable internal 15 pipe, said sheath being obtained by hot extruding a softened layer of a thermoplastic elastomer polymer around said impermeable internal pipe and by cooling said softened layer; according to the invention, said thermoplastic elastomer polymer comprises a thermoplastic polymer based on 20 polypropylene and an elastomer based on a terpolymer of ethylene-propylene-diene monomers, and that said thermoplastic elastomer polymer further comprises a compatibilizing agent added before said hot extrusion to increase the miscibility of said thermoplastic polymer and elastomer during the 25 extrusion, by which the elongation at break of said polymeric sheath is increased. Thus, one characteristic resides in the use of an agent compatibilizing with the thermoplastic polymer and the elastomer during the extrusion, so as to obtain a 30 thermoplastic elastomer polymer which, under the working conditions of pressure and temperature of the tubular structure, has uniform mechanical characteristics throughout the sheath so as to withstand the stresses which it experiences. Advantageously, said compatibilizing agent is 35 a (co)polymer selected from polymers based on polyolefin or - 14 styrene-ethylene-butadiene-styrene (SEBS). These polymers have the advantage of being widely produced in industry, and that they can be obtained at advantageous prices. Furthermore, said thermoplastic elastomer polymer 5 preferably comprises a nucleating agent intended to induce a homogeneous distribution of crystallites over said determined thickness during the cooling phase, and thus obtain spherolites distributed uniformly both in the thickness of the sheath and over the circumference of the 10 sheath. Advantageously, said nucleating agent comprises a phosphate salt and/or a dicarboxylate salt. According to an advantageous characteristic, said thermoplastic elastomer polymer comprises between 40% and 70% by weight of said thermoplastic polymer based on 15 polypropylene, between 10% and 20% by weight of said elastomer based on a terpolymer of ethylene-propylene-diene monomers, and between 1% and 20% by weight of said compatibilizing agent so as to obtain satisfactory mechanical properties and making it possible to avoid the risks of 20 tearing. Furthermore said thermoplastic elastomer polymer advantageously comprises between 0.1% and 1% by weight of nucleating agent. In addition, said polymeric sheath has a thickness of more than 10 mm around said impermeable internal pipe and it has identical mechanical properties at 25 all points. According to a particular embodiment of the invention, said impermeable internal pipe comprises, from the inside to the outside of said pipe, an internal WO 2009/141538 - 15 - PCT/FR2009/000552 polymeric sealing sheath and reinforcing filaments wound around said internal polymeric sealing sheath in order to form at least one reinforcing layer. A flexible tubular pipe commonly used for the offshore 5 transport of hydrocarbons is thus produced. In the present application, the term reinforcing filament equally covers metal wires or filaments of composite material, for example based on glass or carbon fibers, and woven strips or reinforcing cables made of metallic 10 material or of high-strength fiber, for example of the aramid type. Other features and advantages of the invention will become apparent on reading the following description of 15 a particular embodiment of the invention, given by way of indication but without implying limitation and with reference to the appended drawings, in which: - figure 1 is a partial schematic view in perspective 20 and cutaway of a flexible tubular pipe obtained by the method according to the invention, and - figure 2 is a schematic perspective view of an installation for carrying out the method according to 25 the invention. Figure 1 partially illustrates a flexible tubular structure 10, which will be described first before describing its production method for which protection 30 is also sought. This tubular structure is a pipe intended especially for the transport of hydrocarbons and it has, from the inside outward, an impermeable internal pressure sheath 12 inside of which a hydrocarbon can flow. This internal pressure sheath 12 35 is surrounded by an armor layer 14 formed by a short pitch winding of a shaped metal wire which is clamped and intended to take up the internal pressure forces with the internal sheath 12. Around the armor layer 14, WO 2009/141538 - 16 - PCT/FR2009/000552 two layers of tensile armor 16, 18 are wound with a long pitch, these being intended to take up the longitudinal tensile forces to which the pipe is subjected. These two layers of tensile armor 16, 18 5 wound around the armor layer, itself lying around the internal pressure sheath, together constitute the impermeable internal pipe. Lastly, the flexible tubular pipe 10 has an external protective sheath 20 intended to protect the aforementioned reinforcing layers 14, 10 16, 18. The subject matter of the invention more precisely relates to this external protective sheath 20. It will, however, be noted that an intermediate sheath of the same type may be inserted between the reinforcing layers 14, 16, 18, and that it can be 15 produced with the same polymeric materials and according to the same manufacturing method as will be described below. Referring to figure 2, the installation making it 20 possible to manufacture a flexible tubular pipe of the aforementioned type, and more particularly the external protective sheath 20, will be described first. Thus, the installation schematically comprises an 25 extruder 22 having a drive screw 24, which comprises a loading hopper 26 at one of its ends and the injection nozzle 28 at the other of its ends. Unlike extruders equipped with an injection mold, the extruder 22 presented here has a crosshead 30 adapted for a pipe 32 30 being manufactured to pass through it and adapted to be connected to the injection nozzle 28. The pipe is moved from the upstream end 31 of the crosshead 30 to its downstream end 35. Conventionally, the polymers in the form of granules are introduced into the loading hopper 35 26 and they are heated and softened inside the drive screw 24 and driven in molten form through the crosshead 30, which is adapted to form a cylindrical layer 33 of softened polymer over the outermost H:\txb\lnterwovcn\NRPortb\DCC\TXB\5138872 I.doc - 13/5113 - 17 reinforcing layer 18 of the pipe 32 being manufactured. This layer of polymer has a thickness of more than 15 mm. Beyond the downstream end 35 of the crosshead 30, the pipe coated with the cylindrical layer 33 of softened polymer is 5 then cooled, either in air or by passing through a water bath. However, the change from the extrusion temperature, which is more than the glass transition temperature of the polymer and close to the melting temperature, to room temperature is not instantaneous. Thus, as soon as the 10 layer starts to pass through the cooling zone, a radial thermal gradient is set up in the thickness of the external sheath, the outside being colder than the inside. Quite clearly, this gradient disappears after a certain length of time. 15 Thus, the thermoplastic elastomer polymer used for forming the aforementioned external sheath comprises a first mixture including a vulcanized elastomer based on a terpolymer of ethylene-propylene-diene monomers (EPDM) and a thermoplastic polymer based on polypropylene (PP). 20 Advantageously, this first mixture has been manufactured by a dynamic vulcanization method making it possible to obtain a crosslinked elastomer phase distributed in the form of fine particles dispersed in the matrix of the thermoplastic polymer. The mechanical properties of the sheath 20 are 25 improved in this way. This method, which is known to the person skilled in the art, is described particularly in US3037954. This first mixture comprises, by weight, about 60% of thermoplastic polymer and 15% of elastomer. The formulation of this first mixture also includes plasticizers 30 and fillers. It will be noted that this first mixture is marketed in particular under the brand "Santoprene 203-50" by "ExxonMobil"O. Santoprene is a registered trade mark.
- 18 A second mixture including a compatibilizing agent, in the case in point styrene-ethylene-butadiene-styrene (SEBS), is incorporated into this first mixture. The selected SEBS is advantageously a linear triblock copolymer based on styrene 5 and ethylene-butadiene, marketed under the brand "Kraton* G-1650" by "Kraton Polymers"O. This second mixture is generally referred to as a master batch. This second mixture may also include a nucleating agent comprising a phosphate salt or a dicarboxylate salt. For example, this 10 nucleating agent is a bicyclo[2.2.1]heptane dicarboxylate salt. The latter is marketed by "Milliken"* under the reference "HPN-68". Thus, according to a preferred embodiment, a second mixture including, by weight, 46% of compatibilizing agent in the form of a styrene-ethylene 15 butadiene-styrene and 8% of nucleating agent, the bicyclo[2.2.1]heptane dicarboxylate salt, is provided. The first mixture and the second mixture are then mixed together in a ratio of 100 parts by weight of the first mixture to 8 parts of the second mixture, in order to form 20 a third mixture. This operation may be carried out automatically upstream of the extruder with the aid of a known device known as a gravimetric mixing doser. The first and second mixtures are provided in the form of granules which feed the two inlets of the mixing doser, said mixing 25 doser providing a homogeneous mixture of granules in the desired proportions at its outlet. The outlet of the mixing doser is directly connected to the reception part of the ext ruder. Thus, the compatibilizing agent, in the example given here 30 the styrene-ethylene-butadiene-styrene (SEBS), will make it possible to increase the ability of the thermoplastic polymer based on polypropylene and the elastomer when the two polymers are melted together. In WO 2009/141538 - 19 - PCT/FR2009/000552 fact, these two categories of polymer are not very miscible in one another when they are molten. In this way, the first and second mixtures together 5 constitute a third mixture incorporating 55.5% of thermoplastic polymer based on polypropylene, 14% of a terpolymer of ethylene-propylene-diene monomers, 3.4% of compatibilizing agent, i.e. the styrene-ethylene butadiene-styrene, and 0.6% of nucleating agent, i.e. 10 the bicyclo[2.2.1]heptane dicarboxylate salt. It will be noted that the aforementioned formulation is an advantageous formulation, but that other formulations could be suitable. Also, the thermoplastic 15 polymer composition is preferably between 40% and 70% by weight of the total formulation. As regards the elastomer, it is between 10% and 20%. The compatibilizing agent is for its part between 1% and 20%. The nucleating agent, if it is incorporated into 20 the thermoplastic elastomer, is between 0.1% and 1%. Quite clearly, the formulation also comprises conventional and well-known additives such as a thermal stabilizer, antioxidant, anti-UV, fillers or 25 plasticizers. Thus, the third mixture, or final formulation, which is in the form of a mixture of granules, is introduced into the reception hopper 26 of the installation 30 represented in figure 2. In this way, a softened and homogeneous layer of the third mixture is formed by hot extrusion around the outermost reinforcing layer, then this layer is cooled in order to obtain a polymeric sheath with a determined thickness around the 35 reinforcing layer. Tests were carried out in order to verify the performance of this sheath and compare its properties WO 2009/141538 - 20 - PCT/FR2009/000552 with those of sheaths produced according to the prior art. These tests consisted in full-scale extrusion of an external sheath with a thickness varying between 10 mm and 20 mm around a flexible pipe core with a 5 diameter of the order of 225 mm. Said core comprises all the conventional layers of a flexible pipe, apart from the external sheath. Single-screw extruders with a diameter of 150 mm and 155 mm were used. The prior art solutions tested are on the one hand the mixture 10 polypropylene/EPDM without nucleating agent or compatibilizing agent, and on the other hand the mixture polypropylene/EPDM with a nucleating agent but without compatibilizing agent. The nucleating agent used was a bicyclo[2.2.1]heptane dicarboxylate salt 15 according to the teaching of EP1619218. Sheath samples were then taken and analyzed in the laboratory. It was first observed that the sheaths produced according to the present invention have 20 satisfactory mechanical characteristics, even when the thickness of the sheath is more than 15 mm. It would in theory be better to use the value of elongation at the threshold in order to class and select suitable materials, but threshold elongation measurements are 25 not reliable for these highly ductile polymers. Furthermore, it was established with the same sampling and test method that the sheaths produced according to the present invention have a greater elongation at break than those produced according to the prior art, 30 particularly in the case in which the sheath has a thickness of more than 15 mm, typically 20 mm, and when the traction test-pieces are taken in proximity to the internal face. In the most severe cases, the elongation at break of the material according to the present 35 invention may be more than two times greater than that of the materials according to the prior art.
WO 2009/141538 - 21 - PCT/FR2009/000552 In reality, by analyzing the aforementioned advantageous formulation in comparison with the formulations according to the prior art, a certain decline in the mechanical properties of the sheath 5 portions lying in the vicinity of the reinforcing layer was observed when the thickness of the sheath increases. Nevertheless, not only is the elongation at break of these sheath portions with the aforementioned advantageous formulation greater irrespective of the 10 thickness of the sheath, but furthermore the difference between the sheaths obtained from the two formulations increases with the thickness in favor of the sheath produced with the advantageous formulation. Thus, for a sheath with a thickness of 5 mm, the elongation at 15 break of the sheath portions lying in the vicinity of the reinforcing layer is 500% for the sheath obtained with the aforementioned advantageous formulation, and 450% for the sheath obtained with the formulation according to the prior art. When the thickness of the 20 sheath is 10 mm, these elongations are respectively 300% and 200%. When the thickness of the sheath is 20 mm, these elongations at break are respectively found to be 200% and 50%. Furthermore, the two aforementioned solutions of the prior art lead to elongations at break 25 of the same order of magnitude, and adding a nucleating agent does not seem to have a significant effect on the mechanical properties of the sheath, particularly in the case of thick sheaths. Thus, the elongation at break of the material according to the invention is at 30 least 200% in the thickness of the sheath for thicknesses of between 15 and 20 mm, which considerably improves the flexibility of the sheaths produced in this way. 35 Tests were also carried out under conditions similar to those described above, on the one hand using the mixture polypropylene/EPDM with compatibilizing agent but without nucleating agent, and on the other hand the WO 2009/141538 - 22 - PCT/FR2009/000552 mixture polypropylene/EPDM with compatibilizing agent and with nucleating agent. When the thickness of the sheath is 20 mm, the elongations at break are then respectively found to be 200% and 250%. Thus, owing to 5 the combination of a compatibilizing agent and a nucleating agent, the elongation at break of the material according to the invention is at least 250% in the thickness of the sheath, for thicknesses of between 15 and 20 mm, which considerably improves the 10 flexibility of the sheaths produced in this way. It was furthermore checked that the thickness measurement of the sheaths of thermoplastic elastomer material produced in this way could be carried out 15 precisely and reliably with conventional methods of nondestructive inspection by ultrasound echography, which has not always been the case with the thermoplastic elastomer polymers of the prior art. This is because in the sheaths with large thicknesses 20 produced according to the prior art, it was in fact difficult to obtain a reliable measurement of this thickness by these ultrasound methods because the propagation speed of the ultrasound was not homogeneous enough in the thickness of the sheath. Conversely, by 25 virtue of the new material according to the invention, on the one hand the propagation speed of the ultrasound is much more homogeneous in the thickness of the sheath, and on the other hand the ultrasound attenuation is greatly reduced, so that the measurement 30 by ultrasound echography is more reliable and more precise. This nondestructive inspection thus allows the thickness of the thermoplastic elastomer sheath to be measured continuously during the manufacture of the tubular structure. 35 According to another exemplary formulation, the compatibilizing agent was increased to 15% in the third mixture. It was then observed that the elongation at H:\txb\lnterwoven\NRPortbl\DCC\TXB\5138872_I.doc - 13/5/13 - 23 break properties of the sheath were increased. It will, however, be noted that conversely the thermal resistance of the sheath is substantially affected. Now, in certain applications it is necessary to maintain strong thermal 5 insulation properties of the flexible pipe. Thus, it has been shown that the formulation of the third mixture should advantageously include between 2% and 5% of compatibilizing agent based on styrene-ethylene-butadiene-styrene (SEBS). In this way, the thermal conductivity of the polymer of the 10 sheath thus obtained is less than 0.2 W/m.K., which allows the tubular flexible pipe produced in this way to be provided with good thermal insulation. Under other circumstances, a different compatibilizing agent may be incorporated into the formulation so as to 15 replace the polymer based on styrene-ethylene-butadiene styrene (SEBS), in particular a polymer based on polyolefin and more precisely polyethylene. For example, the polyethylene marketed under the brand "Exceed 1018CA"* by "Exxon"* has been used. This is a linear hexene copolymer 20 belonging to the family of linear low density polyethylenes (LLDPE). It was also checked that within the 20% by weight limit of the formulation, the more the proportion of this compatibilizing agent is increased, the more the mechanical 25 properties and in particular the elongation of the polymer of the sheath obtained are improved. According to a particular embodiment of the invention, a tubular structure of the umbilical type is produced. Thus, an internal sealing tube and electrical cables are 30 assembled. Said assembly is carried out by helicoid winding of the tubes and cables so that the umbilical is flexible. The assembly, which then forms an impermeable internal pipe, is surrounded by an external sealing sheath of thermoplastic elastomer polymer WO 2009/141538 - 24 - PCT/FR2009/000552 according to the method of the invention as described above.
Claims (16)
1. A method of manufacturing a flexible tubular structure intended for offshore oil production, said method being: - an impermeable internal pipe is provided; - a thermoplastic elastomer polymer is provided; - a softened layer of said thermoplastic elastomer polymer is formed by hot extrusion around said impermeable internal pipe; - said softened layer is cooled in order to obtain at least one polymeric sheath with a determined thickness around said impermeable internal pipe; characterized in that said thermoplastic elastomer polymer comprises a thermoplastic polymer based on polypropylene (PP) and an elastomer based on a terpolymer of ethylene-propylene diene monomers (EPDM), and in that a compatibilizing agent is added to said thermoplastic elastomer polymer before said hot extrusion to increase the miscibility of said thermoplastic polymer and elastomer during the extrusion, by which the elongation at break of said polymeric sheath is increased.
2. The method as claimed in claim 1, characterized in that a polymer selected from polymers based on polyolefin or styrene-ethylene-butadiene-styrene (SEBS) is provided as the compatibilizing agent.
3. The method as claimed in claim 1 or 2, characterized in that a nucleating agent is furthermore provided, and in that said nucleating agent, said compatibilizing agent, said thermoplastic polymer based on polypropylene and said elastomer based on a terpolymer of ethylene-propylene-diene monomers are mixed together before said hot extrusion. l.b\lntern oen\NRPonb\DCC\TXB5 138872 I.doc.3A)5/2013 - 26
4. The method as claimed in claim 3, characterized in that a nucleating agent comprising a phosphate salt and/or a dicarboxylate salt is provided.
5. The method as claimed in any one of claims 1 to 4, characterized in that a thermoplastic elastomer polymer comprising between 40% and 70% by weight of said thermoplastic polymer based on polypropylene, between 10% and 20% by weight of said elastomer based on a terpolymer of ethylene-propylene diene, and between 1% and 20% by weight of said compatibilizing agent, is provided.
6. The method as claimed in claims 3 or 4 and 5, characterized in that a thermoplastic elastomer polymer furthermore comprising between 0.1% and 1% by weight of nucleating agent is provided.
7. The method as claimed in any one of claims 1 to 6, characterized in that said thermoplastic elastomer polymer is obtained according to a dynamic vulcanization method.
8. The method as claimed in any one of claims 1 to 7, characterized in that a softened layer of said thermoplastic elastomer polymer is formed by hot extrusion around said impermeable internal pipe so as to obtain a polymeric sheath with a thickness of more than 10 mm around said impermeable internal pipe.
9. A flexible tubular structure intended for offshore oil production, said flexible tubular structure comprising an impermeable internal pipe and at least one polymeric sheath with a determined thickness around said impermeable internal pipe, said sheath being obtained by hot extruding a softened layer of a thermoplastic elastomer polymer around said impermeable internal pipe and by cooling said softened layer; H\~b\lmemven\NRPonrl\DCCTXB\$13872_ doc-13A5/201 3 - 27 characterized in that said thermoplastic elastomer polymer comprises a thermoplastic polymer based on polypropylene and an elastomer based on a terpolymer of ethylene-propylene-diene monomers, and that said thermoplastic elastomer polymer further comprises a compatibilizing agent added before said hot extrusion to increase the miscibility of said thermoplastic polymer and elastomer during the extrusion, by which the elongation at break of said polymeric sheath is increased.
10. The flexible tubular structure as claimed in claim 9, characterized in that said compatibilizing agent is a polymer selected from polymers based on polyolefin or styrene-ethylene butadiene-styrene (SEBS), or a mixture of these polymers.
11. The flexible tubular structure as claimed in claim 9 or 10, characterized in that said thermoplastic elastomer polymer comprises a nucleating agent intended to induce a homogeneous distribution of crystallites over said determined thickness.
12. The flexible tubular structure as claimed in claim 11, characterized in that said nucleating agent comprises a phosphate salt and/or a dicarboxylate salt.
13. The flexible tubular structure as claimed in any one of claims 9 to 12, characterized in that said thermoplastic elastomer polymer comprises between 40% and 70% by weight of said thermoplastic polymer based on polypropylene, between 10% and 20% by weight of said elastomer based on a terpolymer of ethylene-propylene-diene monomers, and between 1% and 20% by weight of said compatibilizing agent.
14. The flexible tubular structure as claimed in claims 11 or 12 and 13, characterized in that said thermoplastic IfH.ebmnerwn\NRPorbl\DCC\TXB\513R721 doc.13A3/2013 - 28 elastomer polymer furthermore comprises between 0.1% and 1% by weight of nucleating agent.
15. The flexible tubular structure as claimed in any one of claims 9 to 14, characterized in that said polymeric sheath has a thickness of more than 10 mm around said impermeable internal pipe.
16. The flexible tubular structure as claimed in any one of claims 9 to 15, characterized in that said impermeable internal pipe comprises, from the inside to the outside of said pipe, an internal polymeric sealing sheath and reinforcing filaments wound around said internal polymeric sealing sheath in order to form at least one reinforcing layer.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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FR0802569 | 2008-05-13 | ||
FR0802569A FR2931099B1 (en) | 2008-05-13 | 2008-05-13 | PROCESS FOR PRODUCING A FLEXIBLE TUBULAR STRUCTURE |
PCT/FR2009/000552 WO2009141538A2 (en) | 2008-05-13 | 2009-05-13 | Method of manufacturing a flexible tubular structure |
Publications (2)
Publication Number | Publication Date |
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AU2009248601A1 AU2009248601A1 (en) | 2009-11-26 |
AU2009248601B2 true AU2009248601B2 (en) | 2013-08-22 |
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AU2009248601A Active AU2009248601B2 (en) | 2008-05-13 | 2009-05-13 | Method of manufacturing a flexible tubular structure |
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AU (1) | AU2009248601B2 (en) |
BR (1) | BRPI0912199A2 (en) |
DK (1) | DK178345B1 (en) |
FR (2) | FR2931099B1 (en) |
GB (1) | GB2473357B (en) |
MY (1) | MY150383A (en) |
NO (1) | NO342067B1 (en) |
WO (1) | WO2009141538A2 (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
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FR2957293B1 (en) * | 2010-03-09 | 2012-03-09 | Technip France | EXTRUSION SYSTEM FOR A PLASTIC SHEATH |
EP3371502B1 (en) | 2015-11-03 | 2020-09-02 | National Oilwell Varco Denmark I/S | An unbonded flexible pipe |
FR3068104B1 (en) | 2017-06-22 | 2019-07-19 | Technip France | INSTALLATION FOR MANUFACTURING A REINFORCING STRUCTURE OF A FLEXIBLE CONDUIT, ASSOCIATED METHOD AND SYSTEM COMPRISING SAID INSTALLATION |
US11725098B2 (en) | 2017-12-18 | 2023-08-15 | Celanese International Corporation | Thermoplastic vulcanizate conduits for transporting hydrocarbon fluids |
WO2020068408A1 (en) * | 2018-09-24 | 2020-04-02 | Exxonmobil Chemical Patents Inc. | Thermoplastic blends and composites for flexible pipes |
Citations (3)
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WO1995023685A1 (en) * | 1994-03-04 | 1995-09-08 | Aeroquip Corporation | Composite and tie layer therefor |
WO2003078134A1 (en) * | 2002-03-20 | 2003-09-25 | Nkt Flexibles I/S | Process for the production of a polymer layer of a flexible offshore pipe and a flexible unbonded offshore pipe |
EP1619218A1 (en) * | 2004-07-14 | 2006-01-25 | Advanced Elastomer Systems, L.P. | Thermoplastic vulcanizates with enhanced cooling and articles made therefrom |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US6100334A (en) * | 1999-01-05 | 2000-08-08 | Advanced Elastomer Systems, L.P. | Thermoplastic vulcanizates from a cyclic olefin rubber, a polyolefin, and a compatiblizer |
US6465551B1 (en) * | 2001-03-24 | 2002-10-15 | Milliken & Company | Bicyclo[2.2.1]heptane dicarboxylate salts as polyolefin nucleators |
US20060116474A1 (en) * | 2002-10-07 | 2006-06-01 | Jarus David A | Compatibilized thermoplastic vulcanizate blends and their morphology as determined by atomic force microscopy |
-
2008
- 2008-05-13 FR FR0802569A patent/FR2931099B1/en not_active Expired - Fee Related
-
2009
- 2009-05-13 AU AU2009248601A patent/AU2009248601B2/en active Active
- 2009-05-13 WO PCT/FR2009/000552 patent/WO2009141538A2/en active Application Filing
- 2009-05-13 GB GB1018411.7A patent/GB2473357B/en active Active
- 2009-05-13 BR BRPI0912199A patent/BRPI0912199A2/en not_active Application Discontinuation
- 2009-05-13 FR FR0902307A patent/FR2931098B1/en active Active
- 2009-05-13 MY MYPI2010005184A patent/MY150383A/en unknown
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2010
- 2010-11-03 NO NO20101538A patent/NO342067B1/en unknown
- 2010-11-11 DK DK201070481A patent/DK178345B1/en active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995023685A1 (en) * | 1994-03-04 | 1995-09-08 | Aeroquip Corporation | Composite and tie layer therefor |
WO2003078134A1 (en) * | 2002-03-20 | 2003-09-25 | Nkt Flexibles I/S | Process for the production of a polymer layer of a flexible offshore pipe and a flexible unbonded offshore pipe |
EP1619218A1 (en) * | 2004-07-14 | 2006-01-25 | Advanced Elastomer Systems, L.P. | Thermoplastic vulcanizates with enhanced cooling and articles made therefrom |
Also Published As
Publication number | Publication date |
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WO2009141538A3 (en) | 2010-01-14 |
DK201070481A (en) | 2010-11-11 |
DK178345B1 (en) | 2015-12-21 |
FR2931099A1 (en) | 2009-11-20 |
BRPI0912199A2 (en) | 2015-10-06 |
MY150383A (en) | 2013-12-31 |
GB201018411D0 (en) | 2010-12-15 |
GB2473357B (en) | 2012-08-15 |
FR2931098B1 (en) | 2010-08-20 |
FR2931099B1 (en) | 2010-05-21 |
NO20101538A1 (en) | 2011-01-27 |
NO342067B1 (en) | 2018-03-19 |
GB2473357A (en) | 2011-03-09 |
AU2009248601A1 (en) | 2009-11-26 |
WO2009141538A2 (en) | 2009-11-26 |
FR2931098A1 (en) | 2009-11-20 |
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