WO2011055090A1 - Raidisseur pour conduite flexible - Google Patents
Raidisseur pour conduite flexible Download PDFInfo
- Publication number
- WO2011055090A1 WO2011055090A1 PCT/FR2010/052378 FR2010052378W WO2011055090A1 WO 2011055090 A1 WO2011055090 A1 WO 2011055090A1 FR 2010052378 W FR2010052378 W FR 2010052378W WO 2011055090 A1 WO2011055090 A1 WO 2011055090A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- stiffener
- diisocyanate
- prepolymer
- stiffener according
- polyamine
- Prior art date
Links
- 239000003351 stiffener Substances 0.000 title claims abstract description 68
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 229920000768 polyamine Polymers 0.000 claims abstract description 19
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 45
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 15
- 229920002635 polyurethane Polymers 0.000 claims description 11
- 239000004814 polyurethane Substances 0.000 claims description 11
- 229920005862 polyol Polymers 0.000 claims description 10
- 150000003077 polyols Chemical class 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- -1 isobutyl ester Chemical class 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 claims description 2
- VIOMIGLBMQVNLY-UHFFFAOYSA-N 4-[(4-amino-2-chloro-3,5-diethylphenyl)methyl]-3-chloro-2,6-diethylaniline Chemical compound CCC1=C(N)C(CC)=CC(CC=2C(=C(CC)C(N)=C(CC)C=2)Cl)=C1Cl VIOMIGLBMQVNLY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 2
- UQBRAHLFLCMLBA-UHFFFAOYSA-N N=C=O.N=C=O.CC1=CC=CC(C)=C1 Chemical compound N=C=O.N=C=O.CC1=CC=CC(C)=C1 UQBRAHLFLCMLBA-UHFFFAOYSA-N 0.000 claims 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims 1
- 229920003225 polyurethane elastomer Polymers 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- JIABEENURMZTTI-UHFFFAOYSA-N 1-isocyanato-2-[(2-isocyanatophenyl)methyl]benzene Chemical compound O=C=NC1=CC=CC=C1CC1=CC=CC=C1N=C=O JIABEENURMZTTI-UHFFFAOYSA-N 0.000 abstract 1
- 230000006870 function Effects 0.000 description 13
- 238000004132 cross linking Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000009434 installation Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- OHQOKJPHNPUMLN-UHFFFAOYSA-N n,n'-diphenylmethanediamine Chemical class C=1C=CC=CC=1NCNC1=CC=CC=C1 OHQOKJPHNPUMLN-UHFFFAOYSA-N 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- UPZSGWVELOYWER-UHFFFAOYSA-N 3,5-diamino-4-chlorobenzoic acid Chemical compound NC1=CC(C(O)=O)=CC(N)=C1Cl UPZSGWVELOYWER-UHFFFAOYSA-N 0.000 description 1
- 206010063493 Premature ageing Diseases 0.000 description 1
- 208000032038 Premature aging Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- F16L57/00—Protection of pipes or objects of similar shape against external or internal damage or wear
- F16L57/02—Protection of pipes or objects of similar shape against external or internal damage or wear against cracking or buckling
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B17/00—Drilling rods or pipes; Flexible drill strings; Kellies; Drill collars; Sucker rods; Cables; Casings; Tubings
- E21B17/01—Risers
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B19/00—Handling rods, casings, tubes or the like outside the borehole, e.g. in the derrick; Apparatus for feeding the rods or cables
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B19/00—Handling rods, casings, tubes or the like outside the borehole, e.g. in the derrick; Apparatus for feeding the rods or cables
- E21B19/002—Handling rods, casings, tubes or the like outside the borehole, e.g. in the derrick; Apparatus for feeding the rods or cables specially adapted for underwater drilling
- E21B19/004—Handling rods, casings, tubes or the like outside the borehole, e.g. in the derrick; Apparatus for feeding the rods or cables specially adapted for underwater drilling supporting a riser from a drilling or production platform
-
- 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
- F16L3/00—Supports for pipes, cables or protective tubing, e.g. hangers, holders, clamps, cleats, clips, brackets
- F16L3/01—Supports for pipes, cables or protective tubing, e.g. hangers, holders, clamps, cleats, clips, brackets for supporting or guiding the pipes, cables or protective tubing, between relatively movable points, e.g. movable channels
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/56—Means for preventing chafing or fracture of flexible leads at outlet from coupling part
Definitions
- the invention relates to a stiffener for flexible pipe.
- stiffeners are placed around the pipe at locations where the flexible pipe will undergo heavy stresses induced by the movements of the boat or swell.
- a stiffener consists of a molded plastic structure of conical shape having a length of a few meters and intended to surround the pipe.
- the flexible lines upstream of the fluids (eg hydrocarbons) from the wellhead are connected to the surface installation by passing through a steel guide tube which may be straight or bent, " tube “or” J-tube "respectively in English language.
- a steel guide tube which may be straight or bent, " tube "or” J-tube "respectively in English language.
- Several guide tubes are provided on the surface installation.
- the amplitude of the movements of the flexible pipe generated by the wave movements may cause an alteration of the structure of the flexible pipe in the vicinity of the guide tube for example.
- a stiffener surrounds the flexible pipe in the vicinity of the guide tube. The stiffener is then fixed to the end of the guide tube by a clamp in a known manner.
- the stiffener is usually located under the workstation of the surface installation, in a submerged or partially submerged environment.
- the stiffener undergoes many stresses of elongation and compression generated by the movements of surface installation and the flexible pipe under the effect of sea currents, wind and / or swell.
- the conditions experienced by the stiffener could lead to premature aging of the plastic in the long term which could adversely affect the integrity of the flexible pipe.
- the stiffeners are made from plastic having good characteristics of resistance to hydrolysis and elongation.
- a material that brings together the best features is polyurethane.
- a stiffener is manufactured for example from an Adiprene L167 TDI-polyether of 95 Shore A hardness. For a service life of 20 to 30 years, the maximum temperature of resistance to hydrolysis of material is 50 ° C.
- Classically manufactured stiffeners can be up to several meters long, with thicknesses greater than 200 mm and weighing up to 2 tonnes.
- the polyurethanes are chosen with relatively high hardness typically above 90 shore A.
- An object of the invention is to provide a stiffener which has an improved aging resistance of at least 10 ° C relative to the stiffener of the prior art, while ensuring a good homogeneity of mechanical properties.
- Another object of the invention is to allow the manufacture of a stiffener which has a higher hardness compared to the stiffener of the prior art, 60 shore D for example, while ensuring good homogeneity of mechanical properties.
- a polyurethane elastomer prepared from a prepolymer of diphenylmethane diisocyanate (MDI) and a chain extender selected from polyamines can be used for the manufacture of a stiffener.
- the stiffener thus manufactured then has an even higher resistance to aging compared to the known stiffener as well as improved processability. This improvement in processability allows the realization of a stiffener with higher hardness.
- the polyurethane elastomer is prepared from a prepolymer of diphenylmethane diisocyanate (MDI) and a methylenedianiline salt.
- MDI diphenylmethane diisocyanate
- methylenedianiline salt a methylenedianiline salt.
- This embodiment is particularly advantageous for cold-forming ("cold cast” according to English terminology) of the stiffener.
- the cold molding of the stiffener is particularly advantageous insofar as it does not require a very complex apparatus.
- FIG. 1 is a cross sectional view of a flexible pipe provided with a stiffener according to the invention.
- Figure 1 shows schematically a flexible pipe (10) provided with a stiffener (12).
- the flexible pipe is engaged through the guide tube (14) of the surface installation (not shown).
- the stiffener is located at the pipe so that when connecting the flexible pipe to the surface installation, the stiffener is at the mouth of the guide tube, thus protecting the flexible pipe from damage. during the movements of the boat.
- the stiffener is then fixed by a clamp (not shown) or any other known means around the end of the guide tube.
- the stiffener is made from a new polyurethane composition.
- the polyurethane used to make the stiffener is obtained from a prepolymer composition of diphenylmethane diisocyanate (MDI prepolymer). This prepolymer is then cross-linked with a polyamine to form the formable polyurethane elastomer composition to make the stiffener.
- MDI prepolymer diphenylmethane diisocyanate
- the polyurethane elastomer is thus prepared according to a two-step process. In a first step, an intermediate prepolymer is prepared by condensation of the alcohol functions of a polyol with the isocyanate functions of a polyisocyanate.
- the prepolymer and the crosslinking agent are preheated and mixed in a casting machine, then the mixture is injected into a preheated mold in the form of the stiffener, and finally this mold is kept in temperature in an oven during the duration of the crosslinking ..
- This manufacturing process makes it easier to control the characteristics of the final material which is advantageous when it comes to molding parts requiring large amounts of material as is the case with the stiffener.
- an intermediate prepolymer of diphenylmethane diisocyanate (MDI prepolymer) is synthesized.
- the MDI prepolymer is obtained by reacting a MDI diisocyanate at a temperature between 30 and 150 ° C. with a high molecular weight polyol of for example between 250 and 10,000 g. mol "1.
- the reaction temperature is for example between 30 and 150 ° C.
- the MDI diisocyanate used for the preparation of the MDI prepolymer is selected from 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate or 2,2'-diphenylmethane diisocyanate.
- an aliphatic diisocyanate may be added to the MDI prepolymer composition.
- the aliphatic diisocyanate is then selected from the group consisting of 1,1 '-methylene-bis- (4-isocyanatocyclohexane), 1,4-cyclohexane diisocyanate, isophorone diisocyanate (IPDI), 1,3-xylene diisocyanate hexamethylene diisocyanate and 1,1,4,4-tetramethylxylene diisocyanate or a mixture of one of these compounds.
- the high molecular weight polyol is chosen from the group of polyethers glyco! and polyesterglycol.
- the term "diphenylmethane diisocyanate prepolymer composition” is defined as a composition containing at least 80% of diphenylmethane diisocyanate prepolymer obtained by the reaction of at least one polyol and a diisocynate monomer. and may further comprise an amount of free MDI monomer or other solvent or plasticizer.
- the MDI prepolymer composition is then reacted with a crosslinking agent in a ratio of the order of the stoichiometry selected from polyamines and preferably aromatic polyamines.
- the polyamines are chosen from aromatic polyamines.
- the polyamine may be 4,4'-methylene-bis- (2-chloroaniline), 3,5-diamino-4-chlorobenzoic acid or isobutyl ester or 4,4'-methylenebis - (3-chloro-2,6-diethylaniline).
- the mixture of the prepolymer composition and the crosslinking agent is injected into a preheated mold having the conical shape typical of a stiffener. This mold is maintained in temperature in an oven during the duration of the crosslinking and finally the stiffener is removed from the mold.
- Patent Application EP 1950234 typically discloses a novel polyurethane elastomer that can be used to fabricate a stiffener according to the first embodiment of the invention.
- EP 19550234 discloses in fact a polyurethane elastomer obtained from a pre-polymer comprising diphenylmethane 2,4'-diisocyanate prepared according to a process which comprises the following steps: Reacting diphenylmethane diisocyanate (MDI) comprising more than 80% diphenylmethane 2,4'-diisocyanate with a high molecular weight polyol selected from the group of polyalkylene ether polyols having a molecular weight between 250 and 10,000 g .
- MDI diphenylmethane diisocyanate
- an aliphatic diisocyanate selected from 1,1'-methylenebis (4-isocyanatocyclohexane), 1,4-cyclohexane diisocyanate, isophorone diisocyanate (IPDI), 1,3 xylene diisocyanate, hexamethylene diisocyanate and 1,1,4,4-tetramethylxylene diisocyanate or a mixture of one of these compounds.
- the synthetic method disclosed in EP1950234 is a possible route of obtaining a polyurethane elastomer through the formation of a 2,4'MDI prepolymer composition, crosslinked by an aliphatic or aromatic polyamine and molded to hot to make a stiffener.
- patent application EP1950234 discloses a novel route of synthesis of polyurethane elastomers by reaction. of a composition containing an MDI prepolymer and a polyamine wherein the reaction parameters are controllable.
- the stiffeners prepared from a polyurethane elastomer synthesized by reacting a composition comprising an MDI prepolymer and a polyamine exhibit better hydrolysis resistance and fatigue resistance characteristics than the stiffeners made from the elastomers polyurethane of the prior art, while maintaining homogeneous mechanical properties in areas of high thickness, typically 100 mm to 500 mm.
- the characteristics of the material thus obtained make it possible to achieve a degree of integrity of between 50 Shore D and 70 Shore D while ensuring homogeneous properties within the material.
- Hardness measurements are carried out according to ISO 868 or ASTM D2240 ...
- the obtained material also has a resistance to hydrolysis up to 60 ° C for 30 years, or even 70 ° C for shorter durations, a resistance to fatigue increased by a factor of 2 to 10 depending on the conditions of use.
- the hydrolysis resistance measurements are carried out by tensile tests according to ASTM D638 on specimens having undergone accelerated aging in water, and by extrapolation by Arrhenius law.
- the diisocyanate prepolymer is crosslinked with a particular family of amines whose reactive amino functions are blocked in order to reduce their reactivity with respect to the MDI prepolymer.
- the polyurethane elastomer used to make the stiffener is obtained from a diphenylmethane diisocyanate prepolymer composition (MDI prepolymer) which is then crosslinked with a methylenedianiline (MDA) salt complex to form the elastomer composition. of polyurethane capable of being cold formed to make the stiffener.
- MDI prepolymer diphenylmethane diisocyanate prepolymer composition
- MDA methylenedianiline
- the filling of the mold can be done without the need to pre-heat the mold or even the reagents (except to ensure degassing) and that the crosslinking reaction does not occur during the filling of the mold.
- This allows a slow and controlled filling of the mold, thus avoiding bubble formation, the crosslinking being carried out in a second time during the temperature rise of the material introduced into the mold of the stiffener shape.
- the methylenedianiline salt is a polyamine whose amino functions are blocked in order to decrease the reactivity of the amine with respect to the MDI prepolymer at the time of crosslinking the MDI prepolymer composition and thus to be able to advantageously proceed to the cold molding of the stiffener ("cold cast" in English terminology).
- the amino functions of the MDA salt will be released by a controlled temperature rise to react with the MDI prepolymer composition.
- the progressive release of the amine functions of the MDA salt complex makes it possible to reduce the reactivity of the crosslinking agent and advantageously to implement a cold molding of the stiffener.
- the polyurethane elastomer is prepared according to a three-step process.
- an intermediate prepolymer composition is prepared by condensation of the alcohol functions of a polyol with the isocyanate functions of a polyisocyanate as previously described for the first embodiment of the invention.
- the MDI prepolymer and the MDA salt are mixed preheated around 70 ° C to ensure degassing of the mixture.
- the methylenedianiline salt (MDA) is advantageously the complex of Tris (4,4'-diaminodiphenylmethane), NaCl, obtained between methylene dianiline (MDA) and the salt of sodium chloride.
- this salt may comprise a plasticizer. It is for example proposed under the trademarks CAYTUR 31 TM and CAYTUR 31 -DA TM.
- the mixture is then injected into a mold in the form of a stiffener.
- the mold that has been preheated beforehand is introduced into an oven whose temperature rise is controlled.
- the temperature rise profile of the oven is adjusted to gradually release the amino functions of the MDA salt and crosslink the MDI prepolymer.
- the reaction time leading to the formation of the polyurethane elastomer is longer due to the controlled reactivity of the selected crosslinking agent.
- the stiffener made from the polyurethane elastomer obtained from a MDI prepolymer crosslinked with the methylenedianiline salt (MDA) has mechanical characteristics comparable to those obtained with the stiffener obtained according to the first embodiment. of the invention.
- Patent application WO2009108510 typically discloses a novel polyurethane elastomer that can be used to fabricate a stiffener by the cold molding technique according to the second embodiment of the invention. Also, the teaching of the patent application WO2009108510 is incorporated by reference to the patent application.
- WO2009108510 discloses a polyurethane elastomer composition obtained by reacting an MDI prepolymer and methylenedianiline complexed with a salt of sodium chloride whose mixture is stable over time for several days at the degassing temperature of 70 ° C .
- This mixture is then introduced into a mold in the form of a stiffener and heated to a crosslinking temperature to be determined between 1 and 130 ° C to release the blocked amines of the MDA complex and initiate the crosslinking reaction of the composition of the prepolymer of MDI.
- the crosslinking reaction is carried out under near stoichiometric conditions.
- the stiffener thus obtained has improved properties in a manner identical to that described for the first embodiment of the invention.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DKPA201270238A DK180014B1 (en) | 2009-11-03 | 2010-11-04 | Stiffener for a flexible pipe |
BR112012010421-7A BR112012010421B1 (pt) | 2009-11-03 | 2010-11-04 | enrijecedor para conduto flexível |
NO20120489A NO346686B1 (no) | 2009-11-03 | 2010-11-04 | Avstiver for et fleksibelt rør |
GB1207043.9A GB2487506B (en) | 2009-11-03 | 2010-11-04 | Stiffener for a flexible pipe |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0905254A FR2952118B1 (fr) | 2009-11-03 | 2009-11-03 | Raidisseur pour une conduite flexible |
FR0905254 | 2009-11-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011055090A1 true WO2011055090A1 (fr) | 2011-05-12 |
Family
ID=42144810
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2010/052378 WO2011055090A1 (fr) | 2009-11-03 | 2010-11-04 | Raidisseur pour conduite flexible |
Country Status (7)
Country | Link |
---|---|
BR (1) | BR112012010421B1 (fr) |
DK (1) | DK180014B1 (fr) |
FR (1) | FR2952118B1 (fr) |
GB (1) | GB2487506B (fr) |
MY (1) | MY161125A (fr) |
NO (1) | NO346686B1 (fr) |
WO (1) | WO2011055090A1 (fr) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014052331A2 (fr) * | 2012-09-26 | 2014-04-03 | Dow Global Technologies Llc | Raidisseur de coude en polyuréthane |
GB2519066A (en) * | 2013-09-02 | 2015-04-15 | Balmoral Comtec Ltd | Bend stiffener |
FR3020396B1 (fr) | 2014-04-25 | 2016-05-13 | Saipem Sa | Procede d'installation et mise en œuvre d'un tube rigide depuis un navire ou support flottant |
US11761563B2 (en) * | 2019-03-15 | 2023-09-19 | Gardner T. Baldwin | Reinforced hose end connector having a smooth surface inboard end length |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2671158A1 (fr) * | 1990-12-26 | 1992-07-03 | Coflexip | Raidisseur renforce et son procede de realisation. |
WO2007145532A1 (fr) * | 2006-06-16 | 2007-12-21 | Seaproof Solutions As | Élément raidisseur renforcé par une matrice polymère et procédé de production correspondant |
EP1950234A1 (fr) | 2007-01-29 | 2008-07-30 | Bayer MaterialScience AG | Polyuréthanes durcis avec des amines et leur préparation |
EP1955023A2 (fr) | 2005-12-02 | 2008-08-13 | Pera Odishoo | Procede et dispositif de controle de la quantite restante d'un liquide distribue |
US20090110894A1 (en) * | 2007-10-26 | 2009-04-30 | Nybakken George H | Polyurethane elastomer articles from low free diphenylmethane diisocyanate prepolymers |
-
2009
- 2009-11-03 FR FR0905254A patent/FR2952118B1/fr active Active
-
2010
- 2010-11-04 GB GB1207043.9A patent/GB2487506B/en active Active
- 2010-11-04 MY MYPI2012001877A patent/MY161125A/en unknown
- 2010-11-04 NO NO20120489A patent/NO346686B1/no unknown
- 2010-11-04 WO PCT/FR2010/052378 patent/WO2011055090A1/fr active Application Filing
- 2010-11-04 BR BR112012010421-7A patent/BR112012010421B1/pt active IP Right Grant
- 2010-11-04 DK DKPA201270238A patent/DK180014B1/en active IP Right Grant
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2671158A1 (fr) * | 1990-12-26 | 1992-07-03 | Coflexip | Raidisseur renforce et son procede de realisation. |
EP1955023A2 (fr) | 2005-12-02 | 2008-08-13 | Pera Odishoo | Procede et dispositif de controle de la quantite restante d'un liquide distribue |
WO2007145532A1 (fr) * | 2006-06-16 | 2007-12-21 | Seaproof Solutions As | Élément raidisseur renforcé par une matrice polymère et procédé de production correspondant |
EP1950234A1 (fr) | 2007-01-29 | 2008-07-30 | Bayer MaterialScience AG | Polyuréthanes durcis avec des amines et leur préparation |
US20090110894A1 (en) * | 2007-10-26 | 2009-04-30 | Nybakken George H | Polyurethane elastomer articles from low free diphenylmethane diisocyanate prepolymers |
WO2009108510A1 (fr) | 2008-02-25 | 2009-09-03 | Chemtura Corporation | Articles à base d’élastomères de polyuréthane élaborés à partir de prépolymères à faible taux en diphénylméthane diisocyanate libre |
Also Published As
Publication number | Publication date |
---|---|
NO346686B1 (no) | 2022-11-21 |
BR112012010421A2 (pt) | 2016-03-08 |
DK180014B1 (en) | 2020-01-22 |
GB201207043D0 (en) | 2012-06-06 |
MY161125A (en) | 2017-04-14 |
FR2952118B1 (fr) | 2012-04-06 |
BR112012010421B1 (pt) | 2019-11-12 |
FR2952118A1 (fr) | 2011-05-06 |
GB2487506A (en) | 2012-07-25 |
DK201270238A (en) | 2012-05-10 |
NO20120489A1 (no) | 2012-06-20 |
GB2487506B (en) | 2016-12-14 |
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