NO346686B1 - Stiffener for a flexible pipe - Google Patents
Stiffener for a flexible pipe Download PDFInfo
- Publication number
- NO346686B1 NO346686B1 NO20120489A NO20120489A NO346686B1 NO 346686 B1 NO346686 B1 NO 346686B1 NO 20120489 A NO20120489 A NO 20120489A NO 20120489 A NO20120489 A NO 20120489A NO 346686 B1 NO346686 B1 NO 346686B1
- Authority
- NO
- Norway
- Prior art keywords
- diisocyanate
- bone
- prepolymer
- mixture
- stiffener
- Prior art date
Links
- 239000003351 stiffener Substances 0.000 title claims description 38
- 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 48
- 210000000988 bone and bone Anatomy 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 29
- 229920000768 polyamine Polymers 0.000 claims 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 18
- 229920002635 polyurethane Polymers 0.000 claims description 12
- 239000004814 polyurethane Substances 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 10
- 150000003077 polyols Chemical class 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 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 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 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 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
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-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
- KHUIRIRTZCOEMK-UHFFFAOYSA-N 2-methylpropyl 3,5-diamino-4-chlorobenzoate Chemical compound CC(C)COC(=O)C1=CC(N)=C(Cl)C(N)=C1 KHUIRIRTZCOEMK-UHFFFAOYSA-N 0.000 claims description 2
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical group 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
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 3
- 239000008096 xylene Substances 0.000 claims 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 17
- 238000005266 casting Methods 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000009434 installation Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000002334 glycols Chemical class 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
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 206010063493 Premature ageing Diseases 0.000 description 1
- 208000032038 Premature aging Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- -1 ether polyols Chemical class 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
- 238000005259 measurement Methods 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- OHQOKJPHNPUMLN-UHFFFAOYSA-N n,n'-diphenylmethanediamine Chemical class C=1C=CC=CC=1NCNC1=CC=CC=C1 OHQOKJPHNPUMLN-UHFFFAOYSA-N 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 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
- 238000009864 tensile test Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mining & Mineral Resources (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Polyurethanes Or Polyureas (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Description
AVSTIVER FOR ET FLEKSIBELT RØR STIFFENERS FOR A FLEXIBLE PIPE
Oppfinnelsen angår en bendavstiver for et fleksibelt rør. The invention relates to a leg stiffener for a flexible pipe.
Bendavstivere anbringes rundt rørledningen ved lokasjoner der det fleksible rør kan utsettes for høye belastninger, indusert av bevegelser for båten eller dønninger. En bendavstiver består av en støpt plastkonstruksjon med konisk form med en lengde på noen få meter og som er ment å omgi den angjeldende rørledning. Ved å forsterke det fleksible rør med en bendavstiver på det mest belastede punkt forhindrer man at det skjer bøying ut over den minimale krummingsradius, ut over hvilken rørledningen ville undergå irreversibel skade på strukturen. Bend braces are placed around the pipeline at locations where the flexible pipe may be exposed to high loads, induced by movements of the boat or swells. A leg brace consists of a molded plastic construction with a conical shape with a length of a few meters and which is intended to surround the pipeline in question. By reinforcing the flexible pipe with a leg stiffener at the most stressed point, bending beyond the minimum radius of curvature, beyond which the pipeline would undergo irreversible damage to the structure, is prevented.
De fleksible rør som bringer fluider (for eksempel hydrokarboner) fra brønnhodet er forbundet med overflateinstallasjonen ved å føres gjennom en stålføring som kan være rett eller bøyet, «I-rør» henholdsvis «J-rør». Flere førings- eller lederør er tilveiebragt på overflateinstallasjonen. Under trekking av det fleksible rør er dette ledet og trukket gjennom et lederør for forbinding til enden av røret til overflateinstallasjonen. I drift blir amplituden for bevegelsene for det fleksible rør generert ved bevegelse av følgende som kan føre til en forringelse av konstruksjonen av det fleksible rør nær for eksempel lederøret. For å forhindre slik skade på det fleksible rør omgir en bøyeavstiver det fleksible rør nær lederøret. Bendavstiveren blir så festet til enden av lederøret ved hjelp av i og for seg kjente midler. The flexible pipes that bring fluids (for example hydrocarbons) from the wellhead are connected to the surface installation by passing through a steel guide that can be straight or bent, "I-pipe" or "J-pipe". Several guide or guide pipes are provided on the surface installation. During pulling of the flexible pipe, it is guided and pulled through a guide pipe for connection to the end of the pipe for the surface installation. In operation, the amplitude of the movements of the flexible pipe is generated by the movement of the following which can lead to a deterioration of the construction of the flexible pipe near, for example, the guide pipe. To prevent such damage to the flexible pipe, a bend stiffener surrounds the flexible pipe near the guide pipe. The leg brace is then attached to the end of the guide tube using means known per se.
Publikasjonen WO 2007/145532 A1 beskriver en bendavstiver for en langstrakt struktur som omfatter en elastomer, slik som et polyuretan basert på difenylmetandiisocyanat (MDI). The publication WO 2007/145532 A1 describes a bone stiffener for an elongated structure comprising an elastomer, such as a polyurethane based on diphenylmethane diisocyanate (MDI).
Bendavstiveren er generelt lokalisert under arbeidsstasjonen for overflateinstallasjonen i et nedsenket eller delvis nedsenket medium. Videre blir bendavstiveren utsatt for tallrike forlengelses- og kompresjonsbelastninger som genereres av bevegelsene til overflateinstallasjonen og for det fleksible rør under påvirkning fra havstrømmer, vind og/eller dønninger. De forhold som råder for bendavstiveren kan føre til en for tidlig aldring av plasten, noe som kan skade det fleksible rørs integritet. The leg brace is generally located under the workstation for the surface installation in a submerged or partially submerged medium. Furthermore, the leg brace is subjected to numerous extension and compression loads generated by the movements of the surface installation and of the flexible pipe under the influence of ocean currents, wind and/or swells. The conditions prevailing for the leg brace can lead to premature aging of the plastic, which can damage the integrity of the flexible tube.
For å begrense disse fenomener blir avstiverne fremstilt delvis av et plastmateriale som oppviser gode egenskaper når det gjelder resistens mot hydrolyse og forlengelse. Ett materiale som oppviser de beste egenskaper er polyuretan. I dag blir bendavstivere fremstilt for eksempel fra en Adiprene L167 TDI-polyeter med en Shore A hardhet på 95. For en levetid på 20 til 30 år er den maksimale hydrolyseresistenstemperatur for dette materialet 50 °C. In order to limit these phenomena, the stiffeners are manufactured partly from a plastic material which exhibits good properties in terms of resistance to hydrolysis and elongation. One material that exhibits the best properties is polyurethane. Today, bone braces are manufactured, for example, from an Adiprene L167 TDI polyether with a Shore A hardness of 95. For a lifetime of 20 to 30 years, the maximum hydrolysis resistance temperature for this material is 50 °C.
Bendavstivere slik de konvensjonelt fremstilles kan ha en lengde på flere meter, med tykkelser større enn 200 mm og en vekt som kan overskride 2 tonn. For å begrense størrelsen og vekten for bendavstiverne blir polyuretaner valgt med relativt høy hardhet, karakteristisk over 90 Shore A. Innen dette hardhetsområdet øker vanskeligheten med prosesserbarheten for polyuretanet med hardheten. Særlig gjelder dette at desto høyere hardheten for polyuretanet er, desto kortere er «pot life» til den blanding som fremstilles fra en prepolymer basert på diisocyanat og en kjedeforlenger som polyaminer eller polyalkoholer, noe som nødvendiggjør bruk av maskiner hvis støpehastighet er høy, særlig når det gjelder støping av store deler. Leg braces as they are conventionally manufactured can have a length of several metres, with thicknesses greater than 200 mm and a weight that can exceed 2 tonnes. To limit the size and weight of the bone stiffeners, polyurethanes are chosen with relatively high hardness, typically above 90 Shore A. Within this hardness range, the difficulty of processability for the polyurethane increases with hardness. In particular, this applies that the higher the hardness of the polyurethane, the shorter the "pot life" of the mixture produced from a prepolymer based on diisocyanate and a chain extender such as polyamines or polyalcohols, which necessitates the use of machines whose casting speed is high, especially when it applies to the casting of large parts.
Et formål med oppfinnelsen er å foreslå en bendavstiver som har en aldringsresistens forbedret med minst 10 °C sammenliknet med bendavstivere i henhold til den kjente teknikk, mens det samtidig sikres en god homogenitet for de mekaniske egenskaper. One purpose of the invention is to propose a bone stiffener which has an aging resistance improved by at least 10 °C compared to bone stiffeners according to the known technique, while at the same time ensuring a good homogeneity of the mechanical properties.
Et ytterligere formål med oppfinnelsen er å tillate fremstilling av en avstiver som oppviser en forhøyet hardhet i forhold til avstivere ifølge den kjente teknikk, med Shore 60 D som eksempel, samtidig som det sikres en god homogenitet for de mekaniske egenskaper. A further object of the invention is to allow the production of a stiffener which exhibits an increased hardness compared to stiffeners according to the known technique, with Shore 60 D as an example, while ensuring a good homogeneity of the mechanical properties.
Den tredje fordel er å tillate fremstilling av en bendavstiver, hvis fremstilling forbedres i forhold den kjente teknikk. The third advantage is to allow the production of a leg brace, the production of which is improved compared to the known technique.
Overraskende er det funnet at en polyuretanelastomer, fremstilt fra en difenylmetandiisocyanat (MDI) prepolymer og en kjedeforlenger valgt blant polyaminer kan benyttes for å fremstille en slik bendavstiver. Den således fremstilte bendavstiver har da en enda bedre aldringsresistens sammenliknet med de kjente avstivere og også en forbedret bearbeidbarhet. Denne bearbeidbarhetsforbedring tillater å fremstille en avstiver med forhøyet hardhet. Surprisingly, it has been found that a polyurethane elastomer, prepared from a diphenylmethane diisocyanate (MDI) prepolymer and a chain extender selected from polyamines can be used to produce such a bone stiffener. The bone stiffener produced in this way then has an even better aging resistance compared to the known stiffeners and also an improved workability. This processability improvement allows a stiffener with increased hardness to be produced.
Ifølge oppfinnelsen er det tilveiebrakt en bendavstiver for et fleksibelt rør, fremstilt av polyuretan, der polyuretanet er oppnådd ved å omsette en blanding omfattende minst 80 vekt-% av et difenylmetandiisocyanat (MDI) forpolymer med et polyamin i et forhold mellom 0,7 og 1,2, hvor nevnte forhold er forholdet mellom det totale antall N=CO funksjoner i MDI forpolymerblandingen og det totale antall NH2 funksjoner i reaksjonsblandingen. According to the invention, there is provided a leg stiffener for a flexible pipe, made of polyurethane, where the polyurethane is obtained by reacting a mixture comprising at least 80% by weight of a diphenylmethane diisocyanate (MDI) prepolymer with a polyamine in a ratio between 0.7 and 1 ,2, where said ratio is the ratio between the total number of N=CO functions in the MDI prepolymer mixture and the total number of NH2 functions in the reaction mixture.
Fordelaktige trekk ved oppfinnelsen fremgår av de uselvstendige kravene. Advantageous features of the invention appear from the independent claims.
I henhold til en spesiell utførelsesform av oppfinnelsen blir elastomeren av polyuretanet fremstilt fra en forpolymer av difenylmetandiisocyanat (MDI) og fra et metylendianilinsalt. Denne utførelsesform er spesielt fordelaktig for å fremstille en kald støping av bendavstiveren. Den kalde støpingen av bendavstiveren er spesielt fordelaktig fordi det ikke trengs komplekst utstyr. According to a particular embodiment of the invention, the polyurethane elastomer is produced from a prepolymer of diphenylmethane diisocyanate (MDI) and from a methylene dianiline salt. This embodiment is particularly advantageous for producing a cold cast of the leg brace. The cold casting of the leg brace is particularly advantageous because no complex equipment is needed.
Beskrivelsen vil forstås bedre ut fra den detaljerte beskrivelse av oppfinnelsen som følger nedenfor og under henvisning til den vedlagte figur, der: The description will be better understood from the detailed description of the invention that follows below and with reference to the attached figure, where:
Figur 1 er et snitt av en fleksibel rørledning utstyrt med en bendavstiver ifølge oppfinnelsen. Figure 1 is a section of a flexible pipeline equipped with a leg stiffener according to the invention.
Figur 1 viser skjematisk et fleksibelt rør (10) forsynt med en bendavstiver (12). Det fleksible rør er innført gjennom lederøret (14) på den (ikke-viste) overflateinstallasjonen. Bendavstiveren er anordnet i nivå med røret slik at under sammenkoblingen av det fleksible rør til overflateinstallasjonen, blir bendavstiveren i nivå med munningen til lederøret og beskytter derved det fleksible rør fra eventuelle skader under bevegelser på grunn av båten. Bendavstiveren blir så festet ved hjelp av et (ikke vist) klammer eller på enhver annen kjent måte rundt enden av lederøret. Figure 1 schematically shows a flexible tube (10) provided with a leg stiffener (12). The flexible pipe is inserted through the guide pipe (14) on the (not shown) surface installation. The leg brace is arranged level with the pipe so that during the connection of the flexible pipe to the surface installation, the leg brace is level with the mouth of the guide pipe and thereby protects the flexible pipe from possible damage during movements due to the boat. The leg brace is then attached by means of a clamp (not shown) or in any other known manner around the end of the guide tube.
Ifølge oppfinnelsen fremstilles bendavstiveren med en ny polyuretanblanding. Polyuretanet som benyttes for fremstilling av bendavstiveren, oppnås fra en difenylmetandiisocyanatforpolymer (MDI forpolymer) som preparat. Denne forpolymer blir så fornettet med et polyamin for å danne polyuretanelastomerblandingen som er i stand til å kunne formes for å fremstille bendavstiveren. According to the invention, the leg brace is produced with a new polyurethane mixture. The polyurethane used to manufacture the bone stiffener is obtained from a diphenylmethane diisocyanate prepolymer (MDI prepolymer) as a preparation. This prepolymer is then crosslinked with a polyamine to form the polyurethane elastomer blend which is capable of being molded to produce the bone brace.
Polyuretanelastomeren er således fremstilt i henhold til en to-trinns prosess. I et første trinn blir en første forpolymer fremstilt ved kondensering av alkoholfunksjonene til et polyol med isocyanatfunksjonene på polyisocyanatet. I et andre trinn blir forpolymeren og fornetningsmidlet forvarmet og blandet i en støpemaskin og deretter blir blandingen injisert i en på forhånd oppvarmet støpeform som har form av bendavstiveren, og til slutt blir denne støpeformen holdt ved en temperatur i en ovn gjennom fornetningsvarigheten. The polyurethane elastomer is thus produced according to a two-stage process. In a first step, a first prepolymer is produced by condensing the alcohol functions of a polyol with the isocyanate functions on the polyisocyanate. In a second step, the prepolymer and crosslinking agent are preheated and mixed in a molding machine and then the mixture is injected into a preheated mold shaped like the leg brace, and finally this mold is held at a temperature in an oven for the duration of the crosslinking.
Denne fremstillingsprosess gjør det mulig i større grad å kontrollere egenskapene for sluttmaterialet, noe som har en fordel når det gjelder støping av deler som krever store mengder materiale, slik tilfellet er med bendavstivere. This manufacturing process makes it possible to control the properties of the final material to a greater extent, which has an advantage when it comes to casting parts that require large amounts of material, as is the case with leg braces.
I henhold til et første trinn blir et mellomprodukt difenylmetandiisocyanatforpolymer (MDI forpolymer) syntetisert. According to a first step, an intermediate diphenylmethane diisocyanate prepolymer (MDI prepolymer) is synthesized.
MDI forpolymeren oppnås ved å omsette, ved en temperatur mellom 30 og 150 °C, et MDI diisocyanat med en polyol med høy molekylvekt mellom for eksempel 250 og 10 000 g.mol<-1>. Forholdet mellom antallet N=CO funksjoner og antallet OH funksjoner i reaksjonsblandingen kan være mellom 1,5 og 20. Reaksjonstemperaturen er for eksempel mellom 30 og 150 °C. The MDI prepolymer is obtained by reacting, at a temperature between 30 and 150 °C, an MDI diisocyanate with a polyol with a high molecular weight between, for example, 250 and 10,000 g.mol<-1>. The ratio between the number of N=CO functions and the number of OH functions in the reaction mixture can be between 1.5 and 20. The reaction temperature is, for example, between 30 and 150 °C.
MDI diisocyanatet som benyttes for fremstilling av forpolymeren av MDI velges blant 2,4’-difenylmetandiisocyanat og 4,4’-difenylmetandiisocyanat eller også 2,2’-difenylmetandiisocyanat. The MDI diisocyanate used for the production of the prepolymer of MDI is selected from 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate or 2,2'-diphenylmethane diisocyanate.
Alternativt kan 0 til 20 vekt-% av et alifatisk diisocyanat settes til MDI forpolymerblandingen. Det alifatiske diisocyanat velges så fra gruppen bestående av 1,1’-metylenbis-(4-isocyanatosykloheksan), 1,4-sykloheksandiisocyanat, isoforondiisocyanat (IPDI), 1,3-xylendiisocyanat, heksametylendiisocyanat og 1,1,4,4-tetrametylxylendiisocyanat eller en blanding av en av disse forbindelser. Alternatively, 0 to 20% by weight of an aliphatic diisocyanate can be added to the MDI prepolymer mixture. The aliphatic diisocyanate is then selected from the group consisting of 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.
Fortrinnsvis velges polyolen med høy molekylvekt fra gruppen av polyeterglykoler og polyesterglykoler. Preferably, the high molecular weight polyol is selected from the group of polyether glycols and polyester glycols.
I den gjenværende del av beskrivelsen er uttrykket «diefenylmetandiisocyanatforpolymerpreparat» definert som et preparat som inneholder minst 80 % difenylmetandiisocyanatforpolymer, oppnådd ved omsetning av minst en polyol og en diisocyanatmonomer og som også omfatter en mengde av fri MDI monomer eller en annen solvent eller mykner. In the remaining part of the description, the term "diphenylmethane diisocyanate prepolymer preparation" is defined as a preparation containing at least 80% diphenylmethane diisocyanate prepolymer, obtained by reacting at least one polyol and a diisocyanate monomer and which also includes an amount of free MDI monomer or another solvent or plasticizer.
I henhold til et andre trinn blir MDI forpolymerpreparatet så omsatt med et fornetningsmiddel i et forhold hvorav størrelsesordenen av støkiometrien velges fra polyaminer og fortrinnsvis aromatiske polyaminer. Forholdet mellom det totale antall N=CO funksjoner i MDI forpolymerpreparatet og antallet NH2 funksjoner i reaksjonsblandingen er i det vesentlige i størrelsesorden støkiometri, og er mellom 0,7 og 1,2. According to a second step, the MDI prepolymer preparation is then reacted with a crosslinking agent in a ratio of which the order of magnitude of the stoichiometry is selected from polyamines and preferably aromatic polyamines. The ratio between the total number of N=CO functions in the MDI prepolymer preparation and the number of NH2 functions in the reaction mixture is essentially in the order of stoichiometry, and is between 0.7 and 1.2.
Fortrinnsvis blir polyaminene valgt blant aromatiske polyaminer. Som eksempel kan polyaminet være 4,4’-metylenbis(2-kloranilin), 3,5-diamino-4-klorbenzosyreisobutylester eller sågar 4,4’-metylenbis(3-klor-2,6-dietylanilin). Preferably, the polyamines are selected from among aromatic polyamines. As an example, the polyamine can be 4,4'-methylenebis(2-chloroaniline), 3,5-diamino-4-chlorobenzoic acid isobutyl ester or even 4,4'-methylenebis(3-chloro-2,6-diethylaniline).
Blandingen som består av forpolymerpreparatet og av fornetningsmidlet, injiseres inn i en på forhånd oppvarmet støpeform med konisk form som er typisk for en bendavstiver. Denne støpeform holdes ved en temperatur i en ovn for varigheten av fornetningen og til slutt blir bendavstiveren tatt ut av formen. The mixture consisting of the prepolymer preparation and the crosslinking agent is injected into a pre-heated mold with a conical shape typical of a bone brace. This mold is kept at a temperature in an oven for the duration of the crosslinking and finally the leg brace is removed from the mold.
EP 1 950 234 beskriver typisk en ny polyuretanelastomer som kan benyttes for å fremstille en bendavstiver ifølge den første utførelsesform av oppfinnelsen. EP 1 950 234 typically describes a new polyurethane elastomer which can be used to produce a bone stiffener according to the first embodiment of the invention.
Spesifikt beskriver EP 1 950 234 en polyuretanelastomer som oppnås fra en forpolymer omfattende et 2,4’-difenylmetandiisocyanat fremstilt i henhold til en fremgangsmåte som omfatter de følgende trinn: Specifically, EP 1 950 234 describes a polyurethane elastomer which is obtained from a prepolymer comprising a 2,4'-diphenylmethane diisocyanate produced according to a method comprising the following steps:
(a) Omsetning av difenylmetandiisocyanat (MDI) omfattende mer enn 80% (a) Conversion of diphenylmethane diisocyanate (MDI) comprising more than 80%
2,4’-difenylmetandiisocyanat med en høy molekylvekt polyol valgt fra gruppen bestående av polyalkyleneterpolyoler med en molekylvekt mellom 250 og 10 000 g.mol<-1 >og en temperatur mellom 30 og 150 °C, i et tidsrom tilstrekkelig til å gi 2,4’-MDI forpolymerene og å omsette OH funksjonene i polyolen med et forhold mellom NCO funksjonene og OH funksjonene mellom 1,5:1 og 20:1. (b) Tilsetning til 2,4’-MDI forpolymerene av et alifatisk diisocyanat valgt blant 1,1’-metylenbis(4-isocyanatosykloheksan), 1,4-sykloheksandiisocyanat, isoforondiisocyanat (IPDI), 1,3-xylendiisocyanat, heksametylendiisocyanat og 1,1,4,4-tetrametylxylendiisocyanat eller en blanding av én av disse forbindelser. 2,4'-diphenylmethane diisocyanate with a high molecular weight polyol selected from the group consisting of polyalkylene ether polyols with a molecular weight between 250 and 10,000 g.mol<-1 >and a temperature between 30 and 150 °C, for a period of time sufficient to give 2 ,4'-MDI prepolymers and to convert the OH functions in the polyol with a ratio between the NCO functions and the OH functions between 1.5:1 and 20:1. (b) Addition to the 2,4'-MDI prepolymers of 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.
(c) Tilsetning av en nødvendig mengde av et alifatisk og/eller aromatisk diamin eller et polyamin hvorved bestanddelene vil reagere slik at forholdet mellom ekvivalenten av NCO grupper og summen av frie NCO grupper er mellom 0,8:1 og 1,2:1. (c) Addition of a necessary amount of an aliphatic and/or aromatic diamine or a polyamine whereby the components will react so that the ratio between the equivalent of NCO groups and the sum of free NCO groups is between 0.8:1 and 1.2:1 .
Fremgangsmåtene for syntese som beskrevet i EP 1 950 234 er en mulig vei for å oppnå en polyuretanelastomer ved dannelse av en 2,4’-MDI forpolymerblanding, fornettet med et alifatisk eller aromatisk polyamin, og varmestøpt for å fremstille en bendavstiver. The methods of synthesis described in EP 1 950 234 are one possible way to obtain a polyurethane elastomer by forming a 2,4'-MDI prepolymer mixture, crosslinked with an aliphatic or aromatic polyamine, and heat molded to produce a bone stiffener.
Mens fornetningen tidligere for en MDI forpolymer med et polyamin ble gitt avkall på på grunn av den svært høye reaktivitet med henblikk på MDI’er, beskriver dokumentet EP 1 950 234 en ny vei for syntese av polyuretanelastomerer ved omsetning av et preparat inneholdende en MDI forpolymer og et polyamin der reaksjonsparameterne er kontrollerbare. While the crosslinking previously of an MDI prepolymer with a polyamine was abandoned due to the very high reactivity with regard to MDIs, the document EP 1 950 234 describes a new route for the synthesis of polyurethane elastomers by reacting a preparation containing an MDI prepolymer and a polyamine in which the reaction parameters are controllable.
Bendavstiverne som fremstilles fra en polyuretanelastomer, syntetisert ved omsetning av en blanding omfattende en MDI forpolymer og et polyamin, har bedre hydrolyseresistenskarakteristika og har en bedre utmattingsstyrke enn bendavstivere fremstilt fra polyuretanelastomer ifølge kjent teknikk, mens de samtidig bibeholder homogene, mekaniske egenskaper i områdene med store tykkelser, typisk 100 mm til 500 mm. Videre er det mulig, mens man fremdeles bibeholder homogeniteten for de mekaniske egenskaper, å oppnå bendavstivere med større hardhet. Til slutt er en vesentlig fordel at det er bedre prosesserbarhet for polyuretanet når det gjelder formuleringene basert på MDI forpolymer og et polyamin gjør det mulig, under støping, å sikre en kohesjon mellom den støpte del som allerede er herdet og resten av formuleringen som ennå ikke er herdet. The bone stiffeners made from a polyurethane elastomer, synthesized by reacting a mixture comprising an MDI prepolymer and a polyamine, have better hydrolysis resistance characteristics and have a better fatigue strength than bone stiffeners made from polyurethane elastomers according to the prior art, while at the same time maintaining homogeneous mechanical properties in the areas of large thicknesses, typically 100 mm to 500 mm. Furthermore, it is possible, while still maintaining the homogeneity of the mechanical properties, to achieve bone stiffeners with greater hardness. Finally, a significant advantage is that there is better processability for the polyurethane in the case of the formulations based on MDI prepolymer and a polyamine makes it possible, during casting, to ensure a cohesion between the molded part that has already hardened and the rest of the formulation that has not yet is hardened.
Egenskapene for det således oppnådde materialet gjør det mulig å oppnå en hardhet mellom 50 Shore D og 70 Shore D mens man sikrer homogene egenskaper innen materialet. Hardhetsmålingene gjennomføres i henhold til standarden ISO 868 eller ASTM D2240. Materialet som oppnås har også en hydrolyseresistens på opp til 60 °C i 30 år, eller sågar 70 °C i kortere tid, og en utmattingsstyrke som økes med en faktor 2 til 10 avhengig av arbeidsbetingelsene. Hydrolyseresistensmålingene gjennomføres ved strekkprøver i henhold til standard ASTM D638 på prøvestykker som er underkastet akselerert aldring i vann, og med ekstrapolering i henhold til Arrhenius lov. The properties of the material thus obtained make it possible to achieve a hardness between 50 Shore D and 70 Shore D while ensuring homogeneous properties within the material. The hardness measurements are carried out in accordance with the standard ISO 868 or ASTM D2240. The resulting material also has a hydrolysis resistance of up to 60 °C for 30 years, or even 70 °C for a shorter time, and a fatigue strength that is increased by a factor of 2 to 10 depending on the working conditions. The hydrolysis resistance measurements are carried out by tensile tests according to standard ASTM D638 on test pieces that have been subjected to accelerated aging in water, and with extrapolation according to the Arrhenius law.
En andre, spesiell utførelsesform av oppfinnelsen skal nå beskrives. I denne spesielle utførelsesform av oppfinnelsen er diisocyanatforpolymeren fornettet med en spesiell familie av aminer der de reaktive aminfunksjoner er blokkert for å redusere deres reaktivitet med henblikk på MDI forpolymeren. A second, special embodiment of the invention will now be described. In this particular embodiment of the invention, the diisocyanate prepolymer is crosslinked with a special family of amines where the reactive amine functions are blocked to reduce their reactivity with respect to the MDI prepolymer.
Polyuretanelastomeren som benyttes for fremstilling av bendavstiveren oppnås fra en difenylmetandiisocyanatforpolymer (MDI forpolymer) som en blanding som så fornettes med et kompleks av metylendianilin (MDA) salter for å gi polyuretanelastomerblandingen i stand til å kunne kaldformes for å oppnå bendavstiveren. Uttrykket «kaldforming» skal her forstås til å bety at fyllingen av støpeformen kan skje uten behovet for forvarming av formen og heller ikke reaktantene (bortsett fra å sikre avgassing), og at fornetningsreaksjonen ikke skjer under fylling av støpeformen. Dette muliggjør en langsom og kontrollert fylling av støpeformen og unngår derved dannelse av bobler idet fornetningen skjer i et andre trinn under en økning av temperaturen i materialet som innføres i støpeformen med form av bendavstiveren. The polyurethane elastomer used to produce the bone stiffener is obtained from a diphenylmethane diisocyanate prepolymer (MDI prepolymer) as a mixture which is then cross-linked with a complex of methylene dianiline (MDA) salts to give the polyurethane elastomer mixture the ability to be cold-formed to obtain the bone stiffener. The term "cold forming" shall be understood here to mean that the filling of the mold can take place without the need for preheating the mold or the reactants (except to ensure degassing), and that the crosslinking reaction does not occur during filling of the mold. This enables a slow and controlled filling of the mold and thereby avoids the formation of bubbles as the cross-linking takes place in a second step during an increase in the temperature of the material introduced into the mold in the form of the leg brace.
Metylendianilin (MDA) saltet er et polyamin hvis aminfunksjoner er blokkert for å redusere reaktiviteten for aminet med henblikk på MDI forpolymeren når det gjelder fornetning av MDI forpolymerblandingen og derved å være i stand til fordelaktig å gjennomføre nevnte kaldstøping av bendavstiveren. Under kaldstøpingsfasen vil aminfunksjonene for MDA saltet være ublokkert med en kontrollert økning i temperatur for å reagere med MDI forpolymerblandingen. Den gradvise avblokkering av aminfunksjonene for MDA salt komplekset gjør det mulig å redusere reaktiviteten for fornetningsmidlet og på fordelaktig måte å gjennomføre kaldstøping av bendavstiveren. The methylene dianiline (MDA) salt is a polyamine whose amine functions are blocked in order to reduce the reactivity of the amine with respect to the MDI prepolymer when it comes to crosslinking the MDI prepolymer mixture and thereby be able to advantageously carry out said cold casting of the bone stiffener. During the cold casting phase, the amine functions of the MDA salt will be unblocked with a controlled increase in temperature to react with the MDI prepolymer mixture. The gradual unblocking of the amine functions for the MDA salt complex makes it possible to reduce the reactivity of the cross-linking agent and advantageously carry out cold casting of the bone stiffener.
Polyuretanelastomeren fremstilles i henhold til en tre-trinns prosess. I et første trinn blir et mellomliggende forpolymerpreparat fremstilt ved kondensering av alkoholfunksjonene av en polyol med isocyanatfunksjonene av et polyisocyanat som tidligere beskrevet for den første utførelsesform av oppfinnelsen. The polyurethane elastomer is manufactured according to a three-step process. In a first step, an intermediate prepolymer preparation is produced by condensing the alcohol functions of a polyol with the isocyanate functions of a polyisocyanate as previously described for the first embodiment of the invention.
I et andre trinn blir MDI forpolymeren og MDA saltet blandet, forvarmet til rundt 70 °C for derved å sikre en avgassing av blandingen. In a second step, the MDI prepolymer and the MDA salt are mixed, preheated to around 70 °C to thereby ensure degassing of the mixture.
Saltet av metylendianilin (MDI) er fortrinnsvis tris(4,4’-diaminodifenylmetan)-NaCl komplekset som oppnås mellom metylendianilin (MDA) og natriumkloridsaltet. Eventuelt kan dette salt omfatte en mykner. Det selges, for eksempel, under merkene CAYTUR 31<TM >og CAYTUR 31-DA<TM>. The salt of methylenedianiline (MDI) is preferably the tris(4,4'-diaminodiphenylmethane)-NaCl complex obtained between methylenedianiline (MDA) and the sodium chloride salt. Optionally, this salt may comprise a plasticizer. It is sold, for example, under the brands CAYTUR 31<TM>and CAYTUR 31-DA<TM>.
Blandingen injiseres så i en form tildannet som en bendavstiver. The mixture is then injected into a mold shaped like a bone brace.
I et tredje trinn blir formen, som må kunne forvarmes på forhånd, innført i en ovn og temperaturen økes på kontrollert måte. Under dette siste trinn blir temperaturøkningsprofilen for ovnen justert for gradvis å frigi aminfunksjonene for MDA saltet og å fornette MDI forpolymeren. In a third step, the mold, which must be able to be preheated in advance, is introduced into an oven and the temperature is increased in a controlled manner. During this final step, the oven temperature rise profile is adjusted to gradually release the amine functions of the MDA salt and crosslink the MDI prepolymer.
I denne spesielle utførelsesform er reaksjonstiden som fører til dannelsen av polyuretanelastomeren lengre på grunn av den kontrollerte reaktivitet av det valgte fornetningsmiddel. Således er det ikke nødvendig å benytte støpemaskiner med høyt gjennomløp. Videre har bendavstiveren som fremstilles fra polyuretanelastomeren som oppnås fra en MDI forpolymer som er fornettet med metylendianilin (MDA) saltet mekaniske karakteristika sammenliknbart med de som oppnås med bendavstiveren som oppnås i henhold til oppfinnelsens første utførelsesform. In this particular embodiment, the reaction time leading to the formation of the polyurethane elastomer is longer due to the controlled reactivity of the selected crosslinking agent. Thus, it is not necessary to use casting machines with a high throughput. Furthermore, the bone stiffener produced from the polyurethane elastomer obtained from an MDI prepolymer cross-linked with methylene dianiline (MDA) salt has mechanical characteristics comparable to those obtained with the bone stiffener obtained according to the first embodiment of the invention.
WO 209/108510 beskriver typisk en ny polyuretanelastomer som kan benyttes for å fremstille en bendavstiver ved en kald støpeteknikk i henhold til den andre utførelsesform av oppfinnelsen. WO 209/108510 typically describes a new polyurethane elastomer which can be used to produce a bone stiffener by a cold casting technique according to the second embodiment of the invention.
WO 2009/108510 beskriver en polyuretanelastomerblanding, oppnådd ved omsetning av en MDI forpolymer og metylendianilin, kompleksdannet med et natriumkloridsalt, der blandingen er stabil over tid i flere dager med avgassingstemperaturen på 70 °C. Denne blanding blir så innført i en støpeform som har en utforming som en bendavstiver og varmet opp til en fornetningstemperatur som bestemmes til å være mellom 115 og 130 °C for å frigi de blokkerte aminer av MDA komplekset og å initiere fornetningsreaksjonen for MDI forpolymerblandingen. WO 2009/108510 describes a polyurethane elastomer mixture, obtained by reacting an MDI prepolymer and methylene dianiline, complexed with a sodium chloride salt, where the mixture is stable over time for several days with the degassing temperature of 70 °C. This mixture is then introduced into a mold shaped like a bone stiffener and heated to a crosslinking temperature determined to be between 115 and 130°C to release the blocked amines of the MDA complex and to initiate the crosslinking reaction for the MDI prepolymer mixture.
Fornetningsreaksjonen skjer under så å si støkiometriske betingelser. Støkiometrien oppnås ved forholdet mellom det totale antall N=CO funksjoner i MDI forpolymerblandingen og det totale antall NH2 funksjoner som frigis ved fornetningstemperaturen av MDI forpolymeren. Dette forhold kan lett bestemmes og kan for eksempel være mellom 0,7 og 1,2. The cross-linking reaction takes place under stoichiometric conditions, so to speak. The stoichiometry is obtained by the ratio between the total number of N=CO functions in the MDI prepolymer mixture and the total number of NH2 functions that are released at the crosslinking temperature of the MDI prepolymer. This ratio can be easily determined and can for example be between 0.7 and 1.2.
Bendavstiveren som oppnås på denne måte har forbedrede egenskaper på en måte som er identisk med den som beskrives for oppfinnelsens første utførelsesform. The leg brace obtained in this way has improved properties in a manner identical to that described for the first embodiment of the invention.
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FR0905254A FR2952118B1 (en) | 2009-11-03 | 2009-11-03 | STIFFENER FOR FLEXIBLE DRIVING |
PCT/FR2010/052378 WO2011055090A1 (en) | 2009-11-03 | 2010-11-04 | Stiffener for a flexible pipe |
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FR3020396B1 (en) | 2014-04-25 | 2016-05-13 | Saipem Sa | METHOD FOR INSTALLING AND IMPLEMENTING A RIGID TUBE FROM A VESSEL OR FLOATING SUPPORT |
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2010
- 2010-11-04 DK DKPA201270238A patent/DK180014B1/en active IP Right Grant
- 2010-11-04 GB GB1207043.9A patent/GB2487506B/en active Active
- 2010-11-04 WO PCT/FR2010/052378 patent/WO2011055090A1/en active Application Filing
- 2010-11-04 NO NO20120489A patent/NO346686B1/en unknown
- 2010-11-04 BR BR112012010421-7A patent/BR112012010421B1/en active IP Right Grant
- 2010-11-04 MY MYPI2012001877A patent/MY161125A/en unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007145532A1 (en) * | 2006-06-16 | 2007-12-21 | Seaproof Solutions As | Polymer matrix reinforced stiffening element and method of producing the same |
Also Published As
Publication number | Publication date |
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WO2011055090A1 (en) | 2011-05-12 |
NO20120489A1 (en) | 2012-06-20 |
GB2487506A (en) | 2012-07-25 |
GB201207043D0 (en) | 2012-06-06 |
GB2487506B (en) | 2016-12-14 |
DK201270238A (en) | 2012-05-10 |
BR112012010421A2 (en) | 2016-03-08 |
BR112012010421B1 (en) | 2019-11-12 |
MY161125A (en) | 2017-04-14 |
DK180014B1 (en) | 2020-01-22 |
FR2952118B1 (en) | 2012-04-06 |
FR2952118A1 (en) | 2011-05-06 |
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