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    • 专利摘要:
    METHOD FOR THERMALLY INSULATING AN OBJECT FROM AN ENVIRONMENTAL LIQUID AND PIPE The invention provides an insulation material comprising an epoxy-terminated prepolymer and an amine curing agent. The reaction product of the epoxy-terminated prepolymer and the amine curing agent provides for an elastomer that combines the processing and mechanical properties of polyurethane elastomers with improved thermo-hydrolytic stability. The insulating material is particularly useful as a thermal insulator and coating for subsea oil and gas applications.
    公开号:BR112013005064B1
    申请号:R112013005064-0
    申请日:2011-08-31
    公开日:2020-07-21
    发明作者:Nathan Wilmot；Rajat Duggal；Harshad M. Shah；Alan K. Schrock；Juan Carlos Medina
    申请人:Dow Global Technologies Llc.；
    IPC主号:
    专利说明:

    [0001] [0001] This invention relates to the field of insulated pipes and structures and, in particular, to the field of subsea pipes and structures and pipes for use in deep waters. Background of the invention
    [0002] [0002] Offshore drilling requires the transport of oil from underwater wells to the shore or other surface facilities for additional distribution. The resistance to the flow of liquid products such as oil increases as the temperature decreases. To avoid a substantial reduction in temperature, the pipes are generally insulated. In addition, the underwater environment exposes the equipment to compressive forces, temperatures close to freezing water, possible water absorption, corrosion by salt water, underwater currents and marine life.
    [0003] [0003] Polyurethanes are often used to isolate such subsea applications due to the general ease of processing (two-component molding) and good mechanical properties (tough and tough elastomer). However, such insulation may suffer from hydrolytic degradation when exposed to hot-humid environments. In fields where the oil temperature is high at the wellhead, there is a possibility of degradation of the polymeric lattice if water enters, which would negatively impact the insulating performance of the materials.
    [0004] [0004] Propylene is another type of material also used to insulate such pipes, however, this requires a difficult application process, which is the extrusion of several layers, and such insulation generally does not have the attractive mechanical properties of polyurethane.
    [0005] [0005] Another proposed method for insulating subsea systems is the use of pre-fused sections of rigid epoxy-syntactic foam. This material comprises a rigid epoxy resin mixed with a high volumetric proportion of glass or ceramic spheres. Although this material exhibits excellent thermal conductivity, it is very brittle. Due to its rigidity and fragility of this material, it is easily damaged when subjected to sudden impacts or high levels of stress. To compound this problem, rigid epoxy-syntactic foams are difficult to repair. Removing or replacing this material is extremely difficult because the sections are attached to the surface using adhesives or mechanical fasteners.
    [0006] [0006] With the continued focus on offshore drilling, there remains a need for improvements in materials to insulate pipes and associated equipment. Summary of the invention
    [0007] [0007] This invention provides an amine-cured epoxy elastomeric material that combines the processing and mechanical properties of polyurethane elastomers with improved thermo-hydrolytic stability. In one embodiment, the elastomer is used to thermally isolate any object from a surrounding fluid. In an additional embodiment, the elastomer is used to insulate underwater tubes and wellhead equipment from seawater.
    [0008] (a) um prepolímero terminado por epóxi liquido à temperatura ambiente formado reagindo uma polioxialquilenoamina tendo um peso molecular de 3.000 a 20.000 com um excesso de epóxido, sendo que a polioxialquilenoamina tem pelo menos 3 átomos de hidrogênio ativo e (b) um agente de cura compreendendo pelo menos uma amina ou poliamina tendo um peso equivalente de menos que 200 e tendo 2 a 5 átomos de hidrogênio ativo. [0008] In another embodiment, the invention provides a method for thermally isolating an object from a surrounding fluid, the method comprising interposing the insulating material between the object and the fluid where the insulating material comprises the reaction product of (a) a liquid epoxy-terminated prepolymer at room temperature formed by reacting a polyoxyalkyleneamine having a molecular weight of 3,000 to 20,000 with an excess of epoxide, with polyoxyalkyleneamine having at least 3 active hydrogen atoms and (b) a curing agent comprising at least one amine or polyamine having an equivalent weight of less than 200 and having 2 to 5 active hydrogen atoms.
    [0009] [0009] In another embodiment, the insulating material is a syntactic elastomer containing glass bubbles produced by the reaction of the epoxy-terminated prepolymer and an amine curing agent as described above in the presence of the glass bubbles.
    [0010] [0010] In an additional embodiment, the object insulating material comprises a tube.
    [0011] [0011] In another embodiment, the object is an underwater Christmas tree.
    [0012] [0012] In additional embodiments, the present invention provides tubes, underwater Christmas tree, collector or column at least partially enclosed in the insulating material described above.
    [0013] [0013] This invention also provides amine-cured, elastomeric materials having good flexibility at low temperatures. Detailed description of the invention
    [0014] [0014] The present invention relates to elastomeric materials and synthetic glass elastomers. Elastomeric materials can be used to thermally isolate any object from a surrounding fluid. In particular, such elastomers are suitable for insulating substrates, such as pipelines in cold water and for insulating wellhead equipment. The elastomeric materials of the present invention may also be used to insulate collectors, discharge columns, building joints, configurations designed for Christmas trees, jumpers, winder parts, and other related underwater architectures. Elastomeric materials can also be used to coat robotic parts, devices and vehicles used in subsea applications. In particular, such elastomeric materials are prepared by the amine curing of an epoxy-terminated prepolymer. While elastomers are well suited for objects that are submerged in water, elastomers can be used to coat objects that are not exposed to an aqueous environment.
    [0015] [0015] Elastomeric resins are synthesized in at least two stages: first an epoxy-terminated prepolymer and, in the second stage, the prepolymer is cured with an amine to form the final epoxy-based elastomer. For ease of manufacturing the final product, it is desirable that the prepolymer formed be a liquid under ambient conditions to promote the flow especially when filling complex molds. In a further embodiment, it is desirable that both the epoxy-terminated prepolymer and the amine curing agent are liquid at room temperature. Based on the use of an amine-terminated polyether polyol in the formation of the epoxy prepolymer, followed by curing with an amine, the final elastomer contains "soft" structural segments provided by the polyether. The epoxy portion, when reacted with suitable short polyfunctional amines, provides "hard" structural elements running along the final elastomeric polymeric chain.
    [0016] [0016] The epoxy-based elastomer, not including any fillers, will generally exhibit an elongation greater than 50 percent. In additional embodiments, the epoxy-based elastomer will have an elongation of at least 60, 70 or 80 percent. When a monoamine curing agent, such as an alkanolamine curing agent, is used, the elongation will generally be greater than 100%. In additional embodiments, the epoxy-based elastomer will have an elongation of at least 110 and in additional embodiments of 120% or greater.
    [0017] [0017] In an additional embodiment, the presence of the soft and hard segments provides for an epoxy-based elastomer to have at least a Tg of less than 0 ° C. The term "Tg" is used to mean the glass transition temperature and this is measured via Differential Scanning Calorimetry (DSC). In a further embodiment, the epoxy-based elastomer will have at least a Tg of less than -15 ° C, -20 ° C, -30 ° C, or less than -40 ° C. In a further embodiment, the epoxy-based elastomer will have at least one Tg below -20 ° C and at least one Tg will be above 15 ° C. In an additional embodiment, the appearance of Tg will be greater than 25 ° C.
    [0018] [0018] Furthermore, the epoxy-based elastomers of the present invention can be used to coat tubes or other underwater structures where the temperature of the material transported can vary up to 140 ° C, even up to 150 ° C.
    [0019] [0019] The epoxy resin-based elastomers of the present invention, without the addition of fillers, have a thermal conductivity of less than 0.18 W / m * K, as determined by ASTM C518. In a further embodiment, the elastomers of the present invention have a thermal conductivity of less than 0.16 W / m * K. The thermal conductivity can be further reduced with the addition of hollow spheres, such as glass bubbles.
    [0020] [0020] It was unexpected that an epoxy-based elastomer exhibited the flexibility required for subsea applications, had good hydrolytic stability, exhibited a good curing profile, and had good insulation properties (low thermal conductivity).
    [0021] [0021] In the present invention, the epoxy-terminated prepolymer is formed by the reaction of a polyoxyalkyleneamine with an epoxy resin. Polyoxyalkylene polyamine may also be referred to as an amine-terminated polyether polyol. Generally, polyoxyalkyleneamine will have an average molecular weight of at least 3,000. Generally, polyoxyalkyleneamine will have an average molecular weight of less than 20,000. In a further embodiment, the polyoxyalkyleneamine will have an average molecular weight of at least 3,500. Polyether polyols to produce polyoxyalkyleneamine are generally obtained by adding a C2 to C8 alkylene oxide to an initiator having a nominal functionality of 2 to 6, that is, having 2 to 6 active hydrogen atoms. In additional embodiments, the alkylene oxide will contain 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide and mixtures thereof. When two or more oxides are used, they may be present as random mixtures or as blocks of one or the other polyether. In a preferred embodiment, the polyether polyol will be liquid at room temperatures. In a further embodiment, the alkylene oxide content of the polyether polyol will be less than 30, less than 25, less than 20 or less than 15 weight percent ethylene oxide. In one embodiment, the polyether polyol is a poly (oxypropylene) polyol. The catalysis for the polymerization of an alkylene oxide to an initiator can be either anionic or cationic. Catalysts Commonly used for the polymerization of alkylene oxides include a KOH, CsOH, boron trifluoride catalyst, a double metal cyanide complex (DMC), such as a zinc hexacyanocobaltate or a quaternary phosphazene compound.
    [0022] [0022] Examples of commonly used initiators include glycerol, trimethylol propane, sucrose, sorbitol, pentaerythritol, ethylene diamine, and amino alcohols, such as ethanolamine, diethanolamine, and triethanolamine. In an additional embodiment, the initiator for the polyether contains 3 to 4 active hydrogen atoms. In a further embodiment, the initiator is a polyhydric initiator.
    [0023] [0023] The polyols will have an equivalent weight of at least about 500 and preferably at least about 750 to about 1,500 or up to about 2,000. In one embodiment, polyether polyols having a molecular weight of 4,000 and above are used, based on trihydric initiators.
    [0024] [0024] The conversion of the polyether into a polyoxyalkyleneamine may be carried out by methods known in the art. For example, for a reductive amination, as described, for example, in U.S. Patent No. 3,654,370 the content of which is incorporated herein by reference.
    [0025] [0025] Polyoxyalkyleneamines may be represented by the general formula
    [0026] [0026] Examples of commercially available polyoxyalkylene amines are, for example: JEFFAMINEMR D-4000 and JEFFAMINEMR T-5000 from Huntsman Corporation.
    [0027] [0027] The epoxy resins used to produce the epoxy-terminated prepolymers are compounds containing at least one vicinal epoxy group. The epoxy resin can be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic, and can be replaced. The epoxy resin can also be monomeric or polymeric.
    [0028] [0028] In one embodiment, the epoxy resin component is a polyepoxide. Polyepoxide, as used here, refers to a compound or mixture of compounds where at least one of the compounds contains more than one epoxy portion. Polyepoxide, as used here, also includes advanced or partially advanced epoxy resins, that is, the reaction product of a polyepoxide and a chain extender, where the resulting epoxy reaction product has, on average, more than one unit of epoxide unreacted by molecule. The epoxy resin component can be solid or liquid at room temperature (10 ° C and above). Generally, a "solid epoxy resin" or "SER" is an epoxy-functional resin that has a Tg generally greater than about 30 ° C. While the epoxy resin may be a solid, the final solid epoxy-terminated prepolymer will be a liquid at room temperature. For ease of handling, in one embodiment the epoxy resin will be a liquid at room temperatures.
    [0029] [0029] In one embodiment, the epoxy resin can be represented by the formula
    [0030] [0030] Aliphatic polyepoxides may be prepared from the known reaction of epihalohydrins and polyglycols. Examples of aliphatic epoxides include trimethylolpropane epoxide, and diglycidyl-1,2-cyclohexane dicarboxylate.
    [0031] [0031] Other epoxies that may be employed here include epoxy resins such as, for example, the glycidyl ethers of polyhydric phenols or epoxy resins prepared from an epihalohydrin and a phenol or phenol type compound.
    [0032] [0032] The phenol type compound includes compounds having an average of more than one aromatic hydroxyl group per molecule. Examples of phenol-like compounds include dihydroxy phenols, biphenols, bisphenols, halogenated biphenols, halogenated bisphenols, hydrogenated bisphenols, alkylated biphenols, alkylated bisphenols, trisphenols, phenol-aldehyde resins, novolaca resins (ie, the reaction product and simple aldehydes, preferably formaldehyde), halogenated novolac phenol-aldehyde resins, substituted novolac phenol-aldehyde resins, phenol-hydrocarbon resins, substituted phenol-hydrocarbon resins, phenol-hydroxybenzaldehyde resins, phenol-hydroxybenzaldehyde resins hydrocarbon-phenol resins, halogenated hydrocarbon-phenol resins, alkylated hydrocarbon-phenol resins, or combinations thereof.
    [0033] [0033] Examples of bisphenol A-based epoxy resins useful in the present invention include commercially available resins such as those in the D.E.R.MR 300 series and those in the D.E.R.MR 600 series commercially available from The Dow Chemical Company. Examples of novolac epoxy resins include commercially available resins such as those in the D.E.N.MR 400 series, commercially available from The Dow Chemical Company.
    [0034] [0034] In a further embodiment, the epoxy resin compounds may be an epihalohydrin and resorcinol resin, catechol, hydroquinone, biphenol, bisphenol A, bisphenol AP (1,1-bis (4-hydroxyphenyl) -1-phenyl ethane) , bisphenol F, bisphenol K, bisphenol S, tetrabromobisphenol A, phenol formaldehyde resins novolaca, phenol formaldehyde resins novolaca substituted, phenol formaldehyde resins substituted with alkyl, phenol hydroxybenzaldehyde resins, cresol hydroxy resins dicyclopentadiene-phenol resins, substituted dicyclopentadiene-phenol resins, tetramethylbiphenol, tetramethyl-tetrabomobiphenol, tetramethyltribromobiphenol, tetrachlorobisphenol A, or combinations thereof.
    [0035] [0035] In another embodiment, the epoxy resin includes those resins produced from an epihalohydrin and an amine. Suitable amines include dimethylaminodiphenylmethane, aminophenol, xylene diamine, anilines, and the like, or combinations thereof.
    [0036] [0036] In another embodiment, those resins produced from an epihalohydrin and a carboxylic acid are included. Suitable carboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrahydro- and hexahydrophthalic acid, endomethylene-tetrahydrophthalic acid, isophthalic acid, methylhexahydrophthalic acid, and the like or combinations thereof.
    [0037] [0037] Other useful compounds that can be used in the practice of the present invention are cycloaliphatic epoxides. A cycloaliphatic epoxide consists of a saturated carbon ring having an epoxy oxygen attached to two vicinal atoms in the carbon ring, for example, as illustrated by the following general formula:
    [0038] [0038] The cycloaliphatic epoxide may be a monopoxide, a diepoxide, a polyepoxide, or a mixture of these. For example, any of the cycloaliphatic epoxides described in U.S. Patent No. 3,686,359, incorporated herein by reference, may be used in the present invention. As an illustration, cycloaliphatic epoxides that may be used in the present invention include, for example (3,4-epoxycyclohexyl-methyl carboxylate) -3,4-epoxy-cyclohexane, bis (3,4-epoxycyclohexyl) adipate, monoxide vinylcyclohexene and mixtures thereof.
    [0039] [0039] Another class of useful epoxy resins of the present invention is based on the divinylarene oxide product prepared by the process of the present invention which can be illustrated generally by the general chemical structures I-IV as follows
    [0040] [0040] In the above structures, I, II, III and IV of the divinylarene dioxide product of the present invention, each R1, R2, R3 and R4 individually may be hydrogen, an alkyl, cycloalkyl, aryl or aralkyl group; or an oxidant resistant group including, for example, a halogen, nitro, isocyanate, or RO group, where R may be alkyl, aryl or aralkyl; x can be an integer from 0 to 4; y can be an integer greater than or equal to 2; x + y can be an integer less than or equal to 6; z can be an integer from 0 to 6; and z + y can be an integer less than or equal to 8; and Ar is a fragment of arene including, for example, 1,3-phenylene group.
    [0041] [0041] In certain embodiments of divinylarene dioxide products, the alkyl portion will have from 1 to 36 carbon atoms. In additional embodiments, the alkyl will have less than 24, or less than 18 carbon atoms. In additional embodiments, the alkyl will have 1 to 8 or 1 to 6 carbon atoms. Similarly, cycloalkyl will contain 5 to 36 carbon atoms. Generally, cycloalkyl will contain 5 to 24 carbon atoms.
    [0042] [0042] The aryl portion present in divinylarene dioxide will generally contain 12 carbon atoms or less. An aralkyl group will usually contain 6 to 20 carbon atoms.
    [0043] [0043] The divinylarene dioxide product produced by the process of the present invention may include, for example, alkyl vinyl arene monoxides depending on the presence of alkyl vinyl aryl in the starting material.
    [0044] [0044] In one embodiment of the present invention, the divinylene dioxide produced by the process of the present invention may include, for example, divinylbenzene dioxide, divinylnaphthalene dioxide, divinylbiphenyl dioxide, divinyl diphenyl ether dioxide, and mixtures thereof.
    [0045] [0045] Optionally, the epoxy resin may also contain a halogenated or halogen-containing epoxy resin compound. Halogen-containing epoxy resins are compounds containing at least one vicinal epoxy group and at least one halogen. Halogen may, for example, be chlorine or bromine, and is preferably bromine. Examples of halogen-containing epoxy resins useful in the present invention include diglycidyl ether of tetrabromobisphenol A and derivatives thereof. Examples of epoxy resin useful in the present invention include commercially available resins such as those in the D.E.R.MR 500 series, commercially available from The Dow Chemical Company.
    [0046] [0046] In general, the epoxy resin useful in the present invention has an average molecular weight of about 200 to about 10,000, preferably from about 200 to about 5,000 and more preferably from about 200 to about 1,000.
    [0047] [0047] The epoxy equivalent weight of epoxy resins is generally about 100 to about 8000 and more preferably about 100 to about 4000. As used herein, the term "epoxy equivalent weight" ("EEW") refers to the average molecular weight of the polyepoxide molecule divided by the average number of oxirane groups present in the molecule. The diepoxides useful in the present invention are epoxy resins having an epoxy equivalent weight of about 100 to about 500.
    [0048] [0048] The relative amount of epoxy resin used to make the prepolymer can be varied over wide ranges. Generally, the epoxy resin used must be present in a ratio of at least 3 epoxy groups per hydrogen amine atoms to prevent the prepolymer from gelating. In additional embodiments, the ratio of oxirane portions to amine hydrogen is at least 5, at least 10, and generally up to 20 to 1. In one embodiment, the prepolymer is formed by reacting no less than 4 moles of polyepoxide resin per mole diamine at temperatures in the range of about 80 ° C for no less than 1 hour with constant agitation. Exact duration temperatures will depend on the reactivity of the polyepoxide resins being used.
    [0049] [0049] The conditions for the reaction of the epoxy resin with poliopolypolyalkyleneamine are well known in the art. Generally, when using a polyoxypolyalkyleneamine and epoxy resin that are liquid at room temperatures, no solvent is required. To promote the reaction, the mixture of polypolypolyalkyleneamine and epoxy resin is heated between 70 and 150 ° C for a sufficient time to react with the available active hydrogen atoms. Optionally, the reaction can be carried out in the presence of conventional catalysts that promote the reaction between amines and epoxides. Optionally, the reaction can be carried out in the presence of suitable solvents to dissolve the amine and / or epoxy.
    [0050] [0050] In one embodiment, the final epoxy-terminated prepolymer will be a liquid at room temperature, that is, generally a liquid at 15 ° C and above. In a further embodiment, the epoxy-terminated prepolymer will be a liquid at 10 ° C and above. By liquid, it is inferred that the material is pourable or pumpable.
    [0051] [0051] In a second step to make the epoxy-based elastomer of the present invention, the epoxy prepolymer is reacted with an amine-terminated curing agent. The amine-terminated curing agent will have an equivalent weight of at least 200 and having 2 to 5 active hydrogen atoms. Generally, the amine curing agent will have an equivalent weight of at least 20. The equivalent amino weight means the molecular weight of the curing agent divided by the number of amine active hydrogen atoms. In an additional embodiment, the amine or polyamine will have 2 to 4 active hydrogen atoms. In yet another embodiment, the amine curing agent will have 2 amino active hydrogen atoms.
    [0052] [0052] The curing of the elastomer is generally done at a temperature higher than room temperature. As it is generally desirable to have a short curing time when making articles, the amine curing agent is selected to give a curing time (release) of less than 30 minutes when the molds have been heated to approximately 100 ° C. In an additional embodiment, the curing time is less than 20 minutes. The amine curing agent is generally added to provide 0.8 to 1.5 equivalents of amine (NH) per epoxy reactive group. In an additional embodiment, the ratio is 0.9 to 1.1.
    [0053] [0053] Examples of amine curing agents suitable for use in the present invention include those represented by the following formula:
    [0054] [0054] In one embodiment Z is oxygen. In an additional embodiment, Z is oxygen and R7 is hydrogen. In another embodiment X and Y are both hydrogen.
    [0055] [0055] Cyclic diamines as represented by the following formula can also be used as curing agents in the present invention:
    [0056] [0056] Aromatic amine curing agents can also be used such as toluene-2,4-diamine, toluene-2,6-diamine, phenylene diamine isomers; aniline; and similar.
    [0057] [0057] In another embodiment, the amine curing agent may be the steric and geometric isomers of isophorone diamine, cyclohexaneddihydimethanamine, or cyclohexane diamine.
    [0058] [0058] Specific examples of amine-terminated curing agents include: monoethanolamine; 1-amino-2-propanol; 1-amino-3-propanol; 1-amino-2-butanol; 2-amino-1-butanol; isophorone diamine; piperazine; homopiperazine; butylamine; ethylene diamine; hexamethylene diamine; and mixtures of these. In one embodiment, the curing agent is an alkanolamine.
    [0059] [0059] In a further embodiment, amine-terminated polyethers having an equivalent amine weight of less than 200, such as JEFFAMINEMR D-400 from Huntsman Chemical Company are suitable.
    [0060] [0060] In certain embodiments, the curing agent may contain a combination of an aliphatic and an aromatic curing agent, in order to have a process with stages curing. The combination of amine curing agents allows for a first curing step, usually made at 70 to 80 ° C whereby the aliphatic amine reacts with the epoxy portion to form a prepreg, and a second curing step done in temperatures above 80 ° C to cure aromatic amine.
    [0061] [0061] If desired, the thermal conductivity of the epoxy material can be reduced by adding charges. Suitable fillers include hollow glass spheres, hollow thermoplastic spheres composed of acrylic-type resins such as methyl polymethacrylate, acrylic modified styrene, poly (vinylidene chloride) or styrene copolymer and methyl methacrylate; phenolic resins; silica; ceramic or carbon spheres. Preferred charges are microspheres. The term "hollow" in relation to hollow objects for use in the present invention should be understood as at least 50% of the closed volume being filled with gaseous fluid, optionally, the closed volume being filled only with gaseous fluid. Such filled systems are generally referred to as syntactic materials.
    [0062] [0062] Examples of hollow glass microspheres include, for example, ScotchliteMR GlassBubbles from 3M, polymer microspheres, for example ExpancelMR from Akzo Nobel, or ceramic microspheres, for example CenospheresMR from Sphere Services Inc.
    [0063] [0063] Generally, hollow microspheres provide less than 35% w / w, or less than 25% w / w, of the syntactic coating. In one embodiment, hollow glass beads provide 5 to 15% w / w of the syntactic coating, the weight percentage (% w / w) being relative to the entire formulation.
    [0064] [0064] Generally the microspheres will be well mixed with the epoxy-terminated prepolymer by techniques known in the art. If desired, viscosity modifying agents known in the art may be added. Examples of such additives include diglycidyl butane diol ether, glycidyl fatty acid ethers or natural oils or TEP (triethyl phosphate, (C2H5) 3PO4). If desired, other additives that can be used with the elastomers of the present invention include flame retardant agents, plasticizers, antioxidants, UV stabilizers, adhesion promoters, dyes, fillers, and reinforcing agents.
    [0065] [0065] As previously mentioned, the epoxy-based elastomeric material of the present invention can be used in the isolation of any object from a surrounding fluid. In particular, elastomeric materials are used to insulate oil and gas flow lines, collectors, discharge columns, building joints, configurations designed for Christmas trees, jumpers, winder parts, and other related underwater architectures. The tube that is coated with the elastomeric material can have any outside diameter, inside diameter and length. Usually the outside diameter is at least 10 cm and the length is 1 meter or more.
    [0066] [0066] Underwater Christmas tree structures are well known in the industry and as described, for example, in U.S. patents Nos. 6,520,261 and 6,746,761; portions of such documents disclosing such structures are hereby incorporated by reference. In general, such structures will include a production drilling in communication with the well drilling, a production outlet connected to the production drilling, a flow loop in communication with the production outlet. The structures may include other typical components such as one or more production valves to control the flow through the production outlet. Typically, the insulating material is applied to those portions of the Christmas tree that are most exposed to the surrounding seawater and through which the produced fluids will flow.
    [0067] • prover uma superfície a ser revestida; • prover um prepolímero terminado por epóxi; • prover um agente de cura terminado por amina; • colocar o prepolímero terminado por epóxi e o agente de cura terminado por amina e opcionalmente objetos ocos, em contato com a dita superfície e reagir os ditos prepolímero terminado por epóxi e agente de cura terminado por amina provendo assim um revestimento baseado em epóxi. [0067] In another aspect of the present invention, a process is provided to provide a coating of epoxy-based material for offshore applications. The process comprises the stages of • provide a surface to be coated; • provide an epoxy-terminated prepolymer; • provide an amine-terminated curing agent; • placing the epoxy-terminated prepolymer and the amine-terminated curing agent and optionally hollow objects, in contact with said surface and reacting said epoxy-terminated prepolymer and amine-terminated curing agent thereby providing an epoxy-based coating.
    [0068] [0068] The application of the reaction mixture to the surface to be coated is carried out by methods known in the art. Examples are rotary casting, mold casting and the mixing pot process. See, for example, publications WO 02/072701; WO 2009/085191 and U.S. Patent No. 6,955,778.
    [0069] [0069] When the surface to be coated is a metal tube, such as a steel tube, the tube may be coated with a material in order to provide an anticorrosive layer or an adhesion promoting layer before the addition of the elastomer of the present invention . Examples of protective layers Commonly used in industry include a partially cured or fully cured epoxy or liquid epoxy primers with a glass transition temperature in the range between 70 and 200 ° C. When used, the epoxy primer is generally superimposed with the elastomer of the present invention. Elastomers may also comprise a single layer or multilayer coating for such tubes. For example, the elastomer may be overlaid with an additional layer of material, such as paint, silicone, polyurethane, epoxy, or polyolefin.
    [0070] [0070] When epoxy-based elastomeric material is applied to a complex structure, such as a Christmas tree, a variety of methods known in the art for application can be used. In one method, a mold or shape is built around the object to be isolated. The epoxy-finished prepolymer / amine curing additive / optional additive is carefully mixed and then fused between the object and the mold and allowed to cure. Once the material is cured, the mold is removed. Alternatively, the insulating material can be pre-cast in sections that are shaped to complement the object to be isolated. Once the pre-sections are cured, they can be fixed to the object using adhesives, mechanical fasteners, or any suitable means. The insulating material can also be sprayed on the object.
    [0071] [0071] In the process of rotary casting to coat objects such as tubes, after carefully mixing the epoxy-finished prepolymer, amine curing additive and optional additive (s), the mixture is poured through a nozzle. film on a tube that is rotated around its geometric axis and the desired coating thickness is adjusted via the speed at which the nozzle is advanced. When casting in a mold, a pretreated section of tube is poured into a heated mold, which has generally been treated with release agents, the mold is closed, tilted and filled from the lowest point with a hose until the reagent mixture comes out of the mold by the highest point. When heating, the mold is usually heated to between 80 ° C and 120 ° C. In the mixing bowl process, a reagent dosing machine is introduced into a mixing bowl that is opened at the bottom. At the same time, a defined quantity of hollow microspheres is dosed by means of a screw metering device. The reaction mixture can be applied over a rotating tube or introduced into a mold via an exit orifice.
    [0072] [0072] The coating provided may have a thickness in the range of 100 mm, typically in the range of 10 to 50 mm. In a further embodiment, the coating will have a density of more than 0.5 g / cm3.
    [0073] [0073] The following examples are provided to illustrate the invention, but are not intended to limit its scope. All parts and percentages are by weight, unless otherwise specified. EXAMPLES Example 1: Production of Epoxy Finished Prepolymer
    [0074] [0074] A 20-gallon stainless steel reactor is loaded with 49.6 g of liquid epoxy resin DERMR 383 a reaction product of epichlorohydrin and bisphenol A, commercially available from The Dow Chemical Company (epoxy equivalent weight = 180.1 g / mol) with stirring followed by the addition of 52.3 g of polyalkyleneamine JeffamineMR T5000, a polyoxypropylene triamine with a nominal molar mass of 5000 g / mol commercially available from Huntsman Corp. (equivalent amine weight = 952 g / mol). The vessel is degassed, lined with nitrogen and the temperature is slowly raised to 125 ° C by means of a heated jacket. The internal temperature is maintained at 120 ° C and maintained for three hours. The vessel is then cooled to 80 ° C, the agitator is turned off and the sample is discharged. The epoxy-terminated prepolymer was found to be a viscous liquid at 25 ° C (approximately 90,000 cPs) with a measurable epoxy equivalent weight of 412 g / mol (463 effective). Examples 2 to 5: Preparation of Elastomer:
    [0075] [0075] The epoxy-finished prepolymer prepared in example 1 is added to cups with a lid for use in a FlackTek SpeedMixerMR and the sample was mixed for 30 seconds at 800 rpm, then mixed at 2350 rpm for 1 minute to remove bubbles and then heated in a greenhouse at 54 ° C. The amine curing agent is added according to the formulations in table 1, the values are in parts by weight.
    [0076] [0076] After adding the curing agent, the samples are mixed in a FlackTek SpeedMixer for 30 seconds at 800 rpm followed by 2350 rpm for 1 minute. The mixtures are then poured into closed aluminum molds which are then preheated to 100 ° C and treated with a release agent. The molds are placed back in the oven at 100 ° C and allowed to cure for approximately 1 hour, demoulded and cooled to room temperature for 24 hours. Tensile properties are then measured according to ASTM D1708 and thermal properties are measured by Differential Scanning Calorimetry by cutting samples of approximately 10 mg and placing the samples in aluminum pans. The DSC procedure is to cool the samples to -90 ° C, then ramp to 200 ° C at a rate of 10 ° C / min. The thermal cycle is repeated and the appearance of the glass transition temperatures is measured in the second upward sweep. The measured properties of the elastomers produced are given in table 2.
    [0077] [0077] The results show that the highly functional curing agent (triethylene tetramine) has a deleterious effect on the properties of the elastomers produced. Examples 7 and 8
    [0078] [0078] The epoxy-finished prepolymer prepared in example 1 is added to cups with a lid for use in a FlackTek SpeedMixerMR and the sample was mixed for 30 seconds at 800 rpm, then mixed at 2350 rpm for 1 minute to remove bubbles and then heated in a greenhouse at 54 ° C. The curing agent and DMP 30 (2,4,6-tris (dimethylaminomethyl) phenol) as a catalyst were added according to the formulations in table 3.
    [0079] [0079] After adding the curing agent and catalyst, the samples are mixed in the SpeedMixer for 30 seconds at 800 rpm followed by 2350 rpm for 1 minute. The mixtures are then poured into vertical, closed molds that are preheated to 100 ° C and treated with a release agent. The molds are returned to the oven at 100 ° C, allowed to cure for 12 minutes then demolded and cooled to room temperature over 24 hours. The tensile properties and DSC measurements are made as described above.
    [0080] [0080] The results show that the addition of the catalyst generally improves the resistance and hardness properties of the elastomers without increasing the primary glass transition temperature. In addition the thermal conductivity of examples 7 and 8 are measured according to ASTM and are measured and found to be 10,160 W / m * K and 0.155 W / m * K respectively. Example 9: Thermo-Oxidative Tests of Elastomers according to ASTM D2000
    [0081] [0081] Elastomers prepared according to the procedure of example 2 are tested for oxidative thermostability. Microtension dog bone samples suitable for testing according to ASTM D1708 were cut and these test bodies were aged in a forced air oven for 70 hours at temperatures of 70 100, 125 and 150 ° C. The samples were allowed to cool to room temperature and rest for a minimum of 24 hours before the microtension tests.
    [0082] [0082] Following the aging cycle, there is no significant reduction in the mechanical properties of the elastomers produced indicating good thermo-oxidative stability. Examples 10 and 11
    [0083] [0083] To test the performance of a syntactic elastomer, example 10 is prepared according to the example procedure and example 11 follows the procedure of example 2 except that Scotchlite S38HS glass bubbles (received from 3M Company) (19 grams ) are added to the epoxy-terminated prepolymer prior to the addition of ethanolamine. The glass bubbles are mixed manually in the FlakTek until a homogeneous dispersion is obtained. The molding conditions of the elastomer and the release time are the same as for solid elastomers. The properties of the elastomers produced are given in table 6 (average of 4 samples).
    [0084] [0084] Elastomers produced according to the procedure of examples 2 and 3 are tested for hydrolytic stability. Microtension dog bone shaped samples suitable for testing according to ASTM D1708 are cut from the sample and these test pieces together with several test pieces with dimensions of approximately 5 cm (2 inches) in length 2.54 cm (1 inch) ) in diameter are aged in deionized water in a one gallon stainless steel pressure chamber at 160 ° C for periods of two to four weeks. Following the aging intervals, the test bodies are removed, allowed to cool to approximately 25 ° C, and superficially dried. The cylinders are measured for change in weight and Shore A hardness and compared to non-aged values. Tension test bodies are tested under two conditions. First, the test bodies are re-tested for retention properties within 2 hours of removal from the pressure chamber. Separate sets of test bodies are post-dried in an oven at 60 ° C overnight to remove entrained water, allowed to cool to 25 ° C, and then tested for tension properties. The tension data are reported as an average of 5 test bodies in each interval. The changes in mass and hardness are reported as an average of 3 cylindrical samples. The results of these tests are given in table 7.
    [0085] [0085] The data in example 12 shows that the materials undergo a change from the initial values during the first aging interval of two weeks, but exhibit good stability of all properties from two weeks to four weeks. It can be seen from the elastomer of example 2 that the changes in tension properties are primarily due to the absorption of moisture since after the post-drying step the properties return to values very close to those of the original. This indicates that the materials have good resistance to hydrolytic degradation. Example 13: Coating Preparation
    [0086] [0086] To determine the effectiveness of elastomers as a protective coating, steel plates are coated with the elastomer and property measurements performed according to A1 / A2 systems according to CSA standards (Z245.20-06, External fusion bond epoxy coating for steel pipe).
    [0087] [0087] An epoxy-terminated prepolymer is prepared according to the procedure of example 1 where DER 383 and Jeffamine T5000 are mixed at a molar ratio of 5 to 1. An elastomer is produced according to the procedure of example 2 by mixing 100 g of the prepolymer with 8.15 g of 2-propanol amine as the amine curing agent. The mixture is then melted in a square mold window seated on parallel steel panels, covered with a non-stick aluminum foil, and placed in a greenhouse at 120 ° C. Within a maximum of one hour, the coating is demoulded and cut into two pieces using a general purpose knife. The thickness of the final coating varies between 1.2 mm and 1.5 mm. Performance Results (a) Impact test
    [0088] [0088] The coating test bodies are placed in a freezer and cooled to -30 ° C for a minimum of one hour before testing. The impact test is performed by a mass of 1 kg falling on the panel with an impact energy of at least 3.0 J per mm of effective coating thickness. Three impacts are completed within 30 sec of removing the test body from the freezer. The visual observation of the material coated with the elastomer shows a surface essentially free from surface damage, that is, no delamination or cracks are observed on the surface of the coating. It is believed that the damage resistance of elastomers is due to the presence of soft segments, which are separated in phases from the hard segments, with the glass transition temperature lower than -30 ° C.
    [0089] [0089] For comparison of the impact resistance test, an epoxy coating, based on the formulation given in table 8, is coated with powder on 7.6 x 20.3 cm (3 x 8 inch) steel plates with a approximately 10 mil thickness.
    [0090] [0090] DER 664EU is a solid epoxy resin having an EEW of 900 equivalents per gram and commercially available from The Dow Chemical Company; Amicure CG 1200 is a commercially available dicyandiamide powder from Air Products; Epikure 101 is an imidazole based curing agent and is commercially available from Hexion; Modaflow Powder III is a flow modifier and is commercially available from Solutia Inc .; Vansil W 20 is a wollastonite extender and is commercially available from R.T. Vanderbilt Company, Inc.
    [0091] [0091] The observation of the impact test shows clear impact marks of the fallen mass on the surface coated with FBE. (b) Cathodic detachment test (CD)
    [0092] [0092] A 3.0 mm unpainted space is machined in the center of the test body through the elastomeric coating to expose the steel substrate in a 3% saline solution under two different corrosion conditions: (a) 3.5 V (negative with respect to the reference) at 65 ° C for 48 hours or (b) 1.5 V at 65 ° C for 28 days. After 48 hours, the elastomer coating showed detachment from the steel plates; less than 5 mm in radius. For the 28 days, a detachment radius of 5 mm was observed. (c) Hot wet adhesion test (HWA)
    [0093] [0093] An HWA test is performed by immersing test panels standing in a spout water bath being heated to 75 ° C. The test bodies are removed in 48 hours and a 30 mm x 15 mm rectangle is scratched through the coating using a general purpose knife immediately after removal. Using a knife lever, the coating is forced to peel by inserting the tip of the knife blade under the elastomer at each corner of the rectangle. Only a marginal delamination is created in the FBE and in the elastomer coatings in the corners. (d) Peel adhesion test
    [0094] [0094] The test panel is fixed on the horizontal translational sample level, which virtually slides without friction along the linear rail of a base frame, and installed in an Instron 4505 test instrument at room temperature. A 25 mm wide strip of the elastomer coating is peeled perpendicularly from the steel panel at a constant crosshead speed of 10 mm / min. In addition to this yield point, the peel adhesion force reaches a steady state of 95.3 N. CSA standards require a minimum of 3.0 N and 19.6 N for systems A1 and A2, respectively. (e) Flexibility test at 2.5 °
    [0095] [0095] Elastomer coatings are applied to steel bars of 2.5 cm x 20.3 cm (1 x 8 inches) instead of [; steel for flexibility testing. The bars are cooled to -30 ° C in the freezer and stored for a minimum of one hour before testing. Within 30 s of removal, four points on the test body are subjected to hydraulic compression to achieve a fold of at least 2.5 ° (effective fold of the test bar is 7 °). Visual observation indicates that elastomer coatings do not show any sign of adhesive or cohesive failure. Example 14
    [0096] [0096] To determine the performance of the elastomer in double layer coatings, test bodies are prepared to apply a layer of fusion-bound epoxy (FBE) to the test materials followed by the addition of the elastomeric layer over the FBE. Tests are performed for B1 / B2 systems defined according to CSA standards (Z245.21-06, External polyethylene coating for pipe). The conditions for testing the materials are essentially in accordance with the procedures given in example 13, with the exception of sample sizes that are adjusted according to CSA standards.
    [0097] [0097] Coatings approximately 10 mils thick are applied to 7.6 x 20.3 cm steel plates by a powder coating process. Boards with only the FBE layer serve as the controls. The elastomer is produced according to example 13. The elastomer mixture is melted in a square mold window resting on the panels lined with FBE parallel aligned, covered with a non-adherent aluminum foil, and placed in an oven at 120 ° C. In a maximum of one hour, the coating is demoulded and cut into two pieces using a general purpose knife. The thickness of the final elastomer coating ranges from 1.2 mm to 1.5 mm. Visual observation of test results is as follows: Impact test
    [0098] [0098] The single layer of FBE is considered to be failing due to the clear impact marks of falling mass that exposed the metal under the coatings. The FBE / elastomer coatings exhibit a partial mark on the FBE primer, however no delimitation, cracking or indentation was observed in the elastomer layer. Cathodic detachment test (CD)
    [0099] [0099] The 48 hour results result in showing that less than 5 mm of detachment occurs from the FBE primer of the steel plate for both the FBE and FBE / elastomer coating. A maximum radius of 7 mm of detachment is permitted by CSA standards. Peel adhesion test
    [0100] [0100] The test bodies break before delamination of the FBE primer suggesting that the adhesion force between two layers exceeds the cohesive energy of the elastomer layer. At the yield point, it is consistently observed that the peel adhesion reaches 200 N before the failure which is above the limit (150.0 N) specified in the CSA standards. 2.5 ° flexibility test (4-point folding)
    [0101] [0101] The FBE primer protected with the elastomer coating showed no sign of adhesive or cohesive failure while multiple cracks and delamination were created along the bars coated with a single layer of FBE.
    [0102] [0102] While the above has been directed to embodiments of the invention, other and numerous embodiments of the invention can be envisaged without departing from its basic scope.
    权利要求:
    Claims (11)
    [0001]
    Method for thermally insulating an object from a surrounding liquid, characterized by the fact that it comprises interposing an insulating material between the object and the fluid, the insulating material comprising the reaction product of: (a) a liquid epoxy-terminated prepolymer at room temperature formed by reacting one or more polyoxyalkyleneamine having a molecular weight of 3,000 to 20,000 with a molar excess of epoxide, the polyoxyalkyleneamine having at least 3 active hydrogen atoms; and (b) a curing agent comprising at least one amine or polyamine having an equivalent weight of less than 200 and having 2 to 5 active hydrogen atoms.
    [0002]
    Method, according to claim 1, characterized by the fact that polyoxyalkyleneamine is represented by the formula:
    [0003]
    Method according to claim 2, characterized in that U is an alkyl group having 1 or 2 carbon atoms and T and V are independently hydrogen or an alkyl group containing a carbon.
    [0004]
    Method according to any one of claims 1 to 3, characterized in that the epoxide is at least one or more of the formula:
    [0005]
    Method according to claim 4, characterized in that the epoxide is one or more of diglycidyl ethers of resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis (4-hydroxyphenyl) -1- phenyl ethane), bisphenol F, bisphenol K, bisphenol S, tetrabromobisphenol A, novolaca phenol-formaldehyde resins, alkyl substituted phenol-formaldehyde resins, phenol-hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentol resins dicyclopentadiene-substituted phenol resins, tetramethylbiphenol, tetramethyl-tetrabromobiphenol, tetramethyltribromobiphenol, tetrachlorobisphenol A, or a combination thereof.
    [0006]
    Method according to any one of claims 1 to 3, characterized in that the epoxide is at least one cycloaliphatic epoxide of the formula:
    [0007]
    Method according to any one of claims 1 to 3, characterized in that the epoxide is at least a divinylarene oxide of the following structures:
    [0008]
    Method according to any one of claims 1 to 7, characterized in that the amine curing agent is present in an amount to provide 0.8 to 1.5 equivalents of amine per epoxy reactive group.
    [0009]
    Method according to any one of claims 1 to 8, characterized in that the curing agent is at least one curing agent represented by the formula:
    [0010]
    Method according to any one of claims 1 to 9, characterized in that the amine curing agent is represented by the formula:
    [0011]
    Tube, at least partially enclosed by a thermal insulator, characterized by the fact that the thermal insulator layer comprises the reaction product of: (a) a liquid epoxy-terminated prepolymer at room temperature formed by reacting one or more polyoxyalkyleneamine having a molecular weight of 3,000 to 20,000 with a molar excess of epoxide, with polyoxyalkyleneamine having at least 3 active hydrogens; and (b) a curing agent comprising at least one amine or polyamine having an equivalent weight of less than 200 and having 2 to 5 active hydrogen atoms.
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    同族专利:
    公开号 | 公开日
    EP2611849B1|2015-03-18|
    US8951619B2|2015-02-10|
    MY160149A|2017-02-28|
    AU2011296067A1|2013-04-11|
    BR112013005064A2|2017-07-18|
    DK2611849T3|2015-06-01|
    WO2012030906A1|2012-03-08|
    US20130291992A1|2013-11-07|
    WO2012030339A1|2012-03-08|
    EP2611849A1|2013-07-10|
    PL2611849T3|2015-08-31|
    AU2011296067B2|2015-07-02|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2019-11-19| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2020-05-12| B09A| Decision: intention to grant|
    2020-07-21| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 31/08/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    PCT/US2010/047553|WO2012030339A1|2010-09-01|2010-09-01|Elastomeric insulation materials and the use thereof in subsea applications|
    USPCT/US2010/047553|2010-09-01|
    PCT/US2011/049884|WO2012030906A1|2010-09-01|2011-08-31|Elastomeric insulation materials and the use thereof in subsea applications|
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