• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    swelling article. the present invention relates to an intumescible article, which includes a matrix material and an exfoliable graphene-based material disposed in the matrix material. the exfoliable graphene-based material is operationally arranged to facilitate the swelling of the swellable article upon exposure to a selected fluid through the sorption of particles in the fluid. swelling allows the swelling article to engage an adjacent structure. methods of preparing and using an intumescent article are also included.
    公开号:BR112015002787B1
    申请号:R112015002787-3
    申请日:2013-07-15
    公开日:2021-03-30
    发明作者:Oleg A. Mazyar；James E. Goodson
    申请人:Baker Hughes Incorporated；
    IPC主号:
    专利说明:

    REMISSIVE REFERENCE TO RELATED DEPOSIT REQUESTS
    [001] This application claims the benefit of Application No. U.S. 13/585160, filed on August 14, 2012, which is hereby incorporated in its entirety, by way of reference. BACKGROUND
    [002] Intumescent and fluid materials and absorbents and fluids are used in a multitude of sectors. For example, in the deep drilling and completion sector, intumescible materials are used in various obstruction, insulation, actuation and sealing devices that automatically react upon exposure to certain deep drilling fluids, such as oil and water. Although such intumescible materials are used satisfactorily for various purposes, the technique nevertheless always welcomes advances and alternatives for systems of absorbent and intumescible materials. SUMMARY OF THE INVENTION
    [003] An intumescible article, which includes a matrix material; and an exfoliable graphene-based material disposed in the matrix material, characterized by the fact that the exfoliable graphene-based material is operationally disposed to facilitate intumescence of the intumescible article upon exposure to a fluid selected through the sorption of particles in the fluid, swelling allowing the swelling article to engage an adjacent structure.
    [004] A method of using an intumescible article that includes exposing an intumescible article, as mentioned above, to a selected fluid; dilate the swelling article with the selected fluid; sorb particles in the fluid with the graphene-based material to facilitate swelling; and engaging the swelling article with an adjacent structure after swelling.
    [005] A method of preparing an intumescible article that includes placing a graphene-based material in a matrix material to produce an intumescible material; exfoliate a graphene-based material; and forming the swelling material in an article that is responsibly swelling to a selected fluid, the graphene-based material operatively disposed to facilitate swelling of the swelling article upon exposure to a selected fluid through the sorption of particles in the fluid. BRIEF DESCRIPTION OF THE FIGURES
    [006] The following descriptions should not be considered limiting in any way. With respect to the attached drawings, similar elements are enumerated in a similar way:
    [007] Figure 1 schematically illustrates a process for the preparation and use of an intumescible article; and
    [008] Figure 2 illustrates an example of exfoliation of a graphene-based material from the article in Figure 1 that includes the expansion of an interleaver. DETAILED DESCRIPTION
    [009] A detailed description of one or more modalities of the disclosed apparatus and method are presented in this document as an example and not delimiting in relation to the Figures.
    [0010] Referring now to the Figures, a process of preparation and use of an intumescible article 10 is shown schematically in Figure 1. The process to finally form the article 10 begins with the creation of a material compound based on exfoliable graphene 12. Graphene-based material means graphene, graphite, graphene oxide, graphite oxide, graphite intercalating compounds and their derivative forms to include a functional group, for example, which includes carboxy, epoxy, ether , ketone, amine, hydroxy, alkoxy, alkyl, aryl, aralkyl, alkaryl, lactose, functionalized oligomeric and polymeric groups or a combination comprising at least one of the groups mentioned above. Graphite intercalating compounds can include intercalating agents such as, for example, an acid, metal, binary alloy of an alkali metal with mercury or thallium, binary compound of an alkali metal with a Group V element (for example, P, As , Sb and Bi), metal calcide (including metal oxides, such as chromium trioxide, PbO2, MnO2, metal sulphide and metal selenide), metal peroxide, metal hyperperoxide, metal hydride, hydroxide metal, metals coordinated by nitrogenous compounds, aromatic hydrocarbons (benzene, toluene), aliphatic hydrocarbons (methane, ethane, ethylene, acetylene, n-hexane) and their oxygen derivatives, halogen, fluoride, metal halide, nitrogenous compound, inorganic compound (for example, tritiazil trichloride, thionyl chloride), organometallic compounds, oxidizing compounds (for example, peroxide, permanganate ion, chlorite ion, chlorate ion, perchlorate ion, hypochlorite ion, As2O5 , N2O 5, CH3CIO4, (NH4) 2S2O8, chromate ion, dichromate ion), solvent or a combination comprising at least one of those mentioned above. Exemplary acids include, nitric acid, sulfuric acid, acetic acid, CF3COOH, HSO3F, HSO3CI, HSO3CF3, persulfuric acid (for example, H2SO5, H2S2O8), phosphoric acid, H4P2O7, perchloric acid, HsAsO ^ H2SeO4, HIO4, HIO4, HIO4, HIO4, HIO4, HIO4, HIO4, HIO4, HIO4, HIO4, HIO4, HIO4, HIO4, H2PtCI6, or a combination comprising at least one of those mentioned above. Exemplary metals include alkali metals (eg, lithium, sodium, potassium and the like), alkaline earth metals (eg, magnesium, calcium, strontium and the like), rare earth metals (eg, scandium, yttrium, lanthanide elements and the like ), transition metals (for example, iron, tungsten, vanadium, nickel and the like) and post-transition metals (for example, aluminum, tin and the like). Exemplary metal halides include Nal, FeCI3, CuCI2, AuCI3, MoCI5, SbCI5, and the like. Nitrogen compounds include, for example, ammonia, ammonium, hydrazine, amines and amides. Exemplary halogens include Cl2, Br2, BrCI, ICI, IBr, BrF3, BrF5, and IF5. Exemplary fluorides include halogen fluorides, boron fluoride, hydrogen fluoride, PF5, ASF5, and rare gas fluorides. Exemplary solvents include benzene, toluene, o-xylene, dimethyl sulfoxide, furan, tetrahydrofuran, o-dioxane, m-dioxane, p-dioxane, dimethoxyethane, n-methylpyrrolidone, n, n-dimethylacetamide, y-butyrolactone , 1,3-dimethyl-2-imidazolidinone, benzyl benzoate, hexafluorobenzene, octafluorotolane, pentafluorobenzonitrile, pentafluoropyridine, pyridine, dimethylformamide, hexamethylphosphoramide, nitromethane, and benzonitrile. These materials can be arranged in sheets, layers or sheets, providing extremely high surface areas and oleophilicity. Advantageously, the combination of high surface area and high oleophilicity allows these and other graphene-based materials to adsorb and / or absorb (collectively, "sip") relatively large amounts of certain fluid particles, particularly oil, hydrocarbons and other organic fluids. In turn, this sorption of large amounts of particles facilitates the swelling or swelling of the article 10 when exposed to a fluid that has a component, such as oil or hydrocarbons, which is absorbed by the compound 12.
    [0011] Exfoliable means that the material based on graphene has the ability to undergo an exfoliation process. The exfoliation used in this document refers to the creation of leaves, plans, layers, layers, etc. individual (usually "layers") of a graphene-based material; the delamination of the layers; or widening a flat gap between adjacent layer gaps. In this way, the purpose of exfoliation is to increase the available surface area per unit volume or mass of the graphene-based material. This is particularly useful with larger fluid particles, for example, as in heavy oil, which do not fit between tightly packed layers. Examples of exfoliation include processes, chemical, physical and / or mechanical, such as heating graphite intercalating compounds; graphite sonication, graphite and functionalized graphite intercalation compounds and solvent systems; thermal annealing of graphite oxide; abrasion, shearing, stamping or grinding of graphite particles; removal of layers by adhesive tapes, etc., although those skilled in the art may observe that any other method now known or hereafter discovered can be used to exfoliate a graphene-based material.
    [0012] In one embodiment, compound 12 is formed by combining a graphene-based material 14 (ie, as defined above) and an interleaver 16, as per step 100. As shown in Figure 2, the interleaver or agent interleaver 16 is a solid, liquid or gaseous material that is disposed between two layers 18 of the graphene-based material 14. In one embodiment, the interleaver 16 is formed by potassium and tetrahydrofuran, although other materials can be used. The layers 18 can be as thick as a single atom or as a plurality of atoms. The interleaver 16 results in a flat gap 20, initially designated with the number 20a, formed substantially perpendicularly between the layers 18. By heating the compound 12, according to step 102, the interleaver 16 expands, widening the gap 20, thus way, to a second dimension designated by the number 20b, during the exfoliation of compound 12. As will be described in more detail below, step 102 is shown in its own Figure 2, since the exfoliation of the graphene-based material can occur at various points during the process of Figure 1. In addition, those skilled in the art will be able to readily observe that interleaving represents only one method of forming exfoliable compound 12 and that heating interleaver 16 is just one example of exfoliating compound 12 and any other exfoliable compound and corresponding exfoliation method can be used.
    [0013] Regardless of the method by which compound 12 is formed, compound 12 is combined with a matrix 22 in step 104 to form an intumescible material 24. In one embodiment, compound 12 is ground (for example, cryogenic grinding ) to form powdered compound 12 which is interspersed in matrix 22. Intumescible means that material 24 will swell, enlarge or, if not, change in at least one direction when exposed to a suitable fluid. The matrix 22 can be a material that is also swellable or a non-swellable material. In exemplary embodiments, matrix material 22 is elastomeric, although other materials can be used depending on the purpose of article 10. For example, in one embodiment, matrix 22 is formed from acrylonitrile butylenic rubber, which offers good characteristics sealing and can be adapted to various levels of intumescence. In one embodiment, the matrix 22 and / or the swelling material 24 is prepared to include other additives or materials to adapt the properties of the resulting article 10, such as pressure rate, strength, swelling, elasticity, durability, etc. In one embodiment, matrix 22 and / or material 24 includes carboxymethylcellulose or some water absorbers, water swelling or hydrophilic additives in order to also make article 10 swellable upon exposure to aqueous fluids. In this way, Article 10 can become responsive in an intumescible way to oil, water or double intumescible combinations thereof.
    [0014] The swellable material 24 is then formed in a step 106 in article 10. The formation of step 106 may include the appropriate molding, machining, modeling or other process to give the shape and dimensions to the article 10. In one embodiment, such as noted in this document, the swellable material 24 allows article 10 to be swellable in a fluid that is at least partially defined by oil or hydrocarbons, which are readily absorbed by the graphene-based material in compound 12.
    [0015] According to step 108 of the illustrated embodiment, after forming article 10, a system 26 is formed by arranging article 10 with a tubular 28. In one embodiment, material 24 is directly rolled into the tubular to form a system 26 in a single step that combines the illustrated steps 106 and 108. In one embodiment, the tubular is part of a column, such as a production column or some other component of a well drilling completion. Of course, article 10 can have any other format for installation in or with non-tubular members, article 10 can be installed inwardly radially as opposed to radially, outwardly, as shown, etc. Finally, article 10 is exposed to a suitable fluid in a step 110 in order to increase the volume of article 10. In the illustrated embodiment, the swelling of article 10 allows article 10 to act to engage in order to seal a perforation of well 30 to isolate the drilling of well 30 on opposite sides of article 10. Of course, article 10 can be used in coated well bores or and any annular space formed between adjacent radial structures. In addition, intumescence can be used for any combination of sealing, insulation, actuation, absorption, etc. and one skilled in the art will recognize a myriad of isolation, obstruction, actuation, absorption and sealing devices that can benefit from intumescible materials and articles discussed in this document.
    [0016] As noted above, step 102 can occur at several points in the general process of Figure 1. For example, the graphene-based material can be exfoliated before, during or after steps 100, 104, 106, 108, or 110. It is noted that some of the benefits of exfoliating the graphene-based material can be negated during the formation in step 106, particularly if the material 24 is compressed, for example, in a mold, in order to form the article 10 , as this can cause the graphene / graphite layers (for example, layers 18) to stick together. In a modality that uses the interleaver 16, the exfoliation illustrated in step 102 and Figure 2 occurs after the article 10 is formed in step 106 by heating the article 10. The heating can occur on the surface, deep drilling or any other desired location. In one embodiment, exposure to deep drilling environments provides the necessary heating to exfoliate the graphene-based material by expanding the interleaver 16, while in other modalities, a heat source, such as a heated fluid, exothermic reaction, electric current, etc. is provided. Advantageously, this allows exfoliation to occur after all the forming processes have taken place, so that the graphite / graphene layers are not subjected to any process that can cause them to rejoin, thereby reducing , the surface area that is accessible to the particles (particularly relative to the larger particles) in the fluid to which article 10 is responsive. In another embodiment, the exfoliation of a graphite intercalating compound is obtained by passing an electric current through the intercalated graphite or adjacent metal components. In yet another embodiment, the exfoliation of a graphite intercalating compound is achieved by inductive heating (for example, producing eddy currents in the intercalated graphite / graphene particles). In yet another modality, exfoliation is achieved by applying ultrasonic frequencies to the graphene-based material. Without wishing to stick to any particular theory, sonic frequencies can disturb the connections between adjacent atomic planes in graphene-based materials and / or induce chemical reactions of the intercalating agent within the galleries formed by the graphene planes, which results in an exfoliation of graphene-based materials. Again, without wishing to stick to any particular theory, such effects can be induced by localized and transient disturbances (for example, a hot spot) produced by the rupture of bubbles in the course of the solvent's acoustic cavitation. In yet another embodiment, the exfoliation of the graphite intercalating compounds is obtained by the reaction of the intercalating agent to increase the distance between the adjacent graphene planes in the graphene-based materials. This can be achieved when the occupied dimensions or volumes of the reaction products are greater than the initial dimensions or volumes of the intercalating agent, when a plurality of atoms and molecules of the product or a combination thereof are produced per molecule of the intercalating agent, or when the reaction products formed have high kinetic energy (for example, to heat the graphite intercalating compound and assist in exfoliation). For example, the intercalating agent can be hydrolyzed. In one embodiment, an antimony pentachlorite intercalating agent is hydrolyzed upon contact with water molecules to produce Sb2O5 and hydrochloric acid. Any molecules or atoms of such a product can be further reacted (os) to produce an even greater number of product molecules to assist in the exfoliation process. Of course, any combination including any of those mentioned above can be used.
    [0017] Although the invention has been described with reference to an exemplary modality or modalities, it will be understood by those skilled in the art that several changes can be made and equivalents can be replaced by elements of the same, without deviating from the scope of the invention . In addition, many modifications can be made to adapt a given situation or material with respect to the instructions of the invention without deviating from its essential scope. Therefore, it is intended that the invention is not limited to the particular modality revealed as the best contemplated way to carry out this invention, but that the invention will include all modalities that are within the scope of the appended claims. In addition, in the drawings and description, exemplary modalities of the invention have been revealed and, although specific terms have been used, they are, unless otherwise stated, used only in a general and descriptive sense and not for the purpose of limitation, being the scope of the invention, therefore, not limited to them. In addition, the use of the terms first, second, etc. they do not denote any order or importance, but, on the contrary, the terms first, second, etc. are used to distinguish between one element and another. Additionally, the use of the terms one, one, etc. they do not denote a quantity limitation, but, on the contrary, it denotes the presence of at least one of the items in reference.
    权利要求:
    Claims (31)
    [0001]
    1. Intumescible article characterized by the fact that it comprises: a matrix material; and an exfoliable graphene-based material disposed in the matrix material, and the exfoliable graphene-based material is operationally arranged to expand by applying ultrasonic frequencies to the graphene-based material and to facilitate the swelling of the intumescent article after the exposure to a fluid selected for absorbing hydrocarbons in the fluid, the swelling allowing the intumescent article to engage an adjacent structure, and an intercalant arranged between layers of the graphene-based material; and wherein the intercalant is one or more of the following: a metal selected from an alkali metal, alkaline earth metal, rare earth metal, transition metal and post-transition metal; a binary alloy of an alkali metal with mercury or thallium; a binary compound of an alkali metal with a Group V element; a metal calcide comprising a metal oxide; a metal sulfide; a metal selenide; or a combination thereof, a metal peroxide; a metal hyperoxide; a metal hydride; a metal coordinated by a nitrogenous compound; a halogen comprising Cl2, Br2, BrCl, ICl, IBr, BrF3, BrF5, IF5 or a combination thereof; an acid comprising CF3COOH, HSO3F, HSO3Cl, HSO3CF3, H2S2O8, phosphoric acid, H4P2O7, H3AsO4, H2 SeO4, HIO4, H5IO6, HAuCl4, H2PtCl6 or a combination thereof; or a combination thereof; an oxidant comprising a permanganate ion, a chlorite ion, a chlorate ion, a perchlorate ion, a hypochlorite ion, a chromate ion, a dichromate ion; or a combination thereof; or a solvent comprising benzene, toluene, o-xylene, dimethylsulfoxide, furan, tetrahydrofuran, o-dioxane, m-dioxane, p-dioxane, dimethoxyethane, n-methyl-pyrrolidone, n, n-dimethylacetamide, Y- butyrolactone, 1,3-dimethyl-2-imidazolidinone, benzyl benzoate, hexafluorobenzene, octafluorotoluene, pentafluorobenzonitrile, pentafluoro-pyridine, pyridine, dimethylformamide, hexamethylphosphoramide, nitromethane and benzonitrile, or a combination of the same.
    [0002]
    2. Intumescent article, according to claim 1, characterized by the fact that the matrix material is an electromeric material.
    [0003]
    3. Swelling article, according to claim 2, characterized by the fact that the swelling article is characterized by the fact that it is operationally arranged to create a sealed coupling with the structure after swelling.
    [0004]
    4. Intumescent article, according to claim 3, characterized by the fact that the structure is a well bore, a tubular or a combination that includes at least one of those mentioned above.
    [0005]
    5. Intumescible article, according to claim 1, characterized by the fact that the intumescible article is characterized by the fact that it is configured to expand in a radial direction.
    [0006]
    6. Intumescent article, according to claim 1, characterized by the fact that the interleaver is operationally arranged to expand by applying heat to the interleaver in order to exfoliate the graphene-based material.
    [0007]
    7. Intumescent article, according to claim 1, characterized by the fact that the interleaver is operationally arranged to react with water in order to exfoliate the graphene-based material.
    [0008]
    8. Method of preparing an intumescible article according to claim 1, characterized by the fact that it comprises: arranging a material based on graphene in a matrix material for the production of an intumescible material; exfoliate the graphene-based material; and form the swellable material within an article that is responsibly swellable to a selectable fluid, the graphene-based material operationally arranged to expand with the application of ultrasonic frequencies to the graphene-based material and to facilitate the swelling of the intumescent article by exposure to a selected fluid, absorbing hydrocarbons in the fluid in which the graphene-based material comprises an interlayer disposed between the layers of the graphene-based material; and wherein the intercalant is one or more of the following: a metal selected from an alkali metal, alkaline earth metal, rare earth metal, transition metal and post-transition metal; a binary alloy of an alkali metal with mercury or thallium; a binary compound of an alkali metal with a Group V element; a metal calcide comprising a metal oxide; a metal sulfide; a metal selenide; or a combination thereof, a metal peroxide; a metal hyperoxide; a metal hydride; a metal coordinated by a nitrogenous compound; a halogen comprising Cl2, Br2, BrCl, ICl, IBr, BrF3, BrF5 and IF5, or a combination thereof; an acid comprising CF3COOH, HSO3F, HSO3C1, HSO3CF3, H2S2O8, phosphoric acid, H4P2O7, H3AsO4, H2SeO4, HIO4, H5IO6, HAuCl4, H2PtCl6 or a combination thereof; or a combination thereof; an oxidant comprising a permanganate ion, a chlorite ion, a chlorate ion, a perchlorate ion, a hypochlorite ion, a chromate ion, a dichromate ion or a combination thereof; or a solvent comprising benzene, toluene, o-xylene, dimethylsulfoxide, furan, tetrahydrofuran, o-dioxane, m-dioxane, p-dioxane, dimethoxyethane, n-methyl-pyrrolidone, n, n-dimethylacetamide, Y- butyrolactone, 1,3-dimethyl-2-imidazolidinone, benzyl benzoate, hexafluorobenzene, octafluorotoluene, pentafluorobenzonitrile, pentafluoro-pyridine, pyridine, dimethylformamide, hexamethylphosphoramide, nitromethane and benzonitrile, or a combination of the same.
    [0009]
    9. Method according to claim 8, characterized by the fact that the exfoliation includes heating the graphene-based material in order to expand an interlayer disposed between the layers of the graphene-based material.
    [0010]
    Method according to claim 8, characterized by the fact that the heating includes: passing current through the graphene-based material, the article, a structure adjacent to the article or a combination that includes at least one of those mentioned above; trigger an exothermic reaction; position the article in a deep drilling location; releasing a heated fluid to the article; induce eddy currents in the graphene-based material; or a combination including at least one of those mentioned above.
    [0011]
    11. Method according to claim 8, characterized by the fact that the exfoliation includes reacting an interlayer disposed between the layers of the graphene-based material.
    [0012]
    12. Method according to claim 11, characterized in that the reaction of the interleaver includes producing a plurality of molecules and atoms of the product or a combination of them, per molecule of the interleaver.
    [0013]
    13. Method according to claim 12, characterized in that the production of the plurality of molecules and atoms of the product or the combination of them includes reacting the plurality of molecules and atoms of the product or the combination of them to form at least an additional molecule or atom of the product.
    [0014]
    14. Method, according to claim 11, characterized by the fact that the reaction of the interleaver includes hydrolyzing the interleaver.
    [0015]
    15. Method according to claim 8, characterized by the fact that exfoliation includes applying sonic frequencies to the graphene-based material in order to expand an interleaver disposed between the layers of the graphene-based material.
    [0016]
    16. Method according to claim 8, characterized by the fact that the matrix material is an elastomeric material.
    [0017]
    17. Method, according to claim 8, characterized by the fact that exfoliation occurs before disposing the graphene-based material in the matrix material.
    [0018]
    18. Method, according to claim 8, characterized by the fact that exfoliation occurs before forming the swellable material in the article.
    [0019]
    19. Method, according to claim 8, characterized by the fact that exfoliation occurs after forming the swelling material in the article.
    [0020]
    20. Method, according to claim 19, characterized by the fact that exfoliation occurs after positioning the swelling material in deep drilling.
    [0021]
    21. Method of using an intumescible article characterized by the fact that it comprises: exposing an intumescible article, according to claim 1, to a selected fluid; swelling the swelling article with the selected fluid; sorb particles in the fluid with the graphene-based material to facilitate swelling; and engaging the swelling article with an adjacent structure after swelling.
    [0022]
    22. Method according to claim 21, characterized by the fact that the particles are hydrocarbons.
    [0023]
    23. Method according to claim 21, characterized by the fact that the swellable article forms a sealed coupling with the adjacent structure.
    [0024]
    24. Method according to claim 21, characterized in that the adjacent structure is a well bore, a tubular, column or combination that includes at least one of those mentioned above.
    [0025]
    25. Method according to claim 21, characterized by the fact that the swelling of the swelling article includes expanding the swelling article radially.
    [0026]
    26. Intumescent article according to claim 1, characterized by the fact that the exfoliable graphene-based material is derivatized with a functional group comprising carboxy, epoxy, ether, ketone, amine, hydroxy, alkoxy, alkyl, aryl, aralkyl, alkaryl, lactam, polymeric or oligomeric functionalized group or a combination comprising at least one of the previous items.
    [0027]
    27. Intumescent article according to claim 1, characterized by the fact that the interleaver is one or more of the following: an alkali metal; or an alkaline earth metal.
    [0028]
    28. Intumescent article according to claim 1, characterized by the fact that the intercalant is one or more of the following: a binary alloy of an alkali metal with mercury or thallium; or a binary compound of an alkali metal with a Group V element.
    [0029]
    29. Intumescent article according to claim 1, characterized by the fact that the intercalant is one or more of the following: a metal oxide, a metal sulfide; a metal selenide; a metal peroxide, a metal hyperoxide or a metal hydride.
    [0030]
    30. Intumescent article, according to claim 1, characterized by the fact that the intercalant is a metal coordinated by a nitrogenous compound.
    [0031]
    31. Intumescent article, characterized by the fact that it comprises: a matrix material; an exfoliable graphene-based material, disposed in the matrix material, in which the exfoliable graphene-based material is operationally arranged to expand by applying ultrasonic frequencies to the graphene-based material and to facilitate the swelling of the intumescent article after exposure to a fluid selected for absorbing hydrocarbons in the fluid, the swelling allowing the intumescent article to engage an adjacent structure, and an intercalant disposed between layers of the graphene-based material; and wherein the intercalant is one or more of the following: a halogen comprising Br2; a metal selected from an alkali metal or an alkaline earth metal; a binary alloy of an alkali metal with mercury or thallium; a binary compound of an alkali metal with a Group V element; or a metal coordinated by a nitrogenous compound.
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    同族专利:
    公开号 | 公开日
    CA2880960A1|2014-02-20|
    CN104583530A|2015-04-29|
    US20140051612A1|2014-02-20|
    GB201504187D0|2015-04-29|
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    RU2015108924A|2016-10-10|
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    NO20150171A1|2015-02-06|
    GB2521298B|2019-09-25|
    BR112015002787A2|2017-10-10|
    US9404030B2|2016-08-02|
    CN104583530B|2017-08-25|
    GB2521298A|2015-06-17|
    AU2013303158B2|2016-10-06|
    CA2880960C|2017-06-20|
    AU2013303158A1|2015-02-19|
    WO2014028149A1|2014-02-20|
    RU2634757C2|2017-11-03|
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    法律状态:
    2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-01-14| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-17| B09A| Decision: intention to grant|
    2021-03-30| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/07/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/585,160|2012-08-14|
    US13/585,160|US9404030B2|2012-08-14|2012-08-14|Swellable article|
    PCT/US2013/050477|WO2014028149A1|2012-08-14|2013-07-15|Swellable article|
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