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    • 专利摘要:
    The present invention is directed to a suspension and to a wet powder of reduced graphene oxide (rGO) and an organic solvent, wherein the concentration of the reduced graphene oxide in organic solvent is above 0.3 mg/mL, and wherein the mixture is stable for at least 5 days as measured in a Turbiscan®. The invention further discloses a polymer matrix comprising the rGO of said rGO suspension or wet powder and a polymer, and methods for the preparation of the rGO suspension or wet powder and the polymer matrix.
    公开号:ES2803957A2
    申请号:ES202090034
    申请日:2019-01-23
    公开日:2021-02-01
    发明作者:Escribano Rodrigo Paris；Orta Carolina Ruiz；Elorza Amaia Zurutuza；Murguialday Amaya Ortega；Rodriguez Beatriz Alonso
    申请人:Graphenea S A；
    IPC主号:
    专利说明:

    [0001] A MIXTURE OF REDUCED GRAPHENE OXIDE, POLYMERIC MATRIX
    [0003] FIELD OF THE INVENTION
    [0004] The present invention relates to a stable mixture of a solvent and a reduced graphene oxide (rGO), to a process for its preparation, to a polymeric matrix comprising the rGO and to an article comprising said polymeric matrix.
    [0005] BACKGROUND
    [0006] Graphene has attracted great interest for its excellent mechanical, electrical, thermal and optical properties. It can be produced by various processes such as, for example, highly oriented pyrolytic graphite micromechanical exfoliation, epitaxial growth, chemical vapor deposition and reduction of graphene oxide (GO). A key point in the research and applications of GO is reduction, which partially restores the structure and properties of graphene. Different reduction procedures have been proposed to obtain rGO, which have not provided satisfactory results.
    [0007] MJ Fernández-Merino, et al., J. Phys. Chem. (2010), disclose vitamin C as an ideal substitute for hydrazine in the reduction of graphene oxide suspensions. The document discloses stable suspensions, although they have a maximum rGO concentration of only 0.1 mg / ml. Such low concentrations pose many problems for practical applications. In particular, suspensions of graphene oxide at a concentration of 0.1 mg / ml with vitamin C, at 95 ° C. When the solvent used was water, the pH of the dispersions was adjusted to ~ 9-10. High shear is not disclosed.
    [0008] One of the main problems with the reduction of graphene oxide is the tendency of its flakes to form agglomerates, especially as the concentration of the suspensions increases. Taking advantage of the exceptional physical properties of graphene often requires dispersing it in aqueous or organic media at very low concentration. Dispersion must be achieved at a concentration and stability appropriate for the final application. However, the strong interaction between the graphene sheets causes it to disperse very little except in a few high-boiling organic solvents. Therefore, a truly versatile commercial rGO product has to be stable.
    [0009] Document CN105271191 A discloses a reduced graphene oxide, as well as a preparation process and an application thereof. The preparation process comprises the following preparation steps: vitamin C is added to a 1: 1000 by weight aqueous solution (0.1 mg / ml) of a graphene oxide solution; a uniform mixture is made; then an aqueous solution of ammonia is added; a uniform mixture is made; the mixture is heated to the temperature of 90-100 ° C; After the reaction, filtration is carried out and the filter cake is washed with deionized water until neutral and dried to obtain the dry reduced graphene oxide.
    [0010] Document EP2960205 A1 refers to a stable aqueous graphene suspension and its use in the production of graphene nanocomposites and polymers. It does not provide any disclosure of a highly concentrated in an organic solvent. The authors demonstrate that a polymer filled with a graphene material can be obtained by intimately mixing the graphene material and the monomers before promoting an in situ polymerization, using an aqueous graphene suspension stabilized with an anionic surfactant. In particular, it discloses an aqueous graphene suspension comprising: a liquid suspension medium comprising more than 50 % by weight of water relative to the total amount of liquid suspension medium; at least one graphene material; and at least one anionic surfactant, a part of it being present as a functionalizer of said graphene material, in which the percentage by weight of anionic surfactant with respect to the amount of graphene material is at most equal to 100%. Accordingly, this document does not provide highly concentrated rGO suspensions and, in any case, requires surfactants. It also relates to a process for preparing an aqueous suspension of chemically reduced graphene oxide and a process for manufacturing a nanocomposite of graphene-polymer material and, more specifically, a chemically reduced graphene oxide-polymer nanocomposite from a suspension. Aqueous graphene material and, more specifically, an aqueous suspension of chemically reduced graphene oxide (CRGO) and one or more monomers, said process comprising at least the steps consisting of: (A) an addition of one or more monomers to a suspension and (B) a polymerization of said one or more monomers to give said nanocomposite. The entire procedure, therefore, requires in situ polymerization.
    [0011] Document EP3205624A1 relates to the preparation of a powder of highly dispersible graphene, which has a high specific surface area. This is achieved by using a surface treatment agent having an acid group during the graphene oxide reduction treatment.
    [0012] David W. Johnson, et al., Curr. Opin. Colloid In. (2015), discuss various dispersal (or suspension) strategies. In particular, the effect of shear, solvent and chemical modifications on graphene dispersion is discussed. Also, Johnson, et al., Disclose that the dispersion of graphene into hydrophobic and polymeric engineered products is challenging. The first problem is to get a good dispersion in the polymer. This is addressed by dispersing the graphene in a cosolvent with the polymer prior to coprecipitation or drying to obtain a film, or by dispersing the graphene into a monomer, followed by in situ polymerization. Therefore, this document does not address the problem of providing a highly concentrated rGO in a solvent. In an ideal situation, composite materials processed in a solvent immobilize graphene in a well dispersed form thereof in the solvent; however, it is generally necessary to modify graphene in order to improve its dispersibility and its interaction with the polymer matrix.
    [0013] Recently, Liu et al., RSC Adv. (2014) have used a high-shear mixer in molecular-level (MLM) mixing procedures of rGO / Cu composite materials in aqueous solutions, which are then dried and sintered. No description is given of a highly concentrated rGO suspension in an organic solvent.
    [0014] Liu et al. RSC Adv., 2014, 4, 36464-36470, disclose a suspension of 0.27 mg / ml of rGO in a 40% IPA / water solution. The process comprises subjecting to high shear the rGO already produced in the IPA / water solution. No description is given of a highly concentrated rGO suspension in an organic solvent.
    [0015] Lidong Wang, et al., RSC Adv. (2015) also acknowledge that graphene agglomerates remain the main challenge for producing composite materials. Furthermore, the authors mention that high-shear mixing is a general procedure used in chemistry and food industries, which includes debinding, emulsification and homogenization procedures. High shear mixing is typically used to disperse nanoparticles by breaking down agglomerates of nanoparticles in a liquid. The authors refer to Paton et al., Who demonstrated that the high shear mixture could also be used to exfoliate graphite to graphene suspensions. However, the authors do not recognize the possibility of preparing a highly concentrated suspension of rGO in an organic solvent.
    [0016] M. Ayán-Varela, et al., CARBON, 2014, 75, 390-400, disclose an analysis of the dispersion behavior of reduced graphene oxide in solvents. They describe problems related to the precipitation and agglomeration of reduced graphene oxide. Conventional methodologies for graphene oxide reduction are used, such as those disclosed in Li D, et al., Nat Nanotechnol. 2008, 3 ( 2), 101-5, and Fernández-Merino, et al., J. Phys. Chem. C.
    [0017] 2010, 114 ( 14), 6426-6432.
    [0018] Thus, a need remains in the art to provide highly concentrated forms of rGO and for improved procedures for preparation of rGO, specifically to provide an rGO without the agglomeration usually observed during the chemical reduction of graphene oxide, and to obtain rGO with improved dispersibility in polymeric matrices.
    [0019] SUMMARY
    [0020] The present inventors have found that by effecting the graphene oxide reduction reaction by high shear mixing and preventing the graphene from drying out and by washing with a solvent, the resulting reduced graphene oxide (rGO) mixed with the solvent is surprisingly stable, even in highly concentrated suspensions. Said suspensions are surprisingly stable and do not require the use of surfactants.
    [0021] The high-shear mixing of the graphene oxide (GO) reduction reaction considerably improves the kinetics of the reaction, significantly reducing the reaction times required to complete the reduction. Furthermore, the produced material exfoliates due to the high shear, thus avoiding agglomeration, ie, a reduction in the particle size of the reduced graphene oxide is achieved. Most importantly, the rGO remains remarkably exfoliated for long periods of time. Thus, a first aspect of the invention is a process for the preparation of a suspension of reduced graphene oxide in an organic solvent, in which the concentration of the reduced graphene oxide is greater than 0.3 mg / ml, preferably it is comprised between 0.3 mg / ml and 20.0 mg / ml, for example between 0.3 mg / ml and 15.0 mg / ml (with respect to the total amount of suspension or mixture) and in which the suspension is stable for at least 5 days as measured in a Turbiscan® (meaning stable that the variation in transmittance measured in the Turbiscan® is less than 10 % after 5 days, as will be explained later), comprising said procedure the stages of:
    [0022] (a) reacting an aqueous dispersion of graphene oxide at a temperature between 60 ° C and 150 ° C and at a pH of 7.0 or higher, in the presence of a reducing agent and with high shear to decrease the reaction time required to complete the reduction and to reduce the particle size of the reduced graphene oxide, in order to obtain an aqueous suspension of reduced graphene oxide;
    [0023] (b) washing the aqueous suspension of reduced graphene oxide resulting from step (a) with an organic solvent so that the concentration of the reduced graphene oxide is always greater than 0.3 mg / ml with respect to the total mixture, in order to obtain a wet reduced graphene oxide powder, preferably with a concentration greater than 15.0 mg / ml, for example between 16.0 mg / ml and 25.0 mg / ml; Y
    [0024] (c) redispersing the wet reduced graphene oxide powder obtained in step (b) in an organic solvent to obtain the suspension.
    [0025] The suspension resulting from step (c) is stable for at least 5 days as measured on a Turbiscan®. As far as the inventors know, this is the first time that such stable rGO has been obtained at such a high concentration.
    [0026] Accordingly, a second aspect of the invention is a suspension of reduced graphene oxide in an organic solvent, in which the concentration of the reduced graphene oxide is greater than 0.3 mg / ml, preferably it is between 0, 3 mg / ml and 20.0 mg / ml, for example between 0.3 mg / ml and 15.0 mg / ml and wherein the mixture or suspension is stable for at least 5 days as measured in a Turbiscan® (meaning stable that the variation in transmittance measured in the Turbiscan® is less than 10 % after 5 days, as will be explained later). Said mixture or suspension shows excellent morphology with a very small particle size and a large proportion of single-layer sheets.
    [0027] Furthermore, the inventors have confirmed that even the intermediate reduced graphene oxide wet powder obtained in step (b) can remain stable for long periods of time as long as it is not allowed to dry and, more surprisingly, is easily and efficiently dispersed in polymers. Therefore, a further aspect of the invention is a process for the preparation of a wet powder of reduced graphene oxide in an organic solvent, having a concentration greater than 15.0 mg of reduced graphene oxide per ml (with respect to the total amount of wet reduced graphene oxide powder), preferably between 15.0 mg / ml and 60.0 mg / ml, for example between 15.0 and 25.0 mg / ml, and which is obtainable by a process comprising the stages of:
    [0028] (a) reacting an aqueous dispersion of graphene oxide at a temperature between 60 ° C and 150 ° C and at a pH of 7.0 or higher, in the presence of a reducing agent and with high shear to decrease the reaction time required to complete the reduction and to reduce the reduced graphene oxide particle size, in order to obtain a reduced graphene oxide suspension;
    [0029] (b) washing the aqueous suspension of reduced graphene oxide resulting from step (a) with an organic solvent so that the concentration of the reduced graphene oxide is always greater than 0.3 mg / ml with respect to the total mixture, and adjusting the final amount of organic solvent to obtain the wet reduced graphene oxide powder.
    [0030] Still other aspects of the invention are the reduced graphene oxide wet powder obtained by the above procedure, as well as a reduced graphene oxide wet powder in an organic solvent, having a reduced graphene oxide concentration greater than 15.0 mg / ml, wherein the d90 particle size of the reduced graphene oxide as measured by laser diffraction is between 2 and 70 microns.
    [0031] Also, the inventors have found that the suspension obtained from rGO provides a polymeric matrix, when the rGo of the invention is mixed with a polymer, in which the rGO is dispersed more efficiently while largely maintaining its monolayer structure. More surprising still is the fact that even the intermediate reduced graphene oxide wet powder obtained after the washing of step (b) can also be effectively dispersed in polymers. This opens up an opportunity to provide a stable rGO form with a long shelf life that can be used in various applications. Once mixed in the polymeric matrix, the rGO, whether obtained from the suspension or from the wet powder, maintains its morphological properties and disperses well in the polymeric matrix. Thus, in a third aspect, the invention relates to a matrix polymeric comprising a polymer and the rGO contained in the suspension or in the wet powder as previously defined.
    [0032] The preparation of the polymeric matrix becomes a very simple process, in which the polymer is mixed with the suspension or the wet powder, which is a further aspect of the invention.
    [0033] In another aspect, the invention relates to an article comprising the polymeric matrix comprising the rGO, according to the invention.
    [0034] BRIEF DESCRIPTION OF THE DRAWINGS
    [0035] Figure 1: Macroscopic image of an rGO mixed with a polymeric matrix. Sample (a): rGo dried in a conventional vacuum oven and then mixed with the polymer. Sample (b): rGO according to the invention in the form of a suspension and mixed with the polymer and heated to evaporate the solvent. It can be seen with the naked eye that in sample (b) the rGO is fully integrated into the matrix, while in sample (a) the rGO shows numerous agglomerates.
    [0036] Figure 2: Light microscope images of the samples of Figure 1. Difference between the rGO mixed with a polymer matrix; (a) rGo dried in a conventional vacuum oven; (b) adding it directly to a suspension and evaporating the solvent. It is clearly seen how the addition of the suspension followed by in situ evaporation of the solvent prevents agglomeration of the particles. In images a (i) and b (i) the scale of the bar is 500 microns. In images a (ii) and b (ii) the scale of the bar is 50 microns.
    [0037] Figure 3: Graph of the percentage of variation of the transmittance over time in a suspension or a matrix of a liquid polymer of the invention. The squares represent stable samples, that is, those in which the transmittance does not vary with time. The rhombuses represent unstable samples, in which the transmittance varies with time.
    [0038] Figure 4 : Light microscope image of a mixture of a wet powder according to the invention with an epoxy resin.
    [0039] Figure 5: graphical representation of the stability and instability of emulsions, suspensions, dispersions, etc .: in stable preparations, the particles remain dispersed in the solvent; in unstable preparations, flotation, sedimentation, flocculation or coalescence occurs.
    [0040] Source: Turbiscan® technology explanatory brochure.
    [0041] DETAILED DESCRIPTION OF THE INVENTION
    [0042] The mixtures described herein can therefore form a suspension or a "wet" powder, depending on the concentration of rGO. Thus, at high concentrations of rGO, for example greater than 15.0mg / ml, the mixture is normally a wet powder, although at lower concentrations it normally forms a suspension.
    [0043] In the context of the present invention, when a concentration of the rGO mixture is indicated in mg / ml, it means that per ml of mixture (i.e. rGO suspension or wet rGO powder of the invention), the amount is contained stated in mg. This can be measured, for example, but not limited to, by taking a given amount of mixture (eg 1000 ml), evaporating the organic solvent (or removing it by any other known method) and weighing the remaining rGo. Based on this measurement, the concentration in mg / ml can easily be calculated.
    [0044] The concentration of the reduced graphene oxide in the suspension of According to the invention it is greater than 0.3 mg / ml (that is, 0.3 mg of rGo is contained in 1 ml of the rGO suspension) and, therefore, it can be, for example, greater than 0.4 mg / ml, or greater than 0.5 mg / ml, or greater than 1 mg / ml, or greater than 2.0 mg / ml, or greater than 3.0 mg / ml, or greater than 4.0 mg / ml ml, or greater than 5.0 mg / ml, or greater than 6.0 mg / ml, or greater than 6.5 mg / ml.
    [0045] As will be defined later, if the concentration of the reduced graphene oxide is greater than 15.0 mg / ml, the product is designated as a wet reduced graphene powder. Consequently, the concentration of the reduced graphene oxide in the suspension is generally up to 15.0 mg / ml, or up to 13.0 mg / ml, or up to 12.0 mg / ml, or up to 10.0 mg / ml. ml, or up to 8.0 mg / ml. At higher concentrations, the mixture is designated as a reduced graphene wet powder.
    [0046] In the present application it is intended to include any combination of the upper and lower limits, within the indicated range.
    [0047] For example, the concentration of the reduced graphene oxide in the suspension is, for example, but not limited thereto, between 0.3 mg / ml and 15.0 mg / ml, for example in one of the ranges following: between 0.3 mg / ml and 12.0 mg / ml, between 0.3 mg / ml and 10.0 mg / ml, between 0.4 mg / ml and 13.0 mg / ml, between 0.5 mg / ml and 15.0 mg / ml, between 1.0 mg / ml and 10.0 mg / ml, between 2.0 mg / ml and 10.0 mg / ml, between 3.0 mg / ml and 12.0 mg / ml, between 4.0 mg / ml and 10.0 mg / ml, between 5.0 mg / ml and 8.0 mg / ml, between 6.0 mg / ml and 10.0 mg / ml or between 6.5 mg / ml and 10.0 mg / ml.
    [0048] In the present invention the term "wet" in the term "wet powder" refers to the organic solvent that is present. Thus, a wet reduced graphene oxide powder, or wet rGO, or wet powder, refers to a solid rGO that contains various amounts of solvent, the concentration being greater than 15 mg / ml (i.e., more than 15 mg of rGo per 1 ml of wet reduced graphene oxide powder) and therefore may be, for example, greater than 16 mg / ml, or greater than 20 mg / ml or greater than 25 mg / ml. In general, the concentration will not be higher than 50.0 mg / ml, for example up to 40.0 mg / ml or up to 25.0 mg / ml. The wet powder may have a reduced graphene oxide concentration, for example, but is not limited to, between 16.0 mg / ml and 250.0 mg / ml, for example in one of the following ranges: between 16 mg / ml and 100.0 mg / ml, between 16 mg / ml and 50.0 mg / ml, between 20.0 mg / ml and 60.0 mg / ml, between 20.0 mg / ml and 50.0 mg / ml or between 20.0 mg / ml and 25.0 mg / ml.
    [0049] As indicated above, the suspension of reduced graphene oxide in an organic solvent according to the invention is stable for at least 5 days as measured on a Turbiscan®. The Turbiscan® is an optical dispersion analyzer, used throughout the world to characterize the dispersion state of emulsions, suspensions, dispersions, foams, etc., and is based on static multiple light scattering (25100-Stability -Analyzers /). Changes in terms of size and concentration are monitored (such as, for example, flotation, sedimentation, flocculation or coalescence). The technique consists of sending photons (light) to the sample, for example IR light; These photons, after having been scattered many times by suspended objects (droplets, solid particles, gas bubbles ...) come out of the sample and are detected by the measuring device (which is a transmittance detector) of the Turbiscan® . These measurements make it possible to follow the evolution of the concentration or the average particle diameter during the aging of the product anywhere in the sample and thus the stability of the sample over time, when a sample is measured on a Turbiscan® just after preparation, and at different times thereafter. A stable sample shows a flat curve over time, which means that the transmittance through the sample does not vary with time and therefore the particles are uniformly distributed throughout the suspension without significant changes in any. Given moment. As the suspension becomes unstable, the particles begin to aggregate and settle towards the bottom of the cell. As a result, the measured transmission changes over time.
    [0050] In the present invention, the samples were allowed to stand at 25 ° C in the dark for different periods of time, ranging from a few minutes to months. All measurements were carried out at 25 ° C and 0.10 MPa and always under the same conditions for a given sample. A sample was considered stable if the variation in transmittance was less than 10 % after 5 days (if measurements were compared at different times throughout the suspension and also if measurements were compared at different places or parts of the sample (thus determining whether sedimentation or flotation has occurred, for example; refer to Figure 5) All samples prepared according to the invention with high shear (samples 3, 4, 5 and 6 of Table 1 ) were stable for at least 5 days under the above conditions On the other hand, the mixtures prepared under conventional conditions (comparative samples 1 and 2 of Table 1) were unstable, even after just a few hours.
    [0051] Suitable organic solvents for the mixture of the invention are selected from the group of EtOH, MeOH, iPrOH, BuOH, CH 2 CI 2 , CHCl 3 , ethyl ether, ethyl acetate, DMF, NMP, DMSO. Preferably, the solvents are selected from the group of N, N'-dimethylformamide (DMF), N-methylpyrrolidine (NMP) and alcohols. Preferred solvents are alcohols selected from the group of methanol, ethanol and isopropanol. Most preferably, the selected solvent is methanol. The organic solvent can be a single solvent or a mixture of two or more. In the suspension or wet powder of the invention it is preferred that practically all solvents are organic solvents, although some residual water may be present. However, it is possible to prepare mixtures of the invention in which more than 80 % by volume of the solvent, relative to the total volume of solvent, is an organic solvent, for example more than 90%, preferably more than 95% .
    [0052] A further contribution to achieve the objective of the present invention is made by a polymeric matrix comprising the rGO of the present invention and a polymer.
    [0053] According to the present invention, the polymer can be a liquid polymer at room temperature or soluble in the solvent used in the suspension or the wet powder of the invention. For example, a polyol, a silicone or a polyester. The inventors have obtained matrices of a liquid polymer (for example in polyols) that are stable for at least 15 days as measured in a Turbiscan®. Polyols can be selected from the group consisting of filled polyols (also known as polymer polyols), polyisocyanate polyaddition polymer polyols (PIPA), polytetrahydrofuran (polytetramethylene glycols), polyester polyols, polyols made of poly (caprolactone), polycarbonate polyols, polybutadiene polyols, acrylic polyols, polysiloxane polyols, polyether polyols for rigid polyurethane foams (amino polyols), rigid polyols based on the alkoxylation of aromatic compounds, condensed with aldehydes (polyols of Mannich), Novolac-based polyether polyols, bisphenol A-based polyols, resorcinol-based diols, melamine-based polyols for rigid polyurethanes, aromatic polyester polyols from polyethylene terephthalate residues (bottles, films, fibers), polyols from aromatic polyesters based on phthalic anhydride, polyols from renewable sources, oleochemical polyols, flame retardant polyols, polyols containing chlorine and bromine, phosphorus polyols, ortho-phosphoric acid esters, phosphorous acid esters, phosphonate polyols, polyols phosphine oxide, phosphoramidic polyols, hyperbranched polyols and dendr polyols ytics, and oligopolyols derived from chemical recovery (for example of PU residues, from the hydrolysis of PU polymers, from the glycolysis of PU polymers, from the aminolysis of PU polymers).
    [0054] Any polymer with which the suspension or wet powder can form a mixture is suitable. Non-limiting examples of polymers can be selected from the group consisting of an olefin, an acrylic polymer, a styrenic polymer or a vinyl polymer and copolymers thereof, a polyether, a polyamide (eg, a thermoplastic polyamide), a polyacetal , a polycarbonate, a polyester, a polyurethane, a LCP (liquid crystal polymers), a polyhydroxyalkanoate (PHA), a PEEK (polyarylether ether ketone), an ABS (acrylonitrile butadiene styrene), a polyethersulfone (PES), a PA ( polyamide), a PSU / P / PPSU (polyarylsulfone), a POM (polyoxymethylene), a PPA (polyphthalamide), a PPS (polyphenylene sulfide), a fluoropolymer (eg, polyvinylidene fluoride), and mixtures thereof. For example, the polymer is polylactic acid (PLA), ethylene vinyl alcohol (EVOH), polyethylene terephthalate (PET), polyvinyl alcohol (PVOH), PBT (polybutylene terephthalate), PMMA (polymethyl methacrylate), polyvinyl chloride (PVC ), ANS (acrylonitrile styrene), PEI (polyetherimide) or mixtures thereof.
    [0055] Polyolefins can be selected from homopolymers and copolymers. For example, polypropylene, HDPE, LLDPE, LDPE, UHMWPE, ethylene vinyl acetate copolymer (EVA), ethylene methylacrylate copolymer (EMA), ethylene methyl methacrylate copolymer (EMMA), ethylene acrylate copolymer ethyl (EEA), ethylene propyl acrylate copolymer or ethylene butyl acrylate copolymer (EBA).
    [0056] Also, the polymer can be selected from the group consisting of polyols, epoxy resins, polyester resins, polyurethanes, natural rubbers, polyisoprenes, polychloroprenes, polyacrylates, starch, polyamides, and mixtures thereof. Excellent stability and dispersibility have been obtained, for example, with polyether polyols and the polyurethanes resulting from their reaction with polyisocyanates.
    [0057] Similarly, the polymer can be selected from the group consisting of a polyalkylene carbonate (PAC), a block / random copolymer comprising at least one block of polyolefin, polyacrylic, polystyrene, polyvinyl, polyether, polyamide, polyester, or polyurethane, and an elastomer.
    [0058] PAC (the one used in practice or theoretically) comes from one or more epoxides selected from the group consisting of alkylene oxide (C 2 C 20 ), alkyloxy (C 1 -C 20 ), aryloxy (C 6 -C 20 ), arylalkyloxy (C 6 -C 20 ), cycloalkyloxy (C 4 -C 20 ), cycloalkylene oxide (C 5 - C 20 ) and mixtures thereof. Examples of non-limiting epoxy compounds may be one or more selected from the group consisting of ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, octene oxide, decene oxide, dodecene oxide, tetradecene oxide, hexadecene oxide, octadecene oxide, butadiene monoxide, 1,2-epoxide-7-octene, epifluorohydrin, epichlorohydrin, epibromhydrin, glycidyl methyl ether, glycidyl ethyl ether, glycidyl n-propyl ether, glycidyl sec-butyl ether, glycidyl sec-butyl ether ether, glycidyl n- or isopentyl ether, glycidyl n-hexyl ether, glycidyl n-heptyl ether, glycidyl n-octyl or 2-ethylhexyl ether, glycidyl n- or isononyl ether, glycidyl n-decyl ether, glycidyl n-dodecyl ether, n-tetradecyl glycidyl ether, hexadecyl glycidyl ether-n, noctadecil glycidyl ether, glycidyl n-icocil ether, isopropyl glycidyl ether, butyl glycidyl ether, tert - butyl glycidyl ether, glycidyl ether 2-ethylhexyl, allyl glycidyl ether, cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, cycle oxide dodecene, alpha-pinene oxide, 2,3-epoxy-norbornene, limonene oxide, dieldrin, 2,3-epoxypropylbenzene, styrene oxide, phenylpropylene oxide, stilbene oxide, chlorostilbene oxide, dichlorostilbene oxide, 1, 2-epoxy-3-phenoxypropane, benzyloxymethyl-oxirane, glycidyl methylphenyl ether, chlorophenyl-2,3-epoxypropyl ether, epoxypropyl methoxyphenyl ether, biphenyl glycidyl ether, glycidyl naphthyl ether, glycidyl methylphenyl ether, glycidyl glycidyl acetate glycidyl ester, glycidyl glycidyl ester of glycidyl acetic acid , glycidyl n-pentanoate, glycidyl n-hexanoate, glycidyl heptanoate, glycidyl n-octanoate, glycidyl 2-ethylhexanoate, glycidyl n- nanoate, glycidyl n -decanoate, glycidyl n-dodecanoate, n-tetradecanoate glycidyl, glycidyl nhexadecanoate, glycidyl n-octadecanoate, and glycidyl icosanoate.
    [0059] The elastomer may be an ethylene-based elastomeric compound such as ethylene-propylene rubber (EPR), ethylene-propylene diene monomer rubber (EPDM), or styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-butadiene rubber. (SBR), Styrene-Butadiene-Styrene Block Copolymer (SBS), TPE-E (Thermoplastic Polyester Elastomer) or TPU (Thermoplastic Polyurethanes). Other elastomeric compounds that can be used are acrylonitrile, polychloroprene, polyacrylate rubber, polyurethane, chlorinated polyethylene, polyester, poly (isobutylene), isobutylene and isoprene copolymers, chlorinated isobutylene and isoprene copolymers, butadiene and styrene copolymers, isopolymers of butadiene and styrene, and styrene, butadiene and styrene block copolymers, isoprene and styrene block copolymers, isoprene and vinyltoluene block copolymers, hydrogenated butadiene and styrene copolymers, hydrogenated isoprene and styrene block copolymers, copolymers of acrylonitrile and butadiene copolymers of methacrylonitrile and butadiene, copolymers of acrylonitrile and isoprene and copolymers of methylacrylonitrile and isoprene.
    [0060] Another additional contribution to achieve the objective of the present invention is a process for the preparation of the polymeric matrix, which comprises mixing a polymer with the rGO suspension of the invention. The mixing can be carried out with stirring in solution or by mixing the pure polymer with the mixture of the invention, depending on the rheological characteristics. The process may also comprise suspending the polymer and the mixture of the invention in a suitable solvent or, if the polymer is liquid, mixing the polymer and the mixture of the invention. Mixing is normally carried out at a temperature above 25 ° C to evaporate the organic solvent from the mixture of the invention. If possible, the polymer and the mixture of the invention are mixed with high shear using a high shear device, for example a rotor-stator or a dissolution device, as described above. The high shear provides even better dispersion of the rGO in the polymer and is suitable for liquid polymers, such as polyols (eg, polyether polyol). More stable dispersions were obtained with polyether polyol comprising ethylene oxide and propylene oxide units, for example polyether polyol comprising between 0.1 % by weight and 20 % by weight of ethylene oxide with respect to weight total ethylene oxide and propylene oxide.
    [0061] Likewise, the wet rGO powder according to the invention also provides excellent dispersion and can also be used to prepare said polymeric matrices.
    [0062] The amount of rGO present in the polymeric matrix of the invention can vary according to the specific needs of each case and can be controlled by the person skilled in the art. The amount of rGO present in the polymeric matrix can be between 0.001% by weight and 10% by weight, for example, from 0.1% by weight to 3.0% by weight, relative to the total weight of the polymeric matrix.
    [0063] The temperature at which the mixture of the invention and the polymer are combined is normally between 60 ° C and 150 ° C, preferably between 70 ° C and 130 ° C, preferably between 80 ° C and 120 ° C, is preferably below above 70 ° C, preferably below 120 ° C, preferably between 80 ° C and 100 ° C, preferably between 90 ° C and 100 ° C and is preferably 95 ° C. The heating temperature must be sufficient to melt the polymer (if it is solid) and to evaporate the organic solvent present in the suspension or the wet powder of the invention. Thus, the temperature must be adjusted by the person skilled in the art in each case, depending on the melting point of the polymer, among other factors.
    [0064] Also within the scope of the present disclosure is a mixture (ie a suspension of rGO or a wet powder of rGO according to the invention) that does not comprise surfactants. The compositions disclosed in the prior art, despite their low concentration of graphene, require the use of surfactants to stabilize the suspensions. The inventors have found that the suspensions and wet powders of the present disclosure are stable without the need to use surfactants, even at very high concentrations. Further envisaged within the scope of the present disclosure is a suspension consisting of a reduced graphene oxide and one or more organic solvents, wherein the concentration of the reduced graphene oxide is greater than 0.3 mg / ml, for example is between 0.3 mg / ml and 20.0 mg / ml, and in which the mixture is stable for at least 5 days as measured in a Turbiscan®. Similarly, a wet rGO powder consisting of an organic solvent and rGO and having more than 15.0 mg of reduced graphene oxide per ml is also envisaged within the scope of the present invention, preferably between 15.0 mg / ml and 60 , 0 mg / ml, for example, between 15.0 and 25.0 mg / ml, with respect to the total amount of the wet rGO powder, and which is obtainable by means of a process comprising the steps of:
    [0065] (a) reacting an aqueous dispersion of graphene oxide to a temperature between 60 ° C and 150 ° C and at a pH of 7.0 or higher, in the presence of a reducing agent and with high ash to decrease the reaction time required to complete the reduction and to reduce the particle size of the oxide of reduced graphene, in order to obtain an aqueous suspension of reduced graphene oxide;
    [0066] (b) washing the aqueous suspension of reduced graphene oxide resulting from step (a) with an organic solvent so that, during washing, the concentration of the reduced graphene oxide is always greater than 0.3 mg / ml with respect to to the total mixture, and adjust the final amount of organic solvent to obtain the wet reduced graphene oxide powder.
    [0067] In an alternative aspect of the invention, the suspension of reduced graphene oxide in an organic solvent is a suspension in which the concentration of the reduced graphene oxide with respect to the total mixture is greater than 0.3 mg / ml, preferably it is between 0.3 mg / ml and 20.0 mg / ml, and wherein the d90 particle size of the reduced graphene oxide as measured by laser diffraction is less than 100 microns, preferably less than 80 microns, for example less than 70 microns, preferably less than 50 microns or less than 40 microns. The normal values of d90 that can be obtained in the mixtures of the invention are comprised between 1 micron and 100 microns, for example between 2 microns and 70 microns, or between 5 microns and 60 microns, or between 5 microns and 50 microns, or between 10 microns and 40 microns.
    [0068] In an alternative aspect of the invention, wet graphene powder reduced is a powder having more than 15.0 mg, preferably between 15.0 mg and 60.0 mg, for example between 15.0 mg and 25.0 mg, of reduced graphene oxide per ml of an organic solvent and obtainable by steps (a) and (b) as described herein, and wherein the d90 particle size of the reduced graphene oxide as measured by laser diffraction is less than 100 microns, preferably less than 80 microns, for example less than 70 microns, preferably less than 50 microns or less than 40 microns. The normal values of d90 that can be obtained in the wet powder of the invention are comprised between 1 micron and 100 microns, for example between 2 microns and 70 microns, or between 5 microns and 60 microns, or between 5 microns and 50 microns, or between 10 microns and 40 microns.
    [0069] Procedure
    [0070] The present invention provides a process for the preparation of rGO products with improved reduction reaction kinetics, without agglomeration of the rGO particles and producing an rGO with improved dispersibility in polymeric matrices. Not only is the resulting suspension suitable for effective dispersion in a polymer, so is the intermediate wet powder. The procedure includes:
    [0071] (a) reacting an aqueous dispersion of graphene oxide with high shear, at a temperature between 60 ° C and 150 ° C and at a pH of 7.0 or higher, in the presence of a reducing agent, the high shear contributing to decrease the reaction time required to complete the reduction and to reduce the particle size of the reduced graphene oxide, so as to obtain a reduced graphene oxide suspension;
    [0072] (b) washing the suspension of reduced graphene oxide resulting from step (a) with an organic solvent so that the concentration of the reduced graphene oxide is always greater than 0.3 mg / ml with respect to the total mixture, at in order to obtain a wet reduced graphene oxide powder, preferably with a concentration greater than 15.0 mg / ml, preferably between 15.0 mg / ml and 60.0 mg / ml, for example, between 15.0 mg / ml and 25.0 mg / ml; Y
    [0073] (c) redispersing the wet reduced graphene oxide powder obtained in step (b) in an organic solvent to obtain the suspension.
    [0074] The redispersion of step (c) is preferably carried out with high shear.
    [0075] The present invention also provides a process for the preparation of a wet reduced graphene oxide powder in an organic solvent having a reduced graphene oxide concentration greater than 15.0 mg / ml, comprising the steps of:
    [0076] (a) reacting an aqueous dispersion of graphene oxide at a temperature between 60 ° C and 150 ° C and at a pH of 7.0 or higher, in the presence of a reducing agent and with high shear to decrease the reaction time required to complete the reduction and to reduce the particle size of the reduced graphene oxide, in order to obtain a suspension of reduced graphene oxide;
    [0077] (b) washing the suspension of reduced graphene oxide resulting from step (a) with an organic solvent so that, during washing, the concentration of the reduced graphene oxide is always greater than 0.3 mg / ml with respect to the total mix, and adjust the final amount of organic solvent to obtain the wet reduced graphene oxide powder.
    [0078] The high ash applied in the processes or processes of the present invention (that is, in step (a) of both processes for the preparation of a suspension of rGO and of a wet powder of rGO, or prior to step (a) or during the resuspension of step (c)) it is preferably achieved with a high-shear mixer, preferably a rotor-stator. A high-shear mixer uses a rotating impeller or high-speed rotor, normally powered by an electric motor, that generates flow and shear. In a high shear mixer, the speed of the fluid at the outer diameter of the rotor is greater than the speed at the center of the rotor and it is this speed difference that causes the shear. A stationary component is used in combination with the rotor and is called a stator. The stator creates a free space gap between the rotor and itself and forms an extremely high shear zone for the material as it exits the rotor. Preferably, the high shear mixing is carried out at more than 1000 rpm, preferably at more than 1200 rpm. or more than 1300 r.p.m., for example, between 1000 r.p.m. and 5000 r.p.m.
    [0079] The introduction of the high shear mixture into the processes of the present invention considerably improves the kinetics of the reaction since much shorter reaction times are required to complete the reduction. Furthermore, by using the high shear agglomeration of the reduced graphene oxide is avoided. One of the most critical issues in reducing graphene oxide is the tendency of the flakes to agglomerate, since the Oxygen functionality is reduced in the reduction reaction. Thus, the present invention discloses, in a preferred embodiment, a process in which exfoliation and reduction of graphene oxide are simultaneous.
    [0080] In a preferred embodiment of the methods of the invention, the concentration of the aqueous graphene oxide dispersion of step (a) is between 0.01 mg / ml and 10mg / ml, preferably between 0.05 and 5 mg / ml , preferably between 2 mg / and 5 mg / ml. Preferably, the GO itself has been subjected to a high shear procedure prior to the reduction reaction.
    [0081] In principle, any base can be used to adjust the pH of the high-shear aqueous graphene oxide dispersion. Preferably, the base is selected from NaOH, KOH, RbOH, CsOH, Ca (OH) 2 , Ba (OH) 2 , Mg (OH) 2 , NH 3 , N (C 2 H 5 ) 3 , N (CH 3 ) 3 , pyridine, urea. For example, the base can be ammonia (NH 3 ). The reaction proceeds under basic conditions (pH 7.0 or more), for example between 7.0 and 11.0, preferably between 8.0 and 10.0, more preferably the pH value is about 9.0.
    [0082] Virtually any suitable reducing agent can be used to reduce GO. Suitable reducing agents can be found in CK Chua and M. Pumera, Chem. Soc. Rev. (2014). For example, the reducing agent is selected from the group of borohydrides such as NaBH 4 , NaBH 3 (CN), NaBH (OAc) 3 , NH 3 BH 3 ; aluminum hydride such as LiAlH 4 ; hydrohalic acids such as HI / AcOH, HI / TFA, HI, HBr, HBr-KOtBu; Sulfur containing reducing agents such as thiourea dioxide / NaOH, thiourea dioxide / NaOH / cholate, thiourea dioxide / NH 3 , ethanethiol / AlCb, Lawesson, NaHSO 3 , Na2S2O4 / NaOH, thiourea, thiophene; nitrogen-containing reducing agents such as hydrazine, phenylhydrazine, hydroxylamine / NH 3 , hydroxylamine, pyrrole, benzylamine, p-phenylenediamine, ethylenediamine, urea / NH 3 , dimethyl ketoxime / NH 3 , hexamethylenetetramine, polyelectrolyte, poly (amido amine); reducing agents containing oxygen such as methanol, ethanol, isopropyl alcohol, benzyl alcohol, hydroquinone, L-ascorbic acid / L-tryptophan / NaOH, L-ascorbic acid (vitamin C), L-ascorbic acid / NH 3 , glucose / NH 3 , dextran / NH 3 ; alkali metal combinations such as Zn / NH 3 , Zn / NaOH; amino acids such as L-cysteine, glycine, L-lysine, L-glutathione; plant extracts such as green tea, C. esculenta leaf leaf, M. ferrea Linn leaf, C. sinensis husk , R. damascena; microorganisms such as Shewanella, E. coli culture, E. coli biomass , baker's yeast / NADPH, wild carrot roots; proteins such as bovine serum albumin / NaOH and hormones such as melatonin / NH 3 . Preferably, the reducing agent is selected from the group of hydrazine and vitamin C. More preferably, the reducing agent is vitamin C.
    [0083] Normally, the reduction reaction requires heating, the exact temperature depending on the reagents used and the conditions, and the person skilled in the art can set the ideal temperature in each case. Usually the temperature is between 70 ° C and 130 ° C, for example between 80 ° C and 120 ° C, it is preferably above 70 ° C, preferably below 120 ° C, preferably between 80 ° C and 100 ° C , preferably between 90 ° C and 100 ° C and is preferably 95 ° C.
    [0084] Suitable organic solvents for washing the rGO of step (b) In any of the processes according to the invention they are selected from the group of EtOH, MeOH, iPrOH, BuOH, CH 2 CI 2 , CHCl 3 , ethyl ether, ethyl acetate, DMF, NMP, DMSO. The organic solvent can be a single organic solvent or a mixture of organic solvents. Organic solvents are preferably selected from the group of N, N'-dimethylformamide (DMF), N-methylpyrrolidine (NMP) and alcohols. Preferred organic solvents are alcohols selected from the group of methanol, ethanol and isopropanol. Most preferably, the organic solvent selected is methanol. The washing step involves substituting as much as possible the water in the rGO aqueous suspension obtained in step (a) with the organic solvent. Also, in the washing stage as much as possible of residual reactants is removed, for example reducing agents or residual bases used to adjust the pH in the reduction stage (a). The washing procedure can be adjusted to obtain a mixture having different concentrations of rGO, that is, the final amount of the organic solvent contained in the wet rGO powder can be adjusted. Said washing solvent is normally the same used as organic solvent in the suspension of the invention, that is, in the resuspension of the wet rGO powder.
    [0085] The washing step (b) in any of the processes of the invention is carried out in such a way as to prevent the drying of the rGO. This is accomplished by keeping the concentration of the rGO in the organic solvent above 0.3 mg / ml of mixture at any given time. For example, above 0.5 mg / ml or above 1.0 mg / ml. Washing can be carried out, for example, in a solids extractor. Characteristic extractors are the Soxhlet extractor or the Kumagawa extractor. As indicated above, the final amount of organic solvent can be adjusted in order to obtain the wet rGO powder. As anyone skilled in the art will readily know, this can be achieved inherently by the washing procedure, for example if performed in a Soxhlet extractor, which constantly and simultaneously carries out the washing with the organic solvent and the filtration of the rGO; that is, a wet rGO powder is obtained directly if the washing step (b) is carried out in a Soxhlet extractor or by equivalent procedures. As one skilled in the art will know, alternatively the aqueous suspension of rGO obtained in step (a) can be filtered and the filtered rGO obtained can then be washed with the organic solvent and filtered again. The last steps of washing and filtration can be repeated if deemed necessary, until, as the last step, the amount of organic solvent is adjusted so that a wet rGO powder is obtained (i.e., having a concentration of rGO in organic solvent greater than 15 mg / ml). Equivalent procedures can be used, such as centrifugation and decantation, evaporation, or any other known procedure that allows separating a solid from a liquid, in order to carry out the washing step (b) of the processes of the invention. and reach a final concentration of rGO in the organic solvent greater than 15 mg / ml.
    [0086] Once washed, in the case of preparing an rGO suspension, the wet rGO powder is resuspended in an organic solvent in order to obtain the suspension of the invention. The resuspension preferably comprises high shear. The suspension is stable for long periods of time and, even after some sedimentation, can be re-subjected to a high shear to recover a homogeneous suspension.
    [0087] The suspension thus obtained can be filtered to remove any possible large particles.
    [0088] Another contribution to achieve the objective of the present invention is made by an rGO obtainable by the processes according to the invention.
    [0089] Another contribution to achieve the objective of the present invention is a suspension of a reduced graphene oxide in an organic solvent, in which the concentration of the reduced graphene oxide is greater than 0.3 mg / ml, preferably it is between 0, 3 mg / ml and 20.0 mg / ml, and the suspension being stable for at least 5 days as measured in a Turbiscan®, understanding by stable that the variation in transmittance measured in the Turbiscan® is less than 10% after 5 days; and the mixture being obtainable by a process comprising the steps of:
    [0090] (a) reacting an aqueous dispersion of graphene oxide at a temperature between 60 ° C and 150 ° C and at a pH of 7.0 or higher, in the presence of a reducing agent and with high shear to decrease the reaction time required to complete the reduction and to reduce the particle size of the reduced graphene oxide, in order to obtain an aqueous suspension of reduced graphene oxide;
    [0091] (b) washing the aqueous suspension of reduced graphene oxide resulting from step (a) with an organic solvent so that the concentration of the organic reduced graphene oxide is always greater than 0.3 mg / ml with respect to the total mixture , in order to obtain a wet powder of reduced graphene oxide, preferably with a concentration greater than 15.0 mg / ml, for example between 16.0 mg / ml and 25.0 mg / ml; and (c) redispersing the wet reduced graphene oxide powder obtained in step (b) in an organic solvent to obtain the suspension.
    [0092] Another additional contribution of the present invention is a suspension of a reduced graphene oxide in an organic solvent, in which the concentration of the reduced graphene oxide is greater than 0.3 mg / ml, with respect to the total amount of suspension, and the suspension being stable for at least 5 days as measured in a Turbiscan®, meaning stable that the variation in transmittance measured in the Turbiscan® is less than 10% after 5 days. Preferably, the reduced graphene oxide concentration is greater than 1 mg / ml; for example, the concentration of the reduced graphene oxide is between 1 mg / ml and 10 mg / ml. In the rGO of the invention, the d90 particle size of the reduced graphene oxide as measured by laser diffraction can be between 2 microns and 70 microns. According to a particular embodiment thereof, the organic solvent is methanol.
    [0093] A further contribution of the present invention is a wet powder of a reduced graphene oxide in an organic solvent, that is, having a reduced graphene oxide concentration greater than 15.0 mg / ml, relative to the total amount of the rGO wet powder, wherein the d90 particle size of the reduced graphene oxide as measured by laser diffraction is between 2 and 70 microns. According to a particular embodiment thereof, the concentration of the reduced graphene oxide can be between 16.0 and 25.0 mg / ml with respect to the total amount of the wet rGO powder.
    [0094] The rGO suspensions and reduced graphene oxide wet powder provided in the present invention can be used for different applications, in all fields of medicine, electronics, light processing, energy, sensors or the environment. , for example. Some non-limiting applications are in tissue engineering, as contrast agents, in drug delivery, in transistors, circuits, conductive inks, coatings, paints, pressure sensors, water filtration, composites, and many more.
    [0095] EXAMPLES
    [0096] The following examples are provided with the intention of further illustrating the present invention, but should not be construed as limiting the present invention in any way.
    [0097] Example 1: Synthesis of reduced graphene oxide
    [0098] 1.5 l of a 4 mg / ml graphene oxide dispersion was placed in a 2 l aluminum container. Then 1 ml of NH 3 and 3 g of ascorbic acid were added and the dispersion was mixed at 1600 rpm with high shear in a Dispermat® device and at 95 ° C (heated with a hot plate, temperature controlled by the Dispermat® CN30F2 device ) for 1 h. The reaction was cooled to room temperature and thereafter the suspension was filtered. The wet black powder was then washed in a Soxhlet system with methanol overnight. In this way the sample was never allowed to dry and resulted in a stable wet powder. High shear resuspension of said wet powder in methanol provided a suspension of rGO with a concentration of 8 mg / ml. These rGO suspensions were stable for at least 5 days.
    [0099] Example 2: Synthesis of the polymeric matrix with rGO dispersed therein. Different polymeric matrices were prepared following the following procedure.
    [0100] The polymer (200 g) was placed in a Dispermat® container (high shear). The matrix was heated with a hot plate to 80 ° C and stirred at 800 rpm. The rGO / MeOH dispersion prepared in Example 1 (8 mg / ml) was then added portionwise to the polymer and held overnight to ensure that all the MeOH had evaporated. The final polymer matrix had a concentration of 1 % by weight of rGO.
    [0101] The polymers used in each case were: (i) an epoxy resin; (ii) polyol 1; and (iii) polyol 4 (see example 4 for description).
    [0102] The resulting polymer matrices exhibited much better dispersion. This can be seen with the naked eye, as shown in Figures 1 and 2.
    [0103] Example 3: Results of the mixtures of rGO with solvent and comparison between the mixture of high shear and conventional shear in highly concentrated suspensions of rGO
    [0104] To test the process of the invention and the properties of the rGO thus obtained, different mixtures of rGO in methanol (8 mg / ml) were prepared. First, the reduction step was carried out, using a conventional mechanical stirrer (comparative samples / conditions 1 and 2, table 1) or a high-shear mixer. The starting GO solution had 4.0 mg / ml GO, which is a much higher concentration than those reported in the prior art, which is typically about 0.1 mg / ml. The temperature was kept at 95 ° C, while the different stirring procedures, reaction times and rates. The results are shown in Table 1. This table clearly shows how the high shear mixer improves the mixing between the reactants and cuts the reaction time in half. Even more surprisingly, the high shear provides higher yields. Also, the reduction occurs more efficiently and the oxygen content is lower when using a high shear mixer. This can be seen when comparing the oxygen content of comparative samples 1 and 2 (15% oxygen) with that of samples prepared according to the lrn inv nin -1 xí n procedure.
    [0108] Table 1
    [0110] Also, a notable improvement in particle size (measured by laser diffraction) was observed.
    [0111] The laser diffraction analysis was carried out on a MALVERN equipment Mastersizer 2000. The dispersion medium was methanol. The estimated refractive index for graphene is 2.417. No pretreatment of the samples was performed. Laser diffraction analysis involves taking 5 measurements. The final result corresponds to the average of these 5 results for each sample and is presented in the form of d10, d50 and d90 index (% by volume).
    [0112] Results are shown in table 2.
    [0114]
    [0116] Table 2
    [0118] Furthermore, the smaller particle size of the rGO produced in the invention is clearly visible to the naked eye, indicating less agglomeration of the particles. As shown in Figure 1, in a polymeric matrix prepared according to the present invention by mixing the polymer with a mixture according to the invention (in the form of a wet suspension), the material was fully integrated into the matrix (sample (b)), while agglomerates were observed in sample (a) prepared by mixing dry rGO with the polymer. This improvement was further confirmed by the light microscope, as shown in figure 2.
    [0119] To obtain an accurate measurement of the stability of products Obtained, either a suspension according to the invention or a liquid polymer matrix containing the rGO described herein, the stability was measured on a Turbiscan®. Immediately after preparation, each sample was placed in a cell having a diameter of 2 cm and a height of 40 mm, and analyzed on the Turbiscan®. The Turbiscan® irradiated the sample at a given height of the sample, in this case through the center (20 mm) with a laser wavelength of 800 nm, to establish the initial transmittance (also called "zero"). This procedure was repeated under the same conditions for the sample that was being analyzed at different times. A stable sample exhibits a flat curve over time, which means that the transmittance through the sample does not vary with time and therefore the particles are uniformly distributed throughout the suspension without significant changes in any. Given moment. As the suspension becomes unstable, the particles begin to aggregate and settle towards the bottom of the cell. As a result, the measured transmission changes over time. The variation in transmittance was plotted against time as a percent change per unit time (see Figure 3). The samples were allowed to stand at 25 ° C in the dark for different periods of time, ranging from a few minutes to months. All measurements were carried out at 25 ° C and 0.10 MPa and always under the same conditions for a given sample. A sample was considered stable if the change in transmittance was less than 10 % after 5 days. All samples prepared according to the invention with high shear (samples 3, 4, 5 and 6 of Table 1) were stable for at least 5 days under the above conditions. On the other hand, mixtures prepared under standard conditions (comparative samples 1 and 2 of Table 1) were unstable, even after just a few hours.
    [0120] Example 4: Polymeric matrix using polyol polyethers and thermoplastic polyurethanes
    [0121] In a first trial, the polymers were mixed with dry rGO, resulting in unstable mixtures. On the other hand, a suspension according to the invention was mixed with different polyols with high shear, and the solvent (methanol) was evaporated (total evaporation was tested for mixtures C and E using DSC). The resulting polymeric matrix (1 % by weight of rGO with respect to the total weight of polymer and rGO) was stable throughout the observation period, that is, for at least two months, as measured in a Turbiscan® following the procedures previously described. In ll ^ n nr rnm ri lrl.
    [0125] Polyol 1 (Alcupol F5511): triol copolymer of ethylene oxide and propylene oxide; IOH = 55 mg KOH / g; average molecular weight = 3000 Da; viscosity at 25 ° C = 490 mPa.s
    [0126] Polyol 2 (Alcupol F3231): triol copolymer of ethylene oxide and oxide propylene; HOI = 32 mg KOH / g
    [0127] Polyol 3 (Alcupol F3531): triol copolymer of ethylene oxide and propylene oxide; IOH = 35 mg KOH / g; viscosity at 25 ° C = 800 mPa.s
    [0128] Polyol 4 (Alcupol D2021): polypropylene glycol; average molecular weight = 2000 Da; IHO = 56 mg KOH / g; viscosity at 25 ° C = 300 mPa.s
    [0129] Polyol 5 (Alcupol D1011): polypropylene glycol; average molecular weight = 1000 Da; IHO = 110 mg KOH / g; viscosity at 25 ° C = 150 mPa.s
    [0130] In all polymeric matrices according to the invention, an increase in viscosity was observed with respect to the pure polymer. For example, the viscosity of polyol 1 was 490 mPa.s, while the viscosity of polymeric matrix C was 4079 mPa.s; polyol 5 had a viscosity of 150 mPa.s, while that of polymeric matrix E was 747 mPa.s. Polymeric matrices C and E were used to obtain thermoplastic polyurethane foams by polymerization with methylene diphenyl diisocyanate (MDI) and butanediol (BD).
    [0131] Example 5: Polymeric matrix from a wet rGO powder and an epoxy resin
    [0132] The wet powder obtained in Example 1 (product before resuspension having a concentration of 17 mg / ml) was mixed in a Dispermat® with an epoxy resin and the residual solvent was evaporated. As seen in Figure 4, the light microscope image shows a homogeneous dispersion of fine-grained rGO. Similar results were obtained with rGO wet powder at concentrations up to 200 mg / ml.
    权利要求:
    Claims (19)
    [1]
    1. A process for the preparation of a suspension of a reduced graphene oxide in an organic solvent, wherein the concentration of the reduced graphene oxide is greater than 0.3 mg / ml and wherein the suspension is stable for at least 5 days as measured in a Turbiscan®, understanding by stable that the variation in transmittance measured in the Turbiscan® is less than 10% after 5 days, said procedure comprising the steps of:
    (a) reacting an aqueous dispersion of graphene oxide at a temperature between 60 ° C and 150 ° C and at a pH of 7.0 or higher, in the presence of a reducing agent and with high shear to decrease the reaction time required to complete the reduction and to reduce the particle size of the reduced graphene oxide, in order to obtain an aqueous suspension of reduced graphene oxide;
    (b) washing the aqueous suspension of reduced graphene oxide resulting from step (a) with an organic solvent so that the concentration of the reduced graphene oxide is always greater than 0.3 mg / ml, with respect to the total mixture , to obtain a wet reduced graphene oxide powder; Y
    (c) redispersing the wet reduced graphene oxide powder obtained in step (b) in an organic solvent to obtain the suspension.
    [2]
    2. The process according to any claim 1, wherein the organic solvent of step (b) is the same as the organic solvent of the stage (c).
    [3]
    3. The process according to claim 2, wherein the organic solvent is methanol.
    [4]
    4. The process according to any one of claims 1 to 3, wherein the aqueous suspension of graphene oxide is subjected to high shear before step (a).
    [5]
    5. The process according to any one of claims 1 to 4, wherein the reducing agent is selected from the group consisting of vitamin C and hydrazine.
    [6]
    6. A suspension of reduced graphene oxide in an organic solvent, wherein the concentration of the reduced graphene oxide is greater than 0.3 mg / ml and wherein the suspension is stable for at least 5 days as measured in a Turbiscan®, meaning stable that the variation in transmittance measured in the Turbiscan® is less than 10 % after 5 days.
    [7]
    7. A suspension of reduced graphene oxide in an organic solvent according to claim 6, wherein the concentration of the reduced graphene oxide is greater than 1 mg / ml.
    [8]
    The suspension according to any one of claims 6 and 7, wherein the concentration of the reduced graphene oxide is comprised between 1 mg / ml and 10.0 mg / ml.
    [9]
    The suspension according to any one of claims 6 to 8, wherein the d90 particle size of the reduced graphene oxide as measured by laser diffraction is between 2 and 70 microns.
    [10]
    10. The suspension according to any one of claims 6 to 9, wherein the organic solvent is methanol.
    [11]
    11. A process for the preparation of a wet powder of reduced graphene oxide in an organic solvent having a reduced graphene oxide concentration greater than 15.0 mg / ml, comprising the steps of:
    (a) reacting an aqueous dispersion of graphene oxide at a temperature between 60 ° C and 150 ° C and at a pH of 7.0 or higher, in the presence of a reducing agent and with high shear to decrease the reaction time required to complete the reduction and to reduce the particle size of the reduced graphene oxide, in order to obtain an aqueous suspension of reduced graphene oxide;
    (b) washing the aqueous suspension of reduced graphene oxide resulting from step (a) with an organic solvent so that, during washing, the concentration of the reduced graphene oxide is always greater than 0.3 mg / ml with respect to to the total mixture, and adjust the final amount of organic solvent to obtain the wet reduced graphene oxide powder.
    [12]
    12. A wet powder of reduced graphene oxide in an organic solvent, having a reduced graphene oxide concentration greater than 15.0 mg / ml, wherein the d90 particle size of the reduced graphene oxide as measured by laser diffraction it is between 2 and 70 microns.
    [13]
    The wet graphene oxide powder according to claim 12, having a reduced graphene oxide concentration of between 16.0 and 25.0 mg / ml.
    [14]
    14. A polymeric matrix comprising a polymer and the reduced graphene oxide contained in the suspension defined in any one of claims 6 to 10 or obtained according to any one of claims 1 to 5, or in the wet powder of oxide of reduced graphene defined in any one of claims 12 and 13, or in the reduced graphene oxide wet powder obtained according to the process defined in claim 11.
    [15]
    The polymeric matrix according to claim 14, wherein the reduced graphene oxide is present in the polymeric matrix in an amount ranging from 0.001 % by weight to 10 % by weight, with respect to the total weight of the polymeric matrix.
    [16]
    16. The polymeric matrix according to any one of claims 14 and 15, wherein the polymer is a polyol.
    [17]
    17. A process for the preparation of the polymeric matrix defined in any one of claims 14 to 16, comprising mixing a polymer with the suspension defined in any one of claims 6 to 10 or obtained by the process defined in any one of claims 1 to 5, or with the reduced graphene oxide wet powder defined in any one of claims 12 and 13 or obtained according to the process defined in claim 11, and removing the organic solvent.
    [18]
    18. The method according to claim 17, comprising heating.
    [19]
    19. An article comprising the polymeric matrix defined in any one of claims 14 to 16.
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    同族专利:
    公开号 | 公开日
    WO2019145378A1|2019-08-01|
    US20210047187A1|2021-02-18|
    ES2803957R1|2021-09-20|
    引用文献:
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    KR101264316B1|2010-11-09|2013-05-22|한국전기연구원|manufacturing method of single-layered reduced graphene oxide dispersion solution using shear stress and the single-layered reduced graphene oxide dispersion solution thereby|
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    TWI676594B|2014-10-10|2019-11-11|日商東麗股份有限公司|Graphene powder, electrode paste for lithium ion battery, and electrode for lithium ion battery|
    CN105271191B|2015-10-13|2018-06-22|华南理工大学|A kind of redox graphene and preparation method and application|
    WO2017081688A1|2015-11-10|2017-05-18|B. G. Negev Technologies And Applications Ltd., At Ben-Gurion University|A method of producing graphene quantum dots and a product thereof|CN111570239B|2020-05-14|2021-07-23|中国科学院兰州化学物理研究所|Method for in-situ preparation of graphene coating by reducing graphene oxide through friction in inert environment|
    WO2021248216A1|2020-06-10|2021-12-16|Vale S.A.|Method for producing a polymer nanocomposite, polymer nanocomposite, and use|
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    优先权:
    申请号 | 申请日 | 专利标题
    EP18382036|2018-01-23|
    PCT/EP2019/051671|WO2019145378A1|2018-01-23|2019-01-23|A reduced graphene oxide mixture, polymer matrix containing the same and a process for the preparation thereof|
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