SE2350532A1 - Preparation of graphene - Google Patents
Preparation of grapheneInfo
- Publication number
- SE2350532A1 SE2350532A1 SE2350532A SE2350532A SE2350532A1 SE 2350532 A1 SE2350532 A1 SE 2350532A1 SE 2350532 A SE2350532 A SE 2350532A SE 2350532 A SE2350532 A SE 2350532A SE 2350532 A1 SE2350532 A1 SE 2350532A1
- Authority
- SE
- Sweden
- Prior art keywords
- graphene
- water
- organic compound
- rich
- phase
- Prior art date
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 164
- 238000002360 preparation method Methods 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 106
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 73
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000000839 emulsion Substances 0.000 claims abstract description 43
- 239000002244 precipitate Substances 0.000 claims abstract description 38
- 239000000725 suspension Substances 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000005191 phase separation Methods 0.000 claims abstract description 8
- 239000012071 phase Substances 0.000 claims description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- 239000011877 solvent mixture Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 9
- 239000007858 starting material Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920000867 polyelectrolyte Polymers 0.000 claims description 2
- 239000002952 polymeric resin Substances 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- 229920003002 synthetic resin Polymers 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 22
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 20
- 239000000243 solution Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 229910001629 magnesium chloride Inorganic materials 0.000 description 10
- 238000002156 mixing Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000007900 aqueous suspension Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 230000035508 accumulation Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
- C01B32/196—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Colloid Chemistry (AREA)
Abstract
There is provided a method of preparing graphene starting from a suspension of graphene and then optionally increasing the ionic strength of the suspension so that a graphene rich precipitate forms, and is diluted with water and/or a solvent to form a suspension of graphene in water. There is added at least one selected from i) an emulsion of a first organic compound and ii) a second organic compound. Thereafter at least one selected from a solvent/water ratio, ionic strength, pH and temperature is changed to induce a destabilisation of the emulsion or phase separation.Advantages include that it is possible to provide water free or essentially water free graphene, which is suitable for large scale manufacturing. It is possible to provide graphene so that the distribution of graphene in a finished product becomes more even.
Description
Technical field The present invention relates generally to preparation, purification and treatment of graphene. In particular, it relates to a method of preparing graphene, which is water free or essentially water free.
Background Graphene, one of many two-dimensional materials, has many unique properties regarding for instance thermal and electrical conductivity as well as mechanical properties. It is thus desired to manufacture graphene efficiently in a large scale at a reasonable cost.
WO 2014/140324 discloses a process for exfoliating a 3- dimensional material to produce a two-dimensional material, comprising mixing the 3-dimensional material in a liquid, applying shear force to exfoliate the 3-dimensional material and produce dispersed exfoliated two-dimensional material in solution. A number of additives are disclosed to help the dispersed exfoliated two-dimensional material to remain free and unaggregated in solution.
WO 2014/001519 discloses a different approach for exfoliating a 3-dimenisonal layered material to produce a two-dimensional material, comprising the steps of mixing the layered material in a solvent; applying energy, for example ultrasound, to said mixture, and removing the energy applied to the mixture, such that sedimentation of the two-dimensional material out of solution as a weakly re-aggregated, exfoliated two- dimensional material is produced.
WO 2019/095012 discloses a method for producing nanostructured materials in a thin film reactor (TFR) from lO starting material of inorganic or organic material of layered or two dimensional (2D) structure or inorganic material transformed in situ into 2D material, and a solvent: or liquid phase. The TFR can be a device with spaced first and second fluid contact surfaces, which can be conical, for relative rotation to generate shear stress in the thin film therein between.
WO 2021/204946 discloses a method for manufacturing a two- dimensional material comprising the steps of: a) mixing a starting material with a liquid to form a suspension, and b) forcing the suspension to flow in a space between two opposing surfaces which two surfaces are moving relative to each other.
Water is the preferred solvent for exfoliating graphene. Such methods yield the graphene particles in water.
For some applications, it is necessary to provide the graphene without water. Some applications require water free graphene. Some applications require graphene with a reduced content of water.
Attempts to extract the graphene from water with centrifugation have proven unsuccessful, mainly because the graphene suspensions in water are so stable.
Attempts to dry the aqueous graphene suspension have also proven to be unsuccessful since the graphene particles tend to agglomerate to larger units of graphite-like structures during the drying process. lO It is still also a problem in the prior art to provide water free or essentially water free graphene, especially in a large scale.
Summary It is an object of the present invention to obviate at least some of the disadvantages in the prior art and to provide an improved method for providing water free or essentially water free graphene.
In a first aspect there is provided a method of preparing graphene comprising the sequential steps of: a)providing a suspension of graphene in water, b)optionally increasing the ionic strength and/or adjust pH of the suspension so that a graphene rich precipitate forms, where after the formed graphene rich precipitate is recovered, and where after the recovered graphene rich precipitate is diluted with water and/or a solvent to form a suspension of graphene in water, c)adding at least one selected from the group consisting of i) an emulsion of a first organic compound and ii) a second organic compound, which second organic compound is soluble in water or a water/solvent mixture under some conditions, to the suspension under conditions where the emulsion of the first organic compound is stable and/or the second organic compound is soluble in water or a water/solvent mixture, d)changing at least one selected from the group consisting of a solvent/water ratio, ionic strength, pH and temperature to induce a destabilisation of the emulsion or phase separation so a graphene rich phase forms with lO at least one selected form the first organic compound and the second organic compound and so that a salt rich aqueous phase forms.
In a second aspect there is provided a graphene rich mixture manufactured according to the method described above.
An advantage is that the method provides the possibility of providing water free or essentially water free graphene in a way, which is suitable for large scale manufacturing.
It is possible to provide graphene so that the distribution of graphene in a finished product becomes more even compared to the methods in the state of the art. When the material is used as a starting material for the manufacture of for instance a resin, the distribution of the graphene particles throughout the finished material becomes even and agglomerations and accumulations of graphene particles are reduced.
Detailed description Before the invention is disclosed and described in detail, it is to be understood that this invention is not limited to particular compounds, configurations, method steps, substrates, and materials disclosed herein as such compounds, configurations, method steps, substrates, and materials may vary somewhat. It is also to be understood that the terminology employed herein is used for the purpose of describing particular embodiments only and is not intended to be limiting since the scope of the present invention is limited only by the appended claims.
It must be noted that, as used in this specification and the appended claims, the singular forms "a", "an" and "the" lO include plural referents unless the context clearly dictates otherwise.
If nothing else is defined, any terms and scientific terminology used herein are intended to have the meanings commonly understood by those of skill in the art to which this invention pertains.
All percentages and ratios are calculated by weight throughout the description and the claims, unless otherwise indicated.
In the first aspect there is provided a method of preparing graphene comprising the sequential steps of: a)providing a suspension of graphene in water, b)optionally increasing the ionic strength and/or pH of the suspension so that a graphene rich precipitate forms, where after the formed graphene rich precipitate is recovered, and where after the recovered graphene rich precipitate is diluted with water and/or a solvent to form a suspension of graphene in water, c)adding at least one selected from the group consisting of i) an emulsion of a first organic compound and ii) a second organic compound, which second organic compound is soluble in water or a water/solvent mixture under some conditions, to the suspension under conditions where the emulsion of the first organic compound is stable and/or the second organic compound is soluble in water or a water/solvent mixture, d)changing at least one selected from the group consisting of a solvent/water ratio, ionic strength, pH and temperature to induce a destabilisation of the emulsion lO or phase separation so a graphene rich phase forms with at least one selected form the first organic compound and the second organic compound and so that a salt rich aqueous phase forms.
The graphene is already manufactured and provided in an aqueous suspension. With the method, the graphene is prepared for further processing using the method according to the invention.
In the optional step b) the ionic strength is increased and/or pH is adjusted so that a graphene rich phase is formed as a precipitate. The ionic strength is in one embodiment increased by adding at least one salt. One example of suitable conditions for the precipitation is 0.2 wt% MgCl2. The MgCl2 can suitably be added from a more concentrated solution so that the final concentration becomes for instance 0.2 wt% MgCl2. A skilled person is in the light of this teaching able to find other suitable salts for increasing the ionic strength and precipitate a graphene rich phase.
The precipitate is a graphene rich precipitate, which still comprises water as well as the added salt. This graphene rich precipitate is recovered. The graphene rich precipitate is then diluted with water and/or a solvent to a suspension of suitable for the controlled, relatively high concentration, following steps. If a solvent is used in this step it should be miscible with water. This way it is possible to make sure the salt concentration is low enough to assure a stable there is added at emulsion. To the suspension of graphene, least one of an emulsion of a first organic compound, and a second organic compound. The term graphene rich precipitate also refers to diluted graphene rich precipitate.
When an emulsion is used, i.e. alternative ii) in step c), it may be suitable to dilute the graphene rich precipitate as in step b) in order to ensure stability of the emulsion by controlling the ionic strength. Suitable graphene concentrations in the aqueous suspension of graphene is in the range 0.01 to 1 wt%. A higher concentration of graphene is in general easier to use. A lower concentration generally gives a very dilute graphene rich emulsion and tend to give very small particles. Larger particles are suitably recovered with filtration, whereas smaller particles generally are more suitable to recover by centrifugation.
The step b) is optional and the result of the optional step b) is a suspension of graphene in water. If the optional step b) is utilized, then step c) is carried out with the suspension obtained in step b). If the optional step b) is not carried out, then step c) is carried out with the suspension provided in step a).
If the first organic compound is an emulsion, it should form an emulsion also together with the graphene rich precipitate after the addition. In one embodiment, the first organic compound is a compound which forms an emulsion together with water.
The second organic compound has to be miscible at least to some extent with the graphene rich precipitate. This implies that the second organic compound has to be soluble in water or a water/solvent mixture at least to some extent and at least under some conditions. There should thus exist conditions where the second organic compound is soluble in water or a water/solvent mixture. lO When the first and/or second organic compounds are added the conditions should be such that the emulsion of the first organic compound is stable. The stability is measured over a period of time so that the process can be conducted. In one embodiment, the emulsion is stable for at least l hour. Thus, an emulsion which is unstable over a long time period, but stable over a short time period such as at least one hour can be used.
The conditions should also be such that the second organic compound is miscible with the graphene rich phase, which implies that the second organic compound has to be soluble in water or a water/solvent mixture at least to some extent. If a water/solvent mixture is used, then the solvent should be added as well and selected so that the second organic compound is soluble in the water/solvent mixture when added to the graphene rich phase.
There can be added either the first organic compound or the second organic compound or both the first and second organic compounds. In one embodiment, is added. the first organic compound only In another embodiment, the second organic compound only is added. In yet another embodiment, both the first and the second organic compounds are added.
The first and/or the second organic compounds should be in contact with the graphene rich phase for some time so that a high fraction of the graphene will enrich at the interface and/or enter the phase of the first and/or the second organic This time varies, compounds. but is normally at least a few minutes. In one embodiment, this time is at least one hour. Typically the process where the graphene enters the phase of the first and/or the second organic compounds is very quick, but to ensure that the process is complete it is suitable to lO let the graphene be in contact with the first and/or the second organic compounds for some time.
When the first and/or the second organic compounds are in contact with the graphene rich phase, the conditions are changed so that a phase separation and/or a precipitation is caused. One or more of the solvent/water ratio, the ionic strength, the pH and the temperature is changed to induce a phase separation or destabilisation of the emulsion.
If an emulsion is present, then the emulsion should be destabilized so that a precipitation and/or a phase separation occurs. The skilled person knows how to break an emulsion so that it destabilizes. The result is a two-phase system which is not an emulsion anymore. When the emulsion is added to the graphene rich phase, then it should be a stable emulsion and subsequently the emulsion should be destabilized.
If a second organic compound is used, then a phase separation should occur. When the second organic compound is added to the graphene rich phase, optionally with a co-solvent present, then the second organic compound should be miscible with the graphene rich phase. After changing the conditions in step d) the second organic compound should separate from the water phase to form a two-phase system.
During step c) and before step d) a majority of the graphene will enrich at the interface and/or enter the phase with the first and/or second organic compound. The process can also be described so that the first and/or second organic compound surrounds the graphene and captures the graphene when the first and/or second organic compound is no longer soluble or stable in the solvent.
The first and/or second organic compound form a graphene rich organic compound phase. The other phase is an aqueous salt- rich phase. The graphene rich organic compound phase is recovered for further use. The graphene is now in an organic phase.
In one embodiment, the graphene rich phase obtained in step d) is washed with water. This is made to further reduce the content of ions in the graphene rich phase.
The graphene rich phase can be both solid and liquid depending on the properties of the first and/or the second organic compounds as well as the temperature.
If the graphene rich phase is solid then the graphene rich phase can be further treated by for instance filtration, pressing and/or dried.
In one embodiment, the graphene rich phase obtained in step d) is solid and is filtered to recover it.
In one embodiment, the graphene rich phase obtained in step d) is solid and is pressed to remove at least a part of any remaining water. The pressing can be made for instance on a filter or by other known means.
In one embodiment, the graphene rich phase obtained in step d) is dried at elevated temperature to remove at least a part of any remaining water. The drying at elevated temperature is in one embodiment made in an oven. In one embodiment, the drying temperature is 40-90°C. The drying temperature is determined by the thermal stability of the organic phase. Higher temperatures may be applied upon drying, in particular if the thermal stability of the first and/or second organic compounds allow so. Both a solid and a liquid graphene rich lO ll phase can be dried. In case of a liquid graphene rich phase the drying implies that water is evaporated to leave a liquid graphene rich phase typically with a higher boiling point than water. In case of a solid graphene rich phase the drying implies that water is evaporated to leave a solid graphene rich phase.
Before any pressing and drying the water content of the graphene-rich phase after step d) is still fairly high such as lO - 50 wt%. For some applications, this water content can be tolerated, but for other applications it is necessary to reduce the water content further. In such cases pressing and/or drying is necessary. After pressing a water content of the graphene-rich phase is typically in the range 5 - 30 wt%. For applications, which require even lower water content a drying at elevated temperature is suitable to reduce the water content further. After drying at elevated temperature the water content of the graphene-rich phase is typically less than 2 wt%. For most applications a graphene-rich phase with less than 2 wt% water can be referred to as a water free graphene composition. Thus a graphene-rich phase or a graphene composition is referred to as "water free" if the amount of water is less than 2 wt%.
Thus, the graphene can be used in applications which requires that the graphene is provided an organic phase with little or no water present.
In one embodiment, an alcohol is added to the graphene rich precipitate in step c). This may facilitate for instance dissolution of a second organic compound. In one embodiment, the alcohol is ethanol. In one embodiment, the alcohol is at least partly evaporated after step d). The evaporation of the lO l2 alcohol can be conducted with known methods such as increasing the temperature and/or lowering the pressure.
In one embodiment, the graphene rich organic compound phase is utilized as a starting material in another method. This is suitable for methods where graphene should be provided with little or no water present.
In one embodiment, the ionic strength is increased by adding at least one selected from the group consisting of a salt and a polyelectrolyte.
Examples of first organic compounds include but are not (rubber), (rubber), limited to an emulsion of NBR an emulsion of SBR (rubber), an emulsion of EPDM an emulsion of EVA (ethylene-vinyl acetate copolymers, thermoplastics), an emulsion of EAA (ethylene acrylic acid copolymers, termoplastics) In one embodiment, the second organic compound is a polyol.
In one embodiment, the second organic compound is a { "aï?'I_"1\~íE".-C3 ) . polytítramethylene ether glycol In one embodiment, the second organic compound is a polymer of methyl-vinyl ether.
In one embodiment, the second organic compound has a molecular weight MW in the range 600-2000.
In one embodiment, the second organic compound is at least one selected from the group consisting of bisphenol A and epichlorohydrin.
In one embodiment, the graphene rich organic compound phase is utilized as a starting material for the manufacture of an 13 epoxy polymer resin. This gives a favourable distribution of the graphene in the finished resin compared to other methods of adding the graphene.
In one embodiment, the graphene rich organic compound phase is utilized as a starting material for the manufacture of a polyurethane resin. This also gives a favourable distribution of the graphene in the finished resin compared to other methods of adding the graphene.
In one embodiment, the concentration of graphene in the graphene rich polyol phase is more than 5 wt%, preferably more than 10 wt%, more preferably more than 15 wt%.
In the second aspect there is provided a graphene rich mixture manufactured according to the method described above.
There is further provided a resin manufactured as described above.
It is to be understood that this invention is not limited to the particular embodiments shown here. The embodiments are provided for illustrative purposes and are not intended to limit the scope of the invention since the scope of the present invention is limited only by the appended claims and equivalents thereof.
Examples Example 1 A graphene rich precipitate was obtained by adding a saturated aqueous MgCl2 solution to an aqueous suspension of graphene so that a graphene rich precipitate formed. The graphene rich precipitate was diluted with water to 0.14 wt%. To the diluted graphene suspension was added an EAA polymer (32 wt%) emulsion so that the total graphene content was 10 14 wt% to the EAA polymer. The mix was stirred for 5 minutes before adding 0.2 wt% MgCl2 as a saturated solution in water. The salt solution was added while mixing. The salt destabilized the emulsion and black particles of precipitated polymer containing graphene could be separated from the salt- water solution by filtration. The salt-water solution going through the filter was transparent, containing no or very low amounts of suspended graphene material. The precipitate was washed with water to reduce the salt and other possible contaminants further, pressed on the filter to remove as much water as possible, and lastly dried in an oven at 50°C. Example 2 A graphene rich precipitate was obtained by adding a saturated aqueous MgCl2 solution to an aqueous suspension of graphene so that a graphene rich precipitate formed. The graphene rich precipitate was diluted with water to 0.14 wt%. To the diluted graphene suspension was added an EAA polymer (32 wt%) emulsion so that the total graphene content was 10 wt% to the EAA polymer. The mix was stirred for 5 minutes before adding sulfuric acid to make pH < 2.5. The acid was added while mixing. The lower pH destabilized the emulsion and black particles of precipitated polymer containing graphene could be separated from the water solution by filtration. The water solution going through the filter was transparent, containing no or very low amounts of suspended graphene material. The precipitate was washed with water, pressed on the filter to remove as much water as possible, and lastly dried in an oven at 50°C.
Example 3 A graphene rich precipitate was obtained by adding a saturated aqueous MgCl2 solution to an aqueous suspension of graphene so that a graphene rich precipitate formed. The graphene rich precipitate was diluted to 0.40 wt%. To the diluted graphene suspension was added an NBR emulsion (47.9 wt%) so that the total graphene content was 15 wt% to the NBR. The mix was stirred for 5 minutes before adding 0.2 wt% MgCl2 as a saturated solution in water. The salt solution was added while mixing. The salt destabilized the emulsion and black particles of precipitated rubber containing graphene could be separated from the salt-water solution by filtration. The salt-water solution going through the filter was transparent, containing no or very low amounts of suspended graphene material. The precipitate was washed with water to reduce the salt and other possible contaminants further, pressed on the filter to remove as much water as possible, and lastly dried in an oven at 50°C. Example 4 A graphene rich precipitate was obtained by adding a saturated aqueous MgCl2 solution to an aqueous suspension of graphene so that a graphene rich precipitate formed. The graphene rich precipitate was diluted to 1.20 wt%. To the diluted graphene suspension was added an SBR emulsion (46.0 wt%) so that the total graphene content was 20 wt% to the SBR. The mix was stirred for 5 minutes before adding 0.2 wt% MgCl2 as a saturated solution in water. The salt solution was added while mixing. The salt destabilized the emulsion and black particles of precipitated rubber containing graphene could be separated from the salt-water solution by filtration. The salt-water solution going through the filter was transparent, containing no or very low amounts of suspended graphene material. The precipitate was washed with 16 water to reduce the salt and other possible contaminants further, pressed on the filter to remove as much water as possible, and lastly dried in an oven at 50°C. Example 5 A polyol was heated to 50°C, (PTMEG of molecular weight 2000 g/mol) above the melting temperature for the polyol. A water- based graphene suspension (15%) and ethanol were mixed to a /80 W/E ratio (calculated by weight) and heated to 50°C. The heated polyol was added to the heated water/ethanol mix. The amount of polyol added were calculated to achieve 5 wt% graphene in the polyol, assuming all graphene end up in the polyol phase. The mix was stirred at 50°C for 30 minutes before it was transferred into a container with cold water (5°C), a volume large enough to cool the mix to 15°C, well below the melting temperature of the polyol. The precipitated graphene containing polyol was separated from most of the water/ethanol mix and the remaining small amounts of water and ethanol was removed by evaporation at 60°C in a vacuum OVGH .
Claims (18)
1. Claims lfl A method of preparing graphene comprising the sequential steps of: a) b)
2. The method according to claim 1, providing a suspension of graphene in water, optionally increasing the ionic strength and/or adjust pH of the suspension so that a graphene rich precipitate forms, where after the formed graphene rich precipitate is recovered, and where after the recovered graphene rich precipitate is diluted with water and/or a solvent to form a suspension of graphene in water, adding at least one selected from the group consisting of i) an emulsion of a first organic compound and ii) a second organic compound, which second organic compound is soluble in water or a water/solvent mixture under some conditions, to the suspension under conditions where the emulsion of the first organic compound is stable and/or the second organic compound is soluble in water or a water/solvent mixture, changing at least one selected from the group consisting of a solvent/water ratio, ionic strength, pH and temperature to induce a destabilisation of the emulsion or phase separation so a graphene rich phase forms with at least one selected form the first organic compound and the second organic compound and so that a salt rich aqueous phase forms. wherein an alcohol is added to the suspension in step c).
3. The method according to claim 2, wherein the alcohol is ethanol..The method according to any one of claims 2-3,
4. .The method according to any one of claims 1-4,
5. .The method according to any one of claims 1-5,
6. .The method according to any one
7. .The method according to any one
8. .The method according to any onewherein alcohol is at least partly evaporated after step d). wherein ionic strength is increased by adding at least one selected from the group consisting of a salt and a polyelectrolyte. wherein graphene rich phase obtained in step d) is utilized as starting material in another method. of claims 1-6, wherein graphene rich phase obtained in step d) is washed with water. of claims 1-7, wherein graphene rich phase obtained in step d) filtered to recover it. of claims 1-8, wherein graphene rich phase obtained in step d) is solid and is is solid and is the the the the the the pressed to remove at least a part of any remaining water.
9. The method according to any one of claims 1-9, wherein the graphene rich phase obtained in step d) is dried at elevated temperature to remove at least a part of any remaining water.
10. . The method according to any one of claims 1-10, wherein the second organic compound is a polyol.wherein the second organic compound is a pol ether glycol
11. . The method according to any one of claims 1-11, .r
12. (PTMEGÉ. vtetramethyleno
13. L13. The method according to any one of claims 1-12, wherein the second organic compound has a molecular weight MW in the range 600-
14. The method according to any one of claims 1-13, wherein the second organic compound is at least one selected from the group consisting of bisphenol A and epichlorohydrin.
15. The method according to claim 14, wherein the graphene rich organic compound phase is utilized as a starting material for the manufacture of an epoxy polymer resin.
16. The method according to any one of claims 11-13, wherein the graphene rich organic compound phase is utilized as a starting material for the manufacture of a polyurethane resin.
17. The method according to any one of claims 1-16, wherein the concentration of graphene in the graphene rich organic phase is more than 5 wt%, preferably more thanwt%, more preferably more than 15 wt%.
18. A graphene rich mixture manufactured according to the method of any one of claims 1-17.
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| SE2350532A SE2350532A1 (en) | 2023-05-03 | 2023-05-03 | Preparation of graphene |
| PCT/EP2024/059050 WO2024227550A1 (en) | 2023-05-03 | 2024-04-03 | Treatment of 2d-materials |
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| SE2350532A SE2350532A1 (en) | 2023-05-03 | 2023-05-03 | Preparation of graphene |
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| CN109021286A (en) * | 2018-08-08 | 2018-12-18 | 苏州傅里烨新材料科技有限公司 | A kind of dispersion and dispersing method of graphene |
| CN109455709A (en) * | 2018-12-25 | 2019-03-12 | 中国科学院电工研究所 | A kind of graphene powder material and preparation method thereof |
| CN109957159A (en) * | 2017-12-22 | 2019-07-02 | 北京橡胶工业研究设计院有限公司 | A kind of graphene-styrene-butadiene rubber compound and preparation method thereof |
| CN115650222A (en) * | 2022-11-04 | 2023-01-31 | 中星(广州)纳米材料有限公司 | Method for applying organic acid in graphene preparation process |
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| KR20150036037A (en) | 2012-06-28 | 2015-04-07 | 더 프로보스트, 펠로우스, 파운데이션 스콜라스, 앤드 디 아더 멤버스 오브 보오드 오브 더 칼리지 오브 더 홀리 앤드 언디바이디드 트리니티 오브 퀸 엘리자베스 니어 더블린 | Atomically thin crystals and films and Process for Making Same |
| GB201304770D0 (en) | 2013-03-15 | 2013-05-01 | Provost Fellows Foundation Scholars And The Other Members Of Board Of | A scalable process for producing exfoliated defect-free, non-oxidised 2-dimens ional materials in large quantities |
| JP2021502946A (en) | 2017-11-15 | 2021-02-04 | ２ディー フルイディクス ピーティーワイ エルティーディー | Devices and methods for thin film chemistry |
| GB201800249D0 (en) * | 2018-01-08 | 2018-02-21 | Univ Of Sussex | Pickering emulsions |
| EP3917879B1 (en) | 2020-04-09 | 2023-06-28 | 2D Fab Ab | Manufacture of two-dimensional matter |
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| CN109957159A (en) * | 2017-12-22 | 2019-07-02 | 北京橡胶工业研究设计院有限公司 | A kind of graphene-styrene-butadiene rubber compound and preparation method thereof |
| CN109021286A (en) * | 2018-08-08 | 2018-12-18 | 苏州傅里烨新材料科技有限公司 | A kind of dispersion and dispersing method of graphene |
| CN109455709A (en) * | 2018-12-25 | 2019-03-12 | 中国科学院电工研究所 | A kind of graphene powder material and preparation method thereof |
| CN115650222A (en) * | 2022-11-04 | 2023-01-31 | 中星(广州)纳米材料有限公司 | Method for applying organic acid in graphene preparation process |
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