WO2015182829A1 - Composite de graphène-polymère et son procédé de préparation - Google Patents

Composite de graphène-polymère et son procédé de préparation Download PDF

Info

Publication number
WO2015182829A1
WO2015182829A1 PCT/KR2014/008595 KR2014008595W WO2015182829A1 WO 2015182829 A1 WO2015182829 A1 WO 2015182829A1 KR 2014008595 W KR2014008595 W KR 2014008595W WO 2015182829 A1 WO2015182829 A1 WO 2015182829A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene
polymer composite
amphoteric
polymer
methacrylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2014/008595
Other languages
English (en)
Korean (ko)
Inventor
정한모
다오트렁덩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Ulsan Foundation for Industry Cooperation
Original Assignee
University of Ulsan Foundation for Industry Cooperation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Ulsan Foundation for Industry Cooperation filed Critical University of Ulsan Foundation for Industry Cooperation
Publication of WO2015182829A1 publication Critical patent/WO2015182829A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring

Definitions

  • the present invention relates to a graphene-polymer composite and a method for preparing the same, specifically, a polymer core; And it consists of a shell containing the amphoteric graphene relates to a graphene-polymer composite excellent in electrical conductivity and a method for producing the same.
  • Graphene is a new nanomaterial having excellent physical properties, and researches for applying it in various fields have been actively conducted in recent years. Specifically, graphene has excellent properties such as a modulus of 1 TPa, an electrical conductivity of 10 6 S / cm, a thermal conductivity of 5000 W / m ⁇ K, and a large surface area of 2600 m 2 / g. The potential is excellent.
  • graphene is known to be a material that cannot exist independently. Only theoretical studies have been carried out, but since the Geim Group at the University of Manchester in 2004 confirmed the existence of graphene, graphene is a new conductive nanomaterial. In the spotlight, various studies are being conducted worldwide.
  • composites prepared by mixing graphene with a polymer have been developed in order to use the excellent physical properties of graphene.
  • the composite is not only a variety of physical properties by the graphene, but also to attract the attention as a new material because it can maximize the desired physical properties by appropriately adjusting the structure according to the use.
  • dispersing graphene in a polymer matrix to maximize the interface area between graphene and the polymer, thereby improving the interaction between the graphene and the polymer at the interface can be achieved by optimization.
  • Korean Patent Publication No. 2013-0125388 proposes a composite having a structure in which graphene oxide is dispersed in a polymer matrix using graphene oxide or graphite oxide including a plurality of functional groups on its surface as a catalyst for polymerization. .
  • Korean Patent Laid-Open Publication No. 2010-0109258 proposes an electrically conductive particle coated with graphene by polymer binding the polymer fine particles modified with an ionic functional group and the graphene modified with an ionic functional group on the surface. .
  • Graphene Attached on Microsphere Surface for Thermally Conductive Composite Material Jae-Yong Choi, et.al., Clean Technology, Vol. 19, No. 3, 243
  • a technique for preparing polymethyl methacrylate microparticles having graphene distribution on the surface by using a graphene solution having an interfacial stabilizer introduced through a water dispersion as a water phase is proposed.
  • the structure in which graphene is dispersed in the polymer matrix in terms of electrical conductivity is inferior in physical properties to the composite of the graphene-coated structure, and graphene oxide is also compared with the reduced graphene.
  • when modifying to have a hydrophilicity on the graphene surface in order to improve the dispersibility of the graphene it is accompanied by a modification of the graphene inherent delocalized carbon-carbon double bond to add a separate reaction point, thereby Intrinsic physical properties may be reduced, resulting in insignificant physical properties of the polymer composite.
  • the interfacial stabilizer or dispersion stabilizer there is a problem that the physical properties implemented by the graphene may be reduced by remaining on the surface of the finally prepared polymer composite.
  • An object of the present invention is to provide a graphene-polymer composite having excellent electrical conductivity since the physical properties of graphene are not degraded.
  • Another object of the present invention is to provide a method for producing the graphene-polymer composite that is performed without the use of a stabilizer to improve the dispersibility of graphene.
  • amphoteric graphene provides a graphene-polymer composite including n hydrophilic groups satisfying Equation 1 for 100 graphene carbon atoms:
  • It provides a graphene-polymer composite manufacturing method for producing a graphene-polymer composite by performing a polymerization reaction of a mixture containing a vinyl monomer, an initiator and amphoteric graphene.
  • the graphene-polymer composite according to the present invention has a structure in which a polymer, which is a core, is coated with amphoteric graphene having 0.2 ⁇ n ⁇ 60 hydrophilic groups introduced on its surface with respect to 100 graphene carbon atoms, thereby inherent in graphene. There is no deterioration and excellent electrical conductivity is realized even when a small amount of graphene is contained, and thus may be usefully used in various fields requiring electrical conductivity.
  • Figure 2 is a scanning electron microscope (SEM) analysis of the graphene-polymer composite prepared in one embodiment according to the present invention: (a) is an image of 150 magnification, (b) is a 3,000 magnification Image.
  • SEM scanning electron microscope
  • the terms "comprises” or “having” are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.
  • “phr” refers to the content of amphoteric graphene (Parts per Hundred Resin) used per 100 parts by weight based on the core polymer or the monomer used in the polymerization reaction.
  • stabilizer refers to an additive in which a monomer or polymer used for polymerization is stably maintained in the shape of droplets or fine particles in a polymerization reaction performed with water as a dispersion medium.
  • the stabilizer may include, for example, an emulsifier or a surfactant used in an emulsion polymerization reaction to stably form an emulsion of a reaction solvent and an organic monomer; Dispersants used in the suspension polymerization reaction to stably form droplets of organic monomers in the reaction solvent; Or particle stabilizers used in the dispersion polymerization reaction in order to prevent the fine particles formed by polymerization from agglomerating in the dispersion medium.
  • bilateral means hydrophilicity and hydrophobicity in one molecule or one particle; Or it means showing both hydrophilicity and lipophilic at the same time.
  • bilateral graphene refers to graphene in which both hydrophobicity and hydrophilicity are implemented by imparting hydrophilicity by introducing COO - or SO 3 - to hydrophobic graphene.
  • the present invention relates to a graphene-polymer composite and a preparation method thereof.
  • Graphene is a material that has recently attracted attention in various fields because of its excellent physical properties.
  • the graphite-based materials are not dispersed well in the polymer and are aggregated so that the desired physical properties are not effectively realized.
  • many studies have been conducted to improve this.
  • techniques for improving the dispersibility of water by improving the surface of graphene or controlling the dispersion of graphene using a stabilizer have been published.
  • a separate reaction point is required on the surface, a deformation of carbon-carbon double bonds delocalized on the surface of graphene is accompanied, and when stabilizers are used, stabilizers remain in the finally prepared composite. Since there is a problem that the inherent physical properties of the graphene is implemented in the composite.
  • the present invention proposes a graphene-polymer composite having excellent electrical conductivity and a method of manufacturing the same by minimizing the degradation of inherent properties of graphene.
  • graphene having 0.2 ⁇ n ⁇ 60 hydrophilic groups introduced to the surface of 100 graphene carbon atoms in the preparation of the graphene-polymer composite graphene is not used without using an interfacial stabilizer, dispersion stabilizer, or the like.
  • the invention in one embodiment, a polymer core
  • amphoteric graphene provides a graphene-polymer composite including n hydrophilic groups satisfying Equation 1 for 100 graphene carbon atoms:
  • the graphene-polymer composite may include a shell composed of a polymer core and amphoteric graphene coating the same.
  • the graphene forming the shell may be a hydrophilic group introduced into the surface having an amphoteric.
  • Conventionally performed techniques for introducing a hydrophilic group on the graphene surface deforms the unlocalized carbon-carbon double bond on the graphene surface, thereby degrading the inherent physical properties of the graphene.
  • the amphoteric graphene used in the present invention does not modify carbon-carbon double bonds unlocalized on the graphene surface, and uses reactive groups remaining on the graphene surface, specifically, epoxy groups remaining on the graphene surface.
  • hydrophilic groups may be introduced for 100 graphene carbon atoms. More specifically 0.2 to 40; 0.2 to 30; Or 0.2 to 20 hydrophilic groups may be introduced.
  • the introduction amount of the hydrophilic group can maintain the inherent physical properties of graphene by preventing deformation of the unlocalized carbon-carbon double bond on the graphene surface within the above range, the hydrophilicity imparted to the graphene surface and the hydrophobicity of graphene itself The ratio can be effectively controlled to have amphotericity.
  • the hydrophilic group according to the present invention is not particularly limited as long as it is a substituent capable of inducing hydrophilicity on the surface of graphene, specifically, may include any one or more of COO - M + and SO 3 - M + .
  • M is H; Alkali metals such as Li, Na, K, Rb and Cs; Or quaternary amines.
  • the content of graphene constituting the shell is not particularly limited as long as it is an amount capable of improving the electrical conductivity while stabilizing the water dispersion of the polymer particles as the core. May be 0.1 to 10 phr relative to the polymer core. More specifically 0.1 to 8 phr; 0.2 to 6 phr; Or 0.3 to 5 phr.
  • Equation 2 In evaluating the electrical conductivity (L), the following Equation 2 may be satisfied:
  • the unit of the electrical conductivity (L) is S / cm.
  • the electrical conductivity of the graphene-polymer composite according to the present invention with an amphoteric graphene content of 0.3 to 5.0 phr relative to the polymer core was evaluated.
  • the electrical conductivity was found to be 8.43 X 10 -4 S / cm.
  • the electrical conductivity of the pure polymethyl methacrylate used as the core is 1.75 X 10 -12 S / cm, the electrical conductivity is significantly lower, whereas the graphene-polymer composite according to the present invention is depending on the content of the amphoteric graphene 5.39 X 10 -5 to 1.57 X 10 -1 S / cm, the electrical conductivity of 3.1 X 10 7 to 9.0 X 10 10 times better than that of pure polymethylmethacrylate.
  • Experimental Example 2 shows that shows that of pure polymethylmethacrylate.
  • the graphene-polymer composite according to the present invention can implement excellent electrical conductivity even when the amphoteric graphene is contained in a small amount of 0.1 to 10.0 phr relative to the polymer core, the content of the amphoteric graphene in the polymer core
  • About 1 phr of graphene-polymeric electrical conductivity of the complex is 1.0 ⁇ 10 -8 S / cm or more, specifically 1.0 ⁇ 10 -5 S / cm or higher, more specifically from 1.0 ⁇ 10 -4 S / cm or more, or It turns out that it is 4.0 * 10 ⁇ -4> S / cm or more.
  • the polymer core according to the present invention is not particularly limited in kind, specifically, for example, methyl acrylate (methylacrylate, MA), ethyl acrylate (ethylacrylate, EA), butyl acrylate (butylacrylate, BA), methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate (BMA), 2-ethylhexyl methacrylate (EHMA), glycy Glycidyl methacrylate (GMA), styrene, alpha-methylstyrene, vinyl chloride, vinylidene chloride, ethylene, propylene, etc. It may be a polymer polymerized using at least one vinyl monomer of.
  • the graphene-polymer composite according to the present invention includes an amphoteric graphene having 0.2 ⁇ n ⁇ 60 hydrophilic groups introduced on its surface with respect to 100 graphene carbon atoms, and thus has excellent electrical conductivity. It can be used as a good electrical conductivity.
  • a method for preparing a graphene-polymer composite to prepare a graphene-polymer composite by carrying out a polymerization reaction of a mixture including a vinyl monomer, an initiator and amphoteric graphene.
  • MMA methyl methacrylate
  • AIBN 2,2-azobisisobutyronitrile
  • amphoteric graphene can be mixed in. Thereafter, the mixture may be polymerized at 55 to 85 ° C., the powder formed by the polymerization may be filtered and washed, and then dried to prepare a graphene-polymer composite according to the present invention.
  • the polymerization reaction according to the present invention may be dispersion polymerization, emulsion polymerization or suspension polymerization.
  • the amphoteric graphene has a suitable ratio of hydrophilicity and hydrophobicity (the same as lipophilic) so that the hydrophobic monomer can be stably present in fine particles or droplets in water used as a reaction solvent of a polymerization reaction. Serves as a "Pickering Stabilizer".
  • the “Pickering Stabilizer” refers to micro or nanometer-sized solid particles dispersed in a mixture of two liquids (eg, water and oil) that are different in polarity and do not mix with each other. Solid particles have the function of physically stabilizing to prevent coalescence of emulsion particles. That is, the amphoteric graphene according to the present invention can be stabilized so that the monomer can be formed and polymerized by being located at the interface between the monomer and the water of the dispersion medium in the polymerization reaction of the polymer as the core.
  • the method for preparing the graphene-polymer composite according to the present invention can be performed without using a separate stabilizer by using amphoteric graphene, and therefore, there is no remaining stabilizer in the conventional dispersion polymerization, emulsion polymerization or suspension polymerization. Therefore, it is possible to minimize the deterioration of the physical properties of graphene.
  • the graphene-polymer composite thus prepared may have a structure in which the amphoteric graphene forms a shell by using the polymerized polymer as a core, and some of the amphoteric graphene is polymerized. Alternatively, or depending on the degree of hydrophobicity of the amphoteric graphene, it may be present in the composite together with the polymer that is the core.
  • amphoteric graphene according to the invention may be surface modified with a compound containing a hydrophilic group.
  • the amphoteric graphene may be obtained by oxidizing a commercially available graphite powder, reducing it again to prepare graphene, and then surface modifying the prepared graphene with a compound containing a hydrophilic group.
  • the amphoteric graphene according to the present invention can utilize a functional group containing oxygen remaining in the reduced graphene, that is, an epoxy group, so that when modified, it is inherent to graphene without deformation of the carbon-carbon double bonds delocalized on the graphene surface. Physical property degradation can be minimized and the degree of hydrophilicity and hydrophobicity can be controlled appropriately.
  • the method for oxidizing the graphite powder is, for example, NaClO 3, KClO 3, KMnO 4, etc. can be used alone or in combination, or by electrochemical oxidation method for oxidizing agent.
  • the graphite oxide powder thus prepared may have an element ratio of carbon to oxygen of 1 to 20: 1, but is not limited thereto.
  • the graphite oxide powder has an interlayer distance of about 7 ⁇ s, the 2 ⁇ of the peak observed in the X-ray diffraction analysis may be about 13 ⁇ 1 °, and the error may vary depending on the degree of oxidation and moisture absorption of the graphite oxide powder. May occur.
  • the method of reducing the graphite oxide for example, a heat reduction method of reducing and swelling and peeling off the layers constituting the graphite oxide by heat treatment at a high temperature of 300 °C or more under an inert gas instantaneously;
  • a chemical reduction method may be used in which the graphite oxide is dispersed in a liquid medium and reduced with a reducing agent such as hydrazine, but is not limited thereto.
  • amphoteric graphene according to the present invention is a graphene prepared by reducing the graphite oxide
  • M of the hydrophilic group can be prepared by modifying with a compound containing a hydrophilic group which is H, Li, Na, K, Rb, Cs or quaternary amine.
  • the hydrophobic graphene prepared by reducing graphite oxide may have an epoxy group on a surface thereof. Therefore, the surface of graphene is modified by reacting an epoxy group remaining on the graphene surface with a compound containing a hydrophilic group, a SO 3 ⁇ group and one amine group, for example, 2-aminoethanesulfonic acid, thereby modifying the surface of the graphene. Pins can be manufactured.
  • the hydrophilic group COO - or SO 3 - may perform a function of imparting hydrophilicity to the hydrophobic graphene.
  • the amine group of the compound containing a hydrophilic group may perform a function of reacting with the epoxy group remaining on the graphene surface to modify the surface of the graphene.
  • the compound having one amine group may be used.
  • amphoteric graphene according to the present invention may include n hydrophilic groups satisfying Equation 1 for 100 graphene carbon atoms:
  • the amphoteric graphene according to the present invention is 0.2 to 60, more specifically 0.2 to 40 with respect to 100 graphene carbon atoms; 0.2 to 30; Or 0.2 to 20 hydrophilic groups may be introduced.
  • the amphoteric graphene can efficiently control the hydrophilicity and lipophilicity of the modified graphene by introducing a hydrophilic group within the above range for 100 carbon atoms, and thus, during polymerization of the core polymer, (Pickering Stabilizer) ".
  • the mixing amount of the graphene (graphene) is particularly limited as long as it can stabilize the water dispersion and improve the electrical conductivity of the polymer particles polymerized to form the core.
  • it may be specifically 0.1 to 10 phr relative to the vinyl monomer. More specifically 0.1 to 8 phr; 0.2 to 6 phr; Or 0.3 to 5 phr.
  • the electrical conductivity of the graphene-polymer composite according to the present invention with an amphoteric graphene content of 0.3 to 5.0 phr relative to the polymer core was evaluated.
  • the electrical conductivity of pure polymethyl methacrylate used as the core the electrical conductivity is significantly low as 1.75 X 10 -12 S / cm
  • graphene in accordance with the present invention the polymer composite is 5.39 X 10 -5 to 1.57 Since it exhibits an electrical conductivity of X 10 ⁇ 1 S / cm, it can be confirmed that the electric conductivity is 3.1 X 10 7 to 9.0 X 10 10 times superior to that of pure polymethylmethacrylate (see Experimental Example 2).
  • the graphene-polymer composite according to the present invention realizes excellent electrical conductivity even when the amphoteric graphene contains a small amount of 0.1 to 10.0 phr with respect to the polymer core.
  • the size of the graphene-polymer composite prepared according to the method for producing the graphene-polymer composite according to the present invention may be 0.01 to 10,000 ⁇ m. Specifically, it may be 0.01 to 1000 ⁇ m, 0.1 to 500 ⁇ m, 0.1 to 250 ⁇ m or 1 to 250 ⁇ m.
  • the particle size of the graphene-polymer composite according to the invention was measured in which the amphoteric graphene content is 0.3 to 5.0 phr relative to the polymer core.
  • the particle size of the graphene-polymer composite according to the present invention is about 56.9 to 226.1 ⁇ m, and the graphene-polymer composite has a tendency to decrease the particle size of the prepared composite as the amount of amphoteric graphene increases It can confirm that (refer experimental example 1).
  • the vinyl monomer according to the present invention is not particularly limited in kind, but specifically, for example, methyl acrylate (methyl acrylate, MA), ethyl acrylate (ethyl acrylate, EA), butyl acrylate (butyl acrylate, BA) Methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate (BMA), 2-ethylhexyl methacrylate (EHMA), glycidyl methacrylate Glycidyl methacrylate (GMA), styrene, alpha-methylstyrene, vinyl chloride, vinylidene chloride, ethylene, propylene, etc. Can be.
  • graphite having an average particle size of 280 ⁇ m was expanded for 1 minute. Thereafter, the expanded graphite (10 g) was injected with fuming nitric acid (200 mL) into a 1000 mL reactor equipped with a stirrer and a thermometer, and stirred while maintaining 0 ° C. Potassium chlorate (85 g) was slowly added over 1 hour while stirring, and graphite was oxidized while stirring at room temperature for 24 hours. The oxidized graphite was filtered and washed with distilled water until the pH of the filtrate was 6. The washed graphite oxide was dried at 100 ° C. under vacuum for one day, and the dried graphite oxide was charged into a quartz tube.
  • Step 2 Preparation of Amphoteric Graphene Modified with Sulfonic Acid Group
  • 2-aminoethanesulfonic acid (20.0 g, 0.16 mol) and potassium hydroxide (KOH, 9.0 g, 0.16 mol) were dissolved in water (35 g) and stirred for 30 minutes.
  • graphene (1 g) prepared in step 1 was added to acetone (150 mL) and sonicated for 1 hour to disperse the graphene in acetone.
  • the graphene-dispersed dispersion and the 2-aminoethanesulfonic acid solution were mixed and stirred for 1 hour, the mixed solution was sonicated for 20 minutes, and then stirred at 60 ° C. for 2 days to surface the graphene in the solution. Modified.
  • the mixed solution was filtered to separate graphene, and the separated graphene was washed with acetone mixed with hot water. Thereafter, the mixture was dried under vacuum at 60 ° C. for 1 day to prepare amphoteric graphene modified with a sulfonic acid group which is a hydrophilic group.
  • well-modified amphiphilic average particle size of the pin is 8.4 ⁇ m, and the atom composition yiyeotda C 10 O 1.03 H 1.21 N 0.14 S 0.13.
  • a carboxyl group was modified in the same manner as in Preparation Example 1, except that 6-aminocaproic acid (21.0 g, 0.16 mol) was used instead of 2-aminoethanesulfonic acid in Step 2 of Preparation Example 1. Amphoteric graphene was prepared.
  • the graphene prepared in Preparation Example 1 was added to water (150 g) and sonicated for 1 hour to disperse the graphene, and then methyl methacrylate (MMA, 10 g) as a vinyl monomer and 2,2 as an initiator.
  • MMA methyl methacrylate
  • a solution containing azobisisobutyronitrile (AIBN, 0.15 g) was added to a dispersion in which graphene was dispersed, and stirred at a speed of 2000 rpm for 5 minutes. At this time, the mixed amount of graphene was mixed in 0.3 to 5.0 phr relative to the monomer, as shown in Table 1 below.
  • the temperature was raised to 70 ° C., and the suspension polymerization reaction was performed at 300 rpm for 1 day while maintaining the elevated temperature.
  • the mixed solution was filtered to separate the graphene-coated polymer powder, and the separated powder was dried at 90 ° C. for 1 day under vacuum to prepare a graphene-polymethylmethacrylate composite powder according to the present invention.
  • Example 1 Table 1 Graphene Blending Amount (phr) Example 1 0.3 Example 2 0.5 Example 3 1.0 Example 4 2.0 Example 5 3.0 Example 6 5.0
  • Graphene prepared in Preparation Example 1 was added to acetone (100 g), and sonicated for 1 hour to disperse the graphene. Then, a solution of polymethyl methacrylate (PMMA, 10 g) dissolved in acetone (250 g) was added to the dispersion, stirred and mixed, and then acetone was removed to remove the graphene-polymethyl methacrylate composite powder. Prepared. At this time, as shown in Table 2, the mixed amount of graphene was mixed at 0.0 to 5.0 phr with respect to the vinyl monomer.
  • PMMA polymethyl methacrylate
  • the graphene-polymer composite according to the present invention has a particle form of a shell formed by coating polymethyl methacrylate, which is an amphoteric graphene core, without using a separate stabilizer It can be seen that it is stably produced by the suspension polymerization reaction.
  • FIG. 2 is a scanning electron microscope analysis of the graphene-polymethyl methacrylate complex prepared in Example 5 at 150 magnification, the complex is a rough surface of the spherical It can be confirmed that it is a particle.
  • (b) of FIG. 2 is a 20 times magnification (3,000 magnification) of (a), wherein the modified amphoteric graphene is coated with polymethylmethacrylate to form a shell, and (b) It can be confirmed that it has a form in which some peeled off as indicated in the figure.
  • Example 1 86.4 226.1
  • Example 2 90.8 168.1
  • Example 3 94.4 165.6
  • Example 4 87.4 129.9
  • Example 5 96.6 107.8
  • Example 6 93.8 56.9
  • the polymerization reaction is carried out in an excellent yield of about 85% or more irrespective of the mixed amount of the amphoteric graphene added, the particle size is It can be seen that the polymerization decreases with increasing amount of the amphoteric graphene mixed with methyl methacrylate. This coincides with the reaction tendency of dispersion polymerization, emulsion polymerization or suspension polymerization in which the particle size of the prepared polymer decreases as the amount of dispersion stabilizer increases.
  • the modified amphoteric graphene coats a polymer to form a shell and at the same time plays a role of "pickering stabilizer" in the polymerization reaction.
  • the production method of the graphene-polymer composite according to the present invention by using a composite using a modified amphoteric graphene, it is possible to perform a polymerization reaction stably without using a separate stabilizer, so It can be seen that the composite prepared has the form of polymer particles forming a shell by coating the amphoteric graphene modified on the surface.
  • Example 1 Graphene-polymethyl methacrylate composite particles prepared in Example 1 according to the present invention by compression molding under a pressure condition of 130 °C, 10 MPa to prepare a specimen in the form of a sheet (3.0 cm 3.0 cm ⁇ 100 ⁇ m) It was.
  • the graphene-polymethyl methacrylate composite particles prepared in Examples 2 to 6, and Comparative Examples 1 to 7 were compression molded in the same manner as above to prepare a specimen.
  • the electrical conductivity of the prepared specimens was measured using a four-point probe method, and the results are shown in Table 4 below.
  • the electrical conductivity of a pure poly (methyl methacrylate) prepared in Comparative Example 1 is an insulating, electrical conductivity was found to be 1.75 X 10 -12 S / cm.
  • the composites prepared in Examples 1 to 6 according to the present invention are prepared by adding modified amphoteric graphene to form a graphene shell on the surface of polymethylmethacrylate when polymethylmethacrylate is prepared. It can be seen that the conductivity is improved by 3.1 ⁇ 10 7 to 9.0 ⁇ 10 10 times. In addition, in the case of the composite prepared by mixing the polyacrylate and the amphoteric graphene in Comparative Examples 2 to 7, it can be seen that the 1.2 to 5.7 ⁇ 10 5 times improved.
  • the graphene-polymer composite according to the present invention can achieve a significantly superior electrical conductivity compared to the composite prepared by mixing the polymerized polymer and amphoteric graphene by performing polymerization from a mixture of monomer and amphoteric graphene. It can be seen that.
  • the method for preparing a graphene-polymer composite according to the present invention by using graphene having 0.2 ⁇ n ⁇ 60 hydrophilic groups introduced on the surface of 100 graphene carbon atoms, a separate interfacial stabilizer, dispersion stabilizer, etc.
  • a separate interfacial stabilizer, dispersion stabilizer, etc. In addition to improving the dispersibility of graphene without the use of, it is possible to minimize the deformation of the carbon-carbon double bonds delocalized on the graphene surface. Accordingly, the graphene-polymer composite prepared is excellent in electrical conductivity even if it contains a small amount of graphene, it can be usefully used in various fields that require electrical conductivity.
  • the graphene-polymer composite according to the present invention has a low physical property inherent in graphene, so that excellent electrical conductivity is realized even when a small amount of graphene is contained, and thus may be usefully used in various fields requiring electrical conductivity.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Graft Or Block Polymers (AREA)
  • Polymerisation Methods In General (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention concerne un composite de graphène-polymère et son procédé de préparation. La présente invention peut améliorer la force de dispersion du graphène sans utiliser séparément de tensio-actif ou de stabilisant de dispersion et peut réduire la transformation des doubles liaisons carbone-carbone qui sont délocalisées sur la surface du graphène, en utilisant du graphène ayant une surface sur laquelle n (0,2 ≤ n ≤ 60) groupes hydrophiles sur la base de 100 atomes de carbone de graphène sont introduits, lorsque le composite de graphène-polymère est préparé. Par conséquent, le composite de graphène-polymère préparé présente une excellente conductivité électrique, bien qu'il contienne une faible quantité de graphène, et peut donc être favorablement utilisé dans divers domaines nécessitant une conductivité électrique.
PCT/KR2014/008595 2014-05-26 2014-09-16 Composite de graphène-polymère et son procédé de préparation Ceased WO2015182829A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2014-0063009 2014-05-26
KR1020140063009A KR101590706B1 (ko) 2014-05-26 2014-05-26 그래핀―고분자 복합체 및 이의 제조방법

Publications (1)

Publication Number Publication Date
WO2015182829A1 true WO2015182829A1 (fr) 2015-12-03

Family

ID=54699137

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2014/008595 Ceased WO2015182829A1 (fr) 2014-05-26 2014-09-16 Composite de graphène-polymère et son procédé de préparation

Country Status (2)

Country Link
KR (1) KR101590706B1 (fr)
WO (1) WO2015182829A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108440717A (zh) * 2018-03-15 2018-08-24 厦门大学 一种氧化石墨烯包覆聚甲基丙烯酸缩水甘油酯微球复合防腐涂料助剂及其制备方法
CN108586967A (zh) * 2018-04-29 2018-09-28 武汉工程大学 一种基于细乳液聚合制备石墨烯/苯乙烯-丙烯酸丁酯介电复合材料的方法
CN111620329A (zh) * 2019-02-27 2020-09-04 佳能株式会社 改性石墨烯、其生产方法、改性石墨烯-树脂复合物、改性石墨烯片材和改性石墨烯分散体
CN113336500A (zh) * 2021-06-25 2021-09-03 亚士漆(上海)有限公司 一种粘结砂浆及其制备方法和应用
WO2024220706A1 (fr) * 2023-04-18 2024-10-24 Nano Catalytics, Inc. Nanoparticules et microparticules améliorant les performances physiques de formulations, préparation et produit final

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102464398B1 (ko) * 2015-12-30 2022-11-09 주식회사 상보 그래핀 분산액 및 그래핀-고분자 복합체 제조방법, 및 이를 이용한 배리어 필름 제조방법
KR102739667B1 (ko) * 2021-10-13 2024-12-09 한국자동차연구원 고분자-그래핀 복합소재 제조 방법
KR102814238B1 (ko) * 2024-11-27 2025-06-10 주식회사 케이비엘러먼트 친수성으로 개질된 탄소계 소재를 포함하는 페이스트 조성물 및 이의 제조방법

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100127575A (ko) * 2009-05-26 2010-12-06 한국과학기술연구원 전기 전도성 입자 및 그 제조 방법
KR101029734B1 (ko) * 2010-04-30 2011-04-18 주식회사 라이온켐텍 함산소불소화 처리된 그라핀을 포함하는 전기전도성 고분자 복합재료의 제조방법
KR101051781B1 (ko) * 2010-04-30 2011-07-26 주식회사 라이온켐텍 유무기하이브리드 고분자 복합재료 조성물 및 이를 포함하는 유무기하이브리드 고분자 복합재료

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101018334B1 (ko) 2009-03-31 2011-03-04 한국과학기술연구원 그라펜이 코팅된 전기 전도성 미립자 및 그 제조 방법
WO2012109212A2 (fr) 2011-02-08 2012-08-16 Graphea, Inc. Carbocatalyseurs pour polymérisation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100127575A (ko) * 2009-05-26 2010-12-06 한국과학기술연구원 전기 전도성 입자 및 그 제조 방법
KR101029734B1 (ko) * 2010-04-30 2011-04-18 주식회사 라이온켐텍 함산소불소화 처리된 그라핀을 포함하는 전기전도성 고분자 복합재료의 제조방법
KR101051781B1 (ko) * 2010-04-30 2011-07-26 주식회사 라이온켐텍 유무기하이브리드 고분자 복합재료 조성물 및 이를 포함하는 유무기하이브리드 고분자 복합재료

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XIAOHUI SONG ET AL.: "PS Colloidal Particles Stabilized by Graphene Oxide", LANGMUIR, vol. 27, no. 3, 2011, XP055241091 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108440717A (zh) * 2018-03-15 2018-08-24 厦门大学 一种氧化石墨烯包覆聚甲基丙烯酸缩水甘油酯微球复合防腐涂料助剂及其制备方法
CN108440717B (zh) * 2018-03-15 2020-04-03 厦门大学 一种氧化石墨烯包覆聚甲基丙烯酸缩水甘油酯微球复合防腐涂料助剂及其制备方法
CN108586967A (zh) * 2018-04-29 2018-09-28 武汉工程大学 一种基于细乳液聚合制备石墨烯/苯乙烯-丙烯酸丁酯介电复合材料的方法
CN108586967B (zh) * 2018-04-29 2020-11-27 武汉工程大学 一种基于细乳液聚合制备石墨烯/苯乙烯-丙烯酸丁酯介电复合材料的方法
CN111620329A (zh) * 2019-02-27 2020-09-04 佳能株式会社 改性石墨烯、其生产方法、改性石墨烯-树脂复合物、改性石墨烯片材和改性石墨烯分散体
CN111620329B (zh) * 2019-02-27 2023-08-15 佳能株式会社 改性石墨烯、其生产方法、改性石墨烯-树脂复合物、改性石墨烯片材和改性石墨烯分散体
US12054617B2 (en) 2019-02-27 2024-08-06 Canon Kabushiki Kaisha Modified graphene, method of producing modified graphene, modified graphene-resin composite, modified graphene sheet, and modified graphene dispersion
CN113336500A (zh) * 2021-06-25 2021-09-03 亚士漆(上海)有限公司 一种粘结砂浆及其制备方法和应用
WO2024220706A1 (fr) * 2023-04-18 2024-10-24 Nano Catalytics, Inc. Nanoparticules et microparticules améliorant les performances physiques de formulations, préparation et produit final

Also Published As

Publication number Publication date
KR101590706B1 (ko) 2016-02-01
KR20150135885A (ko) 2015-12-04

Similar Documents

Publication Publication Date Title
WO2015182829A1 (fr) Composite de graphène-polymère et son procédé de préparation
KR101666478B1 (ko) 그래핀의 제조 방법과, 그래핀의 분산 조성물
WO2011078462A2 (fr) Dispersion de graphène et composé de polymère liquide ionique-graphène
KR101348865B1 (ko) 젤화물질을 이용한 나노 구조 복합체의 제조방법
JP2011032156A (ja) グラフェンまたは薄膜グラファイトの製造方法
WO2013133467A1 (fr) Procédé pour produire des nanoparticules de carbone planes, et procédé pour produire un matériau composite d'aluminium/carbone utilisant celles-ci
CN109880294B (zh) 一种单宁酸改性氧化石墨烯的环氧纳米复合材料
WO2011122901A2 (fr) Nanocomposite de polyimide et son procédé de préparation
CN107001047A (zh) 部分氧化石墨烯及其制备方法
WO2020209635A1 (fr) Nanofeuille de graphène dispersible dans l'eau
WO2018236003A1 (fr) Composition d'émulsion de pickering utilisant des particules de polyimide, et son procédé de préparation
CN109929093B (zh) 一种微胶囊型环氧树脂潜伏性固化促进剂及其制备和应用方法
KR20160116112A (ko) 구리-카본계 복합물질 및 그 제조방법
Ayaz et al. Investigation of thermal, mechanical and electrochemical properties of nanocomposites based on CuO modified poly (vinyl chloride)/poly (methyl methacrylate) blend
KR101436016B1 (ko) 개질화된 탄소나노튜브를 포함하는 기계적 물성과 전기 전도성이 우수한 고분자 나노복합재 및 이의 제조방법
WO2023013938A1 (fr) Procédé de production de film mince conducteur utilisant du graphite expansible
KR20170093501A (ko) 환원된 그래핀 옥사이드를 포함하는 복합체 및 이의 제조방법
WO2020032684A1 (fr) Bain de coagulation de filage de graphène par voie humide et procédé de fabrication d'une fibre d'oxyde de graphène l'utilisant
JPS62131068A (ja) 電気的性質を有する有機重合体
CN101177253A (zh) 一种尺寸规整的中空微米碳球的制备方法
KR101312203B1 (ko) 전자 페이퍼용 카본 블랙 안료와 그 분산체 및 제조 방법
CN108285618A (zh) 一种改性石墨烯复合材料的制备方法
WO2023120854A1 (fr) Méthode de production d'oxyde de graphène sur la base d'une exfoliation chimique
WO2020009421A1 (fr) Procédé de production d'oxyde de graphite et d'oxyde de graphène de manière respectueuse de l'environnement en utilisant une réaction d'hydroxylation
CN113773541B (zh) 一种高击穿、低介损的ktn/pi复合薄膜的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14893624

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14893624

Country of ref document: EP

Kind code of ref document: A1