CN111925697A - Graphene/water-soluble polymer composite material and preparation method thereof - Google Patents

Graphene/water-soluble polymer composite material and preparation method thereof Download PDF

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CN111925697A
CN111925697A CN201910393874.0A CN201910393874A CN111925697A CN 111925697 A CN111925697 A CN 111925697A CN 201910393874 A CN201910393874 A CN 201910393874A CN 111925697 A CN111925697 A CN 111925697A
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graphene
water
soluble polymer
membrane
composite material
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CN111925697B (en
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马永梅
庄亚芳
张京楠
郑鲲
叶钢
曹新宇
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Institute of Chemistry CAS
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    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
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    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
    • C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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    • C03C2218/114—Deposition methods from solutions or suspensions by brushing, pouring or doctorblading

Abstract

The invention discloses a graphene/water-soluble polymer composite material and a preparation method thereof, wherein the composite material comprises the following components: graphene accounting for 20-90 wt% of the total mass of the composite material; a modifier accounting for 0.4-70 wt% of the total mass of the composite material; the rest of the composite material is water-soluble polymer; the modifier contains an aromatic ring conjugated structure and is coated on the surface of the graphene. Dissolving a modifier containing an aromatic ring conjugated structure and a hydrophilic group in deionized water, and adding graphene and mixing to obtain a graphene aqueous dispersion with a modified surface; and then mixing the dispersion liquid with an aqueous solution of a water-soluble polymer to obtain a membrane liquid, and crosslinking the coated membrane liquid to obtain the self-supporting graphene/water-soluble polymer composite membrane material. The modifier provided by the invention is mixed with graphene, so that the dispersibility of the graphene in water is improved on the premise of not damaging the chemical structure of the graphene, the prepared composite membrane material has better heat-conducting property, and the mechanical property of the composite membrane material is further improved through crosslinking treatment.

Description

Graphene/water-soluble polymer composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of macromolecules, and particularly relates to a graphene/water-soluble polymer composite material and a preparation method thereof.
Background
With the development of science and technology, the internal structures of high power density electronic devices and high-end electronic industrial devices are more and more complex, the assembly is more and more intensive, and the heat dissipation problem is gradually prominent. It is reported that the service life of an electronic device is shortened by 10% for every 5 ℃ rise of the operating temperature, and the reliability is reduced by 50% for every 10 ℃ rise of the operating temperature, which severely limits the development of the electronic device towards miniaturization and function integration.
The graphene has the characteristics of light weight, high thermal conductivity, strong corrosion resistance and the like, avoids the defects of large density, high thermal expansion coefficient and great reduction of thermal conductivity caused by impure materials of the traditional metal heat conduction material, and becomes one of the important heat conduction materials at present. Meanwhile, the successful development of the graphene film provides an effective way for solving the heat dissipation problem of the high-power electronic device. If the high-thermal-conductivity graphene film is applied to the device needing heat dissipation instead of the traditional metal material, the development of the electronic device towards miniaturization, miniaturization and high power density is facilitated, the weight of the device can be effectively reduced, the effective load is increased, and particularly when high-end electronic device equipment is used, the high-thermal-conductivity graphene film can efficiently dissipate heat, improve safety and prolong the service life.
The graphene film prepared at present is usually required to be subjected to high-temperature graphitization treatment, although the thermal conductivity is high, the mechanical property is poor, self-supporting is difficult, and in some heat conduction fields requiring flexibility, the graphene film cannot meet the use requirements, so that the use range of the graphene film is severely limited. Therefore, how to improve the mechanical properties while maintaining high thermal conductivity is a technical problem to be solved by those skilled in the art.
The application number 201811309101.1 discloses a preparation method of a graphene oxide/polyvinyl alcohol composite coating, which comprises the steps of adding graphene oxide into deionized water, adjusting the pH value of a system to 8.0-14.0 by using alkali, stirring and ultrasonically dispersing the graphene oxide sufficiently to form a single-layer dispersed graphene oxide stripping solution, adding a polyvinyl alcohol solution, a cross-linking agent and an acid catalyst, uniformly mixing to obtain a graphene oxide/polyvinyl alcohol mixed solution, coating the mixed solution on a base film of an organic polymer, drying and curing to form a layer of graphene oxide/polyvinyl alcohol composite coating material on the surface of the base film. Although graphene oxide maintains a certain mechanical property, the thermal conductivity of graphene oxide is poor, and the heat dissipation capability of electronic products cannot be met.
The Chinese patent with the application number of 201510789959.2 discloses a method for preparing a modified graphene/polyvinyl alcohol composite film, wherein 7-amino-4-methylcoumarin is selected as a modifier, and hydrazine hydrate, vitamin C or glucose and other chemical reducing agents are selected; preparing modified graphene, preparing a dispersion solution of the modified graphene, and adding the dispersion solution of the modified graphene into a polyvinyl alcohol aqueous solution to obtain a uniformly dispersed modified graphene-polyvinyl alcohol mixed solution; and finally, pouring the mixed solution into a vessel, and drying at 40-70 ℃ to constant weight in an atmosphere or vacuum environment to obtain the modified graphene/polyvinyl alcohol composite film. Wherein the mass fraction of the modified graphene is 0.1-10%. According to the scheme, although the dispersibility of graphene in water and an organic reagent is improved through the modifier, the problem of poor mechanical property of the film is not solved.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide a graphene/water-soluble polymer composite material and a preparation method thereof, wherein a modifier with an aromatic ring conjugated structure is used for modifying the surface of graphene, and the dispersibility of the graphene in an aqueous dispersion is improved on the premise of not changing the chemical structure of the graphene, so that the composite membrane material has good mechanical property and heat conductivity.
In order to solve the technical problems, the invention adopts the technical scheme that:
the invention provides a graphene/water-soluble polymer composite material, which comprises:
graphene accounting for 20-90 wt% of the total mass of the composite material;
a modifier accounting for 0.4-70 wt% of the total mass of the composite material;
the rest of the composite material is water-soluble polymer;
the modifier contains an aromatic ring conjugated structure and is coated on the surface of the graphene.
In the scheme, the transverse size of the graphene is micron-level (more than or equal to 3 microns), and the thickness of the graphene is less than 10 layers. In the invention, the content of the graphene in the composite material is higher than 20% and can even reach 90% to the maximum, because the adopted modifier improves the compatibility between the surface inert graphene and the water-soluble polymer, and pi-pi interaction is generated between the modifier and the graphene, so that the surface activity of the graphene is improved through the functional group in the modifier. Therefore, the graphene can be uniformly dispersed in a dispersion system, and when the composite material contains a large amount of filler, the compatibility of the filler graphene and a water-soluble polymer matrix is improved, so that the heat-conducting property provided by the graphene in the composite material is greatly improved.
Graphene accounting for 40-65 wt% of the total mass of the composite material;
a modifier accounting for 0.4-60 wt% of the total mass of the composite material;
the rest of the composite material is water-soluble polymer.
The further scheme of the invention is as follows: the mass ratio of the graphene to the modifier is 1: 0.02-3.5, preferably 1: 0.05-2.5; the modifier contains an aromatic ring conjugated structure and a hydrophilic group, and comprises a polymer containing an aromatic ring and a sulfonic acid group.
In the scheme, the graphene has a smooth surface, does not have a functional group, has the problems of difficult dispersion and reaggregation in the polymer, and is weaker in interaction with the polymer molecules. Both of these reasons result in a composite material that is susceptible to stress concentrations. Although graphene has good mechanical strength, such stress concentration limits further improvement of the mechanical properties of the composite material. The modifier containing the aromatic ring conjugated structure provided by the invention not only generates physical interaction with graphene, but also generates hydrogen bond interaction with a water-soluble polymer, so that the graphene is uniformly dispersed in a system, and the interface bonding strength of the graphene/the water-soluble polymer is improved by enhancing the intermolecular interaction, thereby improving the overall mechanical property of the composite material.
The further scheme of the invention is as follows: the aromatic ring-containing polymer comprises but is not limited to one or more of polycyclic aromatic sulfonate formaldehyde condensate, polysulfonic acid calixarene and derivatives thereof, naphthalene sulfonate formaldehyde condensate, sodium polymethine anthracene sulfonate, polyvinylidene fluoride grafted styrene sulfonic acid ethyl ester, polystyrene sulfonic acid, sodium polystyrene sulfonate, polysulfonyl [4, 8-disubstituted- (1,2-b:4, 5-b') benzodithiophene ] - [2, 6-substituted bithiophene ], aromatic polysulphone, sulfonated poly (p-phenylene ethylene), sulfonated polyaniline and water-soluble propane sulfonic acid aramid; preferably, the compound is one or more of aromatic sulfonate formaldehyde condensate, sodium polymethine anthracene sulfonate, aromatic poly-thioether ketone and sulfonated polyaniline.
In the scheme, the modifier is a polymer simultaneously having an aromatic ring conjugated structure and a hydrophilic group. Through the combination of the aromatic ring conjugated structure and the graphene, the surface property of the graphene can be changed by the hydrophilic group, so that the graphene is well dispersed in an aqueous solution. On the basis, the composite compatibility of the graphene and the water-soluble polymer can be further increased.
The further scheme of the invention is as follows: the water-soluble polymer comprises one or more of modified cellulose, modified starch, hydrolyzed polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride, polyquaternary ammonium salt and polyethylene glycol; preferably polyvinyl alcohol. The modified cellulose includes but is not limited to hydroxyl-containing cellulose-hydroxymethyl cellulose, carboxyl-containing cellulose-carboxymethyl cellulose, methyl cellulose, ethyl cellulose, and the modified starch includes but is not limited to carboxyl-containing starch-carboxymethyl starch, and starch acetate.
The invention also provides a preparation method of the graphene/water-soluble polymer composite material, which comprises the following steps:
(1) dissolving a modifier containing an aromatic ring conjugated structure and a hydrophilic group in deionized water, and adding graphene and mixing to obtain a dispersion liquid of the surface modified graphene;
(2) mixing the dispersion liquid of the surface modified graphene obtained in the step (1) with an aqueous solution of a water-soluble polymer to obtain a membrane liquid;
(3) and (3) coating the membrane liquid obtained in the step (2) on a base material in a certain membrane forming mode, then carrying out cross-linking treatment, taking the membrane and drying to obtain the graphene/water-soluble polymer composite membrane material.
In the above preparation method, the crosslinking treatment in the step (3) is: taking a mixture of hydrochloric acid and glutaraldehyde, wherein the concentration of the hydrochloric acid can be selected to be 4.5%, 9%, 18% or 36%, the hydrochloric acid plays a role of a catalyst, and the concentration of the glutaraldehyde can be selected to be 2.5%, 5%, 10% or 15%, and the glutaraldehyde plays a role of a cross-linking agent. And (3) soaking the dried membrane and the base material in a crosslinking solution, crosslinking for a certain time (the membrane and the glass plate can be automatically separated in the soaking process), taking the membrane and drying.
According to the above production method, the step (1) comprises:
a. dissolving one or more of the modifying agents in deionized water, and carrying out physical treatment to obtain a modifying solution;
b. adding graphene into the modifying liquid, and processing by a physical method to obtain the surface-modified graphene dispersion liquid.
According to the preparation method, the physical method is selected from one or more of colloid grinding, ultrasonic treatment, high-speed stirring, homogenization and three-roll grinding.
According to the preparation method, the modifying agent is dissolved into the modifying liquid and then added into the graphene, compared with the method that the modifying agent and the graphene are added into the solution at the same time, the self-aggregation effect of the graphene can be avoided to a great extent, the modifying agent is easier to generate non-covalent bond modification with the surface of the graphene, and therefore the dispersibility of the graphene in water is improved.
According to the preparation method, the ultrasonic treatment conditions are 162-300W, 1s on and 2s off.
According to the preparation method, in the step (1), the mass fraction of the modifier in deionized water is 0.05-10%.
According to the preparation method, the film forming mode in the step (3) comprises a blade coating method, a pulling method or a spin coating method, wherein the blade coating method comprises accumulating the blade coating liquid on the base material for multiple times to obtain a multilayer base film, and performing cross-linking treatment on the base film for 10-50 min to obtain the composite film material.
In the preparation method, the blade coating method is to uniformly scrape and coat the membrane liquid on the surface of the substrate by using a scraper; the spin coating method is a coating process of distributing the film liquid falling on the substrate on the surface of the substrate by means of the centrifugal force and gravity generated when the substrate rotates; the pulling method is a method in which a substrate is immersed in a film solution and pulled at a constant speed to adhere the film solution to the substrate. Preferably a knife coating method.
According to the preparation method, the thickness of the single scraping film on the base material in the step (3) is 0.05-3 mu m, the base film with the thickness of 10-300 mu m is obtained by accumulating the scraping films for multiple times, and the base film is subjected to crosslinking treatment for 10-50 min to obtain the composite film material.
According to the preparation method, the substrate in the step (3) is a material capable of coating the film-scraping solution, and is preferably a glass plate.
In the preparation method, when the glass plate is selected, the piranha washing liquid is adopted to clean the glass plate, then the casting and the film scraping are carried out, and the next film scraping can be carried out after each film scraping and drying.
The preparation method of the graphene/water-soluble polymer composite material provided by the invention specifically comprises the following steps:
(1) weighing a certain weight part of modifier containing aromatic ring conjugated structure, adding the modifier into deionized water, and treating by adopting a physical method to ensure that the modifier is completely dissolved in water to form uniform modifier liquid; adding a certain weight part of graphene into the modification solution to obtain graphene aqueous dispersion with non-covalent bond modified surface;
(2) adding a certain weight part of water-soluble polymer into deionized water for dissolving to obtain a water-soluble polymer solution with a certain concentration, respectively taking the graphene water dispersion liquid with the surface modified by the non-covalent bond in the step (1) and the water-soluble polymer solution according to the selected weight parts, and carrying out ultrasonic treatment to obtain a membrane liquid;
(3) and (3) coating the film liquid prepared in the step (2) on a clean glass plate by adopting a blade coating method, a pulling method or a spin coating method, performing cross-linking treatment on the clean glass plate, taking the film and drying the film to obtain the self-supporting composite film.
Preferably, a multilayer blade coating method is adopted, the glass plate is scraped on a clean glass plate for multiple times with the thickness of 0.05-3 mu m, secondary blade coating is carried out after primary blade coating drying film forming, a basic film with the thickness of 5-300 mu m is obtained through accumulation, crosslinking treatment is carried out for 10-50 min, and the base film is placed in a blast oven for drying at 60 ℃ after film uncovering, so that the composite film material is prepared.
After adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the chemical structure of the graphene is not changed, so that the effect of enhancing the heat-conducting property of the graphene is greatly reserved, and the composite material has good heat-conducting property;
2. according to the graphene/water-soluble polymer composite material provided by the invention, the surface of graphene is modified by the modifier containing a conjugated structure, so that the dispersibility of graphene in a dispersion liquid is improved, the interaction force between the graphene and a water-soluble polymer is improved, and a final composite product has better mechanical property;
3. the content of graphene in the graphene/water-soluble polymer composite material provided by the invention is up to 20-90%, the original structure of the graphene is not changed by the modifier, so that the composite material has excellent thermal conductivity, and the mechanical property of the composite material is further improved by crosslinking treatment;
4. according to the preparation method of the graphene/water-soluble polymer composite material, provided by the invention, the modifier is adopted to treat the graphene, so that the dispersion performance of the graphene in water is improved, an organic reagent is not used for preparing a dispersion liquid, and the harm to the environment is avoided.
The following describes in further detail embodiments of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below, and the following embodiments are used for illustrating the present invention and are not used for limiting the scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The "parts" in the following comparative examples or examples mean parts by weight unless otherwise specified.
Example 1
In this example, a composite film was prepared by the following method:
(1) weighing 5 parts by weight of sulfonated poly-p-phenylene ethylene, adding the sulfonated poly-p-phenylene ethylene into 992.5 parts by weight of deionized water, and mechanically stirring to completely dissolve the sulfonated poly-p-phenylene ethylene in the water to form uniform modification liquid; adding 2.5 parts by weight of graphene into the modifying solution, and carrying out ultrasonic treatment for 30min to obtain an aqueous dispersion with the mass fraction of the graphene being 0.25%, wherein the mass fraction of the modifying agent is 0.5%;
(2) adding 1 part by weight of polyvinyl alcohol into 99 parts by weight of deionized water for dissolving to obtain a polyvinyl alcohol solution, taking 332 parts by weight of the graphene water dispersion liquid with the surface being non-covalently modified in the step (1) and 17 parts by weight of the polyvinyl alcohol solution, and carrying out ultrasonic treatment for 30min (162W,1s on,2s off) to obtain a membrane liquid for membrane scraping;
(3) and (3) scraping and coating the membrane liquid prepared in the step (2) on a clean glass plate for multiple times to obtain a base membrane, carrying out crosslinking treatment for 30min, uncovering the membrane, and then drying in a forced air oven at 60 ℃ to obtain the composite membrane material.
The content of graphene in the composite membrane is 31.20 wt%, the content of a modifier is 62.41 wt%, and the content of polyvinyl alcohol is 6.39 wt%.
Example 2
In this example, a composite film was prepared by the following method:
(1) weighing 5 parts by weight of polysulfonyl [4, 8-disubstituted- (1,2-b:4,5-b ') benzodithiophene ] - [2, 6-substituted bithiophene ], adding the weighed materials into 992.5 parts by weight of deionized water, and mechanically stirring to completely dissolve the polysulfonyl [4, 8-disubstituted- (1,2-b:4, 5-b') benzodithiophene ] - [2, 6-substituted bithiophene ] in the water to form a uniform modification solution; adding 2.5 parts by weight of graphene into the modifying solution, and homogenizing for 30min to obtain an aqueous dispersion with the mass fraction of the graphene being 0.25%, wherein the mass fraction of the modifying agent is 0.5%;
(2) adding 1 part by weight of hydroxy cellulose-hydroxymethyl cellulose into 99 parts by weight of deionized water for dissolving to obtain a hydroxy cellulose-hydroxymethyl cellulose solution, taking 284 parts by weight of graphene water dispersion liquid subjected to surface non-covalent bond modification in the step (1) and 29 parts by weight of the hydroxy cellulose-hydroxymethyl cellulose solution, and performing ultrasonic treatment for 30min (162W,1s on,2s off) to obtain a membrane liquid for scraping a membrane;
(3) and (3) scraping and coating the membrane liquid prepared in the step (2) on a clean glass plate for multiple times to obtain a base membrane, carrying out crosslinking treatment for 30min, uncovering the membrane, and then drying in a forced air oven at 60 ℃ to obtain the composite membrane material.
The content of graphene in the composite membrane is 29.34 wt%, the content of a modifier is 58.68 wt%, and the content of hydroxycellulose-hydroxymethylcellulose is 11.98 wt%.
Example 3
In this example, a composite film was prepared by the following method:
(1) weighing 3 parts by weight of a mixture (1:1) of aromatic poly-thioether ketone and sulfonated polyaniline, adding the mixture into 294 parts by weight of deionized water, and mechanically stirring to completely dissolve the mixture of aromatic poly-thioether ketone and sulfonated polyaniline in water to form a uniform modification solution; adding 3 parts by weight of graphene into the modifying solution, and grinding for 30min by adopting colloid to obtain an aqueous dispersion with the mass fraction of the graphene being 1%, wherein the mass fraction of the modifying agent is 1%;
(2) adding 2 parts by weight of carboxyl-containing starch-carboxymethyl starch into 98 parts by weight of deionized water for dissolving to obtain a carboxyl-containing starch-carboxymethyl starch solution, taking 80 parts by weight of the graphene water dispersion liquid with the surface being non-covalently modified in the step (1) and 10 parts by weight of the carboxyl-containing starch-carboxymethyl starch solution, and performing ultrasonic treatment for 30min (162W,1s on,2s off) to obtain a film liquid for scraping a film;
(3) and (3) scraping and coating the membrane liquid prepared in the step (2) on a clean glass plate for multiple times to obtain a base membrane, carrying out cross-linking treatment for 20min, uncovering the membrane, and then drying in a forced air oven at 60 ℃ to obtain the composite membrane material.
The content of graphene in the composite film is 44.44 wt%, the content of a modifier is 44.44 wt%, and the content of carboxyl-containing starch-carboxymethyl starch is 11.12 wt%.
Example 4
In this example, a composite film was prepared by the following method:
(1) weighing 1 part by weight of a mixture (1:1) of water-soluble propane sulfonic acid aramid fiber and sodium polystyrene sulfonate, adding the mixture into 296 parts by weight of deionized water, and mechanically stirring to completely dissolve the mixture of the water-soluble propane sulfonic acid aramid fiber and the sodium polystyrene sulfonate into the water to form uniform modification liquid; adding 3 parts by weight of graphene into the modifying solution, and stirring at a high speed for 30min to obtain an aqueous dispersion with the graphene mass fraction of 1%, wherein the mass fraction of the modifying agent is 0.33%;
(2) adding 1 part by weight of hydrolyzed polyacrylamide into 99 parts by weight of deionized water for dissolving to obtain a hydrolyzed polyacrylamide solution, taking 67 parts by weight of the graphene water dispersion liquid with the surface being non-covalently modified in the step (1) and 33 parts by weight of the hydrolyzed polyacrylamide solution, and performing ultrasonic treatment for 30min (162W,1s on,2s off) to obtain a membrane liquid for membrane scraping;
(3) and (3) scraping and coating the membrane liquid prepared in the step (2) on a clean glass plate for multiple times to obtain a base membrane, carrying out crosslinking treatment for 30min, uncovering the membrane, and then drying in a forced air oven at 60 ℃ to obtain the composite membrane material.
The content of graphene in the composite membrane is 54.92 wt%, the content of a modifier is 18.03 wt%, and the content of hydrolyzed polyacrylamide is 27.05 wt%.
Example 5
In this example, a composite film was prepared by the following method:
(1) weighing 0.5 part by weight of naphthalene sulfonate formaldehyde condensate, sodium polymethine anthracene sulfonate and sodium polystyrene sulfonate (1:1:1), adding into 98.5 parts by weight of deionized water, and mechanically stirring to completely dissolve the naphthalene sulfonate formaldehyde condensate, the sodium polymethine anthracene sulfonate and the sodium polystyrene sulfonate in the water to form uniform modification liquid; adding 1 part by weight of graphene into the modifying solution, and carrying out ultrasonic treatment for 30min to obtain an aqueous dispersion with the mass fraction of the graphene being 1%, wherein the mass fraction of the modifying agent is 0.5%;
(2) adding 5 parts by weight of polyvinyl alcohol into 95 parts by weight of deionized water for dissolving to obtain a polyvinyl alcohol solution, taking 50 parts by weight of the graphene water dispersion liquid with the surface being non-covalently modified in the step (1) and 10 parts by weight of the polyvinyl alcohol solution, and carrying out ultrasonic treatment for 30min (300W,1s on,2s off) to obtain a membrane liquid for membrane scraping;
(3) and (3) scraping and coating the membrane liquid prepared in the step (2) on a clean glass plate for multiple times to obtain a base membrane, carrying out crosslinking treatment for 30min, uncovering the membrane, and then drying in a forced air oven at 60 ℃ to obtain the composite membrane material.
The content of graphene in the composite membrane is 40 wt%, the content of a modifier is 20 wt%, and the content of polyvinyl alcohol is 40 wt%.
Example 6
In this example, the composite film material was prepared by the following preparation method:
(1) weighing 7 parts by weight of a polycyclic aromatic sulfonate formaldehyde condensate and a polysulfonic acid calixarene mixture (1:1), adding the mixture into 91 parts by weight of deionized water, and mechanically stirring to completely dissolve the polycyclic aromatic sulfonate formaldehyde condensate and the polysulfonic acid calixarene mixture in the water to form a uniform modification solution; adding 2 parts by weight of graphene into the modifying solution, and carrying out ultrasonic treatment for 45min to obtain an aqueous dispersion with the graphene mass fraction of 2%, wherein the mass fraction of the modifying agent in the aqueous dispersion is 7%;
(2) adding 1 part by weight of polymaleic anhydride into 99 parts by weight of deionized water for dissolving to obtain polymaleic anhydride solution, taking 100 parts by weight of graphene water dispersion liquid with non-covalent bond modified surfaces in the step (1) and 100 parts by weight of polymaleic anhydride solution, and performing ultrasonic treatment for 30min (200W,1s on,2s off) to obtain membrane liquid for membrane scraping;
(3) and (3) scraping and coating the membrane liquid prepared in the step (2) on a clean glass plate for multiple times to obtain a base membrane, carrying out cross-linking treatment for 10min, uncovering the membrane, and then drying in a forced air oven at 60 ℃ to obtain the composite membrane material.
The content of graphene in the composite membrane is 20 wt%, the content of the modifier is 70 wt%, and the content of polymaleic anhydride is 10 wt%.
Example 7
In this example, the composite film material was prepared by the following preparation method:
(1) weighing 0.05 part by weight of sulfonated polyaniline, adding the sulfonated polyaniline into 98.95 parts by weight of deionized water, and mechanically stirring to completely dissolve the sulfonated polyaniline in the water to form uniform modification liquid; adding 1 part by weight of graphene into the modifying solution, and grinding for 40min by adopting a multi-roller machine to obtain an aqueous dispersion with the mass fraction of the graphene being 1%, wherein the mass fraction of the modifying agent in the aqueous dispersion is 0.05%;
(2) adding 1 part by weight of polyvinylpyrrolidone into 99 parts by weight of deionized water for dissolving to obtain a polyvinylpyrrolidone solution, taking 900 parts by weight of the graphene water dispersion liquid with the surface being non-covalently modified in the step (1) and 55 parts by weight of the polyvinylpyrrolidone solution, and performing ultrasonic treatment for 30min (200W,1s on,2s off) to obtain a membrane liquid for scraping a membrane;
(3) and (3) scraping and coating the membrane liquid prepared in the step (2) on a clean glass plate for multiple times to obtain a base membrane, carrying out cross-linking treatment for 50min, uncovering the membrane, and then drying in a forced air oven at 60 ℃ to obtain the composite membrane material.
The content of graphene in the composite membrane is 90 wt%, the content of a modifier is 4.5 wt%, and the content of polyvinylpyrrolidone is 5.5 wt%.
Example 8
In this example, the composite film material was prepared by the following preparation method:
(1) weighing 1.3 parts by weight of sodium polymethine anthracene sulfonate, adding into 92.2 parts by weight of deionized water, and mechanically stirring to completely dissolve the sodium polymethine anthracene sulfonate in the water to form a uniform modification solution; adding 6.5 parts by weight of graphene into the modifying solution, and carrying out ultrasonic treatment for 40min to obtain an aqueous dispersion with the mass fraction of the graphene being 6.5%, wherein the mass fraction of the modifying agent in the aqueous dispersion is 1.3%;
(2) adding 2.2 parts by weight of polyvinyl alcohol into 97.8 parts by weight of deionized water for dissolving to obtain a polyvinyl alcohol solution, taking 100 parts by weight of the graphene water dispersion liquid with the surface being non-covalently modified in the step (1) and 100 parts by weight of the polyvinyl alcohol solution, and carrying out ultrasonic treatment for 30min (200W,1s on,2s off) to obtain a membrane liquid for scraping a membrane;
(3) and (3) coating the film liquid prepared in the step (2) on a clean glass plate by adopting a pulling method, carrying out cross-linking treatment for 30min after nitrogen blow drying, uncovering the film, and then placing the film in a blast oven for drying at 60 ℃ to prepare the composite film material.
The content of graphene in the composite membrane is 65 wt%, the content of a modifier is 13 wt%, and the content of polyvinyl alcohol is 22 wt%.
Example 9
In this example, the composite film material was prepared by the following preparation method:
(1) weighing 10 parts by weight of polyvinylidene fluoride grafted ethyl styrene sulfonate, adding the polyvinylidene fluoride grafted ethyl styrene sulfonate into 91 parts by weight of deionized water, and mechanically stirring to completely dissolve the polyvinylidene fluoride grafted ethyl styrene sulfonate in the water to form uniform modification liquid; adding 4 parts by weight of graphene into the modifying solution, and carrying out ultrasonic treatment for 45min to obtain an aqueous dispersion with the mass fraction of the graphene being 4%, wherein the mass fraction of the modifying agent in the aqueous dispersion is 10%;
(2) adding 1.6 parts by weight of polymaleic anhydride into 98.4 parts by weight of deionized water for dissolving to obtain a polymaleic anhydride solution, taking 60 parts by weight of the graphene water dispersion liquid with the surface being non-covalently modified in the step (1) and 100 parts by weight of the polymaleic anhydride solution, and performing ultrasonic treatment for 30min (200W,1s on,2s off) to obtain a membrane liquid for scraping a membrane;
(3) and (3) performing single-time scraping and coating on the membrane liquid prepared in the step (2) on a clean glass plate to obtain a base membrane, performing crosslinking treatment for 10min, uncovering the membrane, and drying in a forced air oven at 60 ℃ to obtain the composite membrane material.
The content of graphene in the composite membrane is 24 wt%, the content of a modifier is 60 wt%, and the content of polymaleic anhydride is 16 wt%.
Example 10
In this example, the composite film material was prepared by the following preparation method:
(1) weighing 0.1 part by weight of a polycyclic aromatic sulfonate formaldehyde condensate and a polysulfonic acid calixarene mixture (1:1), adding the mixture into 99.9 parts by weight of deionized water, and mechanically stirring to completely dissolve the polycyclic aromatic sulfonate formaldehyde condensate and the polysulfonic acid calixarene mixture into the water to form a uniform modification solution; adding 5 parts by weight of graphene into the modifying solution, and carrying out ultrasonic treatment for 45min to obtain an aqueous dispersion with the mass fraction of the graphene being 5%, wherein the mass fraction of the modifying agent in the aqueous dispersion is 0.1%;
(2) adding 7.96 parts by weight of polymaleic anhydride into 92.04 parts by weight of deionized water for dissolving to obtain a polymaleic anhydride solution, taking 40 parts by weight of the graphene water dispersion liquid with the surface being non-covalently modified in the step (1) and 100 parts by weight of the polymaleic anhydride solution, and performing ultrasonic treatment for 30min (200W,1s on,2s off) to obtain a membrane liquid for membrane scraping;
(3) and (3) coating the film liquid prepared in the step (2) on a clean glass plate by adopting a spin-coating method to obtain a base film, carrying out cross-linking treatment for 10min, uncovering the film, and then drying in a forced air oven at 60 ℃ to obtain the composite film material.
The content of graphene in the composite membrane is 20 wt%, the content of a modifier is 0.4 wt%, and the content of polymaleic anhydride is 79.6 wt%.
Comparative example 1
In this comparative example, on the basis of example 5, a composite film was prepared by the following method:
(1) weighing 1 part by weight of graphene, adding the graphene into 95 parts by weight of deionized water, and carrying out ultrasonic treatment for 30min to obtain a graphene aqueous dispersion with the mass fraction of 1%; (ii) a
(2) Adding 5 parts by weight of polyvinyl alcohol into 99 parts by weight of deionized water for dissolving to obtain a polyvinyl alcohol solution, taking 40 parts by weight of the graphene water dispersion liquid with the surface being non-covalently modified in the step (1) and 12 parts by weight of the polyvinyl alcohol solution, and carrying out ultrasonic treatment for 30min (300W,1s on,2s off) to obtain a membrane liquid for membrane scraping;
(3) and (3) scraping and coating the membrane liquid prepared in the step (2) on a clean glass plate for multiple times to obtain a base membrane, carrying out crosslinking treatment for 30min, uncovering the membrane, and then drying in a forced air oven at 60 ℃ to obtain the composite membrane material.
The content of graphene in the composite membrane is 40 wt%, and the content of polyvinyl alcohol in the composite membrane is 60 wt%.
Comparative example 2
In this comparative example, on the basis of example 1, a composite film was prepared by the following method:
(1) weighing 0.25 part by weight of graphene, adding the graphene into 99.75 parts by weight of deionized water, and carrying out ultrasonic treatment for 30min to obtain a graphene water dispersion liquid with the mass fraction of 0.25%;
(2) adding 1 part by weight of polyvinyl alcohol into 99 parts by weight of deionized water for dissolving to obtain a polyvinyl alcohol solution, taking 316 parts by weight of the graphene water dispersion liquid in the step (1) and 172 parts by weight of the polyvinyl alcohol solution, and carrying out ultrasonic treatment for 30min (162W,1s on,2s off) to obtain a membrane liquid for scraping a membrane;
(3) and (3) scraping and coating the membrane liquid prepared in the step (2) on a clean glass plate for multiple times to obtain a base membrane, carrying out crosslinking treatment for 30min, uncovering the membrane, and then drying in a forced air oven at 60 ℃ to obtain the composite membrane material.
The content of graphene in the composite membrane is 31.20 wt%, and the content of polyvinyl alcohol is 68.80 wt%.
Comparative example 3
In this comparative example, on the basis of example 5, a composite film was prepared by the following method:
(1) weighing 0.5 part by weight of naphthalene sulfonate formaldehyde condensate, sodium polymethine anthracene sulfonate and sodium polystyrene sulfonate (1:1:1), adding into 98.5 parts by weight of deionized water, and mechanically stirring to completely dissolve the naphthalene sulfonate formaldehyde condensate, the sodium polymethine anthracene sulfonate and the sodium polystyrene sulfonate in the water to form uniform modification liquid; adding 1 part by weight of graphene into the modifying solution, and carrying out ultrasonic treatment for 30min to obtain an aqueous dispersion with the mass fraction of the graphene being 1%, wherein the mass fraction of the modifying agent is 0.5%;
(2) adding 5 parts by weight of polyvinyl alcohol into 95 parts by weight of deionized water for dissolving to obtain a polyvinyl alcohol solution, taking 50 parts by weight of the graphene water dispersion liquid with the surface being non-covalently modified in the step (1) and 10 parts by weight of the polyvinyl alcohol solution, and carrying out ultrasonic treatment for 30min (300W,1s on,2s off) to obtain a membrane liquid for membrane scraping;
(3) and (3) scraping and coating the membrane liquid prepared in the step (2) on a clean glass plate for multiple times to obtain a base membrane, drying the base membrane in a blast oven at 60 ℃ without crosslinking treatment, and then uncovering the membrane to obtain the composite membrane material.
The content of graphene in the composite membrane is 40 wt%, the content of a modifier is 20 wt%, and the content of polyvinyl alcohol is 40 wt%.
Comparative example 4
In this comparative example, on the basis of example 1, a composite film was prepared by the following method:
(1) weighing 5 parts by weight of sulfonated poly-p-phenylene ethylene, adding the sulfonated poly-p-phenylene ethylene into 992.5 parts by weight of deionized water, and mechanically stirring to completely dissolve the sulfonated poly-p-phenylene ethylene in the water to form uniform modification liquid; adding 2.5 parts by weight of graphene into the modifying solution, and carrying out ultrasonic treatment for 30min to obtain an aqueous dispersion with the mass fraction of the graphene being 0.25%, wherein the mass fraction of the modifying agent is 0.5%;
(2) adding 1 part by weight of polyvinyl alcohol into 99 parts by weight of deionized water for dissolving to obtain a polyvinyl alcohol solution, taking 332 parts by weight of the graphene water dispersion liquid with the surface being non-covalently modified in the step (1) and 17 parts by weight of the polyvinyl alcohol solution, and carrying out ultrasonic treatment for 30min (162W,1s on,2s off) to obtain a membrane liquid for membrane scraping;
(3) and (3) scraping and coating the membrane liquid prepared in the step (2) on a clean glass plate for multiple times to obtain a base membrane, drying the base membrane in a blast oven at 60 ℃ without crosslinking treatment, and then uncovering the membrane to obtain the composite membrane material.
The content of graphene in the composite membrane is 31.20 wt%, the content of a modifier is 62.41 wt%, and the content of polyvinyl alcohol is 6.39 wt%.
Experimental example 1
The thermal conductivity coefficient and the tensile strength of the composite films prepared in examples 1 to 10 and comparative examples 1 to 4 were measured by a thermal conductivity tester, and the results are shown in the following table:
Figure BDA0002057516470000131
Figure BDA0002057516470000141
as can be seen from the above table, the graphene/water-soluble polymer composite materials provided in embodiments 1 to 10 of the present application have excellent thermal conductivity and better mechanical properties, and the above properties of comparative examples 1 to 2 are not as good as those of corresponding embodiments 5 and 1, but the reason for this is that the non-covalent modification is performed on the graphene component, so that the dispersibility of graphene in an aqueous solution is improved, and the composite material formed by the graphene and the water-soluble polymer has a uniform material, and meanwhile, the original structure of the graphene is not changed by the non-covalent modification, so that the thermal conductivity and the mechanical properties of the graphene itself are not lost in the composite material, and the mechanical and thermal properties of the composite material are greatly improved.
Furthermore, the mechanical and thermal properties of comparative examples 3-4 are improved compared with comparative examples 1 and 2, and due to the effect of the modifier in the composite material of comparative examples 3 and 4, the mechanical properties of the film materials of comparative examples 3 and 4 are obviously reduced compared with those of examples 5 and 1 because the film materials are not subjected to crosslinking treatment, and the thermal properties are improved to some extent but are not obviously changed compared with the reduction degree of the mechanical properties. This is because the composite membrane material is not cross-linked in comparative examples 3-4, and the polymer chain can not be changed from a linear structure to a three-dimensional structure, so that the cross-linking ensures the mechanical properties of the composite material with high content of graphene while not obviously reducing the thermal conductivity of the composite material.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. A graphene/water-soluble polymer composite, wherein the composite comprises:
graphene accounting for 20-90 wt% of the total mass of the composite material;
a modifier accounting for 0.4-70 wt% of the total mass of the composite material;
the rest of the composite material is water-soluble polymer;
the modifier contains an aromatic ring conjugated structure and is coated on the surface of graphene.
2. The graphene/water-soluble polymer composite according to claim 1, wherein the composite comprises:
graphene accounting for 40-65 wt% of the total mass of the composite material;
a modifier accounting for 0.4-60 wt% of the total mass of the composite material;
the remainder of the composite is a water-soluble polymer.
3. The graphene/water-soluble polymer composite material according to claim 1 or 2, wherein the mass ratio of graphene to the modifier is 1: 0.02-3.5, preferably 1: 0.05-2.5; the modifier contains an aromatic ring conjugated structure and a hydrophilic group, and comprises a polymer containing an aromatic ring and a sulfonic acid group.
4. The graphene/water-soluble polymer composite material according to claim 3, wherein the polymer containing aromatic rings and hydrophilic groups is selected from one or more of polycyclic aromatic sulfonate formaldehyde condensate, polysulfonic calixarene and its derivatives, naphthalene sulfonate formaldehyde condensate, sodium polymethine anthracene sulfonate, polyvinylidene fluoride-grafted styrene sulfonic acid, polyvinylidene fluoride-grafted ethyl styrene sulfonate, polystyrene sulfonic acid, sodium polystyrene sulfonate, polysulfonyl [4, 8-disubstituted- (1,2-b:4, 5-b') benzodithiophene ] - [2, 6-substituted benzothiophene ], aromatic polythioether ketone, sulfonated poly (p-phenylene ethylene), sulfonated polyaniline, and water-soluble propane sulfonic aramid;
preferably, the compound is one or more of aromatic sulfonate formaldehyde condensate, sodium polymethine anthracene sulfonate, aromatic poly-thioether ketone and sulfonated polyaniline.
5. The graphene/water-soluble polymer composite material according to claim 1 or 2, wherein the water-soluble polymer is selected from one or more of modified cellulose, modified starch, hydrolyzed polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride, polyquaternary ammonium salt and polyethylene glycol.
6. A preparation method of the graphene/water-soluble polymer composite material as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
(1) dissolving a modifier containing an aromatic ring conjugated structure and a hydrophilic group in deionized water, and adding graphene and mixing to obtain a surface-modified graphene dispersion liquid;
(2) mixing the surface-modified graphene dispersion liquid obtained in the step (1) with an aqueous solution of a water-soluble polymer to obtain a membrane liquid;
(3) and (3) coating the membrane liquid obtained in the step (2) on a base material in a certain membrane forming mode, then carrying out cross-linking treatment, taking the membrane and drying to obtain the self-supporting graphene/water-soluble polymer composite membrane material.
7. The method of claim 6, wherein the step (1) comprises:
a. dissolving one or more of the modifying agents in deionized water, and carrying out physical treatment to obtain a modifying solution;
b. adding graphene into the modifying solution, and treating by a physical method to obtain the water dispersion solution of the surface modified graphene.
8. The method of claim 7, wherein the physical method is selected from one or more of colloid milling, sonication, high speed stirring, homogenization, and three-roll milling.
9. The preparation method according to claim 6 or 7, wherein in the step (1), the mass fraction of the modifier in the deionized water is 0.05-10%.
10. The preparation method according to claim 6, wherein the film forming manner in the step (3) comprises a blade coating method, a pulling method or a spin coating method, and the blade coating method comprises accumulating the blade coating liquid on the substrate for multiple times to obtain a multilayer basic film, and performing cross-linking treatment on the basic film for 10-50 min to obtain the composite film material.
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