CN117683251A - Method for dispersing carbon nano material in resin and obtained dispersion material - Google Patents
Method for dispersing carbon nano material in resin and obtained dispersion material Download PDFInfo
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- CN117683251A CN117683251A CN202311811155.9A CN202311811155A CN117683251A CN 117683251 A CN117683251 A CN 117683251A CN 202311811155 A CN202311811155 A CN 202311811155A CN 117683251 A CN117683251 A CN 117683251A
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- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the technical field of composite material preparation, and particularly discloses a method for dispersing a carbon nanomaterial in resin, and relates to an obtained dispersed material. The dispersion method of the carbon nano material in the resin comprises the steps of mixing aqueous dispersion liquid of the carbon nano material with aqueous dispersion liquid of first resin, and then drying to obtain pre-dispersion resin; and uniformly mixing the pre-dispersed resin and the second resin to obtain the carbon nano material resin dispersion material. The method of the invention obtains good dispersing effect of the carbon nano material in the resin, reduces the process cost, and is safe and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to a method for dispersing a carbon nanomaterial in resin, and an obtained dispersed material.
Background
For the last twenty years, carbon nano materials represented by graphene and carbon nano tubes have been widely focused on research aspects of emerging materials such as mechanical enhancement, conductive modification and electromagnetic materials, and have been widely applied in aviation, aerospace, ships and civil fields due to good conductivity, low density and good mechanical properties.
Carbon nanomaterials typically need to be dispersed in other media such as water, N-methylpyrrolidone (NMP), organic resin materials or organic polymeric media for application. Carbon nanotubes and graphene dispersed in a water phase, an N-methylpyrrolidone (NMP) phase have been successfully used as electrode materials in the field of energy storage batteries, and compared with conventional carbon black and graphite, the carbon nanotubes and graphene dispersed in a water phase and an NMP phase can have higher conductivity at lower addition amounts, and the carbon nanotubes dispersed in a water phase and an NMP phase can be used as conductive ink materials. When the polymer is dispersed in an organic polymer, the conductivity of the material can be effectively improved, so that the insulating organic polymer has antistatic property. The conductive resin obtained by dispersing the carbon nano material into the organic resin material is a hot spot for research in the material world, can be used for improving the strength, modulus, conductivity and other properties of the resin, and can be used for further preparing various fiber reinforced composite materials.
In the prior art, carbon nano materials such as carbon nano tubes and graphene are dispersed in other media by adopting methods such as ultrasonic oscillation, high-pressure cavitation, high shearing, ball milling and the like, and the methods generate impact force or shearing force through the impact and flow of liquid, so that the aggregated mass of the carbon nano materials is gradually opened into small aggregates or even single nano materials, and better dispersion is obtained in the media. At present, the methods are successfully applied to the dispersion of carbon nano materials in low-viscosity liquid media such as water, NMP and the like, and because the high shearing action of ultrasonic oscillation and high-pressure cavitation under low viscosity can effectively drive liquid to remotely transfer impact force and shearing force, and thus good dispersion effect is obtained. However, these methods have very limited dispersion effects for resins of relatively high viscosity, and do not achieve good dispersion. At present, the effect of improving the dispersing ability by adding an organic solvent to reduce the viscosity of the resin in the process of dispersing the carbon nanotubes into the resin is reported in the literature. However, after the organic solvent is added into the resin, the solvent is removed under reduced pressure during application, which increases the process cost; the solvent is difficult to remove completely, and a very small amount of residual solvent can be gasified to generate pores in the resin curing process; in addition, the use of large amounts of organic solvents also brings about environmental pollution problems. Therefore, a method of effectively dispersing carbon nanotubes into a resin by adding an organic solvent is still in the experimental stage in most cases. Although the three-roll dispersion method can be used for a high-viscosity resin system, the dispersion effect is generally inferior to that of the ultrasonic dispersion method, and the dispersion process is labor-intensive and takes a long time.
In view of the above, the present invention is to provide a method of efficiently dispersing a carbon nanomaterial in a resin.
Disclosure of Invention
The invention aims to provide a dispersing method of a carbon nano material in resin, and also provides the obtained dispersing material and application thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
In a first aspect, the present invention provides a method for dispersing carbon nanomaterial in a resin, the method comprising the steps of:
(1) Mixing the aqueous dispersion of the carbon nano material and the aqueous dispersion of the first resin, and then drying to obtain pre-dispersion resin;
(2) And uniformly mixing the pre-dispersed resin and the second resin to obtain the carbon nano material resin dispersion material.
In one embodiment of the present invention, the mixing in step (1) is performed by stirring, and the stirring may be mechanical stirring or manual stirring.
In one embodiment of the present invention, the mixing time in step (1) is 3 to 15 minutes, preferably 4 to 10 minutes, and more preferably 4 to 8 minutes.
In the step (2), any one or more of stirring, three-roll dispersion and kneading are used for the mixing.
Preferably, in the step (2), the mixing is performed by any one of stirring, three-roll dispersion and kneading methods. Wherein the stirring is mechanical stirring.
As an embodiment of the present invention, the mixing time in step (2) is 15 to 40 minutes, preferably 20 to 30 minutes. When three-roll dispersion is adopted, mixing is carried out for at least 8 times.
As an embodiment of the invention, the drying in the step (1) can be carried out by adopting the methods of airing, sun drying, spray drying, drying and the like.
As an embodiment of the present invention, the first resin and the second resin are both selected from epoxy resins. For example, it may be selected from the group consisting of epoxy E51, epoxy E54, epoxy AG80, epoxy E44 and epoxy F44.
Wherein the resins represented by the first resin and the second resin may be the same or different.
Preferably, the viscosities of the first resin and the second resin at normal temperature satisfy the condition:
the viscosity is less than or equal to 500Pa.s at the normal temperature and less than or equal to 3.5 Pa.s.
As one embodiment of the invention, the mass percentage content of the carbon nanomaterial in the carbon nanomaterial aqueous dispersion is 2-10%, and the carbon nanomaterial is carbon nanotube and/or graphene. The aqueous carbon nanomaterial dispersion is obtained by dispersing a carbon nanomaterial in water.
As one embodiment of the invention, the aqueous dispersion of the first resin has a mass percentage of the first resin of 20 to 60% and a particle size of the first resin of 50nm to 5 μm. The aqueous dispersion of the first resin is obtained by dispersing the first resin in water.
As one embodiment of the invention, the mass ratio of the first resin to the carbon nanomaterial in the pre-dispersion resin is more than or equal to 5, and preferably the mass ratio of the first resin to the carbon nanomaterial in the pre-dispersion resin is 8-20.
As one embodiment of the present invention, the pre-dispersion resin and the second resin are mixed in a mass ratio of 1: (0.5-10), preferably in a mass ratio of 1: (1-5) mixing.
In one embodiment of the present invention, in step (2), an interface modifier is further added when the pre-dispersed resin is mixed with the second resin, and the interface modifier is selected from amphiphilic polymers. For example, the interfacial modifier may be polyvinylpyrrolidone (PVP), sodium carboxymethylcellulose (CMC-Na), byk-163 dispersant, or the like.
As one embodiment of the present invention, the interfacial modifier is used in an amount of 0.1 to 1.5%, preferably 0.3 to 1.0%, and more preferably 0.3 to 0.8% of the total mass of the first resin and the second resin.
In a second aspect, the present invention provides a carbon nanomaterial resin dispersion obtained by the dispersion method of the present invention.
In a third aspect, the present invention provides the use of the carbon nanomaterial resin dispersion obtained by the dispersion method of the present invention, wherein the use comprises use in an electrically conductive or impact resistant composite.
According to the method for dispersing the carbon nanomaterial in the resin, the resin dispersed in the water system and the carbon nanomaterial dispersed in the water system are uniformly mixed, and then the water is removed, so that the pre-dispersed resin formed by the carbon nanomaterial and the resin micro-droplets is formed; and then blending the pre-dispersed resin with the resin to form a well-dispersed carbon nanomaterial resin dispersion. The invention establishes a method for dispersing the carbon nano material in the resin by mixing the pre-dispersion and the secondary dispersion, skillfully combines the characteristics of easy dispersion of the carbon nano material in the aqueous system, the characteristics of the mature aqueous epoxy resin emulsion system and the characteristics of incompatibility of water and resin, brings advantages when water is completely removed, and obtains the pre-dispersion of the resin emulsion particles and the carbon nano material, namely the pre-dispersion resin through simple blending and drying; the carbon nano material in the pre-dispersion is easy to be mixed and dispersed with the conventional epoxy resin to form the well-dispersed carbon nano material epoxy resin dispersion slurry, namely the pre-dispersion resin and the resin are secondarily dispersed, so that the well-dispersed carbon nano material resin dispersion material can be obtained.
The method of the invention obtains good dispersing effect of the carbon nano material in the epoxy resin, reduces the process cost, and is safe and environment-friendly. In addition, the structure of the dispersion material obtained by the invention is different from that of a dispersion system obtained by the prior method, and the resin casting body prepared from the dispersion material obtained by the invention has better conductivity.
The dispersion method of the carbon nanomaterial in the resin is performed on the system of the existing large-scale industrialized carbon nanomaterial aqueous dispersion slurry and on the basis of the aqueous emulsion epoxy resin, and has the advantages of environmental protection, economy, great simplification of the technological process and the like. Compared with the existing method for improving the dispersibility of the carbon nanomaterial by diluting the resin with the organic solvent, the method has the advantages of simple process, no pollution, simple required equipment and good dispersing effect, and can realize mass preparation instead of laboratory scientific research.
According to the invention, a water-based resin emulsion system is adopted, and in the drying process, a demulsification effect is generated between the carbon nano material (carbon nano tube or graphene) and emulsion particles, so that the emulsion particles and the carbon nano material are separated out together, the carbon nano material and water are subjected to phase separation, the drying speed is obvious after the phase separation, and the water residue is very little. It has been found that this process is prone to occur when the resin has a certain viscosity, for example, a viscosity of the resin of 500Pa.s or less. This is because the formation of a water-oil two-phase structure not only forms a permeation path for water drying, but also the water can sufficiently precipitate from the resin to form free water having a faster drying rate until the water content in the resin is lower than the water absorption of the resin itself, typically lower than 3wt%. In addition, because of water-oil phase separation, the carbon nano material is distributed on the surface of emulsion particles to form micro-nano dispersion, and resin emulsion particles with certain viscosity prevent further agglomeration of the carbon nano material, but the viscosity of the resin at normal temperature is controlled to be more than or equal to 3.5Pa.s, otherwise, the carbon nano material in the formed carbon nano material pre-dispersion system easily overcomes the adhesive acting force of the resin to be aggregated, so that the pre-dispersion effect is poor, and the carbon nano material is difficult to effectively disperse in secondary dispersion. It was found in the study that if the aqueous system employed in the present invention is changed to a water-soluble epoxy resin system such as a polyethylene glycol diglycidyl ether system, the effect of the present invention cannot be achieved, the water-soluble resin system is not only slow in drying speed, but also has a large amount of water residue, and in the drying process, since water and resin are in a co-dissolved state, the solution viscosity is very low, and when the water content is low to a certain extent, the polarity of the solution is changed to be incompatible with the carbon nanomaterial, and the carbon nanomaterial is extremely liable to aggregate in such a low-viscosity solution, resulting in difficulty in dispersion at the time of secondary dispersion.
The application adopts a water-based resin emulsion system, controls the viscosity of the resin to be more than or equal to 3.5Pa.s at normal temperature, and the emulsion microsphere particles of the first resin and the carbon nanomaterial form a pre-dispersion structure after blending and drying, so that the carbon nanomaterial forms a state of being mutually overlapped and not highly aggregated and is distributed on the surface of the emulsion microsphere. The present application found that when the first resin particle size is between 50nm and 5 μm, the carbon nanomaterial can achieve a lap joint state that is most favorable for secondary dispersion. When the diameter of the resin particles is too small, the particle diameter can be compared with the size of carbon nano materials such as carbon nano tubes, so that the carbon nano materials form high-density lap joints among particles, and the secondary dispersion capacity is reduced; when the particle diameter is too large, the specific surface area is small, resulting in a thicker coating layer of the carbon nanomaterial on the particle surface, which is difficult to open in secondary dispersion, thereby reducing the secondary dispersion ability. Also, the case where the coating layer is too thick, resulting in a decrease in secondary dispersibility, is also likely to occur in the pre-dispersion process in which the mass ratio of the first resin to the carbon nanomaterial is less than 5. Therefore, the invention selects the aqueous emulsion containing resin microsphere particles with moderate size to blend with the carbon nanomaterial, and the carbon nanomaterial forms a wrapped pre-dispersion on the microsphere surface after drying, when the carbon nanomaterial is secondarily dispersed with the second resin, the wrapped pre-dispersion of the carbon nanomaterial is easy to disperse, and the carbon nanomaterial is connected with each other to form a conductive network which is easy to form mutual lap joint, so that the percolation threshold is obviously reduced. In the prior art, the carbon nano material is dispersed, and only large agglomerates are dispersed into small agglomerates to form island-shaped distributed agglomerates, so that the carbon nano material resin dispersion material obtained by the method is obviously different from the carbon nano material resin dispersion system structure obtained by the prior art.
In the research, it is also found that the interfacial modifier is added in the secondary dispersion process with the second resin, so that the dispersion degree of the carbon nanomaterial can be further improved, the stability of a conductive network is improved, and the uniformity of the distribution of a conductive medium is improved, but the conductivity is not necessarily improved, so that the addition of the interfacial modifier is more suitable for antistatic application.
In addition, it has been found in the study that the content of the carbon nanomaterial in the aqueous dispersion of the carbon nanomaterial should be 2 to 10wt%, the content of the resin in the aqueous dispersion of the first resin should be 20 to 60wt%, when the concentration of the two is too high, self-polymerization of the carbon nanomaterial and emulsion breaking of the aqueous emulsion easily occur, so that the two are difficult to blend uniformly, and when the concentration of the two is too low, the cost of water evaporation is too high, which is not favorable for practical application.
Drawings
FIG. 1 is an SEM image of resin castings prepared according to example 1 and comparative examples 1-2 of the present invention.
Detailed Description
The technical scheme of the invention is described in further detail below. It should be apparent to those skilled in the art that the detailed description is merely provided to aid in understanding the invention and should not be taken as limiting the invention in any way.
Unless otherwise indicated, the technical means used in the following examples are conventional means well known to those skilled in the art, and all the raw materials used are commercially available conventional products.
Example 1
The embodiment provides a method for dispersing carbon nanotubes in resin, which comprises the following steps:
(1) Mixing the carbon nano tube aqueous dispersion liquid (the mass percentage concentration is 5%) and the aqueous dispersion emulsion of the epoxy resin E51 (the mass percentage concentration is 30%, the size of resin particles is 2 mu m, the viscosity of the resin at normal temperature after water removal is 8.2 Pa.s) according to the volume ratio of 1:2 (the volume of the carbon nano tube aqueous dispersion liquid/the volume of the aqueous dispersion liquid of the epoxy resin E51=1:2), and manually stirring for 5 minutes by using a glass rod to obtain uniformly mixed aqueous carbon nano tube dispersion slurry;
(2) Spreading the uniformly mixed aqueous carbon nanotube dispersion slurry, standing at normal temperature for 15 days, and airing to obtain dried pre-dispersion resin, wherein the moisture content of the dried pre-dispersion resin is 0.7wt%, and the mass ratio of epoxy resin E51 to carbon nanotubes in the pre-dispersion resin is 12:1;
(3) Mixing the pre-dispersion resin prepared in the step (2) with epoxy resin E51 according to a weight ratio of 1:2 (weight of the pre-dispersion resin/weight of the epoxy resin E51=1:2), heating to 45 ℃, and uniformly mixing the mixture for 30min by adopting a mixer mixing method to obtain a carbon nano tube resin dispersion material, wherein the mass percentage content of the carbon nano tubes is 2.56%.
Further mixing the carbon nanotube resin dispersion material obtained in the step (3) with a curing agent 4,4' -diaminodiphenyl sulfone (DDS) and a toughening agent phenolphthalein modified polyaryletherketone (PEK-C) according to a mass ratio of 1:0.32: mixing in a proportion of 0.25, heating to 130 ℃ under stirring, and keeping for 20min until all materials are dissolved uniformly to obtain a casting body. The obtained casting body is scraped into a glue film, and the carbon nanotube modified resin glue film can be used as a glue film for conductive adhesion.
Example 2
The present embodiment provides a method for dispersing carbon nanotubes in a resin, which is different from embodiment 1 only in the step (3), and the step (3) of this embodiment is as follows:
mixing the pre-dispersion resin prepared in the step (2) with epoxy resin E51 according to a weight ratio of 1:10 (weight of the pre-dispersion resin/weight of the epoxy resin E51=1:10), heating to 45 ℃, and uniformly mixing the mixture for 7 times by adopting a three-roller mixing method to obtain a carbon nano tube resin dispersion material, wherein the mass percentage content of the carbon nano tubes is 0.7%.
The prepared carbon nano tube resin dispersion material and dicyandiamide are mixed according to the mass ratio of 10:1 (carbon nano tube resin dispersion material/dicyandiamide=10:1), and after solidification, the unnotched impact strength of the resin casting body is improved by 52.3% compared with the same resin casting body without carbon nano tube, and the carbon nano tube resin casting body reaches 32.8KJ/m 2 Can be used for resin matrix of table tennis bat and golf club made of carbon fiber composite material.
Example 3
The embodiment provides a method for dispersing graphene in resin, which comprises the following steps:
(1) Mixing graphene aqueous dispersion (the mass percentage concentration is 8%) and epoxy resin E54 aqueous dispersion (the mass percentage concentration is 40%, the resin particle size is 1.3 mu m, the viscosity of the resin at normal temperature after water removal is 4.2 Pa.s) according to a volume ratio of 1:3 (the volume of the graphene aqueous dispersion/the volume of the epoxy resin E54 aqueous dispersion=1:3), and manually stirring for 5 minutes by using a glass rod to obtain uniformly mixed aqueous graphene dispersion slurry;
(2) Placing the uniformly mixed aqueous graphene dispersion slurry in a 100 ℃ oven for drying to obtain dried pre-dispersion resin, wherein the moisture content of the dried pre-dispersion resin is 0.37wt%, and the mass ratio of the epoxy resin E54 to the graphene in the pre-dispersion resin is 15:1;
(3) Mixing the pre-dispersion resin prepared in the step (2) with epoxy resin E54 according to a weight ratio of 1:4 (the weight of the pre-dispersion resin/the weight of the epoxy resin E54=1:4), and then uniformly mixing the mixture through a roller for 10 times by adopting a three-roller dispersing machine to obtain graphene resin dispersion materials, wherein the mass percentage content of graphene is 1.25%.
Further stirring the graphene resin dispersion material obtained in the step (3) and the curing agent imidazole and the toughening agent phenoxy resin PKHH for 30 minutes with a reaction kettle according to the proportion of 1:0.04:15, uniformly mixing to obtain matrix resin for the composite material, and preparing prepreg (fiber surface density 135 g/m) after compounding the resin and unidirectional T800 carbon fiber 2 The resin content is 32 wt%) and the composite material prepared by using the prepreg has good antistatic property, and compared with the same composite material without graphene, the flexural modulus is improved by 12%.
Example 4
The embodiment provides a method for dispersing carbon nanomaterial in resin, the method comprising the steps of:
(1) Mixing a carbon nano tube aqueous dispersion (with the mass percentage concentration of 2%), a graphene aqueous dispersion (with the mass percentage concentration of 2%) and an epoxy resin AG80 aqueous dispersion (with the mass percentage concentration of 20%, the resin particle size of 4.5 mu m, and the viscosity of the resin at normal temperature after water removal of 9.2 Pa.s) according to the volume ratio of 1:1:2 (the volume of the carbon nano tube aqueous dispersion/the volume of the graphene aqueous dispersion/the volume of the epoxy resin AG80 aqueous dispersion=1:1:2), and stirring for 5 minutes by using a stirrer to obtain a uniformly mixed aqueous carbon nano material dispersion slurry;
(2) The uniformly mixed aqueous carbon nano material dispersion slurry is subjected to primary drying by adopting a spray drying method, and then is subjected to vacuum drying at normal temperature for 10 hours to obtain dried pre-dispersion resin, wherein the moisture content of the dried pre-dispersion resin is 0.12 weight percent, the mass ratio of epoxy resin AG80 to graphene in the pre-dispersion resin is 20:1, and the mass ratio of AG80 to carbon nano tubes is 20:1;
(3) Mixing the pre-dispersion resin prepared in the step (2) with epoxy resin AG80 according to the weight ratio of 1:1, and then stirring for 30min by adopting a planetary stirrer to uniformly mix to obtain a carbon nano material resin dispersion material, wherein the mass percentage content of carbon nano tubes is 2.27%, and the mass percentage content of graphene is 2.27%.
Further step (3)) The prepared carbonThe nano material resin dispersion material and the DDS are uniformly mixed according to the mass ratio of 1:0.5, so that the high-temperature cured epoxy resin adhesive with good conductivity is obtained, and the conductivity of a cured product reaches 0.17S/m.
Example 5
The embodiment provides a method for dispersing carbon nanomaterial in resin, the method comprising the steps of:
(1) Mixing a carbon nano tube aqueous dispersion (the mass percentage concentration is 3%), a graphene aqueous dispersion (the mass percentage concentration is 8%) and an epoxy resin E44 aqueous dispersion (the mass percentage concentration is 40%, the size of resin particles is 0.77 mu m, the viscosity of the resin after water removal at normal temperature is 30.2 Pa.s) according to a volume ratio of 1:1:2 (the volume of the carbon nano tube aqueous dispersion/the volume of the graphene aqueous dispersion/the volume of the epoxy resin E44 aqueous dispersion = 1:1:2), and stirring for 5 minutes by using a stirring kettle to obtain a uniformly mixed aqueous carbon nano material dispersion slurry;
(2) Heating and drying the uniformly mixed aqueous carbon nano material dispersion slurry to obtain dried pre-dispersion resin, wherein the moisture content of the dried pre-dispersion resin is 0.42wt%, the mass ratio of the epoxy resin E44 to the graphene in the pre-dispersion resin is 10:1, and the mass ratio of the E44 to the carbon nano tube is 80:3;
(3) Mixing the pre-dispersion resin prepared in the step (2) with epoxy resin AG80 according to the weight ratio of 1:1, then adding an interface modifier polyvinylpyrrolidone (PVP), wherein the amount of the interface modifier is 0.5% of the sum of the mass of epoxy resin E44 and the mass of epoxy resin AG80 in the aqueous dispersion liquid of epoxy resin E44 in the step (1), mixing by adopting a mixer, and uniformly mixing the mixture for 20min to obtain a carbon nano material resin dispersion material, wherein the mass percentage content of carbon nano tubes is 1.65%, and the mass percentage content of graphene is 4.40%.
The prepared carbon nano material resin dispersion material can be used as raw materials of antistatic resin casting bodies, antistatic glass fiber composite materials and conductive adhesives.
Example 6
The present embodiment provides a method for dispersing a carbon nanomaterial in a resin, which is different from embodiment 5 only in the step (3), and the step (3) of this embodiment is as follows:
mixing the pre-dispersed resin prepared in the step (2) with epoxy resin AG80 according to the weight ratio of 1:1, then adding an interface modifier sodium carboxymethyl cellulose (CMC-Na), wherein the dosage of the interface modifier is 0.7% of the sum of the mass of epoxy resin E44 and the mass of epoxy resin AG80 in the aqueous dispersion liquid of epoxy resin E44 in the step (1), mixing by adopting a mixer, and uniformly mixing the mixture for 20min to obtain the carbon nano material resin dispersion material.
The prepared carbon nano material resin dispersion material can be used as raw materials of antistatic resin casting bodies, antistatic glass fiber composite materials and conductive adhesives.
Example 7
The embodiment provides a method for dispersing graphene in resin, which comprises the following steps:
(1) Mixing graphene aqueous dispersion (with the mass percentage concentration of 3%) and epoxy resin F44 aqueous dispersion (with the mass percentage concentration of 25%, the resin particle size of 1.25 mu m, and the viscosity of the resin at normal temperature after water removal of 410 Pa.s) according to the volume ratio of 1:1, and stirring for 5 minutes by using a stirrer to obtain uniformly mixed aqueous graphene dispersion slurry;
(2) Spreading the uniformly mixed aqueous graphene dispersion slurry, and evaporating water to obtain dried pre-dispersion resin, wherein the water content after drying is 0.11wt%, and the mass ratio of epoxy resin F44 to graphene in the pre-dispersion resin is 25:3;
(3) Mixing the pre-dispersion resin prepared in the step (2) with epoxy resin F44 according to a weight ratio of 1:3 (the weight of the pre-dispersion resin/the weight of the epoxy resin F44=1:3), heating to 55 ℃, and uniformly mixing the mixture for 25 minutes by adopting a method of mixing by a stirrer to obtain graphene resin dispersion material, wherein the mass percentage content of graphene is 2.88%. Alternatively, a three-roll dispersing method can be adopted, and the mixture is uniformly mixed for 10 times to obtain the well-dispersed graphene resin dispersion material.
It is found that in the step (3), byk-163 dispersing agent (amphiphilic dispersing agent) is added into the mixed system of the pre-dispersed resin and the epoxy resin F44, the amount of the interface modifier is 0.3% of the sum of the mass of the epoxy resin F44 in the aqueous dispersion liquid of the epoxy resin F44 in the step (1) and the mass of the epoxy resin F44 in the step (3), and finally the storage stability of the obtained graphene resin dispersion material is better.
Comparative example 1
The present comparative example provides a method of dispersing a carbon nanomaterial in a resin, the method comprising the steps of: mixing carbon nano tube powder and epoxy resin E54 together according to the mass ratio of 1:99, wherein the mass percentage content of the carbon nano tube is 1%, stirring the mixture for 15 minutes by using a stirrer until the mixture is primarily uniform, then dispersing the mixture for 1 hour by using a high-speed shearing dispersing machine, wherein the model of the high-speed shearing dispersing machine is a product of Process Pilot MK 2000/04plant, IKA company, the rotating speed is 14000 r/min during dispersing, and the temperature is controlled below 80 ℃ during dispersing. After the dispersion is finished, uniformly mixing the epoxy resin E54 dispersed by the carbon nano tube and the DDS according to the mass ratio of 1:0.32, preparing a casting body in an oven according to the curing process of 135 ℃/2h+180 ℃/2h, clamping the casting body to obtain a small block, and observing the fracture morphology of the casting body by using a scanning electron microscope.
Comparative example 2
The present comparative example provides a method of dispersing a carbon nanomaterial in a resin, the method comprising the steps of: mixing carbon nanotube powder, epoxy resin AG80, epoxy resin E54 and epoxy resin 014 together according to a mass ratio of 1:59:20:20, heating to 125 ℃, mutually dissolving and uniformly mixing the three resins, wherein the mass percent of the carbon nanotube is 1%, dispersing the mixture for 100 times by using a three-roll machine, wherein the model of the three-roll machine is EXAKT 80E plus, EXAKT company product, the rotating speed is 120 r/min, and the temperature is controlled below 80 ℃ in the dispersing process. After the dispersion is finished, uniformly mixing the epoxy resin dispersed by the carbon nano tube and the DDS according to the mass ratio of 1:0.37, preparing a casting body in an oven according to a curing process of 135 ℃/2h+180 ℃/2h, clamping the casting body to obtain a small block, and observing the fracture morphology of the casting body by using a scanning electron microscope.
SEM images of the cast bodies prepared in example 1 and comparative examples 1-2 of the present invention are shown in fig. 1. In fig. 1, fig. a and b are sectional SEM images of a casting body prepared in example 1 of the present invention, fig. c is a sectional SEM image of a resin casting body prepared from a dispersion prepared in comparative example 1 of the present invention, and fig. d is a sectional SEM image of a resin casting body prepared from a dispersion prepared in comparative example 2 of the present invention.
From figures a and bTo see, carbonThe dispersion of the nanotubes in the resin is in a certain domain shape, a large number of carbon nanotubes can be seen in a partial region, the carbon nanotubes in the regions are well dispersed in the resin, almost no agglomerates exist, but the carbon nanotubes in the partial region are sparsely distributed, even no carbon nanotubes exist, so the distribution of the carbon nanotubes is in a continuous domain shape. This is because the carbon nanotubes are highly dispersed due to the difference in dispersion state of the carbon nanotubes in the first resin and the second resin, and under the weaker secondary dispersion condition, part of the second resin is not uniformly mixed with the dispersion of the carbon nanotubes/first resin, resulting in no carbon nanotubes in this region. The continuous domain-like dispersion structure has lower percolation threshold and better mechanical property because of no carbon nanotube aggregate (no resin in the aggregate and stacked carbon nanotubes under the action of Van der Waals force).
As can be seen from fig. c, in the carbon nanotube dispersion resin obtained by the conventional high-speed shearing method, a large amount of micron-sized aggregates (the aggregates are free from resin and the carbon nanotubes are stacked by van der waals force) still exist in the system after 1h of dispersion, and the particle size reaches 5 to 20 μm because the liquid flow is still slow at high-speed shearing and the dispersion is not performed for the high-viscosity liquid. FIG. d shows a cross section of a carbon nanotube dispersion resin casting obtained by a three-roll dispersing method, in which more dispersed carbon nanotubes are seen in the resin, but a large amount of carbon nanotube aggregates are also seen.
In summary, as can be seen from fig. 1, the distribution of the cross-section carbon nanotubes shows island-like distribution regardless of the conventional high-speed shearing method or the three-roll dispersing method, which indicates that most of the carbon nanotubes are still not dispersed, the resin is not infiltrated into the agglomerates, and the carbon nanotubes are in a micro-aggregation state, but only the fineness of the aggregate particles is increased. On the resin section diagram of the method, the carbon nano tube aggregates are fully opened, the carbon nano materials are well dispersed, the carbon nano materials are all soaked by the resin, the rare aggregation state exists, and the continuous domain distribution is shown, so that the dispersion characteristics of the carbon nano material dispersion resin are obviously different from those of the prior art, and the dispersion system obtained by the method is different from typical structural characteristics of the dispersion system obtained by other methods.
In the prior art, powdered agglomerated carbon nanotubes or graphene are dispersed into resin, a solvent is often required to be matched, ultrasonic treatment is carried out for a plurality of hours, undispersed carbon nanotubes or graphene are required to be centrifugally separated, finally, the solvent is required to be distilled off, and the carbon nanotubes or graphene are extremely easy to agglomerate in the solvent distillation process, so that the carbon nanotubes or graphene are precipitated from the solvent. Compared with the prior art, the method can obtain the dispersed resin slurry of the carbon nano tube and/or the graphene and the like by simple stirring, three-roller grinding or mixing, the required equipment even only needs a stirrer, the dispersing and mixing time is less than 1h, the operation is very simple, and the time and the labor are saved.
The dispersion obtained by the method has better conductivity. Typically, it was found that when the carbon nanotube content in the dispersion was 1wt%, the volume resistivity of the resin casting was 10 -4 Omega cm. And resin casting dispersed by adopting a high-speed shearing dispersion and three-roller methodWhen the carbon nano tube content reaches 2wt%, the volume resistivity is lower than 10 -6 Omega cm. This is because the dispersion of the well-formed carbon nanotubes in the form of domains greatly reduces the percolation threshold, indicating that the dispersion method of the present invention has significant advantages. The dispersed structure of the carbon nano material with domain shape is also the typical characteristic and the characteristic of the carbon nano material resin dispersed material prepared by the method for dispersing the carbon nano material in the resin.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes or modifications may be made by those skilled in the art within the scope of the appended claims without affecting the spirit of the invention. In the case of no conflict
In the following, embodiments of the present application and features in the embodiments may be arbitrarily combined with each other.
Claims (10)
1. A method of dispersing carbon nanomaterial in a resin, the method comprising the steps of:
(1) Mixing the aqueous dispersion of the carbon nano material and the aqueous dispersion of the first resin, and then drying to obtain pre-dispersion resin;
(2) And uniformly mixing the pre-dispersed resin and the second resin to obtain the carbon nano material resin dispersion material.
2. The method of claim 1, wherein the mixing in step (1) is performed by stirring; and/or in the step (2), any one or more of stirring, three-roller dispersing and mixing methods are adopted for mixing.
3. The method according to claim 1 or 2, wherein the first resin and the second resin are each selected from epoxy resins; the first resin and the second resin represent the same or different resins; and/or the number of the groups of groups,
the viscosities of the first resin and the second resin at normal temperature satisfy the condition:
the viscosity is less than or equal to 500Pa.s at the normal temperature and less than or equal to 3.5 Pa.s.
4. The method according to claim 1, wherein the mass percentage content of the carbon nanomaterial in the aqueous dispersion of the carbon nanomaterial is 2-10%, and the carbon nanomaterial is carbon nanotubes and/or graphene.
5. The method according to claim 1, wherein the aqueous dispersion of the first resin has a mass percentage of the first resin of 20 to 60% and a particle size of the first resin of 50nm to 5 μm.
6. The method according to claim 1, wherein the mass ratio of the first resin to the carbon nanomaterial in the pre-dispersion resin is not less than 5, preferably the mass ratio of the first resin to the carbon nanomaterial in the pre-dispersion resin is 8-20.
7. The method of claim 1, wherein the pre-dispersion resin is present with the second resin in a mass ratio of 1: (0.5-10), preferably in a mass ratio of 1: (1-5) mixing.
8. The method of any one of claims 1-7, wherein in step (2), an interface modifier is further added when the pre-dispersed resin is mixed with the second resin, the interface modifier being selected from amphiphilic polymers; and/or the interface modifier is used in an amount of 0.1 to 1.5%, preferably 0.3 to 1.0%, and more preferably 0.3 to 0.8% of the total mass of the first resin and the second resin.
9. A carbon nanomaterial resin dispersion obtainable by the method of any of claims 1-8.
10. Use of the carbon nanomaterial resin dispersion of claim 9 in a conductive composite or an impact resistant composite.
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