CN114773865B - Carbon nano tube aqueous slurry with functions of emulsifying and solidifying epoxy resin, and preparation and application thereof - Google Patents

Carbon nano tube aqueous slurry with functions of emulsifying and solidifying epoxy resin, and preparation and application thereof Download PDF

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CN114773865B
CN114773865B CN202210590890.0A CN202210590890A CN114773865B CN 114773865 B CN114773865 B CN 114773865B CN 202210590890 A CN202210590890 A CN 202210590890A CN 114773865 B CN114773865 B CN 114773865B
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polyether
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CN114773865A (en
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石红义
戴辉
陈名海
王鹏
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Jiangxi Jiangtong Carbon Nano Material Co ltd
Jiangxi Copper Technology Research Institute Co ltd
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Jiangxi Copper Technology Research Institute Co ltd
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Abstract

The invention belongs to the technical field of carbon nanotube application, and discloses carbon nanotube aqueous slurry with functions of emulsifying and curing epoxy resin, and a preparation method and application thereof. The carbon nano tube aqueous slurry consists of the following components in parts by mass: 1 part of carbon nano tube, 0.6 to 5 parts of epoxy resin co-modified by amino and polyether, 0.4 to 1 part of stabilizer, 0.001 to 0.1 part of defoamer and 6 to 30 parts of water. The carbon nano tube aqueous slurry has good stability, can realize emulsification and solidification of an epoxy resin aqueous system without adding an emulsifying agent and a solidifying agent, has simple components and good compatibility, can be widely applied to the field of carbon nano tube/aqueous epoxy resin functional composite materials, and has important commercial application value.

Description

Carbon nano tube aqueous slurry with functions of emulsifying and solidifying epoxy resin, and preparation and application thereof
Technical Field
The invention belongs to the technical field of carbon nanotube application, and particularly relates to carbon nanotube aqueous slurry with functions of emulsifying and curing epoxy resin, and preparation and application thereof.
Technical Field
Epoxy resins have excellent properties such as excellent adhesion, chemical resistance, thermal stability, mechanical strength, and insulation, and thus are widely used in the fields of surface coating, adhesives, electronic packaging materials, advanced composite materials, aerospace, electronic industry, and the like. However, epoxy resins generally have high viscosity, and a large amount of diluent or organic solvent is often required to be added to facilitate the composite modification and operation processing of the epoxy resins, which can bring great harm to human health and environmental safety. In recent years, with the enhancement of environmental protection consciousness, and the enhancement of environmental protection policy in various countries, aqueous epoxy resins using water as a solvent or a dispersion medium have been increasingly paid attention to.
Carbon Nanotubes (CNTs), also known as bucky tubes, are one-dimensional tubular structured nanomaterials, light in weight, perfectly connected in hexagonal structure, have many excellent mechanical, electrical and thermal properties, etc., and are one of the more ideal polymer-based nanofillers. The carbon nanotube/epoxy resin composite material is a composite material prepared by taking epoxy resin as a matrix and taking carbon nanotubes as a filler. The performance of the material depends largely on the dispersion effect of the carbon nanotubes in the epoxy resin, i.e. the preparation method is a key factor affecting the performance of the composite material. However, due to the van der Waals force effect and the extremely large length-diameter ratio among the carbon nanotubes, the carbon nanotubes are extremely easy to be in an agglomeration state in a solvent or a polymer and difficult to disperse, if the dispersion state of the carbon nanotubes is not good, the performance of a resin matrix is not improved, and even the performance of a composite material is possibly reduced, so that the problem of agglomeration of the carbon nanotubes is a key problem in preparation of the composite material.
In the prior art, the carbon nano tube/epoxy resin composite material is prepared in an auxiliary way by physical blending or adding a dispersing agent. The physical blending mode is generally poor in dispersion, a large amount of the epoxy resin needs to be added to achieve the effect, sometimes even defects occur, and the performance of the epoxy resin is reduced; in addition, a large amount of dispersing agent is generally required to be added to achieve a better dispersing effect, in addition, the problem of compatibility between the dispersing agent and the epoxy resin is also required to be considered, and the dispersing agent can remain in the epoxy resin after the epoxy resin is cured, so that the performance of the composite material can be greatly influenced; in addition, more technologies at present are aimed at organic solution systems, which cause great harm to the environment and human health and are unfavorable for long-term development;
disclosure of Invention
The invention aims to overcome the defects and shortcomings in the prior art and provide the carbon nano tube aqueous slurry with the functions of emulsifying and solidifying epoxy resin.
Another object of the present invention is to provide a method for preparing an aqueous slurry of carbon nanotubes having the function of emulsifying and curing an epoxy resin.
The invention also aims at providing an application of the carbon nano tube aqueous slurry with the functions of emulsifying and curing epoxy resin.
The aim of the invention is achieved by the following technical scheme:
the carbon nano tube aqueous slurry with the functions of emulsifying and curing epoxy resin comprises the following components in parts by weight:
Figure BDA0003667338880000021
the pipe diameter of the carbon nano-tube is 8-60nm, and the length is 3-30 mu m;
the structural formula of the amino-and polyether-containing co-modified epoxy resin is shown in formula I:
Figure BDA0003667338880000022
wherein n is preferably n=8 to 134; r is R 1 Is C 2 H 4 、C 6 H 12 、C 4 H 9 N、C 6 H 14 N 2 、C 8 H 19 N 3 、
Figure BDA0003667338880000023
(x=2.5-85, namely the junction of the epoxy resin polyether amine curing agent after losing two amino groupsThe structure can be a series of products with molecular weight ranging from 230 to 5000),>
Figure BDA0003667338880000024
Figure BDA0003667338880000031
at least one of (a) and (b); />
Figure BDA0003667338880000032
Is epoxy resin->
Figure BDA0003667338880000033
Loss of two epoxy groups->
Figure BDA0003667338880000034
The epoxy resin is phenolic epoxy resin or bisphenol A epoxy resin; r is R 2 Is that
Figure BDA0003667338880000035
Figure BDA0003667338880000036
At least one of (a) and (b); r is R 3 Is H or CH 3 。
The amino-containing and polyether co-modified epoxy resin is more than one type I.
The amino-containing polyether co-modified epoxy resin is prepared by the following method:
step 1) under the protection of inert gas, using a solvent M as a reaction medium, gradually dripping the epoxy resin diluted by the solvent M into a mixed system of an epoxy resin amine curing agent and the solvent M, reacting for 2-5 h at 50-100 ℃,
step 2) gradually dropwise adding the polyalcohol glycidyl ether into a reaction system, continuing to react for 3-6h, and distilling under reduced pressure to remove the solvent M to obtain amino and polyether co-modified epoxy resin;
the solvent M is an organic solvent, preferably one or more of acetone, ethanol, toluene, xylene, propylene glycol monomethyl ether, ethylene glycol butyl ether and N, N' -dimethylformamide;
the epoxy resin is phenolic epoxy resin or bisphenol A type epoxy resin, and the phenolic epoxy resin is F51; the bisphenol A type epoxy resin is one or more of E51 and E44;
the epoxy resin amine curing agent is aliphatic amine, polyether amine or alicyclic amine curing agent, wherein the epoxy resin amine curing agent is preferably at least one of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, isophoronediamine, menthanediamine, 1, 3-bis (aminomethyl) cyclohexane, jeffamine D230 and Jeffamine D400;
the polyalcohol glycidyl ether is one or more of polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether;
one or more of cellulose, acacia, xanthan gum, carrageenan and sodium alginate serving as stabilizing agents;
the defoamer is preferably a mineral oil defoamer or a polysiloxane defoamer. The mineral oil defoamer is preferably at least one of SN-919 (Shanghai Stokes chemical Co., ltd.), BEK-750 (Guangzhou Guanzhu chemical Co., ltd.), or HT-630 (Nantong Tay chemical Co., ltd.). The silicone defoamer is preferably one or more of FY2309, FY2311H or FY-3300 (fluorine edge technologies, inc. of Guangzhou).
The preparation method of the carbon nano tube aqueous slurry with the functions of emulsifying and curing the epoxy resin comprises the following steps:
s1) mixing carbon nano tubes, amino-and polyether-containing co-modified epoxy resin, a stabilizer, a defoaming agent and water, pre-cutting at a high speed, standing and soaking to obtain a premix;
s2) sequentially carrying out sand grinding and high-pressure homogenizing grinding and dispersing on the premix to obtain dispersed carbon nano tube aqueous slurry;
the high-speed pre-shearing in the step S1) is carried out at a shearing speed of 2-40m/S and a treatment time of 30min-6h;
the grinding medium in the step S2) adopts ceramic beads with the diameter of 0.2-2.0mm and the linear speed of a dispersion disc of 2-40m/S; the high-pressure homogenizing treatment pressure is 20-100MPa;
the carbon nano water-based slurry can be used for emulsifying and curing epoxy resin, is used for preparing a carbon nano tube/water-based epoxy composite material, and is applied to conductive or antistatic nano composite coating and adhesive.
Compared with the prior art, the invention has the following advantages and effects:
in the prior art, carbon nanotubes are used as a filler or a pre-dispersion to be added into a system formed by compounding epoxy resin and a curing agent, and the carbon nanotubes are used as an organic solvent system; the epoxy resin co-modified by the amino group-containing polyether can realize the dispersion of the carbon nano tube in a water phase system, can realize the emulsification and the solidification of the epoxy resin water phase system without adding an emulsifying agent and a solidifying agent, has simple components and good compatibility, can be widely applied to the field of carbon nano tube/water-based epoxy resin functional composite materials, and has important commercial application value.
Drawings
FIG. 1 is a block flow diagram of an aqueous slurry of carbon nanotubes with emulsifying and curing epoxy functionality according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto
The invention relates to a carbon nano tube aqueous slurry with the functions of emulsifying and solidifying epoxy resin, which comprises the following components in parts by mass:
Figure BDA0003667338880000041
as shown in fig. 1, the present invention further provides a method for preparing the above-mentioned aqueous slurry of carbon nanotubes having the functions of emulsifying and curing epoxy resin, which specifically comprises the following steps:
s1) respectively weighing carbon nano tubes, epoxy resin co-modified by amino group-containing and polyether, a stabilizer, a defoaming agent and water according to a proportion, mixing, pre-cutting at a high speed, standing and infiltrating to obtain a premix;
s2) sequentially sanding, homogenizing, grinding and dispersing the premix of the S1) under high pressure, and emulsifying and solidifying the carbon nano tube aqueous slurry with the function of epoxy resin.
The high-speed pre-cutting process parameters in the S1) are as follows: the shearing speed is 2-40m/s, and the treatment time is 30min-6h;
the sand grinding and high-pressure homogenizing grinding and dispersing process in the step S2) comprises the following steps:
the sand grinding medium is ceramic beads with the diameter of 0.2-2.0mm, and the linear speed of the dispersion disc is 2-40m/s; the high-pressure homogenizing treatment pressure is 20-100MPa.
The structural formula of the amino-containing polyether co-modified epoxy resin in the S1) is shown in the following formula I:
Figure BDA0003667338880000051
wherein n=8 to 134;
R 1 is C 2 H 4 、C 6 H 12 、C 4 H 9 N、C 6 H 14 N 2 、C 8 H 19 N 3 、
Figure BDA0003667338880000052
/>
Figure BDA0003667338880000053
Figure BDA0003667338880000054
At least one of (a) and (b); />
Figure BDA0003667338880000055
A structure formed by losing two epoxy groups for the epoxy resin;
R 2 is that
Figure BDA0003667338880000061
Figure BDA0003667338880000062
At least one of (a) and (b);
R 3 is H or CH 3 。
The epoxy resin is phenolic epoxy resin or bisphenol A epoxy resin.
The preparation method of the amino-and polyether-containing co-modified epoxy resin specifically comprises the following steps:
step 1) under the protection of inert gas, taking a solvent M as a reaction medium, gradually dropwise adding epoxy resin diluted by the solvent M into a mixed system of an epoxy resin amine curing agent and the solvent M, and reacting for 2-5 h at 50-100 ℃;
step 2) gradually dropwise adding the polyalcohol glycidyl ether into the reaction system in the step 1), continuing to react for 3-6h, and distilling under reduced pressure to remove the solvent M to obtain amino and polyether co-modified epoxy resin; .
The solvent M is an organic solvent;
the epoxy resin is phenolic epoxy resin or bisphenol A epoxy resin;
the epoxy resin amine curing agent is aliphatic amine curing agent, polyether amine curing agent or alicyclic amine curing agent;
the polyalcohol glycidyl ether is one or more of polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether;
the organic solvent is one or more of acetone, ethanol, toluene, xylene, propylene glycol monomethyl ether, ethylene glycol butyl ether and N, N' -dimethylformamide;
the stabilizer in the S1) is one or more of cellulose, acacia, xanthan gum, carrageenan and sodium alginate;
the defoamer is mineral oil defoamer or polysiloxane defoamer.
The carbon nanotube aqueous slurry with the functions of emulsifying and solidifying epoxy resin is applied to the emulsification and solidification of epoxy resin, the preparation of carbon nanotube/aqueous epoxy composite material and the application in conductive or antistatic nano composite coating and adhesive.
Paint film performance testing was performed according to the following criteria:
the pencil hardness of the paint film is measured according to GB/6739-1996; paint film adhesion was determined according to GB/T9286-1998; paint film flexibility was measured according to GB/T1931-1993; the water resistance of the paint film is measured according to GB/1733-1993;
example 1
(1) Preparation of amino group-containing polyether co-modified epoxy resin: 66 parts by mass of epoxy resin E51 and 60 parts by mass of propylene glycol monomethyl ether are uniformly premixed to obtain a propylene glycol monomethyl ether solution of the epoxy resin E51 for standby. 54 parts by mass of triethylene tetramine and 10 parts by mass of propylene glycol monomethyl ether are added into a container, the temperature is raised to 80 ℃, and the propylene glycol monomethyl ether solution of the epoxy resin E51 is dropwise added in the stirring process. After the completion of the dropwise addition, the reaction was carried out at 80℃for 5 hours. Then 20 parts by mass of polyethylene glycol diglycidyl ether is dropwise added into the reaction system, the reaction is continued for 6 hours, and the propylene glycol monomethyl ether is removed by reduced pressure distillation to obtain the amino and polyether co-modified epoxy resin.
(2) Preparation of carbon nano tube aqueous slurry with functions of emulsifying and solidifying epoxy resin: performing high-speed shearing dispersion on 1 part by mass of carbon nano tube, 5 parts by mass of epoxy resin co-modified by amino groups and polyether and 15 parts by mass of water, gradually adding 0.4 part by mass of cellulose and 0.005 part by mass of BEK-750 in the shearing dispersion process, continuing to perform shearing dispersion for 2 hours after the addition is finished, and standing and soaking for 12 hours to obtain a premix; and (3) sanding and dispersing the obtained premix for 2 hours through a rod pin type nano sand mill, wherein a grinding medium adopts ceramic beads with the diameter of 1.0mm and the linear speed of a dispersing disc of 20m/s, and homogenizing for 2 times under the pressure of 70MPa through a high-pressure homogenizer to obtain the carbon nano tube aqueous slurry with the functions of emulsifying and curing epoxy resin.
Example 2
(1) Preparation of amino group-containing polyether co-modified epoxy resin: and uniformly premixing 46 parts by mass of epoxy resin E44 and 40 parts by mass of ethylene glycol butyl ether to obtain an ethylene glycol butyl ether solution of the epoxy resin E44 for later use. 38 parts by mass of isophorone diamine and 20 parts by mass of ethylene glycol butyl ether were added to a vessel, the temperature was raised to 100 ℃, and an ethylene glycol butyl ether solution of epoxy resin E44 was added dropwise during stirring. After the completion of the dropwise addition, the reaction was carried out at 100℃for 3 hours. Then 34 parts by mass of polypropylene glycol diglycidyl ether is dropwise added into the reaction system, the reaction is continued for 3 hours, and the butyl cellosolve is distilled off under reduced pressure to obtain the amino and polyether co-modified epoxy resin.
(2) Preparation of carbon nano tube aqueous slurry with functions of emulsifying and solidifying epoxy resin: carrying out high-speed shearing dispersion on 1 part by mass of carbon nano tube, 2 parts by mass of epoxy resin co-modified by amino group and polyether and 10 parts by mass of water, gradually adding 0.8 part by mass of Arabic gum and 0.01 part by mass of SN-919 in the shearing dispersion process, continuing to conduct shearing dispersion for 4 hours after the addition is finished, and standing and soaking for 12 hours to obtain a premix; and (3) sanding and dispersing the obtained premix for 3 hours through a turbine nano sand mill, wherein a grinding medium adopts ceramic beads with the diameter of 1.0mm and the linear speed of a dispersing disc of 25m/s, and homogenizing for 3 times under the pressure of 50MPa through a high-pressure homogenizer to obtain the carbon nano tube aqueous slurry with the functions of emulsifying and curing epoxy resin.
Example 3
(1) Preparation of amino group-containing polyether co-modified epoxy resin: 60 parts by mass of epoxy resin F51 and 50 parts by mass of toluene are premixed uniformly to obtain a toluene solution of the epoxy resin F51 for standby. 88 parts by mass of Jeffamine D400 and 40 parts by mass of toluene were added to the vessel, the temperature was raised to 90℃and a toluene solution of epoxy F51 was added dropwise during stirring. After the completion of the dropwise addition, the reaction was carried out at 90℃for 4 hours. Then 15 parts by mass of polyethylene glycol diglycidyl ether is added into the reaction system dropwise, the reaction is continued for 4 hours, toluene is removed by reduced pressure distillation, and the amino and polyether co-modified epoxy resin is obtained.
(2) Preparation of carbon nano tube aqueous slurry with functions of emulsifying and solidifying epoxy resin: performing high-speed shearing dispersion on 1 part by mass of carbon nano tube, 4 parts by mass of epoxy resin co-modified by amino and polyether and 30 parts by mass of water, gradually adding 1 part by mass of xanthan gum and 0.001 part by mass of HT-630 in the shearing dispersion process, continuing to perform shearing dispersion for 5 hours after the addition is finished, and standing and soaking for 12 hours to obtain a premix; and (3) sanding and dispersing the obtained premix for 1h through a disc type nano sand mill, wherein a grinding medium adopts ceramic beads with the diameter of 1.0mm and the linear speed of a dispersing disc of 20m/s, and homogenizing for 2 times under the pressure of 100MPa through a high-pressure homogenizer to obtain the carbon nano tube aqueous slurry with the functions of emulsifying and curing epoxy resin.
Example 4
(1) Preparation of amino group-containing polyether co-modified epoxy resin: and uniformly premixing 51 parts by mass of epoxy resin E51 with 50 parts by mass of N, N '-dimethylformamide to obtain an N, N' -dimethylformamide solution of the epoxy resin E51 for later use. 39 parts by mass of Jeffamine D230 and 20 parts by mass of N, N '-dimethylformamide were added to the vessel, the temperature was raised to 70℃and the N, N' -dimethylformamide solution of epoxy resin E51 was added dropwise during stirring. After the completion of the dropwise addition, the reaction was carried out at 70℃for 2 hours. Then, 25 parts by mass of polypropylene glycol diglycidyl ether is dropwise added into the reaction system, the reaction is continued for 5 hours, and N, N' -dimethylformamide is removed by reduced pressure distillation to obtain the amino and polyether co-modified epoxy resin.
(2) Preparation of carbon nano tube aqueous slurry with functions of emulsifying and solidifying epoxy resin: performing high-speed shearing dispersion on 1 part by mass of carbon nano tube, 3 parts by mass of epoxy resin co-modified by amino groups and polyether and 6 parts by mass of water, gradually adding 0.6 part by mass of carrageenan and 0.1 part by mass of FY2309 in the shearing dispersion process, continuing shearing dispersion for 3 hours after the addition is finished, and standing and soaking for 12 hours to obtain a premix; and (3) sanding and dispersing the obtained premix for 2 hours through a rod pin type nano sand mill, wherein a grinding medium adopts ceramic beads with the diameter of 1.0mm and the linear speed of a dispersing disc of 25m/s, and homogenizing for 3 times under the pressure of 60MPa through a high-pressure homogenizer to obtain the carbon nano tube aqueous slurry with the functions of emulsifying and curing epoxy resin.
Example 5
(1) Preparation of amino group-containing polyether co-modified epoxy resin: and uniformly premixing 46 parts by mass of epoxy resin E44 and 40 parts by mass of acetone to obtain an acetone solution of the epoxy resin E44 for later use. 32 parts by mass of 1, 3-bis (aminomethyl) cyclohexane and 30 parts by mass of acetone were added to the vessel, the temperature was raised to 50℃and an acetone solution of epoxy resin E44 was added dropwise during stirring. After the completion of the dropwise addition, the reaction was carried out at 50℃for 3 hours. Then 12 parts by mass of polyethylene glycol diglycidyl ether is added into the reaction system dropwise, the reaction is continued for 3 hours, and acetone is removed by reduced pressure distillation to obtain the amino and polyether co-modified epoxy resin.
(2) Preparation of carbon nano tube aqueous slurry with functions of emulsifying and solidifying epoxy resin: performing high-speed shearing dispersion on 1 part by mass of carbon nano tube, 0.6 part by mass of epoxy resin co-modified by amino groups and polyether and 25 parts by mass of water, gradually adding 0.7 part by mass of sodium alginate and 0.03 part by mass of FY2311H in the shearing dispersion process, continuing to perform shearing dispersion for 30min after the addition is finished, and standing and soaking for 12H to obtain a premix; and (3) sanding and dispersing the obtained premix for 3 hours through a turbine nano sand mill, wherein a grinding medium adopts ceramic beads with the diameter of 1.0mm and the linear speed of a dispersing disc of 20m/s, and homogenizing for 2 times under the pressure of 20MPa through a high-pressure homogenizer to obtain the carbon nano tube aqueous slurry with the functions of emulsifying and curing epoxy resin.
Example 6
(1) Preparation of amino group-containing polyether co-modified epoxy resin: 60 parts by mass of epoxy resin F51 and 50 parts by mass of xylene are premixed uniformly to obtain a xylene solution of the epoxy resin F51 for standby. 43 parts by mass of tetraethylenepentamine and 40 parts by mass of xylene are added to a vessel, the temperature is raised to 60 ℃, and a xylene solution of epoxy resin F51 is added dropwise during stirring. After the completion of the dropwise addition, the reaction was carried out at 60℃for 5 hours. Then 25 parts by mass of polypropylene glycol diglycidyl ether is added into the reaction system dropwise, the reaction is continued for 6 hours, and the xylene is removed by reduced pressure distillation to obtain the amino and polyether co-modified epoxy resin.
(2) Preparation of carbon nano tube aqueous slurry with functions of emulsifying and solidifying epoxy resin: performing high-speed shearing dispersion on 1 part by mass of carbon nano tube, 1 part by mass of epoxy resin co-modified by amino groups and polyether and 20 parts by mass of water, gradually adding 0.5 part by mass of cellulose and 0.06 part by mass of FY-3300 in the shearing dispersion process, continuing to perform shearing dispersion for 6 hours after the addition is finished, and standing and soaking for 12 hours to obtain a premix; and (3) sanding and dispersing the obtained premix for 1h through a disc type nano sand mill, wherein a grinding medium adopts ceramic beads with the diameter of 1.0mm and the linear speed of a dispersing disc of 25m/s, and homogenizing for 3 times under the pressure of 80MPa through a high-pressure homogenizer to obtain the carbon nano tube aqueous slurry with the functions of emulsifying and curing epoxy resin.
The mass ratio of the carbon nano tube aqueous slurry with the functions of emulsifying and curing the epoxy resin to the epoxy resin E51 in the embodiment is 1:1, mixing, high-speed shearing and dispersing to obtain aqueous emulsion, and curing the aqueous emulsion on tin plate to prepare paint by using a brushing method, wherein the performances of the emulsion and a paint film are shown in a table 1:
TABLE 1 examples 1-6 emulsion prepared by curing E51 and Performance test results of coating materials
Figure BDA0003667338880000091
Figure BDA0003667338880000101
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (7)

1. The preparation method of the carbon nano tube aqueous slurry with the functions of emulsifying and curing the epoxy resin comprises the following steps:
s1) respectively weighing carbon nano tubes, epoxy resin co-modified by amino group-containing and polyether, a stabilizer, a defoaming agent and water according to a proportion, mixing, pre-cutting at a high speed, standing and infiltrating to obtain a premix;
the weight portions of the components are as follows: carbon nanotubes: 1 part of amino group-containing polyether co-modified epoxy resin: 0.6-5 parts of stabilizer: 0.4-1 part of defoamer: 0.001-0.1 part of water: 6-30 parts;
the high-speed pre-cutting process parameters are as follows: the shearing speed is 2-40m/s, and the treatment time is 30min-6h;
s2) sequentially sanding, homogenizing, grinding and dispersing the premix of the S1) at high pressure to obtain carbon nano tube aqueous slurry with the functions of emulsifying and curing epoxy resin;
the sand grinding and high-pressure homogenizing grinding dispersing process specifically comprises the following steps:
the sand grinding medium is ceramic beads with the diameter of 0.2-2.0mm, and the linear speed of the dispersion disc is 2-40m/s; the high-pressure homogenizing treatment pressure is 20-100MPa, and is characterized in that: the structural formula of the amino-containing polyether co-modified epoxy resin in the S1) is shown in the following formula I:
Figure FDA0004138908230000011
wherein n=8 to 134;
R 1 is C 2 H 4 、C 6 H 12 、C 4 H 9 N、C 6 H 14 N 2 、C 8 H 19 N 3 、
Figure FDA0004138908230000012
Figure FDA0004138908230000013
At least one of (a) and (b);
Figure FDA0004138908230000021
a structure formed by losing two epoxy groups for the epoxy resin;
R 2 is that
Figure FDA0004138908230000022
Figure FDA0004138908230000023
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Figure FDA0004138908230000024
At least one of (a) and (b);
R 3 is H or CH 3 。
2. The method according to claim 1, characterized in that: the epoxy resin is phenolic epoxy resin or bisphenol A epoxy resin.
3. The method according to claim 1, characterized in that: the preparation method of the amino-and polyether-containing co-modified epoxy resin specifically comprises the following steps:
step 1) under the protection of inert gas, taking a solvent M as a reaction medium, gradually dropwise adding epoxy resin diluted by the solvent M into a mixed system of an epoxy resin amine curing agent and the solvent M, and reacting for 2-5 h at 50-100 ℃;
step 2) gradually dropwise adding the polyalcohol glycidyl ether into the reaction system in the step 1), continuing to react for 3-6h, and distilling under reduced pressure to remove the solvent M to obtain the amino-and polyether-containing co-modified epoxy resin.
4. A method according to claim 3, characterized in that: the solvent M is an organic solvent;
the epoxy resin is phenolic epoxy resin or bisphenol A epoxy resin;
the epoxy resin amine curing agent is aliphatic amine curing agent, polyether amine curing agent or alicyclic amine curing agent;
the polyalcohol glycidyl ether is one or more of polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether.
5. The method according to claim 4, wherein: the organic solvent is one or more of acetone, ethanol, toluene, xylene, propylene glycol monomethyl ether, ethylene glycol butyl ether and N, N' -dimethylformamide.
6. The method according to claim 1, characterized in that: the stabilizer in the S1) is one or more of cellulose, acacia, xanthan gum, carrageenan and sodium alginate;
the defoamer is mineral oil defoamer or polysiloxane defoamer.
7. The carbon nanotube aqueous slurry with the functions of emulsifying and curing epoxy resin prepared by the preparation method according to any one of claims 1-6 is applied to the emulsification and curing of epoxy resin, the preparation of carbon nanotube/aqueous epoxy composite materials or the application of conductive or antistatic nanocomposite coatings and adhesives.
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