CN113549298A - Synthetic resin with strong wear resistance and preparation method thereof - Google Patents
Synthetic resin with strong wear resistance and preparation method thereof Download PDFInfo
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- CN113549298A CN113549298A CN202110830876.9A CN202110830876A CN113549298A CN 113549298 A CN113549298 A CN 113549298A CN 202110830876 A CN202110830876 A CN 202110830876A CN 113549298 A CN113549298 A CN 113549298A
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Abstract
The invention discloses a synthetic resin with strong wear resistance and a preparation method thereof. The preparation method comprises the steps of pretreating a crude carbon nano tube, purifying the pretreated crude carbon nano tube by using alkali liquor and acid liquor, mixing the pretreated crude carbon nano tube with polydopamine, performing ultrasonic treatment, stirring, filtering and drying to obtain a modified carbon nano tube, mixing polyvinylidene fluoride with ethyl acetate, polydopamine and dimethylacetamide, performing stirring reaction, drying the mixture to obtain modified polyvinylidene fluoride, mixing the modified polyvinylidene fluoride with epoxy resin, stirring, standing for defoaming, performing injection molding and curing to obtain modified epoxy resin, mixing the modified carbon nano tube with the modified epoxy resin, performing stirring reaction, adding a curing agent, performing injection molding and curing, and demolding to obtain the synthetic resin with high wear resistance. The synthetic resin with strong wear resistance prepared by the invention has strong wear resistance and excellent mechanical property.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to synthetic resin with strong wear resistance and a preparation method thereof.
Background
The epoxy resin has excellent adhesion performance and is widely applied to the field of synthetic resin, so that the problem of the binding force between the reinforced material and the substrate is well solved. The performance of the synthetic resin, such as mechanical property, wear resistance, corrosion resistance, conductivity and the like, is improved by filling different modified materials. The synthetic resin has wide application prospect in the fields of building, electron, aerospace, petrochemical industry and military affairs.
The carbon nano tube has the characteristics of fibrous structure, large length-diameter ratio, high mechanical strength, low density and the like, and becomes an optimal reinforced modified material of the polymer. The proper amount of carbon nanotube can obviously improve the mechanical property of the synthetic resin, and overcomes the defects that the common inorganic filler has large use amount and can not simultaneously improve certain properties (such as rigidity, heat resistance, dimensional stability, toughness and the like).
Disclosure of Invention
The invention aims to provide a synthetic resin with strong wear resistance and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: the synthetic resin with high wear resistance is characterized by mainly comprising 15-25 parts by weight of modified carbon nanotubes, 15-25 parts by weight of modified polyvinylidene fluoride, 5-8 parts by weight of a curing agent and 30-50 parts by weight of modified epoxy resin.
As optimization, the modified carbon nanotube is prepared by blending purified carbon nanotubes and polydopamine; the purified carbon nano tube is prepared by pretreating a crude carbon nano tube and then purifying the pretreated crude carbon nano tube by using an acid-base solution; the polydopamine is prepared by carrying out polymerization reaction on dopamine under an alkaline condition and then drying.
As optimization, the modified epoxy resin is prepared by mixing epoxy resin E-44, polyvinylidene fluoride and diaminodiphenylmethane; the curing agent is one or a mixture of more of vinyl triamine, m-phenylenediamine, diaminodiphenylmethane and polyamide.
Preferably, the modified polyvinylidene fluoride is prepared by mixing polyvinylidene fluoride with ethyl acetate, polydopamine and dimethylacetamide.
As optimization, the synthetic resin with strong wear resistance mainly comprises the following raw material components in parts by weight: 20 parts of modified carbon nano tube, 22 parts of modified polyvinylidene fluoride, 8 parts of curing agent and 50 parts of modified epoxy resin.
As optimization, the preparation method of the synthetic resin with strong wear resistance mainly comprises the following preparation steps:
(1) pretreating a crude carbon nano tube, then putting the pretreated crude carbon nano tube into a sodium hydroxide solution, stirring, carrying out suction filtration to obtain a filter cake, washing the filter cake to be neutral, drying, and grinding to obtain refined carbon nano tube particles; adding the carbon nano tube into nitric acid for soaking, taking out, washing and drying to obtain a purified carbon nano tube;
(2) adding dopamine into a buffer solution, adjusting the pH value to be alkaline, stirring for reaction to obtain polydopamine, adding a carbon nano tube, performing ultrasonic dispersion, stirring, filtering and drying to obtain a modified carbon nano tube;
(3) mixing the modified polyvinylidene fluoride with epoxy resin, stirring, standing for defoaming, pouring into a mold, and curing to obtain modified epoxy resin;
(4) and (3) mixing the functionalized carbon nanotubes obtained in the step (2) with the modified epoxy resin obtained in the step (3), stirring at a high speed, heating and ultrasonically treating, adding a curing agent, stirring to obtain a black viscous colloid, injecting the black viscous colloid into a mold, curing and molding, and demolding to obtain the synthetic resin with high wear resistance.
As optimization, the preparation method of the synthetic resin with strong wear resistance mainly comprises the following preparation steps:
(1) mixing the pretreated carbon nano tube with 1mol/L sodium hydroxide solution according to the mass ratio of 1:1.2, uniformly stirring at room temperature by magnetic force, then neutralizing, filtering, washing, drying, grinding to obtain the carbon nano tube with the particle size of 30-50 nm, mixing the carbon nano tube with 1mol/L nitric acid solution according to the mass ratio of 1:1, ultrasonically dispersing for 2 hours at 35kHz, continuously soaking for 6 hours, then filtering to obtain a purified carbon nano tube blank, washing the purified carbon nano tube blank with deionized water until the washing solution is neutral, and carrying out vacuum drying on the obtained product at 80 ℃ to obtain the purified carbon nano tube;
(2) dispersing dopamine powder in a buffer solution with the mass of 100-200 times that of the dopamine powder, adjusting the pH value to 8.5, stirring at room temperature for reaction, then adding a purified carbon nanotube with the mass of 0.1 time that of the dopamine powder, ultrasonically dispersing at 30kHz for 30min, magnetically stirring for 24h, filtering, and drying at 80 ℃ for 2h to obtain a modified carbon nanotube;
(3) the modified polyvinylidene fluoride and the epoxy resin are mixed according to the mass ratio of 1: 3-1.2: 3, mixing, stirring at room temperature, standing for defoaming, and obtaining a mixture; finally, pouring the mixture into a silica gel mold and putting the silica gel mold into an oven at 80 ℃ for curing for 12 hours to obtain modified epoxy resin;
(4) mixing the modified carbon nanotube obtained in the step (2) with the modified epoxy resin obtained in the step (3) according to the mass ratio of 1: 100-2: 100, stirring the mixture for 1 hour at 3000rpm by a beater, then carrying out ultrasonic treatment for 2 hours at 100 ℃ and 30kHz, cooling the mixture, adding a curing agent vinyl triamine with the mass of 0.25 time of that of the modified epoxy resin, stirring and mixing the mixture to obtain black viscous colloid, continuing stirring the mixture uniformly by an electric stirrer, injecting the mixture into a mold, curing the mixture for 2 hours at 80 ℃, curing the mixture for 6 hours at 150 ℃, cooling and demolding the mixture to obtain the synthetic resin with strong wear resistance.
Preferably, the pretreatment in the crude carbon nanotubes in the step (1) is to put the crude carbon nanotubes into a ball mill, pulverize the crude carbon nanotubes for 2 hours at a rotation speed of 500rpm, and treat the pulverized crude carbon nanotubes for 30 minutes by using a high-speed airflow of 30m/s to obtain the bulky carbon nanotubes. Mixing the bulked carbon nano tube with ethanol according to the mass ratio of 1:100, cleaning for 30min under 30kHz ultrasound, washing for 3 times by using deionized water, then carrying out suction filtration, drying for 24h at 70 ℃, then putting into a tube furnace, introducing air, burning for 20min at 500 ℃, cooling and then taking out.
Preferably, the buffer solution in the step (2) is prepared by mixing trihydroxymethyl aminomethane and hydrochloric acid with the mass fraction of 30% according to the mass ratio of 1:1.
Optimally, the modified polyvinylidene fluoride in the step (3) is prepared by mixing polyvinylidene fluoride and ethyl acetate according to the mass ratio of 1:10, mixing the mixture in a beaker, adding polydopamine with the mass of 0.3-0.6 time of that of polyvinylidene fluoride and dimethylacetamide with the mass of 0.3-0.6 time of that of polyvinylidene fluoride into the beaker, stirring and reacting, and drying for 2 hours at 70 ℃ to obtain the modified polyvinylidene fluoride.
Compared with the prior art, the invention has the following beneficial effects:
the dopamine modified carbon nano tube is added when the wear-resistant synthetic resin is prepared, and the synthetic resin is prepared by blending epoxy resin and fluorine-containing polymer.
The method comprises the steps of firstly, modifying the carbon nano tube by dopamine, and forming a layer of polydopamine on the surface of the carbon nano tube due to the oxidative self-polymerization action of the dopamine, so that the surface of the carbon nano tube contains rich catechol groups, the conjugation effect between carbon chain molecules and synthetic resin molecules in the carbon nano tube is promoted, and the interface action between a filling material and an epoxy resin matrix is enhanced.
Secondly, diaminodiphenylmethane is added into high-concentration polyvinylidene fluoride, so that high-concentration polyvinylidene fluoride molecules are linked together through the action of partial dehydrofluorination among molecules, and modified polyvinylidene fluoride with a three-dimensional network structure is formed.
Finally, the carbon nano tube is added into the modified epoxy resin as a reinforcement, so that the stress borne by the epoxy resin matrix can be effectively transferred, the product has higher bending strength, the mechanical property is improved, meanwhile, the wall of the carbon nano tube contains a hollow and rolled structure similar to graphene, so that the carbon nano tube can be used as a solid lubricant to reduce the roughness of the surface of the matrix so as to reduce the friction coefficient, and the poly-dopamine and the diamino diphenyl methane can generate Michael addition reaction, so that the polyvinylidene fluoride is connected with the epoxy resin matrix through covalent bonds, a reaction platform is provided for the carbon nano tube, the epoxy resin matrix and the diamino diphenyl methane, the modified carbon nano tube is embedded in a cross-linked network formed by the polyvinylidene fluoride and the epoxy resin and is uniformly dispersed in the modified epoxy resin, and the molecular bonding force between the carbon nano tube and the epoxy resin is improved, further improving the wear resistance of the product.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method of the present invention, the following examples are given, and the method for testing each index of the synthetic resin having high abrasion resistance manufactured in the following examples is as follows:
mechanical properties: the synthetic resins having high abrasion resistance obtained in the respective examples and the products obtained in the comparative examples were cut into resins having a thickness of 15mm, and the compressive strength was measured and the presence or absence of cracks was observed.
The tribological performance is as follows: the synthetic resins with strong wear resistance obtained in each example and the products obtained in the comparative example were tested for tribological properties using an MPX-2000 disc pin type friction and wear tester.
Example 1
The synthetic resin with strong wear resistance mainly comprises 20 parts by weight of modified carbon nano tubes, 22 parts by weight of modified polyvinylidene fluoride, 8 parts by weight of curing agent and 50 parts by weight of modified epoxy resin
A preparation method of synthetic resin with strong wear resistance mainly comprises the following preparation steps:
(1) mixing the pretreated carbon nano tube with 1mol/L sodium hydroxide solution according to the mass ratio of 1:1.2, magnetically stirring uniformly at room temperature, then carrying out suction filtration to obtain a filter cake, washing the filter cake with deionized water until the washing solution is neutral, drying at the temperature of 100 ℃ to constant weight to obtain a carbon nano tube blank, grinding the carbon nano tube blank to obtain a carbon nano tube with the particle size of 40nm, mixing the carbon nano tube with 1mol/L nitric acid solution according to the mass ratio of 1:1, carrying out ultrasonic dispersion at 35kHz for 2 hours, continuing to soak for 6 hours, then carrying out suction filtration to obtain a purified carbon nano tube blank, washing the purified carbon nano tube blank with deionized water until the washing solution is neutral, and carrying out vacuum drying on the obtained product at the temperature of 80 ℃ to obtain a purified carbon nano tube;
(2) dispersing dopamine powder in a buffer solution with the mass 150 times that of the dopamine powder, adjusting the pH value to 8.5, stirring at room temperature for reaction, then adding a purified carbon nanotube with the mass 0.1 time that of the dopamine powder, ultrasonically dispersing at 30kHz for 30min, magnetically stirring for 24h, filtering, and drying at 80 ℃ for 2h to obtain a modified carbon nanotube;
(3) mixing the modified polyvinylidene fluoride and epoxy resin according to the mass ratio of 1:3, stirring at room temperature for reaction, standing for defoaming, and preparing a mixture; finally, pouring the mixture into a silica gel mold and putting the silica gel mold into an oven at 80 ℃ for curing for 12 hours to obtain modified epoxy resin;
(4) mixing the modified carbon nano tube obtained in the step (2) with the modified epoxy resin obtained in the step (3) according to the mass ratio of 1:100, stirring the mixture for 1 hour at 3000rpm by a beater, then carrying out ultrasonic treatment for 2 hours at 100 ℃ and 30kHz, cooling the mixture, adding a curing agent vinyl triamine of which the mass is 0.25 time that of the modified epoxy resin, stirring and mixing the mixture to obtain black viscous colloid, continuously stirring the black viscous colloid uniformly by an electric stirrer, injecting the black viscous colloid into a mold, curing the mixture for 2 hours at 80 ℃, curing the mixture for 6 hours at 150 ℃, cooling and demolding to obtain the synthetic resin with strong wear resistance.
Preferably, the pretreatment in the crude carbon nanotubes in the step (1) is to put the crude carbon nanotubes into a ball mill, pulverize the crude carbon nanotubes for 2 hours at a rotation speed of 500rpm, and treat the pulverized crude carbon nanotubes for 30 minutes by using a high-speed airflow of 30m/s to obtain the bulky carbon nanotubes. Mixing the bulked carbon nano tube with ethanol according to the mass ratio of 1:100, cleaning for 30min under 30kHz ultrasound, washing for 3 times by using deionized water, then carrying out suction filtration, drying for 24h at 70 ℃, then putting into a tube furnace, introducing air, burning for 20min at 500 ℃, cooling and then taking out to obtain the pretreated carbon nano tube.
As optimization, the buffer solution in the step (2) is prepared by mixing trihydroxymethyl aminomethane of which the mass is 0.6 time that of dopamine and hydrochloric acid of which the mass is 0.6 time that of dopamine.
Optimally, the modified polyvinylidene fluoride in the step (3) is prepared by mixing polyvinylidene fluoride and ethyl acetate according to the mass ratio of 1:10, mixing the mixture in a beaker, adding polydopamine with the mass of 0.3 time of that of polyvinylidene fluoride and dimethylacetamide with the mass of 0.3 time of that of polyvinylidene fluoride into the beaker, stirring and reacting, and drying for 2 hours at 70 ℃ to obtain the modified polyvinylidene fluoride.
Example 2
The synthetic resin with strong wear resistance mainly comprises 20 parts by weight of modified carbon nano tubes, 22 parts by weight of modified polyvinylidene fluoride, 8 parts by weight of curing agent and 50 parts by weight of modified epoxy resin
A preparation method of synthetic resin with strong wear resistance mainly comprises the following preparation steps:
(1) mixing the pretreated carbon nano tube with 1mol/L sodium hydroxide solution according to the mass ratio of 1:1.2, uniformly stirring at room temperature by magnetic force, then neutralizing, filtering, washing, drying, grinding to obtain the carbon nano tube with the particle size of 40nm, mixing the carbon nano tube with 1mol/L nitric acid solution according to the mass ratio of 1:1, carrying out ultrasonic dispersion for 2 hours at 35kHz, continuously soaking for 6 hours, cooling, neutralizing, filtering, washing with water to be neutral, and carrying out vacuum drying on the obtained product at 80 ℃ to obtain a purified carbon nano tube;
(2) mixing the modified polyvinylidene fluoride and epoxy resin according to the mass ratio of 1:3, stirring at room temperature for reaction, standing for defoaming, and preparing a mixture; finally, pouring the mixture into a silica gel mold and putting the silica gel mold into an oven at 80 ℃ for curing for 12 hours to obtain modified epoxy resin;
(3) mixing the purified carbon nano tube obtained in the step (1) with the modified epoxy resin obtained in the step (2) according to the mass ratio of 1:100, stirring the mixture for 1 hour at 3000rpm by a beater, then carrying out ultrasonic treatment for 2 hours at 100 ℃ and 30kHz, cooling the mixture, adding a curing agent vinyl triamine which is 0.25 time of the mass of the modified epoxy resin, stirring the mixture for reaction to obtain black viscous colloid, continuously stirring the black viscous colloid uniformly by an electric stirrer, injecting the mixture into a mold, curing the mixture for 2 hours at 80 ℃, curing the mixture for 6 hours at 150 ℃, cooling the mixture, and demolding the obtained product to obtain the synthetic resin with strong wear resistance.
Preferably, the pretreatment in the crude carbon nanotubes in the step (1) is to put the crude carbon nanotubes into a ball mill, pulverize the crude carbon nanotubes for 2 hours at a rotation speed of 500rpm, and treat the pulverized crude carbon nanotubes for 30 minutes by using a high-speed airflow of 30m/s to obtain the bulky carbon nanotubes. Mixing the bulked carbon nano tube with ethanol according to the mass ratio of 1:100, cleaning for 30min under 30kHz ultrasound, washing for 3 times by using deionized water, then carrying out suction filtration, drying for 24h at 70 ℃, then putting into a tube furnace, introducing air, burning for 20min at 500 ℃, cooling and then taking out to obtain the pretreated carbon nano tube.
Optimally, the modified polyvinylidene fluoride in the step (2) is prepared by mixing polyvinylidene fluoride and ethyl acetate according to the mass ratio of 1:10, mixing the mixture in a beaker, adding polydopamine with the mass of 0.3 time of that of polyvinylidene fluoride and dimethylacetamide with the mass of 0.3 time of that of polyvinylidene fluoride into the beaker, stirring and reacting, and drying for 2 hours at 70 ℃ to obtain the modified polyvinylidene fluoride.
Example 3
The synthetic resin with strong wear resistance mainly comprises 20 parts by weight of modified carbon nano tubes, 22 parts by weight of modified polyvinylidene fluoride, 8 parts by weight of curing agent and 50 parts by weight of modified epoxy resin
A preparation method of synthetic resin with strong wear resistance mainly comprises the following preparation steps:
(1) mixing the pretreated carbon nano tube with 1mol/L sodium hydroxide solution according to the mass ratio of 1:1.2, uniformly stirring at room temperature by magnetic force, then neutralizing, filtering, washing, drying, grinding to obtain the carbon nano tube with the particle size of 40nm, mixing the carbon nano tube with 1mol/L nitric acid solution according to the mass ratio of 1:1, carrying out ultrasonic dispersion for 2 hours at 35kHz, continuously soaking for 6 hours, cooling, neutralizing, filtering, washing with water to be neutral, and carrying out vacuum drying on the obtained product at 80 ℃ to obtain a purified carbon nano tube;
(2) dispersing dopamine powder in a buffer solution with the mass 150 times that of the dopamine powder, adjusting the pH value to 8.5, stirring at room temperature for reaction, then adding a purified carbon nanotube with the mass 0.1 time that of the dopamine powder, ultrasonically dispersing at 30kHz for 30min, magnetically stirring for 24h, filtering, and drying at 80 ℃ for 2h to obtain a modified carbon nanotube;
(3) mixing polyvinylidene fluoride and epoxy resin according to the mass ratio of 1:3, stirring at room temperature for reaction, standing for defoaming, and preparing a mixture; finally, pouring the mixture into a silica gel mold and putting the silica gel mold into an oven at 80 ℃ for curing for 12 hours to obtain modified epoxy resin;
(4) stirring the modified epoxy resin obtained in the step (3) at 3000rpm for 1h, then carrying out ultrasonic treatment at 100 ℃ for 2h by using 30kHz, cooling, adding curing agent vinyl triamine with the mass of 0.25 time that of the modified epoxy resin, stirring for reaction to obtain black viscous colloid, continuously stirring uniformly by using an electric stirrer, then injecting into a mold, curing at 80 ℃ for 2h, curing at 150 ℃ for 6h, cooling, and demolding to obtain the synthetic resin with strong wear resistance.
Preferably, the pretreatment in the crude carbon nanotubes in the step (1) is to put the crude carbon nanotubes into a ball mill, pulverize the crude carbon nanotubes for 2 hours at a rotation speed of 500rpm, and treat the pulverized crude carbon nanotubes for 30 minutes by using a high-speed airflow of 30m/s to obtain the bulky carbon nanotubes. Mixing the bulked carbon nano tube with ethanol according to the mass ratio of 1:100, cleaning for 30min under 30kHz ultrasound, washing for 3 times by using deionized water, then carrying out suction filtration, drying for 24h at 70 ℃, then putting into a tube furnace, introducing air, burning for 20min at 500 ℃, cooling and then taking out.
Preferably, the buffer solution in the step (2) is prepared by mixing trihydroxymethyl aminomethane and hydrochloric acid with the mass fraction of 30% according to the mass ratio of 1:1.
Comparative example
The synthetic resin with strong wear resistance mainly comprises 20 parts by weight of modified carbon nano tubes, 22 parts by weight of modified polyvinylidene fluoride, 8 parts by weight of curing agent and 50 parts by weight of modified epoxy resin
A preparation method of synthetic resin with strong wear resistance mainly comprises the following preparation steps:
(1) mixing the pretreated carbon nano tube with 1mol/L sodium hydroxide solution according to the mass ratio of 1:1.2, uniformly stirring at room temperature by magnetic force, then neutralizing, filtering, washing, drying, grinding to obtain the carbon nano tube with the particle size of 40nm, mixing the carbon nano tube with 1mol/L nitric acid solution according to the mass ratio of 1:1, carrying out ultrasonic dispersion for 2 hours at 35kHz, continuously soaking for 6 hours, cooling, neutralizing, filtering, washing with water to be neutral, and carrying out vacuum drying on the obtained product at 80 ℃ to obtain a purified carbon nano tube;
(2) mixing polyvinylidene fluoride and epoxy resin according to the mass ratio of 1:3, stirring at room temperature for reaction, standing for defoaming, and preparing a mixture; finally, pouring the mixture into a silica gel mold and putting the silica gel mold into an oven at 80 ℃ for curing for 12 hours to obtain modified epoxy resin;
(3) mixing the carbon nano tube obtained in the step (1) with the modified epoxy resin obtained in the step (2) according to the mass ratio of 1:100, stirring the mixture for 1 hour at 3000rpm by a beater, then carrying out ultrasonic treatment for 2 hours at 100 ℃ and 30kHz, cooling the mixture, adding a curing agent vinyl triamine which is 0.25 time of the mass of the modified epoxy resin, stirring the mixture for reaction to obtain black viscous colloid, continuously stirring the black viscous colloid uniformly by an electric stirrer, injecting the mixture into a mold, curing the mixture for 2 hours at 80 ℃, curing the mixture for 6 hours at 150 ℃, cooling the mixture, and demolding the obtained product to obtain the synthetic resin with strong wear resistance.
Preferably, the pretreatment in the crude carbon nanotubes in the step (1) is to put the crude carbon nanotubes into a ball mill, pulverize the crude carbon nanotubes for 2 hours at a rotation speed of 500rpm, and treat the pulverized crude carbon nanotubes for 30 minutes by using a high-speed airflow of 30m/s to obtain the bulky carbon nanotubes. Mixing the bulked carbon nano tube with ethanol according to the mass ratio of 1:100, cleaning for 30min under 30kHz ultrasound, washing for 3 times by using deionized water, then carrying out suction filtration, drying for 24h at 70 ℃, then putting into a tube furnace, introducing air, burning for 20min at 500 ℃, cooling and then taking out.
Examples of effects
The following table 1 shows the results of performance analysis of a synthetic resin having high abrasion resistance using examples 1 to 3 of the present invention and a comparative example.
From the comparison of the experimental data of example 1 and comparative example 1 in table 1, it can be found that the mechanical properties and tribological properties of the product can be effectively improved when the modified polyvinylidene fluoride and the modified carbon nanotube are added in the preparation of the synthetic resin with strong wear resistance; from the comparison of the experimental data of example 1 and example 2, it can be found that when the synthetic resin with strong wear resistance is prepared, the carbon nanotubes are not modified, so that the interface bonding force between the carbon nanotubes and the epoxy resin matrix is reduced, and the wear resistance and the mechanical property of the product are reduced; from the comparison of the experimental data of example 1 and example 2, it can be found that when the synthetic resin with strong wear resistance is prepared, the non-modified polyvinylidene fluoride is used, so that the polyvinylidene fluoride is not uniformly dispersed in the epoxy resin, and a firm three-dimensional network structure cannot be formed, thereby the wear resistance of the product is remarkably reduced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The synthetic resin with high wear resistance is characterized by mainly comprising 15-25 parts by weight of modified carbon nanotubes, 15-25 parts by weight of modified polyvinylidene fluoride, 5-8 parts by weight of a curing agent and 30-50 parts by weight of modified epoxy resin.
2. The synthetic resin of claim 1, wherein the modified carbon nanotubes are prepared by blending purified carbon nanotubes with polydopamine; the purified carbon nano tube is prepared by pretreating a crude carbon nano tube and then purifying the pretreated crude carbon nano tube by using an acid-base solution; the polydopamine is prepared by carrying out polymerization reaction on dopamine under an alkaline condition and then drying.
3. The synthetic resin with strong abrasion resistance as claimed in claim 2, wherein the modified epoxy resin is prepared by mixing epoxy resin E-44 with polyvinylidene fluoride and diaminodiphenylmethane; the curing agent is one or a mixture of more of vinyl triamine, m-phenylenediamine, diaminodiphenylmethane and polyamide.
4. The synthetic resin as claimed in claim 3, wherein the modified polyvinylidene fluoride is prepared by mixing polyvinylidene fluoride with ethyl acetate, polydopamine and dimethylacetamide.
5. The synthetic resin with strong wear resistance as claimed in claim 4, wherein the synthetic resin with strong wear resistance mainly comprises the following raw material components in parts by weight: 20 parts of modified carbon nano tube, 22 parts of modified polyvinylidene fluoride, 8 parts of curing agent and 50 parts of modified epoxy resin.
6. The preparation method of the synthetic resin with strong wear resistance is characterized by mainly comprising the following preparation steps:
(1) pretreating a crude carbon nano tube, then putting the pretreated crude carbon nano tube into a sodium hydroxide solution, stirring, carrying out suction filtration to obtain a filter cake, washing the filter cake to be neutral, drying, and grinding to obtain refined carbon nano tube particles; adding the carbon nano tube into nitric acid for soaking, taking out, washing and drying to obtain a purified carbon nano tube;
(2) adding dopamine into a buffer solution, adjusting the pH value to be alkaline, stirring for reaction to obtain polydopamine, adding a carbon nano tube, performing ultrasonic dispersion, stirring, filtering and drying to obtain a dopamine-functionalized carbon nano tube;
(3) mixing the modified polyvinylidene fluoride with epoxy resin, stirring, standing for defoaming, pouring into a mold, and curing to obtain modified epoxy resin;
(4) and (3) mixing the functionalized carbon nanotubes obtained in the step (2) with the modified epoxy resin obtained in the step (3), stirring at a high speed, heating and ultrasonically treating, adding a curing agent, stirring to obtain a black viscous colloid, injecting the black viscous colloid into a mold, curing and molding, and demolding to obtain the synthetic resin with high wear resistance.
7. The method for preparing the synthetic resin with strong abrasion resistance according to claim 6, wherein the method for preparing the synthetic resin with strong abrasion resistance mainly comprises the following steps:
(1) mixing the pretreated carbon nano tube with 1mol/L sodium hydroxide solution according to the mass ratio of 1:1.2, magnetically stirring uniformly at room temperature, then carrying out suction filtration to obtain a filter cake, washing the filter cake with deionized water until the washing solution is neutral, drying at the temperature of 100 ℃ to constant weight to obtain a carbon nano tube blank, grinding the carbon nano tube blank to the particle size of 30-50 nm to obtain a carbon nano tube, mixing the carbon nano tube with 1mol/L nitric acid solution according to the mass ratio of 1:1, carrying out ultrasonic dispersion at 35kHz for 2h, continuing to soak for 6h, then carrying out suction filtration to obtain a purified carbon nano tube blank, washing the purified carbon nano tube blank with deionized water until the washing solution is neutral, and carrying out vacuum drying on the obtained product at the temperature of 80 ℃ to obtain a purified carbon nano tube;
(2) dispersing dopamine powder in a buffer solution with the mass of 100-200 times that of the dopamine powder, adjusting the pH value to 8.5, stirring at room temperature for reaction, then adding a purified carbon nanotube with the mass of 0.1 time that of the dopamine powder, ultrasonically dispersing at 30kHz for 30min, magnetically stirring for 24h, filtering, and drying at 80 ℃ for 2h to obtain a modified carbon nanotube;
(3) the modified polyvinylidene fluoride and the epoxy resin are mixed according to the mass ratio of 1: 3-1.2: 3, mixing, stirring at room temperature, standing for defoaming, and obtaining a mixture; finally, pouring the mixture into a silica gel mold and putting the silica gel mold into an oven at 80 ℃ for curing for 12 hours to obtain modified epoxy resin;
(4) mixing the modified carbon nanotube obtained in the step (2) with the modified epoxy resin obtained in the step (3) according to the mass ratio of 1: 100-2: 100, stirring the mixture for 1 hour at 3000rpm by a beater, then carrying out ultrasonic treatment for 2 hours at 100 ℃ and 30kHz, cooling the mixture, adding a curing agent vinyl triamine with the mass of 0.25 time of that of the modified epoxy resin, stirring and mixing the mixture to obtain black viscous colloid, continuing stirring the mixture uniformly by an electric stirrer, injecting the mixture into a mold, curing the mixture for 2 hours at 80 ℃, curing the mixture for 6 hours at 150 ℃, cooling and demolding to obtain the synthetic resin with strong wear resistance.
8. The method of claim 7, wherein the pre-treating step (1) comprises placing the carbon nanotubes into a ball mill, pulverizing at 500rpm for 2h, and treating with 30m/s high-speed air for 30min to obtain bulked carbon nanotubes; mixing the bulked carbon nano tube with ethanol according to the mass ratio of 1:100, cleaning for 30min under 30kHz ultrasound, washing for 3 times by using deionized water, then carrying out suction filtration, drying for 24h at 70 ℃, then putting into a tube furnace, introducing air, burning for 20min at 500 ℃, cooling and then taking out to obtain the pretreated carbon nano tube.
9. The method for preparing a synthetic resin with high wear resistance according to claim 7, wherein the buffer solution in the step (2) is prepared by mixing tris (hydroxymethyl) aminomethane and 30% hydrochloric acid by mass fraction at a mass ratio of 1:1.
10. The method for preparing the synthetic resin with strong abrasion resistance according to claim 7, wherein the modified polyvinylidene fluoride prepared in the step (3) is prepared by mixing polyvinylidene fluoride and ethyl acetate according to a mass ratio of 1:10, mixing the mixture in a beaker, adding polydopamine with the mass of 0.3-0.6 time of that of polyvinylidene fluoride and dimethylacetamide with the mass of 0.3-0.6 time of that of polyvinylidene fluoride into the beaker, stirring and reacting, and drying for 2 hours at 70 ℃ to obtain the modified polyvinylidene fluoride.
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