CN114773790B - Graphene epoxy resin polymer material and preparation method and application thereof - Google Patents
Graphene epoxy resin polymer material and preparation method and application thereof Download PDFInfo
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Abstract
The application relates to the technical field of plastic toy processing, and particularly discloses a graphene epoxy resin polymer material and a preparation method and application thereof. The graphene epoxy resin polymer material is mainly prepared from the following raw materials in parts by weight: 60-80 parts of epoxy resin, 15-20 parts of butyl glycidyl ether, 80-90 parts of anhydride curing agent, 3-8 parts of accelerator, 1-5 parts of organosilicon defoamer, 6-10 parts of flexibilizer, 2-4 parts of silane coupling agent, 2-4 parts of dispersing agent, 10-20 parts of functionalized graphene and 30-40 parts of silane coupling agent modified spherical silica micropowder; the functionalized graphene is obtained by sequentially treating graphene oxide with silicon dioxide, polyether amine and hydrazine hydrate. The high polymer material has higher tensile strength, fracture toughness and wear resistance, shows excellent comprehensive performance and meets market demands.
Description
Technical Field
The application relates to the technical field of plastic toy processing, in particular to a graphene epoxy resin polymer material and a preparation method and application thereof.
Background
With the development of society, toys have entered into thousands of households. The toy can accompany the growth of children, and can also entertain consumption and relieve pressure. Toys can be classified into metal toys, plastic toys, wooden toys, flannelette toys, etc. according to materials. The plastic toy is generally processed by adopting a high polymer material, and the epoxy resin is widely applied to the processing of the plastic toy due to the advantages of good adhesiveness, low shrinkage and easiness in processing and molding. The raw materials of the existing epoxy resin polymer material are epoxy resin, reactive diluent, curing agent and accelerator. The inventor finds that after the polymer material is processed into the plastic toy in actual processing, the wear resistance is insufficient, the service life of the plastic toy is influenced, and the tensile strength of the plastic toy is still to be further improved.
Disclosure of Invention
In order to increase the wear resistance and tensile strength of a high polymer material, the application provides a graphene epoxy resin high polymer material, and a preparation method and application thereof.
In a first aspect, the application provides a graphene epoxy resin polymer material, which adopts the following technical scheme: the graphene epoxy resin polymer material is mainly prepared from the following raw materials in parts by weight: 60-80 parts of epoxy resin, 15-20 parts of butyl glycidyl ether, 80-90 parts of anhydride curing agent, 3-8 parts of accelerator, 1-5 parts of organosilicon defoamer, 6-10 parts of flexibilizer, 2-4 parts of silane coupling agent, 2-4 parts of dispersing agent, 10-20 parts of functionalized graphene and 30-40 parts of silane coupling agent modified spherical silica micropowder; the functionalized graphene is obtained by sequentially treating graphene oxide with silicon dioxide, polyether amine and hydrazine hydrate.
The graphene epoxy resin polymer material has higher tensile strength and fracture toughness through the synergistic effect between the raw materials, wherein the tensile strength is more than 130MPa, and the fracture toughness is more than 2.1MPa 1/2 . But also has higher wear resistance, and the wear rate is less than 1.3 percent. The high polymer material has good comprehensive performance and meets the market demand.
The functionalized graphene and the silane coupling agent modified spherical silica micropowder are added into the raw materials, so that the tensile strength, fracture toughness and wear resistance of the high polymer material can be improved. Further adding a silane coupling agent, and improving the wettability of the functionalized graphene and the silane coupling agent modified spherical silica micropowder. The dispersing agent is added, so that the surface energy of the spherical silica micropowder modified by the functionalized graphene and the silane coupling agent can be reduced, the dispersing effect is enhanced, and the excellent wetting and flocculation control effects can be achieved. The synergy between the silane coupling agent and the dispersing agent is combined, the fluidity and the interface bonding strength of the raw materials are enhanced, and the mechanical property of the high polymer material is improved.
According to the functionalized graphene disclosed by the application, firstly, graphene oxide is grafted onto silicon dioxide, then polyether amine is utilized to graft polyether amine onto the graphene oxide and the silicon dioxide, and then hydrazine hydrate is utilized to reduce the graphene oxide to form graphene, so that not only is the bonding strength of the graphene and the silicon dioxide increased, but also the compatibility of the functionalized graphene and raw materials is increased, the use effect of the functionalized graphene is improved, the tensile strength, the fracture toughness and the wear resistance of a high polymer material are further enhanced, and the application range is enlarged.
Optionally, the functionalized graphene is prepared by the following method:
s1, adding silicon dioxide into water, and performing ultrasonic treatment for 30-60min to obtain silicon dioxide dispersion liquid;
s2, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide into water, stirring and uniformly mixing, then adding graphene oxide, and carrying out ultrasonic treatment for 30-60min to obtain graphene oxide dispersion liquid;
s3, adding graphene oxide dispersion liquid into the silicon dioxide dispersion liquid, stirring for 20-25 hours, then adding polyether amine, stirring for 30-60 minutes, heating to 50-70 ℃, stirring for 10-15 hours, and concentrating to 0.1-0.3 times of the original volume to obtain a mixture;
s4, adding a hydrazine hydrate solution into water, stirring and uniformly mixing, then adding the mixture, carrying out ultrasonic treatment for 30-60min, heating to 90-100 ℃, stirring for 10-15h, filtering and drying to obtain the functionalized graphene.
Optionally, the weight ratio of the silicon dioxide, the graphene oxide, the polyether amine and the hydrazine hydrate solution is 4 (0.3-0.8), 8-13 and 4-6, and the mass fraction of the hydrazine in the hydrazine hydrate solution is 60-80%.
By adopting the technical scheme, the preparation and control of the functionalized graphene are facilitated. Meanwhile, the silica and the graphene oxide are dispersed in advance, so that uniformity of the dispersion of the silica and the graphene oxide is facilitated. And the silicon dioxide dispersion liquid and the graphene oxide dispersion liquid are mixed, so that uniformity of silicon dioxide and graphene oxide mixed materials is facilitated. When the graphene oxide is dispersed, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide are added, so that the groups on the surface of the graphene oxide can be activated, the interaction between the graphene oxide and silicon dioxide is increased, the interaction between the graphene oxide and polyether amine is also enhanced, and the performance and the use effect of the functionalized graphene are improved.
Further, the weight ratio of graphene oxide to silicon dioxide to polyether amine to hydrazine hydrate solution is 4:0.5:10:5, and the mass fraction of hydrazine in the hydrazine hydrate solution is 80%.
In the step S1, the weight ratio of the silicon dioxide to the water is 4 (150-250).
In the step S2, the weight ratio of graphene oxide to water to 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide to N-hydroxysuccinimide is (0.3-0.8), 150-250, 0.1-0.5 and 0.1-0.5.
In the step S4, the weight ratio of the hydrazine hydrate solution to the water is (4-6) (150-250).
Optionally, the silane coupling agent modified spherical silica micropowder is prepared by the following method: adding the silane coupling agent into water, stirring and uniformly mixing, then adding spherical silicon micropowder, carrying out ultrasonic treatment for 30-60min, heating to 50-70 ℃, stirring for 5-10h, filtering and drying to obtain the silane coupling agent modified spherical silicon micropowder.
Optionally, the weight ratio of the spherical silicon micro powder to the silane coupling agent is 4 (0.5-1).
By adopting the technical scheme, the preparation and control of the silane coupling agent modified spherical silica micropowder are facilitated.
Further, the weight ratio of the spherical silica powder to the silane coupling agent is 4:0.8.
The weight ratio of the spherical silicon micropowder to the water is 4 (150-250).
Optionally, the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane; the dispersing agent is Pick BYK-181.
By adopting the technical scheme, the selection of the silane coupling agent and the dispersing agent is facilitated, the interaction of gamma- (2, 3-glycidoxy) propyl trimethoxy silane, pick BYK-181 and functionalized graphene is improved, and the tensile strength and fracture toughness of the polymer material are improved.
Optionally, the toughening agent is a thermoplastic resin.
By adopting the technical scheme, the toughness of the high polymer material is effectively increased, and the service stability and the service life of the high polymer material are improved.
Further, the thermoplastic resin is one or more of PESU and PES-C, PSU. PESU is preferred.
Optionally, the epoxy resin is a mixture of hydrogenated bisphenol A epoxy resin, tetrahydrodiglycidyl phthalate and bis ((3, 4-epoxycyclohexyl) methyl) adipate, and the weight ratio of the hydrogenated bisphenol A epoxy resin, the tetrahydrodiglycidyl phthalate and the bis ((3, 4-epoxycyclohexyl) methyl) adipate is (4-6): 2-4): 1-3.
By adopting the technical scheme, the hydrogenated bisphenol A epoxy resin is bisphenol epoxy resin, the tetrahydrophthalic acid diglycidyl ester is glycidyl ester epoxy resin, the bis ((3, 4-epoxycyclohexyl) methyl) adipate is alicyclic epoxy resin, and the hydrogenated bisphenol A epoxy resin, the tetrahydrophthalic acid diglycidyl ester and the bis ((3, 4-epoxycyclohexyl) methyl) adipate are utilized to synergistically increase the viscosity and the fluidity of raw materials, so that the raw materials keep good viscosity and fluidity, the influence on the fluidity of the raw materials due to the addition of the functionalized graphene and the silane coupling agent modified spherical silica micropowder is reduced, the dispersion uniformity of the functionalized graphene and the silane coupling agent modified spherical silica micropowder is improved, and the mechanical property of a high polymer material is improved.
Further, the anhydride curing agent is one or more of dodecenyl succinic anhydride, methyl tetrahydrophthalic anhydride and ketobenzene tetracarboxylic dianhydride. Dodecenyl succinic anhydride is preferred, in particular linear LDDSA.
The accelerator is one or more of triphenylphosphine, imidazole accelerator and tertiary amine accelerator. Triphenylphosphine is preferred.
In a second aspect, the present application provides a preparation method of the graphene epoxy resin polymer material, which adopts the following technical scheme:
the preparation method of the graphene epoxy resin polymer material comprises the following steps: at 150-170 ℃, epoxy resin, butyl glycidyl ether, an organosilicon defoamer, a toughening agent, a silane coupling agent, a dispersing agent, functionalized graphene and silane coupling agent modified spherical silica micropowder are stirred for 30-60min; then heating to 180-200 ℃, adding an anhydride curing agent and an accelerator, continuously stirring for 50-100min, and cooling to obtain the high polymer material.
Through adopting above-mentioned technical scheme, mix epoxy, butyl glycidyl ether, organosilicon defoamer, toughener, silane coupling agent, dispersant, functional graphene, silane coupling agent modified spherical silica micropowder in advance, then add anhydride curing agent, accelerator, be convenient for the processing and the control of macromolecular material, help the dispersion of raw materials moreover, improve the homogeneity of compounding, and then increase the performance of macromolecular material.
In a third aspect, the present application provides a plastic toy, which adopts the following technical scheme:
a plastic toy is processed by the graphene epoxy resin polymer material.
By adopting the technical scheme, the application of the graphene epoxy resin polymer material and the processing of the plastic toy are facilitated.
In summary, the application has at least the following advantages:
1. according to the graphene epoxy resin polymer material, through the synergistic effect of the raw materials, the tensile strength is more than 130MPa, and the fracture toughness is more than 2.1MPa.m 1/2 The wear rate is less than 1.3%, the high tensile strength, fracture toughness and wear resistance are shown, the high-strength wear-resistant composite material has excellent comprehensive performance, and the market demand is met.
2. According to the preparation method of the functionalized graphene, the silicon dioxide dispersion liquid and the graphene oxide dispersion liquid are prepared in advance, so that the silicon dioxide and graphene oxide dispersion uniformity and the mixing uniformity are facilitated, and the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and the N-hydroxysuccinimide are added into the graphene oxide dispersion liquid to activate the surface groups, so that the use effect of the functionalized graphene is enhanced, and the mechanical property of the polymer material is improved.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation example
Preparation example 1
A functionalized graphene prepared by the following method:
s1, adding 4kg of silicon dioxide into 200kg of water, and performing ultrasonic treatment for 50min to obtain a silicon dioxide dispersion liquid.
Wherein the silicon dioxide is selected from Hangzhou Cudrania tricuspidata new material.
S2, adding 0.3kg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and 0.3kg of N-hydroxysuccinimide into 200kg of water, and stirring for 30min. Then adding 0.5kg of graphene oxide, and carrying out ultrasonic treatment for 50min to obtain graphene oxide dispersion liquid.
Wherein the graphene oxide is selected from Hangzhou cudrania new materials.
And S3, adding graphene oxide dispersion liquid into the silicon dioxide dispersion liquid, and stirring for 24 hours. Then 10kg of polyetheramine was added and the mixture was stirred for 50min. Heating to 60 ℃, and stirring for 12h. And then concentrated to 0.2 times the original volume to obtain a mixture.
Wherein the polyetheramine is polyetheramine D230 and is selected from Jinan Ming Wei chemical industry.
S4, adding 5kg of hydrazine hydrate solution into 200kg of water, and stirring for 30min. The mixture was then added and sonicated for 50min. Heating to 95 ℃, and stirring for 12h. And filtering and drying to obtain the functionalized graphene.
Wherein the mass fraction of hydrazine in the hydrazine hydrate solution is 80%.
Preparation example 2
A functionalized graphene differs from preparation example 1 in that step S2 is different.
The step S2 specifically comprises the following steps: 0.5kg of graphene oxide is added into 200kg of water, and ultrasonic treatment is carried out for 50min, so as to obtain graphene oxide dispersion liquid.
Preparation example 3
A silane coupling agent modified spherical silicon micropowder is prepared by the following method:
0.8kg of a silane coupling agent was added to 200kg of water, and the mixture was stirred for 30 minutes. Then adding 4kg of spherical silica micropowder, and carrying out ultrasonic treatment for 50min. Heating to 60 ℃, and stirring for 8 hours. Filtering and drying to obtain the silane coupling agent modified spherical silica micropowder.
Wherein the silane coupling agent is gamma- (2, 3-glycidoxy) propyl trimethoxy silane; the spherical silica micropowder is selected from Guangdong Yongfeng chemical industry.
Examples
TABLE 1 content of Polymer materials (Unit: 10 g)
| Examples | Example 1 | Example 2 | Example 3 |
| Epoxy resin | 60 | 70 | 80 |
| Butyl glycidyl ether | 18 | 20 | 15 |
| Anhydride curing agent | 85 | 80 | 90 |
| Accelerating agent | 5 | 3 | 8 |
| Organosilicon defoamer | 2 | 5 | 1 |
| Toughening agent | 8 | 10 | 6 |
| Silane coupling agent | 3 | 2 | 4 |
| Dispersing agent | 3 | 4 | 2 |
| Functionalized graphene | 15 | 20 | 10 |
| Silane coupling agent modified spherical silicon micropowder | 35 | 30 | 40 |
Example 1
The raw material ratio of the graphene epoxy resin polymer material is shown in table 1.
Wherein the epoxy resin is a mixture of hydrogenated bisphenol A epoxy resin, tetrahydrodiglycidyl phthalate and bis ((3, 4-epoxycyclohexyl) methyl) adipate, and the weight ratio of the hydrogenated bisphenol A epoxy resin to the tetrahydrodiglycidyl phthalate to the bis ((3, 4-epoxycyclohexyl) methyl) adipate is 5:3:2. The hydrogenated bisphenol A epoxy resin is selected from Hubei world energy chemical technology.
The anhydride curing agent is dodecenyl succinic anhydride, and specifically is linear LDDSA; the accelerator is triphenylphosphine; the organic silicon defoamer is defoamer THIX-278 and is selected from the technology of Hengxin chemical industry of the tobacco stand; the toughening agent is thermoplastic resin, in particular to PESU E1010 of basf; the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane; the dispersing agent is Pick BYK-181; the functionalized graphene is prepared by adopting a preparation example 1; the silane coupling agent modified spherical silicon micropowder is prepared by adopting a preparation example 3.
The preparation method of the graphene epoxy resin polymer material comprises the following steps:
at 160 ℃, epoxy resin, butyl glycidyl ether, an organosilicon defoamer, a toughening agent, a silane coupling agent, a dispersing agent, functionalized graphene and silane coupling agent modified spherical silica micropowder are stirred for 50min. Then heating to 190 ℃, adding the anhydride curing agent and the accelerator, and continuing stirring for 80min. Cooling to 25 deg.c to obtain polymer material.
Examples 2 to 3
The graphene epoxy resin polymer material is different from the polymer material in example 1 in that the raw material ratio of the polymer material is different, and the raw material ratio of the polymer material is shown in table 1.
Example 4
The graphene epoxy resin polymer material is different from the polymer material in embodiment 1 in that functionalized graphene in the raw material of the polymer material is prepared by adopting preparation example 2.
Example 5
A graphene epoxy resin polymer material is different from the polymer material in example 1 in that the epoxy resin in the raw material of the polymer material is hydrogenated bisphenol A epoxy resin.
Example 6
The graphene epoxy resin polymer material is different from the graphene epoxy resin polymer material in that epoxy resin in the raw material of the polymer material is a mixture of hydrogenated bisphenol A epoxy resin and tetrahydrophthalic acid diglycidyl ester, and the weight ratio of the hydrogenated bisphenol A epoxy resin to the tetrahydrophthalic acid diglycidyl ester is 5:3.
Comparative example
Comparative example 1
A graphene-epoxy polymer material is different from example 1 in that functionalized graphene is not added to the raw material of the polymer material.
Comparative example 2
The graphene epoxy resin polymer material is different from the polymer material in example 1 in that the silane coupling agent modified spherical silica powder is not added in the raw material of the polymer material.
Comparative example 3
The graphene epoxy resin polymer material is different from the polymer material in the embodiment 1 in that functionalized graphene and silane coupling agent modified spherical silica micropowder are not added into the raw materials of the polymer material.
Comparative example 4
A graphene epoxy resin polymer material is different from the polymer material in that the functional graphene is replaced by equivalent graphene in raw materials of the polymer material.
The graphene is prepared by the following method:
to 200kg of water, 5kg of a hydrazine hydrate solution was added, and the mixture was stirred for 30 minutes. Then 0.5kg of graphene oxide was added and sonicated for 50min. Heating to 95 ℃, and stirring for 12h. And (5) filtering, drying and graphene.
Wherein the mass fraction of hydrazine in the hydrazine hydrate solution is 80%; the graphene oxide is selected from Hangzhou cudrania new materials.
Comparative example 5
The difference between the graphene epoxy resin polymer material and the embodiment 1 is that in the preparation method of the functionalized graphene, the step S3 is different from the raw material of the polymer material.
The step S3 specifically comprises the following steps: and adding graphene oxide dispersion liquid into the silicon dioxide dispersion liquid, and stirring for 24 hours. Heating to 60 ℃, and stirring for 12h. And then concentrated to 0.2 times the original volume to obtain a mixture.
Comparative example 6
A graphene epoxy resin polymer material is different from example 1 in that the raw materials of the polymer material and the functionalized graphene are different. The functionalized graphene is prepared by the following method:
s1, adding 0.3kg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and 0.3kg of N-hydroxysuccinimide into 200kg of water, and stirring for 30min. Then adding 0.5kg of graphene oxide, and carrying out ultrasonic treatment for 50min to obtain graphene oxide dispersion liquid.
Wherein the graphene oxide is selected from Hangzhou cudrania new materials.
S3, adding 10kg of polyether amine into the graphene oxide dispersion liquid, and stirring for 50min. Heating to 60 ℃, and stirring for 12h. And then concentrated to 0.2 times the original volume to obtain a mixture.
Wherein the polyetheramine is polyetheramine D230 and is selected from Jinan Ming Wei chemical industry.
S4, adding 5kg of hydrazine hydrate solution into 200kg of water, and stirring for 30min. The mixture was then added and sonicated for 50min. Heating to 95 ℃, and stirring for 12h. And filtering and drying to obtain the functionalized graphene.
Wherein the mass fraction of hydrazine in the hydrazine hydrate solution is 80%.
Comparative example 7
A graphene epoxy resin polymer material is different from example 1 in that a silane coupling agent is not added to the raw material of the polymer material.
Comparative example 8
A graphene epoxy resin polymer material is different from example 1 in that a dispersing agent is not added to the raw material of the polymer material.
Comparative example 9
The graphene epoxy resin polymer material is different from the polymer material in example 1 in that a silane coupling agent, a dispersing agent and functionalized graphene are not added into the raw materials of the polymer material.
Performance test
The polymer materials obtained in examples 1 to 6 and comparative examples 1 to 9 were used as samples, and the following performance tests were carried out on the samples, and the test results are shown in Table 2.
Wherein, the tensile strength is detected according to GB/T1040; the determination of fracture toughness is performed according to ASTM D5045; the abrasion resistance was characterized by abrasion rate, and abrasion rate= (weight before abrasion of sample-weight after abrasion of sample)/weight before abrasion of sample×100%, the lower the abrasion rate, the higher the abrasion resistance was.
TABLE 2 detection results
| Detecting items | Tensile strength/(MPa) | Fracture toughness/(MPa.m) 1/2 ) | Wear rate/(%) |
| Example 1 | 153 | 2.48 | 1.03 |
| Example 2 | 146 | 2.34 | 1.05 |
| Example 3 | 138 | 2.21 | 1.22 |
| Example 4 | 136 | 2.18 | 1.06 |
| Example 5 | 132 | 2.11 | 1.13 |
| Example 6 | 144 | 2.31 | 1.09 |
| Comparative example 1 | 104 | 1.58 | 1.89 |
| Comparative example 2 | 133 | 1.89 | 1.55 |
| Comparative example 3 | 93 | 1.46 | 2.02 |
| Comparative example 4 | 113 | 1.72 | 1.64 |
| Comparative example 5 | 128 | 2.02 | 1.52 |
| Comparative example 6 | 121 | 1.88 | 1.31 |
| Comparative example 7 | 125 | 1.94 | 1.15 |
| Comparative example 8 | 121 | 1.89 | 1.21 |
| Comparative example 9 | 91 | 1.27 | 1.94 |
As can be seen from Table 2, the graphene epoxy resin polymer material has higher tensile strength and fracture toughness, the tensile strength is 132-146MPa, and the fracture toughness is 2.11-2.48MPa.m 1/2 . But also has lower wear rate of 1.03-1.22%, and shows excellent wear resistance. The polymer material has better comprehensive performance and meets the market demand.
Comparing example 1 with comparative examples 1 to 3, it can be seen that the tensile strength, fracture toughness and abrasion resistance of the polymer material can be enhanced by adding functionalized graphene and silane coupling agent modified spherical silica powder to the raw materials and utilizing the synergistic effect therebetween. And then, in combination with comparative examples 7-9, adding a silane coupling agent, a dispersing agent and functionalized graphene into the raw materials, so as to further increase the mechanical properties of the high polymer material and increase the application range of the high polymer material.
Comparing comparative example 1 with comparative example 4, it can be seen that the addition of graphene to the raw material can improve the tensile strength and fracture toughness of the polymer material, and also can increase the abrasion resistance. And in combination with comparative examples 5-6 and example 1, the graphene oxide is further treated by adopting silicon dioxide, polyether amine and hydrazine hydrate, so that the mechanical properties of the polymer material are obviously improved. And in combination with the embodiment 4, the graphene oxide is treated by adopting 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide, so that the groups on the surface of the graphene oxide are activated, and the using effect of the functionalized graphene is effectively improved.
Comparing examples 1 and examples 5-6, it can be seen that the epoxy resin is a mixture of hydrogenated bisphenol A epoxy resin, tetrahydrodiglycidyl phthalate, bis ((3, 4-epoxycyclohexyl) methyl) adipate, and can make the polymer material exhibit better mechanical properties.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (8)
1. A graphene epoxy resin polymer material is characterized in that: the composite material is prepared from the following raw materials in parts by weight: 60-80 parts of epoxy resin, 15-20 parts of butyl glycidyl ether, 80-90 parts of anhydride curing agent, 3-8 parts of accelerator, 1-5 parts of organosilicon defoamer, 6-10 parts of flexibilizer, 2-4 parts of silane coupling agent, 2-4 parts of dispersing agent, 10-20 parts of functionalized graphene and 30-40 parts of silane coupling agent modified spherical silica micropowder; the functionalized graphene is obtained by sequentially treating graphene oxide with silicon dioxide, polyether amine and hydrazine hydrate;
the functionalized graphene is prepared by the following method:
s1, adding silicon dioxide into water, and performing ultrasonic treatment for 30-60min to obtain silicon dioxide dispersion liquid;
s2, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide into water, stirring and uniformly mixing, then adding graphene oxide, and carrying out ultrasonic treatment for 30-60min to obtain graphene oxide dispersion liquid;
s3, adding graphene oxide dispersion liquid into the silicon dioxide dispersion liquid, stirring for 20-25 hours, then adding polyether amine, stirring for 30-60 minutes, heating to 50-70 ℃, stirring for 10-15 hours, and concentrating to 0.1-0.3 times of the original volume to obtain a mixture;
s4, adding a hydrazine hydrate solution into water, stirring and uniformly mixing, then adding the mixture, carrying out ultrasonic treatment for 30-60min, heating to 90-100 ℃, stirring for 10-15h, filtering and drying to obtain the functionalized graphene;
the weight ratio of the silicon dioxide, graphene oxide, polyether amine and hydrazine hydrate solution is 4 (0.3-0.8) (8-13) (4-6), and the mass fraction of hydrazine in the hydrazine hydrate solution is 60-80%.
2. The graphene epoxy resin polymer material according to claim 1, wherein: the silane coupling agent modified spherical silicon micropowder is prepared by the following method: adding the silane coupling agent into water, stirring and uniformly mixing, then adding spherical silicon micropowder, carrying out ultrasonic treatment for 30-60min, heating to 50-70 ℃, stirring for 5-10h, filtering and drying to obtain the silane coupling agent modified spherical silicon micropowder.
3. The graphene epoxy resin polymer material according to claim 2, wherein: the weight ratio of the spherical silicon micro powder to the silane coupling agent is 4 (0.5-1).
4. The graphene epoxy resin polymer material according to claim 1, wherein: the silane coupling agent is gamma- (2, 3-glycidoxy) propyl trimethoxy silane; the dispersing agent is Pick BYK-181.
5. The graphene epoxy resin polymer material according to claim 1, wherein: the toughening agent is thermoplastic resin.
6. The graphene epoxy resin polymer material according to claim 1, wherein: the epoxy resin is a mixture of hydrogenated bisphenol A epoxy resin, tetrahydrodiglycidyl phthalate and bis ((3, 4-epoxycyclohexyl) methyl) adipate, and the weight ratio of the hydrogenated bisphenol A epoxy resin to the tetrahydrodiglycidyl phthalate to the bis ((3, 4-epoxycyclohexyl) methyl) adipate is (4-6): 2-4): 1-3.
7. A method for preparing the graphene epoxy resin polymer material according to any one of claims 1 to 6, which is characterized in that: the method comprises the following steps: at 150-170 ℃, epoxy resin, butyl glycidyl ether, an organosilicon defoamer, a toughening agent, a silane coupling agent, a dispersing agent, functionalized graphene and silane coupling agent modified spherical silica micropowder are stirred for 30-60min; then heating to 180-200 ℃, adding an anhydride curing agent and an accelerator, continuously stirring for 50-100min, and cooling to obtain the high polymer material.
8. A plastic toy, characterized in that: is processed by the graphene epoxy resin polymer material according to any one of claims 1 to 6.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014032378A1 (en) * | 2012-08-25 | 2014-03-06 | 华南理工大学 | Methods for preparing functionalized graphene and the composite electroconductive glue thereof |
| CN103897345A (en) * | 2014-03-10 | 2014-07-02 | 哈尔滨理工大学 | Preparation method of TiO2/PU-EP composite material |
| CN107459774A (en) * | 2017-05-24 | 2017-12-12 | 浙江创元生态环保技术有限公司 | A kind of graphene/nanometer silica/epoxy resin composite material and preparation method thereof |
| CN111944387A (en) * | 2020-09-04 | 2020-11-17 | 沈明晖 | Graphene anticorrosive paint |
| CN113416383A (en) * | 2021-07-08 | 2021-09-21 | 大连理工大学 | Flexible linear polymer and inorganic nanoparticle composite modified graphene oxide-epoxy resin composite material and preparation method thereof |
| CN113956746A (en) * | 2021-11-02 | 2022-01-21 | 国科广化韶关新材料研究院 | Water-based epoxy group anticorrosive paint containing composite functionalized modified graphene oxide and preparation method and application thereof |
Family Cites Families (1)
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|---|---|---|---|---|
| DE112017004473T5 (en) * | 2016-09-06 | 2019-06-27 | Regents Of The University Of Minnesota | SYNERGISTIC VIABILITY IMPROVEMENT OF EPOXY MODIFIED WITH GRAPHS AND BLOCK COPOLYMER |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014032378A1 (en) * | 2012-08-25 | 2014-03-06 | 华南理工大学 | Methods for preparing functionalized graphene and the composite electroconductive glue thereof |
| CN103897345A (en) * | 2014-03-10 | 2014-07-02 | 哈尔滨理工大学 | Preparation method of TiO2/PU-EP composite material |
| CN107459774A (en) * | 2017-05-24 | 2017-12-12 | 浙江创元生态环保技术有限公司 | A kind of graphene/nanometer silica/epoxy resin composite material and preparation method thereof |
| CN111944387A (en) * | 2020-09-04 | 2020-11-17 | 沈明晖 | Graphene anticorrosive paint |
| CN113416383A (en) * | 2021-07-08 | 2021-09-21 | 大连理工大学 | Flexible linear polymer and inorganic nanoparticle composite modified graphene oxide-epoxy resin composite material and preparation method thereof |
| CN113956746A (en) * | 2021-11-02 | 2022-01-21 | 国科广化韶关新材料研究院 | Water-based epoxy group anticorrosive paint containing composite functionalized modified graphene oxide and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Ultralow-Carbon Nanotube-Toughened Epoxy: The Critical Role of a Double-Layer Interface;Liu JW, et al;《Applied Materials & Interfaces》;第10卷;1204-1216 * |
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