CN114773790A - Graphene epoxy resin high polymer material and preparation method and application thereof - Google Patents
Graphene epoxy resin high 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 high polymer material and a preparation method and application thereof. The graphene epoxy resin high 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 an anhydride curing agent, 3-8 parts of an accelerator, 1-5 parts of an organic silicon defoamer, 6-10 parts of a toughening agent, 2-4 parts of a silane coupling agent, 2-4 parts of a dispersing agent, 10-20 parts of functionalized graphene and 30-40 parts of silane coupling agent modified spherical silicon micro powder; the functionalized graphene is obtained by treating graphene oxide with silicon dioxide, polyetheramine and hydrazine hydrate in sequence. The high polymer material has high tensile strength, fracture toughness and wear resistance, shows excellent comprehensive performance and meets market requirements.
Description
Technical Field
The application relates to the technical field of plastic toy processing, in particular to a graphene epoxy resin high 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 be used for entertainment and consumption and pressure reduction. Toys can be classified into metal toys, plastic toys, wooden toys, flannel toys, and the like according to the material. Among them, the plastic toy is generally made of polymer material, and the epoxy resin is widely used for processing the plastic toy due to its advantages of good adhesion, low shrinkage rate and easy processing and forming. The raw materials of the existing epoxy resin high polymer material are epoxy resin, reactive diluent, curing agent and accelerating agent. The inventor finds that after the polymer material is processed into the plastic toy in actual processing, the wear resistance of the plastic toy is insufficient, the service life of the plastic toy is influenced, and the tensile strength of the plastic toy needs 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 present application provides a graphene epoxy resin polymer material, which adopts the following technical scheme: a graphene epoxy resin high 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 an anhydride curing agent, 3-8 parts of an accelerator, 1-5 parts of an organic silicon defoamer, 6-10 parts of a toughening agent, 2-4 parts of a silane coupling agent, 2-4 parts of a dispersing agent, 10-20 parts of functionalized graphene and 30-40 parts of silane coupling agent modified spherical silicon micro powder; the functionalized graphene is obtained by treating graphene oxide with silicon dioxide, polyetheramine and hydrazine hydrate in sequence.
The graphene epoxy resin high polymer material has high tensile strength and fracture toughness through the synergistic effect of the raw materials, wherein the tensile strength is more than 130MPa, and the fracture toughness is more than 2.1MPa1/2. But also has higher wear resistance, and the wear rate is less than 1.3 percent. The polymer material has good comprehensive performance and meets the market demand.
The functional graphene and the silane coupling agent are added into the raw materials to modify the spherical silicon micro powder, so that the tensile strength, the fracture toughness and the wear resistance of the high polymer material can be improved. And a silane coupling agent is further added to improve the wettability of the functionalized graphene and the silane coupling agent modified spherical silicon micro powder. The dispersing agent is added, so that the surface energy of the functionalized graphene and silane coupling agent modified spherical silicon micro powder can be reduced, the dispersing effect is enhanced, and the excellent wetting and flocculation control effects can be achieved. The synergistic interaction 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.
The utility model provides a functional graphene, earlier on graphite oxide grafts to silica, later utilize polyether amine, with polyether amine grafting to graphite oxide, silica, then utilize hydrazine hydrate to reduce graphite oxide and form graphite alkene, not only increase graphite alkene, silica's bonding strength, and increase the compatibility of functional graphite alkene and raw materials, improve functional graphite alkene's result of use, further strengthen macromolecular material's tensile strength, fracture toughness and wearability, enlarge the range of application.
Optionally, the functionalized graphene is prepared by the following method:
s1, adding silicon dioxide into water, and carrying out ultrasonic treatment for 30-60min to obtain a 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 performing ultrasonic treatment for 30-60min to obtain a graphene oxide dispersion liquid;
s3, adding the graphene oxide dispersion liquid into the silicon dioxide dispersion liquid, stirring for 20-25h, then adding polyether amine, stirring for 30-60min, heating to 50-70 ℃, stirring for 10-15h, and then concentrating to 0.1-0.3 time 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 ℃, carrying out stirring treatment 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) to 8-13 to 4-6, and the mass fraction of 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 silicon dioxide and the graphene oxide are dispersed in advance, so that the uniformity of the dispersion of the silicon dioxide and the graphene oxide is facilitated. And the silicon dioxide dispersion liquid and the graphene oxide dispersion liquid are mixed, so that the uniformity of silicon dioxide and graphene oxide mixed materials is facilitated. When the graphene oxide is to be 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 enhanced, and the performance and the using effect of the functionalized graphene are improved.
Furthermore, the weight ratio of the graphene oxide to the silicon dioxide to the polyether amine to the hydrazine hydrate solution is 4:0.5:10:5, and the mass fraction of hydrazine in the hydrazine hydrate solution is 80%.
In step S1, the weight ratio of silicon dioxide to water is 4 (150-) (250).
In step S2, the weight ratio of graphene oxide, water, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide is (0.3-0.8): (150) -250): (0.1-0.5): 0.1-0.5).
In step S4, the weight ratio of hydrazine hydrate solution to water is (4-6): (150-) - (250).
Optionally, the silane coupling agent modified spherical silica micropowder is prepared by the following method: adding a silane coupling agent into water, stirring and uniformly mixing, then adding spherical silicon micro powder, carrying out ultrasonic treatment for 30-60min, heating to 50-70 ℃, carrying out stirring treatment for 5-10h, filtering, and drying to obtain the silane coupling agent modified spherical silicon micro powder.
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 silicon micropowder are facilitated.
Further, the weight ratio of the spherical silicon powder to the silane coupling agent is 4: 0.8.
The weight ratio of the spherical silicon micro powder to the water is 4 (150- & lt 250- & gt).
Optionally, the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane; the dispersant was birk-181.
By adopting the technical scheme, the silane coupling agent and the dispersing agent can be conveniently selected, the interaction of the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, the ByK-181 and the functionalized graphene is improved, and the tensile strength and the fracture toughness of the high 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, the service stability of the high polymer material is improved, and the service life of the high polymer material is prolonged.
Further, the thermoplastic resin is one or more of PESU and PES-C, PSU. Preferably PESU.
Optionally, the epoxy resin is a mixture of hydrogenated bisphenol A epoxy resin, tetrahydrophthalic acid diglycidyl ester and bis ((3, 4-epoxycyclohexyl) methyl) adipate, and the weight ratio of the hydrogenated bisphenol A epoxy resin, the tetrahydrophthalic acid diglycidyl ester 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 type 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 raw materials keep good viscosity and fluidity by utilizing the synergistic effect among the hydrogenated bisphenol A epoxy resin, the tetrahydrophthalic acid diglycidyl ester and the bis ((3, 4-epoxycyclohexyl) methyl) adipate, the influence on the fluidity of the raw materials due to the addition of the functionalized graphene and the silane coupling agent modified spherical silicon micro powder is reduced, the dispersion uniformity of the functionalized graphene and the silane coupling agent modified spherical silicon micro powder can be 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 ketopyromellitic dianhydride. Dodecenyl succinic anhydride, in particular linear LDDSA, is preferred.
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:
a preparation method of the graphene epoxy resin high polymer material comprises the following steps: stirring epoxy resin, butyl glycidyl ether, an organic silicon defoaming agent, a toughening agent, a silane coupling agent, a dispersing agent, functionalized graphene and silane coupling agent modified spherical silicon micro powder for 30-60min at the temperature of 150-; then heating to 180-200 ℃, adding an anhydride curing agent and an accelerant, continuing stirring for 50-100min, and cooling to obtain the polymer material.
By adopting the technical scheme, epoxy resin, butyl glycidyl ether, an organic silicon defoamer, a toughening agent, a silane coupling agent, a dispersing agent, functionalized graphene and silane coupling agent modified spherical silicon micro powder are mixed in advance, and then an anhydride curing agent and an accelerator are added, so that the processing and control of a high polymer material are facilitated, the dispersion of raw materials is facilitated, the uniformity of mixed materials is improved, and the performance of the high polymer material is improved.
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 high polymer material.
By adopting the technical scheme, the application of the graphene epoxy resin high polymer material and the processing of the plastic toy are facilitated.
In summary, the present application has at least the following beneficial effects:
1. the graphene epoxy resin high polymer material has the tensile strength of more than 130MPa and the fracture toughness of more than 2.1MPa through the synergistic effect of the raw materials1/2The wear rate is less than 1.3 percent, and the alloy shows higher tensile strength, fracture toughness and wear resistanceHas excellent comprehensive performance and meets the market demand.
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 dispersion uniformity and the mixing uniformity of the silicon dioxide and the graphene oxide are facilitated, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide are added into the graphene oxide dispersion liquid to activate surface groups, the use effect of the functionalized graphene is enhanced, and the mechanical property of the high polymer material is improved.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation examples
Preparation example 1
A functionalized graphene is prepared by the following method:
s1, adding 4kg of silicon dioxide into 200kg of water, and carrying out ultrasonic treatment for 50min to obtain a silicon dioxide dispersion liquid.
Wherein the silicon dioxide is selected from Hangzhou Cudrania tricuspidata new material.
S2, 0.3kg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and 0.3kg of N-hydroxysuccinimide are added to 200kg of water, and the mixture is stirred for 30 min. Then 0.5kg of graphene oxide is added, and ultrasonic treatment is carried out for 50min to obtain a graphene oxide dispersion liquid.
Wherein the graphene oxide is selected from Hangzhou Cudrania tricuspidata new materials.
And S3, adding the graphene oxide dispersion liquid into the silicon dioxide dispersion liquid, and stirring for 24 hours. Then 10kg of polyetheramine was added and stirred for 50 min. The temperature is increased to 60 ℃, and the stirring treatment is carried out for 12 h. Then, the mixture was concentrated to 0.2 times the original volume to obtain a mixture.
Wherein the polyether amine is polyether amine D230 and is selected from chemical industry of Jinming Jinan.
S4, adding 5kg of hydrazine hydrate solution into 200kg of water, and stirring for 30 min. The mixture was then added and sonicated for 50 min. The temperature is increased to 95 ℃, and the stirring treatment is carried out for 12 h. And filtering and drying to obtain the functionalized graphene.
Wherein the mass fraction of hydrazine in the hydrazine hydrate solution is 80 percent.
Preparation example 2
A functionalized graphene, which is different from preparation example 1 in that step S2 is different.
Step S2 specifically includes: adding 0.5kg of graphene oxide into 200kg of water, and carrying out ultrasonic treatment for 50min to obtain a 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 min. Then 4kg of spherical silicon micro powder is added, and ultrasonic treatment is carried out for 50 min. The temperature is increased to 60 ℃, and the stirring treatment is carried out for 8 hours. Filtering and drying to obtain the silane coupling agent modified spherical silicon micro powder.
Wherein the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane; the spherical silicon micro powder is selected from Guangdong Yongfeng chemical industry.
Examples
TABLE 1 content of each raw material of Polymer materials (unit: 10g)
| Examples | Example 1 | Example 2 | Example 3 |
| Epoxy resin | 60 | 70 | 80 |
| Butyl glycidyl ether | 18 | 20 | 15 |
| Anhydride curing agent | 85 | 80 | 90 |
| Accelerator | 5 | 3 | 8 |
| Organic silicon defoaming agent | 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 proportion of the graphene epoxy resin high polymer material is shown in table 1.
Wherein the epoxy resin is a mixture of hydrogenated bisphenol A epoxy resin, tetrahydrophthalic acid diglycidyl ester and bis ((3, 4-epoxycyclohexyl) methyl) adipate, and the weight ratio of the hydrogenated bisphenol A epoxy resin, the tetrahydrophthalic acid diglycidyl ester and the bis ((3, 4-epoxycyclohexyl) methyl) adipate is 5:3: 2. The hydrogenated bisphenol A epoxy resin is selected from the Hubei world energy chemical technology.
The anhydride curing agent is dodecenyl succinic anhydride, in particular straight-chain LDDSA; the promoter is triphenylphosphine; the organic silicon defoamer is a defoamer THIX-278 and is selected from Nicotiana constant Xin chemical technology; the toughening agent is thermoplastic resin, in particular PASU E1010 of Pasteur; the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane; the dispersant is ByK-181; the functionalized graphene is prepared by adopting preparation example 1; the silane coupling agent modified spherical silica micropowder is prepared by the preparation example 3.
A preparation method of a graphene epoxy resin high polymer material comprises the following steps:
and (3) stirring epoxy resin, butyl glycidyl ether, an organic silicon defoamer, a flexibilizer, a silane coupling agent, a dispersing agent, functionalized graphene and silane coupling agent modified spherical silicon micro powder for 50min at 160 ℃. Then heating to 190 ℃, adding an anhydride curing agent and an accelerant, and continuing stirring for 80 min. And cooling to 25 ℃ to obtain the high polymer material.
Examples 2 to 3
The graphene epoxy resin polymer material is different from that of embodiment 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 that in embodiment 1 in that functionalized graphene in the raw materials of the polymer material is prepared by using preparation example 2.
Example 5
The graphene epoxy resin polymer material is different from that in the embodiment 1 in that the epoxy resin in the raw materials of the polymer material is hydrogenated bisphenol a epoxy resin.
Example 6
The graphene epoxy resin high polymer material is different from the graphene epoxy resin high polymer material in embodiment 1 in that the epoxy resin in the raw materials of the high 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
The graphene epoxy resin polymer material is different from that in embodiment 1 in that functionalized graphene is not added to a raw material of the polymer material.
Comparative example 2
The graphene epoxy resin polymer material is different from that in embodiment 1 in that silane coupling agent modified spherical silicon micro powder is not added to the raw materials of the polymer material.
Comparative example 3
The graphene epoxy resin polymer material is different from that in embodiment 1 in that functionalized graphene and silane coupling agent modified spherical silicon micropowder are not added to the raw materials of the polymer material.
Comparative example 4
The graphene epoxy resin polymer material is different from that in the embodiment 1 in that the raw material of the polymer material is replaced by the same amount of graphene for the functionalized graphene.
The graphene is prepared by the following method:
5kg of hydrazine hydrate solution was added to 200kg of water, and stirred for 30 min. Then 0.5kg of graphene oxide is added, and ultrasonic treatment is carried out for 50 min. The temperature is increased to 95 ℃, and the stirring treatment is carried out for 12 h. And filtering, drying and obtaining graphene.
Wherein the mass fraction of hydrazine in the hydrazine hydrate solution is 80 percent; the graphene oxide is selected from Hangzhou Cudrania tricuspidata new materials.
Comparative example 5
A graphene epoxy resin polymer material, which is different from that in embodiment 1 in that the raw material of the polymer material, in the functionalized graphene preparation method, is different from that in step S3.
Step S3 specifically includes: and adding the graphene oxide dispersion liquid into the silicon dioxide dispersion liquid, and stirring for 24 hours. The temperature is increased to 60 ℃, and the stirring treatment is carried out for 12 h. Then, the mixture was concentrated to 0.2 times the original volume to obtain a mixture.
Comparative example 6
The graphene epoxy resin polymer material is different from the graphene epoxy resin polymer material in embodiment 1 in that the raw material of the polymer material is functionalized graphene. 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 30 min. Then 0.5kg of graphene oxide is added, and ultrasonic treatment is carried out for 50min to obtain graphene oxide dispersion liquid.
Wherein the graphene oxide is selected from Hangzhou Cudrania tricuspidata new materials.
S3, adding 10kg of polyether amine into the graphene oxide dispersion liquid, and stirring for 50 min. The temperature is increased to 60 ℃, and the stirring treatment is carried out for 12 h. Then, the mixture was concentrated to 0.2 times the original volume to obtain a mixture.
Wherein the polyetheramine is polyetheramine D230 and is selected from the chemical industry of Jinming province.
S4, adding 5kg of hydrazine hydrate solution into 200kg of water, and stirring for 30 min. The mixture was then added and sonicated for 50 min. The temperature is increased to 95 ℃, and the stirring treatment is carried out for 12 h. And filtering and drying to obtain the functionalized graphene.
Wherein the mass fraction of hydrazine in the hydrazine hydrate solution is 80 percent.
Comparative example 7
The graphene epoxy resin polymer material is different from the graphene epoxy resin polymer material in that a silane coupling agent is not added to the raw material of the polymer material.
Comparative example 8
The graphene epoxy resin polymer material is different from that in embodiment 1 in that a dispersing agent is not added to a raw material of the polymer material.
Comparative example 9
The graphene epoxy resin polymer material is different from the graphene epoxy resin polymer material in embodiment 1 in that a silane coupling agent, a dispersing agent and functionalized graphene are not added to 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 properties were measured on the samples, and the results are shown in Table 2.
Wherein, the tensile strength is detected according to GB/T1040; testing for fracture toughness according to ASTM D5045; the wear resistance is characterized by the wear rate, and the lower the wear rate, the higher the wear resistance, where (weight before specimen wear-weight after specimen wear)/weight before specimen wear x 100%.
TABLE 2 test 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 ring of the present applicationThe oxygen resin polymer material has higher tensile strength and fracture toughness, wherein the tensile strength is 132-146MPa, and the fracture toughness is 2.11-2.48MPa1/2. But also has lower wear rate, the wear rate is 1.03-1.22%, and the wear resistance is excellent. 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 wear resistance of the polymer material can be enhanced by adding the functionalized graphene and the silane coupling agent modified spherical silica micropowder into the raw materials and utilizing the synergistic effect therebetween. And then, combining with the comparative examples 7-9, adding a silane coupling agent, a dispersing agent and functionalized graphene into the raw materials, further increasing the mechanical property of the high polymer material and increasing 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 materials can improve the tensile strength and fracture toughness of the polymer material, and can also increase the wear resistance. And in combination with comparative examples 5-6 and example 1, the graphene oxide is further treated by silicon dioxide, polyether amine and hydrazine hydrate, so that the mechanical property of the high polymer material is obviously improved. And then combining with the embodiment 4, treating the graphene oxide by adopting 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide to activate groups on the surface of the graphene oxide, thereby effectively increasing the use effect of the functionalized graphene.
Comparing example 1 with examples 5 to 6, it can be seen that when the epoxy resin is a mixture of hydrogenated bisphenol a epoxy resin, diglycidyl tetrahydrophthalate, and bis ((3, 4-epoxycyclohexyl) methyl) adipate, the polymer material can exhibit more excellent mechanical properties.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A graphene epoxy resin high polymer material is characterized in that: the traditional Chinese medicine composition 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 an anhydride curing agent, 3-8 parts of an accelerator, 1-5 parts of an organic silicon defoamer, 6-10 parts of a toughening agent, 2-4 parts of a silane coupling agent, 2-4 parts of a dispersing agent, 10-20 parts of functionalized graphene and 30-40 parts of silane coupling agent modified spherical silicon micro powder; the functionalized graphene is obtained by treating graphene oxide with silicon dioxide, polyetheramine and hydrazine hydrate in sequence.
2. The graphene epoxy resin high polymer material according to claim 1, characterized in that: the functionalized graphene is prepared by the following method:
s1, adding silicon dioxide into water, and carrying out ultrasonic treatment for 30-60min to obtain a 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 performing ultrasonic treatment for 30-60min to obtain a graphene oxide dispersion liquid;
s3, adding the graphene oxide dispersion liquid into the silicon dioxide dispersion liquid, stirring for 20-25h, then adding polyetheramine, stirring for 30-60min, heating to 50-70 ℃, stirring for 10-15h, and then concentrating to 0.1-0.3 time 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 ℃, carrying out stirring treatment for 10-15h, filtering, and drying to obtain the functionalized graphene.
3. The graphene epoxy resin polymer material according to claim 2, wherein: the weight ratio of the silicon dioxide to the graphene oxide to the polyether amine to the hydrazine hydrate solution is 4 (0.3-0.8) to 8-13 to 4-6), and the mass fraction of hydrazine in the hydrazine hydrate solution is 60-80%.
4. The graphene epoxy resin high polymer material according to claim 1, characterized in that: the silane coupling agent modified spherical silicon micropowder is prepared by the following method: adding a silane coupling agent into water, stirring and uniformly mixing, then adding spherical silicon micro powder, carrying out ultrasonic treatment for 30-60min, heating to 50-70 ℃, carrying out stirring treatment for 5-10h, filtering, and drying to obtain the silane coupling agent modified spherical silicon micro powder.
5. The graphene epoxy resin high polymer material according to claim 4, wherein: the weight ratio of the spherical silicon micro powder to the silane coupling agent is 4 (0.5-1).
6. The graphene epoxy resin polymer material according to claim 1, wherein: the silane coupling agent is gamma- (2, 3-epoxy propoxy) propyl trimethoxy silane; the dispersant was birk-181.
7. The graphene epoxy resin high polymer material according to claim 1, characterized in that: the toughening agent is thermoplastic resin.
8. The graphene epoxy resin high polymer material according to claim 1, characterized in that: the epoxy resin is a mixture of hydrogenated bisphenol A epoxy resin, tetrahydrophthalic acid diglycidyl ester and bis ((3, 4-epoxycyclohexyl) methyl) adipate, and the weight ratio of the hydrogenated bisphenol A epoxy resin to the tetrahydrophthalic acid diglycidyl ester to the bis ((3, 4-epoxycyclohexyl) methyl) adipate is (4-6) to (2-4) to (1-3).
9. A method for preparing the graphene epoxy resin high polymer material according to any one of claims 1 to 8, which is characterized in that: the method comprises the following steps: stirring epoxy resin, butyl glycidyl ether, an organic silicon defoamer, a flexibilizer, a silane coupling agent, a dispersing agent, functionalized graphene and silane coupling agent modified spherical silicon micro powder for 30-60min at the temperature of 150-170 ℃; then heating to 180 ℃ and 200 ℃, adding an anhydride curing agent and an accelerant, continuing stirring for 50-100min, and cooling to obtain the polymer material.
10. A plastic toy, characterized in that: the graphene epoxy resin polymer material is processed by the graphene epoxy resin polymer material of any one of claims 1-8.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117801735A (en) * | 2024-03-01 | 2024-04-02 | 广州昊毅新材料科技股份有限公司 | Low-temperature pressure-sensitive lithium battery negative electrode adhesive material and preparation method thereof |
| CN117801735B (en) * | 2024-03-01 | 2024-05-24 | 广州昊毅新材料科技股份有限公司 | Low-temperature pressure-sensitive lithium battery negative electrode adhesive material and preparation method thereof |
Citations (7)
| 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 |
| US20200190312A1 (en) * | 2016-09-06 | 2020-06-18 | Regents Of The University Of Minnesota | Synergistic toughening of epoxy modified by graphene and block copolymer |
| 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 |
-
2022
- 2022-04-23 CN CN202210431884.0A patent/CN114773790B/en active Active
Patent Citations (7)
| 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 |
| US20200190312A1 (en) * | 2016-09-06 | 2020-06-18 | Regents Of The University Of Minnesota | Synergistic toughening of epoxy modified by graphene and block copolymer |
| 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 (2)
| Title |
|---|
| LIU JW, ET AL: "Ultralow-Carbon Nanotube-Toughened Epoxy: The Critical Role of a Double-Layer Interface", 《APPLIED MATERIALS & INTERFACES》, vol. 10, pages 1204 - 1216 * |
| 曹宇臣;郭鸣明;: "石墨烯材料及其应用", 石油化工, no. 10, pages 1149 - 1159 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117801735A (en) * | 2024-03-01 | 2024-04-02 | 广州昊毅新材料科技股份有限公司 | Low-temperature pressure-sensitive lithium battery negative electrode adhesive material and preparation method thereof |
| CN117801735B (en) * | 2024-03-01 | 2024-05-24 | 广州昊毅新材料科技股份有限公司 | Low-temperature pressure-sensitive lithium battery negative electrode adhesive material and preparation method thereof |
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