CN108342177B - Preparation method of high-dispersion graphene oxide reinforced epoxy resin adhesive - Google Patents
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- CN108342177B CN108342177B CN201810269066.9A CN201810269066A CN108342177B CN 108342177 B CN108342177 B CN 108342177B CN 201810269066 A CN201810269066 A CN 201810269066A CN 108342177 B CN108342177 B CN 108342177B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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Abstract
A preparation method of a high-dispersion graphene oxide reinforced epoxy resin adhesive relates to a preparation method of a graphene oxide reinforced epoxy resin adhesive. The invention aims to solve the technical problems of difficult dispersion in the preparation process of the existing graphene oxide reinforced epoxy resin adhesive and environmental pollution caused by organic solvent used in the dispersion process. The invention comprises the following steps: firstly, preparing graphene oxide by a chemical oxidation method; secondly, dispersing graphene oxide in epoxy resin; and thirdly, preparing the graphene oxide reinforced epoxy resin adhesive. The invention utilizes conventional equipment such as a high-speed emulsifying machine, a three-roll grinding machine and the like to prepare the fully-stripped and highly-dispersed graphene oxide reinforced epoxy resin adhesive; the invention does not use organic solvent and any other auxiliary agent in the dispersing process, is beneficial to environmental protection, and simultaneously avoids the adverse effect of the use of the auxiliary agent on other performances of the epoxy resin system.
Description
Technical Field
The invention relates to a preparation method of a graphene oxide reinforced epoxy resin adhesive.
Background
Epoxy resin has the advantages of excellent mechanical property, chemical stability, insulativity and the like, plays a vital role in a plurality of fields such as electronics, machinery, automobiles, buildings, aerospace and the like due to low price and wide applicability, and is one of indispensable basic materials. Epoxy resins have several advantages as well as some disadvantages. Because the epoxy resin forms a high-density cross-linked three-dimensional network structure in the curing process, the epoxy resin has high brittleness and poor toughness, and simultaneously, along with the rapid development of the industry, the performance requirement on the epoxy resin is higher and higher, so that the preparation of the epoxy resin with high toughness, high strength, high modulus and high temperature resistance becomes one of the important development directions of the epoxy resin.
Graphene has excellent mechanical, thermal and electrical conductivity, and is a hot topic of research from discovery to the present. Graphene oxide, an important graphene material, has been widely studied and used in composite materials in various fields because of its easy preparation, large amount of reactive oxygen-containing functional groups, and mechanical properties much higher than those of general polymers. The graphene oxide is used for enhancing the epoxy resin, so that the strength and the modulus are improved, the toughness is improved, and the glass transition temperature and the heat resistance of the epoxy resin can be improved to a certain degree. However, the graphene oxide has a large specific surface area, so that a strong agglomeration phenomenon is shown in the preparation process of the reinforced epoxy resin, and the reinforcing effect is greatly reduced. Although agglomeration can be improved to a certain extent by adding an auxiliary agent such as a surfactant, the addition of the auxiliary agent can adversely affect other properties of the epoxy resin. Therefore, how to disperse the graphene oxide with high efficiency without introducing other auxiliary agents is a difficult problem in the research of the graphene oxide reinforced epoxy resin.
Disclosure of Invention
The invention provides a preparation method of a high-dispersion graphene oxide reinforced epoxy resin adhesive, aiming at solving the technical problems of difficult dispersion in the preparation process of the existing graphene oxide reinforced epoxy resin adhesive and environmental pollution caused by organic solvent used in the dispersion process.
The preparation method of the high-dispersion graphene oxide reinforced epoxy resin adhesive is carried out according to the following steps:
firstly, preparing graphene oxide by a chemical oxidation method:
adding graphite powder into a reaction container, adding 98% concentrated sulfuric acid and 85% phosphoric acid aqueous solution, adding potassium permanganate under the conditions of ice-water bath and stirring, stirring and reacting for 20-60 min under the condition of ice-water bath, then heating the system to 45-50 ℃ by using a heating device, preserving the temperature for 8-20 h under the condition of 45-50 ℃, naturally cooling to room temperature, adding 500-1000 mL of distilled water under the condition of ice-water bath for dilution, dripping hydrogen peroxide at normal temperature until the color becomes golden yellow and no bubbles are generated, centrifuging for 10-30 min under the condition of 2000-4000 rpm of rotation speed, and pouring out supernatant and bottom black substances;
secondly, washing the rest part of the step I by using distilled water, centrifuging for 20-60 min under the condition that the rotating speed is 8000-10000 rpm, and pouring out the supernatant;
thirdly, repeating the step II until the pH value of the centrifuged supernatant is more than 5, and pouring the supernatant after the last centrifugation to obtain viscous graphene oxide suspension;
the mass ratio of the graphite powder to 98% concentrated sulfuric acid is 1 (30-150), the mass ratio of the graphite powder to 85% phosphoric acid aqueous solution is 1 (3-15), and the mass ratio of the graphite powder to potassium permanganate is 1 (5-15);
secondly, dispersing graphene oxide in epoxy resin:
mixing the sticky graphene oxide suspension prepared in the step one with liquid epoxy resin, dispersing the mixture for 5-20 min at the speed of 1000-3000 rpm by using a high-speed emulsifying machine, pouring the mixture into a three-roll grinding machine, grinding the mixture until the mixture is brownish black and transparent under the condition that the ratio of the three-roll speed is 1:3:9 and the gap between the three rolls is 0.1-30 mu m, and finally putting the brownish black and transparent mixture into a vacuum drying box to remove the residual moisture at the temperature of 40-80 ℃; the mass ratio of the liquid epoxy resin in the step two to the pure graphene oxide in the viscous graphene oxide suspension prepared in the step one is 100 (0.1-5);
thirdly, preparing the graphene oxide reinforced epoxy resin adhesive:
and (3) mixing the graphene oxide/epoxy resin mixture with the moisture completely removed in the step two with a curing agent, and uniformly stirring to obtain the high-dispersion graphene oxide reinforced epoxy resin adhesive.
The mixing ratio of the graphene oxide/epoxy resin mixture and the curing agent in the third step and the curing process are determined by the properties of the curing agent, and the method belongs to the conventional technology.
The high-dispersion graphene oxide reinforced epoxy resin adhesive is used for specimen bonding and casting body preparation, and is cured under the curing condition of a curing agent.
The principle of the invention is as follows:
the conventional preparation of graphene oxide reinforced polymer materials uses dried solid graphene oxide, graphene oxide sheets are stacked together again due to volatilization of moisture and are difficult to open, and the fully exfoliated and highly dispersed graphene oxide reinforced materials are difficult to obtain by using mechanical grinding or ultrasonic treatment.
The method comprises the steps of directly mixing the suspension of the graphene oxide with liquid epoxy resin, emulsifying at a high speed, and grinding by using a three-roll grinder. Because the drying process is avoided, graphene oxide lamella layers can not be stacked, and have larger interlayer spacing, and the graphene oxide lamella layers can be easily peeled off and dispersed in an epoxy resin system after three-roller grinding. In addition, most of water can be volatilized in the grinding process, and the fully-stripped and highly-dispersed graphene oxide can be well compatible with the epoxy resin due to the fact that the graphene oxide has a large number of oxygen-containing functional groups, and finally the effect of enhancing the epoxy resin is achieved. The method also avoids using an organic solvent when the graphene oxide is dispersed, and the whole process is environment-friendly and pollution-free. No auxiliary agent is used in the process, and the epoxy resin system is not adversely affected.
The principle of the invention can also be applied to the preparation and production of graphene reinforced other polymers, and has great application and popularization values.
Compared with the prior art, the invention has the advantages that:
1. the raw materials for preparing the graphene oxide are easy to obtain and low in cost, the highest reaction temperature in the process is only 50 ℃, and the preparation method is simple and easy to control;
2. the method is carried out by adopting a common high-speed emulsifying machine and a common three-roller grinding machine for dispersing the graphene oxide, is simple, and is suitable for large-scale production and application;
3. the graphene oxide suspension is used in the dispersing process, the graphene oxide lamella layers are not restacked due to drying, and the graphene oxide lamella layers can be fully stripped and highly dispersed in the epoxy resin by high-speed emulsification and three-roll grinding;
4. in the invention, organic solvent and any other auxiliary agent are not used in the dispersing process, which is beneficial to environmental protection and avoids the adverse effect of the use of the auxiliary agent on other performances of the epoxy resin system;
5. the graphene oxide reinforced epoxy resin adhesive prepared by the invention has excellent performance, the strength, the modulus and the toughness are greatly improved compared with unreinforced epoxy resin, and the heat resistance is also improved to a certain extent.
Drawings
Fig. 1 is a transmission electron microscope picture of a high-dispersion graphene oxide reinforced epoxy resin adhesive prepared in a first test.
Detailed Description
The first embodiment is as follows: the embodiment is a preparation method of a high-dispersion graphene oxide reinforced epoxy resin adhesive, which is specifically carried out according to the following steps:
firstly, preparing graphene oxide by a chemical oxidation method:
adding graphite powder into a reaction container, adding 98% concentrated sulfuric acid and 85% phosphoric acid aqueous solution, adding potassium permanganate under the conditions of ice-water bath and stirring, stirring and reacting for 20-60 min under the condition of ice-water bath, then heating the system to 45-50 ℃ by using a heating device, preserving the temperature for 8-20 h under the condition of 45-50 ℃, naturally cooling to room temperature, adding 500-1000 mL of distilled water under the condition of ice-water bath for dilution, dripping hydrogen peroxide at normal temperature until the color becomes golden yellow and no bubbles are generated, centrifuging for 10-30 min under the condition of 2000-4000 rpm of rotation speed, and pouring out supernatant and bottom black substances;
secondly, washing the rest part of the step I by using distilled water, centrifuging for 20-60 min under the condition that the rotating speed is 8000-10000 rpm, and pouring out the supernatant;
thirdly, repeating the step II until the pH value of the centrifuged supernatant is more than 5, and pouring the supernatant after the last centrifugation to obtain viscous graphene oxide suspension;
the mass ratio of the graphite powder to 98% concentrated sulfuric acid is 1 (30-150), the mass ratio of the graphite powder to 85% phosphoric acid aqueous solution is 1 (3-15), and the mass ratio of the graphite powder to potassium permanganate is 1 (5-15);
secondly, dispersing graphene oxide in epoxy resin:
mixing the sticky graphene oxide suspension prepared in the step one with liquid epoxy resin, dispersing the mixture for 5-20 min at the speed of 1000-3000 rpm by using a high-speed emulsifying machine, pouring the mixture into a three-roll grinding machine, grinding the mixture until the mixture is brownish black and transparent under the condition that the ratio of the three-roll speed is 1:3:9 and the gap between the three rolls is 0.1-30 mu m, and finally putting the brownish black and transparent mixture into a vacuum drying box to remove the residual moisture at the temperature of 40-80 ℃; the mass ratio of the liquid epoxy resin in the step two to the pure graphene oxide in the viscous graphene oxide suspension prepared in the step one is 100 (0.1-5);
thirdly, preparing the graphene oxide reinforced epoxy resin adhesive:
and (3) mixing the graphene oxide/epoxy resin mixture with the moisture completely removed in the step two with a curing agent, and uniformly stirring to obtain the high-dispersion graphene oxide reinforced epoxy resin adhesive.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the graphite powder in the first step is flaky graphite powder, and the particle size is 80-400 meshes. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the liquid epoxy resin in the second step is one or a mixture of more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin and alicyclic epoxy resin. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: in step two, the mixture was dispersed for 10min using a high speed emulsifier at 2000 rpm. The rest is the same as one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the curing agent in the third step is one or a mixture of more of polyamide, aliphatic amine, polyether amine and alicyclic amine. The rest is the same as one of the first to fourth embodiments.
The invention was verified with the following tests:
test one: the test is a preparation method of a high-dispersion graphene oxide reinforced epoxy resin adhesive, and the preparation method is specifically carried out according to the following steps:
firstly, preparing graphene oxide by a chemical oxidation method:
adding graphite powder into a reaction container, adding 98% concentrated sulfuric acid and 85% phosphoric acid aqueous solution by mass, adding potassium permanganate under the conditions of ice-water bath and stirring, stirring and reacting for 60min under the conditions of ice-water bath, then heating the system to 50 ℃ by using a heating device, preserving heat for 10h at 50 ℃, naturally cooling to room temperature, adding 500mL of distilled water under the conditions of ice-water bath for dilution, dropwise adding hydrogen peroxide at normal temperature until the color becomes golden yellow and no bubbles are generated, centrifuging for 30min at the rotating speed of 2000rpm, and pouring out supernatant and bottom black substances;
secondly, washing the rest part in the first step by using distilled water, centrifuging for 30min at the rotation speed of 8000rpm, and pouring out the supernatant;
thirdly, repeating the step II until the pH value of the centrifuged supernatant is more than 5, and pouring the supernatant after the last centrifugation to obtain viscous graphene oxide suspension;
the mass ratio of the graphite powder to 98% concentrated sulfuric acid is 1:50, the mass ratio of the graphite powder to 85% phosphoric acid aqueous solution is 1:10, and the mass ratio of the graphite powder to potassium permanganate is 1: 7;
secondly, dispersing graphene oxide in epoxy resin:
mixing the viscous graphene oxide suspension prepared in the step one with liquid epoxy resin, dispersing the mixture for 5min at the speed of 1000rpm by using a high-speed emulsifying machine, pouring the mixture into a three-roll grinding machine, grinding the mixture until the mixture is brownish black and transparent under the condition that the ratio of the three-roll speed is 1:3:9 and the gap between the three rolls is 5 mu m, and finally putting the brownish black and transparent mixture into a vacuum drying box to remove residual moisture at the temperature of 40 ℃; the mass ratio of the liquid epoxy resin in the step two to the pure graphene oxide in the viscous graphene oxide suspension prepared in the step one is 100: 1;
thirdly, preparing the graphene oxide reinforced epoxy resin adhesive:
and (3) mixing the graphene oxide/epoxy resin mixture with the moisture completely removed in the step two with a curing agent, and uniformly stirring to obtain the high-dispersion graphene oxide reinforced epoxy resin adhesive.
The graphite powder in the first step is flaky graphite powder with the particle size of 325 meshes;
the liquid epoxy resin in the second step is glycidyl ether epoxy resin E51;
the curing agent in the third step is a polyamide curing agent V140, and the mass ratio of the graphene oxide/epoxy resin mixture with the moisture completely removed in the second step to the curing agent is 101: 50;
and (2) test II: preparation and test of aluminum alloy bonding piece and casting body:
an aluminum sheet having a specification of 60mm × 20mm × 3mm was sanded with 80-mesh sandpaper, subjected to chemical oxidation treatment using a chromic acid washing solution, and then rinsed with tap water and dried. The high-dispersion graphene oxide reinforced epoxy resin adhesive prepared in the first test is used for bonding test pieces and preparing a casting body, is cured at the temperature of 80 ℃/4h, and then is used for testing the 120 ℃ shear strength, the tensile strength, the impact strength and the glass transition temperature of the adhesive of the test pieces.
In the first test, the shear strength of the prepared high-dispersion graphene oxide reinforced epoxy resin adhesive at 120 ℃ is 10.3MPa, and is increased by 56.3% compared with the unreinforced epoxy adhesive; the tensile strength is 66.4MPa, which is improved by 9 percent compared with the unreinforced epoxy adhesive; the modulus is 2.90Gpa, which is improved by 10.3 percent compared with the unreinforced epoxy adhesive; the impact strength is 15.7 kJ.m-2Compared with the unreinforced epoxy adhesive, the epoxy adhesive is improved by 89.5 percent; the glass transition temperature is 100.2 ℃, which is improved by 4.2 ℃ compared with the unreinforced epoxy adhesive.
Fig. 1 is a transmission electron microscope picture of a high dispersion graphene oxide reinforced epoxy resin adhesive prepared in a first test, and it can be seen that graphene oxide is fully peeled off and highly dispersed in the epoxy resin adhesive, and well combined with an epoxy resin matrix. Due to the excellent performance and good dispersion of the graphene oxide, the adhesive has higher strength, modulus and toughness, and the heat resistance is improved. Therefore, the invention can obtain the high-dispersion graphene oxide reinforced epoxy resin adhesive with good performance.
Claims (5)
1. A preparation method of a high-dispersion graphene oxide reinforced epoxy resin adhesive is characterized by comprising the following steps:
firstly, preparing graphene oxide by a chemical oxidation method:
adding graphite powder into a reaction container, adding 98% concentrated sulfuric acid and 85% phosphoric acid aqueous solution, adding potassium permanganate under the conditions of ice-water bath and stirring, stirring and reacting for 20-60 min under the condition of ice-water bath, then heating the system to 45-50 ℃ by using a heating device, preserving the temperature for 8-20 h under the condition of 45-50 ℃, naturally cooling to room temperature, adding 500-1000 mL of distilled water under the condition of ice-water bath for dilution, dripping hydrogen peroxide at normal temperature until the color becomes golden yellow and no bubbles are generated, centrifuging for 10-30 min under the condition of 2000-4000 rpm of rotation speed, and pouring out supernatant and bottom black substances;
secondly, washing the rest part of the step I by using distilled water, centrifuging for 20-60 min under the condition that the rotating speed is 8000-10000 rpm, and pouring out the supernatant;
thirdly, repeating the step II until the pH value of the centrifuged supernatant is more than 5, and pouring the supernatant after the last centrifugation to obtain viscous graphene oxide suspension;
the mass ratio of the graphite powder to 98% concentrated sulfuric acid is 1 (30-150), the mass ratio of the graphite powder to 85% phosphoric acid aqueous solution is 1 (3-15), and the mass ratio of the graphite powder to potassium permanganate is 1 (5-15);
secondly, dispersing graphene oxide in epoxy resin:
mixing the sticky graphene oxide suspension prepared in the step one with liquid epoxy resin, dispersing the mixture for 5-20 min at the speed of 1000-3000 rpm by using a high-speed emulsifying machine, pouring the mixture into a three-roll grinding machine, grinding the mixture until the mixture is brownish black and transparent under the condition that the ratio of the three-roll speed is 1:3:9 and the gap between the three rolls is 0.1-30 mu m, and finally putting the brownish black and transparent mixture into a vacuum drying box to remove the residual moisture at the temperature of 40-80 ℃; the mass ratio of the liquid epoxy resin in the step two to the pure graphene oxide in the viscous graphene oxide suspension prepared in the step one is 100 (0.1-5);
thirdly, preparing the graphene oxide reinforced epoxy resin adhesive:
and (3) mixing the graphene oxide/epoxy resin mixture with the moisture completely removed in the step two with a curing agent, and uniformly stirring to obtain the high-dispersion graphene oxide reinforced epoxy resin adhesive.
2. The preparation method of the highly dispersed graphene oxide reinforced epoxy resin adhesive according to claim 1, wherein the graphite powder in the first step is flaky graphite powder, and the particle size is 80-400 meshes.
3. The method for preparing the highly dispersed graphene oxide reinforced epoxy resin adhesive according to claim 1, wherein the liquid epoxy resin in the second step is one or a mixture of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin and alicyclic epoxy resin.
4. The method for preparing the highly dispersed graphene oxide reinforced epoxy resin adhesive according to claim 1, wherein the mixture is dispersed for 10min at 2000rpm by using a high speed emulsifying machine in the second step.
5. The method for preparing the highly dispersed graphene oxide reinforced epoxy resin adhesive according to claim 1, wherein the curing agent in step three is one or a mixture of more of polyamide, aliphatic amine, polyether amine and alicyclic amine.
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| CN110484158B (en) * | 2019-08-12 | 2021-09-07 | 江南大学 | Adhesive layer based on epoxy adhesive |
| CN110699026B (en) * | 2019-10-22 | 2022-11-18 | 亿铖达（深圳）新材料有限公司 | Flexible epoxy pouring sealant |
| CN111117164A (en) * | 2020-01-08 | 2020-05-08 | 广东墨睿科技有限公司 | Preparation method of graphene oxide modified epoxy resin |
| CN113214606A (en) * | 2020-01-21 | 2021-08-06 | 常州第六元素材料科技股份有限公司 | Graphene-epoxy resin composite material and preparation method thereof |
| CN115386048A (en) * | 2021-10-14 | 2022-11-25 | 常州全睿聚合物新材料有限公司 | Weather-resistant water-based epoxy resin and preparation method and application thereof |
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