CN111647263A - Preparation method of graphene modified polyurethane composite material - Google Patents
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Abstract
The invention discloses a preparation method of a graphene modified polyurethane composite material. The method comprises the following steps: (1) oxidizing graphite serving as a raw material to obtain graphene oxide; (2) modifying the obtained graphene oxide by a reducing agent and hydrochloric acid to obtain modified graphene oxide; (3) ultrasonically dispersing the modified graphene oxide in deionized water, adding a photoinitiator, and curing in a photocuring machine to obtain the graphene-polyurethane composite material. The preparation method is simple, the problem of internal stress concentration of the composite material caused by secondary agglomeration generated by Van der Waals force between graphene and polyurethane is solved by modifying the graphene, and the strength is improved. The modified graphene oxide has a good reinforcing effect on polyurethane, and the prepared graphene-polyurethane composite material is excellent in performance, water resistance and erosion resistance.
Description
Technical Field
The invention relates to the field of composite materials, and particularly relates to a preparation method of a graphene modified polyurethane composite material.
Background
Since 2004, graphene was discovered, and applications related to graphene are increasingly widespread. The appearance of the nano material provides a new idea and a new method for preparing the high-performance polymer composite material, and the excellent physical, chemical and mechanical properties of the graphene become good modifiers for preparing the nano composite material. However, many properties of graphene still need to be studied, such as superconductivity, magnetism, etc., so that the performance and application of polymer nanocomposites prepared by graphene modification still have many challenges.
At present, the synthesis of graphene nanocomposites and the research on the related applications thereof have been greatly advanced, but a lot of problems and challenges are still faced to truly realize the large-scale synthesis and industrial application of graphene nanocomposites. Firstly, how to prepare high-quality graphene on a large scale is also a premise on the basis; secondly, the graphene is functionalized in a controllable manner to improve the dispersibility of the graphene in the polymer, so that the modification effect of the graphene in the polymer can be fully exerted, and the interaction mechanism between the graphene and the polymer in the composite material is further studied so as to further explore the possible new performance and new application due to the synergistic effect between the polymer and the graphene; finally, the preparation method of the polymer nano composite material can be improved, and the types of the nano composite material are enriched, so that the nano composite material is more diversified and functionalized. It is believed that with the development of nano-composite materials with more excellent properties, the nano-composite materials will perform better in a plurality of fields.
The natural graphite is neither hydrophilic nor oleophilic, and the graphene prepared by the oxidation-reduction method does not undergo chemical treatment before reduction, but can be quickly gathered together in the reduction process to regenerate blocky graphite, so that the desired lamellar graphene is difficult to obtain. Even a small amount of lamellar graphene is obtained, the lamellar graphene also has the properties of non-hydrophilicity and non-lipophilicity, so that the lamellar graphene cannot be well compounded with other materials, the wide application of the graphene is limited, and the composite material cannot fully exert the excellent performance of the graphene. We therefore first considered surface intercalation modification of graphene oxide prior to preparation of graphene and proved to be feasible. This is because graphene prepared by a chemical method is obtained by reducing graphite oxide, and the graphite oxide sheet structure contains carbonyl and carboxyl groups at the periphery and contains highly active oxygen-containing functional groups such as hydroxyl and epoxy groups in the middle. The functional groups can be used for carrying out chemical treatments such as grafting, coating and the like on graphene with excellent performance to obtain graphene oxide containing certain specific functional groups, and then the specific functional groups can be used for reacting with other high polymers to form the functional polymer nanocomposite with chemical bond connection. The modified graphene oxide can be stably dispersed in an organic solvent through the observation of a settleability experiment.
After modifying graphene oxide, we finally modify polyurethane with the modified functionalized graphene oxide. It is known that although polyurethane itself has many excellent properties such as low temperature resistance, abrasion resistance, etc., there are many disadvantages such as poor water resistance, poor erosion resistance, low strength, etc., in order to improve these disadvantages, a more excellent material is obtained to meet our needs.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene modified polyurethane composite material, which is simple and the obtained graphene modified polyurethane composite material has good water resistance and erosion resistance.
The invention is realized by the following technical scheme:
a preparation method of a graphene modified polyurethane composite material comprises the following steps:
firstly, preparing graphene oxide:
(1) adding acid and sodium salt into a container, cooling, adding graphite powder and an oxidant, stirring, heating for reaction, and adding deionized water after reaction;
(2) then adding a hydrogen peroxide solution, filtering, washing a product with hydrochloric acid until no acid radical exists in the filtrate, washing the product to be neutral, and finally centrifuging, drying and freezing to obtain graphene oxide;
secondly, preparing modified graphene oxide:
(1) ultrasonically dispersing graphene oxide in deionized water, adding a reducing agent and hydrochloric acid, and stirring;
(2) then heating, removing excessive reducing agent, washing, filtering, drying and grinding to obtain modified graphene oxide;
thirdly, preparing the composite material:
(1) ultrasonically dispersing the modified graphene oxide in polyurethane to obtain a graphene-polyurethane dispersion liquid;
(2) and adding a photoinitiator into the graphene-polyurethane dispersion liquid, stirring to obtain a mixed liquid, pouring the mixed liquid into a reaction kettle, standing, heating, and finally curing to obtain the graphene-polyurethane composite material.
Further, preparation of graphene oxide: in the step (1), the mass-to-volume ratio of the sodium salt to the acid is 0.025-0.05g/ml, and the mass ratio of the graphite powder to the oxidant is 1: (5-8), wherein the mass ratio of the sodium salt to the graphite powder is 1: 1, the volume ratio of the acid to the deionized water is 1: (5-10).
Further, preparation of graphene oxide: in the step (1), the acid is concentrated sulfuric acid, the sodium salt is sodium nitrate, and the oxidant is potassium permanganate.
Further, preparation of graphene oxide: in the step (1), the cooling is carried out by adopting ice water bath cooling, the cooling is carried out to 5-10 ℃, the stirring time is 1-3 hours, the temperature after the temperature rise is 30-40 ℃, and the reaction time is 2-3 hours.
Further, preparation of graphene oxide: in the step (2), the mass fraction of hydrogen peroxide in the hydrogen peroxide solution is 30%, and the volume ratio of the hydrogen peroxide solution to the acid is 1: (8-10), wherein the hydrochloric acid is dilute hydrochloric acid with the concentration of 5%.
Further, preparation of modified graphene oxide: in the step (1), the reducing agent is aluminum powder, the mass volume ratio of the graphene oxide to the deionized water is 0.001-0.00125g/ml, and the mass ratio of the graphene oxide to the reducing agent is 1: (20-30), the mass volume ratio of the reducing agent to the hydrochloric acid is 0.05-0.1g/ml, the hydrochloric acid is concentrated hydrochloric acid with the concentration of 37%, and the stirring time is 1-3 hours.
Further, preparation of modified graphene oxide: in the step (2), the heating temperature is 70-90 ℃, and the heating time is 1-3 hours.
Further, preparation of the composite material: in the step (1), the mass ratio of the modified graphene oxide to the polyurethane is (1-5): 200.
further, preparation of the composite material: in the step (2), the mass ratio of the photoinitiator to the graphene-polyurethane dispersion liquid is (1-2): 20, stirring under the condition of keeping out light and at room temperature.
Further, preparation of the composite material: in the step (2), the reaction kettle is a polytetrafluoroethylene reaction kettle, the standing time is 20-24 hours, the heating temperature is 60-80 ℃, the heating time is 8-12 hours, and the curing is carried out in a photocuring machine.
The invention has the beneficial effects that:
the preparation method is simple, the problem of internal stress concentration of the composite material caused by secondary agglomeration generated by Van der Waals force between graphene and polyurethane is solved through modification of graphene, and the strength is increased. According to the invention, the performance of the polyurethane is effectively enhanced by compounding the modified graphene oxide and the polyurethane, which shows that the graphene and the polyurethane can be used for preparing the composite material with excellent performance. The modified graphene oxide is added into polyurethane to prepare the composite material, and researches show that the modified graphene oxide has an obvious reinforcing effect on the water resistance and the corrosion resistance of the polyurethane, the modified graphene oxide has a good reinforcing effect on the polyurethane, and the prepared graphene-polyurethane composite material is excellent in performance, strong in water resistance, good in erosion resistance and high in strength.
Drawings
FIG. 1 is a scanning electron micrograph of polyurethane;
fig. 2 is a scanning electron microscope image of the graphene-polyurethane composite material.
Detailed Description
The invention is illustrated in detail below with reference to specific examples:
example 1
A preparation method of a graphene modified polyurethane composite material comprises the following steps:
firstly, preparing graphene oxide:
(1) adding 200ml of 98% concentrated sulfuric acid and 5g of sodium nitrate into a dry beaker, cooling to 5 ℃ with ice water, then adding 5g of graphite powder and 30g of potassium permanganate into the beaker, stirring for 2 hours (when the potassium permanganate is added, the graphite powder and the potassium permanganate are slowly added, and the temperature of a reaction system is controlled not to exceed 15 ℃), after stirring is finished, heating to 35 ℃ and reacting for 2 hours, after the reaction is finished, adding 1000ml of deionized water, and stirring for 30 minutes (when the deionized water is added, the temperature is controlled to be between 90 and 98 ℃);
(2) then adding 20ml of hydrogen peroxide solution (wherein the mass fraction of hydrogen peroxide is 30%) into the reaction system in the step (1), filtering while hot, washing the filtered product with 5% hydrochloric acid, washing until no sulfate radical exists in the filtrate of the product (no precipitate is detected through the solution, namely no sulfate radical exists), washing the product with deionized water to be neutral after washing with hydrochloric acid, centrifuging, drying at 60 ℃ for 2 hours, and finally freezing to obtain graphene oxide;
secondly, preparing modified graphene oxide:
(1) taking 0.1g of the prepared graphene oxide, ultrasonically dispersing the graphene oxide in 100ml of deionized water, then adding 2.0g of aluminum powder and 40ml of hydrochloric acid with the concentration of 37%, and stirring for 2 hours;
(2) stirring, heating to 80 ℃ for reaction for 2 hours, adding a proper amount of dilute hydrochloric acid after the reaction to remove excessive aluminum powder in the reaction system, washing with deionized water, filtering, drying at 60 ℃ for 1 hour, and finally grinding the product to obtain modified graphene oxide;
thirdly, preparing the composite material:
(1) taking 0.05g of modified graphene oxide, and ultrasonically dispersing the modified graphene oxide in 10g of polyurethane to obtain a graphene-polyurethane dispersion liquid;
(2) taking 5g of graphene-polyurethane dispersion liquid, adding 0.25g of ammonium persulfate into the graphene-polyurethane dispersion liquid, stirring for 1 hour under the condition of keeping out of the sun and room temperature to obtain a mixed liquid, then pouring the mixed liquid into a polytetrafluoroethylene reaction kettle, standing for 24 hours, heating to 60 ℃ after standing for reaction for 10 hours, and finally curing in a photocuring machine to obtain the graphene-polyurethane composite material.
Example 2
A preparation method of a graphene modified polyurethane composite material comprises the following steps:
firstly, preparing graphene oxide:
(1) adding 200ml of 98% concentrated sulfuric acid and 8g of sodium nitrate into a dry beaker, cooling to 10 ℃ with ice water, then adding 8g of graphite powder and 64g of potassium permanganate into the beaker, stirring for 1 hour (when the potassium permanganate is added, slowly adding the graphite powder and controlling the temperature of a reaction system to be not more than 15 ℃), after stirring is finished, heating to 30 ℃ and reacting for 3 hours, after the reaction is finished, adding 1500ml of deionized water, and stirring for 30 minutes (when the deionized water is added, controlling the temperature to be between 90 and 98 ℃);
(2) adding 23ml of hydrogen peroxide solution (wherein the mass fraction of hydrogen peroxide is 30%) into the reaction system in the step (1), filtering while hot, washing the filtered product with 5% hydrochloric acid, washing until no sulfate radical exists in the filtrate of the product (no precipitate is detected through the solution, namely no sulfate radical exists), washing the product with deionized water to be neutral after washing with hydrochloric acid, centrifuging, drying at 60 ℃ for 2 hours, and finally freezing to obtain graphene oxide;
secondly, preparing modified graphene oxide:
(1) taking 0.1g of the prepared graphene oxide, ultrasonically dispersing the graphene oxide in 80ml of deionized water, then adding 2.5g of aluminum powder and 31ml of hydrochloric acid with the concentration of 37%, and stirring for 1 hour;
(2) stirring, heating to 70 ℃ for reaction for 3 hours, adding a proper amount of dilute hydrochloric acid after the reaction to remove excessive aluminum powder in the reaction system, washing with deionized water, filtering, drying at 60 ℃ for 1 hour, and finally grinding the product to obtain modified graphene oxide;
thirdly, preparing the composite material:
(1) taking 0.1g of modified graphene oxide, and ultrasonically dispersing the modified graphene oxide in 10g of polyurethane to obtain a graphene-polyurethane dispersion liquid;
(2) taking 5g of graphene-polyurethane dispersion liquid, adding 0.5g of ammonium persulfate into the graphene-polyurethane dispersion liquid, stirring for 1 hour under the condition of keeping out of the sun and room temperature to obtain a mixed liquid, then pouring the mixed liquid into a polytetrafluoroethylene reaction kettle, standing for 22 hours, heating to 70 ℃ after standing for reaction for 12 hours, and finally curing in a photocuring machine to obtain the graphene-polyurethane composite material.
Example 3
A preparation method of a graphene modified polyurethane composite material comprises the following steps:
firstly, preparing graphene oxide:
(1) adding 200ml of 98% concentrated sulfuric acid and 10g of sodium nitrate into a dry beaker, cooling to 7 ℃ with ice water, then adding 10g of graphite powder and 50g of potassium permanganate into the beaker, stirring for 3 hours (when the potassium permanganate is added, slowly adding the mixture and controlling the temperature of a reaction system not to exceed 15 ℃), after stirring is finished, heating to 40 ℃ and reacting for 1 hour, after the reaction is finished, adding 2000ml of deionized water, and stirring for 30 minutes (when the deionized water is added, controlling the temperature to be between 90 and 98 ℃);
(2) then adding 25ml of hydrogen peroxide solution (wherein the mass fraction of hydrogen peroxide is 30%) into the reaction system in the step (1), filtering while hot, washing the filtered product with 5% hydrochloric acid, washing until no sulfate radical exists in the product filtrate (no precipitate is detected through the solution, namely no sulfate radical exists), washing the product filtrate with deionized water to be neutral after washing with hydrochloric acid, centrifuging, drying at 60 ℃ for 2 hours, and finally freezing to obtain graphene oxide;
secondly, preparing modified graphene oxide:
(1) taking 0.1g of the prepared graphene oxide, ultrasonically dispersing the graphene oxide in 90ml of deionized water, then adding 3.0g of aluminum powder and 30ml of 37% hydrochloric acid, and stirring for 3 hours;
(2) stirring, heating to 90 ℃ for reaction for 1 hour, adding a proper amount of dilute hydrochloric acid after the reaction to remove excessive aluminum powder in the reaction system, washing with deionized water, filtering, drying at 60 ℃ for 1.5 hours, and finally grinding the product to obtain modified graphene oxide;
thirdly, preparing the composite material:
(1) taking 0.1g of modified graphene oxide, and ultrasonically dispersing the modified graphene oxide in 4g of polyurethane to obtain a graphene-polyurethane dispersion liquid;
(2) taking 4g of graphene-polyurethane dispersion liquid, adding 0.3g of ammonium persulfate into the graphene-polyurethane dispersion liquid, stirring for 1 hour under the condition of keeping out of the sun and room temperature to obtain a mixed liquid, then pouring the mixed liquid into a polytetrafluoroethylene reaction kettle, standing for 20 hours, heating to 80 ℃ after standing for reaction for 8 hours, and finally curing in a photocuring machine to obtain the graphene-polyurethane composite material.
Example 4
Taking polyurethane and the graphene-polyurethane composite material prepared in the above example 1 respectively for SEM characterization: and obtaining a polyurethane scanning electron microscope image shown in fig. 1 and a graphene-polyurethane composite material scanning electron microscope image shown in fig. 2. It can be seen from the scanning electron microscope image of polyurethane in fig. 1 that the surface of polyurethane has pores and voids, and from the scanning electron microscope image of graphene-polyurethane composite material in fig. 2, it can be seen that the modified graphene oxide is uniformly distributed on the surface of polyurethane, and the addition of the modified graphene oxide improves the compactness of the surface of the composite material, so that the water resistance is improved.
Example 5
Polyurethane and the graphene-polyurethane composite materials prepared in the above examples 1 to 3 were respectively taken, and then a nano indenter was used to perform a strength test, and the results are shown in table 1:
| type of material | Hardness value/Mpa |
| Polyurethane | 16.2 |
| Example 1 | 23.8 |
| Example 2 | 23.4 |
| Example 3 | 23.5 |
TABLE 1
From table 1, it can be seen that the strength of the graphene-polyurethane composite material prepared by the present invention is significantly enhanced, because the modified graphene oxide is uniformly dispersed on the surface of the polyurethane after being added into the polyurethane, a covalent crosslinking reaction occurs between the modified graphene oxide and the polyurethane molecular chains to form a network structure, external stress can be effectively transferred from the matrix to the modified graphene oxide, and the addition of the modified graphene oxide fills up the defect of the micro-pores of the polyurethane caused by curing, such that the obtained composite material can better resist the external force effect, and the strength is increased.
Example 6
The graphene-polyurethane composite material prepared in the above example 1 is subjected to a simulated sand erosion test to test erosion resistance, which is specifically shown in table 2:
| sand discharge rate | Percentage of erosion reduction |
| 30g/min | 49.19％ |
| 45g/min | 46.54％ |
| 50g/min | 44.40％ |
TABLE 2
As can be seen from table 2, the erosion rate of the graphene-polyurethane composite material is significantly reduced under different test conditions. On one hand, the modified graphene oxide is added into the polyurethane and then has better interaction with the polyurethane, so that the strength of the composite material is improved, the flexibility of the composite material is not lost, the sand erosion resistance of the coating is stronger, and the erosion rate is reduced; on the other hand, the modified graphene oxide can play a certain lubricating role, so that the friction force generated when sand grains are contacted with the surface of the material is reduced, the cutting damage of the sand grains to the material is reduced, and the effect of reducing the erosion rate is also played.
The above-mentioned preferred embodiments of the present invention are provided for illustration only and not for the purpose of limiting the invention. Obvious variations or modifications of the present invention are within the scope of the present invention.
Claims (10)
1. A preparation method of a graphene modified polyurethane composite material is characterized by comprising the following steps:
firstly, preparing graphene oxide:
(1) adding acid and sodium salt into a container, cooling, adding graphite powder and an oxidant, stirring, heating for reaction, and adding deionized water after reaction;
(2) then adding a hydrogen peroxide solution, filtering, washing a product with hydrochloric acid until no acid radical exists in the filtrate, washing the product to be neutral, and finally centrifuging, drying and freezing to obtain graphene oxide;
secondly, preparing modified graphene oxide:
(1) ultrasonically dispersing graphene oxide in deionized water, adding a reducing agent and hydrochloric acid, and stirring;
(2) then heating, removing excessive reducing agent, washing, filtering, drying and grinding to obtain modified graphene oxide;
thirdly, preparing the composite material:
(1) ultrasonically dispersing the modified graphene oxide in polyurethane to obtain a graphene-polyurethane dispersion liquid;
(2) and adding a photoinitiator into the graphene-polyurethane dispersion liquid, stirring to obtain a mixed liquid, pouring the mixed liquid into a reaction kettle, standing, heating, and finally curing to obtain the graphene-polyurethane composite material.
2. The preparation method of the graphene modified polyurethane composite material according to claim 1, wherein the preparation of graphene oxide is as follows: in the step (1), the mass-to-volume ratio of the sodium salt to the acid is 0.025-0.05g/ml, and the mass ratio of the graphite powder to the oxidant is 1: (5-8), wherein the mass ratio of the sodium salt to the graphite powder is 1: 1, the volume ratio of the acid to the deionized water is 1: (5-10).
3. The preparation method of the graphene modified polyurethane composite material according to claim 1, wherein the preparation of graphene oxide is as follows: in the step (1), the acid is concentrated sulfuric acid, the sodium salt is sodium nitrate, and the oxidant is potassium permanganate.
4. The preparation method of the graphene modified polyurethane composite material according to claim 1, wherein the preparation of graphene oxide is as follows: in the step (1), the cooling is carried out by adopting ice water bath cooling, the cooling is carried out to 5-10 ℃, the stirring time is 1-3 hours, the temperature after the temperature rise is 30-40 ℃, and the reaction time is 2-3 hours.
5. The preparation method of the graphene modified polyurethane composite material according to claim 1, wherein the preparation of graphene oxide is as follows: in the step (2), the mass fraction of hydrogen peroxide in the hydrogen peroxide solution is 30%, and the volume ratio of the hydrogen peroxide solution to the acid is 1: (8-10), wherein the hydrochloric acid is dilute hydrochloric acid with the concentration of 5%.
6. The preparation method of the graphene-modified polyurethane composite material according to claim 1, wherein the preparation of the modified graphene oxide is as follows: in the step (1), the reducing agent is aluminum powder, the mass volume ratio of the graphene oxide to the deionized water is 0.001-0.00125g/ml, and the mass ratio of the graphene oxide to the reducing agent is 1: (10-20), the mass-to-volume ratio of the reducing agent to the hydrochloric acid is 0.05-0.1g/ml, and the stirring time is 1-3 hours.
7. The preparation method of the graphene-modified polyurethane composite material according to claim 1, wherein the preparation of the modified graphene oxide is as follows: in the step (2), the heating temperature is 70-90 ℃, and the heating time is 1-3 hours.
8. The preparation method of the graphene modified polyurethane composite material according to claim 1, wherein the preparation of the composite material comprises the following steps: in the step (1), the mass ratio of the modified graphene oxide to the polyurethane is (1-5): 200.
9. the preparation method of the graphene modified polyurethane composite material according to claim 1, wherein the preparation of the composite material comprises the following steps: in the step (2), the photoinitiator is ammonium persulfate, and the mass ratio of the photoinitiator to the graphene-polyurethane dispersion liquid is (1-2): 20, stirring under the condition of keeping out light and at room temperature.
10. The preparation method of the graphene modified polyurethane composite material according to claim 1, wherein the preparation of the composite material comprises the following steps: in the step (2), the reaction kettle is a polytetrafluoroethylene reaction kettle, the standing time is 20-24 hours, the heating temperature is 60-80 ℃, the heating time is 8-12 hours, and the curing is carried out in a photocuring machine.
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| CN112897706A (en) * | 2021-01-13 | 2021-06-04 | 北京大学 | Enhanced carboxylated graphene modified polyurethane carrier and preparation method and application thereof |
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| CN112897706A (en) * | 2021-01-13 | 2021-06-04 | 北京大学 | Enhanced carboxylated graphene modified polyurethane carrier and preparation method and application thereof |
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Application publication date: 20200911 |