CN110862700A - Preparation method of oil-water amphiphilic powder and powder prepared by same - Google Patents
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Abstract
The invention provides a preparation method of oil-water amphiphilic powder, which comprises the following steps: adding the original powder into a vacuum reactor, and carrying out heat treatment and primary vacuumizing treatment; carrying out heat treatment on the vacuum reactor to a reaction temperature of 0-500 ℃ to obtain a vacuum reactor to be reacted; introducing gas containing fluorine simple substance into a vacuum reactor to be reacted, reacting at a reaction temperature to obtain a reacted vacuum reactor, and opening the reacted vacuum reactor to obtain oil-water amphiphilic powder; the original powder is inorganic powder which can be used as an additive to be added into an organic matrix to improve the performance of a terminal product. The preparation method can be used for preparing oil-water amphiphilic powder, has higher surface energy, can be used as an additive to be added into an organic matrix material, has good compatibility with various materials such as resin and the like, has simple preparation method and low cost, and can permanently improve the performance of the generated powder.
Description
Technical Field
The invention belongs to the technical field of additive preparation, and particularly relates to a preparation method of oil-water amphiphilic powder and the oil-water amphiphilic powder.
Background
Inorganic powders are increasingly being tried as additives to organic substrates such as coatings, rubbers, resins, etc. for improving the properties of end products because of their special properties. However, these inorganic powders generally have problems such as easy agglomeration and poor compatibility and adhesion with a matrix system. Generally, these inorganic materials are modified by means of a modifier, oxidation, or the like, but the powder of these inorganic materials is chemically stable, and the desired effect may not be obtained by the above modification method.
The introduction of the fluorine-containing group into the material can increase the lipophilicity of the material, and the carbon-fluorine bond is a strong polar bond, so that the material has the oil-water amphiphilic characteristic if the carbon-fluorine bond can be introduced into the material in a proper way, and the material has excellent interface performances such as good dispersibility and adhesiveness in most solvents and base materials. However, the surface energy of the conventional fluorine-containing materials such as polytetrafluoroethylene, polyvinylidene fluoride and the like is obviously lower than that of the conventional materials, and even the conventional materials show super-hydrophobic characteristics, and the powder material of the conventional fluorine-containing materials has the characteristics of easy agglomeration and difficult adhesion. The applicant verifies through a large number of experiments that the material contains strong polar carbon-fluorine bonds with better symmetry, which shows stronger non-polarity, and the lipophilicity of the material is greatly reduced.
Therefore, the development of a process for modifying inorganic powders by introducing fluorine into the powders in a random manner is urgent.
The invention provides a method for solving the defects in the prior art.
Disclosure of Invention
The invention aims to provide a preparation method of oil-water amphiphilic powder, which comprises the steps of adjusting reaction conditions and time, reacting a fluorine simple substance with original powder, randomly replacing a part of elements on the surface of the original powder to form irregular carbon-fluorine bonds, enabling the modified inorganic powder to have higher surface activity, and improving lipophilicity due to introduction of the fluorine element, so that the modified inorganic powder has hydrophile lipophilicity. Compared with the conventional modification process, the powder obtained by the method has good modification effect, and the performance after modification lasts for a long time, even reaches permanent aging.
The invention also aims to provide powder obtained by the preparation method, which has hydrophilic and lipophilic properties and high surface performance, can be added into an organic matrix as a modified material, has good compatibility with base materials such as various resins and the like, and can be used for modifying the materials such as the resins.
In order to achieve the purpose, the technical scheme of the invention is a preparation method of oil-water amphiphilic powder, which comprises the following steps:
adding original powder into a vacuum reactor, and carrying out heat treatment and primary vacuumizing treatment; wherein the vacuum reactor is subjected to heat treatment to a reaction temperature of 0-500 ℃ to obtain a vacuum reactor to be reacted;
introducing gas containing fluorine simple substance into a vacuum reactor to be reacted, reacting at a reaction temperature to obtain a reacted vacuum reactor, and opening the reacted vacuum reactor to obtain oil-water amphiphilic powder;
the original powder is inorganic powder which can be used as an additive to be added into an organic matrix to improve the performance of a terminal product.
According to the method of the present invention, preferably, in the step (1), the raw powder is one or more selected from graphite, graphene, carbon nanotubes, fullerene, molybdenum disulfide, silicon carbide, titanium carbide, boron nitride and alumina.
According to the method of the present invention, preferably, in the step (1), the pressure in the vacuum reactor to be reacted is-0.1 to 0 Mpa.
According to the method of the present invention, preferably, in the step (2), the gas containing elemental fluorine is selected from elemental fluorine, or a mixed gas of elemental fluorine and an inert gas; wherein the mass ratio of the fluorine simple substance in the gas containing the fluorine simple substance to the original powder is 1: 1000-10.
According to the method of the present invention, preferably, in the step (2), the reaction is carried out at a reaction temperature for 10min to 5 hr.
According to the method of the present invention, preferably, in the step (2), the vacuum reactor after the reaction is subjected to a second vacuum treatment before being opened, and the gas extracted during the second vacuum treatment absorbs a small amount of HF and residual elemental fluorine contained therein through the adsorbent.
According to the method of the present invention, preferably, in the step (1), the vacuum reactor is a static vacuum reactor made of monel material, the raw powder is placed on a gas permeable tray, and the tray is made of a material selected from metal or polyethylene; or
In the step (1), the vacuum reactor is a rotary or vibrating vacuum reactor made of Monel material.
According to the method of the invention, preferably, in the step (1), the first vacuum-pumping treatment comprises filling inert gas, and vacuumizing to a pressure of-0.1 to 0 Mpa; repeating the steps for 1-5 times.
According to the method of the invention, preferably, in the step (2), the second vacuum-pumping treatment comprises filling inert gas, and vacuumizing to-0.1-0 Mpa; repeating the steps for 1-5 times.
In addition, the invention also provides powder and the oil-water amphiphilic powder prepared by the preparation method.
The invention has the beneficial effects that:
the preparation method can be used for preparing oil-water amphiphilic powder, has higher surface energy, can be used as an additive to be added into an organic matrix material, has good compatibility with various materials such as resin and the like, has simple preparation method and low cost, and can permanently improve the performance of the generated powder.
Drawings
Fig. 1 is a schematic diagram of modified graphene dispersed in polyol according to the present invention.
Fig. 2 is a comparison graph of graphene before modification and graphene after modification dispersed in water respectively and standing for 24 hours.
Fig. 3 is a comparison graph of the modified graphene of example 1 of the present invention and the modified graphene of the comparative example.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below.
The pressure in the present invention refers to the relative pressure.
The preparation method of the oil-water amphiphilic powder comprises the following steps: (1) a preparation step of a vacuum reactor to be reacted; (2) and (3) a vacuum reactor reaction step.
< preparation step of vacuum reactor to be reacted >
Adding original powder into a vacuum reactor, and carrying out primary vacuumizing treatment and heating treatment; and heating to a reaction temperature which is not higher than the melting point of the powder, and preparing the vacuum reactor to be reacted through the steps. In the invention, the original powder is selected from one or more mixtures of graphite, graphene, carbon nano tube, fullerene, molybdenum disulfide, silicon carbide, titanium carbide, boron nitride and alumina; preferably, the original powder is selected from one or more of graphite, graphene, carbon nano tube, fullerene, molybdenum disulfide and silicon carbide; more preferably, the raw powder is selected from one of graphene and silicon carbide. By adopting the original powder, the original powder can be better modified, and particularly the surface energy rising range is larger.
In the invention, the median particle size of the powder is 0.01 mu m-1 mm; preferably, the median particle size of the powder is 0.1-500 μm; more preferably, the median particle diameter of the powder is 20 to 200. mu.m.
In the invention, after the vacuum reactor to be reacted is subjected to heat treatment and first vacuumizing treatment, the pressure in the vacuum reactor to be reacted is-0.1-0 Mpa; preferably, the pressure in the vacuum reactor to be reacted is between-0.1 and-0.05 MPa; more preferably, the pressure in the vacuum reactor to be reacted is between-0.1 and-0.08 MPa. Carrying out heat treatment on a vacuum reactor to be reacted to reach the reaction temperature of 0-500 ℃; preferably, the reaction temperature is 0 ℃ to 300 ℃; more preferably, the reaction temperature is 20 ℃ to 300 ℃; further preferably, the reaction temperature is 60 ℃ to 300 ℃. According to one embodiment of the present invention, the pressure in the vacuum reactor to be reacted is-0.1 to-0.08 MPa, and the reaction temperature is 60 to 300 ℃. By adopting the pressure range, gas impurities in the vacuum reactor, including oxygen, existing moisture and the like, can be removed better, particularly, the moisture is removed completely, the moisture reacts violently with the fluorine simple substance and releases heat, and irritant oxygen fluoride is generated. The reaction equation of water and fluorine and the reaction equation of oxygen and fluorine are shown in the following formulas (1) and (2):
2F2+2H2O＝2HF+O2(1)
O2+F2＝OF2(2)
because the reaction of the fluorine simple substance and the original powder is exothermic, the reaction temperature range can be adopted to promote the reaction of the fluorine simple substance and the original powder, and the reaction speed can be controlled to control the exothermic rate, so that the generation of a symmetrical structure of a fluorinated bond caused by excessive reaction is prevented.
In one embodiment of the present invention, the vacuum reactor is a static vacuum reactor made of monel material, and the raw powder is placed on a gas permeable tray made of metal or polyethylene. The Monel vacuum reactor has better tolerance to fluorine simple substances, and other materials can be selected and need to be passivated to prevent the adsorption and release of potential impurities to reaction gas in the reaction process. The air-permeable tray can enable the fluorine simple substance to contact the original powder of each layer more uniformly, so that the fluorine simple substance can react with the original powder more uniformly and fully. In another embodiment of the present invention, the vacuum reactor is a rotary or vibrating vacuum reactor of monel material. The vacuum reactor can be used for realizing more uniform reaction of powder by stirring, throwing and other modes of the powder.
In the invention, the first vacuum-pumping treatment comprises filling inert gas at-0.05-0.1 Mpa, and pumping vacuum to-0.1-0 Mpa; repeating the above steps 0-5 times, preferably repeating the above steps 1-4 times, more preferably 2-3 times. According to an embodiment of the present invention, the first vacuuming process comprises filling inert gas to a relative pressure of 0Mpa, vacuuming to-0.095 Mpa, and repeating the above steps 2 times. The inert gas is preferably one or a mixture of two of nitrogen and argon.
< vacuum reactor reaction step >
The invention leads gas containing fluorine simple substance into a vacuum reactor to be reacted, and the reaction is carried out at the reaction temperature to obtain the reacted vacuum reactor, and the reacted vacuum reactor is opened to obtain oil-water amphiphilic powder. The fluorine exists in the form of fluorine ions, taking graphene as an example, and the reaction equation in the vacuum reactor is (3):
in the invention, the gas containing the elemental fluorine is selected from elemental fluorine or a mixed gas of the elemental fluorine and an inert gas, preferably a mixed gas of the elemental fluorine and the inert gas, more preferably a mixed gas of the elemental fluorine and nitrogen, and a mixed gas of the elemental fluorine and argon. In one embodiment of the present invention, the concentration of the elemental fluorine in the mixed gas of the elemental fluorine and the inert gas is 1 vol% to 99 vol%, preferably 1 vol% to 50 vol%; more preferably 10 vol% -30 vol%, and the reaction rate is controlled by controlling the proportion of the fluorine simple substance and the inert gas, so that the phenomenon that the reaction is too fast or too slow, the reaction time is too long, and the reaction is too fast, so that the local part is easy to generate excessive reaction, the excessive fluorine simple substance is consumed, and the other parts are insufficient in reaction, and the overall performance of the modified powder is seriously influenced is prevented.
In the invention, the median particle size of the powder is 0.01 mu m-1 mm; preferably, the median particle size of the powder is 0.1-500 μm; more preferably, the median particle diameter of the powder is 20 to 200. mu.m.
In the invention, the mass ratio of the fluorine simple substance in the gas containing the fluorine simple substance to the original powder is 1: 000-10; preferably, the mass ratio is 1: 500-20; more preferably, the mass ratio is 1: 300-20. By adopting the mass ratio, the appearance of symmetrical carbon-fluorine bonds can be avoided on the premise of ensuring higher fluorine content in the oil-water amphiphilic powder, namely the surface energy of the oil-water amphiphilic powder is increased. In the present invention, the vacuum reactor to be reacted is reacted at a reaction temperature for 10min to 5hr, preferably, for 20min to 3hr, more preferably, for 30min to 2 hr; by adopting the reaction time, the appearance of symmetrical carbon-fluorine bonds can be avoided on the premise of ensuring higher fluorine content in the oil-water amphiphilic powder, namely the surface energy of the oil-water amphiphilic powder is increased. Experiments prove that the performance of the oil-water amphiphilic powder obtained after the reaction of the fluorine simple substance and the original powder in the mass ratio for 1hr is well improved, the performance is basically stable after the reaction for 3hr, the surface energy of the oil-water amphiphilic powder begins to decrease along with the continuous lapse of the reaction time, and the applicant believes that after the reaction time is 3hr, symmetrical carbon-fluorine bonds begin to appear and randomly-appearing carbon-fluorine bonds begin to decrease along with the continuous progress of the reaction.
In the invention, the vacuum reactor after reaction is subjected to secondary vacuum treatment before being opened, and the gas extracted during the secondary vacuum treatment absorbs a small amount of HF and residual fluorine contained in the gas through the adsorbent. Preferably, the adsorbent is selected from water, calcium carbonate particles, activated carbon particles; more preferably, the adsorbent is selected from calcium carbonate particles.
The second vacuumizing treatment comprises the steps of filling inert gas until the pressure is-0.05-0.1 Mpa, and vacuumizing until the pressure is-0.1-0 Mpa; repeating the steps for 1-5 times. Preferably, the above steps are repeated 1 to 4 times, more preferably 2 to 3 times. According to one embodiment of the present invention, the second evacuation process comprises filling inert gas at 0.1MPa, evacuating to-0.1 MPa, and repeating the above steps for 2 times. The inert gas is preferably one or a mixture of two of nitrogen and argon.
As an optional step, the oil-water amphiphilic powder obtained by opening the vacuum reactor after the reaction is further subjected to a heating post-treatment step, wherein the heating post-treatment step comprises the steps of heating the oil-water amphiphilic powder to 20-300 ℃, heating for 10-120min, and removing hydrogen fluoride attached to the surface of the oil-water amphiphilic powder; preferably, the oil-water amphiphilic powder is heated to 50-150 ℃ for 40-60 min. Some hydrogen fluoride remains in the oil-water amphiphilic powder after the reaction, the hydrogen fluoride is acidic, the subsequent use of the powder can be affected, and the human body is damaged to a certain extent.
< oil-water amphiphilic powder >
The oil-water amphiphilic powder is prepared by the preparation method, and details are not repeated here. The oil-water amphiphilic powder prepared by the preparation method is introduced with fluorine elements in a random mode, breaks through the convention of symmetrical appearance of fluorine-containing structures, greatly increases the polarity and surface energy of the powder, and permanently improves the compatibility of the powder and a compound matrix.
Introduction to test methods
And (3) testing the dispersion performance:
1. filling 1/2-2/3 of solvent (water or organic solvent) into a transparent bottle, and pouring a small amount of powder into the transparent bottle (the small amount of powder is 1/2 which is smaller than the volume of the solvent in the transparent bottle, so that the state of the powder in the water can be observed conveniently);
2. screwing the bottle cap and shaking for 10 s;
3. the powder in the solvent is carefully observed, and if no agglomeration phenomenon exists, the modification effect is good.
Example 1: modification of graphene
Material sources are as follows: sichuan university tin-free graphene application research center
The trade mark is as follows: g201
Layer number: 3 to 5
Volume of the reactor: 20L
Volume of the reactor: 20L static vacuum reactor with gas-filled pipe and vacuum-pumping pipe
The content of fluorine in the mixed gas of fluorine and nitrogen is 10vol percent
Preparation method
Step 1, paving 4g of graphene powder in a tray, and paving a layer of breathable filter cloth on the upper surface of the paved graphene to prevent the graphene powder from being blown away by gas;
step 2, placing the tray in a static vacuum reactor;
step 3, heating the temperature of the vacuum reactor to 200 ℃ by using a jacket and stabilizing for 1 hour;
step 4, carrying out vacuum pumping treatment on the interior of the vacuum reactor, wherein the pressure reaches-0.095 Mpa;
step 5, filling nitrogen into the vacuum reactor until the pressure is 0 Mpa;
step 6, repeating the steps 4, 5 and 2 times in sequence;
step 7, standing for 1 hour to ensure that the temperature of the powder is balanced at the temperature required by the reaction;
step 8, carrying out vacuum pumping treatment on the vacuum reactor until the pressure reaches-0.095 MPA;
step 9, filling a fluorine-nitrogen mixed gas with the fluorine content of 10 vol% into a vacuum reactor until the relative pressure in the vacuum reactor reaches-0.085 mpa (the mass of the introduced fluorine simple substance is 0.19g calculated by the following calculation method), namely the mass ratio of the fluorine simple substance to the powder is 1: 20;
step 10, standing the vacuum reactor for 2 hours (keeping the temperature of the vacuum reactor at 200 ℃) to allow the reaction to fully proceed;
step 11, after reacting for 2 hours, vacuumizing the vacuum reactor to the relative pressure of-0.095 Mpa;
step 12, filling nitrogen into the vacuum reactor to normal pressure;
step 13, vacuumizing the vacuum reactor to-0.095 Mpa;
step 14, repeating the steps 12, 13 and 2 times in sequence, wherein the steps can remove residues in the vacuum reactor as far as possible;
step 15, filling inert gas (or dry air) into the vacuum reactor to normal pressure;
step 16, opening the vacuum reactor and taking out the powder in the vacuum reactor;
step 17, placing the powder in a constant-temperature drying box at 80 ℃ for standing for 2 hours to remove residual hydrogen fluoride in the powder; and obtaining the modified graphene powder.
The modified graphene powder passes a dispersion performance test, and the modified graphene powder has good dispersibility in water and polyhydric alcohol. The schematic diagram of the dispersion condition of the modified graphene powder in the polyol is shown in fig. 1, wherein black spots with bright light are bubbles and are not agglomerated. As can be seen from FIG. 1, the modified graphene has good dispersibility in the polyol and no agglomeration phenomenon. Fig. 2 is a comparison graph of graphene before modification and graphene after modification dispersed in water respectively and left to stand for 24 hours. As can be seen from fig. 2, after the graphene before modification is stood for 24 hours, a precipitation phenomenon occurs, but the modified graphene is still uniformly dispersed in water after being stood for 24 hours, which further proves that the introduction of fluorine element increases the surface energy of the graphene, thereby improving the hydrophilicity and the dispersibility of the graphene.
Example 2: modification of silicon carbide powder
Material sources are as follows: jiangsu university
The trade mark is as follows: w07
Particle size: 7 μm
Volume of the reactor: 400L static vacuum reactor
The content of fluorine in the mixed gas of fluorine and nitrogen is 20vol percent
The preparation method comprises the following steps:
step 1, spreading 1500g of silicon carbide powder in a tray, wherein the thickness of the silicon carbide powder is about 5 cm;
step 2, placing the tray in a vacuum reactor;
step 3, heating the temperature of the vacuum reactor to 150 ℃ by using a jacket and stabilizing for 2 hours;
step 4, carrying out vacuum pumping treatment on the interior of the vacuum reactor until the pressure reaches-0.095 Mpa;
step 5, filling nitrogen into the vacuum reactor to normal pressure;
step 6, repeating the steps 4, 5 and 2 times in sequence;
step 7, standing the vacuum reactor for 1 hour to ensure that the temperature of the powder is balanced at the temperature required by the reaction;
step 8, carrying out vacuum pumping treatment on the reactor, wherein the pressure reaches-0.095 Mpa;
step 9, filling a fluorine-nitrogen mixed gas with 20 vol% of fluorine content into a vacuum reactor until the relative pressure in the vacuum reactor reaches-0.05 Mpa (the mass of the introduced fluorine simple substance is 39g calculated by the following calculation method), namely the mass ratio of the fluorine simple substance to the powder is about 1: 38;
step 10, standing for 3 hours (keeping the temperature of the vacuum reactor at 150 ℃) to allow the reaction to be fully carried out;
step 11, vacuumizing the vacuum reactor to the relative pressure of-0.095 Mpa;
step 12, filling nitrogen into the vacuum reactor to normal pressure;
step 13, vacuumizing the vacuum reactor to-0.095;
step 14, repeating the steps 13, 14 and 2 times in sequence to ensure that residues in the vacuum reactor are removed as clean as possible;
step 15, filling inert gas (or dry air) into the vacuum reactor to normal pressure;
step 16, opening the vacuum reactor and taking out the powder in the vacuum reactor;
step 17, placing the powder in a constant-temperature drying box at 120 ℃ for standing for 2 hours to remove residual hydrogen fluoride in the powder; obtaining the modified silicon carbide powder.
The modified silicon carbide powder passes the dispersion performance test, and the modified silicon carbide powder has good dispersibility in water and polyol.
Comparative example:
the difference from example 1 is: in the step 9, the charged fluorine-nitrogen mixed gas is a fluorine-nitrogen mixed gas with a fluorine content of 30 vol% to-0.085 Mpa (the mass of the introduced fluorine simple substance is 0.58g calculated by the following calculation method), namely the mass ratio of the fluorine simple substance to the powder is about 1: 7; in step 10, the reaction was allowed to stand for 5 hours (while maintaining the vacuum reactor temperature at 200 ℃ C.) to allow the reaction to proceed sufficiently. The final product appeared whitish, grayish (see fig. 3 right), rather than the original grayish black color of graphene (see fig. 3 left). The modified graphene prepared in example 1 and the comparative example is uniformly dispersed in water and stands for 24 hours, and experiments prove that the modified graphene prepared in the comparative example 1 has poor dispersibility in water and has even more agglomeration phenomenon than the graphene raw material before modification. This indicates the probability of occurrence of a carbon-fluorine bond that is significantly symmetrical in the mass ratio of elemental fluorine-containing substance to graphene.
According to the analysis, by the preparation method, the fluorine element is introduced to the surface of the original powder in a random manner by adjusting the mass ratio of the fluorine simple substance to the original powder, the reaction conditions and other influencing elements, so that the surface energy of the original powder is improved, and the hydrophilicity of the original powder is improved; and the introduction of fluorine improves the lipophilicity, so the powder prepared by the preparation method has oil-water amphiphilicity.
Note: mass m of fluorine used in the present inventionfThe calculation method is as follows:
mf＝(p2-p1)*VM/R/(T+273)*F*106
wherein p is1(Mpa) the pressure in the reactor before filling the fluorine/inert gas mixture;
p2(Mpa): pressure in the reactor after filling the fluorine/inert gas mixture;
f (vol%): the fluorine content in the fluorine/inert gas mixed gas;
V(m3): a reactor volume;
m is the molar mass of the fluorine simple substance is 38 g/mol;
r is gas constant 8.314;
t (. degree. C.) is the reaction temperature.
Claims (10)
1. The preparation method of the oil-water amphiphilic powder is characterized by comprising the following steps:
adding original powder into a vacuum reactor, and carrying out heat treatment and primary vacuumizing treatment; carrying out heat treatment on the vacuum reactor to a reaction temperature which is not higher than the melting point of the original powder to obtain a vacuum reactor to be reacted;
introducing gas containing fluorine simple substance into a vacuum reactor to be reacted, reacting at a reaction temperature to obtain a reacted vacuum reactor, and opening the reacted vacuum reactor to obtain oil-water amphiphilic powder;
the original powder is inorganic powder which can be used as an additive to be added into an organic matrix to improve the performance of a terminal product.
2. The method according to claim 1, wherein in step (1), the raw powder is selected from one or more of graphite, graphene, carbon nanotubes, fullerene, molybdenum disulfide, silicon carbide, titanium carbide, boron nitride and alumina.
3. The method according to claim 1, wherein in the step (1), the pressure in the vacuum reactor to be reacted is-0.1 to 0MPa, and the reaction temperature is 0 to 500 ℃.
4. The method according to claim 1, wherein in the step (2), the gas containing elemental fluorine is selected from elemental fluorine, or a mixed gas of elemental fluorine and an inert gas; wherein the mass ratio of the fluorine simple substance in the gas containing the fluorine simple substance to the original powder is 1: 1000-10.
5. The method according to claim 1, wherein in the step (2), the reaction is carried out at the reaction temperature for 10min to 5 hr.
6. The method according to claim 1, wherein in the step (2), the vacuum reactor after the reaction is subjected to a second vacuumizing treatment before being opened, and the gas extracted in the second vacuumizing treatment absorbs a small amount of HF and residual elemental fluorine contained in the gas through an adsorbent.
7. The method according to any one of claims 1 to 6, wherein in step (1), the vacuum reactor is a static vacuum reactor of Monel material, and the raw powder is placed on a gas permeable tray, and the tray is made of a material selected from metal or polyethylene; or
In the step (1), the vacuum reactor is a rotary or vibrating vacuum reactor made of Monel material.
8. The method according to any one of claims 1 to 6, wherein in the step (1), the first vacuum treatment comprises filling inert gas, and vacuumizing to a pressure of-0.1 to 0 MPa; repeating the steps for 1-5 times.
9. The method according to any one of claims 1 to 6, wherein in the step (2), the second vacuuming treatment comprises filling inert gas, and vacuumizing to-0.1 to 0 MPa; repeating the steps for 1-5 times.
10. A powder characterized by being an oil-water amphiphilic powder prepared by the method of claims 1-9.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1259978A (en) * | 1997-07-14 | 2000-07-12 | 美国3M公司 | Microporous fluorinated silica agglomerate and method of preparing and using same |
| CN1297470A (en) * | 1998-02-20 | 2001-05-30 | 范蒂科股份公司 | Organophilic phyllosilicates |
| CN102280368A (en) * | 2011-05-06 | 2011-12-14 | 中国科学院研究生院 | Patterned ultraviolet screening film preparation method |
| CN102581274A (en) * | 2012-03-08 | 2012-07-18 | 中国工程物理研究院化工材料研究所 | Method for coating micro/nano-metal powder by chemical vapor deposition |
| CN102730664A (en) * | 2012-07-04 | 2012-10-17 | 四川大学 | Carbon nano-tube with fluorine-containing surface and preparation method thereof |
| CN103086366A (en) * | 2013-01-16 | 2013-05-08 | 天津工业大学 | Preparation method of amphiphilic fluorinated-oxidized graphene |
| CN103420352A (en) * | 2013-08-08 | 2013-12-04 | 四川大学 | High-fluoride-content graphite fluoride and preparation method thereof |
| CN106672939A (en) * | 2016-12-05 | 2017-05-17 | 四川大学 | Fluorinated graphene with large surface area and high thermal stability and preparation method thereof |
| CN107500275A (en) * | 2017-10-20 | 2017-12-22 | 山东重山光电材料股份有限公司 | A kind of method for producing different Oil repellent fluorinated graphenes in enormous quantities |
| CN109179395A (en) * | 2018-10-23 | 2019-01-11 | 湖北工程学院 | A kind of fluorinated graphene and preparation method thereof, application |
| CN110240814A (en) * | 2019-06-18 | 2019-09-17 | 山东大学 | A kind of amphiphilic graphene oxide and preparation method thereof and the application in water paint |
| CN110343406A (en) * | 2019-06-20 | 2019-10-18 | 宁波锋成先进能源材料研究院 | A kind of fluorine containing silane modified graphene oxide and its preparation method and application |
-
2019
- 2019-12-03 CN CN201911223019.1A patent/CN110862700A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1259978A (en) * | 1997-07-14 | 2000-07-12 | 美国3M公司 | Microporous fluorinated silica agglomerate and method of preparing and using same |
| CN1297470A (en) * | 1998-02-20 | 2001-05-30 | 范蒂科股份公司 | Organophilic phyllosilicates |
| CN102280368A (en) * | 2011-05-06 | 2011-12-14 | 中国科学院研究生院 | Patterned ultraviolet screening film preparation method |
| CN102581274A (en) * | 2012-03-08 | 2012-07-18 | 中国工程物理研究院化工材料研究所 | Method for coating micro/nano-metal powder by chemical vapor deposition |
| CN102730664A (en) * | 2012-07-04 | 2012-10-17 | 四川大学 | Carbon nano-tube with fluorine-containing surface and preparation method thereof |
| CN103086366A (en) * | 2013-01-16 | 2013-05-08 | 天津工业大学 | Preparation method of amphiphilic fluorinated-oxidized graphene |
| CN103420352A (en) * | 2013-08-08 | 2013-12-04 | 四川大学 | High-fluoride-content graphite fluoride and preparation method thereof |
| CN106672939A (en) * | 2016-12-05 | 2017-05-17 | 四川大学 | Fluorinated graphene with large surface area and high thermal stability and preparation method thereof |
| CN107500275A (en) * | 2017-10-20 | 2017-12-22 | 山东重山光电材料股份有限公司 | A kind of method for producing different Oil repellent fluorinated graphenes in enormous quantities |
| CN109179395A (en) * | 2018-10-23 | 2019-01-11 | 湖北工程学院 | A kind of fluorinated graphene and preparation method thereof, application |
| CN110240814A (en) * | 2019-06-18 | 2019-09-17 | 山东大学 | A kind of amphiphilic graphene oxide and preparation method thereof and the application in water paint |
| CN110343406A (en) * | 2019-06-20 | 2019-10-18 | 宁波锋成先进能源材料研究院 | A kind of fluorine containing silane modified graphene oxide and its preparation method and application |
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