CN111718603A - Silicon dioxide surface modification method - Google Patents

Silicon dioxide surface modification method Download PDF

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CN111718603A
CN111718603A CN202010618202.8A CN202010618202A CN111718603A CN 111718603 A CN111718603 A CN 111718603A CN 202010618202 A CN202010618202 A CN 202010618202A CN 111718603 A CN111718603 A CN 111718603A
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silicon dioxide
sample
coupling agent
dioxide sample
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CN111718603B (en
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刘月田
何宇廷
柴汝宽
薛亮
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China University of Petroleum Beijing
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China University of Petroleum Beijing
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract

The invention provides a silicon dioxide surface modification method, which comprises the following steps: cleaning the surface of a silicon dioxide sample; and continuously heating the silicon dioxide sample at 490-510 ℃ for 30-35 minutes. Hydroxylating the surface of a silicon dioxide sample; putting a silicon dioxide sample into an electrolytic cell filled with 0.025-0.030% calcium chloride or magnesium chloride solution, electrically exciting the surface of the silicon dioxide by using direct current of 1.5-1.7V/cm to promote the breaking of Si-O-Si bonds and the H in water+、OH‑And (4) combining. Alkylating the silicon dioxide sample; the silica sample after hydroxylation by electro-stimulation was placed in the preferred KH 560: benzene: methanol 1: (9-11): (0.5-0.7) in the reaction solution of the novel silane coupling agent, finishing alkylation reaction to obtain surface modificationThe silica sample of (3). After the silicon dioxide sample is modified by using the silicon dioxide surface modification method provided by the invention, the wetting angle of deionized water on the surface of the silicon dioxide sample is obviously increased, and the hydrophobicity of the surface of the silicon dioxide sample is greatly improved.

Description

Silicon dioxide surface modification method
Technical Field
The invention relates to the technology of inorganic non-metallic materials, in particular to a silicon dioxide surface modification method.
Background
Silica is a main mineral of sandstone oil reservoirs, and the surface wettability of the silica directly influences the occurrence and migration characteristics of oil and water in pores. In order to accurately research the action effect and the action mechanism of different wettabilities, effective regulation of the surface wettability of the silicon dioxide substrate needs to be realized. The structure of the common silicon dioxide contains more silicon hydroxyl groups, so that the surface of the common silicon dioxide shows stronger hydrophilic property, and the silicon hydroxyl groups are easily combined with water molecules in the environment, thereby leading the surface of the silicon dioxide to adsorb and combine more water molecules and polar substances. The surface modification of silica can change the wettability of the silica surface and further improve the hydrophobicity of silica, which is called the modification of the silica surface.
At present, the silicon dioxide surface modification method mainly comprises an alcohol ester modification method, a polymer grafting method and a silane coupling agent method, and aims to reduce silicon hydroxyl groups on the surface of silicon dioxide and form a bonding layer of an organic matrix-a silane coupling agent-an inorganic matrix on the surface so as to achieve the hydrophobic and oleophilic specific effect. Neither the alcohol ester modification method nor the polymer grafting method pretreats the surface of the silicon dioxide, so that the surface of the silicon dioxide has fewer active reaction sites for grafting hydroxyl, the number of grafting functional groups is very limited, and the modification effect of the silicon dioxide is poor. The silane coupling agent method has the problems that the surface of silicon dioxide is not thoroughly cleaned and the hydroxylation of the silicon dioxide is insufficient, besides, the silane coupling agent is strongly hydrolyzed, hydrolysis products are strongly agglomerated, so that a large number of silane coupling agents are ineffective, grafting functional groups cannot be combined with hydroxyl groups on the surface of the silicon dioxide, and the problem of poor silicon dioxide modification effect is caused.
In conclusion, the traditional silicon dioxide surface modification technology has the problem of poor modification effect.
Disclosure of Invention
The invention provides a silicon dioxide surface modification method, which is used for solving the problem of poor modification effect of the traditional silicon dioxide surface modification technology. The silicon dioxide modified by the silicon dioxide surface modification method has the advantages that the wetting angle of the surface water phase is greatly increased, and the hydrophobicity is greatly improved.
In one aspect, the present invention provides a method for modifying a silica surface, comprising:
heating the cleaned silicon dioxide sample to 490-510 ℃ at high temperature, and continuously heating for 30-35 minutes to remove residual organic pollutants and adsorbed water on the surface of the silicon dioxide sample to the maximum extent; then, carrying out electric excitation hydroxylation treatment on the silicon dioxide sample; the direct current electrically excites the surface of the silicon dioxide to promote the breaking of the Si-O-Si bond and the H in the water+、OH-In combination, the surface hydroxyl groups of the silicon dioxide are effectively increased;
after the electric excitation hydroxylation treatment is finished, placing a silicon dioxide sample in a novel silane coupling agent reaction solution containing a coupling agent KH560, benzene and methanol, sequentially carrying out oscillation treatment and constant-temperature alkylation reaction to finish the alkylation reaction, and obtaining a surface-modified silicon dioxide sample after the reaction is finished.
In the method provided by the invention, in the stage of cleaning the silicon dioxide sample, the silicon dioxide sample is placed in a muffle furnace, and is heated to 490-510 ℃ at high temperature and is continuously heated for 30-35 minutes, so that water molecules, pollutants, impurities and the like adsorbed on the surface of the sample are thoroughly removed.
After the surface of the silicon dioxide sample is cleaned at high temperature, the silicon dioxide sample is electrically stimulated to hydroxylate, as shown in figure 1, the silicon dioxide sample is placed in a reaction vessel filled with electrolyte solution, and a direct current power supply is connected to two sides of the silicon dioxide sample. In the electro-active hydroxylation treatment, an inorganic salt solution may be used as the electrolytic medium. The inventors found that when the electrolyte solution of the electric excitation hydroxylation treatment is a magnesium chloride solution with a mass fraction of 0.025% to 0.030% or a calcium chloride solution with a mass fraction of 0.025% to 0.030% and the voltage on a unit length of the silica sample is in a range of 1.2V to 1.7V, the wetting angle is improved more remarkably. Preferably, the voltage of the electric excitation hydroxylation treatment is 1.6V/cm, and the corresponding electrolyte is a calcium chloride solution with the mass fraction of 0.025%.
After the electric excitation hydroxylation treatment is finished, preparing a novel coupling agent reaction solution containing a coupling agent KH560, benzene and methanol, and oscillating the novel coupling agent reaction solution. Adding a coupling agent KH560, benzene and methanol into a beaker, mixing, and then oscillating for 3-5 minutes, wherein the oscillating treatment is ultrasonic oscillating treatment. The oscillation in the preparation process of the novel coupling agent reaction liquid is beneficial to fully dispersing the methanol in the coupling agent, inhibiting the hydrolysis of the coupling agent KH560 and the condensation reaction of the hydrolysis product, and enhancing the dispersion stability of the reaction liquid.
And placing the silicon dioxide sample subjected to electric excitation hydroxylation treatment in a novel coupling agent reaction solution containing a coupling agent KH560, benzene and methanol for sequential oscillation treatment and constant-temperature alkylation reaction, wherein the oscillation treatment is ultrasonic oscillation, and the time of the ultrasonic oscillation treatment is 3-5 minutes. In the ultrasonic oscillation process, the methanol can effectively inhibit the hydrolysis of the coupling agent KH560 and the condensation reaction of the hydrolysis product, enhance the dispersion stability of the solution, and promote the effective alkylation reaction of the coupling agent KH560 and the hydroxyl on the surface of the silicon dioxide sample, thereby improving the hydrophobicity of the surface of the silicon dioxide sample. The constant-temperature alkylation reaction is to place a silicon dioxide sample in the novel coupling agent reaction liquid for alkylation reaction, the temperature of the alkylation reaction can be 90 ℃, and the time of the alkylation reaction can be 6-8 hours.
According to the method provided by the invention, before a silicon dioxide sample is placed in the novel coupling agent reaction solution, the novel coupling agent reaction solution is required to be prepared. The novel coupling agent reaction liquid must comprise a coupling agent KH560, benzene and methanol, wherein the coupling agent KH560 is used for alkylating the surface of a silica sample, the methanol is used for inhibiting the hydrolysis of the coupling agent KH560 and inhibiting the condensation reaction of the hydrolysate of the coupling agent KH560, and the benzene is used as a reagent for dispersing the coupling agent KH560 and the methanol. When a reagent of a novel coupling agent reaction solution is selected, the benzene-dispersed coupling agent KH560 and methanol are selected to effectively improve the hydrophobicity of the surface of the silicon dioxide sample.
In the experiment of the reagent of selecting novel coupling agent reaction liquid, the selective reagent is ethanol, n-hexane and benzene respectively to be tested, through a large amount of experiments, the selective reagent is determined to be benzene, and after the silica sample is obtained through oscillation treatment and constant temperature alkylation reaction, the wetting angle of deionized water on the surface of the silica sample can be further improved when the reagent is benzene, and the hydrophobicity of the surface of the silica sample is stronger.
In one embodiment, in the novel coupling agent reaction solution, the volume ratio of the coupling agent KH560 to the benzene to the methanol is 1: (9-11): (0.5 to 0.7).
Preferably, when the coupling agent KH560, the volume ratio of benzene to methanol is 1:10:0.6, the voltage corresponding to the electric excitation hydroxylation treatment is 1.6V/cm, and the electrolyte is a calcium chloride solution with the mass fraction of 0.025%, the hydroxylation effect of the silicon dioxide sample is better.
In one embodiment, the time of the electric stimulation hydroxylation treatment is 1-1.5 hours.
The hydroxylation effect can be reduced when the time of the electric excitation hydroxylation is too short, and the silicon hydroxyl active reaction sites for grafting on the surface of the silicon dioxide sample can be effectively increased when the time of the electric excitation hydroxylation treatment is 1-1.5 hours.
In one embodiment, the electrical stimulation hydroxylation treatment is performed after the cleaned silica sample is heated to 500 ℃ at high temperature for 30 minutes.
The washed silica samples were heated to 490 deg.C, 500 deg.C, 510 deg.C, 520 deg.C, 530 deg.C for 30min, respectively. And (3) cooling to normal temperature in a vacuum drying oven, and then measuring the wetting angle of deionized water on the surface of a silicon dioxide sample, namely the surface of a quartz glass slide, as follows: 38.01 °, 36.244 °, 37.481 °, 39.657 °, 40.314 °. Experiments can obtain that: the minimum wetting angle can be reached at 500 ℃, the surface cleaning is most thorough, and the pretreatment is most sufficient. Therefore, 500 ℃ is the optimum heating temperature.
In one embodiment, the constant-temperature alkylation reaction is carried out at 90 ℃ for 6-8 hours.
It should be noted that the constant-temperature alkylation reaction time is 6-8 hours, and too short time causes low efficiency of grafting the silane coupling agent on the surface of the silica. And when the temperature of the constant-temperature alkylation reaction is 90 ℃ and the reaction time is 6-8 hours, the coupling agent KH560 and silicon hydroxyl groups on the surface of the silicon dioxide sample, which can be grafted, are subjected to alkylation reaction, so that the hydrophobicity of the surface of the silicon dioxide sample is improved.
In one embodiment, the shaking time is 3-5 minutes.
It is understood that the time of the oscillation treatment can be selected by the experimenter according to the actual needs. The oscillation treatment time of 3-5 minutes is beneficial to fully dispersing the methanol in the coupling agent, and can help the methanol to effectively inhibit the hydrolysis of the coupling agent KH560 and the condensation between hydrolysis products.
In one embodiment, the silica sample is sequentially subjected to ultrasonic cleaning by using acetone and deionized water, so as to obtain the cleaned silica sample.
The number of times of ultrasonic cleaning is 3, and the cleaning time is 3-5 minutes each time. It can be understood that proper cleaning is beneficial to thoroughly remove impurities on the surface of the silicon dioxide, and the influence on the experimental result is reduced.
In one embodiment, after the constant-temperature alkylation reaction, the method further comprises:
and cleaning the silicon dioxide sample subjected to the constant-temperature alkylation reaction by using ethanol, and drying to obtain the surface-modified silicon dioxide sample.
The invention provides a silicon dioxide surface modification method, which comprises the steps of heating a cleaned silicon dioxide sample to 490-510 ℃ at high temperature, continuously heating for 30-35 minutes, and then carrying out electric excitation hydroxylation treatment on the silicon dioxide sample; after the electric excitation hydroxylation treatment is finished, placing the silicon dioxide sample in a novel coupling agent reaction solution containing a coupling agent KH560, benzene and methanol to carry out oscillation treatment and constant-temperature alkylation reaction in sequence to obtain a surface-modified silicon dioxide sample. The silicon dioxide surface modification method provided by the invention can greatly increase the wetting angle of deionized water on the surface of a silicon dioxide sample, thereby greatly improving the hydrophobicity of the surface of the silicon dioxide sample. The method has good application effect on micro-etching models made of common silicon dioxide base materials, the regulation and control of the surface wettability of micro-fluidic chips and the modification inside silicon dioxide capillaries in the industries of oil gas and the like.
Drawings
FIG. 1 is a schematic representation of an electro-stimulated hydroxylation process.
Fig. 2 is a test chart before modification of the silica sample.
FIG. 3 is a test chart of a modified silica sample.
With the foregoing drawings in mind, certain embodiments of the disclosure have been shown and described in more detail below. These drawings and written description are not intended to limit the scope of the disclosed concepts in any way, but rather to illustrate the concepts of the disclosure to those skilled in the art by reference to specific embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The silica surface modification method of this example was carried out as follows:
1. and (3) ultrasonically cleaning the silicon dioxide sample by using acetone and deionized water in sequence, wherein the cleaning times are 3 times, and each cleaning time is 5 minutes, so that the cleaned silicon dioxide sample is obtained.
2. And (3) carrying out high-temperature heating treatment on the cleaned silicon dioxide sample by using a muffle furnace, and continuously heating the silicon dioxide sample at 490 ℃ for 30 min. And (3) carrying out high-temperature heating treatment on the cleaned silicon dioxide sample for 30 minutes, wherein the temperature of the high-temperature heating treatment is 490 ℃, so as to obtain the cleaned silicon dioxide sample, and the high-temperature heating treatment is carried out in a muffle furnace.
3. After the surface of the silicon dioxide sample after the high-temperature heating treatment is cleaned, the silicon dioxide sample is placed in an electrolytic cell for electric excitation hydroxylation treatment. Wherein the electrolyte is a calcium chloride solution with the mass fraction of 0.030%, the voltage is 1.6V/cm, and after 1h, the silicon dioxide sample subjected to electric excitation hydroxylation treatment is obtained.
4. The coupling agent KH560, benzene and methanol were mixed at a volume ratio of 1:9:0.5, and shaken for 5 minutes to obtain the novel coupling agent reaction solution of this example.
And then the silicon dioxide sample after the electric excitation hydroxylation treatment is placed in the fully dispersed novel coupling agent reaction solution, and is subjected to oscillation treatment for 5 minutes, so that the methanol can effectively inhibit the hydrolysis of the coupling agent KH560 and the condensation reaction of the hydrolysis product. And then putting the novel coupling agent reaction liquid and the silicon dioxide sample placed in the novel coupling agent reaction liquid into a reaction kettle, and then putting the reaction kettle into a vacuum drying oven to carry out constant-temperature alkylation reaction, wherein the constant-temperature alkylation reaction is modification at the temperature of 90 ℃ for 6 hours.
5. And taking out the silica sample in the vacuum drying oven, washing with ethanol, and drying to complete the modification of the silica sample.
And (3) product determination:
the wetting angle is measured by a sitting drop method, and the method comprises the following specific steps: washing a quartz glass slide by using deionized water, drying in vacuum, and then placing the quartz glass slide on a sample platform; the adjustment platform is kept horizontal, the light source is turned on, and the quartz glass slide on the sample platform is adjusted to appear at the center of the screen. And titrating deionized water on the surface of the quartz glass slide by using a needle, photographing in real time by using a CCD (charge coupled device) camera to record the oil drop form, and determining the wetting angle. And measuring for 3 times, and calculating to obtain the average value of the wetting angle, namely the measured wetting angle of the product. The wetting angle of the deionized water on the surface of the modified silica sample of this example was measured to be 119.79 °. The larger the wetting angle of the water droplet on the silica sample, the better the hydrophobicity of the silica sample.
Example 2
The silica surface modification method of this example was carried out as follows:
1. and (3) ultrasonically cleaning the silicon dioxide sample by using acetone and deionized water in sequence, wherein the cleaning times are 3 times, and each cleaning time is 5 minutes, so that the cleaned silicon dioxide sample is obtained.
2. And (3) carrying out high-temperature heating treatment on the cleaned silicon dioxide sample by using a muffle furnace, and continuously heating the silicon dioxide sample at 500 ℃ for 30 min. And (3) carrying out high-temperature heating treatment on the cleaned silicon dioxide sample for 30 minutes, wherein the temperature of the high-temperature heating treatment is 500 ℃, so as to obtain the cleaned silicon dioxide sample, and the high-temperature heating treatment is carried out in a muffle furnace.
3. After the surface of the silicon dioxide sample after the high-temperature heating treatment is cleaned, the silicon dioxide sample is placed in an electrolytic cell for electric excitation hydroxylation treatment. Wherein the electrolyte is a magnesium chloride solution with the mass fraction of 0.025%, the voltage is 1.2V/cm, and after 1h, the silicon dioxide sample subjected to electric excitation hydroxylation treatment is obtained.
4. The coupling agent KH560, benzene and methanol were mixed at a volume ratio of 1:10:0.6, and the mixture was shaken for 5 minutes to obtain the novel coupling agent reaction solution of this example.
And then the silicon dioxide sample after the electric excitation hydroxylation treatment is placed in the fully dispersed novel coupling agent reaction solution, and is subjected to oscillation treatment for 5 minutes, so that the methanol can effectively inhibit the hydrolysis of the coupling agent KH560 and the condensation reaction of the hydrolysis product. And then putting the novel coupling agent reaction liquid and the silicon dioxide sample placed in the novel coupling agent reaction liquid into a reaction kettle, and then putting the reaction kettle into a vacuum drying oven to carry out constant-temperature alkylation reaction, wherein the constant-temperature alkylation reaction is modification at the temperature of 90 ℃ for 6 hours.
5. And taking out the silica sample in the vacuum drying oven, washing with ethanol, and drying to complete the modification of the silica sample.
And (3) product determination:
the wetting angle is measured by a sitting drop method, and the method comprises the following specific steps: washing a quartz glass slide by using deionized water, drying in vacuum, and then placing the quartz glass slide on a sample platform; the adjustment platform is kept horizontal, the light source is turned on, and the quartz glass slide on the sample platform is adjusted to appear at the center of the screen. And titrating deionized water on the surface of the quartz glass slide by using a needle, photographing in real time by using a CCD (charge coupled device) camera to record the oil drop form, and determining the wetting angle. And measuring for 3 times, and calculating to obtain the average value of the wetting angle, namely the measured wetting angle of the product. The wetting angle of the deionized water on the surface of the modified silica sample of this example was measured to be 119.077 °. The larger the wetting angle of the water droplet on the silica sample, the better the hydrophobicity of the silica sample.
Example 3
The silica surface modification method of this example was carried out as follows:
1. and (3) ultrasonically cleaning the silicon dioxide sample by using acetone and deionized water in sequence, wherein the cleaning times are 3 times, and each cleaning time is 5 minutes, so that the cleaned silicon dioxide sample is obtained.
2. And (3) carrying out high-temperature heating treatment on the cleaned silicon dioxide sample by using a muffle furnace, and continuously heating the silicon dioxide sample at 490 ℃ for 30 min. And (3) carrying out high-temperature heating treatment on the cleaned silicon dioxide sample for 30 minutes, wherein the temperature of the high-temperature heating treatment is 490 ℃, so as to obtain the cleaned silicon dioxide sample, and the high-temperature heating treatment is carried out in a muffle furnace.
3. After the surface of the silicon dioxide sample after the high-temperature heating treatment is cleaned, the silicon dioxide sample is placed in an electrolytic cell for electric excitation hydroxylation treatment. Wherein the electrolyte is a magnesium chloride solution with the mass fraction of 0.030%, the voltage is 1.4V/cm, and after 1h, the silicon dioxide sample subjected to electric excitation hydroxylation treatment is obtained.
4. The coupling agent KH560, benzene and methanol were mixed at a volume ratio of 1:9:0.5, and shaken for 5 minutes to obtain the novel coupling agent reaction solution of this example.
And then the silicon dioxide sample after the electric excitation hydroxylation treatment is placed in the fully dispersed novel coupling agent reaction solution, and is subjected to oscillation treatment for 5 minutes, so that the methanol can effectively inhibit the hydrolysis of the coupling agent KH560 and the condensation reaction of the hydrolysis product. And then putting the novel coupling agent reaction liquid and the silicon dioxide sample placed in the novel coupling agent reaction liquid into a reaction kettle, and then putting the reaction kettle into a vacuum drying oven to carry out constant-temperature alkylation reaction, wherein the constant-temperature alkylation reaction is modification at the temperature of 90 ℃ for 6 hours.
5. And taking out the silica sample in the vacuum drying oven, washing with ethanol, and drying to complete the modification of the silica sample.
And (3) product determination:
the wetting angle is measured by a sitting drop method, and the method comprises the following specific steps: washing a quartz glass slide by using deionized water, drying in vacuum, and then placing the quartz glass slide on a sample platform; the adjustment platform is kept horizontal, the light source is turned on, and the quartz glass slide on the sample platform is adjusted to appear at the center of the screen. And titrating deionized water on the surface of the quartz glass slide by using a needle, photographing in real time by using a CCD (charge coupled device) camera to record the oil drop form, and determining the wetting angle. And measuring for 3 times, and calculating to obtain the average value of the wetting angle, namely the measured wetting angle of the product. The wetting angle of the deionized water on the surface of the modified silica sample of this example was measured to be 119.912 °. The larger the wetting angle of the water droplet on the silica sample, the better the hydrophobicity of the silica sample.
Example 4
The silica surface modification method of this example was carried out as follows:
1. and (3) ultrasonically cleaning the silicon dioxide sample by using acetone and deionized water in sequence, wherein the cleaning times are 3 times, and each cleaning time is 5 minutes, so that the cleaned silicon dioxide sample is obtained.
2. And (3) carrying out high-temperature heating treatment on the cleaned silicon dioxide sample by using a muffle furnace, and continuously heating the silicon dioxide sample at 500 ℃ for 30 min. And (3) carrying out high-temperature heating treatment on the cleaned silicon dioxide sample for 30 minutes, wherein the temperature of the high-temperature heating treatment is 500 ℃, so as to obtain the cleaned silicon dioxide sample, and the high-temperature heating treatment is carried out in a muffle furnace.
3. After the surface of the silicon dioxide sample after the high-temperature heating treatment is cleaned, the silicon dioxide sample is placed in an electrolytic cell for electric excitation hydroxylation treatment. Wherein the electrolyte is a magnesium chloride solution with the mass fraction of 0.025%, the voltage is 1.6V/cm, and after 1h, the silicon dioxide sample subjected to electric excitation hydroxylation treatment is obtained.
4. The coupling agent KH560, benzene and methanol were mixed at a volume ratio of 1:10:0.6, and the mixture was shaken for 5 minutes to obtain the novel coupling agent reaction solution of this example.
And then the silicon dioxide sample after the electric excitation hydroxylation treatment is placed in the fully dispersed novel coupling agent reaction solution, and is subjected to oscillation treatment for 5 minutes, so that the methanol can effectively inhibit the hydrolysis of the coupling agent KH560 and the condensation reaction of the hydrolysis product. And then putting the novel coupling agent reaction liquid and the silicon dioxide sample placed in the novel coupling agent reaction liquid into a reaction kettle, and then putting the reaction kettle into a vacuum drying oven to carry out constant-temperature alkylation reaction, wherein the constant-temperature alkylation reaction is modification at the temperature of 90 ℃ for 6 hours.
5. And taking out the silica sample in the vacuum drying oven, washing with ethanol, and drying to complete the modification of the silica sample.
And (3) product determination:
the wetting angle is measured by a sitting drop method, and the method comprises the following specific steps: washing a quartz glass slide by using deionized water, drying in vacuum, and then placing the quartz glass slide on a sample platform; the adjustment platform is kept horizontal, the light source is turned on, and the quartz glass slide on the sample platform is adjusted to appear at the center of the screen. And titrating deionized water on the surface of the quartz glass slide by using a needle, photographing in real time by using a CCD (charge coupled device) camera to record the oil drop form, and determining the wetting angle. And measuring for 3 times, and calculating to obtain the average value of the wetting angle, namely the measured wetting angle of the product. Referring to fig. 2 and 3, fig. 2 shows the wetting angle of a water drop on the surface of an unmodified silica sample, and fig. 3 shows the wetting angle of a water drop on the surface of a silica sample modified by the method provided in this example, which is 122.152 °. The larger the wetting angle of the water droplet on the silica sample, the better the hydrophobicity of the silica sample.
Example 5
The silica surface modification method of this example was carried out as follows:
1. and (3) ultrasonically cleaning the silicon dioxide sample by using acetone and deionized water in sequence, wherein the cleaning times are 3 times, and each cleaning time is 5 minutes, so that the cleaned silicon dioxide sample is obtained.
2. And (3) carrying out high-temperature heating treatment on the cleaned silicon dioxide sample by using a muffle furnace, and continuously heating the silicon dioxide sample at 500 ℃ for 30 min. And (3) carrying out high-temperature heating treatment on the cleaned silicon dioxide sample for 30 minutes, wherein the temperature of the high-temperature heating treatment is 500 ℃, so as to obtain the cleaned silicon dioxide sample, and the high-temperature heating treatment is carried out in a muffle furnace.
3. After the surface of the silicon dioxide sample after the high-temperature heating treatment is cleaned, the silicon dioxide sample is placed in an electrolytic cell for electric excitation hydroxylation treatment. Wherein the electrolyte is a calcium chloride solution with the mass fraction of 0.030%, the voltage is 1.8V/cm, and after 1h, the silicon dioxide sample subjected to electric excitation hydroxylation treatment is obtained.
4. The coupling agent KH560, benzene and methanol were mixed at a volume ratio of 1:9:0.5, and shaken for 5 minutes to obtain the novel coupling agent reaction solution of this example.
And then the silicon dioxide sample after the electric excitation hydroxylation treatment is placed in the fully dispersed novel coupling agent reaction solution, and is subjected to oscillation treatment for 5 minutes, so that the methanol can effectively inhibit the hydrolysis of the coupling agent KH560 and the condensation reaction of the hydrolysis product. And then putting the novel coupling agent reaction liquid and the silicon dioxide sample placed in the novel coupling agent reaction liquid into a reaction kettle, and then putting the reaction kettle into a vacuum drying oven to carry out constant-temperature alkylation reaction, wherein the constant-temperature alkylation reaction is modification at the temperature of 90 ℃ for 6 hours.
5. And taking out the silica sample in the vacuum drying oven, washing with ethanol, and drying to complete the modification of the silica sample.
And (3) product determination:
the wetting angle is measured by a sitting drop method, and the method comprises the following specific steps: washing a quartz glass slide by using deionized water, drying in vacuum, and then placing the quartz glass slide on a sample platform; the adjustment platform is kept horizontal, the light source is turned on, and the quartz glass slide on the sample platform is adjusted to appear at the center of the screen. And titrating deionized water on the surface of the quartz glass slide by using a needle, photographing in real time by using a CCD (charge coupled device) camera to record the oil drop form, and determining the wetting angle. And measuring for 3 times, and calculating to obtain the average value of the wetting angle, namely the measured wetting angle of the product. The wetting angle of the deionized water on the surface of the modified silica sample of this example was measured to be 120.663 °. The larger the wetting angle of the water droplet on the silica sample, the better the hydrophobicity of the silica sample.
Example 6
The silica surface modification method of this example was carried out as follows:
1. and (3) ultrasonically cleaning the silicon dioxide sample by using acetone and deionized water in sequence, wherein the cleaning times are 3 times, and each cleaning time is 5 minutes, so that the cleaned silicon dioxide sample is obtained.
2. And (3) carrying out high-temperature heating treatment on the cleaned silicon dioxide sample by using a muffle furnace, and continuously heating the silicon dioxide sample at 510 ℃ for 30 min. And (3) carrying out high-temperature heating treatment on the cleaned silicon dioxide sample for 30 minutes, wherein the temperature of the high-temperature heating treatment is 510 ℃, so as to obtain the cleaned silicon dioxide sample, and the high-temperature heating treatment is carried out in a muffle furnace.
3. After the surface of the silicon dioxide sample after the high-temperature heating treatment is cleaned, the silicon dioxide sample is placed in an electrolytic cell for electric excitation hydroxylation treatment. Wherein the electrolyte is a calcium chloride solution with the mass fraction of 0.025%, the voltage is 1.6V/cm, and after 1h, the silicon dioxide sample subjected to electric excitation hydroxylation treatment is obtained.
4. The coupling agent KH560, benzene and methanol were mixed at a volume ratio of 1:10:0.6, and the mixture was shaken for 5 minutes to obtain the novel coupling agent reaction solution of this example.
And then the silicon dioxide sample after the electric excitation hydroxylation treatment is placed in the fully dispersed novel coupling agent reaction solution, and is subjected to oscillation treatment for 5 minutes, so that the methanol can effectively inhibit the hydrolysis of the coupling agent KH560 and the condensation reaction of the hydrolysis product. And then putting the novel coupling agent reaction liquid and the silicon dioxide sample placed in the novel coupling agent reaction liquid into a reaction kettle, and then putting the reaction kettle into a vacuum drying oven to carry out constant-temperature alkylation reaction, wherein the constant-temperature alkylation reaction is modification at the temperature of 90 ℃ for 6 hours.
5. And taking out the silica sample in the vacuum drying oven, washing with ethanol, and drying to complete the modification of the silica sample.
And (3) product determination:
the wetting angle is measured by a sitting drop method, and the method comprises the following specific steps: washing a quartz glass slide by using deionized water, drying in vacuum, and then placing the quartz glass slide on a sample platform; the adjustment platform is kept horizontal, the light source is turned on, and the quartz glass slide on the sample platform is adjusted to appear at the center of the screen. And titrating deionized water on the surface of the quartz glass slide by using a needle, photographing in real time by using a CCD (charge coupled device) camera to record the oil drop form, and determining the wetting angle. And measuring for 3 times, and calculating to obtain the average value of the wetting angle, namely the measured wetting angle of the product. The wetting angle of deionized water on the surface of the modified silica sample of this example was measured to be 119.62 °. The larger the wetting angle of the water droplet on the silica sample, the better the hydrophobicity of the silica sample.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (8)

1. A method for modifying the surface of silica, comprising:
heating the cleaned silicon dioxide sample to 490-510 ℃ at high temperature, and continuously heating for 30-35 minutes to remove the silicon dioxide sample to the maximumResidual organic pollutants and adsorbed moisture on the surface of the silicon dioxide sample; then, carrying out electric excitation hydroxylation treatment on the silicon dioxide sample; the direct current electrically excites the surface of the silicon dioxide to promote the breaking of the Si-O-Si bond and the H in the water+、OH-In combination, the surface hydroxyl groups of the silicon dioxide are effectively increased;
after the electric excitation hydroxylation treatment is finished, placing a silicon dioxide sample in a novel silane coupling agent reaction solution containing a coupling agent KH560, benzene and methanol, sequentially carrying out oscillation treatment and constant-temperature alkylation reaction, and obtaining a surface-modified silicon dioxide sample after the reaction is finished.
2. The method according to claim 1, wherein the novel coupling agent reaction solution has a volume ratio of the coupling agent KH560 to the benzene to the methanol of 1: (9-11): (0.5-0.7), the hydrolysis of KH560 can be effectively inhibited by adding proper methanol, mutual condensation of free coupling agent KH560 hydrolysate in the solution is weakened, and the dispersion stability of the silane coupling agent in the solution is enhanced.
3. The method according to any one of claims 1 to 2, wherein in the electrical stimulation hydroxylation treatment, the voltage is 1.5V/cm to 1.7V/cm, and the electrolyte is a magnesium chloride solution with a mass fraction of 0.025% to 0.030% or a calcium chloride solution with a mass fraction of 0.025% to 0.030%.
4. The method according to claim 3, wherein the time for the electrical stimulation hydroxylation treatment is 1-1.5 hours.
5. The method according to claim 1, wherein the electrical stimulation hydroxylation treatment is performed after heating the washed silica sample to 500 ℃ at an elevated temperature for 30 minutes.
6. The method according to claim 1 or 5, wherein the isothermal alkylation reaction is carried out at a temperature of 90 ℃ for 6-8 hours.
7. The method according to claim 1 or 5, wherein the shaking treatment time is 3 to 5 minutes.
8. The method of claim 1, wherein after the isothermal alkylation reaction, further comprising:
and cleaning the silicon dioxide sample subjected to the constant-temperature alkylation reaction by using ethanol, and drying to obtain the surface-modified silicon dioxide sample.
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