CN108147416B - The preparation method and nanometer titanium dioxide silica aerogel of nanometer titanium dioxide silica aerogel - Google Patents
The preparation method and nanometer titanium dioxide silica aerogel of nanometer titanium dioxide silica aerogel Download PDFInfo
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- CN108147416B CN108147416B CN201810048941.0A CN201810048941A CN108147416B CN 108147416 B CN108147416 B CN 108147416B CN 201810048941 A CN201810048941 A CN 201810048941A CN 108147416 B CN108147416 B CN 108147416B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
- C01B33/158—Purification; Drying; Dehydrating
- C01B33/1585—Dehydration into aerogels
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/16—Preparation of silica xerogels
- C01B33/163—Preparation of silica xerogels by hydrolysis of organosilicon compounds, e.g. ethyl orthosilicate
Abstract
The invention discloses a kind of preparation method of nanometer titanium dioxide silica aerogel and nanometer titanium dioxide silica aerogels, are related to SiO2Aeroge technical field.This method comprises: 1:(0.5~1 by volume (a) system A and system B) ratio be sufficiently mixed, obtain wet gel；Wherein, system A is for organic silicon source, dissolved with ethylization-beta-cyclodextrin low-carbon alcohol solution, acid and water with 1:(10~50): (0.5~1): the molar ratio mixing of (2~8)；System B is dissolved with ethylization-beta-cyclodextrin low-carbon alcohol solution, silane coupling agent, alkali and water with 10:(0.5~1): (0.05~0.2): the molar ratio mixing of (0.2~3)；(b) wet gel is dry.The present invention alleviates the SiO that existing method obtains2Aeroge hydrophobicity and the bad problem of physical property.By using SiO made from the method for the present invention2Aeroge not only excellent physical properties, and hydrophobicity is good.
Description
Technical field
The present invention relates to aerosil technical fields, in particular to a kind of nanometer titanium dioxide silica aerogel
Preparation method and nanometer titanium dioxide silica aerogel.
Background technique
Aeroge is mutually to assemble to be constituted nanoporous network structure with nanometer scale ultramicro powder, and in network pore
Lightweight nano solid material full of gaseous state decentralized medium.The most common aeroge is aerosil, silica gas
Gel is a kind of light nanoporous amorphous solid material that solar heat protection heat-proof quality is very outstanding, and porosity is up to 80-
99.8%, the typical sizes of hole are 1-100nm, specific surface area 200-1000m2/ g, and density can be down to 3kg/m3, room temperature
Thermal coefficient can be down to 0.012W/ (mk).Make aerogel material in calorifics, acoustics, optics, micro- electricity just because of these features
There is very wide application potential in terms of son, particle detection.
The preparation method of aerosil is predominantly by silica precursor such as waterglass or tetraethoxysilane
(TEOS) wet gel is prepared, then in the case where not destroying its microstructure by removing the liquid component preparation in wet gel
Aeroge.Aerosil can be divided into three kinds of powder, particle and material all in one piece canonical forms.
Since gel structure characteristic and physical property reduce when aerosil absorbs moisture, needing to develop one kind can
Muchly to prevent from absorbing the method for the moisture in air, to be easy to use in the industry.It has proposed at present by two
Silica aerogel surface carries out hydrophobic treatment to prepare the method with permanent hydrophobic aerosil, usually leads to
Crossing has hydrophobic aerosil using surface modifier preparation.But this method, which is difficult to control surface, to be modified instead
It answers, productivity is lower, and obtained aerosil hydrophobicity and physical property is bad.
In view of this, the present invention is specifically proposed.
Summary of the invention
One of the objects of the present invention is to provide a kind of preparation method of nanometer titanium dioxide silica aerogel, prepared by this method
Journey is simple, by the way that ethylization-beta-cyclodextrin is added, is able to participate SiO2The formation of gel network, enhances nanometer titanium dioxide
The hydrophobicity of silica aerogel.
The second object of the present invention is that the preparation method for providing a kind of above-mentioned nanometer titanium dioxide silica aerogel is prepared
Nanometer titanium dioxide silica aerogel, by using nanometer titanium dioxide silica aerogel obtained by the above method, not only physical property is excellent
It is different, and obtain higher hydrophobicity.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of preparation method of nanometer titanium dioxide silica aerogel, comprising the following steps:
(a) 1:(0.5~1 by volume system A and system B) ratio be sufficiently mixed, obtain wet gel；
Wherein, system A be organic silicon source, dissolved with ethylization-beta-cyclodextrin low-carbon alcohol solution, acid and water with 1:(10~
50): (0.5~1): what the molar ratio of (2~8) was mixed to get；
System B be dissolved with ethylization-beta-cyclodextrin low-carbon alcohol solution, silane coupling agent, alkali and water with 10:(0.5~
1): (0.05~0.2): what the molar ratio of (0.2~3) was mixed to get；
(b) wet gel of step (a) is dried, obtains nanometer titanium dioxide silica aerogel.
Further, on the basis of technical solution provided by the invention, dissolved with ethylization-beta-cyclodextrin low-carbon alcohol solution
The concentration of middle ethylization-beta-cyclodextrin be 0.01~0.05g/mL, preferably 0.02~0.05g/mL, further preferred 0.02~
0.04g/mL。
Preferably, on the basis of technical solution provided by the invention, ethylization-beta-cyclodextrin is prepared by the following method
It obtains:
Beta-cyclodextrin is dissolved in aqueous slkali, 95% ethyl alcohol is added, dithyl sulfate is added dropwise and is reacted, is adjusted after reaction
Reaction solution pH6~7 obtain ethylization-beta-cyclodextrin after extracted, dry；
Preferably, the molar concentration of aqueous slkali is 8~12mol/L, and the alkali of 18~20mL is added in every 2~3g beta-cyclodextrin
Solution, 75~95% ethyl alcohol of 1~3mL and the dithyl sulfate of 22~25mL；
Preferably, reaction temperature is 50~65 DEG C, and the reaction time is 8~12h；
It is further preferred that reaction temperature is 55~65 DEG C, the reaction time is 10~12h.
Further, on the basis of technical solution provided by the invention, step (a) carries out aging after being sufficiently mixed；
Preferably, aging temperature is 50~90 DEG C, and ageing time is 1~10h；
It is further preferred that aging temperature is 60~90 DEG C, ageing time is 5~8h.
Preferably, on the basis of technical solution provided by the invention, primary emulsion is straight-chain alkyl sulfate, straight chain alkane
One or more of arylsulphonate, straight chain fatty acid polyoxyethylene ether sulfate or straight chained alkyl sulphosuccinates.
Preferably, on the basis of technical solution provided by the invention, the organic silicon source is selected from methyl orthosilicate, positive silicon
One of acetoacetic ester, tetrachloro silicane, industrial raw material E-40, E32 or E28 are a variety of；
Preferably, the low-carbon alcohol solution is selected from one of methanol, ethyl alcohol or propyl alcohol or a variety of；
Preferably, the acid is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, oxalic acid or acetic acid.
Preferably, on the basis of technical solution provided by the invention, the silane coupling agent be selected from trim,ethylchlorosilane,
One or more of hexamethyldisilazane, dimethyldichlorosilane, methyltriethoxysilane or fluoric silane, preferably six
Methyl disilazane；
Preferably, the alkali is selected from one or more of ammonium hydroxide, monoethanolamine, diethanol amine or triethanolamine.
Preferably, on the basis of technical solution provided by the invention, step (a) be sufficiently mixed after mixed system pH value
It is 7~12, preferably 8~12, further preferred 9~12.
Preferably, on the basis of technical solution provided by the invention, the drying is supercritical drying；
Preferably, for supercritical drying using methanol as dried medium, supercritical temperature is 260~280 DEG C, and supercritical pressure is
10~12MPa；
Preferably, supercritical drying is with CO2For dried medium, supercritical temperature is 30~35 DEG C, supercritical pressure 10
~20MPa.
A kind of nanometer titanium dioxide silica aerogel of the preparation method preparation of above-mentioned nanometer titanium dioxide silica aerogel.
Further, on the basis of technical solution provided by the invention, the vibration density of the nanometer titanium dioxide silica aerogel
Degree is 0.05~0.12g/mL；
The nanometer titanium dioxide silica aerogel contains the carbon of 10~15 weight %.
Compared with the prior art, the invention has the following beneficial effects:
(1) preparation method of nanometer titanium dioxide silica aerogel of the present invention is first respectively by organic silicon source, dissolved with ethylization-β-ring
Low-carbon alcohol solution, acid and the water of dextrin are mixed in a certain proportion, and form system A；It will be dissolved with ethylization-beta-cyclodextrin low-carbon alcohols
Solution, silane coupling agent, alkali and water are mixed in a certain proportion, and form system B, then system A and system B is mixed, system A is organic
Silicon source hydrolysis is gradually condensed, and forms colloidal sol, then mixing with system B further makes network structure stabilization form gel, while system
The silane coupling agent of B is able to carry out that surface is modified, helps to obtain physical property and the good nanometer two of hydrophobicity using this method
Silica aerogel.
(2) preparation method of nanometer titanium dioxide silica aerogel of the present invention is by being added ethylization-beta-cyclodextrin, ethylization-
Beta-cyclodextrin is able to participate due to being capable of providing a large amount of active site with numerous hydroxyls as a kind of skeletal support
In the formation of whole network structure, being reached by a large amount of ethyl group improves the hydrophobic purpose of network structure, further increases
The strong hydrophobicity of nanometer titanium dioxide silica aerogel.
(3) the nanometer titanium dioxide silica aerogel excellent physical properties obtained by using the method for the present invention have lower
Tap density and higher specific surface area, tap density is 0.05~0.12g/mL, and hydrophobicity is good, and carbon with higher contains
Amount, carbon content are 10~15 weight %.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
According to the first aspect of the invention, a kind of preparation method of nanometer titanium dioxide silica aerogel is provided, including with
Lower step:
(a) 1:(0.5~1 by volume system A and system B) ratio be sufficiently mixed, obtain wet gel；
Wherein, system A be organic silicon source, dissolved with ethylization-beta-cyclodextrin low-carbon alcohol solution, acid and water with 1:(10~
50): (0.5~1): what the molar ratio of (2~8) was mixed to get；
System B be dissolved with ethylization-beta-cyclodextrin low-carbon alcohol solution, silane coupling agent, alkali and water with 10:(0.5~
1): (0.05~0.2): what the molar ratio of (0.2~3) was mixed to get；
(b) wet gel of step (a) is dried, obtains nanometer titanium dioxide silica aerogel.
In general, dry aerosil keeps lower thermal conductivity immediately after the drying, but due to being present in
Hydrophilic silane alcohol radical (Si-OH) on silica surface absorbs the water in air, and thermal conductivity can be gradually increased.Therefore, it needs
The surface of aerosil is modified as hydrophobicity to keep lower thermal conductivity.
It has proposed to prepare by carrying out hydrophobic treatment on aerosil surface with permanent hydrophobicity at present
Aerosil method, usually by using surface modifier preparation have hydrophobic aerosil.
But this method is difficult to control surface modification reaction, productivity is lower, obtained aerosil hydrophobicity and physics
Performance is bad.
Then the preparation method of nanometer titanium dioxide silica aerogel of the invention is proposed:
Step 1) first obtains system A and system B respectively, and system A and system B are mixed to get wet solidifying by step 2) in proportion again
Glue, step 3) is dry by wet gel, obtains nanometer titanium dioxide silica aerogel.
System A
System A is organic silicon source, dissolved with ethylization-beta-cyclodextrin low-carbon alcohol solution, acid and water.
Organic silicon source is not particularly limited, and prepares the common organic silicon source of aerosil i.e. using this field
Can, typical but non-limiting organic silicon source is, for example, methyl orthosilicate, ethyl orthosilicate or tetrachloro silicane.
Refer to dissolved with ethylization-beta-cyclodextrin low-carbon alcohol solution and ethylization-beta-cyclodextrin is dissolved in low-carbon alcohols and is obtained
's.Ethylization-beta-cyclodextrin is that beta-cyclodextrin carries out the derivative arrived after ethylization modification, can select commercially available conventional second
Base-beta-cyclodextrin.Low-carbon alcohols are not particularly limited, typical but non-limiting low-carbon alcohol solution be methanol, ethyl alcohol or
Propyl alcohol.
Ethylization-beta-cyclodextrin concentration in ethylization-beta-cyclodextrin low-carbon alcohol solution is not particularly limited, only
Ethylization-beta-cyclodextrin can be made to be dissolved completely in low-carbon alcohols in solubility range.
Acid plays the role of catalyzing hydrolysis, creates environment and sol gel reaction is made to be easy to carry out, can control reaction ring
Border pH.Acid is not particularly limited, typical but non-limiting acid is, for example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, grass
Acid or acetic acid.
Organic silicon source, dissolved with ethylization-beta-cyclodextrin low-carbon alcohol solution, acid and water molar ratio be 1:(10~50):
(0.5~1): (2~8), such as 1:10:1:2,1:50:0.5:8,1:10:0.5:2,1:50:1:2,1:30:0.8:5 or 1:20:
0.6:6 etc..
System B
System B is ethylization-beta-cyclodextrin low-carbon alcohol solution, silane coupling agent, alkali and water.
Ethylization-beta-cyclodextrin low-carbon alcohol solution is identical as the description in system A, low to ethylization-beta-cyclodextrin
Ethylization-beta-cyclodextrin concentration is not particularly limited in carbon alcoholic solution, as long as can make ethylization-in solubility range
Beta-cyclodextrin is dissolved completely in low-carbon alcohols, can be using ethylization-beta-cyclodextrin low-carbon with system A same concentration
Alcoholic solution.
Silane coupling agent is not particularly limited silane coupling agent as surface modifier, typical but non-limiting
Silane coupling agent be, for example, trim,ethylchlorosilane, hexamethyldisilazane, dimethyldichlorosilane, methyltriethoxysilane or
Fluoric silane, preferably hexamethyldisilazane.
It so that network structure is stablized by the way that alkali is added, form gel, while activating silane coupling agent, pass through table
The hydrophobicity of the modified enhancing gel in face.Alkali is not particularly limited, typical but non-limiting alkali is, for example, ammonium hydroxide, an ethyl alcohol
Amine, diethanol amine or triethanolamine.
Low-carbon alcohol solution, silane coupling agent, alkali and water molar ratio be 10:(0.5~1): (0.05~0.2): (0.2~
, such as 10:0.5:0.2:0.2,10:1:0.05:3,10:0.5:0.05:3,10:0.8:0.1:0.25 or 10:0.6:0.15 3):
0.25 etc..
The volume ratio that system A is mixed with system B is 1:(0.5~1), such as 1:0.5,1:0.6,1:0.7,1:0.8,1:
0.9 or 1:1.
System A and system B are sufficiently mixed, wet gel is obtained.
Wet gel is dry, solvent is removed, aerosil is obtained, dry mode is not particularly limited,
It can be using freeze-drying, supercritical drying or constant pressure and dry etc..
The preparation method of nanometer titanium dioxide silica aerogel of the present invention is first pasted by organic silicon source, dissolved with ethylization-β-ring respectively
Low-carbon alcohol solution, acid and the water of essence are mixed in a certain proportion, and form system A；It will be molten dissolved with ethylization-beta-cyclodextrin low-carbon alcohols
Liquid, silane coupling agent, alkali and water are mixed in a certain proportion, and form system B, then system A and system B is mixed, system A organosilicon
Source hydrolysis is gradually condensed, and forms colloidal sol, then mixing with system B further makes network structure stabilization form gel, while system B
Silane coupling agent to be able to carry out surface modified, increase gel surface hydrophobicity, while by the way that ethylization-beta-cyclodextrin is added,
Ethylization-beta-cyclodextrin is due to being capable of providing a large amount of active site with numerous hydroxyls, thus as a kind of skeletal support energy
It enough participates in the formation of whole network structure, being reached by a large amount of ethyl group improves the hydrophobic purpose of network structure,
Further enhance the hydrophobicity of nanometer titanium dioxide silica aerogel entirety.The nanometer titanium dioxide obtained by using the preparation method
Silica aerogel not only excellent physical properties, but also hydrophobicity with higher.
In a preferred embodiment, it is pasted dissolved with ethylization-β in ethylization-beta-cyclodextrin low-carbon alcohol solution-ring
The concentration of essence is 0.01~0.05g/mL, preferably 0.02~0.05g/mL, further preferred 0.02~0.04g/mL.
The typical but non-limiting concentration of ethylization-beta-cyclodextrin low-carbon alcohol solution is, for example, 0.01g/mL, 0.02g/
ML, 0.03g/mL, 0.04g/mL or 0.05g/mL.
Ethylization-beta-cyclodextrin low-carbon alcohol solution by using concentration in 0.01~0.05g/mL carries out reaction acquisition
Aerosil physical property and hydrophobicity it is excellent.
In a preferred embodiment, ethylization-beta-cyclodextrin is prepared by the following method to obtain:
Beta-cyclodextrin is dissolved in aqueous slkali, 75~95% ethyl alcohol are added, dithyl sulfate is added dropwise and is reacted, after reaction
Reaction solution pH6~7 are adjusted, obtain ethylization-beta-cyclodextrin after extracted, dry.
The preparation of ethylization-beta-cyclodextrin uses dithyl sulfate method, and beta-cyclodextrin forms negative oxygen ion in highly basic, so
The secondary carbon nucleophilic attack of backward dithyl sulfate, sloughs ethyl sulphate, completes ethylation reaction.
75~95% ethyl alcohol refer to volume fraction.
Preferably, the molar concentration of aqueous slkali is 8~12mol/L, and the alkali of 18~20mL is added in every 2~3g beta-cyclodextrin
Solution, 95% ethyl alcohol of 1~3mL and the dithyl sulfate of 22~25mL；
Preferably, reaction temperature is 50~65 DEG C, and the reaction time is 8~12h；
It is further preferred that reaction temperature is 55~65 DEG C, the reaction time is 10~12h.
Ethylation reaction need to carry out in strong base solution, and there are reaction in concentration, reaction temperature, reaction time of alkali etc. larger
It influences, by optimizing reaction condition, reacts fully, improve the quality and yield of product, ethylization-beta-cyclodextrin parent of acquisition
Lipid is high, and hygroscopicity is low.
Specifically, ethylization-beta-cyclodextrin is prepared by the following method to obtain: 2~3g beta-cyclodextrin is taken, it is dissolved in 8~
In 12mol/L 18~20mL NaOH solution, add 1~3mL, 95% ethyl alcohol, 55 DEG C are stirred continuously down, and 22~25mL sulfuric acid is added dropwise
Diethylester continues 8~12h of stirring after dripping off, add 4~5mL of ammonium hydroxide, and 55 DEG C are stirred 5 hours, decomposes excessive dithyl sulfate
Completely, it is neutralized with hydrochloric acid to pH6, three times (30,25,25mL), extracting solution is washed with water twice chloroform recovery, dry with anhydrous sodium sulfate
To clarify up to solution, chloroform is recycled within dry 2 hours, residue 10~15mL dehydrated alcohol is dissolved, filtered through glass funnel, filtrate
Be concentrated under reduced pressure, obtain white powder crystallization, 80 DEG C drying 24 hours.
The ethylization for using this method to obtain-beta-cyclodextrin degree of substitution is 1.83, average molecular weight 1496.
It is good by using ethylization obtained by the above method-beta-cyclodextrin hydrophobicity, it is able to participate the shape of gel network
Cheng Zhong helps to construct hydrophobic type three-dimensional net structure.
In a preferred embodiment, aging is carried out after step (a) is sufficiently mixed；
Preferably, aging temperature is 50~90 DEG C, and ageing time is 1~10h；
It is further preferred that aging temperature is 60~90 DEG C, ageing time is 5~8h.
Aging is not particularly limited, typical but non-limiting aging temperature is, for example, 50 DEG C, 60 DEG C, 70 DEG C, 80
DEG C or 90 DEG C, typical but non-limiting ageing time is, for example, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h.
Silica wet gel is set more securely to form reticular structure by aging, pore property is more excellent.
Preferably, organic silicon source is selected from methyl orthosilicate, ethyl orthosilicate, tetrachloro silicane, industrial raw material E-40, E32
Or one of E28 or a variety of；
Preferably, low-carbon alcohol solution is selected from one of methanol, ethyl alcohol or propyl alcohol or a variety of；
Preferably, acid is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, oxalic acid or acetic acid；
Preferably, silane coupling agent is selected from trim,ethylchlorosilane, hexamethyldisilazane, dimethyldichlorosilane, methyl
One or more of triethoxysilane or fluoric silane, preferably hexamethyldisilazane；
Preferably, the alkali is selected from one or more of ammonium hydroxide, monoethanolamine, diethanol amine or triethanolamine.
Mixed system pH value after in a preferred embodiment, step (a) is sufficiently mixed is 7~12, such as 7,
8,9,10,11 or 12, preferably 8~12, further preferred 9~12.
By controlling the pH value of mixed system, reaction system can be advanced optimized, acquisition performance is more preferable, structure is more steady
Fixed gel rubber system.
In a preferred embodiment, dry is supercritical drying；
Gas-liquid interface can disappear liquid medium at high temperature under high pressure, form the homogeneous (uniform) fluid between gas-liquid, medium
This state is known as supercriticality.Surface tension has not just existed when medium reaches supercriticality, thus by overcritical
Aeroge skeleton structure caused by systolic pressure is collapsed when greatly can reduce dry, and then obtains excellent aeroge.Pass through
The complete of aeroge skeleton structure can be guaranteed using supercritical drying mode.
Preferably, for supercritical drying using methanol as dried medium, supercritical temperature is 260~280 DEG C, and supercritical pressure is
10~12MPa；
When using methanol, as dried medium, supercritical temperature is, for example, 260 DEG C, 270 DEG C or 280 DEG C, supercritical pressure
For 10MPa, 11MPa or 12MPa.
Preferably, supercritical drying is with CO2For dried medium, supercritical temperature is 30~35 DEG C, supercritical pressure 10
~20MPa.
When use carbon dioxide as dried medium, supercritical temperature be, for example, 30 DEG C, 31 DEG C, 32 DEG C, 33 DEG C, 34 DEG C or
35 DEG C, supercritical pressure 10MPa, 12MPa, 14MPa, 16MPa, 18MPa or 20MPa.
Use carbon dioxide lower as dried medium required temperature, drying effect is good and highly-safe.
Preferably, it can be washed before drying.
According to another aspect of the present invention, a kind of preparation method by above-mentioned nanometer titanium dioxide silica aerogel is provided
The nanometer titanium dioxide silica aerogel of preparation.
The tap density of the nanometer titanium dioxide silica aerogel of an embodiment according to the present invention can for 0.05~
0.12g/mL and the carbon of 10~15 weight % can be contained.
Since the aerosil of embodiment according to the present invention is prepared by above-mentioned preparation method, root
Can have higher hydrophobicity and excellent physical property according to the aerosil of embodiment of the present invention, such as compared with
Low tap density.
Hereinafter, by according to following specific embodiment and comparative example, the present invention will be described in more detail.However, providing following
Embodiment and comparative example be only used for illustrate the present invention, the scope of the present invention is not limited thereto, each raw material of the present invention
Pass through commercially available acquisition.
Ethylization-beta-cyclodextrin that embodiment and comparative example uses is prepared by the following method to obtain: taking 2.5g β-ring paste
Essence is dissolved in 10mol/L 20mLNaOH solution, adds 95% ethyl alcohol of 2mL, and 55 DEG C are stirred continuously down, and 25mL sulfuric acid diethyl is added dropwise
Ester continues stirring 12 hours after dripping off, add ammonium hydroxide 4mL, and 55 DEG C are stirred 5 hours, decomposes excessive dithyl sulfate completely, uses
Hydrochloric acid is neutralized to pH6, and three times (30,25,25mL), extracting solution is washed with water twice chloroform recovery, 2 hours dry with anhydrous sodium sulfate
To clarify up to solution, chloroform is recycled, residue 10mL dehydrated alcohol is dissolved, filtered through glass funnel, and filtrate decompression concentration obtains
White powder crystallization, 80 DEG C of dryings obtain for 24 hours.
Embodiment 1
A kind of preparation method of nanometer titanium dioxide silica aerogel, comprising the following steps:
(1) methyl orthosilicate, dissolved with ethylization-beta-cyclodextrin ethanol solution, hydrochloric acid and water with mole of 1:10:1:2
Than the system A being mixed to get；
(2) dissolved with ethylization-beta-cyclodextrin ethanol solution, hexamethyldisilazane, ammonium hydroxide and water with 10:1:0.05:3
The system B that is mixed to get of molar ratio；
(3) ratio of system A and system B 1:0.5 by volume is sufficiently mixed, and mixed system pH value is 10, is placed and is carried out
Aging, aging temperature are 60 DEG C, and ageing time 5h obtains wet gel；
(4) supercritical drying processing is carried out to the wet gel of step (3), dried medium is methanol, supercritical temperature 260
DEG C, supercritical pressure 10MPa obtains nanometer titanium dioxide silica aerogel.
Wherein, step (1) and step (2) can exchange, dissolved with ethylization-beta-cyclodextrin in step (1) and step (2)
Ethylization-beta-cyclodextrin concentration is 0.03g/mL in ethanol solution.
Embodiment 2
A kind of preparation method of nanometer titanium dioxide silica aerogel, comprising the following steps:
(1) methyl orthosilicate, dissolved with ethylization-beta-cyclodextrin methanol solution, sulfuric acid and water rubbing with 1:50:0.5:8
The system A that your ratio is mixed to get；
(2) dissolved with ethylization-beta-cyclodextrin methanol solution, hexamethyldisilazane, ammonium hydroxide and water with 10:0.5:0.2:
The system B that 0.2 molar ratio is mixed to get；
(3) ratio of system A and system B 1:1 by volume is sufficiently mixed, and mixed system pH value is 9, place carry out it is old
Change, aging temperature is 80 DEG C, and ageing time 4h obtains wet gel；
(4) supercritical drying processing is carried out to the wet gel of step (3), dried medium is methanol, supercritical temperature 280
DEG C, supercritical pressure 12MPa obtains nanometer titanium dioxide silica aerogel.
Wherein, step (1) and step (2) can exchange, dissolved with ethylization-beta-cyclodextrin in step (1) and step (2)
Ethylization-beta-cyclodextrin concentration is 0.01g/mL in methanol solution.
Embodiment 3
A kind of preparation method of nanometer titanium dioxide silica aerogel, comprising the following steps:
(1) methyl orthosilicate, dissolved with ethylization-beta-cyclodextrin ethanol solution, nitric acid and water rubbing with 1:10:0.5:2
The system A that your ratio is mixed to get；
(2) dissolved with ethylization-beta-cyclodextrin ethanol solution, trim,ethylchlorosilane, ammonium hydroxide and water with 10:0.5:0.05:3
The system B that is mixed to get of molar ratio；
(3) ratio of system A and system B 1:0.8 by volume is sufficiently mixed, and mixed system pH value is 11, is placed and is carried out
Aging, aging temperature are 60 DEG C, and ageing time 8h obtains wet gel；
(4) supercritical drying processing is carried out to the wet gel of step (3), dried medium is methanol, supercritical temperature 270
DEG C, supercritical pressure 11MPa obtains nanometer titanium dioxide silica aerogel.
Wherein, step (1) and step (2) can exchange, dissolved with ethylization-beta-cyclodextrin in step (1) and step (2)
Ethylization-beta-cyclodextrin concentration is 0.05g/mL in ethanol solution.
Embodiment 4
A kind of preparation method of nanometer titanium dioxide silica aerogel, comprising the following steps:
(1) ethyl orthosilicate, dissolved with ethylization-beta-cyclodextrin methanol solution, phosphoric acid and water with mole of 1:50:1:2
Than the system A being mixed to get；
(2) dissolved with ethylization-beta-cyclodextrin methanol solution, trim,ethylchlorosilane, triethanolamine and water with 10:0.5:
The system B that the molar ratio of 0.05:3 is mixed to get；
(3) ratio of system A and system B 1:0.6 by volume is sufficiently mixed, and mixed system pH value is 12, is placed and is carried out
Aging, aging temperature are 70 DEG C, and ageing time 5h obtains wet gel；
(4) supercritical drying processing, dried medium CO are carried out to the wet gel of step (3)2, supercritical temperature 30
DEG C, supercritical pressure 10MPa obtains nanometer titanium dioxide silica aerogel.
Wherein, step (1) and step (2) can exchange, dissolved with ethylization-beta-cyclodextrin in step (1) and step (2)
Ethylization-beta-cyclodextrin concentration is 0.02g/mL in methanol solution.
Embodiment 5
A kind of preparation method of nanometer titanium dioxide silica aerogel, comprising the following steps:
(1) ethyl orthosilicate, dissolved with ethylization-beta-cyclodextrin ethanol solution, oxalic acid and water rubbing with 1:30:0.8:5
The system A that your ratio is mixed to get；
(2) dissolved with ethylization-beta-cyclodextrin ethanol solution, dimethyldichlorosilane, triethanolamine and water with 10:0.8:
The system B that the molar ratio of 0.1:0.25 is mixed to get；
(3) ratio of system A and system B 1:0.8 by volume is sufficiently mixed, and mixed system pH value is 8, place carry out it is old
Change, aging temperature is 50 DEG C, and ageing time 10h obtains wet gel；
(4) supercritical drying processing, dried medium CO are carried out to the wet gel of step (3)2, supercritical temperature 35
DEG C, supercritical pressure 20MPa obtains nanometer titanium dioxide silica aerogel.
Wherein, step (1) and step (2) can exchange, dissolved with ethylization-beta-cyclodextrin in step (1) and step (2)
Ethylization-beta-cyclodextrin concentration is 0.04g/mL in ethanol solution.
Embodiment 6
A kind of preparation method of nanometer titanium dioxide silica aerogel, comprising the following steps:
(1) ethyl orthosilicate, dissolved with ethylization-beta-cyclodextrin methanol solution, acetic acid and water rubbing with 1:20:0.6:6
The system A that your ratio is mixed to get；
(2) dissolved with ethylization-beta-cyclodextrin methanol solution, dimethyldichlorosilane, triethanolamine and water with 10:0.6:
The system B that the molar ratio of 0.15:0.25 is mixed to get；
(3) ratio of system A and system B 1:0.7 by volume is sufficiently mixed, and mixed system pH value is 10, is placed and is carried out
Aging, aging temperature are 90 DEG C, and ageing time 1h obtains wet gel；
(4) supercritical drying processing, dried medium CO are carried out to the wet gel of step (3)2, supercritical temperature 32
DEG C, supercritical pressure 15MPa obtains nanometer titanium dioxide silica aerogel.
Wherein, step (1) and step (2) can exchange, dissolved with ethylization-beta-cyclodextrin in step (1) and step (2)
Ethylization-beta-cyclodextrin concentration is 0.035g/mL in methanol solution.
Embodiment 7
A kind of preparation method of nanometer titanium dioxide silica aerogel, in addition to step (1) and step (2) use dissolved with ethyl
Ethylization-beta-cyclodextrin concentration is except 0.002g/mL, with same as Example 1 in change-beta-cyclodextrin ethanol solution
Mode prepares nanometer titanium dioxide silica aerogel.
Embodiment 8
A kind of preparation method of nanometer titanium dioxide silica aerogel, in addition to step (1) and step (2) use dissolved with ethyl
Ethylization-beta-cyclodextrin concentration is except 0.2g/mL, with side same as Example 1 in change-beta-cyclodextrin ethanol solution
Formula prepares nanometer titanium dioxide silica aerogel.
Embodiment 9
A kind of preparation method of nanometer titanium dioxide silica aerogel, in addition to step (3) aging temperature be 40 DEG C other than, with reality
It applies the identical mode of example 2 and prepares nanometer titanium dioxide silica aerogel.
Embodiment 10
A kind of preparation method of nanometer titanium dioxide silica aerogel, in addition to step (3) mixed system pH value be 7 other than, with
The identical mode of embodiment 3 prepares nanometer titanium dioxide silica aerogel.
Comparative example 1
A kind of preparation method of nanometer titanium dioxide silica aerogel, in addition to by step (1) and step (2) dissolved with ethylization-β-
The ethanol solution of cyclodextrin replaces with except ethanol solution, prepares nano silica airsetting in the same manner as example 1
Glue.
Comparative example 2
A kind of preparation method of nanometer titanium dioxide silica aerogel, in addition to by step (1) and step (2) dissolved with ethylization-β-
The methanol solution of cyclodextrin replaces with except methanol solution, prepares nano silica airsetting in the same way as in example 2
Glue.
Comparative example 3
A kind of preparation method of nanometer titanium dioxide silica aerogel, in addition to by step (1) and step (2) dissolved with ethylization-β-
The ethanol solution of cyclodextrin replaces with except ethanol solution, prepares nano silica airsetting in mode same as Example 3
Glue.
Comparative example 4
A kind of preparation method of nanometer titanium dioxide silica aerogel, in addition to by step (1) and step (2) dissolved with ethylization-β-
The methanol solution of cyclodextrin replaces with except methanol solution, prepares nano silica airsetting in mode same as Example 4
Glue.
Comparative example 5
A kind of preparation method of nanometer titanium dioxide silica aerogel, in addition to by step (1) and step (2) dissolved with ethylization-β-
The ethanol solution of cyclodextrin replaces with except ethanol solution, prepares nano silica airsetting in mode same as Example 5
Glue.
Comparative example 6
A kind of preparation method of nanometer titanium dioxide silica aerogel, in addition to by step (1) and step (2) dissolved with ethylization-β-
The methanol solution of cyclodextrin replaces with except methanol solution, prepares nano silica airsetting in the same manner as in example 6
Glue.
Comparative example 7
A kind of preparation method of nanometer titanium dioxide silica aerogel, in addition to step (1) methyl orthosilicate, dissolved with ethylization-β-
Except the system A that ethanol solution, hydrochloric acid and the water of cyclodextrin are mixed to get with the molar ratio of 1:5:2:1, with same as Example 1
Mode prepare nanometer titanium dioxide silica aerogel.
Comparative example 8
A kind of preparation method of nanometer titanium dioxide silica aerogel, other than saving the silane coupling agent in step (2), with
Mode same as Example 1 prepares nanometer titanium dioxide silica aerogel.
Test example
For the physical property of the nanometer titanium dioxide silica aerogel prepared in comparing embodiment 1-10 and comparative example 1-8, survey
The tap density (g/ml) and carbon content (weight %) of fixed each aeroge.The results are shown in following table 1.
(1) tap density (g/ml)
Tap density is measured using tap density tester (STAV II, Enge 1smann AG).
Specifically, by each aeroge is put into standard cylinder (25ml) measure each aeroge weight it
Afterwards, cylinder is fixed on tap density tester, closes blimp, and set 2,500 vibrations.After vibration measurement,
The volume for measuring each aeroge in cylinder measures density by calculating the ratio of the weight and volume that had previously measured.
(2) carbon content (weight %)
Carbon content is measured using carbon analyzer (carbon-sulphur content analyzer CS-2000, El tra GmbH).
The physical property of the nanometer titanium dioxide silica aerogel of 1 embodiment and comparative example of table preparation
| Sample | Tap density (g/ml) | Carbon content (weight %) |
| Embodiment 1 | 0.08 | 14 |
| Embodiment 2 | 0.09 | 13 |
| Embodiment 3 | 0.06 | 12 |
| Embodiment 4 | 0.05 | 13 |
| Embodiment 5 | 0.09 | 15 |
| Embodiment 6 | 0.10 | 14 |
| Embodiment 7 | 0.09 | 11 |
| Embodiment 8 | 0.10 | 10 |
| Embodiment 9 | 0.12 | 11 |
| Embodiment 10 | 0.11 | 10 |
| Comparative example 1 | 0.15 | 5 |
| Comparative example 2 | 0.13 | 6 |
| Comparative example 3 | 0.14 | 6 |
| Comparative example 4 | 0.18 | 5 |
| Comparative example 5 | 0.16 | 7 |
| Comparative example 6 | 0.14 | 6 |
| Comparative example 7 | 0.11 | 10 |
| Comparative example 8 | 0.09 | 9 |
As shown in table 1, it can be verified that compared with the nanometer titanium dioxide silica aerogel of comparative example 1-8 preparation, pass through basis
The nanometer titanium dioxide silica aerogel of the embodiment 1-10 of the preparation method preparation of embodiment of the present invention generally has lower
Tap density, tap density is in 0.05~0.12g/mL, while hydrophobicity is good, carbon content with higher, carbon content 10~
15 weight %.
Specifically, other than whether adding ethylization-beta-cyclodextrin, embodiment 1 and right is prepared at identical conditions
The nanometer titanium dioxide silica aerogel of ratio 1, the nanometer titanium dioxide silica aerogel of embodiment 2 and comparative example 2, embodiment 3 and comparison
The nanometer titanium dioxide silica aerogel of example 3, the nanometer titanium dioxide silica aerogel of embodiment 4 and comparative example 4, embodiment 5 and comparative example 5
Nanometer titanium dioxide silica aerogel and embodiment 6 and comparative example 6 nanometer titanium dioxide silica aerogel, as comparison result,
The carbon content of the aerosil of embodiment 1-6 increases, while compared with the aerosil of comparative example 1-6, real
The aerosil tap density for applying a 1-6 is substantially reduced.
Further analysis shows that in addition to ethylization-beta-cyclodextrin in ethylization-beta-cyclodextrin ethanol solution for using
Except concentration is different, the nanometer titanium dioxide silica aerogel of embodiment 1, embodiment 7 and embodiment 8 is prepared at identical conditions,
As comparison result, the tap density of the aerosil of embodiment 1 is suitable with embodiment 7-8, but carbon content is more real
Apply that a 7-8 is higher, and hydrophobicity is more preferable.As it can be seen that being pasted by ethylization-β-ring that a certain range content is added in ethanol solution
The hydrophobicity of essence, the aeroge enabled to is more preferable.
Further analysis shows that preparing embodiment 2 and embodiment at identical conditions other than aging temperature is different
9 nanometer titanium dioxide silica aerogel, as comparison result, the tap density of the aerosil of embodiment 2 is relatively implemented
Example 9 is lower, while carbon content is higher, it is seen then that aging temperature influences the final physical property and hydrophobicity of aeroge, by one
Determine to carry out aging at temperature, can obtain that density is lower, the higher aerosil of hydrophobicity.
Further analysis shows that preparing embodiment 3 and reality at identical conditions other than mixed system pH value is different
The nanometer titanium dioxide silica aerogel for applying example 10, as comparison result, the tap density of the aerosil of embodiment 3 compared with
Embodiment 10 is lower, while carbon content is higher, it is seen then that mixed system pH value influences the final physical property of aeroge and hydrophobic
Property, it is more preferable by the aerosil performance that in regulation system pH to a certain range after mixing, reaction can obtain.
Comparative example 7 is compared with Example 1, methyl orthosilicate in step (1), molten dissolved with ethylization-beta-cyclodextrin ethyl alcohol
Liquid, hydrochloric acid are different with the ratio of water, and finally obtained aerosil physical property is declined, while hydrophobicity is
Reduce, this is because using a certain proportion of organic silicon source, dissolved with ethylization-beta-cyclodextrin low-carbon alcohol solution, acid catalyst
It is mixed with water, entirely reaction hydrolysis, condensation can be made more complete, obtain more stable, performance preferably hydrophobic dioxy
SiClx aeroge network structure.
Comparative example 8 compared with Example 1, saves the silane coupling agent in step (2), obtained aerosil object
It is little to manage performance change, but hydrophobicity is declined, is modified, has this is because being able to carry out surface by addition silane coupling agent
Help obtain the better nanometer titanium dioxide silica aerogel of hydrophobicity.
In conclusion the preparation method of nanometer titanium dioxide silica aerogel of the present invention first obtains system A and system B respectively, then
System A and system B are mixed, the hydrolysis of system A organic silicon source is gradually condensed, and forms colloidal sol, then mix with system B and further make
Network structure, which is stablized, forms gel, while the silane coupling agent of system B is able to carry out surface and is modified, and it is hydrophobic to increase gel surface
Property, while by the way that ethylization-beta-cyclodextrin is added, ethylization-beta-cyclodextrin with numerous hydroxyls due to being capable of providing largely
Active site, thus be able to participate in the formation of whole network structure as a kind of skeletal support, pass through a large amount of ethyl base
Group, which reaches, improves the hydrophobic purpose of network structure, further enhances the hydrophobicity of nanometer titanium dioxide silica aerogel entirety.It is logical
The nanometer titanium dioxide silica aerogel obtained using the preparation method not only excellent physical properties are crossed, but also with higher hydrophobic
Property.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that wrapping in the following claims
Include all such changes and modifications belonged in the scope of the invention.
Claims (25)
1. a kind of preparation method of nanometer titanium dioxide silica aerogel, which comprises the following steps:
(a) 1:(0.5~1 by volume system A and system B) ratio be sufficiently mixed, obtain wet gel；
Wherein, system A is for organic silicon source, dissolved with ethylization-beta-cyclodextrin low-carbon alcohol solution, acid and water with 1:(10~50):
(0.5~1): what the molar ratio of (2~8) was mixed to get；
System B is dissolved with ethylization-beta-cyclodextrin low-carbon alcohol solution, silane coupling agent, alkali and water with 10:(0.5~1):
(0.05~0.2): what the molar ratio of (0.2~3) was mixed to get；
(b) wet gel of step (a) is dried, obtains nanometer titanium dioxide silica aerogel.
2. the preparation method of nanometer titanium dioxide silica aerogel described in accordance with the claim 1, which is characterized in that dissolved with ethylization-
Ethylization-beta-cyclodextrin concentration is 0.01~0.05g/mL in the low-carbon alcohol solution of beta-cyclodextrin.
3. the preparation method of nanometer titanium dioxide silica aerogel according to claim 2, which is characterized in that dissolved with ethylization-
Ethylization-beta-cyclodextrin concentration is 0.02~0.05g/mL in the low-carbon alcohol solution of beta-cyclodextrin.
4. the preparation method of nanometer titanium dioxide silica aerogel described in accordance with the claim 3, which is characterized in that dissolved with ethylization-
Ethylization-beta-cyclodextrin concentration is 0.02~0.04g/mL in the low-carbon alcohol solution of beta-cyclodextrin.
5. the preparation method of nanometer titanium dioxide silica aerogel described in accordance with the claim 1, which is characterized in that ethylization-β-ring
Dextrin is prepared by the following method to obtain:
Beta-cyclodextrin is dissolved in aqueous slkali, 75~95% ethyl alcohol are added, dithyl sulfate is added dropwise and is reacted, is adjusted after reaction
Reaction solution pH6~7 obtain ethylization-beta-cyclodextrin after extracted, dry.
6. the preparation method of nanometer titanium dioxide silica aerogel according to claim 5, which is characterized in that mole of aqueous slkali
Concentration is 8~12mol/L, every 2~3g beta-cyclodextrin, be added the aqueous slkali of 18~20mL, 95% ethyl alcohol of 1~3mL and 22~
The dithyl sulfate of 25mL.
7. the preparation method of nanometer titanium dioxide silica aerogel according to claim 5, which is characterized in that reaction temperature 50
~65 DEG C, the reaction time is 8~12h.
8. the preparation method of nanometer titanium dioxide silica aerogel according to claim 7, which is characterized in that reaction temperature 55
~65 DEG C, the reaction time is 10~12h.
9. according to the preparation method of the described in any item nanometer titanium dioxide silica aerogels of claim 1-8, which is characterized in that step
(a) aging is carried out after being sufficiently mixed.
10. the preparation method of nanometer titanium dioxide silica aerogel according to claim 9, which is characterized in that aging temperature is
50~90 DEG C, ageing time is 1~10h.
11. the preparation method of nanometer titanium dioxide silica aerogel according to claim 10, which is characterized in that aging temperature is
60~90 DEG C, ageing time is 5~8h.
12. according to the preparation method of the described in any item nanometer titanium dioxide silica aerogels of claim 1-8, which is characterized in that institute
It states organic silicon source and is selected from one of methyl orthosilicate, ethyl orthosilicate, tetrachloro silicane, industrial raw material E-40, E32 or E28
Or it is a variety of.
13. the preparation method of nanometer titanium dioxide silica aerogel according to claim 12, which is characterized in that the low-carbon alcohols
Solution is selected from one of methanol, ethyl alcohol or propyl alcohol or a variety of.
14. the preparation method of nanometer titanium dioxide silica aerogel according to claim 13, which is characterized in that the acid is selected from
One or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, oxalic acid or acetic acid.
15. according to the preparation method of the described in any item nanometer titanium dioxide silica aerogels of claim 1-8, which is characterized in that institute
State silane coupling agent be selected from trim,ethylchlorosilane, hexamethyldisilazane, dimethyldichlorosilane, methyltriethoxysilane or
One or more of fluoric silane.
16. the preparation method of nanometer titanium dioxide silica aerogel according to claim 15, which is characterized in that the silane is even
Connection agent is hexamethyldisilazane.
17. the preparation method of nanometer titanium dioxide silica aerogel according to claim 15, which is characterized in that the alkali is selected from
One or more of ammonium hydroxide, monoethanolamine, diethanol amine or triethanolamine.
18. according to the preparation method of the described in any item nanometer titanium dioxide silica aerogels of claim 1-8, which is characterized in that step
Suddenly the mixed system pH value after (a) is sufficiently mixed is 7~12.
19. the preparation method of nanometer titanium dioxide silica aerogel according to claim 18, which is characterized in that step (a) is filled
Dividing mixed mixed system pH value is 8~12.
20. the preparation method of nanometer titanium dioxide silica aerogel according to claim 18, which is characterized in that step (a) is filled
Dividing mixed mixed system pH value is 9~12.
21. according to the preparation method of the described in any item nanometer titanium dioxide silica aerogels of claim 1-8, which is characterized in that institute
Stating dry is supercritical drying.
22. according to the preparation method of the nanometer titanium dioxide silica aerogel described in claim 21, which is characterized in that supercritical drying
Using methanol as dried medium, supercritical temperature is 260~280 DEG C, and supercritical pressure is 10~12MPa.
23. according to the preparation method of the nanometer titanium dioxide silica aerogel described in claim 21, which is characterized in that supercritical drying
With CO2For dried medium, supercritical temperature is 30~35 DEG C, and supercritical pressure is 10~20MPa.
24. nano-silica prepared by a kind of preparation method of described in any item nanometer titanium dioxide silica aerogels of claim 1-23
SiClx aeroge.
25. according to the nanometer titanium dioxide silica aerogel described in claim 24, which is characterized in that the nano silica airsetting
The tap density of glue is 0.05~0.12g/mL；
The nanometer titanium dioxide silica aerogel contains the carbon of 10~15 weight %.
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| CN104548114A (en) * | 2014-12-23 | 2015-04-29 | 西安交通大学 | Preparation method of inorganic-organic compound aerogel drug carrier |
| CN106495169A (en) * | 2016-10-28 | 2017-03-15 | 浙江省普瑞科技有限公司 | A kind of hydrophobic type aerosil and preparation method thereof |
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| CN104140553A (en) * | 2014-07-18 | 2014-11-12 | 天津大学 | Hydrophobic chitosan-silicon dioxide composite aerogel and preparation method and oil absorption application thereof |
| CN104548114A (en) * | 2014-12-23 | 2015-04-29 | 西安交通大学 | Preparation method of inorganic-organic compound aerogel drug carrier |
| CN106495169A (en) * | 2016-10-28 | 2017-03-15 | 浙江省普瑞科技有限公司 | A kind of hydrophobic type aerosil and preparation method thereof |
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