CN108147416A - The preparation method of nanometer titanium dioxide silica aerogel and nanometer titanium dioxide silica aerogel - Google Patents
The preparation method of nanometer titanium dioxide silica aerogel and nanometer titanium dioxide silica aerogel Download PDFInfo
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- CN108147416A CN108147416A CN201810048941.0A CN201810048941A CN108147416A CN 108147416 A CN108147416 A CN 108147416A CN 201810048941 A CN201810048941 A CN 201810048941A CN 108147416 A CN108147416 A CN 108147416A
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- titanium dioxide
- nanometer titanium
- silica aerogel
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- dioxide silica
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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 includes：(a) system A and system B by volume 1:The ratio of (0.5~1) is sufficiently mixed, and obtains wet gel；Wherein, system A be organic silicon source, dissolved with ethylatedβ cyclodextrins low-carbon alcohol solution, acid and water with 1:(10~50):(0.5~1):The molar ratio mixing of (2~8)；System B is with 10 dissolved with the low-carbon alcohol solution of ethylatedβ cyclodextrins, silane coupling agent, alkali and water:(0.5~1):(0.05~0.2):The molar ratio mixing of (0.2~3)；(b) wet gel is dried.The present invention alleviates the SiO that existing method obtains2The problem of aeroge hydrophobicity and bad physical property.By using SiO made from the method for the present invention2Aeroge not only excellent physical properties, but also hydrophobicity is good.
Description
Technical field
The present invention relates to aerosil technical field, in particular to a kind of nanometer titanium dioxide silica aerogel
Preparation method and nanometer titanium dioxide silica aerogel.
Background technology
Aeroge is mutually to assemble to be formed nanoporous network structure, and in network hole with nanometer scale ultramicro powder
Lightweight nano solid material full of gaseous state decentralized medium.Most common aeroge be aerosil, silica gas
Gel is a kind of very outstanding light nanoporous amorphous solid material of solar heat protection heat-proof quality, 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 conductivity factor 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, is then prepared in the case where not destroying its microstructure by removing the liquid component 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, need exploitation one kind can
Muchly to prevent from absorbing the method for the moisture in air, easily 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 logical
It crosses to prepare using surface modifier and there is hydrophobic aerosil.But this method, which is difficult to control surface, to be modified instead
Should, productivity is relatively low, and obtained aerosil hydrophobicity and physical property is bad.
In view of this, it is special to propose the present invention.
Invention content
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 adding in ethylization-beta-cyclodextrin, can participate in SiO2The formation of gel network, enhances nanometer titanium dioxide
The hydrophobicity of silica aerogel.
The second object of the present invention is that providing a kind of preparation method of above-mentioned nanometer titanium dioxide silica aerogel is prepared
Nanometer titanium dioxide silica aerogel, not only physical property is excellent for the nanometer titanium dioxide silica aerogel obtained by using the above method
It is different, and obtain higher hydrophobicity.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of preparation method of nanometer titanium dioxide silica aerogel, includes the following steps：
(a) system A and system B by volume 1:The ratio of (0.5~1) is sufficiently mixed, and obtains 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 is with 10 dissolved with the low-carbon alcohol solution of ethylization-beta-cyclodextrin, silane coupling agent, alkali and water:(0.5~
1):(0.05~0.2):What the molar ratio of (0.2~3) was mixed to get；
(b) processing is dried to the wet gel of step (a), obtains nanometer titanium dioxide silica aerogel.
Further, on the basis of technical solution provided by the invention, dissolved with the low-carbon alcohol solution of ethylization-beta-cyclodextrin
A concentration of 0.01~0.05g/mL of middle ethylization-beta-cyclodextrin, 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, adds in 95% ethyl alcohol, 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 be 8~12mol/L, every 2~3g beta-cyclodextrins, add in 18~20mL alkali
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
It is one or more in acetoacetic ester, tetrachloro silicane, industrial raw material E-40, E32 or E28；
Preferably, the low-carbon alcohol solution is one or more in methanol, ethyl alcohol or propyl alcohol；
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.
Nanometer titanium dioxide silica aerogel prepared by a kind of preparation method 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
It spends for 0.05~0.12g/mL；
The nanometer titanium dioxide silica aerogel contains the carbon of 10~15 weight %.
Compared with the prior art, the present invention has the advantages that：
(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 with certain proportion, form system A；It will be dissolved with the low-carbon alcohols of ethylization-beta-cyclodextrin
Solution, silane coupling agent, alkali and water are mixed with certain proportion, 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 mixed with system B and further stablize network structure to form gel, while system
The silane coupling agent of B can carry out surface modification, contribute 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 adding in ethylization-beta-cyclodextrin, ethylize-
Beta-cyclodextrin can be participated in 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 relatively low
Tap density and higher specific surface area, tap density is 0.05~0.12g/mL, and hydrophobicity is good, and there is higher carbon to contain
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, the condition suggested according to normal condition or manufacturer carry out.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, provide a kind of preparation method of nanometer titanium dioxide silica aerogel, including with
Lower step：
(a) system A and system B by volume 1:The ratio of (0.5~1) is sufficiently mixed, and obtains 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 is with 10 dissolved with the low-carbon alcohol solution of ethylization-beta-cyclodextrin, silane coupling agent, alkali and water:(0.5~
1):(0.05~0.2):What the molar ratio of (0.2~3) was mixed to get；
(b) processing is dried to the wet gel of step (a), obtains nanometer titanium dioxide silica aerogel.
In general, dry aerosil keeps relatively low 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 relatively low thermal conductivity.
It has proposed to prepare with permanent hydrophobicity by carrying out hydrophobic treatment on aerosil surface at present
Aerosil method, usually by using surface modifier prepare have hydrophobic aerosil.
But this method is difficult to control surface modification reaction, productivity is relatively low, obtained aerosil hydrophobicity and physics
Performance is bad.
Then the preparation method of the nanometer titanium dioxide silica aerogel of the present 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) dry wet gel, obtain nanometer titanium dioxide silica aerogel.
System A
System A is organic silicon source, low-carbon alcohol solution, acid and water dissolved with ethylization-beta-cyclodextrin.
Organic silicon source is not particularly limited, and the common organic silicon source of aerosil is prepared 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 ethylization-beta-cyclodextrin is dissolved in low-carbon alcohols and obtained dissolved with the low-carbon alcohol solution of ethylization-beta-cyclodextrin
'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 for methanol, ethyl alcohol or
Propyl alcohol.
The concentration of ethylization-beta-cyclodextrin in the low-carbon alcohol solution of ethylization-beta-cyclodextrin 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 easily carried 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, the low-carbon alcohol solution dissolved with ethylization-beta-cyclodextrin, 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 low-carbon alcohol solution, silane coupling agent, alkali and the water of ethylization-beta-cyclodextrin.
The low-carbon alcohol solution of ethylization-beta-cyclodextrin is identical with the description in system A, to the low of ethylization-beta-cyclodextrin
The concentration of ethylization-beta-cyclodextrin is not particularly limited in carbon alcoholic solution, if can make in solubility range ethylization-
Beta-cyclodextrin is dissolved completely in low-carbon alcohols, and the low-carbon with ethylization-beta-cyclodextrin of system A same concentrations may be used
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 further can stablize network structure by adding in alkali, form gel, while activate silane coupling agent, pass through table
Face is modified the hydrophobicity of enhancing gel.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 3):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:
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, obtain wet gel.
Wet gel is dried, solvent is removed, obtains aerosil, dry mode is not particularly limited,
Freeze-drying, supercritical drying or constant pressure and dry etc. may be used.
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 with certain proportion, form system A；It will be molten dissolved with the low-carbon alcohols of ethylization-beta-cyclodextrin
Liquid, silane coupling agent, alkali and water are mixed with certain proportion, form system B, then system A and system B is mixed, system A organosilicons
Source hydrolysis is gradually condensed, and forms colloidal sol, then mixed with system B and further stablize network structure to form gel, while system B
Silane coupling agent can carry out surface modification, increase gel surface hydrophobicity, while by adding in ethylization-beta-cyclodextrin,
Ethylization-beta-cyclodextrin is used as a kind of skeletal support energy due to being capable of providing a large amount of active site with numerous hydroxyls
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 with higher hydrophobicity.
In a preferred embodiment, it is pasted dissolved with ethylization-β in the low-carbon alcohol solution of ethylization-beta-cyclodextrin-ring
A concentration of 0.01~the 0.05g/mL, preferably 0.02~0.05g/mL, further preferred 0.02~0.04g/mL of essence.
The typical but non-limiting concentration of low-carbon alcohol solution of ethylization-beta-cyclodextrin is, for example, 0.01g/mL, 0.02g/
ML, 0.03g/mL, 0.04g/mL or 0.05g/mL.
Reaction acquisition is carried out by using low-carbon alcohol solution of the concentration in ethylization-beta-cyclodextrin of 0.01~0.05g/mL
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, adds in 75~95% ethyl alcohol, dithyl sulfate is added dropwise and is reacted, after reaction
Reaction solution pH6~7 are adjusted, ethylization-beta-cyclodextrin is obtained 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 be 8~12mol/L, every 2~3g beta-cyclodextrins, add in 18~20mL alkali
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-cyclodextrins are taken, it is dissolved in 8~
In 12mol/L 18~20mL NaOH solutions, 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, 55 DEG C are stirred 5 hours, decompose 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, is done with anhydrous sodium sulfate
To be clarified up to solution, chloroform is recycled, residue 10~15mL absolute ethyl alcohols are dissolved, filtered through glass funnel, filtrate within dry 2 hours
It is concentrated under reduced pressure, obtains white powder crystallization, 80 DEG C of dryings 24 hours.
Ethylization-beta-cyclodextrin degree of substitution that this method obtains is used as 1.83, average molecular weight 1496.
The ethylization obtained by using the above method-beta-cyclodextrin hydrophobicity is good, can participate in the shape of gel network
Cheng Zhong helps to build 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 made 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
It is or one or more in E28；
Preferably, low-carbon alcohol solution is one or more in methanol, ethyl alcohol or propyl alcohol；
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,
8th, 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, it is dry for 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 is caved in caused by systolic pressure when greatly can reduce dry, and then obtains excellent aeroge.Pass through
The complete of aeroge skeleton structure can be ensured 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 using 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.
Relatively low using carbon dioxide as dried medium required temperature, drying effect is good and 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 be 0.05~
0.12g/mL and can the carbon containing 10~15 weight %.
Since the aerosil of embodiment according to the present invention is prepared by above-mentioned preparation method, root
According to embodiment of the present invention aerosil can have higher hydrophobicity and excellent physical property, such as compared with
Low tap density.
Hereinafter, will the present invention be more fully described according to following specific embodiment and comparative example.However, it provides 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：Take 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 diethyls are added dropwise
Ester continues stirring 12 hours after dripping off, add ammonium hydroxide 4mL, and 55 DEG C are stirred 5 hours, are decomposed excessive dithyl sulfate complete, are used
Hydrochloric acid is neutralized to pH6, and three times (30,25,25mL), extracting solution is washed with water twice chloroform recovery, is dried 2 hours with anhydrous sodium sulfate
To be clarified up to solution, chloroform is recycled, residue 10mL absolute ethyl alcohols are dissolved, filtered through glass funnel, and filtrate decompression concentration obtains
White powder crystallizes, and 80 DEG C of dryings obtain for 24 hours.
Embodiment 1
A kind of preparation method of nanometer titanium dioxide silica aerogel, includes the following steps：
(1) methyl orthosilicate, dissolved with ethylization-beta-cyclodextrin ethanol solution, hydrochloric acid and water with 1:10:1:2 mole
Than the system A being mixed to get；
(2) dissolved with the ethanol solution of ethylization-beta-cyclodextrin, hexamethyldisilazane, ammonium hydroxide and water with 10:1:0.05:3
The system B that is mixed to get of molar ratio；
(3) system A and system B by volume 1:0.5 ratio is sufficiently mixed, and mixed system pH value is 10, places and carries 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)
A concentration of 0.03g/mL of ethylization-beta-cyclodextrin in ethanol solution.
Embodiment 2
A kind of preparation method of nanometer titanium dioxide silica aerogel, includes the following steps：
(1) methyl orthosilicate, dissolved with ethylization-beta-cyclodextrin methanol solution, sulfuric acid and water with 1:50:0.5:8 rub
The system A that your ratio is mixed to get；
(2) dissolved with the methanol solution of ethylization-beta-cyclodextrin, hexamethyldisilazane, ammonium hydroxide and water with 10:0.5:0.2:
The system B that 0.2 molar ratio is mixed to get；
(3) system A and system B by volume 1:1 ratio is sufficiently mixed, and mixed system pH value is 9, places and carries out always
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)
A concentration of 0.01g/mL of ethylization-beta-cyclodextrin in methanol solution.
Embodiment 3
A kind of preparation method of nanometer titanium dioxide silica aerogel, includes the following steps：
(1) methyl orthosilicate, dissolved with ethylization-beta-cyclodextrin ethanol solution, nitric acid and water with 1:10:0.5:2 rub
The system A that your ratio is mixed to get；
(2) dissolved with the ethanol solution of ethylization-beta-cyclodextrin, 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) system A and system B by volume 1:0.8 ratio is sufficiently mixed, and mixed system pH value is 11, places and carries 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)
A concentration of 0.05g/mL of ethylization-beta-cyclodextrin in ethanol solution.
Embodiment 4
A kind of preparation method of nanometer titanium dioxide silica aerogel, includes the following steps：
(1) ethyl orthosilicate, dissolved with ethylization-beta-cyclodextrin methanol solution, phosphoric acid and water with 1:50:1:2 mole
Than the system A being mixed to get；
(2) dissolved with the methanol solution of ethylization-beta-cyclodextrin, trim,ethylchlorosilane, triethanolamine and water with 10:0.5:
0.05:The system B that 3 molar ratio is mixed to get；
(3) system A and system B by volume 1:0.6 ratio is sufficiently mixed, and mixed system pH value is 12, places and carries 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)
A concentration of 0.02g/mL of ethylization-beta-cyclodextrin in methanol solution.
Embodiment 5
A kind of preparation method of nanometer titanium dioxide silica aerogel, includes the following steps：
(1) ethyl orthosilicate, dissolved with ethylization-beta-cyclodextrin ethanol solution, oxalic acid and water with 1:30:0.8:5 rub
The system A that your ratio is mixed to get；
(2) dissolved with the ethanol solution of ethylization-beta-cyclodextrin, dimethyldichlorosilane, triethanolamine and water with 10:0.8:
0.1:The system B that 0.25 molar ratio is mixed to get；
(3) system A and system B by volume 1:0.8 ratio is sufficiently mixed, and mixed system pH value is 8, places and carries out always
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)
A concentration of 0.04g/mL of ethylization-beta-cyclodextrin in ethanol solution.
Embodiment 6
A kind of preparation method of nanometer titanium dioxide silica aerogel, includes the following steps：
(1) ethyl orthosilicate, dissolved with ethylization-beta-cyclodextrin methanol solution, acetic acid and water with 1:20:0.6:6 rub
The system A that your ratio is mixed to get；
(2) dissolved with the methanol solution of ethylization-beta-cyclodextrin, dimethyldichlorosilane, triethanolamine and water with 10:0.6:
0.15:The system B that 0.25 molar ratio is mixed to get；
(3) system A and system B by volume 1:0.7 ratio is sufficiently mixed, and mixed system pH value is 10, places and carries 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)
A concentration of 0.035g/mL of ethylization-beta-cyclodextrin 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
In the ethanol solution of change-beta-cyclodextrin except a concentration of 0.002g/mL of ethylization-beta-cyclodextrin, with same as Example 1
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
In the ethanol solution of change-beta-cyclodextrin except a concentration of 0.2g/mL of ethylization-beta-cyclodextrin, with side same as Example 1
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 is other than 40 DEG C, 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 is other than 7, 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 is replaced with except ethanol solution, prepares nano silicon dioxide 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 is replaced with except methanol solution, prepares nano silicon dioxide 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 is replaced with except ethanol solution, and nano silicon dioxide airsetting is prepared in a manner of 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 is replaced with except methanol solution, and nano silicon dioxide airsetting is prepared in a manner of 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 is replaced with except ethanol solution, and nano silicon dioxide airsetting is prepared in a manner of 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 is replaced with except methanol solution, prepares nano silicon dioxide 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-
Ethanol solution, hydrochloric acid and the water of cyclodextrin are with 1:5:2:Except the system A that 1 molar ratio is mixed to get, 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 nanometer titanium dioxide silica aerogel prepared in comparing embodiment 1-10 and comparative example 1-8, survey
The fixed tap density (g/ml) of each aeroge and carbon content (weight %).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 measured in standard cylinder (25ml) weight of each aeroge it
Afterwards, cylinder is fixed on tap density tester, closes blimp, and set 2,500 vibrations.After vibration measurement,
The volume of each aeroge in cylinder is measured, density is measured by calculating the ratio of the weight previously measured and volume.
(2) carbon content (weight %)
Carbon content is measured using carbon analyzer (carbon-sulphur content analyzer CS-2000, El tra GmbH).
The physical property of nanometer titanium dioxide silica aerogel prepared by 1 embodiment and comparative example of table
| 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 nanometer titanium dioxide silica aerogel prepared by comparative example 1-8, pass through basis
The nanometer titanium dioxide silica aerogel of embodiment 1-10 prepared by the preparation method of embodiment of the present invention generally has relatively low
Tap density, tap density is in 0.05~0.12g/mL, while hydrophobicity is good, has a higher carbon content, 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 the nanometer titanium dioxide silica aerogel of embodiment 6 and comparative example 6, as result of the comparison,
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 the ethanol solution of ethylization-beta-cyclodextrin that uses
Except concentration difference, the nanometer titanium dioxide silica aerogel of embodiment 1, embodiment 7 and embodiment 8 is prepared at identical conditions,
As result of the comparison, the tap density of the aerosil of embodiment 1 is suitable with embodiment 7-8, but carbon content is more real
A 7-8 highers are applied, hydrophobicity is more preferable.As it can be seen that it is pasted by ethylization-β-ring that a certain range content is added in ethanol solution
Essence, the hydrophobicity of the aeroge enabled to are more preferable.
Further analysis shows that other than aging temperature difference, embodiment 2 and embodiment are prepared at identical conditions
9 nanometer titanium dioxide silica aerogel, as result of the comparison, the tap density of the aerosil of embodiment 2 is relatively implemented
Example 9 is lower, while carbon content 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 other than mixed system pH value difference, embodiment 3 and reality are prepared at identical conditions
Apply the nanometer titanium dioxide silica aerogel of example 10, as result of the comparison, the tap density of the aerosil of embodiment 3 compared with
Embodiment 10 is lower, while carbon content higher, it is seen then that mixed system pH value influences the final physical property of aeroge and hydrophobic
Property, by that in regulation system pH to a certain range, can make aerosil performance obtained by the reaction more preferable after mixing.
Comparative example 7 compared with Example 1, methyl orthosilicate in step (1), dissolved with ethylization-beta-cyclodextrin ethyl alcohol it is molten
Liquid, hydrochloric acid are different with the ratio of water, and the aerosil physical property finally obtained is declined, while hydrophobicity is
It reduces, this is because using a certain proportion of organic silicon source, the low-carbon alcohol solution dissolved with ethylization-beta-cyclodextrin, acid catalyst
It is mixed with water, entire 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, this is because can carry out surface modification by adding silane coupling agent, is had
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 sources is gradually condensed, and forms colloidal sol, then is mixed with system B and further made
Network structure is stablized to form gel, while the silane coupling agent of system B can carry out surface modification, and it is hydrophobic to increase gel surface
Property, while by adding in ethylization-beta-cyclodextrin, ethylization-beta-cyclodextrin with numerous hydroxyls due to being capable of providing largely
Active site, thus can be participated 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
Cross the nanometer titanium dioxide silica aerogel obtained using the preparation method not only excellent physical properties, 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 the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that it wraps in the following claims
Include all such changes and modifications belonged in the scope of the invention.
Claims (10)
1. a kind of preparation method of nanometer titanium dioxide silica aerogel, which is characterized in that include the following steps：
(a) system A and system B by volume 1:The ratio of (0.5~1) is sufficiently mixed, and obtains 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 is with 10 dissolved with the low-carbon alcohol solution of ethylization-beta-cyclodextrin, silane coupling agent, alkali and water:(0.5~1):
(0.05~0.2):What the molar ratio of (0.2~3) was mixed to get；
(b) processing is dried to the wet gel of step (a), 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 ethylize-
A concentration of 0.01~0.05g/mL of ethylization-beta-cyclodextrin, preferably 0.02~0.05g/ in the low-carbon alcohol solution of beta-cyclodextrin
ML, further preferred 0.02~0.04g/mL.
3. 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, adds in 75~95% ethyl alcohol, 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 be 8~12mol/L, every 2~3g beta-cyclodextrins, add in 18~20mL aqueous slkali,
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.
4. according to the preparation method of claim 1-3 any one of them nanometer titanium dioxide silica aerogels, which is characterized in that step
(a) aging is carried out 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.
5. according to the preparation method of claim 1-3 any one of them nanometer titanium dioxide silica aerogels, which is characterized in that described
One kind in methyl orthosilicate, ethyl orthosilicate, tetrachloro silicane, industrial raw material E-40, E32 or E28 of organic silicon source or
It is a variety of；
Preferably, the low-carbon alcohol solution is one or more in methanol, ethyl alcohol or propyl alcohol；
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.
6. according to the preparation method of claim 1-3 any one of them nanometer titanium dioxide silica aerogels, which is characterized in that described
Silane coupling agent is selected from trim,ethylchlorosilane, hexamethyldisilazane, dimethyldichlorosilane, methyltriethoxysilane or fluorine
For one or more of silane, preferably hexamethyldisilazane；
Preferably, the alkali is selected from one or more of ammonium hydroxide, monoethanolamine, diethanol amine or triethanolamine.
7. according to the preparation method of claim 1-3 any one of them nanometer titanium dioxide silica aerogels, which is characterized in that step
(a) the mixed system pH value after being sufficiently mixed is 7~12, preferably 8~12, further preferred 9~12.
8. according to the preparation method of claim 1-3 any one of them nanometer titanium dioxide silica aerogels, which is characterized in that described
Dry is supercritical drying；
Preferably, supercritical drying is using methanol as dried medium, and supercritical temperature is 260~280 DEG C, supercritical pressure for 10~
12MPa；
Preferably, supercritical drying is with CO2For dried medium, supercritical temperature is 30~35 DEG C, supercritical pressure for 10~
20MPa。
9. nanometer titanium dioxide prepared by a kind of preparation method of claim 1-8 any one of them nanometer titanium dioxide silica aerogel
Silica aerogel.
10. according to the nanometer titanium dioxide silica aerogel described in claim 9, which is characterized in that the nano silicon dioxide 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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| CN112875711A (en) * | 2021-01-26 | 2021-06-01 | 西南科技大学 | Preparation method of gradient density hydrophobic silica aerogel |
| CN115010140A (en) * | 2022-07-20 | 2022-09-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of super-hydrophobic silica aerogel |
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