CN109592689A - Silica aerogel, preparation method and application based on linear organosilicon oligomer - Google Patents
Silica aerogel, preparation method and application based on linear organosilicon oligomer Download PDFInfo
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- 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
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- C01B33/113—Silicon oxides; Hydrates thereof
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- C01P2006/90—Other properties not specified above
Abstract
The invention discloses a kind of silica aerogels based on linear organosilicon oligomer, preparation method and application.The silica aerogel is mainly formed by linear organosilicon oligomer through polycondensation, gelation, constant pressure and dry, and the contact angle with water, oil is 0 °, and oil absorption, water absorption are in 100wt% or more.The preparation method includes: that organosiloxane, acidic aqueous solution are uniformly mixed and are heated with alcohol, and the sol precursor containing linear organosilicon oligomer is prepared；The sol precursor is mixed with diluent, and catalyst is added, gel is formed after standing, stands aging again later；Gel mechanical after aging is crushed, is dry, obtains silica aerogel.The present invention is replaced without any solvent, also need not any modifying process, also need not freeze-drying or supercritical drying, directly dry under normal pressure, compared with aeroge prepared by other all constant pressure and dries, which can not only oil suction, moreover it is possible to absorb a large amount of water.
Description
Technical field
The present invention relates to a kind of silica aerogels more particularly to a kind of prepared using constant pressure and dry technology to have nanometer more
Pore structure, silica aerogel based on linear organosilicon oligomer and preparation method thereof and its application, it is more to belong to nanometer
Porous materials technical field.
Background technique
Aeroge is a kind of porous nano material, is that the current world improves quality solid most light, that heat-proof quality is best
Material.Since silica aerogel has high-specific surface area (400~1500m2/ g), it is high porosity (80~99.8%), low close
Spend (0.003~0.6g/cm3) and the features such as lower thermal conductivity (0.013~0.038W/mk), make it in high temperature resistant heat insulation, ultralow close
The fields such as degree, acoustic impedance coupling, gas absorption and filtering, catalyst carrier, pharmaceutical carrier have very important application.
The common method for preparing silica aerogel is supercritical drying, for example, publication CN102583407A and
CN102642842B discloses the method for preparing aeroge using supercritical drying, is displaced by supercritical fluid wet
Solvent in gel can be good at keeping the original structure of gel after final drying.But usual supercritical drying needs to use
It to special equipment, and need to be operated under high pressure-temperature, the equipment on the one hand used is expensive, and operating difficulties, at high cost；It is another
There is also great security risks for aspect.Therefore, although aeroge has above-mentioned excellent properties, due to being prepared into
Ben Taigao, to limit its extensive use in daily life.
For this purpose, the emphasis of industry research staff's numerous studies just focuses on being produced into for reduction silica aerogel at present
This, such as publication CN101503195, CN102020285A and CN103043673A is individually disclosed using constant pressure and dry
The method for preparing aeroge: by repeatedly exchanging the fluid exchange in gel duct with multi-solvents as low surface tension
Solvent, such as n-hexane, then the surface in duct is modified as hydrophobicity, the capillary force in gel duct is substantially reduced, from
And during drying gel contraction very little, can substantially keep original form in this way.But since constant pressure and dry needs
Multiple gel duct exchange of solvent and surface-hydrophobicized processing are wanted, manufacturing cycle is very very long, and cumbersome, thus is difficult
Realize industrialization production.
On the other hand, hydrophobic modification is passed through by silica aerogel prepared by atmosphere pressure desiccation all unavoidablely,
Increase preparation process, and increase cost, and the pollution of hydrophobic reagent bring and by-product etc..Further, since by hydrophobic
Change and is modified, it is all so far that super-hydrophobicity is all shown as by the silica aerogel that atmosphere pressure desiccation prepares, although can absorb
A large amount of oil, but water cannot be absorbed.
Summary of the invention
In view of the deficiencies of the prior art with the limitation of material, the main purpose of the present invention is to provide a kind of super hydrophilic bases
In the silica aerogel and its constant pressure and dry preparation method of linear organosilicon oligomer.
Another object of the present invention is to provide the aforementioned super hydrophilic silica aerogel based on linear organosilicon oligomer
Purposes.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The embodiment of the invention provides a kind of preparation method of silica aerogel based on linear organosilicon oligomer,
Include:
(1) organosiloxane, acidic aqueous solution are uniformly mixed and are heated with alcohol, be prepared containing linear organosilicon oligomerization
The sol precursor of object；
(2) sol precursor is mixed with diluent, and catalyst is added, form gel, Zhi Houzai after standing
Stand aging；
(3) gel mechanical after step (2) obtained aging is crushed, is dry, obtaining silica aerogel.
The embodiment of the invention also provides a kind of silica aerogel based on linear organosilicon oligomer, the silica
Aeroge is mainly formed by linear organosilicon oligomer through polycondensation, gelation, constant pressure and dry.
In some preferred embodiments, the silica aerogel is powder, and average grain diameter is 50nm~1000 μm.
Further, the aperture of hole contained by the silica aerogel be 1~500nm, specific surface area be 150~
2200m20.5~6cm of/g, Kong Rongwei3/ g, the contact angle with water, oil is 0 °.
The embodiment of the invention also provides the methods that a kind of pair of body surface carries out super hydrophilic modification comprising: it will be aforementioned
The silica aerogel even application based on linear organosilicon oligomer apply 0.5 in body surface, and after the completion of coating
The pressure of~10MPa forms super-hydrophilic coating.
Compared with prior art, advantages of the present invention at least that:
(1) the super hydrophilic silica aerogel micro mist of one kind of the invention, while there is oleophylic and hydrophily, and by normal pressure
Drying prepares, and synthetic method has the characteristics that simple process, production cycle are extremely short, at low cost, utilizes method of the invention
All solvent replacement process in existing atmosphere pressure desiccation can be exempted, it, also need not freeze-drying also without any modifying process
Or supercritical drying, it directly dries under normal pressure, substantially reduces manufacturing cycle, economize on resources；
(2) compared with aeroge prepared by other all constant pressure and dries, by the silica gas of method acquisition of the invention
Gel micro mist, has amphiphilic, and oil suction and water absorption are high, and particle diameter distribution is relatively narrow, the excellent properties such as high-specific surface area；
(3) present invention develops modification application method of the aeroge as super-hydrophilic coating for the first time, has easy to operate, suitable
With various interfaces or even bioelectric interface, mechanical resistant friction, stability is strong, is easy to the advantages such as removing；And the super-hydrophilic coating is not only
It can be used for traditional inorganic interface, it may also be used for life interface, while there is excellent abrasion resistance energy.
Detailed description of the invention
Mass spectrogram of the Fig. 1 by obtaining sol precursor in the embodiment of the present invention 1.
Schematic arrangement of the Fig. 2 by obtaining sol precursor in 1-6 of the embodiment of the present invention.
Isothermal nitrogen adsorption desorption curve graph of the Fig. 3 by obtaining silica aerogel micro mist in the embodiment of the present invention 1.
Pore size distribution curve figure of the Fig. 4 by obtaining silica aerogel micro mist in the embodiment of the present invention 1.
Scanning electron microscope diagram of Fig. 5 a by obtaining silica aerogel micro mist in the embodiment of the present invention 1.
Contact angle photo of Fig. 5 b by obtaining silica aerogel micro mist in the embodiment of the present invention 1.
Isothermal nitrogen adsorption desorption curve graph of the Fig. 6 by obtaining silica aerogel micro mist in the embodiment of the present invention 2.
Pore size distribution curve figure of the Fig. 7 by obtaining silica aerogel micro mist in the embodiment of the present invention 2.
Scanning electron microscope diagram of the Fig. 8 by obtaining silica aerogel micro mist in the embodiment of the present invention 2.
Isothermal nitrogen adsorption desorption curve graph of the Fig. 9 by obtaining silica aerogel micro mist in the embodiment of the present invention 3.
Pore size distribution curve figure of the Figure 10 by obtaining silica aerogel micro mist in the embodiment of the present invention 3.
Scanning electron microscope diagram of the Figure 11 by obtaining silica aerogel micro mist in the embodiment of the present invention 3.
Isothermal nitrogen adsorption desorption curve graph of the Figure 12 by obtaining silica aerogel micro mist in the embodiment of the present invention 4.
Pore size distribution curve figure of the Figure 13 by obtaining silica aerogel micro mist in the embodiment of the present invention 4.
Scanning electron microscope diagram of the Figure 14 by obtaining silica aerogel micro mist in the embodiment of the present invention 4.
Isothermal nitrogen adsorption desorption curve graph of the Figure 15 by obtaining silica aerogel micro mist in the embodiment of the present invention 5.
Pore size distribution curve figure of the Figure 16 by obtaining silica aerogel micro mist in the embodiment of the present invention 5.
Scanning electron microscope diagram of the Figure 17 by obtaining silica aerogel micro mist in the embodiment of the present invention 5.
Isothermal nitrogen adsorption desorption curve graph of the Figure 18 by obtaining silica aerogel micro mist in the embodiment of the present invention 6.
Pore size distribution curve figure of the Figure 19 by obtaining silica aerogel micro mist in the embodiment of the present invention 6.
Scanning electron microscope diagram of the Figure 20 by obtaining silica aerogel micro mist in the embodiment of the present invention 6.
Figure 21 is in reference examples 1 to the striograph of blade modified experimental facilities acquisition.
Figure 22 is the striograph of the modified experimental facilities acquisition of opponent in reference examples 1.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution.Present invention firstly provides a kind of amphiphilic silica aerogel micro mists and its preparation method and application.
The preparation of hydrophily silica aerogel still depends on supercritical drying, i.e., the silica of non-hydrophobization is wet solidifying
Glue can prepare hydrophilic silicas aeroge through supercritical drying.Pass through atmosphere pressure desiccation preparation hydrophilic and oleophylic oxidation simultaneously
Silica aerogel (i.e. amphiphilic silica aerogel), while reducing preparation cost, application range can also be from heat-insulated expansion
The fields such as biological medicine, cosmetics are opened up, there is important science and practical application value.
The one aspect of the embodiment of the present invention provides a kind of silica aerogel based on linear organosilicon oligomer
Preparation method, including three key steps:
(1) synthesis of sol precursor；(2) synthesis and aging of gel；(3) drying of gel.
Specifically, the preparation method of the silica aerogel based on linear organosilicon oligomer includes:
(1) organosiloxane, acidic aqueous solution are uniformly mixed and are heated with alcohol, be prepared containing linear organosilicon oligomerization
The sol precursor of object；
(2) sol precursor is mixed with diluent, and catalyst is added, form gel, Zhi Houzai after standing
Stand aging；
(3) gel mechanical after step (2) obtained aging is crushed, is dry, obtaining silica aerogel.
In some embodiments, the organosiloxane includes ethyl orthosilicate, methyl orthosilicate, methyl trimethoxy oxygroup silicon
In alkane, methyltriethoxysilane, dimethyl methoxy silane, dimethylethoxysilane etc. any one or it is two or more
Combination, and it is without being limited thereto.
Further, the acidic aqueous solution includes the weak solution of hydrochloric acid, sulfuric acid, oxalic acid, acetic acid or nitric acid, and is not limited to
This.
Further, H in the acidic aqueous solution+Content is 10-6~10-1mol/L。
Further, the alcohol include in methanol, ethyl alcohol, isopropanol, propyl alcohol, butanol, tert-butyl alcohol etc. any one or
Two or more combinations, and it is without being limited thereto.
Further, the silicon atom number of the organosilicon oligomer is 5~10, and the Si in skeleton is connected by Si-O-Si key
It connects and forms linear molecule.
Further, the molar ratio of organosiloxane, acidic aqueous solution and alcohol described in step (1) is 1:1.8~2.2:1
~10.
Further, the temperature of the heating is 80~150 DEG C, and the time is 5~12 hours.
Among some particularly preferred embodiments, the synthesis of sol precursor include: by the organosiloxane of 1mol,
The alcohol heating stirring after mixing of the acidic aqueous solution of 1.8~2.2mol, 1~10mol, is prepared few containing linear organosilicon
The sol precursor of polymers.
In some embodiments, the volume ratio of sol precursor, diluent and catalyst described in step (2) is 1:0.1
~3:0.01~0.5.
Further, the time for standing aging is in 5h or more.
Further, the temperature for standing aging is boiling temperature of the room temperature to the catalyst.
Among some particularly preferred embodiments, the synthesis of gel includes mixing sol precursor and diluent with aging
It closes, catalyst is added after being sufficiently stirred, forms gel after standing, stands aging again after gel.
Further, the diluent includes methanol, ethyl alcohol, isopropanol, propyl alcohol, butanol, the tert-butyl alcohol, n-hexane, hexamethylene
Any one in alkane, normal heptane, acetonitrile, toluene, tetrahydrofuran, different benzyl alcohol and perfluoroalkanes etc. or two or more groups
The composite solution of conjunction or the above solution, and it is without being limited thereto.
Further, the catalyst includes sodium hydroxide, potassium hydroxide, urea, ammonium hydroxide, pyridine, trimethyl ammonium chloride
It is and without being limited thereto with any one or the two or more combinations in triethylamine etc..
Further, the dosage of the catalyst is the 1%~50% of sol precursor volume fraction.
In some embodiments, step (3) specifically includes: the gel mechanical after step (2) obtained aging is crushed, it is natural
5~10h is dried, finally dry 5~10h dries aeroge thoroughly in forced air drying equipment, obtains silica aerogel.
Further, described be mechanically pulverized includes that roller press crushes, machine mixer crushes, colloid mill crushes, cutting vibration
Crushing, fruit juice mixer crushing etc. are swung, and without being limited thereto.
Further, the environmental pressure that dries is an atmospheric pressure, and temperature is room temperature, is placed at dry and ventilated.
Further, the temperature of the forced air drying equipment is 80~250 DEG C.
Further, the time of the forced air drying is 5~10h.
To sum up, the present invention synthesizes a kind of linear short chain of organosilicon polymer (oligomer) by structure design, poly- with this
The gel that object is precursor synthesis is closed, super hydrophilic oxidation can be obtained by convection drying (i.e. constant pressure and dry) under an atmospheric pressure
Silica aerogel.This method breaches the functional limitation that conventional atmospheric seasoning prepares aeroge, as prepared by conventional atmospheric seasoning
Aeroge be all it is hydrophobic, and aeroge prepared by the present invention be Superhydrophilic, greatly extend its application range.
The other side of the embodiment of the present invention additionally provides a kind of silica airsetting based on linear organosilicon oligomer
Glue, the silica aerogel are mainly formed by linear organosilicon oligomer through polycondensation, gelation, constant pressure and dry, primary chemical
Composition is SiO2。
Further, the silica aerogel is powder, and average grain diameter is 50nm~1000 μm.
Further, the silica aerogel has porous structure, and the aperture of hole contained by the porous structure is 1~
500nm, specific surface area are 150~2200m20.5~6cm of/g, Kong Rongwei3/ g, the contact angle with water, oil is 0 °.
Further, which has amphiphilic, while having oil suction (such as gasoline, kerosene, benzene and its derivative, each
Kind of alkane, alkene etc.) and water absorbing properties, aeroge absorb liquid to after being saturated, which obtained using precision balance weighing and calculating
The oil absorption and water absorption of gel reach 100wt% or more.
Further, the oil includes gasoline, kerosene, benzene and/or benzene derivate, alkane or alkene etc., and not
It is limited to this.
To sum up, silica aerogel micro mist of the invention, has amphiphilic, and oil suction and water absorption are high, and particle diameter distribution is relatively narrow,
The excellent properties such as high-specific surface area.
The other side of the embodiment of the present invention additionally provides the silica gas above-mentioned based on linear organosilicon oligomer
The purposes of gel.
The other side of the embodiment of the present invention additionally provides the method that a kind of pair of body surface carries out super hydrophilic modification,
Include: by the silica aerogel even application above-mentioned based on linear organosilicon oligomer in body surface, and is being coated
At the rear pressure for applying 0.5~10MPa, super-hydrophilic coating is formed.
One of as a preferred option, the amphiphilic silica aerogel micro mist is placed in the body surface that need to be modified,
Apply setting pressure to the amphiphilic silica aerogel micro mist again, keeps the amphiphilic silica aerogel micro mist uniform
It is coated on body surface, and forms super-hydrophilic coating.
Further, the dosage of the silica aerogel micro mist is 0.1~20g/m2。
Further, the body surface is dry anhydrous smooth or rough surface.
Further, the object includes glass, metal, polymer fiber, plastic foil, rubber, timber, leaf, insect
Any one in body surface, feather etc., and it is without being limited thereto.
Further, modified surface is all super hydrophilic, and moisture absorption is strong, and has certain anti-fog function.
In conclusion the silica aerogel based on linear organosilicon oligomer is used for by the present invention as super-hydrophilic coating
It is modified, have it is easy to operate, be applicable in various interfaces even bioelectric interface, that mechanical resistant friction, stability is strong, is easy to remove etc. is excellent
Gesture；And the super-hydrophilic coating can be not only used for traditional inorganic interface, it may also be used for life interface, while there is excellent resist
Attriting performance.
Below by way of several embodiments and in conjunction with the attached drawing technical solution that present invention be described in more detail.However, selected
Embodiment be merely to illustrate the present invention, and do not limit the scope of the invention.
Embodiment 1
(1) synthesis of sol precursor: the methyl orthosilicate of 1mol is taken, (content of hydrochloric acid is the aqueous hydrochloric acid solution of 1.8mol
10-4Mol), the ethyl alcohol of 1mol after mixing by three stirs 12 hours in 80 DEG C, obtains the line that silicon atom number is 5~10
Shape organosilicon polymer presoma.The mass spectrum of the presoma is referring to Fig. 1, and schematic arrangement is referring to fig. 2.Need herein explanation be
The molar ratio of what methyl orthosilicate and water is 1:1.8, if the two molar ratio is 1:(< 1.8) when, it can be only formed ring-type after hydrolysis
Silane, and molar ratio is 1:(> 2.2) when, hydrolysate functional group is easily crosslinked too much, and it is short can not all to form linear silicon polymerization
Chain.
(2) synthesis and aging of gel: taking 10 parts of sol precursor obtained above, then takes 30 parts of ethyl alcohol, by the two
5 parts of sodium hydroxide is added after being sufficiently mixed, stirs 20 minutes at room temperature, forms gel in 5 hours after standing.Again by gel
It is placed in 50 DEG C of baking oven, aging 6 hours.
(3) preparation of silica aerogel --- constant pressure and dry: after the gel after above-mentioned aging is smashed using colloid mill,
It dries at room temperature 8 hours, most of solvent naturally can be dry net at this time, and gel is then transferred to 250 DEG C of forced air drying
In case, any pressure or decompression device is not needed, is taken out after 5 hours dry, obtains super hydrophilic silica aerogel micro mist.Through
BET isothermal adsorption characterization, it is found that the silica aerogel micro mist has nano-porous structure, this silica aerogel is micro-
For the isothermal adsorption desorption curve of powder referring to Fig. 3, pore-size distribution refers to Fig. 4, scanning electron microscope (SEM) photograph please refers to Fig. 5 a, contact angle photo
Fig. 5 b is please referred to, other physical parameters such as specific surface area, pore size, Kong Rong, density, contact angle etc. see table 1.Aeroge is inhaled
Receive liquid to be saturated after, use precision balance weighing and calculating obtain the oil absorption of the aeroge, water absorption 100wt% with
On.
(4) gained aeroge micro mist 100mg is taken to be placed in 0.5 square metre of lotus leaf surface, with smooth plastic plate airsetting
Glue micro mist is evenly applied to blade face, obtains super hydrophilic lotus leaf, and modified agrochemical can be spread in blade face, kills germ,
And unmodified super-hydrophobic blade face, aqueous agricultural-chemical can not be sprawled.
Embodiment 2
(1) synthesis of sol precursor: the ethyl orthosilicate of 1mol is taken, (content of hydrochloric acid is the aqueous hydrochloric acid solution of 2.2mol
10-6Mol), the methanol of 10mol after mixing by three stirs 5 hours in 150 DEG C, obtains the line that silicon atom number is 5~10
Shape organosilicon polymer presoma.The schematic arrangement of the presoma is referring to fig. 2.Need herein explanation why ethyl orthosilicate
It is 1:2.2 with the molar ratio of water, if the two molar ratio is 1:(< 1.8) when, it can be only formed cyclic silane after hydrolysis, and mole
Than for 1:(> 2.2) when, hydrolysate functional group is easily crosslinked too much, can not all be formed linear silicon and be polymerize short chain.
(2) synthesis and aging of gel: taking 10 parts of sol precursor obtained above, then takes 1 part of methanol, and the two is filled
Divide after mixing and 0.1 part of urea is added, stirs 30 minutes at room temperature, form gel in 5 hours after standing.Gel is placed in again
80 DEG C of baking oven, aging 9 hours.
(3) preparation of silica aerogel --- constant pressure and dry: after the gel after above-mentioned aging is smashed using colloid mill,
It dries at room temperature 5 hours, most of solvent naturally can be dry net at this time, and gel is then transferred to 150 DEG C of forced air drying
In case, any pressure or decompression device is not needed, is taken out after 10 hours dry, obtains super hydrophilic silica aerogel micro mist.
It is characterized through BET isothermal adsorption, it is found that the silica aerogel micro mist has nano-porous structure, this silica aerogel
The isothermal adsorption desorption curve of micro mist is referring to Fig. 6, pore-size distribution refers to Fig. 7, and scanning electron microscope (SEM) photograph is referring to Fig. 8, other physics
Parameter such as specific surface area, pore size, Kong Rong, density, contact angle etc. sees table 1.
(4) gained aeroge micro mist 50mg is taken, is placed on plastic foil (PET), then with smooth metal plate that aeroge is uniform
Coated on plastic film, amphiphilic plastic foil is obtained, becomes super hydrophilic super oil-wet film.
Embodiment 3
(1) synthesis of sol precursor: the methyl orthosilicate of 1mol is taken, (sulfuric acid content is the aqueous sulfuric acid of 2.0mol
10-3Mol), the ethyl alcohol of 2mol after mixing by three stirs 12 hours in 100 DEG C, obtains the line that silicon atom number is 5~10
Shape organosilicon polymer presoma.The schematic arrangement of the presoma is referring to fig. 2.Need herein explanation why methyl orthosilicate
It is 1:2 with the molar ratio of water, if the two molar ratio is 1:(< 1.8) when, it can be only formed cyclic silane after hydrolysis, and molar ratio
For 1:(> 2.2) when, hydrolysate functional group is easily crosslinked too much, can not all be formed linear silicon and be polymerize short chain.
(2) synthesis and aging of gel: taking 10 parts of sol precursor obtained above, then takes 30 parts of tetrahydrofuran, will
5 trimethyl ammonium chlorides are added in the two after being sufficiently mixed, stir 30 minutes at room temperature, form gel in 5 hours after standing.Again will
Gel is placed in 50 DEG C of baking oven, and aging 8 hours.
(3) preparation of silica aerogel --- constant pressure and dry: after the gel after above-mentioned aging is smashed using colloid mill,
It dries at room temperature 6 hours, most of solvent naturally can be dry net at this time, and gel is then transferred to 80 DEG C of air dry oven
In, any pressure or decompression device is not needed, is taken out after 10 hours dry, obtains super hydrophilic silica aerogel micro mist.Through
BET isothermal adsorption characterization, it is found that the silica aerogel micro mist has nano-porous structure, this silica aerogel is micro-
The isothermal adsorption desorption curve of powder is referring to Fig. 9, pore-size distribution referring to Figure 10, and scanning electron microscope (SEM) photograph please refers to Figure 11, other physics
Parameter such as specific surface area, pore size, Kong Rong, density, contact angle etc. sees table 1.
(4) it takes gained aeroge micro mist 500mg to be placed on rubber gloves, then aeroge is applied to rubber gloves with glass plate
Surface obtains super hydrophilic gloves, contact angle 0o.
Embodiment 4
(1) methyltriethoxysilane of 1mol, the aqueous acetic acid (acetic acid of 2.1mol the synthesis of sol precursor: are taken
Solubility is 10-5Mol), the propyl alcohol of 2mol, after mixing by three, in 80 DEG C stir 12 hours, obtain silicon atom number be 5~
10 linear organosilicon polymer presoma.The schematic arrangement of the presoma is referring to fig. 2.Need herein explanation why methyl
The molar ratio of triethoxysilane and water is 1:2.1, if the two molar ratio is 1:(< 1.8) when, it can be only formed ring-type after hydrolysis
Silane, and molar ratio is 1:(> 2.2) when, hydrolysate functional group is easily crosslinked too much, and it is short can not all to form linear silicon polymerization
Chain.
(2) synthesis and aging of gel: taking 10 parts of sol precursor obtained above, then takes 5 parts of n-hexane, by the two
1 part of ammonium hydroxide is added after being sufficiently mixed, stirs 20 minutes at room temperature, forms gel in 5 hours after standing.Gel is placed in again
30 DEG C of baking oven, aging 6 hours.
(3) preparation of silica aerogel --- constant pressure and dry: after the gel after above-mentioned aging is smashed using colloid mill,
It dries at room temperature 8 hours, most of solvent naturally can be dry net at this time, and gel is then transferred to 120 DEG C of forced air drying
In case, any pressure or decompression device is not needed, is taken out after 8 hours dry, obtains super hydrophilic silica aerogel micro mist.Through
BET isothermal adsorption characterization, it is found that the silica aerogel micro mist has nano-porous structure, this silica aerogel is micro-
The isothermal adsorption desorption curve of powder please refers to Figure 12, and pore-size distribution referring to Figure 13, scanning electron microscope (SEM) photograph please refers to Figure 14, other physics
Parameter such as specific surface area, pore size, Kong Rong, density, contact angle etc. sees table 1.
(4) it takes gained aeroge micro mist 5mg to be placed in ginkgo leaf surface, then wears plastic glove, aeroge is lightly applied to
Folium Ginkgo surface obtains amphiphilic ginkgo leaf, contact angle 0o.
Embodiment 5
(1) synthesis of sol precursor: the methyltrimethoxysilane of 1mol is taken, (formic acid contains the formic acid solution of 1.9mol
Amount is 10-1Mol), the butanol of 8mol after mixing by three stirs 12 hours in 100 DEG C, and obtaining silicon atom number is 5~10
Linear organosilicon polymer presoma.The schematic arrangement of the presoma is referring to fig. 2.Need herein explanation why methyl three
Methoxy silane and the molar ratio of water are 1:1.9, if the two molar ratio is 1:(< 1.8) when, it can be only formed cyclic annular silicon after hydrolysis
Alkane, and molar ratio is 1:(> 2.2) when, hydrolysate functional group is easily crosslinked too much, and it is short can not all to form linear silicon polymerization
Chain.
(2) synthesis and aging of gel: taking 10 parts of sol precursor obtained above, then takes 30 parts of isopropanol, by two
9 parts of ammonium hydroxide is added in person after being sufficiently mixed, stir 20 minutes at room temperature, form gel in 5 hours after standing.Gel is set again
In 90 DEG C of baking oven, aging 6 hours.
(3) preparation of silica aerogel --- constant pressure and dry: after the gel after above-mentioned aging is smashed using colloid mill,
It dries at room temperature 8 hours, most of solvent naturally can be dry net at this time, and gel is then transferred to 180 DEG C of forced air drying
In case, any pressure or decompression device is not needed, is taken out after 7 hours dry, obtains super hydrophilic silica aerogel micro mist.Through
BET isothermal adsorption characterization, it is found that the silica aerogel micro mist has nano-porous structure, this silica aerogel is micro-
The isothermal adsorption desorption curve of powder please refers to Figure 15, and pore-size distribution referring to Figure 16, scanning electron microscope (SEM) photograph please refers to Figure 17, other physics
Parameter such as specific surface area, pore size, Kong Rong, density, contact angle etc. sees table 1.
Embodiment 6
(1) synthesis of sol precursor: the methyl orthosilicate of 1mol is taken, (nitric acid content is the aqueous solution of nitric acid of 2.0mol
10-3Mol), the methanol of 2mol after mixing by three stirs 10 hours in 110 DEG C, obtains the line that silicon atom number is 5~10
Shape organosilicon polymer presoma.The schematic arrangement of the presoma is referring to fig. 2.Need herein explanation why methyl orthosilicate
It is 1:2 with the molar ratio of water, if the two molar ratio is 1:(< 1.8) when, it can be only formed cyclic silane after hydrolysis, and molar ratio
For 1:(> 2.2) when, hydrolysate functional group is easily crosslinked too much, can not all be formed linear silicon and be polymerize short chain.
(2) synthesis and aging of gel: 10 parts of sol precursor obtained above are taken, then takes 10 parts of methanol, the two is filled
Divide after mixing and 9 parts of triethylamine is added, stirs 30 minutes at room temperature, form gel in 5 hours after standing.Gel is placed in again
40 DEG C of baking oven, aging 6 hours.
(3) preparation of silica aerogel --- constant pressure and dry: after the gel after above-mentioned aging is smashed using colloid mill,
It dries at room temperature 10 hours, most of solvent naturally can be dry net at this time, and gel is then transferred to 150 DEG C of forced air drying
In case, any pressure or decompression device is not needed, is taken out after 10 hours dry, obtains super hydrophilic silica aerogel micro mist.
It is characterized through BET isothermal adsorption, it is found that the silica aerogel micro mist has nano-porous structure, this silica aerogel
The isothermal adsorption desorption curve of micro mist please refers to Figure 18, and pore-size distribution referring to Figure 19, scanning electron microscope (SEM) photograph please refers to Figure 20, other objects
Reason parameter such as specific surface area, pore size, Kong Rong, density, contact angle etc. sees table 1.
Reference examples 1
The silica aerogel prepared using nonlinear organosilicon oligomer, the common oxygen being both prepared by constant pressure and dry
SiClx aeroge is modified blade, hand using same method respectively, the results showed that the modified contact angle with water is
1500, it cannot achieve the super hydrophilic property, the image of blade modified experimental facilities acquisition referred to Figure 21 (non-photograph), it is right
The image of the modified experimental facilities acquisition of hand refers to Figure 22 (non-photograph).
The structure and performance parameters of obtained silica aerogel micro mist in 1 embodiment 1-6 of table
In conclusion there is Gao Bibiao by the super hydrophilic silica aerogel micro mist that technical solution of the present invention obtains
The performances such as area, super hydrophilic；And the present invention develops modification application method of the aeroge as parents' coating for the first time, has behaviour
Make it is simple, be applicable in various interfaces even bioelectric interface, the advantages such as mechanical resistant friction, stability is strong, is easy to remove；And the super parents
Coating can be not only used for traditional inorganic interface, it may also be used for life interface, while there is excellent abrasion resistance energy.
In addition, inventor also refers to the mode of embodiment 1- embodiment 6, with other raw materials listed in this specification
It is tested with condition, and has equally been made and has amphiphilic, oil suction and water absorption are high, and particle diameter distribution is relatively narrow, high-ratio surface
The silica aerogel based on linear organosilicon oligomer of the excellent properties such as product.
It should be appreciated that above-described is only some embodiments of the present invention, it is noted that for the common of this field
For technical staff, under the premise of not departing from concept of the invention, other modification and improvement can also be made, these are all
It belongs to the scope of protection of the present invention.
Claims (10)
1. a kind of preparation method of the silica aerogel based on linear organosilicon oligomer, characterized by comprising:
(1) organosiloxane, acidic aqueous solution are uniformly mixed and are heated with alcohol, be prepared containing linear organosilicon oligomer
Sol precursor；
(2) sol precursor is mixed with diluent, and catalyst is added, formed gel after standing, stand again later
Aging；
(3) gel mechanical after step (2) obtained aging is crushed, is dry, obtaining silica aerogel.
2. preparation method according to claim 1, it is characterised in that: the organosiloxane includes ethyl orthosilicate, just
Methyl silicate, methyltrimethoxysilane, methyltriethoxysilane, dimethyl methoxy silane, dimethylethoxysilane
In any one or two or more combinations；And/or the acidic aqueous solution includes hydrochloric acid, sulfuric acid, oxalic acid, acetic acid or nitre
The weak solution of acid；And/or H in the acidic aqueous solution+Content is 10-6~10-1mol/L；And/or the alcohol include methanol,
Ethyl alcohol, isopropanol, propyl alcohol, butanol, any one or two or more combinations in the tert-butyl alcohol；And/or the organosilicon oligomerization
The silicon atom number of object is 5~10, and the Si in skeleton is keyed by Si-O-Si and forms linear molecule.
3. preparation method according to claim 1, it is characterised in that: organosiloxane described in step (1), acidity are water-soluble
The molar ratio of liquid and alcohol is 1:1.8~2.2:1~10；And/or the temperature of the heating is 80~150 DEG C, the time is 5~1h.
4. preparation method according to claim 1, it is characterised in that: sol precursor described in step (2), diluent with
The volume ratio of catalyst is 1:0.1~3:0.01~0.5；And/or the time for standing aging is in 5h or more；And/or institute
Stating and standing the temperature of aging is boiling temperature of the room temperature to the catalyst.
5. preparation method according to claim 1, it is characterised in that: the diluent include methanol, ethyl alcohol, isopropanol,
Propyl alcohol, butanol, the tert-butyl alcohol, n-hexane, hexamethylene, normal heptane, acetonitrile, toluene, tetrahydrofuran, different benzyl alcohol and perfluoroalkanes
In any one or two or more combinations；And/or the catalyst include sodium hydroxide, potassium hydroxide, urea, ammonium hydroxide,
Any one in pyridine, trimethyl ammonium chloride and triethylamine or two or more combinations.
6. preparation method according to claim 1, which is characterized in that step (3) specifically includes: step (2) is obtained always
Gel mechanical after change crushes, and naturally dry 5~10h, last 5~10h of forced air drying obtain silica aerogel.
7. preparation method according to claim 6, it is characterised in that: described be mechanically pulverized includes that roller press crushes, is mechanical
Blender crushes, colloid mill crushes, cutting oscillation crushes or fruit juice mixer crushes；And/or the temperature of the forced air drying be 80~
250℃。
8. a kind of silica aerogel based on linear organosilicon oligomer, it is characterised in that: the silica aerogel is main
It is formed by linear organosilicon oligomer through polycondensation, gelation, constant pressure and dry；Preferably, the silica aerogel is powder, is put down
Equal partial size is 50nm~1000 μm；Preferably, the aperture of hole contained by the silica aerogel is 1~500nm, specific surface area
For 150~2200m20.5~6cm of/g, Kong Rongwei3/ g, the contact angle with water, oil is 0 °；Preferably, the silica airsetting
The oil absorption of glue, water absorption are in 100wt% or more；Preferably, the oil includes the derivative of gasoline, kerosene, benzene and/or benzene
Object, alkane or alkene.
9. the method that a kind of pair of body surface carries out super hydrophilic modification, characterized by comprising: be based on according to any one of claims 8
The silica aerogel even application of linear organosilicon oligomer applies 0.5~10MPa in body surface after the completion of coating
Pressure, formed super-hydrophilic coating.
10. the method according to claim 9 for carrying out super hydrophilic modification to body surface, it is characterised in that: the oxidation
The dosage of silica aerogel micro mist is 0.1~20g/m2；And/or the body surface is dry anhydrous smooth or rough surface；
And/or the object includes glass, metal, polymer fiber, plastic foil, rubber, timber, leaf, insect body surface or feather.
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