CN103304814B - Intrinsic hydrophobic polyimide aerogel and preparation method thereof and application - Google Patents
Intrinsic hydrophobic polyimide aerogel and preparation method thereof and application Download PDFInfo
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Abstract
The invention discloses and a kind of there is polyimide aerogels of intrinsic hydrophobic property and preparation method thereof and application.The structure of this aerogel is such as formula shown in I.The present invention by introducing the hydrophobic property that the specific groups such as hydrophobicity fluoro-containing group, low polar lipid cyclic group imparts polyimide aerogels material high in polyimide molecule structure.In addition, this kind of polyimide aerogels also have that porosity is high, thermal conductivity is low, density is low, specific surface area is large, specific inductivity and the characteristic such as dielectric loss is low.Therefore, in field, all there is important using value in the anti-heat insulating member of the spacecraft such as aircraft, satellite, super large-scale integration interlevel dielectric material, the anti-insulating of building, environment protection, deep-sea detecting, petroleum prospecting, energy saving building and household electrical appliances, insulation garment, sports equipment etc.
Description
Technical field
The invention belongs to high-performance polyimide material field, relate to a kind of intrinsic hydrophobic polyimide aerogel and preparation method thereof and application.
Background technology
The dry state gelatinous material of aerogel to be a class dispersion medium be air, its solid-phase and pore texture are nanometer scale.Aerogel is become this constitutional features and the minimum solid material of former world upper density (minimumly reaches 0.0002g/cm
3), be also that the solid material that thermal conductivity is minimum in the world (can reach 0.002W/m in air
-1k
-1, under room temperature in vacuo, can 0.001W/m be reached
-1k
-1), aerogel also has very low specific inductivity (1.0-2.0) and dielectric loss simultaneously.Above-mentioned characteristic makes aerogel to have a wide range of applications in fields such as unicircuit, energy-conservation, aerospace (AegerterMA, LeventisN, KoebelM (eds) .Aerogelshandbook.SpringerScience+BusinessMedia:NewYork, 2011)
Although aerogel has the excellent anti-heat insulation and characteristic such as low density, low-k, but its height micro hole structure (~ 10nm) causes it to have the specific surface area of the even thousands of meters squared per gram of hundreds of, so high specific surface area makes it very easily absorb moisture in air and moisture.The moisture absorbed not only can make the specific inductivity of aerogel significantly increase, but also can cause at the stronger capillary force of aerogel inside generation.For crisp for matter, frangible inorganic aerogels (as aerosil etc.), this surface tension directly can cause the fragmentation of aerogel material.Therefore, surface-hydrophobicized process must be carried out to aerogel in practical application.Common process for hydrophobicizing comprises employing chlorosilane or alkoxysilane compound containing trialkylsilyl group in molecular structure steam processes, and hexamethyldisilazane (HMDZ) steam also can be adopted to process.
Polyimide (PI) is the organic polymer material that a class has excellent comprehensive performance.The aerogel be made up of PI has the characteristics such as temperature resistant grade is high, good mechanical performance, therefore obtains in recent years and develops (MeadorMAB, etal.ACSApplMaterInterfaces, 2012,4:536-544) fast.But coventional type PI molecular structure has very strong polarity, the aerogel therefore prepared is easy to the moisture absorption equally.Because PI aerogel has good mechanics snappiness, although the PI aerogel of the moisture that therefore absorbs water can not as inorganic SiO
2there is fragmentation in aerogel, but can cause the increase of density and specific inductivity like that, thus affect its effect.And adopt conventional hydrophobic metallization processes effectively can't improve the wetting ability of PI aerogel.
Summary of the invention
Polyimide (PI) aerogel that the object of this invention is to provide a kind of intrinsic hydrophobic property and preparation method thereof and application.
Compound provided by the invention or aerogel, its general structure such as formula shown in I,
Formula I
In described formula I, R
1for dianhydride monomer fragment, be selected from following radicals any one:
with
R
2for diamine monomer fragment, be selected from following radicals any one:
with
T is amino-terminated substrate section, is selected from any one in following radicals:
with
N is the integer of 1-100, specifically can be the integer of the integer of 20-30, the integer of 30-40 or 20-40, is more specifically 30.
Shown in preparation formula I provided by the invention, the method for compound or aerogel, comprises the steps:
1) aromatic diamine monomer is mixed with excessive alicyclic dianhydride monomer in organic solvent carry out condensation polymerization reaction, react the complete polyamic acid solution obtaining acid anhydride base end-blocking;
2) to described step 1) add in gained solution and carry out amidate action containing the mixing of amino polyfunctional group end-capping reagent, obtain the polyamic acid solution be cross-linked;
3) to described step 2) add diacetyl oxide in the crosslinked polyamic acid solution of gained and pyridine stirs, carry out dehydration reaction in the mould that reinjects, react the complete gel obtained containing compound shown in formula I;
4) by step 3) in gained gel be placed in solvent and soak, then carry out supercritical co drying, after drying, obtain described aerogel.
The step 1 of aforesaid method) in, described step 1) in, alicyclic dianhydride is selected from 1,2,3,4-tetramethylene tetracarboxylic dianhydride (CBDA), 1,2,4,5-pentamethylene tetracarboxylic dianhydride (CPDA), 1,2,4,5-hexanaphthene tetracarboxylic dianhydride (CHDA), dicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride and dicyclo [2.2.2] octane-2, at least one in 3,5,6-tetracarboxylic dianhydride;
Described aromatic diamine is selected from 2,3,5,6-tetrafluoro Ursol D (TFPDA), 3,3 ', 5,5 '-four fluoro-4,4 '-benzidine, octafluoro benzidine, 3,5-diamido-benzotrifluorides (TFMDA) and 2, at least one in 2 '-bis-(trifluoromethyl)-4,4 '-benzidine (TFDB);
Described organic solvent is selected from N-Methyl pyrrolidone (NMP), meta-cresol, N, dinethylformamide (DMF), N, at least one in N-N,N-DIMETHYLACETAMIDE (DMAc), dimethyl sulfoxide (DMSO) (DMSO), specifically be selected from least one in N-Methyl pyrrolidone (NMP) and N,N-dimethylacetamide (DMAc);
The molar ratio of described alicyclic dianhydride and aromatic diamine is 1.00: (0.90 ~ 0.99), is specially 1.00: (0.95 ~ 0.98), is more specifically 1.00: 0.97;
Described step 1) in condensation polymerization reactions steps, the time is 10 ~ 30 hours, is specially 20 ~ 25 hours, is more specifically 24 hours;
Temperature is 0 ~ 35 DEG C, concrete 15 ~ 25 DEG C.
Described step 2) in, the described polyfunctional group end-capping reagent containing amino is selected from 1,3,5-tri-(amino) benzene, 1,3, at least one in 5-tri-(amino-benzene oxygen) benzene (TAB), 2,6-two (4 '-aminophenyl)-4-(4 '-aminophenyl) pyridines (TAPP), eight (aminophenyl) polysilsesquioxane (OAPS);
Described step 2) in amidation reaction steps, the time is 10 ~ 30 hours, is specially 20 ~ 25 hours, is more specifically 24 hours;
Temperature is 0 ~ 35 DEG C, is specially 15 ~ 25 DEG C.
Described step 3) in, the molar ratio of described diacetyl oxide and alicyclic dianhydride is (2.00 ~ 10.00): 1.00, is specially (3.00 ~ 5.00): 1.00;
The molar ratio of described pyridine and alicyclic dianhydride is (2.00 ~ 8.00): 1.00, is specially (3.00 ~ 5.00): 1.00;
In described dehydration reaction step, the time of stirring is 10 minutes ~ 30 minutes, is specially 15 minutes ~ 20 minutes; In described dehydration reaction step, the time is 1 hour ~ 10 hours, is specially 1 hour ~ 5 hours.
Temperature is 0-35 DEG C, is specially 15-25 DEG C.
Described step 4) in, at least one in described solvent selected from methanol, ethanol, Virahol and acetone;
In described supercritical co drying step, pressure is 10 ~ 20MPa, is specially 15 ~ 18MPa;
Temperature is 30 ~ 80 DEG C, is specially 40 ~ 60 DEG C, is more specifically 45 DEG C.
Compound shown in the formula I provided by the invention described above or aerogel, as the interlevel dielectric material of anti-lagging material, super large-scale integration and the application of heat insulating material formed middle at least one, also belong to protection scope of the present invention.Wherein, this application specifically can be the application in the anti-insulating of the anti-heat insulating member preparing the spacecraft such as aircraft, satellite, super large-scale integration interlevel dielectric material, building, environment protection, deep-sea detecting, petroleum prospecting, the field such as energy saving building and household electrical appliances, insulation garment, sports equipment.
Polyimide aerogels provided by the invention, its preparation technology comprises first employing alicyclic structure dianhydride monomer, fluorinated aromatic diamine monomer and polyfunctional group aminocompound linking agent and prepares polyimide gel, then adopts supercritical co to carry out drying.The present invention by introducing the hydrophobic property that the specific groups such as hydrophobicity fluoro-containing group, low polar lipid cyclic group imparts polyimide aerogels material high in polyimide molecule structure.In addition, this kind of polyimide aerogels also have that porosity is high, thermal conductivity is low, density is low, specific surface area is large, specific inductivity and the characteristic such as dielectric loss is low.Therefore, in field, all there is important using value in the anti-heat insulating member of the spacecraft such as aircraft, satellite, super large-scale integration interlevel dielectric material, the anti-insulating of building, environment protection, deep-sea detecting, petroleum prospecting, energy saving building and household electrical appliances, insulation garment, sports equipment etc.
Accompanying drawing explanation
Fig. 1 is the infrared spectra that embodiment 1 prepares gained polyimide aerogels.
Fig. 2 is the electron scanning micrograph that embodiment 1 prepares gained polyimide aerogels.
Fig. 3 is the N that embodiment 1 prepares gained polyimide aerogels
2the attached curve of absorption-desorption.
Fig. 4 is x-ray photoelectron spectroscopy (XPS) spectrogram that embodiment 1 prepares gained polyimide aerogels.
Fig. 5 is the water contact angle that embodiment 1 prepares gained polyimide aerogels.
Fig. 6 is thermal weight loss (TGA) curve that embodiment 1 prepares gained polyimide aerogels.
Fig. 7 is specific inductivity and the dielectric loss test curve that embodiment 1 prepares gained polyimide aerogels.
Fig. 8 is the water contact angle that embodiment 2 prepares gained polyimide aerogels.
Fig. 9 is the water contact angle that embodiment 3 prepares gained polyimide aerogels.
Figure 10 is the water contact angle that comparative example 1 prepares gained polyimide aerogels.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described material all can obtain from open commercial sources if no special instructions.
N
2the attached curve of absorption-desorption adopts ASAP2000 surface-area and pore size distribution analysis-e/or determining, and the gas adsorbed is N
2, sample is before testing through 80 DEG C of Fruit storages 10 hours.
XPS Analysis (XPS) adopts VGScientificESCALab220i-XL type photoelectron spectrograph, and excitaton source is MgK α X-ray, and power is about 300W, and base vacuum during analysis is 3 × 10
-9mbar, the electron binding energy C1s peak (284.8eV) of external carbon corrects.
Water contact angle measures in DataphysicsOCA-20 contact angle instrument under room temperature (25 DEG C), by 2 μ L water droplet instillation testees, reads contact angle values with instrument.
Specific inductivity and dielectric loss adopt Agilent vector analysis instrument to measure, and measure sample is of a size of 50mm × 30mm × 2mm, and test frequency is 2-12GHz
Thermogravimetric analysis (TGA) adopts U.S. TA company Q-50 thermal analyzer to measure, and temperature rise rate is 20 DEG C/min, and test environment is nitrogen atmosphere.
Embodiment 1
1) be furnished with in the there-necked flask of mechanical stirring, temperature and nitrogen inlet at one and add 1.9741g (6.16mmol) 2,2 '-bis-(trifluoromethyl)-4, the N-Methyl pyrrolidone (NMP) that 4 '-benzidine (TFDB) and 25g newly distill, passes into nitrogen.After TFDB dissolves completely, add the NMP of 1.2479g (6.36mmol) 1,2,3,4-tetramethylene tetracarboxylic dianhydride (CBDA) and 25g, carry out condensation polymerization reaction 24h in 25 DEG C, obtain the polyamic acid solution of acid anhydride base end-blocking.
2) in system, add polyfunctional group end-capping reagent eight (aminophenyl) polysilsesquioxane (OAPS) containing amino of 0.0574g (0.0497mmol), carry out amidate action 24h in 25 DEG C, obtain the polyamic acid solution be cross-linked.
3) in step 2) add 2.52g (31.82mmol) pyridine and 3.25g (31.82mmol) diacetyl oxide in the crosslinked polyamic acid solution of gained, stir 20min, be cast in mould and carry out dehydration reaction, system, at 4h inner gel, obtains the gel containing formula II compound.
4) by step 3) the polyimide gel that obtains takes out from mould, repeatedly soaks 3 times with ethanol.The polyimide wet gel obtained is joined supercritical CO
2carry out drying in reactor, at 45 DEG C, dry 6h under 15MPa condition, obtain polyimide aerogels.
The structure of this aerogel is such as formula shown in II:
Formula II
Wherein T is:
n is 30.
As shown in Figure 1, as from the foregoing, this aerogel structure is correct, for belonging to the compound of formula II for the infrared spectra of this aerogel.
The electron scanning micrograph of this aerogel material, N
2the attached curve of absorption-desorption, x-ray photoelectron spectroscopy (XPS), water contact angle, thermal weight loss (TGA), specific inductivity and dielectric loss test result are respectively as shown in Fig. 2, Fig. 3, Fig. 4, Fig. 5, Fig. 6 and Fig. 7.
As can be seen from above-mentioned test result, this embodiment has successfully prepared the PI aerogel of expected structure, this aerogel microtexture is the nanometer fibrous of winding mutually, and the diameter of fiber is between 10-100nm, and in aerogel, volume shared by air (porosity) is 86%.
The surface-area of this aerogel is 407m
2/ g, volume density (ρ
b) be 0.22g/cm
3, water surface contact angle is 135 °, and 5% thermal weight loss temperature is 442 DEG C, and the specific inductivity under 2.75GHz is 1.19, and dielectric loss is 0.0011.
And can not noticeable change be there is along with the increase of ambient moisture in the specific inductivity of this PI aerogel and dielectric loss.
Therefore, a kind of PI aerogel with intrinsic hydrophobic property has been prepared in the present embodiment.The hydrophobic property that this material is good and the relatively low molecular structure of polarity and high porosity structure impart this PI aerogel low-k and low-loss characteristic.
Embodiment 2
1) be furnished with in the there-necked flask of mechanical stirring, temperature and nitrogen inlet at one and add 1.1102g (6.16mmol) 3, the N-Methyl pyrrolidone (NMP) that 5-diamido-benzotrifluoride (TFMDA) and 25g newly distill, passes into nitrogen.1.2479g (6.36mmol) 1 is added after TFMDA dissolves completely, the NMP of 2,3,4-tetramethylene tetracarboxylic dianhydride (CBDA) and 25g, carry out condensation polymerization reaction 24h in room temperature (25 DEG C), obtain the polyamic acid solution of acid anhydride base end-blocking.
2) in step 1) add eight (aminophenyl) polysilsesquioxane (OAPS) of 0.0574g (0.0497mmol) in system, carry out amidate action 24h in room temperature (25 DEG C), obtain the polyamic acid solution be cross-linked.
3) in step 2) add 2.52g (31.82mmol) pyridine and 3.25g (31.82mmol) diacetyl oxide in the crosslinked polyamic acid solution of gained.Stir 20min, be cast in mould and carry out dehydration reaction, system, at 1h inner gel, obtains the gel containing formula III compound.
4) by step 3) the polyimide gel that obtains will obtain gel and take out from mould, repeatedly soak 3 times with ethanol.The polyimide wet gel obtained is joined supercritical CO
2carry out drying in reactor, at 45 DEG C, under 15MPa condition, dry 6h, obtains polyimide aerogels.
The structure of this aerogel as shown in formula III,
Formula III
Wherein T is:
n is 30.
The water contact angle of this aerogel material as shown in Figure 8.This aerogel microtexture is the nanofiber string-like be mutually wound around, and the diameter of fiber is between 10-50nm, and in aerogel, volume shared by air (porosity) is 88%.The surface-area of this aerogel is 386m
2/ g, volume density (ρ
b) be 0.25g/cm
3, water surface contact angle is 99 °, and 5% thermal weight loss temperature is 466 DEG C, and the specific inductivity under 2.75GHz is 1.21, and dielectric loss is 0.0016, and the specific inductivity of this PI aerogel and dielectric loss noticeable change can not occur along with the increase of ambient moisture.
Embodiment 3
1) be furnished with in the there-necked flask of mechanical stirring, temperature and nitrogen inlet at one and add 1.0858g (6.16mmol) 2,3, the N-Methyl pyrrolidone (NMP) that 5,6-tetrafluoro Ursol D (TFPDA) and 25g newly distill, passes into nitrogen.The NMP of 1.2479g (6.36mmol) 1,2,3,4-tetramethylene tetracarboxylic dianhydride (CBDA) and 25g is added after TFPDA dissolves completely.Carry out condensation poly-reaction 24h in room temperature (25 DEG C), obtain the polyamic acid solution of acid anhydride base end-blocking.
2) in step 1) add eight (aminophenyl) polysilsesquioxane (OAPS) of 0.0574g (0.0497mmol) in system, carry out amidate action 24h in room temperature (25 DEG C), obtain the polyamic acid solution be cross-linked.
3) in step 2) add 2.52g (31.82mmol) pyridine and 3.25g (31.82mmol) diacetyl oxide in the crosslinked polyamic acid solution of gained.Stir 20min, be cast in mould and carry out dehydration reaction, system, at 1h inner gel, obtains the gel containing formula IV compound.
4) by step 3) gel that obtains takes out from mould, repeatedly soaks 3 times with ethanol.The polyimide wet gel obtained is joined supercritical CO
2carry out drying in reactor, at 45 DEG C, under 15MPa condition, dry 6h, obtains polyimide aerogels.
The structure of this aerogel such as formula shown in IV,
Formula IV
Wherein T is:
n is 30.
The water contact angle of this aerogel material as shown in Figure 9.This aerogel water surface contact angle is 100 °, and the specific inductivity under 2.75GHz is 1.20, and dielectric loss is 0.0014, and the specific inductivity of this PI aerogel and dielectric loss noticeable change can not occur along with the increase of ambient moisture.
Comparative example 1
Add 1.3268g (6.25mmol) 4 being furnished with in churned mechanically there-necked flask, the nitrogen methyl-2-pyrrolidone (NMP) that 4 '-diamino-2,2 '-dimethyl-1,1 '-biphenyl (DMBZ) and 25g newly distill, passes into nitrogen.1.8987g (6.45mmol) 3,3 ', 4 is added, 4 '-oxydiphthalic (BPDA) and 25gNMP after DMBZ dissolves completely.Reaction 24h obtains necessarily thick solution, 0.0581g (0.05mmol) eight (aminophenyl) polysilsesquioxane (OAPS) is added in system, reaction 24h, adds 2.55g pyridine and 3.29g diacetyl oxide in reaction system.Stir 20min, be cast in mould, gel ethanol, at 2h inner gel, exchanges by system, the wet gel after exchange at 45 DEG C, the supercritical CO of 15MPa
2in reactor, dry 6h, obtains polyimide aerogels.
The structure of this aerogel such as formula shown in V,
Formula V
Wherein T is:
n is 30.
The water contact angle of this aerogel material as shown in Figure 10.Can find out, the water contact angle of this PI aerogel is 73 °, it is a class hydrophilic PI aerogel, specific inductivity under its 2.75GHz is 1.33, dielectric loss is 0.0032, and specific inductivity increases along with the increase of ambient moisture, this mainly causes the moisture in its absorption environment due to the water-wet behavior of this kind of PI aerogel, thus causes the increase of specific inductivity.
Table 1 summarizes the salient features of the present invention and comparative example gained PI aerogel.
The performance of table 1, polyimide aerogels
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Water contact angle (°) | 135 | 99 | 100 | 73 |
| Specific inductivity (2.75GHz) | 1.11 | 1.21 | 1.20 | 1.33 |
| Dielectric loss (2.75GHz) | 0.0011 | 0.0016 | 0.0014 | 0.0032 |
As seen from table, PI aerogel prepared by the present invention has higher contact angle, show that this aerogel-like has intrinsic hydrophobicity, PI aerogel prepared by the present invention is in the dielectric constant range of 2.75GHz at 1.11-1.33, and dielectric loss has ultralow specific inductivity and dielectric loss.
In sum, the PI aerogel performance prepared by the present invention meets the application demand in the anti-insulating of the anti-heat insulating member preparing the spacecraft such as aircraft, satellite, super large-scale integration interlevel dielectric material, building, environment protection, deep-sea detecting, petroleum prospecting, the field such as energy saving building and household electrical appliances, insulation garment, sports equipment.
Claims (13)
1. aerogel shown in formula I,
In described formula I, R
1for dianhydride monomer fragment, be selected from following radicals any one:
R
2for diamine monomer fragment, be selected from following radicals any one:
T is amino-terminated substrate section, is selected from any one in following radicals:
N is the integer of 1-100.
2. aerogel according to claim 1, is characterized in that: described n is the integer of 20-40.
3. aerogel according to claim 2, is characterized in that: described n is the integer of 20-30 or the integer of 30-40.
4. prepare a method for aerogel shown in arbitrary described formula I in claim 1-3, comprise the steps:
1) aromatic diamine monomer is mixed with excessive alicyclic dianhydride monomer in organic solvent carry out condensation polymerization reaction, react the complete polyamic acid solution obtaining acid anhydride base end-blocking;
2) to described step 1) add in gained solution and carry out amidate action containing the mixing of amino polyfunctional group end-capping reagent, obtain the polyamic acid solution be cross-linked;
3) to described step 2) add in the crosslinked polyamic acid solution of gained after diacetyl oxide and pyridine stir, carry out dehydration reaction in the mould that reinjects, react the complete gel obtained containing compound shown in formula I;
4) by step 3) in gained gel be placed in solvent and soak, then carry out supercritical co drying, after drying, obtain described aerogel.
5. method according to claim 4, is characterized in that: described step 1) in, alicyclic dianhydride is selected from 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,4,5-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, dicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride and dicyclo [2.2.2] octane-2, at least one in 3,5,6-tetracarboxylic dianhydride; Or,
Described aromatic diamine is selected from 2,3,5,6-tetrafluoro Ursol D, 3, fluoro-4, the 4'-benzidines of 3', 5,5'-tetra-, octafluoro benzidine, 3, the at least one of 5-diamino trifluoromethylbenzene and 2,2'-two (trifluoromethyl)-4,4'-in benzidine; Or,
Described organic solvent is selected from least one in N-Methyl pyrrolidone, meta-cresol, DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO); Or,
The molar ratio of described alicyclic dianhydride and aromatic diamine is 1.00:(0.90 ~ 0.99); Or,
Described step 1) in condensation polymerization reactions steps, the reaction times is 10 ~ 30 hours; Or,
Temperature is 0 ~ 35 DEG C.
6. method according to claim 5, is characterized in that: the molar ratio of described alicyclic dianhydride and aromatic diamine is 1.00:(0.95 ~ 0.98); Or,
Described step 1) in condensation polymerization reactions steps, the reaction times is 20 ~ 25 hours; Or,
Temperature is 15 ~ 25 DEG C.
7. method according to claim 4, it is characterized in that: described step 2) in, the described polyfunctional group end-capping reagent containing amino is selected from 1,3,5-tri-(amino) benzene, 1, at least one in 3,5-tri-(amino-benzene oxygen) benzene, 2,6-two (4'-aminophenyl)-4-(4'-aminophenyl) pyridines, eight (aminophenyl) polysilsesquioxane; Or,
Described step 2) in amidation reaction steps, the time is 10 ~ 30 hours; Or,
Temperature is 0 ~ 35 DEG C.
8. method according to claim 7, is characterized in that: described step 2) in amidation reaction steps, the time is 20 ~ 25 hours; Or,
Temperature is 15 ~ 25 DEG C.
9. method according to claim 4, is characterized in that: described step 3) in, the molar ratio of described diacetyl oxide and alicyclic dianhydride is (2.00 ~ 10.00): 1.00; Or,
The molar ratio of described pyridine and alicyclic dianhydride is (2.00 ~ 8.00): 1.00; Or,
Described step 3) in dehydration reaction step, the time of stirring is 10 minutes ~ 30 minutes; Or,
In described dehydration reaction step, the time is 1 hour ~ 10 hours; Or,
Temperature is 0-35 DEG C.
10. method according to claim 9, is characterized in that: described step 3) in, the molar ratio of described diacetyl oxide and alicyclic dianhydride is (3.00 ~ 5.00): 1.00; Or,
The molar ratio of described pyridine and alicyclic dianhydride is (3.00 ~ 5.00): 1.00; Or,
Described step 3) in dehydration reaction step, the time of stirring is 15 minutes ~ 20 minutes; Or,
In described dehydration reaction step, the time is 1 hour ~ 5 hours; Or,
Temperature is 15-25 DEG C.
11., according to described method arbitrary in claim 4-10, is characterized in that: described step 4) in, at least one in described solvent selected from methanol, ethanol, Virahol and acetone; Or,
In described supercritical co drying step, pressure is 10 ~ 20MPa; Or,
Temperature is 30 ~ 80 DEG C.
12. methods according to claim 11, is characterized in that: in described supercritical co drying step, and pressure is 15 ~ 18MPa; Or,
Temperature is 40 ~ 60 DEG C.
Aerogel shown in the arbitrary described formula I of 13. claim 1-3 is as the interlevel dielectric material of anti-lagging material, super large-scale integration and the application of heat insulating material formed middle at least one; Or,
The application of aerogel at least one in deep-sea detecting, environment protection and petroleum prospecting shown in the arbitrary described formula I of claim 1-3.
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