CN106947252A - Coated type polyimides strengthens the preparation method of aerosil - Google Patents

Coated type polyimides strengthens the preparation method of aerosil Download PDF

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Publication number
CN106947252A
CN106947252A CN201710172349.7A CN201710172349A CN106947252A CN 106947252 A CN106947252 A CN 106947252A CN 201710172349 A CN201710172349 A CN 201710172349A CN 106947252 A CN106947252 A CN 106947252A
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aerosil
solution
coated type
type polyimides
preparation
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CN106947252B (en
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杨自春
费志方
李昆锋
陈国兵
陈俊
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Naval University of Engineering PLA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
    • C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
    • C08J2205/026—Aerogel, i.e. a supercritically dried gel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

Abstract

Strengthen the preparation method of aerosil, aerosil preparing technical field the invention discloses a kind of coated type polyimides.The polyamic acid solution of elder generation's synthesizing silane coupler end-blocking of the invention, then imidization is carried out to polyamic acid, and the acetic acid generated using imidization carries out the prehydrolysis of silicon source as the acid catalyst of silicon source hydrolysis, secondly, the ammoniacal liquor for adding dilution is used as the base catalyst of polycondensation reaction, collosol and gel is completed by soda acid two-step catalysis, obtain coated type polyimides enhancing silica wet gel, finally, coated type polyimides enhancing aerosil is obtained to wet gel progress aging, displacement, supercritical drying.Coated type polyimides prepared by present invention enhancing aerosil high temperature resistant, low fragility, non-breakable and not shedding and scaling-off, and preparation technology of the present invention is simple, preparation process is not in phase separation and separates out precipitation, and overall production cost is relatively low, it is easy to industrialized production.

Description

Coated type polyimides strengthens the preparation method of aerosil
Technical field
The present invention relates to aerosil preparing technical field, more particularly to a kind of coated type polyimides enhancing The preparation method of aerosil.
Background technology
Aerosil has the pore structure of nanoscale and the continuous solid phase particles in space, and it is unique microcosmic Structure assigns its many special property, there is important application in different fields, be most widely used at present, it is ripe not Excessively adiabatic heat-insulation field.However, pure silicon dioxide aeroge low intensity, fragility are big, easily crush, it is difficult to which directly engineering should With, it is necessary to carry out mechanics modification to it.Common inorganic fiber-reinforcement silicon dioxide aerogel composite, changes though mechanical property has It is kind, but there are problems in the application, on the one hand it is that fiber and aeroge interface cohesion are bad, is shown as in " de- Powder ", " scaling-off " phenomenon are serious；On the other hand, the introducing of fiber causes the increase of material system density more.Therefore, it is badly in need of exploring A kind of new mechanics Enhancement Method, solves pure silicon dioxide aeroge low intensity, broken, fiber-reinforcement silicon dioxide airsetting Glue density is big, easy shedding defect.
Publication No. discloses a kind of polyimide/silicon dioxide airsetting rubber powder for CN10580220A Chinese invention patent The preparation method of bluk recombination aerogel material, the invention is by the hybrid mode of organic/inorganic that aerosil is micro- Grain and heat-resistant polymer polyimides carry out it is compound obtain, with applicability extensively, raw material is easy to get, course of reaction is simple, total The features such as body low cost, and the invention can solve pure silicon dioxide aerogel powder easily " dry linting " the problem of and with excellent material Expect heat-proof quality and toughness, mixed however, the recombination process of polyimides and silicon dioxide aerogel powder is simple physics Mixed, interface is physical bond, is unfavorable for the lifting of resistance to elevated temperatures.
Notification number discloses a kind of crosslinked polyimide silica for CN104341594B Chinese invention patent and mixed Close the preparation method of aeroge, the invention using collosol and gel it is organic-method of inorganic hybridization, silane coupler will be contained Organic silicon source mixed with polyamic acid, through imidization formed wet gel, with reference to supercritical drying process, prepare cross-linking type gather Acid imide silica mixing aerogel material.There is wide adaptation range, raw material to be easy to get for the invention, with low cost, reaction time Short the features such as, and the invention prepare crosslinked polyimide silica mixing aeroge have high intensity, high-specific surface area, The nanoporous network structure of low-density and many fraction shapes, it is big, frangible to solve pure silicon dioxide aeroge fragility, organic enhancing The problem of specific surface area is low afterwards.However, the present invention uses double [3- (trimethoxy silicon substrate) propyl group], amine is coupling agent, methyl trimethoxy TMOS is silicon source, and the cost of raw material is of a relatively high, although and the introducing of methyl is conducive to the lifting of material flexibility, meeting The resistance to elevated temperatures of expendable material.
The content of the invention
It is an object of the invention to overcome above-mentioned prior art to there is problem, there is provided a kind of high temperature resistant, mechanical property are good, no Broken and not shedding and scaling-off coated type polyimides strengthen the preparation method of aerosil.
To achieve the above object, the present invention is adopted the following technical scheme that：
Coated type polyimides strengthens the preparation method of aerosil, comprises the following steps：
1) polyamic acid solution of synthesizing silane coupler end-blocking：Diamines is added into organic solvent, stir at room temperature to Be completely dissolved, then slowly, add dianhydride in batch, continue to stir, reaction 3h generation polyamic acid solutions are designated as solution A, so Silane coupler is added dropwise in backward solution A, 1h is stirred at room temperature, solution B, wherein diamines, dianhydride and silane coupler is designated as Mol ratio be：1: (2~2.05): (2~2.05)；
2) imidization of polyamic acid：To step 1) obtained by solution B in add dehydrating agent and catalyst solution, reaction one The section time, obtain solution C；
3) prehydrolysis of silicon source is mixed：Silicon source, silane coupler, deionized water are dissolved in organic solvent, solution D is designated as, Then by step 2) obtained by solution C mixed with solution D, stir 20min at room temperature, stand a period of time, obtain solution E, its The mol ratio of middle silicon source, silane coupler and deionized water is：1: (0.1~0.4): (3~4)；
4) coated type polyimides enhancing silica wet gel is prepared：To step 3) obtained by solution E in be added dropwise dilution Ammonia spirit, stir, adjust pH value, coated type polyimides enhancing silica wet gel is obtained after standing, wherein The volume ratio of ammoniacal liquor and organic solvent is：1∶10；
5) coated type polyimides enhancing aerosil is prepared：By step 4) obtained by coated type polyimides increase Strong silica wet gel progress aging, displacement, supercritical drying obtain coated type polyimides enhancing aerosil.
Further, the step 1) in diamines be 4,4 '-diaminodiphenyl ether, dianhydride is pyromellitic acid anhydride, Silane coupler is the hexyloxy silane of 3- aminopropyls-three, and organic solvent is 1-METHYLPYRROLIDONE.
Further, the step 2) in dehydrating agent and catalyst solution be pyridine and acetic anhydride mixed solution, its In acetic anhydride may participate in the imidization of polyamic acid reaction generation acetic acid, it can be as step 3) in mixing silicon source Carry out the acid catalyst of prehydrolysis.
Further, the step 2) in the reaction time be 5~10min, can prevent the reaction time from too short causing imidization Not exclusively, the reaction time long causes polyimides gel.
Further, the step 3) in silicon source be tetraethyl orthosilicate, silane coupler be the hexyloxy of 3- aminopropyls-three Silane, both material feedstocks are easy to get and cheap, it is possible to decrease coated type polyimides strengthens the whole of aerosil Body cost of manufacture.
Further, the step 3) in time of repose be 24h, it is ensured that mixing silicon source obtain sufficient prehydrolysis.
Further, the step 4) in pH value be 7.0~7.5, in the pH range, can further reduce gel bag The type of applying polyimides strengthens the acquisition time of silica wet gel, and can further improve the acquisition effect and gel of gel Network structure uniformity.
The invention has the advantages that：
1st, the present invention passes through friendship as enhancing from temperature tolerance, the preferable polyimides of mechanical property with aeroge skeleton Connection reaction forms chemical bonds, and a strata acid imide clad, the primary grain of increase are formed on silica primary particles surface Contact area between son, effectively reinforces the weakness of primary particle interface cohesion, this mechanics method of modifying is from molecular level pair Aeroge carries out mechanics enhancing, overcomes that pure silicon dioxide aeroge fragility is big, broken and traditional inorfil enhancing two Silica aerogel " shedding ", the defect of " scaling-off ".It is this kind of that aerosil mechanical property is strengthened using chemical crosslinking Method is expected to be engineered the brand-new road of application as silica.
2nd, the present invention is catalyzed the pre-hydrolysis process of silicon source by the use of the acetic acid that polyamic acid imidization is generated as acid catalyst, Acid catalyst need not be it is possible to additionally incorporate, preparation process is simplified, and the present invention to the reaction time, solution ph be precisely controlled it is favourable Precipitated in reacting abundant, avoiding being separated and avoid separating out.
3rd, the coated type polyimides enhancing silica aerogel material density that prepared by the present invention is 0.06g/cm3~ 0.17g/cm3, 288~321m of specific surface area2/ g, aperture size is 13~27nm, and modulus of compressibility reaches as high as 6MPa (strains 50%), the minimum 0.028W/ of normal temperature thermal conductivity (mK), initial pyrolyzation temperature is more than 400 DEG C, and weight-loss ratio is at 700 DEG C 20%, with preferable heat-resisting quantity.
4th, raw material of the present invention is easy to get, cheap, and preparation process is simple, has lower entirety raw compared to prior art Produce cost, it is easy to industrialized production, and coated type polyimides enhancing silica aerogel material performance prepared by the present invention It is excellent, it can be widely applied to adiabatic heat-insulation field.
Brief description of the drawings
Fig. 1 is that the coated type polyimides of the embodiment of the present invention 1~3 strengthens the photo of aerosil；
Fig. 2 is that the coated type polyimides of the embodiment of the present invention 2 strengthens the FTIR spectrum figure of aerosil；
Fig. 3 is that the coated type polyimides of the embodiment of the present invention 1 strengthens the electron microscope photo scanning of aerosil；
Fig. 4 is that the coated type polyimides of the embodiment of the present invention 2 strengthens the electron microscope photo scanning of aerosil；
Fig. 5 is the nitrogen suction of the coated type polyimides enhancing aerosil of the embodiment of the present invention 3, desorption curve figure With pore size distribution curve；
Fig. 6 is that compression stress-strain of the coated type polyimides enhancing aerosil of the embodiment of the present invention 3 is bent Line.
Embodiment
In order to be better understood from the present invention, the present invention is further described below by embodiment, embodiment is only used In explaining the present invention, any limit is not constituted to the present invention.
Embodiment 1
Coated type polyimides strengthens the preparation method of aerosil, comprises the following steps：
1) diamines (4,4 '-diaminodiphenyl ether) is added into 10mL organic solvents (1-METHYLPYRROLIDONE), at room temperature Stirring to being completely dissolved, then slowly, add dianhydride (pyromellitic acid anhydride) in batch, continue to stir, reaction 3h generations are poly- Acid amides acid solution, is designated as solution A, and 0.14mL silane coupler (the hexyloxy silicon of 3- aminopropyls-three is then added dropwise into solution A Alkane), 1h is stirred at room temperature, is obtained the polyamic acid of silane coupler end-blocking, solution B is designated as, wherein 4,4 '-diaminourea hexichol Ether：Pyromellitic acid anhydride=0.3mmol: 0.61mmol；
2) to step 1) obtained by solution B in add 0.43mL dehydrating agents and catalyst solution (acetic anhydride: pyridine= , rapidly stir 5min, obtain solution C 0.23mL: 0.20mL)；
3) by 6.8mL silicon sources (tetraethyl orthosilicate), 0.85mL silane couplers (the hexyloxy silane of 3- aminopropyls-three), 2.16mL deionized waters are dissolved in 15mL organic solvents (1-METHYLPYRROLIDONE), are designated as solution D, then by step 2) obtained by it is molten Liquid C is mixed with solution D, and 20min is stirred at room temperature, is stood 24h, is obtained solution E；
4) to step 3) obtained by solution E in be added dropwise dilution ammonia spirit (ammoniacal liquor: 1-METHYLPYRROLIDONE=1mL: 10mL), stir, regulation pH value is 7.0 or so, coated type polyimides enhancing silica wet gel is obtained after standing；
5) by step 4) obtained by coated type polyimides enhancing silica wet gel aging 24h after take out, use N- first Base pyrrolidones is replaced 1 time, and the mixed solution of 1-METHYLPYRROLIDONE and acetone is replaced 3 times, finally replaces 1 with acetone soln Secondary, 8~12h, supercritical drying is carried out after being replaced every time, obtains coated type polyimides enhancing aerosil.
The coated type polyimides for using the above method to prepare strengthens aerosil density for 0.06g/cm3, tool There is good flexibility and resilience, shown in sample photo such as Fig. 1 (a).
Embodiment 2
Coated type polyimides strengthens the preparation method of aerosil, comprises the following steps：
1) diamines (4,4 '-diaminodiphenyl ether) is added into 10mL organic solvents (1-METHYLPYRROLIDONE), at room temperature Stirring to being completely dissolved, then slowly, add dianhydride (pyromellitic acid anhydride) in batch, continue to stir, reaction 3h generations are poly- Acid amides acid solution, is designated as solution A, and 0.31mL silane coupler (the hexyloxy silicon of 3- aminopropyls-three is then added dropwise into solution A Alkane), 1h is stirred at room temperature, is obtained the polyamic acid of silane coupler end-blocking, solution B is designated as, wherein 4,4 '-diaminourea hexichol Ether：Pyromellitic acid anhydride=0.65mmol: 1.33mmol；
2) to step 1) obtained by solution B in add 0.92mL dehydrating agents and catalyst solution (acetic anhydride: pyridine= , rapidly stir 7.5min, obtain solution C 0.5mL: 0.42mL)；
3) by 6.8mL silicon sources (tetraethyl orthosilicate), 0.85mL silane couplers (the hexyloxy silane of 3- aminopropyls-three), 2.16mL deionized waters are dissolved in 15mL organic solvents (1-METHYLPYRROLIDONE), are designated as solution D, then by step 2) obtained by it is molten Liquid C is mixed with solution D, and 20min is stirred at room temperature, is stood 24h, is obtained solution E；
4) to step 3) obtained by solution E in be added dropwise dilution ammonia spirit (ammoniacal liquor: 1-METHYLPYRROLIDONE=1mL: 10mL), stir, regulation pH value is 7.5 or so, coated type polyimides enhancing silica wet gel is obtained after standing；
5) by step 4) obtained by coated type polyimides enhancing silica wet gel aging 24h after take out, use N- first Base pyrrolidones is replaced 1 time, and the mixed solution of 1-METHYLPYRROLIDONE and acetone is replaced 3 times, finally replaces 1 with acetone soln Secondary, 8~12h, supercritical drying is carried out after being replaced every time, obtains coated type polyimides enhancing aerosil.
The coated type polyimides for using the above method to prepare strengthens aerosil density for 0.14g/cm3, sample Shown in product photo such as Fig. 1 (b).
Embodiment 3
Coated type polyimides strengthens the preparation method of aerosil, comprises the following steps：
1) diamines (4,4 '-diaminodiphenyl ether) is added into 90mL organic solvents (1-METHYLPYRROLIDONE), at room temperature Stirring to being completely dissolved, then slowly, add dianhydride (pyromellitic acid anhydride) in batch, continue to stir, reaction 3h generations are poly- Acid amides acid solution, is designated as solution A, and 9.65mL silane coupler (the hexyloxy silicon of 3- aminopropyls-three is then added dropwise into solution A Alkane), 1h is stirred at room temperature, is obtained the polyamic acid of silane coupler end-blocking, solution B is designated as, wherein 4,4 '-diaminourea hexichol Ether：Pyromellitic acid anhydride=20mmol: 41mmol；
2) to step 1) obtained by solution B in add 28.32mL dehydrating agents and catalyst solution (acetic anhydride: pyridine= , rapidly stir 10min, obtain solution C 15.28mL: 13.04mL)；
3) by 6.8mL silicon sources (tetraethyl orthosilicate), 0.85mL silane couplers (the hexyloxy silane of 3- aminopropyls-three), 2.16mL deionized waters are dissolved in 15mL organic solvents (1-METHYLPYRROLIDONE), are designated as solution D, then by step 2) obtained by it is molten Liquid C is mixed with solution D, and 20min is stirred at room temperature, is stood 24h, is obtained solution E；
4) to step 3) obtained by solution E in be added dropwise dilution ammonia spirit (ammoniacal liquor: 1-METHYLPYRROLIDONE=1mL: 10mL), stir, regulation pH value is 7.5 or so, coated type polyimides enhancing silica wet gel is obtained after standing；
5) by step 4) obtained by coated type polyimides enhancing silica wet gel aging 24h after take out, use N- first Base pyrrolidones is replaced 1 time, and the mixed solution of 1-METHYLPYRROLIDONE and acetone is replaced 3 times, finally replaces 1 with acetone soln Secondary, 8~12h, supercritical drying is carried out after being replaced every time, obtains coated type polyimides enhancing aerosil.
The coated type polyimides for using the above method to prepare strengthens aerosil density for 0.17g/cm3, tool There is good flexibility and resilience, shown in sample photo such as Fig. 1 (c).
Fig. 2 is that the coated type polyimides of the embodiment of the present invention 2 strengthens the FTIR spectrum figure of aerosil, As seen from Figure 2：1777cm-1、1726cm-1、1380cm-1And 725cm-1Locate the infrared signature peak for polyimides, 1073cm-1Locate the characteristic peak for silica, illustrate coated type polyimides enhancing aerosil prepared by the present invention, Containing polyimides and silica silicon because in preparation method of the present invention the imido grpup of alkane coupling agent first with polyamides End capping reaction occurs for amino acid, mixes, by soda acid two-step catalysis, is carried out with the silicon source of prehydrolysis after polyamic acid dehydration imidization The Si-O-Si spacial frameworks that cohydrolysis, polycondensation reaction are crosslinked, and generate polyimides by cross-linking reaction with Silica primary particles surface is combined.
Fig. 3 and Fig. 4 are respectively the coated type polyimides enhancing aerosil of Example 1 and Example 2 of the present invention Electron microscope photo scanning, can be seen that by Fig. 3 and Fig. 4：Coated type polyimides enhancing silica airsetting prepared by the present invention Glue is porous material, possesses three-dimensional nano space network structure, and polyimides is coated on silica primary particles surface, increase Contact area between primary particle, plays a part of reinforcing and support gel rubber skeleton, improves the mechanics of aerosil Performance.And the hole of the coated type polyimides enhancing aerosil of embodiment 1 is openr, material possesses preferably Flexible and resilience, and the bore hole size of the coated type polyimides enhancing aerosil of embodiment 2 is smaller, material is overall It is more closely knit, possess higher intensity.
Fig. 5 is the nitrogen suction of the coated type polyimides enhancing aerosil of the embodiment of the present invention 3, desorption curve figure With pore size distribution curve, as seen from Figure 5：Coated type polyimides enhancing aerosil prepared by the present invention compares table Area is 287m2/ g, pore volume is 1.9cm3/ g, average pore size is 26nm.
Fig. 6 is that compression stress-strain of the coated type polyimides enhancing aerosil of the embodiment of the present invention 3 is bent Line, as seen from Figure 6：, the coated type polyimides for preparing of the present invention strengthens aerosil in elastic deformation area most Big strain illustrates possess preferable elasticity up to 50% or so.

Claims (7)

1. a kind of coated type polyimides strengthens the preparation method of aerosil, it is characterised in that：Comprise the following steps：
1) polyamic acid solution of synthesizing silane coupler end-blocking：Diamines is added into organic solvent, is stirred at room temperature to complete Dissolving, then slowly, add dianhydride in batch, continue to stir, reaction 3h generation polyamic acid solutions are designated as solution A, Ran Houxiang Silane coupler is added dropwise in solution A, 1h is stirred at room temperature, it is designated as solution B, wherein diamines, dianhydride and silane coupler rubs You are at ratio：1: (2~2.05): (2~2.05)；
2) imidization of polyamic acid：To step 1) obtained by solution B in add dehydrating agent and catalyst solution, during one section of reaction Between, obtain solution C；
3) prehydrolysis of silicon source is mixed：Silicon source, silane coupler, deionized water are dissolved in organic solvent, solution D is designated as, then By step 2) obtained by solution C mixed with solution D, stir 20min at room temperature, stand a period of time, obtain solution E, wherein silicon The mol ratio in source, silane coupler and deionized water is：1: (0.1~0.4): (3~4)；
4) coated type polyimides enhancing silica wet gel is prepared：To step 3) obtained by solution E in the ammonia of dilution is added dropwise The aqueous solution, stirs, and adjusts and coated type polyimides enhancing silica wet gel, wherein ammoniacal liquor are obtained after pH value, standing Volume ratio with organic solvent is：1∶10；
5) coated type polyimides enhancing aerosil is prepared：By step 4) obtained by coated type polyimides enhancing two Silica wet gel progress aging, displacement, supercritical drying obtain coated type polyimides enhancing aerosil.
2. coated type polyimides according to claim 1 strengthens the preparation method of aerosil, its feature exists In：The step 1) in diamines be 4,4 '-diaminodiphenyl ether, dianhydride is pyromellitic acid anhydride, and silane coupler is 3- The hexyloxy silane of aminopropyl-three, organic solvent is 1-METHYLPYRROLIDONE.
3. coated type polyimides according to claim 1 strengthens the preparation method of aerosil, its feature exists In：The step 2) in dehydrating agent and catalyst solution be pyridine and acetic anhydride mixed solution.
4. coated type polyimides according to claim 1 strengthens the preparation method of aerosil, its feature exists In：The step 2) in the reaction time be 5~10min.
5. coated type polyimides according to claim 1 strengthens the preparation method of aerosil, its feature exists In：The step 3) in silicon source be tetraethyl orthosilicate, silane coupler be the hexyloxy silane of 3- aminopropyls-three.
6. coated type polyimides according to claim 1 strengthens the preparation method of aerosil, its feature exists In：The step 3) in time of repose be 24h.
7. coated type polyimides according to claim 1 strengthens the preparation method of aerosil, its feature exists In：The step 4) in pH value be 7.0~7.5.
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CN108793172A (en) * 2018-06-11 2018-11-13 四川科宁泰科技有限公司 A kind of preparation method of aerosil
CN109593228A (en) * 2018-11-16 2019-04-09 同济大学 A kind of polyimides-organosiloxane aerogel composite and preparation method thereof
CN110481105A (en) * 2019-07-06 2019-11-22 肖时云 A kind of preparation method of Warm-keeping heat-insulating tent compound fabric
CN111239860A (en) * 2020-02-26 2020-06-05 中国工程物理研究院激光聚变研究中心 Frequency tripling antireflection film for high-power laser device and preparation method and application thereof
CN113265085A (en) * 2021-04-29 2021-08-17 同济大学 Polymethylsilsesquioxane-polyimide composite aerogel material and preparation and application thereof
CN113683812A (en) * 2021-08-27 2021-11-23 北京宇程科技有限公司 Flame-retardant and heat-insulating polyimide nanofiber aerogel and preparation method thereof

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CN108793172A (en) * 2018-06-11 2018-11-13 四川科宁泰科技有限公司 A kind of preparation method of aerosil
CN109593228A (en) * 2018-11-16 2019-04-09 同济大学 A kind of polyimides-organosiloxane aerogel composite and preparation method thereof
CN109593228B (en) * 2018-11-16 2021-06-04 同济大学 Polyimide-organosiloxane composite aerogel material and preparation method thereof
CN110481105A (en) * 2019-07-06 2019-11-22 肖时云 A kind of preparation method of Warm-keeping heat-insulating tent compound fabric
CN111239860A (en) * 2020-02-26 2020-06-05 中国工程物理研究院激光聚变研究中心 Frequency tripling antireflection film for high-power laser device and preparation method and application thereof
CN113265085A (en) * 2021-04-29 2021-08-17 同济大学 Polymethylsilsesquioxane-polyimide composite aerogel material and preparation and application thereof
CN113265085B (en) * 2021-04-29 2022-06-21 同济大学 Polymethylsilsesquioxane-polyimide composite aerogel material and preparation and application thereof
CN113683812A (en) * 2021-08-27 2021-11-23 北京宇程科技有限公司 Flame-retardant and heat-insulating polyimide nanofiber aerogel and preparation method thereof

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