CN106866997A - A kind of preparation method of nanoporous polyimides aeroge - Google Patents
A kind of preparation method of nanoporous polyimides aeroge Download PDFInfo
- Publication number
- CN106866997A CN106866997A CN201710032330.2A CN201710032330A CN106866997A CN 106866997 A CN106866997 A CN 106866997A CN 201710032330 A CN201710032330 A CN 201710032330A CN 106866997 A CN106866997 A CN 106866997A
- Authority
- CN
- China
- Prior art keywords
- polyimides
- nanoporous
- aeroge
- preparation
- dianhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- 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
-
- 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
- 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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- 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
- C08K3/346—Clay
-
- 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
- C08K7/00—Use of ingredients characterised by shape
-
- 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
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
-
- 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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention relates to a kind of preparation method of nanoporous polyimides aeroge, including：Under nitrogen atmosphere, diamine monomer is added in solvent, 0660 DEG C of 3~6h of stirring is subsequently adding dianhydride monomer, obtains mixed solution, reacts 2~6h, obtains PAA stostes；Then by ultraviolet curable agent and it is attapulgite modified be added in PAA stostes, add chemical imidization agent, obtain polyimide solution, be subsequently poured into mould, ultraviolet light polymerization, obtain polyimides wet gel；By polyimides wet gel at room temperature in mould it is aging, then carry out solvent displacement, supercritical carbon dioxide is dried, and obtains nanoporous polyimides aeroge.Method of the present invention process is simple, extensively, the nanoporous polyimides aeroge for obtaining is expected to be applied to high temperature insulating field raw material sources.
Description
Technical field
The invention belongs to the preparation field of aeroge, more particularly to a kind of preparation side of nanoporous polyimides aeroge
Method.
Background technology
Aeroge is a solid material that class density is low, porosity is big, specific surface area is high, and air accounts for material volume
80%-99.8%.The unique three-dimensional netted loose structure of aerogel material make its show high porosity, high-specific surface area,
The premium properties such as low-density, lower thermal conductivity.With SiO2Aeroge be representative traditional inorganic aerogels have it is excellent heat-resisting steady
Qualitative (1000 DEG C of ＞), but matter is crisp, frangible, mechanical property is relatively poor, can only carry out activeness and quietness by materials such as fiber cloths；
And organic aerogel haves the shortcomings that heat endurance is poor, the application of aeroge is greatly limit.
Polyimides is the high performance material containing imide ring in a class backbone structure, and it is because with excellent resistance to height
Warm, low temperature resistant, good mechanical performance, chemical stability and the low performance of dielectric constant, are widely used in Aeronautics and Astronautics, engineering
The high-tech areas such as plastics, microelectronics, coating and photoresist.Polyimide aerogels as in a class formation containing having more than 90%
The special material of nanoscale (10-40nm) stomata, its overall characteristic for having aeroge and polyimide material concurrently, including machinery is strong
Degree is high, heat endurance is good, density is low, absorb sound, dielectric constant and dielectric loss are low, mechanics pliability is good and heat-proof quality is excellent
Deng.Traditional inorganic aerogels and the respective shortcoming of organic aerogel are solved, the range of application of aeroge has been expanded.Additionally, poly-
The distinctive Molecular Design flexibility of acid imide material allows that people carry out functionalization to it as needed.Above-mentioned characteristic
So that polyimide aerogels have a wide range of applications in modern industry.
The characteristics of due on supercritical drying process and aerogel structure, make the manufacturing cycle of aeroge considerably long, and
And the common crosslinking agent used in preparation process such as 1,3,5- tri- (amino-benzene oxygen) benzene (TAB) and eight (aminophenyl) cage types are poly-
Expensive (the ACS Applied Materials＆Interfaces, 2012,4 such as silsesquioxane (OAPS):536).Therefore,
Find the task of top priority that quick, cheap aeroge preparation method is material supply section scholar.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of preparation method of nanoporous polyimides aeroge, should
Attapulgite in method is a kind of rich reserves, cheap inorganic nano-fiber, is easily modified, and overcomes conventional polyamides sub-
The expensive shortcoming of crosslinking agent in amine aeroge preparation process.
A kind of preparation method of nanoporous polyimides aeroge of the invention, including：
(1) under nitrogen atmosphere, diamine monomer is added in solvent, 0~60 DEG C of 3~6h of stirring is subsequently adding dianhydride list
Body, obtains mixed solution, reacts 2~6h, obtains polyamic acid PAA stostes；Then by ultraviolet curable agent and modified attapulgite
Soil is added in PAA stostes as crosslinking agent, adds chemical imidization agent to slough CO2Or slough H2O, obtains polyimide solution,
Poured into mould after 10min, ultraviolet light polymerization, obtain polyimides wet gel；Wherein, it is attapulgite modified for AT-NCO or
AT-NH2；
(2) by the polyimides wet gel in step (1) at room temperature in mould fully it is aging, then carry out solvent and put
Change, supercritical carbon dioxide is dried, and obtains nanoporous polyimides aeroge.
Diamine monomer is p-phenylenediamine PPD, 4,4'- diaminodiphenyl ether ODA, 4,4'- diaminourea two in the step (1)
At least one in phenylmethane MDA and 4,4'- diaminourea -2,2'- dimethyl -1,1'- biphenyl DMBZ；Structural formula is respectively：
The dianhydride is double phthalic anhydride ODPA, 3,3'4,4'- biphenyl of benzophenone tetracarboxylic dianhydride BTDA, 4,4- oxygen
At least one in double (3,4- dicarboxylic acids) the hexafluoropropane dianhydride 6FDA of tetracarboxylic dianhydride BPDA and 2,2'-；Structural formula is respectively：
The quality of diamines and dianhydride monomer and 7~20wt% of mixed solution gross mass is accounted in the step (1)；Diamines with
The mol ratio of dianhydride monomer is n：(n+1)；Wherein, the scope of n is 10~30；N is the number of repeat unit, when diamines and dianhydride
The mol ratio of monomer is n：(n+1) when, the polyamic acid oligomer thing of anhydride group end-blocking is obtained, with AT-NH2Or AT-NCO is crosslinked
Reaction obtains the polyamic acid solution with cross-linked structure.
Solvent in the step (1) is 1-METHYLPYRROLIDONE NMP, dimethylformamide DMF or dimethylacetylamide
DMAC。
Ultraviolet curable agent is 4- phenylene-ethynylenes phthalic anhydride, 4- (phenylacetylene base) aniline in the step (1)
At least one in (2,4- diamino-phenyls)-[4- (2- phenylacetylene bases) phenyl] ethyl ketone；Structural formula is respectively：
The addition of the ultraviolet curable agent (accounts for the percentage of dianhydride and diamine monomer gross mass for 0.2wt%~3wt%
Than).
Attapulgite modified preparation method is in the step (1)：Per 100g attapulgite AT raw ores and 0.25~
0.5mol HCl are blended, and through centrifugation, washing, dry, and acid activation AT is obtained；Then with silane coupler or diisocyanate
NMP dispersion liquids are blended, and through backflow, filtering, dry, and obtain attapulgite modified AT-NH2Or AT-NCO.
The silane coupler or diisocyanate and the mass ratio of attapulgite are 2~10：90~98.
The silane coupler is aminopropyl trimethoxysilane or aminopropyl triethoxysilane；Two isocyanic acid
Ester is Toluene-2,4-diisocyanate, 4- diisocyanate (2,4-TDI), Toluene-2,4-diisocyanate, 6- diisocyanate (2,6-TDI) or diphenyl methane two
Isocyanates (MDI).
Attapulgite modified addition (accounts for dianhydride and the total matter of diamine monomer for 1wt%~5wt% in the step (1)
The percentage of amount).
In the step (1) chemical imidization agent by pyridine and acetic anhydride with mol ratio 1:1 composition；Wherein, dianhydride, pyridine with
The mol ratio of acetic anhydride is 1：5：5, to ensure that polyamic acid is fully cyclized into polyimides.
The condition of ultraviolet light polymerization is in the step (1)：3~20s of ultraviolet light irradiation.
Solvent is replaced into the step (2)：The solvent displacement of one week is carried out in acetone, ethanol or methyl alcohol.
The dry condition of supercritical carbon dioxide is in the step (2)：Pressure is 10~15MPa, and temperature is 30~60
DEG C, the time is 3~6h.
The density of the nanoporous polyimides aeroge in the step (2) is 0.05~0.2g/cm3, specific surface area
It is 300-600m2/g。
Polyimide aerogels density prepared by the present invention is low up to 0.05-0.2g/cm3, specific surface area is up to 520m2/ g, receives
Shrinkage is less than 10%, and thermal conductivity is low up to 25mW/ (mK), and dielectric constant is minimum up to 1.15；It is this kind of with three-dimensional netted solid
The polyimide aerogels material of structure is expected to be applied to high temperature insulating field.
Beneficial effect
(1), with attapulgite modified for crosslinking agent prepares polyimide aerogels material, process is simple can be quantitative for the present invention
Control the degree of cross linking of polyimides；
(2) solvent for use small toxicity of the present invention；
(3) attapulgite that the present invention is used is a kind of wide material sources, cheap inorganic clay, the letter of its modifying process
Single, reactivity is higher, and overcomes the shortcoming of crosslinking agent costliness in conventional polyimide aeroge preparation process；Meanwhile, it is recessed
The nano bar-shape structure of convex rod soil is also played a supporting role on the nanoscale of polyimide aerogels, and aeroge is increased
By force, high intensity low density polyimide aerogels are prepared, and is suitable to industrialized production.
Brief description of the drawings
Fig. 1 is polyimide aerogels nitrogen adsorption desorption curve：(A) embodiment 1；(B) embodiment 2；
Fig. 2 is polyimide aerogels pore size distribution curve：(A) embodiment 1；(B) embodiment 2；
Fig. 3 is the measurement curve of polyimide aerogels：(A) embodiment 1；(B) embodiment 4；
Fig. 4 is nanoporous polyimides aeroge scanning electron microscope diagram piece in embodiment 1.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
100g attapulgites (AT) raw ore is blended with 0.25mol HCl, through centrifugation, washing, dries, and acid activation AT is obtained；
Then the NMP dispersion liquids (concentration is 2g/ml) with 100ml silane coupler aminopropyl trimethoxysilanes are blended, through backflow, mistake
Attapulgite modified (AT-NH is obtained after filter, drying and other steps2)。
Under nitrogen de-oxygen, by dianhydride and diamines (3,3'4,4'- biphenyl tetracarboxylic dianhydride and 4,4'- diaminourea two
The mol ratio 31 of phenylate:30) it is dissolved in the 1-METHYLPYRROLIDONE of 50ml (NMP), synthesizing polyamides acid solution, adds account for afterwards
The AT-NH of dianhydride and diamine monomer gross mass 1wt%2With the ultraviolet curable agent 4- phenylene-ethynylene O-phthalics of 0.2wt%
Acid anhydrides, cyclizing agent is added after stirring 10mins, and (mol ratio is 1:1 acetic anhydride and triethylamine), poured into mould after rapid stirring
Gel is waited after uv light irradiation solidification 3s, it is mixed with acetone with 1-METHYLPYRROLIDONE after aging 24h at room temperature is placed in afterwards
Closing solution carries out solvent displacement, each 12h, then 5 solvent displacements are carried out with pure acetone.Finally in pressure 10MPa, temperature 45 C
Under carry out supercritical carbon dioxide and dry 3h, obtain nanoporous polyimides aeroge；Sample rate is 0.10g/cm3, than
Surface area is 425m2Shown in/g, such as Fig. 1 (A) and Fig. 2 (A), polyimide aerogels show typical IV type and inhale de- in figure
Attached thermoisopleth, shows to exist in material substantial amounts of mesoporous, is typical mesoporous material；As shown in Fig. 3 (A), the dielectric of aeroge
Constant is 1.25.
Embodiment 2
100g attapulgites (AT) raw ore is blended with 0.3mol HCl, through centrifugation, washing, dries, and acid activation AT is obtained；And
Afterwards with 150ml Toluene-2,4-diisocyanates, NMP dispersion liquids (concentration is 5g/ml) blending of 4- diisocyanate (2,4-TDI), through backflow, mistake
Attapulgite modified (AT-NCO) is obtained after filter, drying and other steps.
Under nitrogen de-oxygen, by dianhydride and diamines (3,3'4,4'- biphenyl tetracarboxylic dianhydride and 4,4'- diaminourea -2,
The mol ratio 26 of 2'- dimethyl -1,1'- biphenyl:25) it is dissolved in the dimethylacetylamide of 50ml (DMAC), synthesizing polyamides acid
Solution, adds the ultraviolet curable agent (2,4- of the AT-NCO and 0.5wt% that account for dianhydride and diamine monomer gross mass 2wt% afterwards
Diamino-phenyl)-[4- (2- phenylacetylene bases) phenyl] ethyl ketone, cyclizing agent is added after stirring 10mins, and (mol ratio is 1:1 acetic acid
Acid anhydride and triethylamine), poured into after rapid stirring in mould and wait gel after uv light irradiation solidification 12s, it is placed in afterwards old at room temperature
After changing 24h, solvent displacement, each 12h are carried out with the mixed solution of 1-METHYLPYRROLIDONE and acetone, then 5 are carried out with pure acetone
Secondary solvent displacement.Finally carrying out supercritical carbon dioxide under pressure 12MPa, temperature 50 C dries 4h, obtains porous polyamides sub-
Amine aeroge；Sample rate is 0.13g/cm3, specific surface area is 580m2/ g, dielectric constant is 1.20；The polyimides gas for obtaining
Shown in gel pore size distribution curve such as Fig. 2 (B), shown in nitrogen adsorption desorption curve such as Fig. 1 (B).
Embodiment 3
100g attapulgites (AT) raw ore is blended with 0.45mol HCl, through centrifugation, washing, dries, and acid activation AT is obtained；
Then the NMP dispersion liquids (concentration is 3g/ml) with 80ml silane coupler aminopropyl triethoxysilanes are blended, through backflow, mistake
Attapulgite modified (AT-NH is obtained after filter, drying and other steps2)。
Under nitrogen de-oxygen, by dianhydride and the diamines (mol ratio 21 of benzophenone tetracarboxylic dianhydride and p-phenylenediamine:
20) it is dissolved in the dimethylformamide of 50ml (DMF), synthesizing polyamides acid solution, addition accounts for dianhydride and diamine monomer is total afterwards
The AT-NH of quality 3wt%2With ultraviolet curable agent (2,4- diamino-phenyls)-[4- (2- phenylacetylene bases) phenyl] of 1.2wt%
Ethyl ketone, cyclizing agent is added after stirring 10mins, and (mol ratio is 1:1 acetic anhydride and triethylamine), poured into mould after rapid stirring
Gel is waited after uv light irradiation solidification 20s, after aging 24h at room temperature is placed in afterwards, with 1-METHYLPYRROLIDONE and methyl alcohol
Mixed solution carries out solvent displacement, each 12h, then 5 solvent displacements are carried out with pure methyl alcohol.Finally in pressure 15MPa, temperature 60
Supercritical carbon dioxide is carried out at DEG C and dries 5h, obtain porous polyimide aeroge；Sample rate is 0.08g/cm3, compare table
Area is 505m2/ g, dielectric constant is 1.29.
Embodiment 4
100g attapulgites (AT) raw ore is blended with 0.5mol HCl, through centrifugation, washing, dries, and acid activation AT is obtained；And
The NMP dispersion liquids (concentration is 4g/ml) with 120ml methyl diphenylene diisocyanates (MDI) are blended afterwards, through backflow, filtering, do
Attapulgite modified (AT-NCO) is obtained after the step such as dry.
Under nitrogen de-oxygen, by dianhydride and diamines (2,2'- double (3,4- dicarboxylic acids) hexafluoropropane dianhydrides and 4,4'-
The mol ratio 16 of diaminodiphenyl ether:15) it is dissolved in the 1-METHYLPYRROLIDONE of 50ml (NMP), synthesizing polyamides acid solution, it
The ultraviolet curable agent 4- (phenylacetylene base) of the AT-NCO and 2.0wt% that account for dianhydride and diamine monomer gross mass 5wt% is added afterwards
Aniline, cyclizing agent is added after stirring 10mins, and (mol ratio is 1:1 acetic anhydride and triethylamine), poured into mould after rapid stirring
Gel is waited after uv light irradiation solidification 18s, after aging 24h at room temperature is placed in afterwards, with 1-METHYLPYRROLIDONE and acetone
Mixed solution carries out solvent displacement, each 12h, then 5 solvent displacements are carried out with pure acetone.Finally in pressure 13MPa, temperature 45
Supercritical carbon dioxide is carried out at DEG C and dries 6h, obtain porous polyimide aeroge；Sample rate is 0.11g/cm3, compare table
Area is 438m2Shown in/g, such as accompanying drawing 3 (B), the dielectric constant of aeroge is 1.15.
Claims (10)
1. a kind of preparation method of nanoporous polyimides aeroge, including：
(1) under nitrogen atmosphere, diamine monomer is added in solvent, 0~60 DEG C of 3~6h of stirring is subsequently adding dianhydride monomer, obtains
To mixed solution, 2~6h is reacted, obtain polyamic acid PAA stostes；Then using ultraviolet curable agent and it is attapulgite modified as
Crosslinking agent is added in PAA stostes, adds chemical imidization agent to slough CO2Or slough H2O, obtains polyimide solution, then falls
Enter in mould, ultraviolet light polymerization obtains polyimides wet gel；Wherein, it is attapulgite modified for AT-NCO or AT-NH2；
(2) by the polyimides wet gel in step (1) at room temperature in mould it is aging, then carry out solvent displacement, it is super to face
Boundary's carbon dioxide is dried, and obtains nanoporous polyimides aeroge.
2. the preparation method of a kind of nanoporous polyimides aeroge according to claim 1, it is characterised in that described
Diamine monomer is p-phenylenediamine PPD, 4,4'- diaminodiphenyl ether ODA, 4,4'- diaminodiphenyl-methane MDA in step (1)
With at least one in 4,4'- diaminourea -2,2'- dimethyl -1,1'- biphenyl DMBZ；Dianhydride is benzophenone tetracarboxylic dianhydride
Double (the 3,4- dicarboxyls of double phthalic anhydride ODPA, 3,3'4,4'- biphenyl tetracarboxylic dianhydride BPDA and 2,2'- of BTDA, 4,4- oxygen
Acid) at least one in hexafluoropropane dianhydride 6FDA.
3. the preparation method of a kind of nanoporous polyimides aeroge according to claim 1, it is characterised in that described
The quality of diamines and dianhydride monomer and 7~20wt% of mixed solution gross mass is accounted in step (1)；Diamines rubs with dianhydride monomer
You are than being n：(n+1)；Wherein, the scope of n is 10~30.
4. the preparation method of a kind of nanoporous polyimides aeroge according to claim 1, it is characterised in that described
Solvent in step (1) is 1-METHYLPYRROLIDONE NMP, dimethylformamide DMF or dimethylacetylamide DMAC.
5. the preparation method of a kind of nanoporous polyimides aeroge according to claim 1, it is characterised in that described
Ultraviolet curable agent is 4- phenylene-ethynylenes phthalic anhydride, 4- (phenylacetylene base) aniline and (2,4- diaminourea in step (1)
Phenyl) at least one in-[4- (2- phenylacetylene bases) phenyl] ethyl ketone；The addition of ultraviolet curable agent accounts for dianhydride and diamines list
0.2wt%~the 3wt% of body gross mass.
6. the preparation method of a kind of nanoporous polyimides aeroge according to claim 1, it is characterised in that described
Attapulgite modified preparation method is in step (1)：It is blended with 0.25~0.5mol HCl per 100g attapulgite AT raw ores,
Through centrifugation, washing, dry, acid activation AT is obtained；Then the NMP dispersion liquids with silane coupler or diisocyanate are blended,
Through backflow, filtering, dry, obtain attapulgite modified AT-NH2Or AT-NCO.
7. the preparation method of a kind of nanoporous polyimides aeroge according to claim 1, it is characterised in that described
Attapulgite modified addition accounts for the 1wt%~5wt% of dianhydride and diamine monomer gross mass in step (1).
8. the preparation method of a kind of nanoporous polyimides aeroge according to claim 1, it is characterised in that described
In step (1) chemical imidization agent by pyridine and acetic anhydride with mol ratio 1:1 composition；Wherein, dianhydride, pyridine and acetic anhydride mole
Than being 1：5：5.
9. the preparation method of a kind of nanoporous polyimides aeroge according to claim 1, it is characterised in that described
The condition of ultraviolet light polymerization is in step (1)：3~20s of ultraviolet light irradiation.
10. the preparation method of a kind of nanoporous polyimides aeroge according to right asks 1, it is characterised in that described
The dry condition of supercritical carbon dioxide is in step (2)：Pressure be 10~15MPa, temperature be 30~60 DEG C, the time be 3~
6h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710032330.2A CN106866997A (en) | 2017-01-16 | 2017-01-16 | A kind of preparation method of nanoporous polyimides aeroge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710032330.2A CN106866997A (en) | 2017-01-16 | 2017-01-16 | A kind of preparation method of nanoporous polyimides aeroge |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106866997A true CN106866997A (en) | 2017-06-20 |
Family
ID=59158194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710032330.2A Pending CN106866997A (en) | 2017-01-16 | 2017-01-16 | A kind of preparation method of nanoporous polyimides aeroge |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106866997A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109250738A (en) * | 2018-09-19 | 2019-01-22 | 西南科技大学 | The preparation method of high temperature resistant block alumina aerogels |
| CN110437492A (en) * | 2018-05-04 | 2019-11-12 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of polyimide aerogels and the preparation method and application thereof with petal effect |
| CN111041589A (en) * | 2019-12-03 | 2020-04-21 | 东华大学 | Preparation method of polyimide aerogel fiber |
| CN111114035A (en) * | 2019-12-04 | 2020-05-08 | 中车青岛四方机车车辆股份有限公司 | Carbon fiber sandwich composite material and preparation method and application thereof |
| CN113024994A (en) * | 2021-02-08 | 2021-06-25 | 厦门大学 | Preparation method of nano attapulgite/phenolic aerogel and application of nano attapulgite/phenolic aerogel in preparation of wear-resistant automobile tires |
| CN113652214A (en) * | 2021-10-19 | 2021-11-16 | 山东德仕化工有限公司 | Supercritical carbon dioxide channeling sealing agent and preparation technology and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304814A (en) * | 2013-06-08 | 2013-09-18 | 中国科学院化学研究所 | Intrinsic hydrophobic polyimide aerogel and preparation method as well as application thereof |
-
2017
- 2017-01-16 CN CN201710032330.2A patent/CN106866997A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304814A (en) * | 2013-06-08 | 2013-09-18 | 中国科学院化学研究所 | Intrinsic hydrophobic polyimide aerogel and preparation method as well as application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张颖: ""聚酰亚胺/凹凸棒土（PI/AT）复合材料的制备及其性能研究"", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
| 龚永林: ""新产品与新技术（49）-降低聚酰亚胺基材介电常数的新技术"", 《印制电路信息》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437492A (en) * | 2018-05-04 | 2019-11-12 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of polyimide aerogels and the preparation method and application thereof with petal effect |
| CN110437492B (en) * | 2018-05-04 | 2022-03-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | Polyimide aerogel with petal effect as well as preparation method and application thereof |
| CN109250738A (en) * | 2018-09-19 | 2019-01-22 | 西南科技大学 | The preparation method of high temperature resistant block alumina aerogels |
| CN109250738B (en) * | 2018-09-19 | 2021-03-09 | 西南科技大学 | Preparation method of high-temperature resistant block alumina aerogel |
| CN111041589A (en) * | 2019-12-03 | 2020-04-21 | 东华大学 | Preparation method of polyimide aerogel fiber |
| CN111114035A (en) * | 2019-12-04 | 2020-05-08 | 中车青岛四方机车车辆股份有限公司 | Carbon fiber sandwich composite material and preparation method and application thereof |
| CN113024994A (en) * | 2021-02-08 | 2021-06-25 | 厦门大学 | Preparation method of nano attapulgite/phenolic aerogel and application of nano attapulgite/phenolic aerogel in preparation of wear-resistant automobile tires |
| CN113024994B (en) * | 2021-02-08 | 2021-12-10 | 厦门大学 | Preparation method of nano attapulgite/phenolic aerogel and application of nano attapulgite/phenolic aerogel in preparation of wear-resistant automobile tires |
| US11597809B2 (en) | 2021-02-08 | 2023-03-07 | Xiamen University | Method for preparing nano attapulgite and phenolic aerogel and method for preparing abrasion-resistant vehicle tire |
| CN113652214A (en) * | 2021-10-19 | 2021-11-16 | 山东德仕化工有限公司 | Supercritical carbon dioxide channeling sealing agent and preparation technology and application thereof |
| CN113652214B (en) * | 2021-10-19 | 2022-03-08 | 山东德仕化工有限公司 | Supercritical carbon dioxide channeling sealing agent and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106866997A (en) | A kind of preparation method of nanoporous polyimides aeroge | |
| CN108727818B (en) | Hydrophobic silicon dioxide/polyimide aerogel composite material and preparation method thereof | |
| CN106674560B (en) | A kind of polyimide containing crown ether micropore is from tool microporous polymer membranes and preparation method thereof | |
| CN105289337B (en) | A kind of crosslinkable polyimide gas separation membrane and preparation method | |
| CN107551835B (en) | Preparation method of high-flux graphene oxide/polyimide mixed matrix membrane material | |
| CN103304814B (en) | Intrinsic hydrophobic polyimide aerogel and preparation method thereof and application | |
| CN105968354B (en) | A kind of CO2The absorption preparation method of polyimide aerogels | |
| CN103846022A (en) | Preparation method of copolyimide hollow fiber gas separation membrane | |
| CN104211980B (en) | A kind of low dielectric coefficient polyimide film and preparation method thereof | |
| CN109942848B (en) | Preparation method of hydrophobic polyimide aerogel film with surface structure | |
| KR102082635B1 (en) | Method for Manufacturing Polyimide Aerogels cross-linked with amino-functionalized hollow mesoporous silica particles | |
| US10047207B2 (en) | Microporous polyimide sponge and method for producing the same | |
| CN107698794A (en) | A kind of preparation method of crosslinked polyimide aeroge | |
| CN114854083B (en) | Ultralight hydrophobic polyimide aerogel and preparation method and application thereof | |
| CN114891209B (en) | Low-dielectric-constant organic silicon modified polyimide film and preparation method thereof | |
| CN106237862A (en) | Ho llow fiber membrane for gas separation and preparation method thereof | |
| Wu et al. | Preparation and characterization of highly hydrophobic fluorinated polyimide aerogels cross-linked with 2, 2′, 7, 7′-Tetraamino-9, 9′-spirobifluorene | |
| CN109833784A (en) | A kind of Silicone Containing Polyimides gas separation membrane and preparation method | |
| Dasgupta et al. | Gas transport properties of fluorinated poly (ether imide) membranes containing indan moiety in the main chain | |
| CN108745006A (en) | Fluorinated polyimide hollow-fibre membrane and preparation method thereof | |
| CN108384047A (en) | A kind of transparent, High Strength Polyimide aeroge and preparation method thereof | |
| Xi et al. | Moisture‐Resistant and Mechanically Strong Polyimide‐Polymethylsilsesquioxane Hybrid Aerogels with Tunable Microstructure | |
| CN113831582B (en) | Cross-linked polyimide-based composite aerogel and preparation method thereof | |
| Wang et al. | Sub-Tg cross-linked thermally rearranged polybenzoxazole derived from phenolphthalein diamine for natural gas purification | |
| KR102086646B1 (en) | Micro-pored polyimide sponge and method for preparation of the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170620 |