CN107698794A - A kind of preparation method of crosslinked polyimide aeroge - Google Patents
A kind of preparation method of crosslinked polyimide aeroge Download PDFInfo
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- CN107698794A CN107698794A CN201610640949.7A CN201610640949A CN107698794A CN 107698794 A CN107698794 A CN 107698794A CN 201610640949 A CN201610640949 A CN 201610640949A CN 107698794 A CN107698794 A CN 107698794A
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- preparation
- crosslinked polyimide
- polyamic acid
- solvent
- wet gel
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 63
- 229920001721 polyimide Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011240 wet gel Substances 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 19
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 238000000352 supercritical drying Methods 0.000 claims abstract description 6
- 229920005575 poly(amic acid) Polymers 0.000 claims description 27
- 238000004132 cross linking Methods 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000008064 anhydrides Chemical group 0.000 claims description 11
- 150000004984 aromatic diamines Chemical class 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000000499 gel Substances 0.000 claims description 10
- 238000012643 polycondensation polymerization Methods 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229940113088 dimethylacetamide Drugs 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 3
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical class CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 125000006159 dianhydride group Chemical group 0.000 claims 1
- 150000002466 imines Chemical class 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims 1
- 239000004964 aerogel Substances 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 3
- 150000004985 diamines Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000004952 Polyamide Substances 0.000 abstract 1
- 229920002647 polyamide Polymers 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000012024 dehydrating agents Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001757 thermogravimetry curve Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical class CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- 239000004965 Silica aerogel Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- -1 Tetracarboxylic acid dianhydride Chemical class 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000011938 amidation process Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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
- 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
- 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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
-
- 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
- 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
- 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
Abstract
The present invention proposes a kind of preparation method of crosslinked polyimide aeroge, using sol-gal process, i.e. using dianhydride and diamines as monomer synthesizing polyamides acid, using triamido monomer as crosslinking agent, polyimides wet gel is formed through solvent hot imidization, with reference to supercritical drying process, crosslinked polyimide aerogel material is prepared.The present invention has the characteristics that applicability is extensive, raw material are cheap and easily-available, course of reaction is simple, overall cost is low, and resulting material has the multistage microstructural of nanoscale.
Description
Technical field
The present invention relates to a kind of preparation method of crosslinked polyimide aeroge, belong to aeroge preparing technical field.
Background technology
The fast-developing demand for efficiently anti-/ heat-barrier material of space technology is increasingly urgent.Aerogel material is light with its
The characteristics such as matter, super heat-insulated, superinsulation and receive more and more extensive attention, be increasingly becoming the first choice of efficiently anti-/ heat-barrier material
One of kind.Polyimide aerogels are a kind of with high temperature resistant, high fire-retardance, high insulation, high adiabatic, low-k and dielectric
The organic aerogel of loss, there is good mechanical property and flexility compared with purely inorganic aeroge, while there is low-heat
Conductance, manufactured film has good pliability, flexible, fold, fold spacecraft, aerospace craft heat control system,
Space suit etc. has boundless application prospect.
Aspen companies of the U.S. are prepared for the polyimide aerogels of linear structure first, and this kind of material has preferably heat
Stability and good mechanical property, 560 DEG C of heat decomposition temperature, than the mechanical property of general organic polymer enhancing silica aerogel
It is high.But shrinkage factor during this material supercritical drying is big, be not suitable for industrial production.In order to improve polyimide aerogels hole knot
The stability of structure, reduces the linear shrinkage ratio of material, and scientific research personnel has carried out the research work of cross-linked structure polyimide aerogels again
Make.The B2 of United States Patent (USP) US 9109088 disclose a kind of method for preparing crosslinked polyimide aeroge, i.e., using excess
The acid amides acid-sol of anhydride group end-blocking is first made with diamine monomer for dianhydride monomer, adds crosslinking agent --- polyamino monomer, through changing
Imidization (pyridine is catalyzed, and acetic anhydride is dehydrating agent) is learned, forms polyimides wet gel, with reference to supercritical drying process, is prepared
Crosslinked polyimide aerogel material, this method turn into the common method for preparing crosslinked polyimide aeroge at present,
Such as patent CN104693477A, CN105384950A.But there is also inborn deficiency, the catalyst pyrrole of chemical imidization for this method
Pyridine and dehydrating agent acetic anhydride before sol system gel, it is necessary to add, and now, dehydrating agent acetic anhydride can be unreacted with crosslinking agent
End capping reaction quickly occurs for amino, whole reaction system can not be formed perfect cross-linked network, and the gel ultimately formed is poly-
After compound imidization in the solution decreased solubility and separate out formation, the linear wet gel that its structure is formed like physical connection.
Therefore, how to realize that real cross-linked structure turns into the bottleneck problem for restricting polyimide aerogels Materials.
The content of the invention
It is an object of the invention to overcome prior art insufficient, there is provided a kind of applied widely, technique is simple and convenient to operate
With the preparation method of the crosslinked polyimide aerogel material suitable for industrialized production.
The technical solution of the present invention：A kind of preparation method of crosslinked polyimide aeroge, passes through following steps
Realize：
The first step, prepare polyamic acid solution；
Aromatic diamine monomer is well mixed be condensed with the aromatic dianhydride monomer of excess in organic solvent and gathered
Reaction is closed, obtains the polyamic acid solution of anhydride group end-blocking after completion of the reaction；
The present invention is not particularly limited to the species of aromatic diamine and aromatic dianhydride, and aromatic diamine can use normal
4,4'- diamino anisoles (ODA), 2,2'- dimethyl -4,4'- benzidines (DMBZ) for condensation polymerization reaction etc.；
Aromatic dianhydride can use the 3,3', 4,4'- BPDAs, 3,3' for being usually used in condensation polymerization reaction, 4,4'- diphenyl ether
Tetracarboxylic acid dianhydride, 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s etc..
The present invention is not particularly limited to the species of organic solvent, can be commonly used for the N- methyl pyrroles of condensation polymerization reaction
Pyrrolidone (NMP), N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO) etc..
Aromatic dianhydride and the mol ratio of aromatic diamine are 1：(0.4~0.85)；In condensation polymerization reactions steps, the time
For 8~32 hours, temperature was 0~40 DEG C.
Condensation polymerization reaction of the present invention is known in the art technology, and those skilled in the art can enter as the case may be
The selection of row raw material and technological parameter.
Second step, the polyamic acid wet gel of crosslinking is prepared,
Crosslinking agent triamido monomer is added in polyamic acid solution prepared by the first step, after being well mixed at room temperature,
Stand, after question response system gel, heat up aging, the polyamic acid wet gel being crosslinked；
The present invention is not particularly limited to type of crosslinking agent, can prepare the conventional triamido list of polyimide aerogels
Double (the 4'- aminophenyls) -4- (4'- of body, such as 1,3,5- tri- (amino) benzene, 1,3,5- tri- (amino-benzene oxygen) benzene (TAB), 2,6-
Aminophenyl) pyridine (TAPP) etc..
The dosage of crosslinking agent ensures amino total amount (in aromatic diamine and crosslinking agent on the basis of the amount of aromatic dianhydride
Amino total content) with anhydride group total amount (contained anhydride group total amount in aromatic dianhydride) equimolar ratio.Present invention determine that aromatic series
The mol ratio of dianhydride and aromatic diamine is 1：(0.4~0.85), on the premise of ensureing amino with anhydride group equimolar ratio, if fragrant
Fragrant race's diamine contents are too many, then dosage of crosslinking agent will very little, and the density of the polyamic acid wet gel internal crosslinking point of preparation is too
Small, during the 3rd step carries out imidization by solvent heat, polyamic acid wet gel can dissolve in a solvent again, can not
Polyimides wet gel is formed, and then the polyimide aerogels of cross-linking type can not be formed；If aromatic diamine content is very little,
Dosage of crosslinking agent will be too many, then sol system gel can be caused too fast, be unfavorable for operating.In the range of application claims,
Aromatic diamine dosage is fewer, and the dosage of crosslinking agent is more, increases with dosage of crosslinking agent, polyimide aerogels internal crosslinking point
Density be consequently increased, molcohesion increase, thus the linear shrinkage ratio of aeroge is consequently increased, and the density of sample has increasing
Big trend；The increase of the degree of cross linking, ratio of the micropore in pore structure can be also improved, thus specific surface area has becoming for increase
Gesture；The motion of the increase meeting restriction molecule chain of the degree of cross linking, while the stability of molecular structure is improved, thus the vitrifying of aeroge
Transition temperature and heat endurance have the trend of growth.
The present invention carries out heating aging to polyamic acid wet gel, to promote the cross-linked network of wet gel more perfect, carries
The intensity of high wet gel.Aging temperature is 40~80 DEG C, and ageing time is not less than 24 hours.If aging temperature is too low, to promoting
The complete amino of unreacted and the polycondensation reaction DeGrain of anhydride group in gel rubber system；Aging temperature is too high, can promote wet solidifying
A large amount of volatilizations of glue internal solvent, cause the contraction and structural damage of wet gel；Ageing time is too short, can not make gel rubber system
Polycondensation reaction fully occurs for the complete amino of middle unreacted and anhydride group；Ageing time is oversize, also results in wet gel internal solvent
A large amount of volatilizations, while reduce preparation efficiency.
3rd step, the polyamic acid wet gel for the crosslinking that second step is obtained carry out Asia under air-proof condition by solvent heat
Amination, obtain polyimides wet gel；
The time that imidization is carried out by solvent heat is no less than 8 hours, and temperature is 100~250 DEG C.Entered by solvent heat
The time of row imidization is too short, and it is complete to be unfavorable for imidization；Time is oversize, is unfavorable for improving preparation efficiency；Temperature is too low, unfavorable
It is complete in imidization；Temperature is too high, and solvent can acutely seethe with excitement, and can destroy the structure of wet gel.
Solvent heat is known technology, and solvent heat technology of preparing is that Bibby etc. starts to adopt in non-aqueous system during synthetic zeolite
, it is with nonaqueous solvents (NH3、C2H5OH、CO2、C6H6) reaction medium is used as, it is anti-that chemistry is carried out under high-temperature and high-pressure conditions
Should.The present invention has used for reference solvent thermal technology in imidization, and principle is consistent with known technology, simply the solvent in the present invention
The solvent that heat uses must with polyamic acid solution is prepared in the first step used by solvent it is identical, and ensure that solvent soaks completely
Do not have polyamic acid wet gel.
4th step, polyimides wet gel carry out solvent displacement, supercritical drying, obtain crosslinked polyimide airsetting
Glue.
Solvent displacement, supercritical drying are known in the art technology, and solvent can be conventional ethanol or acetone etc., ability
Field technique personnel carry out solvent and process choice as the case may be.
The beneficial effect of the present invention compared with prior art：
(1) present invention enters by preparing the intermediate product (polyamic acid wet gel) with cross-linked network, then through solvent heat
Row imidization makes it be converted to the polyimides wet gel of cross-linked form, and really crosslinking knot can not be obtained in the prior art by overcoming
The problem of polyimide aerogels of structure；
(2) present invention has the characteristics that applicability is extensive, raw material are cheap and easily-available, course of reaction is simple, overall cost is low,
Resulting material has the multistage microstructural of nanoscale.
Brief description of the drawings
Fig. 1 is flow chart of the present invention；
Fig. 2 is polyimide aerogels infrared spectrogram prepared by the embodiment of the present invention 1；
Fig. 3 is the stereoscan photograph of polyimide aerogels prepared by the embodiment of the present invention 1；
Fig. 4 is the polyimide aerogels that polyimide aerogels prepared by the embodiment of the present invention 1 are prepared with comparative example 1
TGA curves.
Embodiment
With reference to instantiation and accompanying drawing, the present invention is described in detail.
Embodiment 1
Preparation method by following steps as shown in figure 1, realized：
1st, by 2.94g (10mmol) 3,3', 4,4'- BPDA, 1.70g (8.5mmol) 4,4'- diaminobenzene first
Ether is dissolved in 93mL NMP, and condensation polymerization reaction 24h is carried out in 25 DEG C, obtains the polyamic acid solution of anhydride group end-blocking.
2nd, 0.40g (1mmol) crosslinking agent 1,3,5- tri- (amino-benzene oxygen) benzene is added in polyamic acid solution system
(TAB) 5min, is stirred in 25 DEG C, is cast in mould and stands, after question response system gel, be warming up to 60 DEG C of aging 24h, obtain
The polyamic acid wet gel of crosslinking.
3rd, a small amount of NMP is added into the mould of step 2, the surface of polyamic acid wet gel is covered by NMP, then by mould
Sealing, solvent hot imidization 18h is carried out in 220 DEG C, obtains polyimides wet gel.
4th, the polyimides wet gel that step 3 obtains is removed from the molds, soaked repeatedly with ethanol 3 times, then surpassed
Critical CO2Dry, 8h is dried under the conditions of 40 DEG C, 15MPa, obtains the polyimide aerogels of cross-linking type.
The test result data for the crosslinked polyimide aeroge performance that the present embodiment obtains is listed in Table 1 below, infrared light
Spectrogram is shown in accompanying drawing 2, and SEM photograph is shown in accompanying drawing 3, and TGA curves are shown in accompanying drawing 4.
It can be seen that from Fig. 2 spectrogram, in 1367cm-1、1715cm-1And 1775cm-1The feature that polyimides occurs in place is inhaled
Peak is received, in 1660cm-1And 1535cm-1There is not the characteristic absorption peak of polyamic acid in place, it was demonstrated that solvent heat treatment can make to gather
Amic acid imidization is complete；It was found from Fig. 3 stereoscan photograph, the cross-linking type that the embodiment is successfully prepared expected structure gathers
Acid imide aeroge, the aeroge microstructure is nanometer fibrous mutually to wind, and fibre diameter is between 10-50nm, gas
Volume shared by air (porosity) is 95% in gel；It was found from Fig. 4 is TGA curve of the embodiment 1 with comparative example 1, the present invention
Crosslinked polyimide aeroge prepared by method has higher heat endurance compared with prepared by conventional method.
Embodiment 2
Except the quality of 4, the 4'- diamino anisoles of addition is 1.40g (7mmol), NMP volume is 95mL, crosslinking agent
The quality of 1,3,5- tri- (amino-benzene oxygen) benzene (TAB) be 0.80g (2mmol) outside, the preparation of crosslinked polyimide aeroge
Condition and process are same as Example 1, and crosslinked polyimide aeroge the performance test results data are listed in Table 1 below.
Embodiment 3
Except the quality of 4, the 4'- diamino anisoles of addition is 1.10g (5.5mmol), NMP volume is 97mL, crosslinking
Agent 1,3, the quality of 5- tri- (amino-benzene oxygen) benzene (TAB) for 1.20g (3mmol) outside, the system of crosslinked polyimide aeroge
Standby condition and process are same as Example 1, and crosslinked polyimide aeroge the performance test results data are listed in Table 1 below.
Embodiment 4
Except the quality of 4, the 4'- diamino anisoles of addition is 0.80g (4mmol), NMP volume is 99mL, crosslinking agent
The quality of 1,3,5- tri- (amino-benzene oxygen) benzene (TAB) be 1.60g (4mmol) outside, the preparation of crosslinked polyimide aeroge
Condition and process are same as Example 1, and crosslinked polyimide aeroge the performance test results data are listed in Table 1 below.
Comparative example 1
Crosslinked polyimide aeroge is prepared using conventional method
1st, by 2.94g (10mmol) 3,3', 4,4'- BPDA, 1.70g (8.5mmol) 4,4'- diaminobenzene first
Ether is dissolved in 93mL NMP, is carried out amidation process 24h in 25 DEG C, is obtained the polyamic acid solution of anhydride group end-blocking.
2nd, 0.40g (1mmol) (amino-benzene oxygen) benzene (TAB) of crosslinking agent 1,3,5- tri- is added in system, in 25 DEG C
5min is stirred, adds imidization catalyst pyridine 7mL (80mmol) and dehydrating agent acetic anhydride 8mL (80mmol) stirring 1min,
It is cast in mould and stands, after question response system gel, in 25 DEG C of aging 24h, obtains polyimides wet gel.
3rd, the polyimides wet gel that step 2) obtains is removed from the molds, soaked repeatedly with ethanol 3 times, then surpassed
Critical CO2Dry, 8h is dried under the conditions of 40 DEG C, 15MPa, obtains polyimide aerogels.
The test result data of polyimide aerogels performance prepared by comparative example 1 is listed in Table 1 below, and TGA curves are shown in accompanying drawing
4。
The specific surface area of embodiment 1~4 and comparative example 1 (sample before testing through 80 DEG C of Fruit storages 10 hours),
(heating rate is 20 DEG C/min, nitrogen flow 100mL/min, temperature range by room temperature thermal conductivity factor, DSC：100~360 DEG C)
(heating rate is 20 DEG C/min, nitrogen flow 100mL/min, temperature range with TGA：100~800 DEG C) test result is shown in Table
1。
Table 1
It was found from the performance data of the embodiment of table 1, crosslinked polyimide aeroge prepared by the inventive method is being kept
While good heat-proof quality and low-density, its glass transition temperature and 5% thermal weight loss temperature exceed conventional method system
More than 40 DEG C of standby polyimide aerogels material, thus there is higher SC service ceiling temperature.
Embodiment 1-4 performance difference is the different result of crosslinked polyimide aeroge internal crosslinking degree, with friendship
Join the increase of agent content, the density of polyimide aerogels internal crosslinking point is consequently increased, and the density of sample has becoming for increase
Gesture, specific surface area have the trend of increase, and the glass transition temperature and heat endurance of sample have the trend of growth.
Unspecified part of the present invention is known to the skilled person technology.
Claims (9)
1. a kind of preparation method of crosslinked polyimide aeroge, it is characterised in that realized by following steps：
The first step, prepare polyamic acid solution；
By aromatic diamine monomer with excess aromatic dianhydride monomer be well mixed in organic solvent progress condensation polymerization it is anti-
Should, the polyamic acid solution that anhydride group blocks is obtained after completion of the reaction；
Second step, the polyamic acid wet gel of crosslinking is prepared,
Crosslinking agent triamido monomer is added in polyamic acid solution prepared by the first step, after being well mixed at room temperature, is stood,
After question response system gel, heat up aging, the polyamic acid wet gel being crosslinked；
3rd step, the polyamic acid wet gel for the crosslinking that second step is obtained carry out imines under air-proof condition by solvent heat
Change, obtain polyimides wet gel；
4th step, polyimides wet gel carry out solvent displacement, supercritical drying, obtain crosslinked polyimide aeroge.
A kind of 2. preparation method of crosslinked polyimide aeroge according to claim 1, it is characterised in that：Described
Aromatic dianhydride and the mol ratio of aromatic diamine are 1 in one step：(0.4~0.85).
A kind of 3. preparation method of crosslinked polyimide aeroge according to claim 1, it is characterised in that：Described
Crosslinking agent uses triamido monomer in two steps, and for dosage of crosslinking agent on the basis of the amount of aromatic dianhydride, amino total amount and anhydride group are total
Measure equimolar ratio.
A kind of 4. preparation method of crosslinked polyimide aeroge according to claim 1, it is characterised in that：Described
Polyamic acid wet gel carries out heating aging in two steps, and aging temperature is 40~80 DEG C, and ageing time is not less than 24 hours.
A kind of 5. preparation method of crosslinked polyimide aeroge according to claim 1, it is characterised in that：Described
The time that three steps carry out imidization by solvent heat is no less than 8 hours, and temperature is 100~250 DEG C.
A kind of 6. preparation method of crosslinked polyimide aeroge according to claim 1, it is characterised in that：Described
The solvent that solvent heat uses in three steps must with polyamic acid solution is prepared in the first step used by solvent it is identical, solvent will
Polyamic acid wet gel is totally submerged.
A kind of 7. preparation method of crosslinked polyimide aeroge according to claim 1, it is characterised in that：Described
Aromatic diamine is 4,4'- diamino anisoles (ODA) or 2,2'- dimethyl -4,4'- benzidines (DMBZ) in one step；
Aromatic dianhydride is 3,3', 4,4'- BPDAs, 3,3', 4,4'- diphenyl ether tetraformic dianhydrides or 3,3', 4,4'- hexichol
Ketone tetracarboxylic acid dianhydride.
A kind of 8. preparation method of crosslinked polyimide aeroge according to claim 1, it is characterised in that：Described
Organic solvent is 1-METHYLPYRROLIDONE (NMP), N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide in one step
(DMAc) dimethyl sulfoxide (DMSO) (DMSO) such as.
A kind of 9. preparation method of crosslinked polyimide aeroge according to claim 1, it is characterised in that：Described
The time that condensation polymerization is reacted in one step is 8~32 hours, and temperature is 0~40 DEG C.
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| CN108586403A (en) * | 2018-04-19 | 2018-09-28 | 吉林大学 | A kind of side chain dianhydride monomer containing phenylacetylene and its synthetic method and application |
| CN109731533A (en) * | 2019-01-22 | 2019-05-10 | 北京交通大学 | A kind of polyimide nano-fiber aeroge and its preparation method and application |
| CN110951107A (en) * | 2019-12-12 | 2020-04-03 | 山东省科学院新材料研究所 | Controllable preparation of PI aerogel material and photocatalytic reduction of CO2In (1) |
| WO2020085830A1 (en) * | 2018-10-26 | 2020-04-30 | 한국전기연구원 | Polyimide aerogel having controlled particle size and pore structure, and method for producing same |
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| CN108586403A (en) * | 2018-04-19 | 2018-09-28 | 吉林大学 | A kind of side chain dianhydride monomer containing phenylacetylene and its synthetic method and application |
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| CN110951107B (en) * | 2019-12-12 | 2023-03-07 | 山东省科学院新材料研究所 | Controllable preparation of PI aerogel material and photocatalytic reduction of CO 2 In (1) |
| CN110951107A (en) * | 2019-12-12 | 2020-04-03 | 山东省科学院新材料研究所 | Controllable preparation of PI aerogel material and photocatalytic reduction of CO2In (1) |
| CN112062989A (en) * | 2020-08-10 | 2020-12-11 | 航天特种材料及工艺技术研究所 | Polyimide aerogel lithium battery diaphragm and preparation method thereof |
| CN112062989B (en) * | 2020-08-10 | 2022-09-23 | 航天特种材料及工艺技术研究所 | Polyimide aerogel lithium battery diaphragm and preparation method thereof |
| CN114015194A (en) * | 2021-10-19 | 2022-02-08 | 航天特种材料及工艺技术研究所 | Polybenzoxazine aerogel and preparation method thereof |
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| CN115818616A (en) * | 2022-11-28 | 2023-03-21 | 四川大学 | Polyimide-based carbon aerogel and preparation method and application thereof |
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