CN108794766A - A kind of crosslinked polyimide aeroge and preparation method - Google Patents
A kind of crosslinked polyimide aeroge and preparation method Download PDFInfo
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- CN108794766A CN108794766A CN201710310163.3A CN201710310163A CN108794766A CN 108794766 A CN108794766 A CN 108794766A CN 201710310163 A CN201710310163 A CN 201710310163A CN 108794766 A CN108794766 A CN 108794766A
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- polyamic acid
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- wet gel
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- crosslinked polyimide
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 64
- 229920001721 polyimide Polymers 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 40
- 239000011240 wet gel Substances 0.000 claims abstract description 37
- 150000008064 anhydrides Chemical group 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 23
- 125000003368 amide group Chemical group 0.000 claims abstract description 20
- 238000007789 sealing Methods 0.000 claims abstract description 20
- 239000013067 intermediate product Substances 0.000 claims abstract description 11
- 238000000352 supercritical drying Methods 0.000 claims abstract description 7
- 238000006073 displacement reaction Methods 0.000 claims abstract description 5
- 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 description 22
- 150000004984 aromatic diamines Chemical class 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 238000004132 cross linking Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 16
- 238000012643 polycondensation polymerization Methods 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 8
- 239000000499 gel Substances 0.000 claims description 8
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 6
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000002466 imines Chemical class 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims 1
- 239000004964 aerogel Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 description 13
- 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 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012024 dehydrating agents Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 3
- 238000003483 aging Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- -1 Tetracarboxylic acid dianhydride Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MRAKLTZPBIBWFH-ARJAWSKDSA-N (z)-2-ethenylbut-2-enedioic acid Chemical compound OC(=O)\C=C(\C=C)C(O)=O MRAKLTZPBIBWFH-ARJAWSKDSA-N 0.000 description 1
- 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 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
- 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 description 1
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 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
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 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
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- 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
- C08J3/246—Intercrosslinking of at least two polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
- C08J2335/06—Copolymers with vinyl aromatic monomers
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
- C08J2435/06—Copolymers with vinyl aromatic monomers
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- C08J2479/00—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 C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
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Abstract
A kind of crosslinked polyimide aeroge of present invention proposition and preparation method, it is crosslinked to obtain intermediate product with more anhydride group crosslinking agents by the polyamic acid of amido sealing end, intermediate product obtains polyimides wet gel, then be made through solvent displacement, supercritical drying through solvent hot imidization；The intermediate product is the polyamic acid wet gel with cross-linked structure.The present invention passes through intermediate product (polyamic acid wet gel) of the preparation with cross-linked network, again the problem of imidization makes it be converted to the polyimides wet gel of cross-linked form, overcomes the polyimide aerogels for being unable to get real cross-linked structure in the prior art is carried out through solvent heat.
Description
Technical field
The present invention relates to a kind of crosslinked polyimide aeroge and preparation methods, belong to aeroge preparing technical field.
Background technology
Aeroge is mutually to be coalesced to constitute nanoporous network structure by colloidal particle or high-polymer molecular, and in nano-pore
A kind of high dispersive solid nano material of gaseous state decentralized medium is full of in gap.Aeroge has low-density, high-specific surface area, low-heat
The features such as conductance and low acoustic impedance.Polyimide aerogels are one kind of organic aerogel, are had compared with purely inorganic aeroge
Good mechanical property and flexility, while having lower thermal conductivity, manufactured film have a good flexibility, flexible,
It folds, there is boundless application folding spacecraft, aerospace craft heat control system, space suit, base camp tent etc.
Foreground.
Polyimide aerogels can be divided into two kinds of line style and cross-linking type.The polyimide aerogels of linear structure are faced super
Larger volume contraction often occurs for volume in boundary's drying process, is not suitable for industrial production；And crosslinked polyimide airsetting
Glue is analyzed from principle, can be with shape since the introducing of crosslinking agent makes polyimide polymer chain be combined by covalent bond
At tridimensional network, the density and thermal coefficient of sample can be reduced, while promoting its heat, mechanical property.
9109088 B2 of United States Patent (USP) US disclose a kind of method preparing crosslinked polyimide aeroge, that is, use
The amide acid-sol of anhydride group sealing end is first made with diamine monomer for excessive dianhydride monomer, adds crosslinking agent --- polyamino list
Body forms polyimides wet gel, in conjunction with supercritical drying work through chemical imidization (pyridine is catalyzed, and acetic anhydride is dehydrating agent)
Skill prepares crosslinked polyimide aerogel material, and this method has become prepares the normal of crosslinked polyimide aeroge at present
With method, such as patent CN104693477A, CN105384950A.But this method is there is also inborn deficiency, chemical imidization
Catalyst pyridine and dehydrating agent acetic anhydride need to be added before sol system gel, at this point, the meeting of dehydrating agent acetic anhydride and crosslinking agent
End capping reaction quickly occurs for unreacted amino, makes entire reaction system that can not form perfect cross-linked network, finally formed
Gel be after polymer imidization in the solution decreased solubility and formation is precipitated, structure forms linear like physical connection
Wet gel.Therefore, how to realize that real cross-linked structure has become the bottleneck problem for restricting polyimide aerogels Materials.
Meanwhile the price of the crosslinking agent of polyamino monomer is very expensive, or need to obtain by complicated synthesis technology, this
Also the large-scale production and application of crosslinked polyimide aeroge are further limited.
Invention content
It is an object of the invention to overcome the shortage of prior art, provide that a kind of manufacturing cost is low, applied widely, technique is simple
Single, easy to operate and crosslinked polyimide aeroge and preparation method suitable for industrialized production.
Technical solution of the invention：A kind of crosslinked polyimide aeroge, by amido sealing end polyamic acid with
More anhydride group crosslinking agents are crosslinked to obtain intermediate product, and intermediate product obtains polyimides wet gel through solvent hot imidization, then
It is made through solvent displacement, supercritical drying, the intermediate product is the polyamic acid wet gel with cross-linked structure.
The polyamic acid of the amido sealing end is by aromatic dianhydride monomer with excessive aromatic diamine monomer in organic
Mixing progress condensation polymerization is obtained by the reaction in solvent, and the molar ratio of aromatic diamine and aromatic dianhydride is 1：(0.30~
0.90)。
Anhydride group number is more than or equal to 3 on the unimolecule of more anhydride group crosslinking agents, and dosage is with the amount of aromatic diamine
On the basis of, ensure anhydride group total amount (aromatic dianhydride and the anhydride group total content in crosslinking agent) with amido total amount (in aromatic diamine
Institute's amino-contained total amount) equimolar ratio.
A kind of crosslinked polyimide aeroge preparation method, is realized by following steps：
The first step prepares the polyamic acid solution of amido sealing end；
Aromatic dianhydride monomer is uniformly mixed be condensed in organic solvent with excessive aromatic diamine monomer and is gathered
Reaction is closed, obtains the polyamic acid solution of amido sealing end after completion of the reaction；
The present invention is not particularly limited the type of aromatic diamine and aromatic dianhydride, and aromatic diamine may be used often
4,4'- diamino anisoles (ODA), 2,2'- dimethyl -4,4'- benzidines (DMBZ) for being reacted for condensation polymerization etc.；
The 3,3', 4,4'- biphenyltetracarboxylic dianhydride, 3,3' for being usually used in condensation polymerization reaction, 4,4'- diphenyl ether may be used in aromatic dianhydride
Tetracarboxylic acid dianhydride, 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s etc..
The present invention is not particularly limited the type of organic solvent, can be commonly used for the N- methyl of condensation polymerization reaction
Pyrrolidones (NMP), N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO)
Deng.
The molar ratio of aromatic diamine and aromatic dianhydride is 1：(0.30~0.90)；In condensation polymerization reaction step, when
Between be 4~72 hours, temperature be 0~40 DEG C.
Condensation polymerization of the present invention reaction is known in the art technology, those skilled in the art can as the case may be, into
The selection of row raw material and technological parameter.
The present invention is to overcome current more amines catalysts expensive or prepare the unfavorable factors such as complexity, is abandoned existing usual
The polyamic acid solution of the anhydride group sealing end of production, is changed to carry out using excessive aromatic diamine monomer and aromatic dianhydride monomer
Condensation polymerization is reacted, and the polyamic acid solution of amido sealing end is obtained, to make it possible novel, the cheap catalyst of selection.
Second step prepares crosslinked polyamic acid wet gel,
More anhydride group crosslinking agents are added in the polyamic acid solution of amido sealing end prepared by the first step, mixing is equal at room temperature
It after even, stands, after reaction system gel, heat up aging, obtains crosslinked polyamic acid wet gel；
Anhydride group number on the unimolecule of more anhydride group crosslinking agents has to be larger than equal to three, multiple anhydride groups on strand, can be with
It is reacted with the polyamic acid of amido sealing end, forms cross-linked network.
More anhydride group crosslinking agent optimization styrene-copolymer-maleic anhydrides, styrene-maleic anhydride copolymer raw material is cheap,
It is easily-synthesized, and styrene and maleic anhydride is easily made to form alternate copolymer, facilitate the control of maleic anhydride content, most preferably benzene
Ethylene-maleic acid alternate copolymer is not particularly limited its molecular weight.
The dosage of more anhydride group crosslinking agents ensures anhydride group total amount (aromatic dianhydride and friendship on the basis of the amount of aromatic diamine
Join the anhydride group total content in agent) and amido total amount (institute's amino-contained total amount in aromatic diamine) equimolar ratio.Present invention determine that
The molar ratio of aromatic diamine and aromatic dianhydride is 1：(0.30~0.90), ensure amido and anhydride group equimolar than premise
Under, if aromatic dianhydride content is too many, dosage of crosslinking agent will be very little, the polyamic acid wet gel internal crosslinking point of preparation
Density is too small, and during third step carries out imidization by solvent heat, polyamic acid wet gel can be dissolved in solvent again
In, polyimides wet gel can not be formed, and then the polyimide aerogels of cross-linking type can not be formed；If aromatic dianhydride content
Very little, then dosage of crosslinking agent will be too many, and molcohesion is caused to increase, and wet gel is acutely shunk in ageing process, finally
Polyimide aerogels density is caused to increase.The present invention claims in the range of, aromatic dianhydride dosage is fewer, the use of crosslinking agent
Amount is more, increases with dosage of crosslinking agent, and the density of polyimide aerogels internal crosslinking point is consequently increased, and molcohesion increases
Greatly, thus the linear shrinkage ratio of aeroge is consequently increased, and the density of sample has increased trend；The increase of the degree of cross linking can also carry
Ratio of the high micropore in pore structure, thus specific surface area has increased trend；The increase meeting restriction molecule chain of the degree of cross linking
Movement, while the stability of molecular structure is improved, thus the glass transition temperature of aeroge has the tendency that growth.
The present invention carries out aging to polyamic acid wet gel, to promote the cross-linked network of wet gel more perfect, improves wet
The intensity of gel.Aging temperature and time, gel aging was known in the art technology, this field depending on the reactivity of monomer
Technical staff selects according to actual requirement.
Third walks, and the crosslinked polyamic acid wet gel that second step is obtained is carried out under air-proof condition by solvent heat sub-
Amination obtains 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.By solvent heat into
The time of row imidization is too short, and it is complete to be unfavorable for imidization；Time is too long, is unfavorable for improving preparation efficiency；Temperature is too low, unfavorable
It is complete in imidization；Temperature is too high, and solvent can acutely boil, and can destroy the structure of wet gel.
The present invention has used for reference solvent thermal technology in imidization, and principle is consistent with known technology, only in the present invention
The solvent that uses of solvent heat must be identical as solvent used by polyamic acid solution is prepared in the first step, and ensure solvent
It is totally submerged 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 common ethyl alcohol or acetone etc., ability
Field technique personnel carry out solvent and process choice as the case may be.
The advantageous effect of the present invention compared with prior art：
(1) present invention by preparation with cross-linked network intermediate product (polyamic acid wet gel), then through solvent heat into
Row imidization makes it be converted to the polyimides wet gel of cross-linked form, overcomes and is unable to get really crosslinking knot in the prior art
The problem of polyimide aerogels of structure；
(2) present invention has the characteristics that applicability is extensive, raw material are cheap and easily-available, reaction process is simple, overall cost is low,
Obtained material has the multistage microstructural of nanoscale；
(3) it the present invention overcomes the defect of the rare costliness of crosslinking agent in crosslinked polyimide aeroge preparation process, gets rid of
The polyamic acid solution for abandoning the existing anhydride group sealing end usually produced, is changed to using excessive aromatic diamine monomer and aromatic series two
Anhydride monomer carries out condensation polymerization reaction, the polyamic acid solution of amido sealing end is obtained, to make the catalyst that selection is novel, cheap
It is possibly realized.
Description of the drawings
Fig. 1 is polyimide aerogels infrared spectrogram prepared by the embodiment of the present invention 2；
Fig. 2 is the stereoscan photograph of polyimide aerogels prepared by the embodiment of the present invention 2.
Fig. 3 is flow chart of the present invention.
Specific implementation mode
With reference to specific example and attached drawing, the present invention is described in detail.
Embodiment 1
Preparation method by following steps as shown in Figure 1, realized：
1, by 2.0024g (10mmol) 4,4'- diamino anisoles, 2.6480g (9mmol) 3,3', 4,4'- biphenyl tetracid
Dianhydride is dissolved in the NMP of 93mL, and condensation polymerization reaction is carried out in 25 DEG C for 24 hours, obtains the polyamic acid solution of anhydride group sealing end.
2, crosslinking styrene-maleic anhydride that 0.4044g (2mmol anhydride groups) is added in polyamic acid solution system is handed over
For copolymer, 5min is stirred in 25 DEG C, is cast in mold and stands, after reaction system gel, be warming up to 60 DEG C of agings for 24 hours,
Obtain crosslinked polyamic acid wet gel.
3, a small amount of NMP is added into the mold of step 2, the surface of polyamic acid wet gel is made to be covered by NMP, then by mold
Sealing carries out solvent hot imidization 18h in 220 DEG C, obtains polyimides wet gel.
4, the polyimides wet gel that step 3 obtains is removed from the molds, is impregnated repeatedly with ethyl alcohol 3 times, then surpassed
Critical CO2Dry, dry 8h, obtains the polyimide aerogels of cross-linking type under the conditions of 40 DEG C, 15MPa.The present embodiment obtains
The test result data of crosslinked polyimide aeroge performance be listed in table 1.
Embodiment 2
Except the quality of the 3,3' of addition, 4,4'- biphenyltetracarboxylic dianhydride is 2.0595g (7mmol), the volume of NMP is
97mL, outside for 1.2133g (6mmol anhydride groups), cross-linking type polyamides is sub- for the quality of crosslinking styrene-maleic anhydride alternate copolymer
The preparation condition and process of amine aeroge are same as Example 1, crosslinked polyimide aeroge the performance test results data row
In table 1, infrared spectrogram is shown in that attached drawing 1, SEM photograph are shown in attached drawing 2.
It can be seen that from the spectrogram of Fig. 1, in 1365cm-1、1707cm-1And 1777cm-1The feature that polyimides occurs in place is inhaled
Peak is received, in 1660cm-1There is not the characteristic absorption peak of polyamic acid in place, it was demonstrated that polyamic acid imidization is complete；From sweeping for Fig. 2
Electromicroscopic photograph is retouched it is found that the embodiment is successfully prepared the crosslinked polyimide aeroge of expected structure, the aeroge is microcosmic
Structure is the nanosphere string-like mutually wound, fibre diameter about 30nm, and air is filled between nanofiber and particle, this knot
Structure imparts the very low density of aeroge.
Embodiment 3
Except the quality of the 3,3' of addition, 4,4'- biphenyltetracarboxylic dianhydride is 1.6182g (5.5mmol), the volume of NMP is
100mL, the quality of crosslinking styrene-maleic anhydride alternate copolymer be 1.8199g (9mmol anhydride groups) outside, cross-linking type polyamides
The preparation condition and process of imines aeroge are same as Example 1, crosslinked polyimide aeroge the performance test results data
It is listed in Table 1 below.
Embodiment 4
Except the quality of the 3,3' of addition, 4,4'- biphenyltetracarboxylic dianhydride is 0.8827g (3mmol), the volume of NMP is
105mL, the quality of crosslinking styrene-maleic anhydride alternate copolymer be 2.8309g (14mmol anhydride groups) outside, cross-linking type polyamides
The preparation condition and process of imines aeroge are same as Example 1, crosslinked polyimide aeroge the performance test results data
It is listed in Table 1 below.
The specific surface area (sample before testing through 80 DEG C of Fruit storages 10 hours) of Examples 1 to 4, room temperature heat conduction system
(heating rate is 20 DEG C/min, nitrogen flow 100mL/min, temperature range by number and DSC：100~400 DEG C) test result
It is shown in Table 1.
Comparative example 1
Crosslinked polyimide aeroge is prepared using conventional method
1, by 2.9422g (10mmol) 3,3', 4,4'- biphenyltetracarboxylic dianhydride, 1.8022g (9mmol) 4,4'- diamino
Methyl phenyl ethers anisole is dissolved in the NMP of 93mL, is carried out amidation process for 24 hours in 25 DEG C, is obtained the polyamic acid solution of anhydride group sealing end.
2, crosslinking agent 1,3,5- tri- (amino-benzene oxygen) benzene of 0.2663g (0.6667mmol) is added in system
(TAB), 5min is stirred in 25 DEG C, adds imidization catalyst pyridine 7mL (80mmol) and dehydrating agent acetic anhydride 8mL
(80mmol) stirs 1min, is cast in mold and stands, and after reaction system gel, for 24 hours in 25 DEG C of agings, obtains polyamides Asia
Amine wet gel.
3, the polyimides wet gel that step 2) obtains is removed from the molds, is impregnated repeatedly with ethyl alcohol 3 times, then surpassed
Critical CO2Dry, dry 8h, obtains polyimide aerogels under the conditions of 40 DEG C, 15MPa.
The specific surface area (sample before testing through 80 DEG C of Fruit storages 10 hours) of comparative example 1, room temperature thermal coefficient
(heating rate is 20 DEG C/min, nitrogen flow 100mL/min, temperature range with DSC：100~400 DEG C) test result is shown in
Table 1.
Table 1
From the performance data of 1 embodiment of table it is found that crosslinked polyimide aeroge prepared by the method for the present invention is being kept
While good heat-proof quality and low-density, there is higher glass transition temperature, glass transition temperature is beyond biography
40 DEG C of polyimide aerogels material or more prepared by system method, thus there is higher SC service ceiling temperature.
The performance difference of embodiment 1-4 is that crosslinked polyimide aeroge internal crosslinking degree is different as a result, with friendship
Join the increase of agent content, the density of polyimide aerogels internal crosslinking point is consequently increased, the density of sample have it is increased become
Gesture, specific surface area have increased trend, the glass transition temperature of sample to have the tendency that growth.
Unspecified part of the present invention is known to the skilled person technology.
Claims (10)
1. a kind of crosslinked polyimide aeroge, it is characterised in that：Polyamic acid by amido sealing end and more anhydride group crosslinking agents
It being crosslinked to obtain intermediate product, intermediate product obtains polyimides wet gel through solvent hot imidization, then replaced through solvent,
Supercritical drying is made；The intermediate product is the polyamic acid wet gel with cross-linked structure.
2. a kind of crosslinked polyimide aeroge according to claim 1, it is characterised in that：The amido sealing end
Polyamic acid is mixed that carry out condensation polymerization anti-by aromatic dianhydride monomer and excessive aromatic diamine monomer in organic solvent
It should obtain, the molar ratio of aromatic diamine and aromatic dianhydride is 1：(0.30~0.90).
3. a kind of crosslinked polyimide aeroge according to claim 2, it is characterised in that：More anhydride groups crosslinking
Anhydride group number is more than or equal to 3 on the unimolecule of agent, and dosage ensures anhydride group total amount and amido on the basis of the amount of aromatic diamine
Total amount equimolar ratio.
4. a kind of crosslinked polyimide aeroge according to claim 1, it is characterised in that：More anhydride groups crosslinking
Agent is alternate styrene-maleic anhydride copolymer.
5. a kind of crosslinked polyimide aeroge preparation method, which is characterized in that realized by following steps：
The first step prepares the polyamic acid solution of amido sealing end；
Second step prepares crosslinked polyamic acid wet gel,
More anhydride group crosslinking agents are added in the polyamic acid solution of amido sealing end prepared by the first step, is uniformly mixed and waits for reaction system
After gel, heat up aging, obtains crosslinked polyamic acid wet gel；
Third walks, and the crosslinked polyamic acid wet gel that second step obtains is carried out imines under air-proof condition by solvent heat
Change, obtains polyimides wet gel；
4th step, polyimides wet gel carry out solvent displacement, supercritical drying, obtain crosslinked polyimide aeroge.
6. a kind of crosslinked polyimide aeroge preparation method according to claim 5, it is characterised in that：Described first
The polyamic acid solution that amido blocks in step is by aromatic dianhydride monomer and excessive aromatic diamine monomer in organic solvent
Middle condensation polymerization is obtained by the reaction.
7. a kind of crosslinked polyimide aeroge preparation method according to claim 6, it is characterised in that：Described first
The molar ratio of aromatic diamine and aromatic dianhydride is 1 in step：(0.30~0.90).
8. a kind of crosslinked polyimide aeroge preparation method according to claim 5, it is characterised in that：Described second
The anhydride group number walked on the unimolecule of more anhydride group crosslinking agents has to be larger than equal to 3.
9. a kind of crosslinked polyimide aeroge preparation method described according to claim 6 or 7, it is characterised in that：It is described
The dosage of more anhydride group crosslinking agents ensures anhydride group total amount and amido total amount equimolar on the basis of the amount of aromatic diamine in second step
Than.
10. a kind of crosslinked polyimide aeroge preparation method according to claim 5, 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, the solvent that solvent heat uses
It is identical as solvent used by the polyamic acid solution for preparing amido sealing end in the first step, and ensure that solvent is totally submerged polyamides
Amino acid wet gel.
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