CN110483994A - A kind of silica enhancing polyimide aerogels micro mist and preparation method thereof - Google Patents
A kind of silica enhancing polyimide aerogels micro mist and preparation method thereof Download PDFInfo
- Publication number
- CN110483994A CN110483994A CN201910708254.1A CN201910708254A CN110483994A CN 110483994 A CN110483994 A CN 110483994A CN 201910708254 A CN201910708254 A CN 201910708254A CN 110483994 A CN110483994 A CN 110483994A
- Authority
- CN
- China
- Prior art keywords
- micro mist
- polyimide aerogels
- preparation
- silica
- solution
- 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.)
- Granted
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silicon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a kind of silica enhancing polyimide aerogels micro mists and preparation method thereof, belong to nano-porous materials and thermal isolation technique field.The preparation method includes: respectively to dissolve the dilute base ether-copolymer-maleic anhydride of methyl second, 3-aminopropyltriethoxysilane and aromatic diamine in a solvent；Three kinds of solution are mixed in a certain ratio again, after mixing evenly arrest reaction, form gel, micro mist gel is prepared using mechanical crushing method, then by soak in dehydrating agent；The displacement of dewatered gel solvent, supercritical drying are finally obtained into the linear polyimide aerogels micro mist of silica nano particle enhancing.The polyimide aerogels micro mist that the present invention obtains is brown, has organic and inorganic dual network structure, the toughness of rigidity and polyimides with silica, the low (0.03~0.3g/cm of density3), specific surface area height (200~600m2/ g), the good characteristics such as high temperature resistance is good.
Description
Technical field
The present invention relates to a kind of linear polyimide aerogels micro mists and preparation method thereof of silica enhancing, belong to nanometer
Porous material and thermal isolation technique field.
Background technique
Aeroge is a kind of porous nano material, is that the current world improves quality solid most light, that heat-proof quality is best
Material.Since silica aerogel has high-specific surface area (400~1500m2/ g), it is high porosity (80~99.8%), low close
Spend (0.003~0.6g/cm3) and the features such as lower thermal conductivity (0.013~0.038W/mk), make it in high temperature resistant heat insulation, ultralow close
The fields such as degree, acoustic impedance coupling, gas absorption and filtering, catalyst carrier, pharmaceutical carrier have very important application.So far
Until, various types of aeroges, including aerosil are prepared for by chemical crosslink technique
(CN102424538A；CN102633269A), chitosan aeroge (CN102417606A), carbon aerogels (CN102423668A；
CN102430369A), metal oxide and its composite aerogel (CN102513041A), multielement composite aerogel
(CN102584010A), graphene and carbon nanotube aerogel (CN102674315A), titania aerogel
(CN102671587A) etc..Above-mentioned aeroge mechanical strength is weak, brittleness is big, and not fire-retardant, not radiation hardness etc., therefore urgency
It need to invent with excellent in mechanical performance, while there is the aeroge of excellent radiation hardness, weatherability, the performances such as do not burn, with reality
Existing application of the aeroge in aviation and civil field.
Polyimides is a kind of organic polymer that main chain contains imide ring, has high mechanical strength, thermal stability good
And the advantages that wear-resistant.Either as structural material or functional material, significant superiority is adequately recognized
Know.In recent years, the research of polyimide aerogels has attracted much attention, compared with other polymer aerogels, polyimide aerogels
The unique property such as excellent strength, rigid adjustable, high temperature resistant, resistance to extremely low temperature, radiation hardness, fire-retardant, therefore from 2006
Just extensive concern has been obtained since the invention for the first time of (USP7074880,2006) polyimide aerogels.Just because of this, U.S. NASA
Polyimide aerogels preparation and application aspect carry out numerous studies (document ACS Appl.Mater.Interfaces,
2012,4,536-544).However, existing polyimide aerogels, since toughness is higher, powder processed is difficult, powder filler can not be used as
Use, in addition traditional polyimide aerogels are with high costs, and skeleton structure is organic principle, it is slight it is poor, intensity is low.
Summary of the invention
In view of the deficiencies of the prior art with the limitation of material, the main purpose of the present invention is to provide a kind of increasings of silica
Strong linear polyimide aerogels micro mist and preparation method thereof.
To realize aforementioned invention purpose, The technical solution adopted by the invention is as follows:
A kind of preparation method of silica enhancing polyimide aerogels micro mist, comprising the following steps:
Step (1), by methyl vinyl ether-maleic acid copolymer, 3-aminopropyltriethoxysilane and aromatic series
Diamines dissolves respectively obtains methyl vinyl ether-maleic acid copolymer solution, 3- aminopropyl triethoxysilicane in a solvent
Alkane solution and aromatic diamine solution；
Step (2), by the methyl vinyl ether-maleic acid copolymer solution, 3-aminopropyltriethoxysilane
Solution and aromatic diamine solution stand after being stirred by a certain percentage and form gel, then the soak of formation is being dehydrated
The sub- amidation of chemistry is carried out in agent, obtains sub- amidation gel；
The sub- amidation gel is obtained silica nano particle through crushing, solvent displacement, drying process by step (3)
The linear polyimide aerogels micro mist of enhancing.
In an alternative embodiment, step (1) described aromatic diamine includes p-phenylenediamine, m-phenylene diamine (MPD), 4,4 '-diamines
Base biphenyl, 4,4'- methylene dianiline (MDA), any one or two or more combinations in 4,4'- diaminodiphenyl ether.
In an alternative embodiment, step (1) the methyl vinyl ether-maleic acid copolymer number-average molecular weight is
50000-200000.4, the preparation method of silica enhancing polyimide aerogels micro mist according to claim 1, it is special
Sign is that step (1) described solvent includes n,N-Dimethylformamide, n,N-dimethylacetamide, dimethyl sulfoxide or N- first
At least one of base pyrrolidones.
In an alternative embodiment, the concentration of methyl vinyl ether-maleic acid copolymer solution described in step (1) is
0.1~0.3g/cm3, 3-aminopropyltriethoxysilane solution concentration be 0.01~0.2g/cm3, aromatic diamine solution it is dense
Degree is 0.05~0.2g/cm3, methyl vinyl ether-maleic acid copolymer solution described in step (2), 3- aminopropyl three
The volume ratio of Ethoxysilane solution and aromatic diamine solution is 100:4~6:25~35.
It in an alternative embodiment, is stood at 0~80 DEG C in step (2) and forms gel, the dehydrating agent is pyridine, three
Ethamine, acetic anhydride, picoline, chloroacetic chloride, thionyl chloride, the halide of phosphorus or in Dicyclohexylcarbodiimide at least one
Kind.
In an alternative embodiment, crushing described in step (3) includes: first to squeeze under 20-50 DEG C, 0.5-3MPa pressure
Then 1-5h stirs 2~4h with the revolving speed of 800-3000 turns/min, obtains wet gel micro mist.
In an alternative embodiment, the displacement of solvent described in step (3) includes: to be replaced to crush with methanol, ethyl alcohol or acetone
Gel afterwards, displacement number is no less than twice.
In an alternative embodiment, drying means described in step (3) is faced using carbon dioxide, ethyl alcohol or methanol as super
Boundary's fluid is 40-250 DEG C in temperature, carries out supercritical drying, drying time 2-10h under conditions of pressure >=8MPa.
The silica that above-mentioned preparation method is prepared enhances polyimide aerogels micro mist, which is characterized in that and it is brown,
With organic and inorganic dual network structure, density is 0.03~0.3g/cm3, specific surface area is 200~600m2/g.With existing skill
Art is compared, the invention has the following beneficial effects:
The present invention using linear polyanhydride as monomer, have many advantages, such as that low in cost, functional group is numerous, thus with
While diamines is cross-linked to form polyimides gel, organosiloxane etc. can be introduced, forms organic second gel network, and two
Kind network chemical bonding forms the synergy that mechanics enhancing and thermostabilization enhance, prepared polyimide aerogels micro mist
It is not only at low cost but also there is rigid pore structure.
Detailed description of the invention
Scanning electron microscope diagram of the Fig. 1 by obtaining polyimide aerogels micro mist in the embodiment of the present invention 1.
Scanning electron microscope diagram of the Fig. 2 by obtaining polyimide aerogels micro mist in the embodiment of the present invention 2.
Scanning electron microscope diagram of the Fig. 3 by obtaining polyimide aerogels micro mist in the embodiment of the present invention 3.
Scanning electron microscope diagram of the Fig. 4 by obtaining polyimide aerogels micro mist in the embodiment of the present invention 4.
Scanning electron microscope diagram of the Fig. 5 by obtaining polyimide aerogels micro mist in the embodiment of the present invention 5.
Scanning electron microscope diagram of the Fig. 6 by obtaining polyimide aerogels micro mist in the embodiment of the present invention 6.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution.Further detailed description is done to the present invention with reference to the accompanying drawings and examples:
A kind of preparation method of the linear polyimide aerogels micro mist of silica enhancing, comprising the following steps:
Step (1), by methyl vinyl ether-maleic acid copolymer, 3-aminopropyltriethoxysilane and aromatic series
Diamines dissolves respectively obtains methyl vinyl ether-maleic acid copolymer solution, 3- aminopropyl triethoxysilicane in a solvent
Alkane solution and aromatic diamine solution；
Step (2), by the methyl vinyl ether-maleic acid copolymer solution, 3-aminopropyltriethoxysilane
Solution and aromatic diamine solution stand after being stirred by a certain percentage and form gel, then the soak of formation is being dehydrated
The sub- amidation of chemistry is carried out in agent, obtains sub- amidation gel；
The sub- amidation gel is obtained silica nano particle through crushing, solvent displacement, drying process by step (3)
The linear polyimide aerogels micro mist of enhancing.
Wherein, the preferred p-phenylenediamine of step (1) aromatic diamine, m-phenylene diamine (MPD), 4,4 '-benzidines, 4,4'-
Methylene dianiline (MDA), any one in 4,4'- diaminodiphenyl ethers or two or more combinations；Step (1) the methyl second
Alkene ether-copolymer-maleic anhydride number-average molecular weight preferred 50000-200000, more preferable 80000；Step (1) described solvent is excellent
Select at least one of N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide or N-Methyl pyrrolidone；
In an alternative embodiment, the concentration of methyl vinyl ether-maleic acid copolymer solution described in step (1) is
0.1~0.3g/cm3, 3-aminopropyltriethoxysilane solution concentration be 0.01~0.2g/cm3, aromatic diamine solution it is dense
Degree is 0.05~0.2g/cm3, methyl vinyl ether-maleic acid copolymer solution described in step (2), 3- aminopropyl three
The volume ratio of Ethoxysilane solution and aromatic diamine solution is 100:4~6:25~35.Under the reaction conditions, 3- ammonia
Base propyl-triethoxysilicane is reacted with the dilute base ether-copolymer-maleic anhydride of methyl second generates alkoxysilane-modified functionality
High molecular polymer, for further hydrolytic condensation at the dual network system of molecule rank, macromolecule network is direct with silica network
By chemical bonds, the two interface is eliminated, intensity greatly improves.
It in an alternative embodiment, is stood at 0~80 DEG C in step (2) and forms gel, the dehydrating agent is pyridine, three
Ethamine, acetic anhydride, picoline, chloroacetic chloride, thionyl chloride, the halide of phosphorus or in Dicyclohexylcarbodiimide at least one
Kind.
In an alternative embodiment, crushing described in step (3) includes: first to squeeze under 20-50 DEG C, 0.5-3MPa pressure
Then 1-5h stirs 2~4h with the revolving speed of 800-3000 turns/min, obtains wet gel micro mist.Inventor is of the invention in realization
Long-term a large amount of experimental study has been carried out in the process, and research is found when being crushed under this condition, both can be to avoid extruding
Pressure is too small, granularity caused by excessively slow etc. factors of mixing speed is irregular and big, and is avoided that since squeeze pressure is uncomfortable or stirs
Mix the breakage that the factors such as excessive velocities cause gel internal structure, it is ensured that obtain high-quality aeroge.
Specifically, the displacement of solvent described in step (3) includes: to replace smashed gel with methanol, ethyl alcohol or acetone, is set
Change number no less than twice；Drying means described in step (3) using carbon dioxide, ethyl alcohol or methanol as supercritical fluid,
It is 40-250 DEG C in temperature, carries out supercritical drying, drying time 2-10h under conditions of pressure >=8MPa.
The silica enhancing polyimide aerogels being prepared the embodiment of the invention also provides above-mentioned preparation method are micro-
Powder, it is brown, there is organic and inorganic dual network structure, density is 0.03~0.3g/cm3, specific surface area be 200~600m2/g。
The following are several specific embodiments of the invention, and the raw materials used embodiment of the present invention is commercial product:
Wherein, methyl vinyl ether-maleic acid copolymer number-average molecular weight used in Examples 1 to 6 is 80000；
Embodiment 1
(1) configuration of monomer solution: 10g methyl vinyl ether-maleic acid copolymer, 1g 3- aminopropyl are taken respectively
Triethoxysilane, 5g p-phenylenediamine, and be dissolved in 100ml N-Methyl pyrrolidone respectively, being configured to concentration is respectively
0.1,0.01,0.05g/cm3Solution.
(2) synthesis of gel: taking above-mentioned solution 100,5 and 30ml respectively, is uniformly mixed, in 0 DEG C of formation gel, then will coagulate
Glue is soaked in the mixed solution of pyridine and acetic anhydride (volume ratio 1:1) and is dehydrated.
(3) preparation of polyimide aerogels micro mist --- it crushes, solvent displacement is with drying: by above-mentioned dewatered gel
(sub- amidation gel) first squeezes 3h under 30 DEG C, 2MPa pressure, then stirs 3h with the revolving speed of 1000 turns/min, obtains wet solidifying
Glue micro mist, the methanol for being then soaked in 2 times of volumes carry out solvent displacement, change a methanol within every 5 hours, replaces 3 times altogether.It will displacement
Gel afterwards is 10 hours dry in 40 DEG C, the supercritical carbon dioxide of 10MPa, and the oxygen that average grain diameter is 9.8um is prepared
The linear polyimide aerogels micro mist of SiClx enhancing.It is characterized through BET isothermal adsorption, SEM etc., the polyimide aerogels micro mist
With nano-porous structure, the scanning electron micrograph of this polyimide aerogels micro mist is referring to Fig. 1, other physical parameters
Such as specific surface area, density refer to table 1.
Embodiment 2
(1) configuration of monomer solution: 30g methyl vinyl ether-maleic acid copolymer, 5g 3- aminopropyl are taken respectively
Triethoxysilane, 20g p-phenylenediamine, and be dissolved in 100ml n,N-dimethylacetamide respectively, it is configured to concentration difference
It is 0.3,0.05,0.2g/cm3Solution.
(2) synthesis of gel: taking above-mentioned solution 100,5 and 30ml respectively, is uniformly mixed, in 40 DEG C of formation gels, then will
Soak is dehydrated in the mixed solution of triethylamine and acetic anhydride (volume ratio 1:1).
(3) preparation of polyimide aerogels micro mist --- it crushes, solvent displacement is with drying: by above-mentioned dewatered gel
1h first is squeezed under 50 DEG C, 3MPa pressure, 2h is then stirred with the revolving speed of 2000 turns/min, wet gel micro mist is obtained, then soaks
The ethyl alcohol steeped in 2 times of volumes carries out solvent displacement, changes an ethyl alcohol within every 10 hours, replaces 3 times altogether.By the gel after displacement 45
DEG C, 10 hours dry in the supercritical carbon dioxide of 8MPa, it is the linear of 64.6um silica enhancing that average grain diameter, which is prepared,
Polyimide aerogels micro mist.It is characterized through BET isothermal adsorption, SEM etc., which has nanoporous knot
Structure, the scanning electron micrograph of this polyimide aerogels micro mist is referring to Fig. 2, other physical parameters such as specific surface area, close
Degree etc. refers to table 1.
Embodiment 3
(1) configuration of monomer solution: 30g methyl vinyl ether-maleic acid copolymer, 10g 3- aminopropyl are taken respectively
Triethoxysilane, 15g p-phenylenediamine, and be dissolved in 100ml dimethyl sulfoxide respectively, being configured to concentration is respectively 0.3,
0.1,0.15g/cm3Solution.
(2) synthesis of gel: taking above-mentioned solution 100,5 and 30ml respectively, is uniformly mixed, in 40 DEG C of formation gels, then will
Soak is dehydrated in chloroacetic chloride.
(3) preparation of polyimide aerogels micro mist --- it crushes, solvent displacement is with drying: by above-mentioned dewatered gel
3h first is squeezed under 30 DEG C, 2MPa pressure, 3h is then stirred with the revolving speed of 1000 turns/min, obtains wet gel micro mist, is then soaked
The ethyl alcohol steeped in 1 times of volume carries out solvent displacement, changes an ethyl alcohol within every 9 hours, replaces 3 times altogether.By the gel after displacement 245
DEG C, it is 10 hours dry in the Supercritical Ethanol of 9MPa, the linear poly- of the silica enhancing that average grain diameter is 86.8um is prepared
Acid imide aeroge micro mist.It is characterized through BET isothermal adsorption, SEM etc., which has nanoporous knot
Structure, the scanning electron micrograph of this polyimide aerogels micro mist is referring to Fig. 3, other physical parameters such as specific surface area, close
Degree etc. refers to table 1.
Embodiment 4
(1) configuration of monomer solution: 30g methyl vinyl ether-maleic acid copolymer, 20g 3- aminopropyl are taken respectively
Triethoxysilane, 10g p-phenylenediamine, and be dissolved in 100ml dimethyl sulfoxide respectively, being configured to concentration is respectively 0.3,
0.2,0.1g/cm3Solution.
(2) synthesis of gel: taking above-mentioned solution 100,5 and 30ml respectively, is uniformly mixed, in 60 DEG C of formation gels, then will
Soak is dehydrated in the mixed solution of picoline and acetic anhydride (1:1).
(3) preparation of polyimide aerogels micro mist --- it crushes, solvent displacement is with drying: by above-mentioned dewatered gel
3h first is squeezed under 30 DEG C, 2MPa pressure, 3h is then stirred with the revolving speed of 1000 turns/min, wet gel micro mist is obtained, then soaks
The acetone steeped in 1 times of volume carries out solvent displacement, changes an acetone for every eight hours, replaces 3 times altogether.By the gel after displacement 42
DEG C, it is 10 hours dry in the supercritical carbon dioxide of 9MPa, the line that the silica that average grain diameter is 164.4um enhances is prepared
Shape polyimide aerogels micro mist.It is characterized through BET isothermal adsorption, SEM etc., which has nanoporous
Structure, the scanning electron micrograph of this polyimide aerogels micro mist referring to Fig. 4, other physical parameters such as specific surface area,
Density etc. refers to table 1.
Embodiment 5
(1) configuration of monomer solution: 30g methyl vinyl ether-maleic acid copolymer, 20g 3- aminopropyl are taken respectively
Triethoxysilane, 20g p-phenylenediamine, and be dissolved in 100ml N-Methyl pyrrolidone respectively, being configured to concentration is respectively
0.3,0.2,0.2g/cm3Solution.
(2) synthesis of gel: taking above-mentioned solution 100,5 and 30ml respectively, is uniformly mixed, in 80 DEG C of formation gels, then will
Soak is dehydrated in Dicyclohexylcarbodiimide.
(3) preparation of polyimide aerogels micro mist --- it crushes, solvent displacement is with drying: by above-mentioned dewatered gel
3h first is squeezed under 30 DEG C, 2MPa pressure, 3h is then stirred with the revolving speed of 1000 turns/min, obtains wet gel micro mist, then impregnate
Solvent displacement is carried out in the methanol of 1 times of volume, a methanol is changed for every eight hours, replaces 3 times altogether.By the gel after displacement 245
DEG C, it is 10 hours dry in the supercritical methanol under 9MPa, the linear of the silica enhancing that average grain diameter is 200.5um is prepared
Polyimide aerogels micro mist.It is characterized through BET isothermal adsorption, SEM etc., which has nanoporous knot
Structure, the scanning electron micrograph of this polyimide aerogels micro mist is referring to Fig. 5, other physical parameters such as specific surface area, close
Degree etc. refers to table 1.
Embodiment 6
(1) configuration of monomer solution: 20g methyl vinyl ether-maleic acid copolymer, 10g 3- aminopropyl are taken respectively
Triethoxysilane, 10g p-phenylenediamine, and be dissolved in 100ml N-Methyl pyrrolidone respectively, being configured to concentration is respectively
0.2,0.1,0.1g/cm3Solution.
(2) synthesis of gel: taking above-mentioned solution 100,5 and 30ml respectively, is uniformly mixed, in 70 DEG C of formation gels, then will
Soak is dehydrated in thionyl chloride.
(3) preparation of polyimide aerogels micro mist --- it crushes, solvent displacement is with drying: by above-mentioned dewatered gel
3h first is squeezed under 30 DEG C, 2MPa pressure, 3h is then stirred with the revolving speed of 1000 turns/min, wet gel micro mist is obtained, is immersed in 1
The methanol of times volume carries out solvent displacement, changes a methanol for every eight hours, replaces 3 times altogether.By the gel after displacement at 40 DEG C,
It is 10 hours dry in supercritical carbon dioxide under 10MPa, the line that the silica that average grain diameter is 268.6um enhances is prepared
Shape polyimide aerogels micro mist.It is characterized through BET isothermal adsorption, SEM etc., which has nanoporous
Structure, the scanning electron micrograph of this polyimide aerogels micro mist referring to Fig. 6, other physical parameters such as specific surface area,
Density etc. refers to table 1.
Embodiment 7
Preparation method and embodiment 3 are consistent, unique the difference is that methyl vinyl ether-maleic acid used in embodiment 7 is total
Polymers number-average molecular weight is 50000；Gained silica enhancing linear polyimide aerogels micro mist average grain diameter be
156.4um.Other physical parameters such as specific surface area, density etc. refer to table 1.
Embodiment 8
Preparation method and embodiment 3 are consistent, unique the difference is that methyl vinyl ether-maleic acid used in embodiment 7 is total
Polymers number-average molecular weight is 150000.Gained silica enhancing linear polyimide aerogels micro mist average grain diameter be
298.4um.Other physical parameters such as specific surface area, density etc. refer to table 1.
The structure and performance parameters of the polyimide aerogels micro mist of obtained silica enhancing in 1 embodiment 1-8 of table
The above, a specific embodiment only of the invention, but scope of protection of the present invention is not limited thereto, appoints
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of, all by what those familiar with the art
It is covered by the protection scope of the present invention.
Unspecified part of the present invention belongs to common sense well known to those skilled in the art.
Claims (10)
1. a kind of preparation method of silica enhancing polyimide aerogels micro mist, it is characterised in that the following steps are included:
Step (1), by methyl vinyl ether-maleic acid copolymer, 3-aminopropyltriethoxysilane and aromatic diamine
Dissolve that obtain methyl vinyl ether-maleic acid copolymer solution, 3-aminopropyltriethoxysilane in a solvent molten respectively
Liquid and aromatic diamine solution；
Step (2), by the methyl vinyl ether-maleic acid copolymer solution, 3-aminopropyltriethoxysilane solution
It is stood after being stirred by a certain percentage with aromatic diamine solution and forms gel, then by the soak of formation in dehydrating agent
The sub- amidation of chemistry is carried out, sub- amidation gel is obtained；
The sub- amidation gel is obtained silica nano particle enhancing through crushing, solvent displacement, drying process by step (3)
Linear polyimide aerogels micro mist.
2. the preparation method of silica enhancing polyimide aerogels micro mist according to claim 1, which is characterized in that step
Suddenly (1) described aromatic diamine includes p-phenylenediamine, m-phenylene diamine (MPD), 4,4 '-benzidines, 4,4'- methylene dianiline (MDA), 4,
Any one in 4'- diaminodiphenyl ether or two or more combinations.
3. the preparation method of silica enhancing polyimide aerogels micro mist according to claim 1, which is characterized in that step
Suddenly (1) described methyl vinyl ether-maleic acid copolymer number-average molecular weight is 50000-200000.
4. the preparation method of silica enhancing polyimide aerogels micro mist according to claim 1, which is characterized in that step
Suddenly (1) described solvent includes N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide or N-Methyl pyrrolidone
At least one of.
5. the preparation method of silica enhancing polyimide aerogels micro mist according to claim 1, which is characterized in that step
Suddenly the concentration of methyl vinyl ether-maleic acid copolymer solution described in (1) is 0.1~0.3g/cm3, 3- aminopropyl three
Ethoxysilane solution concentration is 0.01~0.2g/cm3, aromatic diamine solution concentration be 0.05~0.2g/cm3, step (2)
Described in methyl vinyl ether-maleic acid copolymer solution, 3-aminopropyltriethoxysilane solution and aromatic diamine
The volume ratio of solution is 100:4~6:25~35.
6. the preparation method of silica enhancing polyimide aerogels micro mist according to claim 1, which is characterized in that step
Suddenly it is stood at 0~80 DEG C in (2) and forms gel, the dehydrating agent is pyridine, triethylamine, acetic anhydride, picoline, acetyl
At least one of chlorine, thionyl chloride, the halide of phosphorus or Dicyclohexylcarbodiimide.
7. the preparation method of silica enhancing polyimide aerogels micro mist according to claim 1, which is characterized in that step
Suddenly crushing described in (3) includes: first to squeeze 1-5h under 20-50 DEG C, 0.5-3MPa pressure, then with 800-3000 turns/min's
Revolving speed stirs 2~4h, obtains wet gel micro mist.
8. the preparation method of silica enhancing polyimide aerogels micro mist according to claim 1, which is characterized in that step
Suddenly the displacement of solvent described in (3) includes: to replace smashed gel with methanol, ethyl alcohol or acetone, and displacement number is no less than twice.
9. the preparation method of silica enhancing polyimide aerogels micro mist according to claim 1, which is characterized in that step
Suddenly drying means described in (3) is 40-250 DEG C in temperature using carbon dioxide, ethyl alcohol or methanol as supercritical fluid, pressure
Supercritical drying, drying time 2-10h are carried out under conditions of power >=8MPa.
10. polyimide aerogels micro mist is enhanced by the silica that the preparation method of any one of claim 1~9 is prepared,
It is characterized in that, brown, there is organic and inorganic dual network structure, density is 0.03~0.3g/cm3, specific surface area 200
~600m2/g。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910708254.1A CN110483994B (en) | 2019-08-01 | 2019-08-01 | Silicon oxide reinforced polyimide aerogel micro powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910708254.1A CN110483994B (en) | 2019-08-01 | 2019-08-01 | Silicon oxide reinforced polyimide aerogel micro powder and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110483994A true CN110483994A (en) | 2019-11-22 |
| CN110483994B CN110483994B (en) | 2022-01-04 |
Family
ID=68549076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910708254.1A Active CN110483994B (en) | 2019-08-01 | 2019-08-01 | Silicon oxide reinforced polyimide aerogel micro powder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110483994B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4623578A (en) * | 1985-04-04 | 1986-11-18 | Westinghouse Electric Corp. | Epoxy crosslinked copolymers of polyanhydrides and laminates therefrom |
| JP2003335858A (en) * | 2002-03-11 | 2003-11-28 | Sumitomo Bakelite Co Ltd | Polyimide resin |
| US20140272358A1 (en) * | 2013-03-14 | 2014-09-18 | Ohio Aerospace Institute | Porous cross-linked polyimide-urea networks |
| CN104211881A (en) * | 2013-06-03 | 2014-12-17 | 联茂电子股份有限公司 | Organic-inorganic hybrid material film and making method thereof |
| US20150038039A1 (en) * | 2013-08-01 | 2015-02-05 | Iteq Corporation | Organic-inorganic hybrid material film and method for manufacturing the same |
| CN104341594A (en) * | 2014-10-20 | 2015-02-11 | 同济大学 | Preparation method of crosslinked polyimide silicon dioxide mixed gas gel |
| CN104693477A (en) * | 2015-03-30 | 2015-06-10 | 上海大音希声新型材料有限公司 | Preparation method for crosslinking type polyimide aerogel |
| CN108384047A (en) * | 2018-03-13 | 2018-08-10 | 航天材料及工艺研究所 | A kind of transparent, High Strength Polyimide aeroge and preparation method thereof |
| CN108794766A (en) * | 2017-05-05 | 2018-11-13 | 航天特种材料及工艺技术研究所 | A kind of crosslinked polyimide aeroge and preparation method |
-
2019
- 2019-08-01 CN CN201910708254.1A patent/CN110483994B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4623578A (en) * | 1985-04-04 | 1986-11-18 | Westinghouse Electric Corp. | Epoxy crosslinked copolymers of polyanhydrides and laminates therefrom |
| JP2003335858A (en) * | 2002-03-11 | 2003-11-28 | Sumitomo Bakelite Co Ltd | Polyimide resin |
| US20140272358A1 (en) * | 2013-03-14 | 2014-09-18 | Ohio Aerospace Institute | Porous cross-linked polyimide-urea networks |
| CN104211881A (en) * | 2013-06-03 | 2014-12-17 | 联茂电子股份有限公司 | Organic-inorganic hybrid material film and making method thereof |
| US20150038039A1 (en) * | 2013-08-01 | 2015-02-05 | Iteq Corporation | Organic-inorganic hybrid material film and method for manufacturing the same |
| CN104341594A (en) * | 2014-10-20 | 2015-02-11 | 同济大学 | Preparation method of crosslinked polyimide silicon dioxide mixed gas gel |
| CN104693477A (en) * | 2015-03-30 | 2015-06-10 | 上海大音希声新型材料有限公司 | Preparation method for crosslinking type polyimide aerogel |
| CN108794766A (en) * | 2017-05-05 | 2018-11-13 | 航天特种材料及工艺技术研究所 | A kind of crosslinked polyimide aeroge and preparation method |
| CN108384047A (en) * | 2018-03-13 | 2018-08-10 | 航天材料及工艺研究所 | A kind of transparent, High Strength Polyimide aeroge and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| HAIQUAN GUO ET AL.: "Poly(maleic anhydride) cross-linked polyimide aerogels: synthesis and properties", 《RSC ADVANCES》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110483994B (en) | 2022-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110437492A (en) | A kind of polyimide aerogels and the preparation method and application thereof with petal effect | |
| CN105110313B (en) | A kind of polyimide-based compound carbon aerogels and preparation method thereof | |
| CN104772048B (en) | Inorganic-organic hybrid film that a kind of inorganic filler is combined with dopamine and its production and use | |
| CN106987019A (en) | A kind of polyimide aerogels of functionalisation of surfaces nano-particle crosslinking and preparation method thereof | |
| CN104693477A (en) | Preparation method for crosslinking type polyimide aerogel | |
| Qiao et al. | Facile strategy to prepare polyimide nanofiber assembled aerogel for effective airborne particles filtration | |
| Ding et al. | Flexible, Mechanically Stable, Porous Self‐Standing Microfiber Network Membranes of Covalent Organic Frameworks: Preparation Method and Characterization | |
| CN106633171B (en) | Preparation method of amino phenyl silsesquioxane crosslinked polyimide aerogel material | |
| Wang et al. | Fabrication of porous polyacrylamide/polystyrene fibrous membranes for efficient oil-water separation | |
| Wu et al. | Solution-processable polyimide aerogels with high hydrophobicity | |
| CN104906966A (en) | Cellulose acetate/functionalized graphene mixed media hollow fiber positive osmotic membrane | |
| CN102153102A (en) | Polyimide reinforced clay aerogel material and preparation method thereof | |
| CN103469362A (en) | Porous polyethyleneimine and chitosan blend fiber and preparation method and applications thereof | |
| CN113388150B (en) | Method for preparing aerogel containing para-aramid nanofibers, aerogel containing para-aramid nanofibers | |
| CN109251412A (en) | A kind of super-hydrophobic composite microporous foam of polytetrafluoroethylene (PTFE)/high molecular material and preparation method thereof | |
| CN104031386B (en) | A kind of composite aerogel and preparation method thereof | |
| Feng et al. | Polyamide-imide reinforced polytetrafluoroethylene nanofiber membranes with enhanced mechanical properties and thermal stabilities | |
| CN104446304A (en) | Aerogel composite material with multi-scale and multi-network composite structure and preparation method of aerogel composite material | |
| CN105968354A (en) | Preparation method of polyimide aerogel for CO2 adsorption | |
| CN112500565B (en) | Preparation method of functional cross-linked polyimide aerogel heat-insulating material | |
| CN110437470B (en) | Polyimide aerogel with lotus leaf effect and preparation method and application thereof | |
| Zu et al. | Transparent, ultraflexible, and superinsulating nanofibrous biocomposite aerogels via ambient pressure drying | |
| CN108298519A (en) | A kind of preparation method using the enhanced charcoal-aero gel of Ludox | |
| CN104028121B (en) | Sulfonated polyether-ether-ketone-amido modified titanium nanotube hybridized film and preparation and application | |
| Arumugham et al. | PFOM fillers embedded PVDF/cellulose dual-layered membranes with hydrophobic–hydrophilic channels for desalination via direct contact membrane distillation process |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |