CN106916304A - Silicon dioxide microparticle, the constituent for forming polyimide aerogels, polyimide aerogels and its manufacture method, composite - Google Patents
Silicon dioxide microparticle, the constituent for forming polyimide aerogels, polyimide aerogels and its manufacture method, composite Download PDFInfo
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- 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
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Abstract
Constituent, polyimide aerogels and its manufacture method, composite that the present invention provides a kind of silicon dioxide microparticle, forms polyimide aerogels, the silicon dioxide microparticle containing amino is that the alkoxy silane as shown in formula (I) is obtained in the presence of catalyst with the alkoxy silane shown in formula (II) through hydrolysis-condensation reaction, wherein in formula (I), R1It is the alkyl that carbon number is 1 to 10, and in formula (II), Y is the alkyl that carbon number is 1 to 10 or the alkenyl that carbon number is 2 to 10, R2It is the alkyl that carbon number is 1 to 10, m is 1 to 3 integer.The present invention makes polyimide aerogels have the characteristics such as high porosity, well insulated, good flexibility, anti-flammability, uv-resistance, endurance and low-k, without the use of low-surface-energy solvent and Co 2 supercritical fluids such as n-hexane, pentanes in processing procedure, and it is suitably applied in composite.Si(OR1)4Formula (I)；(NH2-Y)m-Si(OR2)4-mFormula (II).
Description
Technical field
It is the present invention relates to a kind of silicon dioxide microparticle and sub- using polyamides prepared by the silicon dioxide microparticle
Amine aeroge, more particularly to a kind of silicon dioxide microparticle containing amino, the group of formation polyimide aerogels
Into thing, polyimide aerogels and its manufacture method, composite.
Background technology
Aeroge is the distinct solids with high porosity.Porosity high causes that aeroge has surface high
The characteristic of product, low-refraction, low-k, loss coefficient low in calories and bass speed transmitting medium etc..
Therefore, aeroge has a wide range of applications in fields such as integrated circuit, energy-conservation, aviations.
In the method for conventionally manufactured aeroge, in order to avoid loose structure is collapsed in drying process, lead to
Often need to use the low-surface-energy such as n-hexane, pentane solvent to carry out solvent displacement or use carbon dioxide
Supercritical fluid carries out solvent displacement and/or drying.However, the low-surface-energy solvent is because of tool nerve high
Toxicity and harmfulness is high, and using Co 2 supercritical fluid carry out solvent displacement and/or drying need height
Compacting journey, thereby not only power consumption also needs to the equipment of the tolerable postcritical special device of investment etc. and causes
It is more expensive to manufacture, is also required to put into substantial amounts of manpower and time in addition.
The content of the invention
In consideration of it, the present invention a kind of silicon dioxide microparticle is provided, the constituent that forms polyimide aerogels,
Polyimide aerogels and its manufacture method, composite, not only make polyimide aerogels have hole high
Gap rate, well insulated, good flexibility, anti-flammability, uv-resistance, endurance and low dielectric system
The characteristics such as number, also face in processing procedure without the use of the low-surface-energy solvents such as n-hexane, pentane and carbon dioxide are super
Boundary's fluid, and be suitably applied in composite.
Silicon dioxide microparticle containing amino of the invention is the alkoxy silane and formula (II) institute as shown in formula (I)
The alkoxy silane for showing is obtained in the presence of catalyst through hydrolysis-condensation reaction：
Si(OR1)4Formula (I),
(NH2-Y)m-Si(OR2)4-mFormula (II),
Wherein in formula (I), R1It is the alkyl that carbon number is 1 to 10, and in formula (II), Y is that carbon number is 1
To 10 alkyl or carbon number be 2 to 10 alkenyl, R2Be the alkyl that carbon number is 1 to 10, m be 1 to 3 it is whole
Number.
In one embodiment of the present invention, the amino in the above-mentioned silicon dioxide microparticle containing amino work as
Amount number is 5mmol/g to 10mmol/g.
In one embodiment of the present invention, the alkoxy silane shown in above-mentioned formula (I) includes tetraethoxy
Silane, and alkoxy silane shown in formula (II) includes APTES.
The constituent for being used to be formed polyimide aerogels of the invention includes diamine monomer, tetracarboxylic dianhydride
Monomer, foregoing silicon dioxide microparticle and solvent containing amino.Diamine monomer and tetracarboxylic dianhydride
The mol ratio of monomer is 1：1 to 1：1.5.To be used to be formed the gross weight of the constituent of polyimide aerogels
Gauge, the percentage by weight of the silicon dioxide microparticle containing amino is 10wt% to 40wt%.
In one embodiment of the present invention, the above-mentioned constituent for being used to be formed polyimide aerogels
Solid content is 5wt% to 20wt%.
In one embodiment of the present invention, above-mentioned diamine monomer is 4,4 '-diamino-diphenyl ether
(ODA), 3,3 '-dimethyl diphenyl diamines (DMB), p-phenylenediamine (p-PDA), m-phenylene diamine (MPD)
(m-PDA), double [4- (4- the aminophenoxy phenyls)] propane (BAPP) of 2,2'- or the (trifluoros of 2,2- bis-
Methyl) benzidine (TFMB), and above-mentioned tetracarboxylic dianhydride's monomer is 3,3 ', 4,4 '-biphenyl
Tetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride
(BTDA), diphenyl ether tetraformic dianhydride (ODPA) or hexafluorodianhydride (6FDA) (6FDA).
In one embodiment of the present invention, above-mentioned solvent is selected from 1-METHYLPYRROLIDONE, dimethyl second
At least one of acid amides, dimethylformamide, tetrahydrofuran and phenol.
The manufacture method of polyimide aerogels of the invention is comprised the following steps.By diamine monomer, tetracarboxylic acid
Acid dianhydride monomer is well mixed with the silicon dioxide microparticle containing amino in solvent, foregoing to obtain
It is used to be formed the constituent of polyimide aerogels.Entered using the constituent for forming polyimide aerogels
Row condensation polymerization and cyclization, to form wet gel.Wet gel is entered with the mixed liquor of water using acetone
Row Solvent exchange drying.To being dried treatment through the wet gel after Solvent exchange drying.
In one embodiment of the present invention, in the mixed liquor of above-mentioned acetone and water, acetone and water
Volume ratio is 10：90 to 90：10.
In one embodiment of the present invention, the manufacture method of above-mentioned polyimide aerogels is additionally included in
Before carrying out Solvent exchange drying, crosslinking agent is added in wet gel, wherein with the gross weight meter of wet gel,
The addition of crosslinking agent is 1wt% to 10wt%.
In one embodiment of the present invention, above-mentioned crosslinking agent is diisocyanate system crosslinking agent, diamines
Crosslinking agent, three amine crosslinkers or glycol system crosslinking agent.
In one embodiment of the present invention, the manufacture method of above-mentioned polyimide aerogels is also included in
Surfactant is added in acetone and the mixed liquor of water, wherein with acetone and the gross weight meter of the mixed liquor of water,
The addition of surfactant is 0.01wt% to 1wt%.
In one embodiment of the present invention, above-mentioned surfactant is fluorine system surfactant.
Polyimide aerogels of the invention are made by the manufacture method of foregoing polyimide aerogels
Make.
In one embodiment of the present invention, the porosity of above-mentioned polyimide aerogels is 85% to 95
%.
In one embodiment of the present invention, the thickness of above-mentioned polyimide aerogels is 0.1mm to 1
mm。
Composite containing polyimide aerogels of the invention includes fabric and foregoing polyamides
Imines aeroge, wherein fabric are mutually combined with polyimide aerogels.
Based on above-mentioned, in the present invention, by using including the diamines list with special ratios relation extents
Body and tetracarboxylic dianhydride's monomer, and the alkoxy silane as shown in formula (I) with certain content scope with
The constituent of the silicon dioxide microparticle containing amino prepared by alkoxy silane shown in formula (II) manufactures polyamides
Imines aeroge, is not only without the use of to low-surface-energy solvent and titanium dioxides such as n-hexane, pentanes in processing procedure
Carbon supercritical fluid, and polyimide aerogels have high porosity, well insulated, good deflection
The characteristic such as property, anti-flammability, uv-resistance, endurance and low-k
It is that features described above of the invention and advantage can be become apparent, implementation method cited below particularly is specifically
It is bright as follows.
Specific embodiment
Herein, the scope for being represented by " numerical value to another numerical value ", is that one kind is avoided in the description
Enumerate the summary representation of all numerical value in the scope.Therefore, a certain special value scope
Record, cover any number in the number range and defined by any number in the number range
The relatively fractional value scope for going out, as write out any number in plain text in the description and being somebody's turn to do compared with fractional value scope
Equally.
In order to prepare with molten without the use of low-surface-energies such as n-hexane, pentanes in good physical property, processing procedure
Agent and Co 2 supercritical fluid and the polyimide aerogels of composite are suitably applied, the present invention
Propose a kind of silicon dioxide microparticle containing amino, including the silicon dioxide microparticle containing amino to shape
Into the constituent of polyimide aerogels, and by the constituent for being used to form polyimide aerogels
Obtained polyimide aerogels can reach above-mentioned advantage.Hereinafter, this hair is described in detail especially exemplified by implementation method
The bright silicon dioxide microparticle containing amino, it is used to form the constituent of polyimide aerogels, polyimides
Aeroge and its manufacture method and the composite containing polyimide aerogels, as the present invention
The example that can actually implement according to this.
[silicon dioxide microparticle containing amino]
The silicon dioxide microparticle containing amino of one embodiment of the present invention is the alkoxyl silicone as shown in formula (I)
Alkane is obtained in the presence of catalyst with the alkoxy silane shown in formula (II) through hydrolysis-condensation reaction：
Si(OR1)4Formula (I),
(NH2-Y)m-Si(OR2)4-mFormula (II).
In formula (I), R1It is the alkyl that carbon number is 1 to 10.Specifically, the alkoxyl silicone shown in formula (I)
The example of alkane is for example but not limited to：Tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane or
Four butoxy silanes.The example of the alkoxy silane shown in formula (I) is preferably tetraethoxysilane.
In formula (II), Y is for alkyl that carbon number is 1 to 10 or be alkenyl that carbon number is 2 to 10；R2
It is the alkyl that carbon number is 1 to 10；And the integer that m is 1 to 3.Specifically, shown in formula (II)
The example of alkoxy silane is for example but not limited to：3- TSL 8330s, 3- aminopropyls three
Ethoxysilane, 3- aminoethylaminopropyls trimethoxy silane or 3- aminoethylaminopropyl triethoxysilanes.
The example of the alkoxy silane shown in formula (II) is preferably APTES.
Catalyst is, for example, acid catalyst or base catalyst.Specifically, acid catalyst is included but is not limited to：
The inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid, chloric acid, chlorous acid, hypochlorous acid；Or
Person, acetic acid, formic acid, propionic acid, ethanedioic acid, malonic acid, succinic acid, citric acid, malic acid, oneself two
The organic carboxyl acid class such as acid, azelaic acid.Base catalyst is included but is not limited to：Lithium hydroxide, NaOH,
The alkali metal hydroxides such as potassium hydroxide；The ammonium compounds such as ammonium hydroxide, ammonium chloride, ammonium bromide；Inclined phosphorus
The alkaline phosphatase sodium salt such as sour sodium, sodium pyrophosphate, sodium polyphosphate；Allyl amine, diallylamine, triolefin
Propyl group amine, isopropylamine, diisopropylamine, ethylamine, diethylamide, triethylamine, 2- ethyl hexyls
Base amine, 3- ethoxycarbonyl propyls amine, diisobutyl amine, 3- (diethylamino) propyl group amine, two -2- ethylhexyls
Amine, 3- (dibutylamino) propyl group amine, tetramethylethylenediamine, tri-butylamine, the second butylamine, propyl group
Amine, 3- (methylamino) propyl group amine, 3- (dimethylamino) propyl group amine, 3- Methoxyamines, dimethyl ethanol
The aliphatic amine such as amine, methyl diethanolamine, diethanol amine, triethanolamine；Or, morpholine, N- first
Base morpholine, 2- methyl morpholines, piperazine and its derivative, piperidines and its derivative, imidazole and its derivants
Deng nitrogen-containing hetero ring-type compounds.In addition, the usage amount of catalyst is, for example, regarding above-mentioned hydrolysis-condensation reaction
PH value depending on, wherein acid catalyst is for example adapted for for reaction condition being adjusted to pH=2~4, and alkali is urged
Agent is for example adapted for for reaction condition being adjusted to pH=10~12.
In addition, the hydrolysis-condensation reaction is to carry out in a solvent, and it is used in usable art
Carried out with technological means.For example, the method for condensation reaction of being hydrolyzed is comprised the following steps：It is first
First, at 25 DEG C to 35 DEG C, by the alkoxy silane shown in formula (I), the alkoxy silane shown in formula (II)
It is dissolved in solvent.Then, at 25 DEG C to 35 DEG C, stir while adding catalyst, and stir
Mix reaction 3 hours to 5 hours.In addition, after the completion of hydrolysis-condensation reaction, can further be done
Dry treatment, to remove solvent.The method of dried process is, for example, using heating plate or heated air circulation type baking oven
Heated, wherein temperature conditionss are, for example, 60 DEG C to 80 DEG C, and time conditions be, for example, 3 hours extremely
5 hours.
There is no particular restriction for above-mentioned solvent, as long as the alkoxy silane shown in formula (I), formula (II) institute can be dissolved
The alkoxy silane for showing and catalyst.Specifically, in the present embodiment, solvent include but not
It is limited to：Water；The alcohols such as methyl alcohol, ethanol, normal propyl alcohol, 2- propyl alcohol, n-butanol, 2- butanol, the 3rd butanol
Solvent；Dimethylacetamide amine solvent；Or, N- methylpyrrole ketone solvents.In addition, solvent can be single
Solely or be used in mixed way.
In addition, optionally, pH adjuster can be added to adjust the pH of solution, with sharp hydrolytic condensation
Reaction is carried out.PH adjuster is for example including the acid such as the buffer such as boric acid or phosphoric acid, hydrochloric acid or sulfuric acid, hydrogen
The alkali such as sodium oxide molybdena or potassium hydroxide.
In addition, in the present embodiment, the equivalents of the amino in the silicon dioxide microparticle containing amino is 5
Mmol/g to 10mmol/g, preferably 6mmol/g to 8mmol/g.Specifically, if containing amino
The equivalents of the amino in silicon dioxide microparticle is less than 5mmol/g, then cross-linking reaction can be incomplete；And
If the equivalents of the amino in the silicon dioxide microparticle containing amino be higher than 10mmol/g, because excess and caused by
Reagent waste.
[being used to be formed the constituent of polyimide aerogels]
The constituent for being used to be formed polyimide aerogels of one embodiment of the present invention includes diamines list
Silicon dioxide microparticle containing amino in body, tetracarboxylic dianhydride's monomer, any one aforementioned embodiments and
Solvent, the wherein mol ratio of diamine monomer and tetracarboxylic dianhydride's monomer are 1：1 to 1：1.5, preferably 1：
1 to 1：1.1, and to be used to be formed the gross weight meter of the constituent of polyimide aerogels, containing amino
The percentage by weight of silicon dioxide microparticle is 10wt% to 40wt%, preferably 20wt% to 30wt%.
Specifically, the example of diamine monomer is for example but not limited to：4,4 '-diamino-diphenyl ether
(ODA), 3,3 '-dimethyl diphenyl diamines (DMB), p-phenylenediamine (p-PDA), m-phenylene diamine (MPD)
(m-PDA), double [4- (4- the aminophenoxy phenyls)] propane (BAPP) of 2,2'- or the (trifluoros of 2,2- bis-
Methyl) benzidine (TFMB).The example of diamine monomer is preferably 4,4 '-diamino-diphenyl ether
Or 3,3 '-dimethyl diphenyl diamines.
The example of tetracarboxylic dianhydride's monomer is for example but not limited to：3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride
(BPDA), pyromellitic dianhydride (PMDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA),
Diphenyl ether tetraformic dianhydride (ODPA) or hexafluorodianhydride (6FDA) (6FDA).The example of tetracarboxylic dianhydride's monomer
Preferably 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA).
The associated description of the silicon dioxide microparticle containing amino is at large said in aforementioned embodiments
It is bright, therefore repeated no more in this.
There is no particular restriction for solvent, as long as can dissolve diamine monomer, tetracarboxylic dianhydride's monomer and contain amino
Silicon dioxide microparticle.In the present embodiment, solvent be, for example, selected from 1-METHYLPYRROLIDONE,
At least one of dimethylacetylamide, dimethylformamide, tetrahydrofuran and phenol.Specifically,
The example of phenol include between phenol.
In addition, the solid content for being used to be formed the constituent of polyimide aerogels is 5wt% to 20wt%,
Preferably 8wt% to 15wt%.Specifically, if being used to be formed the constituent of polyimide aerogels
Solid content is less than 5wt%, then viscosity is too low, it is impossible to process；And if being used to form polyimides airsetting
The solid content of the constituent of glue is higher than 20wt%, then can reduce formed polyimides because viscosity is too high
The porosity of aeroge.
[polyimide aerogels and its manufacture method]
The manufacture method of the polyimide aerogels of one embodiment of the present invention is comprised the following steps.First,
Prepare the constituent for being used to be formed polyimide aerogels in any one aforementioned embodiments.Specifically,
It is used to be formed the preparation method of the constituent of polyimide aerogels to be included at 0 DEG C to 35 DEG C, by diamines
Monomer, tetracarboxylic dianhydride's monomer are well mixed with the silicon dioxide microparticle containing amino in solvent.Mixing
There is no particular restriction for method, as long as diamine monomer, tetracarboxylic dianhydride's monomer can be made with the titanium dioxide containing amino
Silicon particle is well mixed in solvent and is reacted with the sharp follow-up condensation polymerization that carries out.In addition, being used to be formed
Diamine monomer, tetracarboxylic dianhydride's monomer in the constituent of polyimide aerogels, the titanium dioxide containing amino
The associated description of silicon particle and solvent at large illustrated in aforementioned embodiments, therefore in this no longer
Repeat.
Then, condensation polymerization and cyclization are carried out using the constituent for forming polyimide aerogels,
To form wet gel.Specifically, in this step, diamine monomer and the silicon dioxide microparticle containing amino
Amino all can carry out condensation polymerization and cyclization with the acid anhydride of tetracarboxylic dianhydride's monomer and form acyl
Imines is bonded.That is, in the present embodiment, wet gel is included, and there is acid imide to be bonded and have
The plural gel solid content of mobility.
More specifically, in the present embodiment, the method for forming wet gel is included in 0 DEG C to 35 DEG C
Under, chemical catalyst pyridine is persistently stirred and added using the constituent for forming polyimide aerogels
And acetic anhydride, to carry out condensation polymerization and cyclization 3 hours to 8 hours, wherein pyridine and acetic anhydride
Volume ratio be about 2:1.
Then, Solvent exchange drying is carried out to wet gel using the mixed liquor of acetone and water.At solvent displacement
Reason is the step of solvent in wet gel is replaced into the solvent for being suitable for being removed in follow-up dried process.In detail
For thin, in the present embodiment, the solvent as acetone for being suitable for being removed in follow-up dried process
With the mixed liquor of water.That is, Solvent exchange drying and without the use of Co 2 supercritical fluid or
Being the low-surface-energy solvents such as the highly toxic n-hexane of tool, pentane is carried out, thereby polyimides of the invention
The manufacture method of aeroge has low manufacturing cost and the time, and can avoid making environment, biology etc.
Application is improved into harm.
In the present embodiment, in the mixed liquor of acetone and water, acetone is 10 with the volume ratio of water：
90 to 90：10, preferably 10：70 to 70：30.Specifically, if the volume ratio of acetone and water
Less than 10：90 or higher than 90：When 10, then follow-up formed polyimide aerogels can produce inequality
The situation of even contraction.
In addition, any method in the usable art of Solvent exchange drying well known to technical staff
Come carry out.For example, at 0 DEG C to 35 DEG C, wet gel is placed in mixed liquor of the acetone with water
Row immersion 1 hour to 8 hours, to carry out Solvent exchange drying.Wherein, acetone and the mixed liquor of water
There is no particular restriction for usage amount, as long as the amount that the solvent in wet gel can be sufficiently displaced from.One
In implementation method, the usage amount of the mixed liquor of acetone and water can be 1 times of the volume relative to wet gel extremely
3 times of amount.
Then, to being dried treatment through the wet gel after Solvent exchange drying, polyamides can thereby be obtained
Imines aeroge.In the present embodiment, the method for dried process is to use direct drying method or freezing dry
Dry method is carried out.That is, dried process and carried out without the use of Co 2 supercritical fluid,
Thereby the manufacture method of polyimide aerogels of the invention has low manufacturing cost and the time.
With regard to reduce manufacturing cost viewpoint for, can be used direct drying method, the direct drying method be in
The method of standing and drying under normal temperature and pressure, that is, be not necessary to additionally apply pressure or heating be dried.In addition,
Freeze-drying can be carried out using any method well known to technical staff in art.Citing
For, the method for carrying out freeze-drying includes：Make through the wet gel after Solvent exchange drying in -10 DEG C extremely
After being freezed at 0 DEG C, it is dried under vacuum (0.01atm to 0.03atm).
In addition, in the present embodiment, being increased by the structural strength of polyimide aerogels to avoid in dry
For there is the viewpoint of void collapse in dry treatment, the manufacture method of polyimide aerogels be additionally included in into
Before the row Solvent exchange drying, crosslinking agent is added in wet gel.Specifically, with wet gel
Gross weight meter, the addition of crosslinking agent is 1wt% to 10wt%, preferably 1wt% to 5wt%.Separately
Outward, the example of crosslinking agent is for example but not limited to：Diisocyanate system crosslinking agent, diamine crosslinker, three
Amine crosslinker or glycol system crosslinking agent.Wherein, above-mentioned diisocyanate system crosslinking agent be such as, but not limited to be
Methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), IPDI, dicyclohexyl
Methane diisocyanate or LDI.
In addition, in the present embodiment, just reduce between surface surface can with suppress polyimide aerogels in
Shunk in dried process for the viewpoint of phenomenon, the manufacture method of polyimide aerogels is also included in
Surfactant is added in the acetone and the mixed liquor of water.Specifically, with acetone and the mixed liquor of water
Gross weight meter, the addition of surfactant is 0.01wt% to 5wt%, preferably 0.1wt% to 3
Wt%.In addition, surfactant is, for example, fluorine system surfactant.The present invention is not particularly limited fluorine system table
The species of face activating agent, also can be used commercially available product, such as model NovecTM4200、NovecTM4300、
FC-4430、FC-4434、FC-5120、S-111n、S-113、S-121、S-131、S-132、S-141、
S-145, SA-100, S-381 and S-393 etc. commercially available fluorine system surfactant.
Another embodiment of the present invention also provides a kind of polyimide aerogels, the polyimides airsetting
Glue is manufactured by the manufacture method of the polyimide aerogels in any one aforementioned embodiments.In detail
For, the porosity of polyimide aerogels is about 85% to 95%, and the thickness of polyimide aerogels is about
It is 0.1mm to 1mm, and the heat transfer coefficient of polyimide aerogels is about 30mW/mk to 80
mW/m·k。
In addition, when the external force for bestowing 1 kilogram bends polyimide aerogels, polyimide aerogels
Maximum bent angle be about 270 degree to 360 degree.That is, polyimides airsetting of the invention
Glue has good flexibility.
It is noted that as it was noted above, by using including with special ratios relation extents two
Amine monomers and tetracarboxylic dianhydride's monomer, and the alkoxyl silicone as shown in formula (I) with certain content scope
Alkane is manufactured with the constituent of the silicon dioxide microparticle containing amino of the alkoxy silane preparation shown in formula (II)
Polyimide aerogels, are not only without the use of to low-surface-energy solvents and two such as n-hexane, pentanes in processing procedure
Carbonoxide supercritical fluid, and polyimide aerogels have high porosity, well insulated, well may be used
The characteristics such as flexibility, anti-flammability, uv-resistance, endurance and low-k.Consequently, it is possible to this hair
Bright polyimide aerogels have while there is existing aeroge to be difficult to reach excellent productivity and
The advantage of physical property.
Furthermore, because polyimide aerogels have above-mentioned advantage, it can be applied to multiple fields,
For example textile industry, building field, traffic and transport field, family's electrical article, semiconductor applications, industry are used
Equipment etc..Hereinafter, it is illustrated so that polyimide aerogels are applied to textile industry as an example.
[composite containing polyimide aerogels]
The composite containing polyimide aerogels of one embodiment of the present invention includes fabric and appoints
A kind of polyimide aerogels in aforementioned embodiments, wherein fabric are mutually multiple with polyimide aerogels
Close.Specifically, the example of fabric is for example but not limited to：Woven, knitted fabric, stereo fabric or
Adhesive-bonded fabric etc..The associated description of polyimide aerogels at large illustrated in aforementioned embodiments,
Therefore repeated no more in this.In addition, the method for making fabric mutually compound with polyimide aerogels for example includes
After through the wet gel coating after Solvent exchange drying or being impregnated in fabric, treatment is dried.Coating
Method can be used the rubbing method for typically being carried out, such as Dipcoat method, spin-coating method, spraying process, bristle
Rubbing method, roller transfer method, screen painting method, ink-jet method or flexographic printing process.The dried process can be with
The dried process carried out during manufacture polyimide aerogels is identical, and associated description is in aforementioned embodiments
In at large illustrated, therefore repeated no more in this.
What deserves to be explained is, as it was noted above, polyimide aerogels have well insulated, anti-flammability,
Uv-resistance and endurance, thereby improve thermal insulation, anti-flammability, uv-resistance and the endurance of fabric,
Imply that the composite containing polyimide aerogels also has thermal insulation, anti-flammability, uv-resistance and resistance to
The property changed；Polyimide aerogels have high porosity, thereby cause compound containing polyimide aerogels
Material is able to reach lightweight, lightening；Polyimide aerogels have good flexibility, thereby make
Obtaining the composite containing polyimide aerogels has good workability and application.From another viewpoint and
Speech, the composite containing polyimide aerogels is by mutually multiple with polyimide aerogels by fabric
Close and obtain, therefore compared to fabric or polyimide aerogels, the composite containing polyimide aerogels
With preferably obdurability.Consequently, it is possible to the composite containing polyimide aerogels have can conduct
The purposes of outdoor cloth film, protective garment, firefighting clothing, space suit, flame proof cloth etc..
Below in reference to embodiment 1 to embodiment 3, feature of the invention is more specifically described.Although retouching
Following examples are stated, but in the case of insurmountability scope, can suitably change material used
Material, its amount and ratio, treatment details and handling process etc..Therefore, should not be by reality hereinafter described
Example is applied to explain restricting property of the present invention.
Embodiment 1
The preparation of the silicon dioxide microparticle containing amino
At room temperature, by the tetraethoxysilane (being produced by Acros companies) and 1.11g of 4.17g
APTES (being produced by Acros companies) be dissolved in as the 10g's of solvent
In DMAc.Then, stir at room temperature while in being added as the 0.5g of catalyst in 30 minutes
NaOH.Then, it is lasting to stir the condensation reaction 4 hours that is hydrolyzed at 30 DEG C.Afterwards, profit
Solvent is removed with centrifugation, you can obtain the silicon dioxide microparticle containing amino of embodiment 1, wherein institute
The equivalents for stating the amino in the silicon dioxide microparticle containing amino is 8.5mmol/g.
It is used to be formed the preparation of the constituent of polyimide aerogels
By 3,3 '-dimethyl diphenyl diamines (hereinafter referred to as DMB), 3.0893 of 2.1229g (0.01mol)
3,3 ', the 4,4 '-biphenyl tetracarboxylic dianhydride (hereinafter referred to as BPDA) of g (0.0105mol), the reality of 1.7374g
Apply the silicon dioxide microparticle containing amino of example 1 and organic as the NMP adding apparatus of the 65g of solvent
In the three-neck flask of the 100mL of tool stirring, and in nitrogen environment and at room temperature, be stirred 8 hours with
DMB, BPDA is set to be well mixed in solvent with the silicon dioxide microparticle containing amino of embodiment 1, i.e.,
The constituent for being used to be formed polyimide aerogels of the embodiment 1 that solid content is 10wt% can be obtained.
The preparation of polyimide aerogels
In under 30 DEG C and nitrogen environment, making the constituent for being used to be formed polyimide aerogels of embodiment 1
Persistently stirring and add catalyst pyridine 5mL and acetic anhydride 10ml carries out condensation polymerization and cyclization 8
Hour, to form the wet gel of embodiment 1.Then, by the diisocyanate system crosslinking agent (two of 0.15g
Methylenebis phenyl isocyanate) add embodiment 1 wet gel in, and prepares 200mL acetone and
The volume ratio of water is 7：3 acetone and the mixed liquor of water.Then, by the fluorine system surface-active of 0.5g
Agent (trade name 3MTMNovecTM4200, produced by 3M companies) add the mixing of foregoing acetone and water
In liquid.Then, at 30 DEG C, the wet gel of gained embodiment 1 is placed in gained acetone mixed with water
Soaked 4 hours in conjunction liquid, to carry out Solvent exchange drying.Afterwards, in normal temperature and pressure (30 DEG C, 1atm)
Under, by through the 4 hours mixed liquors to remove acetone and water of wet gel standing and drying after Solvent exchange drying,
Thereby obtain the polyimide aerogels of embodiment 1.Then, to the polyimide aerogels of embodiment 1
The measurement of thickness is carried out, thickness about 0.5mm is obtained.
Embodiment 2
The preparation of the silicon dioxide microparticle containing amino
The silicon dioxide microparticle containing amino of embodiment 2 is manufactured according to fabrication schedule same as Example 1.
It is used to be formed the preparation of the constituent of polyimide aerogels
By 4,4 '-diamino-diphenyl ether (hereinafter referred to as ODA), 3.0893 of 2.0024g (0.01mol)
The silicon dioxide microparticle and work containing amino of the embodiment 2 of BPDA, 1.6972g of g (0.0105mol)
In having a three-neck flask of churned mechanically 100mL for the NMP adding apparatus of the 61g of solvent, and in nitrogen
Compression ring border and at room temperature, be stirred 8 hours so that ODA, BPDA and embodiment 2 containing amino
Silicon dioxide microparticle is well mixed in solvent, you can obtain solid content being used to for the embodiment 2 of 10wt%
Form the constituent of polyimide aerogels.
The preparation of polyimide aerogels
In under 30 DEG C and nitrogen environment, making the composition for being used to be formed polyimide aerogels of embodiment 2
Thing is persistently stirred and adds catalyst pyridine 5mL and acetic anhydride 10mL carries out condensation polymerization and cyclisation is anti-
Answer 8 hours, to form the wet gel of embodiment 2.Then, the diisocyanate system of 0.15g is crosslinked
Agent (methyl diphenylene diisocyanate) is added in the wet gel of embodiment 2, and prepare 200mL third
Ketone is 7 with the volume ratio of water：3 acetone and the mixed liquor of water.Then, by the fluorine system surface of 0.05g
Activating agent (trade name 3MTMNovecTM4200, produced by 3M companies) foregoing acetone is added with water
In mixed liquor.Then, at 30 DEG C, the wet gel of gained embodiment 2 is placed in gained acetone and water
Mixed liquor in soak 4 hours, to carry out Solvent exchange drying.Afterwards, in normal temperature and pressure (30 DEG C,
Under 1atm), by through the wet gel standing and drying 4 hours after Solvent exchange drying removing acetone and water
Mixed liquor, the polyimide aerogels of embodiment 2 are thereby obtained, wherein sub- to the polyamides of embodiment 2
Amine aeroge carries out the measurement of thickness, obtains thickness about 0.5mm.
Embodiment 3
The preparation of the silicon dioxide microparticle containing amino
The silicon dioxide microparticle containing amino of embodiment 3 is manufactured according to fabrication schedule same as Example 1.
It is used to be formed the preparation of the constituent of polyimide aerogels
By BPDA, 1.7374g of DMB, 3.0893g (0.0105mol) of 2.1229g (0.01mol)
Embodiment 3 the silicon dioxide microparticle containing amino and the NMP adding apparatus of the 65g as solvent
In having a three-neck flask of churned mechanically 100mL, and in nitrogen environment and at room temperature, it is stirred 8
Hour is so that DMB, BPDA mix with the silicon dioxide microparticle containing amino of embodiment 3 in solvent
It is even, you can it is the constituent for being used to be formed polyimide aerogels of the embodiment 3 of 10wt% to obtain solid content.
The preparation of polyimide aerogels
In under 30 DEG C and nitrogen environment, making the constituent for being used to be formed polyimide aerogels of embodiment 3
Persistently stirring and add catalyst pyridine 5mL and acetic anhydride 10mL carries out condensation polymerization and cyclization 8
Hour, to form the wet gel of embodiment 3.Then, by the diisocyanate system crosslinking agent (two of 0.15g
Methylenebis phenyl isocyanate) add embodiment 3 wet gel in, and prepares 200mL acetone and
The volume ratio of water is 3：7 acetone and the mixed liquor of water.Then, by the fluorine system surface-active of 0.05g
Agent (trade name 3MTMNovecTM4200, produced by 3M companies) add the mixing of foregoing acetone and water
In liquid.Then, at 30 DEG C, the wet gel of gained embodiment 3 is placed in the mixing of gained acetone and water
Soaked 4 hours in liquid, to carry out Solvent exchange drying.Afterwards, make through wet solidifying after Solvent exchange drying
Glue after being freezed at -20 DEG C, in be dried under vacuum (0.1atm) 8 hours with remove acetone with
The mixed liquor of water, thereby obtains the polyimide aerogels of embodiment 3, wherein to the polyamides of embodiment 3
Imines aeroge carries out the measurement of thickness, obtains thickness about 0.5mm.
Afterwards, respectively the polyimide aerogels of embodiment 1-3 are carried out with porosity, heat transfer coefficient, most
The measure of big bent angle and dielectric constant.Foregoing measure is described as follows, and the result for determining shows
In table 1.
The measure ＞ of ＜ porositys
First, the polyimide aerogels of embodiment 1-3 are fabricated to length and width size for 3cm × 1cm respectively
Membrane material, and measure its density.It is then used by apparent density measurement instrument (device name Micromeritics
AccuPyc 1330) apparent density measurement is carried out, using helium or argon gas filled polyimide aeroge, with
Measure its apparent density (apparent density).Afterwards, it is then density and the conversion of apparent density ratio is i.e. available
Polyimide aerogels porosity.The hole rate score of polyimide aerogels is lower to represent that void content is better,
It is better with respect to insulating characteristicses.
The measure ＞ of ＜ heat transfer coefficients
Coefficient of heat conduction analyzer is providing constant power under the conditions of the thermal source of material sample, measures sample
The ability that heat source is gone out.When the temperature of object and the external world is inconsistent, hot-cast socket will be produced
Situation, the circulation way of heat mainly include conduction (Conduction), convection current (Convection) and
Radiation (Radiation).First, the polyimide aerogels of embodiment 1-3 are fabricated to length and width respectively
Size is the membrane material of 10cm × 10cm.It is then used by heat conduction analysis device (device name Hot Disk
TPS 2500) those membrane materials are carried out with the measurement of heat flow, application method is the experiment of transition plane heat source method
Operation or work standard, the heat transfer coefficient numerical value of polyimide aerogels is lower to represent that thermal insulation is better.
The measure ＞ of the maximum bent angles of ＜
First, the polyimide aerogels of embodiment 1-3 are fabricated to length and width size for 5cm × 5cm respectively
Membrane material.Then, 1 kilogram of external force is bestowed to the membrane material respectively and bends it, and measure membrane material not
Maximum bent angle when being broken.In the standard in the industry cycle setting, when maximum bent angle is
At 360 degree, that is, representing membrane material can be with reflexed.
The measure ＞ of ＜ dielectric constants
First, the polyimide aerogels of embodiment 1-3 are fabricated to length and width size for 10cm × 10 respectively
The membrane material of cm.Then, using Dielectric Coefficient device (device name Agilent -8722ES) to this
The dielectric constant of a little membrane materials is measured, wherein it is 0~1GHz to measure frequency.The standard in the industry cycle setting
In, the dielectric constant of polyimide aerogels is preferably less than 1.5, and the lower expression dielectric property of numerical value
Better.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Porosity (%) | 87 | 87 | 88 |
| Heat transfer coefficient (mW/mk) | 43 | 43 | 42 |
| Maximum bent angle (degree) | 360 | 360 | 320 |
| Dielectric constant | 1.2 | 1.3 | 1.1 |
As shown in Table 1, embodiment 1 to the polyimide aerogels of embodiment 3 pass system in porosity, heat
There is good behaviour in several, maximum bent angle and dielectric constant each side.This is represented by using bag
Diamine monomer and tetracarboxylic dianhydride monomer of the proportionate relationship in particular range are included, and content is in specific model
Alkoxy silane as shown in formula (I) in enclosing and the alkoxy silane shown in formula (II) prepare containing amino
The constituent of silicon dioxide microparticle manufactures polyimide aerogels, enables to the polyimide aerogels to have
There are high porosity, well insulated, good flexibility and low-k.
Although the present invention is disclosed as above with implementation method, so it is not limited to the present invention, Ren Hesuo
Those of ordinary skill in category technical field, it is without departing from the spirit and scope of the present invention, a little when that can make
Change and retouching, therefore protection scope of the present invention depending on appended claims confining spectrum when being defined.
Claims (19)
1. a kind of silicon dioxide microparticle containing amino, it is characterised in that the alkoxy silane as shown in formula (I)
Obtained through hydrolysis-condensation reaction in the presence of catalyst with the alkoxy silane shown in formula (II)：
Si(OR1)4Formula (I),
(NH2-Y)m-Si(OR2)4-mFormula (II),
Wherein in formula (I), R1It is the alkyl that carbon number is 1 to 10；And
In formula (II), Y is the alkyl that carbon number is 1 to 10 or the alkenyl that carbon number is 2 to 10, R2For carbon number is
1 to 10 alkyl, m is 1 to 3 integer.
2. the silicon dioxide microparticle containing amino according to claim 1, it is characterised in that described to contain
The equivalents of the amino in the silicon dioxide microparticle of amino is 5mmol/g to 10mmol/g.
3. the silicon dioxide microparticle containing amino according to claim 1, it is characterised in that formula (I) institute
The alkoxy silane for showing includes tetraethoxysilane, and alkoxy silane shown in formula (II) includes 3- amino
Propyl-triethoxysilicane.
4. a kind of constituent for being used to form polyimide aerogels, it is characterised in that including：
Diamine monomer；
The mol ratio of tetracarboxylic dianhydride's monomer, the diamine monomer and tetracarboxylic dianhydride's monomer is 1：1
To 1：1.5；
Silicon dioxide microparticle containing amino according to any one of claim 1 to 3, with the use
To form the gross weight meter of the constituent of polyimide aerogels, the silicon dioxide microparticle containing amino
Percentage by weight is 10wt% to 40wt%；And
Solvent.
5. the constituent for being used to form polyimide aerogels according to claim 4, its feature exists
In the solid content of the constituent for being used to be formed polyimide aerogels is 5wt% to 20wt%.
6. the constituent for being used to form polyimide aerogels according to claim 4, its feature exists
In, the diamine monomer be 4,4 '-diamino-diphenyl ether, 3,3 '-dimethyl diphenyl diamines, to benzene two
Double [4- (4- the aminophenoxy phenyls)] propane of amine, m-phenylene diamine (MPD), 2,2'- or 2,2- bis- (trifluoromethyl) two
Aminobphenyl, tetracarboxylic dianhydride's monomer is 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, Pyromellitic Acid
Acid anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, diphenyl ether tetraformic dianhydride or hexafluorodianhydride (6FDA).
7. the constituent for being used to form polyimide aerogels according to claim 4, its feature exists
In the solvent is selected from 1-METHYLPYRROLIDONE, dimethylacetylamide, dimethylformamide, tetrahydrochysene furan
Mutter and at least one of phenol.
8. a kind of manufacture method of polyimide aerogels, it is characterised in that including：
Diamine monomer, tetracarboxylic dianhydride's monomer are mixed with the silicon dioxide microparticle containing amino in solvent
It is even, to obtain the group that being used to as any one of claim 4 to 7 to form polyimide aerogels
Into thing；
The constituent for being used to be formed polyimide aerogels is set to carry out condensation polymerization and cyclization, with
Form wet gel；
Solvent exchange drying is carried out to the wet gel using the mixed liquor of acetone and water；And
To being dried treatment through the wet gel after the Solvent exchange drying.
9. the manufacture method of polyimide aerogels according to claim 8, it is characterised in that in
In the mixed liquor of the acetone and water, acetone is 10 with the volume ratio of water：90 to 90：10.
10. the manufacture method of polyimide aerogels according to claim 8, it is characterised in that also
It is included in before carrying out the Solvent exchange drying, crosslinking agent is added in the wet gel.
The manufacture method of 11. polyimide aerogels according to claim 10, it is characterised in that
With the gross weight meter of the wet gel, the addition of the crosslinking agent is 1wt% to 10wt%.
The manufacture method of 12. polyimide aerogels according to claim 10, it is characterised in that
The crosslinking agent is the crosslinking of diisocyanate system crosslinking agent, diamine crosslinker, three amine crosslinkers or glycol system
Agent.
The manufacture method of 13. polyimide aerogels according to claim 8, it is characterised in that also
It is included in the mixed liquor of the acetone and water and adds surfactant.
The manufacture method of 14. polyimide aerogels according to claim 13, it is characterised in that
With the acetone and the gross weight meter of the mixed liquor of water, the addition of the surfactant is 0.01wt%
To 1wt%.
The manufacture method of 15. polyimide aerogels according to claim 13, it is characterised in that
The surfactant is fluorine system surfactant.
16. a kind of polyimide aerogels, it is characterised in that as any one of claim 8 to 15
Polyimide aerogels manufacture method manufactured by.
17. polyimide aerogels according to claim 16, it is characterised in that the polyamides is sub-
The porosity of amine aeroge is 85% to 95%.
18. polyimide aerogels according to claim 16, it is characterised in that the polyamides is sub-
The thickness of amine aeroge is 0.1mm to 1mm.
A kind of 19. composites containing polyimide aerogels, it is characterised in that including：
Fabric；And
Polyimide aerogels according to any one of claim 16 to 18, wherein the fabric with
The polyimide aerogels are mutually combined.
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