CN110527293A - A kind of Kapton and preparation method thereof of basalt scale fibre modification - Google Patents

A kind of Kapton and preparation method thereof of basalt scale fibre modification Download PDF

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Publication number
CN110527293A
CN110527293A CN201910841637.6A CN201910841637A CN110527293A CN 110527293 A CN110527293 A CN 110527293A CN 201910841637 A CN201910841637 A CN 201910841637A CN 110527293 A CN110527293 A CN 110527293A
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basalt scale
basalt
kapton
dianhydride
fiber
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CN110527293B (en
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苏桂明
姜海健
方雪
陈明月
崔向红
张晓臣
马宇良
宫禹
刘晓东
李天智
宋美慧
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Institute of Advanced Technology of Heilongjiang Academy of Sciences
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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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

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  • Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

A kind of Kapton and preparation method thereof of basalt scale fibre modification has more low water absorption, higher intensity and better heat resistance than unmodified identical films.The present invention makes it easily generate reunion in a polymer matrix to solve the interlaminar action power of basalt scale fiber, it is not easy the technical issues of dispersing, it is modified that surface is carried out to basalt scale fiber using Amino End Group silane coupling agent, change the surface roughness of basalt scale fiber by microwave liquid phase auxiliary law, the effect that the infiltration of Amino End Group silane coupling agent can be made modified gets a promotion, improve the grafting rate of amido functional group, it is bonded the amino of modified basalt scale fiber surface with monomer dianhydride by in-situ polymerization again, it is scattered in inorganic matter fiber is uniform and stable in a manner of being chemically bonded in polyimides system, avoid the reunion of scale fiber, this method is suitable for various using diamines and dianhydride as the home position polymerization reaction of monomer.The invention belongs to polyimide film fields.

Description

A kind of Kapton and preparation method thereof of basalt scale fibre modification
Technical field
The invention patent relates to a kind of Kaptons and preparation method thereof of basalt scale fibre modification.
Background technique
Basalt scale is a kind of novel scale material, transparent or bottle green laminated structure is presented, thickness is generally on 3 μm of left sides The right side, size is generally in 25 μm~3mm or so.Since ferriferous oxide, titanium dioxide, aluminium oxide, calcium oxide contain in basalt scale Amount is high and wherein basic anhydride content is less, therefore can not only generate screen effect, and in acid and alkali-resistance and corrosion resistance Aspect also has unique advantage.This characteristic makes it have extensive industrial application prospect in waterproof Waterproof corrosion erosion field, but Basalt scale fiber belongs to lamella fiber type, and interlaminar action power makes its easily generate reunion in a polymer matrix, is not easy point It dissipates.
Summary of the invention
The purpose of the present invention is to solve the interlaminar action power of basalt scale fiber to make fiber in a polymer matrix Easily generate and reunite, be not easy the technical issues of dispersing, provide a kind of basalt scale fibre modification Kapton and Preparation method, the method are suitable for the various home position polymerization reactions that PI is prepared using diamines as monomer.
A kind of Kapton of basalt scale fibre modification is comprising mass fraction in the Kapton 1~5% basalt scale fiber modified through Amino End Group coupling agent surface.
The preparation method of basalt scale fibre modification Kapton follows the steps below:
One, basalt scale fiber is added to absolute ethanol, ultrasonic disperse, cleaning are obtained by the pretreated Black Warrior Rock scale fiber；
Two, Amino End Group silane coupling agent is added in ethyl alcohol, is configured to immersion fluid, be added and pass through pretreated basalt Scale fiber stirs at low speed 1h under ultrasound condition, dries at being rinsed 3 times, 80 DEG C after taking-up with soaked in absolute ethyl alcohol, obtains idol Join agent treated basalt scale fiber；
Three, first that molfraction is fine for the basalt scale after 1 part of diamine monomer and coupling agent treatment at 0 DEG C~5 DEG C Dimension is added in solvent, and solvent adding amount is 15% calculating according to product solid content mass fraction, is stirred to after being completely dissolved, so The dianhydride monomer that molfraction is 1.1 is added portionwise afterwards, home position polymerization reaction is carried out and (notices that each inventory excessive not made It is sudden and violent poly- that generation can not be dissolved at local monomer), after addition, sustained response 1-12h obtains polyamic acid solution；
Four, 200 mesh copper mesh of polyamic acid solution are filtered, carries out film on a glass using automatic film applicator, applied Film thickness is 0.5mm, in clean room drying at room temperature for 24 hours after, be put into air dry oven echelon heating carry out hot imidization, obtain Basalt scale fibre modification Kapton.
Amino End Group siloxanes described in step 2 is gamma-aminopropyl-triethoxy-silane, γ-aminopropyl trimethoxy silicon Alkane, N- β (aminoethyl)-aminopropyl trimethoxysilane, N- β (aminoethyl)-aminopropyltriethoxy dimethoxysilane, N- β (ammonia second Base)-aminopropyl triethoxysilane or N- β (aminoethyl)-aminopropyltriethoxy diethoxy silane or other contain Amino End Group official One of silane coupling agent can be rolled into a ball.
Coupling agent mass fraction is 5%~10% in the ethyl alcohol immersion fluid prepared in step 2, and surface is modified in step 2 Method is microwave liquid phase auxiliary law.
Modified basalt scale fiber additional amount is put into monomer gross mass 1%~5% in step 3.
Diamines described in step 3 is diaminodiphenyl ether, p-phenylenediamine, benzidine or benzophenone tetracid dianhydride；
Dianhydride described in step 3 is benzophenone tetracid dianhydride, pyromellitic dianhydride or diphenyl ether tetracid dianhydride.
Diamines described in step 3 is fluorinated diamine or alicyclic diamine monomer.
Dianhydride described in step 3 is fluorine-containing dianhydride or alicyclic dianhydride monomer.
Organic solvent described in step 3 is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone And one or more of tetrahydrofuran a mixture of arbitrary proportions.
The purpose of the invention is to prepare a kind of basalt scale fibre modification PI film, modified caudacoria has better The basalt scale of surface attachment amido functional group is added in heat resistance and lower water absorption rate, the present invention in polyimides system Fiber, amido functional group are chemically reacted with anhydride monomers, are dispersed in polyimides system in the form of chemical bond.It improves The dispersibility of basalt scale in a polymer matrix needs to be surface modified basalt scale, and it is compatible to improve interface Property, it is chemically bonded.Surface grafting has the basalt scale fiber of amino group can be with the acid anhydrides in polyimide monomers It is chemically reacted, is dispersed in polyimides system.It, can be bright since basalt scale is fibroplastic " labyrinth effect " The osmotic-pressure-tolerant and corrosion resistance of aobvious enhancing polymeric matrix, so as to improve the water resistance, impervious with enhancing Kapton Permeability, corrosion resistance and mechanical property.
The present invention changes the surface roughness of basalt scale fiber by microwave liquid phase auxiliary law, can make Amino End Group silicon The modified effect of alkane coupling agent infiltration gets a promotion, and improves the grafting rate of amido functional group, then the method for using in-situ polymerization, makes Basalt scale fiber is uniform and stable in a manner of being chemically bonded to be scattered in polyimides system, and scale coma is avoided It is poly- to be negatively affected caused by polymer performance.
Detailed description of the invention
Fig. 1 be in experiment one before modified after basalt fibre infrared spectrum analysis figure；
Fig. 2 is modified PI membrane forces section basalt fibre distribution stereoscan photograph in experiment two；
Fig. 3 is modified polyimide film TG test chart in experiment two.
Specific embodiment
The technical solution of the present invention is not limited to the following list, further includes between each specific embodiment Any combination.
Specific embodiment 1: a kind of Kapton of basalt scale fibre modification of present embodiment, described poly- The basalt scale fiber modified through Amino End Group coupling agent surface for being 1~5% comprising mass fraction in imide membrane.
Specific embodiment 2: a kind of polyimides of basalt scale fibre modification described in specific embodiment one is thin Film, it is characterised in that the preparation method of the film is as follows
One, basalt scale fiber is added to absolute ethanol, ultrasonic disperse, cleaning are obtained by the pretreated Black Warrior Rock scale fiber；
Two, Amino End Group silane coupling agent is added in ethyl alcohol, is configured to immersion fluid, be added and pass through pretreated basalt Scale fiber stirs at low speed 1h under ultrasound condition, dries at being rinsed 3 times, 80 DEG C after taking-up with soaked in absolute ethyl alcohol, obtains idol Join agent treated basalt scale fiber；
Three, first that molfraction is fine for the basalt scale after 1 part of diamine monomer and coupling agent treatment at 0 DEG C~5 DEG C Dimension is added in solvent, and solvent adding amount is 15% calculating according to product solid content mass fraction, is stirred to after being completely dissolved, so The dianhydride monomer that molfraction is 1.1 is added portionwise afterwards, carries out home position polymerization reaction, after addition, sustained response 1- 12h obtains polyamic acid solution；
Four, 200 mesh copper mesh of polyamic acid solution are filtered, carries out film on a glass using automatic film applicator, applied Film thickness is 0.5mm, in clean room drying at room temperature for 24 hours after, be put into air dry oven echelon heating carry out hot imidization, obtain Basalt scale fibre modification Kapton.
Specific embodiment 3: present embodiment and Amino End Group silicon described in step 2 unlike specific embodiment two Oxygen alkane is gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- β (aminoethyl)-aminopropyl trimethoxy Silane, N- β (aminoethyl)-aminopropyltriethoxy dimethoxysilane, N- β (aminoethyl)-aminopropyl triethoxysilane or N- β (aminoethyl)-aminopropyltriethoxy diethoxy silane other contains one of Amino End Group functional silanes coupling agent.Other It is identical with embodiment two.
Specific embodiment 4: the second that present embodiment is prepared in step 2 unlike specific embodiment two or three Coupling agent mass fraction is 5%~10% in alcohol immersion fluid, and surface modifying method is microwave liquid phase auxiliary law in step 2.Other It is identical as specific embodiment two or three.
Specific embodiment 5: modified in step 3 unlike one of present embodiment and specific embodiment two to four Basalt scale fiber additional amount is put into monomer gross mass 1%~5% afterwards.One of other and specific embodiment two to four It is identical.
Specific embodiment 6: unlike one of present embodiment and specific embodiment two to five described in step 3 Diamines be diaminodiphenyl ether (ODA), p-phenylenediamine, benzidine or benzophenone tetracid dianhydride；Two described in step 3 Acid anhydride is benzophenone tetracid dianhydride, pyromellitic dianhydride or diphenyl ether tetracid dianhydride.One of other and specific embodiment two to five It is identical.
Specific embodiment 7: unlike one of present embodiment and specific embodiment two to six described in step 3 Diamines be fluorinated diamine or alicyclic diamine monomer.Other are identical as one of specific embodiment two to six.
Specific embodiment 8: unlike one of present embodiment and specific embodiment two to seven described in step 3 Dianhydride be fluorine-containing dianhydride or alicyclic dianhydride monomer.Other are identical as one of specific embodiment two to seven.
Specific embodiment 9: having described in step 3 unlike one of present embodiment and specific embodiment two to eight Solvent be one of N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone and tetrahydrofuran or Several a mixture of arbitrary proportions.Other are identical as one of specific embodiment two to eight.
It is any ratio between ingredient when organic solvent described in present embodiment is mixture.
Specific embodiment 10: heat is sub- in step 4 unlike one of present embodiment and specific embodiment two to nine Amination Technique are as follows: 120 DEG C of constant temperature 1.5h, 180 DEG C of constant temperature 1h, 240 DEG C of constant temperature 1h, 280 DEG C of constant temperature 1h.Other and specific embodiment party One of formula two to nine is identical.
Using following experimental verifications effect of the present invention:
Experiment one:
It is configured to the immersion fluid that mass fraction is 5% using amino silane KH-550 and dehydrated alcohol, ultrasonic wave is dispersed Treated, and basalt scale fiber is immersed in immersion fluid, and 1h is stirred at low speed under ultrasound condition, is soaked after taking-up with dehydrated alcohol Modified basalt scale fiber is obtained at bubble rinses 3 times, 80 DEG C after dry out solvent.
N is passed through in the 1000ml three-necked flask equipped with stirring, thermometer2After dry 3min, by 39g diaminodiphenyl ether It is added in n,N-dimethylacetamide with modified basalt scale fiber, stirring and dissolving, obtains mixed liquor, modified basalt scale The additional amount of fiber is the 1% of two kinds of reaction monomers gross masses, using the cooling reaction kettle of sub-cooled circulating pump to 0-5 DEG C, is claimed Pyromellitic acid anhydride 44g is taken, is added in solution in batches, is added once according to the about every 15min of reaction kettle viscosity, until being added It finishes, reacting 12h after the completion can be obtained pale yellow transparent polyamic acid solution.
Obtained polyamic acid solution is after the filtering of 200 mesh copper mesh, using automatic film applicator on clean glass plate Carry out film, coating thickness 0.5mm, in clean room drying at room temperature for 24 hours after, be put into air dry oven echelon heating carry out heat Imidization, process conditions are 120 DEG C of constant temperature 1.5h, obtain micro- Huang after 180 DEG C of constant temperature 1h, 240 DEG C of constant temperature 1h, 280 DEG C of constant temperature 1h Clear polyimides modified film.
Experiment two:
It is configured to the immersion fluid that mass fraction is 10% using amino silane KH-550 and dehydrated alcohol, ultrasonic wave is dispersed Treated, and basalt scale fiber is immersed in immersion fluid, and 1h is stirred at low speed under ultrasound condition, is soaked after taking-up with dehydrated alcohol Modified basalt scale fiber is obtained at bubble rinses 3 times, 80 DEG C after dry out solvent.
N is passed through in the 1000ml three-necked flask equipped with stirring, thermometer2After dry 3min, by 39g diaminodiphenyl ether It is added in n,N-dimethylacetamide with modified basalt scale fiber, stirring and dissolving, obtains mixed liquor, modified basalt scale The additional amount of fiber is the 3% of two kinds of reaction monomers gross masses, using the cooling reaction kettle of sub-cooled circulating pump to 0-5 DEG C, is claimed Pyromellitic acid anhydride 44g is taken, is added in solution in batches, is added once according to the about every 15min of reaction kettle viscosity, until being added It finishes, reacting 12h after the completion can be obtained pale yellow transparent polyamic acid solution.
Obtained polyamic acid solution is after the filtering of 200 mesh copper mesh, using automatic film applicator on clean glass plate Carry out film, coating thickness 0.5mm, in clean room drying at room temperature for 24 hours after, be put into air dry oven echelon heating carry out heat Imidization, process conditions are 120 DEG C of constant temperature 1.5h, obtain micro- Huang after 180 DEG C of constant temperature 1h, 240 DEG C of constant temperature 1h, 280 DEG C of constant temperature 1h Clear polyimides modified film.
Water absorption rate test, mechanical strength test, the survey of thin-membrane section SEM scanning electron microscope are carried out to one, two product films of experiment The test such as examination, infrared spectrum analysis and thermogravimetic analysis (TGA) is to determine basalt fibre modified effect.
Top curve is unmodified basalt fibre infrared spectrogram in Fig. 1, and lower curve is to use KH-550 coupling agent Basalt fibre infrared spectrum after modification, both comparisons can be found that unmodified basalt in 908cm-1There is shape in place The round and smooth and broad peak of shape, this is the common trait of silicate infrared spectroscopy, belongs to the flexible vibration of Si-O and Si-O-Si structure Dynamic peak, the wave number at this peak is smaller than the wave number of normal Si-O vibration peak, and peak width has reached 400cm-1, this is because the Black Warrior Al in rock fiber replaces Si occupy-place, and since the vibration frequency of the degree of order official post Si-O key of Al reduces, peak type broadens.It is modified Basalt fibre afterwards is in 3300-3600cm-1Occur being different from multiple weak absorbing peaks before modified in range, belongs to coupling - NH after agent grafting2And the disperse peak that ion is formed, 2972cm-1And 2921cm-1It is symmetrical and anti-that place is attributed to the C-H on methyl Symmetrical stretching vibration peak, additionally, due to the addition of Si-O key in silane coupling agent, the 908cm of script-1The list circle broad peak division at place For 1074cm-1And 959cm-1That locates is bimodal, these features all demonstrate the graft effect of method of modifying of the present invention.
It is the mechanics section SEM sem test figure for testing two products therefrom films shown in Fig. 2, it can be seen that Highly uniform, the only minimal amount of particle agglomeration for the distribution that basalt scale fiber is distributed on thin-membrane section, because of experiment two In doping it is bigger, so the electromicroscopic photograph of its fiber distribution is more representative, illustrate the method that uses of the present invention to the Black Warrior Rock fiber is dispersed with good improvement effect in resin matrix.
Fig. 3 show two resulting PI film thermogravimetic analysis (TGA) test and comparisons of unmodified PI film and experiment, theoretically profound The addition of military rock fiber should have positive contribution to the heat resistance of material, and Fig. 3 top curve is unmodified PI film, Td5% The temperature of (5%loss) is 526 DEG C, and lower curve is that the modification PI film that mass fraction is 3% basalt fibre is added, weightless Temperature Td5% is 537 DEG C, and the heat resistance of material is improved.
As the result is shown with the increase of basalt scale fiber additional amount, water absorption rate is substantially reduced water absorption rate test in table 1. Embodiment product PI film stretching intensity is listed in table 2, it can be seen that increase of its numerical value with basalt fibre, tensile strength Increase, test result proves that the addition of basalt fibre can reduce the water imbibition of PI film and enhance its mechanical strength.
Table 1 before modified after PI film water absorption rate data comparison
Table 2 before modified after PI film stretching intensity contrast

Claims (10)

1. a kind of Kapton of basalt scale fibre modification, it is characterized in that: including matter in the Kapton Measure the basalt scale fiber modified through Amino End Group coupling agent surface that score is 1~5%.
2. a kind of Kapton of basalt scale fibre modification described in claim 1, it is characterised in that the film Preparation method is as follows
One, basalt scale fiber is added to absolute ethanol, ultrasonic disperse, cleaning, is obtained by pretreated basalt squama Piece fiber；
Two, Amino End Group silane coupling agent is added in ethyl alcohol, is configured to immersion fluid, be added and pass through pretreated basalt scale Fiber stirs at low speed 1h under ultrasound condition, dries at being rinsed 3 times, 80 DEG C after taking-up with soaked in absolute ethyl alcohol, obtains coupling agent Treated basalt scale fiber；
Three, at 0 DEG C~5 DEG C, first molfraction is added for the basalt scale fiber after 1 part of diamine monomer and coupling agent treatment Enter into solvent, solvent adding amount is 15% calculating according to product solid content mass fraction, is stirred to after being completely dissolved, and then will The dianhydride monomer that molfraction is 1.1 is added portionwise, and carries out home position polymerization reaction, after addition, sustained response 1-12h is obtained To polyamic acid solution；
Four, 200 mesh copper mesh of polyamic acid solution are filtered, carries out film on a glass using automatic film applicator, applies film thickness Degree be 0.5mm, in clean room drying at room temperature for 24 hours after, be put into air dry oven echelon heating carry out hot imidization, obtain the Black Warrior Rock scale fibre modification Kapton.
3. the preparation method of basalt scale fibre modification Kapton according to claim 2, it is characterised in that step Amino End Group siloxanes described in rapid two is gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- β (ammonia second Base)-aminopropyl trimethoxysilane, N- β (aminoethyl)-aminopropyltriethoxy dimethoxysilane, N- β (aminoethyl)-aminopropyl Triethoxysilane or N- β (aminoethyl)-aminopropyltriethoxy diethoxy silane are other even containing Amino End Group functional silanes Join one of agent.
4. the preparation method of basalt scale fibre modification Kapton according to claim 2, it is characterised in that step Coupling agent mass fraction is 5%~10% in the ethyl alcohol immersion fluid prepared in rapid two, and surface modifying method is microwave in step 2 Liquid phase auxiliary law.
5. the preparation method of basalt scale fibre modification Kapton according to claim 2, it is characterised in that step Modified basalt scale fiber additional amount is put into monomer gross mass 1%~5% in rapid three.
6. the preparation method of basalt scale fibre modification Kapton according to claim 2, it is characterised in that step Diamines described in rapid three is diaminodiphenyl ether, p-phenylenediamine, benzidine or benzophenone tetracid dianhydride；
Dianhydride described in step 3 is benzophenone tetracid dianhydride, pyromellitic dianhydride or diphenyl ether tetracid dianhydride.
7. the preparation method of basalt scale fibre modification Kapton according to claim 2, it is characterised in that step Diamines described in rapid three is fluorinated diamine or alicyclic diamine monomer.
8. the preparation method of basalt scale fibre modification Kapton according to claim 2, it is characterised in that step Dianhydride described in rapid three is fluorine-containing dianhydride or alicyclic dianhydride monomer.
9. the preparation method of basalt scale fibre modification Kapton according to claim 2, it is characterised in that step Rapid three organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone and tetrahydrofuran One or more of a mixture of arbitrary proportions.
10. the preparation method of basalt scale fibre modification Kapton according to claim 2, it is characterised in that step Hot imidization technique in rapid four are as follows: 120 DEG C of constant temperature 1.5h, 180 DEG C of constant temperature 1h, 240 DEG C of constant temperature 1h, 280 DEG C of constant temperature 1h.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110843294A (en) * 2019-12-04 2020-02-28 中国科学院兰州化学物理研究所 Preparation method of high-speed working condition self-lubricating fabric liner composite material
CN112426619A (en) * 2020-10-26 2021-03-02 广东泰宝医疗科技股份有限公司 Quantum energy fiber modified ion induction matrix material
CN114656690A (en) * 2022-02-28 2022-06-24 海南联塑科技实业有限公司 Modified basalt flake material, preparation method thereof and HDPE double-wall corrugated pipe containing modified basalt flake material

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