CN1760244A - Hybrid film of polyimide of modified by silicon dioxide tube and preparation method thereof - Google Patents
Hybrid film of polyimide of modified by silicon dioxide tube and preparation method thereof Download PDFInfo
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- CN1760244A CN1760244A CN 200410083919 CN200410083919A CN1760244A CN 1760244 A CN1760244 A CN 1760244A CN 200410083919 CN200410083919 CN 200410083919 CN 200410083919 A CN200410083919 A CN 200410083919A CN 1760244 A CN1760244 A CN 1760244A
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Abstract
The present invention relates to the hybrid film of polyimide and the method for making of the modification of a kind of silica nanometer pipe, adopt coupling agent treatment, ultrasonic dispersing, in-situ polymerization and coating process to make; Its matrix is a polyimide resin, and filler is the powder material silicon-dioxide tubulose material of 30～350 nanometers for the internal diameter that adopts the template self-assembling method to prepare; After this powder material seasoning, join in proportion and stir reaction down in the solution that contains coupling agent; Add the ODA monomer again and carry out ultra-sonic dispersion, stir then and add monomer PMDA down and carry out home position polymerization reaction, the gained mixing liquid is poured on films on the sheet glass, puts into baking oven after drying under the room temperature and carries out hot imidization and handle and obtain.This film has under the broad temperature territory can adjust specific inductivity, and filler is the hollow silicon dioxide tubular material that utilizes the self-assembling technique preparation; Its method is simple, economic, practical, need not special solvent, and cost is low, is easy to apply.
Description
Invention field
The invention belongs to polymer based nanocomposites and preparing technical field thereof, hybrid film of polyimide of particularly a kind of silica nanometer pipe modification and preparation method thereof.
Background technology
Kapton is called as " gold film " as a kind of special engineering plastics film, be by raw materials such as pyromellitic acid anhydride and diaminodiphenyl oxide in high polar solvent polycondensation again through film forming and the speciality polymer film.Kapton is owing to have good resistant of high or low temperature, high strength, high insulation, low-k and low-dielectric loss, low thermal coefficient of expansion, radiation resistance, resistance to medium, can be in-269 ℃～250 ℃ temperature range excellent comprehensive performance such as life-time service, thereby be widely used in aviation, space flight, microelectronics, electric, the energy, high-technology fields such as traffic, in particular for the high-temperature insulation material of various motors and ic substrate and the cryogenic insulation material and the H class B insulation electrical equipment of high-temperature superconductive cable and other cryogenic engineerings, phase insulation, layer insulation and print circuit plates making etc. are the large-scale integrated circuit microelectronic devices, motor, electric wire, computer and digital electrical apparatus, national defence, vehicle, the instrument communication, the irreplaceable key base mateiral of industries such as petrochemical complex.This technology is mainly grasped by minority producers such as du pont company, Japanese clock deep pool chemical companies at present.The U.S., West Europe and Japan in 2000 consume more than 6000 ton altogether in the world.China's polyimide goods in 2000 demand reaches more than 1000 ton, and to Kapton product demand every year with 10.9% speed increase.Its use field is expanded to ultra-filtration, reverse osmosis and membrane sepn process by the high-temperature resistant insulation.For many years, the Kapton of China is because production technique falls behind main dependence on import.China's consumption per capita intends near developed country's level, and the market application potential is huge.Therefore greatly develop novel polyimide film material, can promote the fast development of national high performance insulating material and relevant industries thereof, bright development prospect is arranged with independent intellectual property right.
Yet its performance of existing polyimide film has certain limitation, because prescription is single thereby performance can not satisfy many-sided needs.Therefore has the polyimide hybrid film of performance designability because concern and the development that has excellent comprehensive performance more and obtained domestic and international investigator in recent years.Investigators adopt mineral filler to improve thermal characteristics, mechanical property, barrier properties for gases and the water absorption energy etc. of Kapton, and relevant research is at document
[1-9]In more detailed report is arranged.
[1]K.Yano，A.Usuki，A.Okada，J.Polym.Sci.Polym.Chem.1997，35，2289.
[2]M.H.Tsai，W.T.Whang，Polymer?2001，42，4197.
[3]R.Magaraphan，W.Lilayuthalert，A.Sirivat，J.W.Schwank，Comp.Sci.Tech.2001，61，1253.
[4]P.C.Chiang，W.T.Whang，M.H.Tsai，S.C.Wu，Thin?solid?films?2004，447，359.
[5]H.L.Tyan，Y.C.Liu，K.H.Wei，Chem.Mater.1999，11，1942.
[6]J.C.Huang，Z.K.Zhu，X.D.Ma，X.F.Qian，J.Yin，Mater.Sci.Eng.2001，36，871.
[7]H.L.Tyan，C.M.Leu，K.H.Wei，Chem.Mater.2001，13，222.
[8]A.B.Morgan，J.W.Gilman，C.L.Jackson，Macromolecules?2001，34，2735.
[9]H.L.Tyan，K.H.Wei，T.E.Hsieh，J.Polym.Sci.Poly.Phys.2000，38，2873.
As a kind of important dielectric materials, in order to obtain various dielectric properties to adapt to different requirements, people attempt to utilize the complex effect of polyimide organic/inorganic hybridization material, change its dielectric properties by adding various mineral fillers.The performance of hybrid film of polyimide is different because of the difference of contained inorganics dielectric properties, and its inorganics has layered silicate, pottery etc.As E.Kang and its co-worker
[10][E.Kang, Y.S.Kwon, W.J.Cho, C.Cho, M.Chang, M.Ree, T.Cang, C.S.Ha, Synth.Metal.1997,85,1399.]; Y.Kim and its co-worker
[11][Y.Kim, W.K.Lee, W.J.Cho, C.S.Ha, Polym.Int.1997,43,129.] adopt colloidal sol-gel process to improve the dielectric properties of Kapton by the adding silica dioxide granule respectively, but found that the increase along with silicon dioxide granule content, the specific inductivity of Kapton increases always.L.Y.Jiang and its co-worker
[12][L.Y.Jiang, C.M.Leu, K.H.Wei, Adv.Mat.14 (2002) 426.] find that in the research of mica modified polyimide film the dependence between dielectric properties and the mica content does not have rule, that is be uncontrollable.And at present dielectric properties under the single temperature have only been reported about the research of hybrid film of polyimide.
Have a lot about the report that adopts self-assembling technique to prepare nano material.Because the one dimension semiconductor inorganic materials with nanometer and submicrometer structure comprises materials such as fiber with certain length-to-diameter ratio, band, rod, pipe, line.Have character such as certain power, heat, light, electricity, magnetic because of its its specific structure, can be applicable to energy conversion device, optical waveguides, microreactor, field effect transistor, gas sensor, functional stuffing, receive/field such as microelectronics such as micro element and optics.Be that template adopts self-assembling technique or preparation methods such as gas evaporation, deposition to be subjected to domestic and international investigator's attention in recent years with the tensio-active agent.Since finding carbon nanotube in 1991, various novel tubular nanometer material such as SiO
2,
[13,14][13.B.C.Satishkumar, A.Govindaraj, J.Mater.Res.1997,12,604.] [14.F.Miyaji, Y.Watanabe, Y.Suyama, Mater.Res.Bull.2003,38,1669.]; V
2O
5 [15][M.E.Spahr, R.Stoschitizki, P.Bitterci, R.Nesper.Angew Chem Int Ed.1998,37,1263.] and MoS
2 [16][Y.Tdldman, E.Wasserman, D.J.Srolovitz, R.Tenne, Science 1995,267, and 222.] occur in succession.These novel tubular materials make them may be used as aspects such as functional stuffing, energy storage material or nano-reactor template owing to have big surface-area and hollow structure.
Self-assembling technique such as document
[17][Whitesides G M, Mathias J P, Seto C T.Molecularself-assembly and nanochemistry:a chemical strategy for the synthesis of nanostructures.Science, 1991,254:1312-1319] in introduced, be meant by than the key less a little less than the covalent linkage with directivity, as the synergy of ionic linkage, hydrogen bond and Van der Waals force (van der Waals), spontaneous group of molecules is dressed up has a fixed structure, stable, non covalent bond bonded aggregate.Self assembling process finish following three steps of general needs: at first, by the synthetic intermediate of orderly covalent linkage with definite structure; Form big, stable aggregate by the interaction between hydrogen bond, Van der Waals force and other non covalent bond then; At last, be structural unit with one or more molecule aggregatess or polymkeric substance, repeat to organize to arrange to make required nanostructure.If will make the existence that the nanostructure that makes can be stable, must satisfy following two conditions: the first, there are enough non covalent bonds to exist to keep the stable of system; The secondth, this power that combines with non covalent bond is greater than the reactive force between they and the solvent between the molecule, to guarantee that aggregate can not be dissociated into disordered structure.
As far back as nineteen forty-six Zisman
[18][Bigelow W C, Pickett D L, Zisman W A.J.ColloidInterface Sci., 1946,1:513-538.] delivered by absorption (self-assembly) a kind of tensio-active agent, the cleaning the metallic surface be prepared into unimolecular layer membrane, reported first the self-assembly phenomenon, but possible people are not familiar with and predict the meaning of self-assembly, do not cause big concern at that time.In addition, early stage work also has SagivJ. in 1980
[19]The C of [J.Am.Chem.Soc., 1980,102:92-98.] report
18H
37Cl
3(OTS) film forming on sheet glass and Kuhn utilize silane derivative in the assembling of carrying out on glass.Nineteen eighty-three, Nuzzo
[20]Deng [Nuzzo R G, Allara D L.J.Am.Chem.Soc., 1983,105:4481-4483.] method, on gold surface, prepared fine and close mercaptan self-assembled monolayer by in two sulphur compound dilute solutions, adsorbing.The work that the silane compound rotten with utilizing the easy moisture absorption assembled is compared, and their work has initiative meaning undoubtedly.
Be seen in silica nano material and the submicron material that reported in literature studies at present and mainly contain spherical granules, nano wire, porous membrane, pipe, rod etc.Wherein, the silicon-dioxide line makes by the melt drawing technology, and spherical granules is to make by sol-gel technique or hydrothermal method, and porous membrane, pipe, rod etc. make by self-assembling technique.In recent years, Chinese Academy of Sciences's chemistry is cooperated with U.S. Tulane university, makes important progress at 1-dimention nano hole composite material and array research field thereof.They adopt porous-film is template, in conjunction with the sol/gel of inorganics and the self assembling process of segmented copolymer, has prepared silica fiber and the pipe and the array system thereof of 1-dimention nano pore structure.By the wettability of control template hole surface and the concentration of segmented copolymer, can realize the controllable adjustment of product pattern and nano-pore structure.Composite functional matter respectively in the microcavity of nanoporous and hollow tube combines the serial new function structure and material of will deriving with the character and the functional of material of nanoporous.
About adopting the template self-assembling method to prepare silica fiber, the research of this respect can be referring to the article of the 3587-3595 pages or leaves of " chemical material " magazine 13 phases of calendar year 2001 of the U.S. " porous silica fiber: synthetic, internal structure and growth mechanism ".The investigator utilizes this method to obtain the porous silica fiber of diameter for the 2-40 micron.This document has mainly been studied the influence of different silica sources to mesoporous silicon oxide form and internal structure, discovers that the hole all is closelypacked to being six sides around fibre axis under all situations, and non-circular hole.By observing visual solid product, the process of growth of fiber can be divided into 5 stages, but the formation kinetics of silica fiber and products distribution are mainly decided by the interpolation quantity of silicon source and oil phase, use different silicon sources and oil phase can obtain ratio between the different shaped particles.The last fiber of which kind of oil phase that don't work always forms at aqueous phase, and fiber can also can form on the top at interface in the bottom at interface when promptly using different oil phases.
But fibrous, particle that above-mentioned technology is prepared and tubulose silicon-dioxide are not found it and polyimide is compound and as the report of dielectric materials or other purposes material.The preparation and the application thereof of the hybrid film of polyimide of the modified by silicon dioxide tube of employing self-assembling technique preparation do not appear in the newspapers.
Summary of the invention
The objective of the invention is to overcome prior art can only adopt silica dioxide granule that Kapton is carried out the deficiency of modification and the defective that particle can not reach some service requirements, adopt the silica nanometer pipe of self-assembling technique preparation that Kapton is carried out modification, obtain a kind of novel hybrid film of polyimide material that use, that can regulate dielectric properties that has in wide temperature territory.The present invention can provide the preparation method of a kind of economy, simple, practical self-assembled silicon dioxide nanotube, this preparation method can prepare the self-assembled silicon dioxide tubular material that its diameter is 30～400 nanometers, and this self-assembled silicon dioxide tubular material can be applicable to functional materials such as modified fillers such as the enhancing, dielectric of organic-inorganic nanocomposite and absorption, energy storage, microreactor template.
The objective of the invention is to be achieved through the following technical solutions:
The hybrid film of polyimide of modified by silicon dioxide tube provided by the invention adopts coupling agent treatment, ultrasonic dispersing, in-situ polymerization and coating process to make; Its matrix is a polyimide resin, and filler is 30～400 nano silicon tubular materials for the internal diameter that adopts the template self-assembling method to prepare;
Its preparation method comprises the steps:
1) with the surfactant templates material dissolves in water and alcoholic acid solution, by volume volumetric molar concentration is that 5mmol/L～25mmol/L is made into the template aqueous solution, and under agitation add the silicon ester of 0.1mol/L～3mol/L, under 15～40 ℃, left standstill self-assembly 20-80 minute; The strong aqua that adds 1mol/L～5mol/L in this mixing solutions left standstill 20-70 minute, products therefrom separates with testing sieve or filtering membrane, obtains white powder material after massive laundering is washed, and is viewed as the superfine silicon dioxide tubular material under the Electronic Speculum, caliber is 30～350 nanometers, is shaped as hollow tube; The weight percent concentration of described ammoniacal liquor is 25～28%.
2), take by weighing in proportion to join and under agitation carry out reaction treatment in the solution that contains coupling agent with after this powder material seasoning; The consumption of described coupling agent is 0.1-1g/L;
3) above-mentioned treatment solution is added the ODA monomer and carry out ultra-sonic dispersion, adding monomer PMDA and solvent carry out home position polymerization reaction under stirring then, and the gained mixing liquid is poured on films on the sheet glass;
4) put into baking oven after drying under the room temperature and carry out the hot imidization solidification treatment, obtain the hybrid film of polyimide of the silicon-dioxide tubulose modification that can adjust specific inductivity of different silicon-dioxide tubulose fillers.
The tensio-active agent of described step 1) is anion surfactant or cats product; Wherein anion surfactant is selected from AOT, tartrate and OP-10; Cats product is selected from alkylsulfonate and quaternary ammonium salt; Described silicon ester is selected from tetraethoxy, positive silicic acid propyl ester, butyl silicate and the positive own ester of silicic acid.
Described coupling agent is silane coupling agent or titanate coupling agent.The temperature of the hot imidization solidification treatment of described step 4) is 50-350 ℃.Silicon dioxide tube weight percent content in the hybrid film of polyimide of this modified by silicon dioxide tube is 0.1-30%, uses warm territory to be 150--150 ℃, and specific inductivity is 2.8-3.8.
Hybrid film of polyimide of the present invention can at room temperature be deposited standby.
The preparation method of the hybrid film of polyimide of modified by silicon dioxide tube provided by the invention comprises the steps:
1) with the surfactant templates material dissolves in water and alcoholic acid solution, by volume volumetric molar concentration is that 5mmol/L～25mmol/L is made into the template aqueous solution, and under agitation add the silicon ester of 0.1mol/L～3mol/L, under 15～40 ℃, left standstill self-assembly 20-80 minute; The ammoniacal liquor that adds 1mol/L～5mol/L in this mixing solutions left standstill 20-70 minute, products therefrom separates with testing sieve or filtering membrane, obtains white powder material after massive laundering is washed, and is viewed as the superfine silicon dioxide tubular material under the Electronic Speculum, caliber is 30～400 nanometers, is shaped as hollow tube; The weight percent concentration of described ammoniacal liquor is 25～28%;
2), join after taking by weighing in proportion and under agitation carry out reaction treatment in the solution that contains coupling agent with after this powder material seasoning; The consumption of described coupling agent is 0.1-1g/L;
3) above-mentioned treatment solution is added the ODA monomer and carry out ultra-sonic dispersion, adding monomer PMDA and solvent carry out home position polymerization reaction under stirring then, and the gained mixing liquid is poured on films on the sheet glass;
4) put into baking oven after drying under the room temperature and carry out the hot imidization solidification treatment, obtain the hybrid film of polyimide of the silicon-dioxide tubulose modification that can adjust specific inductivity of different silicon-dioxide tubulose fillers.
The tensio-active agent of described step 1) is anion surfactant or cats product; Wherein anion surfactant is selected from AOT, tartrate and OP-10; Cats product is selected from alkylsulfonate and quaternary ammonium salt; Described silicon ester is selected from tetraethoxy, positive silicic acid propyl ester, butyl silicate and the positive own ester of silicic acid.
Described coupling agent is silane coupling agent or titanate coupling agent.The temperature of the hot imidization solidification treatment of described step 4) is 50-350 ℃.
The invention has the advantages that:
The present invention is by the ratio of option table surface-active agent template compound, solvent and silicon source compound, can self-assembly obtain silicon-dioxide tubulose material, adopt resulting silicon-dioxide tubulose material after the coupling agent surface treatment, polyimide to be carried out modification, finally obtain in wide temperature territory, can adjusting the hybrid film of polyimide of the modified by silicon dioxide tube of specific inductivity.
Compare with the existing polyimide film, the advantage of the hybrid film of polyimide of modified by silicon dioxide tube provided by the present invention is: the hybrid film of polyimide of modified by silicon dioxide tube provided by the invention is for adjusting the hybrid film of polyimide of specific inductivity under broad temperature territory, adopt ultra-sonic dispersion and in-situ polymerization novel process, all fillers are the hollow silicon dioxide tubular material that utilizes the self-assembling technique preparation; In addition, thin film preparation process provided by the invention and general thin-film technique are basic identical, and used silicon-dioxide tubulose material is to make by the template self-assembly, and its method is simple, economic, practical, need not special solvent, and cost is low, is easy to apply.
Description of drawings
Fig. 1 is the stereoscan photograph of the silicon dioxide tube of embodiment 1 preparation;
Fig. 2 is the transmission electron microscope photo of the silicon dioxide tube of embodiment 2 preparations.
Fig. 3 be the hybrid film of polyimide of modified by silicon dioxide tube of embodiment 1 preparation in the time of 150 ℃ specific inductivity with the curve of frequency change;
Fig. 4 be the hybrid film of polyimide of modified by silicon dioxide tube of embodiment 3 preparation in the time of-150 ℃ specific inductivity with the curve of frequency change;
Fig. 5 is the curve that the dielectric constant with temperature of the modified by silicon dioxide tube hybrid film of polyimide of embodiment 4 preparations changes.
Embodiment
Further describe the present invention below in conjunction with drawings and Examples:
1) the alkylsulfonate cats product is dissolved in water and the alcoholic acid solution, by volume volumetric molar concentration is 5mmol/L～25mmol/L, be preferably 5mmol/L～8mmol/L, be made into the template aqueous solution and under agitation add the silicon ester of 0.1mol/L～3mol/L, under 15～40 ℃, left standstill self-assembly 40 minutes; In this mixing solutions, add 1mol/L～5mol/L, the strong aqua that is preferably 2mol/L～3mol/L 25～28% (weight percent concentration) left standstill 20-70 minute, products therefrom separates with testing sieve or filtering membrane, after washing, massive laundering obtains white powder material, be viewed as the superfine silicon dioxide tubular material under the Electronic Speculum, caliber is 30～350 nanometers, is shaped as hollow tube.See Fig. 1;
2), join after taking by weighing in the ratio of the 1-3% of resin content in the solution of certain density coupling agent and stir reaction treatment down with after this powder material seasoning; The weight part proportioning of powder material and coupling agent is 100: 0.5;
3) above-mentioned treatment solution is added the ODA monomer and carry out ultra-sonic dispersion, adding monomer PMDA and solvent carry out in-situ polymerization under stirring then, and the gained mixing liquid is poured on and films on the sheet glass behind the reaction certain hour;
4) putting into baking oven after drying under the room temperature carries out hot imidization and handles the hybrid film of polyimide that obtains 1-3% silicon-dioxide tubulose filler.The scope of its specific inductivity is 2.8-3.1 after tested, sees Fig. 3.
Embodiment 2
Press the step of embodiment 1, the 4mmol succsinic acid is dissolved in water and the alcoholic acid solution, stir preparation mould material solution down, its molality is 6mmol/kg; The silicon ester that under agitation adds 0.1mol/L～3mol/L left standstill self-assembly 40 minutes under 15～40 ℃; 25～28% (weight percent concentration) strong aqua strong aqua that adds 2mol/L～3mol/L in this mixing solutions left standstill 20-70 minute, products therefrom separates with testing sieve or filtering membrane, after washing, massive laundering obtains white powder material, be viewed as the superfine silicon dioxide tubular material under the Electronic Speculum, caliber is 40～50 nanometers, is shaped as hollow tube.See Fig. 2.
2) stir reaction treatment down with joining after taking by weighing in the ratio of the 3-5% of resin content after this powder material seasoning in the solution of certain density coupling agent; The weight part proportioning of powder material and coupling agent is 100: 0.5;
3) above-mentioned treatment solution is added the ODA monomer and carry out ultra-sonic dispersion, adding monomer PMDA and solvent carry out in-situ polymerization under stirring then, and the gained mixing liquid is poured on and films on the sheet glass behind the reaction certain hour;
4) putting into baking oven after drying under the room temperature carries out hot imidization and handles the hybrid film of polyimide that obtains 3-5% silicon-dioxide tubulose filler.The scope of its specific inductivity is 2.8-3.2 after tested, referring to Fig. 4.
Press the step of embodiment 1,3mmol tartrate is dissolved in water and the alcoholic acid solution, stir preparation mould material solution down, its molality is 6mmol/kg; The silicon ester that under agitation adds 0.1mol/L～3mol/L left standstill self-assembly 40 minutes under 15～40 ℃; The strong aqua strong aqua that adds 25～28% (weight percent concentration) of 2.5mol/L～3.5mol/L in this mixing solutions left standstill 20-70 minute, products therefrom separates with testing sieve or filtering membrane, after washing, massive laundering obtains white powder material, be viewed as the superfine silicon dioxide tubular material under the Electronic Speculum, caliber is 80～300 nanometers, is shaped as hollow tube.See Fig. 1.
2) stir reaction treatment down with joining after taking by weighing in 10% ratio of resin content after this powder material seasoning in the solution of certain density coupling agent; The weight part proportioning of powder material and coupling agent is 100: 12.
3) above-mentioned treatment solution is added the ODA monomer and carry out ultra-sonic dispersion, adding monomer PMDA and solvent carry out in-situ polymerization under stirring then, and the gained mixing liquid is poured on and films on the sheet glass behind the reaction certain hour;
4) putting into baking oven after drying under the room temperature carries out hot imidization and handles the hybrid film of polyimide that obtains 10% silicon-dioxide tubulose filler.The scope of its specific inductivity is 3.0-3.3 after tested, referring to Fig. 4.
Embodiment 4
Press the step of embodiment 1, the 3mmol citric acid is dissolved in water and the alcoholic acid solution, stir preparation mould material solution down, its molality is 5mmol/kg; The silicon ester that under agitation adds 0.1mol/L～3mol/L left standstill self-assembly 40 minutes under 15～40 ℃; The strong aqua strong aqua that adds 25～28% (weight percent concentration) of 2mol/L～3mol/L in this mixing solutions left standstill 20-70 minute, products therefrom separates with testing sieve or filtering membrane, after washing, massive laundering obtains white powder material, be viewed as the superfine silicon dioxide tubular material under the Electronic Speculum, caliber is 90～350 nanometers, is shaped as hollow tube.See Fig. 1.
2) stir reaction treatment down with joining after taking by weighing in 20% ratio of resin content after this powder material seasoning in the solution of certain density coupling agent; The weight part proportioning of powder material and coupling agent is 100: 20.
3) above-mentioned treatment solution is added the ODA monomer and carry out ultra-sonic dispersion, adding monomer PMDA and solvent carry out in-situ polymerization under stirring then, and the gained mixing liquid is poured on and films on the sheet glass behind the reaction certain hour;
4) putting into baking oven after drying under the room temperature carries out hot imidization and handles the hybrid film of polyimide that obtains 20% silicon-dioxide tubulose filler.The scope of its specific inductivity is 3.2-3.8 after tested, referring to Fig. 5.
Claims (11)
1, a kind of hybrid film of polyimide of modified by silicon dioxide tube adopts coupling agent treatment, ultrasonic dispersing, in-situ polymerization and coating process to make; Its matrix is a polyimide resin, and filler is 30～350 nano silicon tubular materials for the internal diameter that adopts the template self-assembling method to prepare;
Its preparation method comprises the steps:
1) with the surfactant templates material dissolves in water and alcoholic acid solution, by volume volumetric molar concentration is that 5mmol/L～25mmol/L is made into the template aqueous solution, and under agitation add the silicon ester of 0.1mol/L～3mol/L, under 15～40 ℃, left standstill self-assembly 20-80 minute; The ammoniacal liquor that adds 1mol/L～5mol/L in this mixing solutions left standstill 20-70 minute, products therefrom separates with testing sieve or filtering membrane, obtains white powder material after massive laundering is washed, and is viewed as the superfine silicon dioxide tubular material under the Electronic Speculum, caliber is 30～350 nanometers, is shaped as hollow tube;
2), take by weighing in proportion to join and under agitation carry out reaction treatment in the solution that contains coupling agent with after this powder material seasoning; The consumption of described coupling agent is 0.1-1g/L;
3) above-mentioned treatment solution is added the ODA monomer and carry out ultra-sonic dispersion, adding monomer PMDA and solvent carry out home position polymerization reaction under stirring then, and the gained mixing liquid is poured on films on the sheet glass;
4) put into baking oven after drying under the room temperature and carry out the hot imidization solidification treatment, obtain the hybrid film of polyimide of the silicon-dioxide tubulose modification that can adjust specific inductivity of different silicon-dioxide tubulose fillers.
2, by the hybrid film of polyimide of the described modified by silicon dioxide tube of claim 1, it is characterized in that the tensio-active agent of described step 1) is anion surfactant or cats product; Wherein anion surfactant is selected from AOT, tartrate and OP-10; Cats product is selected from alkylsulfonate and quaternary ammonium salt; Described silicon ester is selected from tetraethoxy, positive silicic acid propyl ester, butyl silicate and the positive own ester of silicic acid.
3, by the hybrid film of polyimide of the described modified by silicon dioxide tube of claim 1, it is characterized in that described coupling agent is silane coupling agent or titanate coupling agent.
4, by the hybrid film of polyimide of the described modified by silicon dioxide tube of claim 1, it is characterized in that the temperature of the hot imidization solidification treatment of described step 4) is 50-350 ℃.
5, by the hybrid film of polyimide of the described modified by silicon dioxide tube of claim 1, it is characterized in that the weight percent concentration of described ammoniacal liquor is 25～28%.
6, press the hybrid film of polyimide of the described modified by silicon dioxide tube of claim 1, it is characterized in that, silicon dioxide tube weight percent content in the hybrid film of polyimide of this modified by silicon dioxide tube is 0.1-30%, uses warm territory to be 150--150 ℃, and specific inductivity is 2.8-3.8.
7, the preparation method of the hybrid film of polyimide of the described modified by silicon dioxide tube of a kind of claim 1 comprises the steps:
1) with the surfactant templates material dissolves in water and alcoholic acid solution, by volume volumetric molar concentration is that 5mmol/L～25mmol/L is made into the template aqueous solution, and under agitation add the silicon ester of 0.1mol/L～3mol/L, under 15～40 ℃, left standstill self-assembly 20-80 minute; The strong aqua that adds 1mol/L～5mol/L in this mixing solutions left standstill 20-70 minute, products therefrom separates with testing sieve or filtering membrane, obtains white powder material after massive laundering is washed, and is viewed as the superfine silicon dioxide tubular material under the Electronic Speculum, caliber is 30～350 nanometers, is shaped as hollow tube;
2), take by weighing in proportion to join and under agitation carry out reaction treatment in the solution that contains coupling agent with after this powder material seasoning; The consumption of described coupling agent is 0.1-1g/L;
3) above-mentioned treatment solution is added the ODA monomer and carry out ultra-sonic dispersion, adding monomer PMDA and solvent carry out home position polymerization reaction under stirring then, and the gained mixing liquid is poured on films on the sheet glass;
4) put into baking oven after drying under the room temperature and carry out the hot imidization solidification treatment, obtain the hybrid film of polyimide of the silicon-dioxide tubulose modification that can adjust specific inductivity of different silicon-dioxide tubulose fillers.
8, press the preparation method of the hybrid film of polyimide of the described modified by silicon dioxide tube of claim 7, it is characterized in that the tensio-active agent of described step 1) is anion surfactant or cats product; Wherein anion surfactant is selected from AOT, tartrate and OP-10; Cats product is selected from alkylsulfonate and quaternary ammonium salt; Described silicon ester is selected from tetraethoxy, positive silicic acid propyl ester, butyl silicate and the positive own ester of silicic acid.
9, press the preparation method of the hybrid film of polyimide of the described modified by silicon dioxide tube of claim 7, it is characterized in that described coupling agent is silane coupling agent or titanate coupling agent.
10, press the preparation method of the hybrid film of polyimide of the described modified by silicon dioxide tube of claim 7, it is characterized in that the temperature of the hot imidization solidification treatment of described step 4) is 50-350 ℃.
11, by the hybrid film of polyimide of the described modified by silicon dioxide tube of claim 7, it is characterized in that the weight percent concentration of described ammoniacal liquor is 25～28%.
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| CN1760244A true CN1760244A (en) | 2006-04-19 |
| CN100340594C CN100340594C (en) | 2007-10-03 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100537854C (en) * | 2007-04-03 | 2009-09-09 | 中国科学院理化技术研究所 | A kind of preparation method of silica nanometer pipe |
| CN102558875A (en) * | 2011-12-16 | 2012-07-11 | 天津大学 | Silicon rubber composite material and method for improving dielectric properties |
| CN105017958A (en) * | 2015-07-31 | 2015-11-04 | 中国科学院合肥物质科学研究院 | Composite insulating paint and preparation method thereof |
| CN105949768A (en) * | 2016-05-23 | 2016-09-21 | 东莞珂洛赫慕电子材料科技有限公司 | Heat-insulation polyimide composite film for electric-heating film substrates |
| CN108047498A (en) * | 2017-12-05 | 2018-05-18 | 马鞍山市东方仪表有限公司 | A kind of processing technology of filler for automobile instrument macromolecular component |
| CN108395577A (en) * | 2017-02-08 | 2018-08-14 | 台虹科技股份有限公司 | Nano powder and polyimide resin composition |
| CN112480407A (en) * | 2020-11-30 | 2021-03-12 | 浙江中科玖源新材料有限公司 | Low-dielectric and low-loss polyimide film and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3486325B2 (en) * | 1997-06-26 | 2004-01-13 | 日本電信電話株式会社 | Polyamic acid solution, polyimide film and method for controlling characteristics of polyimide film |
| CN1218999C (en) * | 2002-02-07 | 2005-09-14 | 四川大学 | Prepn of lateral hydroxyl group containing polyimide/SiO2 hybrid film |
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- 2004-10-13 CN CNB2004100839198A patent/CN100340594C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100537854C (en) * | 2007-04-03 | 2009-09-09 | 中国科学院理化技术研究所 | A kind of preparation method of silica nanometer pipe |
| CN102558875A (en) * | 2011-12-16 | 2012-07-11 | 天津大学 | Silicon rubber composite material and method for improving dielectric properties |
| CN105017958A (en) * | 2015-07-31 | 2015-11-04 | 中国科学院合肥物质科学研究院 | Composite insulating paint and preparation method thereof |
| CN105949768A (en) * | 2016-05-23 | 2016-09-21 | 东莞珂洛赫慕电子材料科技有限公司 | Heat-insulation polyimide composite film for electric-heating film substrates |
| WO2017201847A1 (en) * | 2016-05-23 | 2017-11-30 | 东莞珂洛赫慕电子材料科技有限公司 | Heat-insulating polyimide composite film used in electric heating film substrate |
| CN108395577A (en) * | 2017-02-08 | 2018-08-14 | 台虹科技股份有限公司 | Nano powder and polyimide resin composition |
| CN108047498A (en) * | 2017-12-05 | 2018-05-18 | 马鞍山市东方仪表有限公司 | A kind of processing technology of filler for automobile instrument macromolecular component |
| CN112480407A (en) * | 2020-11-30 | 2021-03-12 | 浙江中科玖源新材料有限公司 | Low-dielectric and low-loss polyimide film and preparation method thereof |
| CN112480407B (en) * | 2020-11-30 | 2023-07-04 | 浙江中科玖源新材料有限公司 | Polyimide film with low dielectric and low loss and preparation method thereof |
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