CN102161826B - Polyimide resin based ternary hybrid material and preparation method thereof - Google Patents
Polyimide resin based ternary hybrid material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of organic/ inorganic hybrid materials, and discloses a polyimide resin based ternary hybrid material and a preparation method thereof. The hybrid material comprises the following raw materials in parts by weight: 100 parts of polyimide, 2-50 parts of barium titanate and 0.2-15 parts of graphite oxide. According to the preparation method disclosed by the invention, the synergistic action of graphite and barium titanate is fully utilized, so that the material has higher electroconductibility when the content of inorganic matters is lower so as to keep the flexibility and the excellent thermal performance of matrix resin.
Description
Technical field
The invention belongs to the organic/inorganic hybridization material field, be specifically related to a kind of polyimide resin based ternary hybrid material with conductivity and preparation method thereof.
Background technology
Polyimide, because of its performance and synthetic aspect outstanding feature, no matter be as structured material or as functional material, its huge application prospect is familiar with fully.It has high thermostability, high strength and high-modulus, low thermal coefficient of expansion and solvent resistance etc. and is widely used in the industrial circles such as aerospace, military affairs, electric and electronic.There is the polyimide of conductivity at electromagnetic shielding material, the electrostatic adhesion film, the aspects such as electrode materials of antistatic agent and battery also have broad application prospects.
Because polyimide itself belongs to the category of isolator, pass through often directly to introduce the electroconductibility inorganics so there is the polyimide of conductivity, as: carbon black, graphite, metallics, metal oxide etc. obtain.In order to obtain better conductivity, also have and attempt the composite use of two or more conducting material.As: the research of Chinese gongwu institute shows (aerospace material technique, the 4th phase in 2009), and expanded graphite (70wt%) and the composite introducing polyimide of carbon fiber (10wt%) (20wt%) can be obtained to higher specific conductivity.
Although prior art has the simple advantage of technique, but also there is a very large deficiency, that is: excessive to the inorganics amount of introducing in matrix resin, with original polymer phase ratio, the high addition of inorganics makes the density of matrix material increase, flexibility descends, the mechanical property variation, and then has limited the widespread use of this class matrix material.
CN200910184128.7 discloses a kind of polyimide/graphite hybrid material with high dielectric constant, and a small amount of graphite is introduced to polyimide to improve the matrix dielectric properties.The follow-up study discovery, as hope obtains the hybrid material with electroconductibility, the content of graphite needs to increase, and follows content of graphite to improve, and the original part mechanical property of polyimide worsens, and the second-order transition temperature appearance descends.
Summary of the invention
In order to overcome the existing deficiency prepared in conductivity polyimide technology, the invention provides a kind of polyimide resin based ternary hybrid material, when providing and thering is the high conductance matrix material, overcome to a certain extent existing polymer composites makes composite materials property descend deficiency because inorganic content is high.
Another object of the present invention is to provide the above-mentioned preparation method with polyimide resin based ternary hybrid material of conductivity.
Purpose of the present invention can reach by following measures:
A kind of polyimide-based ternary hybrid material with conductivity, its raw material is comprised of following mass parts component:
Polyimide 100
Barium titanate (BaTiO
3) 2～50
Graphite oxide 0.2～15.
When the barium titanate mass fraction is greater than 30 and the mass fraction of graphite oxide while being greater than 10, although the specific conductivity of ternary hybrid material reaches a higher level, but high inorganic content may make the mechanical property of material obviously descend, fragility increases, poor processability.Consider the balance between specific conductivity and mechanical property, the mass fraction of barium titanate is preferably 10～30, and the mass fraction of graphite oxide is preferably 0.5～10.
In polyimide-based ternary hybrid material with conductivity of the present invention, polyimide is comprised of dicarboxylic anhydride monomer and diamine monomer, and the mol ratio of diamine monomer and dicarboxylic anhydride monomer is 1: 1～1.20.In order to obtain the hybrid material of good mechanical performance, the mol ratio of diamine monomer and dicarboxylic anhydride monomer is preferably 1: 1.02～and 1.05.
In the described polyimide-based ternary hybrid material with conductivity, the preferable particle size of barium titanate (BaTiO3) is 50～500 nanometers, because if particle diameter is greater than 500 nanometers, may appears in polymeric matrix and be difficult to finely dispersed problem; If be less than 50 nanometers, may cause the rising of raw materials cost.It is coupling agent modified without silane surface or through silane coupler modified that barium titanate can be.Modification silane coupling agent used is Union carbide A-162, methyltrimethoxy silane, ethyl triethoxysilane, ethyl trimethoxy silane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane or γ-[(2,3)-epoxy the third oxygen] propyl trimethoxy silicane etc.Wherein, the method for modifying of barium titanate is according to described in CN 100999589A.Its main process is: barium titanate and the ethanolic soln of appropriate silane coupling agent are placed in to there-necked flask, and at 60～70 ℃ of temperature, reaction refluxed more than 4～5 hours, and filtration washing obtains the barium titanate of modification.Based on simplifying technique, the angle reduced costs is considered, the barium titanate of preferred long time without surface modification.
In order to make graphite flake layer disperse more evenly in polyimide matrix, before natural flake graphite or expanded graphite introducing polyimide, want first through the oxidation lift-off processing, by oxidizing reaction, make natural flake graphite or expanded graphite surface introduce a large amount of oxy radicals, obtain the higher graphite oxide of effective ratio area.By atomic force microscope, characterize, resulting oxidized graphite flake thickness 1～20 nanometer, radius-thickness ratio is 100～2000.
Dicarboxylic anhydride monomer of the present invention, there is no particular limitation, but, for obtaining preferably material of performance, be preferably the aromatic diacid anhydride monomer.Described aromatic diacid anhydride monomer is pyromellitic acid anhydride (PMDA) more preferably, 3, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3, 3 ', 4, 4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 3, 3 ', 4, 4 '-BPDA (BPDA), 2, 2-is two, and [4-(3 ', 4 '-dicarboxylic acid phenoxyl) phenyl] propane dianhydride (BPADA), 1, 4, 5, 8-naphthalene tetracarboxylic dianhydride (NTDA), 3, 3 ', 4, 4 '-sulfobenzide tetracarboxylic acid dicarboxylic anhydride (DSDA), 3, 3 ', 4, 4 '-diphenyl sulfide tetracarboxylic dianhydride (TDPA), triphen bis ether tetracarboxylic acid dianhydride (HQDPA), two (3, 4 phthalate anhydrides) dimethylsilane (SiDA), or 4, 4 '-(hexafluoro propylidene) two-Tetra hydro Phthalic anhydride (6FDA).
From cost, the acquisition difficulty or ease equal angles of material, consider, in above-mentioned aromatic diacid acid anhydride, particularly preferably: pyromellitic acid anhydride (PMDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA) or 3,3 ', 4,4 '-BPDA (BPDA).
Diamine monomer of the present invention, there is no particular limitation, can be aliphatic diamine monomers or aromatic diamine monomer.But for obtaining preferably material of performance, optimization aromatic diamine monomer.Described aromatic diamine monomer more preferably 4,4 '-diaminodiphenyl oxide (ODA), p-phenylenediamine (PPD), m-phenylenediamine (MPD), 4,4 '-diamino-diphenyl propane (IDPA), 4,4 '-diaminodiphenyl-methane (MDA), 4,4 '-diamino-diphenyl thioether (SDA), 3,3 '-diamino diphenyl sulfone (DDS) or 1,5-diaminonaphthalene (1,5-NDA).
From cost, acquisition difficulty or ease and the toxicity equal angles of material, consider, in above-mentioned aromatic diamine monomer, particularly preferably: 4,4 '-diaminodiphenyl oxide (ODA), p-phenylenediamine (PPD) or m-phenylenediamine (MPD).
A kind ofly prepare the above-mentioned method with polyimide-based ternary hybrid material of conductivity, it comprises the following steps:
(1) graphite oxide is scattered in organic solvent, it being uniformly dispersed under room temperature ultrasonic 2～20 hours becomes the graphite oxide dispersion liquid;
(2) barium titanate is added in the graphite oxide dispersion liquid, it being uniformly dispersed under room temperature ultrasonic 3～6 hours becomes graphite oxide-barium titanate dispersions;
(3) under the protection of rare gas element, diamine monomer is added in graphite oxide-barium titanate dispersions, stir, add wherein the dicarboxylic anhydride monomer after to be dissolved; After having fed in raw material, under the protection of rare gas element, react under 10～35 ℃ 10～30 hours, obtain polyamic acid/graphite oxide-barium titanate hydridization solution;
(4) after polyamic acid/graphite oxide-barium titanate hydridization solution being carried out under 280～350 ℃ to the imidization reaction of 2～4 hours, the polyimide-based ternary hybrid material that obtains having electroconductibility.
In aforesaid method, the mass parts of graphite oxide is 0.2-15; The mass parts of barium titanate is 2-50.
The mass fraction of diamine monomer and dicarboxylic anhydride monomer and be 100 in aforesaid method step (3), wherein the consumption mol ratio of diamine monomer and dicarboxylic anhydride monomer is 1: 1～1.20, be preferably 1: 1.02～1.05, its reaction times, consider over-all properties stable of final material, preferably 12-24h.
Each raw material adopted in the preparation method with and ratio the same.Wherein graphite oxide is 10 by particle diameter
3～10
6purpose natural flake graphite or expanded graphite carry out oxidation and peel off and prepare.Concrete preparation method can the described (J.Am.Chem.Soc.1958 of reference, 80:1339), main process is: natural flake graphite or expanded graphite, SODIUMNITRATE, potassium permanganate are joined to 98% vitriol oil that is placed in ice bath, keep constantly stirring 1 hour, obtain mixed solution.Remove ice bath, mixed solution is placed in to 35 ℃ of water-bath constant temperature 4 hours.With deionized water dilution, make mixed solution 90 ℃ of holding temperatures 15 minutes.With the deionized water dilution, add hydrogen peroxide filtered while hot again.Be washed till sulfate radical-free ion (SO with deionized water
4 2-) get final product.
Described in aforesaid method step (1), organic solvent is N,N-dimethylacetamide, DMF, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO).The ultrasonic graphite oxide that refers to that the hyperacoustic method of employing is difficult to ordinary method to disperse used in the preparation method is disperseed, therefore the present invention there is no particular requirement to the ultrasonic wave of specifically selecting which kind of frequency and power, as long as graphite oxide fully can be disperseed.Consider the difference of different hyperacoustic dispersion effects, dispersion efficiency and energy consumption, the present invention is defined as 2～20 hours by ultrasonic time simultaneously.
The polyimide-based ternary hybrid material with conductivity of present method gained can be by making polyamic acid/graphite oxide-barium titanate hydridization solution in stainless steel plate, sheet glass, silicon chip, metal aluminum foil, tetrafluoroethylene or other stromal surface film forming or being molded into then imidization shaping of mould.Manufacturing process commonly used is film forming on sheet glass or silicon chip.
Of the present invention have the polyimide-based ternary hybrid material of conductivity with polyimide, graphite oxide and barium titanate are that raw material is prepared, graphite oxide is reduced to graphite flake layer in the imidization reaction process, and the form that therefore final product is scattered in polyimide matrix with graphite exists.
Beneficial effect of the present invention: the composite electroconductibility of improving polyimide of selective oxidation graphite of the present invention and barium titanate, utilize the synergistic effect between graphite and barium titanate, realize adding the matrix material that less inorganics obtains high conductance, overcome in traditional method, inorganics adds the shortcoming that the valency amount is high.The polyimide-based ternary hybrid material of conductivity of the present invention (material particularly prepared according to method of the present invention), not only have higher specific conductivity, and kept the original flexibility of polyimide matrix and excellent mechanical property.
There is the polyimide-based ternary hybrid material of conductivity at electromagnetic shielding material, the electrostatic adhesion film, the aspects such as electrode materials of antistatic agent and battery also have broad application prospects.
Embodiment
The present invention can obtain by the embodiment by following preferred embodiment, but these embodiment only are to illustrate, and scope of the present invention is not made and being defined.
The starting material that use in embodiment:
A) graphite oxide, concrete preparation method is as follows:
98% vitriol oil of getting 400 mass parts is placed in ice bath, adds 10 mass parts natural flake graphites or expanded graphite, 5 mass parts SODIUMNITRATE, 30 mass parts potassium permanganate, mechanical stirring 1 hour, and keep mixeding liquid temperature lower than 20 ℃.Remove ice bath, by mixed solution be placed in 35 ℃ of water-bath constant temperature after 4 hours with 500 mass parts deionized waters dilutions, make mixed solution 90 ℃ of holding temperatures 15 minutes.With deionized water 900 mass parts dilutions, add 60 mass parts hydrogen peroxide filtered while hot.With deionized water, be washed till without SO
4 2-ion.
Wherein as the natural flake graphite of raw material or expanded graphite particle diameter between 10
3～10
6order.After peroxidation is peeled off, resulting oxidized graphite flake thickness is 1～20 nanometer, and radius-thickness ratio is 100～2000.
B) barium titanate: Guangdong Fenghua High Technology Co., Ltd; Particle diameter is 50～500 nanometers.
C) organic monomer: pyromellitic acid anhydride (PMDA): Chemical Reagent Co., Ltd., Sinopharm Group; 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA): Co., Ltd in SIGMA-Aldrich; 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA): Co., Ltd in SIGMA-Aldrich; 3,3 ', 4,4 '-BPDA (BPDA): Co., Ltd in SIGMA-Aldrich; 4,4 '-diaminodiphenyl ether (ODA): Chemical Reagent Co., Ltd., Sinopharm Group; P-phenylenediamine (PPD): Chemical Reagent Co., Ltd., Sinopharm Group; M-phenylenediamine (MPD): Chemical Reagent Co., Ltd., Sinopharm Group;
D) organic solvent: N,N-dimethylacetamide (DMAc): Chemical Reagent Co., Ltd., Sinopharm Group; N-Methyl pyrrolidone (NMP): Chemical Reagent Co., Ltd., Sinopharm Group; Dimethyl sulfoxide (DMSO) (DMSO): Chemical Reagent Co., Ltd., Sinopharm Group; DMF (DMF): Chemical Reagent Co., Ltd., Sinopharm Group;
The measuring method of the specific conductivity of polyimide-based ternary hybrid material and second-order transition temperature in embodiment and Comparative Examples:
A) mensuration of specific conductivity: under 22 ℃, Novocontrol wideband dielectric and impedance spectrometer (BDS-40 Germany), adopt 2 centimetres of electrode diameters, test frequency scope: 0.01Hz～10MHz, impressed voltage: 1V.Before test, sample surfaces through metalized (sputter or brush elargol) with guarantee between sample and test electrode contact good.The mean value that the resulting materials specific conductivity is three sample test results.
B) room temperature storage modulus and second-order transition temperature test: Dynamic Viscoelastic spectrometer (the TA Q800 U.S.), test frequency 1Hz, probe temperature: room temperature～450 ℃, 3 ℃/min of heat-up rate.The test specimen in use is film forming on sheet glass, then takes off, and is tested after being cut into batten (size: wide 6.30mm, length>20mm, thickness is surveyed).
Embodiment 1
(1) 0.106g (1 mass parts) graphite oxide is dispersed in the 81ml N-Methyl pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 15 hours becomes the graphite oxide dispersion liquid;
(2) the barium titanate 2.12g that is the 50-100 nanometer by particle diameter (20 mass parts) is dispersed in above-mentioned graphite oxide dispersion liquid, and ultrasonic 4 hours of room temperature, obtain graphite oxide-barium titanate dispersions;
(3) under the protection of rare gas element, by 5.0g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned graphite oxide-barium titanate dispersions, stirs, and slowly adds wherein 5.6g pyromellitic acid anhydride (PMDA) after to be dissolved; After having fed in raw material, under the protection of rare gas element, under 25 ℃, react 16 hours, obtain polyamic acid/graphite oxide-barium titanate hydridization solution;
(4) by polyamic acid/graphite oxide of obtaining-barium titanate hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 2 hours under 300 ℃ after, obtain polyimide-based ternary hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 1.6 * 10
-5s/cm.396.5 ℃ of the second-order transition temperatures of hybrid material.
Comparative Examples 1
(1) 0.106g (1 mass parts) graphite oxide is dispersed in the 81ml N-Methyl pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 15 hours becomes the graphite oxide dispersion liquid;
(2) under the protection of rare gas element, by 5.0g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned graphite oxide dispersion liquid, stirs, and slowly adds wherein 5.6g pyromellitic acid anhydride (PMDA) after to be dissolved; After having fed in raw material, under the protection of rare gas element, under 25 ℃, react 16 hours, obtain polyamic acid/graphite hydridization solution;
(3) by polyamic acid/barium titanate of obtaining-graphite hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 2 hours under 300 ℃ after, obtain polyimide/graphite hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 1.6 * 10
-8s/cm.393.5 ℃ of the second-order transition temperatures of hybrid material.Its specific conductivity is starkly lower than the polyimide-based ternary hybrid material in embodiment 1.
Comparative Examples 2
(1) the barium titanate 2.12g that is the 50-100 nanometer by particle diameter (20 mass parts) is dispersed in the 81ml N-Methyl pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 4 hours becomes barium titanate dispersions;
(2) under the protection of rare gas element, by 5.0g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned barium titanate dispersions, stirs, and slowly adds wherein 5.6g pyromellitic acid anhydride (PMDA) after to be dissolved; After having fed in raw material, under the protection of rare gas element, under 25 ℃, react 16 hours, obtain polyamic acid/barium titanate hydridization solution;
(3) by the polyamic acid that obtains/barium titanate hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 2 hours under 300 ℃ after, obtain polyimide/barium titanate hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 3.0 * 10
-15s/cm.395.9 ℃ of the second-order transition temperatures of hybrid material.Its specific conductivity is starkly lower than the polyimide-based ternary hybrid material in embodiment 1.
Comparative Examples 3
(1) under the protection of rare gas element, by 5.0g 4,4 '-diaminodiphenyl ether (ODA) adds in the 81ml N-Methyl pyrrolidone, stirs, and slowly adds wherein 5.6g pyromellitic acid anhydride (PMDA) after to be dissolved; After having fed in raw material, under the protection of rare gas element, under 22 ℃, react 16 hours, obtain the polyamic acid solution of homogeneous;
(2) by the polyamic acid solution film forming that obtains on stainless steel plate, carry out the imidization reaction of 2 hours under 300 ℃ after, obtain pure polyimide film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 3.9 * 10
-13s/cm.397.6 ℃ of the second-order transition temperatures of polyimide film.Its specific conductivity is starkly lower than the polyimide-based ternary hybrid material in embodiment 1.
Embodiment 2
(1) 0.164g (1.5 mass parts) graphite oxide is dispersed in the 84ml N,N-dimethylacetamide, and it being uniformly dispersed under room temperature ultrasonic 3 hours becomes the graphite oxide dispersion liquid;
(2) the barium titanate 3.27g that is the 100-200 nanometer by particle diameter (30 mass parts) is dispersed in above-mentioned graphite oxide dispersion liquid, and ultrasonic 5 hours of room temperature, obtain graphite oxide-barium titanate dispersions;
(3) under the protection of rare gas element, 2.7g mphenylenediamine (MPD) is added in above-mentioned graphite oxide-barium titanate dispersions, stir, slowly add wherein 8.2g 3 after to be dissolved, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After having fed in raw material, under the protection of rare gas element, under 27 ℃, react 15 hours, obtain polyamic acid/graphite oxide-barium titanate hydridization solution;
(4) by polyamic acid/graphite oxide of obtaining-barium titanate hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 3 hours under 320 ℃ after, obtain polyimide-based ternary hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 9.6 * 10
-4s/cm.303.6 ℃ of the second-order transition temperatures of hybrid material.
Comparative Examples 4
(1) 0.164g (1.5 mass parts) graphite oxide is dispersed in the 84ml N,N-dimethylacetamide, and it being uniformly dispersed under room temperature ultrasonic 3 hours becomes the graphite oxide dispersion liquid;
(2) under the protection of rare gas element, 2.7g mphenylenediamine (MPD) is added in above-mentioned graphite oxide dispersion liquid, stir, slowly add wherein 8.2g 3 after to be dissolved, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After having fed in raw material, under the protection of rare gas element, under 27 ℃, react 15 hours, obtain polyamic acid/graphite hydridization solution;
(3) by the polyamic acid that obtains/graphite hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 3 hours under 320 ℃ after, obtain polyimide/graphite hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 6.6 * 10
-8s/cm.300.2 ℃ of the second-order transition temperatures of hybrid material.Its specific conductivity is starkly lower than the polyimide-based ternary hybrid material in embodiment 2.
Comparative Examples 5
(1) under the protection of rare gas element, 2.7g mphenylenediamine (MPD) is added in the 84ml N,N-dimethylacetamide, stir, slowly add wherein 8.2g 3 after to be dissolved, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After having fed in raw material, under the protection of rare gas element, under 27 ℃, react 15 hours, obtain the polyamic acid solution of homogeneous;
(2) by the polyamic acid solution film forming that obtains on stainless steel plate, carry out the imidization reaction of 3 hours under 320 ℃ after, obtain pure polyimide film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 8.2 * 10
-13s/cm.300.0 ℃ of the second-order transition temperatures of polyimide film.Its specific conductivity is starkly lower than the polyimide-based ternary hybrid material in embodiment 2.
Embodiment 3
(1) 0.40g (4 mass parts) graphite oxide is dispersed in the 78ml N-Methyl pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 9 hours becomes the graphite oxide dispersion liquid;
(2) barium titanate that is the 200-500 nanometer by particle diameter is placed in there-necked flask with the ethanolic soln of appropriate silane coupling agent, and at 70 ℃ of temperature, reaction refluxes 5 hours, and filtration washing obtains the barium titanate of modification.1.02g (10 mass parts) modified barium carbonate is dispersed in above-mentioned graphite oxide dispersion liquid, and ultrasonic 3 hours of room temperature, obtain graphite oxide-barium titanate dispersions;
(3) under the protection of rare gas element, 2.7g Ursol D (PPD) is added in above-mentioned graphite oxide-barium titanate dispersions, stir, slowly add wherein 7.5g 3 after to be dissolved, 3 ', 4,4 '-BPDA (BPDA); After having fed in raw material, under the protection of rare gas element, under 20 ℃, react 20 hours, obtain polyamic acid/graphite oxide-barium titanate hydridization solution;
(4) by polyamic acid/graphite oxide of obtaining-barium titanate hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 3 hours under 350 ℃ after, obtain polyimide-based ternary hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 5.3 * 10
-4s/cm.The second-order transition temperature of hybrid material>450 ℃ (higher than the highest probe temperature of DMA).
Comparative Examples 6
(1) 0.40g (4 mass parts) graphite oxide is dispersed in the 78ml N-Methyl pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 9 hours becomes the graphite oxide dispersion liquid;
(2) under the protection of rare gas element, 2.7g Ursol D (PPD) is added in above-mentioned graphite oxide dispersion liquid, stir, slowly add wherein 7.5g 3 after to be dissolved, 3 ', 4,4 '-BPDA (BPDA); After having fed in raw material, under the protection of rare gas element, under 20 ℃, react 20 hours, obtain polyamic acid/graphite hydridization solution;
(3) by the polyamic acid that obtains/graphite hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 3 hours under 350 ℃ after, obtain polyimide/graphite hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out the dielectric properties test, and under 100Hz, specific conductivity 9.1 * 10
-8s/cm.The second-order transition temperature of hybrid material>450 ℃ (higher than the highest probe temperature of DMA).Its specific conductivity is starkly lower than the polyimide-based ternary hybrid material in embodiment 3.
Embodiment 4
(1) 0.79g (6 mass parts) graphite oxide is dispersed in the 101ml N-Methyl pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 20 hours becomes the graphite oxide dispersion liquid;
(2) the barium titanate 3.28g that is the 100-200 nanometer by particle diameter (25 mass parts) is dispersed in above-mentioned graphite oxide dispersion liquid, and ultrasonic 6 hours of room temperature, obtain graphite oxide-barium titanate dispersions;
(3), under the protection of rare gas element, by 5.00g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned graphite oxide-barium titanate dispersions, stir, slowly add wherein 8.1g3,3 ' after to be dissolved, 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA); After having fed in raw material, under the protection of rare gas element, under 12 ℃, react 24 hours, obtain polyamic acid/graphite oxide-barium titanate hydridization solution;
(4) by polyamic acid/graphite oxide of obtaining-barium titanate hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 4 hours under 300 ℃ after, obtain polyimide-based ternary hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 8.7 * 10
-5s/cm.270.9 ℃ of the second-order transition temperatures of hybrid material.
Comparative Examples 7
(1) 0.79g (6 mass parts) graphite oxide is dispersed in the 101ml N-Methyl pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 20 hours becomes the graphite oxide dispersion liquid;
(2) under the protection of rare gas element, by 5.00g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned graphite oxide dispersion liquid, stirs, and slowly adds wherein 8.1g3 after to be dissolved, and 3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA); After having fed in raw material, under the protection of rare gas element, under 12 ℃, react 24 hours, obtain polyamic acid/graphite hydridization solution;
(3) by the polyamic acid that obtains/graphite hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 4 hours under 300 ℃ after, obtain polyimide/graphite hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 5.7 * 10
-7s/cm.The second-order transition temperature of hybrid material is 267.3 ℃.Its specific conductivity is starkly lower than the polyimide-based ternary hybrid material in embodiment 4.
Comparative Examples 8
(1) the barium titanate 3.28g that is the 100-200 nanometer by particle diameter (25 mass parts) is dispersed in the 101mlN-methyl-2-pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 6 hours becomes barium titanate dispersions;
(2) under the protection of rare gas element, by 5.00g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned barium titanate dispersions, stirs, and slowly adds wherein 8.1g 3 after to be dissolved, and 3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA); After having fed in raw material, under the protection of rare gas element, under 12 ℃, react 24 hours, obtain polyamic acid/barium titanate hydridization solution;
(3) by the polyamic acid that obtains/barium titanate hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 4 hours under 300 ℃ after, obtain polyimide/barium titanate hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, 100Hz specific conductivity 9.3 * 10
-14s/cm.The second-order transition temperature of polyimide film is 269.5 ℃.Its specific conductivity is starkly lower than the polyimide-based ternary hybrid material in embodiment 4.
Embodiment 5
(1) 0.066g (0.5 mass parts) graphite oxide is dispersed in the 102ml N,N-dimethylacetamide, and it being uniformly dispersed under room temperature ultrasonic 3 hours becomes the graphite oxide dispersion liquid;
(2) the barium titanate 1.98g that is the 50-150 nanometer by particle diameter (15 mass parts) is dispersed in above-mentioned graphite oxide dispersion liquid, and ultrasonic 5 hours of room temperature, obtain graphite oxide-barium titanate dispersions;
(3), under the protection of rare gas element, by 5.0g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned graphite oxide-barium titanate dispersions, stir, slowly add wherein 8.2g3,3 ' after to be dissolved, 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After having fed in raw material, under the protection of rare gas element, under 20 ℃, react 20 hours, obtain polyamic acid/graphite oxide-barium titanate hydridization solution;
(4) by polyamic acid/graphite oxide of obtaining-barium titanate hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 2 hours under 300 ℃ after, obtain polyimide-based ternary hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 6.9 * 10
-8s/cm.309.5 ℃ of the second-order transition temperatures of hybrid material.
Embodiment 6
(1) 0.10g (0.75 mass parts) graphite oxide is dispersed in the 102mlN-methyl-2-pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 8 hours becomes the graphite oxide dispersion liquid;
(2) the barium titanate 2.66g that is the 50-150 nanometer by particle diameter (20 mass parts) is dispersed in above-mentioned graphite oxide dispersion liquid, and ultrasonic 6 hours of room temperature, obtain graphite oxide-barium titanate dispersions;
(3), under the protection of rare gas element, by 5.0g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned graphite oxide-barium titanate dispersions, stir, slowly add wherein 8.3g3,3 ' after to be dissolved, 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After having fed in raw material, under the protection of rare gas element, under 15 ℃, react 18 hours, obtain polyamic acid/graphite oxide-barium titanate hydridization solution;
(4) by polyamic acid/graphite oxide of obtaining-barium titanate hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 2 hours under 300 ℃ after, obtain polyimide-based ternary hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 6.6 * 10
-6s/cm.301.8 ℃ of the second-order transition temperatures of hybrid material.
Embodiment 7
(1) 0.134g (1 mass parts) graphite oxide is dispersed in the 102ml dimethyl sulfoxide (DMSO), and it being uniformly dispersed under room temperature ultrasonic 16 hours becomes the graphite oxide dispersion liquid;
(2) the barium titanate 2.68g that is the 100-200 nanometer by particle diameter (20 mass parts) is dispersed in above-mentioned graphite oxide dispersion liquid, and ultrasonic 5 hours of room temperature, obtain graphite oxide-barium titanate dispersions;
(3), under the protection of rare gas element, by 5.0g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned graphite oxide-barium titanate dispersions, stir, slowly add wherein 8.4g3,3 ' after to be dissolved, 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After having fed in raw material, under the protection of rare gas element, under 30 ℃, react 12 hours, obtain polyamic acid/graphite oxide-barium titanate hydridization solution;
(4) by polyamic acid/graphite oxide of obtaining-barium titanate hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 2 hours under 300 ℃ after, obtain polyimide-based ternary hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 1.3 * 10
-5s/cm.298.7 ℃ of the second-order transition temperatures of hybrid material.
Embodiment 8
(1) 0.066g (0.5 mass parts) graphite oxide is dispersed in 102mlN, and in dinethylformamide, it being uniformly dispersed under room temperature ultrasonic 20 hours becomes the graphite oxide dispersion liquid;
(2) the barium titanate 6.60g that is the 50-150 nanometer by particle diameter (50 mass parts) is dispersed in above-mentioned graphite oxide dispersion liquid, and ultrasonic 6 hours of room temperature, obtain graphite oxide-barium titanate dispersions;
(3), under the protection of rare gas element, by 5.0g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned graphite oxide-barium titanate dispersions, stir, slowly add wherein 8.2g3,3 ' after to be dissolved, 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After having fed in raw material, under the protection of rare gas element, under 25 ℃, react 24 hours, obtain polyamic acid/graphite oxide-barium titanate hydridization solution;
(4) by polyamic acid/graphite oxide of obtaining-barium titanate hydridization solution film forming on sheet glass, carry out the imidization reaction of 3 hours under 300 ℃ after, obtain polyimide-based ternary hybridized film.
Film is taken off, and the thickness of lower surface sputter thereon is about the gold layer of 0.1 micron, carries out electric performance test, and under 100Hz, specific conductivity 1.4 * 10
-9s/cm.291.8 ℃ of the second-order transition temperatures of hybrid material.
Embodiment 9
(1) 0.04g (0.3 mass parts) graphite oxide is dispersed in the 102mlN-methyl-2-pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 12 hours becomes the graphite oxide dispersion liquid;
(2) the barium titanate 0.4g that is the 100-200 nanometer by particle diameter (3 mass parts) is dispersed in above-mentioned graphite oxide dispersion liquid, and ultrasonic 3 hours of room temperature, obtain graphite oxide-barium titanate dispersions;
(3), under the protection of rare gas element, by 5.0g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned graphite oxide-barium titanate dispersions, stir, slowly add wherein 8.3g3,3 ' after to be dissolved, 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After having fed in raw material, under the protection of rare gas element, under 15 ℃, react 18 hours, obtain polyamic acid/graphite oxide-barium titanate hydridization solution;
(4) by polyamic acid/graphite oxide of obtaining-barium titanate hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 2 hours under 350 ℃ after, obtain polyimide-based ternary hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 8.5 * 10
-9s/cm.297.8 ℃ of the second-order transition temperatures of hybrid material.
Embodiment 10
(1) 1.73g (13 mass parts) graphite oxide is dispersed in the 162mlN-methyl-2-pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 20 hours becomes the graphite oxide dispersion liquid;
(2) the barium titanate 5.99g that is the 50-150 nanometer by particle diameter (45 mass parts) is dispersed in above-mentioned graphite oxide dispersion liquid, and ultrasonic 6 hours of room temperature, obtain graphite oxide-barium titanate dispersions;
(3), under the protection of rare gas element, by 5.0g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned graphite oxide-barium titanate dispersions, stir, slowly add wherein 8.3g3,3 ' after to be dissolved, 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After having fed in raw material, under the protection of rare gas element, under 23 ℃, react 20 hours, obtain polyamic acid/graphite oxide-barium titanate hydridization solution;
(4) by polyamic acid/graphite oxide of obtaining-barium titanate hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 2 hours under 300 ℃ after, obtain polyimide-based ternary hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 1.6 * 10
-4s/cm.306.8 ℃ of the second-order transition temperatures of hybrid material.
Embodiment 11
(1) 1.86g (14 mass parts) graphite oxide is dispersed in the 180mlN-methyl-2-pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 20 hours becomes the graphite oxide dispersion liquid;
(2) the barium titanate 0.67g that is the 50-150 nanometer by particle diameter (5 mass parts) is dispersed in above-mentioned graphite oxide dispersion liquid, and ultrasonic 6 hours of room temperature, obtain graphite oxide-barium titanate dispersions;
(3), under the protection of rare gas element, by 5.0g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned graphite oxide-barium titanate dispersions, stir, slowly add wherein 8.3g3,3 ' after to be dissolved, 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After having fed in raw material, under the protection of rare gas element, under 24 ℃, react 28 hours, obtain polyamic acid/graphite oxide-barium titanate hydridization solution;
(4) by polyamic acid/graphite oxide of obtaining-barium titanate hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 2 hours under 300 ℃ after, obtain polyimide-based ternary hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 1.8 * 10
-4s/cm.323.3 ℃ of the second-order transition temperatures of hybrid material.
Embodiment 12
(1) 1.00g (7.5 mass parts) graphite oxide is dispersed in the 110mlN-methyl-2-pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 18 hours becomes the graphite oxide dispersion liquid;
(2) the barium titanate 3.33g that is the 50-150 nanometer by particle diameter (25 mass parts) is dispersed in above-mentioned graphite oxide dispersion liquid, and ultrasonic 5 hours of room temperature, obtain graphite oxide-barium titanate dispersions;
(3), under the protection of rare gas element, by 5.0g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned graphite oxide-barium titanate dispersions, stir, slowly add wherein 8.3g3,3 ' after to be dissolved, 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After having fed in raw material, under the protection of rare gas element, under 25 ℃, react 18 hours, obtain polyamic acid/graphite oxide-barium titanate hydridization solution;
(4) by polyamic acid/graphite oxide of obtaining-barium titanate hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 2 hours under 320 ℃ after, obtain polyimide-based ternary hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 1.6 * 10
-4s/cm.327.3 ℃ of the second-order transition temperatures of hybrid material.
Embodiment 13
(1) 1.33g (10 mass parts) graphite oxide is dispersed in the 120mlN-methyl-2-pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 16 hours becomes the graphite oxide dispersion liquid;
(2) the barium titanate 1.33g that is the 50-150 nanometer by particle diameter (10 mass parts) is dispersed in above-mentioned graphite oxide dispersion liquid, and ultrasonic 6 hours of room temperature, obtain graphite oxide-barium titanate dispersions;
(3), under the protection of rare gas element, by 5.0g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned graphite oxide-barium titanate dispersions, stir, slowly add wherein 8.3g3,3 ' after to be dissolved, 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After having fed in raw material, under the protection of rare gas element, under 26 ℃, react 12 hours, obtain polyamic acid/graphite oxide-barium titanate hydridization solution;
(4) by polyamic acid/graphite oxide of obtaining-barium titanate hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 2 hours under 280 ℃ after, obtain polyimide-based ternary hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 1.3 * 10
-5s/cm.327.7 ℃ of the second-order transition temperatures of hybrid material.
Embodiment 14
(1) 0.67g (5 mass parts) graphite oxide is dispersed in the 102mlN-methyl-2-pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 8 hours becomes the graphite oxide dispersion liquid;
(2) the barium titanate 2.68g that is the 50-150 nanometer by particle diameter (20 mass parts) is dispersed in above-mentioned graphite oxide dispersion liquid, and ultrasonic 5 hours of room temperature, obtain graphite oxide-barium titanate dispersions;
(3), under the protection of rare gas element, by 5.0g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned graphite oxide-barium titanate dispersions, stir, slowly add wherein 8.4g3,3 ' after to be dissolved, 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After having fed in raw material, under the protection of rare gas element, under 34 ℃, react 11 hours, obtain polyamic acid/graphite oxide-barium titanate hydridization solution;
(4) by polyamic acid/graphite oxide of obtaining-barium titanate hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 2 hours under 300 ℃ after, obtain polyimide-based ternary hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 6.9 * 10
-5s/cm.292.2 ℃ of the second-order transition temperatures of hybrid material.
Embodiment 15
(1) 0.268g (2 mass parts) graphite oxide is dispersed in the 102mlN-methyl-2-pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 4 hours becomes the graphite oxide dispersion liquid;
(2) the barium titanate 4.02g that is the 50-150 nanometer by particle diameter (30 mass parts) is dispersed in above-mentioned graphite oxide dispersion liquid, and ultrasonic 6 hours of room temperature, obtain graphite oxide-barium titanate dispersions;
(3), under the protection of rare gas element, by 5.0g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned graphite oxide-barium titanate dispersions, stir, slowly add wherein 8.4g3,3 ' after to be dissolved, 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After having fed in raw material, under the protection of rare gas element, under 12 ℃, react 25 hours, obtain polyamic acid/graphite oxide-barium titanate hydridization solution;
(4) by polyamic acid/graphite oxide of obtaining-barium titanate hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 2 hours under 350 ℃ after, obtain polyimide-based ternary hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 1.2 * 10
-5s/cm.283.7 ℃ of the second-order transition temperatures of hybrid material.
Comparative Examples 9
(1) under the protection of rare gas element, by 5.00g 4,4 '-diaminodiphenyl ether (ODA) adds in the 102ml N-Methyl pyrrolidone, stirs, and slowly adds wherein 8.3g3 after to be dissolved, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After having fed in raw material, under the protection of rare gas element, under 20 ℃, react 20 hours, obtain the polyamic acid solution of homogeneous;
(2) by the polyamic acid solution film forming that obtains on stainless steel plate, carry out the imidization reaction of 2 hours under 300 ℃ after, obtain pure polyimide film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 5.7 * 10
-13s/cm.299.6 ℃ of the second-order transition temperatures of polyimide film.Its specific conductivity is starkly lower than the polyimide-based ternary hybrid material in embodiment 5-15.
Comparative Examples 10
(1) the barium titanate 6.70g that is the 50-150 nanometer by particle diameter (50 mass parts) is dispersed in the 102mlN-methyl-2-pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 6 hours becomes barium titanate dispersions;
(2) under the protection of rare gas element, by 5.0g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned barium titanate dispersions, stirs, and slowly adds wherein 8.4g 3 after to be dissolved, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After having fed in raw material, under the protection of rare gas element, under 20 ℃, react 20 hours, obtain polyamic acid/barium titanate hydridization solution;
(3) by the polyamic acid that obtains/barium titanate hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 2 hours under 300 ℃ after, obtain polyimide/barium titanate hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 9.0 * 10
-13s/cm.298.0 ℃ of the second-order transition temperatures of hybrid material.Its specific conductivity is starkly lower than the polyimide-based ternary hybrid material in embodiment 5-15.
Comparative Examples 11
(1) 0.67g (5 mass parts) graphite oxide is dispersed in the 102mlN-methyl-2-pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 15 hours becomes the graphite oxide dispersion liquid;
(2) under the protection of rare gas element, by 5.0g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned graphite oxide dispersion liquid, stirs, and slowly adds wherein 8.4g 3 after to be dissolved, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After having fed in raw material, under the protection of rare gas element, under 20 ℃, react 20 hours, obtain polyamic acid/graphite oxide hydridization solution;
(3) by the polyamic acid that obtains/graphite oxide hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 2 hours under 300 ℃ after, obtain polyimide/graphite hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 1.5 * 10
-7s/cm.284.6 ℃ of the second-order transition temperatures of hybrid material.Its specific conductivity is starkly lower than the polyimide-based ternary hybrid material in embodiment 14.
Comparative Examples 12
(1) 2.14g (16 mass parts) graphite oxide is dispersed in the 190mlN-methyl-2-pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 20 hours becomes the graphite oxide dispersion liquid;
(2) under the protection of rare gas element, by 5.0g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned graphite oxide dispersion liquid, stirs, and slowly adds wherein 8.4g 3 after to be dissolved, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After having fed in raw material, under the protection of rare gas element, under 23 ℃, react 15 hours, obtain polyamic acid/graphite oxide hydridization solution;
(3) by the polyamic acid that obtains/graphite oxide hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 2 hours under 300 ℃ after, obtain polyimide/graphite hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 1.6 * 10
-4s/cm.Because hybrid material fragility is very large, can not carry out cutting acquisition DMA and test required sample, therefore second-order transition temperature does not obtain.Although its specific conductivity is higher, because of the too high levels of graphite oxide, make final hybrid material lose the original snappiness of polyimide matrix.
Comparative Examples 13
(1) 2.14g (16 mass parts) graphite oxide is dispersed in the 200mlN-methyl-2-pyrrolidone, and it being uniformly dispersed under room temperature ultrasonic 20 hours becomes the graphite oxide dispersion liquid;
(2) the barium titanate 7.37g that is the 50-150 nanometer by particle diameter (55 mass parts) is dispersed in above-mentioned graphite oxide dispersion liquid, and ultrasonic 6 hours of room temperature, obtain graphite oxide-barium titanate dispersions;
(3), under the protection of rare gas element, by 5.0g 4,4 '-diaminodiphenyl ether (ODA) adds in above-mentioned graphite oxide-barium titanate dispersions, stir, slowly add wherein 8.4g3,3 ' after to be dissolved, 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA); After having fed in raw material, under the protection of rare gas element, under 15 ℃, react 24 hours, obtain polyamic acid/graphite oxide-barium titanate hydridization solution;
(4) by polyamic acid/graphite oxide of obtaining-barium titanate hydridization solution film forming on stainless steel plate, carry out the imidization reaction of 2 hours under 300 ℃ after, obtain polyimide-based ternary hybridized film.
Directly a layer thickness of surface painting thereon is about the elargol layer of 0.5 micron, after elargol solidifies fully, carries out electric performance test, and under 100Hz, specific conductivity 3.1 * 10
-4s/cm.Because hybrid material fragility is very large, can not carry out cutting acquisition DMA and test required sample, therefore second-order transition temperature does not obtain.Although the polyimide-based ternary hybrid material of part in its specific conductivity and embodiment 5-15 is suitable, because of the too high levels of inorganics, make final hybrid material lose the original snappiness of polyimide matrix.
By the contrast of the concrete numerical value of material property in embodiment and Comparative Examples, the mass fraction that the mass fraction that barium titanate in polyimide-based ternary hybrid material is described is 2-50, graphite oxide is 0.2-15; When the mass fraction that particularly mass fraction of barium titanate is 10-30, graphite oxide is 0.5-10, due to the synergy of graphite and barium titanate, make material when thering is high electrical conductivity, kept the flexible and excellent thermal characteristics of matrix resin.With pure polyimide, polyimide/barium titanate and polyimide/graphite composite material are compared, and the specific conductivity of hybrid material has raising significantly, and its specific conductivity can reach 10
-4s/cm.But in polyimide-based ternary hybrid material, the mass fraction of barium titanate is greater than 50, the mass fraction of graphite oxide is while being greater than 15, due to the too high levels of inorganics, makes final hybrid material lose the original snappiness of polyimide matrix.
Claims (10)
1. the polyimide-based ternary hybrid material with conductivity, it is characterized in that: the raw material of this hybrid material is comprised of following mass parts component:
Polyimide 100
Barium titanate 2～30
Graphite oxide 0.2～10.
2. the polyimide-based ternary hybrid material with conductivity according to claim 1, it is characterized in that: described polyimide is comprised of dicarboxylic anhydride monomer and diamine monomer, and wherein the mol ratio of diamine monomer and dicarboxylic anhydride monomer is 1:1～1.20.
3. the polyimide-based ternary hybrid material with conductivity according to claim 1, it is characterized in that: the particle diameter of described barium titanate is 50～500 nanometers.
4. the polyimide-based ternary hybrid material with conductivity according to claim 1, it is characterized in that: the radius-thickness ratio of described graphite oxide is 100～2000.
5. the polyimide-based ternary hybrid material with conductivity according to claim 2, it is characterized in that: described dicarboxylic anhydride monomer is pyromellitic acid anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride or 3,3', 4,4'-BPDA.
6. the polyimide-based ternary hybrid material with conductivity according to claim 2, is characterized in that described diamine monomer is 4,4 '-diaminodiphenyl oxide, p-phenylenediamine or m-phenylenediamine.
7. one kind prepares the method with polyimide-based ternary hybrid material of conductivity claimed in claim 1, it is characterized in that: comprise the following steps:
(1) graphite oxide is scattered in organic solvent, it being uniformly dispersed under room temperature ultrasonic 2～20 hours becomes the graphite oxide dispersion liquid;
(2) barium titanate is added in the graphite oxide dispersion liquid, it being uniformly dispersed under room temperature ultrasonic 3～6 hours becomes graphite oxide-barium titanate dispersions;
(3) under the protection of rare gas element, diamine monomer is added in graphite oxide-barium titanate dispersions, stir, add wherein the dicarboxylic anhydride monomer after to be dissolved; After having fed in raw material, under the protection of rare gas element, react under 10～35 ℃ 10～30 hours, obtain polyamic acid/graphite oxide-barium titanate hydridization solution;
(4) after polyamic acid/graphite oxide-barium titanate hydridization solution being carried out under 280～350 ℃ to the imidization reaction of 2～4 hours, the polyimide-based ternary hybrid material that obtains having electroconductibility.
8. method according to claim 7, is characterized in that described graphite oxide is 10 by particle diameter
3～10
6purpose natural flake graphite or expanded graphite prepare after oxidation is peeled off.
9. method according to claim 7, is characterized in that described organic solvent is N,N-dimethylacetamide, DMF, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO).
10. method according to claim 7, is characterized in that described dicarboxylic anhydride monomer is pyromellitic acid anhydride, 3,3 ', 4, and 4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride or 3,3', 4,4'-BPDA; Described diamine monomer is 4,4 '-diaminodiphenyl ether, p-phenylenediamine or m-phenylenediamine; The mol ratio of diamine monomer and dicarboxylic anhydride monomer is 1:1～1.20.
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| CN101283048A (en) * | 2005-10-12 | 2008-10-08 | E.I.内穆尔杜邦公司 | Compositions comprising polyimide and hydrophobic epoxy, and methods relating thereto |
| CN101333320A (en) * | 2007-06-25 | 2008-12-31 | 晟茂（青岛）先进材料有限公司 | Conductive heat conducting material and method for manufacturing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20070231588A1 (en) * | 2006-03-31 | 2007-10-04 | Karthikeyan Kanakarajan | Capacitive polyimide laminate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101283048A (en) * | 2005-10-12 | 2008-10-08 | E.I.内穆尔杜邦公司 | Compositions comprising polyimide and hydrophobic epoxy, and methods relating thereto |
| CN101333320A (en) * | 2007-06-25 | 2008-12-31 | 晟茂（青岛）先进材料有限公司 | Conductive heat conducting material and method for manufacturing same |
Non-Patent Citations (4)
| Title |
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| Dielectric behavior of three phase polyimide percolative nanocomposites;Naga Gopi Devaraju,et al.;《Journal of applied science》;20060111;第99卷;第3018-3022页 * |
| Naga Gopi Devaraju,et al..Dielectric behavior of three phase polyimide percolative nanocomposites.《Journal of applied science》.2006,第99卷 |
| 耐高温聚酰亚胺导电复合材料的性能;郭乔辉等;《高分子材料科学与工程》;20090228;第25卷(第2期);第52-54,58页 * |
| 郭乔辉等.耐高温聚酰亚胺导电复合材料的性能.《高分子材料科学与工程》.2009,第25卷(第2期), |
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| CN102161826A (en) | 2011-08-24 |
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