CN104788676A - Preparation method for low-dielectric-constant polyimide/multilayer graphene oxide composite film - Google Patents
Preparation method for low-dielectric-constant polyimide/multilayer graphene oxide composite film Download PDFInfo
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Abstract
The invention discloses a preparation method for a low-dielectric-constant polyimide/multilayer graphene oxide composite film. The method comprises the following steps: (1) modifying graphene oxide with a silane coupling agent; (2) in a room-temperature and nitrogen atmosphere environment, adding diamine and dianhydride with a molar ratio being 1:1 into a high-boiling-point polar aprotic solvent to prepare a solution with the solid content of 5-15 wt%; (3) adding modified graphene oxide obtained in the step (1) into the solution obtained in the step (2), ultrasonically dispersing, producing a continuous stirring reaction at a room temperature for 18-24 hours, and obtaining a polyamide acid viscous fluid; (4) pouring the polyamide acid viscous fluid prepared in the step (3) into a mould; (5) performing vacuum-drying on the mould at 80-100 DEG C for 2-3 hours, heating to 130-160 DEG C, performing vacuum-drying for 2-3 hours, and obtaining a polyamide acid gel film; (6) continuously heating the polyamide acid gel film obtained in the step (5) to 180-200 DEG C, performing vacuum-drying for 1-3 hours, heating to 240-280 DEG C, performing vacuum-drying for 1-3 hours, and obtaining the polyimide/multilayer graphene oxide composite film.
Description
Technical field
The invention belongs to composite polyimide material technical field, be specifically related to the preparation method of a kind of low dielectric coefficient polyimide/multilayer graphene composite thin film.
Background technology
As high-performance polymer, polyimide (PI) is the macromolecular material that a class has high temperature resistant, low temperature resistant, radiation hardness, excellent chemical stability and good mechanical strength, is used widely in high-tech sectors such as photoelectricity, space flight and aviation, electric and electronics.Polyimide, owing to having low specific inductivity, is very important material for power industry.As crucial insulated part in inverter motor, the serviceability of polyimide and inverter motor is directly related.Now, along with the high-voltage of inverter motor and the development of insulation level, the performance of Kapton especially specific inductivity becomes one of topmost problem at industrial circle, but existing Kapton still can not meet the needs of inverter motor development.
Graphene is the splendid strongthener of a kind of performance, have high mechanical strength, thermal conductivity and specific conductivity, but its application is still in development, does not also have and can go into operation by business-like product.Graphene-based matrix material is counted as Graphene by one of field of the application that takes the lead in.Especially Graphene has typical two-dimension plane structure, will produce directed reinforced effects for the mechanical property of Kapton and conductive characteristic.
Publication number is the preparation method that the Chinese patent of CN102534858A discloses a kind of graphene/polyimide composite fibers, although the conjugated fibre that the preparation method of this graphene/polyimide composite fibers prepares improves mechanical property to a certain extent, but, the over-all properties of conjugated fibre does not reach ideal value, its mechanical property, resistance toheat and conductivity can not be taken into account simultaneously, the reason of this problem is caused to mainly contain: conjugated fibre exists Graphene from reuniting in preparation process, causes graphene dispersion uneven; And Graphene and polyimide matrix bounding force poor, cause stress concentration.
Summary of the invention
In view of this, the object of the present invention is to provide the preparation method of a kind of low dielectric coefficient polyimide/multilayer graphene composite thin film, the polyimide/multilayer graphene composite thin film adopting the method to prepare has lower specific inductivity and over-all properties.
For achieving the above object, the invention provides following technical scheme:
A preparation method for low dielectric coefficient polyimide/multilayer graphene composite thin film, comprises the steps:
1) silane coupler modified graphene oxide is used: be that the graphene oxide of 0.1%-1% joins in ethanolic soln by massfraction, the band amino silicane coupling agent that massfraction is 1%-10% is added after ultrasonic disperse, at 60-80 DEG C after stirring reaction 3-10h, obtain modified graphene oxide through centrifugation, washing drying;
2) under room temperature and nitrogen atmosphere environment, be that diamines and the dianhydride of 1: 1 joins in high boiling point polar aprotic solvent by mol ratio, be mixed with the solution of solid content 5-15wt%;
3) modified graphene oxide obtained in step 1) is joined step 2) in the solution that obtains, ultrasonic disperse, and at room temperature continuously stirring reaction 18-24h, obtain viscous fluid of polyamide acid;
4) viscous fluid of polyamide acid that step 3) is obtained is poured on mould;
5) by mould at 80-100 DEG C after vacuum-drying 2-3h, vacuum-drying 2-3h again at being warming up to 130-160 DEG C, obtains polyamic acid gel-film;
6) after polyamic acid gel-film step 5) obtained continues to be warming up to 180-200 DEG C of vacuum-drying 1-3h, then be warming up to vacuum-drying 1-3h at 240-280 DEG C of temperature, obtain product polyimide/multilayer graphene composite thin film.
Further, in described step 1), the silane coupling agent of band amino is γ aminopropyltriethoxy silane.
Further, in described step 1), the mass concentration of ethanolic soln is 95%.
Further, in described step 1), be separated 10 minutes with the centrifugation of 4500 revs/min, and wash, dry 3-4 time.
Further, described step 2) in, high boiling point polar aprotic solvent is METHYLPYRROLIDONE, DMF or N,N-dimethylacetamide.
Further, described step 2) in, diamines is 4,4 ,-diaminodiphenyl oxide, 4,4 ,-bis-(4-amino-benzene oxygen) sulfobenzide, two [3,5-dimethyl-4-(4-is amino) phenol] methane or hexanediamine or diaminodiphenylmethane.
Further, described step 2) in, dianhydride is BP-3,3,3 ', 4,4 '-tetramethyl-dianhydride, pyromellitic acid anhydride, 4,4, the two-Tetra hydro Phthalic anhydride of-(hexafluoro propylidene), bisphenol A-type dianhydride, BPDA or two (3,4-phthalate anhydride) dimethylsilane.
Further, in described step 3), in the quality of the described modified graphene oxide added and described step 6), the ratio of final obtained polyimide/multilayer graphene composite thin film total mass is less than or equal to 0.26%.
Beneficial effect of the present invention is:
The preparation method of low dielectric coefficient polyimide of the present invention/multilayer graphene composite thin film, by the standby graphene oxide of the Hummers legal system improved, and obtain the suspension of graphene oxide in water and high boiling point polar aprotic solvent by ultrasonic dispersion, prepare polyimide/multilayer graphene composite thin film in conjunction with situ aggregation method; The principle of preparation method of the present invention adopts ultrasonic wave, mechanical blending means, makes nanoparticle dispersed in polymer monomer (or its performed polymer), then trigger monomer polymerization in situ under certain condition; Due to the modifying surface to graphene nano particle, can guarantee that nanoparticulate dispersed evenly and do not reunite, therefore, the mechanical property of the laminated film prepared and resistance toheat are all higher, namely improve the over-all properties of laminated film; Conventional surface modifying method is surface chemical modification, namely by surface-modifying agent as coupling agent, unsaturated organic acid etc. and the mode that particle surface carries out chemical reaction or chemisorption have come; Result shows, and the polyimide of isolator is transformed to electroconductibility good polyimide/multilayer graphene composite thin film;
The specific inductivity of polyimide composite film is reduced by introducing graphene oxide; And along with the increase of graphene oxide introduction volume, graphene oxide also can be more and more obvious on the impact of specific inductivity; There is amino by the surface of graphene oxide that KH-550 coupling agent surface modification is crossed, can be dispersed in polyamic acid solution smoothly through stirring and having children outside the state plan; Therefore, utilize preparation method of the present invention to prepare to have the polyimide/multilayer graphene composite thin film of low-k, this material is while maintaining the thermal property of polyimide, reduce its specific inductivity, its specific inductivity is along with the increase of graphene oxide mass content, and specific inductivity presents the trend first reducing increasing, simultaneously, the Schwellenwert of specific inductivity, also along with different diamines and dianhydride monomer change, occurs when the mass content that graphene oxide is different.
Accompanying drawing explanation
In order to make object of the present invention, technical scheme and beneficial effect clearly, the invention provides following accompanying drawing and being described:
Fig. 1 is the transmission electron microscope photo of the graphene oxide in the preparation method of low dielectric coefficient polyimide of the present invention/multilayer graphene composite thin film;
Fig. 2 a-Fig. 2 c is the structure iron of polyimide/multilayer graphene composite thin film under the graphene oxide of Different Weight per-cent adopting preparation method of the present invention to prepare; Wherein, Fig. 2 a represents non-oxidation Graphene, and Fig. 2 b represents a small amount of graphene oxide, and Fig. 2 c is excessive graphene oxide.
Fig. 3 is the polyimide/multilayer graphene composite thin film specific inductivity at different frequencies adopting preparation method of the present invention to prepare;
Fig. 4 is the specific inductivity of polyimide/multilayer graphene composite thin film under the graphene oxide of Different Weight per-cent adopting preparation method of the present invention to prepare.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described, can better understand the present invention and can be implemented, but illustrated embodiment is not as a limitation of the invention to make those skilled in the art.
embodiment 1
The preparation method of the low dielectric coefficient polyimide/multilayer graphene composite thin film of the present embodiment, comprises the steps:
1) use silane coupler modified graphene oxide: by massfraction be 0.1% graphene oxide join in ethanolic soln, every one hour with the ultrasonic disperse 20 minutes of 50W, 40kHz, after add the band amino silicane coupling agent that massfraction is 5%, with after 1000 revs/min of stirring reaction 5h at 60 DEG C, and be separated 10 minutes with the centrifugation of 4500 revs/min, washing, drying 3 times, obtain modified graphene oxide; Wherein, the mass concentration of ethanolic soln is 95%, the silane coupling agent employing γ aminopropyltriethoxy silane that band is amino.
Concrete, the preparation process of the graphene oxide of the present embodiment is: the mix and blend in the sulfuric acid (98%) of 115ml by 5g graphite and 2.5g SODIUMNITRATE; Then in ice bath, 2h is cooled, add 15g potassium permanganate afterwards and stir 4h energetically, after sample is heated to 35 DEG C of maintenance 30min, reaction mixture reaches room temperature, then pours in the deionized water containing 250ml, is heated to 70 DEG C further, after maintaining constant temperature 15min, pour in the deionized water of 1L, add the hydrogen peroxide of 3%, remove unreacted potassium permanganate and Manganse Dioxide; Then move in other containers by the mixture of reaction, the graphene oxide of acquisition purifies through centrifugation repeatedly and redispersion in deionized water; Before using, graphene oxide need under 60 DEG C of vacuum states dry 48h.
2) under room temperature and nitrogen atmosphere environment, be that diamines and the dianhydride of 1: 1 joins in high boiling point polar aprotic solvent by mol ratio, be mixed with the solution of solid content 10wt%; Wherein, the diamines of the present embodiment and dianhydride are 0.001mol.High boiling point polar aprotic solvent is METHYLPYRROLIDONE, DMF or N,N-dimethylacetamide, and the high boiling point polar aprotic solvent of the present embodiment adopts METHYLPYRROLIDONE; Diamines can adopt 4,4 ,-diaminodiphenyl oxide, 4,4 ,-bis-(4-amino-benzene oxygen) sulfobenzide, two [3,5-dimethyl-4-(4-amino) phenol] methane or hexanediamine or diaminodiphenylmethane; Dianhydride can adopt BP-3,3,3 ', 4,4 '-tetramethyl-dianhydride, pyromellitic acid anhydride, 4,4, the two-Tetra hydro Phthalic anhydride of-(hexafluoro propylidene), bisphenol A-type dianhydride, BPDA or two (3,4-phthalate anhydride) dimethylsilane, the diamines of the present embodiment adopts two [3,5-dimethyl-4-(4-is amino) phenol] methane, and dianhydride adopts BP-3.
The preparation process of two [3.5-dimethyl-4-(4-is amino) phenol] methane (BDAPM) of the present embodiment is: by the N of 28.1g salt of wormwood and 300ml, dinethylformamide mixes, add 25.6g bismethane and 31.5g parachloronitrobenzene, at 150 DEG C ~ 160 DEG C, maintain 12h synthesis two [3.5-dimethyl-4-(4-is amino) nitrophenol] methane (BDNPM).To pour in distilled water after reacted solution cool to room temperature, by filtering and dry acquisition yellow powder under 80 DEG C of conditions; Then 50ml hydrazine hydrate is dropwise joined the BDNPM of 25.9g 70 DEG C time, the iron(ic) chloride of 3.1g, in the mixture of the dehydrated alcohol composition of Pd/C and 200ml of 0.3g; At 80 DEG C ~ 90 DEG C, maintain 14h subsequently, carry out recrystallize acquisition product finally by filtration with dehydrated alcohol, prepare yellow BDAPM crystal through purification.
3) modified graphene oxide obtained in step 1) is joined step 2) in the solution that obtains, with the ultrasonic disperse of 50W, 40kHz, and at room temperature continuously stirring reaction 24h, obtain viscous fluid of polyamide acid; Wherein, the quality of the modified graphene oxide added is 0.13% of the laminated film total mass finally prepared.
4) viscous fluid of polyamide acid that step 3) is obtained is poured in glass board mould.
5) by mould at 80 DEG C after vacuum-drying 2h, vacuum-drying 2h again at being warming up to 150 DEG C, obtains polyamic acid gel-film after desolvation.
6) after polyamic acid gel-film step 5) obtained continues to be warming up to 200 DEG C of vacuum-drying 1.5h, then be warming up to vacuum-drying 1.5h at 240 DEG C of temperature, obtain product polyimide/multilayer graphene composite thin film; Wherein, vacuum pressure is-0.1MPa.
Test with HIOKI 3532-50 electric impedance analyzer, from the polyimide prepared/specific inductivity of multilayer graphene composite thin film and the relation of frequency, under 1MHz frequency, be that the specific inductivity of the laminated film of 0.13% is 1.80 containing graphene oxide weight percent.Than under 1MHz frequency, the specific inductivity 2.21 of the film of oxygen-free functionalized graphene is low.
embodiment 2
The preparation method of the low dielectric coefficient polyimide/multilayer graphene composite thin film of the present embodiment, comprises the steps:
1) use silane coupler modified graphene oxide: by massfraction be 1% graphene oxide join in ethanolic soln, every one hour with the ultrasonic disperse 20 minutes of 50W, 40kHz, after add the band amino silicane coupling agent that massfraction is 10%, with after 500 revs/min of stirring reaction 3h at 80 DEG C, and be separated 10 minutes with the centrifugation of 4500 revs/min, washing, drying 4 times, obtain modified graphene oxide; Wherein, the mass concentration of ethanolic soln is 95%, the silane coupling agent employing γ aminopropyltriethoxy silane that band is amino.
2) under room temperature and nitrogen atmosphere environment, be that diamines and the dianhydride of 1: 1 joins in high boiling point polar aprotic solvent by mol ratio, be mixed with the solution of solid content 5wt%; Wherein, the diamines of the present embodiment and dianhydride are 0.001mol.High boiling point polar aprotic solvent is METHYLPYRROLIDONE, DMF or N,N-dimethylacetamide, and the high boiling point polar aprotic solvent of the present embodiment adopts METHYLPYRROLIDONE; Diamines can adopt 4,4 ,-diaminodiphenyl oxide, 4,4 ,-bis-(4-amino-benzene oxygen) sulfobenzide, two [3,5-dimethyl-4-(4-amino) phenol] methane or hexanediamine or diaminodiphenylmethane; Dianhydride can adopt BP-3,3,3 ', 4,4 '-tetramethyl-dianhydride, pyromellitic acid anhydride, 4,4, two-the Tetra hydro Phthalic anhydride of-(hexafluoro propylidene), bisphenol A-type dianhydride, BPDA or two (3,4-phthalate anhydride) dimethylsilane, the diamines of the present embodiment adopts 4,4,-bis-(4-amino-benzene oxygen) sulfobenzide, dianhydride adopts 4,4 '-tetramethyl-dianhydride.
3) modified graphene oxide obtained in step 1) is joined step 2) in the solution that obtains, with the ultrasonic disperse of 50W, 40kHz, and at room temperature continuously stirring reaction 12h, obtain viscous fluid of polyamide acid; Wherein, the quality of the modified graphene oxide added is 0.19% of the laminated film total mass finally prepared.
4) viscous fluid of polyamide acid that step 3) is obtained is poured in glass board mould.
5) by mould at 100 DEG C after vacuum-drying 3h, vacuum-drying 3h again at being warming up to 130 DEG C, obtains polyamic acid gel-film after desolvation.
6) after polyamic acid gel-film step 5) obtained continues to be warming up to 180 DEG C of vacuum-drying 1h, then be warming up to vacuum-drying 1h at 280 DEG C of temperature, obtain product polyimide/multilayer graphene composite thin film; Wherein, vacuum pressure is-0.1MPa.
Test with HIOKI 3532-50 electric impedance analyzer, from the polyimide prepared/specific inductivity of multilayer graphene composite thin film and the relation of frequency, under 1MHz frequency, be that the specific inductivity of the laminated film of 0.19% is 1.41 containing graphene oxide weight percent.Than under 1MHz frequency, the specific inductivity 2.21 of the film of oxygen-free functionalized graphene is low.
embodiment 3
The preparation method of the low dielectric coefficient polyimide/multilayer graphene composite thin film of the present embodiment, comprises the steps:
1) use silane coupler modified graphene oxide: by massfraction be 0.5% graphene oxide join in ethanolic soln, every one hour with the ultrasonic disperse 20 minutes of 50W, 40kHz, after add the band amino silicane coupling agent that massfraction is 1%, with after 800 revs/min of stirring reaction 10h at 70 DEG C, and be separated 10 minutes with the centrifugation of 4500 revs/min, washing, drying 4 times, obtain modified graphene oxide; Wherein, the mass concentration of ethanolic soln is 95%, the silane coupling agent employing γ aminopropyltriethoxy silane that band is amino.
2) under room temperature and nitrogen atmosphere environment, be that diamines and the dianhydride of 1: 1 joins in high boiling point polar aprotic solvent by mol ratio, be mixed with the solution of solid content 15wt%; Wherein, the diamines of the present embodiment and dianhydride are 0.001mol.High boiling point polar aprotic solvent is METHYLPYRROLIDONE, DMF or N,N-dimethylacetamide, and the high boiling point polar aprotic solvent of the present embodiment adopts DMF; Diamines can adopt 4,4 ,-diaminodiphenyl oxide, 4,4 ,-bis-(4-amino-benzene oxygen) sulfobenzide, two [3,5-dimethyl-4-(4-amino) phenol] methane or hexanediamine or diaminodiphenylmethane; Dianhydride can adopt BP-3,3,3 ', 4,4 '-tetramethyl-dianhydride, pyromellitic acid anhydride, 4,4, the two-Tetra hydro Phthalic anhydride of-(hexafluoro propylidene), bisphenol A-type dianhydride, BPDA or two (3,4-phthalate anhydride) dimethylsilane, the diamines of the present embodiment adopts two [3,5-dimethyl-4-(4-is amino) phenol] methane, and dianhydride adopts pyromellitic acid anhydride.
3) modified graphene oxide obtained in step 1) is joined step 2) in the solution that obtains, with the ultrasonic disperse of 50W, 40kHz, and at room temperature continuously stirring reaction 8h, obtain viscous fluid of polyamide acid; Wherein, the quality of the modified graphene oxide added is 0.26% of the laminated film total mass finally prepared.
4) viscous fluid of polyamide acid that step 3) is obtained is poured in glass board mould.
5) by mould at 90 DEG C after vacuum-drying 2.5h, vacuum-drying 2.5h again at being warming up to 160 DEG C, obtains polyamic acid gel-film after desolvation.
6) after polyamic acid gel-film step 5) obtained continues to be warming up to 190 DEG C of vacuum-drying 3h, then be warming up to vacuum-drying 3h at 260 DEG C of temperature, obtain product polyimide/multilayer graphene composite thin film; Wherein, vacuum pressure is-0.1MPa.
Test with HIOKI 3532-50 electric impedance analyzer, from the polyimide prepared/specific inductivity of multilayer graphene composite thin film and the relation of frequency, under 1MHz frequency, be that the specific inductivity of the laminated film of 0.26% is 1.70 containing graphene oxide weight percent.Than under 1MHz frequency, the specific inductivity 2.21 of the film of oxygen-free functionalized graphene is low.
embodiment 4
The preparation method of the low dielectric coefficient polyimide/multilayer graphene composite thin film of the present embodiment, comprises the steps:
1) use silane coupler modified graphene oxide: by massfraction be 0.7% graphene oxide join in ethanolic soln, every one hour with the ultrasonic disperse 20 minutes of 50W, 40kHz, after add the band amino silicane coupling agent that massfraction is 8%, with after 600 revs/min of stirring reaction 8h at 75 DEG C, and be separated 10 minutes with the centrifugation of 4500 revs/min, washing, drying 3 times, obtain modified graphene oxide; Wherein, the mass concentration of ethanolic soln is 95%, the silane coupling agent employing γ aminopropyltriethoxy silane that band is amino.
2) under room temperature and nitrogen atmosphere environment, be that diamines and the dianhydride of 1: 1 joins in high boiling point polar aprotic solvent by mol ratio, be mixed with the solution of solid content 8wt%; Wherein, the diamines of the present embodiment and dianhydride are 0.001mol.High boiling point polar aprotic solvent is METHYLPYRROLIDONE, DMF or N,N-dimethylacetamide, and the high boiling point polar aprotic solvent of the present embodiment adopts N,N-dimethylacetamide; Diamines can adopt 4,4 ,-diaminodiphenyl oxide, 4,4 ,-bis-(4-amino-benzene oxygen) sulfobenzide, two [3,5-dimethyl-4-(4-amino) phenol] methane or hexanediamine or diaminodiphenylmethane; Dianhydride can adopt BP-3,3,3 ', 4,4 '-tetramethyl-dianhydride, pyromellitic acid anhydride, 4,4, the two-Tetra hydro Phthalic anhydride of-(hexafluoro propylidene), bisphenol A-type dianhydride, BPDA or two (3,4-phthalate anhydride) dimethylsilane, the diamines of the present embodiment adopts hexanediamine or diaminodiphenylmethane, and dianhydride adopts two (3,4-phthalate anhydride) dimethylsilane.
3) modified graphene oxide obtained in step 1) is joined step 2) in the solution that obtains, with the ultrasonic disperse of 50W, 40kHz, and at room temperature continuously stirring reaction 20h, obtain viscous fluid of polyamide acid; Wherein, the quality of the modified graphene oxide added is 1% of the laminated film total mass finally prepared.
4) viscous fluid of polyamide acid that step 3) is obtained is poured in glass board mould.
5) by mould at 85 DEG C after vacuum-drying 3h, vacuum-drying 3h again at being warming up to 140 DEG C, obtains polyamic acid gel-film after desolvation.
6) after polyamic acid gel-film step 5) obtained continues to be warming up to 185 DEG C of vacuum-drying 2h, then be warming up to vacuum-drying 1.5h at 250 DEG C of temperature, obtain product polyimide/multilayer graphene composite thin film; Wherein, vacuum pressure is-0.1MPa.
Test with HIOKI 3532-50 electric impedance analyzer, from the polyimide prepared/specific inductivity of multilayer graphene composite thin film and the relation of frequency, under 1MHz frequency, be that the specific inductivity of the laminated film of 0.01% is 2.20 containing graphene oxide weight percent.Than under 1MHz frequency, the specific inductivity 2.21 of the film of oxygen-free functionalized graphene is low.
embodiment 5
The preparation method of the low dielectric coefficient polyimide/multilayer graphene composite thin film of the present embodiment, comprises the steps:
1) use silane coupler modified graphene oxide: by massfraction be 0.3% graphene oxide join in ethanolic soln, every one hour with the ultrasonic disperse 20 minutes of 50W, 40kHz, after add the band amino silicane coupling agent that massfraction is 3%, with after 900 revs/min of stirring reaction 7h at 65 DEG C, and be separated 10 minutes with the centrifugation of 4500 revs/min, washing, drying 3 times, obtain modified graphene oxide; Wherein, the mass concentration of ethanolic soln is 95%, the silane coupling agent employing γ aminopropyltriethoxy silane that band is amino.
2) under room temperature and nitrogen atmosphere environment, be that diamines and the dianhydride of 1: 1 joins in high boiling point polar aprotic solvent by mol ratio, be mixed with the solution of solid content 12wt%; Wherein, the diamines of the present embodiment and dianhydride are 0.001mol.High boiling point polar aprotic solvent is METHYLPYRROLIDONE, DMF or N,N-dimethylacetamide, and the high boiling point polar aprotic solvent of the present embodiment adopts N,N-dimethylacetamide; Diamines can adopt 4,4 ,-diaminodiphenyl oxide, 4,4 ,-bis-(4-amino-benzene oxygen) sulfobenzide, two [3,5-dimethyl-4-(4-amino) phenol] methane, hexanediamine or diaminodiphenylmethane; Dianhydride can adopt BP-3,3,3 ', 4,4 '-tetramethyl-dianhydride, pyromellitic acid anhydride, 4,4, two-the Tetra hydro Phthalic anhydride of-(hexafluoro propylidene), bisphenol A-type dianhydride, BPDA or two (3,4-phthalate anhydride) dimethylsilane, the diamines of the present embodiment adopts two [3,5-dimethyl-4-(4-is amino) phenol] methane, dianhydride adopts 4,4, the two-Tetra hydro Phthalic anhydride of-(hexafluoro propylidene).
3) modified graphene oxide obtained in step 1) is joined step 2) in the solution that obtains, with the ultrasonic disperse of 50W, 40kHz, and at room temperature continuously stirring reaction 16h, obtain viscous fluid of polyamide acid; Wherein, the quality of the modified graphene oxide added is 0.1% of the laminated film total mass finally prepared.
4) viscous fluid of polyamide acid that step 3) is obtained is poured in glass board mould.
5) by mould at 95 DEG C after vacuum-drying 2.8h, vacuum-drying 2.5h again at being warming up to 150 DEG C, obtains polyamic acid gel-film after desolvation.
6) after polyamic acid gel-film step 5) obtained continues to be warming up to 200 DEG C of vacuum-drying 2h, then be warming up to vacuum-drying 2h at 270 DEG C of temperature, obtain product polyimide/multilayer graphene composite thin film; Wherein, vacuum pressure is-0.1MPa.
Test with HIOKI 3532-50 electric impedance analyzer, from the polyimide prepared/specific inductivity of multilayer graphene composite thin film and the relation of frequency, under 1MHz frequency, be that the specific inductivity of the laminated film of 0.1% is 1.93 containing graphene oxide weight percent.Than under 1MHz frequency, the specific inductivity 2.21 of the film of oxygen-free functionalized graphene is low.
The above embodiment is only that protection scope of the present invention is not limited thereto in order to absolutely prove the preferred embodiment that the present invention lifts.The equivalent alternative or conversion that those skilled in the art do on basis of the present invention, all within protection scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (8)
1. a preparation method for low dielectric coefficient polyimide/multilayer graphene composite thin film, is characterized in that: comprise the steps:
1) silane coupler modified graphene oxide is used: be that the graphene oxide of 0.1%-1% joins in ethanolic soln by massfraction, the band amino silicane coupling agent that massfraction is 1%-10% is added after ultrasonic disperse, at 60-80 DEG C after stirring reaction 3-10h, obtain modified graphene oxide through centrifugation, washing drying;
2) under room temperature and nitrogen atmosphere environment, be that diamines and the dianhydride of 1: 1 joins in high boiling point polar aprotic solvent by mol ratio, be mixed with the solution of solid content 5-15wt%;
3) modified graphene oxide obtained in step 1) is joined step 2) in the solution that obtains, ultrasonic disperse, and at room temperature continuously stirring reaction 18-24h, obtain viscous fluid of polyamide acid;
4) viscous fluid of polyamide acid that step 3) is obtained is poured on mould;
5) by mould at 80-100 DEG C after vacuum-drying 2-3h, vacuum-drying 2-3h again at being warming up to 130-160 DEG C, obtains polyamic acid gel-film;
6) after polyamic acid gel-film step 5) obtained continues to be warming up to 180-200 DEG C of vacuum-drying 1-3h, then be warming up to vacuum-drying 1-3h at 240-280 DEG C of temperature, obtain product polyimide/multilayer graphene composite thin film.
2. the preparation method of low dielectric coefficient polyimide according to claim 1/multilayer graphene composite thin film, is characterized in that: in described step 1), and the silane coupling agent of band amino is γ aminopropyltriethoxy silane.
3. the preparation method of low dielectric coefficient polyimide according to claim 1/multilayer graphene composite thin film, is characterized in that: in described step 1), and the mass concentration of ethanolic soln is 95%.
4. the preparation method of low dielectric coefficient polyimide according to claim 1/multilayer graphene composite thin film, is characterized in that: in described step 1), is separated 10 minutes with the centrifugation of 4500 revs/min, and wash, dry 3-4 time.
5. the preparation method of low dielectric coefficient polyimide according to claim 1/multilayer graphene composite thin film, it is characterized in that: described step 2) in, high boiling point polar aprotic solvent is METHYLPYRROLIDONE, DMF or N,N-dimethylacetamide.
6. the preparation method of low dielectric coefficient polyimide according to claim 1/multilayer graphene composite thin film, it is characterized in that: described step 2) in, diamines is 4,4,-diaminodiphenyl oxide, 4,4 ,-bis-(4-amino-benzene oxygen) sulfobenzide, two [3,5-dimethyl-4-(4-amino) phenol] methane or hexanediamine or diaminodiphenylmethane.
7. the preparation method of low dielectric coefficient polyimide according to claim 1/multilayer graphene composite thin film, it is characterized in that: described step 2) in, dianhydride is BP-3,3,3 ', 4,4 '-tetramethyl-dianhydride, pyromellitic acid anhydride, 4,4, two-the Tetra hydro Phthalic anhydride of-(hexafluoro propylidene), bisphenol A-type dianhydride, BPDA or two (3,4-phthalate anhydride) dimethylsilane.
8. the preparation method of low dielectric coefficient polyimide according to claim 1/multilayer graphene composite thin film, it is characterized in that: in described step 3), in the quality of the described modified graphene oxide added and described step 6), the ratio of final obtained polyimide/multilayer graphene composite thin film total mass is less than or equal to 0.26%.
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| CN105197909A (en) * | 2015-09-24 | 2015-12-30 | 复旦大学 | Graphene nanoribbon/carbon nanotube/polyimide-based compound carbon aerogel and preparation method thereof |
| CN105601921A (en) * | 2016-01-26 | 2016-05-25 | 华南理工大学 | Preparation method of low dielectric constant enhanced graphene oxide/polyimide composite film |
| CN107488348A (en) * | 2017-09-04 | 2017-12-19 | 杭州高烯科技有限公司 | A kind of preparation method of graphene polyimides black film |
| CN109269394A (en) * | 2018-10-26 | 2019-01-25 | 钟祥博谦信息科技有限公司 | It is a kind of using PDMS as conductive film of base material and preparation method thereof |
| CN109456481A (en) * | 2018-11-22 | 2019-03-12 | 桂林电子科技大学 | A kind of preparation method of graphene oxide/polyimides black film |
| CN109897199A (en) * | 2019-02-22 | 2019-06-18 | 黑龙江省科学院石油化学研究院 | The polyimide precursor gel and its preparation method and application for inhaling wave and heat resistant poly acid imide lightweight labyrinth can be prepared |
| CN110527293A (en) * | 2019-09-06 | 2019-12-03 | 黑龙江省科学院高技术研究院 | A kind of Kapton and preparation method thereof of basalt scale fibre modification |
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| CN105197909A (en) * | 2015-09-24 | 2015-12-30 | 复旦大学 | Graphene nanoribbon/carbon nanotube/polyimide-based compound carbon aerogel and preparation method thereof |
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| CN107488348A (en) * | 2017-09-04 | 2017-12-19 | 杭州高烯科技有限公司 | A kind of preparation method of graphene polyimides black film |
| CN109269394A (en) * | 2018-10-26 | 2019-01-25 | 钟祥博谦信息科技有限公司 | It is a kind of using PDMS as conductive film of base material and preparation method thereof |
| CN109456481A (en) * | 2018-11-22 | 2019-03-12 | 桂林电子科技大学 | A kind of preparation method of graphene oxide/polyimides black film |
| CN109456481B (en) * | 2018-11-22 | 2021-07-20 | 桂林电子科技大学 | Preparation method of graphene oxide/polyimide black film |
| CN109897199A (en) * | 2019-02-22 | 2019-06-18 | 黑龙江省科学院石油化学研究院 | The polyimide precursor gel and its preparation method and application for inhaling wave and heat resistant poly acid imide lightweight labyrinth can be prepared |
| CN110527293A (en) * | 2019-09-06 | 2019-12-03 | 黑龙江省科学院高技术研究院 | A kind of Kapton and preparation method thereof of basalt scale fibre modification |
| CN110527293B (en) * | 2019-09-06 | 2022-03-15 | 黑龙江省科学院高技术研究院 | Basalt flake fiber modified polyimide film |
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