CN105601964A - Preparation method of polyimide film with ultralow dielectric constant and low dielectric loss - Google Patents

Preparation method of polyimide film with ultralow dielectric constant and low dielectric loss Download PDF

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Publication number
CN105601964A
CN105601964A CN201511024047.2A CN201511024047A CN105601964A CN 105601964 A CN105601964 A CN 105601964A CN 201511024047 A CN201511024047 A CN 201511024047A CN 105601964 A CN105601964 A CN 105601964A
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hbpsi
preparation
silane
dielectric
monomer
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张秋禹
雷星锋
乔明涛
田力冬
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Northwestern Polytechnical University
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Northwestern Polytechnical University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/005—Hyperbranched macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Abstract

The invention relates to a preparation method of a polyimide film with an ultralow dielectric constant and low dielectric loss. HBPSi (Hyperbranched Polysiloxane) is first obtained by adopting a hydrolytic cocondensation method and multistep purification; finally, an HBPSi structure is introduced into a PI (Polyimide) molecular main chain in the form of a chemical bond; the modification on a PI material on a molecular level is realized; the dielectric constant of the PI material is obviously decreased; the inherent advantage of the PI material is maintained better. A PI film is excellent in dielectric property, favorable in heat resistance, outstanding in mechanical strength, low in water absorption, high in surface evenness, mild in reaction condition in a preparation process and lower in research and development costs, and is beneficial to large-scale commercial production. In comparison with a Kapton standard film which is currently used generally, the dielectric constant of an HBPSi-PI film is decreased by 30 percent to 40 percent in an equal test condition; a lowest dielectric constant is even approximate to 2.0; the level of the ultralow dielectric constant is reached; the active demand of the development of a microelectronic industry in the future can be met.

Description

The preparation method of ultralow dielectric, low-dielectric loss Kapton
Technical field
The invention belongs to the preparation method of Kapton, be specifically related to a kind of ultralow dielectric, low-dielectric lossThe preparation method of Kapton, relates to the preparation of amido modified hyperbranched polyorganosiloxane (HBPSi) and containsThere are the ultralow dielectric of HBPSi structure, the preparation method of low-dielectric loss Kapton.
Background technology
Microelectric technique is the core technology of modern science and technology information industry, is to be accompanied by integrated circuit, particularly super large ruleThe research and development of vlsi die and a new technology growing up. In recent years, in order further to improve integrated circuit justTake the signaling rate in formula communication equipment, microelectric technique is gradually towards high integration more, more low-power consumption and moreHigh performance future development. But in improving integrated circuit integrated level, integrated circuit size is also in progressively contractingLittle, this is the easier phase mutual interference of connection wire causing in integrated circuit, and then causes the electricity such as signal hysteresis and cross-talkSubsignal disturbs obviously to be increased. Because signal hysteresis and cross-talk increase the dielectric constant (D with interlayer dielectric materialk)Linear, this means can be by reducing the D of interlayer dielectric mediumkSolving signal hysteresis and cross-talk etc. asksTopic, and then reduce energy loss and improve signal transmission quality.
Polyimides (PI) material is owing to having higher mechanical strength, outstanding heat resistance and good chemically-resistantCorrosive medium, is widely used in encapsulating material, photic etching material, flexible circuit board in microelectronics industry fieldMatrix material and the aligning film material of liquid crystal display etc. Regrettably, although business-like PI material at microelectronicsIn industry, obtain application comparatively widely, but at its relatively high D of integrated circuit fieldskBecome restriction PIThe factor of extensive use. Therefore, exploitation has ultralow DkPI material become domestic and international researcher's extensive concernProblem.
At present, the dielectric constant of reduction PI material mainly concentrates on the following aspects: (1) adopts lower mole of polarizationThe diamines of rate or dianhydride monomer, as introduced fluoro-containing group etc.; (2) in PI matrix, introduce air-gap or prepare microporePI material; (3) adopt and there is significantly sterically hindered, can to improve PI material free volume diamines or dianhydride monomer, asThe monomer of introducing the non-copline of distortion or containing larger side base. Adopt the monomer of low mole of polarizability to prepare low dielectric PIMaterial can be traced back to the sixties in last century the earliest, and du pont company adopts fluorinated diamine and fluorine-containing dianhydride to synthesize oneFluoridize PI, the D of this material in the time of 1MHzkBe 2.7, and there is lower hygroscopicity (< 1.0%). But,Along with the introducing of fluorine element in PI strand, the defect of this material is also following, as creep resisting ability declines, mechanicsPerformance reduction, medium corrosion resistance variation etc. In addition, the exploitation of fluorine-containing PI has also increased R&D costs greatly, noBe beneficial to mass production. In recent years, consider that the relative dielectric constant of air approaches 1, researcher adopts respectively both at home and abroadWith thermal degradation, be separated, the means such as chemical etching prepare the PI material with microcellular structure. The general tool of micropore PIThere is lower Dk(2.3 – 2.6), even can reach ultralow D for some systemkCategory (Dk< 2.0). But,Due to the existence of a large amount of microcellular structures, such PI film General Mechanics poor-performing, and pore structure is in hot conditionsThere is the tendency of caving in, be difficult to meet the demand of microelectronics industry, and then limited the extensive use of micropore PI film. FoundationThe POLARIZATION MECHANISM of material internal polarisation unit (interfacial polarization, dipole polarization, atom polarization, electronic polarization) is known,Microcosmic accumulation shape by controlled material, to increase the free volume of material internal, just can reduce the utmost point in unit volumeChange cell density, reduce D thereby reachkObject. Wei etc. have prepared a kind of side chain and have contained cage-type silsesquioxane(POSS) the hybrid polyimide material of structure (K.H.Weietal., Macromolecules, 2003,36,9122 – 9127). Because POSS has larger sterically hinderedly, can significantly improve free body after introducing PI resin matrixLong-pending, and the distinctive cavity structure of POSS also increased the microporosity of material, and therefore this kind of hydridization PI material isReveal lower dielectric constant (2.32 – 2.86). But this PI material mechanical performance is not good enough, and synthetic POSSTechnique comparatively complicated, R&D costs are higher, limited the extensive use of such material.
Summary of the invention
The technical problem solving
For fear of the deficiencies in the prior art part, the present invention proposes a kind of ultralow dielectric, low-dielectric loss polyamidesThe preparation method of imines film, the technical scheme adopting is: (i) synthesizing containing amino HBPSi; (ii) containThe preparation of the low dielectric PI hybrid film of HBPSi structure.
Technical scheme
A preparation method for ultralow dielectric, low-dielectric loss Kapton, is characterized in that step is as follows:
Step 1, prepare polyamic acid PAA:
Be that 0.1～2:1 will add reactor containing amino hyperbranched polyorganosiloxane HBPSi and aromatic diamine according to mass ratioIn, then add polar non-solute, stir in nitrogen protection; After monomer dissolves, maintain reaction system temperatureDegree is for-5～5 DEG C, and adds aromatic dibasic acid acid anhydride, continues stirring reaction 24～48h, obtains containing HBPSi structurePAA Solution H BPSi-PAA, system solid content is controlled at as 10wt.%～20wt.%; Described aromatic dibasic acid acid anhydrideWith the mol ratio of amido functional group be 1:2;
Step 2, prepare hybrid film:
Step 1 gained HBPSi-PAA solution is coated on glass plate, in 80 DEG C～100 DEG C environment, processes 2～5H is placed on and in baking oven, carries out imidization; Described imidization technique is: 100 DEG C/30min, and 150 DEG C/1h, 200 DEG C/ 0.5h, 250 DEG C/0.5h, 300 DEG C/0.5h, 380 DEG C/0.5h, 420～480 DEG C/2min, heating rate is 1～4 DEG C/min；
After imidization finishes, with the rate of temperature fall of 2～4 DEG C/min, system temperature is down to 25 DEG C, takes out glass plate,Soak 24h in deionized water after, take off film, and at 150 DEG C vacuum drying 24h, obtain low dielectric PI thinFilm HBPSi-PI.
The described synthetic step containing amino hyperbranched polyorganosiloxane HBPSi is:
Step (1): add successively polar solvent, four degree of functionality silane monomers in container, three-functionality-degree silane monomerWith containing amino silane monomer, start simultaneously and stir and lower the temperature to system; The matter of described polar solvent and three kinds of silane monomersAmount is than being 0.5～3:1, and the mol ratio of four degree of functionality silane monomers and three-functionality-degree silane monomer is 0.1～2:10, four sensesDegree silane monomer is 0.5～3:1 with the mol ratio containing amino silane monomer;
Step (2): in the time that temperature is down to 0～5 DEG C, distilled water is splashed in 1～3h in step 1 system; FinishAfter, maintain reaction condition constant, continue to stir 1～4h, be then warming up to 30～50 DEG C, continue reaction 5～10h;The mol ratio of described distilled water and three kinds of silane monomers is 1～4:1;
Step (3): reaction finishes rear rotary evaporation, and temperature is controlled at 55～80 DEG C, and pressure is 0.1 atmospheric pressure,Remove volatile matter and obtain thick product E;
Step (4): adopt ethanol and toluene mixture liquid cleaning product E2～3 time of 50～100mL0 DEG C, obtain and produceProduct F; The volume ratio of described ethanol and toluene is 3:1～2;
Step (5): product F be dissolved in the chloroform of 20～50mL and use tetrafluoro filter element filtering, then using 200～400The ethanol precipitating of mL0 DEG C is also filtered; Repeat this operation 2～5 times, obtain product G;
Step (6): by be dried 48～60h under product G normal temperature in vacuum drying oven, obtain containing amino hyperbranched poly siliconOxygen alkane HBPSi.
The aperture of the tetrafluoro filter core of described step (5) is 220nm.
Described polar solvent is any one or its combination in oxolane, chloroform or carrene.
Described four degree of functionality silane monomers are silicon tetrachloride SiCl4, ethyl orthosilicate TEOS or methyl silicate TMOSIn any one or its combination; The structure of described four degree of functionality silane monomer B is as follows:
Described three-functionality-degree silane monomer is phenyl trimethoxy silicon PTMS, phenyl triethoxysilane PTES, methylTrimethoxy silane MTMS, MTES MTES, phenyl trichlorosilane PTCS, methyl trichlorine siliconAlkane MTCS, vinyltrimethoxy silane CG-151M, VTES CG-151E, propyl group front threeAny one or its combination in TMOS CG-123M or propyl-triethoxysilicane CG-123E; Described three officialsThe structural formula of energy degree silane monomer C is as follows:
The described amino silane monomer that contains is: γ-aminopropyltrimethoxysilane APSM, gamma-aminopropyl-triethoxy-silaneAPSE, p-aminophenyl trimethoxy silane ABSM, p-aminophenyl triethoxysilane ABSE, N-β (ammoniaEthyl)-γ-aminopropyltrimethoxysilane UP-900M, N-β (aminoethyl)-gamma-aminopropyl-triethoxy-silaneUP-900E, γ-aminopropyl methyl dimethoxysilane APMDM, γ-aminopropyl methyldiethoxysilane APMDE,In γ-aminopropyl ethyl dimethoxy silane APEDM or γ-aminopropyl ethyl diethoxy silane APEDE any onePlant or its combination; The described structural formula containing amino silane monomer D is as follows:
Described polar non-solute is: DMF DMF, DMA DMAc, twoAny one or its combination in methyl sulfoxide DMSO or 1-METHYLPYRROLIDONE NMP.
Described aromatic diamine monomer is any one or its combination in following several monomer; The change of described several monomersStructural formula is as follows:
Described aromatic dibasic acid acid anhydride is any one or its combination in following several monomer; The chemistry of described several monomersStructural formula is as follows:
Beneficial effect
A kind of ultralow dielectric that the present invention proposes, the preparation method of low-dielectric loss Kapton, adopt waterSeparate that cocondensation is legal has synthesized amido modified hyperbranched polyorganosiloxane (HBPSi), and by this structure by the side of copolycondensationMethod is introduced PI molecular backbone, has significantly improved the internal freedom volume of PI material, has given the dielectricity of material excellenceCan, reach the D that reduces PI materialk, and make the preparation of low dielectric PI material towards future development capable of being industrialized.
In addition, the prepared HBPSi of the present invention has realized the modification on molecular level to PI, thus with PI resinMatrix has presented good compatibility, so obtained that dielectric loss is little, excellent heat resistance, mechanical strength are outstanding,The hybrid film that hygroscopicity is little, optical transparence is good, thus ensure that such PI film can better serve micro-electricitySub-industry.
The invention has the beneficial effects as follows: the present invention adopts legal having synthesized of hydrolysis cocondensation to contain amino HBPSi, finally to changeLearn the form of key hyperbranched polyorganosiloxane structure is introduced to PI molecular backbone, realized on molecular level PI materialModification, significantly reduced the dielectric constant of PI material, and kept preferably the intrinsic advantage of PI material. This PIThin-film dielectric performance excellence, excellent heat resistance, mechanical strength is outstanding, and water absorption rate is low, and surface smoothness is high, and film is saturatingBright property is good, and preparation process reaction condition gentleness, and R&D costs are lower, are conducive to large-scale industrial production. With orderBefore the Kapton standard film that generally uses compare, the reduced dielectric constant of HBPSi-PI film under equal test condition30%～40%, lowest dielectric constant even approaches 2.0, reaches the level of ultralow dielectric, can meet futureThe active demand of microelectronic industry development.
Brief description of the drawings
Fig. 1 is the synthetic route of amido modified hyperbranched polyorganosiloxane (HBPSi);
Fig. 2 is that the ultralow dielectric that contains HBPSi structure, the preparation flow of low-dielectric loss Kapton showIntention;
Fig. 3 is the dielectric properties of the Kapton of different HBPSi content: (a) dielectric constant becomes with test frequencyChange curve; (b) dielectric loss is with test frequency change curve; (c) Kapton of different HBPSi content existsDielectric constant when test frequency is 1MHz and dielectric loss;
Fig. 4 is the Kapton thermal weight loss in (a) air and (b) argon gas respectively of different HBPSi content(TGA) curve;
Fig. 5 is mechanical property (a) load-deformation curve of the Kapton of different HBPSi content; (b) drawStretch intensity and fracture elongation.
Detailed description of the invention
Now in conjunction with the embodiments, the invention will be further described for accompanying drawing:
Embodiment 1
(1) synthesizing containing amino hyperbranched polyorganosiloxane (HBPSi)
Add successively 20g oxolane, 1.4476gSiCl to being equipped with in the container of magnetic stirring apparatus4，16.8964gPTMS and 1.6559gAPSM start simultaneously and stir and lower the temperature to system. In the time that system temperature is down to 2 DEG C, by 3.68G distilled water splashes in above-mentioned system in 1h. After end, maintain reaction condition constant, continue to stir 1h, thenBe warming up to 40 DEG C, continue reaction 5h. After reaction finishes, rotary evaporation, temperature is controlled at 60 DEG C, and pressure is 0.1Individual atmospheric pressure, removes volatile matter, obtains thick product E. By ethanol/toluene mixed liquor (ethanol and the first of 50mL0 DEG CThe volume ratio of benzene is 3:1) cleaning product E2 time, obtain product F. Product F is dissolved in the chloroform of 20mL alsoThe tetrafluoro filter element filtering that is 220nm with aperture, then also filters by the ethanol precipitating of 200mL0 DEG C. Repeat this behaviourDo 3 times, obtain product G. By be dried 50h under product G normal temperature in vacuum drying oven, obtain finished product H,HBPSi, amino content is 0.35mmol/g.
(2) preparation of the low dielectric PI hybrid film that contains HBPSi structure
Take 2.8571gHBPSi and 3.6947gBAPP in reactor, add 53.8gDMAc and start and stirMix nitrogen protection. After monomer dissolves, maintain temperature of reaction system at 0 DEG C, the disposable 2.9422gBPDA that adds.Maintain reaction condition constant, continue stirring reaction 30h, obtain the PAA solution that contains HBPSi structure(HBPSi-PAA). Gained HBPSi-PAA solution is evenly coated on glass plate, in 80 DEG C of environment, processes3h is placed on and in baking oven, carries out imidization. Concrete imidization technique is: 100 DEG C/30min, and 150 DEG C/1h, 200 DEG C/ 0.5h, 250 DEG C/0.5h, 300 DEG C/0.5h, 380 DEG C/0.5h, 420 DEG C/2min, heating rate is 2 DEG C/min.After imidization finishes, with the rate of temperature fall of 3 DEG C/min, system temperature is down to 25 DEG C, take out glass plate, go fromAfter soaking 24h in sub-water, take off film, and at 150 DEG C vacuum drying 24h, obtain low dielectric PI film(HBPSi-PI)。
Embodiment 2
(1) synthesizing containing amino hyperbranched polyorganosiloxane (HBPSi)
Add successively 20g chloroform, 1.4628gTEOS to being equipped with in the container of magnetic stirring apparatus, 17.31gPTES with1.66gAPSE starts simultaneously and stirs and lower the temperature to system. In the time that system temperature is down to 2 DEG C, by 3.52g distilled waterIn 1h, splash in above-mentioned system. After end, maintain reaction condition constant, continue to stir 2h, be then warming up to 45 DEG C,Continue reaction 6h. After reaction finishes, rotary evaporation, temperature is controlled at 60 DEG C, and pressure is 0.1 atmospheric pressure, removesRemove volatile matter, obtain thick product E. With the ethanol/toluene mixed liquor of 50mL0 DEG C, (volume ratio of ethanol and toluene is3:1) cleaning product E2 time, obtains product F. Product F is dissolved in the chloroform of 20mL and with aperture be 220nmTetrafluoro filter element filtering, then by the ethanol precipitating of 200mL0 DEG C and filter. Repeat this operation 4 times, producedProduct G. By be dried 50h under product G normal temperature in vacuum drying oven, obtain finished product H, i.e. HBPSi, amino contentFor 0.20mmol/g.
(2) preparation of the low dielectric PI hybrid film that contains HBPSi structure
Take 2.0gHBPSi and 3.209g6FBA in reactor, add 32.6gDMAc and start stirring,Nitrogen protection. After monomer dissolves, maintain temperature of reaction system at 0 DEG C, the disposable 2.9422ga-BPDA that adds.Maintain reaction condition constant, continue stirring reaction 24h, obtain the PAA solution that contains HBPSi structure(HBPSi-PAA). Gained HBPSi-PAA solution is evenly coated on glass plate, in 80 DEG C of environment, processes3h is placed on and in baking oven, carries out imidization. Concrete imidization technique is: 100 DEG C/30min, and 150 DEG C/1h, 200 DEG C/ 0.5h, 250 DEG C/0.5h, 300 DEG C/0.5h, 380 DEG C/0.5h, 430 DEG C/2min, heating rate is 2 DEG C/min.After imidization finishes, with the rate of temperature fall of 2 DEG C/min, system temperature is down to 25 DEG C, take out glass plate, go fromAfter soaking 24h in sub-water, take off film, and at 150 DEG C vacuum drying 24h, obtain low dielectric PI film(HBPSi-PI)。
Embodiment 3
(1) synthesizing containing amino hyperbranched polyorganosiloxane (HBPSi)
Add successively 20g chloroform, 5.7677gTEOS, 25.8069gMTMS to being equipped with in the container of magnetic stirring apparatusStart simultaneously and stir and lower the temperature to system with 8.4252gUP-900M. In the time that system temperature is down to 0 DEG C, by 4.59gDistilled water splashes in above-mentioned system in 1h. After end, maintain reaction condition constant, continue to stir 2h, then riseTemperature, to 40 DEG C, continues reaction 6h. After reaction finishes, rotary evaporation, temperature is controlled at 60 DEG C, and pressure is 0.1Atmospheric pressure, removes volatile matter, obtains thick product E. With ethanol/toluene mixed liquor (ethanol and the toluene of 50mL0 DEG CVolume ratio be 3:2) cleaning product E2 time, obtain product F. Product F be dissolved in the chloroform of 20mL and useAperture is the tetrafluoro filter element filtering of 220nm, then also filters by the ethanol precipitating of 200mL0 DEG C. Repeat this operation3 times, obtain product G. By be dried 50h under product G normal temperature in vacuum drying oven, obtain finished product H, i.e. HBPSi,Amino content is 0.30mmol/g.
(2) preparation of the low dielectric PI hybrid film that contains HBPSi structure
Take 0.6667gHBPSi and 1.0188gOTDA in reactor, add 23.7gDMF and start stirring,Nitrogen protection. After monomer dissolves, maintain temperature of reaction system at 0 DEG C, the disposable 1.5511gODPA that adds.Maintain reaction condition constant, continue stirring reaction 24h, obtain the PAA solution that contains HBPSi structure(HBPSi-PAA). Gained HBPSi-PAA solution is evenly coated on glass plate, in 80 DEG C of environment, processes3h is placed on and in baking oven, carries out imidization. Concrete imidization technique is: 100 DEG C/30min, and 150 DEG C/1h, 200 DEG C/ 0.5h, 250 DEG C/0.5h, 300 DEG C/0.5h, 380 DEG C/0.5h, 420 DEG C/2min, heating rate is 2 DEG C/min.After imidization finishes, with the rate of temperature fall of 2 DEG C/min, system temperature is down to 25 DEG C, take out glass plate, go fromAfter soaking 24h in sub-water, take off film, and at 150 DEG C vacuum drying 24h, obtain low dielectric PI film(HBPSi-PI)。
Embodiment 4
(1) synthesizing containing amino hyperbranched polyorganosiloxane (HBPSi)
Add successively 20g carrene, 1.4275gSiCl to being equipped with in the container of magnetic stirring apparatus4，9.9878gMTES and 3.5847gABSM start simultaneously and stir and lower the temperature to system. In the time that system temperature is down to 5 DEG C, will1.5859g distilled water splashes in above-mentioned system in 2h. After end, maintain reaction condition constant, continue to stir 2h,Then be warming up to 40 DEG C, continue reaction 6h. After reaction finishes, rotary evaporation, temperature is controlled at 60 DEG C, pressureBe 0.1 atmospheric pressure, remove volatile matter, obtain thick product E. By the ethanol/toluene mixed liquor (second of 50mL0 DEG CThe volume ratio of alcohol and toluene is 3:2) cleaning product E3 time, obtain product F. Product F is dissolved in to the chlorine of 20mLThe tetrafluoro filter element filtering that is also 220nm with aperture in imitative, then also filters by the ethanol precipitating of 200mL0 DEG C. HeavyMultiple this operation 3 times, obtains product G. By be dried 50h under product G normal temperature in vacuum drying oven, obtain finished product H,Be HBPSi, amino content is 0.45mmol/g.
(2) preparation of the low dielectric PI hybrid film that contains HBPSi structure
Take 1.1111gHBPSi and 0.8922gDDM in reactor, add 32.5gDMF and start stirring,Nitrogen protection. After monomer dissolves, maintain temperature of reaction system at 0 DEG C, the disposable 1.6112gBTDA that adds. DimensionHold reaction condition constant, continue stirring reaction 24h, obtain the PAA solution (HBPSi-PAA) that contains HBPSi structure.Gained HBPSi-PAA solution is evenly coated on glass plate, in 80 DEG C of environment, processes 3h and be placed in baking ovenCarry out imidization. Concrete imidization technique is: 100 DEG C/30min, and 150 DEG C/1h, 200 DEG C/0.5h, 250 DEG C/0.5H, 300 DEG C/0.5h, 380 DEG C/0.5h, 430 DEG C/2min, heating rate is 3 DEG C/min. After imidization finishes,System temperature is down to 25 DEG C by rate of temperature fall with 2 DEG C/min, takes out glass plate, soaks 24h in deionized waterAfter take off film, and at 150 DEG C vacuum drying 24h, obtain low dielectric PI film (HBPSi-PI).
Embodiment 5
(1) synthesizing containing amino hyperbranched polyorganosiloxane (HBPSi)
Add successively 20g chloroform, 1.6155gTEOS, 16.4041gPTCS to being equipped with in the container of magnetic stirring apparatusStart simultaneously and stir and lower the temperature to system with 1.9804gABSE. In the time that system temperature is down to 2 DEG C, 1.96g is steamedHeat up in a steamer water splashes in above-mentioned system in 1h. After end, maintain reaction condition constant, continue to stir 2h, then heat upTo 40 DEG C, continue reaction 6h. After reaction finishes, rotary evaporation, temperature is controlled at 60 DEG C, pressure be 0.1 largeAir pressure, removes volatile matter, obtains thick product E. With the ethanol/toluene mixed liquor of 50mL0 DEG C (ethanol and tolueneVolume ratio is 3:1) cleaning product E2 time, obtain product F. Product F be dissolved in the chloroform of 20mL and use holeFootpath is the tetrafluoro filter element filtering of 220nm, then also filters by the ethanol precipitating of 200mL0 DEG C. Repeat this operation 3Inferior, obtain product G. By be dried 50h under product G normal temperature in vacuum drying oven, obtain finished product H, i.e. HBPSi,Amino content is 0.17mmol/g.
(2) preparation of the low dielectric PI hybrid film that contains HBPSi structure
Take 0.5882gHBPSi and 1.5692g6FDMB in reactor, add 23.6gDMAc and start and stirMix nitrogen protection. After monomer dissolves, maintain temperature of reaction system at 0 DEG C, the disposable 2.0116gHQDPA that adds.Maintain reaction condition constant, continue stirring reaction 24h, obtain the PAA solution that contains HBPSi structure(HBPSi-PAA). Gained HBPSi-PAA solution is evenly coated on glass plate, in 80 DEG C of environment, processes3h is placed on and in baking oven, carries out imidization. Concrete imidization technique is: 100 DEG C/30min, and 150 DEG C/1h, 200 DEG C/ 0.5h, 250 DEG C/0.5h, 300 DEG C/0.5h, 380 DEG C/0.5h, 420 DEG C/2min, heating rate is 2 DEG C/min.After imidization finishes, with the rate of temperature fall of 2 DEG C/min, system temperature is down to 25 DEG C, take out glass plate, go fromAfter soaking 24h in sub-water, take off film, and at 150 DEG C vacuum drying 24h, obtain low dielectric PI film(HBPSi-PI)。
Embodiment 6
(1) synthesizing containing amino hyperbranched polyorganosiloxane (HBPSi)
Add successively 20g oxolane, 4.2532gTMOS, 21.7296g to being equipped with in the container of magnetic stirring apparatusMTCS and 3.8443gUP-900E start simultaneously and stir and lower the temperature to system. In the time that system temperature is down to 2 DEG C, will5.10g distilled water splashes in above-mentioned system in 1h. After end, maintain reaction condition constant, continue to stir 2h,Then be warming up to 40 DEG C, continue reaction 6h. After reaction finishes, rotary evaporation, temperature is controlled at 60 DEG C, pressureBe 0.1 atmospheric pressure, remove volatile matter, obtain thick product E. By the ethanol/toluene mixed liquor (second of 50mL0 DEG CThe volume ratio of alcohol and toluene is 3:2) cleaning product E3 time, obtain product F. Product F is dissolved in to the chlorine of 20mLThe tetrafluoro filter element filtering that is also 220nm with aperture in imitative, then also filters by the ethanol precipitating of 200mL0 DEG C. HeavyMultiple this operation 3 times, obtains product G. By be dried 48h under product G normal temperature in vacuum drying oven, obtain finished product H,Be HBPSi, amino content is 0.27mmol/g.
(2) preparation of the low dielectric PI hybrid film that contains HBPSi structure
Take 0.3704gHBPSi and 1.0403gDMBZ in reactor, add 25.1gDMSO and start and stirMix nitrogen protection. After monomer dissolves, maintain temperature of reaction system at 0 DEG C, the disposable 2.0116gRsDPA that adds.Maintain reaction condition constant, continue stirring reaction 24h, obtain the PAA solution that contains HBPSi structure(HBPSi-PAA). Gained HBPSi-PAA solution is evenly coated on glass plate, in 100 DEG C of environment, processes5h is placed on and in baking oven, carries out imidization. Concrete imidization technique is: 100 DEG C/30min, and 150 DEG C/1h, 200 DEG C/ 0.5h, 250 DEG C/0.5h, 300 DEG C/0.5h, 380 DEG C/0.5h, 420 DEG C/2min, heating rate is 1 DEG C/min.After imidization finishes, with the rate of temperature fall of 2 DEG C/min, system temperature is down to 25 DEG C, take out glass plate, go fromAfter soaking 24h in sub-water, take off film, and at 150 DEG C vacuum drying 24h, obtain low dielectric PI film(HBPSi-PI)。
Embodiment 7
(1) synthesizing containing amino hyperbranched polyorganosiloxane (HBPSi)
Add successively 20g carrene, 2.6182gSiCl to being equipped with in the container of magnetic stirring apparatus4，11.4219gCG-151M and 5.9597gAPMDM start simultaneously and stir and lower the temperature to system. In the time that system temperature is down to 2 DEG C,6.66g distilled water is splashed in above-mentioned system in 2h. After end, maintain reaction condition constant, continue to stir 2h,Then be warming up to 40 DEG C, continue reaction 6h. After reaction finishes, rotary evaporation, temperature is controlled at 60 DEG C, pressureBe 0.1 atmospheric pressure, remove volatile matter, obtain thick product E. By the ethanol/toluene mixed liquor (second of 50mL0 DEG CThe volume ratio of alcohol and toluene is 3:1) cleaning product E3 time, obtain product F. Product F is dissolved in to the chlorine of 20mLThe tetrafluoro filter element filtering that is also 220nm with aperture in imitative, then also filters by the ethanol precipitating of 200mL0 DEG C. HeavyMultiple this operation 3 times, obtains product G. By be dried 50h under product G normal temperature in vacuum drying oven, obtain finished product H,Be HBPSi, amino content is 0.75mmol/g.
(2) preparation of the low dielectric PI hybrid film that contains HBPSi structure
Take 0.1333gHBPSi and 1.2167gDDS in reactor, add 19.8gDMF and start stirring,Nitrogen protection. After monomer dissolves, maintain temperature of reaction system at 0 DEG C, the disposable 2.1515g6FBPDA that adds.Maintain reaction condition constant, continue stirring reaction 24h, obtain the PAA solution that contains HBPSi structure(HBPSi-PAA). Gained HBPSi-PAA solution is evenly coated on glass plate, in 80 DEG C of environment, processes3h is placed on and in baking oven, carries out imidization. Concrete imidization technique is: 100 DEG C/30min, and 150 DEG C/1h, 200 DEG C/ 0.5h, 250 DEG C/0.5h, 300 DEG C/0.5h, 380 DEG C/0.5h, 420 DEG C/2min, heating rate is 3 DEG C/min.After imidization finishes, with the rate of temperature fall of 2 DEG C/min, system temperature is down to 25 DEG C, take out glass plate, go fromAfter soaking 24h in sub-water, take off film, and at 150 DEG C vacuum drying 24h, obtain low dielectric PI film(HBPSi-PI)。
Embodiment 8
(1) synthesizing containing amino hyperbranched polyorganosiloxane (HBPSi)
Add successively 20g oxolane, 3.0318gTEOS, 22.1567g to being equipped with in the container of magnetic stirring apparatusCG-151E and 4.8115gAPEDE start simultaneously and stir and lower the temperature to system. In the time that system temperature is down to 2 DEG C,4.1354g distilled water is splashed in above-mentioned system in 1h. After end, maintain reaction condition constant, continue to stir 2H, is then warming up to 40 DEG C, continues reaction 6h. After reaction finishes, rotary evaporation, temperature is controlled at 60 DEG C, pressesPower is 0.1 atmospheric pressure, removes volatile matter, obtains thick product E. By the ethanol/toluene mixed liquor (second of 50mL0 DEG CThe volume ratio of alcohol and toluene is 3:2) cleaning product E3 time, obtain product F. Product F is dissolved in to the chlorine of 20mLThe tetrafluoro filter element filtering that is also 220nm with aperture in imitative, then also filters by the ethanol precipitating of 200mL0 DEG C. HeavyMultiple this operation 3 times, obtains product G. By be dried 52h under product G normal temperature in vacuum drying oven, obtain finished product H,Be HBPSi, amino content is 0.68mmol/g.
(2) preparation of the low dielectric PI hybrid film that contains HBPSi structure
Take 1.4706gHBPSi and 2.6311g1,3,4-APB, in reactor, adds 25.1gDMSO and opensMoving stirring, nitrogen protection. After monomer dissolves, maintain temperature of reaction system at 0 DEG C, the disposable 2.1812g that addsPMDA. Maintain reaction condition constant, continue stirring reaction 24h, obtain the PAA solution that contains HBPSi structure(HBPSi-PAA). Gained HBPSi-PAA solution is evenly coated on glass plate, in 100 DEG C of environment, processes5h is placed on and in baking oven, carries out imidization. Concrete imidization technique is: 100 DEG C/30min, and 150 DEG C/1h, 200 DEG C/ 0.5h, 250 DEG C/0.5h, 300 DEG C/0.5h, 380 DEG C/0.5h, 420 DEG C/2min, heating rate is 1 DEG C/min.After imidization finishes, with the rate of temperature fall of 2 DEG C/min, system temperature is down to 25 DEG C, take out glass plate, go fromAfter soaking 24h in sub-water, take off film, and at 150 DEG C vacuum drying 24h, obtain low dielectric PI film(HBPSi-PI)。
Embodiment 9
(1) synthesizing containing amino hyperbranched polyorganosiloxane (HBPSi)
Add successively 20g carrene, 3.4148gSiCl to being equipped with in the container of magnetic stirring apparatus4，33.0203gCG-123M and 3.5641gAPEDM start simultaneously and stir and lower the temperature to system. In the time that system temperature is down to 2 DEG C,7.7g distilled water is splashed in above-mentioned system in 2h. After end, maintain reaction condition constant, continue to stir 2h,Then be warming up to 40 DEG C, continue reaction 6h. After reaction finishes, rotary evaporation, temperature is controlled at 60 DEG C, pressureBe 0.1 atmospheric pressure, remove volatile matter, obtain thick product E. By the ethanol/toluene mixed liquor (second of 50mL0 DEG CThe volume ratio of alcohol and toluene is 3:1) cleaning product E3 time, obtain product F. Product F is dissolved in to the chlorine of 20mLThe tetrafluoro filter element filtering that is also 220nm with aperture in imitative, then also filters by the ethanol precipitating of 200mL0 DEG C. HeavyMultiple this operation 3 times, obtains product G. By be dried 50h under product G normal temperature in vacuum drying oven, obtain finished product H,Be HBPSi, amino content is 0.35mmol/g.
(2) preparation of the low dielectric PI hybrid film that contains HBPSi structure
Take 0.5714gHBPSi and 0.9612gODA in reactor, add 37.2gNMP and start stirring,Nitrogen protection. After monomer dissolves, maintain temperature of reaction system at 0 DEG C, the disposable 2.6025gBPADA that adds.Maintain reaction condition constant, continue stirring reaction 24h, obtain the PAA solution that contains HBPSi structure(HBPSi-PAA). Gained HBPSi-PAA solution is evenly coated on glass plate, in 80 DEG C of environment, processes3h is placed on and in baking oven, carries out imidization. Concrete imidization technique is: 100 DEG C/30min, and 150 DEG C/1h, 200 DEG C/ 0.5h, 250 DEG C/0.5h, 300 DEG C/0.5h, 380 DEG C/0.5h, 420 DEG C/2min, heating rate is 3 DEG C/min.After imidization finishes, with the rate of temperature fall of 2 DEG C/min, system temperature is down to 25 DEG C, take out glass plate, go fromAfter soaking 24h in sub-water, take off film, and at 150 DEG C vacuum drying 24h, obtain low dielectric PI film(HBPSi-PI)。
Embodiment 10
(1) synthesizing containing amino hyperbranched polyorganosiloxane (HBPSi)
Add successively 20g chloroform, 2.0319gTEOS, 16.1016g to being equipped with in the container of magnetic stirring apparatusCG-123E and 1.8663gAPMDE start simultaneously and stir and lower the temperature to system. In the time that system temperature is down to 2 DEG C,3.51g distilled water is splashed in above-mentioned system in 1h. After end, maintain reaction condition constant, continue to stir 2h,Then be warming up to 40 DEG C, continue reaction 6h. After reaction finishes, rotary evaporation, temperature is controlled at 60 DEG C, pressureBe 0.1 atmospheric pressure, remove volatile matter, obtain thick product E. By the ethanol/toluene mixed liquor (second of 50mL0 DEG CThe volume ratio of alcohol and toluene is 3:2) cleaning product E2 time, obtain product F. Product F is dissolved in to the chlorine of 20mLThe tetrafluoro filter element filtering that is also 220nm with aperture in imitative, then also filters by the ethanol precipitating of 200mL0 DEG C. HeavyMultiple this operation 3 times, obtains product G. By be dried 50h under product G normal temperature in vacuum drying oven, obtain finished product H,Be HBPSi, amino content is 0.40mmol/g.
(2) preparation of the low dielectric PI hybrid film that contains HBPSi structure
Take 0.5gHBPSi and 0.8844gBz in reactor, add 20.4gDMAc and start stirring, nitrogenGas protection. After monomer dissolves, maintain temperature of reaction system at 0 DEG C, the disposable 2.2212g6FDA that adds. MaintainReaction condition is constant, continues stirring reaction 24h, obtains the PAA solution (HBPSi-PAA) that contains HBPSi structure.Gained HBPSi-PAA solution is evenly coated on glass plate, in 80 DEG C of environment, processes 3h and be placed in baking ovenCarry out imidization. Concrete imidization technique is: 100 DEG C/30min, and 150 DEG C/1h, 200 DEG C/0.5h, 250 DEG C/0.5H, 300 DEG C/0.5h, 380 DEG C/0.5h, 420 DEG C/2min, heating rate is 2 DEG C/min. After imidization finishes,System temperature is down to 25 DEG C by rate of temperature fall with 2 DEG C/min, takes out glass plate, soaks 24h in deionized waterAfter take off film, and at 150 DEG C vacuum drying 24h, obtain low dielectric PI film (HBPSi-PI).

Claims (10)

1. a preparation method for ultralow dielectric, low-dielectric loss Kapton, is characterized in that step is as follows:
Step 1, prepare polyamic acid PAA:
Be that 0.1～2:1 will add reactor containing amino hyperbranched polyorganosiloxane HBPSi and aromatic diamine according to mass ratioIn, then add polar non-solute, stir in nitrogen protection; After monomer dissolves, maintain reaction system temperatureDegree is for-5～5 DEG C, and adds aromatic dibasic acid acid anhydride, continues stirring reaction 24～48h, obtains containing HBPSi structurePAA Solution H BPSi-PAA, system solid content is controlled at as 10wt.%～20wt.%; Described aromatic dibasic acid acid anhydrideWith the mol ratio of amido functional group be 1:2;
Step 2, prepare hybrid film:
Step 1 gained HBPSi-PAA solution is coated on glass plate, in 80 DEG C～100 DEG C environment, processes 2～5H is placed on and in baking oven, carries out imidization; Described imidization technique is: 100 DEG C/30min, and 150 DEG C/1h, 200 DEG C/ 0.5h, 250 DEG C/0.5h, 300 DEG C/0.5h, 380 DEG C/0.5h, 420～480 DEG C/2min, heating rate is 1～4 DEG C/min；
After imidization finishes, with the rate of temperature fall of 2～4 DEG C/min, system temperature is down to 25 DEG C, takes out glass plate,Soak 24h in deionized water after, take off film, and at 150 DEG C vacuum drying 24h, obtain low dielectric PI thinFilm HBPSi-PI.
2. the preparation method of ultralow dielectric, low-dielectric loss Kapton according to claim 1, its spyLevy and be: the described synthetic step containing amino hyperbranched polyorganosiloxane HBPSi is:
Step (1): add successively polar solvent, four degree of functionality silane monomers in container, three-functionality-degree silane monomerWith containing amino silane monomer, start simultaneously and stir and lower the temperature to system; The matter of described polar solvent and three kinds of silane monomersAmount is than being 0.5～3:1, and the mol ratio of four degree of functionality silane monomers and three-functionality-degree silane monomer is 0.1～2:10, four sensesDegree silane monomer is 0.5～3:1 with the mol ratio containing amino silane monomer;
Step (2): in the time that temperature is down to 0～5 DEG C, distilled water is splashed in 1～3h in step 1 system; FinishAfter, maintain reaction condition constant, continue to stir 1～4h, be then warming up to 30～50 DEG C, continue reaction 5～10h;The mol ratio of described distilled water and three kinds of silane monomers is 1～4:1;
Step (3): reaction finishes rear rotary evaporation, and temperature is controlled at 55～80 DEG C, and pressure is 0.1 atmospheric pressure,Remove volatile matter and obtain thick product E;
Step (4): adopt ethanol and toluene mixture liquid cleaning product E2～3 time of 50～100mL0 DEG C, obtain and produceProduct F; The volume ratio of described ethanol and toluene is 3:1～2;
Step (5): product F be dissolved in the chloroform of 20～50mL and use tetrafluoro filter element filtering, then using 200～400The ethanol precipitating of mL0 DEG C is also filtered; Repeat this operation 2～5 times, obtain product G;
Step (6): by be dried 48～60h under product G normal temperature in vacuum drying oven, obtain containing amino hyperbranched poly siliconOxygen alkane HBPSi.
3. the preparation method of ultralow dielectric, low-dielectric loss Kapton according to claim 2, its spyLevy and be: the aperture of the tetrafluoro filter core of described step (5) is 220nm.
4. the preparation method of ultralow dielectric according to claim 1, low-dielectric loss Kapton, itsBe characterised in that: described polar solvent is any one or its combination in oxolane, chloroform or carrene.
5. the preparation method of ultralow dielectric according to claim 1, low-dielectric loss Kapton, itsBe characterised in that: described four degree of functionality silane monomers are silicon tetrachloride SiCl4, ethyl orthosilicate TEOS or positive silicic acidAny one or its combination in methyl esters TMOS.
6. the preparation method of ultralow dielectric according to claim 1, low-dielectric loss Kapton, itsBe characterised in that: described three-functionality-degree silane monomer is phenyl trimethoxy silicon PTMS, phenyl triethoxysilanePTES, MTMS MTMS, MTES MTES, phenyl trichlorosilane PTCS,Methyl trichlorosilane MTCS, vinyltrimethoxy silane CG-151M, VTESIn CG-151E, propyl trimethoxy silicane CG-123M or propyl-triethoxysilicane CG-123E any onePlant or its combination.
7. the preparation method of ultralow dielectric according to claim 1, low-dielectric loss Kapton, itsBe characterised in that: the described amino silane monomer that contains is: γ-aminopropyltrimethoxysilane APSM, γ-aminopropyl three secondTMOS APSE, p-aminophenyl trimethoxy silane ABSM, p-aminophenyl triethoxysilaneABSE, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane UP-900M, N-β (aminoethyl)-γ-aminopropylTriethoxysilane UP-900E, γ-aminopropyl methyl dimethoxysilane APMDM, γ-aminopropyl methyl diethylTMOS APMDE, γ-aminopropyl ethyl dimethoxy silane APEDM or γ-aminopropyl ethyl diethoxyAny one or its combination in silane APEDE.
8. the preparation method of ultralow dielectric according to claim 1, low-dielectric loss Kapton, itsBe characterised in that: described polar non-solute is: DMF DMF, DMAAny one or its combination in DMAc, dimethyl sulfoxide (DMSO) DMSO or 1-METHYLPYRROLIDONE NMP.
9. the preparation method of ultralow dielectric according to claim 1, low-dielectric loss Kapton, itsBe characterised in that: described aromatic diamine monomer is any one or its combination in following several monomer; Described severalThe chemical structural formula of planting monomer is as follows:
10. the preparation method of ultralow dielectric according to claim 1, low-dielectric loss Kapton, itsBe characterised in that: described aromatic dibasic acid acid anhydride is any one or its combination in following several monomer; Described severalThe chemical structural formula of monomer is as follows:
CN201511024047.2A 2015-12-30 2015-12-30 Preparation method of polyimide film with ultralow dielectric constant and low dielectric loss Pending CN105601964A (en)

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CN106479182A (en) * 2016-11-04 2017-03-08 东华大学 A kind of BPADA type BDADTBHQ branched polyimide resin film and preparation method thereof
CN106519682A (en) * 2016-11-04 2017-03-22 东华大学 HQDA type bisphenol A tetramine branched polyimide resin film and preparation method thereof
CN106633875A (en) * 2016-11-04 2017-05-10 东华大学 HQDA type 14BDAPB branched polyimide resin film and preparation method thereof
CN106633867A (en) * 2016-11-04 2017-05-10 东华大学 BTDA-type 14BDAPB branched polyimide resin thin film and preparation method thereof
CN106832278A (en) * 2017-02-08 2017-06-13 常州市明卓新材料科技有限公司 One class high transparency copoly type fluorine-containing polyimide film material and preparation method thereof
CN111995782A (en) * 2020-09-01 2020-11-27 无锡高拓新材料股份有限公司 Low-dielectric-constant polyimide hybrid film under high frequency and preparation method thereof
WO2021193530A1 (en) * 2020-03-24 2021-09-30 東レ株式会社 Resin film, method for producing same, resin composition, display and method for producing same
CN113736259A (en) * 2021-09-06 2021-12-03 上海海事大学 Low dielectric loss negative dielectric material and preparation method thereof
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CN106519682A (en) * 2016-11-04 2017-03-22 东华大学 HQDA type bisphenol A tetramine branched polyimide resin film and preparation method thereof
CN106633875A (en) * 2016-11-04 2017-05-10 东华大学 HQDA type 14BDAPB branched polyimide resin film and preparation method thereof
CN106633867A (en) * 2016-11-04 2017-05-10 东华大学 BTDA-type 14BDAPB branched polyimide resin thin film and preparation method thereof
CN106832278A (en) * 2017-02-08 2017-06-13 常州市明卓新材料科技有限公司 One class high transparency copoly type fluorine-containing polyimide film material and preparation method thereof
WO2021193530A1 (en) * 2020-03-24 2021-09-30 東レ株式会社 Resin film, method for producing same, resin composition, display and method for producing same
CN111995782A (en) * 2020-09-01 2020-11-27 无锡高拓新材料股份有限公司 Low-dielectric-constant polyimide hybrid film under high frequency and preparation method thereof
CN113736259A (en) * 2021-09-06 2021-12-03 上海海事大学 Low dielectric loss negative dielectric material and preparation method thereof
CN113736259B (en) * 2021-09-06 2024-03-29 上海海事大学 Low-dielectric-loss negative dielectric material and preparation method thereof
CN115044204A (en) * 2022-04-24 2022-09-13 华南理工大学 Preparation method of low-dielectric all-organic crosslinked polyimide film

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