CN112094425A - Surface compact type low-dielectric constant porous polyimide composite film and preparation method thereof - Google Patents
Surface compact type low-dielectric constant porous polyimide composite film and preparation method thereof Download PDFInfo
- Publication number
- CN112094425A CN112094425A CN202011019267.7A CN202011019267A CN112094425A CN 112094425 A CN112094425 A CN 112094425A CN 202011019267 A CN202011019267 A CN 202011019267A CN 112094425 A CN112094425 A CN 112094425A
- Authority
- CN
- China
- Prior art keywords
- film
- polyamic acid
- porous
- solution
- fluorinated graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 229920001721 polyimide Polymers 0.000 title claims abstract description 54
- 239000004642 Polyimide Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 61
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000004985 diamines Chemical class 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 32
- 239000010410 layer Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical group C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 6
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 239000002344 surface layer Substances 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 230000001112 coagulating effect Effects 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 150000004984 aromatic diamines Chemical class 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 2
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000009423 ventilation Methods 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims 4
- 239000002253 acid Substances 0.000 claims 4
- 229920002647 polyamide Polymers 0.000 claims 4
- 239000000463 material Substances 0.000 abstract description 6
- 238000004377 microelectronic Methods 0.000 abstract description 3
- 238000000614 phase inversion technique Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 58
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 230000008054 signal transmission Effects 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Classifications
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/365—Coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—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 C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
Abstract
The invention discloses a surface compact type low dielectric constant porous polyimide composite film and a preparation method thereof; preparing a polyamic acid solution and a composite solution thereof by taking dianhydride, diamine and fluorinated graphene as raw materials, preparing a polyimide porous film with a three-layer structure in a layer-by-layer coating mode, taking the polyimide or the fluorinated graphene/polyimide composite film as a compact outer surface enhancement layer, and taking porous polyimide prepared by a phase inversion method as a middle core low dielectric constant layer; the method has the advantages of simple operation, no pollution and low cost, and the prepared film has adjustable thickness, compact surface, low dielectric constant and excellent overall mechanical and thermal properties, and can be used in the fields of chemical products, microelectronic components, aerospace devices and the like with special requirements on the dielectric properties of materials.
Description
Technical Field
The invention relates to the field of polymer dielectric materials, in particular to a surface compact type low-dielectric-constant porous polyimide composite film and a preparation method thereof.
Background
The flexible circuit board has three-dimensional assembly characteristics of dynamic deflection and static deflection, and has light structure, thin thickness and high flexibility, so that the flexible circuit board is widely applied to high-performance electronic products. With the advent of the 5G era, electronic products are developing toward high frequency and high speed digitization of signal transmission, and the demand for high frequency and high speed of flexible circuit boards as signal transmission carriers is increasing. Research shows that reducing the dielectric constant of insulating medium material in circuit board is the most effective and direct means to raise the transmission speed and efficiency of microelectronic device and promote the high frequency and high speed development of flexible circuit board. The insulating medium layer connected between metals is widely applied to the preparation and processing of electronic devices. However, the intrinsic dielectric constant of the polyimide film is high (3.1-3.5), and the conventional polyimide film cannot meet the requirements of the development of the current integrated circuit and high-frequency printed circuit. Therefore, low-dielectric and low-modification of polyimide has become one of the research hotspots in the field of high-frequency and high-speed signal transmission at home and abroad; the development of a novel low-dielectric polyimide material for preparing the flexible copper clad laminate has important theoretical and practical significance for the development and application of polyimide in the field of 5G communication.
For polyimide materials, the ways to reduce the dielectric constant can be mainly classified into two types: one is to reduce the polarizability itself by introducing fluorine atoms or alicyclic structures, etc.: one is to reduce the number of polarized molecules per unit volume by increasing the free volume by constructing a large skeletal structure or by indirectly and directly introducing air. Air has a low dielectric constant (r = 1), and therefore, its dielectric constant can be greatly reduced by appropriately introducing air into the polyimide material. The introduction of air to construct the void containing structure is also currently recognized as the most effective method for lowering the dielectric constant. CN111087634A discloses a nano-composite porous polyimide film and a preparation method thereof. The polyimide solution and the modified nano particles are mixed, emulsified and dried to obtain the low dielectric polyimide containing air holes, but the air holes obtained by the method penetrate through the whole film, so that the moisture absorption performance of the low dielectric polyimide is improved, and the application of the low dielectric polyimide on electronic devices is limited. CN108329689A discloses a polyimide porous membrane with low dielectric constant and a preparation method thereof. The porous low-dielectric polyimide film is obtained by a self-assembly method taking water drops as templates, but the method also can improve the moisture absorption performance of the surface of the film and reduce the comprehensive use performance of the film.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides a surface compact type low-dielectric constant porous polyimide composite film and a preparation method thereof, so as to improve the mechanical and moisture absorption properties of the polyimide porous film.
In order to achieve the above object, the present invention is achieved by the following technical solutions.
The surface compact type low-dielectric constant porous polyimide composite film is a three-layer composite film, the bottom layer of the composite film is a fluorinated graphene/polyamic acid composite compact film, the middle layer is a fluorinated graphene/polyamic acid composite porous film or a polyamic acid porous film, and the surface layer is a fluorinated graphene/polyamic acid composite compact film.
The preparation method of the surface compact type low-dielectric constant porous polyimide composite film comprises the following steps:
a) preparing a bottom dense film: coating the fluorinated graphene/polyamic acid composite solution on a substrate, heating to 60-83 ℃ in vacuum, preserving heat for 1-3h, then heating to 120 ℃ and 220 ℃ in a ventilating manner in sequence, and preserving heat for 1-3h at each stage, thereby obtaining a bottom layer compact film.
b) Preparation of the intermediate porous membrane: coating the fluorinated graphene/polyamic acid composite solution or the polyamic acid solution on the compact film of the bottom layer, dipping the compact film in a coagulating bath at the temperature of 0-65 ℃ for 0.5-3h to form a porous wet film, heating the porous wet film to the temperature of 60-83 ℃ in vacuum, preserving the heat for 1-3h, then heating the porous wet film to the temperature of 100-220 ℃ in sequence by ventilation, and preserving the heat for 1-3h in each stage to further obtain the porous polyamic acid double-layer film.
c) Preparing a dense film of the surface layer: coating the fluorinated graphene/polyamic acid composite solution on the middle porous membrane, heating to 60-83 ℃ in vacuum, preserving heat for 1-3h, then heating to 100-; and finally, soaking the compounded film in boiling water for 10-50 min, and removing the film to obtain the low dielectric porous polyimide film with a compact surface.
Further, the preparation method of the fluorinated graphene/polyamic acid composite solution comprises the following steps: preparing a graphite fluoride raw material and an N-methyl pyrrolidone solvent into a graphite fluoride solution of 3-8 mg/ml; then, heating and refluxing the solution at 40-80 ℃ for 2-5 h to fully disperse the graphite fluoride; finally, carrying out ultrasonic stripping on the refluxed solution for 2-8 hours to obtain a fluorinated graphene dispersion solution; adding the fluorinated graphene dispersion liquid into a polyamic acid solution, and fully and mechanically stirring to obtain a fluorinated graphene/polyamic acid composite solution; wherein the content of the fluorinated graphene is 0-2 wt%.
Further, the preparation method of the polyamic acid solution comprises the following steps: rapidly stirring 5-40 mmol of diamine and 40-120 ml of organic solvent for 10-60 min, adding 5-40.8 mmol of dianhydride for 3-10 times, and continuously stirring for 3-24 h to obtain the polyamic acid solution with solid content of 8-25 wt%.
Preferably, the dianhydride is pyromellitic dianhydride or/and 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride.
Preferably, the diamine is 4, 4' -diaminodiphenyl ether or/and long-chain flexible aromatic diamine.
Preferably, the organic solvent is one or any combination of N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, N-diethylacetamide, and 1, 4-butyrolactone (GBL).
Preferably, the coagulating bath is one or any combination of water, ethanol and acetone.
Compared with the prior art, the invention has the following beneficial effects:
the invention aims to provide a preparation method of a polyimide film with compact surface, low dielectric constant and excellent mechanical and thermal properties. The polyimide porous film with a three-layer structure is prepared by a layer-by-layer coating method, the fluorinated graphene/polyimide composite film is used as a compact outer surface enhancement layer, and the porous polyimide prepared by a phase inversion method is used as a middle core low dielectric constant layer. The method is simple and strong in operability, can greatly improve the mechanical and moisture absorption performance of the polyimide porous film, and does not influence the overall low dielectric property of the polyimide porous film.
The method has the advantages of safe process, no need of expensive equipment and simple operation flow, and the polyimide film prepared by the method has the advantages of smooth and compact surface, excellent mechanical property, thermal stability and puncture resistance while keeping the low dielectric constant of the porous material.
The polyimide porous composite film with the low dielectric constant prepared by the invention has controllable overall thickness, and the thicknesses of the compact outer surface layer and the middle porous layer can be respectively adjusted by controlling the coating thicknesses of the polyamic acid and the fluorinated graphene/polyamic acid composite solution. The polyimide film with low dielectric constant can be applied to the fields of chemical products, microelectronic components, aerospace devices and the like which have special requirements on dielectric properties of materials.
Drawings
The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which,
FIG. 1 is a dielectric test chart of a polyimide film obtained by preparation according to example 1 of the present invention.
FIG. 2 is a cross-sectional electron micrograph of a film obtained according to example 1 of the present invention after being broken.
FIG. 3 is a cross-sectional and surface electron microscope image of a surface dense type low-k porous polyimide film prepared according to example 1 of the present invention, wherein (1) is a cross-sectional electron microscope image of the porous polyimide film, (2) is a lower surface electron microscope image of the porous polyimide film, and (3) is an upper surface electron microscope image of the porous polyimide film.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail with reference to the embodiments and the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The technical solution of the present invention is described in detail below with reference to the embodiments and the drawings, but the scope of protection is not limited thereto.
The invention is illustrated by way of example for a better understanding.
Example 1
1) Preparation of polyamic acid solution
In a 250 mL three-necked flask, 10 mmol of 4, 4' -diaminodiphenyl ether and 40 mL of N, N-dimethylacetamide were added, and the mixture was rapidly stirred for 30 min. And adding 10.2 mmol of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride six times, and stirring for 3 hours to obtain the polyamic acid solution.
2) Preparation of fluorinated graphene/polyamic acid composite solution
Dispersing 0.5 g of graphite fluoride in 100 ml of N-methylpyrrolidone solvent; subsequently, the solution was heated at 60 ℃ for 2h under reflux; and finally, carrying out ultrasonic stripping on the refluxed solution for 3 hours to obtain the fluorinated graphene dispersion liquid.
Adding 2.5 ml of the fluorinated graphene dispersion liquid into 20 ml of the polyamic acid solution prepared in the step 1), and fully and mechanically stirring to obtain a fluorinated graphene/polyamic acid composite solution.
3) Preparation of compact Polyamic acid film
Coating the fluorinated graphene/polyamic acid composite solution prepared in the step 2) on a clean glass substrate, heating to 60 ℃ in vacuum, preserving heat for 2h, then heating to 100 ℃ and 200 ℃ in sequence in a ventilating manner, and preserving heat for 1 h in each stage to obtain a compact polyamic acid film.
4) Preparation of polyimide double-layer porous film
Coating the composite solution prepared in the step 2) on the polyamic acid film in the step 3), soaking in a solidification water bath at 0 ℃ for 0.5 h to form a porous wet film, heating to 60 ℃ in vacuum, preserving heat for 2h, then heating to 100 ℃ and 200 ℃ in sequence in a ventilating manner, and preserving heat for 1 h in each stage to further obtain the porous polyamic acid double-layer film.
5) Preparation of low-dielectric three-layer porous film with compact surface
Coating the composite solution prepared in the step 2) on the porous polyamic acid double-layer film in the step 4), heating to 60 ℃ in vacuum, preserving heat for 2 hours, then heating to 100 ℃, 200 ℃ and 300 ℃ in sequence in a ventilating manner, and preserving heat for 1 hour in each stage. And finally, soaking the membrane in boiling water for 10 min, and uncovering the membrane to obtain a thin film with the thickness of about 78 mu m.
Example 2
1) Preparation of polyamic acid solution
10 mmol of 4, 4' -diaminodiphenyl ether, 10 ml of 1, 4-butyrolactone and 30 ml of N, N-dimethylacetamide are added to a 250 ml three-necked flask and stirred rapidly for 30 min. And adding 10.2 mmol of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride six times, and stirring for 3 hours to obtain the polyamic acid solution.
2) Preparation of fluorinated graphene/polyamic acid composite solution
Dispersing 0.5 g of graphite fluoride in 100 ml of N-methylpyrrolidone solvent; subsequently, the solution was heated at 60 ℃ for 2h under reflux; and finally, carrying out ultrasonic stripping on the refluxed solution for 3 hours to obtain the fluorinated graphene dispersion liquid.
10 mmol of 4, 4' -diaminodiphenyl ether and 40 ml of N, N-dimethylacetamide are added to a 250 ml three-necked flask and stirred rapidly for 30 min. And adding 10.2 mmol of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride six times, and continuing stirring for 3 hours until the reaction is stopped, thus obtaining the polyamic acid solution for compounding. And adding 1 ml of the fluorinated graphene dispersion liquid into 10 ml of polyamic acid solution for compounding, and fully and mechanically stirring to obtain the fluorinated graphene/polyamic acid composite solution.
3) Preparation of compact Polyamic acid film
Coating the fluorinated graphene/polyamic acid composite solution prepared in the step 2) on a clean glass substrate, heating to 60 ℃ in vacuum, preserving heat for 2h, then heating to 100 ℃ and 220 ℃ in sequence in a ventilating manner, and preserving heat for 1 h in each stage to obtain a compact polyamic acid film.
4) Preparation of polyimide double-layer porous film
Coating the solution prepared in the step 1) on the polyamic acid film in the step 3), soaking in a solidification water bath at 0 ℃ for 0.5 h to form a porous wet film, heating to 60 ℃ in vacuum, preserving heat for 2h, then heating to 100 ℃ and 200 ℃ in sequence in a ventilating manner, and preserving heat for 1 h in each stage to further obtain the porous polyamic acid double-layer film.
5) Preparation of low-dielectric three-layer porous film with compact surface
Coating the solution prepared in the step 2) on the porous polyamic acid double-layer film in the step 4), heating to 60 ℃ in vacuum, preserving heat for 2 hours, then heating to 100 ℃, 200 ℃ and 300 ℃ in sequence in a ventilating manner, and preserving heat for 1 hour in each stage. And finally, soaking the film in boiling water for 10 min, and removing the film to obtain the low dielectric porous polyimide film with a compact surface.
Example 3
1) Preparation of polyamic acid solution
In a 250 mL three-necked flask, 10 mmol of 4, 4' -diaminodiphenyl ether and 40 mL of N, N-dimethylacetamide were added, and the mixture was rapidly stirred for 30 min. And adding 10.2 mmol of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride six times, and stirring for 3 hours to obtain the polyamic acid solution.
2) Preparation of fluorinated graphene/polyamic acid composite solution
Dispersing 0.5 g of graphite fluoride in 100 ml of N-methylpyrrolidone solvent; subsequently, the solution was heated at 60 ℃ for 2h under reflux; and finally, carrying out ultrasonic stripping on the refluxed solution for 3 hours to obtain the fluorinated graphene dispersion liquid.
Adding 2.5 ml of the fluorinated graphene dispersion liquid into 20 ml of the polyamic acid solution prepared in the step 1), and fully and mechanically stirring to obtain a fluorinated graphene/polyamic acid composite solution.
3) Preparation of compact Polyamic acid film
Coating the fluorinated graphene/polyamic acid composite solution prepared in the step 2) on a clean glass substrate, heating to 60 ℃ in vacuum, preserving heat for 2h, then heating to 120 ℃ and 210 ℃ in sequence in a ventilating manner, and preserving heat for 2h at each stage to obtain a compact polyamic acid film.
4) Preparation of polyimide double-layer porous film
Coating the composite solution prepared in the step 2) on the polyamic acid film in the step 3), soaking in a solidification water bath at 0 ℃ for 0.5 h to form a porous wet film, heating to 60 ℃ in vacuum, preserving heat for 2h, then heating to 120 ℃ and 210 ℃ in sequence in a ventilating manner, and preserving heat for 1 h in each stage to further obtain the porous polyamic acid double-layer film.
5) Preparation of low-dielectric three-layer porous film with compact surface
Coating the composite solution prepared in the step 2) on the porous polyamic acid double-layer film in the step 4), heating to 80 ℃ in vacuum, preserving heat for 1.5h, then heating to 110 ℃, 210 ℃ and 330 ℃ in sequence in a ventilating manner, and preserving heat for 2h in each stage. And finally, soaking the membrane in boiling water for 30 min, and uncovering the membrane, wherein the thickness of the membrane is about 80 mu m.
While the invention has been described in further detail with reference to specific preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. The surface compact type low-dielectric constant porous polyimide composite film is characterized by being a three-layer composite film, wherein the bottom layer of the composite film is a fluorinated graphene/polyamide acid composite compact film, the middle layer of the composite film is a fluorinated graphene/polyamide acid composite porous film or polyamide acid porous film, and the surface layer of the composite film is a fluorinated graphene/polyamide acid composite compact film.
2. The method for preparing the surface compact type low-dielectric-constant porous polyimide composite film according to claim 1, comprising the following steps:
a) preparing a bottom dense film: coating the fluorinated graphene/polyamic acid composite solution on a substrate, heating to 60-83 ℃ in vacuum, preserving heat for 1-3h, then heating to 120 ℃ and 220 ℃ in a ventilating manner in sequence, and preserving heat for 1-3h at each stage to obtain a bottom layer compact film;
b) preparation of the intermediate porous membrane: coating a fluorinated graphene/polyamic acid composite solution or a polyamic acid solution on a compact film of a bottom layer, dipping the compact film in a coagulating bath at the temperature of 0-65 ℃ for 0.5-3h to form a porous wet film, heating the porous wet film to the temperature of 60-83 ℃ in vacuum, preserving heat for 1-3h, then heating the porous wet film to the temperature of 100-220 ℃ in sequence by ventilation, and preserving heat for 1-3h in each stage to further obtain a porous polyamic acid double-layer film;
c) preparing a dense film of the surface layer: coating the fluorinated graphene/polyamic acid composite solution on the middle porous membrane, heating to 60-83 ℃ in vacuum, preserving heat for 1-3h, then heating to 100-; and finally, soaking the compounded film in boiling water for 10-50 min, and removing the film to obtain the low dielectric porous polyimide film with a compact surface.
3. The preparation method of the surface compact type low-dielectric-constant porous polyimide composite film according to claim 2, wherein the preparation method of the fluorinated graphene/polyamic acid composite solution comprises the following steps: preparing a graphite fluoride raw material and an N-methyl pyrrolidone solvent into a graphite fluoride solution of 3-8 mg/ml; then, heating and refluxing the solution at 40-80 ℃ for 2-5 h to fully disperse the graphite fluoride; finally, carrying out ultrasonic stripping on the refluxed solution for 2-8 hours to obtain a fluorinated graphene dispersion solution; adding the fluorinated graphene dispersion liquid into a polyamic acid solution, and fully and mechanically stirring to obtain a fluorinated graphene/polyamic acid composite solution; wherein the content of the fluorinated graphene is 0-2 wt%.
4. The preparation method of the surface compact type low-dielectric-constant porous polyimide composite film according to claim 2, wherein the preparation method of the polyamic acid solution comprises the following steps: rapidly stirring 5-40 mmol of diamine and 40-120 ml of organic solvent for 10-60 min, adding 5-40.8 mmol of dianhydride for 3-10 times, and continuously stirring for 3-24 h to obtain the polyamic acid solution with solid content of 8-25 wt%.
5. The method for preparing the surface dense type low-dielectric constant porous polyimide composite film according to claim 4, wherein the dianhydride is pyromellitic dianhydride or/and 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride.
6. The method for preparing a surface dense type low-dielectric constant porous polyimide composite film according to claim 4, wherein the diamine is 4, 4' -diaminodiphenyl ether or/and long-chain flexible aromatic diamine.
7. The method for preparing the surface compact type low dielectric constant porous polyimide composite film according to claim 4, wherein the organic solvent is one or any combination of N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, and 1, 4-butyrolactone.
8. The method for preparing the surface compact type low-dielectric-constant porous polyimide composite film according to claim 4, wherein the coagulating bath is one or any combination of water, ethanol and acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011019267.7A CN112094425A (en) | 2020-09-24 | 2020-09-24 | Surface compact type low-dielectric constant porous polyimide composite film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011019267.7A CN112094425A (en) | 2020-09-24 | 2020-09-24 | Surface compact type low-dielectric constant porous polyimide composite film and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112094425A true CN112094425A (en) | 2020-12-18 |
Family
ID=73756139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011019267.7A Pending CN112094425A (en) | 2020-09-24 | 2020-09-24 | Surface compact type low-dielectric constant porous polyimide composite film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112094425A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114379176A (en) * | 2022-02-11 | 2022-04-22 | 哈尔滨工程大学 | Low-dielectric polyimide composite sheet and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04235034A (en) * | 1991-01-10 | 1992-08-24 | Nippon Telegr & Teleph Corp <Ntt> | Polyimide multilayer film and preparation thereof |
| CN1911985A (en) * | 2006-08-21 | 2007-02-14 | 浙江大学 | Ultralow dielectric constant polyimide film and its preparation method |
| CN103613927A (en) * | 2013-11-26 | 2014-03-05 | 哈尔滨工业大学 | Polyimide/fluorinated graphene composite film and preparation method thereof |
| CN103747609A (en) * | 2013-12-17 | 2014-04-23 | 上海洁晟环保科技有限公司 | Polyimide nano fiber composite film, and preparation method and application thereof |
| CN103772981A (en) * | 2013-12-30 | 2014-05-07 | 四川大学 | Low-dielectric-constant polymer/fluorinated graphene composite material and preparation method thereof |
| CN103879105A (en) * | 2014-04-18 | 2014-06-25 | 东南大学 | Method for preparing carbon material and polyimide compounded sandwich film |
| CN103965503A (en) * | 2014-05-07 | 2014-08-06 | 哈尔滨工业大学 | Preparation method of polyimide film |
| CN109251334A (en) * | 2017-07-14 | 2019-01-22 | 天津大学 | A kind of high light transmission and low dielectric fluorinated graphene/polyimide composite film preparation method |
-
2020
- 2020-09-24 CN CN202011019267.7A patent/CN112094425A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04235034A (en) * | 1991-01-10 | 1992-08-24 | Nippon Telegr & Teleph Corp <Ntt> | Polyimide multilayer film and preparation thereof |
| CN1911985A (en) * | 2006-08-21 | 2007-02-14 | 浙江大学 | Ultralow dielectric constant polyimide film and its preparation method |
| CN103613927A (en) * | 2013-11-26 | 2014-03-05 | 哈尔滨工业大学 | Polyimide/fluorinated graphene composite film and preparation method thereof |
| CN103747609A (en) * | 2013-12-17 | 2014-04-23 | 上海洁晟环保科技有限公司 | Polyimide nano fiber composite film, and preparation method and application thereof |
| CN103772981A (en) * | 2013-12-30 | 2014-05-07 | 四川大学 | Low-dielectric-constant polymer/fluorinated graphene composite material and preparation method thereof |
| CN103879105A (en) * | 2014-04-18 | 2014-06-25 | 东南大学 | Method for preparing carbon material and polyimide compounded sandwich film |
| CN103965503A (en) * | 2014-05-07 | 2014-08-06 | 哈尔滨工业大学 | Preparation method of polyimide film |
| CN109251334A (en) * | 2017-07-14 | 2019-01-22 | 天津大学 | A kind of high light transmission and low dielectric fluorinated graphene/polyimide composite film preparation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114379176A (en) * | 2022-02-11 | 2022-04-22 | 哈尔滨工程大学 | Low-dielectric polyimide composite sheet and preparation method thereof |
| CN114379176B (en) * | 2022-02-11 | 2023-08-22 | 哈尔滨工程大学 | Low-dielectric polyimide composite sheet and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107108926B (en) | Method for producing polyimide film using porous particles and low dielectric constant polyimide film | |
| JP6567590B2 (en) | Film for millimeter wave antenna | |
| JP6567591B2 (en) | Film for millimeter wave antenna | |
| CN100445322C (en) | Ultralow dielectric constant polyimide film and its preparation method | |
| CN106750435B (en) | A kind of preparation method of the ordered porous Kapton of low-k | |
| CN103613927A (en) | Polyimide/fluorinated graphene composite film and preparation method thereof | |
| CN112679770B (en) | Low-dielectric-constant polyimide film and preparation method thereof | |
| CN103224705A (en) | Nano-modified polyimide composite film and preparation method thereof | |
| CN109942851A (en) | A kind of low dielectric coefficient polyimide hybrid film and application | |
| CN105601923A (en) | Fluorine-containing flexible-rigid polyimide film, and preparation method and application thereof | |
| CN113717524A (en) | Polyimide film for preparing graphite film and preparation method thereof | |
| CN112898614A (en) | High-dielectric-constant polyimide three-phase composite material and preparation method thereof | |
| CN112094425A (en) | Surface compact type low-dielectric constant porous polyimide composite film and preparation method thereof | |
| CN114605153A (en) | Preparation method of high-thermal-conductivity graphite film | |
| CN112646372B (en) | Polyimide film with low dielectric constant and application thereof | |
| CN100422243C (en) | Method of preparing ultra low dielectric constant polyimide membrane by polyamide ester precursor phase transformation | |
| JP2006160934A (en) | Paste composition and dielectric composition | |
| CN115612097A (en) | Nano composite material with low dielectric constant and high strength and preparation method thereof | |
| TWI742945B (en) | Low-dissipation flexible copper-coated laminate, manufacturing method thereof, and electronic device | |
| CN108264766A (en) | A kind of preparation method of Kapton | |
| CN113150547A (en) | Polyimide composite film with electromagnetic shielding function and preparation method and application thereof | |
| CN113402746A (en) | Matte insulating polyimide black film and preparation method thereof | |
| CN115368734B (en) | Preparation method of high-heat-conductivity polyimide composite film material | |
| CN114410111A (en) | Method for improving dielectric constant of composite film by graphitized multi-walled carbon nano-tube | |
| CN113072743B (en) | Porous module high temperature resistant hot plate for auxiliary control device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201218 |
|
| RJ01 | Rejection of invention patent application after publication |