WO2023015705A1 - 一种三明治结构聚酰亚胺复合纳米纤维膜及其制备方法 - Google Patents

一种三明治结构聚酰亚胺复合纳米纤维膜及其制备方法 Download PDF

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WO2023015705A1
WO2023015705A1 PCT/CN2021/122787 CN2021122787W WO2023015705A1 WO 2023015705 A1 WO2023015705 A1 WO 2023015705A1 CN 2021122787 W CN2021122787 W CN 2021122787W WO 2023015705 A1 WO2023015705 A1 WO 2023015705A1
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polyimide
membrane
polytetrafluoroethylene
polyvinylidene fluoride
preparation
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程丝
于嘉诚
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Suzhou University
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
    • D01D5/0084—Coating by electro-spinning, i.e. the electro-spun fibres are not removed from the collecting device but remain integral with it, e.g. coating of prostheses
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4318—Fluorine series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4374—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece using different kinds of webs, e.g. by layering webs
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/542—Adhesive fibres
    • D04H1/551—Resins thereof not provided for in groups D04H1/544 - D04H1/55
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/559—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving the fibres being within layered webs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B17/00—Insulators or insulating bodies characterised by their form
    • H01B17/56—Insulating bodies
    • H01B17/60—Composite insulating bodies
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/02—Moisture-responsive characteristics
    • D10B2401/021—Moisture-responsive characteristics hydrophobic

Definitions

  • the invention belongs to the technical field of polymer dielectric materials, and in particular relates to a sandwich-structured polyimide composite nanofiber membrane and a preparation method thereof.
  • the main methods of structural design of modified polyimide substrate MPI include two kinds: (1) multi-level structure design of polyimide: introducing substituent groups with low polarizability, such as trifluoromethyl, Alicyclic structure, siloxane structural unit, etc., to reduce the polarization ability of dipoles in the molecule; (2) Microscopic morphology modification of polyimide: introduce micro-nano pore structure to increase porosity. Since the molar polarizability P value of fluorine atoms and fluorine-containing substituents is small, introducing a high content of fluorine into the material can significantly reduce the dielectric constant of PI.
  • FPIs Current low-dielectric fluorinated polyimides
  • 6FDA 4,4′-(hexafluoroisopropylene) diphthalic anhydride
  • BDAF fluorinated diamine
  • fluorine-containing monomers are expensive and difficult to synthesize, and a large number of fluorine-containing groups with low surface energy will lead to a decrease in the adhesion between the surface of the polyimide film and copper foil in subsequent applications, which is not conducive to subsequent use. Therefore, the preparation process of FPI needs to control the addition of fluorine-containing monomers.
  • the introduction of micropores into the interior of PI films to reduce the dielectric constant usually leads to a decrease in the mechanical strength of the film and an increase in water absorption.
  • Patent CN200610131651.X utilizes the electrospinning method to prepare a variety of single-component low-permittivity polymer fiber membranes with large porosity.
  • the dielectric constant of the obtained membranes is between 1.53-2.23, but it is found in actual research that , because the dielectric constant of a single polyimide fiber membrane is limited, the water absorption is still high, and the strength of the membrane is low.
  • the patent does not address dielectric loss, which becomes more severe in materials at high frequencies. Therefore, in order to adapt to high frequency applications, low dielectric loss is more important than low dielectric constant.
  • Patent CN202011023007.7 has prepared a sandwich structure in which the upper and lower layers are a honeycomb porous structure containing cage polysilsesquioxane and the middle layer is a flat polyimide film, which reduces the dielectric constant of the polyimide film. At the same time, the mechanical properties of the film are maintained. However, its dielectric constant has a limited decrease, and at the same time, due to the introduction of microporous structure, the water absorption rate is still very large.
  • the present invention provides a polyimide composite nanofiber membrane with a sandwich structure and a preparation method thereof.
  • a sandwich structure polyimide composite nanocomposite fiber membrane the composite nanofiber membrane includes two layers of polyimide nanofiber membranes and a polyvinylidene fluoride-polyethylene Tetrafluoroethylene nanofiber membrane.
  • the dielectric constant of the nanocomposite fiber membrane is 1.11-2.36; the dielectric loss is 0.001-0.005; and the water absorption is 0.5%-1%.
  • Step 1 Using electrospinning technology, first electrospin the polyimide acid solution to obtain polyimide acid electrospun membrane, and then directly electrospin the polytetrafluoroethylene-polyvinylidene fluoride mixed solution on the above obtained
  • the upper layer is polytetrafluoroethylene-polyvinylidene fluoride electrospun membrane
  • the lower layer is a composite electrospun membrane of polyimide acid electrospun membrane, and then the polyimide acid
  • the solution is directly electrospun on the other side of the polytetrafluoroethylene-polyvinylidene fluoride electrospun membrane of the composite electrospun membrane to obtain a sandwich structure composite membrane;
  • Step 2 heating the sandwich-structured composite membrane in step 1 for thermal imidization to obtain the composite nanofiber membrane.
  • step 1 the polytetrafluoroethylene-polyvinylidene fluoride mixed solution is prepared by the following method:
  • polytetrafluoroethylene powder and polyvinylidene fluoride powder into the mixed organic solvent, and stir at room temperature for 2-4 hours to obtain the polytetrafluoroethylene-polyvinylidene fluoride mixed solution.
  • the size of the polytetrafluoroethylene powder is 20nm-5 ⁇ m.
  • the mass ratio of polytetrafluoroethylene fine powder to polyvinylidene fluoride powder is 0.5:1-1:1.
  • the mass ratio of N-N dimethylformamide or/and N-N dimethylacetamide to acetone is 0.5:1-2:1.
  • the preparation method of the polyimide acid solution is that the mass ratio of polyimide acid to N-N dimethylacetamide solution is 0.5:1 ⁇ 1.5:1 Mix, heat and stir at 80°C for 30 minutes until completely mixed and homogeneous.
  • the mass concentration of the polytetrafluoroethylene-polyvinylidene fluoride mixed solution is 6%-12%.
  • step 1 the volume ratio of the polyimide acid solution, polytetrafluoroethylene-polyvinylidene fluoride mixed solution and polyimide acid solution is 1:0.5:1 ⁇ 1:2:1.
  • the electrospinning parameters are voltage of 9-15KV, distance between the spinneret and the receiving substrate of 8-12cm, and feeding speed of 0.5-2mL/h.
  • the thermal imidization conditions are as follows: heat up to 350-380°C within 30-60min, keep warm at 350-380°C for 15-30min, and cool to room temperature 25°C .
  • the advantage of the present invention is that the electrospinning technology introduces randomly interlaced PI and PVDF/PTFE nanofibers, and has a nanofiber skeleton structure while introducing fluorine-containing polymers and micro-nano hole structures, which can fully ensure the nanofiber film.
  • Mechanical properties and low hygroscopicity The sandwich structure can control the fluorine-containing groups inside the film, and maintain the bonding performance of the outer surface of the film while reducing the dielectric constant.
  • the introduction of fluorine groups can also improve the hydrophobicity of the film and improve the degradation of the dielectric properties of the film due to moisture absorption.
  • the preparation method of the sandwich structure ultra-low dielectric constant film of the present invention is obtained by two key steps of electrospinning to prepare a sandwich structure film and heating imidization treatment.
  • the prepared sample has excellent dielectric properties and physical and mechanical properties.
  • the mechanical properties of conventional electrospun polyimide films are improved, and the dielectric constant, dielectric loss and excessive water absorption are reduced.
  • the special sandwich structure ultra-low dielectric constant membrane of the present invention has a dense porous structure, and the introduction of the intermediate hydrophobic fluorine-containing layer can avoid the disadvantages of a single polyimide electrospun membrane with a high dielectric constant and a high water absorption rate.
  • an ultra-low dielectric constant film with a sandwich structure can be obtained, and the preparation process is easy to implement.
  • the ultra-low dielectric film of the present invention can be used as a high-performance insulating material in the 5G field due to its low dielectric constant and excellent heat resistance and hydrophobic properties.
  • the present invention directly utilizes segmental electrospinning technology to prepare a three-layer film, fibers are formed between each layer to form an interpenetrating network, and each layer is firmly bonded.
  • Fig. 1 is the physical figure of the corresponding product of embodiment 1 of the present invention.
  • Fig. 2 is a scanning electron micrograph of the electrospun layer corresponding to Example 1 of the present invention.
  • Fig. 3 is the dielectric constant and dielectric loss spectrum of the electrospun membrane corresponding to Example 1 of the present invention.
  • Fig. 4 is the dielectric constant and dielectric loss spectrum of the electrospun membrane corresponding to Comparative Example 1 of the present invention.
  • the spinning parameters adopted in the electrospinning process of polyimide acid electrospinning solution are: the voltage is 15KV, the distance between the spinneret and the receiving substrate is 10cm, and the feeding speed is 1mL/h.
  • the spinning parameters used in the electrospinning process of polytetrafluoroethylene-polyvinylidene fluoride mixed electrospinning liquid are: the voltage is 12KV, the distance between the spinneret and the receiving substrate is 12cm, and the feeding speed is 1mL/h.
  • Dielectric performance test Novocontrol CONCEPT 80 broadband dielectric impedance spectrometer was used to test the dielectric constant and dielectric loss of the obtained film.
  • the room temperature is 25°C, and the frequency range is controlled at 10-10 7 Hz.
  • polyimide acid electrospinning solution Using an electrospinning device, first spin 4mL polyimide acid solution to make an electrospun membrane, and then directly electrospin 2mL polytetrafluoroethylene-polyvinylidene fluoride mixed solution on the polyimide electrospun membrane Finally, 4 mL of polyimide acid solution was spun into an electrospun membrane to obtain a composite membrane with a sandwich structure.
  • the spinning parameters adopted in the electrospinning process of polyimide acid electrospinning solution are: the voltage is 15KV, the distance between the spinneret and the receiving substrate is 10cm, and the feeding speed is 1mL/h.
  • the spinning parameters used in the electrospinning process of polytetrafluoroethylene-polyvinylidene fluoride mixed electrospinning liquid are: the voltage is 12KV, the distance between the spinneret and the receiving substrate is 12cm, and the feeding speed is 1mL/h.
  • Dielectric performance test Novocontrol CONCEPT 80 broadband dielectric impedance spectrometer was used to test the dielectric constant and dielectric loss of the obtained film.
  • the room temperature is 25°C, and the frequency range is controlled at 10-10 7 Hz.
  • polyimide acid electrospinning solution Using an electrospinning device, first spin 4mL polyimide acid solution to make an electrospun membrane, and then directly electrospin 8mL polytetrafluoroethylene-polyvinylidene fluoride mixed solution on the polyimide electrospun membrane Finally, 4 mL of polyimide acid solution was spun into an electrospun membrane to obtain a composite membrane with a sandwich structure.
  • the spinning parameters adopted in the electrospinning process of polyimide acid electrospinning solution are: the voltage is 15KV, the distance between the spinneret and the receiving substrate is 10cm, and the feeding speed is 1mL/h.
  • the spinning parameters adopted in the electrospinning process of polytetrafluoroethylene-polyvinylidene fluoride mixed electrospinning solution are: the voltage is 12KV, the distance between the spinneret and the receiving substrate is 12cm, and the feeding speed is 1mL/h.
  • Dielectric performance test Novocontrol CONCEPT 80 broadband dielectric impedance spectrometer was used to test the dielectric constant and dielectric loss of the obtained film.
  • the room temperature is 25°C, and the frequency range is controlled at 10-10 7 Hz.
  • polyimide acid electrospinning solution Using an electrospinning device, first spin 4mL polyimide acid solution to make an electrospun membrane, and then directly electrospin 8mL polytetrafluoroethylene-polyvinylidene fluoride mixed solution on the polyimide electrospun membrane Finally, 4 mL of polyimide acid solution was spun into an electrospun membrane to obtain a composite membrane with a sandwich structure.
  • the spinning parameters adopted in the electrospinning process of polyimide acid electrospinning solution are: the voltage is 15KV, the distance between the spinneret and the receiving substrate is 10cm, and the feeding speed is 1mL/h.
  • the spinning parameters used in the electrospinning process of polytetrafluoroethylene-polyvinylidene fluoride mixed electrospinning liquid are: the voltage is 12KV, the distance between the spinneret and the receiving substrate is 12cm, and the feeding speed is 1mL/h.
  • Dielectric performance test Novocontrol CONCEPT 80 broadband dielectric impedance spectrometer was used to test the dielectric constant and dielectric loss of the obtained film.
  • the room temperature is 25°C, and the frequency range is controlled at 10-10 7 Hz.
  • the spinning parameters used in the electrospinning process of polyimide acid electrospinning solution are: the voltage is 15KV, the distance between the spinneret and the receiving substrate is 10cm, and the feeding speed is 1mL/h.
  • Dielectric performance test Novocontrol CONCEPT 80 broadband dielectric impedance spectrometer was used to test the dielectric constant and dielectric loss of the obtained film.
  • the room temperature is 25°C, and the frequency range is controlled at 10-10 7 Hz.
  • dielectric constant and dielectric loss value of above-mentioned embodiment and comparative example at 1MHz frequency are summarized in table 1, find through comparison, the dielectric constant of pure polyimide nanofiber membrane and dielectric loss are compared with the present invention. On the high side, it proves that the introduction of polyvinylidene fluoride-polytetrafluoroethylene nanofiber layer does have the effect of reducing the dielectric constant and dielectric loss.

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Abstract

一种三明治结构聚酰亚胺复合纳米纤维膜及其制备方法，属于聚合物介电材料领域。本发明所得三明治结构的聚酰亚胺复合纳米纤维膜，包含三层结构，依次为聚酰亚胺纳米纤维膜层/聚偏氟乙烯-聚四氟乙烯纳米纤维膜层/聚酰亚胺纳米纤维膜层。本发明通过对材料结构的调整，同时引入含氟聚合物和多孔结构，从而使聚酰亚胺纳米纤维膜的介电常数和介电损耗大幅度降低。

Description

一种三明治结构聚酰亚胺复合纳米纤维膜及其制备方法 技术领域
本发明属于聚合物介电材料技术领域，尤其涉及一种三明治结构聚酰亚胺复合纳米纤维膜及其制备方法。
背景技术
随着5G通信技术的发展，对材料提出了更高要求。研究表明，与传统移动通信模式相比，5G信号传送的高频和高速化会使信号传输的损耗变得更严重。要想满足5G要求，需要材料具有更低的介电常数(Dk)和介电损耗(Df)。普通纯聚酰亚胺薄膜在4G通讯领域得到广泛应用，但其介电常数(3.4)和介电损耗(0.02)比较大，难以适应5G高频、高速信号传输需求。要想满足5G应用要求，需对聚酰亚胺进行改性处理，从而获得低介电的改性聚酰亚胺(MPI)。目前，市场上商品化的MPI其介电常数通常在2.8-3.2,介电损耗多在0.0025-0.006之间。
目前，改性聚酰亚胺基材MPI的结构设计的主要方法包括两种：(1)聚酰亚胺的多层次结构设计：引入低极化能力的取代基团，如三氟甲基、脂环结构、硅氧烷结构单元等，以降低分子中偶极子的极化能力；(2)聚酰亚胺的微观形貌改性：引入微纳孔结构，增加孔隙率。由于氟原子及含氟取代基的摩尔极化度P值较小，因此在材料中引入高含量的氟元素能使PI的介电常数明显下降。目前的低介电含氟聚酰亚胺(FPI)主要是基于商业化含氟二酐如4,4′-(六氟异丙烯)双邻苯二甲酸酐(6FDA)或含氟二胺、2,2′-双[4-(4-氨基苯氧基苯基)]六氟丙烷(BDAF)单体的PI材料。但含氟单体价格昂贵，合成困难，且大量的低表面能的含氟基团会导致聚酰亚胺膜表面与后续应用中铜箔的粘接性能下降，不利于后续使用。所以FPI的制备过程，需 要控制含氟单体的加入量。而向PI薄膜内部引入微孔来降低介电常数通常会导致薄膜的机械强度下降和吸水率的增加。
专利CN200610131651.X利用静电纺丝法制备了多种单一组分的具有大孔隙率的低介电常数高分子纤维膜，所得膜的介电常数在1.53-2.23之间，但在实际研究中发现，因为单一的聚酰亚胺纤维膜介电常数降低有限，吸水率依旧偏高，而且膜的强度偏低。另外，该专利并没有涉及介电损耗，而高频下材料的介电损耗会变得更严重。因此为适应高频下应用，低的介电损耗比低介电常数更为重要。专利CN202011023007.7制备了上下两层为含笼型聚倍半硅氧烷的蜂巢状多孔结构和中间层为聚酰亚胺平膜的三明治型结构，实现降低聚酰亚胺薄膜介电常数的同时，保持了薄膜的力学性能。但其介电常数下降有限，同时由于微孔结构的引入，吸水率依旧很大。
发明内容
为解决上述技术问题，本发明提供了一种三明治结构聚酰亚胺复合纳米纤维膜及其制备方法。
一种三明治结构聚酰亚胺复合纳米复合纤维膜，所述复合纳米纤维膜包括两层聚酰亚胺纳米纤维膜和设置在两层聚酰亚胺纳米纤维膜中间的聚偏氟乙烯-聚四氟乙烯纳米纤维膜。
在本发明的一个实施例中，所述纳米复合纤维膜的介电常数为1.11-2.36；介电损耗在0.001-0.005；吸水率在0.5％-1％。
在本发明的一个实施例中，包括以下步骤，
步骤1：采用静电纺丝技术，先将聚酰亚胺酸溶液进行电纺得到聚酰亚胺酸电纺膜，而后将聚四氟乙烯-聚偏氟乙烯混合溶液直接电纺在上述所得到的聚酰亚胺酸电纺膜上，得到上层为聚四氟乙烯-聚偏氟乙烯电纺膜、下层为聚酰亚胺酸电纺膜的复合电纺膜，再将聚酰亚胺酸溶液直接电纺在上述复合电纺膜的聚四氟乙烯-聚偏氟乙烯电纺膜另一侧，得到三明治结构复合膜；
步骤2：将步骤1中所述三明治结构复合膜加热进行热亚胺化，得到所述复合纳米纤维膜。
在本发明的一个实施例中，步骤1中，所述聚四氟乙烯-聚偏氟乙烯混合溶液通过以下方法制备得到：
将N-N二甲基甲酰胺或/和N-N二甲基乙酰胺与丙酮进行混合得到混合有机溶剂；
将聚四氟乙烯粉末与聚偏氟乙烯粉末加入到混合有机溶剂中，在室温下搅拌2-4小时，得到所述聚四氟乙烯-聚偏氟乙烯混合溶液。其中聚四氟乙烯粉末的尺寸在20nm-5μm。
在本发明的一个实施例中，所述聚四氟乙烯微粉末与聚偏氟乙烯粉末质量比为0.5:1-1:1。
在本发明的一个实施例中，所述N-N二甲基甲酰胺或/和N-N二甲基乙酰胺与丙酮的质量比为0.5:1-2:1。
在本发明的一个实施例中，步骤1中，所述聚酰亚胺酸溶液的配制方法为将聚酰亚胺酸与N-N二甲基乙酰胺溶液的质量比为0.5:1～1.5:1混合，在80℃下加热搅拌30min，直至完全混合均匀。
在本发明的一个实施例中，步骤1中，所述聚四氟乙烯-聚偏氟乙烯混合溶液的质量浓度为6％-12％。
在本发明的一个实施例中，步骤1中，所述聚酰亚胺酸溶液、聚四氟乙烯-聚偏氟乙烯混合溶液与聚酰亚胺酸溶液的体积比为1:0.5:1～1:2:1。
在本发明的一个实施例中，步骤1中，所述电纺参数为电压为9-15KV，喷丝头与接收基板的距离为8-12cm，供料速度0.5-2mL/h。
在本发明的一个实施例中，步骤2中，所述热亚胺化的条件为：30-60min内升温到350-380℃，在350-380℃下保温15-30min，冷却至室温25℃。
本发明的上述技术方案相比现有技术具有以下优点：
本发明的优势在于静电纺丝技术引入了无规交错的PI和PVDF/PTFE纳米纤维，在引入含氟聚合物和微纳孔洞结构的同时具有纳米纤维的骨架结构，能充分保证纳米纤维薄膜的力学性能和低的吸湿性。三明治结构可以将含氟基团控制在薄膜内部，在降低介电常数的同时维持了薄膜外表面的粘结性能。此外，氟基团的引入还能提高薄膜的疏水性能，改善薄膜因吸湿造成介电性能发生劣化的情况。
本发明所述三明治结构超低介电常数膜的制备方法由电纺制备三明治结构薄膜及加热亚胺化处理两个关键步骤制得，所制备的样品具有优良的介电性能和物理机械性能，改善了常规静电纺丝聚酰亚胺薄膜力学性能，降低了介电常数、介电损耗和过高的吸水率。
本发明的特殊的三明治结构超低介电常数膜，具有致密多孔结构，中间疏水含氟层的引入可避免了单一聚酰亚胺电纺膜介电常数较高和吸水率偏大的缺点。按照本发明的制备工艺，可以得到具有三明治结构的超低介电常数膜，且制备工艺易于实现。本发明的超低介电膜由于低的介电常数和优良的耐热、疏水等性能使其能够作为高性能绝缘材料应用于5G领域。
本发明直接利用分段静电纺丝技术，制备三层薄膜，在各层之间形成了纤维可形成互穿网络，各层之间粘结牢固。
附图说明
为了使本发明的内容更容易被清楚的理解，下面根据本发明的具体实施例并结合附图，对本发明作进一步详细的说明，其中
图1是本发明实施例1相应的产品的实物图。
图2是本发明实施例1相应的电纺层的扫描电镜照片。
图3是本发明实施例1相应的电纺膜的介电常数和介电损耗谱图。
图4是本发明对照例1相应的电纺膜的介电常数和介电损耗谱图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术 人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
实施例1
1)将20g聚酰亚胺酸溶于20g DMAC溶液，在80℃下加热搅拌30min，直至完全混合均匀，获得聚酰亚胺酸纺丝液。分别取0.6g聚四氟乙烯微纳粉、0.6g聚偏氟乙烯微粉、4.4g DMF、4.4g丙酮，先将DMF与丙酮混合均匀，然后依次加入聚四氟乙烯微纳粉和聚偏氟乙烯微粉，在室温下搅拌3h，充分混合均匀，制得聚四氟乙烯-聚偏氟乙烯纺丝液。
2)利用静电纺丝装置，先纺4mL聚酰亚胺酸溶液，制成电纺膜，再将4mL聚四氟乙烯-聚偏氟乙烯混合溶液直接电纺在聚酰亚胺电纺膜膜上，最后再将4mL聚酰亚胺酸溶液纺成电纺膜，获得三明治结构复合膜。其中聚酰亚胺酸电纺液静电纺丝过程中所采用的纺丝参数为：电压为15KV，喷丝头与接收基板的距离为10cm，供料速度1mL/h。聚四氟乙烯-聚偏氟乙烯混合电纺液静电纺丝过程中所采用的纺丝参数为：电压为12KV，喷丝头与接收基板的距离为12cm，供料速度1mL/h。
3)将三明治结构薄膜整理平整，放入烘箱中进行热亚胺化。设置烘箱运行程序，首先在30min内将烘箱温度升至350℃进行初步亚胺化，然后在350℃下保温15min，使聚酰亚胺酸进一步转变为聚酰亚胺，最后冷却至室温获得聚酰亚胺/聚偏氟乙烯-聚四氟乙烯/聚酰亚胺三明治薄膜。
介电性能测试：采用Novocontrol CONCEPT 80型号的宽频介电阻抗谱仪对所得膜进行介电常数和介电损耗的测试。室温25℃，频率范围控制在10-10 7Hz。
实施例2
1)将20g聚酰亚胺酸溶于20g DMAC溶液，在80℃下加热搅拌30min，直至完全混合均匀，获得聚酰亚胺酸纺丝液。分别取0.6g聚四氟乙烯微纳粉、0.6g聚偏氟乙烯微粉、4.4g DMF、4.4g丙酮，先将DMF与丙酮混合均匀，然后依次加入聚四氟乙烯微纳粉和聚偏氟乙烯微粉，在室温下搅拌3 h，充分混合均匀，制得聚四氟乙烯-聚偏氟乙烯纺丝液。
2)利用静电纺丝装置，先纺4mL聚酰亚胺酸溶液，制成电纺膜，再将2mL聚四氟乙烯-聚偏氟乙烯混合溶液直接电纺在聚酰亚胺电纺膜膜上，最后再将4mL聚酰亚胺酸溶液纺成电纺膜，获得三明治结构复合膜。其中聚酰亚胺酸电纺液静电纺丝过程中所采用的纺丝参数为：电压为15KV，喷丝头与接收基板的距离为10cm，供料速度1mL/h。聚四氟乙烯-聚偏氟乙烯混合电纺液静电纺丝过程中所采用的纺丝参数为：电压为12KV，喷丝头与接收基板的距离为12cm，供料速度1mL/h。
3)将三明治结构薄膜整理平整，放入烘箱中进行热亚胺化。设置烘箱运行程序，首先在30min内将烘箱温度升至350℃进行初步亚胺化，然后在350℃下保温15min，使聚酰亚胺酸进一步转变为聚酰亚胺，最后冷却至室温获得聚酰亚胺/聚偏氟乙烯-聚四氟乙烯/聚酰亚胺三明治薄膜。
介电性能测试：采用Novocontrol CONCEPT 80型号的宽频介电阻抗谱仪对所得膜进行介电常数和介电损耗的测试。室温25℃，频率范围控制在10-10 7Hz。
实施例3
1)将20g聚酰亚胺酸溶于20g DMAC溶液，在80℃下加热搅拌30min，直至完全混合均匀，获得聚酰亚胺酸纺丝液。分别取0.6g聚四氟乙烯微纳粉、0.6g聚偏氟乙烯微粉、4.4g DMF、4.4g丙酮，先将DMF与丙酮混合均匀，然后依次加入聚四氟乙烯微纳粉和聚偏氟乙烯微粉，在室温下搅拌3h，充分混合均匀，制得聚四氟乙烯-聚偏氟乙烯纺丝液。
2)利用静电纺丝装置，先纺4mL聚酰亚胺酸溶液，制成电纺膜，再将8mL聚四氟乙烯-聚偏氟乙烯混合溶液直接电纺在聚酰亚胺电纺膜膜上，最后再将4mL聚酰亚胺酸溶液纺成电纺膜，获得三明治结构复合膜。其中聚酰亚胺酸电纺液静电纺丝过程中所采用的纺丝参数为：电压为15KV，喷丝头与接收基板的距离为10cm，供料速度1mL/h。聚四氟乙烯-聚偏氟乙烯混合电纺液静电纺丝过程中所采用的纺丝参数为：电压为12KV，喷丝头与 接收基板的距离为12cm，供料速度1mL/h。
3)将三明治结构薄膜整理平整，放入烘箱中进行热亚胺化。设置烘箱运行程序，首先在30min内将烘箱温度升至350℃进行初步亚胺化，然后在350℃下保温15min，使聚酰亚胺酸进一步转变为聚酰亚胺，最后冷却至室温获得聚酰亚胺/聚偏氟乙烯-聚四氟乙烯/聚酰亚胺三明治薄膜。
介电性能测试：采用Novocontrol CONCEPT 80型号的宽频介电阻抗谱仪对所得膜进行介电常数和介电损耗的测试。室温25℃，频率范围控制在10-10 7Hz。
实施例4
1)将20g聚酰亚胺酸溶于20g DMAC溶液，在80℃下加热搅拌30min，直至完全混合均匀，获得聚酰亚胺酸纺丝液。分别取0.3g聚四氟乙烯微纳粉、0.6g聚偏氟乙烯微粉、4.4g DMF、4.4g丙酮，先将DMF与丙酮混合均匀，然后依次加入聚四氟乙烯微纳粉和聚偏氟乙烯微粉，在室温下搅拌3h，充分混合均匀，制得聚四氟乙烯-聚偏氟乙烯纺丝液。
2)利用静电纺丝装置，先纺4mL聚酰亚胺酸溶液，制成电纺膜，再将8mL聚四氟乙烯-聚偏氟乙烯混合溶液直接电纺在聚酰亚胺电纺膜膜上，最后再将4mL聚酰亚胺酸溶液纺成电纺膜，获得三明治结构复合膜。其中聚酰亚胺酸电纺液静电纺丝过程中所采用的纺丝参数为：电压为15KV，喷丝头与接收基板的距离为10cm，供料速度1mL/h。聚四氟乙烯-聚偏氟乙烯混合电纺液静电纺丝过程中所采用的纺丝参数为：电压为12KV，喷丝头与接收基板的距离为12cm，供料速度1mL/h。
3)将三明治结构薄膜整理平整，放入烘箱中进行热亚胺化。设置烘箱运行程序，首先在30min内将烘箱温度升至350℃进行初步亚胺化，然后在350℃下保温15min，使聚酰亚胺酸进一步转变为聚酰亚胺，最后冷却至室温获得聚酰亚胺/聚偏氟乙烯-聚四氟乙烯/聚酰亚胺三明治薄膜。
介电性能测试：采用Novocontrol CONCEPT 80型号的宽频介电阻抗谱仪对所得膜进行介电常数和介电损耗的测试。室温25℃，频率范围控制在 10-10 7Hz。
对比例1
1)将20g聚酰亚胺酸溶于20g DMAC溶液，在80℃下加热搅拌30min，直至完全混合均匀，获得聚酰亚胺酸纺丝液。
2)利用静电纺丝装置，纺制10mL聚酰亚胺酸溶液，制成电纺膜。聚酰亚胺酸电纺液静电纺丝过程中所采用的纺丝参数为：电压为15KV，喷丝头与接收基板的距离为10cm，供料速度1mL/h。
3)将聚酰亚胺酸薄膜整理平整，放入烘箱中进行热亚胺化。设置烘箱运行程序，首先在30min内将烘箱温度升至350℃进行初步亚胺化，然后在350℃下保温15min，使聚酰亚胺酸进一步转变为聚酰亚胺，最后冷却至室温获得纯聚酰亚胺纳米纤维膜。
介电性能测试：采用Novocontrol CONCEPT 80型号的宽频介电阻抗谱仪对所得膜进行介电常数和介电损耗的测试。室温25℃，频率范围控制在10-10 7Hz。
上述实施例和对比例在1MHz频率下的介电常数和介电损耗值汇总于表1，经过对比发现，纯聚酰亚胺纳米纤维膜的介电常数和介电损耗与本发明相比均偏高，证明引入聚偏氟乙烯-聚四氟乙烯纳米纤维层确实具有降低介电常数和介电损耗的效果。
表1 实施例和对比例的介电常数和介电损耗值对比(@1MHz)
样品 实施例1 实施例2 实施例3 实施例4 对比例1
介电常数 1.38 2.36 1.11 1.54 2.45
介电损耗 0.0038 0.0175 0.0041 0.0033 0.045
显然，上述实施例仅仅是为清楚地说明所作的举例，并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式变化或变动。这里无需也无法对所有的实施方式予以穷举。而 由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (10)

  1. 一种三明治结构聚酰亚胺复合纳米纤维膜，其特征在于，所述复合纳米纤维膜包括两层聚酰亚胺纳米纤维膜和设置在两层聚酰亚胺纳米纤维膜中间的聚偏氟乙烯-聚四氟乙烯纳米纤维膜。
  2. 根据权利要求1所述的三明治结构聚酰亚胺复合纳米纤维膜，其特征在于，所述纳米复合纤维膜的介电常数为1.11-2.36；介电损耗在0.001-0.005；吸水率在0.5％-1％。
  3. 一种三明治结构聚酰亚胺复合纳米纤维膜的制备方法，其特征在于，包括以下步骤，
    步骤1：采用静电纺丝技术，先将聚酰亚胺酸溶液进行电纺得到聚酰亚胺酸电纺膜，而后将聚四氟乙烯-聚偏氟乙烯混合溶液电纺在上述所得聚酰亚胺酸电纺膜上，得到复合电纺膜，再将聚酰亚胺酸溶液电纺在所述复合电纺膜的聚四氟乙烯-聚偏氟乙烯电纺膜另一侧，得到三明治结构复合膜；
    步骤2：将步骤1中所述三明治结构复合膜加热进行热亚胺化，得到所述复合纳米纤维膜。
  4. 根据权利要求3所述的制备方法，其特征在于，步骤1中，所述聚四氟乙烯-聚偏氟乙烯混合溶液通过以下方法制备得到：
    将N-N二甲基甲酰胺或/和N-N二甲基乙酰胺与丙酮进行混合得到混合有机溶剂；
    将聚四氟乙烯粉末与聚偏氟乙烯粉末加入到混合有机溶剂中，在室温下搅拌2-4小时，得到所述聚四氟乙烯-聚偏氟乙烯混合溶液。
  5. 根据权利要求4所述的制备方法，其特征在于，所述聚四氟乙烯粉末与聚偏氟乙烯粉末质量比为0.5:1-1:1。
  6. 根据权利要求4所述的制备方法，其特征在于，所述N-N二甲基甲酰 胺或/和N-N二甲基乙酰胺与丙酮的质量比为0.5:1-2:1。
  7. 根据权利要求3所述的制备方法，其特征在于，步骤1中，所述聚酰亚胺酸溶液的配制方法为将聚酰亚胺酸与N-N二甲基乙酰胺溶液的质量比为0.5:1～1.5:1混合，加热搅拌直至完全混合均匀。
  8. 根据权利要求3所述的制备方法，其特征在于，步骤1中，所述聚四氟乙烯-聚偏氟乙烯混合溶液的质量浓度为6％-12％。
  9. 根据权利要求3所述的制备方法，其特征在于，步骤1中，所述聚酰亚胺酸溶液、聚四氟乙烯-聚偏氟乙烯混合溶液与聚酰亚胺酸溶液的体积比为1:0.5:1～1:2:1。
  10. 根据权利要求3所述的制备方法，其特征在于，步骤2中，所述热亚胺化的条件为：30-60min内升温到350-380℃，在350-380℃下保温15-30min，冷却至室温25℃。
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