CN111976236B - Preparation method of multi-layer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate - Google Patents

Preparation method of multi-layer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate Download PDF

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CN111976236B
CN111976236B CN202010901197.1A CN202010901197A CN111976236B CN 111976236 B CN111976236 B CN 111976236B CN 202010901197 A CN202010901197 A CN 202010901197A CN 111976236 B CN111976236 B CN 111976236B
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fiber cloth
layer
graphene oxide
electronic fiber
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CN111976236A (en
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向中荣
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Wuxi Relong New Material Technology Co ltd
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    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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    • B32B2457/08—PCBs, i.e. printed circuit boards
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Abstract

The invention provides a multi-layer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate and a preparation method thereof. The multi-layer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate provided by the invention has a middle layer graphene oxide metallization reinforced nano fiber layer with the microscopic form conversion of crystalline metal oxide and amorphous metal and electronic fiber cloth layers which are positioned at two sides of the middle layer graphene oxide metallization reinforced nano fiber layer and coated by polymer copolymers with the microscopic structures of amorphous state and crystalline state and are used as three layers of films, and finally, the three layers of films are pressed with a first copper foil and a second copper foil on the outer layer to form the multi-layer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate which has good tensile property, elastic modulus and bending strength, can effectively block ultraviolet light and improve the light transmittance of.

Description

Preparation method of multi-layer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate
Technical Field
The invention belongs to the technical field of high-frequency copper-clad plates, and particularly relates to a preparation method of a multi-layer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate.
Background
With the rapid development of information science and technology, various electronic consumer products with high-speed information processing function have strong market demand, and continuously put forward higher technical requirements, such as high-speed information transmission, integrity, product multi-functionalization and miniaturization, and the like, so that the continuous development of high-frequency and high-speed application technology is promoted. Modern electronic products tend to be miniaturized and multifunctional, which requires high-density and high-performance high-frequency copper-clad Plates (PCB). The flexible board and the rigid-flexible combination board with special structures can obviously reduce the volume of electronic products and realize dense assembly and three-dimensional assembly. As a polyimide film (PI film) mainly enhancing flexibility, for example, chinese patent 201010621313.0, a flexible copper clad laminate manufactured by using the PI film has a high glass transition temperature, is not suitable for rigid-flexible transformation at room temperature, has poor light transmittance and ultraviolet light blocking effect, easily causes a high rejection rate of the manufactured copper clad laminate, has a large number of poor adhesion degrees with an outer copper foil, has poor high temperature impact resistance and mechanical properties, and has low bending strength.
Disclosure of Invention
Aiming at the defects, the invention provides a multilayer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate which is provided with a middle layer graphene oxide metallization reinforced nanofiber layer with the conversion of the microscopic forms of crystalline metal oxide and amorphous metal and an electronic fiber cloth layer which is positioned on two sides of the middle layer graphene oxide metallization reinforced nanofiber layer and is coated with a conductive high polymer-insulating high polymer copolymer with the microscopic structures of amorphous state and crystalline state and serves as a three-layer film, and is finally pressed with a first copper foil and a second copper foil on the outer layer to form the multilayer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate which has good tensile property, elastic modulus and bending strength, can effectively block ultraviolet light, can improve the bonding strength of a light-transmitting copper foil and has low peeling strength.
The invention provides the following technical scheme: a multilayer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate comprises a graphene oxide metallization reinforced nanofiber layer positioned in a middle layer, a conductive high polymer-insulating high polymer copolymer coated electronic fiber cloth layer positioned on two sides of the graphene oxide metallization reinforced nanofiber layer, and a first copper foil layer and a second copper foil layer positioned on two sides of the conductive high polymer-insulating high polymer copolymer coated electronic fiber cloth layer.
Further, the graphene oxide metallized reinforced nanofiber layer comprises the following components in parts by weight:
Figure BDA0002659815470000021
further, the inorganic metal salt or the hydrate of the inorganic metal salt is one or more of nitrate, acetate, sulfate or hydrochloride of a metal element, and the metal element is one or more of Gd, Co, Fe, Ni or Zr; the inorganic metal salt hydrate may be Co (NO)3)2·6H2O、CoSO4·7H2O、Co(CH3COO)2·4H2O、CoCl2·6H2O，Gd2(SO4)3·8H2O、Gd(CH3COO)3·4H2O、GdCl3·6H2O、NiCl2·6H2O、NiSO4·6H2O、Ni(CH3COO)2·4H2O、Ni(NO3)2·6H2O、Fe(NO3)3·9H2O、Fe2(SO4)3·7H2O、FeCl3·6H2O、Zr(NO3)4·5H2O、Zr(SO4)2·4H2O。
Further, the preparation method of the graphene oxide metallized reinforced nanofiber comprises the following steps:
b1: ultrasonically dissolving the graphene oxide powder with the weight component in half of ethylene glycol with the weight component at the frequency of 50 Hz-100 Hz to obtain graphene oxide dispersion liquid;
b2: dissolving the weight component of inorganic metal salt hydrate and the weight component of urea in the remaining half of the weight component of ethylene glycol to form an inorganic metal salt hydrate organic solution, and dissolving the graphene oxide dispersion liquid obtained in the step B1 in the inorganic metal salt hydrate organic solution;
b3: adding the alkali of the weight component into the mixed solution obtained in the step B2, and adjusting the pH to 10-13;
b4: transferring the mixture obtained in the step B3 to a polytetrafluoroethylene stainless steel autoclave preheated to 200-250 ℃, reacting for 3-4 h to obtain graphene oxide-metal oxide particles, and after the autoclave is cooled to room temperature after the reaction is finished, cleaning the graphene oxide-metal oxide particles for 3-4 times by using a mixed solution of distilled water and ethanol with a volume ratio of 1: 3-1: 2;
b5: the cleaned graphene oxide-metal oxide particles obtained in the step B4 are placed at the temperature of 500-700 ℃ for 30cm2/min～50cm2Calcining for 1-1.5 hours under a hot air flow of/min to obtain graphene oxide particles attached to the crystalline metal oxide;
b6: dissolving the crystalline metal oxide-attached graphene oxide particles obtained in the step B5 in hydrazine hydrate of the weight component;
b7: dissolving the hydroxymethyl nanocellulose whiskers of the weight components in tetrahydrofuran of the weight components, mixing the obtained mixture with the mixture obtained in the step B6, and freeze-drying at-15 to-10 ℃ for 10 to 30min to obtain the graphene oxide metallized reinforced nanofibers, wherein the graphene oxide metallized reinforced nanofibers are the hydroxymethyl nanocelluloses reinforced by alternately filling graphene oxide attached to crystal oxides.
Further, the conductive high molecular polymer-insulating high molecular polymer copolymer coated electronic fiber cloth layer comprises the following components in parts by weight:
35-45 parts of conductive high molecular polymer-insulating high molecular polymer copolymer;
Figure BDA0002659815470000041
the curing agent is one or more of triphenylphosphine, imidazole, 2-methylimidazole or 2-phenylimidazole.
Further, the preparation method of the conductive high molecular polymer-insulating high molecular polymer copolymer coated electronic fiber cloth layer comprises the following steps:
m1: dissolving the conductive high molecular polymer-insulating high molecular polymer copolymer of the weight component in the isopropanol of the weight component, and stirring for 10min to 15min at 40 ℃ to 50 ℃ and 400rpm to 450 rpm;
m2: adding the organosilicon adhesive with the weight components into the mixture obtained in the step M1, and stirring at the temperature of 35-40 ℃ for 10-15 min at the rpm of 100-150;
m3: dissolving the curing agent in the weight components in a mixed solution of distilled water and ethanol with a volume ratio of 1: 2-1: 1, and uniformly stirring to obtain a curing agent solution;
m4: and (3) mixing the mixture obtained in the step M2 with the curing agent solution obtained in the step M3, uniformly coating the mixture on the electronic fiber cloth with the weight components, heating the electronic fiber cloth at 250-300 ℃ for 20min, then cooling the electronic fiber cloth to 150-180 ℃ at the speed of 10 ℃/min, then keeping the temperature, heating the electronic fiber cloth for 10-15 min, then heating the electronic fiber cloth to 300-350 ℃ at the speed of 15 ℃/min, continuing to heat the electronic fiber cloth for 15-20 min, and naturally cooling the electronic fiber cloth to room temperature to obtain the conductive high polymer-insulating high polymer copolymer coated electronic fiber cloth layer.
Further, the conductive high molecular polymer-insulating high molecular polymer copolymer comprises the following components in parts by weight:
Figure BDA0002659815470000042
Figure BDA0002659815470000051
further, the conductive high molecular polymer is one or more of polypyrrole, poly (3-butylthiophene), poly (3, 4-ethyldioxythiophene) or polyacetylene; the insulating high polymer material is one or more of polyurethane, polyethylene terephthalate or polyvinyl alcohol.
Further, the preparation method of the conductive high molecular polymer-insulating high molecular polymer copolymer comprises the following steps:
a1: dissolving the conductive high molecular polymer monomer with the weight component in HCl solution with the concentration of 1M, stirring at 200-300 rpm at-10-5 ℃ for 1.5-2 h, and dropwise adding ammonium persulfate with the weight component in the stirring process;
a2: adding the insulating high molecular polymer monomer with the weight component into the mixture obtained in the step A1, adding the acetone with the weight component, stirring at the temperature of 35-45 ℃ for 30-40 min at the speed of 150-200 rpm, and standing in the dark at the temperature of-1 ℃ for 10-15 min;
a3: dissolving the ethylene carbonate and dimethyl carbonate in the weight ratio of (1:3) - (2:3) to 95% of ethanol and NH3·H2Forming a mixed solution of ethylene carbonate and dimethyl carbonate in the mixed solution of O;
a4: dissolving the mixture obtained in the step A1 and the mixture obtained in the step A2 in the mixed solution of the ethylene carbonate and the dimethyl carbonate obtained in the step A3, and performing ultrasonic oscillation for 20-30 min at the frequency of 20-25 kHZ;
a5: refrigerating the mixture obtained in the step A4 at-4 to-2 ℃ for 18 to 32 hours to complete the cross-linking copolymerization of the conductive high molecular polymer and the insulating high molecular polymer and obtain a conductive high molecular polymer-insulating high molecular polymer prepolymer;
a6: and (2) dissolving the ammonium hydroxide with the weight components in 100ml of distilled water to form an ammonium hydroxide solution, immersing the prepolymer obtained in the step A5 in the ammonium hydroxide solution, and pretreating the prepolymer to increase the solubility of the prepolymer.
A7: the prepolymer pretreated in the step A6 is placed at 15cm under the relative humidity of 30-40% and the temperature of 25-28 DEG C2/min～20cm2And drying for 1-2 h under air flow of/min to obtain the conductive high molecular polymer-insulating high molecular polymer copolymer.
The invention also provides a preparation method of the multilayer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate, which comprises the following steps:
s1: dissolving 2.5-5 parts by weight of sodium dodecyl benzene sulfonate in an ethanol solution to form a sodium dodecyl benzene sulfonate ethanol solution with the mass fraction of 15-30%, adding the graphene oxide metallized reinforced nanofiber layer into the sodium dodecyl benzene sulfonate ethanol solution, and immersing for 10-15 min to obtain a graphene oxide metallized reinforced nanofiber layer with negative charges on the surface;
s2: respectively dissolving 3-5 parts of dibutyltin dilaurate and 5-10 parts of triethanolamine in distilled water according to weight components to form a dibutyltin dilaurate aqueous solution with the concentration of 0.5-1.5M and a triethanolamine aqueous solution with the concentration of 1.5-2M, and mixing the dibutyltin dilaurate aqueous solution and the triethanolamine aqueous solution to obtain an association catalyst;
s3: immersing the conductive high molecular polymer-insulating high molecular polymer copolymer coated electronic fiber cloth layer in the association catalyst obtained in the step S2 for 10-15 min, and then taking out and cleaning for 2-3 times by using methanol;
s4: stacking the immersed conductive high molecular polymer-insulating high molecular polymer copolymer coated electronic fiber cloth layer obtained in the step S3 on the graphene oxide metalized reinforced nanofiber layer with negative charges on the surface obtained in the step S1, and drying at 100-150 ℃ for 20min to obtain a three-layer film with an intermediate layer of the graphene oxide metalized reinforced nanofiber layer (1) and conductive high molecular polymer-insulating high molecular polymer copolymer coated electronic fiber cloth layers (2) positioned at two sides of the graphene oxide metalized reinforced nanofiber layer (1);
s5: and (3) stacking a first copper foil (3-1) and a second copper foil (3-2) to two sides of the three-layer film obtained in the step S4, then placing the two sides between two steel plates, and carrying out vacuum hot pressing for 1.5-2.0 h at the temperature of 350-390 ℃ under the pressure of 600 PSI-1200 PSI for molding to obtain the multi-layer polymerized surface function modified electronic fiber cloth flexible high-frequency copper-clad plate.
The invention has the beneficial effects that:
1. in the preparation process of the graphene oxide metallization reinforced nanofiber layer which is the intermediate layer of the multi-layer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate provided by the invention, graphene oxide particles with crystal metal oxide adhesion are prepared by using inorganic salt of metal, and the nanoparticles are doped and filled in hydroxyl nanocellulose in a staggered mode.
The formed crystalline metal oxide is an amorphous alloy oxide, has good anisotropy and orderliness, can have the characteristics of amorphous alloy metal plastic and crystalline metal oxide when the external temperature changes, and improves the conversion capacity between crystals and non-crystals; the glass has good photocatalytic activity when in a crystal metal oxide form, so that the silicon-oxygen value in the glass component in the crystal metal oxide is reduced, the oxygen bridge bond is broken, and the network structure is relaxed, thereby relieving the problem of difficult solubility of the flexible glass; has a low glass transition temperature (T) when in an amorphous alloy stategValue), and further can perform rigid-flexible transformation at a lower temperature (15 ℃ to 30 ℃), and has the characteristics of supercooled liquid to perform superplastic deformation, and further has properties similar to those of ordinary polymer glass, and has good tensile properties, elastic modulus and bending strength.
2. The graphene oxide attached with the crystalline metal oxide with the conductive capability is doped, the graphene has high conductivity, high mechanical property and high thermal conductivity, and the crystalline metal oxide is attached, so that the conductivity, the mechanical property and the heat dispersion and impedance capability of the graphene oxide can be further improved by the crystalline metal oxide, and the thermal shock resistance, the electrical property and the mechanical property of the flexible copper-clad plate can be further improved doubly.
3. The graphene oxide particles with crystal metal oxide adhesion prepared by using inorganic salt of metal can enable the path of photo-generated electrons and holes to be shorter from the inside of the particles to the surface, the average time required is shorter under the condition of a certain migration rate, so that the recombination rate of photo-generated carriers is reduced, the activity of a photocatalytic material is improved, the light transmittance of a flexible copper clad laminate is increased, the transmittance of ultraviolet light is reduced, the mutual interference of two-side circuit patterns is avoided, the condition of waste products is caused, the ultraviolet light is absorbed by utilizing the group with photocatalytic activity, and the effects of blocking the ultraviolet light and increasing the light transmittance are achieved.
4. The conductive high molecular polymer-insulating high molecular polymer copolymer positioned outside the graphene oxide metalized reinforced nanofiber layer at the center coats the conductive high molecular polymer-insulating high molecular polymer copolymer in the electronic fiber cloth, and has semi-crystalline (amorphous) and crystalline properties; the crystalline property maintains the dimensional stability and mechanical property of the copolymer, the amorphous property provides the capability of capturing a large amount of conductive electrons, so that good insulating property is achieved, the microstructure between the amorphous state and the crystalline property improves the porosity of the copper-clad plate, and the bonding capability of the three-layer film with the first copper foil and the second copper foil can be improved under the high temperature condition (300-350 ℃) of the S5 step in the preparation process, the bonding strength with the copper foils is good, and the peeling strength (N/mm) is low.
5. Meanwhile, the graphene oxide metallized reinforced nanofiber layer positioned in the center of the three layers of films and the conductive high polymer-insulating high polymer copolymer coated electronic fiber cloth on the outer layer can be soaked in different solvents and then stacked, and finally are pressed with the first copper foil and the second copper foil, so that the thickness of the cured copolymer coating layer with good uniformity can be obtained, and etching ripples are reduced.
Drawings
The invention will be described in more detail hereinafter on the basis of embodiments and with reference to the accompanying drawings. Wherein:
fig. 1 is a cross-sectional structural diagram of a high-frequency copper-clad plate provided in embodiments 1 to 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The multilayer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate provided by the embodiment comprises a graphene oxide metallization reinforced nanofiber layer 1 positioned in a middle layer, a polypyrrole-polyethylene terephthalate copolymer coated electronic fiber cloth layer 2 positioned on two sides of the graphene oxide metallization reinforced nanofiber layer 1, and a first copper foil layer 3-1 and a second copper foil layer 3-2 positioned on two sides of the polypyrrole-polyethylene terephthalate copolymer coated electronic fiber cloth layer 2.
The graphene oxide metallized reinforced nanofiber comprises the following components in parts by weight:
Figure BDA0002659815470000091
Figure BDA0002659815470000101
the preparation method of the graphene oxide metallized reinforced nanofiber comprises the following steps:
b1: ultrasonically dissolving 30 parts of graphene oxide powder in 3.5 parts of ethylene glycol at the frequency of 50Hz to obtain a graphene oxide dispersion liquid;
b2: 10 parts of Co (NO)3)2·6H2O, 10 parts of Gd (CH)3COO)3·4H2O and 2 parts of urea are dissolved in the remaining 3.5 parts of ethylene glycol to form Co (NO)3)2·6H2O and Gd (CH)3COO)3·4H2O, dissolving the graphene oxide dispersion liquid obtained in the step B1 in Co (NO)3)2·6H2O and Gd (CH)3COO)3·4H2O in a mixed organic solution;
b3: adding 7 parts of KOH into the mixed solution obtained in the step B2, and adjusting the pH value to 10;
b4: transferring the mixture obtained in the step B3 to a polytetrafluoroethylene stainless steel autoclave preheated to 200 ℃, and reacting for 3h to obtain graphene oxide-Co3O4/Gd2O3After the reaction is finished, cooling the autoclave to room temperature, and then carrying out graphene oxide-Co oxidation3O4/Gd2O3Washing the particles for 3 times by using a mixed solution of distilled water and ethanol in a volume ratio of 1: 2;
b5: the cleaned graphene oxide-Co obtained in the step B43O4/Gd2O3The granules are 30cm at 500 deg.C2Calcining for 1h under hot air flow of/min to obtain crystal Co3O4/Gd2O3Attached graphene oxide particles;
b6: the crystal Co obtained in the step B53O4/Gd2O3Dissolving the attached graphene oxide particles in 10 parts of hydrazine hydrate;
b7: dissolving 40 parts of hydroxymethyl nano cellulose whisker in 5 parts of tetrahydrofuran, mixing the obtained mixture with the mixture obtained in the step B6, and freeze-drying at-15 ℃ for 30min to obtain the graphene oxide metallized reinforced nano fiber which is crystalline Co3O4/Gd2O3The attached graphene oxide is filled in a staggered mode to further strengthen the hydroxymethyl nanocellulose.
The polypyrrole-polyethylene glycol terephthalate copolymer coated electronic fiber cloth layer comprises the following components in parts by weight:
Figure BDA0002659815470000111
the preparation method of the polypyrrole-polyethylene terephthalate copolymer coated electronic fiber cloth layer comprises the following steps:
m1: dissolving 35 parts of polypyrrole-polyethylene terephthalate copolymer in 40 parts of isopropanol, and stirring at 40 ℃ and 400rpm for 10 min;
m2: adding 1 part of organic silicon adhesive into the mixture obtained in the step M1, and stirring at 100rpm at 35 ℃ for 10 min;
m3: dissolving 5 parts of curing agent triphenylphosphine in a mixed solution of distilled water and ethanol in a volume ratio of 1:2, and uniformly stirring to obtain a curing agent triphenylphosphine solution;
m4: and (3) mixing the mixture obtained in the step M2 with the curing agent triphenylphosphine solution obtained in the step M3, uniformly coating the mixture on 30 parts of electronic fiber cloth, heating the electronic fiber cloth at 250 ℃ for 20min, then cooling the electronic fiber cloth to 150 ℃ at the speed of 10 ℃/min, preserving heat, heating the electronic fiber cloth for 10min, heating the electronic fiber cloth to 300 ℃ at the speed of 15 ℃/min, continuing to heat the electronic fiber cloth for 15min, and naturally cooling the electronic fiber cloth to room temperature to obtain the polypyrrole-polyethylene terephthalate copolymer coated electronic fiber cloth layer.
The polypyrrole-polyethylene terephthalate copolymer comprises the following components in parts by weight:
Figure BDA0002659815470000112
Figure BDA0002659815470000121
a preparation method of polypyrrole-polyethylene terephthalate copolymer comprises the following steps:
a1: dissolving 20 parts of polypyrrole monomer into 1M HCl solution, stirring at 200rpm at-10 ℃ for 2h, and dropwise adding 5 parts of ammonium persulfate during stirring;
a2: adding 5 parts of polyethylene terephthalate monomer and 3 parts of acetone into the mixture obtained in the step A1, stirring at 150rpm at 35 ℃ for 30min, and standing in the dark at-1 ℃ for 15 min;
a3: 6 parts of ethylene carbonate and 6 parts of dimethyl carbonate are dissolved in 95% by volume fraction ethanol and NH in a volume ratio of 1:33·H2Forming a mixed solution of ethylene carbonate and dimethyl carbonate in the mixed solution of O;
a4: dissolving the mixture obtained in the step A1 and the mixture obtained in the step A2 in the mixed solution of ethylene carbonate and dimethyl carbonate obtained in the step A3, and performing ultrasonic oscillation for 20min at the frequency of 20 kHZ;
a5: refrigerating the mixture obtained in the step A4 at-4 ℃ for 32h to complete the cross-linking copolymerization of polypyrrole and polyethylene glycol terephthalate to obtain a polypyrrole-polyethylene glycol terephthalate copolymer;
a6: and 4 parts of ammonium hydroxide is dissolved in 100ml of distilled water to form an ammonium hydroxide solution, the prepolymer obtained in the step A5 is immersed in the ammonium hydroxide solution, and the prepolymer is pretreated to increase the solubility of the prepolymer.
A7: pre-polymer pretreated by the step A6 is put at 15cm under the relative humidity of 30 percent and the temperature of 25 DEG C2And drying for 2h under the air flow of/min to obtain the polypyrrole-polyethylene terephthalate copolymer.
The preparation method of the multilayer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate provided by the embodiment comprises the following steps:
s1: 2.5 parts of sodium dodecyl benzene sulfonate is dissolved in an ethanol solution to form a sodium dodecyl benzene sulfonate ethanol solution with the mass fraction of 15%, and the graphene oxide metallized reinforced nanofiber layer is added into the sodium dodecyl benzene sulfonate ethanol solution and immersed for 10min to obtain a graphene oxide metallized reinforced nanofiber layer with negative charges on the surface;
s2: respectively dissolving 3 parts of dibutyltin dilaurate and 5 parts of triethanolamine in distilled water to form a 0.5M dibutyltin dilaurate aqueous solution and a 1.5M triethanolamine aqueous solution, and mixing the dibutyltin dilaurate aqueous solution and the triethanolamine aqueous solution to obtain an association catalyst;
s3: immersing a polypyrrole-polyethylene terephthalate copolymer coated electronic fiber cloth layer in the association catalyst obtained in the step S2 for 10min, and then taking out and cleaning for 2-3 times by using methanol;
s4: stacking the electronic fiber cloth layer coated with the immersed polypyrrole-polyethylene terephthalate copolymer obtained in the step S3 on the graphene oxide metalized reinforced nanofiber layer with negative charges on the surface obtained in the step S1, and drying at 100 ℃ for 20min to obtain a three-layer film, wherein the middle layer of the three-layer film is the graphene oxide metalized reinforced nanofiber layer 1 and the electronic fiber cloth layer 2 coated with the polypyrrole-polyethylene terephthalate copolymer on two sides of the graphene oxide metalized reinforced nanofiber layer 1;
s5: and (3) overlapping the first copper foil 3-1 and the second copper foil 3-2 to two sides of the three-layer film obtained in the step S4, then placing the three-layer film between two steel plates, and carrying out vacuum hot pressing for 1.5 hours at 350 ℃ under 1200PSI pressure to form the multi-layer polymerized surface function modified electronic fiber cloth flexible high-frequency copper-clad plate.
Example 2
The multilayer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate provided by the embodiment comprises a graphene oxide metallization reinforced nanofiber layer 1 positioned in a middle layer, a poly (3-butylthiophene) -polyurethane copolymer coated electronic fiber cloth layer 2 positioned on two sides of the graphene oxide metallization reinforced nanofiber layer 1, and a first copper foil layer 3-1 and a second copper foil layer 3-2 positioned on two sides of the poly (3-butylthiophene) -polyurethane copolymer coated electronic fiber cloth layer 2.
The graphene oxide metallized reinforced nanofiber comprises the following components in parts by weight:
Figure BDA0002659815470000141
the preparation method of the graphene oxide metallized reinforced nanofiber comprises the following steps:
b1: ultrasonically dissolving 35 parts of graphene oxide powder in 7.5 parts of ethylene glycol at the frequency of 100Hz to obtain a graphene oxide dispersion liquid;
b2: 22.5 parts of NiCl2·6H2O and 5 parts of urea are dissolved in the remaining 7.5 parts of ethylene glycol to form NiCl2·6H2O organic solution, dissolving the graphene oxide dispersion liquid obtained in the step B1 in NiCl2·6H2O in organic solution;
b3: adding 15 parts of NaOH into the mixed solution obtained in the step B2, and adjusting the pH value to be 13;
b4: transferring the mixture obtained in the step B3 to a polytetrafluoroethylene stainless steel autoclave preheated to 250 ℃, reacting for 4 hours to obtain graphene oxide-NiO particles, and after the autoclave is cooled to room temperature after the reaction is finished, cleaning the graphene oxide-NiO particles for 4 times by adopting a mixed solution of distilled water and ethanol with a volume ratio of 1: 3;
b5: the cleaned graphene oxide-NiO particles obtained in the step B4 are placed at 700 ℃ for 50cm2Calcining for 1.5h under a hot air flow of/min to obtain oxidized graphene particles attached with crystal NiO;
b6: dissolving the graphene oxide particles attached with the crystal NiO obtained in the step B5 in 15 parts of hydrazine hydrate;
b7: and (3) dissolving 45 parts of hydroxymethyl nanocellulose whiskers in 10 parts of tetrahydrofuran, mixing the obtained mixture with the mixture obtained in the step B6, and freeze-drying at-10 ℃ for 10min to obtain the graphene oxide metallized reinforced nanofiber, wherein the graphene oxide metallized reinforced nanofiber is the hydroxymethyl nanocellulose reinforced by alternately filling graphene oxide attached to crystalline NiO.
The poly (3-butylthiophene) -polyurethane copolymer coating electronic fiber cloth layer comprises the following components in parts by weight:
Figure BDA0002659815470000151
the preparation method of the electronic fiber cloth layer coated with the poly (3-butylthiophene) -polyurethane copolymer comprises the following steps:
m1: dissolving the weight component of poly (3-butyl thiophene) -polyurethane copolymer in the weight component of isopropanol, and stirring at 45 ℃ and 425rpm for 13 min;
m2: adding 3 parts of organic silicon adhesive into the mixture obtained in the step M1, and stirring at 125rpm at 38 ℃ for 12 min;
m3: dissolving 7.5 parts of curing agent imidazole in a mixed solution of distilled water and ethanol in a volume ratio of 2:3, and uniformly stirring to obtain a curing agent imidazole solution;
m4: and (3) mixing the mixture obtained in the step M2 with the curing agent imidazole solution obtained in the step M3, uniformly coating the mixture on electronic fiber cloth with weight components, heating the electronic fiber cloth at 275 ℃ for 20min, then cooling the electronic fiber cloth to 165 ℃ at the speed of 10 ℃/min, preserving heat, heating the electronic fiber cloth for 13min, heating the electronic fiber cloth to 325 ℃ at the speed of 15 ℃/min, continuing to heat the electronic fiber cloth for 17min, and naturally cooling the electronic fiber cloth to room temperature to obtain the poly (3-butylthiophene) -polyurethane copolymer coated electronic fiber cloth layer.
The poly (3-butylthiophene) -polyurethane copolymer comprises the following components in parts by weight:
Figure BDA0002659815470000161
a preparation method of a poly (3-butylthiophene) -polyurethane copolymer comprises the following steps:
a1: dissolving 25 parts of poly (3-butylthiophene) monomer in 1M HCl solution, stirring at 300rpm at-5 ℃ for 1.5h, and dropwise adding 10 parts of ammonium persulfate in the stirring process;
a2: adding 15 parts of polyurethane monomer and 5 parts of acetone into the mixture obtained in the step A1, stirring at 200rpm at 45 ℃ for 40min, and standing in the dark at 1 ℃ for 10 min;
a3: 12 parts of ethylene carbonate and 12 parts of dimethyl carbonate are dissolved in 95% by volume fraction ethanol and NH in a volume ratio of 2:33·H2Forming a mixed solution of ethylene carbonate and dimethyl carbonate in the mixed solution of O;
a4: dissolving the mixture obtained in the step A1 and the mixture obtained in the step A2 in the mixed solution of ethylene carbonate and dimethyl carbonate obtained in the step A3, and performing ultrasonic oscillation for 30min at the frequency of 25 kHZ;
a5: refrigerating the mixture obtained in the step A4 at-2 ℃ for 18h to complete the cross-linking copolymerization of poly (3-butylthiophene) and polyurethane to obtain a poly (3-butylthiophene) -polyurethane copolymer prepolymer;
a6: and (3) dissolving 8 parts of ammonium hydroxide in 100ml of distilled water to form an ammonium hydroxide solution, immersing the prepolymer obtained in the step A5 in the ammonium hydroxide solution, and pretreating the prepolymer to increase the solubility of the prepolymer.
A7: pre-polymer pretreated by A6 step is put at 40% relative humidity and 2At 8 ℃ at 20cm2Drying for 1h under an air stream of/min to obtain the poly (3-butylthiophene) -polyurethane copolymer.
The embodiment also provides a preparation method of the multilayer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate, which comprises the following steps:
s1: dissolving 3.75 parts by weight of sodium dodecyl benzene sulfonate in an ethanol solution to form an ethanol solution of sodium dodecyl benzene sulfonate with the mass fraction of 18%, adding the graphene oxide metallized reinforced nanofiber layer into the ethanol solution of sodium dodecyl benzene sulfonate, and immersing for 12min to obtain a graphene oxide metallized reinforced nanofiber layer with negative charges on the surface;
s2: respectively dissolving 4 parts of dibutyltin dilaurate and 7.5 parts of triethanolamine in distilled water according to weight components to form a 1.0M dibutyltin dilaurate aqueous solution and a 1.75M triethanolamine aqueous solution, and mixing the dibutyltin dilaurate aqueous solution and the triethanolamine aqueous solution to obtain an association catalyst;
s3: immersing a poly (3-butylthiophene) -polyurethane copolymer-coated electronic fiber cloth layer in the association catalyst obtained in the step S2 for 12min, and then taking out and cleaning for 3 times by using methanol;
s4: stacking the immersed electronic fiber cloth layer coated with the poly (3-butylthiophene) -polyurethane copolymer obtained in the step S3 on the graphene oxide metalized reinforced nanofiber layer with negative charges on the surface obtained in the step S1, and drying at 125 ℃ for 20min to obtain a three-layer film, wherein the middle layer of the three-layer film is the graphene oxide metalized reinforced nanofiber layer 1 and the electronic fiber cloth layer 2 coated with the poly (3-butylthiophene) -polyurethane copolymer on the two sides of the graphene oxide metalized reinforced nanofiber layer 1;
s5: and (3) overlapping the first copper foil 3-1 and the second copper foil 3-2 to two sides of the three-layer film obtained in the step S4, then placing the three-layer film between two steel plates, and carrying out vacuum hot pressing for 1.8h at 370 ℃ under the pressure of 900PSI to form the multi-layer polymerized surface function modified electronic fiber cloth flexible high-frequency copper-clad plate.
Example 3
The multilayer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate provided by the embodiment comprises a graphene oxide metallization reinforced nanofiber layer 1 positioned in a middle layer, a polyacetylene-polyvinyl alcohol copolymer coated electronic fiber cloth layer 2 positioned on two sides of the graphene oxide metallization reinforced nanofiber layer 1, and a first copper foil layer 3-1 and a second copper foil layer 3-2 positioned on two sides of the polyacetylene-polyvinyl alcohol copolymer coated electronic fiber cloth layer 2.
The graphene oxide metallized reinforced nanofiber comprises the following components in parts by weight:
Figure BDA0002659815470000181
the preparation method of the graphene oxide metallized reinforced nanofiber comprises the following steps:
b1: ultrasonically dissolving 32.5 parts of graphene oxide powder in 5.5 parts of ethylene glycol at the frequency of 75Hz to obtain a graphene oxide dispersion liquid;
b2: mixing 11 parts of Fe2(SO4)3·7H2O, 10 parts of Zr (SO)4)2·4H2O and 3.5 parts of urea are dissolved in the remaining 5.5 parts of ethylene glycol to form Fe2(SO4)3·7H2O and Zr (SO)4)2·4H2O mixed organic solution, and the graphene oxide dispersion liquid obtained in the step B1 is dissolved in Fe2(SO4)3·7H2O and Zr (SO)4)2·4H2O is mixed with the organic solution;
b3: adding 11 parts of KOH into the mixed solution obtained in the step B2, and adjusting the pH value to 12;
b4: transferring the mixture obtained in the step B3 to a polytetrafluoroethylene stainless steel autoclave preheated to 225 ℃, and reacting for 3.5h to obtain graphene oxide-Fe3O4/ZrO2After the reaction is finished, cooling the autoclave to room temperature, and then carrying out graphene oxide-Fe oxidation3O4/ZrO2Washing the particles for 3 times by using a mixed solution of distilled water and ethanol in a volume ratio of 2: 5;
b5: washing the graphene oxide-Fe obtained in the step B43O4/ZrO2The granules are 40cm at 600 DEG C2Calcining for 1.3h under hot air flow of/min to obtain crystalline Fe3O4/ZrO2Attached graphene oxide particles;
b6: the crystal Fe obtained in the step B53O4/ZrO2Dissolving the attached graphene oxide particles in 12.5 parts of hydrazine hydrate;
b7: dissolving 42.5 parts of hydroxymethyl nano cellulose whisker in 7.5 parts of tetrahydrofuran, mixing the obtained mixture with the mixture obtained in the step B6, and freeze-drying at-12 ℃ for 20min to obtain graphene oxide metallized reinforced nano fiber which is crystalline Fe3O4/ZrO2The attached graphene oxide is filled in a staggered mode to further strengthen the hydroxymethyl nanocellulose.
The polyacetylene-polyvinyl alcohol copolymer coated electronic fiber cloth layer comprises the following components in parts by weight:
Figure BDA0002659815470000191
the preparation method of the electronic fiber cloth layer coated with the polyacetylene-polyvinyl alcohol copolymer comprises the following steps:
m1: dissolving 45 parts of polyacetylene-polyvinyl alcohol copolymer in 50 parts of isopropanol, and stirring at 50 ℃ and 450rpm for 15 min;
m2: adding 5 parts of organic silicon adhesive into the mixture obtained in the step M1, and stirring at 150rpm at 40 ℃ for 15 min;
m3: dissolving 10 parts of curing agent 2-phenylimidazole in a mixed solution of distilled water and ethanol in a volume ratio of 1:1, and uniformly stirring to obtain a curing agent 2-phenylimidazole solution;
m4: and (3) mixing the mixture obtained in the step M2 with the curing agent 2-phenylimidazole solution obtained in the step M3, uniformly coating the mixture on electronic fiber cloth with weight components, heating the electronic fiber cloth at 250-300 ℃ for 20min, then cooling to 150-180 ℃ at the speed of 10 ℃/min, preserving heat, heating for 10-15 min, then heating to 300-350 ℃ at the speed of 15 ℃/min, continuing to heat for 15-20 min, and naturally cooling to room temperature to obtain the conductive high polymer-insulating high polymer copolymer coated electronic fiber cloth layer.
The polyacetylene-polyvinyl alcohol copolymer comprises the following components in parts by weight:
Figure BDA0002659815470000201
the preparation method of the polyacetylene-polyvinyl alcohol copolymer comprises the following steps:
a1: dissolving 22.5 parts of polyacetylene monomer in 1M HCl solution, stirring at 250rpm at-8 ℃ for 1.8h, and dropwise adding 7.5 parts of ammonium persulfate during stirring;
a2: adding 10 parts of polyvinyl alcohol monomer and 4 parts of acetone into the mixture obtained in the step A1, stirring at 175rpm at 40 ℃ for 35min, and standing in the dark at 0 ℃ for 12 min;
a3: 9 parts of ethylene carbonate and 9 parts of dimethyl carbonate are dissolved in 95% by volume fraction ethanol and NH in a volume ratio of 2:53·H2Forming a mixed solution of ethylene carbonate and dimethyl carbonate in the mixed solution of O;
a4: dissolving the mixture obtained in the step A1 and the mixture obtained in the step A2 in the mixed solution of ethylene carbonate and dimethyl carbonate obtained in the step A3, and performing ultrasonic oscillation for 25min at the frequency of 22.5 kHZ;
a5: refrigerating the mixture obtained in the step A4 at-3 ℃ for 25h to complete the crosslinking copolymerization of the polyacetylene and the polyvinyl alcohol to obtain a polyacetylene-polyvinyl alcohol copolymer prepolymer;
a6: and (3) dissolving 6 parts of ammonium hydroxide in 100ml of distilled water to form an ammonium hydroxide solution, immersing the prepolymer obtained in the step A5 in the ammonium hydroxide solution, and pretreating the prepolymer to increase the solubility of the prepolymer.
A7: pre-polymer pretreated by the step A6 is put under 35 percent relative humidity and 26 ℃ in17cm2And drying for 1.5h under the air flow of/min to obtain the polyacetylene-polyvinyl alcohol copolymer.
The invention also provides a preparation method of the multilayer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate, which comprises the following steps:
s1: dissolving 5 parts by weight of sodium dodecyl benzene sulfonate in an ethanol solution to form a 30% sodium dodecyl benzene sulfonate ethanol solution, adding the graphene oxide metallized reinforced nanofiber layer into the sodium dodecyl benzene sulfonate ethanol solution, and immersing for 15min to obtain a graphene oxide metallized reinforced nanofiber layer with negative charges on the surface;
s2: respectively dissolving 5 parts of dibutyltin dilaurate and 10 parts of triethanolamine in distilled water according to weight components to form a 1.5M dibutyltin dilaurate aqueous solution and a 2M triethanolamine aqueous solution, and mixing the dibutyltin dilaurate aqueous solution and the triethanolamine aqueous solution to obtain an association catalyst;
s3: immersing a polyacetylene-polyvinyl alcohol copolymer coated electronic fiber cloth layer in the association catalyst obtained in the step S2 for 15min, and then taking out and cleaning for 3 times by using methanol;
s4: stacking the electronic fiber cloth layer coated with the immersed polyacetylene-polyvinyl alcohol copolymer obtained in the step S3 on the graphene oxide metallized reinforced nanofiber layer with the surface having negative charges obtained in the step S1, and drying at 150 ℃ for 20min to obtain a three-layer film, wherein the middle layer of the three-layer film is a graphene oxide metallized reinforced nanofiber layer 1 and a polyacetylene-polyvinyl alcohol copolymer coated electronic fiber cloth layer 2 positioned at two sides of the graphene oxide metallized reinforced nanofiber layer 1;
s5: and (3) overlapping the first copper foil 3-1 and the second copper foil 3-2 to two sides of the three-layer film obtained in the step S4, then placing the three-layer film between two steel plates, and carrying out vacuum hot pressing for 2.0 hours at 390 ℃ under the pressure of 600PSI to form the multi-layer polymerized surface function modified electronic fiber cloth flexible high-frequency copper-clad plate.
Comparative example 1
Measuring the graphene oxide metallized reinforced nanofiber layer of the high-frequency copper-clad plate in the embodiment 1-3 of the invention and the polyimide film high-flexibility flexible base material coated with the bonding glue prepared in the embodiment 1 of Chinese patent 201010621313.0 as characteristic temperatures and corresponding amorphous forming capability parameter values in the heating crystallization process of the comparative embodiment 1 by adopting a differential scanning calorimeter with the model of DSC-500C of Shanghai's Kangjin scientific instruments Co., Ltd; the method comprises the steps of measuring the Young-type elastic modulus, the shear modulus and the volume modulus of a sample which is a copper-clad plate prepared in embodiments 1-3 of the invention and a copper-clad plate finally prepared from a polyimide film coated with bonding glue prepared in embodiment 1 of Chinese patent 201010621313.0 by adopting an IET-1600VP high-temperature elastic modulus tester of a Luoyang Zongsheng detection instrument Co., Ltd; the bending strength of the copper-clad plate prepared in the embodiments 1-3 of the invention and the copper-clad plate finally prepared from the polyimide film coated with the bonding glue prepared in the embodiment 1 of the Chinese patent 201010621313.0 are tested by adopting a microcomputer-controlled bending strength tester with the model number of WDW-200/300/600 of Beijing Zhonghang time instrument and equipment Limited company. The results are shown in Table 1.
TABLE 1
Index (I) Example 1 Example 2 Example 3 Comparative example 1
Glass transition temperature Tg 15.7℃ 20.3℃ 27.8℃ 56.8℃
Amorphous crystallization temperature Tx 12.6℃ 15.1℃ 19.8℃ 54.5℃
Supercooled liquid region Δ Tx 3.1℃ 5.2℃ 8.0℃ 2.3℃
Young's modulus of elasticity 69.33GPa 76.54GPa 87.69GPa 46.87GPa
Shear modulus 36.88GPa 41.20GPa 49.65GPa 26.55GPa
Bulk modulus 26.47GPa 30.42GPa 35.64GPa 10.56GPa
Flexural Strength (MPa) 85.67MPa 88.54MPa 90.34MPa MPa
Comparative example 2
The high-frequency copper-clad plate in the embodiment 1-3 of the invention and the high-flexibility flexible base material of the adhesive-coated polyimide film prepared in the embodiment 1 of the Chinese patent 201010621313.0 are used as the expansion coefficient values of the temperature range of 20-150 ℃ in the comparative example 2, and the smaller the thermal expansion coefficient value is, the stronger the thermal shock resistance and the thermal cycle resistance are; the high-frequency copper clad laminate of examples 1 to 3 of the present invention and the adhesive-coated polyimide film high-flexibility flexible substrate prepared in example 1 of chinese patent 201010621313.0 were measured for peel strength, solder dip resistance (300 ℃) and etching waviness as comparative example 2. The results are shown in Table 2.
TABLE 2
Figure BDA0002659815470000231
Figure BDA0002659815470000241
Comparative example 3
The high-frequency copper clad laminate of examples 1 to 3 of the present invention and the adhesive-coated polyimide film high-flexibility flexible substrate prepared in example 1 of chinese patent 201010621313.0 were measured for light transmittance and ultraviolet ray blocking rate as comparative example 3. The results are shown in Table 3.
TABLE 3
Index (I) Example 1 Example 2 Example 3 Comparative example 3
Light transmittance 85.49％ 87.64％ 89.36％ 65.97％
Ultraviolet light blocking ratio 75.02％ 77.56％ 79.84％ 26.31％
While the invention has been described with reference to a preferred embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In particular, the technical features mentioned in the embodiments can be combined in any way as long as there is no structural conflict. It is intended that the invention not be limited to the particular embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims (8)

1. The multilayer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate is characterized by comprising a graphene oxide metallization reinforced nanofiber layer (1) positioned in a middle layer, a conductive high polymer-insulating high polymer copolymer coating electronic fiber cloth layer (2) positioned at two sides of the graphene oxide metallization reinforced nanofiber layer (1), and a first copper foil layer (3-1) and a second copper foil layer (3-2) positioned at two sides of the conductive high polymer-insulating high polymer copolymer coating electronic fiber cloth layer (2);
the graphene oxide metallized reinforced nanofiber layer comprises the following components in parts by weight:
Figure FDA0002908924390000011
the preparation method of the graphene oxide metallized reinforced nanofiber comprises the following steps:
b1: ultrasonically dissolving the graphene oxide powder with the weight component in half of ethylene glycol with the weight component at the frequency of 50 Hz-100 Hz to obtain graphene oxide dispersion liquid;
b2: dissolving the weight component of inorganic metal salt hydrate and the weight component of urea in the remaining half of the weight component of ethylene glycol to form an inorganic metal salt hydrate organic solution, and dissolving the graphene oxide dispersion liquid obtained in the step B1 in the inorganic metal salt hydrate organic solution;
b3: adding the alkali of the weight component into the mixed solution obtained in the step B2, and adjusting the pH to 10-13;
b4: transferring the mixture obtained in the step B3 to a polytetrafluoroethylene stainless steel autoclave preheated to 200-250 ℃, reacting for 3-4 h to obtain graphene oxide-metal oxide particles, and after the autoclave is cooled to room temperature after the reaction is finished, cleaning the graphene oxide-metal oxide particles for 3-4 times by using a mixed solution of distilled water and ethanol with a volume ratio of 1: 3-1: 2;
b5: the cleaned graphene oxide-metal oxide particles obtained in the step B4 are placed at the temperature of 500-700 ℃ for 30cm2/min～50cm2Calcining for 1-1.5 h under hot air flow of/min to obtain graphite oxide attached with crystal metal oxideAn alkene particle;
b6: dissolving the crystalline metal oxide-attached graphene oxide particles obtained in the step B5 in hydrazine hydrate of the weight component;
b7: dissolving the hydroxymethyl nanocellulose whiskers of the weight components in tetrahydrofuran of the weight components, mixing the obtained mixture with the mixture obtained in the step B6, and freeze-drying at-15 to-10 ℃ for 10 to 30min to obtain the graphene oxide metallized reinforced nanofibers, wherein the graphene oxide metallized reinforced nanofibers are the hydroxymethyl nanocelluloses reinforced by alternately filling graphene oxide attached to crystal oxides.
2. The flexible high-frequency copper-clad plate with multi-layer polymerized surface function modified electronic fiber cloth according to claim 1, wherein the inorganic metal salt or inorganic metal salt hydrate is one or more of nitrate, acetate, sulfate or hydrochloride of metal elements, and the metal elements are one or more of Gd, Co, Fe, Ni or Zr.
3. The flexible high-frequency copper-clad plate with multi-layer polymerized surface function modified electronic fiber cloth according to claim 1, wherein the electronic fiber cloth layer coated with the conductive high molecular polymer-insulating high molecular polymer copolymer comprises the following components in parts by weight:
Figure FDA0002908924390000021
Figure FDA0002908924390000031
the curing agent is one or more of triphenylphosphine, imidazole, 2-methylimidazole or 2-phenylimidazole.
4. The high-frequency copper-clad plate with the multi-layer polymerized surface function modified electronic fiber cloth flexible according to claim 3, wherein the preparation method of the electronic fiber cloth layer coated with the conductive high molecular polymer-insulating high molecular polymer copolymer comprises the following steps:
m1: dissolving the conductive high molecular polymer-insulating high molecular polymer copolymer of the weight component in the isopropanol of the weight component, and stirring for 10min to 15min at 40 ℃ to 50 ℃ and 400rpm to 450 rpm;
m2: adding the organosilicon adhesive with the weight components into the mixture obtained in the step M1, and stirring at the temperature of 35-40 ℃ for 10-15 min at the rpm of 100-150;
m3: dissolving the curing agent in the weight components in a mixed solution of distilled water and ethanol with a volume ratio of 1: 2-1: 1, and uniformly stirring to obtain a curing agent solution;
m4: and (3) mixing the mixture obtained in the step M2 with the curing agent solution obtained in the step M3, uniformly coating the mixture on the electronic fiber cloth with the weight components, heating the electronic fiber cloth at 250-300 ℃ for 20min, then cooling the electronic fiber cloth to 150-180 ℃ at the speed of 10 ℃/min, then keeping the temperature, heating the electronic fiber cloth for 10-15 min, then heating the electronic fiber cloth to 300-350 ℃ at the speed of 15 ℃/min, continuing to heat the electronic fiber cloth for 15-20 min, and naturally cooling the electronic fiber cloth to room temperature to obtain the conductive high polymer-insulating high polymer copolymer coated electronic fiber cloth layer.
5. The flexible high-frequency copper-clad plate with multi-layer polymerized surface function modified electronic fiber cloth according to claim 3, wherein the conductive high molecular polymer-insulating high molecular polymer copolymer comprises the following components in parts by weight:
Figure FDA0002908924390000032
Figure FDA0002908924390000041
6. the flexible high-frequency copper-clad plate with multi-layer polymerized surface function modified electronic fiber cloth according to claim 5, wherein the conductive high molecular polymer is one or more of polypyrrole, poly (3-butylthiophene), poly (3, 4-ethyldioxythiophene) or polyacetylene; the insulating high polymer material is one or more of polyurethane, polyethylene terephthalate or polyvinyl alcohol.
7. The flexible high-frequency copper-clad plate with multi-layer polymerized surface function modified electronic fiber cloth according to claim 5, wherein the preparation method of the conductive high molecular polymer-insulating high molecular polymer copolymer comprises the following steps:
a1: dissolving the conductive high molecular polymer monomer with the weight component in HCl solution with the concentration of 1M, stirring at 200-300 rpm at-10-5 ℃ for 1.5-2 h, and dropwise adding ammonium persulfate with the weight component in the stirring process;
a2: adding the insulating high molecular polymer monomer with the weight component into the mixture obtained in the step A1, adding the acetone with the weight component, stirring at the temperature of 35-45 ℃ for 30-40 min at the speed of 150-200 rpm, and standing in the dark at the temperature of-1 ℃ for 10-15 min;
a3: dissolving the ethylene carbonate and dimethyl carbonate in the weight ratio of (1:3) - (2:3) to 95% of ethanol and NH3·H2Forming a mixed solution of ethylene carbonate and dimethyl carbonate in the mixed solution of O;
a4: dissolving the mixture obtained in the step A1 and the mixture obtained in the step A2 in the mixed solution of the ethylene carbonate and the dimethyl carbonate obtained in the step A3, and performing ultrasonic oscillation for 20-30 min at the frequency of 20-25 kHZ;
a5: refrigerating the mixture obtained in the step A4 at-4 to-2 ℃ for 18 to 32 hours to complete the cross-linking copolymerization of the conductive high molecular polymer and the insulating high molecular polymer and obtain a conductive high molecular polymer-insulating high molecular polymer prepolymer;
a6: dissolving ammonium hydroxide with the weight components in 100ml of distilled water to form an ammonium hydroxide solution, immersing the prepolymer obtained in the step A5 in the ammonium hydroxide solution, and pretreating the prepolymer to increase the solubility of the prepolymer;
a7: the prepolymer pretreated in the step A6 is placed at 15cm under the relative humidity of 30-40% and the temperature of 25-28 DEG C2/min～20cm2And drying for 1-2 h under air flow of/min to obtain the conductive high molecular polymer-insulating high molecular polymer copolymer.
8. The preparation method of the multi-layer polymerization surface function modified electronic fiber cloth flexible high-frequency copper-clad plate according to any one of claims 1 to 7, characterized by comprising the following steps:
s1: dissolving 2.5-5 parts by weight of sodium dodecyl benzene sulfonate in an ethanol solution to form a sodium dodecyl benzene sulfonate ethanol solution with the mass fraction of 15-30%, adding the graphene oxide metallized reinforced nanofiber layer into the sodium dodecyl benzene sulfonate ethanol solution, and immersing for 10-15 min to obtain a graphene oxide metallized reinforced nanofiber layer with negative charges on the surface;
s2: respectively dissolving 3-5 parts of dibutyltin dilaurate and 5-10 parts of triethanolamine in distilled water according to weight components to form a dibutyltin dilaurate aqueous solution with the concentration of 0.5-1.5M and a triethanolamine aqueous solution with the concentration of 1.5-2M, and mixing the dibutyltin dilaurate aqueous solution and the triethanolamine aqueous solution to obtain an association catalyst;
s3: immersing the conductive high molecular polymer-insulating high molecular polymer copolymer coated electronic fiber cloth layer in the association catalyst obtained in the step S2 for 10-15 min, and then taking out and cleaning for 2-3 times by using methanol;
s4: stacking the immersed conductive high molecular polymer-insulating high molecular polymer copolymer coated electronic fiber cloth layer obtained in the step S3 on the graphene oxide metalized reinforced nanofiber layer with negative charges on the surface obtained in the step S1, and drying at 100-150 ℃ for 20min to obtain a three-layer film with an intermediate layer of the graphene oxide metalized reinforced nanofiber layer (1) and conductive high molecular polymer-insulating high molecular polymer copolymer coated electronic fiber cloth layers (2) positioned at two sides of the graphene oxide metalized reinforced nanofiber layer (1);
s5: and (3) stacking a first copper foil (3-1) and a second copper foil (3-2) to two sides of the three-layer film obtained in the step S4, then placing the two sides between two steel plates, and carrying out vacuum hot pressing for 1.5-2.0 h at the temperature of 350-390 ℃ under the pressure of 600 PSI-1200 PSI for molding to obtain the multi-layer polymerized surface function modified electronic fiber cloth flexible high-frequency copper-clad plate.
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