CN116656091A - Electrostatic spinning fiber prepreg and preparation method thereof - Google Patents
Electrostatic spinning fiber prepreg and preparation method thereof Download PDFInfo
- Publication number
- CN116656091A CN116656091A CN202310507433.5A CN202310507433A CN116656091A CN 116656091 A CN116656091 A CN 116656091A CN 202310507433 A CN202310507433 A CN 202310507433A CN 116656091 A CN116656091 A CN 116656091A
- Authority
- CN
- China
- Prior art keywords
- prepreg
- resin
- fiber
- electrostatic spinning
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 108
- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 74
- 239000011347 resin Substances 0.000 claims abstract description 74
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 20
- 239000003292 glue Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 238000009987 spinning Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005510 Diuron Substances 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- 239000002861 polymer material Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000012783 reinforcing fiber Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000005686 electrostatic field Effects 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000009719 polyimide resin Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000009736 wetting Methods 0.000 claims description 2
- 238000004804 winding Methods 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 15
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 238000000465 moulding Methods 0.000 abstract description 4
- 238000005470 impregnation Methods 0.000 abstract description 3
- 230000002787 reinforcement Effects 0.000 abstract description 3
- 238000000748 compression moulding Methods 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 12
- 239000004744 fabric Substances 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 5
- 230000008595 infiltration Effects 0.000 description 5
- 238000001764 infiltration Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/246—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using polymer based synthetic fibres
-
- 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
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/34—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated alcohols, acetals or ketals as the major constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/18—Homopolymers or copolymers of nitriles
- C08J2433/20—Homopolymers or copolymers of acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
Abstract
The invention provides an electrostatic spinning fiber prepreg and a preparation method thereof, which belong to the technical field of preparation of fiber prepregs, and aims to introduce electrostatic spinning fibers on the basis of the traditional prepreg, so that resin can be more uniformly soaked in the reinforced fibers, the fibers can be more uniformly distributed in the resin, the generation of bubbles in the preparation process of the prepreg is reduced, and the thickness of the prepreg is reduced. The invention is formed by interlacing and connecting a plurality of intricate fibers, which is beneficial to the uniform impregnation of a resin matrix and reduces impurities such as bubbles and the like in the preparation process of the prepreg; the fiber prepreg containing the electrostatic spinning can improve the performance of the resin, strengthen the interface characteristic between the fiber and the resin, realize the reinforcement of the composite material on the nanometer scale, and can be used as the prepreg of the composite material for structures or functions such as layering autoclave molding, compression molding, vacuum bag non-autoclave molding and the like; has excellent physical and mechanical properties, and greatly enhances the application of the fiber composite material.
Description
Technical Field
The invention belongs to the technical field of preparation of fiber prepregs, and relates to an electrostatic spinning fiber prepreg and a preparation method thereof.
Background
Prepregs are compositions of resin matrix and reinforcement made of resin matrix impregnated with fibers or fabrics under tightly controlled conditions, and are intermediate materials for the manufacture of composite materials. The fiber prepreg is widely applied to the fields of aerospace, construction, sports, agriculture and the like by virtue of light weight, high strength, chemical corrosion resistance and good electrical property. In the fiber resin prepreg, a fiber reinforced material is usually added, and the matrix resin is solidified to bond the fiber reinforced material into a whole, so that the fiber resin prepreg plays a role in load transmission and gives the composite material various excellent comprehensive properties such as electrical insulation, corrosion resistance, high temperature resistance, oxidation resistance, manufacturability and the like.
The current method for preparing the fiber resin prepreg mainly comprises the following steps: (1) applying liquid matrix resin to the fiber cloth in a brushing mode, penetrating the resin material into the fiber cloth through the wettability of the resin material, and solidifying the matrix resin in a cooling solidification mode, a chemical crosslinking solidification mode or a UV solidification mode and the like to obtain a fiber resin prepreg, and forming a composite board through a multi-layer brushing fiber resin prepreg or a lamination process; (2) the thermoplastic resin film and the fiber cloth are laminated and hot pressed, and the thermoplastic resin film is melted at high temperature, so that the fiber cloth and the thermoplastic resin are mutually infiltrated to prepare the fiber resin prepreg. The method is widely applied, but the existing preparation method has higher requirements on the viscosity, fluidity, affinity between the resin and the fiber cloth and the like of the resin, and if the viscosity of the resin is higher, the fluidity is poor or the affinity is poor, the resin is difficult to flow on the fiber cloth sufficiently when the resin and the fiber cloth are soaked, so that the problems of insufficient soaking, bubble formation and the like are caused, and the performance of the fiber resin prepreg is poor.
At present, patent CN 109468852a discloses a fiber prepreg, a fiber prepreg board and a preparation method of the fiber prepreg, and the preparation method of the fiber prepreg provided by the patent CN 109468852a can effectively reduce the requirements on the viscosity, flowability and affinity of resin, but has poor and satisfactory reinforcing effect and a complex preparation process. Patent CN 105164192a, prepreg and method for producing the same, a resin composition is impregnated into a reinforcing fiber layer to obtain a 1-time prepreg, then a sheet of the resin composition is laminated on one side or both sides of the 1-time prepreg, and the 1-time prepreg is integrated with the sheet of the resin composition by hot pressing. The conductive particles contained in the resin composition of the surface layer thereof do not deposit to the inner layer but stay on the surface layer of the prepreg, enhancing conductivity and impact resistance. However, the prepreg has poor storage stability and uneven distribution of reinforcing fibers. Because of the need to develop a simple and convenient resin prepreg preparation technology and method with uniform impregnation and uniform fiber distribution.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides an electrostatic spinning fiber prepreg and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the electrostatic spinning fiber prepreg is introduced based on the traditional prepreg, and the technical effect achieved is that the resin can be more uniformly soaked in the reinforcing fiber, the fiber can be more uniformly distributed in the resin, the generation of bubbles in the preparation process of the prepreg is reduced, and the thickness of the prepreg is reduced.
A method for preparing an electrospun fiber prepreg, comprising the steps of:
first, preparing an electrospun fiber
1.1 Preparing an electrostatic spinning solution.
At room temperature, adding 1-10 parts by weight of polymer material into 10-100 parts by weight of organic solvent, and stirring until the polymer material is completely dissolved to obtain uniform and stable spinning solution.
1.2 Preparing the electrostatic spinning fiber by adopting an electrostatic spinning process.
And (3) placing the spinning solution obtained in the step (I) into an injector of an electrostatic spinning machine at room temperature, setting processing parameters of the electrostatic spinning machine, and obtaining the single-layer electrostatic spinning fiber with the thickness of 0.2-1.5 mm after spinning.
And secondly, preparing the fiber prepreg by using a solvent method.
2.1 Firstly, mixing 5-10 parts by weight of resin, 1-2 parts by weight of accelerator and 1-2 parts by weight of curing agent, preparing into an impregnated resin matrix at the temperature of 10-25 ℃ to obtain a resin mixed solution, and injecting the resin mixed solution into a glue groove.
2.2 Immersing the electrospun fiber obtained in the step one into a resin mixed solution to prepare the fiber prepreg containing the electrospun fiber. The method comprises the following steps: firstly, unreeling the fiber obtained in the first step to obtain a tiled structure, and placing the tiled structure in a glue tank into which a resin solution is injected in the second step for glue dipping, wherein the smoothness of the fiber and the stability of the wetting rate are maintained in the glue dipping process. And then placing the PE film into a hot air type prepreg machine to remove redundant solvents, and carrying out traction and winding after covering the PE film up and down through a cooling and traction device, so that the phenomenon of mutual adhesion among prepreg fibers can be avoided. Finally obtaining the fiber prepreg containing the electrostatic spinning, wherein the thickness of the prepreg is in the range of 0.5mm-1.5mm.
3.2 The porosity of the electrospun fibrous prepregs can be tested, and the flow and wettability of the resin during the prepreg preparation can be observed.
Further, in the step 1.1), the organic solvent is any one of N-N dimethylformamide, phenol, toluene, sulfuric acid, ethanol or methanol; the polymer is any one of Polyacrylonitrile (PAN), polyurethane (PU), polyaniline (PANi), polyvinylpyrrolidone (PVP), polymethyl methacrylate (PMMA) and the like.
Further, in the step 1.2), the processing parameters are specifically: the inner diameter of the stainless steel needle head of the injector is 0.4mm-1.6mm; the distance from the needle head to the collector is 10-20cm; the electrostatic field voltage is-10 kV-20kV, the pushing speed of the spinning solution is 1-5mL/h, the receiving mode is roller receiving, and the rotating speed of the roller is 300-800rpm. The post-treatment process comprises the following steps: and drying the prepared fiber in a vacuum drying oven to remove redundant organic solvents, wherein the temperature is 60-80 ℃, the heat preservation time is 10-12h, and the vacuum pressure is-0.5 MPa.
Further, in the step 2.1), the resin is any one of epoxy resin including E-51, E-44, E-42, E-20, E-12, etc., cyanate resin, polyurethane resin, phenolic resin, polyimide resin and bismaleimide resin; any one of the accelerator diuron, diuron and TDI urea or a mixture thereof according to any proportion; any one of dicyandiamide micropowder, T31, polyamide, ethylenediamine and the like.
The beneficial effects of the invention are as follows: in the invention, the electrostatic spinning fiber consists of a plurality of staggered and connected fibers, which is beneficial to the uniform impregnation of a resin matrix and the reduction of impurities such as bubbles in the preparation process of the prepreg; the fiber prepreg containing the electrostatic spinning can improve the performance of the resin, strengthen the interface characteristic between the fiber and the resin, realize the reinforcement of the composite material on the nanometer scale, and can be used as the prepreg of the composite material for structures or functions such as layering autoclave molding, compression molding, vacuum bag non-autoclave (OOA) molding and the like; has excellent physical and mechanical properties in complex environment, and greatly enhances the application of the fiber composite material. The invention adopts the solvothermal method to prepare the prepreg, has small environmental pollution and high production efficiency of products.
Drawings
FIG. 1 is a scan of PAN-based electrospun fibers prepared according to example 1 of the present invention;
FIG. 2 is a drawing showing the formation of electrospun fibers prepared in example 1 of the present invention.
Detailed Description
The invention will be further illustrated by the following examples, which are given solely for the purpose of illustration and are not to be construed as limiting the invention in any way.
Example 1:
(1) Preparing an electrostatic spinning solution: to 10 parts of N-N Dimethylformamide (DMF) was added 1 part of Polyacrylonitrile (PAN) as a polymer material and stirred until completely dissolved, resulting in a uniform, stable spinning solution.
(2) An electrostatic spinning process is set: the inner diameter of the stainless steel needle head is 0.4mm, and the distance from the needle head to the collector is 20cm; the electrostatic field voltage is-10 kV-20kV, the pushing speed is 1mL/h, the receiving mode is roller receiving, and the roller rotating speed is 300rpm.
(3) The prepared fiber was dried in a vacuum oven. The temperature is 60 ℃, the heat preservation time is 12 hours, the vacuum pressure is-0.5 MPa, and the thickness of the fiber is 0.2mm.
(4) Preparing a solvent impregnating resin solution: firstly, 5 parts of E51 epoxy resin, 1 part of diuron and 1 part of T31 curing agent are mixed, and are prepared into an impregnated resin matrix in a glue tank at the temperature of 10 ℃ to obtain a resin mixed solution.
(5) And (3) placing the 0.2mm electrostatic spinning fibers prepared in the step (3) on an unreeling device for tiling, controlling the tension of the fibers by adopting a tension controller, enabling the fibers to enter the glue groove in the step (4) at a uniform speed for infiltration, reasonably combining under reasonable pressure, tension and speed, and obtaining the prepreg, wherein a layer of isolating paper is paved on the lower layer of the prepreg for preventing resin from dripping.
(6) And then the prepreg obtained in the step 5 is placed into a hot air type prepreg machine to remove the solvent, and after being covered with PE films up and down by a cooling and traction device, the prepreg is drawn and rolled to obtain the film-added prepreg, so that the phenomenon of mutual adhesion among prepreg fibers is avoided, and the thickness of the prepreg is 0.5mm.
(7) The fiber prepreg containing the electrostatic spinning was tested for porosity of less than 1.0%, and resin flow and wettability during the preparation of the prepreg were observed. The method has the advantages of smaller porosity, small bubble generation amount, stronger wettability in the process of fusing resin and fiber, smaller performance thickness of the prepreg and larger promotion space for application of the composite material.
Example 2:
(1) Preparing an electrostatic spinning solution: 10 parts of polyvinylpyrrolidone (PVP) as a polymer material was added to 100 parts of ethanol solution and stirred until completely dissolved, to obtain a uniform and stable spinning solution.
(2) An electrostatic spinning process is set: the inner diameter of the stainless steel needle head is 1.6mm, and the distance from the needle head to the collector is 10cm; the electrostatic field voltage is-1 kV-18kV, the pushing speed is 5mL/h, the receiving mode is roller receiving, and the roller rotating speed is 800rpm.
(3) And drying the prepared fiber in a vacuum drying oven after spinning is finished, wherein the temperature is 80 ℃, the heat preservation time is 8 hours, the vacuum pressure is-0.5 MPa, and the thickness of the fiber is 1.5mm.
(4) Preparing a solvent impregnating resin solution: firstly, 10 parts of E12 epoxy resin, 2 parts of diuron accelerator and 2 parts of ethylenediamine curing agent are mixed, and a resin matrix is prepared to be impregnated in a glue tank at the temperature of 10 ℃ to obtain a resin mixed solution.
(5) Placing the 1.5mm electrostatic spinning fiber prepared in the step 3 on an unreeling device for tiling, controlling the tension of the fiber yarn by adopting a tension controller, enabling the fiber to enter the glue groove in the step 4 at a uniform speed for infiltration, reasonably combining under reasonable pressure, tension and speed to obtain the prepreg, and paving a layer of isolating paper on the lower layer of the prepreg for preventing resin from dripping.
(8) And then the prepreg obtained in the step 5 is placed into a hot air type prepreg machine to remove the solvent, and after being covered with PE films up and down by a cooling and traction device, the prepreg is drawn and rolled to obtain the film-added prepreg, so that the phenomenon of mutual adhesion among prepreg fibers is avoided, and the thickness of the prepreg is 1.5mm.
(6) The porosity of the fiber prepreg containing the electrostatic spinning is lower than 1.1%, larger holes basically do not exist after the preparation is finished, and the flow and wettability of the resin in the preparation process of the prepreg are obviously improved. The lower thickness is also beneficial to further preparation and application of the fiber composite material containing electrostatic spinning.
Example 3:
(1) Preparing an electrostatic spinning solution: to 50 parts of phenol, 2 parts of Polyurethane (PU) as a polymer material was added and stirred until completely dissolved, to obtain a uniform and stable spinning solution.
(2) In the electrostatic spinning process, the inner diameter of a stainless steel needle is 1.45mm, and the distance from the needle to a collector is 15cm; the electrostatic field voltage is-1 kV-15kV, the pushing speed is 2.5mL/h, the receiving mode is roller receiving, and the roller rotating speed is 500rpm.
(3) The prepared fiber is dried in a vacuum drying oven at the temperature of 70 ℃ for 10 hours under the vacuum pressure of-0.5 MPa, and the thickness of the fiber is 1mm.
(4) Preparing a solvent impregnating resin solution: firstly, 10 parts of phenolic resin, 2 parts of a diuron accelerant and 2 parts of a polyamide curing agent are mixed, and are prepared into an impregnated resin matrix in a glue tank at the temperature of 15 ℃ to obtain a resin mixed solution.
(5) Placing the 1mm electrostatic spinning fiber prepared in the step 3 on an unreeling device for tiling, controlling the tension of the fiber yarn by adopting a tension controller, enabling the fiber to enter the glue groove in the step 4 at a uniform speed for infiltration, reasonably combining under reasonable pressure, tension and speed, and obtaining the prepreg, wherein a layer of isolating paper is paved on the lower layer of the prepreg for preventing resin from dripping.
(6) And (3) putting the prepreg obtained in the step (5) into a hot air type prepreg machine to remove the solvent, and carrying out cooling and traction on the prepreg by a traction device, wherein PE films are covered up and down, and then, the prepreg with the film is obtained through traction and rolling, so that the phenomenon of mutual adhesion among prepreg fibers is avoided, and the thickness of the prepreg is 0.6mm.
(7) The porosity of the fiber prepreg containing the electrostatic spinning is lower than 0.8%, the flowing permeability of the resin in the preparation process of the prepreg is obviously improved compared with the traditional method, and the thickness thinning effect is obvious.
Comparative example 1:
(1) Melting hot-melt epoxy resin at 80 ℃ and uniformly mixing the hot-melt epoxy resin with 2 mass percent of T31 curing agent;
(2) Casting the mixed solution in the step 1 into a film machine to prepare a film; the rubber roll degree of the rubber film machine is 70-110 ℃.
(3) Uniformly mixing the adhesive film in the step 3 and the reinforcing material conventional carbon fiber, and continuously carrying out hot pressing infiltration to obtain the wave-absorbing prepreg, wherein the hot pressing infiltration temperature is 80 ℃ and the pressure is 10kg/cm 2 . But the reinforcing material carbon fiber in the preparation process of the prepregThe distribution of the dimensions was not uniform, more bubbles were generated during the prepreg period, and the thickness of the prepreg was large (about 2-3 mm).
Comparative example 2:
(1) Carrying out hot melting on epoxy resin at 100 ℃, and adding three-dimensional graphene to prepare a mixture, wherein the volume of the added three-dimensional graphene is 3% of the volume of the epoxy resin; setting the rubber roll degree to 100 ℃ in a rubber film machine, and preparing the mixture into a rubber film; continuously hot-pressing and impregnating quartz fiber cloth and adhesive film on an impregnating machine to prepare wave-absorbing prepreg, wherein the thickness of the quartz fiber cloth is 0.1mm, and the impregnating temperature of the impregnating machine is 11 ℃ and the pressure is 10kg/cm 2 。
(2) And paving 30 layers of prepared prepreg layer by layer, and curing and forming by a vacuum bag under the conditions of the pressure of 0.1Mpa and the curing temperature of 15 ℃ for 2 hours to prepare the wave-absorbing composite material. After the temperature is reduced to room temperature, the wave-absorbing composite material is cut into 300mm specifications, and the reflectivity is measured in a wave-absorbing darkroom by adopting a bow-frame method, so that the reflectivity is-23 dB at 17-1 GHz. The mixing of quartz fiber and epoxy resin belongs to mechanical mixing, and the phenomenon of uneven mixing and powder precipitation is unavoidable.
Analysis of results of comparative example 1 and example 1: the fibers prepared by electrostatic spinning are in a net structure and are mutually interweaved and connected, and the flow property of the resin is obviously improved in the process of impregnating the resin. In the process of preparing the prepreg by using the solvent method, the generation of bubbles can be reduced, the porosity is reduced, and the resin and the fiber are tightly combined, so that the composite material shows smaller thickness under the same condition.
Analysis of results of comparative example 2 and example 3: compared with artificial mechanical mixing, the electrostatic spinning can realize uniform distribution of the reinforcing fibers, and simultaneously realize construction of a three-dimensional reticular structure of the reinforcing fibers, thereby being beneficial to uniform flowing and soaking of resin. The problems of powder precipitation and the like are reduced, and simultaneously, the mesh fibers of the electrostatic spinning are connected, so that the resin flow is enhanced, and the use amount of the resin can be reduced, thereby being beneficial to thinning the composite material.
The examples described above represent only embodiments of the invention and are not to be understood as limiting the scope of the patent of the invention, it being pointed out that several variants and modifications may be made by those skilled in the art without departing from the concept of the invention, which fall within the scope of protection of the invention.
Claims (7)
1. The electrostatic spinning fiber prepreg is characterized in that electrostatic spinning fibers are introduced on the basis of the traditional prepreg, so that resin can uniformly soak reinforcing fibers, the fibers can be distributed in the resin more uniformly, the generation of bubbles in the preparation process of the prepreg is reduced, and the thickness of the prepreg is reduced.
2. A method of preparing an electrospun fibrous prepreg according to claim 1, comprising the steps of:
first, preparing an electrospun fiber
1.1 Preparing an electrostatic spinning solution;
adding 1-10 parts by weight of polymer material into 10-100 parts by weight of organic solvent at room temperature, and stirring until the polymer material is completely dissolved to obtain uniform and stable spinning solution;
1.2 Preparing electrostatic spinning fiber by adopting an electrostatic spinning process;
placing the spinning solution obtained in the first step into an injector of an electrostatic spinning machine at room temperature, setting processing parameters of the electrostatic spinning machine, and obtaining a single-layer electrostatic spinning fiber with the thickness of 0.2mm-1.5mm after spinning;
secondly, preparing a fiber prepreg by using a solvent method;
2.1 Firstly, mixing 5-10 parts by weight of resin, 1-2 parts by weight of accelerator and 1-2 parts by weight of curing agent, preparing into an impregnated resin matrix at the temperature of 10-25 ℃ to obtain a resin mixed solution, and injecting the resin mixed solution into a glue tank;
2.2 Immersing the electrospun fiber obtained in the first step into a resin mixed solution to prepare the fiber prepreg containing the electrospun fiber.
3. The method for preparing an electrospun fiber prepreg according to claim 2, wherein in the step 1.1), the organic solvent is any one of N-N dimethylformamide, phenol, toluene, sulfuric acid, ethanol or methanol.
4. The method for preparing an electrospun fiber prepreg according to claim 2, wherein in the step 1.1), the polymer is any one of polyacrylonitrile PAN, polyurethane PU, polyaniline PANi, polyvinylpyrrolidone PVP, polymethyl methacrylate PMMA.
5. The method for preparing an electrospun fiber prepreg according to claim 2, wherein in the step 1.2), the processing parameters are specifically: the inner diameter of the stainless steel needle head of the injector is 0.4mm-1.6mm; the distance from the needle head to the collector is 10-20cm; the electrostatic field voltage is-10 kV-20kV, the pushing speed of the spinning solution is 1-5mL/h, the receiving mode is roller receiving, and the rotating speed of the roller is 300-800rpm; the post-treatment process comprises the following steps: and drying the prepared fiber in a vacuum drying oven to remove redundant organic solvents, wherein the temperature is 60-80 ℃, the heat preservation time is 10-12h, and the vacuum pressure is-0.5 MPa.
6. The method for preparing an electrospun fiber prepreg according to claim 2, wherein in the step 2.1), the resin is any one of epoxy resin including E-51, E-44, E-42, E-20, E-12, cyanate resin, polyurethane resin, phenolic resin, polyimide resin and bismaleimide resin; any one of the accelerator diuron, diuron and TDI urea or a mixture thereof according to any proportion; any one of dicyandiamide micropowder, T31, polyamide, ethylenediamine and the like.
7. The method for preparing an electrospun fiber prepreg according to claim 2, wherein the step 2.2) comprises the following steps: firstly, unreeling the fiber obtained in the first step to obtain a tiled structure, and placing the tiled structure in a glue tank injected with a resin solution in the second step for glue dipping, wherein the smoothness of the fiber and the stability of the wetting rate are maintained in the glue dipping process; then, placing the mixture into a hot air type prepreg machine to remove redundant solvents, and carrying out traction and winding after covering PE films up and down through a cooling and traction device to avoid the phenomenon of mutual adhesion among prepreg fibers; finally, the fiber prepreg containing the electrostatic spinning is obtained, and the thickness of the prepreg ranges from 0.5mm to 1.5mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310507433.5A CN116656091A (en) | 2023-05-08 | 2023-05-08 | Electrostatic spinning fiber prepreg and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310507433.5A CN116656091A (en) | 2023-05-08 | 2023-05-08 | Electrostatic spinning fiber prepreg and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116656091A true CN116656091A (en) | 2023-08-29 |
Family
ID=87725129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310507433.5A Pending CN116656091A (en) | 2023-05-08 | 2023-05-08 | Electrostatic spinning fiber prepreg and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116656091A (en) |
-
2023
- 2023-05-08 CN CN202310507433.5A patent/CN116656091A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2799470B1 (en) | Carbon fiber base, prepreg, and carbon-fiber-reinforced composite material | |
| CN102099403B (en) | Method for the preparation of a reinforced thermoset polymer composite | |
| CN106671525B (en) | The highly conductive and high Reinforced structure composite material and preparation method of hybrid modification | |
| CN103554530A (en) | Electric conductive continuous fiber-reinforced fabric or prepreg and electric conductive treatment method | |
| CN109206905B (en) | Graphene bismaleimide resin composite material and preparation method thereof | |
| CN107323025A (en) | Vertical orientated composite of a kind of interlayer high heat conduction fine hair and preparation method thereof | |
| WO2011064707A3 (en) | Fiber reinforced polymeric composites with tailorable electrical resistivities and process for preparing the same | |
| CN102514206A (en) | Production method of phenol formaldehyde epoxy vinyl ester resin/carbon fiber composite material | |
| CN107856325A (en) | One kind is used for continuous fiber reinforced thermoplastic matrix composite and preparation method | |
| CN105802136A (en) | Preparation method of three-dimensional fabric enhanced porous composite material | |
| CN108081691B (en) | Aramid short fiber reinforced carbon fiber prepreg, preparation method and application | |
| CN109651635B (en) | Preparation method of recycled carbon fiber prepreg | |
| CN116656091A (en) | Electrostatic spinning fiber prepreg and preparation method thereof | |
| CN108384188A (en) | A kind of prepreg and its application based on engineering plastics non-woven cloth | |
| CN111890771A (en) | Damping intercalation and continuous fiber reinforced composite material with strong interface and wide temperature range | |
| CN111004407A (en) | Prepreg and preparation method thereof | |
| CN112176499A (en) | Three-dimensional fabric reinforcement, preparation method thereof and polymer-based composite material | |
| CN113650388B (en) | Z-direction high-heat-conductivity epoxy resin-based continuous fiber reinforced composite material laminated board | |
| CN115195215A (en) | Interlaminar toughening method for composite material laminated plate | |
| CN111037781B (en) | Wave-absorbing prepreg and preparation method thereof | |
| CN110997290A (en) | Fiber fabric reinforced composite material and preparation method thereof | |
| CN113652073A (en) | Continuous carbon fiber reinforced poly (arylene ether nitrile) composite prepreg tape and preparation method thereof | |
| CN115366492B (en) | Conductive high-temperature-resistant polyimide composite adhesive film and preparation method thereof | |
| CN115195216B (en) | Zinc oxide nanowire-loaded electrostatic spinning membrane interlayer reinforced and toughened continuous fiber reinforced resin matrix composite material and preparation method thereof | |
| CN110272587A (en) | A kind of cold-resistant High-temperature-resflamet flamet retardant composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |