CN114874605A - Continuous carbon fiber reinforced thermosetting resin prepreg filament and preparation method and application thereof - Google Patents
Continuous carbon fiber reinforced thermosetting resin prepreg filament and preparation method and application thereof Download PDFInfo
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- CN114874605A CN114874605A CN202210496924.XA CN202210496924A CN114874605A CN 114874605 A CN114874605 A CN 114874605A CN 202210496924 A CN202210496924 A CN 202210496924A CN 114874605 A CN114874605 A CN 114874605A
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 159
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 159
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 229920005989 resin Polymers 0.000 title claims abstract description 107
- 239000011347 resin Substances 0.000 title claims abstract description 107
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910021389 graphene Inorganic materials 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 14
- 238000010146 3D printing Methods 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 239000003822 epoxy resin Substances 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 9
- 238000004513 sizing Methods 0.000 claims description 7
- 229920001971 elastomer Polymers 0.000 claims description 6
- 239000007767 bonding agent Substances 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 3
- 229920006311 Urethane elastomer Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 24
- 241001391944 Commicarpus scandens Species 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 239000003733 fiber-reinforced composite Substances 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 20
- 238000005470 impregnation Methods 0.000 description 12
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 5
- 229920003225 polyurethane elastomer Polymers 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 3
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- 239000000243 solution Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
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- 239000011208 reinforced composite material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 238000005491 wire drawing Methods 0.000 description 1
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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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- 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
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2463/02—Polyglycidyl ethers of bis-phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
Abstract
The invention provides a continuous carbon fiber reinforced thermosetting resin prepreg yarn and a preparation method and application thereof, belonging to the technical field of fiber reinforced composite materials. According to the invention, the carbon fiber bundle is wrapped by the thermoplastic rubber to increase the toughness of the carbon fiber, and simultaneously a small amount of thermoplastic rubber is impregnated into the fiber bundle to realize effective bonding among fiber filaments, so that the fiber bundle is prevented from being broken in the use process, and the problems that the surface of the carbon fiber is brittle and easy to break and is difficult to impregnate and draw wires are effectively solved. The results of the examples show that the prepreg filaments provided by the invention are not easy to break, and have thermal conductivity of 40.594 w/m.K and good thermal conductivity.
Description
Technical Field
The invention relates to the technical field of fiber reinforced composite materials, in particular to a continuous carbon fiber reinforced thermosetting resin prepreg filament and a preparation method and application thereof.
Background
The fiber or fabric is usually soaked in a molten matrix with certain viscosity, and then is cooled, dried and taken up to finally prepare the composite material prepreg filament, which has high strength and light weight and can be widely applied to the fields of aerospace, military materials, sports equipment and the like. At present, common fibers are thermoplastic materials such as glass fibers, but for high-temperature places or 3D printing application fields requiring rapid heat transfer, the materials are required to have good heat resistance and thermal conductivity, and the low-melting-point characteristic of the thermoplastic materials limits the application of the thermoplastic materials in high-temperature environments.
In the existing fibers, the pitch-based carbon fibers have good thermal conductivity, the thermal conductivity coefficient can reach more than 800 w/m.K, even exceeds 1000 w/m.K, is much higher than that of metal aluminum and metal copper, and can meet the requirements of high-temperature environments. However, the pitch-based carbon fiber shows high thermal conductivity due to high carbonization and also causes high brittleness, so that the pitch-based carbon fiber is very easy to break in the prepreg filament preparation process and the 3D printing forming process, which increases the difficulty of material preparation and forming, and is also a major technical bottleneck that the pitch-based carbon fiber cannot be used for 3D printing forming at present.
Therefore, a prepreg filament of pitch-based carbon fiber reinforced composite material that can be used for 3D printing molding is needed.
Disclosure of Invention
The invention aims to provide a continuous carbon fiber reinforced thermosetting resin prepreg filament and a preparation method and application thereof. The carbon fiber reinforced thermosetting resin prepreg silk provided by the invention can be used for 3D printing and has good heat-conducting property.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a continuous carbon fiber reinforced thermosetting resin prepreg yarn, which comprises a carbon fiber bundle, thermoplastic rubber and thermosetting resin which are sequentially arranged from inside to outside;
the carbon fiber bundle is formed by bonding carbon fibers through a bonding agent;
the thermoplastic rubber is wrapped outside the carbon fiber bundles and is impregnated inside the carbon fiber bundles;
the thermosetting resin is wrapped outside the thermoplastic rubber.
Preferably, the volume fraction of the carbon fiber bundles in the continuous carbon fiber reinforced thermosetting resin prepreg filaments is 1-50%.
Preferably, the volume fraction of the thermoplastic rubber in the continuous carbon fiber reinforced thermosetting resin prepreg filaments is 20-70%.
Preferably, the thermoplastic rubber comprises a polyurethane rubber, a polyolefin elastomer or a polyester rubber.
Preferably, the thermosetting resin comprises a resin matrix, a curing agent and graphene.
Preferably, the resin matrix comprises an epoxy resin, a phenolic resin, an unsaturated polyester resin or a polyimide.
Preferably, the mass ratio of the resin matrix to the curing agent to the graphene is 100: (1-15): (0.1 to 1).
Preferably, the volume fraction of the thermosetting resin in the continuous carbon fiber reinforced thermosetting resin prepreg filaments is 10-40%.
The invention provides a preparation method of the continuous carbon fiber reinforced thermosetting resin prepreg yarn in the technical scheme, which comprises the following steps:
(1) sizing the carbon fiber yarns by using a binder to obtain carbon fiber bundles;
(2) impregnating the carbon fiber bundles obtained in the step (1) into molten thermoplastic rubber, and drying to obtain carbon fiber bundles wrapped by the thermoplastic rubber;
(3) and (3) impregnating the thermoplastic rubber-coated carbon fiber bundles obtained in the step (2) into molten thermosetting resin to obtain continuous carbon fiber reinforced thermosetting resin prepreg filaments.
The invention also provides the application of the continuous carbon fiber reinforced thermosetting resin prepreg filament in the technical scheme or the continuous carbon fiber reinforced thermosetting resin prepreg filament prepared by the preparation method in the technical scheme in 3D printing.
The invention provides a continuous carbon fiber reinforced thermosetting resin prepreg yarn, which comprises a carbon fiber bundle, thermoplastic rubber and thermosetting resin which are sequentially arranged from inside to outside; the carbon fiber bundle is formed by bonding carbon fibers through a bonding agent; the thermoplastic rubber is wrapped outside the carbon fiber bundles and is impregnated inside the carbon fiber bundles; the thermosetting resin is wrapped outside the thermoplastic rubber. According to the invention, the fiber bundles are carded and bundled by adopting the binder to obtain the gathered and undispersed carbon fiber bundles, then the carbon fiber bundles are wrapped by the thermoplastic rubber to increase the toughness of the carbon fibers, and simultaneously a small amount of thermoplastic rubber is impregnated into the fiber bundles to realize effective bonding among the fibers, so that the fiber bundles are prevented from being broken in the use process, the problems that the surfaces of the carbon fibers are brittle and easy to break and difficult to impregnate and draw the fibers are effectively solved, and finally the thermosetting resin is wrapped to improve the high temperature resistance of the prepreg fibers. The results of the examples show that the prepreg filaments provided by the invention are not easy to break, can be used for 3D printing, have thermal conductivity of 40.594 w/m.K and have good thermal conductivity.
Drawings
FIG. 1 is a schematic view of the flow of the preparation method and the structure of a continuous carbon fiber reinforced thermosetting resin prepreg filament according to example 1 of the present invention;
FIG. 2 is a schematic view of an apparatus in step (1) in example 1 of the present invention;
FIG. 3 is a schematic view of an apparatus in step (2) in example 1 of the present invention;
FIG. 4 is a schematic view of an apparatus in step (3) in example 1 of the present invention;
FIG. 5 is a macroscopic view of a continuous carbon fiber reinforced thermosetting resin prepreg filament according to example 1 of the present invention;
fig. 6 is an SEM image of continuous carbon fiber reinforced thermosetting resin prepreg filaments according to example 1 of the present invention.
Detailed Description
The invention provides a continuous carbon fiber reinforced thermosetting resin prepreg yarn, which comprises a carbon fiber bundle, thermoplastic rubber and thermosetting resin which are sequentially arranged from inside to outside;
the carbon fiber bundle is formed by bonding carbon fibers through a bonding agent;
the thermoplastic rubber is wrapped outside the carbon fiber bundles and is impregnated inside the carbon fiber bundles;
the thermosetting resin is wrapped outside the thermoplastic rubber.
The continuous carbon fiber reinforced thermosetting resin prepreg filament provided by the invention comprises carbon fiber bundles.
In the invention, the carbon fiber bundle is formed by bonding carbon fibers through a bonding agent.
In the present invention, the carbon fiber is preferably a continuous pitch-based carbon fiber. In the present invention, the pitch-based carbon fiber has good thermal conductivity.
In the present invention, the binder preferably includes a polyvinyl alcohol emulsion, an acrylic emulsion, or an aqueous polyurethane. In the invention, the binder is used for carding and bundling the carbon fiber yarns to obtain the gathered and undispersed carbon fiber bundles.
In the invention, the volume ratio of the binder to the carbon fiber bundles in the carbon fiber bundles is preferably (1-5): 100, more preferably (1-3): 100. the present invention can reduce the number of voids in the carbon fiber bundle by limiting the volume ratio of the binder to the carbon fiber bundle to the above range.
In the invention, the volume fraction of the carbon fiber bundles in the continuous carbon fiber reinforced thermosetting resin prepreg filaments is preferably 1-50%, more preferably 5-40%, and most preferably 6-15%. According to the invention, the volume fraction of the carbon fiber bundles in the continuous carbon fiber reinforced thermosetting resin prepreg filaments is limited within the range, so that the prepreg filaments have high heat conductivity.
The continuous carbon fiber reinforced thermosetting resin prepreg filament provided by the invention also comprises thermoplastic rubber.
In the present invention, the thermoplastic rubber is wrapped around the carbon fiber bundle and impregnated into the carbon fiber bundle.
In the present invention, the thermoplastic rubber preferably includes urethane rubber, polyolefin elastomer, or polyester rubber. In the invention, the thermoplastic rubber can increase the toughness of the carbon fiber, and simultaneously a small amount of thermoplastic rubber is impregnated into the fiber bundle to realize effective bonding among the fiber yarns, thereby avoiding the fiber bundle from being broken in the use process, and effectively solving the problems that the surface of the carbon fiber is brittle and easy to break and is difficult to impregnate and draw wires.
In the invention, the volume fraction of the thermoplastic rubber in the continuous carbon fiber reinforced thermosetting resin prepreg filament is preferably 20-70%, more preferably 30-70%, and most preferably 50-70%. According to the invention, the volume fraction of the thermoplastic rubber in the continuous carbon fiber reinforced thermosetting resin prepreg filaments is limited within the range, so that the toughness of the carbon fibers can be further increased, and the occurrence of fracture can be avoided.
The continuous carbon fiber reinforced thermosetting resin prepreg filament provided by the invention also comprises thermosetting resin.
In the present invention, the thermosetting resin is wrapped around the outside of the thermoplastic rubber.
In the present invention, the thermosetting resin preferably includes a resin matrix, a curing agent, and graphene. According to the invention, the thermosetting resin is wrapped on the outermost surface of the prepreg filaments, so that the high-temperature resistance of the prepreg filaments can be improved, and the thermal conductivity of graphene can be further improved.
In the present invention, the resin matrix preferably includes an epoxy resin, a phenol resin, an unsaturated polyester resin, or a polyimide, and more preferably an epoxy resin.
In the present invention, the curing agent preferably includes a dicyandiamide curing agent or a 2,4, 6-tris (dimethylaminomethyl) phenol DMP-30 curing agent. The present invention limits the kinds of the resin matrix and the curing agent within the above range, enabling the resin matrix to have a faster curing rate.
In the present invention, the mass ratio of the resin matrix, the curing agent, and the graphene is preferably 100: (1-15): (0.1 to 1), more preferably 100: (3-12): (0.2 to 0.8), most preferably 100: (4-10): (0.4-0.6). According to the invention, the mass ratio of the resin matrix to the curing agent to the graphene is limited within the range, so that the thermosetting resin has appropriate curing time and fluidity, and the impregnation effect and the 3D printing performance of the prepreg silks are improved.
In the invention, the volume fraction of the thermosetting resin in the continuous carbon fiber reinforced thermosetting resin prepreg filament is preferably 10-40%, more preferably 20-40%, and most preferably 30-40%. According to the invention, the volume fraction of the thermosetting resin in the continuous carbon fiber reinforced thermosetting resin prepreg filaments is limited within the range, so that the heat conduction performance and the high temperature resistance of the prepreg filaments can be further improved.
According to the invention, the fiber bundles are carded and bundled by adopting the binder to obtain the gathered and undispersed carbon fiber bundles, then the carbon fiber bundles are wrapped by the thermoplastic rubber to increase the toughness of the carbon fibers, and meanwhile, a small amount of thermoplastic rubber is impregnated into the fiber bundles to realize effective bonding among the fibers, so that the fiber bundles are prevented from being broken in the using process, the problems that the surfaces of the carbon fibers are fragile and easy to break and the carbon fibers are difficult to impregnate and draw wires are effectively solved, and finally the thermosetting resin is wrapped to improve the high temperature resistance of the prepreg filaments, control the composition and the dosage of each component and the like, and further improve the heat conduction performance and the 3D printing performance of the prepreg filaments.
The invention provides a preparation method of the continuous carbon fiber reinforced thermosetting resin prepreg yarn in the technical scheme, which comprises the following steps:
(1) sizing the carbon fiber yarns by using a binder to obtain carbon fiber bundles;
(2) impregnating the carbon fiber bundles obtained in the step (1) into molten thermoplastic rubber, and drying to obtain carbon fiber bundles wrapped by the thermoplastic rubber;
(3) and (3) impregnating the thermoplastic rubber-coated carbon fiber bundles obtained in the step (2) into molten thermosetting resin to obtain continuous carbon fiber reinforced thermosetting resin prepreg filaments.
In the present invention, the sources of the components are not particularly limited, unless otherwise specified, and commercially available products known to those skilled in the art may be used.
The carbon fiber bundle is obtained by sizing the carbon fiber yarns by using the binder.
The diameter of the carbon fiber filament is not particularly limited in the present invention, and a carbon fiber filament having a diameter well known to those skilled in the art may be used.
The operation of sizing is not particularly limited in the invention, and the sizing technical scheme known to those skilled in the art can be adopted.
In the present invention, the sizing apparatus is preferably as shown in fig. 2, and the carbon fiber yarn sequentially passes through a binder impregnation tank, a drying apparatus and a yarn collecting apparatus to obtain a carbon fiber bundle.
After obtaining the carbon fiber bundle, the invention soaks the carbon fiber bundle into the molten thermoplastic rubber and then dries the carbon fiber bundle to obtain the carbon fiber bundle wrapped by the thermoplastic rubber.
In the present invention, the temperature of the molten thermoplastic rubber is preferably 200 to 220 ℃, and more preferably 210 ℃.
In the invention, the time for soaking is preferably 5-20 s, and more preferably 8-16 s.
In the invention, the drying temperature is preferably 80-120 ℃, and more preferably 100 ℃.
In the present invention, the apparatus for obtaining the carbon fiber bundle wrapped with the thermoplastic rubber by drying the carbon fiber bundle after impregnating the carbon fiber bundle into the molten thermoplastic rubber is preferably, as shown in fig. 3, a carbon fiber bundle sequentially passes through a thermoplastic rubber impregnation tank and a filament collecting apparatus, wherein the impregnation tank and the filament collecting apparatus have a certain distance therebetween, and the molten thermoplastic rubber is sufficiently solidified.
After the carbon fiber bundles wrapped by the thermoplastic rubber are obtained, the carbon fiber bundles wrapped by the thermoplastic rubber are impregnated into the molten thermosetting resin to obtain the continuous carbon fiber reinforced thermosetting resin prepreg filaments.
In the present invention, the method for preparing the molten thermosetting resin is preferably: mixing the resin matrix, the curing agent and the graphene, and heating.
In the present invention, the temperature of the molten thermosetting resin is preferably 80 to 120 ℃, and more preferably 100 ℃.
In the invention, the time for soaking is preferably 1-10 s, and more preferably 5-8 s.
After the impregnation is finished, the impregnated product is preferably cured to obtain the continuous carbon fiber reinforced thermosetting resin prepreg filaments.
The operation of the curing is not particularly limited in the present invention, and a thermosetting resin curing method known to those skilled in the art may be used.
In the present invention, the apparatus for impregnating the thermoplastic rubber-wrapped carbon fiber bundles with the molten thermosetting resin to obtain the carbon fiber reinforced thermosetting resin prepreg filaments is preferably as shown in fig. 4, wherein the carbon fiber bundles sequentially pass through a thermosetting resin impregnation tank and a filament collecting apparatus, wherein the impregnation tank and the filament collecting apparatus have a certain distance therebetween, and the molten thermosetting resin is sufficiently cured.
The preparation method of the continuous carbon fiber reinforced thermosetting resin prepreg filament and the structure of the prepared prepreg filament are preferably shown in figure 1, the fiber filament is sized to obtain a fiber bundle, then thermoplastic rubber is adopted to toughen the fiber bundle, and then thermosetting resin is impregnated to obtain the continuous carbon fiber reinforced thermosetting resin prepreg filament, wherein 1 is asphalt-based fiber, 2 is a thermoplastic rubber toughening layer, and 3 is a thermosetting resin reinforcing layer.
The invention also provides the application of the continuous carbon fiber reinforced thermosetting resin prepreg filament in the technical scheme or the continuous carbon fiber reinforced thermosetting resin prepreg filament prepared by the preparation method in the technical scheme in 3D printing.
The operation of the application of the continuous carbon fiber reinforced thermosetting resin prepreg filament in 3D printing is not particularly limited, and the technical scheme of the application of the continuous carbon fiber reinforced thermosetting resin prepreg filament in 3D printing, which is well known to those skilled in the art, can be adopted.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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 continuous carbon fiber reinforced thermosetting resin prepreg filament is composed of carbon fiber bundles, thermoplastic polyurethane rubber and thermosetting resin which are sequentially arranged from inside to outside; the carbon fiber bundle is formed by bonding continuous asphalt-based carbon fibers by a waterborne polyurethane adhesive; the thermoplastic polyurethane rubber is wrapped outside the carbon fiber bundles and is impregnated inside the carbon fiber bundles; the thermosetting resin is wrapped outside the thermoplastic rubber; the thermosetting resin consists of epoxy resin E-20, a dicyandiamide curing agent and graphene; wherein the volume fraction of the carbon fiber bundles in the carbon fiber reinforced prepreg filaments is 8.2 percent, the volume fraction of the thermoplastic polyurethane rubber is 61.2 percent, and the volume fraction of the thermosetting resin is 30.6 percent;
the preparation flow and the structure of the prepared prepreg silk are shown in figure 1, and the preparation method comprises the following steps: (1) adopting equipment shown in figure 2, passing 1 thousand continuous asphalt-based carbon fiber filaments (with monofilament diameter of 12 mu m) through an aqueous polyurethane impregnation tank (viscosity of 320mPa · S and solid content of 32%), drying by using a hot air gun in the wire drawing process, wherein the drying temperature is 220 ℃, and collecting by an active wire collecting device at the speed of 1.2r/min, wherein the diameter of the carbon fiber bundles after collection is 0.6mm, and the volume ratio of polyurethane to carbon fiber filaments in the carbon fiber bundles is 1.2: 100;
(2) the carbon fiber bundle obtained in step (1) was passed through a molten urethane rubber (hardness 95A, tensile strength 250 Kgf/cm) using an apparatus shown in FIG. 3 2 The melt index is 20g/10minS) soaking tank (the soaking time is 8s), wherein the temperature of the molten polyurethane rubber is 210 ℃, then the molten polyurethane rubber is collected by an active wire collecting device through a nozzle of the soaking tank with the diameter of 1.2mm at the speed of 1.2r/min, and then the molten polyurethane rubber is placed into an electrothermal blowing drying oven to be dried for 5min at the temperature of 100 ℃;
(3) mixing and adding epoxy resin E-20, a dicyandiamide curing agent and graphene into an impregnation tank according to the mass ratio of 100:4:0.5 by adopting equipment shown in figure 4, wherein the melting point of the dicyandiamide curing agent is 210 ℃, the granularity D50 of the graphene is 8um, and the sheet resistance is 5.6m omega cm, passing the fiber bundle containing the polyurethane rubber obtained in the step (2) through the impregnation tank, wherein the temperature of the impregnation tank is 100 ℃, the impregnation time is 5s, passing through a 1.5mm nozzle, and collecting by active filament collecting equipment at the speed of 1.2r/min to obtain the continuous carbon fiber reinforced thermosetting resin prepreg filament.
The prepreg filament of test example 1 has a thermal conductivity of 40.549 w/m.K, and has good thermal conductivity.
The macroscopic view of the prepreg filaments of example 1 is shown in fig. 5, and the SEM view of the prepreg filaments is shown in fig. 6.
Example 2
The mass ratio of the epoxy resin E-20, the dicyandiamide curing agent and the graphene in the step (3) of the example 1 is replaced by 100:5:0.5, and other parameters are the same as those in the example 1.
Example 3
The resin system in the step (3) of the example 1 is replaced by epoxy resin E-44, a DMP-30 curing agent (the viscosity is 80-200 mPa.s at 25 ℃) and graphene, the mass ratio of the epoxy resin E-44 to the DMP-30 curing agent to the graphene is 100:12:0.5, and other parameters are the same as those of the example 1.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (10)
1. A continuous carbon fiber reinforced thermosetting resin prepreg yarn comprises a carbon fiber bundle, thermoplastic rubber and thermosetting resin which are sequentially arranged from inside to outside;
the carbon fiber bundle is formed by bonding carbon fibers through a bonding agent;
the thermoplastic rubber is wrapped outside the carbon fiber bundles and is impregnated inside the carbon fiber bundles;
the thermosetting resin is wrapped outside the thermoplastic rubber.
2. The continuous carbon fiber reinforced thermosetting resin prepreg filament according to claim 1, wherein the volume fraction of the carbon fiber bundles in the continuous carbon fiber reinforced thermosetting resin prepreg filament is 1 to 50%.
3. The continuous carbon fiber reinforced thermosetting resin prepreg filament according to claim 1, wherein the volume fraction of the thermoplastic rubber in the continuous carbon fiber reinforced thermosetting resin prepreg filament is 20-70%.
4. The continuous carbon fiber reinforced thermosetting resin prepreg filament according to claim 1 or 3, wherein the thermoplastic rubber comprises a urethane rubber, a polyolefin elastomer, or a polyester rubber.
5. The continuous carbon fiber reinforced thermosetting resin prepreg filament of claim 1, wherein the thermosetting resin comprises a resin matrix, a curing agent, and graphene.
6. The continuous carbon fiber reinforced thermosetting resin prepreg filament of claim 5, wherein the resin matrix comprises an epoxy resin, a phenolic resin, an unsaturated polyester resin, or a polyimide.
7. The continuous carbon fiber reinforced thermosetting resin prepreg filament according to claim 5, wherein the mass ratio of the resin matrix, the curing agent and the graphene is 100: (1-15): (0.1 to 1).
8. The continuous carbon fiber reinforced thermosetting resin prepreg filament according to any one of claims 1 and 5 to 7, wherein the volume fraction of the thermosetting resin in the continuous carbon fiber reinforced thermosetting resin prepreg filament is 10 to 40%.
9. The method for preparing the continuous carbon fiber reinforced thermosetting resin prepreg filament according to any one of claims 1 to 8, comprising the steps of:
(1) sizing the carbon fiber yarns by using a binder to obtain carbon fiber bundles;
(2) impregnating the carbon fiber bundles obtained in the step (1) into molten thermoplastic rubber, and drying to obtain carbon fiber bundles wrapped by the thermoplastic rubber;
(3) and (3) impregnating the thermoplastic rubber-coated carbon fiber bundles obtained in the step (2) into molten thermosetting resin to obtain continuous carbon fiber reinforced thermosetting resin prepreg filaments.
10. Use of the continuous carbon fiber reinforced thermosetting resin prepreg filament according to any one of claims 1 to 8 or the continuous carbon fiber reinforced thermosetting resin prepreg filament prepared by the preparation method according to claim 9 in 3D printing.
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