CN111662535A - Resin for pultrusion carbon fiber composite material, preparation and use method - Google Patents
Resin for pultrusion carbon fiber composite material, preparation and use method Download PDFInfo
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- CN111662535A CN111662535A CN202010577989.8A CN202010577989A CN111662535A CN 111662535 A CN111662535 A CN 111662535A CN 202010577989 A CN202010577989 A CN 202010577989A CN 111662535 A CN111662535 A CN 111662535A
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- 239000003292 glue Substances 0.000 claims description 8
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- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 4
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- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 3
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- ITZGNPZZAICLKA-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylate Chemical compound C1C2OC2CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 ITZGNPZZAICLKA-UHFFFAOYSA-N 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
- B29C70/523—Pultrusion, i.e. forming and compressing by continuously pulling through a die and impregnating the reinforcement in the die
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
- B29C70/525—Component parts, details or accessories; Auxiliary operations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/009—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive fibres, e.g. metal fibres, carbon fibres, metallised textile fibres, electro-conductive mesh, woven, non-woven mat, fleece, cross-linked
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- 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
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- C08K2201/001—Conductive additives
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- 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
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a resin for pultrusion of a carbon fiber composite material, which comprises 30-60% of an epoxy resin system, 10-30% of an unsaturated resin system, 2-5% of a toughening agent, 3-5% of an internal release agent, 5-10% of an active diluent and 3-8% of chopped conductive fibers. The invention can be used for the requirements of low reaction viscosity, high activity and good strength of a resin system for meeting the process requirements in the pultrusion of the electromagnetic shielding carbon fiber composite material, and can supplement the defect of improving the electromagnetic performance of the material by reinforcing fiber by utilizing the fiber conductive reinforcing agent in the resin system. By preferably selecting the resin combination of the invention and combining with the pultrusion electromagnetic shielding carbon fiber plate, the effect of being more than 40dB under the shielding effectiveness of 150 KHz-18 GHz is realized. Meanwhile, due to the particularity of the fiber conductive reinforcing agent in the resin, the invention provides a pultrusion process method using the resin system.
Description
Technical Field
The invention relates to the field of electromagnetic shielding materials and the technical field of advanced composite materials, in particular to a resin for pultrusion of a carbon fiber composite material, and preparation and use methods thereof.
Background
With the increasingly stringent requirements for weight reduction of various protective equipment in the field of electromagnetic shielding, the application of new materials in various shielding products is gradually increased, but at present, light-weight metal alloy materials are researched more. Advanced composite materials represented by carbon fiber composite materials are influenced by electrical properties, and the development of the advanced composite materials in the field is limited. How to apply new materials with excellent mechanical properties and lower density to the field of weight reduction and electromagnetic protection has become a key point of attention. At present, the processing modes based on the reinforcement of the electromagnetic shielding capability of the carbon fiber composite material mainly comprise three types: the first is that the conductive performance of the composite material is increased by filling conductive particles, fibers and the like in the resin matrix of the composite material; secondly, the surface conductivity of the composite material is increased by means of chemical plating, electroplating, vapor deposition and the like; thirdly, conductive fibers, conductive metal nets, metal films and the like are used as composite material layers to enhance the conductivity between the inner layers of the composite material layers.
The pultrusion process is an important process method for manufacturing composite material products, and has the advantages of high production efficiency and good product continuity. The key to the realization of the pultrusion electromagnetic shielding carbon fiber composite product is how to combine the pultrusion process with the characteristics of the electromagnetic shielding composite material design. And the design of a resin system meeting the process design method is an important research direction for ensuring the pultrusion electromagnetic shielding carbon fiber composite product. At present, pultrusion resin used in the field of electromagnetic shielding is less researched, and the requirements of pultrusion technology on low viscosity, high activity, excellent performance and electromagnetic performance compensation of resin systems are not reported.
Chinese patent application CN 110951369A discloses a coating for electromagnetic shielding, a preparation method and a use method thereof. The shielding coating resin system is composed of an organic carrier composed of polyurethane resin, polyester resin phenolic resin, epoxy resin and the like, and conductive fillers composed of graphene and flaky silver-coated copper powder. The preferred embodiment of the system achieves a shielding effect of 60 dB.
The Chinese patent application CN 104448243A discloses a solvent-free high-temperature-resistant modified epoxy system pultrusion resin and a preparation method thereof. The pultrusion resin consists of epoxy resin, reactive diluent, curing agent and accelerator, and is suitable for manufacturing and producing carbon fiber and glass fiber reinforced pultrusion composite materials.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the resin for the pultrusion carbon fiber composite material, and the preparation and use methods thereof, wherein the resin is mainly used for electromagnetic shielding carbon fiber products of pultrusion processes, and can be extended to parts such as shielding cabins, shielding case skins, wall plates and the like to play the effects of weight reduction and electromagnetic shielding.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a resin for pultrusion carbon fiber composite materials is prepared from the following components in percentage by mass: 30-60% of epoxy resin system, 10-30% of unsaturated resin system, 2-5% of toughening agent, 3-5% of internal release agent, 5-10% of reactive diluent and 3-8% of chopped conductive fibers; the epoxy resin system comprises epoxy resin and a corresponding curing agent, and the unsaturated resin system comprises unsaturated resin and a corresponding curing agent. The viscosity of a resin system is adjusted through the unsaturated resin component, and the curing of the epoxy component is promoted by utilizing the characteristic of high activity of the unsaturated resin and the curing heat.
Further, the toughening agent is any one or combination of polyethylene glycol diglycidyl ether, carboxyl-terminated liquid nitrile rubber and polyurethane. The impact strength requirement of the product is met through the toughening agent.
Further, the reactive diluent is any one or combination of 1, 4-butyrolactone, butyl glycidyl ether and ethylene glycol diglycidyl ether. The viscosity requirement of the resin system is achieved through the reactive diluent.
Further, the short-cut conductive fiber is any one or combination of nickel-plated carbon fiber, stainless steel fiber, magnetic nano modified zinc oxide whisker and nickel-plated carbon nanotube. The space network formed by the cured conductive fibers in the resin plays roles in electromagnetic shielding and electrical property compensation, and can form a richer space conductive network with the continuous fibers in the carbon fiber pultrusion product.
Further, the chopped conductive fibers are conductive and magnetic conductive fibers with the length of less than 1 mm.
A method of preparing a resin for pultruded carbon fiber composites, comprising the steps of:
s1, sequentially adding the epoxy resin system, the unsaturated resin system and the internal release agent according to the mass percent, and dispersing for 5-10 min by using a high-speed stirrer to obtain a composite resin system;
s2, adding the toughening agent and the reactive diluent into the composite resin system in the S1 according to mass percent, and dispersing for 5min-10min by using a high-speed stirrer to prepare a low-viscosity composite resin system;
and S3, adding the chopped conductive fibers into the low-viscosity composite resin system in the S2 according to the mass percentage, and dispersing for 30min by using a high-speed stirrer to obtain the composite resin system, thereby obtaining the pultrusion electromagnetic shielding carbon fiber composite material resin.
A method for using resin for pultrusion of carbon fiber composite materials comprises the steps of placing the pultrusion carbon fiber composite material resin in a resin impregnation tank, introducing the impregnated resin into a preforming mold through a glue injection pipe by adopting a glue injection pump, and continuously reinforcing fibers.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a resin for pultrusion carbon fiber composite material, a preparation method and a use method, wherein an epoxy and unsaturated resin composite resin system is adopted, so that the viscosity and the reaction activity of the resin meet the requirements of process characteristics, the rapid curing is ensured, and the viscosity and the low permeability are good; the chopped conductive fibers are used as a conductive reinforcement, a space network formed by the conductive fibers in the cured resin plays roles in electromagnetic shielding and electrical property compensation, and a richer space conductive network can be formed with the continuous fibers in the carbon fiber pultrusion product. The preparation process is simple, the designed resin components are uniformly mixed, the chopped conductive fibers are added, and the mixture is stirred by a high-speed stirrer, so that the preparation method is suitable for large-batch preparation and production. The use method of the pultrusion electromagnetic shielding carbon fiber composite resin provided by the invention avoids the filtering effect of surface felts and surface cloth of pultrusion products on chopped fiber reinforcements in a resin system, and can realize that the conductive reinforcements are dispersed in the material instead of being concentrated on the surface.
Drawings
FIG. 1 is a schematic representation of the method of use of the pultruded carbon fiber composite resin prepared in accordance with the present invention.
In the figure: 11 is carbon fiber cloth, 12 is carbon fiber yarn, 2 is a resin impregnation tank, 3 is an injection pump, 4 is an injection pipe, 5 is a preforming mold, and 6 is a curing mold.
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.
A resin for pultrusion carbon fiber composite materials is prepared from the following components in percentage by mass: 30-60% of epoxy resin system, 10-30% of unsaturated resin system, 2-5% of toughening agent, 3-5% of internal release agent, 5-10% of reactive diluent and 3-8% of chopped conductive fibers; the epoxy resin system comprises epoxy resin and a corresponding curing agent, and the unsaturated resin system comprises unsaturated resin and a corresponding curing agent. In this embodiment, the toughening agent is any one or a combination of polyethylene glycol diglycidyl ether, carboxyl-terminated liquid nitrile rubber, and polyurethane. The reactive diluent is any one or combination of 1, 4-butyrolactone, butyl glycidyl ether and ethylene glycol diglycidyl ether. The short-cut conductive fibers are conductive and magnetic conductive fibers with the length less than 1 mm. The short-cut conductive fiber is any one or combination of nickel-plated carbon fiber, stainless steel fiber, magnetic nano modified zinc oxide whisker and nickel-plated carbon nano tube.
A method of preparing a resin for pultruded carbon fiber composites, comprising the steps of:
s1, sequentially adding the epoxy resin system, the unsaturated resin system and the internal release agent according to the mass percent, and dispersing for 5-10 min by using a high-speed stirrer to obtain a composite resin system;
s2, adding the toughening agent and the reactive diluent into the composite resin system in the S1 according to mass percent, and dispersing for 5min-10min by using a high-speed stirrer to prepare a low-viscosity composite resin system;
and S3, adding the chopped conductive fibers into the low-viscosity composite resin system in the S2 according to the mass percentage, and dispersing for 30min by using a high-speed stirrer to obtain the composite resin system, thereby obtaining the pultrusion electromagnetic shielding carbon fiber composite material resin.
A method for using resin for pultrusion of carbon fiber composite materials comprises the steps of placing the pultrusion carbon fiber composite material resin in a resin impregnation tank, introducing the impregnated resin into a preforming mold through a glue injection pipe by adopting a glue injection pump, and continuously reinforcing fibers.
Example 1
The embodiment provides a pultrusion electromagnetic shielding carbon fiber composite material resin which comprises the following components in percentage by mass:
weighing 30 parts of epoxy resin E51, 20 parts of methyl tetrahydrophthalic anhydride, 30 parts of unsaturated resin, 2 parts of benzoyl peroxide, 5 parts of 1, 4-butyrolactone, 3 parts of carboxyl-terminated liquid nitrile rubber, 3 parts of internal mold release agent, 5 parts of 1 mm-length short-cut nickel-plated carbon fiber and 2 parts of 1mm stainless steel fiber in sequence, and adding the materials into a stirring barrel to be uniformly stirred for later use;
the viscosity of the resin system is measured as follows: 650 mPa.s;
pultrusion electromagnetic shielding carbon fiber composite material preparation, design fibre volume content 65%, as figure 1, overspeed device tensioner from the top down sets gradually to carbon cloth 11, carbon fiber yarn 12 and carbon fiber cloth 11, preforming mould 5 and curing mold 6 have set gradually in the carbon fiber flowing water direction, grouting pump 3 pours into preforming mould 5 into with resin in resin impregnation tank 2 through injecting glue pipe 4 in, carbon fiber yarn 12 is under draw gear's traction, get into and impregnate in preforming mould 5 after gathering together through the yarn guide plate, finally accomplish the resin curing at curing mold 6 with carbon fiber cloth 11, realize the combined material shaping. To prevent the filtering effect of the chopped conductive fibers by the reinforcing fiber cloth, only the continuous reinforcing carbon fiber yarns 12 are passed through the preforming mold 5.
Under the traction force of a pultrusion machine, the reinforced fiber is impregnated and then is cured and molded through a curing mold, wherein the curing temperature is 85 ℃ in one section, 135 ℃ in two sections and 150 ℃ in three sections. The traction speed is 0.01 m/min. And curing and cutting to obtain the pultruded carbon fiber electromagnetic shielding composite material plate.
The tensile strength of the electromagnetic shielding carbon fiber composite material is measured as follows: 890 MPa;
the shielding effectiveness of the electromagnetically shielding carbon fiber composite material was measured as shown in Table 1
TABLE 1 Shielding effectiveness
| Frequency of | 150KHz | 30MHz | 200MHz | 1GHz | 3GHz | 6GHz | 10GHz | 18GHz |
| Shielding effectiveness | 40dB | 55 dB | 65 dB | 80 dB | 75 dB | 75 dB | 60 dB | 55 dB |
Example 2
The embodiment provides a pultrusion electromagnetic shielding carbon fiber composite material resin which comprises the following components in percentage by mass:
50 parts of epoxy resin TDE-85, 5 parts of dimethyl imidazole, 20 parts of unsaturated resin, 2 parts of benzoyl peroxide, 5 parts of butyl glycidyl ether, 5 parts of ethylene glycol diglycidyl ether, 3 parts of carboxyl-terminated liquid nitrile rubber, 5 parts of an internal mold release agent, 3 parts of short-cut nickel-plated carbon fiber with the length of 1mm and 2 parts of magnetic nano modified zinc oxide whisker are weighed in sequence. Adding the mixture into a stirring barrel and stirring the mixture evenly for later use;
the viscosity of the resin system is measured as follows: 450 mPa.s;
electromagnetic shield carbon-fibre composite preparation of pultrusion, design fibre content 60% (volume content), as figure 1, overspeed device tensioner from the top down sets gradually carbon cloth 11, carbon fiber yarn 12 and carbon fiber cloth 11, at carbon fiber flowing water direction, preforming mould 5 and curing mold 6 have set gradually, grouting pump 3 pours into preforming mould 5 into with resin in the resin impregnation groove 2 through injecting glue pipe 4, carbon fiber yarn 12 is under draw gear's traction, get into and impregnate in preforming mould 5 after gathering together through the yarn guide plate, finally accomplish the resin curing at curing mold 6 with carbon fiber cloth 11, realize the combined material shaping.
Under the traction force of a pultrusion machine, the reinforced fiber is impregnated and then is cured and molded through a curing mold, wherein the curing temperature is 85 ℃ in one section, 130 ℃ in two sections and 140 ℃ in three sections. The traction speed is 0.06 m/min. And curing and cutting to obtain the pultruded carbon fiber electromagnetic shielding composite material plate.
The tensile strength of the electromagnetic shielding carbon fiber composite material is measured as follows: 850 MPa;
the shielding effectiveness of the electromagnetically shielding carbon fiber composite material was measured as shown in Table 2
TABLE 2 Shielding effectiveness
| Frequency of | 150KHz | 30MHz | 200MHz | 1GHz | 3GHz | 6GHz | 10GHz | 18GHz |
| Shielding effectiveness | 45dB | 55 dB | 60 dB | 75 dB | 70 dB | 75 dB | 65 dB | 58 dB |
The method for testing the performance of the prepared pultrusion electromagnetic shielding carbon fiber composite material resin in the embodiment comprises the following steps:
(1) viscosity: according to the GB/T22314-;
(2) tensile strength: according to the tensile property test method of GBT 1447-;
(3) electromagnetic shielding performance: according to the method for measuring the shielding effectiveness of the GBT 12190-2006 electromagnetic shielding chamber, the size of the sample plate is 300mm × 4mm 1.
Although only the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art, and all changes are encompassed in the scope of the present invention.
Claims (7)
1. The resin for pultrusion of the carbon fiber composite material is characterized by being prepared from the following components in percentage by mass: 30-60% of epoxy resin system, 10-30% of unsaturated resin system, 2-5% of toughening agent, 3-5% of internal release agent, 5-10% of reactive diluent and 3-8% of chopped conductive fibers; the epoxy resin system comprises epoxy resin and a corresponding curing agent, and the unsaturated resin system comprises unsaturated resin and a corresponding curing agent.
2. A resin for pultruded carbon fibre composite material according to claim 1, characterized in that: the toughening agent is any one or combination of polyethylene glycol diglycidyl ether, carboxyl-terminated liquid nitrile rubber and polyurethane.
3. A resin for pultruded carbon fibre composite material according to claim 1, characterized in that: the reactive diluent is any one or combination of 1, 4-butyrolactone, butyl glycidyl ether and ethylene glycol diglycidyl ether.
4. A resin for pultruded carbon fibre composite material according to claim 1, characterized in that: the short-cut conductive fiber is any one or combination of nickel-plated carbon fiber, stainless steel fiber, magnetic nano modified zinc oxide whisker and nickel-plated carbon nano tube.
5. A resin for pultruded carbon fibre composite according to claim 1 or 4, characterized in that: the short-cut conductive fibers are conductive and magnetic conductive fibers with the length less than 1 mm.
6. A method for preparing resin for pultrusion of carbon fiber composite material is characterized by comprising the following steps:
s1, sequentially adding the epoxy resin system, the unsaturated resin system and the internal release agent according to the mass percent, and dispersing for 5-10 min by using a high-speed stirrer to obtain a composite resin system;
s2, adding the toughening agent and the reactive diluent into the composite resin system in the S1 according to mass percent, and dispersing for 5min-10min by using a high-speed stirrer to prepare a low-viscosity composite resin system;
and S3, adding the chopped conductive fibers into the low-viscosity composite resin system in the S2 according to the mass percentage, and dispersing for 30min by using a high-speed stirrer to obtain the composite resin system, thereby obtaining the pultrusion electromagnetic shielding carbon fiber composite material resin.
7. A method of using a resin for pultrusion of carbon fiber composite material, characterized in that: and placing the pultruded carbon fiber composite resin into a resin impregnation tank, and introducing the impregnated resin into a preforming mold through a glue injection pipe by using a glue injection pump to continuously reinforce the fiber.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778706A (en) * | 2021-01-05 | 2021-05-11 | 中国电子科技集团公司第三十三研究所 | Pultruded carbon fiber electromagnetic shielding composite material section and manufacturing method thereof |
| CN112810190A (en) * | 2020-12-31 | 2021-05-18 | 南京海拓新材料科技有限公司 | Preparation device and method for achieving electromagnetic shielding effect of novel FRP (fiber reinforced plastic) material |
| CN113150499A (en) * | 2021-04-27 | 2021-07-23 | 嘉兴恒隆复合材料有限公司 | Epoxy resin composition for pultrusion and preparation method thereof |
| CN113265120A (en) * | 2021-05-17 | 2021-08-17 | 武汉本邦复合材料科技有限公司 | Epoxy resin composition suitable for drawing agent process and epoxy resin drawing agent method |
| CN114635291A (en) * | 2022-02-25 | 2022-06-17 | 哈尔滨工业大学 | Thermosetting resin coated inorganic nonmetal fiber composite bundle and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965582A (en) * | 2014-04-24 | 2014-08-06 | 山东省阳信丰源科技有限公司 | Carbon nano dual-cured resin matrix for pultrusion process and composite of carbon nano dual-cured resin matrix |
-
2020
- 2020-06-23 CN CN202010577989.8A patent/CN111662535A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965582A (en) * | 2014-04-24 | 2014-08-06 | 山东省阳信丰源科技有限公司 | Carbon nano dual-cured resin matrix for pultrusion process and composite of carbon nano dual-cured resin matrix |
Non-Patent Citations (1)
| Title |
|---|
| 闫丽丽;乔妙杰;雷忆三;王富强;王东红;陈佳;: "化学镀镍碳纤维/环氧树脂复合材料电磁屏蔽性能" * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112810190A (en) * | 2020-12-31 | 2021-05-18 | 南京海拓新材料科技有限公司 | Preparation device and method for achieving electromagnetic shielding effect of novel FRP (fiber reinforced plastic) material |
| CN112778706A (en) * | 2021-01-05 | 2021-05-11 | 中国电子科技集团公司第三十三研究所 | Pultruded carbon fiber electromagnetic shielding composite material section and manufacturing method thereof |
| CN113150499A (en) * | 2021-04-27 | 2021-07-23 | 嘉兴恒隆复合材料有限公司 | Epoxy resin composition for pultrusion and preparation method thereof |
| CN113265120A (en) * | 2021-05-17 | 2021-08-17 | 武汉本邦复合材料科技有限公司 | Epoxy resin composition suitable for drawing agent process and epoxy resin drawing agent method |
| CN114635291A (en) * | 2022-02-25 | 2022-06-17 | 哈尔滨工业大学 | Thermosetting resin coated inorganic nonmetal fiber composite bundle and preparation method thereof |
| CN114635291B (en) * | 2022-02-25 | 2023-10-13 | 哈尔滨工业大学 | Thermosetting resin coated inorganic nonmetallic fiber composite bundle and preparation method thereof |
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Application publication date: 20200915 |