CN112980026A - Preparation method of carbon nanotube modified fiber reinforced thermosetting resin-based prepreg - Google Patents
Preparation method of carbon nanotube modified fiber reinforced thermosetting resin-based prepreg Download PDFInfo
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- CN112980026A CN112980026A CN202110252944.8A CN202110252944A CN112980026A CN 112980026 A CN112980026 A CN 112980026A CN 202110252944 A CN202110252944 A CN 202110252944A CN 112980026 A CN112980026 A CN 112980026A
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 125
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 117
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 229920005989 resin Polymers 0.000 title claims abstract description 67
- 239000011347 resin Substances 0.000 title claims abstract description 67
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 47
- 239000000835 fiber Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003822 epoxy resin Substances 0.000 claims description 53
- 229920000647 polyepoxide Polymers 0.000 claims description 53
- 238000003756 stirring Methods 0.000 claims description 49
- 239000006185 dispersion Substances 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000002313 adhesive film Substances 0.000 claims description 7
- 239000003292 glue Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000012745 toughening agent Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 3
- 239000011342 resin composition Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229920005992 thermoplastic resin Polymers 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 28
- 238000002156 mixing Methods 0.000 abstract description 7
- 230000006835 compression Effects 0.000 abstract description 5
- 238000007906 compression Methods 0.000 abstract description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 12
- 239000005011 phenolic resin Substances 0.000 description 12
- 229920001568 phenolic resin Polymers 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 8
- 238000009775 high-speed stirring Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 239000004695 Polyether sulfone Substances 0.000 description 4
- -1 carbon nanotube modified carbon fiber Chemical class 0.000 description 4
- 229920006393 polyether sulfone Polymers 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
Classifications
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- 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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- 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
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
- C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2481/06—Polysulfones; Polyethersulfones
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a preparation method of a carbon nanotube modified fiber reinforced thermosetting resin-based prepreg. The carbon nanotube modified fiber reinforced thermosetting resin-based prepreg is prepared by mixing carbon nanotubes and thermosetting resin in proportion, and has the advantages of high comprehensive mechanical property, particularly high compressive strength, capability of effectively solving the problem of compression resistance of a composite material as a main bearing part, capability of improving the transverse tensile strength of the composite material, effectively improving the mechanical property among fibers of the composite material and widening the application range of the composite material on structural parts which require high bearing in three-dimensional and multi-dimensional directions. In addition, the preparation method has the advantages of convenient operation, good repeatability and the like.
Description
Technical Field
The invention relates to the field of composite material preparation, in particular to a preparation method of a carbon nanotube modified fiber reinforced thermosetting resin-based prepreg.
Background
With the continuous development of composite materials, it is of great significance to apply the light and high-strength advanced resin-based composite material as a main bearing part to replace alloy materials. The fiber unidirectional or two-dimensional fabric reinforced resin matrix composite material has the advantages of high specific strength, high specific rigidity, strong designability, fatigue resistance, corrosion resistance and the like, and replaces the traditional metal material in many fields. However, the characteristics of high specific strength and high specific modulus of the composite material are mainly reflected in the fiber direction, the mechanical properties among fibers are poor, damage failure among fibers is an important damage form and cause of the composite material, and the further wide application of the composite material is limited due to the low compressive strength of the composite material.
In order to solve the problem of the mechanical property of the composite material, scientific researchers can improve the mechanical property of the composite material by improving the property of a resin matrix, and the method can improve the mechanical property of the composite material to a certain extent. But the defects are that the improvement of the resin matrix performance is difficult, and the performance of the resin matrix can be improved only to a small extent by trying a lot of efforts, so that the mechanical property of the composite material is not greatly improved, the improvement of the resin matrix performance cannot be effectively transferred to the composite material, and the compressive strength of the composite material cannot be greatly improved. Carbon nanotubes have been widely studied for their excellent mechanical properties as a nano-reinforcing material. The enhancement of the mechanical property of the carbon nano tube to the fiber composite material can be divided into two categories: first, the carbon nanotubes can significantly improve the mechanical properties of the resin by enhancing the toughness of the resin matrix. After the carbon nano tubes are added, the surface energy of the resin is reduced, the wettability of the fiber is improved, the interface combination between the resin and the fiber is enhanced, and the carbon nano tubes with proper length can be effectively inserted between the fiber yarns to play a role in binding the fiber yarns, so that the compressive strength and the transverse tensile strength of the fiber composite material can be effectively enhanced; second, the reinforcement is achieved by grafting carbon nanotubes onto the surface of the fiber.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a carbon nanotube modified fiber reinforced thermosetting resin-based prepreg.
In order to solve the technical problems, the invention adopts the following technical scheme: according to the design proportion of the composite material, carbon nanotubes with certain mass, a carbon nanotube resin dispersant and a thermosetting resin composition are mixed to prepare a carbon nanotube resin pre-dispersion liquid, the carbon nanotube resin pre-dispersion liquid is stirred at a high speed and ground by three rollers for re-dispersion, then is stirred and mixed with a curing agent in a stirring kettle to form a curing system, the curing system is frozen and then is coated with glue to form a film, and a resin adhesive film is compounded with fibers through a prepreg compounding production line to form the carbon nanotube-containing fiber/thermosetting resin-based prepreg.
The invention relates to a preparation method of a carbon nanotube modified fiber reinforced thermosetting resin-based prepreg, which comprises the following steps:
1) preparing a toughening agent of thermosetting resin and heat-resistant thermoplastic resin with a mass ratio of 25-50: 1, weighing proper mass for later use;
2) according to the following steps of 1: respectively weighing the carbon nano tube and the carbon nano tube resin dispersant in a mass ratio of 0.3-0.8, wherein the mass content of the carbon nano tube is 0.5-2.0% of the total weight of the thermosetting resin for later use;
3) heating the weighed thermosetting resin composition in an environment of 100-130 ℃, and adding the weighed carbon nano tube and the carbon nano tube dispersing agent under the low-speed stirring of the rotating speed not more than 100rpm when the viscosity is not more than 1.3Pa & s; after the solution is heated to the preset temperature, maintaining the temperature, and continuously stirring for 30-60min to prepare a carbon nano tube/thermosetting resin dispersion liquid;
3) preparing the carbon nano tube/thermosetting resin dispersion liquid into a thermosetting resin curing system containing the carbon nano tube;
4) freezing the prepared thermosetting resin curing system containing the carbon nano tube for not less than 24 hours, and then coating the glue at the temperature of 50-60 ℃ to prepare an epoxy resin glue film containing the carbon nano tube;
5) and compounding the prepared thermosetting resin adhesive film containing the carbon nano tube with fibers to prepare the carbon nano tube modified fiber reinforced thermosetting resin prepreg.
The invention relates to a preparation method of a carbon nanotube modified fiber reinforced thermosetting resin-based prepreg, which is characterized by comprising the following steps: before the step of preparing the thermosetting resin curing system containing the carbon nano tube, the prepared carbon nano tube/thermosetting resin dispersion liquid is firstly dispersed for 30-60min by a high-speed stirrer with the rotating speed higher than 7000rpm under the condition that the viscosity is not more than 0.8 Pa.s; and grinding and dispersing for at least three times by using a three-roll grinder.
The invention relates to a preparation method of a carbon nanotube modified fiber reinforced thermosetting resin-based prepreg, which is characterized by comprising the following steps: the mass content of the carbon nano tube is 1.2 percent of the total weight of the thermosetting resin.
The invention relates to a preparation method of a carbon nanotube modified fiber reinforced thermosetting resin-based prepreg, which is characterized by comprising the following steps: the thermosetting resin is epoxy resin, and when an epoxy resin curing system containing the carbon nano tube is prepared, a proper amount of curing agent and accelerating agent are added into the carbon nano tube/epoxy resin dispersion liquid at the temperature of 70-85 ℃ and the rotating speed of 50-80rpm according to the curing molding requirement of the epoxy resin.
The invention relates to a preparation method of a carbon nanotube modified fiber reinforced thermosetting resin-based prepreg, which is characterized by comprising the following steps: the carbon nanotube has a length of 70 to 100 μm and a diameter of 15 to 30 nm.
According to the invention, the carbon nano tubes are mixed with the thermosetting resin, and the carbon nano tubes are dispersed by adding the carbon nano tube resin dispersing agent, high-speed stirring dispersion and three-roll grinding dispersion, so that the problem of poor dispersion of the carbon nano tubes can be effectively solved. In addition, the preparation method has the advantages of convenient operation, good repeatability and the like.
Detailed Description
The present invention will be further described with reference to the following examples, which are not intended to limit the scope of the present invention. The invention is not limited to the embodiments described above, but rather, various modifications and changes may be made by those skilled in the art without departing from the scope of the invention.
Example one
A5000 ml beaker is placed in a heating sleeve, a JJ-1 type electric stirrer is placed in the beaker, the set rotating speed is 60rpm, and the heating temperature of the heating sleeve is set to be 110 ℃.
AFG-90MH and polyether sulfone resin PES toughening agent in a mass ratio of 50:1 are mixed to prepare an epoxy resin composition, 3000g of the epoxy resin composition is weighed, and the epoxy resin composition is added into a beaker.
45.18g of CNTs having a length of 70 μm and a diameter of 15nm were weighed out for use.
13.554g of carbon nanotube resin dispersant JCCHDS was weighed out for use.
Starting a heating sleeve and an electric stirrer, adding weighed CNTs and JCCHDS when the viscosity of the solution is 1.2 Pa.s, and continuously stirring until the solution is uniform and black; and after the temperature of the solution reaches 110 ℃, continuously stirring for 60min to prepare the carbon nano tube/epoxy resin pre-dispersion liquid.
Placing the prepared carbon nano tube/epoxy resin pre-dispersion liquid with the viscosity of 0.7 Pa.s under an A30 high-speed stirring disperser, setting the rotating speed to 7000rpm, and stirring at high speed for 30min to obtain the carbon nano tube/epoxy resin dispersion liquid.
And immediately taking out the prepared carbon nano tube/epoxy resin dispersion liquid, grinding the carbon nano tube/epoxy resin dispersion liquid for 3 times in a ZYTR-30 three-roller grinder, and collecting the carbon nano tube/epoxy resin dispersion liquid with better dispersity.
And placing the prepared carbon nano tube/epoxy resin dispersion liquid with better dispersibility into a DLH-10 stirring kettle, wherein the temperature of the stirring kettle is set to be 70 ℃, and the stirring speed is set to be 50 rpm. Starting the stirring kettle to start heating, stopping operation when the temperature in the kettle reaches 70 ℃, adding 750g of 4, 4-diamino diphenyl sulfone curing agent and 15g of boron trifluoride ethylamine accelerator into the kettle, continuously starting the stirring kettle, and vacuumizing to-0.1 MPa, so as to remove bubbles generated in the stirring and mixing process. And under the vacuum state of-0.1 MPa, continuously stirring and mixing the mixture in the stirring kettle for 30min, stopping running, and extruding the uniformly mixed carbon nano tube/epoxy resin system from the stirring kettle to obtain the carbon nano tube/epoxy resin curing system.
The prepared carbon nanotube/epoxy resin curing system is frozen and stored for 24 hours, then the glue is coated at 50 ℃ to prepare a carbon nanotube/epoxy resin adhesive film, and the carbon nanotube modified carbon fiber reinforced epoxy resin prepreg is prepared by using a hot melting method and continuous carbon fibers.
The carbon nanotube modified carbon fiber reinforced epoxy resin prepreg prepared in the embodiment is cut into appropriate sizes to be subjected to layering and mould pressing to prepare a composite material, and a longitudinal compression failure experiment and a transverse tension failure experiment are performed on a composite material sample according to GB/T3856-.
Example two
A5000 ml beaker is placed in a heating sleeve, a JJ-1 type electric stirrer is placed in the beaker, the set rotating speed is 100rpm, and the heating temperature of the heating sleeve is set to be 130 ℃.
AFG-90H and polyether sulfone resin PES toughening agent in a mass ratio of 100:3 are mixed to prepare an epoxy resin composition, 3000g of the epoxy resin composition is weighed, and the epoxy resin composition is added into a beaker.
75.3g of CNTs having a length of 100 μm and a diameter of 30nm were weighed out for use.
60.24g of carbon nanotube resin dispersant JCCHDS was weighed out for use.
Starting a heating sleeve and an electric stirrer, adding weighed CNTs and JCCHDS when the viscosity of the solution is 1.3 Pa.s, and continuously stirring until the solution is uniform and black; and after the temperature of the solution reaches 130 ℃, continuously stirring for 60min to prepare the carbon nano tube/epoxy resin pre-dispersion liquid.
Placing the prepared carbon nano tube/epoxy resin pre-dispersion liquid with the viscosity of 0.8 Pa.s under an A30 high-speed stirring disperser, setting the rotating speed to 10000rpm, and stirring at high speed for 60min to obtain the carbon nano tube/epoxy resin dispersion liquid.
And (3) when the temperature of the prepared carbon nano tube/epoxy resin pre-dispersion liquid is reduced to 50 ℃, placing the carbon nano tube/epoxy resin pre-dispersion liquid under a ZYTR-30 three-roll grinder for grinding for 6 times, and collecting the carbon nano tube/epoxy resin pre-dispersion liquid with better dispersibility.
And placing the prepared carbon nano tube/epoxy resin dispersion liquid with better dispersibility into a DLH-10 stirring kettle, wherein the temperature of the stirring kettle is set to be 85 ℃, and the stirring speed is 80 rpm. Starting the stirring kettle to start heating, stopping operation when the temperature in the kettle reaches 85 ℃, adding 750g of 4, 4-diamino diphenyl sulfone curing agent and 15g of boron trifluoride ethylamine accelerator into the kettle, continuously starting the stirring kettle, vacuumizing to-0.1 MPa, and removing bubbles generated in the stirring and mixing process. And under the vacuum state of-0.1 MPa, continuously stirring and mixing the mixture in the stirring kettle for 60min, stopping running, and extruding the uniformly mixed carbon nano tube/epoxy resin system from the stirring kettle to obtain the carbon nano tube/epoxy resin curing system.
After the carbon nanotube/epoxy resin curing system prepared in this embodiment is frozen for 48 hours, the carbon nanotube/epoxy resin adhesive film is prepared by gluing at 60 ℃, and the carbon nanotube-modified carbon fiber-reinforced epoxy resin prepreg is prepared by using a hot melting method with continuous carbon fibers.
The prepreg prepared in the embodiment is cut into a proper size to be subjected to layering and mould pressing to prepare the composite material, and a longitudinal compression failure experiment and a transverse tension failure experiment are performed on a composite material sample according to GB/T3856-.
EXAMPLE III
A5000 ml beaker is placed in a heating sleeve, a JJ-1 type electric stirrer is placed in the beaker, the set rotating speed is 80rpm, and the heating temperature of the heating sleeve is set to be 100 ℃.
BR6216 and polyether sulfone PES toughening agent in a mass ratio of 25:1 are prepared into a phenolic resin composition, 3000g is weighed, and the weighed phenolic resin composition is added into a beaker.
30g of CNTs with a length of 80 μm and a diameter of 20nm are weighed for use.
15g of carbon nanotube resin dispersant XFZ32 was weighed out for use.
Starting a heating sleeve and an electric stirrer, adding weighed CNTs and XFZ32 when the solution is heated to the viscosity of 1.0 Pa.s, and continuously stirring until the solution is uniform and black; and after the temperature of the solution reaches 100 ℃, continuously stirring for 45min to prepare the carbon nano tube/phenolic resin pre-dispersion liquid.
The prepared carbon nano tube/phenolic resin pre-dispersion liquid with the viscosity of 0.5 Pa.s is placed under an A30 high-speed stirring dispersion machine, the rotating speed is set to be 9000rpm, and the high-speed stirring is carried out for 45min to obtain the carbon nano tube/phenolic resin dispersion liquid.
Grinding the prepared carbon nano tube/phenolic resin dispersion liquid for 4 times by a ZYTR-30 three-roll grinder, and collecting to obtain the carbon nano tube/phenolic resin dispersion liquid with better dispersibility.
And placing the prepared carbon nano tube/epoxy resin dispersion liquid with better dispersibility into a DLH-10 stirring kettle, wherein the temperature of the stirring kettle is set to be 75 ℃, and the stirring speed is 65 rpm. Starting the stirring kettle to start heating, continuing to start the stirring kettle when the temperature in the kettle reaches 75 ℃, vacuumizing to-0.1 MPa, and removing bubbles generated in the stirring and mixing process. And (3) stopping running after the stirring kettle is continuously stirred and mixed for 45min, and extruding the uniformly mixed carbon nano tube/phenolic resin system from the stirring kettle to obtain the carbon nano tube/phenolic resin curing system.
After the carbon nanotube/phenolic resin curing system prepared in this example is frozen for 36 hours, the adhesive is applied at 55 ℃ to prepare a carbon nanotube/phenolic resin adhesive film, and the carbon nanotube-modified glass fiber reinforced phenolic resin prepreg is prepared by using a hot melting method and continuous glass fibers.
The prepreg prepared in the embodiment is cut into a proper size to be subjected to layering and mould pressing to prepare the composite material, and a longitudinal compression failure experiment and a transverse tension failure experiment are performed on a composite material sample according to GB/T3856-.
Example four
A5000 ml beaker is placed in a heating sleeve, a JJ-1 type electric stirrer is placed in the beaker, the set rotating speed is 50rpm, and the heating temperature of the heating sleeve is set to be 115 ℃.
Preparing an epoxy resin composition from AFG-90MH and a polyimide PI flexibilizer in a mass ratio of 100:3, weighing 3000g, and adding into a beaker.
16.395g of CNTs 90 μm long and 25nm in diameter were weighed out for use.
9.837g of carbon nanotube resin dispersant XFZ32 was weighed for use.
Starting a heating sleeve and an electric stirrer, adding weighed CNTs and XFZ32 when the solution is heated to the viscosity of 1.2 Pa.s, and continuously stirring until the solution is uniform and black; and after the temperature of the solution reaches 115 ℃, continuously stirring for 30min to prepare the carbon nano tube/epoxy resin pre-dispersion liquid.
The prepared carbon nano tube/epoxy resin pre-dispersion liquid with the viscosity of 0.6 Pa.s is placed under an A30 high-speed stirring dispersion machine, the set rotating speed is 8000rpm, and the high-speed stirring is carried out for 40min to obtain the carbon nano tube/epoxy resin dispersion liquid.
Grinding the prepared carbon nano tube/epoxy resin dispersion liquid for 6 times by a ZYTR-30 three-roll grinder, and collecting to obtain the carbon nano tube/epoxy resin dispersion liquid with better dispersibility.
And placing the prepared carbon nano tube/epoxy resin dispersion liquid with better dispersibility into a DLH-10 stirring kettle, wherein the temperature of the stirring kettle is set to be 70 ℃, and the stirring speed is 65 rpm. Starting the stirring kettle to start heating, stopping operation when the temperature in the kettle reaches 70 ℃, adding 70g of m-phenylenediamine curing agent and 9g of boron trifluoride second-future complex accelerator into the kettle, continuously starting the stirring kettle, vacuumizing to-0.1 MPa, and removing bubbles generated in the stirring and mixing process. And (3) stopping running after the stirring kettle is continuously stirred and mixed for 30min, and extruding the uniformly mixed carbon nano tube/epoxy resin system from the stirring kettle to obtain the carbon nano tube/epoxy resin curing system.
The carbon nanotube/epoxy resin curing system prepared in this embodiment is frozen for 24 hours, then coated with a glue at 55 ℃ to prepare a carbon nanotube/epoxy resin adhesive film, and then prepared with continuous carbon fibers into a carbon nanotube modified carbon fiber reinforced epoxy resin prepreg by a hot-melt method.
The prepreg prepared in the embodiment is cut into a proper size to be subjected to layering and mould pressing to prepare the composite material, and a longitudinal compression failure experiment and a transverse tension failure experiment are performed on a composite material sample according to GB/T3856-.
Claims (5)
1. A preparation method of a carbon nanotube modified fiber reinforced thermosetting resin-based prepreg comprises the following steps:
1) preparing a toughening agent of thermosetting resin and heat-resistant thermoplastic resin with a mass ratio of 25-50: 1, weighing proper mass for later use;
2) according to the following steps of 1: respectively weighing the carbon nano tube and the carbon nano tube resin dispersant in a mass ratio of 0.3-0.8, wherein the mass content of the carbon nano tube is 0.5-2.0% of the total weight of the thermosetting resin for later use;
3) heating the weighed thermosetting resin composition in an environment of 100-130 ℃, and adding the weighed carbon nano tube and the carbon nano tube resin dispersant under the low-speed stirring of the rotating speed not more than 100rpm when the viscosity is not more than 1.3Pa & s; after the solution is heated to the preset temperature, maintaining the temperature, and continuously stirring for 30-60min to prepare a carbon nano tube/thermosetting resin dispersion liquid;
4) preparing the carbon nano tube/thermosetting resin dispersion liquid into a thermosetting resin curing system containing the carbon nano tube;
5) freezing the prepared thermosetting resin curing system containing the carbon nano tube for not less than 24 hours, and then coating the glue at the temperature of 50-60 ℃ to prepare a thermosetting resin glue film containing the carbon nano tube;
6) and compounding the prepared thermosetting resin adhesive film containing the carbon nano tube with fibers to prepare the carbon nano tube modified fiber reinforced thermosetting resin prepreg.
2. The method for preparing the carbon nanotube modified fiber reinforced thermosetting resin-based prepreg according to claim 1, which is characterized by comprising the following steps: before the step of preparing the thermosetting resin curing system containing the carbon nano tube, the prepared carbon nano tube/thermosetting resin dispersion liquid is firstly dispersed for 30-60min by a high-speed stirrer with the rotating speed higher than 7000rpm under the condition that the viscosity is not more than 0.8 Pa.s; and grinding and dispersing for at least three times by using a three-roll grinder.
3. The method for preparing the carbon nanotube modified fiber reinforced thermosetting resin-based prepreg according to claim 1 or 2, characterized in that: the mass content of the carbon nano tube is 1.2 percent of the total weight of the thermosetting resin.
4. The method for preparing the carbon nanotube modified fiber reinforced thermosetting resin-based prepreg according to claim 1, which is characterized by comprising the following steps: the thermosetting resin is epoxy resin, and when an epoxy resin curing system containing the carbon nano tube is prepared, a proper amount of curing agent and accelerating agent are added into the carbon nano tube/epoxy resin dispersion liquid at the temperature of 70-85 ℃ and the rotating speed of 50-80rpm according to the curing molding requirement of the epoxy resin.
5. The method for preparing the carbon nanotube modified fiber reinforced thermosetting resin-based prepreg according to claim 1, which is characterized by comprising the following steps: the carbon nanotube has a length of 70 to 100 μm and a diameter of 15 to 30 nm.
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