CN117447741A - High-temperature-resistant antioxidant hot-melt polyimide prepreg, composite material and preparation method thereof - Google Patents
High-temperature-resistant antioxidant hot-melt polyimide prepreg, composite material and preparation method thereof Download PDFInfo
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 133
- 239000012943 hotmelt Substances 0.000 title claims abstract description 125
- 239000004642 Polyimide Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 17
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 17
- 239000009719 polyimide resin Substances 0.000 claims abstract description 89
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000003647 oxidation Effects 0.000 claims abstract description 40
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 40
- 239000002313 adhesive film Substances 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000003292 glue Substances 0.000 claims abstract description 13
- 239000012779 reinforcing material Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000010030 laminating Methods 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- 239000004744 fabric Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- XWASSENKVFJRFR-UHFFFAOYSA-N [SiH4].C1(=CC=CC=C1)C#C Chemical compound [SiH4].C1(=CC=CC=C1)C#C XWASSENKVFJRFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 abstract description 21
- 239000011347 resin Substances 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 9
- 230000002787 reinforcement Effects 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000009827 uniform distribution Methods 0.000 abstract description 3
- 238000004321 preservation Methods 0.000 description 18
- 238000013329 compounding Methods 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 7
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- UPGRRPUXXWPEMV-UHFFFAOYSA-N 5-(2-phenylethynyl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C#CC1=CC=CC=C1 UPGRRPUXXWPEMV-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
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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
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
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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
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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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
- C08J2379/00—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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
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Abstract
The invention relates to a high-temperature-resistant antioxidant hot-melt polyimide prepreg, a composite material and a preparation method thereof; the method comprises the following steps: heating a hot-melt polyimide resin to melt the hot-melt polyimide resin; mixing the melted hot-melt polyimide resin with carborane-containing phenylacetylene end-capped oligomer, and stirring at a temperature of more than or equal to 60 ℃ to prepare a glue film; laminating the adhesive film and the reinforcing material, and heating to obtain the high-temperature-resistant oxidation-resistant hot-melt polyimide prepreg; the preparation method of the high-temperature-resistant antioxidant hot-melt polyimide prepreg is provided to solve the problems that the existing preparation of the prepreg by adopting a solution method in the prior art is difficult to accurately control the resin content in the prepreg and the uniform distribution of the resin matrix on the reinforcement is difficult to realize; the content of volatile matters is difficult to control, and the volatilization of solvents such as DMAc and the like can cause environmental pollution.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a high-temperature-resistant oxidation-resistant hot-melt polyimide prepreg, a composite material and a preparation method thereof.
Background
Polyimide is one of organic polymer with optimal comprehensive performance, and its heat resisting temperature can reach 600 deg.c and long term use temperature range of 200-500 deg.c. Currently, polyimide resin prepregs are generally prepared by a wet process (generally in the form of manual brushing), and the phenomenon of uneven brushing caused by human factors exists.
In order to further improve the temperature resistance and oxidation resistance of the polyimide resin-based composite material, the published literature shows that the introduction of carborane groups and silane groups into polyimide resin can improve the temperature resistance and oxidation resistance of the polyimide resin; under the high-temperature air condition, a boron oxide protective film can be formed to improve the oxidation resistance of the material, but the prepreg is prepared by adopting a solution method, so that the resin content in the prepreg is difficult to accurately control, and the uniform distribution of the resin matrix on the reinforcement is difficult to realize; the content of volatile matters is difficult to control, and the volatilization of solvents such as DMAc and the like can cause environmental pollution.
Accordingly, there is an urgent need for providing a high temperature resistant and oxidation resistant hot melt polyimide prepreg, a composite material and a method for preparing the same.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant oxidation-resistant hot-melt polyimide prepreg, a composite material and a preparation method thereof, and the preparation method of the high-temperature-resistant oxidation-resistant hot-melt polyimide prepreg is provided to solve the problems that the existing preparation of the prepreg by adopting a solution method in the prior art is difficult to accurately control the resin content in the prepreg and the uniform distribution of resin matrix on a reinforcement is difficult to realize; the content of volatile matters is difficult to control, and the volatilization of solvents such as DMAc and the like can cause environmental pollution.
The invention provides a preparation method of high-temperature-resistant antioxidant hot-melt polyimide prepreg, which comprises the following steps:
heating a hot-melt polyimide resin to melt the hot-melt polyimide resin;
mixing the melted hot-melt polyimide resin with carborane-containing phenylacetylene end-capped oligomer, and stirring at a temperature of more than or equal to 60 ℃ to prepare a glue film;
and laminating the adhesive film and the reinforcing material, and heating to obtain the high-temperature-resistant and oxidation-resistant hot-melt polyimide prepreg.
Preferably, the carborane-containing phenylacetylene-terminated oligomer is added in an amount of 10-30% by weight of the hot melt polyimide resin.
Preferably, the method further comprises adding phenylacetylene silane when the hot-melt polyimide resin is mixed with carborane-containing phenylacetylene end-capped oligomer.
Preferably, the total weight of carborane-containing phenylacetylene end-capped oligomer and phenylacetylene silane is 10% -30% of the weight of the hot melt polyimide resin.
Preferably, the reinforcing material is one of quartz fiber cloth, carbon fiber cloth or glass fiber cloth.
Preferably, the hot-melt polyimide resin is heated at a temperature of 60 to 80 ℃ for 1 to 3 hours to melt the hot-melt polyimide resin.
Preferably, a film coating production device is adopted, the mixture of the hot-melt polyimide resin and the antioxidant auxiliary agent is coated into a film with uniform thickness, and the film surface density is controlled by adjusting the roller clearance and the film coating speed.
Preferably, the thickness of the adhesive film is 0.1mm.
The invention also provides a high-temperature-resistant and oxidation-resistant polyimide resin prepreg obtained based on the preparation method of the high-temperature-resistant and oxidation-resistant hot-melt polyimide prepreg.
The invention also provides a polyimide resin matrix composite material, which comprises the high-temperature-resistant and oxidation-resistant polyimide resin prepreg.
Compared with the prior art, the preparation method of the high-temperature-resistant antioxidant hot-melt polyimide prepreg and the composite material provided by the invention has the following steps:
1. the invention provides a preparation method of high-temperature-resistant antioxidant hot-melt polyimide prepreg, which is characterized in that the prepreg is prepared from a hot-melt polyimide resin matrixAdding carborane-containing phenylacetylene end-capped oligomer, and in the heating process of the carborane-containing phenylacetylene end-capped oligomer, making chemical reaction to produce B 2 O 3 And the like to produce B 2 O 3 A layer of protective film is formed on the surface of the matrix, so that the matrix is protected, the matrix is prevented from being oxidized, the resin matrix can be uniformly distributed on the reinforcement, and the content of volatile matters can be controlled to have small influence on the environment.
2. Compared with the polyimide resin-based composite material obtained by singly adopting hot-melt polyimide resin, the polyimide resin-based composite material obtained by adopting the high-temperature-resistant and oxidation-resistant polyimide resin prepreg has the advantages of high bending strength, high glass transition temperature and high 5% weight loss temperature, and can be used as functions or structural members of ultrahigh-speed aircrafts.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation method of the high-temperature-resistant oxidation-resistant hot-melt polyimide prepreg provided by the embodiment comprises the following steps:
s1) heating the hot-melt polyimide resin to melt the hot-melt polyimide resin;
s2) mixing the melted hot-melt polyimide resin with carborane-containing phenylacetylene end-capped oligomer, and stirring at a temperature of more than or equal to 60 ℃ to prepare a glue film;
s3) laminating the adhesive film and the reinforcing material, and heating to obtain the high-temperature-resistant and oxidation-resistant hot-melt polyimide prepreg.
Specifically, the addition weight of the carborane-containing phenylacetylene terminated oligomer is 10-30% of the weight of the hot melt polyimide resin.
Specifically, when the hot-melt polyimide resin is mixed with carborane-containing phenylacetylene end-capped oligomer, phenylacetylene silane is also added.
Specifically, the total weight of the carborane-containing phenylacetylene end-capped oligomer and the phenylacetylene silane is 10-30% of the weight of the hot melt polyimide resin.
Specifically, the reinforcing material is one of quartz fiber cloth, carbon fiber cloth or glass fiber cloth.
Specifically, the hot-melt polyimide resin is heated at a temperature of 60 to 80 ℃ for 1 to 3 hours to melt the hot-melt polyimide resin.
Specifically, a coating production device is adopted to coat the mixture of the hot-melt polyimide resin and the antioxidant auxiliary agent into a glue film with uniform thickness, and the surface density of the glue film is controlled by adjusting the roller clearance and the coating speed.
Specifically, the thickness of the adhesive film was 0.1mm.
The invention provides a high-temperature-resistant and oxidation-resistant polyimide resin prepreg based on the preparation method of the high-temperature-resistant and oxidation-resistant hot-melt polyimide prepreg.
The polyimide resin-based composite material provided by the invention comprises the high-temperature-resistant and oxidation-resistant polyimide resin prepreg.
According to the preparation method of the high-temperature-resistant antioxidant hot-melt polyimide prepreg, carborane-containing phenylacetylene end-capped oligomer is added into a hot-melt polyimide resin matrix, and chemical reaction is carried out in the heating process of the carborane-containing phenylacetylene end-capped oligomer to generate B 2 O 3 And the like to produce B 2 O 3 A layer of protective film is formed on the surface of the matrix, so that the matrix is protected, the matrix is prevented from being oxidized, the resin matrix can be uniformly distributed on the reinforcement, and the content of volatile matters can be controlled to have small influence on the environment.
Compared with the polyimide resin-based composite material obtained by singly adopting hot-melt polyimide resin, the polyimide resin-based composite material obtained by adopting the high-temperature-resistant and oxidation-resistant polyimide resin prepreg has the advantages of high bending strength, high glass transition temperature and high 5% weight loss temperature, and can be used as functions or structural members of ultrahigh-speed aircrafts.
Example 1
The preparation method of the high-temperature-resistant antioxidant hot-melt polyimide prepreg comprises the following steps:
101 Heating the hot-melt polyimide resin at 70 ℃ for 2 hours to melt the hot-melt polyimide resin;
102 Mixing the melted hot-melt polyimide resin with the carborane-containing phenylacetylene-terminated oligomer by adopting a star stirrer, stirring at the temperature of more than or equal to 60 ℃, and mixing the melted hot-melt polyimide resin with the carborane-containing phenylacetylene-terminated oligomer to prepare a glue film by adopting a hot-melt prepreg coating production device; wherein the addition amount of the carborane-containing phenylacetylene-terminated oligomer is 25% of the mass part of the hot melt polyimide resin, the thickness of the adhesive film is 0.1mm, the gap between rollers is 0.3mm, the coating speed is 4 m/min, the surface density of the adhesive film is regulated, and the surface density of the adhesive film is controlled to be 100g/m 2 。
103 A hot-melt prepreg machine is used for compounding production, a layer of adhesive film is respectively placed on the upper part and the lower part of the hot-melt prepreg machine at the temperature of 80 ℃ by a compression roller, quartz fiber cloth is placed in the middle of the hot-melt prepreg machine as a reinforcing material, and the high-temperature-resistant and oxidation-resistant hot-melt polyimide prepreg is obtained by hot-press compounding.
The polyimide resin matrix composite material is prepared by placing 40 layers of high temperature resistant and oxidation resistant hot melt polyimide prepreg (350 mm multiplied by 350 mm) in a mould, and curing the prepreg on a hot press according to a system of heat preservation of 120+/-10 min at 260+/-3 ℃, heat preservation of 30+/-10 min at 320+/-3 ℃ and heat preservation of 120+/-5 min at 370+/-3 ℃ on a hot press, wherein the physical properties are shown in table 1.
Preparation method of carborane-containing phenylacetylene end-capped oligomer
3g of 4-phenylethynyl phthalic anhydride is added into absolute ethanol solvent, reflux is carried out for 4 hours, an esterified product is obtained, the esterified product is cooled to room temperature, 28.12g of triamine compound containing a tri-carborane cage structure synthesized in patent CN 111606936B is added, and carborane-containing phenylacetylene end-capped oligomer is obtained through reaction.
Example two
The preparation method of the high-temperature-resistant antioxidant hot-melt polyimide prepreg comprises the following steps:
201 Heating the hot-melt polyimide resin at a temperature of 60 ℃ for 3 hours to melt the hot-melt polyimide resin;
202 Mixing the melted hot-melt polyimide resin with carborane-containing phenylacetylene-terminated oligomer (carborane-containing phenylacetylene-terminated oligomer in the first embodiment) by using a star stirrer, stirring at a temperature of more than or equal to 60 ℃, and mixing the melted hot-melt polyimide resin with the carborane-containing phenylacetylene-terminated oligomer to prepare a glue film by using a hot-melt prepreg coating production device; wherein the addition amount of the carborane-containing phenylacetylene-terminated oligomer is 10% of the mass part of the hot melt polyimide resin, the thickness of the adhesive film is 0.1mm, the gap between rollers is 0.3mm, the coating speed is 4 m/min, the surface density of the adhesive film is regulated, and the surface density of the adhesive film is controlled to be 100g/m 2 。
203 A hot-melt prepreg machine is used for compounding production, a layer of adhesive film is respectively placed on the upper part and the lower part of the hot-melt prepreg machine at the temperature of 80 ℃ by a compression roller, carbon fiber cloth is placed in the middle of the hot-melt prepreg machine as a reinforcing material, and the high-temperature-resistant and oxidation-resistant hot-melt polyimide prepreg is obtained by hot-press compounding.
The polyimide resin matrix composite material is prepared by placing 40 layers of high temperature resistant and oxidation resistant hot melt polyimide prepreg (350 mm multiplied by 350 mm) in a mould, and curing the prepreg on a hot press according to a system of heat preservation of 120+/-10 min at 260+/-3 ℃, heat preservation of 30+/-10 min at 320+/-3 ℃ and heat preservation of 120+/-5 min at 370+/-3 ℃ on a hot press, wherein the physical properties are shown in table 1.
Example III
The preparation method of the high-temperature-resistant antioxidant hot-melt polyimide prepreg comprises the following steps:
301 Heating the hot-melt polyimide resin at 80 ℃ for 3 hours to melt the hot-melt polyimide resin;
302 Mixing the melted hot-melt polyimide resin with carborane-containing phenylacetylene-terminated oligomer (carborane-containing phenylacetylene-terminated oligomer in the first embodiment) by using a star stirrer, stirring at a temperature of more than or equal to 60 ℃, and mixing the melted hot-melt polyimide resin with the carborane-containing phenylacetylene-terminated oligomer by using a hot-melt prepreg coating production device to prepare a glue film; wherein the addition amount of the carborane-containing phenylacetylene end-capped oligomer is hot melt20% of polyimide resin, wherein the thickness of the adhesive film is 0.1mm, the gap of a roller is adjusted to be 0.3mm, the coating speed is 4 m/min, the surface density of the adhesive film is adjusted, and the surface density of the adhesive film is controlled to be 100g/m 2 。
303 A hot-melt prepreg machine is used for compounding production, a layer of adhesive film is respectively placed on the upper part and the lower part of the hot-melt prepreg machine at the temperature of 80 ℃ by a compression roller, glass fiber cloth is placed in the middle of the hot-melt prepreg machine as a reinforcing material, and the high-temperature-resistant and oxidation-resistant hot-melt polyimide prepreg is obtained by hot-press compounding.
The polyimide resin matrix composite material is prepared by placing 40 layers of high temperature resistant and oxidation resistant hot melt polyimide prepreg (350 mm multiplied by 350 mm) in a mould, and curing the prepreg on a hot press according to a system of heat preservation of 120+/-10 min at 260+/-3 ℃, heat preservation of 30+/-10 min at 320+/-3 ℃ and heat preservation of 120+/-5 min at 370+/-3 ℃ on a hot press, wherein the physical properties are shown in table 1.
Example IV
The preparation method of the high-temperature-resistant antioxidant hot-melt polyimide prepreg comprises the following steps:
401 Heating the hot-melt polyimide resin at 80 ℃ for 3 hours to melt the hot-melt polyimide resin;
402 Mixing the melted hot-melt polyimide resin with carborane-containing phenylacetylene-terminated oligomer (carborane-containing phenylacetylene-terminated oligomer in the first embodiment) by using a star stirrer, stirring at a temperature of more than or equal to 60 ℃, and mixing the melted hot-melt polyimide resin with the carborane-containing phenylacetylene-terminated oligomer to prepare a glue film by using a hot-melt prepreg coating production device; wherein the addition amount of the carborane-containing phenylacetylene-terminated oligomer is 30% of the mass part of the hot melt polyimide resin, the thickness of the adhesive film is 0.1mm, the gap between rollers is 0.3mm, the coating speed is 4 m/min, the surface density of the adhesive film is regulated, and the surface density of the adhesive film is controlled to be 100g/m 2 。
403 A hot-melt prepreg machine is used for compounding production, a layer of adhesive film is respectively placed on the upper part and the lower part of the hot-melt prepreg machine at the temperature of 80 ℃ by a compression roller, quartz fiber cloth is placed in the middle of the hot-melt prepreg machine as a reinforcing material, and the high-temperature-resistant and oxidation-resistant hot-melt polyimide prepreg is obtained by hot-press compounding.
The polyimide resin matrix composite material is prepared by placing 40 layers of high temperature resistant and oxidation resistant hot melt polyimide prepreg (350 mm multiplied by 350 mm) in a mould, and curing the prepreg on a hot press according to a system of heat preservation of 120+/-10 min at 260+/-3 ℃, heat preservation of 30+/-10 min at 320+/-3 ℃ and heat preservation of 120+/-5 min at 370+/-3 ℃ on a hot press, wherein the physical properties are shown in table 1.
Example five
The preparation method of the high-temperature-resistant antioxidant hot-melt polyimide prepreg comprises the following steps:
501 Heating the hot-melt polyimide resin at 70 ℃ for 3 hours to melt the hot-melt polyimide resin;
502 Mixing the melted hot-melt polyimide resin with carborane-containing phenylacetylene-terminated oligomer (carborane-containing phenylacetylene-terminated oligomer in embodiment one) and phenylacetylene silane by using a star stirrer, stirring at a temperature of more than or equal to 60 ℃, and mixing the melted hot-melt polyimide resin with the carborane-containing phenylacetylene-terminated oligomer by using a hot-melt prepreg coating production device to prepare a glue film; wherein the total addition amount of the carborane-containing phenylacetylene end-capped oligomer and the phenylacetylene silane is 25% of the mass part of the hot melt polyimide resin (the mass ratio of the carborane-containing phenylacetylene end-capped oligomer to the phenylacetylene silane is 1:1), the thickness of the adhesive film is 0.1mm, the gap between rollers is adjusted to be 0.3mm, the coating speed is 4 m/min, the surface density of the adhesive film is adjusted, and the surface density of the adhesive film is controlled to be 100g/m 2 。
503 A hot-melt prepreg machine is used for compounding production, a layer of adhesive film is respectively placed on the upper part and the lower part of the hot-melt prepreg machine at the temperature of 80 ℃ by a compression roller, quartz fiber cloth is placed in the middle of the hot-melt prepreg machine as a reinforcing material, and the high-temperature-resistant and oxidation-resistant hot-melt polyimide prepreg is obtained by hot-press compounding.
The polyimide resin matrix composite material is prepared by placing 40 layers of high temperature resistant and oxidation resistant hot melt polyimide prepreg (350 mm multiplied by 350 mm) in a mould, and curing the prepreg on a hot press according to a system of heat preservation of 120+/-10 min at 260+/-3 ℃, heat preservation of 30+/-10 min at 320+/-3 ℃ and heat preservation of 120+/-5 min at 370+/-3 ℃ on a hot press, wherein the physical properties are shown in table 1.
Comparative example
D1. Heating the hot-melt polyimide resin at 70 ℃ for 3 hours to completely melt the hot-melt polyimide resin;
D2. coating a film production device by adopting a hot-melt prepreg machine, coating hot-melt polyimide resin into a film with uniform thickness, wherein the thickness of the film is 0.1mm, the gap between rollers is adjusted to be 0.3mm, the coating speed is 4 m/min, the surface density of the film is adjusted, and the surface density of the film is controlled to be 100g/m 2 ;
D3. And (3) using a hot-melting prepreg machine to compound production device, placing a layer of adhesive film on the upper part and the lower part respectively and placing quartz fiber cloth in the middle as a reinforcing material under the condition of heating the pressing roller to 80 ℃, and obtaining the prepreg through hot-pressing compounding.
S4, placing 40 layers of prepregs (350 mm multiplied by 350 mm) in a mould and placing the mould on a hot press; curing according to a system of (260+ -3) DEG C heat preservation for 120+ -10 min, (320+ -3) DEG C heat preservation for (30+ -10) min and (370+ -3) DEG C heat preservation for (120+ -5) min to prepare the polyimide resin matrix composite, wherein the physical properties are shown in table 1.
TABLE 1 physical Properties of polyimide resin matrix composite
| Test item | Example 1 | Example two | Example III | Example IV | Example five | Comparative example |
| Density (g/m 3) | 1.65 | 1.64 | 1.65 | 1.64 | 1.66 | 1.64 |
| Bending strength at room temperature (MPa) | 613 | 605 | 544 | 573 | 597 | 568 |
| Glass transition temperature | 502℃ | 478℃ | 479℃ | 496℃ | 472℃ | 418℃ |
| 5% weight loss temperature (under air atmosphere) | 653℃ | 593℃ | 607℃ | 638℃ | 624℃ | 541℃ |
Compared with the comparative examples, the polyimide resin matrix composite materials obtained in the first, second, third, fourth and fifth embodiments have significantly higher room temperature flexural strength, glass transition temperature and 5% weight loss temperature (under air atmosphere), and can be used as functions or structural members of ultra-high-speed aircrafts.
And moreover, by compounding phenylacetylene silane and carborane-containing phenylacetylene end-capped oligomer, the resin wettability can be increased, the surface roughness of the prepreg is reduced, and the appearance and uniformity of the prepreg are ensured.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A preparation method of a high-temperature-resistant antioxidant hot-melt polyimide prepreg is characterized by comprising the following steps of: the method comprises the following steps:
heating a hot-melt polyimide resin to melt the hot-melt polyimide resin;
mixing the melted hot-melt polyimide resin with carborane-containing phenylacetylene end-capped oligomer, and stirring at a temperature of more than or equal to 60 ℃ to prepare a glue film;
and laminating the adhesive film and the reinforcing material, and heating to obtain the high-temperature-resistant and oxidation-resistant hot-melt polyimide prepreg.
2. The method for preparing the high-temperature-resistant and oxidation-resistant hot-melt polyimide prepreg according to claim 1, which is characterized in that:
the added weight of the carborane-containing phenylacetylene end-capped oligomer is 10-30% of the weight of the hot melt polyimide resin.
3. The method for preparing the high-temperature-resistant and oxidation-resistant hot-melt polyimide prepreg according to claim 1, which is characterized in that:
the method also comprises the step of adding phenylacetylene silane when the hot-melt polyimide resin is mixed with carborane-containing phenylacetylene end-capped oligomer.
4. The method for preparing the high temperature resistant and oxidation resistant hot melt polyimide prepreg according to claim 3, which is characterized in that:
the total weight of the carborane-containing phenylacetylene end-capped oligomer and the phenylacetylene silane is 10-30% of the weight of the hot melt polyimide resin.
5. The method for preparing the high-temperature-resistant and oxidation-resistant hot-melt polyimide prepreg according to claim 1, which is characterized in that:
the reinforcing material is one of quartz fiber cloth, carbon fiber cloth or glass fiber cloth.
6. The method for preparing the high-temperature-resistant and oxidation-resistant hot-melt polyimide prepreg according to claim 1, which is characterized in that:
the hot-melt polyimide resin is heated for 1-3 hours at the temperature of 60-80 ℃ to melt the hot-melt polyimide resin.
7. The method for preparing the high-temperature-resistant and oxidation-resistant hot-melt polyimide prepreg according to claim 1, which is characterized in that:
and (3) coating the mixture of the hot-melt polyimide resin and the antioxidant auxiliary agent into a glue film with uniform thickness by adopting a coating production device, and controlling the surface density of the glue film by adjusting the gap between rollers and the coating speed.
8. The method for preparing the high-temperature-resistant and oxidation-resistant hot-melt polyimide prepreg according to claim 1, which is characterized in that: the thickness of the adhesive film is 0.1mm.
9. A high temperature resistant and oxidation resistant polyimide resin prepreg obtained based on the method for preparing a high temperature resistant and oxidation resistant hot melt polyimide prepreg according to any one of claims 1 to 8.
10. A polyimide resin-based composite material is characterized in that: a high temperature resistant and oxidation resistant polyimide resin prepreg according to claim 9.
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