CN113004690A - Bismaleimide resin composition, preparation method and application thereof - Google Patents
Bismaleimide resin composition, preparation method and application thereof Download PDFInfo
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- C08L79/00—Compositions 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
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- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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- 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
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- 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 bismaleimide resin composition, a preparation method and an application thereof. Belonging to the technical field of high polymer materials, the bismaleimide resin composition is prepared from the following raw materials in parts by weight: 50-70 parts of a bismaleimide monomer; 5-15 parts of cyanate ester resin; 15-35 parts of allyl compounds; 7-32 parts of imidazolyl-containing poly (arylene ether nitrile) resin; 0.02-0.8 part of imidazole accelerator. In the bismaleimide resin composition provided by the invention, the imidazolyl-containing polyarylether nitrile resin is matched with other components to perform synergistic action, so that the toughness of the obtained composite material can be improved, and the bismaleimide resin composition can obtain higher tensile strength and modulus after being cured. In addition, the carbon fiber composite material prepared from the bismaleimide resin composition has high interlaminar shear strength and excellent toughness, and is suitable for high use temperature.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a bismaleimide resin composition, a preparation method and an application thereof.
Background
The high-modulus carbon fiber has the advantages of light weight, high strength, low thermal expansion coefficient, good dimensional stability and the like. With the rapid development of domestic high-modulus carbon fiber technology in recent years, the batch preparation technology of high-modulus carbon fibers such as domestic T800, M40, M40J and M55J is broken through successively. However, the matrix resin matched with the high-modulus carbon fiber still has the technical problem to be solved urgently. When the modulus and the toughness of the resin are insufficient, the resin cannot be matched with the modulus and the fracture deformation of high-modulus carbon fibers, and when the resin is subjected to external force, the resin matrix cannot effectively transfer stress, yield failure occurs, and the performance of high-modulus carbon fibers is limited, so that the mechanical property of the carbon fiber resin matrix composite material can be effectively improved by improving the modulus and the toughness of the resin matrix.
The bismaleimide resin has the characteristics of excellent comprehensive mechanical property, high temperature resistance, flame retardance, radiation resistance, easiness in molding and processing and the like, and an advanced composite material taking the bismaleimide resin as a matrix is widely applied to the fields of aviation, aerospace and the like. The high-temperature-resistant bismaleimide resin has high crosslinking density and is brittle, and generally is toughened and modified by a temperature-resistant thermoplastic resin. However, the conventional thermoplastic resin toughening agents such as polyetherimide, polysulfone, polyethersulfone, phenolphthalein polyarylethersulfone and the like generally have low modulus (2.5-2.8 GPa) and glass transition temperature lower than 265 ℃, and the use temperature and the modulus of the bismaleimide resin can be reduced after blending modification. The high-modulus high-temperature-resistant thermoplastic polyimide resin is basically insoluble in a bismaleimide resin system or has high cost, so that the industrial popularization is difficult. At present, no bismaleimide resin system for high-modulus carbon fiber composite materials with the use temperature of more than 300 ℃ has been developed.
CN102702482A discloses a high-strength and high-modulus thermosetting resin composition, wherein the cured product has higher strength and modulus, but the applicable use temperature of the system is lower, and the process is complex. CN103804908B, a Chinese patent of invention, discloses bismaleimide/polythioetherimide alloy and a preparation method thereof, and the resin has the comprehensive properties of high heat resistance, high modulus, high strength, high impact and excellent flame retardance, and can be used as an advanced resin matrix composite material matrix. But the curing pressure of the resin is large, the process time is long, the glass transition temperature of the polythioetherimide is still lower than 300 ℃, and the bending strength of the resin system is lower than 50 MPa. CN108084435A discloses a high-modulus high-temperature-resistant bismaleimide resin composition which can be cured at 200 ℃ and has a tensile modulus of 5.3GPa, but does not give related properties of a carbon fiber composite material, and according to the report of the prior document, the impact resistance of the composite material is hardly improved when a simple thermosetting resin composition is used for a carbon fiber composite material resin matrix.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a bismaleimide resin composition, a preparation method and an application thereof, wherein the bismaleimide resin composition provided by the present invention can obtain higher tensile strength and modulus after being cured; the carbon fiber composite material prepared from the bismaleimide resin composition has high interlaminar shear strength and excellent toughness, and is suitable for high use temperature.
The invention provides a bismaleimide resin composition which is prepared from the following raw materials in parts by weight:
the bismaleimide resin composition comprises the following components in parts by weight:
66-109 parts of a prepolymerization product and 6-28 parts of imidazolyl-containing poly (arylene ether nitrile) resin; 5-15 parts of cyanate ester resin; 0.02-0.8 part of imidazole accelerator.
The prepolymerization product is composed of bismaleimide monomer, allyl compound and polyarylether nitrile resin containing imidazolyl, wherein:
50-70 parts of bismaleimide monomer;
15-35 parts of allyl compounds;
1-4 parts of imidazolyl-containing poly (arylene ether nitrile) resin;
preferably, the bismaleimide monomer includes one of 4,4 ' -diphenylmethane bismaleimide, 4 ' -diphenyl ether bismaleimide and 4,4 ' -diphenyl sulfone bismaleimide.
Preferably, the cyanate ester resin comprises one or more of bisphenol a cyanate ester, bisphenol M cyanate ester and bisphenol E cyanate ester.
Preferably, the allyl compound comprises one or more of diallyl bisphenol A, bisphenol A diallyl ether and allyl phenol.
Preferably, the imidazolyl-containing polyarylene ether nitrile resin has a structure represented by formula (I):
in the formula, Ar is selected from
One of (1);
m is more than or equal to 0 and less than or equal to 0.9, n is more than or equal to 0 and less than or equal to 0.9, x is more than or equal to 0.1 and less than or equal to 0.9, y is more than or equal to 0.1 and less than or equal to 0.9, and m + n + x + y is equal to 1.
Preferably, the powder particle size of the bismaleimide resin composition is 8-30 μm.
The present invention also provides a method for preparing the bismaleimide resin composition, which comprises the following steps:
A) uniformly mixing the heated allyl compound with a part of the polyarylether nitrile resin containing the imidazolyl to obtain a homogeneous solution;
B) pre-polymerizing the homogeneous solution and a bismaleimide monomer at 125-135 ℃ to obtain a pre-polymerization product;
C) and grinding and uniformly mixing the cooled prepolymer, cyanate ester resin, imidazole accelerator and the rest polyarylether nitrile resin containing imidazole groups to obtain the bismaleimide resin composition.
Preferably, in the step a), the temperature of the heated allylic compound is 130 to 150 ℃.
Preferably, in the step B), the prepolymerization time is 20-40 min.
The invention also provides a carbon fiber composite material which is prepared from the following raw materials in parts by weight:
25-40 parts of a bismaleimide resin composition;
60-75 parts of carbon fiber;
the bismaleimide resin composition includes the bismaleimide resin composition described above or a bismaleimide resin composition prepared by the preparation method described above.
The carbon fiber composite material is prepared according to the following method:
and (2) molding the carbon fiber and bismaleimide resin composition by a hot melting method to prepare a prepreg, and heating and curing to obtain the carbon fiber composite material.
The invention provides a bismaleimide resin composition which is prepared from the following raw materials in parts by weight: 50-70 parts of a bismaleimide monomer; 5-15 parts of cyanate ester resin; 15-35 parts of allyl compounds; 7-32 parts of imidazolyl-containing poly (arylene ether nitrile) resin; 0.02-0.8 part of imidazole accelerator. In the bismaleimide resin composition provided by the invention, the imidazolyl-containing polyarylether nitrile resin is matched with other components to perform synergistic action, so that the toughness of the obtained composite material can be improved, and meanwhile, the obtained bismaleimide resin composition is cured to obtain higher tensile strength and modulus and is suitable for higher use temperature. In addition, the carbon fiber composite material prepared from the bismaleimide resin composition has high interlaminar shear strength and excellent toughness, and is suitable for high use temperature.
Experimental results show that the tensile strength of the bismaleimide resin composition provided by the invention after curing is not lower than 85MPa, and the modulus is not lower than 4.2 GPa. And (2) forming the carbon fibers and the bismaleimide resin composition by a hot melting method to prepare a prepreg, and heating and curing to obtain the carbon fiber composite material. Through detection, the glass transition temperature of the carbon fiber composite material is greater than 300 ℃, and the carbon fiber composite material is suitable for higher use temperature; the interlaminar shear strength is not lower than 95MPa, and the toughness is better; the compression strength after impact is not lower than 300MPa, and the impact resistance is better.
Drawings
FIG. 1 is an infrared spectrum of an imidazolyl-containing polyarylene ether nitrile resin of example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood 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.
The invention provides a bismaleimide resin composition which is prepared from the following raw materials in parts by weight:
the raw material of the bismaleimide resin composition provided by the invention comprises a bismaleimide monomer. The weight part of the bismaleimide monomer is 50-70 parts. In certain embodiments of the present invention, the weight fraction of the bismaleimide monomer is 50 parts or 60 parts.
In certain embodiments of the present invention, the bismaleimide monomer comprises one of 4,4 ' -diphenylmethane bismaleimide, 4 ' -diphenyl ether bismaleimide, and 4,4 ' -diphenylsulfone bismaleimide.
The raw materials of the bismaleimide resin composition provided by the invention also comprise cyanate ester resin. The cyanate ester resin is 5-15 parts by weight. In certain embodiments of the present invention, the cyanate ester resin is present in an amount of 5 parts, 10 parts, or 15 parts by weight.
In certain embodiments of the present invention, the cyanate ester resin comprises one or more of bisphenol a type cyanate ester, bisphenol M type cyanate ester, and bisphenol E type cyanate ester. In certain embodiments, the bisphenol a type cyanate ester can be bisphenol a dicyanate; the bisphenol E type cyanate ester can be bisphenol E type dicyanate.
The raw material of the bismaleimide resin composition provided by the invention also comprises an allyl compound. The allyl compound is 15-35 parts by weight. In certain embodiments of the present invention, the allylic compound is 15 parts, 20 parts, or 25 parts by weight.
In certain embodiments of the present invention, the allylic compound comprises one or more of diallylbisphenol A, bisphenol A diallyl ether, and allylphenol. In the present invention, the allyl compound is a curing agent.
The raw material of the bismaleimide resin composition provided by the invention also comprises an imidazolyl-containing polyarylether nitrile resin. The imidazole-group-containing polyarylether nitrile resin is 7-32 parts by weight. In certain embodiments of the present invention, the imidazole group-containing polyarylene ether nitrile resin is 15 parts, 20 parts or 22 parts by weight.
In an embodiment of the present invention, the imidazolyl-containing polyarylene ether nitrile resin has a structure represented by formula (i):
in the formula, Ar is selected from
One of (1);
m is more than or equal to 0 and less than or equal to 0.9, n is more than or equal to 0 and less than or equal to 0.9, x is more than or equal to 0.1 and less than or equal to 0.9, y is more than or equal to 0.1 and less than or equal to 0.9, and m + n + x + y is equal to 1.
In certain embodiments of the present invention, m is 0, n is 0, x is 0.2, and y is 0.8; or m is 0, n is 0, x is 0.3, and y is 0.7; or m is 0.1, n is 0.3, x is 0.2, and y is 0.4.
In the invention, the imidazolyl-containing polyarylether nitrile resin is used as a toughening agent, so that the toughness of the obtained composite material can be improved, and other components are matched, so that the bismaleimide resin composition obtained after curing has high tensile strength and modulus, and is suitable for high use temperature.
The bismaleimide resin composition provided by the invention also comprises an imidazole accelerator as a raw material. The weight part of the imidazole accelerator is 0.02-0.8. In certain embodiments of the present invention, the parts by weight of the imidazole-based accelerator is 0.06 parts, 0.1 parts, or 0.4 parts.
In certain embodiments of the present invention, the imidazole-based accelerator comprises one or more of 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole. In the invention, the imidazole accelerator has an accelerating effect on reducing the curing temperature of bismaleimide resin.
In an embodiment of the present invention, the powder particle size of the bismaleimide resin composition is 8 to 30 μm.
In the bismaleimide resin composition provided by the invention, the imidazolyl-containing polyarylether nitrile resin is matched with other components to perform synergistic action, so that the toughness of the obtained composite material can be improved, and meanwhile, the obtained bismaleimide resin composition is cured to obtain higher tensile strength and modulus and is suitable for higher use temperature. In addition, the carbon fiber composite material prepared from the bismaleimide resin composition has high interlaminar shear strength and excellent toughness, and is suitable for high use temperature.
The present invention also provides a method for preparing the bismaleimide resin composition, which comprises the following steps:
A) uniformly mixing the heated allyl compound with a part of the polyarylether nitrile resin containing the imidazolyl to obtain a homogeneous solution;
B) pre-polymerizing the homogeneous solution and a bismaleimide monomer at 125-135 ℃ to obtain a pre-polymerization product;
C) and grinding and uniformly mixing the cooled prepolymer, cyanate ester resin, imidazole accelerator and the rest polyarylether nitrile resin containing imidazole groups to obtain the bismaleimide resin composition.
In the preparation method, the components and the proportion of the raw materials are the same as above, and are not described again. In the present invention, the source of the raw material is not particularly limited, and may be generally commercially available.
The method comprises the step of uniformly mixing the heated allyl compound with a part of the polyarylether nitrile resin containing the imidazolyl to obtain a homogeneous solution. In certain embodiments of the invention, the blending may be stirred blending.
In some embodiments of the present invention, the heated allylic compound has a temperature of 130 to 150 ℃. In certain embodiments, the heated allylic compound has a temperature of 150 ℃ or 130 ℃.
In certain embodiments of the present invention, the mass ratio of the part of the imidazole group-containing polyarylene ether nitrile resin to the rest of the imidazole group-containing polyarylene ether nitrile resin is 4 to 5: 11 to 18. In certain embodiments, the mass ratio of the portion of the imidazole group-containing polyarylene ether nitrile resin to the remaining imidazole group-containing polyarylene ether nitrile resin is 4: 11. 5: 15 or 4: 18.
according to the invention, a part of the polyarylether nitrile resin containing the imidazolyl is mixed and dissolved firstly, so that a tackifying effect can be achieved, and the subsequent carbon fiber prepreg forming is facilitated.
And after obtaining a homogeneous solution, carrying out prepolymerization on the homogeneous solution and a bismaleimide monomer at 125-135 ℃ to obtain a prepolymerization product.
In the invention, the prepolymerization temperature is 125-135 ℃. In certain embodiments of the invention, the temperature of the prepolymerization is 130 ℃ or 135 ℃. In some embodiments of the present invention, the prepolymerization time is 20 to 40 min. In certain embodiments, the prepolymerization time is 30min, 20min, or 40 min.
After obtaining the prepolymer, the present invention preferably further comprises cooling the prepolymer. In certain embodiments of the present invention, the temperature of the cooled prepolymer is 70 to 100 ℃. In certain embodiments, the temperature of the cooled prepolymer product is 80 ℃.
And grinding and uniformly mixing the cooled prepolymer, cyanate ester resin, imidazole accelerator and the rest polyarylether nitrile resin containing imidazole groups to obtain the bismaleimide resin composition. Specifically, the following may be mentioned: and adding cyanate ester resin and imidazole accelerator into the cooled prepolymer, uniformly mixing, adding the rest polyarylether nitrile resin containing imidazole group, grinding and uniformly mixing to obtain the bismaleimide resin composition.
In certain embodiments of the invention, the milling is performed in a three-roll mill.
The invention also provides a carbon fiber composite material which is prepared from the following raw materials in parts by weight:
25-40 parts of a bismaleimide resin composition;
60-75 parts of carbon fiber;
the bismaleimide resin composition includes the bismaleimide resin composition described above or a bismaleimide resin composition prepared by the preparation method described above.
In certain embodiments of the present invention, the carbon fibers may be M40J carbon fibers or T800 carbon fibers.
In the invention, the carbon fiber composite material is prepared according to the following method:
and (2) molding the carbon fiber and bismaleimide resin composition by a hot melting method to prepare a prepreg, and heating and curing to obtain the carbon fiber composite material.
The components and the proportion of the carbon fiber and the bismaleimide resin composition are the same as above, and are not described again.
The steps and parameters of the hot-melt molding method are not particularly limited, and those well known to those skilled in the art can be used.
The temperature-rising curing step and parameters are not particularly limited in the present invention, and those well known to those skilled in the art can be used.
In certain embodiments of the present invention, the carbon fiber composite is prepared according to the following method:
and compounding the bismaleimide resin composition and carbon fibers to prepare a prepreg with the thickness of 100-140 microns, and performing presetting, pressurizing at 0.1-0.4 MPa, and gradient heating and curing to obtain the carbon fiber composite material.
The invention provides a bismaleimide resin composition which is prepared from the following raw materials in parts by weight: 50-70 parts of a bismaleimide monomer; 5-15 parts of cyanate ester resin; 15-35 parts of allyl compounds; 7-32 parts of imidazolyl-containing poly (arylene ether nitrile) resin; 0.02-0.8 part of imidazole accelerator. In the bismaleimide resin composition provided by the invention, the imidazolyl-containing polyarylether nitrile resin is matched with other components to perform synergistic action, so that the toughness of the obtained composite material can be improved, and meanwhile, the obtained bismaleimide resin composition is cured to obtain higher tensile strength and modulus and is suitable for higher use temperature. In addition, the carbon fiber composite material prepared from the bismaleimide resin composition has high interlaminar shear strength and excellent toughness, and is suitable for high use temperature.
Experimental results show that the tensile strength of the bismaleimide resin composition provided by the invention after curing is not lower than 85MPa, and the modulus is not lower than 4.2 GPa. And (2) forming the carbon fibers and the bismaleimide resin composition by a hot melting method to prepare a prepreg, and heating and curing to obtain the carbon fiber composite material. Through detection, the glass transition temperature of the carbon fiber composite material is greater than 300 ℃, and the carbon fiber composite material is suitable for higher use temperature; the interlaminar shear strength is not lower than 95MPa, and the toughness is better; the compression strength after impact is not lower than 300MPa, and the impact resistance is better.
In order to further illustrate the present invention, the bismaleimide resin composition, the preparation method and the application thereof provided by the present invention are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
The starting materials used in the following examples are all generally commercially available.
Example 1
The imidazolyl-containing polyarylene ether nitrile resin has a structure represented by formula (1):
in formula (1), x is 0.2 and y is 0.8.
Weighing 15g of diallyl bisphenol A, heating to 150 ℃, adding 4g of the imidazolyl-containing polyarylether nitrile resin, and stirring to completely dissolve to obtain a homogeneous solution;
pre-polymerizing the homogeneous solution and 50g of 4, 4' -diphenylmethane bismaleimide at 130 ℃ for 30min to obtain a pre-polymerization product;
and cooling the prepolymerization product to 80 ℃, adding 5g of bisphenol A dicyanate and 0.06g of 2-ethyl-4-methylimidazole, uniformly stirring, continuously adding 11g of the imidazolyl-containing polyarylether nitrile resin, and uniformly blending by a three-roller machine to obtain the bismaleimide resin composition.
In this example, infrared analysis was performed on the imidazole group-containing polyarylene ether nitrile resin having a structure represented by formula (1) to obtain an infrared spectrum shown in FIG. 1. FIG. 1 is an infrared spectrum of an imidazolyl-containing polyarylene ether nitrile resin of example 1 of the present invention. As can be seen from FIG. 1, 3064cm-1Is located at 2230cm of C-H stretching vibration peak on benzene ring-1Vibration absorption peak at CN, 1732cm-1And the position is a C ═ O vibration absorption peak on the imidazole ring, and the obtained product is the target product.
The obtained bismaleimide resin composition is solidified (130 ℃/1h +150 ℃/1h +180 ℃/2h +200 ℃/2h +230 ℃/3h) to obtain a cast body of the bismaleimide resin composition. The tensile strength of the cast body was 95MPa and the modulus was 4.3GPa, as determined according to the standard GB/T2567-2008.
And compounding the bismaleimide resin composition with M40J carbon fibers to prepare a prepreg with the thickness of 120 mu M, and performing presetting, pressurizing at 0.3MPa, and gradient heating and curing to obtain the carbon fiber composite material.
According to the detection of the standard ASTM D7028-07, the glass transition temperature of the carbon fiber composite material is 318 ℃, and the carbon fiber composite material is suitable for higher use temperature; according to the test of the standard ASTM D2344/D2344M-16, the interlaminar shear strength of the carbon fiber composite material is 102MPa, and the toughness is better; according to the test of the standard ASTM D7137/D7137M-17, the compression strength of the carbon fiber composite material after impact is 305MPa, and the impact resistance is better.
Example 2
The imidazolyl-containing polyarylene ether nitrile resin has a structure represented by formula (2):
in formula (2), x is 0.3 and y is 0.7.
Weighing 25g of bisphenol A diallyl ether, heating to 130 ℃, adding 5g of the imidazolyl-containing polyarylether nitrile resin, and stirring to completely dissolve the imidazolyl-containing polyarylether nitrile resin to obtain a homogeneous solution;
prepolymerizing the homogeneous solution and 60g of 4, 4' -diphenyl ether bismaleimide at 135 ℃ for 20min to obtain a prepolymerization product;
and cooling the prepolymerization product to 80 ℃, adding 10g of bisphenol E dicyanate and 0.1g of 2-phenylimidazole, uniformly stirring, continuously adding 15g of the imidazolyl-containing polyarylether nitrile resin, and uniformly blending by a three-roller machine to obtain the bismaleimide resin composition.
The obtained bismaleimide resin composition is solidified (130 ℃/1h +150 ℃/1h +180 ℃/2h +200 ℃/2h +230 ℃/3h) to obtain a cast body of the bismaleimide resin composition. The tensile strength of the cast product was 85MPa and the modulus was 4.2GPa, as determined according to GB/T2567.
And compounding the bismaleimide resin composition with T800 carbon fibers to prepare a prepreg with the thickness of 120 mu m, and performing presetting, pressurizing by 0.3MPa, and gradient heating and curing to obtain the carbon fiber composite material.
According to the test of the standard ASTM D7028, the glass transition temperature of the carbon fiber composite material is 305 ℃, and the carbon fiber composite material is suitable for higher use temperature; the detection is carried out according to the standard ASTM D2344, so that the interlaminar shear strength of the carbon fiber composite material is 95MPa, and the toughness is better; according to the test of the standard ASTM D7137, the compression strength of the carbon fiber composite material after impact is 320MPa, and the impact resistance is better.
Example 3
The imidazolyl-containing polyarylene ether nitrile resin has a structure represented by formula (3):
in formula (3), m is 0.1, n is 0.3, x is 0.2, and y is 0.4.
Weighing 25g of bisphenol A diallyl ether and 5g of allyl phenol, heating to 150 ℃, adding 4g of the imidazolyl-containing polyarylether nitrile resin, and stirring to completely dissolve the imidazolyl-containing polyarylether nitrile resin to obtain a homogeneous solution;
pre-polymerizing the homogeneous solution and 60g of 4, 4' -diphenylmethane bismaleimide at 130 ℃ for 40min to obtain a pre-polymerization product;
and cooling the prepolymerization product to 80 ℃, adding 15g of bisphenol A dicyanate and 0.4g of 2-phenyl-4-methylimidazole, uniformly stirring, continuously adding 18g of the imidazolyl-containing polyarylether nitrile resin, and uniformly blending by a three-roller machine to obtain the bismaleimide resin composition.
The obtained bismaleimide resin composition is solidified (130 ℃/1h +150 ℃/1h +180 ℃/2h +200 ℃/2h +230 ℃/3h) to obtain a cast body of the bismaleimide resin composition. The tensile strength of the cast product was 80MPa and the modulus was 4.4GPa, as determined according to GB/T2567.
And compounding the bismaleimide resin composition with T800 carbon fibers to prepare a prepreg with the thickness of 120 mu m, and performing presetting, pressurizing by 0.3MPa, and gradient heating and curing to obtain the carbon fiber composite material.
According to the test of the standard ASTM D7028, the glass transition temperature of the carbon fiber composite material is 330 ℃, and the carbon fiber composite material is suitable for higher use temperature; the detection is carried out according to the standard ASTM D2344, so that the interlaminar shear strength of the carbon fiber composite material is 98MPa, and the toughness is better; according to the test of the standard ASTM D7137, the compression strength of the carbon fiber composite material after impact is 325MPa, and the impact resistance is better.
Experimental results show that the tensile strength of the bismaleimide resin composition provided by the invention after curing is not lower than 85MPa, and the modulus is not lower than 4.2 GPa. And (2) forming the carbon fibers and the bismaleimide resin composition by a hot melting method to prepare a prepreg, and heating and curing to obtain the carbon fiber composite material. Through detection, the glass transition temperature of the carbon fiber composite material is greater than 300 ℃, and the carbon fiber composite material is suitable for higher use temperature; the interlaminar shear strength is not lower than 95MPa, and the toughness is better; the compression strength after impact is not lower than 300MPa, and the impact resistance is better.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The bismaleimide resin composition is characterized by being prepared from the following raw materials in parts by weight:
2. the bismaleimide resin composition of claim 1 wherein the bismaleimide monomer comprises one of 4,4 ' -diphenylmethane bismaleimide, 4 ' -diphenyl ether bismaleimide and 4,4 ' -diphenyl sulfone bismaleimide.
3. The bismaleimide resin composition as claimed in claim 1, wherein the cyanate ester resin comprises one or more of bisphenol a cyanate ester, bisphenol M cyanate ester, and bisphenol E cyanate ester.
4. The bismaleimide resin composition of claim 1 wherein the allylic compound comprises one or more of diallyl bisphenol a, bisphenol a diallyl ether, and allyl phenol.
5. The bismaleimide resin composition of claim 1 wherein the imidazolyl-containing polyarylene ether nitrile resin has a structure represented by formula (i):
in the formula, Ar is selected from
One of (1);
m is more than or equal to 0 and less than or equal to 0.9, n is more than or equal to 0 and less than or equal to 0.9, x is more than or equal to 0.1 and less than or equal to 0.9, y is more than or equal to 0.1 and less than or equal to 0.9, and m + n + x + y is equal to 1.
6. The bismaleimide resin composition according to claim 1, wherein a powder particle diameter of the bismaleimide resin composition is 8 to 30 μm.
7. The method for preparing the bismaleimide resin composition as claimed in claim 1, comprising the steps of:
A) uniformly mixing the heated allyl compound with a part of the polyarylether nitrile resin containing the imidazolyl to obtain a homogeneous solution;
B) pre-polymerizing the homogeneous solution and a bismaleimide monomer at 125-135 ℃ to obtain a pre-polymerization product;
C) and grinding and uniformly mixing the cooled prepolymer, cyanate ester resin, imidazole accelerator and the rest polyarylether nitrile resin containing imidazole groups to obtain the bismaleimide resin composition.
8. The method according to claim 7, wherein the temperature of the heated allylic compound in step A) is 130 to 150 ℃.
9. The method according to claim 7, wherein the prepolymerization time in step B) is 20-40 min.
10. The carbon fiber composite material is characterized by being prepared from the following raw materials in parts by weight:
25-40 parts of a bismaleimide resin composition;
60-75 parts of carbon fiber;
the bismaleimide resin composition comprises the bismaleimide resin composition as claimed in any one of claims 1 to 6 or the bismaleimide resin composition prepared by the preparation method as claimed in any one of claims 7 to 9.
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| CN114349994A (en) * | 2022-01-10 | 2022-04-15 | 长春长光宇航复合材料有限公司 | Modified bismaleimide carbon fiber prepreg, composite material and preparation method thereof |
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| CN114349994A (en) * | 2022-01-10 | 2022-04-15 | 长春长光宇航复合材料有限公司 | Modified bismaleimide carbon fiber prepreg, composite material and preparation method thereof |
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