CN110294931B - Bismaleimide resin matrix and preparation method and application thereof - Google Patents
Bismaleimide resin matrix and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a bismaleimide resin matrix and a preparation method and application thereof, belonging to the technical field of prepreg preparation. The bismaleimide resin matrix comprises the following components: the thermoplastic polyimide composite material comprises bismaleimide resin monomers, a composite process modifier, thermoplastic resin and thermoplastic polyimide micron-sized particles, wherein the composite process modifier is composed of diallyl bisphenol A and liquid epoxy resin, the thermoplastic resin is dissolved in the composite process modifier, and the thermoplastic polyimide micron-sized particles are swelled in the composite process modifier. The resin matrix improves the interface bonding force of the thermoplastic resin and the thermosetting resin through the phase angle, and improves the anti-microcrack capability after the resin matrix is combined with the fiber; the composite material prepared by the resin matrix has the CAI as high as 340MPa, and meanwhile, the resin matrix has good manufacturability and spreadability, and can meet the requirement of the aerospace field on high impact toughness of the carbon fiber composite material.
Description
Technical Field
The invention relates to the technical field of prepreg preparation, and particularly provides a bismaleimide resin matrix and a preparation method and application thereof.
Background
Bismaleimide resin (BMI) is a highly crosslinked polymer with a three-dimensional network structure, and the network structure endows the bismaleimide resin with excellent high temperature resistance, radiation resistance, humidity resistance, good mechanical properties, dimensional stability and other excellent characteristics, so that the bismaleimide resin and the hot-melt prepreg thereof are widely applied to main sections of aviation and aerospace and composite material structural members. However, the poor toughness of the bismaleimide resin matrix and the poor impact damage resistance of the corresponding carbon fiber composite material are important factors influencing the further expanded application of the bismaleimide resin matrix.
The most common method for improving the impact resistance of carbon fiber reinforced composite materials is to improve the toughness of matrix resin (bismaleimide), and soluble thermoplastic resin is often adopted to carry out toughening through reaction induced phase separation. Although the method improves the toughness of the matrix resin to a certain extent, the addition of a large amount of thermoplastic resin can change the hand feeling viscosity of the matrix resin, influence the technological performance of the matrix resin, increase the operation difficulty when the carbon/bismaleimide prepreg is used for preparing the composite material, have non-ideal toughening effect and cannot effectively inhibit the failure of the composite material laminated board.
Disclosure of Invention
Aiming at the problems in the prior art, the embodiment of the invention provides a bismaleimide resin matrix and a preparation method and application thereof, wherein the resin matrix improves the interface bonding force of thermoplastic resin and thermosetting resin through a phase angle, and improves the anti-microcrack capability after the resin matrix is bonded with fibers; the impact compression strength of the composite material prepared by the resin matrix and the carbon fiber reinforcement is obviously improved; meanwhile, the resin matrix has good manufacturability and spreadability, and can meet the requirement of the aerospace field on high impact toughness of the carbon fiber composite material.
The technical solution of the invention is as follows:
the bismaleimide resin matrix comprises the following raw materials:
the modified bismaleimide resin comprises bismaleimide resin monomers, a composite process modifier, thermoplastic resin and thermoplastic polyimide micron-sized particles, wherein the composite process modifier is composed of diallyl bisphenol A and liquid epoxy resin, the thermoplastic resin is dissolved in the composite process modifier, and the thermoplastic polyimide micron-sized particles are swelled in the composite process modifier.
In an optional embodiment, the mass ratio of the bismaleimide resin monomer, the composite process modifier, the thermoplastic resin and the thermoplastic polyimide micron-sized particles is 100: 60-90: 5-15: 10 to 45.
In an alternative embodiment, the mass ratio of the diallyl bisphenol a to the epoxy resin is 75: 5 to 15.
In an alternative embodiment, the bismaleimide resin monomer is one or more of diphenylmethane diamine type bismaleimide monomer, toluene diamine type bismaleimide monomer, m-phenylene diamine type bismaleimide monomer or diphenyl ether diamine type bismaleimide monomer.
In an optional embodiment, the bismaleimide resin monomer is formed by mixing a diphenylmethane diamine monomer and a toluene diamine monomer according to a mass ratio of 50: 30-60.
In an alternative embodiment, the thermoplastic resin is one or more of polyarylethersulfone, polyaryletherketone, or polyphenylene oxide.
In an alternative embodiment, the thermoplastic polyimide micron-sized particles have an average particle size of 5 to 40 μm.
In an alternative embodiment, the liquid epoxy resin is one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, and hydrogenated bisphenol a epoxy resin.
A method for preparing a bismaleimide resin matrix comprises the following steps:
(1) weighing the following raw materials according to the mixture ratio:
(2) mixing the weighed bismaleimide resin monomer and a composite process modifier for pre-polymerization, adding the weighed thermoplastic resin, and mixing to obtain a dissolved phase;
(3) and adding the weighed thermoplastic polyimide micron-sized particles into the dissolved phase, mixing, and cooling to obtain the bismaleimide resin matrix.
In an optional embodiment, in the step (2), the weighed bismaleimide resin monomer and the composite process modifier are mixed, then the mixture is subjected to thermal insulation prepolymerization at the temperature of 120-130 ℃ for 20-40min, the temperature is reduced to 80-120 ℃, then the weighed thermoplastic resin is added and stirred for 20-60min, and the mixture is mixed to obtain a dissolved phase.
In an alternative embodiment, the temperature of the dissolved phase is maintained at 60-90 ℃ in step (3), the weighed thermoplastic polyimide micron-sized particles are added and stirred for 10-30min, and the mixture is mixed to form the swelling phase.
The bismaleimide resin matrix is applied to the hot-melt prepreg.
In an optional embodiment, the reinforcing fibers of the prepreg are carbon fibers, and the gel content is 30-50%.
Compared with the prior art, the invention has the beneficial effects that:
compared with the traditional toughening method of the bismaleimide resin composite material matrix, the method has higher practicability and toughening effect. The basic toughening of the resin system is realized by selecting the soluble thermoplastic resin to form a single soluble phase in the bismaleimide resin system, which is beneficial to the transmission of the load of the carbon fiber composite material; by adding the swellable thermoplastic micron-sized particles into the resin system, the interface bonding force between the thermoplastic particles and the bismaleimide resin system is improved because the particles swell in the composite process modifier, and when the resin system is compounded with the reinforcing fibers, the thermoplastic micron-sized particles can migrate to the surface of the reinforcing fibers in the curing process because the thermoplastic micron-sized particles swell instead of being dissolved in the matrix resin, so that efficient in-situ toughening is realized. The toughness of the matrix and the impact damage resistance capability of the composite material thereof are obviously improved by a 'dissolution-swelling' binary phase state synergistic toughening method (the compression strength after impact can reach 340 MPa). Compared with the traditional method, the thermoplastic micron-sized particles are not dissolved in a bismaleimide resin system, so that the influence on the viscosity of a resin matrix and the viscosity at room temperature is small, the viscosity at room temperature of the resin system is 20,000-80,000 Pa.s, the lowest viscosity in the temperature rise process is 2-10 Pa.s, and the good manufacturability of the prepreg hot-melt method resin system is ensured on the basis of realizing the high toughening of the composite material. The toughening method provided by the invention is simple and feasible, and is suitable for engineering preparation of high-toughness bismaleimide resin and large-scale batch production of hot-melt prepreg thereof.
Drawings
FIG. 1 is the rheological property curve (swelling phase-soluble phase binary phase toughening) of bismaleimide resin matrix obtained in example 1 (25 deg.C-180 deg.C, 1 deg.C/min);
FIG. 2 is the rheological property curve (homogeneous solution phase toughening) of bismaleimide resin matrix obtained in comparative example 1 (25 deg.C-180 deg.C, 1 deg.C/min).
Detailed Description
The following detailed description of embodiments of the invention will be made with reference to the accompanying drawings.
The embodiment of the invention provides a bismaleimide resin matrix which comprises the following raw materials:
the thermoplastic polyimide composite material comprises bismaleimide resin monomers, a composite process modifier, thermoplastic resin and thermoplastic polyimide micron-sized particles, wherein the composite process modifier is composed of diallyl bisphenol A and liquid epoxy resin, the thermoplastic resin is dissolved in the composite process modifier, and the thermoplastic polyimide micron-sized particles are swelled in the composite process modifier.
Specifically, the mass ratio of the bismaleimide resin monomer, the composite process modifier, the thermoplastic resin and the thermoplastic polyimide micron-sized particles is 100: 60-90: 5-15: 10 to 45. When the components are prepared according to the proportion, the good manufacturability and the good spreadability (the room temperature viscosity of the resin is 20,000-80,000 Pa.s, and the lowest viscosity in the temperature rising process is 2-10 Pa.s) of the hot-melt prepreg prepared by the bismaleimide resin matrix can be ensured, and the compression strength of the composite material prepared by the hot-melt prepreg can be ensured to reach 340MPa after impact.
Specifically, the mass ratio of the diallyl bisphenol A to the epoxy resin is 75: 5 to 15. When the proportion is adopted for mixing, the full dissolution of the thermoplastic resin can be ensured, and the swelling of the thermoplastic polyimide micron-sized particles can also be ensured.
The bismaleimide resin monomer is preferably one or more of a diphenylmethane diamine type bismaleimide monomer, a toluene diamine type bismaleimide monomer, a m-phenylenediamine type bismaleimide monomer or a diphenyl ether diamine type bismaleimide monomer, more preferably the diphenylmethane diamine type bismaleimide monomer and the toluene diamine type bismaleimide monomer are mixed according to the mass ratio of 50: 30-60, and a resin system with a reduced melting point can be obtained by mixing the two optimized bismaleimide monomers according to the above ratio; the thermoplastic resin is preferably one or more of polyarylethersulfone, polyaryletherketone or polyphenyl ether, more preferably polyarylethersulfone or polyetheretherketone; the liquid epoxy resin is one or the combination of more than one of bisphenol A type epoxy resin, bisphenol F type epoxy resin and hydrogenated bisphenol A type epoxy resin, and the liquid epoxy resin can endow a resin system with good viscosity at room temperature, has proper reaction activity and can ensure that the resin has a prolonged storage period. Specifically, the average particle diameter of the thermoplastic polyimide micron-sized particles is preferably 5 to 40 μm, more preferably 5 to 20 μm. The polyimide particles with the particle size range can improve the in-situ toughening effect of the swelling particles and further improve the impact resistance of the material.
The embodiment of the invention also provides a preparation method of the bismaleimide resin matrix, which comprises the following steps:
step (1): weighing the raw materials according to the raw material proportion provided by the embodiment;
for detailed description of raw materials and corresponding beneficial effects, reference is made to the above raw material examples, which are not described herein again;
step (2): mixing the weighed bismaleimide resin monomer and a composite process modifier for pre-polymerization, adding the weighed thermoplastic resin, and mixing to obtain a dissolved phase;
specifically, in the step (2) in the embodiment of the invention, the weighed bismaleimide resin monomer and the composite process modifier are preferably mixed, and then the mixture is subjected to heat preservation and prepolymerization at the temperature of 120-130 ℃ for 20-40min, and then the mixture is cooled to the temperature of 80-120 ℃, and then the weighed thermoplastic resin is added, subjected to heat preservation and stirring for 20-60min, and mixed to obtain a uniform dissolved phase; when the method is adopted for mixing, the uniform mixing can be ensured, and the controllable rheological property of a resin system and the good manufacturability in the forming process can be ensured.
And (3): and (3) adding the weighed thermoplastic polyimide micron-sized particles into the dissolved phase in the step (2), mixing and stirring for 10-30min to further form a uniform swelling phase with the composite process modifier, and thus obtaining the high-toughness bismaleimide resin matrix.
Specifically, in the embodiment of the present invention, the temperature during the mixing and stirring in step (3) is maintained at 60 to 90 ℃, and the weighed thermoplastic polyimide micron-sized particles are added and stirred for 10 to 30min, and then mixed to obtain the swelling phase. When the method is adopted for mixing, the uniform mixing can be ensured, and the difficult formation of a swelling phase caused by improper temperature can be avoided.
The embodiment of the invention also provides application of the bismaleimide resin matrix in hot-melt prepreg.
The prepreg is characterized in that the reinforcing fibers of the prepreg are carbon fibers, and the gel content is 30-50%.
The following are several specific examples of the present invention, and the raw materials used in each example are all commercially available products:
example 1
The embodiment provides a high-toughness bismaleimide resin matrix, which is prepared by the following specific steps:
step (1): 100kg of bismaleimide resin monomer (diphenylmethane diamine monomer, BMI-01, 50 kg; tolylenediamine monomer, BMI-05, 50 kg; Honghu bismaleimide New Material science and technology Co., Ltd.), 10kg of polyarylethersulfone thermoplastic resin (PES 5003P, Nippon Sumitomo chemical Co., Ltd.), 75kg of diallyl bisphenol A, 5kg of epoxy resin (bisphenol F epoxy resin, NPEF-170, Nanyao epoxy resin (Kunshan) Co., Ltd.), 45kg of polyimide thermoplastic microparticles (PI2080, average particle diameter 10 μm, Upjohn, USA) were weighed;
step (2): mixing the weighed bismaleimide resin monomer with a composite process modifier consisting of diallyl bisphenol A and epoxy resin, carrying out heat preservation and prepolymerization for 20min at 130 ℃, cooling to 120 ℃, adding the weighed polyarylethersulfone thermoplastic resin, carrying out heat preservation and stirring for 30min, and preparing a uniform dissolved phase;
and (3) adding the weighed thermoplastic polyimide microparticles into the uniform dissolved phase obtained in the step (2) at 82 ℃, and stirring for 20min to uniformly disperse the thermoplastic polyimide microparticles and the composite process modifier to form a uniform swelling phase. And cooling to room temperature to finally obtain the bismaleimide resin matrix for the prepreg, which is in a 'dissolving-swelling binary phase state' and is toughened synergistically.
Fracture toughness K of resin castingICIs 2.4J/m2(ii) a The bismaleimide resin matrix and domestic TG800-12k unidirectional carbon fibers are impregnated to prepare a hot-melt prepreg, the content of glue in the hot-melt prepreg is 35%, the hot-melt prepreg has good spreadability and viscosity (the room-temperature viscosity of the matrix resin is 20,000 Pa.s, the lowest viscosity in the temperature rise process is 7.9 Pa.s), and the post-impact compressive strength of the cured test composite material is 340 MPa.
Comparative example 1
The base resin system was identical to example 1 except that the same amount of thermoplastic polyethersulfone was used in place of the polyimide particles in (2). Obtaining the toughened bismaleimide resin matrix for the prepreg, which is toughened by the thermoplastic resin polyether sulfone through a single dissolved phase. Fracture toughness K of resin castingICIs 2.0J/m2The prepreg is impregnated with domestic TG800-12k unidirectional carbon fibers to prepare a hot-melt prepreg, the dry spreading property of the prepreg is poor (the room temperature viscosity of a resin matrix is 110,000 Pa.s, the lowest viscosity in the temperature rise process is 14 Pa.s), and the post-impact compressive strength of the cured test composite material is 180 MPa.
Comparative example 2
The matrix resin system except for step (2) was prepared using an equivalent amount of a completely insoluble polyamideimide PAI (Solvay Corp.)
4000TF) was used instead of the thermoplastic polyimide particles, the other resin components were exactly the same as in example 1 except that the swollen phase could not be formed due to complete insolubilization. Obtaining the toughened bismaleimide resin matrix for the prepreg toughened by the polyether sulfone and the polyamide polyimide thermoplastic resin. Fracture toughness K of resin castingICIs 1.4J/m2The hot-melt prepreg prepared by impregnating the composite material with T800 unidirectional carbon fiber has good spreadability and operability, but because PAI is insoluble and non-swelling in the mixing and curing processes, the interfacial bonding force is weak, and the impact of the composite material is tested after curingThe post-compressive strength was 130 MPa.
Example 2
The embodiment provides a high-toughness bismaleimide resin matrix, which is prepared by the following specific steps:
step (1): weighing 100kg of bismaleimide resin monomer (diphenylmethane diamine type bismaleimide monomer, BDM, northwest chemical research institute), 10kg of polyaryletherketone thermoplastic resin (PEK-C, Xuzhou engineering plastics factory), 80kg of diallyl bisphenol A, 10kg of epoxy resin (bisphenol A epoxy resin, CYD-115, Yueyang petrochemical epoxy resin factory), and 40kg of polyimide particles (PI molding powder SS100P, 10 microns, Hangzhou plastic Germing Technology Co., Ltd.);
step (2): mixing the weighed bismaleimide resin monomer with a composite process modifier consisting of diallyl bisphenol A and epoxy resin, carrying out heat preservation and prepolymerization at 120 ℃ for 20min, cooling to 110 ℃, adding the weighed polyaryletherketone thermoplastic resin, carrying out heat preservation and stirring for 60min, and preparing a uniform dissolved phase; and (3) adding the weighed polyimide particles into the uniform dissolved phase obtained in the step (2) at 90 ℃, and stirring for 10min to disperse the polyimide particles and the composite process modifier to form a swelling phase. And cooling to room temperature to finally obtain the bismaleimide resin matrix for the prepreg, which is in a 'dissolving-swelling binary phase state' and is toughened synergistically.
Fracture toughness K of resin castingICIs 2.1J/m2(ii) a The bismaleimide resin matrix and the T700 unidirectional carbon fiber are impregnated to prepare the hot-melt prepreg, the content of the hot-melt prepreg is 30%, the hot-melt prepreg has good spreadability and viscosity (the room temperature viscosity of the matrix resin is 30,000 Pa.s, the lowest viscosity in the temperature rise process is 4 Pa.s), and the post-impact compressive strength of the cured test composite material is 280 MPa.
Example 3
The embodiment provides a high-toughness bismaleimide resin matrix, which is prepared by the following specific steps:
step (1): weighing 100kg of bismaleimide monomer (m-phenylenediamine monomer, Tianyi chemical engineering limited company in Yangyang Henan), 12kg of polyarylethersulfone thermoplastic resin (PES 3200, Beijing Kary New Material science and technology limited company), 70kg of diallyl bisphenol A, 12kg of epoxy resin (bisphenol F epoxy resin, NPEF-170, Nanyao epoxy resin (Kunshan) limited company) and 25kg of polyimide particles (SK-0180, 10 microns, Changzhou Shangshouke New Material limited company);
step (2): mixing the weighed bismaleimide resin monomer with a composite process modifier consisting of diallyl bisphenol A and epoxy resin, carrying out heat preservation and prepolymerization at 120 ℃ for 30min, cooling to 100 ℃, adding the weighed polyaryletherketone thermoplastic resin, carrying out heat preservation and stirring for 40min, and preparing a uniform dissolved phase; and (3) adding the weighed polyimide particles into the uniform dissolved phase obtained in the step (2) at 75 ℃, and stirring for 10min to disperse the polyimide particles and the composite process modifier to form a swelling phase. And cooling to room temperature to finally obtain the bismaleimide resin matrix for the prepreg, which is in a 'dissolving-swelling binary phase state' and is toughened synergistically.
Fracture toughness K of resin castingICIs 2.2J/m2(ii) a The bismaleimide resin matrix and the T300 unidirectional carbon fiber are impregnated to prepare the hot-melt prepreg, the content of the hot-melt prepreg is 35%, the hot-melt prepreg has good spreadability and viscosity (the room temperature viscosity of the matrix resin is 35,000 Pa.s, the lowest viscosity in the temperature rise process is 8 Pa.s), and the post-impact compressive strength of the cured test composite material is 260 MPa.
In each example, the viscosity of the resin system (change in viscosity rheology during temperature rise, measured from room temperature) was measured using a Physica MCR 301 rheometer from Anton Paar, with a temperature rise rate of 1 deg.C/min, in the range of 25 deg.C to 180 deg.C. The mechanical properties of the resins and composites were measured by a universal material tester from Instron, USA, and the fracture toughness K of the resin casting was determinedICThe test was done according to ASTM D5045-99, the Compression After Impact strength (Compression After Impact) of the composite was used to characterize the Impact damage resistance of the composite, the Impact energy was 6.67J/mm, and the test was done according to GB/T21239-2007.
The above description is only one embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
The invention has not been described in detail in part of the common general knowledge of those skilled in the art.
Claims (9)
1. The bismaleimide resin matrix is characterized by comprising the following raw materials:
the thermoplastic polyimide composite material comprises bismaleimide resin monomers, a composite process modifier, thermoplastic resin and thermoplastic polyimide micron-sized particles, wherein the composite process modifier is composed of diallyl bisphenol A and liquid epoxy resin, the thermoplastic resin is dissolved in the composite process modifier, and the thermoplastic polyimide micron-sized particles are swelled in the composite process modifier; the thermoplastic resin is one or more of polyarylethersulfone, polyaryletherketone or polyphenyl ether; the average particle size of the thermoplastic polyimide micron-sized particles is 5-40 mu m;
the mass ratio of the bismaleimide resin monomer, the composite process modifier, the thermoplastic resin and the thermoplastic polyimide micron-sized particles is 100: 60-90: 5-15: 10-45;
the mass ratio of the diallyl bisphenol A to the liquid epoxy resin is 75: 5 to 15.
2. The bismaleimide resin matrix of claim 1 wherein the bismaleimide resin monomer is one or a combination of more than one of a diphenylmethane diamine type bismaleimide monomer, a toluene diamine type bismaleimide monomer, a m-phenylene diamine type bismaleimide monomer, or a diphenyl ether diamine type bismaleimide monomer.
3. The bismaleimide resin matrix of claim 2 wherein the bismaleimide resin monomer is a mixture of a diphenylmethane diamine monomer and a toluene diamine monomer at a mass ratio of 50:30 to 60.
4. The bismaleimide resin matrix of claim 1 wherein the liquid epoxy resin is one or a combination of more than one of bisphenol a epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol a epoxy resin.
5. A preparation method of a bismaleimide resin matrix is characterized by comprising the following steps:
(1) weighing the raw materials according to the raw material ratio provided by any one of claims 1 to 4:
(2) mixing the weighed bismaleimide resin monomer and a composite process modifier for pre-polymerization, adding the weighed thermoplastic resin, and mixing to obtain a dissolved phase;
(3) and adding the weighed thermoplastic polyimide micron-sized particles into the dissolved phase, mixing, and cooling to obtain the bismaleimide resin matrix.
6. The method for preparing bismaleimide resin matrix as claimed in claim 5, wherein the bismaleimide resin monomer weighed in step (2) is mixed with the composite process modifier, pre-polymerized at 120-130 ℃ for 20-40min, cooled to 80-120 ℃, added with the weighed thermoplastic resin, stirred for 20-60min, and mixed to obtain the dissolved phase.
7. The method for preparing bismaleimide resin matrix as claimed in claim 6, wherein the temperature of the dissolved phase in step (3) is maintained at 60-90 ℃, and the weighed thermoplastic polyimide micron-sized particles are added and stirred for 10-30min, and mixed to form the swelling phase.
8. Use of a bismaleimide resin matrix according to any one of claims 1 to 4 in a hot melt prepreg.
9. Use according to claim 8, wherein the reinforcing fibres of the prepreg are carbon fibres and the gel content is between 30% and 50%.
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