CN111978727B - A high-strength and high-modulus hot-melt bismuth resin composition, preparation method, prepreg, and composite material - Google Patents

Abstract

The invention relates to a high-strength and high-modulus hot-melt bisquer resin composition, a preparation method, a prepreg, and a composite material. The composition comprises a bisquer resin monomer, a process modifier, an aromatic amine curing agent, and inorganic nanoparticles And thermoplastic resin, the bis-horse resin monomer is: one or more of the diphenylmethane diamine-type bis-horse monomer IA, m-phenylenediamine-type bis-horse monomer IB or toluenediamine-type bis-horse monomer IC , and the composition of benzoic anilide-type bis-horse monomer ID, the resin matrix improves the modulus of the resin matrix through the angle of intermolecular force and molecular packing density, and improves the process characteristics of the resin matrix by selecting thermoplastic resins with different active groups and the interface bonding force with the reinforced carbon fiber, while adding surface-activated nano-inorganic silica particles to improve the modulus of the matrix, a hard interface phase is formed between the high-modulus resin and the fiber; the composite material prepared by the resin matrix and the carbon fiber is 0° The compressive strength is up to 2100MPa, and the compressive/tensile coefficient of the material is up to 0.83.

Description

A high-strength and high-modulus hot-melt bismuth resin composition, preparation method and prepreg, composite composite material

technical field

The invention relates to a high-strength and high-modulus hot-melt bismuth resin composition, a preparation method, a prepreg and a composite material, and belongs to the technical field of hot-melt prepreg manufacturing for structural composite materials.

Background technique

Carbon fiber reinforced resin matrix composites have a series of excellent properties such as high specific strength, high specific modulus, good designability, fatigue resistance and good shock absorption performance. They can be manufactured into large-scale complex components and are widely used in aviation aerospace field.

In the actual use process, the requirements for composite materials are quite different in different application occasions and use environments. Specifically, from the perspective of the service mechanical environment of resin-based composite materials for aerospace weapons and equipment, the complex cabin of land-based strategic missiles is represented, which mainly bears compression conditions. The new generation of strategic missiles needs to continue to significantly reduce the weight of the missile body structure, and the dynamic compression load is higher than that of the existing models, which puts forward more stringent requirements for the compression performance of the missile body structure.

The tensile strength and modul The compressive performance is unbalanced (compression/tensile matching coefficient is about 0.62), and the insufficient compressive strength has become the bottleneck of design and application, restricting the development of aerospace weapons and equipment. Therefore, structural composite materials for missile weapons are in urgent need of high-performance resin-based composite materials with better compression properties and good balance between compression and tension.

In view of the mismatch between the compressive strength and tensile strength of composite materials, technicians in the field of composite materials have carried out exploratory research on improving the compressive strength and improving the balance between compression and tension of high-performance carbon fiber composites. Liu Wei et al. obtained the corresponding hot-melt prepreg by blending m-aminophenol epoxy resin and bisphenol A epoxy resin and using 4,4-diaminodiphenylsulfone (4,4-DDS) as the curing agent. The 0° compressive strength of the composite material can reach up to 1466MPa, and the research on improving the compressive properties of the resin matrix composite material mainly focuses on the epoxy resin composite material. There are no reports on the improvement of the compression properties of Shuangma resin composites. To sum up, the 0° compressive strength of the current Shuangma resin composite material is still low, which has become the bottleneck technology for its further expansion.

SUMMARY OF THE INVENTION

The purpose of the present invention is to overcome the above-mentioned defects of the prior art, and to provide a high-strength and high-modulus hot-melt bismuth resin composition and a preparation method thereof. , 0° compressive strength/0° tensile strength coefficient is as high as 0.83; at the same time, the resin matrix has good manufacturability and layability, which can meet the design requirements of high-pressure tensile matching of carbon fiber composite materials in the aerospace field.

Another object of the present invention is to provide a prepreg and a composite material comprising the high-strength and high-modulus hot-melt bismuth resin composition.

The above-mentioned purpose of the present invention is mainly achieved through the following technical solutions:

A high-strength and high-modulus hot-melt bismuth resin composition comprises the following components in parts by mass:

Wherein, the described bis-horse resin monomer is: any one or several of the diphenylmethane diamine type bis-horse monomer IA, m-phenylenediamine type bis-horse monomer IB or toluenediamine type bis-horse monomer IC Kind, with the composition of benzoic anilide type two horse monomer ID, concrete structural formula is as follows:

In the above-mentioned high-strength and high-modulus hot-melt bihorse resin composition, in the bimbar resin monomer composition, the mass percentage content of benzilide-type bimbar monomer ID is 10%-50%.

In the above-mentioned high-strength and high-modulus hot-melt bihorse resin composition, the process modifier is a combination of diallyl bisphenol A and triglycidyl m-aminophenol, and the mass ratio of the two is 1:0.5- 1.5.

In the above-mentioned high-strength and high-modulus hot-melt bismuth resin composition, the inorganic nanoparticles are silica nanoparticles with amino surface activation or epoxy surface activation; the particle size of the silica nanoparticles is 20-100 nm .

In the above-mentioned high-strength and high-modulus hot-melt bihorse resin composition, the aromatic amine curing agent is 3,3-diaminodiphenyl sulfone; the particle size of the aromatic amine curing agent is 5-20 μm.

In the above-mentioned high-strength and high-modulus hot-melt bismuth resin composition, the tensile modulus of the thermoplastic resin is greater than or equal to 3.2 GPa.

In the above-mentioned high-strength and high-modulus hot-melt bismuth resin composition, the thermoplastic resin is one or a combination of polyarylethersulfone or polyimide.

The preparation method of the above-mentioned high-strength and high-modulus hot-melt bismuth resin composition comprises the steps:

(1), according to 100 parts of double horse resin monomer, 40-80 parts of process modifier, 5-15 parts of aromatic amine curing agent, 1-5 parts of inorganic nanoparticles, 5-25 parts of thermoplastic resin, weigh each raw material ;

(2) After heating the process modifier and thermoplastic resin to 120-150°C and mechanical stirring for 30-120min, after the complete dissolution, add inorganic nanoparticles and stir for 20-40min until the dispersion is uniform, adjust the temperature to 100-120°C and add Shuangma The resin monomer is stirred until it is melted and transparent;

(3), cooling the components obtained in step (2) to 80-95° C., adding aromatic amine curing agent, stirring for 20-40 min, and mixing evenly, cooling to room temperature to obtain a high-strength and high-modulus hot-melt bihorse resin composition.

A hot-melt prepreg material, comprising the above-mentioned high-strength and high-modulus hot-melt bismuth resin composition and reinforcing fibers.

In the above hot-melt prepreg, the mass percentage content of the high-strength and high-modulus hot-melt bismuth resin composition is 30%-36%; the reinforcing fibers are carbon fibers.

A composite material is prepared by using the above-mentioned hot-melt prepreg.

In the above composite materials, the 0° compressive strength is greater than or equal to 1850 MPa, and the 0° compressive strength/0° tensile strength matching coefficient of the composite material is greater than or equal to 0.7.

Compared with the prior art, the present invention has the following beneficial effects:

(1), the present invention provides a high-strength and high-modulus hot-melt bismuth resin matrix and a preparation method thereof. The resin matrix improves the modulus of the resin matrix through the angle of intermolecular force and molecular packing density. The resin improves the process characteristics of the resin matrix and its interface bonding force with the reinforced carbon fiber; at the same time, the addition of surface-activated nano-inorganic silica particles further improves the matrix modulus, and further forms a hard interface phase between the high-modulus resin and the fiber. Through the above-mentioned various designs, the compressive-tensile balance characteristics of the composite material prepared by the resin matrix and carbon fiber reinforcement have been significantly improved, and the 0° compressive strength/0° tensile strength coefficient is as high as 0.83; at the same time, the resin matrix has good manufacturability It can meet the design requirements of high-pressure tensile matching of carbon fiber composite materials in the aerospace field.

(2), the bis-horse resin monomer of the present invention selects the composition of two or more bis-horse monomers, and one of them is the benzoic anilide type bis-horse monomer ID, by the pair of bis-horse resin monomer group The optimized design of the composition and content, by improving the intermolecular force of the resin system (containing amide hydrogen bond bis-horse monomer) and the bulk density (free volume radius of 0.222nm, resin system density of 1.39g/cm ³ ), effectively improved the The modulus of the resin matrix and its interfacial bonding force with carbon fibers, and high-modulus thermoplastic resin is used as the rheological control component to meet the requirements of the hot-melt process and minimize the loss of the resin matrix modulus. The resin matrix finally obtained It has higher matching with high-strength carbon fiber.

(3), the inorganic nanoparticles that the present invention adopts are the silica nanoparticles of amino surface activation or epoxy surface activation to further improve the matrix modulus, and further form a hard interface phase between the high-modulus resin and the fiber; A thermoplastic resin with an elongation modulus ≥ 3.2GPa, specifically one or a combination of polyarylethersulfone or polyimide, and the process characteristics of the resin matrix and its interface with the reinforced carbon fiber are improved by selecting thermoplastic resins with different active groups. Binding force;

(4), the tensile strength of the high-strength and high-modulus hot-melt bismuth resin of the present invention is ≥80MPa, and the modulus is ≥4.8GPa. Its 0° compressive strength can be as high as 2100MPa, and the compressive/tensile coefficient of the material can be as high as 0.83, 0° compressive strength/0° tensile strength ≥ 0.7, which is significantly improved compared with the existing resin-based composite materials. It can meet the design requirements of new aerospace equipment.

(5) The design and preparation method of the bismuth resin matrix system for improving the compression/tensile matching of high-strength carbon fiber reinforced resin-based composite materials provided by the present invention is simple and easy to implement, and is suitable for the engineering of high-strength and high-modulus hot-melt bismuth resins Preparation, large-scale batch production and engineering application of hot melt prepregs.

Description of drawings

Fig. 1 is the stress-strain curve of the compressive properties of TG800-high-strength and high-modulus hot-melt bismuth resin composite material obtained in Example 1 of the present invention;

FIG. 2 is a CT scanning topography of the fracture surface of a typical compression sample of TG800-high-strength and high-modulus hot-melt bismuth resin composite material obtained in Example 1 of the present invention.

Detailed ways

Below in conjunction with accompanying drawing and specific embodiment, the present invention is described in further detail:

The invention provides a high-strength and high-modulus hot-melt bismuth resin matrix, the raw material of which includes the following components:

Wherein, the described bis-horse resin monomer is: any one or several of the diphenylmethane diamine type bis-horse monomer IA, m-phenylenediamine type bis-horse monomer IB or toluenediamine type bis-horse monomer IC Kind, with the composition of benzoic anilide type two horse monomer ID, concrete structural formula is as follows:

In the double horse resin monomer composition, the mass percentage content of the benzoic anilide type double horse monomer ID is 10%-50%.

When the components are prepared according to the above proportions, it can ensure that the hot-melt prepreg prepared by the double horse resin matrix has good manufacturability and layability (the viscosity of the resin at room temperature is 20,000-100,000 Pa·s, and the minimum temperature during the heating process is The viscosity is 1.0-6.0Pa·s), which can ensure that the obtained bismuth resin matrix has the characteristics of high strength and high modulus, and the compressive strength/tensile matching coefficient of the prepared carbon fiber reinforced composite material can reach up to 0.83.

Among them, in the combination of bis-horse resin monomers, the IB and IC imide groups are meta-positions, which can provide higher stacking efficiency and packing density. Benzoanilide bis-horse monomer ID has molecular hydrogen bonds, which can enhance the Intermolecular force, the above combination can synergistically improve the modulus of the bis-horse resin system. The process modifier is the composition of diallyl bisphenol A and triglycidyl m-aminophenol, and the ratio of the two is 1:0.5-1.5, which can further improve the stacking efficiency of the cured product of the bis-horse resin system .

The aromatic amine curing agent is 3,3-diaminodiphenylsulfone, and the particle size of the aromatic amine curing agent is 5-20 μm. Due to the existence of cis and trans spatial conformations of the -NH2 functional group, further improved stacking can be obtained. Therefore, a high-strength and high-modulus bismuth resin matrix can be obtained and the compression/tensile matching coefficient of the composite material is further improved. At the same time, the bismuth resin system using the above curing agent has suitable reactivity, which can ensure that the resin has a prolonged period of time. storage period.

Inorganic nanoparticles are silica nanoparticles with amino surface activation or epoxy surface activation, which have good compatibility with the bis-horse resin system. At the same time, the nanoparticles are inorganic particles, which can improve the performance of the bis-horse resin matrix. Stiffness, forms a hard interface phase in the composite material, further improves the failure mode of the composite material during compression failure, and increases the 0° compressive strength of the material.

The thermoplastic resin rheology control component is preferably one or more combinations of polyarylethersulfone and polyimide, more preferably polyarylethersulfone or polyimide with tensile modulus ≥ 3.2GPa, using the The high-modulus thermoplastic resin not only controls the process rheology of the dual-horse resin system to meet the requirements of the hot-melt process, but also minimizes the sacrifice of the overall resin matrix modulus.

The present invention also provides a method for preparing a high-strength and high-modulus hot-melt bismuth resin matrix, comprising the following steps:

(1), according to 100 parts of double horse resin monomer, 40-80 parts of process modifier, 5-15 parts of aromatic amine curing agent, 1-5 parts of inorganic nanoparticles, 5-25 parts of thermoplastic resin, weigh each raw material ;

(2) After heating the process modifier and thermoplastic resin to 120-150°C and mechanical stirring for 30-120min, after the complete dissolution, add inorganic nanoparticles and stir for 20-40min until the dispersion is uniform, adjust the temperature to 100-120°C and add Shuangma The resin monomer is stirred until it is melted and transparent;

Specifically, when this method is used for mixing, it can not only ensure full dissolution of thermoplastic resin, uniform dispersion of inorganic nanoparticles and melting of bismuth monomer, but also ensure that the room temperature viscosity and rheological properties of the resin system are controllable.

(3), cooling the components obtained in step (2) to 80-95° C., adding aromatic amine curing agent, stirring for 20-40 min, and mixing evenly, cooling to room temperature to obtain a high-strength and high-modulus hot-melt bihorse resin composition.

Specifically, when this method is used for mixing, it can not only ensure uniform mixing, but also avoid poor processability caused by excessive prepolymerization degree or long time caused by unsuitable temperature.

The invention also provides the application of the above-mentioned high-strength and high-modulus hot-melt bismuth resin matrix in hot-melt prepreg. Wherein, the prepreg material includes the above-mentioned high-strength and high-modulus hot-melt bismuth resin composition and reinforcing fibers, and the glue content is 30%-36%. The reinforcing fibers are carbon fibers.

The present invention also provides a high-strength carbon fiber reinforced composite material prepared by using the prepreg, which has a 0° compressive strength of ≥1850 MPa, a 0° tensile strength of ≥2500 MPa, and a compression/tensile matching coefficient of the material ≥0.7.

In the following examples, the viscosity of the resin system (measured from room temperature, the viscosity rheological properties change during the heating process) was tested using the Physica MCR 301 rheological analyzer of Anton Paar Company, the heating rate was 1°C/min, and the test range It is 25℃-225℃. The mechanical properties of resin and composite materials were tested by the universal material testing machine of Instron Company in the United States. The tensile strength and modulus of resin castings were tested according to ASTM D 695, and the 0° tensile strength test of composite materials was performed according to ASTM D 3039, 0 °Compressive strength test according to ASTM D 3410/6641. Compression/tensile matching factor for composites = 0° compressive strength/0° tensile strength (unitless).

Example 1

This embodiment provides a high-strength and high-modulus hot-melt bismaleimide resin matrix, and the specific preparation method includes:

Step (1), take raw material according to proportioning;

Step (2), 40kg diallyl bisphenol A and 40kg triglycidyl m-aminophenol, 10kg thermoplastic polyimide P84STD are heated to 120 ℃ of mechanical stirring 60min and dissolve to transparent state, add 3kg amino-modified nanometer two Silica particles (SNL, Institute of Chemistry, Chinese Academy of Sciences, with an average particle size of 60nm) were stirred for 20-40min until uniformly dispersed; the temperature was lowered to 110°C, and 50kg of m-phenylenediamine-type bis-horse monomer (IB) and 50kg of benzoic acid were added. The mixture in the aniline bis-horse monomer (ID) is stirred to a melted state;

In step (3), the components obtained in step (2) are cooled to 85° C., 15kg of 3,3-diaminodiphenylsulfone aromatic amine curing agent is added, stirred for 30 minutes, and mixed evenly, and cooled to room temperature to obtain a high-strength and high-modulus bisma resin mixture.

The tensile strength of the resin casting body is 90MPa, and the tensile modulus is 5.0GPa; the obtained high-strength and high-modulus hot-melt bismuth resin is impregnated with domestic TG800-12k unidirectional carbon fiber to make a hot-melt prepreg. The hot-melt prepreg contains The amount of glue is 32%, and it has good spreadability and viscosity (the viscosity of the matrix resin at room temperature is 22,000Pa s). The stretch match factor is 0.83.

Figure 1 shows the stress-strain curve of the compressive properties of the TG800-high-strength and high-modulus hot-melt bismuth resin composite material obtained in Example 1 of the present invention.

Figure 2 shows the CT scanning topography of the fracture surface of a typical compression sample of the TG800-high-strength and high-modulus hot-melt bismuth resin composite material obtained in Example 1 of the present invention.

Example 2

This embodiment provides a high-strength and high-modulus hot-melt bismaleimide resin matrix, and the specific preparation method includes:

Step (1), take raw material according to proportioning;

Step (2), 30kg diallyl bisphenol A and 45kg triglycidyl m-aminophenol, 8kg polyaryl ether sulfone PES-C are heated to 120 ℃ mechanical stirring 30min and dissolve to transparent state, add 2kg amino modified nanometer Silica particles (SNL, Institute of Chemistry, Chinese Academy of Sciences, with an average particle size of 60nm) were stirred for 20-40min until uniformly dispersed; cooled to 105°C, added 20kg of diphenylmethanediamine-type bisma monomer (IA), 40kg of The mixture in the phenylenediamine-type bis-horse monomer (IB) and 40kg of benzoic anilide-type bis-horse monomer (ID) is stirred to a melted state;

In step (3), the components obtained in step (2) are cooled to 80° C., 10 kg of 3,3-diaminodiphenylsulfone aromatic amine curing agent is added, stirred for 20 minutes, and mixed evenly, and cooled to room temperature to obtain a high-strength and high-modulus bisma resin mixture.

The tensile strength of the resin casting body is 100MPa, and the tensile modulus is 5.3GPa; the obtained high-strength and high-modulus hot-melt bismuth resin is impregnated with domestic TG800-12k unidirectional carbon fiber to make a hot-melt prepreg. The hot-melt prepreg contains The amount of glue is 32%, and it has good spreadability and viscosity (the viscosity of the matrix resin at room temperature is 30,000Pa s). The stretch match factor is 0.76.

Example 3

This embodiment provides a high-strength and high-modulus hot-melt bismaleimide resin matrix, and the specific preparation method includes:

Step (1), take raw material according to proportioning;

Step (2), 50kg diallyl bisphenol A and 30kg triglycidyl m-aminophenol, 5kg polyaryl ether sulfone PES-C are heated to 120 ℃ mechanical stirring 30min and dissolve to transparent state, add 5kg amino modified nanometer Silica particles (SNL, Institute of Chemistry, Chinese Academy of Sciences, with an average particle size of 60nm) were stirred for 20-40min until uniformly dispersed; the temperature was lowered to 105°C, and 60kg of toluenediamine-type bis-horse monomer (IC) and 40kg of benzoic acid were added. The mixture in the aniline bis-horse monomer (ID) is stirred to a melted state;

In step (3), the components obtained in step (2) were cooled to 80° C., 10 kg of 3,3-diaminodiphenylsulfone aromatic amine curing agent was added, stirred for 40 minutes, and the mixture was evenly mixed, and cooled to room temperature to obtain a high-strength and high-modulus bisma resin mixture.

The tensile strength of the resin casting body is 95MPa, and the tensile modulus is 4.9GPa; the obtained high-strength and high-modulus hot-melt bismuth resin is impregnated with domestic TG800-12k unidirectional carbon fiber to make a hot-melt prepreg. The hot-melt prepreg contains The amount of glue is 32%, and it has good spreadability and viscosity (the viscosity of the matrix resin at room temperature is 18,000Pa s). The stretch match factor is 0.80.

The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited to this. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, All should be included within the protection scope of the present invention.

The parts of the present invention that are not described in detail belong to the common knowledge of those skilled in the art.

Claims (11)

1. A high-strength high-modulus hot-melt bismaleimide resin composition is characterized in that: the composition comprises the following components in parts by mass:

wherein the bismaleimide resin monomer is: the composition of any one or more of diphenylmethane diamine type bismaleimide monomer IA, m-phenylenediamine type bismaleimide monomer IB or toluene diamine type bismaleimide monomer IC and phenylanilide type bismaleimide monomer ID has the following specific structural formula:

in the bismaleimide resin monomer composition, the mass percentage content of the benzanilide type bismaleimide monomer ID is 10-50%.

2. A high-strength high-modulus hot-melt bismaleimide resin composition as claimed in claim 1, wherein: the process modifier is a combination of diallyl bisphenol A and triglycidyl meta-aminophenol, and the mass ratio of the diallyl bisphenol A to the triglycidyl meta-aminophenol is 1: 0.5-1.5.

3. A high-strength high-modulus hot-melt bismaleimide resin composition as claimed in claim 1, wherein: the inorganic nano particles are silicon dioxide nano particles with amino surface activated or epoxy surface activated; the particle size of the silicon dioxide nano particles is 20-100 nm.

4. A high-strength high-modulus hot-melt bismaleimide resin composition as claimed in claim 1, wherein: the aromatic amine curing agent is 3, 3-diaminodiphenyl sulfone; the particle size of the aromatic amine curing agent is 5-20 mu m.

5. A high-strength high-modulus hot-melt bismaleimide resin composition as claimed in claim 1, wherein: the tensile modulus of the thermoplastic resin is more than or equal to 3.2 GPa.

6. A high-strength high-modulus hot-melt bismaleimide resin composition as claimed in claim 5 wherein: the thermoplastic resin is one or a combination of polyarylethersulfone and polyimide.

7. A method for preparing a high-strength high-modulus hot-melt bismaleimide resin composition as claimed in any one of claims 1 to 6, wherein: the method comprises the following steps:

(1) weighing each raw material according to 100 parts of bismaleimide resin monomer, 40-80 parts of process modifier, 5-15 parts of aromatic amine curing agent, 1-5 parts of inorganic nano particles and 5-25 parts of thermoplastic resin;

(2) heating the process modifier and the thermoplastic resin to the temperature of 120-;

(3) and (3) cooling the components obtained in the step (2) to 80-95 ℃, adding an aromatic amine curing agent, stirring for 20-40min, uniformly mixing, and cooling to room temperature to obtain the high-strength high-modulus hot melt bismaleimide resin composition.

8. A hot melt prepreg characterized by: a high-strength high-modulus hot-melt bismaleimide resin composition comprising the high-modulus hot-melt bismaleimide resin composition as claimed in any one of claims 1 to 6 and a reinforcing fiber.

9. A hot melt prepreg according to claim 8, wherein: the high-strength high-modulus hot-melt bismaleimide resin composition comprises 30-36% by mass; the reinforcing fibers are carbon fibers.

10. A composite material characterized by: prepared using the hot melt prepreg according to claim 8 or 9.

11. The composite material of claim 10, wherein: the 0-degree compressive strength is more than or equal to 1850MPa, and the 0-degree compressive strength/0-degree tensile strength matching coefficient of the composite material is more than or equal to 0.7.

Images