CN110218417B - Hierarchical pore boron nitride structural member/epoxy resin composite material - Google Patents
Hierarchical pore boron nitride structural member/epoxy resin composite material Download PDFInfo
- Publication number
- CN110218417B CN110218417B CN201910530843.5A CN201910530843A CN110218417B CN 110218417 B CN110218417 B CN 110218417B CN 201910530843 A CN201910530843 A CN 201910530843A CN 110218417 B CN110218417 B CN 110218417B
- Authority
- CN
- China
- Prior art keywords
- boron nitride
- structural member
- epoxy resin
- nitride structural
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
A hierarchical pore boron nitride structural member/epoxy resin composite material comprises the following components in percentage by mass: aryl ester type liquid crystal epoxy resin, a hierarchical pore boron nitride structural member, phenolic resin, a curing agent and an accelerator. The preparation method comprises the following steps: heating, melting and uniformly stirring aryl ester type liquid crystal epoxy resin, phenolic resin, a curing agent and an accelerant, then soaking the mixture on a hierarchical pore boron nitride structural member formed by SLS and a degreasing process to obtain a prepreg base, and then placing the prepreg base in a vacuum oven for curing to obtain the hierarchical pore boron nitride structural member/epoxy resin composite material. The hierarchical pore boron nitride structural member/epoxy resin composite material has extremely high thermal conductivity and ultrahigh strength, simultaneously has good toughness and rigidity, is simple in forming process and high in flexibility, can realize the abnormity of the composite material, meets the requirements of different occasions, and realizes the complete controllability of filler dispersion in the forming process.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a hierarchical pore boron nitride structural member/epoxy resin composite material, in particular to a hierarchical pore boron nitride structural member/epoxy resin composite material for a high-power searchlight backseat and a high-power motor shell.
Background
High power equipment must be accompanied with the high heat, if the heat that produces can't in time spill, equipment operating temperature is too high, not only increases the energy consumption, still can influence the stability that equipment used. Therefore, a polymer having a high thermal conductivity and high strength is essential.
According to the modern microscopic theory of solid physical heat conduction, the high heat conduction material can also be prepared by doping metal oxide or inorganic non-metal powder with higher heat conductivity into the polymer matrix material to prepare the high heat conduction polymer matrix composite material. For filled thermally conductive polymer-based materials, the thermal conductivity depends on the synergy of the polymer resin matrix and the thermally conductive filler. When the amount of the filler added is relatively low, the filler exists mainly in an isolated form in the polymer matrix, and does not contact with each other and affect each other. In this case, the continuous phase is also the polymer matrix and the filler is encapsulated as a dispersed phase by the polymer matrix, much like the "sea-island two-phase system" structure in polymer blend systems. When the addition amount of the heat-conducting filler reaches a specific value, the particles are contacted with each other to form a passage, so that the high polymer is converted from a poor heat conductor to a good heat conductor. This transition is known as "percolation". Once the addition amount of the filler reaches the percolation threshold or more, the filler and the filler or the filler aggregate and the aggregate are mutually contacted, and a local heat conduction chain or a local heat conduction net is formed in the composite material; if the amount of the filler is further increased, the local heat conduction chains or heat conduction nets can be mutually connected and penetrated to form a heat conduction network penetrating through the whole polymer matrix material, so that the polymer and the filler can be both continuous phases, and the filler aggregate heat conduction network and the polymer matrix can form a mutually penetrated network structure, so that the heat conduction performance of the filled composite material is remarkably improved. This means that the presence of the filler has little influence on the thermal conductivity when the amount of the filler does not reach the threshold value, and even when the amount of the filler exceeds the threshold value, a part of the filler is in an isolated state and does not contribute to the improvement of the thermal conductivity. Based on this, it is proposed to make the fillers contact each other as much as possible to form a heat conducting network, i.e. to lower the "threshold value", by controlling the dispersion state of the fillers in the matrix without increasing the amount of the fillers, thereby generating the "isolated dispersed heat conduction" theory.
Although the modification method in the prior art can effectively construct the heat-conducting network, the fillers forming the heat-conducting network are only gathered together by external pressure and lack the connection of bonding force (such as intermolecular acting force, chemical bond and the like), so that the mechanical property of the material is inevitably reduced, and pores exist among the fillers, so that the heat-conducting property is reduced.
The heat conductivity coefficient of the current commercial heat-conducting resin is mostly about 1W/(mK), which is far away from the practical application requirement. Further, since the amount of the additive is high, the mechanical properties and processability of the product are deteriorated, and the product cannot be used in a limited environment.
The Chinese patent application No. CN201811469670.2 discloses a preparation method of a high-thermal-conductivity hexagonal boron nitride/epoxy resin composite material, which takes hexagonal boron nitride and epoxy resin as raw materials, prepares the high-thermal-conductivity hexagonal boron nitride/epoxy resin composite material through solvent dispersion, vacuum filtration, tabletting treatment and curing treatment, has a complex process, is only gathered together by external pressure, lacks binding force, can cause the mechanical property of the material to be reduced, and has air holes among fillers to reduce the thermal conductivity.
Chinese patent application No. CN201811004019.8 discloses a method for preparing a boron nitride/epoxy resin composite material with a three-dimensional structure, which has a complex process and low thermal conductivity.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects, the invention aims to provide the hierarchical pore boron nitride structural member/epoxy resin composite material which has extremely high heat conductivity and ultrahigh strength, simultaneously has good toughness and rigidity, is simple in forming process and high in flexibility, can realize the abnormity of the composite material, meets the requirements of different occasions, and realizes the complete controllability of filler dispersion in the forming process.
The purpose of the invention is realized by the following technical scheme:
a hierarchical pore boron nitride structural member/epoxy resin composite material comprises the following components in percentage by mass:
43-63 wt% of an aryl ester type liquid crystal epoxy resin,
10wt% of the multi-level hole boron nitride structural member,
9-17 wt% of phenolic resin,
12-20 wt% of curing agent and accelerator.
Further, in the hierarchical pore boron nitride structure/epoxy resin composite material, the aryl ester type liquid crystal epoxy resin is epoxy 4, 4' -di-p-hydroxybenzoic acid hydroquinone diglycidyl ether.
Furthermore, in the hierarchical pore boron nitride structural member/epoxy resin composite material, the hierarchical pore boron nitride structural member is a special-shaped hierarchical pore boron nitride structural member with a porous and efficient heat-conducting network structure.
The hierarchical porous boron nitride structural member is a special-shaped hierarchical porous structure, so that boron nitride and a filler can directly and fully contact with each other to form a heat-conducting network penetrating through the whole polymer matrix material, the polymer and the filler can form a continuous phase, the filler aggregate heat-conducting network and the polymer matrix can form a mutually-penetrating network structure, and the heat-conducting property of the filled composite material is remarkably improved.
Furthermore, in the hierarchical porous boron nitride structural member/epoxy resin composite material, the special-shaped hierarchical porous boron nitride structural member is honeycomb-shaped, the porosity is 35-70%, and the specific surface area is 165-527 m2/g。
The special-shaped hierarchical porous boron nitride structural member is honeycomb-shaped, the porosity is 35-70%, and the specific surface area is 165-527 m2And g, the boron nitride and the filler can directly and fully contact with each other, and the heat-conducting property of the hierarchical pore boron nitride structural member/epoxy resin composite material is further improved remarkably.
Further, in the hierarchical pore boron nitride structural member/epoxy resin composite material, the phenolic resin is bisphenol a formaldehyde phenolic resin.
Further, in the hierarchical pore boron nitride structural member/epoxy resin composite material, the accelerant is boron trifluoride ethylamine complex and/or quaternary ammonium salt accelerant.
Further, in the above hierarchical porous boron nitride structure/epoxy resin composite material, the quaternary ammonium salt accelerator is one or more of benzyltriethylammonium chloride, dodecyldimethylbenzylammonium chloride or benzyltributylammonium chloride.
The invention also relates to a preparation method of the hierarchical pore boron nitride structural member/epoxy resin composite material, which comprises the following steps:
(1) preparing a hierarchical pore boron nitride structural member;
(2) heating, melting and uniformly stirring aryl ester type liquid crystal epoxy resin, phenolic resin, a curing agent and an accelerant, and then impregnating the mixture on the hierarchical pore boron nitride structural member to obtain a hierarchical pore boron nitride structural member/epoxy resin prepreg;
(3) and curing the prepreg base in a vacuum oven to obtain the hierarchical pore boron nitride structural member/epoxy resin composite material.
Further, according to the preparation method of the hierarchical pore boron nitride structural member/epoxy resin composite material, the hierarchical pore boron nitride structural member is a honeycomb-shaped boron nitride structural member formed finally through SLS technology and polymer adhesive auxiliary molding, solvent and high-temperature degreasing.
Through the SLS process, the boron nitride structure can be designed, the optimal structure is designed according to the performance requirements of different occasions, the performance is improved to the maximum extent, and the method is simple in process, high in material utilization rate, high in forming speed and high in forming precision.
Further, according to the preparation method of the hierarchical pore boron nitride structural member/epoxy resin composite material, the preparation of the hierarchical pore boron nitride structural member further comprises the following steps:
(1) mixing boron nitride powder and PA12 powder in a volume ratio of 1: 1-3, blending, and printing and forming at 150-170 ℃;
(2) and taking out the printed part, placing the printed part in a muffle furnace, heating to 900-1300 ℃ at the speed of 10-30 ℃/min, preserving heat for 30-60 min, and naturally cooling to obtain the honeycomb type hierarchical hole boron nitride structural member.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention discloses a hierarchical pore boron nitride structural member/epoxy resin composite material, and the use of the hierarchical pore boron nitride structural member provided by the invention ensures the toughness of the material, and simultaneously improves the heat-conducting property and the strength of the material to the maximum extent, so that the hierarchical pore boron nitride structural member can be stably used in a limit environment.
(2) The hierarchical pore boron nitride structural member reinforced epoxy resin high-thermal-conductivity composite material provided by the invention realizes complete controllability of filler dispersion in the molding process, and is a brand-new processing and molding process.
(3) The forming process of the hierarchical pore boron nitride structural member reinforced epoxy resin high-thermal-conductivity composite material is simple and has high flexibility, and by designing the boron nitride structure, the composite material can be shaped to meet various shapes required by different occasions.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to specific experimental data, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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 following embodiment provides a hierarchical pore boron nitride structural member/epoxy resin composite material, which comprises the following components in percentage by mass: 43-63 wt% of aromatic ester type liquid crystal epoxy resin, 10wt% of a hierarchical pore boron nitride structural member, 9-17 wt% of phenolic resin and 12-20 wt% of a curing agent and an accelerator.
The aryl ester type liquid crystal epoxy resin is epoxy 4, 4' -di-p-hydroxybenzoic acid hydroquinone diglycidyl ether.
The hierarchical porous boron nitride structural member is a special-shaped hierarchical porous boron nitride structural member with a porous and efficient heat conducting network structure.
The special-shaped hierarchical porous boron nitride structural member is honeycomb-shaped, and the porosity is 35-70 percentThe surface area is 165-527 m2/g。
The phenolic resin is bisphenol A formaldehyde phenolic resin.
The accelerant is boron trifluoride ethylamine complex and/or quaternary ammonium salt accelerant.
The quaternary ammonium salt accelerant is one or more of benzyltriethylammonium chloride, dodecyl dimethyl benzyl ammonium chloride or benzyltributylammonium chloride.
Example 1
Mixing boron nitride powder and PA12 powder according to the volume ratio of 1: 1, uniformly blending, putting into an SLS printer, wherein the temperature of a material box is 150 ℃, the temperature of a printing surface is 170 ℃, the scanning speed is 700mm/s, taking out a workpiece after printing is finished, and cleaning the surface of the workpiece by using air blowing.
And putting the workpiece into a muffle furnace, heating the workpiece from room temperature to 400 ℃ at the speed of 10 ℃/min, preserving the heat for 30min, heating the workpiece from 400 ℃ to 900 ℃ at the speed of 10 ℃/min, preserving the heat for 10min, and naturally cooling the workpiece to the room temperature to obtain the honeycomb type boron nitride structural member.
Heating, mixing and stirring 43wt% of aryl ester type liquid crystal epoxy resin and 27wt% of phenolic resin uniformly, then adding 20wt% of curing agent and accelerator, and stirring uniformly; the thus prepared epoxy resin composition was impregnated into a treated 10wt% honeycomb boron nitride structure to obtain a hierarchical porous boron nitride structure/epoxy resin prepreg. Placing the prepreg base in a vacuum oven according to a curing system: and curing at the pressure of 1-2 MPa, wherein the temperature is 80 ℃/2h +135 ℃/2h +165 ℃/2h, and the hierarchical pore boron nitride structural member/epoxy resin composite material is obtained.
Example 2
Mixing boron nitride powder and PA12 powder according to the volume ratio of 1: 2, uniformly blending, putting into an SLS printer, controlling the temperature of a material box to be 150 ℃, the temperature of a printing surface to be 175 ℃ and the scanning speed to be 650mm/s, taking out the workpiece after printing is finished, and cleaning the surface of the workpiece by air blowing.
And putting the workpiece into a muffle furnace, heating the workpiece from room temperature to 400 ℃ at the speed of 10 ℃/min, preserving the heat for 30min, heating the workpiece from 400 ℃ to 900 ℃ at the speed of 10 ℃/min, preserving the heat for 10min, and naturally cooling the workpiece to the room temperature to obtain the honeycomb type boron nitride structural member.
Heating, mixing and stirring 48wt% of aryl ester type liquid crystal epoxy resin and 25wt% of phenolic resin uniformly, then adding 17wt% of curing agent and accelerator, and stirring uniformly; the thus prepared epoxy resin composition was impregnated into a treated 10wt% honeycomb boron nitride structure to obtain a hierarchical porous boron nitride structure/epoxy resin prepreg. Placing the prepreg base in a vacuum oven according to a curing system: and curing at the pressure of 1-2 MPa, wherein the temperature is 80 ℃/2h +135 ℃/2h +165 ℃/2h, and the hierarchical pore boron nitride structural member/epoxy resin composite material is obtained.
Example 3
Mixing boron nitride powder and PA12 powder according to the volume ratio of 1: 3, uniformly blending, putting into an SLS printer, wherein the temperature of a material box is 150 ℃, the temperature of a printing surface is 175 ℃, the scanning speed is 600mm/s, taking out the workpiece after printing is finished, and cleaning the surface of the workpiece by using air blowing.
And putting the workpiece into a muffle furnace, heating the workpiece from room temperature to 400 ℃ at the speed of 10 ℃/min, preserving the heat for 30min, heating the workpiece from 400 ℃ to 900 ℃ at the speed of 10 ℃/min, preserving the heat for 10min, and naturally cooling the workpiece to the room temperature to obtain the honeycomb type boron nitride structural member.
Heating, mixing and stirring 53wt% of aryl ester type liquid crystal epoxy resin and 22wt% of phenolic resin uniformly, then adding 15wt% of curing agent and accelerator, and stirring uniformly; the thus prepared epoxy resin composition was impregnated into a treated 10wt% honeycomb boron nitride structure to obtain a hierarchical porous boron nitride structure/epoxy resin prepreg. Placing the prepreg base in a vacuum oven according to a curing system: and curing at the pressure of 1-2 MPa, wherein the temperature is 80 ℃/2h +135 ℃/2h +165 ℃/2h, and the hierarchical pore boron nitride structural member/epoxy resin composite material is obtained.
Example 4
Mixing boron nitride powder and PA12 powder according to the volume ratio of 1: 1, uniformly blending, putting into an SLS printer, wherein the temperature of a material box is 150 ℃, the temperature of a printing surface is 170 ℃, the scanning speed is 700mm/s, taking out a workpiece after printing is finished, and cleaning the surface of the workpiece by using air blowing.
And putting the workpiece into a muffle furnace, heating the workpiece from room temperature to 400 ℃ at the speed of 10 ℃/min, preserving the heat for 30min, heating the workpiece from 400 ℃ to 1100 ℃ at the speed of 10 ℃/min, preserving the heat for 10min, and naturally cooling the workpiece to the room temperature to obtain the honeycomb type boron nitride structural member.
Heating, mixing and stirring 55wt% of aryl ester type liquid crystal epoxy resin and 20wt% of phenolic resin uniformly, then adding 15wt% of curing agent and accelerator, and stirring uniformly; the thus prepared epoxy resin composition was impregnated into a treated 10wt% honeycomb boron nitride structure to obtain a hierarchical porous boron nitride structure/epoxy resin prepreg. Placing the prepreg base in a vacuum oven according to a curing system: and curing at the pressure of 1-2 MPa, wherein the temperature is 80 ℃/2h +135 ℃/2h +165 ℃/2h, and the hierarchical pore boron nitride structural member/epoxy resin composite material is obtained.
Example 5
Mixing boron nitride powder and PA12 powder according to the volume ratio of 1: 1, uniformly blending, putting into an SLS printer, wherein the temperature of a material box is 150 ℃, the temperature of a printing surface is 170 ℃, the scanning speed is 700mm/s, taking out a workpiece after printing is finished, and cleaning the surface of the workpiece by using air blowing.
And putting the workpiece into a muffle furnace, heating the workpiece from room temperature to 400 ℃ at the speed of 10 ℃/min, preserving the heat for 30min, heating the workpiece from 400 ℃ to 1300 ℃ at the speed of 10 ℃/min, preserving the heat for 10min, and naturally cooling the workpiece to the room temperature to obtain the honeycomb type boron nitride structural member.
Heating, mixing and stirring 58wt% of aryl ester type liquid crystal epoxy resin and 19wt% of phenolic resin uniformly, then adding 13wt% of curing agent and accelerator, and stirring uniformly; the thus prepared epoxy resin composition was impregnated into a treated 10wt% honeycomb boron nitride structure to obtain a hierarchical porous boron nitride structure/epoxy resin prepreg. Placing the prepreg base in a vacuum oven according to a curing system: and curing at the pressure of 1-2 MPa, wherein the temperature is 80 ℃/2h +135 ℃/2h +165 ℃/2h, and the hierarchical pore boron nitride structural member/epoxy resin composite material is obtained.
Example 6
Mixing boron nitride powder and PA12 powder according to the volume ratio of 1: 1, uniformly blending, putting into an SLS printer, wherein the temperature of a material box is 150 ℃, the temperature of a printing surface is 170 ℃, the scanning speed is 700mm/s, taking out a workpiece after printing is finished, and cleaning the surface of the workpiece by using air blowing.
And putting the workpiece into a muffle furnace, heating the workpiece from room temperature to 400 ℃ at a speed of 20 ℃/min, preserving heat for 30min, heating the workpiece from 400 ℃ to 900 ℃ at a speed of 20 ℃/min, preserving heat for 10min, and naturally cooling the workpiece to room temperature to obtain the honeycomb type boron nitride structural member.
Heating, mixing and stirring 43wt% of liquid bisphenol A type epoxy resin E-51 (Shanghai resin factory) epoxy resin and 10wt% of solid bisphenol A type epoxy resin CYD-012 (Baling petrochemical company) epoxy resin uniformly, adding 17wt% of phenolic resin and 0.5wt% of benzyltriethylammonium chloride, and stirring uniformly; the thus prepared epoxy resin composition was impregnated into a treated 10wt% honeycomb boron nitride structure to obtain a hierarchical porous boron nitride structure/epoxy resin prepreg. Placing the prepreg base in a vacuum oven according to a curing system: and curing at the pressure of 1-2 MPa, wherein the temperature is 80 ℃/2h +135 ℃/2h +165 ℃/2h, and the hierarchical pore boron nitride structural member/epoxy resin composite material is obtained.
Example 7
Mixing boron nitride powder and PA12 powder according to the volume ratio of 1: 1, uniformly blending, putting into an SLS printer, wherein the temperature of a material box is 150 ℃, the temperature of a printing surface is 170 ℃, the scanning speed is 700mm/s, taking out a workpiece after printing is finished, and cleaning the surface of the workpiece by using air blowing.
And putting the workpiece into a muffle furnace, heating the workpiece from room temperature to 400 ℃ at the speed of 20 ℃/min, preserving the heat for 30min, heating the workpiece from 400 ℃ to 1100 ℃ at the speed of 20 ℃/min, preserving the heat for 10min, and naturally cooling the workpiece to the room temperature to obtain the honeycomb type boron nitride structural member.
Heating, mixing and stirring 60wt% of aryl ester type liquid crystal epoxy resin and 18wt% of phenolic resin uniformly, then adding 12wt% of curing agent and accelerator, and stirring uniformly; the thus prepared epoxy resin composition was impregnated into a treated 10wt% honeycomb boron nitride structure to obtain a hierarchical porous boron nitride structure/epoxy resin prepreg. Placing the prepreg base in a vacuum oven according to a curing system: and curing at the pressure of 1-2 MPa, wherein the temperature is 80 ℃/2h +135 ℃/2h +165 ℃/2h, and the hierarchical pore boron nitride structural member/epoxy resin composite material is obtained.
Example 8
Mixing boron nitride powder and PA12 powder according to the volume ratio of 1: 1, uniformly blending, putting into an SLS printer, wherein the temperature of a material box is 150 ℃, the temperature of a printing surface is 170 ℃, the scanning speed is 700mm/s, taking out a workpiece after printing is finished, and cleaning the surface of the workpiece by using air blowing.
And putting the workpiece into a muffle furnace, heating the workpiece from room temperature to 400 ℃ at a speed of 20 ℃/min, preserving heat for 30min, heating the workpiece from 400 ℃ to 1300 ℃ at a speed of 20 ℃/min, preserving heat for 10min, and naturally cooling the workpiece to room temperature to obtain the honeycomb type boron nitride structural member.
Heating, mixing and stirring 63wt% of aryl ester type liquid crystal epoxy resin and 13wt% of phenolic resin uniformly, then adding 14wt% of curing agent and accelerator, and stirring uniformly; the thus prepared epoxy resin composition was impregnated into a treated 10wt% honeycomb boron nitride structure to obtain a hierarchical porous boron nitride structure/epoxy resin prepreg. Placing the prepreg base in a vacuum oven according to a curing system: and curing at the pressure of 1-2 MPa, wherein the temperature is 80 ℃/2h +135 ℃/2h +165 ℃/2h, and the hierarchical pore boron nitride structural member/epoxy resin composite material is obtained.
Effect verification:
the composite materials obtained in example 1, example 2, example 3, example 4, example 5, example 6, example 7 and example 8 were tested for their properties according to the following criteria, and the test results are shown in table 1.
Tensile properties the bars are measured according to ISO 527 and are rated 150mm X10 mm X4 mm.
The bending properties are determined according to ISO 527 with the standard 80 mm. times.10 mm. times.4 mm.
The impact strength is determined according to ISO 178 with a bar standard of 80 mm. times.10 mm. times.4 mm.
The thermal conductivity of the bars is measured according to ISO22007-2, with a standard of 50mm by 35mm by 2 mm.
TABLE 1 sample Performance test results
| Performance of | Flexural Strength (MPa) | Flexural modulus (GPa) | Tensile Strength (MPa) | Coefficient of thermal conductivity (W/mK) |
| Example 1 | 394 | 19.0 | 137.5 | 6.78 |
| Example 2 | 408 | 19.4 | 141.7 | 7.31 |
| Example 3 | 412 | 21.4 | 143.2 | 8.42 |
| Example 4 | 406 | 24.6 | 139.5 | 9.92 |
| Example 5 | 398 | 22.4 | 137.9 | 11.23 |
| Example 6 | 404 | 22.0 | 138.6 | 10.35 |
| Example 7 | 386 | 22.6 | 142.7 | 10.03 |
| Example 8 | 411 | 21.7 | 143.1 | 9.78 |
The invention has many applications, and the above description is only a preferred embodiment of the invention. It should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention and these modifications are to be considered within the scope of the invention.
Claims (5)
1. The hierarchical pore boron nitride structural member/epoxy resin composite material is characterized in that: the composite material comprises the following components in percentage by mass:
43-63 wt% of an aryl ester type liquid crystal epoxy resin,
10wt% of the multi-level hole boron nitride structural member,
9-17 wt% of phenolic resin,
12-20 wt% of a curing agent and an accelerator;
the total amount of all the components is 100 wt%;
the hierarchical pore boron nitride structural component is a special-shaped hierarchical pore boron nitride structural component;
the special-shaped hierarchical porous boron nitride structural member is honeycomb-shaped, the porosity is 35-70%, and the specific surface area is 165-527 m2/g；
The preparation method of the hierarchical pore boron nitride structural member/epoxy resin composite material comprises the following steps:
(1) preparing a hierarchical pore boron nitride structural member;
(2) heating, melting and uniformly stirring aryl ester type liquid crystal epoxy resin, phenolic resin, a curing agent and an accelerant, and then impregnating the mixture on the hierarchical pore boron nitride structural member to obtain a hierarchical pore boron nitride structural member/epoxy resin prepreg;
(3) curing the prepreg base in a vacuum oven to obtain the hierarchical pore boron nitride structural member/epoxy resin composite material;
the preparation method of the hierarchical pore boron nitride structural member comprises the following steps:
(1) mixing boron nitride powder and PA12 powder in a volume ratio of 1: 1-3, mixing, putting into an SLS printer, and printing and molding at 150-170 ℃;
(2) and taking out the printed part, placing the printed part in a muffle furnace, heating to 900-1300 ℃ at the speed of 10-30 ℃/min, preserving heat for 30-60 min, and naturally cooling to obtain the honeycomb type hierarchical hole boron nitride structural member.
2. The multi-graded hole boron nitride structural member/epoxy composite material of claim 1, wherein: the aryl ester type liquid crystal epoxy resin is 4, 4' -di-p-hydroxybenzoic acid hydroquinone diglycidyl ether.
3. The multi-graded hole boron nitride structural member/epoxy composite material of claim 1, wherein: the phenolic resin is bisphenol A formaldehyde phenolic resin.
4. The multi-graded hole boron nitride structural member/epoxy composite material of claim 1, wherein: the accelerant is boron trifluoride ethylamine complex and/or quaternary ammonium salt accelerant.
5. The multi-graded hole boron nitride structural member/epoxy composite material of claim 4, wherein: the quaternary ammonium salt accelerant is one or more of benzyltriethylammonium chloride, dodecyl dimethyl benzyl ammonium chloride or benzyltributylammonium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910530843.5A CN110218417B (en) | 2019-06-19 | 2019-06-19 | Hierarchical pore boron nitride structural member/epoxy resin composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910530843.5A CN110218417B (en) | 2019-06-19 | 2019-06-19 | Hierarchical pore boron nitride structural member/epoxy resin composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110218417A CN110218417A (en) | 2019-09-10 |
| CN110218417B true CN110218417B (en) | 2022-04-15 |
Family
ID=67817789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910530843.5A Active CN110218417B (en) | 2019-06-19 | 2019-06-19 | Hierarchical pore boron nitride structural member/epoxy resin composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110218417B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104647760A (en) * | 2015-02-12 | 2015-05-27 | 华中科技大学 | 3D printing and manufacturing method of short-fiber reinforced thermosetting resin composite product |
| CN109206854A (en) * | 2018-08-30 | 2019-01-15 | 桂林电子科技大学 | A kind of boron nitride/epoxy resin composite material preparation method with three-dimensional structure |
| CN109280332A (en) * | 2018-08-03 | 2019-01-29 | 吉林大学 | A kind of preparation method of boron nitride/epoxy resin heat conductive insulating composite material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10471507B2 (en) * | 2015-04-24 | 2019-11-12 | Halliburton Energy Services, Inc. | Methods of fabricating ceramic or intermetallic parts |
| CN105399428B (en) * | 2015-12-09 | 2019-02-12 | 中国建筑材料科学研究总院 | A kind of ceramic slurry and ceramic material 3D printing forming method |
| CN106316440B (en) * | 2016-08-19 | 2020-01-14 | 华中科技大学 | Preparation method of porous ceramic with complex structure based on selective laser sintering |
-
2019
- 2019-06-19 CN CN201910530843.5A patent/CN110218417B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104647760A (en) * | 2015-02-12 | 2015-05-27 | 华中科技大学 | 3D printing and manufacturing method of short-fiber reinforced thermosetting resin composite product |
| CN109280332A (en) * | 2018-08-03 | 2019-01-29 | 吉林大学 | A kind of preparation method of boron nitride/epoxy resin heat conductive insulating composite material |
| CN109206854A (en) * | 2018-08-30 | 2019-01-15 | 桂林电子科技大学 | A kind of boron nitride/epoxy resin composite material preparation method with three-dimensional structure |
Non-Patent Citations (1)
| Title |
|---|
| "高导热液晶环氧树脂的合成及性能研究";唐杰等;《第十四届覆铜板技术.市场研讨会论文集》;20130930;第44-48页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110218417A (en) | 2019-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Park et al. | Thermal stability of carbon-MoSi2-carbon composites by thermogravimetric analysis | |
| CN101508824B (en) | Oxatyl-containing lateral group polyarylether cured modified epoxy resin composition and method for producing the same | |
| CN104559148A (en) | High-thermal-diffusion-coefficient high molecular material and preparation method thereof | |
| CN108250747B (en) | Thermoplastic polyetherimide insulating and heat-conducting composite material and preparation method thereof | |
| JP2008050526A (en) | Resin composition, prepreg and laminated board using the same | |
| CN105647123A (en) | Thermosetting resin composition as well as prepreg, metal foil-coated lamination board and printed circuit board containing same | |
| CN114103305B (en) | high-Tg high-heat-conductivity metal-based copper-clad plate and processing technology thereof | |
| CN103862589A (en) | Method for preparing polyamide-based heat conduction composite material through melt blending | |
| CN105419142A (en) | Electroplated PC (Poly Carbonate)/ABS (Acrylonitrile Butadiene StyreneAcrylonitrile Butadiene Styrene) alloy material and preparation method thereof | |
| CN106751390A (en) | One kind plating PC/ABS alloy materials and preparation method thereof | |
| CN110218417B (en) | Hierarchical pore boron nitride structural member/epoxy resin composite material | |
| CN108623999A (en) | A kind of composite material for wind power generator blade and preparation method thereof | |
| Guan et al. | Interface compatibility and mechanisms of improved mechanical performance of starch/poly (lactic acid) blend reinforced by bamboo shoot shell fibers | |
| CN106700436A (en) | High-plasticity heat-conducting composite material and preparation method thereof | |
| CN104177827A (en) | Polysulfonamide-based carbon fiber reinforced composite material and preparation method thereof | |
| CN110330765B (en) | Process for preparing heat-conducting polymer material by SLS (selective laser sintering) molded porous ceramic heat-conducting network | |
| KR101838848B1 (en) | Epoxy Resin Compositions for Bulk Mold Compound Dispersed Carbon Nano Tube | |
| CN103963381B (en) | Metal-based copper-clad plate and preparation method thereof | |
| CN107163489A (en) | A kind of high intensity high heat conduction PC/ABS plastics and preparation method thereof | |
| JP2008248048A (en) | Molding material of high heat conductive thermoplastic resin | |
| CN111040380A (en) | Heat-conducting modified epoxy resin-based composite material and preparation method thereof | |
| CN112795094A (en) | PP alloy material capable of releasing negative oxygen ions and preparation method and application thereof | |
| CN109096730A (en) | A kind of high temperature resistant conduction PPO/PS alloy material and preparation method thereof | |
| CN104017385A (en) | Resin composition, prepreg, composite plate, and preparation method and applications of the composite plate | |
| CN109355975A (en) | A kind of heat-resisting vulcan fibre and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |