CN114479065A - Flame-retardant composite material, preparation method thereof and electronic equipment - Google Patents
Flame-retardant composite material, preparation method thereof and electronic equipment Download PDFInfo
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- CN114479065A CN114479065A CN202210184151.1A CN202210184151A CN114479065A CN 114479065 A CN114479065 A CN 114479065A CN 202210184151 A CN202210184151 A CN 202210184151A CN 114479065 A CN114479065 A CN 114479065A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- 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
- C08K9/00—Use of pretreated ingredients
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a flame-retardant composite material, a preparation method thereof and electronic equipment. The flame-retardant composite material comprises a three-dimensional porous framework material, polyamide and magnesium hydroxide; the three-dimensional porous framework material has a three-dimensional reticular porous structure formed by self-assembly of graphene oxide and a reinforcing material; at least part of polyamide and magnesium hydroxide are loaded on the surface of the three-dimensional porous framework material, and at least part of polyamide and magnesium hydroxide are embedded into or penetrate through holes on the surface of the three-dimensional porous framework material to form a three-dimensional interpenetrating network structure; wherein the reinforcing material is selected from at least one of carbon nanotubes and graphene fibers; the mass of the three-dimensional porous framework material is 0.5-15% of the mass of the polyamide, and the mass of the magnesium hydroxide is 5-30% of the mass of the polyamide. The flame-retardant composite material has high thermal conductivity, high flame retardance and excellent mechanical property.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a flame-retardant composite material, a preparation method thereof and electronic equipment.
Background
With the development of electronic devices toward high integration, high performance, miniaturization, and functionalization, the heat dissipation problem of devices becomes increasingly important. Polyamide 6(PA6) is often used as engineering plastic to be widely applied to the preparation of electronic equipment due to its characteristics of excellent mechanical properties, better electrical properties, wear resistance, oil resistance, self-lubrication, corrosion resistance, good processability, etc., but its thermal conductivity (thermal conductivity coefficient is only 0.23W/m · k) and flame retardancy (limiting oxygen index is only 22%) are low, and further improvement is still needed.
In the prior art, a graphene modified polyamide composite material is prepared by in-situ polymerization of three-dimensional graphene aerogel and polyamide PA6 monomers, but the three-dimensional graphene aerogel formed by self-assembly inevitably undergoes structural collapse in a freeze drying process, the pore diameter is enlarged, part of graphene is repeatedly stacked, the performance of the graphene cannot be fully exerted, and the prepared graphene modified polyamide composite material cannot meet the requirements of the modern technology on the mechanical property, the thermal conductivity and the flame retardant property of a device material.
Therefore, the prior art still remains to be developed.
Disclosure of Invention
Based on the above, the invention provides a flame-retardant composite material, a preparation method thereof and electronic equipment, wherein the flame-retardant composite material has high thermal conductivity, high flame retardance and excellent mechanical properties.
The technical scheme of the invention is as follows.
In one aspect of the invention, a flame retardant composite is provided, comprising a three-dimensional porous skeletal material, polyamide and magnesium hydroxide; the three-dimensional porous framework material has a three-dimensional reticular porous structure formed by self-assembly of graphene oxide and a reinforcing material;
at least part of the polyamide and the magnesium hydroxide are loaded on the surface of the three-dimensional porous framework material, and at least part of the polyamide and the magnesium hydroxide are embedded into or penetrate through holes on the surface of the three-dimensional porous framework material to form a three-dimensional interpenetrating network structure;
wherein the reinforcing material is selected from at least one of carbon nanotubes and graphene fibers; the mass of the three-dimensional porous framework material is 0.5-15% of the mass of the polyamide, and the mass of the magnesium hydroxide is 5-30% of the mass of the polyamide.
In some of the embodiments, the magnesium hydroxide is surface-modified magnesium hydroxide having amino groups, and the amino groups of the magnesium hydroxide are bonded to carboxyl groups on the surface of the three-dimensional porous skeleton material.
In some of these embodiments, the amino groups of the polyamide are bonded to the carboxyl groups on the surface of the three-dimensional porous skeletal material; and/or
The carboxyl group of the polyamide is bonded to the amino group on the surface of the magnesium hydroxide.
In some of these embodiments, the mass of the three-dimensional porous skeleton material is 5% to 15% of the mass of the polyamide; and/or
The mass of the magnesium hydroxide is 10-25% of the mass of the polyamide.
In some embodiments, in the three-dimensional porous skeleton material, the mass of the reinforcing material is 1% to 12% of the mass of the graphene oxide.
In some embodiments, the reinforcing material includes carbon nanotubes and graphene fibers, and in the three-dimensional porous skeleton material, the mass of the carbon nanotubes is 1% to 1.2% of the mass of the graphene oxide, and the mass of the graphene fibers is 8% to 10% of the mass of the graphene oxide.
In some of the embodiments, the tube length of the carbon nanotube is 1 μm to 16 μm, and the length of the graphene fiber is 10 μm to 15 μm; and/or
The particle size of the three-dimensional porous framework material is 15-30 μm.
In another aspect of the present invention, there is provided a method for preparing the flame retardant composite material as described above, comprising the steps of:
mixing the reinforcing material, the graphene oxide and a solvent, carrying out self-assembly treatment, and then freeze-drying to obtain the three-dimensional porous framework material;
and mixing the three-dimensional porous framework material, the magnesium hydroxide and the polyamide monomers, and performing reaction extrusion to obtain the flame-retardant composite material.
In some of these embodiments, the step of reactive extrusion is performed under the action of an initiator and an activator; and/or
The step of reactive extrusion is carried out in a reactive extruder, and the temperature of the reactive extruder is as follows according to the advancing direction of materials: 120 deg.C, 140 deg.C, 160 deg.C, 180 deg.C, 200 deg.C and 200 deg.C; and/or
The temperature of the self-assembly treatment is 180-200 ℃, and the time is 10-12 h.
In yet another aspect of the present invention, there is provided an electronic device comprising the flame retardant composite material as described above.
The flame-retardant composite material comprises a three-dimensional porous framework material, polyamide and magnesium hydroxide; the three-dimensional porous framework material has a three-dimensional reticular porous structure formed by self-assembling graphene oxide and a reinforcing material, the reinforcing material is selected from at least one of carbon nano tubes and graphene fibers, and when the graphene oxide and the reinforcing material are self-assembled, the reinforcing material is used as a substrate to play a role in supporting physical cross-linking points, so that the formed three-dimensional porous framework material has a stable structure, more uniform pore diameter and higher cell strength, can effectively conduct heat and resist flame, and avoids structural collapse; meanwhile, at least part of polyamide and magnesium hydroxide are loaded on the surface of the three-dimensional porous framework material, and at least part of polyamide and magnesium hydroxide are embedded into or penetrate through holes on the surface of the three-dimensional porous framework material to form a three-dimensional interpenetrating network structure, and the quality of the three-dimensional porous framework material, the quality of polyamide and the quality of magnesium hydroxide are controlled, so that the prepared flame-retardant composite material has high thermal conductivity, high flame retardance and excellent mechanical properties.
Further, the magnesium hydroxide is surface-modified magnesium hydroxide with amino groups, and the amino groups of the magnesium hydroxide are bonded with carboxyl groups on the surface of the three-dimensional porous framework material; therefore, the magnesium hydroxide is tightly combined with the three-dimensional porous framework material, and the mechanical property of the flame-retardant composite material is further improved on the basis of keeping excellent heat conduction and flame retardance.
Further, the amino group of the polyamide is bonded with the carboxyl group on the surface of the three-dimensional porous framework material; and/or the carboxyl of the polyamide is bonded with the amino on the surface of the magnesium hydroxide, so that the bonding force among the polyamide, the magnesium hydroxide and the three-dimensional porous framework material is further improved, the synergistic effect of the polyamide, the magnesium hydroxide and the three-dimensional porous framework material is fully exerted, and the flame-retardant composite material is improved to have high thermal conductivity, high flame retardance and excellent mechanical property.
According to the preparation method of the flame-retardant composite material, firstly, the reinforcing material, the graphene oxide and the solvent are mixed and subjected to self-assembly treatment, and then the mixture is subjected to freeze drying, wherein the reinforcing material is selected from at least one of carbon nano tubes and graphene fibers, the dispersibility of the reinforcing material is good, and when the graphene oxide and the reinforcing material are subjected to self-assembly, the reinforcing material serves as a substrate to play a role in supporting a physical cross-linking point, so that the formed three-dimensional porous framework material is stable in structure, uniform in pore diameter and high in cell strength, and structural collapse in the subsequent freeze drying process can be avoided; so as to form a three-dimensional reticular porous structure and obtain the three-dimensional porous framework material with effective heat conduction; and then mixing the three-dimensional porous framework material, magnesium hydroxide and polyamide monomers, performing reactive extrusion, polymerizing the polyamide monomers to form polyamide in the reactive extrusion process, loading at least part of the polyamide and the magnesium hydroxide on the surface of the three-dimensional porous framework material, embedding or penetrating at least part of the polyamide and the magnesium hydroxide into or through holes on the surface of the three-dimensional porous framework material to form a three-dimensional interpenetrating network structure, and simultaneously controlling the mixture ratio of the materials to obtain the flame-retardant composite material with high thermal conductivity, high flame retardance and excellent mechanical property.
Compared with the traditional method for carrying out self-polymerization in solution, the preparation method directly mixes the monomers of the three-dimensional porous framework material, the magnesium hydroxide and the polyamide and then carries out reaction extrusion for carrying out in-situ polymerization, has high reaction speed and high production efficiency, can carry out continuous production, and has high molecular weight and narrow molecular weight distribution of the product; at the same time, the residence time of the product in the extruder is short, and therefore the degree of thermal degradation is low. Further, part of residual monomers and trace moisture can be directly removed through a vacuumizing and exhausting process and then recovered.
The electronic equipment comprises the flame-retardant composite material, and the flame-retardant composite material has high thermal conductivity, high flame retardance and excellent mechanical property, and is favorable for improving the thermal conductivity and the flame retardant mechanical property of the electronic equipment, so that the service life of the electronic equipment is prolonged.
Drawings
FIG. 1 is a schematic structural analysis diagram of the flame-retardant composite material of the present invention.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
One embodiment of the present invention provides a flame retardant composite material comprising a three-dimensional porous skeletal material, polyamide and magnesium hydroxide; the three-dimensional porous framework material has a three-dimensional reticular porous structure formed by self-assembly of graphene oxide and a reinforcing material; at least part of polyamide and magnesium hydroxide are loaded on the surface of the three-dimensional porous framework material, and at least part of polyamide and magnesium hydroxide are embedded into or penetrate through holes on the surface of the three-dimensional porous framework material to form a three-dimensional interpenetrating network structure;
wherein the reinforcing material is selected from at least one of carbon nanotubes and graphene fibers; the mass of the three-dimensional porous framework material is 0.5-15% of the mass of the polyamide, and the mass of the magnesium hydroxide is 5-30% of the mass of the polyamide.
The components of the flame-retardant composite material comprise a three-dimensional porous framework material, polyamide and magnesium hydroxide; the three-dimensional porous framework material has a three-dimensional reticular porous structure formed by self-assembling graphene oxide and a reinforcing material, the reinforcing material is selected from at least one of carbon nano tubes and graphene fibers, and when the graphene oxide and the reinforcing material are self-assembled, the reinforcing material is used as a substrate to play a role in supporting physical cross-linking points, so that the formed three-dimensional porous framework material has a stable structure, more uniform pore diameter and higher cell strength, can effectively conduct heat and resist flame, and avoids structural collapse; meanwhile, at least part of polyamide and magnesium hydroxide are loaded on the surface of the three-dimensional porous framework material, and at least part of polyamide and magnesium hydroxide are embedded into or penetrate through holes on the surface of the three-dimensional porous framework material to form a three-dimensional interpenetrating network structure, and the quality of the three-dimensional porous framework material, the quality of polyamide and the quality of magnesium hydroxide are controlled, so that the prepared flame-retardant composite material has high thermal conductivity, high flame retardance and excellent mechanical properties.
It should be noted that, in the above-mentioned polyamide and magnesium hydroxide supported on the portion of the surface of the three-dimensional porous skeleton material and the polyamide and magnesium hydroxide embedded in or passed through the portion of the pores of the surface of the three-dimensional porous skeleton material, the mass of the two portions is not particularly required, and the materials of the two portions may have overlapping portions, for example, single chains of the polyamide may be supported on the surface of the three-dimensional porous skeleton material while passing through the pores of the surface of the three-dimensional porous skeleton material.
Specifically, referring to fig. 1, fig. 1 is a schematic view of a dissected structure of the flame retardant composite material, wherein graphene oxide and a reinforcing material are self-assembled to form a three-dimensional network porous structure, a portion of polyamide and magnesium hydroxide are loaded on the surface of the three-dimensional porous framework material, and a portion of polyamide and magnesium hydroxide are embedded in or penetrate through pores on the surface of the three-dimensional porous framework material to form a three-dimensional interpenetrating network structure.
The magnesium hydroxide is surface-modified magnesium hydroxide with amino, and the amino of the magnesium hydroxide is bonded with carboxyl on the surface of the three-dimensional porous framework material; therefore, the magnesium hydroxide is tightly combined with the three-dimensional porous framework material, and the mechanical property of the flame-retardant composite material is further improved on the basis of keeping excellent heat conduction and flame retardance.
It can be understood that: in the three-dimensional porous framework material formed by self-assembly of the graphene oxide and the reinforcing material, a large number of oxygen-containing functional groups which are not reduced, such as carboxyl, are distributed among layers or on the surface of the graphene oxide. The above "bonding" may refer to bonding between atoms in different forms, including but not limited to: van der waals forces, molecular forces and even atomic forces, or the formation of covalent bonds, hydrogen bonds, and the like. For example, the amino group on the surface of the magnesium hydroxide may be bonded to the carboxyl group on the surface of the three-dimensional porous skeleton material, and the amino group may react with the carboxyl group to form a covalent bond, or the amino group may form a hydrogen bond with the carboxyl group, or both of them may be present.
In some of the embodiments, the flake magnesium hydroxide is modified by a silane coupling agent.
Specifically, the silane coupling agent is KH 550.
The modification method can adopt dry modification or wet modification, and further can adopt a magnesium hydroxide surface modifier commonly used in the field to replace a silane coupling agent as long as the surface of the magnesium hydroxide can form amino.
Specifically, the magnesium hydroxide is a flaky magnesium hydroxide.
With continued reference to FIG. 1, the amino groups of the polyamide are bonded to the carboxyl groups on the surface of the three-dimensional porous skeleton material; and/or the carboxyl group of the polyamide is bonded with the amino group on the surface of the magnesium hydroxide.
It can be understood that: the molecular chain of the polyamide at least contains one terminal amino group and one terminal carboxyl group, the amino group can be bonded with the carboxyl group on the surface of the three-dimensional porous framework material, and the carboxyl group can be bonded with the amino group on the surface of the magnesium hydroxide, so that the bonding force among the polyamide, the magnesium hydroxide and the three-dimensional porous framework material can be further improved, the synergistic effect of the three can be fully exerted, and the flame-retardant composite material is improved to have high thermal conductivity, high flame retardance and excellent mechanical property.
In some of these embodiments, the polyamide is selected from at least one of PA6 and PA 66. Specifically, the polyamide is PA 6.
It should be noted that when a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range as well as each value between such minimum and maximum values. For example, "0.5% to 15%" includes but is not limited to: 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%; "5% to 30%" includes but is not limited to: 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%.
In some embodiments, the mass of the three-dimensional porous skeleton material is 5-15% of the mass of the polyamide.
In some of these embodiments, the magnesium hydroxide is present in an amount of 10% to 25% by mass of the polyamide.
The heat conductivity, the flame retardance and the mechanical property of the flame-retardant composite material are further improved by further adjusting the mass ratio of the components.
In some embodiments, in the three-dimensional porous skeleton material, the mass of the reinforcing material is 1% to 12% of the mass of the graphene oxide.
The heat conduction and mechanical properties of the three-dimensional porous framework material are further improved by controlling the specific proportion of the reinforcing material.
In some embodiments, the reinforcing material includes carbon nanotubes and graphene fibers, and in the three-dimensional porous skeleton material, the mass of the carbon nanotubes is 1% to 1.2% of the mass of the graphene oxide, and the mass of the graphene fibers is 8% to 10% of the mass of the graphene oxide.
The variety and the proportion of the reinforcing material are further regulated and controlled, the synergistic effect of the carbon nano tube and the graphene fiber is exerted, and the mechanical property of the flame-retardant composite material is further improved while high heat conductivity and high flame retardance are kept.
In some embodiments, the carbon nanotubes have a tube length of 1 μm to 16 μm, and the graphene fibers have a length of 10 μm to 15 μm.
The length of the reinforced material is further regulated and controlled, so that the reinforced material can fully play the supporting role of the physical cross-linking point, and the mechanical property of the flame-retardant composite material is further improved.
In some embodiments, the diameter of the carbon nanotube is 7nm to 15nm, and the monofilament diameter of the graphene fiber is 1 μm to 10 μm.
In some of these embodiments, the carbon nanotubes are multi-walled carbon nanotubes.
In some embodiments, the graphene oxide is a sheet-like graphene oxide; further, the sheet diameter of the graphene oxide is 3 to 10 μm.
In some embodiments, the particle size of the three-dimensional porous skeleton material is 15 μm to 30 μm.
An embodiment of the present invention provides a method for preparing the flame retardant composite material, including the following steps S10 to S20.
And step S10, mixing the reinforcing material, the graphene oxide and the solvent, carrying out self-assembly treatment to form a three-dimensional reticular porous structure, and then carrying out freeze drying to obtain the three-dimensional porous framework material.
And step S20, mixing the three-dimensional porous framework material, magnesium hydroxide and polyamide monomers, and performing reaction extrusion to obtain the flame-retardant composite material.
According to the preparation method of the flame-retardant composite material, firstly, the reinforcing material, the graphene oxide and the solvent are mixed and subjected to self-assembly treatment, and then the mixture is subjected to freeze drying, wherein the reinforcing material is selected from at least one of carbon nano tubes and graphene fibers, the dispersibility of the reinforcing material is good, and when the graphene oxide and the reinforcing material are subjected to self-assembly, the reinforcing material serves as a substrate to play a role in supporting a physical cross-linking point, so that the formed three-dimensional porous framework material is stable in structure, uniform in pore diameter and high in cell strength, and structural collapse in the subsequent freeze drying process can be avoided; so as to form a three-dimensional reticular porous structure and obtain the three-dimensional porous framework material with effective heat conduction; and then mixing the three-dimensional porous framework material, magnesium hydroxide and polyamide monomers, performing reactive extrusion, polymerizing the polyamide monomers to form polyamide in the reactive extrusion process, loading the polyamide and the magnesium hydroxide on the surface of the three-dimensional porous framework material, and embedding or penetrating through holes on the surface of the three-dimensional porous framework material to form a three-dimensional interpenetrating network structure, and simultaneously controlling the mixture ratio of the materials to obtain the flame-retardant composite material with high thermal conductivity, high flame retardance and excellent mechanical properties.
Compared with the traditional method of carrying out self-polymerization in solution, the preparation method directly mixes the monomers of the three-dimensional porous framework material, the magnesium hydroxide and the polyamide and then carries out reaction extrusion for in-situ polymerization, has high reaction speed and high production efficiency, can carry out continuous production, and has high molecular weight and narrow molecular weight distribution of the product; at the same time, the residence time of the product in the extruder is short, and therefore the degree of thermal degradation is low. Further, part of residual monomers and trace moisture can be directly removed through a vacuumizing and exhausting process and then recovered.
In some of these embodiments, the solvent is water.
In some embodiments, the step of mixing in step S10 is as follows:
firstly, mixing graphene oxide and a solvent to obtain a graphene oxide solution; and then dispersing the reinforcing material in the graphene oxide solution.
Further, the concentration of the graphene oxide solution is about 2mg/mL to 3 mg/mL.
Further, the self-assembly treatment is carried out under the action of the aqueous dispersant; specifically, an aqueous dispersant is mixed with a graphene oxide solution.
In some embodiments, the aqueous dispersant is 0.5% to 1% by mass of the graphene oxide solution.
Specifically, the aqueous dispersant is at least one selected from sodium dodecylbenzene sulfonate and sodium dodecyl sulfate.
The order of adding the reinforcing material and the aqueous dispersant into the graphene oxide solution is not specific, and may be performed sequentially or simultaneously.
In some of these embodiments, the mixing step is performed under ultrasonic conditions.
In some embodiments, the self-assembly treatment is carried out at 180-200 ℃ for 10-12 h.
In some of these examples, the freeze-drying was carried out at-60 ℃ for 48 hours.
In some embodiments, step S10 further includes a step of water washing the self-assembly product after the self-assembly treatment and before the step of freeze-drying.
In some embodiments, in step S10, after the step of freeze-drying, a step of crushing and drying the freeze-dried product is further included to remove moisture carried in the product.
Furthermore, the drying temperature is 100-120 ℃, and the drying time is 3-5 h.
It can be understood that: in step S10, the quality of the reinforcing material and the graphene oxide in the prepared three-dimensional porous framework material can be controlled by adjusting the quality of the raw material reinforcing material and the graphene oxide.
In some of the embodiments, in step S20, the temperature controlled in the step of reactive extrusion is, in order, according to the reaction in which the material advances: 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ and 200 ℃.
Specifically, the step of reactive extrusion is carried out in a reactive extruder; in other words, the temperature controlled in the above step of reactive extrusion is, in turn, the temperature of the feeding section to the head.
In some of these embodiments, the step of reactive extrusion is performed under the action of an initiator and an activator.
The initiator initiates polymerization of the monomers of the polyamide and the activator facilitates polymerization.
In some of these embodiments, the initiator inorganic base described above; further, a hydroxide of an alkali metal; including but not limited to: sodium hydroxide, potassium hydroxide, and the like.
In some of these embodiments, the activator is an isocyanate.
Taking the polymerization of polyamide 6 as an example: the monomer caprolactam reacts with initiator alkali to generate caprolactam anion, the caprolactam reacts with activator isocyanate to generate caprolactam isocyanate, then the caprolactam anion attacks the caprolactam isocyanate and generates a ring opening reaction to generate another active anion, the caprolactam reacts with the active anion to generate active caprolactam cyanate to realize chain growth, and then the caprolactam anion attacks the caprolactam cyanate to open the ring, thus the circulation is continued, and finally the polyamide polymer with the required relative molecular mass is obtained.
In some embodiments, the step of mixing and reactive extruding the three-dimensional porous skeleton material, the magnesium hydroxide and the polyamide monomer in the step S20 specifically includes the following steps S21 to S22.
Step S21, dividing the polyamide monomer into two parts, wherein one part is mixed with the initiator and the three-dimensional porous framework material to obtain a first mixture; another part of the melt of the polyamide is mixed with the activator to obtain a second mixture.
Further, the first mixture was distilled to remove water, and a trace amount of water was removed therefrom by distillation under reduced pressure at 120 ℃.
In some of these embodiments, the ratio of moles of polyamide monomer, initiator, and activator is: 1:0.02:0.0035.
And step S22, respectively placing the first mixture and the second mixture into feeding tanks A and B, feeding magnesium hydroxide into a side feeding tank, and simultaneously feeding polarity reaction extrusion.
In some embodiments, step S20 is further performed by, after the step of reactive extrusion, sequentially performing dicing, boiling water extraction and drying on the product of reactive extrusion.
The extraction with boiling water can remove the incompletely reacted monomers or impurities generated in the reactive extrusion process.
In some embodiments, the time for extracting with boiling water is 10-20 h, and the drying temperature is 105-120 ℃.
An embodiment of the present invention also provides an electronic device including the flame retardant composite material as described above.
When the flame-retardant composite material is used for preparing electronic equipment, the flame-retardant composite material can be used as a coating material for preparing a device coating layer of the electronic equipment, and can also be used as an engineering raw material for preparing a structural component in an electronic device.
The flame-retardant composite material has high thermal conductivity, high flame retardance and excellent mechanical property, and is beneficial to improving the thermal conductivity, flame retardance and mechanical property of electronic equipment, so that the service life of the electronic equipment is prolonged.
While the present invention will be described with respect to particular embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover by the appended claims the scope of the invention, and that certain changes in the embodiments of the invention will be suggested to those skilled in the art and are intended to be covered by the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
(1) Adding 0.018g of carbon nano tube (the tube diameter is 7-15 nm, the tube length is 1.5 mu m) into 500mL of 3mg/mL GO aqueous solution, simultaneously adding 5g of dispersant sodium dodecyl benzene sulfonate, stirring uniformly, and continuing ultrasonic dispersion for 30min to obtain a mixed solution; adding the mixed solution into a high-pressure hydrothermal reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 180-200 ℃ for 12h, opening the reaction kettle after the reaction kettle is fully cooled to room temperature to obtain graphene hydrogel doped with carbon nanotubes, washing with deionized water for three times, then carrying out freeze drying at-60 ℃ for 48h to obtain a three-dimensional porous framework material which has a three-dimensional reticular porous structure and is in an open-cell foam shape, finally crushing the three-dimensional porous framework material into powder particles with the particle size of 15-30 mu m, placing the powder particles at 100-120 ℃ for drying for 5h, and removing residual moisture in pores to obtain the dried three-dimensional porous framework material; in the three-dimensional porous framework material, the mass of the carbon nano tube is 1.2% of that of the graphene oxide.
(2) Dividing 1000g of monomer caprolactam into 500g of the same amount, adding 7g of initiator sodium hydroxide and 5g of the three-dimensional porous framework material prepared in the step (1) into 500g of the monomer caprolactam, heating to 120 ℃, and distilling under reduced pressure to remove trace moisture to obtain a first mixture; heating another 500g of the mixture to 120 ℃, distilling the mixture under reduced pressure to remove trace moisture, preparing a melt, and adding 5.4g of TDI to obtain a second mixture; wherein n (caprolactam): n (sodium hydroxide): n (tdi) 1:0.02: 0.0035.
(3) Adding the first mixture and the second mixture into constant-temperature feeding tanks A and B at 120 ℃ respectively, and feeding 150g of modified magnesium hydroxide powder into a side feeding tank; starting a preheated reactive double-screw exhaust extruder, opening feeding valves of a feeding tank A and a feeding tank B to enable materials to enter the extruder at the same flow rate, wherein the temperatures from a feeding section of the extruder to a machine head are respectively 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ and 200 ℃, and simultaneously opening a side feeding and adjusting the feeding proportion to perform reactive extrusion, and cooling and pelletizing an extruded product; and extracting for 15 hours by boiling water, drying at 105 ℃, and performing injection molding to obtain a standard sample strip, thereby obtaining the flame-retardant composite material. Wherein the mass of the three-dimensional porous framework material accounts for 0.5 percent of the mass of the PA6, and the mass of the magnesium hydroxide accounts for 15 percent of the mass of the PA 6.
Example 2
Example 2 is essentially the same as example 1, except that: example 2 step (2) 30g of three-dimensional porous skeleton material was added, and in the flame-retardant composite material prepared in step (3), the mass of the three-dimensional porous skeleton material was 3% of the mass of PA6, and the mass of magnesium hydroxide was 15% of the mass of PA6
The remaining steps and process conditions were the same as in example 1.
Example 3
Example 3 is essentially the same as example 1, except that: example 3 step (2) of adding 50g of three-dimensional porous skeleton material, in the flame-retardant composite material prepared in step (3), the mass of the three-dimensional porous skeleton material was 5% of the mass of PA6, and the mass of magnesium hydroxide was 15% of the mass of PA6
The remaining steps and process conditions were the same as in example 1.
Example 4
Example 4 is essentially the same as example 1, except that: example 4 step (2) of adding 100g of three-dimensional porous skeleton material, in the flame-retardant composite material prepared in step (3), the mass of the three-dimensional porous skeleton material was 10% of the mass of PA6, and the mass of magnesium hydroxide was 15% of the mass of PA6
The remaining steps and process conditions were the same as in example 1.
Example 5
Example 5 is essentially the same as example 1, except that: example 5 in the flame-retardant composite material prepared by adding 50g of the three-dimensional porous framework material in the step (2) and 50g of the magnesium hydroxide in the step (3), the mass of the three-dimensional porous framework material accounts for 5% of the mass of the PA6, and the mass of the magnesium hydroxide accounts for 5% of the mass of the PA 6.
The remaining steps and process conditions were the same as in example 1.
Example 6
Example 6 is essentially the same as example 1, except that: example 6 adding 50g of three-dimensional porous skeleton material in step (2) and 300g of magnesium hydroxide in step (3) to obtain a flame-retardant composite material, wherein the mass of the three-dimensional porous skeleton material is 5% of the mass of PA6, and the mass of the magnesium hydroxide is 30% of the mass of PA6
The remaining steps and process conditions were the same as in example 1.
Example 7
Example 7 is essentially the same as example 3, except that: example 7 step (1) carbon nanotubes were replaced with graphene fibers (length 10 to 15 μm, monofilament diameter 1.6 μm), and the mass of graphene fibers in the prepared three-dimensional porous framework material was 10% of the mass of graphene oxide.
The remaining steps and process conditions were the same as in example 3.
Example 8
Example 8 is essentially the same as example 3, except that: example 8 the reinforcing material of step (1) was a mixture of carbon nanotubes and graphene fibers, the mass of the carbon nanotubes and the mass of the graphene fibers accounting for 1% and 5% of the mass of the graphene oxide, respectively.
The remaining steps and process conditions were the same as in example 3.
Example 9
Example 9 is essentially the same as example 3, except that: example 9 the particle size of the three-dimensional porous skeleton material of step (1) is 5 to 15 μm.
The remaining steps and process conditions were the same as in example 3.
Example 10
Example 10 is essentially the same as example 3, except that: example 10 the particle size of the three-dimensional porous skeleton material of step (1) was 30 to 50 μm.
The remaining steps and process conditions were the same as in example 3.
Example 11
Example 11 is essentially the same as example 3, except that: example 11 step (2) the mass of the three-dimensional porous skeleton material accounted for 15% of the mass of PA 6.
The remaining steps and process conditions were the same as in example 3.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that: step (1) is not carried out, and the three-dimensional porous framework material is not added in step (2).
The remaining steps and process conditions were the same as in example 1.
Comparative example 2
Comparative example 2 is substantially the same as example 3 except that: the carbon nano tube is not added in the step (1).
The remaining steps and process conditions were the same as in example 3.
Comparative example 3
Comparative example 3 is substantially the same as example 3 except that: magnesium hydroxide is not added in the step (3). The remaining steps and process conditions were the same as in example 3.
Comparative example 4
Comparative example 4 is substantially the same as example 3 except that: in the step (3), the mass of the magnesium hydroxide accounts for 50% of the mass of the PA 6.
The remaining steps and process conditions were the same as in example 3.
Note: the magnesium hydroxide used in the above examples and comparative examples was a magnesium hydroxide sheet dry-modified with a silane coupling agent.
In the performance test, the flame-retardant composite material samples prepared in the above examples and comparative examples are all injection-molded into sample bars with standard sizes, and the thermal conductivity test sample pieces are injection-molded round pieces with the diameters of 3cm and the thicknesses of 2 mm; limit oxygen index test sample size was 80mm 10mm 4mm injection molded bars; the tensile strength test specimens are dumbbell type I specimens with a tensile rate of 50 mm/min. Wherein, a DRL-III thermal conductivity tester is adopted to test the over-surface thermal conductivity according to the ASTM D5470 standard; testing the limiting oxygen index LOI by using an oxygen index tester according to GB/T2406.2-2009 standard; and testing the tensile strength by using a universal tester according to the GB/T1040.1-2018 standard. The test results are shown in table 1.
TABLE 1
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (10)
1. The flame-retardant composite material is characterized by comprising a three-dimensional porous framework material, polyamide and magnesium hydroxide; the three-dimensional porous framework material has a three-dimensional reticular porous structure formed by self-assembly of graphene oxide and a reinforcing material;
at least part of the polyamide and the magnesium hydroxide are loaded on the surface of the three-dimensional porous framework material, and at least part of the polyamide and the magnesium hydroxide are embedded into or penetrate through holes on the surface of the three-dimensional porous framework material to form a three-dimensional interpenetrating network structure;
wherein the reinforcing material is selected from at least one of carbon nanotubes and graphene fibers; the mass of the three-dimensional porous framework material is 0.5-15% of the mass of the polyamide, and the mass of the magnesium hydroxide is 5-30% of the mass of the polyamide.
2. The flame-retardant composite material according to claim 1, wherein the magnesium hydroxide is surface-modified magnesium hydroxide having amino groups, and the amino groups of the magnesium hydroxide are bonded to carboxyl groups on the surface of the three-dimensional porous skeleton material.
3. The flame retardant composite of claim 2, wherein the amino groups of the polyamide are bonded to the carboxyl groups on the surface of the three-dimensional porous skeleton material; and/or
The carboxyl group of the polyamide is bonded to the amino group on the surface of the magnesium hydroxide.
4. The flame retardant composite of any one of claims 1 to 3, wherein the mass of the three-dimensional porous skeleton material is 5% to 15% of the mass of the polyamide; and/or
The mass of the magnesium hydroxide is 10-25% of the mass of the polyamide.
5. The flame-retardant composite material according to any one of claims 1 to 3, wherein the mass of the reinforcing material in the three-dimensional porous skeleton material is 1 to 12% of the mass of the graphene oxide.
6. The flame-retardant composite material according to any one of claims 1 to 3, wherein the reinforcing material comprises carbon nanotubes and graphene fibers, and in the three-dimensional porous framework material, the mass of the carbon nanotubes is 1% to 1.2% of the mass of the graphene oxide, and the mass of the graphene fibers is 8% to 10% of the mass of the graphene oxide.
7. The flame-retardant composite material according to any one of claims 1 to 3, wherein the carbon nanotubes have a tube length of 1 μm to 16 μm, and the graphene fibers have a length of 10 μm to 15 μm; and/or
The particle size of the three-dimensional porous framework material is 15-30 μm.
8. The method for preparing the flame-retardant composite material according to any one of claims 1 to 7, comprising the steps of:
mixing the reinforcing material, the graphene oxide and a solvent, carrying out self-assembly treatment, and then freeze-drying to obtain the three-dimensional porous framework material;
and mixing the three-dimensional porous framework material, the magnesium hydroxide and the polyamide monomers, and performing reaction extrusion to obtain the flame-retardant composite material.
9. The method of preparing a flame retardant composite of claim 8 wherein the step of reactive extrusion is performed under the action of an initiator and an activator; and/or
The step of reactive extrusion is carried out in a reactive extruder, and the temperature of the reactive extruder is as follows according to the advancing direction of materials: 120 deg.C, 140 deg.C, 160 deg.C, 180 deg.C, 200 deg.C and 200 deg.C; and/or
The temperature of the self-assembly treatment is 180-200 ℃, and the time is 10-12 h.
10. An electronic device, characterized in that the electronic device comprises the flame-retardant composite material according to any one of claims 1 to 7.
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