CN114479065B - 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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- CN114479065B CN114479065B CN202210184151.1A CN202210184151A CN114479065B CN 114479065 B CN114479065 B CN 114479065B CN 202210184151 A CN202210184151 A CN 202210184151A CN 114479065 B CN114479065 B CN 114479065B
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- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 239000003063 flame retardant Substances 0.000 title claims abstract description 61
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Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
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 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. 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
As electronic devices move toward higher integration, higher performance, miniaturization, and functionalization, the problem of heat dissipation from the devices becomes increasingly important. Polyamide 6 (PA 6) is widely used as engineering plastics for preparing electronic equipment due to the characteristics of excellent mechanical properties, better electrical properties, wear resistance, oil resistance, self-lubrication, corrosion resistance, good processability and the like, but has lower heat conduction (the heat conduction coefficient is only 0.23W/m.k) and flame retardant property (the limiting oxygen index is only 22%), and still needs to be further improved.
In the prior art, graphene modified polyamide composite materials are prepared by in-situ polymerization of monomers of three-dimensional graphene aerogel and polyamide PA6, but the three-dimensional graphene aerogel formed by self-assembly inevitably collapses in structure in the freeze drying process, the pore diameter becomes large, partial graphene is repeatedly stacked and cannot fully exert the performance of graphene, and the prepared graphene modified polyamide composite materials cannot meet the requirements of the modern technology on the mechanical performance, the thermal conductivity and the flame retardant performance of device materials.
Thus, the prior art is still 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, the flame retardant composite comprising a three-dimensional porous skeletal material, polyamide and magnesium hydroxide; the three-dimensional porous framework material is provided with 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 these 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 skeletal material.
In some of these embodiments, the amino groups of the polyamide are bonded to the carboxyl groups of the surface of the three-dimensional porous scaffold material; and/or
The carboxyl of the polyamide is bonded with the amino on the surface of the magnesium hydroxide.
In some of these embodiments, the mass of the three-dimensional porous scaffold 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, the reinforcing material is 1% -12% of the graphene oxide in the three-dimensional porous skeletal material.
In some embodiments, the reinforcing material comprises carbon nanotubes and graphene fibers, and in the three-dimensional porous skeletal material, the mass of the carbon nanotubes is 1% -1.2% of the mass of the graphene oxide, and the mass of the graphene fibers is 8% -10% of the mass of the graphene oxide.
In some of these 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; and/or
The particle size of the three-dimensional porous framework material is 15-30 mu m.
In another aspect of the present invention, there is provided a method of preparing the flame retardant composite material as described above, comprising the steps of:
mixing the reinforcing material, the graphene oxide and the solvent, performing 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 monomer, 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 reaction extrusion step is carried out in a reaction extruder, and the temperature of the reaction extruder is as follows in sequence according to the advancing direction of the materials: 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ and 200 ℃; 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, an electronic device is provided that includes a flame retardant composite 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, wherein the reinforcing material is 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 a physical crosslinking point, so that the formed three-dimensional porous framework material has a stable structure, a more uniform pore diameter and larger cell strength, can effectively conduct heat and resist flame, and can avoid structural collapse; at the same time, at least part of the polyamide and the magnesium hydroxide are loaded on the surface of the three-dimensional porous framework material, 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, and the quality of the three-dimensional porous framework material, the quality of the polyamide and the quality of the 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 magnesium hydroxide with amino groups modified on the surface, 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 groups of the polyamide are bonded with carboxyl groups 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 is fully exerted, and the flame-retardant composite material is improved, and has high thermal conductivity, high flame retardance and excellent mechanical property.
In the preparation method of the flame-retardant composite material, the reinforcing material, the graphene oxide and the solvent are mixed and subjected to self-assembly treatment, and then freeze-drying is carried out, wherein the reinforcing material is at least one of carbon nano tubes and graphene fibers, the dispersibility is good, and when the graphene oxide and the reinforcing material are subjected to self-assembly, the reinforcing material is used as a substrate to play a supporting role of a physical crosslinking point, so that the formed three-dimensional porous framework material has a stable structure, a more uniform pore diameter and a larger bubble 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 a three-dimensional porous framework material with effective heat conduction; and then mixing and reacting and extruding monomers of the three-dimensional porous framework material, magnesium hydroxide and polyamide, polymerizing the monomers of the polyamide to form polyamide in the process of reacting and extruding, loading at least part of polyamide and magnesium hydroxide on the surface of the three-dimensional porous framework material, embedding or penetrating at least part of polyamide and magnesium hydroxide into holes on the surface of the three-dimensional porous framework material to form a three-dimensional interpenetrating network structure, and controlling the proportion of each material 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 has the advantages that the three-dimensional porous framework material, the magnesium hydroxide and the polyamide monomer are directly mixed and then are subjected to reaction extrusion for in-situ polymerization, the reaction speed is high, the production efficiency is high, continuous production can be carried out, and the molecular weight of the product is high and the molecular weight distribution is narrow; meanwhile, the residence time of the product in the extruder is short, so the thermal degradation degree 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 properties, is beneficial to improving the thermal conductivity and the flame retardant mechanical properties of the electronic equipment, and further improves the service life of the electronic equipment.
Drawings
FIG. 1 is a schematic structural analysis of the flame retardant composite of the present invention.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention, and preferred embodiments of the present invention are set forth. 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 herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
An embodiment of the invention provides a flame-retardant composite material, which 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 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.
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, wherein the reinforcing material is 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 a physical crosslinking point, so that the formed three-dimensional porous framework material has a stable structure, a more uniform pore diameter and larger cell strength, can effectively conduct heat and resist flame, and can avoid structural collapse; at the same time, at least part of the polyamide and the magnesium hydroxide are loaded on the surface of the three-dimensional porous framework material, 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, and the quality of the three-dimensional porous framework material, the quality of the polyamide and the quality of the magnesium hydroxide are controlled, so that the prepared flame-retardant composite material has high thermal conductivity, high flame retardance and excellent mechanical properties.
In the polyamide and the magnesium hydroxide which are supported on the surface of the three-dimensional porous skeleton material and the polyamide and the magnesium hydroxide which are embedded in or pass through the holes on the surface of the three-dimensional porous skeleton material, the mass of the two parts is not particularly required, and the two parts may have overlapped parts, for example, single strands of the polyamide may be supported on the surface of the three-dimensional porous skeleton material while passing through the holes on the surface of the three-dimensional porous skeleton material.
Referring to fig. 1 specifically, fig. 1 is a schematic diagram of a analysis 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 part of polyamide and magnesium hydroxide are loaded on the surface of a three-dimensional porous skeleton material, and a part of polyamide and magnesium hydroxide are embedded into or pass through holes on the surface of the three-dimensional porous skeleton material to form a three-dimensional interpenetrating network structure.
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.
It can be understood that: in the three-dimensional porous framework material formed by self-assembly of graphene oxide and the reinforcing material, a large number of unreduced oxygen-containing functional groups, such as carboxyl groups, are distributed between 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, 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 by a reaction between the amino group and the carboxyl group to form a covalent bond, by a reaction between the amino group and the carboxyl group to form a hydrogen bond, or both.
In some embodiments, the platy magnesium hydroxide is magnesium hydroxide modified with a silane coupling agent.
Specifically, the silane coupling agent is KH550.
The modification method can adopt dry modification or wet modification, and further can adopt magnesium hydroxide surface modifier commonly used in the field to replace silane coupling agent, so long as the magnesium hydroxide surface can form amino groups.
Specifically, the magnesium hydroxide is a sheet-like 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 framework material; and/or the carboxyl groups of the polyamide are bonded with the amino groups 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 is fully exerted, and the flame-retardant composite material has 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 PA6.
It is noted that when a range of values is disclosed herein, the range is considered to be continuous and includes the minimum and maximum values of the range, as well as each value between such minimum and maximum values. For example, "0.5% -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% -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 framework material is 5% -15% of the mass of the polyamide.
In some of these embodiments, the mass of magnesium hydroxide is 10% to 25% of the 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 each component.
In some embodiments, in the three-dimensional porous framework material, the reinforcing material has a mass of 1% -12% of the mass of 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% -1.2% of the mass of the graphene oxide, and the mass of the graphene fibers is 8% -10% of the mass of the graphene oxide.
The types and the proportions of the reinforcing materials are further regulated, the synergistic effect of the carbon nano tube and the graphene fiber is exerted, and the mechanical properties of the flame-retardant composite material are further improved while the high heat conduction and the high flame retardance are maintained.
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 so that the reinforced material fully plays the supporting role of a physical crosslinking point, and the mechanical property of the flame-retardant composite material is further improved.
In some embodiments, the diameter of the carbon nanotube is 7 nm-15 nm, and the diameter of the graphene fiber filament is 1 μm-10 μm.
In some embodiments, the carbon nanotubes are multiwall carbon nanotubes.
In some embodiments, the graphene oxide is a flake graphene oxide; further, the graphene oxide has a sheet diameter of 3 to 10 μm.
In some embodiments, the three-dimensional porous skeletal material has a particle size of 15 μm to 30 μm.
An embodiment of the present invention provides a method for preparing the flame retardant composite material as described above, including the following steps S10 to S20.
And S10, mixing the reinforcing material, graphene oxide and a solvent, performing self-assembly treatment to form a three-dimensional reticular porous structure, and then performing freeze drying to obtain the three-dimensional porous framework material.
And step S20, mixing the three-dimensional porous framework material, the magnesium hydroxide and the polyamide monomer, and performing reaction extrusion to obtain the flame-retardant composite material.
In the preparation method of the flame-retardant composite material, the reinforcing material, the graphene oxide and the solvent are mixed and subjected to self-assembly treatment, and then freeze-drying is carried out, wherein the reinforcing material is at least one of carbon nano tubes and graphene fibers, the dispersibility is good, and when the graphene oxide and the reinforcing material are subjected to self-assembly, the reinforcing material is used as a substrate to play a supporting role of a physical crosslinking point, so that the formed three-dimensional porous framework material has a stable structure, a more uniform pore diameter and a larger bubble 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 a three-dimensional porous framework material with effective heat conduction; and then mixing and reacting and extruding monomers of the three-dimensional porous framework material, magnesium hydroxide and polyamide, and polymerizing the monomers of the polyamide to form polyamide in the process of reacting and extruding, so that the polyamide and the magnesium hydroxide are loaded on the surface of the three-dimensional porous framework material and are embedded into or pass through holes on the surface of the three-dimensional porous framework material to form a three-dimensional interpenetrating network structure, and simultaneously controlling the proportion of each material 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 has the advantages that the three-dimensional porous framework material, the magnesium hydroxide and the polyamide monomer are directly mixed and then are subjected to reaction extrusion for in-situ polymerization, the reaction speed is high, the production efficiency is high, continuous production can be carried out, and the molecular weight of the product is high and the molecular weight distribution is narrow; meanwhile, the residence time of the product in the extruder is short, so the thermal degradation degree 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 embodiments, the solvent is water.
In some embodiments, the step of mixing in step S10 is as follows:
firstly, mixing graphene oxide with a solvent to obtain a graphene oxide solution; the reinforcing material is then dispersed in the graphene oxide solution described above.
Further, the concentration of the graphene oxide solution is about 2 mg/mL-3 mg/mL.
Further, the self-assembly treatment is performed under the action of the water-based dispersing agent; specifically, an aqueous dispersant is mixed with a graphene oxide solution.
In some of these embodiments, the mass of the aqueous dispersant is 0.5% to 1% of the mass of the graphene oxide solution.
Specifically, the aqueous dispersant is at least one selected from sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
The order of adding the reinforcing material and the aqueous dispersing agent into the graphene oxide solution is not particularly sequential, and the reinforcing material and the aqueous dispersing agent can be sequentially or simultaneously performed.
In some of these embodiments, the above mixing step is performed under ultrasound conditions.
In some embodiments, the self-assembly process is performed at a temperature of 180-200 ℃ for a time of 10-12 hours.
In some embodiments, the freeze-drying temperature is-60 ℃ for 48 hours.
In some of these embodiments, step S10 further comprises a step of washing the self-assembled product with water after the self-assembly process and before the step of freeze-drying.
In some embodiments, in step S10, after the step of freeze-drying, a step of pulverizing and drying the freeze-dried product is further included to remove moisture carried in the product.
Further, the drying temperature is 100-120 ℃ and the drying time is 3-5 h.
It can be understood that: in the step S10, the quality of the reinforcing material and the quality of 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 quality of the graphene oxide.
In some embodiments, in step S20, according to the reaction of advancing the material, the temperature controlled in the step of reactive extrusion is: 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ and 200 ℃.
Specifically, the step of reactive extrusion is performed in a reactive extruder; in other words, the temperature controlled in the step of reactive extrusion described above is in turn the temperature of the feed section to the head.
In some of these embodiments, the step of reactive extrusion is performed under the influence of an initiator and an activator.
The initiator initiates the polymerization of the polyamide monomers, and the activator can promote the polymerization.
In some of these embodiments, the initiator described above is an inorganic base; further, is an alkali metal hydroxide; 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 anions, the caprolactam reacts with activator isocyanate to generate caprolactam isocyanate, then the caprolactam anions attack the caprolactam isocyanate and undergo ring opening reaction to generate another active anion, the caprolactam reacts with the active anions to generate active caprolactam cyanate so as to realize chain extension, and then the caprolactam is attacked by the caprolactam anions to open the ring, so that the polyamide polymer with the required relative molecular mass is obtained through continuous circulation.
In some embodiments, in the step S20, the step of mixing and reactive extruding the three-dimensional porous skeleton material, the magnesium hydroxide, and the monomer of the polyamide specifically includes the following steps S21 to S22.
Step S21, uniformly dividing a polyamide monomer into two parts, wherein one part is mixed with an initiator and a three-dimensional porous framework material to obtain a first mixture; another part of the melt of polyamide is mixed with an activator to obtain a second mixture.
Further, the first mixture is distilled to remove water, and reduced pressure distillation is carried out at 120 ℃ to remove trace moisture.
In some of these embodiments, the ratio of the moles of polyamide monomer, initiator, and activator is: 1:0.02:0.0035.
And S22, respectively placing the first mixture and the second mixture in a feeding tank A and a feeding tank B, feeding the magnesium hydroxide into a side feeding tank, and simultaneously feeding and polar reaction extrusion.
In some embodiments, in step S20, after the step of reactive extrusion, the steps of granulating, boiling water extraction, and drying the reactive extruded product are further included in this order.
The monomer which is not completely reacted in the reaction extrusion process or the generated impurities can be removed by boiling water extraction.
In some embodiments, the boiling water extraction time is 10-20 hours, and the drying temperature is 105-120 ℃.
An embodiment of the present invention also provides an electronic device comprising the flame retardant composite 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.
The invention will be described in connection with specific embodiments, but the invention is not limited thereto, and it will be appreciated that the appended claims outline the scope of the invention, and those skilled in the art, guided by the inventive concept, will appreciate that certain changes made to the embodiments of the invention will be covered by the spirit and scope of the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
(1) Adding 0.018g of carbon nanotube (with the pipe diameter of 7-15 nm and the pipe length of 1.5 mu m) into 500mL of GO aqueous solution with the concentration of 3mg/mL, adding 5g of dispersing agent 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 polytetrafluoroethylene lining, carrying out hydrothermal treatment for 12 hours at 180-200 ℃, 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 freeze-drying at-60 ℃ for 48 hours to obtain a three-dimensional porous framework material, wherein the three-dimensional porous framework material 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, and drying the powder particles at 100-120 ℃ for 5 hours to remove 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 percent of that of the graphene oxide.
(2) Dividing 1000g of monomeric caprolactam into 500g of equal amount, adding 7g of initiator sodium hydroxide and 5g of three-dimensional porous framework material prepared in the step (1) into 500g of monomeric caprolactam, heating to 120 ℃ and distilling under reduced pressure to remove trace moisture to obtain a first mixture; heating 500g to 120 ℃ for reduced pressure distillation 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) Respectively adding the first mixture and the second mixture into a constant temperature charging tank A and a constant temperature charging tank B at 120 ℃, and charging 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, enabling materials in the feeding valves to enter the extruder at the same flow rate, enabling the temperature from a feeding section of the extruder to a machine head to be 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ and 200 ℃, simultaneously starting a side feeding and adjusting feeding ratio to perform reactive extrusion, and cooling and granulating an extruded product; and then extracting with boiling water for 15 hours, drying at 105 ℃, and injection molding into standard sample bars to obtain the flame-retardant composite material. Wherein the mass of the three-dimensional porous framework material accounts for 0.5% of the mass of the PA6, and the mass of the magnesium hydroxide accounts for 15% of the mass of the PA6.
Example 2
Example 2 is substantially the same as example 1, except that: example 2 step (2) 30g of a three-dimensional porous skeleton Material was added, and in the flame retardant composite material obtained 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 substantially the same as example 1, except that: example 3 step (2) 50g of three-dimensional porous skeleton Material was added, and in the flame retardant composite material obtained 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 substantially the same as example 1, except that: example 4 step (2) 100g of three-dimensional porous skeleton Material was added, and in the flame retardant composite material obtained 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 substantially the same as example 1, except that: example 5 step (2) 50g of three-dimensional porous skeleton material was added, and step (3) 50g of magnesium hydroxide was added, whereby a flame retardant composite material was produced in which the mass of the three-dimensional porous skeleton material was 5% of the mass of PA6 and the mass of magnesium hydroxide was 5% of the mass of PA6.
The remaining steps and process conditions were the same as in example 1.
Example 6
Example 6 is substantially the same as example 1, except that: example 6 step (2) 50g of three-dimensional porous skeleton Material was added, and 300g of magnesium hydroxide was added in step (3), and in the flame retardant composite material obtained, the mass of the three-dimensional porous skeleton material was 5% of the mass of PA6, and the mass of magnesium hydroxide was 30% of the mass of PA6
The remaining steps and process conditions were the same as in example 1.
Example 7
Example 7 is substantially the same as example 3, except that: example 7 step (1) the carbon nanotubes were replaced with graphene fibers (length 10 μm to 15 μm, filament diameter 1.6 μm), and the mass of the graphene fibers in the prepared three-dimensional porous scaffold 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 substantially the same as example 3, except that: example 8 step (1) the reinforcing material 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 graphene oxide, respectively.
The remaining steps and process conditions were the same as in example 3.
Example 9
Example 9 is substantially the same as example 3, except that: example 9 the three-dimensional porous skeletal material of step (1) has a particle size of 5 μm to 15 μm.
The remaining steps and process conditions were the same as in example 3.
Example 10
Example 10 is substantially the same as example 3, except that: example 10 the three-dimensional porous skeletal material of step (1) had a particle size of 30 μm to 50. Mu.m.
The remaining steps and process conditions were the same as in example 3.
Example 11
Example 11 is substantially the same as example 3, except that: example 11 the mass of the three-dimensional porous scaffold material of step (2) was 15% of the mass of PA6.
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 a 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: in the step (1), no carbon nanotubes are added.
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: in the step (3), no magnesium hydroxide is added. 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 PA6.
The remaining steps and process conditions were the same as in example 3.
Note that: the magnesium hydroxide used in the above examples and comparative examples was a magnesium hydroxide sheet dry-modified with a silane coupling agent.
Performance test the flame retardant composite samples prepared in the above examples and comparative examples were injection molded into standard size bars, with the thermal conductivity test coupon being a 3cm diameter, 2mm thick injection molded disc; limiting oxygen index test sample size is 80mm x 10mm x 4mm injection molded spline; the tensile strength test bars are dumbbell type I specimens with a tensile rate of 50mm/min. Wherein, a DRL-III thermal conductivity tester is adopted to test the surface thermal conductivity according to the ASTM D5470 standard; adopting an oxygen index determinator to test limiting oxygen index LOI according to GB/T2406.2-2009 standard; the tensile strength is tested according to GB/T1040.1-2018 standard by using a universal testing machine. The test results are shown in Table 1.
TABLE 1
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by 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 is provided with a three-dimensional reticular porous structure formed by self-assembly of graphene oxide and a reinforcing material; the polyamide is selected from at least one of PA6 and PA 66;
part of the polyamide and the magnesium hydroxide are loaded on the surface of the three-dimensional porous framework material, and 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 3% -15% of the mass of the polyamide, and the mass of the magnesium hydroxide is 5% -30% of the mass of the polyamide;
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;
in the three-dimensional porous framework material, the mass of the reinforcing material is 1% -12% of the mass of the graphene oxide;
the preparation method of the flame-retardant composite material comprises the following steps:
mixing the three-dimensional porous framework material, the magnesium hydroxide and the polyamide monomer, and extruding through reaction.
2. The flame retardant composite of claim 1, wherein the amino groups of the polyamide are bonded to the carboxyl groups of the surface of the three-dimensional porous skeletal material.
3. The flame retardant composite of claim 1, wherein the carboxyl groups of the polyamide are bonded to the amino groups of the magnesium hydroxide surface.
4. A flame retardant composite according to 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. A flame retardant composite material according to any one of claims 1 to 3, wherein the reinforcing material is carbon nanotubes and graphene fibers, and in the three-dimensional porous skeleton material, the mass of the carbon nanotubes is 1% -1.2% of the mass of the graphene oxide, and the mass of the graphene fibers is 8% -10% of the mass of the graphene oxide.
6. A flame retardant composite 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.
7. A flame retardant composite according to any one of claims 1 to 3, wherein the three-dimensional porous matrix material has a particle size of 15 μm to 30 μm.
8. The method for preparing a 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 the solvent, performing 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 monomer, 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 reaction extrusion step is carried out in a reaction extruder, and the temperature of the reaction extruder is as follows in sequence according to the advancing direction of the materials: 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ and 200 ℃; and/or
The temperature of the self-assembly treatment is 180-200 ℃ and the time is 10-12 h.
10. An electronic device comprising the flame retardant composite of any one of claims 1-7.
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