CN110804245A - Flame-retardant composite material and preparation method thereof - Google Patents

Flame-retardant composite material and preparation method thereof Download PDF

Info

Publication number
CN110804245A
CN110804245A CN201911129791.7A CN201911129791A CN110804245A CN 110804245 A CN110804245 A CN 110804245A CN 201911129791 A CN201911129791 A CN 201911129791A CN 110804245 A CN110804245 A CN 110804245A
Authority
CN
China
Prior art keywords
graphene oxide
flame
composite material
magnesium hydroxide
retardant composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201911129791.7A
Other languages
Chinese (zh)
Inventor
刘志启
郭凡
李娜
李丽娟
姬连敏
宋雪雪
聂锋
曾忠民
时东
宋福根
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qinghai Institute of Salt Lakes Research of CAS
Original Assignee
Qinghai Institute of Salt Lakes Research of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qinghai Institute of Salt Lakes Research of CAS filed Critical Qinghai Institute of Salt Lakes Research of CAS
Priority to CN201911129791.7A priority Critical patent/CN110804245A/en
Publication of CN110804245A publication Critical patent/CN110804245A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a flame-retardant composite material and a preparation method thereof. The preparation method of the flame-retardant composite material comprises the following steps: adding a soluble divalent magnesium salt into a graphene oxide solution to obtain a mixed solution; adding alkali into the mixed solution, and reacting to obtain mixed slurry; solid-liquid separation of the mixed slurry to obtain a magnesium hydroxide/graphene oxide hybrid material in a solid phase; and adding the magnesium hydroxide/graphene oxide hybrid material into polypropylene to prepare the flame-retardant composite material. The flame-retardant composite material provided by the invention comprises the magnesium hydroxide/graphene oxide hybrid material and polypropylene which are mixed with each other, and the flame-retardant composite material has excellent heat-conducting property and flame-retardant property. Meanwhile, the preparation method of the flame-retardant composite material provided by the invention is simple, efficient and low in cost, and can be well applied to industrial production.

Description

Flame-retardant composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of flame-retardant materials, and particularly relates to a flame-retardant composite material and a preparation method thereof.
Background
Magnesium hydroxide is the most common inorganic flame retardant, the decomposition temperature is about 340 ℃, and magnesium oxide and water generated after decomposition belong to non-toxic and harmless substances and environment-friendly flame retardants, so the application prospect is very wide. However, magnesium hydroxide has the disadvantages of easy agglomeration and low flame-retardant efficiency, and the addition amount of the magnesium hydroxide in a polymer is very large, and the polymer can reach the flame-retardant level when the addition amount is usually more than 50%. However, such a large amount of addition has greatly affected the mechanical properties of the polymer, and severely limits the application of magnesium hydroxide in particular fields. In order to reduce the amount of magnesium hydroxide added to a polymer, improvement of magnesium hydroxide is required.
There are many methods for improving magnesium hydroxide, including making the magnesium hydroxide flame retardant additive into nanometer size, considering the synergistic effect of magnesium hydroxide flame retardant and other materials, and surface treatment and modification of magnesium hydroxide flame retardant to reduce the addition of magnesium hydroxide flame retardant in the polymer. Research shows that when the nano-scale magnesium hydroxide is used as a flame retardant of a high polymer material, the required filling amount is small, the nano-scale magnesium hydroxide has good compatibility with the high polymer material, and the nano-scale magnesium hydroxide also has a certain enhancing effect on the mechanical property of the high polymer material.
Among inorganic flame retardants, carbon nanomaterials are also a commonly used flame retardant, and graphene has attracted attention of researchers due to its excellent mechanical properties and synergistic flame retardant properties. The two-dimensional structure of the graphene can play a role of a protective layer, the graphitization degree of the residual carbon layer can be greatly improved when the graphene is added into a high polymer material, the thermal stability of the residual carbon layer is improved, and the flame retardant effect is achieved.
Chinese patent application (publication No. CN 106191901A) discloses a preparation method of a magnesium hydroxide/graphene composite material with a high specific surface area, which takes bischofite as a magnesium source, then adds graphene for ultrasonic dispersion, adjusts the pH value of the solution, takes a graphite plate as a cathode, and takes metal or alloy material thereof as an anode to electrolyze magnesium chloride/graphene electrolyte to obtain a product. The method has complex experimental process, adopts an electrolytic method to prepare the composite material, has higher production cost and higher difficulty in realizing industrial production. Chinese patent application (CN106430172A) discloses a preparation method of a magnesium hydroxide/graphene oxide composite material, which uses a supergravity method to prepare the magnesium hydroxide/graphene oxide composite material by taking graphene oxide dispersion liquid, magnesium salt solution and alkali solution as raw materials. But the invention has to use special supergravity equipment, and the production cost is high.
Disclosure of Invention
In order to solve the problems that the preparation cost of the magnesium hydroxide/graphene oxide composite material in the prior art is high, and the prepared material cannot have excellent heat conduction and flame retardant properties, the invention adopts a simple and low-cost preparation method to prepare the flame retardant composite material with excellent heat conduction property and excellent flame retardant property.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a flame retardant composite comprising a magnesium hydroxide/graphene oxide hybrid material and polypropylene intermixed.
Preferably, in the magnesium hydroxide/graphene oxide hybrid material, the mass fraction of graphene oxide is 0.1-10%.
Preferably, in the flame-retardant composite material, the mass fraction of the magnesium hydroxide/graphene oxide hybrid material is 10-50%.
The invention also provides a preparation method of the flame-retardant composite material, which comprises the following steps:
s1, adding a soluble divalent magnesium salt into the graphene oxide solution to obtain a mixed solution;
s2, adding alkali into the mixed solution, and reacting to obtain mixed slurry;
s3, separating solid from liquid to obtain mixed slurry, and obtaining the magnesium hydroxide/graphene oxide hybrid material in the solid phase;
s4, adding the magnesium hydroxide/graphene oxide hybrid material into polypropylene to obtain the flame-retardant composite material.
Preferably, the reaction time of step S2 is 0.5-1 h.
Further preferably, the mixed slurry in step S2 is subjected to hydrothermal reaction at a reaction temperature of 100 to 200 ℃ for 0.5 to 48 hours.
Preferably, the soluble divalent magnesium salt is magnesium chloride, magnesium nitrate, magnesium sulfate, or a hydrate thereof.
Further preferably, the concentration of magnesium ions in the mixed solution is 0.5-2.0 mol/L.
Preferably, the base is a solid base or a lye base.
Further preferably, the concentration of the alkali liquor is 1-4 mol/L.
The flame-retardant composite material provided by the invention comprises the magnesium hydroxide/graphene oxide hybrid material and polypropylene which are mixed with each other, and has excellent heat-conducting property and flame-retardant property. Meanwhile, the preparation method of the flame-retardant composite material provided by the invention is simple, efficient and low in cost, and can be well applied to industrial production.
Drawings
The above and other aspects, features and advantages of embodiments of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
fig. 1 is an XRD pattern of graphene oxide of example 1 of the present invention;
fig. 2 is an SEM image of graphene oxide of example 1;
FIG. 3 is an XRD pattern of the product obtained in example 1;
FIGS. 4 and 5 are TEM images of the product obtained in example 1 at different magnifications;
FIGS. 6 and 7 are SEM images of the magnesium hydroxide/graphene oxide hybrid material in example 1 at different magnifications;
FIG. 8 is a graph of heat release rate for PP materials and the flame retardant composite of examples 1-3;
FIG. 9 is a graph showing the total heat release of PP material and the flame retardant composite of examples 1 to 3;
FIG. 10 is a graph of smoke release rate for PP material and the flame retardant composite of examples 1-3;
FIG. 11 is a graph showing the total smoke emission of PP material and the flame retardant composite of examples 1 to 3;
FIG. 12 is an XRD pattern of the product obtained in example 5;
FIG. 13 is an SEM photograph of the product obtained in example 5;
FIG. 14 is an XRD pattern of the product obtained in example 6;
FIGS. 15 and 16 are SEM images of the product obtained in example 6 at different magnifications.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided to explain the principles of the invention and its practical application to thereby enable others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated.
The inventor of the invention provides a flame-retardant composite material with excellent heat conduction performance and flame retardance performance based on the problems that a magnesium hydroxide/graphene oxide composite material in the prior art cannot have excellent heat conduction performance and flame retardance performance, is high in preparation cost and is complex in preparation method, and provides a preparation method of the flame-retardant composite material.
The two-dimensional structure of the graphene can play a role of a protective layer, and the graphitization degree of the residual carbon layer can be greatly improved by adding the graphene into a high polymer material, so that the thermal stability of the residual carbon layer is improved, and the flame retardant effect is achieved. The surface of the graphene oxide contains a large number of active groups, and the organic-inorganic hybrid composite material can be prepared through non-covalent interaction, wherein the preparation mechanism of the flame-retardant composite material is as follows: firstly, stripping graphite oxide into graphene oxide by a chemical method; then, adsorbing metal cations on the surface of the graphene oxide; then, adding a precipitator to enable the metal ions adsorbed on the surface to be self-combined into a metal oxide/graphene oxide composite material; and finally, adding the composite material into a high polymer material to obtain the high polymer flame-retardant composite material.
The preparation method of the flame-retardant composite material provided by the invention comprises the following steps:
s1, adding a soluble divalent magnesium salt into the graphene oxide solution to obtain a mixed solution;
the soluble divalent magnesium salt is selected from various kinds, and may be magnesium chloride, magnesium nitrate, magnesium sulfate or their hydrates.
The Graphene Oxide (GO) is prepared from natural crystalline flake graphene by a chemical oxidation method.
The magnesium ion concentration is low, which is beneficial to the dispersion of magnesium hydroxide, but the output efficiency of the product is low; the magnesium ion concentration is high, the yield is high, but the agglomeration of magnesium hydroxide is serious. Therefore, in order to integrate the output efficiency and the agglomeration problem, the concentration of magnesium ions in the mixed solution is preferably 0.5-2.0 mol/L.
And S2, adding alkali into the mixed solution, and reacting to obtain mixed slurry.
The alkali can be selected from solid alkali or alkali liquor, and when the alkali liquor is used, the concentration of the alkali liquor is preferably 1-4 mol/L.
The specific method comprises the following steps: firstly, reacting alkali and magnesium salt for a period of time to generate a magnesium hydroxide crystal nucleus in a reaction system, wherein the reaction time of the nucleation is preferably 0.5-1 h; and then preferably transferring the mixed system of the primary reaction into a high-pressure reaction kettle for hydrothermal reaction, wherein the preferred temperature of the hydrothermal reaction is 100-200 ℃, and the preferred time of the hydrothermal reaction is 0.5-48 h. The hydrothermal reaction is carried out in a closed reaction kettle, so that hexagonal flaky magnesium hydroxide can be formed, and the magnesium hydroxide with the morphology has a good flame retardant effect in application.
S3, separating solid from liquid, mixing the slurry, and obtaining the magnesium hydroxide/graphene oxide hybrid material in the solid phase.
There are various solid-liquid separation methods, and the present invention does not limit the specific selection thereof, and may employ suction filtration, drying, centrifugal separation, and the like.
S4, adding the magnesium hydroxide/graphene oxide hybrid material into polypropylene to obtain the flame-retardant composite material.
The embodiment of the invention provides a flame-retardant composite material which comprises a magnesium hydroxide/graphene oxide hybrid material and polypropylene which are mixed with each other.
In the magnesium hydroxide/graphene oxide hybrid material, the mass fraction of the graphene oxide is 0.1-10%.
In the flame-retardant composite material, the mass fraction of the magnesium hydroxide/graphene oxide hybrid material is preferably 10-50%.
It is worth to be noted that polypropylene (PP) contains a large amount of methyl groups, which results in a limited oxygen index (LOI value) of only 17.4%, and is a flammable polymer material. In addition, a large amount of black smoke and toxic gas are generated in the combustion process of PP, and the molten drops are dripped, so that great threat is brought to the life and property safety of people, and potential safety hazards exist when the PP material is used alone. Compared with a pure PP material, the flame-retardant composite material disclosed by the invention has higher thermal conductivity and lower smoke release amount, the smoke release rate and the heat release rate are both obviously reduced, and the excellent heat conduction and flame retardance properties enable the flame-retardant composite material to have great application value.
According to the invention, magnesium hydroxide is attached to the surface of graphene oxide by adopting a simple and efficient non-covalent effect to form a magnesium hydroxide/graphene oxide hybrid material, and then the hybrid material is added into polypropylene. The particle size of the magnesium hydroxide/graphene oxide hybrid material is in a nanometer scale and is about 50nm, so that the magnesium hydroxide/graphene oxide hybrid material has a good nanometer effect, and the thermal conductivity of the graphene oxide is good, so that the obtained flame-retardant composite material has high thermal conductivity and high flame-retardant performance, and particularly, the dispersion performance of the material is greatly improved by adding the graphene oxide.
The above flame-retardant composite material and the method for preparing the same according to the present invention will be described below with reference to specific examples, and it will be understood by those skilled in the art that the following examples are only specific examples of the above flame-retardant composite material and the method for preparing the same according to the present invention, and are not intended to limit the entirety thereof.
Example 1
(1) The soluble divalent magnesium salt is magnesium chloride hexahydrate (MgCl)2·6H2O), and preparing graphene oxide with the initial concentration of 14 mg/mL.
The X-ray diffraction (XRD) scan was performed on the graphene oxide, and the results are shown in fig. 1. As can be seen from FIG. 1, the used graphene oxide XRD spectrogram has no impurity peak, high crystallinity, single product and high purity.
Further, the graphene oxide was scanned by a Scanning Electron Microscope (SEM), and the obtained results are shown in fig. 2. It can be seen from fig. 2 that the graphene oxide has a typical graphene wrinkle morphology.
(2) 800mL of distilled water was placed in a three-necked flask, and 20.4mL of an aqueous graphene oxide solution was sucked up into the three-necked flask by a pipette.
(3) 97.6g of magnesium chloride hexahydrate was weighed into a three-necked flask and stirred magnetically at 60 ℃ for 1 hour (magnesium ion concentration: 0.5 mol/L).
(4) 38.4g of sodium hydroxide solution is dissolved in 240mL of deionized water (the concentration of sodium hydroxide is 4mol/L), added into a three-neck flask at a certain feeding speed to obtain gray slurry, continuously stirred for 0.5h and then transferred into a hydrothermal reaction kettle.
(5) Reacting for 6h at 140 ℃, taking out reactants, naturally cooling, filtering, washing, drying for 8h in a constant temperature air blast drying oven at 80 ℃, grinding and sieving to obtain the product.
XRD scanning of the product gave the results shown in FIG. 3. From fig. 3, it can be seen that the XRD spectrum of the product has only the diffraction peak of magnesium hydroxide, and no graphene oxide peak and other impurity peaks appear. The product has no diffraction peak of graphene oxide, and the agglomeration of graphene oxide is prevented probably due to the existence of magnesium hydroxide, or the mass fraction of graphene oxide is too small to be detected.
The analysis of the above products by Transmission Electron Microscopy (TEM) gave the results shown in FIGS. 4 and 5 at different magnifications. It can be seen from FIGS. 4 and 5 that the particle size of the product produced is small, about 50 nm; it can also be seen that magnesium hydroxide is attached to the graphene oxide sheet, and there is substantially no agglomeration and very good dispersion. Therefore, it can be seen that the product obtained in this example is a magnesium hydroxide/graphene oxide hybrid material.
SEM scans of different magnifications were performed on the above magnesium hydroxide/graphene oxide hybrid material, and the obtained result graphs are shown in fig. 6 and 7. As can be seen from FIGS. 6 and 7, the magnesium hydroxide/graphene oxide hybrid material has uniform morphology, good dispersibility and nano-scale particle sizes.
In the magnesium hydroxide/graphene oxide hybrid material, graphene oxide accounts for 1% of the mass of magnesium hydroxide.
(6) Heating the torque rheometer to 180 ℃, adding polypropylene until the polypropylene is molten, then adding the magnesium hydroxide/graphene oxide hybrid material, and controlling the mass ratio of the polypropylene to the magnesium hydroxide/graphene oxide hybrid material to be 90: 10. And mixing the mixture for 15min to obtain the polypropylene-containing flame-retardant composite material, and tabletting and slicing to obtain a sample strip.
Example 2
Steps (1) to (5) of example 2 are the same as steps (1) to (5) of example 1, and graphene oxide accounts for 1% of the mass of magnesium hydroxide in the obtained magnesium hydroxide/graphene oxide hybrid material.
Different from the embodiment 1 in the step (6), the mass ratio of the polypropylene to the magnesium hydroxide/graphene oxide hybrid material is controlled to be 70: 30.
Example 3
Steps (1) to (5) of example 3 are the same as steps (1) to (5) of example 1, and graphene oxide accounts for 1% of the mass of magnesium hydroxide in the obtained magnesium hydroxide/graphene oxide hybrid material.
The procedure of step (6) of example 3 was the same as that of example 1, except that the mass ratio of polypropylene to the magnesium hydroxide/graphene oxide hybrid material was controlled to 50: 50.
Performance testing of the materials of examples 1-3
The heat conductivity of the pure PP and the specimens from examples 1 to 3 was measured:
the thermal conductivity of the pure PP material is 0.25W/(m.K), and the Limiting Oxygen Index (LOI) is 17.4%.
The flame-retardant composite material obtained in example 1 had a thermal conductivity of 0.29W/(m.K), which was 1.16 times that of pure PP, and a Limiting Oxygen Index (LOI) of 18.9%, which was 1.09 times that of pure PP.
The flame-retardant composite material obtained in example 2 had a thermal conductivity of 0.38W/(m.K), which was 1.52 times that of pure PP, and a Limiting Oxygen Index (LOI) of 21% which was 1.21 times that of pure PP.
The thermal conductivity of the flame-retardant composite material obtained in example 3 is 0.65W/(m.K), which is 2.6 times that of pure PP, and the Limiting Oxygen Index (LOI) is 27.8% which is 1.60 times that of pure PP.
The particle size of the prepared magnesium hydroxide/graphene oxide hybrid material is smaller and is about 50nm (as can be seen from a TEM image), and due to the nanometer effect of the magnesium hydroxide/graphene oxide hybrid material and the better thermal conductivity of GO, the flame-retardant composite material obtained by compounding the magnesium hydroxide and the graphene oxide hybrid material has excellent thermal conductivity, the mass fraction of GO in the flame-retardant composite material is continuously improved, and the thermal conductivity can be further improved.
Flame retardancy tests were performed on pure PP and the sample strips of examples 1 to 3, and a Heat Release Rate (HRR) curve, a total heat release amount (THR) curve, a smoke release rate (SPR) curve, and a total smoke release amount (TSP) curve were obtained as shown in fig. 8 to 11, respectively. Wherein "MGO" represents a magnesium hydroxide/graphene oxide hybrid material.
As can be seen from FIG. 8, the heat release rate of the flame-retardant composite material is obviously reduced, and after 30 wt% of MGO is added, the peak value of the heat release rate of the flame-retardant composite material is 799.7kW/m of pure PP2Reduced to 289.8kW/m2The reduction is 64%; after the addition of 50 wt% of MGO, the peak value of the heat release rate of the flame-retardant composite material is reduced to 156.3kW/m2And the reduction is 80 percent.
From FIG. 9, it can be seen that the total heat release of the flame retardant composite decreases with the increase of the MGO content, and at the addition of 30 wt% of MGO, the total heat release of the flame retardant composite is reduced from 115.3MJ/m of pure PP2Reduced to 108.6MJ/m2The reduction is 6.3%; at the addition amount of 50 wt% of MGO, the total heat release of the flame-retardant composite material is reduced to 79.8MJ/m2And the reduction is 30.8 percent.
As can be seen from FIG. 10, the smoke release rate of MGO gradually decreases with increasing MGO content, and at 30 wt% of the MGO addition, the peak smoke release rate of the flame retardant composite material is 0.28m of that of pure PP2The/s is reduced to 0.09m2The/s is reduced by 67 percent; at the addition amount of 50 wt%, the peak value of the smoke release rate of the composite material is reduced to 0.06m2And/s, reduced by 79%.
From FIG. 11, it can be seen that the total smoke release of the polypropylene composite material is lower and lower with the increase of MGO, and at the addition of 30 wt% of MGO, the total smoke release is 46.4m of that of pure PP2Reduced to 34.4m2The reduction is 26%; at the addition of 50 wt%, the total smoke release of the composite material is reduced to 20.1m2And the reduction is 57%.
Example 4
(1) The soluble divalent magnesium salt is magnesium chloride hexahydrate (MgCl)2·6H2O), and preparing graphene oxide with the initial concentration of 14 mg/mL.
(2) 800mL of distilled water was placed in a three-necked flask, and 81.6mL of an aqueous graphene oxide solution was sucked up into the three-necked flask by a pipette.
(3) 390.4g of magnesium chloride hexahydrate was weighed into a three-necked flask, and stirred magnetically at 60 ℃ for 1 hour (magnesium ion concentration: 2 mol/L).
(4) 153.6g of sodium hydroxide solution is dissolved in 960mL of deionized water (the concentration of sodium hydroxide is 4mol/L), added into a three-neck flask at a certain feeding speed to obtain gray slurry, continuously stirred for 0.5h and transferred into a hydrothermal reaction kettle.
(5) Reacting for 6 hours at 180 ℃, taking out reactants, naturally cooling, filtering, washing, drying for 8 hours in a constant-temperature air-blast drying oven at 80 ℃, grinding, and sieving to obtain the magnesium hydroxide/graphene oxide hybrid material.
In the magnesium hydroxide/graphene oxide hybrid material, graphene oxide accounts for 1% of the mass of magnesium hydroxide.
(6) Heating the torque rheometer to 180 ℃, adding polypropylene until the polypropylene is molten, then adding the magnesium hydroxide/graphene oxide hybrid material, and controlling the mass ratio of the polypropylene to the magnesium hydroxide/graphene oxide hybrid material to be 50: 50. And mixing the mixture for 15min to obtain the polypropylene-containing flame-retardant composite material, and tabletting and slicing to obtain a sample strip.
Example 5
(1) The soluble divalent magnesium salt is magnesium nitrate hexahydrate (Mg (NO)3)2·6H2O), and preparing graphene oxide with the initial concentration of 14 mg/mL.
(2) 400mL of distilled water was put in a three-neck flask, and 204mL of the graphene oxide aqueous solution was sucked into the three-neck flask by a pipette.
(3) 123.1g of magnesium nitrate hexahydrate is weighed and transferred to a three-necked flask, and stirred at 60 ℃ for 1h with a magneton (magnesium ion concentration of 1 mol/L).
(4) 38.4g of sodium hydroxide solution is dissolved in 960mL of deionized water (the concentration of sodium hydroxide is 1mol/L), added into a three-neck flask at a certain feeding speed to obtain gray slurry, continuously stirred for 0.5h and then transferred into a hydrothermal reaction kettle.
(5) Reacting at 200 ℃ for 6h, taking out the reactant, naturally cooling, filtering, washing, drying in a constant-temperature air-blast drying oven at 80 ℃ for 8h, grinding, and sieving to obtain the product.
XRD scanning of the product gave the results shown in FIG. 12. Comparing fig. 12 with the XRD spectrum of graphene oxide (i.e. fig. 1), it can be seen that the peak labeled (002) in the XRD spectrum of the product of this example corresponds to the peak position of graphene oxide in fig. 1, and the diffraction peak of magnesium hydroxide is also shown in fig. 12, so that the product obtained in this example is a magnesium hydroxide/graphene oxide hybrid material containing graphene oxide and magnesium hydroxide.
The result of SEM scanning of the magnesium hydroxide/graphene oxide hybrid material is shown in fig. 13. As can be seen from FIG. 13, the material has uniform morphology, good dispersibility and nano-scale particle size.
In the magnesium hydroxide/graphene oxide hybrid material, graphene oxide accounts for 10% of the mass of magnesium hydroxide.
(6) Heating the torque rheometer to 180 ℃, adding polypropylene until the polypropylene is molten, then adding the magnesium hydroxide/graphene oxide hybrid material, and controlling the mass ratio of the polypropylene to the magnesium hydroxide/graphene oxide hybrid material to be 30: 70. And mixing the mixture for 15min to obtain the polypropylene-containing flame-retardant composite material, and tabletting and slicing to obtain a sample strip.
Example 6
(1) The soluble divalent magnesium salt is magnesium sulfate heptahydrate (MgSO)4·7H2O), and preparing graphene oxide with the initial concentration of 14 mg/mL.
(2) 200mL of distilled water was placed in a three-necked flask, and 2.04mL of an aqueous graphene oxide solution was sucked up by a pipette into the three-necked flask.
(3) 118.4g of magnesium sulfate heptahydrate were weighed into a three-necked flask, and stirred at 60 ℃ for 1 hour with a magneton (magnesium ion concentration: 2 mol/L).
(4) 38.4g of sodium hydroxide solution is dissolved in 240mL of deionized water (the concentration of sodium hydroxide is 4mol/L), added into a three-neck flask at a certain feeding speed to obtain gray slurry, continuously stirred for 0.5h and then transferred into a hydrothermal reaction kettle.
(5) Reacting for 6h at 100 ℃, taking out reactants, naturally cooling, filtering, washing, drying for 8h in a constant temperature air blast drying oven at 80 ℃, grinding and sieving to obtain the product.
XRD scanning of the product gave the results shown in FIG. 14. From fig. 14, it can be seen that the XRD spectrum of the product has only the diffraction peak of magnesium hydroxide, and no graphene oxide peak and other impurity peaks appear, which is mainly due to the fact that the mass fraction of graphene oxide is too small, and it only accounts for 0.1% of the mass of magnesium hydroxide.
SEM scanning of the above product gave results at different magnifications as shown in FIGS. 15 and 16. As can be seen from fig. 15, the dispersion of magnesium hydroxide in the product at low GO mass fraction is not ideal, and as compared to fig. 6 in example 1, the increase in GO content greatly improves the dispersion properties of the product without the addition of other dispersion aids. As can be seen from fig. 16, in the obtained product, magnesium hydroxide all exhibited hexagonal plate-like morphology.
(6) Heating the torque rheometer to 180 ℃, adding polypropylene until the polypropylene is molten, then adding the magnesium hydroxide/graphene oxide hybrid material, and controlling the mass ratio of the polypropylene to the magnesium hydroxide/graphene oxide hybrid material to be 50: 50. And mixing the mixture for 15min to obtain the polypropylene-containing flame-retardant composite material, and tabletting and slicing to obtain a sample strip.
While the invention has been shown and described with reference to certain embodiments, those skilled in the art will understand that: various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.

Claims (10)

1. The flame-retardant composite material is characterized by comprising a magnesium hydroxide/graphene oxide hybrid material and polypropylene which are mixed with each other.
2. The flame retardant composite material according to claim 1, wherein the mass fraction of graphene oxide in the magnesium hydroxide/graphene oxide hybrid material is 0.1-10%.
3. The flame-retardant composite material according to claim 1 or 2, wherein the mass fraction of the magnesium hydroxide/graphene oxide hybrid material in the flame-retardant composite material is 10-50%.
4. A method for preparing a flame retardant composite material according to any one of claims 1 to 3, comprising the steps of:
s1, adding a soluble divalent magnesium salt into the graphene oxide solution to obtain a mixed solution;
s2, adding alkali into the mixed solution, and reacting to obtain mixed slurry;
s3, separating solid from liquid to obtain mixed slurry, and obtaining the magnesium hydroxide/graphene oxide hybrid material in the solid phase;
s4, adding the magnesium hydroxide/graphene oxide hybrid material into polypropylene to obtain the flame-retardant composite material.
5. The method according to claim 4, wherein the reaction time of step S2 is 0.5-1 h.
6. The method according to claim 4 or 5, wherein the mixed slurry obtained in step S2 is further subjected to hydrothermal reaction at a reaction temperature of 100 to 200 ℃ for a reaction time of 0.5 to 48 hours.
7. The method according to claim 4, wherein the soluble divalent magnesium salt is magnesium chloride, magnesium nitrate, magnesium sulfate, or a hydrate thereof.
8. The method according to claim 4, wherein the concentration of magnesium ions in the mixed solution is 0.5 to 2.0 mol/L.
9. The method according to claim 4 or 8, wherein the base is a solid base or an alkaline solution.
10. The preparation method of claim 9, wherein the concentration of the alkali liquor is 1-4 mol/L.
CN201911129791.7A 2019-11-18 2019-11-18 Flame-retardant composite material and preparation method thereof Pending CN110804245A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911129791.7A CN110804245A (en) 2019-11-18 2019-11-18 Flame-retardant composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911129791.7A CN110804245A (en) 2019-11-18 2019-11-18 Flame-retardant composite material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN110804245A true CN110804245A (en) 2020-02-18

Family

ID=69490410

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911129791.7A Pending CN110804245A (en) 2019-11-18 2019-11-18 Flame-retardant composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110804245A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113072082A (en) * 2021-03-31 2021-07-06 珠海格力新材料有限公司 Preparation method and application of magnesium oxide flame retardant
CN113121915A (en) * 2021-04-21 2021-07-16 广东宇豪新材料科技有限公司 Halogen-free flame-retardant graphene modified flame-retardant polypropylene material for household appliances
CN113150446A (en) * 2021-05-19 2021-07-23 广东宇豪新材料科技有限公司 Polypropylene material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106430172A (en) * 2015-08-07 2017-02-22 北京化工大学 Magnesium hydroxide/graphene oxide composite material, preparation method and applications thereof
CN106496632A (en) * 2016-10-14 2017-03-15 复旦大学 A kind of preparation method of magnesium oxide Graphene composite heat-conducting insulating packing

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106430172A (en) * 2015-08-07 2017-02-22 北京化工大学 Magnesium hydroxide/graphene oxide composite material, preparation method and applications thereof
CN106496632A (en) * 2016-10-14 2017-03-15 复旦大学 A kind of preparation method of magnesium oxide Graphene composite heat-conducting insulating packing

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113072082A (en) * 2021-03-31 2021-07-06 珠海格力新材料有限公司 Preparation method and application of magnesium oxide flame retardant
CN113121915A (en) * 2021-04-21 2021-07-16 广东宇豪新材料科技有限公司 Halogen-free flame-retardant graphene modified flame-retardant polypropylene material for household appliances
CN113121915B (en) * 2021-04-21 2022-03-04 广东宇豪新材料科技有限公司 Halogen-free flame-retardant graphene modified flame-retardant polypropylene material for household appliances
CN113150446A (en) * 2021-05-19 2021-07-23 广东宇豪新材料科技有限公司 Polypropylene material
CN113150446B (en) * 2021-05-19 2022-03-04 广东宇豪新材料科技有限公司 Polypropylene material

Similar Documents

Publication Publication Date Title
CN110804245A (en) Flame-retardant composite material and preparation method thereof
Lv et al. Controlled synthesis of magnesium hydroxide nanoparticles with different morphological structures and related properties in flame retardant ethylene–vinyl acetate blends
KR100200082B1 (en) Composite metal hydroxide and its use
JP5686563B2 (en) Magnesium hydroxide fine particles and magnesium oxide fine particles, and methods for producing them
Ni et al. Phase-controllable synthesis of nanosized nickel phosphides and comparison of photocatalytic degradation ability
Wu et al. Synthesis and characterization of superfine magnesium hydroxide with monodispersity
Nouroozi et al. Synthesis and characterization of brush-like ZnO nanorods using albumen as biotemplate
JP5347139B2 (en) Method for producing carbon nanotube
JP2012509389A (en) Synthetic inorganic flame retardants, methods for their preparation and their use as flame retardants
CN102660220A (en) Preparation method of graphene supported ferriferrous oxide nanocomposite
JP4288452B2 (en) Method for producing Mg-Al hydrotalcite-type particle powder, chlorine-containing resin stabilizer and chlorine-containing resin composition
Yang et al. Controllable crystal growth of Mg (OH) 2 hexagonal flakes and their surface modification using graft polymerization
CN112266485B (en) Universal two-dimensional rare earth MOFs material, solvent-free chemical stripping method and application thereof
Tu et al. Waste to resource: preparation of an efficient adsorbent and its sustainable utilization in flame retardant polyurethane composites
CN113023730A (en) Preparation method of silicon-containing layered double hydroxide
CN116178795A (en) Multifunctional phosphorus-nickel doped graphite-like carbon nitride nano sheet, preparation method thereof and ABS material
Santhosh et al. A facile hydrous mechano-synthesis of magnesium hydroxide [Hy-Mg (OH) 2] nano fillers for flame-retardant polyester composites
CN112919431B (en) Hexagonal boron nitride nano-sheet with high yield and high crystallinity and preparation method thereof
Samberg et al. PbO networks composed of single crystalline nanosheets synthesized by a facile chemical precipitation method
CN109575363B (en) 2 MgO-B2O 3-H2O/RGO nano composite flame retardant
Shen et al. Rapid synthesis of SnSe nanowires via an ethylenediamine-assisted polyol route
CN110104666B (en) Method for preparing anhydrous magnesium carbonate based on hydrothermal carbonization reaction
CN109906202A (en) Particle complex metal hydroxide, its firing object, its manufacturing method and its resin combination
CN103074056A (en) Preparation method for SrB6O10/5H2O:Eu<3> luminous material
CN113493215B (en) Preparation method of active magnesium hydroxide

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200218