CN108238595B - Flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel and preparation method thereof - Google Patents
Flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel and preparation method thereof Download PDFInfo
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Abstract
A flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel and a preparation method thereof relate to the field of composite aerogels and preparation thereof. Firstly, synthesizing hydroxyapatite nanorods by a hydrothermal method, dispersing the hydroxyapatite nanorods in deionized water to prepare hydroxyapatite dispersion, then using sodium hydroxide/urea aqueous solution as a solvent, using epoxy chloropropane as a cross-linking agent to prepare microcrystalline cellulose solution, and finally preparing the flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel which has a honeycomb structure and is formed by uniformly dispersing the hydroxyapatite nanorods with the diameter of 1-100nm and the length of 10-300nm in a microcrystalline cellulose matrix by a solution blending method and vacuum freeze drying. The prepared composite aerogel has obvious flame retardant effect and smoke release inhibition effect, the fire safety of the aerogel is obviously improved, and the adopted microcrystalline cellulose and hydroxyapatite raw materials have excellent biocompatibility and environmental friendliness.
Description
Technical Field
The invention relates to the field of composite aerogel and preparation thereof, in particular to microcrystalline cellulose/hydroxyapatite composite aerogel with excellent flame retardance and smoke suppression performance obtained by hydroxyapatite and a preparation method thereof.
Background
The aerogel is a high-dispersion solid nano material which is in a nano porous network structure formed by mutually aggregating colloidal particles or polymer molecules and is filled with gaseous dispersion media in nanopores. The aerogel has the characteristics of low density, high specific surface area, high porosity and the like, so that the aerogel has excellent heat insulation, heat preservation, sound resistance, adsorption and other performances, and plays a significant role in the fields of mechanics, thermal, optics, electromagnetism, electrochemistry and the like. Aerogels can be classified into inorganic aerogels, organic aerogels, and inorganic/organic composite aerogels according to their composition. Inorganic aerogels such as silica aerogels attract attention due to excellent heat insulation, incombustibility and the like, but the mechanical properties, particularly the compression property, of the inorganic aerogels are far lower than the theoretical values, and although the preparation technology is mature, the preparation method is complex and is always a difficult problem in industrial production. The organic aerogel has the characteristics of good mechanical property, flexibility, low thermal conductivity and the like, but has the defect of poor thermal stability, so that the use temperature of the organic aerogel has certain limitation. The inorganic/organic composite aerogel combines the advantages of inorganic aerogel and organic aerogel, and has very wide application prospect in high-technology fields such as spacecrafts, space suits, military tents and the like.
Cellulose is a natural biological polymer with wide sources, and has the advantages of excellent biological friendliness, biodegradability, mechanical strength and the like. Cellulosic aerogel materials are considered as a third generation of aerogel materials, independent of inorganic aerogel materials and organic polymeric aerogel materials, with biological advantages and high mechanical strength not comparable to traditional aerogel materials. With the aggravation of global energy crisis, the development of the cellulose aerogel is beneficial to realizing green environmental protection, energy conservation and consumption reduction, and the sustainable development is promoted. The microcrystalline cellulose is a pure cellulose depolymerization product, has the characteristics of unique fluidity, water absorption and the like, and is a natural high-molecular functional material with a great application prospect. However, microcrystalline cellulose is extremely easy to burn in case of fire, so that the fire accident caused by the burning can threaten human life and property, and the use of the microcrystalline cellulose in the fields of life, industry and the like is greatly limited. The addition of phosphorus-nitrogen flame retardants, halogen flame retardants, polysilicate flame retardants, and phosphorus flame retardants to cellulose substrates (chinese patent application 201611166003.8) is one of the important ways to improve the flame retardant properties of cellulose, but still has the problem of easily generating secondary environmental pollution. Therefore, the environment-friendly halogen-free, low-smoke and efficient flame retardant is adopted to carry out flame retardant treatment on the microcrystalline cellulose aerogel, so that the fire safety of the microcrystalline cellulose aerogel is improved, and the flame retardant is a research hotspot in the field.
Hydroxyapatite is a bioactive material in calcium phosphate ceramics, belongs to the field of biocompatible materials, has chemical compositions and structures extremely similar to inorganic apatite serving as a human bone tissue, and is widely used as a bone tissue repair and filling material. In addition, hydroxyapatite is also used as a flame retardant raw material to improve the flame retardant property of the material. The Chinese patent application 201610390184.6 provides a flame-retardant damping coating prepared by compounding hydroxyapatite ultra-long nanowires and a damping coating as raw materials, and the coating has the effects of flame retardance, mechanical enhancement, shock absorption, noise reduction and the like, and has good application prospects in multiple fields of airplanes, rail trains and the like.
So far, no public report is found in the domestic and external research of preparing the composite aerogel by using hydroxyapatite and microcrystalline cellulose.
Disclosure of Invention
The invention aims to provide the microcrystalline cellulose/hydroxyapatite composite aerogel which is prepared by taking hydroxyapatite nanorods as raw materials and has good biocompatibility, environmental friendliness and excellent flame retardant property. Meanwhile, the invention also provides a preparation method of the composite aerogel.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel has a honeycomb structure and is formed by uniformly dispersing hydroxyapatite nanorods with the diameter of 1-100nm and the length of 10-300nm in a microcrystalline cellulose matrix.
A method for preparing a flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel comprises the following steps:
1) and preparing a hydroxyapatite dispersion liquid:
adding a precursor soluble calcium salt of hydroxyapatite and ammonium dihydrogen phosphate into deionized water, stirring uniformly, adjusting the pH value with ammonia water, reacting in a water bath, and transferring to a hydrothermal reaction kettle for hydrothermal reaction; centrifuging, washing and drying the precipitate after the hydrothermal reaction; dispersing the synthesized hydroxyapatite nano rod in deionized water, and preparing stable and uniformly dispersed hydroxyapatite dispersion liquid after ultrasonic combined mechanical stirring; the molar ratio of Ca/P in the precursor is 5: 3; adjusting the pH value to 10 by using ammonia water; the water bath temperature is 35-55 ℃, and the water bath reaction time is 0.5-1.5 h; the hydrothermal reaction temperature is 160-200 ℃, and the hydrothermal reaction time is 12-24 h; the content of hydroxyapatite in the hydroxyapatite nanorod dispersion liquid is 5-15%;
2) and preparing a microcrystalline cellulose solution:
preparing a mixed aqueous solution of sodium hydroxide and urea, prefreezing the mixed aqueous solution in a refrigerator, slowly adding microcrystalline cellulose into the prefreezed solution, stirring the solution until the microcrystalline cellulose is completely dissolved, transferring the solution into a low-temperature water tank, and slowly dropwise adding a cross-linking agent epichlorohydrin while stirring to prepare a microcrystalline cellulose solution; the mass ratio of the sodium hydroxide to the urea to the deionized water to the microcrystalline cellulose to the epichlorohydrin is 7: 12: 81: 3-7: 3.5 to 6; the temperature of the low-temperature water tank is 0 ℃;
3) and preparing the flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel:
mixing and uniformly stirring a microcrystalline cellulose solution and a hydroxyapatite nanorod dispersion liquid, wherein the mass percentage of hydroxyapatite in the microcrystalline cellulose/hydroxyapatite composite aerogel is 25-50%; placing the mixed solution in a constant-temperature drying box for standing to prepare microcrystalline cellulose/hydroxyapatite composite hydrogel; and leaching the hydrogel with water until the pH value is 7, freezing, and drying in a vacuum freeze dryer to obtain the microcrystalline cellulose/hydroxyapatite composite aerogel.
As a preferred embodiment of the present invention, in the above preparation method, the anion of the calcium salt in step 1) is NO3 -Or Cl-(ii) a The rotating speed of the centrifugal machine is 4000-8000 r/min, and the centrifugal time is 5-10 min; the drying temperature is 60-80 ℃, and the drying time is 12-24 h; the ultrasonic stirring time is 1-3 h. In the step 2), the pre-freezing temperature is-12 ℃, the pre-freezing time is 15-30 min, and the microcrystalline cellulose is slowly added into the pre-freezing solution and then stirred for 20-40 min. The temperature of the constant-temperature drying box in the step 3) is 50 ℃, and the standing time is 10-15 hours; the temperature of the frozen hydrogel is-56 ℃, and the freezing time is 8-15 h; the vacuum freeze drying time is 96-120 h.
Firstly, synthesizing hydroxyapatite nanorods by a hydrothermal method, dispersing the hydroxyapatite nanorods in deionized water to prepare hydroxyapatite dispersion, then using a sodium hydroxide/urea aqueous solution as a solvent, using epoxy chloropropane as a cross-linking agent to prepare microcrystalline cellulose solution, and finally preparing the flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel by a solution blending method and vacuum freeze drying. The beneficial effects are mainly shown as follows:
1) according to the flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel, the hydroxyapatite nanorods have excellent dispersibility and good interface acting force with microcrystalline cellulose, and can be uniformly dispersed in a microcrystalline cellulose matrix to form a honeycomb structure.
2) The microcrystalline cellulose/hydroxyapatite composite aerogel prepared by the invention has low heat release rate and smoke release rate, and the fire safety of the material is obviously improved.
3) The microcrystalline cellulose and the hydroxyapatite adopted by the invention have low cost, excellent biocompatibility and environmental friendliness.
Drawings
FIG. 1 is a SEM photograph of hydroxyapatite prepared in example 1.
Fig. 2 is a field emission scanning electron microscope photograph of the flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel prepared in example 5.
FIG. 3 is a heat release rate curve of the microcrystalline cellulose aerogel prepared in example 2 and the flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel prepared in examples 3 to 5.
FIG. 4 is a smoke release rate curve of the microcrystalline cellulose aerogel prepared in example 2 and the flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel prepared in examples 3 to 5.
Detailed Description
The following provides further details of the flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel and the preparation method thereof according to the present invention with reference to the following examples and accompanying drawings.
Example 1
5.904g of calcium nitrate [ Ca (NO) were weighed out3)2·4H2O]Dissolved in 25mL of deionized water, 1.725g of ammonium dihydrogen phosphate (NH) was weighed4H2PO4) Dissolving the two solutions in 25mL of deionized water, and mixing and uniformly stirring the two solutions, wherein the molar ratio of Ca/P is 5: 3; adjusting the pH value of the mixed solution to 10 by using 25% ammonia water, and reacting for 1h in a water bath at the temperature of 40 ℃; transferring the solution to a reaction kettle at 180 deg.CReacting for 16 h; after the reaction is finished, cooling to room temperature, opening the kettle, centrifuging the solution, washing with deionized water for 3 times, wherein the centrifugal rotation speed is 6000r/min, the time is 8min, and finally drying in an oven at 70 ℃ for 24h to obtain the product, namely the hydroxyapatite nanorod. 2.5g of hydroxyapatite nanorods are weighed and dispersed in 22.5mL of water, the content of hydroxyapatite is 10%, and the hydroxyapatite dispersion liquid with uniform dispersion is prepared after ultrasonic stirring for 2 h.
Figure 1 shows the field emission scanning electron microscope image of the product hydroxyapatite prepared in example 1. As can be seen from FIG. 1, the hydroxyapatite has a regular rod-like structure, a diameter of 20-60 nm and a length of 80-200 nm.
Example 2
Weighing 7g of sodium hydroxide and 12g of urea, dissolving in 81mL of deionized water, placing the solution in a refrigerator at-12 ℃ for precooling for 20min, weighing 6g of microcrystalline cellulose, slowly adding the microcrystalline cellulose into the solution, stirring for 0.5h until the microcrystalline cellulose is completely dissolved, transferring the solution into a three-necked bottle provided with a mechanical stirring device, placing the three-necked bottle in a low-temperature water tank at 0 ℃, slowly dropwise adding 4mL of epoxy chloropropane, and mechanically stirring for 1h to obtain the microcrystalline cellulose solution.
Placing the solution in a constant-temperature drying oven at 50 ℃ and standing for 12 hours to prepare microcrystalline cellulose hydrogel; and (3) leaching the hydrogel with water to pH 7, freezing the hydrogel in a freezer at-56 ℃ for 12 hours, and drying the hydrogel in a vacuum freeze dryer for 120 hours to obtain the microcrystalline cellulose aerogel.
Example 3
Weighing 25.4g of microcrystalline cellulose solution prepared in the example 2 and 4.6g of hydroxyapatite dispersion prepared in the example 1, mixing the two solutions, uniformly stirring, wherein the content of hydroxyapatite in the microcrystalline cellulose/hydroxyapatite composite aerogel is 25%, and standing in a constant-temperature drying oven at 50 ℃ for 12 hours to prepare microcrystalline cellulose/hydroxyapatite composite hydrogel; and leaching the hydrogel with water until the pH value is 7, freezing the hydrogel in a freezer at the temperature of-56 ℃ for 12 hours, and then drying the hydrogel in a vacuum freeze dryer for 96 hours to obtain the flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel.
Example 4
Weighing 23.6g of microcrystalline cellulose solution prepared in example 2 and 6.4g of hydroxyapatite dispersion prepared in example 1, mixing and uniformly stirring the two solutions, wherein the content of hydroxyapatite in the microcrystalline cellulose/hydroxyapatite composite aerogel is 33.3%, and standing the mixture in a constant-temperature drying oven at 50 ℃ for 10 hours to prepare microcrystalline cellulose/hydroxyapatite composite hydrogel; and (3) leaching the hydrogel with water until the pH value is 7, freezing the hydrogel in a freezer at the temperature of-56 ℃ for 8 hours, and then drying the hydrogel in a vacuum freeze dryer for 105 hours to obtain the flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel.
Example 5
Weighing 19.4g of microcrystalline cellulose solution prepared in example 2 and 10.6g of hydroxyapatite dispersion prepared in example 1, mixing and uniformly stirring the two solutions, wherein the content of hydroxyapatite in the microcrystalline cellulose/hydroxyapatite composite aerogel is 50%, and standing the mixture in a constant-temperature drying oven at 50 ℃ for 15 hours to prepare microcrystalline cellulose/hydroxyapatite composite hydrogel; and leaching the hydrogel with water until the pH value is 7, freezing the hydrogel in a freezer at the temperature of-56 ℃ for 15 hours, and then drying the hydrogel in a vacuum freeze dryer for 120 hours to obtain the flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel.
FIG. 2 shows the SEM photo of the flame retardant microcrystalline cellulose/hydroxyapatite aerogel composite prepared in example 5. As can be seen from fig. 2, the microcrystalline cellulose/hydroxyapatite composite aerogel has a typical honeycomb structure; the hydroxyapatite and the microcrystalline cellulose have good interfacial force, and no hydroxyapatite aggregate can be observed.
Fig. 3 and 4 respectively show a heat release rate curve and a smoke release rate curve of the microcrystalline cellulose aerogel prepared in example 2 and the flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel prepared in examples 3 to 5. It can be known from the change curve (fig. 3) of the heat release rate with time obtained by the cone calorimeter that, compared with the microcrystalline cellulose aerogel prepared in example 2, the peak values of the heat release rates of the flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogels prepared in examples 3, 4 and 5 are respectively reduced by 51.5%, 51.8 and 93.7%, and the flame retardant property of the composite aerogel is remarkably improved; it can be known from the change curve (fig. 4) of the smoke release rate with time obtained by the cone calorimeter that compared with the microcrystalline cellulose aerogel prepared in example 2, the peak values of the smoke release rates of the flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogels prepared in examples 3, 4 and 5 are respectively reduced by 6.2%, 20% and 54.8%, and the smoke release of the composite aerogel is effectively inhibited. The flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel prepared by the invention has excellent fire safety.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (4)
1. A preparation method of flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel is characterized by comprising the steps of firstly synthesizing hydroxyapatite nanorods by a hydrothermal method and dispersing the hydroxyapatite nanorods in deionized water to prepare hydroxyapatite dispersion liquid, then using a sodium hydroxide/urea aqueous solution as a solvent, using epoxy chloropropane as a cross-linking agent to prepare microcrystalline cellulose solution, and finally preparing the flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel by combining a solution blending method and vacuum freeze drying; the preparation method comprises the following steps:
1) and preparing a hydroxyapatite dispersion liquid:
adding a precursor soluble calcium salt of hydroxyapatite and ammonium dihydrogen phosphate into deionized water, stirring uniformly, adjusting the pH value with ammonia water, reacting in a water bath, and transferring to a hydrothermal reaction kettle for hydrothermal reaction; centrifuging, washing and drying the precipitate after the hydrothermal reaction; dispersing the synthesized hydroxyapatite nano rod in deionized water, and preparing stable and uniformly dispersed hydroxyapatite dispersion liquid after ultrasonic combined mechanical stirring; the molar ratio of Ca/P in the precursor is 5: 3; adjusting the pH value to 10 by using ammonia water; the water bath temperature is 35-55 ℃, and the water bath reaction time is 0.5-1.5 h; the hydrothermal reaction temperature is 160-200 ℃, and the hydrothermal reaction time is 12-24 h; the content of hydroxyapatite in the hydroxyapatite nanorod dispersion liquid is 5-15%;
2) and preparing a microcrystalline cellulose solution:
preparing a mixed aqueous solution of sodium hydroxide and urea, prefreezing the mixed aqueous solution in a refrigerator, slowly adding microcrystalline cellulose into the prefreezed solution, stirring the solution until the microcrystalline cellulose is completely dissolved, transferring the solution into a low-temperature water tank, and slowly dropwise adding a cross-linking agent epichlorohydrin while stirring to prepare a microcrystalline cellulose solution; the mass ratio of the sodium hydroxide to the urea to the deionized water to the microcrystalline cellulose to the epichlorohydrin is 7: 12: 81: 3-7: 3.5 to 6; the temperature of the low-temperature water tank is 0 ℃;
3) and preparing the flame-retardant microcrystalline cellulose/hydroxyapatite composite aerogel:
mixing and uniformly stirring a microcrystalline cellulose solution and a hydroxyapatite nanorod dispersion liquid, wherein the mass percentage of hydroxyapatite in the microcrystalline cellulose/hydroxyapatite composite aerogel is 25-50%; placing the mixed solution in a constant-temperature drying box for standing to prepare microcrystalline cellulose/hydroxyapatite composite hydrogel; leaching the hydrogel with water until the pH is =7, freezing, and drying in a vacuum freeze dryer to obtain microcrystalline cellulose/hydroxyapatite composite aerogel;
the prepared microcrystalline cellulose/hydroxyapatite composite aerogel has a honeycomb structure and is formed by uniformly dispersing hydroxyapatite nanorods with the diameter of 1-100nm and the length of 10-300nm in a microcrystalline cellulose matrix.
2. The method according to claim 1, wherein the anion of the calcium salt in step 1) is NO3 -Or Cl-(ii) a The rotating speed of the centrifugal machine is 4000-8000 r/min, and the centrifugal time is 5-10 min; the drying temperature is 60-80 ℃, and the drying time is 12-24 h; the ultrasonic stirring time is 1-3 h.
3. The preparation method according to claim 1, wherein the prefreezing temperature in the step 2) is-12 ℃, the prefreezing time is 15-30 min, and the stirring time is 20-40 min after the microcrystalline cellulose is slowly added to the prefreezing liquid.
4. The preparation method of claim 1, wherein the temperature of the constant-temperature drying oven in the step 3) is 50 ℃, and the standing time is 10-15 h; the temperature of the frozen hydrogel is-56 ℃, and the freezing time is 8-15 h; the vacuum freeze drying time is 96-120 h.
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| CN112194816B (en) * | 2020-09-16 | 2022-05-27 | 陕西科技大学 | Preparation method of modified cellulose aerogel for separating glycoprotein |
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