CN112225940A - Organic/inorganic material composite flame-retardant aerogel board prepared by taking ramie stalks as raw materials and preparation method thereof - Google Patents
Organic/inorganic material composite flame-retardant aerogel board prepared by taking ramie stalks as raw materials and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an organic/inorganic material composite flame-retardant aerogel board prepared by taking ramie stalks as raw materials and a preparation method thereof, wherein the board is prepared by taking the ramie stalks as the raw materials, firstly extracting cellulose in the ramie stalks and then carrying out acidolysis on the cellulose to prepare cellulose whiskers; then uniformly mixing the self-made aluminum hydroxide colloid, the polypropylene fiber and the cellulose whisker to prepare wet gel, and freeze-drying to prepare the cellulose-based aerogel plate; and finally, reacting the cellulose-based aerogel board with a self-made organic flame retardant to obtain the composite material. The organic/inorganic material composite flame-retardant aerogel board prepared by the invention contains the aluminum hydroxide inorganic flame retardant and the phenyl dichlorophosphate organic flame retardant, so that the board has safe fireproof performance in application; the polypropylene fiber is doped to realize stronger mechanical property. The organic/inorganic material composite flame-retardant aerogel board disclosed by the invention is simple in preparation process, wide in raw material source and good in market prospect.
Description
Technical Field
The invention belongs to the technical field of aerogel preparation, and particularly relates to an organic/inorganic material composite flame-retardant aerogel board prepared by taking ramie stalks as raw materials and a preparation method thereof.
Background
The aerogel is a novel material formed by forming a gel by chemically or physically crosslinking organic or inorganic molecules, and replacing the liquid state filled in a gel network with gas by a drying method and the like. The aerogel has the characteristics of small density, large specific surface area, high porosity and the like, and has excellent performances in the aspects of heat, mechanics, acoustics, electricity, optics and the like, so the aerogel has good application potential in the fields of sound insulation materials, adsorption catalysis, heat insulation materials, sensors, filtering materials, acoustic impedance coupling materials, fuel cells and the like.
Aerogels are one of the lightest materials known at present and can be classified into organic, inorganic and composite systems. Compared with the traditional organic aerogel, the cellulose aerogel has the advantages of high toughness, degradability, wide source and the like, so that the high-performance cellulose aerogel is most expected to replace the organic aerogel and is used in the fields of heat preservation, sound and heat insulation and the like. Cellulose aerogels have been extensively studied in many fields, such as: chinese patent application No. 201410024893.3 discloses a preparation method of a super-light, hydrophobic and high-oil-absorption nano fibrillated cellulose aerogel; chinese patent application No. 201610686477.9 discloses a modified cellulose aerogel capable of purifying urine and a preparation method thereof. However, the mechanical strength of the pure cellulose aerogel is not high, and the pure cellulose aerogel is easy to collapse during bearing, so that the application of the pure cellulose aerogel in specific fields such as buildings, furniture and plates is limited, and therefore, the further improvement of the mechanical properties of the cellulose aerogel is very important. In addition, the cellulose aerogel is flammable, and when the cellulose aerogel is used in the fields of buildings, furniture, plates and the like, a fire disaster is easy to happen, which is also a difficult problem to overcome.
Aiming at the defects of weak mechanical property and flammability of the cellulose aerogel, in order to widely apply the cellulose aerogel in specific fields such as buildings, furniture, plates and the like, effective methods must be found to solve the two defects.
Disclosure of Invention
The present invention proposes a solution in this respect to the problem of weak mechanical properties and flammability of cellulose aerogels. The invention aims to overcome the defects of the prior art and provides an organic/inorganic material composite flame-retardant aerogel board prepared by taking ramie stalks as raw materials and a preparation method thereof. The organic/inorganic material composite flame-retardant aerogel board prepared by the invention has better mechanical property and flame retardant property, and is a good material for building boards and the like.
The invention aims to provide an organic/inorganic material composite flame-retardant aerogel plate prepared by taking ramie stalks as raw materials, wherein the plate is prepared by taking the ramie stalks as the raw materials, extracting cellulose in the ramie stalks and preparing aluminum hydroxide colloid; secondly, cellulose is acidolyzed to prepare cellulose whiskers; then uniformly mixing aluminum hydroxide colloid, polypropylene fiber (PP fiber) and cellulose whisker to prepare wet gel, and freeze-drying to prepare the cellulose-based aerogel plate; and finally reacting the cellulose-based aerogel board with an organic flame retardant to obtain the composite material.
The invention also aims to provide a preparation method of the organic/inorganic material composite flame-retardant aerogel board prepared by taking the ramie stalks as raw materials, which comprises the following steps:
(1) preparation of aluminum hydroxide colloid: mixing and reacting an aluminum chloride solution and ammonia water to generate aluminum hydroxide, stirring and curing the generated aluminum hydroxide on a magnetic stirrer at 70-80 ℃, wherein the curing time is 8-10 h; placing the cured sol in a condensation reflux device, and refluxing for 24-48 h at 80-95 ℃ in a water bath kettle; and filtering the refluxed sol by using a 0.45 mu m acetate fiber filter membrane to obtain aluminum hydroxide colloid.
Preferably, the concentration of the aluminum chloride solution is 1-3 mol/L, the concentration of the ammonia water is 1-3 mol/L, and the volume ratio of the aluminum chloride solution to the ammonia water is as follows: 1: 2-4; the rotating speed of the magnetic stirrer is 200-300 r/min.
(2) Preparing an aqueous solution of cellulose whiskers: and (2) carrying out acidolysis on cellulose by using 60-70% of sulfuric acid at room temperature for 8-12 h, filtering, washing with distilled water to be neutral, and carrying out vacuum drying to obtain the cellulose whisker. Preferably, the mass to volume ratio of cellulose (g) to sulfuric acid (mL) is: 1: 5-10.
(3) Mixing of aluminum hydroxide colloid with cellulose solution: mixing the aluminum hydroxide colloid, the PP fibers and the cellulose whiskers prepared in the step (1) in a proper proportion, dissolving the mixture in deionized water, and putting the mixed solution into a mold for ultrasonic treatment until the mixed solution becomes wet gel; then soaking the wet gel into 20-40 times of volume of absolute ethyl alcohol at 20-25 ℃ for treatment for 3-4 days, and changing the solution every 24 hours to obtain cellulose ethyl alcohol wet gel; finally, freeze-drying at-50-60 ℃; a cellulose-based aerogel board was obtained.
Preferably, the mold is a 50cm x 30cm x 10cm glass container article; the mass-volume ratio of the aluminum hydroxide colloid (mL) to the PP fiber (g) to the cellulose whisker (g) is as follows: 1: 5-10; the mass-to-volume ratio of the cellulose whiskers (g) to the deionized water (mL) is as follows: 1: 20-30.
(4) Finishing of the organic flame retardant: and (3) soaking the single cellulose-based aerogel board prepared in the step (3) into a dimethyl sulfoxide solution in which a flame retardant and urea are dissolved, reacting for 4-6 hours at 90-100 ℃, then carrying out water-based reaction until the water-based reaction is neutral, and drying.
Preferably, the mass-to-volume ratio of the flame retardant (g), urea (g) and dimethyl sulfoxide (mL) is: 1: 2-4: 20-30.
The preparation method of the cellulose in the step (2) comprises the following steps:
step 101: sawing dry ramie stalks, wherein the length of each section is about 5-10 cm after sawing; under normal pressure, adding ramie stalks into a sodium hydroxide solution of 5-20 g/L, wherein the bath ratio of the ramie stalks to the sodium hydroxide solution is 1: 30-50, the boiling-off temperature is 60-90 ℃, and the boiling-off time is 90-120 min; repeatedly washing with tap water to neutrality after boiling off;
step 102: soaking the ramie stalks treated in the step 101 in a sulfuric acid solution with the mass concentration of 1-3 g/L at the solid-liquid bath ratio of 1: 30-50 and the temperature of 50-60 ℃ for 20-40 min; after soaking, repeatedly washing the mixture to be neutral by using tap water;
step 103: soaking the ramie stalks treated in the step 102 in a mixed solution of 1-3 g/L of pectinase and 1-3 g/L of laccase in a solid-liquid bath ratio of 1: 30-50, controlling the pH value to be 6-7, controlling the temperature to be 50-60 ℃, and soaking for 3-5 hours; after soaking, repeatedly washing the mixture to be neutral by using tap water;
step 104: soaking the ramie stalks treated in the step 103 in an ethanol solution, wherein the bath ratio of solid to liquid is 1: 30-50, the temperature is controlled to be 30-50 ℃, and the stirring is continuously carried out for 2-5 hours; after stirring, filtering to remove filtrate;
step 105: putting the straw stalks treated in the step 104 into a high-temperature high-pressure closed aqueous solution, wherein the bath ratio of solid to liquid is 1: 30-50, the treatment temperature is 180-220 ℃, the pressure is 6-12 atm, and the treatment time is 2-3 hours; and (3) repeatedly washing the solid flocculent substance to be neutral by using tap water, and naturally airing in the air.
The preparation method of the flame retardant in the step (4) comprises the following steps: adding ethylenediamine and phenyl dichloro phosphate into a flask provided with a strong stirring device and a reflux condensing device, and reacting for 2-3 hours; and after the reaction is finished, pouring a proper amount of acetone solution into the reaction product, shaking and mixing, standing for layering, leaving a layer of white solution, washing for 3-5 times by using acetone, performing suction filtration to obtain a white powdery product, and drying for 4-5 hours at 70-80 ℃ to obtain the flame retardant.
Preferably, the volume ratio of ethylenediamine (mL) to phenyl dichlorophosphate (mL) is: 1: 2-4.
The invention has the following remarkable characteristics:
(1) according to the invention, the PP fiber is added in the process of preparing the organic/inorganic material composite flame-retardant aerogel board, so that the organic/inorganic material composite flame-retardant aerogel board has better strength and toughness, and can be used for building boards.
(2) The invention successfully extracts the cellulose in the ramie stalks, and realizes the high-efficiency utilization of the ramie stalks.
(3) The organic/inorganic material composite flame-retardant aerogel board prepared by the invention contains the aluminum hydroxide inorganic flame retardant and the phenyl dichlorophosphate organic flame retardant, so that the board has safe fireproof performance in application.
Drawings
Fig. 1 is an electron microscope image of an organic/inorganic material composite flame retardant aerogel board a prepared in example 1.
Detailed Description
The examples described below illustrate the invention in detail.
Example 1
In this embodiment, the organic/inorganic material composite flame-retardant aerogel board prepared by using ramie stalks as raw materials is prepared by the following method, which includes the following steps:
(1) preparation of aluminum hydroxide colloid: mixing 10mL of 2mol/L aluminum chloride solution and 30mL of 2mol/L ammonia water for reaction to generate aluminum hydroxide, and stirring and curing the generated aluminum hydroxide solution at 75 ℃ on a magnetic stirrer with the rotation speed of 250r/min for 9 h; putting the cured sol into a condensation reflux device, and refluxing for 36 hours at 90 ℃ in a water bath; and filtering the refluxed sol by using a 0.45 mu m acetate fiber filter membrane to obtain aluminum hydroxide colloid.
(2) Preparing an aqueous solution of cellulose whiskers: and (2) carrying out acidolysis on 10g of cellulose by using 75mL of sulfuric acid with the mass fraction of 65% at room temperature for 10h, filtering, washing with distilled water to be neutral, and carrying out vacuum drying to obtain the cellulose whisker.
(3) Mixing of aluminum hydroxide colloid with cellulose solution: mixing 300mL of the aluminum hydroxide colloid prepared in the step (1), 120g of PP fiber and 160g of cellulose whisker, dissolving in 4000mL of deionized water, and putting the mixed solution into a mold for ultrasonic treatment until the mixed solution becomes wet gel; then soaking the wet gel into 30 times volume of absolute ethyl alcohol at 23 ℃ for 3 days, and changing the solution every 24 hours to obtain cellulose ethyl alcohol wet gel; finally, freeze drying at-55 deg.C; obtaining a cellulose-based aerogel board; the mold is a 30cm x 15cm x 5cm glass container article.
(4) Finishing of the organic flame retardant: and (3) soaking the single cellulose-based aerogel board prepared in the step (3) into 3000mL of dimethyl sulfoxide solution in which 55g of flame retardant and 165g of urea are dissolved, reacting for 5h at 95 ℃, then carrying out water-based to neutral reaction, and drying to obtain the organic/inorganic material composite flame-retardant aerogel board a, wherein an electron microscope image of the organic/inorganic material composite flame-retardant aerogel board a is shown in figure 1.
The preparation method of the cellulose in the step (2) comprises the following steps:
step 101: sawing dry ramie stalks, wherein the length of each section is about 5-10 cm after sawing; under normal pressure, adding ramie stalks into 15g/L sodium hydroxide solution, wherein the bath ratio of the ramie stalks to the sodium hydroxide solution is 1: 40, the boiling-off temperature is 70 ℃, and the boiling-off time is 100 min; repeatedly washing with tap water to neutrality after boiling off;
step 102: soaking the ramie stalks treated in the step 101 in a sulfuric acid solution with the mass concentration of 2g/L at the bath ratio of 1: 40 and the temperature of 55 ℃ for 30 min; after soaking, repeatedly washing the mixture to be neutral by using tap water;
step 103: soaking the ramie stalks treated in the step 102 in a mixed solution of 2g/L of pectinase and 2g/L of laccase, wherein the bath ratio of solid to liquid is 1: 40, the pH value is controlled to be 6.5, the temperature is controlled to be 55 ℃, and the soaking time is 4 hours; after soaking, repeatedly washing the mixture to be neutral by using tap water;
step 104: soaking the ramie stalks treated in the step 103 in an ethanol solution, wherein the bath ratio of solid to liquid is 1: 40, the temperature is controlled at 40 ℃, and the stirring is continuously carried out for 3 hours; after stirring, filtering to remove filtrate;
step 105: putting the straw stalks treated in the step 104 into a high-temperature high-pressure closed aqueous solution, wherein the bath ratio of solid to liquid is 1: 40, the treatment temperature is 200 ℃, the pressure is 10atm, and the treatment time is 2.5 hours; and (3) repeatedly washing the solid flocculent substance to be neutral by using tap water, and naturally airing in the air.
The preparation method of the flame retardant in the step (4) comprises the following steps: adding 20mL of ethylenediamine and 30mL of phenyl dichlorophosphate into a flask provided with a strong stirring device and a reflux condensing device, and reacting for 2.5 hours; and after the reaction is finished, pouring a reaction product into a proper amount of acetone solution, shaking and mixing, standing for layering to leave a layer of white solution, washing for 4 times by using acetone, performing suction filtration to obtain a white powdery product, and drying for 4.5 hours at 75 ℃ to obtain the flame retardant.
Example 2
In this embodiment, the organic/inorganic material composite flame-retardant aerogel board prepared by using ramie stalks as raw materials is prepared by the following method, which includes the following steps:
(1) preparation of aluminum hydroxide colloid: mixing 10mL of 1mol/L aluminum chloride solution and 30mL of 1mol/L ammonia water for reaction to generate aluminum hydroxide, and stirring and curing the generated aluminum hydroxide solution at 80 ℃ on a magnetic stirrer with the rotation speed of 250r/min for 9 h; putting the cured sol into a condensation reflux device, and refluxing for 36 hours at 90 ℃ in a water bath; and filtering the refluxed sol by using a 0.45 mu m acetate fiber filter membrane to obtain aluminum hydroxide colloid.
(2) Preparing an aqueous solution of cellulose whiskers: and (2) carrying out acidolysis on 10g of cellulose by 50mL of sulfuric acid with the mass fraction of 70% at room temperature for 8h, filtering, washing with distilled water to be neutral, and carrying out vacuum drying to obtain the cellulose whisker.
(3) Mixing of aluminum hydroxide colloid with cellulose solution: mixing 300mL of the aluminum hydroxide colloid prepared in the step (1), 120g of PP fiber and 180g of cellulose whisker, dissolving in 3600mL of deionized water, and putting the mixed solution into a mold for ultrasonic treatment until the mixed solution becomes wet gel; then soaking the wet gel into 20 times volume of absolute ethyl alcohol at 22 ℃ for 3 days, and changing the solution every 24 hours to obtain cellulose ethyl alcohol wet gel; finally, freeze drying at-60 deg.C; obtaining a cellulose-based aerogel board; the mold is a 30cm x 15cm x 5cm glass container article.
(4) Finishing of the organic flame retardant: and (3) soaking the single cellulose-based aerogel board prepared in the step (3) into 3000mL of dimethyl sulfoxide solution in which 50g of flame retardant and 100g of urea are dissolved, reacting for 5h at 95 ℃, then carrying out water-based to neutral reaction, and drying to obtain the organic/inorganic material composite flame-retardant aerogel board b.
The preparation method of the cellulose in the step (2) comprises the following steps:
step 101: sawing dry ramie stalks, wherein the length of each section is about 5-10 cm after sawing; under normal pressure, adding ramie stalks into 10g/L sodium hydroxide solution, wherein the bath ratio of the ramie stalks to the sodium hydroxide solution is 1: 30, the boiling-off temperature is 80 ℃, and the boiling-off time is 110 min; repeatedly washing with tap water to neutrality after boiling off;
step 102: soaking the ramie stalks treated in the step 101 in a sulfuric acid solution with the mass concentration of 1g/L at the solid-liquid bath ratio of 1: 30 and the temperature of 55 ℃ for 30 min; after soaking, repeatedly washing the mixture to be neutral by using tap water;
step 103: soaking the ramie stalks treated in the step 102 in a mixed solution of 1g/L of pectinase and 1g/L of laccase in a solid-liquid bath ratio of 1: 30, controlling the pH value to be 6.0, controlling the temperature to be 55 ℃, and soaking for 4 h; after soaking, repeatedly washing the mixture to be neutral by using tap water;
step 104: soaking the ramie stalks processed in the step 103 in an ethanol solution at a bath ratio of 1: 30 and a temperature of 30 ℃, and continuously stirring for 3 hours; after stirring, filtering to remove filtrate;
step 105: putting the straw stalks treated in the step 104 into a high-temperature high-pressure closed aqueous solution, wherein the bath ratio of solid to liquid is 1: 30, the treatment temperature is 180 ℃, the pressure is 9atm, and the treatment time is 2 hours; and (3) repeatedly washing the solid flocculent substance to be neutral by using tap water, and naturally airing in the air.
The preparation method of the flame retardant in the step (4) comprises the following steps: adding 20mL of ethylenediamine and 40mL of phenyl dichlorophosphate into a flask provided with a strong stirring device and a reflux condensing device, and reacting for 2 hours; and after the reaction is finished, pouring a reaction product into a proper amount of acetone solution, shaking and mixing, standing for layering to leave a layer of white solution, washing for 4 times by using acetone, performing suction filtration to obtain a white powdery product, and drying for 4 hours at 70 ℃ to obtain the flame retardant.
Example 3
In this embodiment, the organic/inorganic material composite flame-retardant aerogel board prepared by using ramie stalks as raw materials is prepared by the following method, which includes the following steps:
(1) preparation of aluminum hydroxide colloid: mixing 10mL of 1mol/L aluminum chloride solution and 40mL of 2mol/L ammonia water for reaction to generate aluminum hydroxide, and stirring and curing the generated aluminum hydroxide solution at 80 ℃ on a magnetic stirrer with the rotating speed of 300r/min for 9 h; putting the cured sol into a condensation reflux device, and refluxing for 36h at 95 ℃ in a water bath; and filtering the refluxed sol by using a 0.45 mu m acetate fiber filter membrane to obtain aluminum hydroxide colloid.
(2) Preparing an aqueous solution of cellulose whiskers: and (2) carrying out acidolysis on 10g of cellulose by using 100mL of sulfuric acid with the mass fraction of 70% at room temperature for 12h, filtering, washing with distilled water to be neutral, and carrying out vacuum drying to obtain the cellulose whisker.
(3) Mixing of aluminum hydroxide colloid with cellulose solution: mixing 300mL of the aluminum hydroxide colloid prepared in the step (1), 120g of PP fiber and 135g of cellulose whisker, dissolving in 4000mL of deionized water, and putting the mixed solution into a mold for ultrasonic treatment until the mixed solution becomes wet gel; then soaking the wet gel into 40 times volume of absolute ethyl alcohol at 25 ℃ for treatment for 4 days, and changing the solution every 24 hours to obtain cellulose ethyl alcohol wet gel; finally, freeze drying at-60 deg.C; obtaining a cellulose-based aerogel board; the mold is a 30cm x 15cm x 5cm glass container article.
(4) Finishing of the organic flame retardant: and (3) soaking the single cellulose-based aerogel board prepared in the step (3) into 3000mL of dimethyl sulfoxide solution in which 60g of flame retardant and 240g of urea are dissolved, reacting for 6 hours at 100 ℃, then carrying out water-based to neutral reaction, and drying to obtain the organic/inorganic material composite flame-retardant aerogel board c.
The preparation method of the cellulose in the step (2) comprises the following steps:
step 101: sawing dry ramie stalks, wherein the length of each section is about 5-10 cm after sawing; under normal pressure, adding ramie stalks into 20g/L sodium hydroxide solution, wherein the bath ratio of the ramie stalks to the sodium hydroxide solution is 1: 50, the boiling-off temperature is 80 ℃, and the boiling-off time is 120 min; repeatedly washing with tap water to neutrality after boiling off;
step 102: soaking the ramie stalks treated in the step 101 in a sulfuric acid solution with the mass concentration of 3g/L at the solid-liquid bath ratio of 1: 50 and the temperature of 55 ℃ for 30 min; after soaking, repeatedly washing the mixture to be neutral by using tap water;
step 103: soaking the ramie stalks treated in the step 102 in a mixed solution of 3g/L of pectinase and 3g/L of laccase, wherein the bath ratio of solid to liquid is 1: 50, the pH value is controlled to be 6.0, the temperature is 60 ℃, and the soaking time is 5 hours; after soaking, repeatedly washing the mixture to be neutral by using tap water;
step 104: soaking the ramie stalks processed in the step 103 in an ethanol solution at a bath ratio of 1: 50 and a temperature of 45 ℃, and continuously stirring for 3 hours; after stirring, filtering to remove filtrate;
step 105: putting the straw stalks treated in the step 104 into a high-temperature high-pressure closed aqueous solution, wherein the bath ratio of solid to liquid is 1: 50, the treatment temperature is 180 ℃, the pressure is 12atm, and the treatment time is 3 hours; and (3) repeatedly washing the solid flocculent substance to be neutral by using tap water, and naturally airing in the air.
The preparation method of the flame retardant in the step (4) comprises the following steps: adding 20mL of ethylenediamine and 80mL of phenyl dichlorophosphate into a flask provided with a strong stirring device and a reflux condensing device, and reacting for 3 hours; and after the reaction is finished, pouring a reaction product into a proper amount of acetone solution, shaking and mixing, standing for layering to leave a layer of white solution, washing for 5 times by using acetone, performing suction filtration to obtain a white powdery product, and drying for 5 hours at 80 ℃ to obtain the flame retardant.
Claims (8)
1. A preparation method of an organic/inorganic material composite flame-retardant aerogel board prepared by taking ramie stalks as raw materials is characterized by comprising the following steps:
(1) preparation of aluminum hydroxide colloid: mixing and reacting an aluminum chloride solution and ammonia water to generate aluminum hydroxide, stirring and curing the generated aluminum hydroxide on a magnetic stirrer at 70-80 ℃, wherein the curing time is 8-10 h; placing the cured sol in a condensation reflux device, and refluxing for 24-48 h at 80-95 ℃ in a water bath kettle; filtering the refluxed sol by using a 0.45 mu m acetate fiber filter membrane to obtain aluminum hydroxide colloid;
(2) preparing an aqueous solution of cellulose whiskers: carrying out acidolysis on cellulose by using 60-70% sulfuric acid by mass at room temperature for 8-12 h, filtering, washing the cellulose to be neutral by using distilled water, and carrying out vacuum drying to obtain cellulose whiskers;
(3) mixing of aluminum hydroxide colloid with cellulose solution: mixing the aluminum hydroxide colloid, the PP fibers and the cellulose whiskers prepared in the step (1) in a proper proportion, dissolving the mixture in deionized water, and putting the mixed solution into a mold for ultrasonic treatment until the mixed solution becomes wet gel; then soaking the wet gel into 20-40 times of volume of absolute ethyl alcohol at 20-25 ℃ for treatment for 3-4 days, and changing the solution every 24 hours to obtain cellulose ethyl alcohol wet gel; finally, freeze-drying at-50-60 ℃; obtaining a cellulose-based aerogel board;
(4) finishing of the organic flame retardant: and (3) soaking the single cellulose-based aerogel board prepared in the step (3) into a dimethyl sulfoxide solution in which a flame retardant and urea are dissolved, reacting for 4-6 hours at 90-100 ℃, then carrying out water-based reaction until the water-based reaction is neutral, and drying.
2. The method for preparing the organic/inorganic material composite flame-retardant aerogel board prepared by taking ramie stalks as raw materials according to claim 1, is characterized by comprising the following steps of: in the step (1), the concentration of the aluminum chloride solution is 1-3 mol/L, the concentration of the ammonia water is 1-3 mol/L, and the volume ratio of the aluminum chloride solution to the ammonia water is as follows: 1: 2-4; the rotating speed of the magnetic stirrer is 200-300 r/min.
3. The method for preparing the organic/inorganic material composite flame-retardant aerogel board prepared by taking ramie stalks as raw materials according to claim 1, is characterized by comprising the following steps of: the preparation method of the cellulose in the step (2) comprises the following steps:
step 101: sawing dry ramie stalks, wherein the length of each section is about 5-10 cm after sawing; under normal pressure, adding ramie stalks into a sodium hydroxide solution of 5-20 g/L, wherein the bath ratio of the ramie stalks to the sodium hydroxide solution is 1: 30-50, the boiling-off temperature is 60-90 ℃, and the boiling-off time is 90-120 min; repeatedly washing with tap water to neutrality after boiling off;
step 102: soaking the ramie stalks treated in the step 101 in a sulfuric acid solution with the mass concentration of 1-3 g/L at the solid-liquid bath ratio of 1: 30-50 and the temperature of 50-60 ℃ for 20-40 min; after soaking, repeatedly washing the mixture to be neutral by using tap water;
step 103: soaking the ramie stalks treated in the step 102 in a mixed solution of 1-3 g/L of pectinase and 1-3 g/L of laccase in a solid-liquid bath ratio of 1: 30-50, controlling the pH value to be 6-7, controlling the temperature to be 50-60 ℃, and soaking for 3-5 hours; after soaking, repeatedly washing the mixture to be neutral by using tap water;
step 104: soaking the ramie stalks treated in the step 103 in an ethanol solution, wherein the bath ratio of solid to liquid is 1: 30-50, the temperature is controlled to be 30-50 ℃, and the stirring is continuously carried out for 2-5 hours; after stirring, filtering to remove filtrate;
step 105: putting the straw stalks treated in the step 104 into a high-temperature high-pressure closed aqueous solution, wherein the bath ratio of solid to liquid is 1: 30-50, the treatment temperature is 180-220 ℃, the pressure is 6-12 atm, and the treatment time is 2-3 hours; and (3) repeatedly washing the solid flocculent substance to be neutral by using tap water, and naturally airing in the air.
4. The method for preparing the organic/inorganic material composite flame-retardant aerogel board prepared by taking ramie stalks as raw materials according to claim 1, is characterized by comprising the following steps of: the mass-to-volume ratio of the cellulose (g) to the sulfuric acid (mL) in the step (2) is as follows: 1: 5-10.
5. The method for preparing the organic/inorganic material composite flame-retardant aerogel board prepared by taking ramie stalks as raw materials according to claim 1, is characterized by comprising the following steps of: the mould in the step (3) is a glass container product with the thickness of 50cm multiplied by 30cm multiplied by 10 cm; the mass-volume ratio of the aluminum hydroxide colloid (mL) to the PP fiber (g) to the cellulose whisker (g) is as follows: 1: 5-10; the mass-to-volume ratio of the cellulose whiskers (g) to the deionized water (mL) is as follows: 1: 20-30.
6. The method for preparing the organic/inorganic material composite flame-retardant aerogel board prepared by taking ramie stalks as raw materials according to claim 1, is characterized by comprising the following steps of: the preparation method of the flame retardant in the step (4) comprises the following steps: adding ethylenediamine and phenyl dichloro phosphate into a flask provided with a strong stirring device and a reflux condensing device, and reacting for 2-3 hours; after the reaction is finished, pouring a reaction product into an appropriate amount of acetone solution, shaking and mixing, standing for layering to leave a layer of white solution, washing for 3-5 times by using acetone, performing suction filtration to obtain a white powdery product, and drying for 4-5 hours at 70-80 ℃ to obtain a flame retardant; the volume ratio of the ethylenediamine (mL) to the phenyl dichlorophosphate (mL) is as follows: 1: 2-4.
7. The method for preparing the organic/inorganic material composite flame-retardant aerogel board prepared by taking ramie stalks as raw materials according to claim 1, is characterized by comprising the following steps of: the mass-volume ratio of the flame retardant (g), the urea (g) and the dimethyl sulfoxide (mL) in the step (4) is as follows: 1: 2-4: 20-30.
8. An organic/inorganic material composite flame-retardant aerogel board prepared by taking ramie stalks as raw materials is characterized by being prepared by adopting the preparation method of the organic/inorganic material composite flame-retardant aerogel board prepared by taking the ramie stalks as the raw materials according to any one of claims 1 to 7.
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| WO2018221987A1 (en) * | 2017-05-31 | 2018-12-06 | 알이엠텍 주식회사 | Aerogel sheet and insulation material comprising same |
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