CN110898772B - Preparation method and application of composite organic aerogel - Google Patents
Preparation method and application of composite organic aerogel Download PDFInfo
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- CN110898772B CN110898772B CN201911108844.7A CN201911108844A CN110898772B CN 110898772 B CN110898772 B CN 110898772B CN 201911108844 A CN201911108844 A CN 201911108844A CN 110898772 B CN110898772 B CN 110898772B
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Abstract
The invention provides a preparation method of a composite organic aerogel, which comprises the following steps: carrying out polycondensation reaction on a silicon source and a boron source in the presence of an acidic catalyst and an alcohol solvent; the polycondensation product is activated by active carbon and light calcination under alkaline environment to form a sol with SiCOB skeleton structure; then, the polar solvent in the sol is replaced by a non-polar solvent, and the sol is obtained by normal pressure gradient pyrolysis treatment under the protection of inert gas; the light calcination adopts ultraviolet light with the wavelength of 170-190nm, and the pyrolysis temperature does not exceed 600 ℃. The preparation method can improve the adsorption capacity and the hydrophilicity of the product, increase the pore forming diversity and the pore volume of the product, enhance the mechanical strength and the tensile stability of the product, save the production cost and reduce the energy consumption. The obtained aerogel has improved high-temperature resistance and high-temperature oxidation resistance, and improved breaking strength, flexibility and deformation resistance; the composite material has application as an insulating material and/or preparation of an insulating material, as a carrier in the aspect of waste water and/or air purification.
Description
Technical Field
The invention belongs to the technical field of material science, and particularly relates to a preparation method and application of a composite organic aerogel.
Background
The silica aerogel is an amorphous solid porous material with adjustable structure, has extremely low density, high specific surface area and porosity, good adsorption performance and very low thermal conductivity. It is known to use organic or inorganic aerogels as core materials in vacuum insulation panels because of their low thermal conductivity making them increasingly used in the field of thermal insulation. However, the narrow pore size distribution of aerogels, rigid and fragile structures, low mechanical and tensile strength, poor water wettability of hydrophobic aerogels and poor mixing with aqueous solutions, and the depth of organic removal from aerogels that can be difficult or not well controlled, limit their use in various applications (e.g., flexibility and certain strength requirements, necessary hydrophilic properties, etc.). However, the aerogels used in the prior art are aerogels which have high production costs and are difficult to manufacture, requiring long and expensive supercritical CO2The drying stage, therefore, the expensive preparation cost of the aerogel, the difficult disadvantages of low strength and high brittleness of the material itself become the bottleneck restricting the wide application.
More and more research is being applied to the preparation and modification of aerogels, among which SiCO aerogels are a more important class of aerogel materials, compared to SiO2The aerogel has a firm tetrahedral molecular structure formed by a silicon-oxygen network structure, so that the aerogel network structure can be strengthened and the aerogel condensation can be improvedThermal and mechanical properties of the glue material. However, the SiCO aerogel begins to generate a carbon thermal reduction reaction in an environment with oxygen at about 1000 ℃ to cause decomposition of an aerogel structure, so that the heat insulation effect of the aerogel is influenced, and the application of the SiCO aerogel material is limited due to low temperature resistance and poor high-temperature oxidation resistance. How to improve the temperature resistance and the high-temperature oxidation resistance of the aerogel heat insulation composite material to improve the high-temperature heat insulation effect is still a technical problem which is very concerned by the technical personnel in the field.
Disclosure of Invention
The invention aims to provide a method for accelerating the reaction process and improving the reaction efficiency; the adsorption capacity and the hydrophilic performance of the composite aerogel product can be improved, and particularly the adsorption capacity to hydrophilic pollutants can be improved; the collapse and cracking of the pore channel can be avoided in the pyrolysis so as to increase the pore forming diversity and pore volume of the product and enhance the mechanical strength and tensile stability of the product; the preparation method of the composite organic aerogel saves the production cost and reduces the energy consumption. The aerogel prepared by the method has a hierarchical pore structure with micropores and mesopores as main components, the high temperature resistance and the high temperature oxidation resistance are obviously improved, the maximum use temperature can reach 1500 ℃, the breaking strength of the material is obviously improved, and the aerogel has better flexibility and deformation resistance.
The invention also aims to provide the application of the composite organic aerogel in the aspects of serving as an insulating material and/or preparing the insulating material, treating wastewater, purifying wastewater and purifying air, and preparing the composite material loaded with substances such as medicines, catalysts and the like by taking the porous particles as carriers.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the preparation method of the composite organic aerogel comprises the following steps: a, performing polycondensation reaction on a silicon source and a boron source in the presence of an acid catalyst and an alcohol solvent; b, calcining and activating the polycondensation product by activated carbon and light in an alkaline environment to form a sol with a SiCOB skeleton structure; c, replacing the polar solvent in the sol with the SiCOB skeleton structure by using a nonpolar solvent, and then carrying out normal-pressure gradient pyrolysis treatment under the protection of inert gas to obtain the SiCOB sol; the light calcination activation adopts ultraviolet with the wavelength of 170-190nmAnd (3) carrying out light radiation treatment, wherein the pyrolysis temperature is not more than 600 ℃. The aerogel prepared by the method has a hierarchical pore structure with micropores and mesopores as main components, is high in high-temperature stability and heat resistance, has certain hydrophilic performance and larger adsorption capacity, is improved in mechanical strength and tensile stability, has better flexibility and deformation resistance, and can be dried at normal pressure, so that supercritical CO is avoided2The complex process of drying or ultrahigh temperature thermal cracking is beneficial to improving the yield and production scale of the aerogel, saving the production cost and reducing the energy consumption.
For the present invention, the weight ratio of the silicon source, the boron source and the acidic catalyst is 1:0.5-1: 0.05-0.2. The silicon source is tetraalkoxysilane Si (OR)1)4Or silylated compounds wherein R1Is a saturated or unsaturated radical containing from 1 to 12 carbon atoms; the boron source is represented by the formula B (OR)2)3N-boric acid ester of (1), wherein R2Is a saturated or unsaturated group containing 1 to 12 carbon atoms; the acidic catalyst is selected from the group consisting of aqueous solutions of hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, acetic acid, phosphoric acid, acrylic acid, toluenesulfonic acid, dichloroacetic acid or formic acid, preferably, the acidic catalyst is acrylic acid. The addition of the acidic catalyst enables the silicon source to be hydrolyzed, thereby carrying out crosslinking and polycondensation reactions with the boron source. The SiOB structure formed by introducing boron atoms into the aerogel structure can prevent SiO2The SiCO aerogel collapses at high temperature, provides a more complex and stable structure, can enhance the high-temperature stability and heat resistance of the aerogel product under the condition of less influence on the heat conductivity, enhances the application range of the product, and reduces the loss of the product caused by high temperature in use.
For the purposes of the present invention, the polycondensation reaction conditions are: the temperature is 55-65 ℃, the ultrasonic power is 600- & lt1000 & gt W, and the reaction time is 120- & lt210 & gt min.
For the present invention, the pH of the alkaline environment is 10-14; the ultraviolet radiation treatment conditions are as follows: the power of the ultraviolet lamp is 60-500W, and the time is 120-240 min. It should be noted that the time for the ultraviolet radiation treatment is related to the power of the ultraviolet lamp, the higher the power of the ultraviolet lamp, the shorter the radiation treatment time. The alkali liquor activates hydrophobic groups in the sol, free oxygen groups generated under the action of ultraviolet light shuttle in the limited depth of a substrate of a condensation polymerization product SiOB precursor, so that the atomic distance between activated carbon and the substrate structure is reduced, and further, the activated carbon and the substrate structure are polymerized to form a SiCOB framework structure, thereby enhancing the hierarchical pore structure and the hydrophilic performance in the aerogel product and improving the adsorption capacity of the composite aerogel product.
For the invention, the weight ratio of the active carbon to the silicon source is 0.5-1.5: 1; the light calcination activation is carried out by aid of auxiliary agents, wherein the auxiliary agents comprise glyoxal, polyhydroxy benzene and N, N-dimethylformamide, and the addition amounts of the glyoxal, the polyhydroxy benzene and the N, N-dimethylformamide are respectively 1-5%, 0.5-1% and 0.03-0.1% of the weight of the activated carbon. The polyhydroxybenzene is preferably a di-or trihydroxybenzene, examples of which include, but are not limited to, resorcinol, catechol, hydroquinone, phloroglucinol, and mixtures thereof, preferably the polyhydroxybenzene is phloroglucinol. The hydrophilic performance of the aerogel product can be enhanced by activated carbon and photo-calcination, the addition of the auxiliary agent can accelerate the etching of the activated carbon on an SiOB precursor framework, promote the activated carbon to be embedded into the precursor framework and perform polycondensation so as to form a SiCOB three-dimensional network-shaped framework structure, improve the reaction rate, and simultaneously, the auxiliary agent utilizes the expansion effect of photo-calcination and pyrolysis in the framework, so that the internal groups of the aerogel product have higher activity, the combination pore structure has stronger adsorption capacity, and particularly the aerogel product has larger adsorption capacity on hydrophilic pollutants (such as phenol).
For the present invention, the nonpolar solvent contains n-hexane or carbon tetrachloride; the non-polar solvent also comprises 0.1-0.5wt% of an auxiliary agent, and the auxiliary agent comprises 2, 4-toluene diisocyanate and glycol dimethyl ether in a weight ratio of 1: 0.5-1. The surface tension of the nonpolar solvent is smaller, the contraction of gel is more difficult to cause than the polar solvent under the common drying condition, the aerogel framework collapse and the structure damage can not be caused in the drying process, the auxiliary agent permeates into the colloid framework when the solvent is replaced, the secondary particles in the cross-linked colloid are hung on the framework in parallel, when the high-temperature pyrolysis is carried out, the auxiliary agent can reduce the sensitivity of the secondary particles to the temperature, so that the secondary particles have weaker sliding phenomenon at high temperature, the formed micropores and mesopores in the aerogel material are difficult to collapse and crack, the pore diversity and the pore volume are increased, meanwhile, the auxiliary agent can gather the active atoms diffused by the pyrolysis in the neck area of the secondary particles, the atomic weight deposited in the neck area is increased, when the neck area is subjected to the external force, the neck area has stronger impact resistance protection without fracture, and the mechanical strength and the tensile stability of the aerogel product are enhanced, thereby having better flexibility and deformation resistance.
For the present invention, the solvent replacement operation is: soaking the sol colloid by a nonpolar solvent for 12-24 h; before the solvent replacement operation, the sol colloid is firstly aged, and the aging conditions are as follows: standing at 55-65 deg.C for 12-36 h. The sol is further stabilized by aging to ensure that the composite gel can form a complete network structure, thereby obtaining a colloidal precipitate with complete crystal form, large particle size and purity. After polar solvent in the sol colloid is exchanged by utilizing the smaller surface tension of the nonpolar solvent, the colloid can be dried at normal pressure, thereby avoiding supercritical CO2The complex process of drying or ultrahigh temperature thermal cracking is beneficial to improving the yield and production scale of the aerogel, saving the production cost and reducing the energy consumption.
For the purposes of the present invention, the inert gas is N2Ar or He, and the flow rate of the inert gas is 100-500 mL/min.
For the invention, the specific operation of the normal pressure gradient pyrolysis treatment is as follows: heating to 250-300 ℃ at the heating rate of 5-15 ℃/min, keeping the temperature for 1-2h, heating to 450-550 ℃ at the heating rate of 5-15 ℃/min, keeping the temperature for 1-2h, and naturally cooling. During gradient pyrolysis, each atom in the SiCOB backbone is activated. Along with the increase of temperature, the inter-atomic distance in the skeleton structure is changed, so that the inter-atomic expansion effect and the attraction are changed, the carbon-silicon material layers are bent to form unrecoverable pores and channels, and the gradient heat preservation mode is favorable for forming and maintaining the mesoporous structure in the material, so that the aerogel product forms a hierarchical pore structure mainly comprising micropores and mesopores, the specific surface area and the porosity of the material are increased, and the composite organic aerogel material with lower heat conductivity is obtained.
The invention also discloses the composite organic aerogel prepared by the method, wherein oxygen and boron elements are introduced into a silicon source to form an SiOB precursor, and the SiOB precursor is activated by activated carbon and light calcination to form an SiCOB skeleton structure, so that the composite organic aerogel material with a hierarchical pore structure mainly comprising micropores and mesopores is obtained.
For the purposes of the present invention, composite organic aerogels exhibit: a porosity of 80-95%, and/or 500m2/g-1500m2Specific surface per gram, and/or 0.5cm3/g-3.5cm3Pore volume per gram, and/or average pore diameter of 1nm to 40nm, and/or 0.05 to 0.3g/cm3The density of (c). The aerogel particles have uniform particle size distribution, uniform and non-collapsed pore channel structure and concentrated pore size distribution, and have excellent adsorption performance and easy regeneration performance. The material has an adsorption and removal effect on water, air and harmful pollutants (such as organic solvents, grease and the like) in the surrounding environment, can separate adsorbed substances from the composite organic aerogel, realizes multiple cyclic utilization of the material, and has wide application prospects and market prospects in the aspects of wastewater treatment, wastewater purification and air purification.
For the purposes of the present invention, composite organic aerogels exhibit: the thermal conductivity at normal temperature is 10-45 mW/(mK), and the lowest thermal conductivity at 1000 deg.C, 1200 deg.C, 1500 deg.C is 0.032W/mK, 0.057W/mK, 0.283W/mK. The composite organic aerogel has the characteristics of high porosity and low density, the thermal conductivity of the material is low, the thermal insulation performance is good, the high temperature resistance and the high temperature oxidation resistance are obviously improved, and the maximum use temperature can reach 1500 ℃. After the composite organic aerogel material is treated in an aerobic environment at 1000 ℃ for 2 hours, the appearance is unchanged, and no obvious shrinkage exists in the plane direction and the thickness direction.
For the purposes of the present invention, composite organic aerogels exhibit: the breaking strength is 10-25MPa, and the compression modulus is 300-900 MPa. The breaking strength of the aerogel material is remarkably improved, so that the stretching elasticity and the stretching stability of the aerogel material are improved, the aerogel material has better flexibility and deformation resistance compared with other materials, has resilience after unloading, and overcomes or improves the limitation of the defects of low strength and high brittleness of common aerogel materials on the application of the aerogel material.
The invention also discloses application of the composite organic aerogel prepared by the method, and application of the composite organic aerogel serving as an insulating material and/or in preparation of the insulating material. Such insulating materials include thermal and acoustic insulating materials.
For the purposes of the present invention, composite organic aerogels also include use in wastewater treatment, wastewater purification and air purification. The purpose of removing pollutants is achieved by utilizing the excellent adsorption performance of the composite organic aerogel, the material is regenerated and recycled, the treatment effect is good, the material recycling rate is high, and the material loss is reduced.
For the purposes of the present invention, composite organic aerogels also include the use in the form of porous particles as carriers for the preparation of composite materials loaded with substances such as drugs, catalysts, etc. Specifically, the composite organic aerogel can load a photocatalyst and is used for removing pollutants in the air under the irradiation of visible light so as to achieve the aim of purifying the environment; the composite organic aerogel can load medicines, has large loading capacity, and realizes the controllable release of the medicines.
The invention has the beneficial effects that:
1) the preparation method can accelerate the reaction process, improve the reaction efficiency, enhance the high-temperature stability and the heat resistance of the aerogel product, improve the adsorption capacity and the hydrophilic performance of the composite aerogel product, particularly have larger adsorption capacity for hydrophilic pollutants (such as phenol), prevent pore channels from collapsing and cracking easily in the pyrolysis process, increase the pore-forming diversity and the pore volume of the product, and enhance the mechanical strength and the tensile stability of the aerogel product;
2) the preparation method adopts the synergistic cooperation of nonpolar solvent replacement and normal pressure gradient pyrolysis, so that the colloid can be dried at normal pressure, thereby avoiding supercritical CO2The complex process of drying or ultrahigh temperature thermal cracking is beneficial to improving the yield and production scale of the aerogel, has low raw material and production cost, short production period, production cost saving and production cost reductionEnergy consumption;
3) the aerogel disclosed by the invention has a hierarchical pore structure with micropores and mesopores as main components, has excellent adsorption performance and easy regeneration performance, can realize repeated cyclic utilization of materials, has the characteristics of high porosity, low density and low thermal conductivity, is good in heat insulation performance, is remarkably improved in high temperature resistance and high temperature oxidation resistance, has the highest use temperature of 1500 ℃, is remarkably improved in breaking strength, has better flexibility and deformation resistance, has resilience capability after unloading, and overcomes or improves the limitation of the application of the defects of low strength and high brittleness of a common aerogel material;
4) the composite organic aerogel has application value in the aspects of serving as an insulating material and/or preparing the insulating material, and also has application value in the aspects of wastewater treatment, wastewater purification and air purification, and in the aspect of preparing the composite material loaded with substances such as medicines, catalysts and the like by taking a porous particle form as a carrier.
The preparation method and the application of the composite organic aerogel provided by the invention adopt the technical scheme, make up for the defects of the prior art, and have the advantages of reasonable design and convenience in operation.
Drawings
FIG. 1 is a nitrogen adsorption isotherm for a composite organic aerogel material;
FIG. 2 is a plot of the pore size distribution of a composite organic aerogel material;
FIG. 3 is a schematic diagram of stress-strain curves for compression and tensile tests of composite organic aerogel materials, A-
Example 1, B-example 3, C-control;
FIG. 4 is a schematic diagram of adsorption isotherms of the composite organic aerogel material for phenol at 25 ℃.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
the preparation method of the composite organic aerogel comprises the following steps: a, performing polycondensation reaction on a silicon source and a boron source in the presence of an acid catalyst and an alcohol solvent; b, subjecting the polycondensation product toActivated by activated carbon and light calcination in an alkaline environment to form a sol with a SiCOB skeleton structure; c, replacing the polar solvent in the sol with the SiCOB skeleton structure by using a nonpolar solvent, and then carrying out normal-pressure gradient pyrolysis treatment under the protection of inert gas to obtain the SiCOB sol; the light calcination activation is carried out by ultraviolet radiation with the wavelength of 170-190nm, and the pyrolysis temperature is not more than 600 ℃. The aerogel prepared by the method has a hierarchical pore structure with micropores and mesopores as main components, is high in high-temperature stability and heat resistance, has certain hydrophilic performance and larger adsorption capacity, is improved in mechanical strength and tensile stability, has better flexibility and deformation resistance, and can be dried at normal pressure, so that supercritical CO is avoided2The complex process of drying or ultrahigh temperature thermal cracking is beneficial to improving the yield and production scale of the aerogel, saving the production cost and reducing the energy consumption.
For the purposes of the present invention, the weight ratio of silicon source, boron source and acidic catalyst is from 1:0.5 to 1:0.05 to 0.2, for example 1:0.5:0.05, 1:0.7:0.1, 1:0.8:0.08, etc.
The silicon source is tetraalkoxysilane Si (OR)1)4Or silylated compounds wherein R1Is a saturated or unsaturated radical containing from 1 to 12 carbon atoms; examples of tetraalkoxysilanes include, but are not limited to, methyl orthosilicate, ethyl orthosilicate, silylated compounds include silanes, alkoxysilanes, alkoxyalkyl silanes, disiloxanes, and combinations thereof, examples of which include, but are not limited to, phenylethyldiethoxysilane, trimethylbutoxysilane, trivinyltrimethylcyclotrisiloxane, hexaethyldisiloxane, divinyldipropoxysilane, vinyldimethylmethoxysilane, hexamethyldisiloxane.
The boron source is represented by the formula B (OR)2)3N-boric acid ester of (1), wherein R2Is a saturated or unsaturated group containing 1 to 12 carbon atoms; examples include, but are not limited to, trimethyl borate, triethyl borate.
The acidic catalyst is selected from hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, acetic acid, phosphoric acid, acrylic acid, toluenesulfonic acid, dichloroacetic acid or methyl acetateAn aqueous acid solution, preferably the acidic catalyst is acrylic acid. The addition of the acidic catalyst enables the silicon source to be hydrolyzed, thereby carrying out crosslinking and polycondensation reactions with the boron source. The SiOB structure formed by introducing boron atoms into the aerogel structure can prevent SiO2The SiCO aerogel collapses at high temperature, provides a more complex and stable structure, can enhance the high-temperature stability and heat resistance of the aerogel product under the condition of less influence on the heat conductivity, enhances the application range of the product, and reduces the loss of the product caused by high temperature in use.
The alcohol solvent is ethanol or isopropanol.
For the purposes of the present invention, the polycondensation reaction conditions are: the temperature is 55-65 ℃, the ultrasonic power is 600- & lt1000 & gt W, and the reaction time is 120- & lt210 & gt min.
For the present invention, the pH of the alkaline environment is 10-14; the ultraviolet radiation treatment conditions are as follows: the power of the ultraviolet lamp is 60-500W, and the time is 120-240 min. It should be noted that the time for the ultraviolet radiation treatment is related to the power of the ultraviolet lamp, the higher the power of the ultraviolet lamp, the shorter the radiation treatment time. Examples of the above-mentioned alkali liquors include, but are not limited to, sodium carbonate, sodium bicarbonate, potassium carbonate, ammonium carbonate, lithium carbonate, ammonium hydroxide, potassium hydroxide, and sodium hydroxide. The alkali liquor activates hydrophobic groups in the sol, free oxygen groups generated under the action of ultraviolet light shuttle in the limited depth of a substrate of a condensation polymerization product SiOB precursor, so that the atomic distance between activated carbon and the substrate structure is reduced, and further, the activated carbon and the substrate structure are polymerized to form a SiCOB framework structure, thereby enhancing the hierarchical pore structure and the hydrophilic performance in the aerogel product and improving the adsorption capacity of the composite aerogel product.
For the invention, the weight ratio of the active carbon to the silicon source is 0.5-1.5: 1; the light calcination activation is carried out by aid of auxiliary agents, wherein the auxiliary agents comprise glyoxal, polyhydroxy benzene and N, N-dimethylformamide, and the addition amounts of the glyoxal, the polyhydroxy benzene and the N, N-dimethylformamide are respectively 1-5%, 0.5-1% and 0.03-0.1% of the weight of the activated carbon. The polyhydroxybenzene is preferably a di-or trihydroxybenzene, examples of which include, but are not limited to, resorcinol, catechol, hydroquinone, phloroglucinol, and mixtures thereof, preferably the polyhydroxybenzene is phloroglucinol. The hydrophilic performance of the aerogel product can be enhanced by activated carbon and photo-calcination, the addition of the auxiliary agent can accelerate the etching of the activated carbon on an SiOB precursor framework, promote the activated carbon to be embedded into the precursor framework and perform polycondensation so as to form a SiCOB three-dimensional network-shaped framework structure, improve the reaction rate, and simultaneously, the auxiliary agent utilizes the expansion effect of photo-calcination and pyrolysis in the framework, so that the internal groups of the aerogel product have higher activity, the combination pore structure has stronger adsorption capacity, and particularly the aerogel product has larger adsorption capacity on hydrophilic pollutants (such as phenol).
For the present invention, the nonpolar solvent contains n-hexane or carbon tetrachloride; the non-polar solvent also comprises 0.1-0.5wt% of an auxiliary agent, and the auxiliary agent comprises 2, 4-toluene diisocyanate and glycol dimethyl ether in a weight ratio of 1: 0.5-1. The surface tension of the nonpolar solvent is smaller, the contraction of gel is more difficult to cause than the polar solvent under the common drying condition, the aerogel framework collapse and the structure damage can not be caused in the drying process, the auxiliary agent permeates into the colloid framework when the solvent is replaced, the secondary particles in the cross-linked colloid are hung on the framework in parallel, when the high-temperature pyrolysis is carried out, the auxiliary agent can reduce the sensitivity of the secondary particles to the temperature, so that the secondary particles have weaker sliding phenomenon at high temperature, the formed micropores and mesopores in the aerogel material are difficult to collapse and crack, the pore diversity and the pore volume are increased, meanwhile, the auxiliary agent can gather the active atoms diffused by the pyrolysis in the neck area of the secondary particles, the atomic weight deposited in the neck area is increased, when the neck area is subjected to the external force, the neck area has stronger impact resistance protection without fracture, and the mechanical strength and the tensile stability of the aerogel product are enhanced, thereby having better flexibility and deformation resistance.
For the present invention, the solvent replacement operation is: soaking the sol colloid by a nonpolar solvent for 12-24 h; before the solvent replacement operation, the sol colloid is firstly aged, and the aging conditions are as follows: standing at 55-65 deg.C for 12-36 h. The sol is further stabilized by aging to ensure that the composite gel can form a complete network structure, thereby obtainingObtain colloid precipitate with complete crystal form, large particle size and purity. After polar solvent in the sol colloid is exchanged by utilizing the smaller surface tension of the nonpolar solvent, the colloid can be dried at normal pressure, thereby avoiding supercritical CO2The complex process of drying or ultrahigh temperature thermal cracking is beneficial to improving the yield and production scale of the aerogel, saving the production cost and reducing the energy consumption.
For the purposes of the present invention, the inert gas is N2Ar or He, and the flow rate of the inert gas is 100-500 mL/min.
For the invention, the specific operation of the normal pressure gradient pyrolysis treatment is as follows: heating to 250-300 ℃ at the heating rate of 5-15 ℃/min, keeping the temperature for 1-2h, heating to 450-550 ℃ at the heating rate of 5-15 ℃/min, keeping the temperature for 1-2h, and naturally cooling. During gradient pyrolysis, each atom in the SiCOB backbone is activated. Along with the increase of temperature, the inter-atomic distance in the skeleton structure is changed, so that the inter-atomic expansion effect and the attraction are changed, the carbon-silicon material layers are bent to form unrecoverable pores and channels, and the gradient heat preservation mode is favorable for forming and maintaining the mesoporous structure in the material, so that the aerogel product forms a hierarchical pore structure mainly comprising micropores and mesopores, the specific surface area and the porosity of the material are increased, and the composite organic aerogel material with lower heat conductivity is obtained.
For the invention, the specific preparation steps of the composite organic aerogel are as follows:
(1) adding a silicon source, a boron source and an acid catalyst into an alcohol solvent, stirring for 60-120min at the temperature of 35-55 ℃ and the stirring speed of 600-1000r/min, and then carrying out a polycondensation reaction for 120-210min under the ultrasonic environment with the temperature of 55-65 ℃ and the power of 600-1000W-plus to obtain SiOB precursor sol, wherein the dosage of the alcohol solvent is 5-10 times of that of the silicon source;
(2) adding alkali liquor into the SiOB precursor sol, adjusting the pH value to 10-14, then adding activated carbon, glyoxal, polyhydroxy benzene and N, N-dimethylformamide into the SiOB precursor sol, uniformly stirring, and then placing the SiOB precursor sol under an ultraviolet lamp with the power of 60-500W for 120-240min to obtain sol with a SiCOB framework structure;
(3) standing and aging SiCOB sol at the constant temperature of 55-65 ℃ for 12-36h, taking out the sol, soaking the sol in 3-5 times of nonpolar solvent for 12-24h for solvent exchange, and then performing normal-pressure gradient pyrolysis treatment under the protection of inert gas to obtain the composite organic aerogel.
The invention also discloses the composite organic aerogel prepared by the method, wherein oxygen and boron elements are introduced into a silicon source to form an SiOB precursor, and the SiOB precursor is activated by activated carbon and light calcination to form an SiCOB skeleton structure, so that the composite organic aerogel material with a hierarchical pore structure mainly comprising micropores and mesopores is obtained.
For the purposes of the present invention, composite organic aerogels exhibit: a porosity of 80-95%, and/or 500m2/g-1500m2Specific surface per gram, and/or 0.5cm3/g-3.5cm3Pore volume per gram, and/or average pore diameter of 1nm to 40nm, and/or 0.05 to 0.3g/cm3The density of (c). The aerogel particles have uniform particle size distribution, uniform and non-collapsed pore channel structure and concentrated pore size distribution, and have excellent adsorption performance and easy regeneration performance. The material has an adsorption and removal effect on water, air and harmful pollutants (such as organic solvents, grease and the like) in the surrounding environment, can separate adsorbed substances from the composite organic aerogel, realizes multiple cyclic utilization of the material, and has wide application prospects and market prospects in the aspects of wastewater treatment, wastewater purification and air purification.
For the purposes of the present invention, composite organic aerogels exhibit: the thermal conductivity at normal temperature is 10-45 mW/(mK), and the lowest thermal conductivity at 1000 deg.C, 1200 deg.C, 1500 deg.C is 0.032W/mK, 0.057W/mK, 0.283W/mK. The composite organic aerogel has the characteristics of high porosity and low density, the thermal conductivity of the material is low, the thermal insulation performance is good, the high temperature resistance and the high temperature oxidation resistance are obviously improved, and the maximum use temperature can reach 1500 ℃. After the composite organic aerogel material is treated in an aerobic environment at 1000 ℃ for 2 hours, the appearance is unchanged, and no obvious shrinkage exists in the plane direction and the thickness direction.
For the purposes of the present invention, composite organic aerogels exhibit: the breaking strength is 10-25MPa, and the compression modulus is 300-900 MPa. The breaking strength of the aerogel material is remarkably improved, so that the stretching elasticity and the stretching stability of the aerogel material are improved, the aerogel material has better flexibility and deformation resistance compared with other materials, has resilience after unloading, and overcomes or improves the limitation of the defects of low strength and high brittleness of common aerogel materials on the application of the aerogel material.
For purposes of the present invention, other auxiliary materials, such as methylcellulose, starch, polyvinyl alcohol, and/or wax emulsions can also be included in the composite organic aerogel to enhance properties of the material such as biocompatibility. In addition, IR opacifiers, such as carbon black, titanium dioxide, iron oxide, or zirconium dioxide, or mixtures thereof, can also be included in the composite organic aerogel; preferably, the opacifier is titanium dioxide, iron oxide or zirconium dioxide. Opacifiers reduce the effect of radiation on thermal conductivity, particularly when used at high temperatures.
The invention also discloses application of the composite organic aerogel prepared by the method, and application of the composite organic aerogel serving as an insulating material and/or in preparation of the insulating material. Such insulating materials include thermal and acoustic insulating materials.
For the purposes of the present invention, composite organic aerogels also include use in wastewater treatment, wastewater purification and air purification. The purpose of removing pollutants is achieved by utilizing the excellent adsorption performance of the composite organic aerogel, the material is regenerated and recycled, the treatment effect is good, the material recycling rate is high, and the material loss is reduced.
For the purposes of the present invention, composite organic aerogels also include the use in the form of porous particles as carriers for the preparation of composite materials loaded with substances such as drugs, catalysts, etc. Specifically, the composite organic aerogel can load a photocatalyst and is used for removing pollutants in the air under the irradiation of visible light so as to achieve the aim of purifying the environment; the composite organic aerogel can load medicines, has large loading capacity, and realizes the controllable release of the medicines.
For the purposes of the present invention, uses of composite organic aerogels include, but are not limited to: monoliths, building blocks, optical waveguides, cladding, matting media, structural composite panels, fiberglass reinforced panels, windows, partitions, composite walls, insulation panels, acoustical panels, moisture resistant articles, syntactic foams, or any industrial article containing aerogel particles of the present invention.
It is to be understood that the foregoing description is to be considered illustrative or exemplary and not restrictive, and that changes and modifications may be made by those skilled in the art within the scope and spirit of the appended claims. In particular, the present invention covers other embodiments having any combination of features from the different embodiments described above and below, without the scope of the invention being limited to the specific examples below.
Example 1:
the preparation method of the composite organic aerogel comprises the following specific steps:
(1) adding tetraethoxysilane, trimethyl borate and acrylic acid into ethanol solvent, stirring for 120min at the stirring speed of 1000r/min at 50 ℃, and then carrying out polycondensation reaction for 180min under the ultrasonic environment with the temperature of 60 ℃ and the power of 1000W to obtain SiOB precursor sol, wherein the weight ratio of the tetraethoxysilane to the trimethyl borate to the acrylic acid is 1:0.7:0.05, and the dosage of the ethanol solvent is 5 times of that of the tetraethoxysilane;
(2) adding sodium hydroxide into SiOB precursor sol, adjusting the pH value to 12, then adding activated carbon, glyoxal, phloroglucinol and N, N-dimethylformamide into the SiOB precursor sol, uniformly stirring the mixture, and then placing the mixture under an ultraviolet lamp with the power of 400W for radiation for 150min to obtain sol with a SiCOB framework structure, wherein the weight ratio of the activated carbon to tetraethoxysilane is 0.7:1, and the addition amounts of the glyoxal, the phloroglucinol and the N, N-dimethylformamide in the auxiliary agent for light calcination and activation are respectively 1.5%, 0.5% and 0.05% of the weight of the activated carbon;
(3) standing and aging SiCOB sol at a constant temperature of 60 ℃ for 36h, taking out the sol, soaking in 5 times of nonpolar solvent for 24h for solvent exchange, introducing inert gas Ar at the flow rate of 300mL/min, heating to 300 ℃ at the heating rate of 10 ℃/min under the protection of the inert gas and normal pressure, keeping the temperature for 1.5h, heating to 500 ℃ at the heating rate of 15 ℃/min, keeping the temperature for 2h, and naturally cooling to obtain the composite organic aerogel, wherein the nonpolar solvent is n-hexane and contains 0.5wt% of auxiliary agent, and the auxiliary agent comprises 2, 4-toluene diisocyanate and ethylene glycol dimethyl ether in a weight ratio of 1: 0.5.
The pore structure parameters and basic properties of the obtained composite organic aerogel are as follows: a porosity of 93.7%, and 1238m2Specific surface area per gram, and 2.8cm3Pore volume per g, and average pore diameter of 22nm, and 0.13g/cm3The density of (3) and the thermal conductivity at normal temperature were 23 mW/(mK).
Example 2:
the preparation method of the composite organic aerogel is different from the preparation method of the embodiment 1 only in the following specific steps: the adjuvant for activating the photo-calcination in the step (2) comprises glyoxal, but polyhydroxy benzene and N, N-dimethylformamide are not added.
Example 3:
the preparation method of the composite organic aerogel is different from the preparation method of the embodiment 1 only in the following specific steps: in the step (3), an auxiliary agent comprising 2, 4-toluene diisocyanate and ethylene glycol dimethyl ether is not added into the nonpolar solvent.
Example 4:
the preparation method of the composite organic aerogel is different from the preparation method of the embodiment 1 only in the following specific steps: in the step (3), the synergistic cooperation of non-polar solvent replacement and normal-pressure gradient pyrolysis is not adopted for aerogel drying, but CO is adopted2Supercritical drying, which comprises the following steps:
placing the aged colloid in supercritical fluid drying equipment, and pre-charging 3.5MPa N2Then CO was introduced at a flow rate of 600mL/h2Keeping the pressure in the equipment stable during drying, heating to 250 deg.C at a speed of 10 deg.C/min, maintaining for 2.5h, slowly releasing pressure at a speed of 50kPa/min, and finally N2And flushing and sweeping for 30min to obtain the composite organic aerogel material.
Example 5:
the preparation method of the composite organic aerogel is different from the preparation method of the embodiment 1 only in the following specific steps: in the step (3), the aerogel is dried by adopting an ultrahigh temperature thermal cracking method instead of adopting the synergistic cooperation of nonpolar solvent replacement and normal pressure gradient pyrolysis, and the specific steps are as follows:
and (3) placing the aged colloid in a pyrolysis furnace, introducing argon at the flow rate of 50mL/min, heating to 950 ℃ at the speed of 10 ℃/min, keeping the temperature for 2 hours, and cooling to room temperature to obtain the composite organic aerogel.
Test example 1:
characterization of composite organic aerogel material pore structure
The test samples were: composite organic aerogel materials obtained in examples 1, 3, 4 and 5.
The test method comprises the following steps: the nitrogen desorption isotherm at 77K was used for the Autosorb-IQ test samples, the specific surface area of the samples was calculated by the BET method and the pore volume and pore size distribution of the samples were calculated by the DFT method. See figures 1, 2 and table 1 for details.
Fig. 1 is a nitrogen adsorption isotherm for a composite organic aerogel material, and fig. 2 is a pore size distribution curve for a composite organic aerogel material. As can be seen from FIG. 1, the composite organic aerogel material samples of the examples simultaneously exhibit partial characteristics of type I and type IV adsorption isotherms, and exhibit a hysteresis loop of type H4 in a pressure range of 0.5-1.0, indicating that the material has a mesoporous structure and is in a low pressure range (P/P)0<0.1), both samples present a certain amount of adsorption, indicating that there is a certain amount of microporous structure in the material. The samples from examples 1 and 3 were P/P higher than the samples from examples 4 and 50<The sharp increase in adsorption capacity in the range of 0.1 is due to the large number of micropores filled in the samples of examples 1 and 3, indicating that the preparation methods of examples 1 and 3 can protect the microporous structure in the aerogel colloid from collapse at high temperature; example 1 compared to example 3 samples in P/P0In the range of more than 0.5, the area of the hysteresis loop is larger, and the pore size distribution of the example 1 in fig. 2 is more diversified than that of the example 3, which indicates that more mesopores exist in the example 1, and indicates that the preparation method of the example 1 can better protect the colloid mesoporous pore channel from collapse and cracking at high temperature than that of the example 3, increase the pore forming diversity, and form a hierarchical pore structure mainly comprising mesopores and micropores.
TABLE 1 pore Structure parameters of composite organic aerogel materials
| Average pore diameter nm | Specific surface area m2/g | Pore volume cm3/g | Porosity% | |
| Example 1 | 22.1 | 1238.4 | 2.8 | 93.7 |
| Example 3 | 21.2 | 1055.8 | 2.4 | 85.3 |
| Example 4 | 19.8 | 928.5 | 1.8 | 78.2 |
| Example 5 | 20.3 | 937.8 | 2.1 | 78.1 |
As can be seen from Table 1, examples 1 and 3 show high specific surface area and pore volume, and the porosity reaches more than 85%, which indicates that the preparation method can increase the specific surface area, the porosity and the pore volume of the material, and is beneficial to reducing the thermal conductivity of the material; compared with example 3, the preparation method of example 1 can increase the diversity of the pore structure and improve the porosity and pore volume of the material.
Test example 2:
compression and tensile property test of composite organic aerogel material
The test samples were: examples 1 and 3 gave composite organic aerogel materials.
The test method comprises the following steps: samples were tested for mechanical properties in terms of three-point compression and in terms of tension using ASTM C165-07 using a MTS tensile/compression tester, a commercially available silica aerogel was used as a control. The results are shown in FIG. 3.
Fig. 3 is a graph showing the stress-strain curves of compression and tensile tests of composite organic aerogel materials, a-example 1, B-example 3, C-control. As can be seen from FIG. 3, the curve has no yield stage, the compression resistance of the material is much better than the tensile resistance, and the obtained aerogel material has the property of a brittle material; the maximum stress value which can be borne by the material in the example 1 in the stretching process is the highest, the maximum stress value of the control group is the lowest after the material in the example 1 is stretched for 3 times, and the preparation method of the material obtained in the example 1 is shown to enable the flexibility and the deformation resistance of the aerogel to be remarkably improved, and the application range and the value of the aerogel can be increased.
Table 2 compression test results for composite organic aerogel materials
As can be seen from Table 2, the material of example 1 has the highest breaking strength in compression, the material of example 3 times has the lowest breaking strength in comparison, and the preparation method of the material obtained in example 1 is demonstrated to enable the breaking strength and the mechanical strength of the aerogel to be remarkably improved, so that the application range and the value of the aerogel can be increased.
Test example 3:
adsorption capacity test of composite organic aerogel material
The test samples were: the composite organic aerogel materials obtained in examples 1 and 2 were prepared by using a commercially available silica aerogel as a control.
The test method comprises the following steps: 10g of the sample was taken, and the adsorption isotherm of phenol at 25 ℃ at room temperature was measured using an intelligent gravimetric adsorption apparatus IGA-002, and the results are shown in FIG. 4.
FIG. 4 is a schematic diagram of adsorption isotherms of the composite organic aerogel material for phenol at 25 ℃. As can be seen from the figure, example 1 has the highest adsorption capacity for phenol, the equilibrium adsorption capacity for phenol at 25 ℃ is 419mg/g, example 2 has 307mg/g, and the control group has only 183mg/g, which indicates that the aerogel prepared by the present invention has better adsorption capacity, and also indicates that example 1 can increase and enhance the adsorption capacity for hydrophilic contaminants (such as phenol) more than the preparation method of example 2, and has wider application in wastewater treatment, wastewater purification and air purification.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (8)
1. A composite organic aerogel exhibiting: the porosity is 80-95%, the thermal conductivity at normal temperature is 10-45 mW/(m.K), the breaking strength is 10-25MPa, and the compression modulus is 300-900 MPa;
the preparation method of the composite organic aerogel comprises the following steps:
a, performing polycondensation reaction on a silicon source and a boron source in the presence of an acid catalyst and an alcohol solvent;
b, calcining and activating the polycondensation product by activated carbon and light in an alkaline environment to form a sol with a SiCOB skeleton structure;
c, replacing the polar solvent in the sol with the SiCOB skeleton structure by using a non-polar solvent, and then carrying out normal-pressure gradient pyrolysis treatment under the protection of inert gas to obtain the SiCOB sol;
the light calcination activation is carried out by adopting ultraviolet radiation with the wavelength of 170-190nm, and the pyrolysis temperature is not more than 600 ℃;
the pH of the alkaline environment is 10-14; the ultraviolet radiation treatment conditions are as follows: the power of the ultraviolet lamp is 60-500W, and the time is 120-240 min;
the weight ratio of the active carbon to the silicon source is 0.5-1.5: 1;
the nonpolar solvent contains n-hexane or carbon tetrachloride; the nonpolar solvent also comprises 0.1-0.5wt% of an auxiliary agent, and the auxiliary agent comprises 2, 4-toluene diisocyanate and glycol dimethyl ether in a weight ratio of 1: 0.5-1.
2. The composite organic aerogel according to claim 1, characterized in that: the weight ratio of the silicon source to the boron source to the acid catalyst is 1:0.5-1: 0.05-0.2; the silicon source is tetraalkoxysilane Si (OR)1)4Or a silylated compound; the boron source is B (OR)2)3N-borate esters of (1).
3. The composite organic aerogel according to claim 1, characterized in that: the polycondensation reaction conditions are as follows: the temperature is 55-65 ℃, the ultrasonic power is 600- & lt1000 & gt W, and the reaction time is 120- & lt210 & gt min.
4. The composite organic aerogel according to claim 1, characterized in that: the light calcination activation is carried out by aid of auxiliary agents, wherein the auxiliary agents comprise glyoxal, polyhydroxy benzene and N, N-dimethylformamide, and the addition amounts of the glyoxal, the polyhydroxy benzene and the N, N-dimethylformamide are respectively 1-5%, 0.5-1% and 0.03-0.1% of the weight of the activated carbon.
5. The composite organic aerogel according to claim 1, characterized in that: the solvent replacement operation is: soaking the sol colloid by a nonpolar solvent for 12-24 h; before the solvent replacement operation, the sol colloid is firstly aged, and the aging conditions are as follows: standing at 55-65 deg.C for 12-36 h.
6. The composite organic aerogel according to claim 1, characterized in that: the inert gas is N2Ar or He, and the flow rate of the inert gas is 100-500 mL/min.
7. The composite organic aerogel according to claim 1, characterized in that: the specific operation of the normal pressure gradient pyrolysis treatment is as follows: heating to 250-300 ℃ at the heating rate of 5-15 ℃/min, keeping the temperature for 1-2h, heating to 450-550 ℃ at the heating rate of 5-15 ℃/min, keeping the temperature for 1-2h, and naturally cooling.
8. Use of the composite organic aerogel according to any of claims 1 to 7 as an insulation material and/or for the preparation of an insulation material, for wastewater treatment and air purification, for the preparation of a composite material loaded with a drug or catalyst substance in the form of porous particles as a carrier.
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