CN113735556B - Silicon-containing aerogel composite material and preparation method and application thereof - Google Patents
Silicon-containing aerogel composite material and preparation method and application thereof Download PDFInfo
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- CN113735556B CN113735556B CN202110931338.9A CN202110931338A CN113735556B CN 113735556 B CN113735556 B CN 113735556B CN 202110931338 A CN202110931338 A CN 202110931338A CN 113735556 B CN113735556 B CN 113735556B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B30/00—Compositions for artificial stone, not containing binders
- C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/06—Use of materials for tobacco smoke filters
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
- C01B33/158—Purification; Drying; Dehydrating
- C01B33/1585—Dehydration into aerogels
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
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Abstract
The invention relates to the field of gel materials, and discloses a silicon-containing aerogel composite material as well as a preparation method and application thereof. The material is compounded by aerogel containing silicon and fibers. The material provided by the invention has the advantages of low density, high adsorption rate, high porosity, excellent elasticity and excellent processability, and does not fall off powder, so that the material does not cause inhalation risk to smokers. The method for preparing the silicon-containing aerogel composite material has the advantages of simple process, short preparation period and wide industrial prospect, and the cigarette filter tip prepared from the material prepared by the method has excellent adsorption effect on total particulate matters, tar and nicotine in smoke.
Description
Technical Field
The invention relates to the field of gel materials, in particular to a silicon-containing aerogel composite material and a preparation method and application thereof.
Background
In recent years, with the sharp increase of the smoking health problem, the tobacco industry in China is developing towards the direction of low tar and low harm, and a brand new material is needed to realize the tobacco industry. The method is characterized in that a nano material with an adsorption function is added into a cigarette filter stick, so that the harm of harmful substances in smoke to smokers can be reduced, and the taste of the cigarette filter stick is not lost.
However, after the nano powder material is added into the cigarette filter stick, the nano powder material is easy to enter the mouth of a smoker along with smoke, so that a new potential safety hazard is caused, and meanwhile, the nano powder material is difficult to realize industrialization, so that the application of the nano powder material in the cigarette filter stick is severely restricted.
CN102423132A discloses a plant polysaccharide cigarette filter tip and a preparation method thereof, wherein the prepared filter tip does not fall off powder, and can reduce the content of tar and nicotine, but a large amount of bubbles are generated in the preparation process. The existence of a large amount of bubbles can generate local effect, influence the normal operation of reaction and cause the uneven structure and pore diameter of the formed material. Therefore, it is usually necessary to add a defoaming agent or to use defoaming equipment, resulting in a complicated process.
CN111974356A discloses a composite aerogel type cigarette filter tip material, its preparation method and application, the method is to mix the nano-cellulose suspension and nano-silica suspension uniformly, then pre-freeze at low temperature, and freeze-dry to obtain the composite material, although the material has strong adsorbability to tar, nicotine and other substances in the smoke, and does not fall off powder, its preparation period is long, the process is complex, it needs to grind the raw materials for many times, and the freeze-drying period is long.
Therefore, there is a need for a method of preparing cigarette filter material that overcomes the above-mentioned drawbacks.
Disclosure of Invention
The invention aims to solve the problems that the nano powder material added into a cigarette filter stick in the prior art causes powder falling, has inhalation risk to smokers and is difficult to realize industrialization.
In order to achieve the above object, a first aspect of the present invention provides a silicon-containing aerogel composite, the aerogel compositeThe material is formed by compounding silicon-containing aerogel and fibers, wherein the content weight ratio of the silicon-containing aerogel to the fibers is 1:2-5, the density of the material is 48.9-70.1g/cm 3 The pore diameter is 500nm-1.0 μm, the porosity is 90% -93%, and the adsorption rate is 8.5-10.7g/g.
A second aspect of the present invention provides a method of preparing the silicon-containing aerogel composite of the first aspect, comprising:
in the presence of a solvent I, carrying out a first reaction on a silicon source I, an acidic catalyst I and a surfactant I to obtain silica sol I; in the presence of a solvent II, carrying out a second reaction on a silicon source II, an acid catalyst II and a surfactant II to obtain silica sol II; in the presence of a solvent III, carrying out a third reaction on a silicon source III, an acidic catalyst III and a surfactant III to obtain silica sol III;
carrying out a fourth reaction on the silica sol I, the silica sol II and the silica sol III with a pore size control agent, and adjusting the pH value to 8.0-10.0 by using an alkaline catalyst to obtain a first mixture;
dipping and mixing fibers with the first mixture to obtain a second mixture, and contacting the second mixture with an alcohol solvent to be aged and dried sequentially to obtain the silicon-containing aerogel composite material; the drying is CO2 supercritical drying;
wherein the silicon source I is selected from at least one of silicate ester, the silicon source II is selected from at least one of alkyl trialkoxysilane, and the silicon source III is selected from at least one of dialkyl dialkoxysilane.
A third aspect of the invention provides the use of a silica-containing aerogel composite as described in the previous first aspect in the manufacture of a cigarette filter.
The silicon-containing aerogel composite material provided by the invention has the advantages of low density, high adsorption rate, high porosity, excellent elasticity and excellent processability, and the material provided by the invention has the advantage of no powder falling, so that no inhalation risk is caused to smokers.
The method for preparing the silicon-containing aerogel composite material has the advantages of simple process, short preparation period and wide industrial prospect, and the cigarette filter tip prepared from the material prepared by the method has excellent adsorption effect on total particulate matters, tar and nicotine in smoke.
Drawings
FIG. 1 is an SEM image of a silicon-containing aerogel sample provided in accordance with a preferred embodiment 1 of the present invention; wherein the left image is the SEM image of the silicon-containing aerogel sample at a magnification of 6.00K, and the right image is the SEM image of the silicon-containing aerogel sample at a magnification of 3.00K.
FIG. 2 is an exemplary diagram of a sample of a silicon-containing aerogel provided in accordance with preferred embodiment 1 of the present invention; wherein, the left graph is the silicon-containing aerogel sample before bending, and the right graph is the silicon-containing aerogel sample after bending.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
As described above, in the first aspect of the present invention, a silicon-containing aerogel composite material is provided, which is formed by compounding a silicon-containing aerogel and fibers, wherein the content weight ratio of the silicon-containing aerogel to the fibers is 1:2 to 5, the density of the material is 48.9 to 70.1g/cm < 3 >, the pore diameter is 500nm to 1.0 mu m, the porosity is 90 to 93 percent, and the adsorption rate is 8.5 to 10.7g/g.
In the present invention, the adsorption rate is a ratio of the mass of a substance adsorbed when a material having an adsorption capacity per unit mass reaches an adsorption equilibrium to the mass of the material itself.
In the invention, the porosity is the percentage of the volume of the internal pores of the porous material in the total volume of the porous material, and the porosity can indicate the number of the pores of the porous material.
The present invention is not particularly limited to a specific method for preparing the silicon-containing aerogel composite material according to the first aspect, as long as the silicon-containing aerogel composite material having the above-mentioned characteristic parameters can be obtained, and those skilled in the art can combine the methods known in the art. But in order to obtain a better processibility and higher porosity of the silicon containing aerogel composite. The present invention provides a preferred method for preparing the silicon-containing aerogel composite described in the foregoing first aspect, and as described above, the second aspect of the present invention provides a method for preparing the silicon-containing aerogel composite described in the foregoing first aspect, the method comprising:
in the presence of a solvent I, carrying out a first reaction on a silicon source I, an acidic catalyst I and a surfactant I to obtain silica sol I; in the presence of a solvent II, carrying out a second reaction on a silicon source II, an acid catalyst II and a surfactant II to obtain silica sol II; in the presence of a solvent III, carrying out a third reaction on a silicon source III, an acidic catalyst III and a surfactant III to obtain silica sol III;
carrying out a fourth reaction on the silica sol I, the silica sol II and the silica sol III with a pore size control agent, and adjusting the pH value to 8.0-10.0 by using an alkaline catalyst to obtain a first mixture;
dipping and mixing fibers with the first mixture to obtain a second mixture, and contacting the second mixture with an alcohol solvent to be aged and dried sequentially to obtain the silicon-containing aerogel composite material; the drying is CO2 supercritical drying;
wherein the silicon source I is at least one selected from silicate ester, the silicon source II is at least one selected from alkyl trialkoxysilane, and the silicon source III is at least one selected from dialkyl dialkoxysilane.
In the present invention, preferably, the alkyl group in the alkyltrialkoxysilane means an alkyl group having a total number of carbon atoms of 1 to 10 in the alkyl group, and the alkyl group in the dialkyldialkoxysilane means an alkyl group having a total number of carbon atoms of 1 to 10 in the alkyl group, including straight-chain alkyl groups and branched-chain alkyl groups. Integers from 1 to 10 include 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10. Illustrative may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, and the like.
In the present invention, preferably, the alkoxy group in the alkyltrialkoxysilane refers to an alkyl group having a total number of carbon atoms of 1 to 10 in the alkoxy group, and the alkoxy group in the dialkyldialkoxysilane refers to an alkyl group having a total number of carbon atoms of 1 to 10 in the alkoxy group, including a linear alkoxy group and a branched alkoxy group. Integers from 1 to 10 include 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10. Illustrative may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy, and the like.
The inventor of the invention finds that the silicon-containing aerogel composite material prepared by the preparation method has better processing performance and higher porosity.
Preferably, the solvent I, the solvent II and the solvent III are each independently selected from at least one of methanol, ethanol, n-butanol, isopropanol.
Preferably, the acidic catalyst I, the acidic catalyst II and the acidic catalyst III are each independently selected from at least one of hydrochloric acid, oxalic acid, hydrofluoric acid, glacial acetic acid.
Preferably, the surfactant I, the surfactant II and the surfactant III are each independently selected from at least one of an anionic surfactant, a cationic surfactant and an amphoteric surfactant.
More preferably, the surfactant I, the surfactant II and the surfactant III are each independently selected from at least one of cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulphate, poloxamer.
Preferably, the silicon source I is at least one selected from the group consisting of methyl orthosilicate, ethyl orthosilicate, butyl orthosilicate, methyl polysilicate, ethyl polysilicate, and butyl polysilicate.
Preferably, the silicon source II is selected from at least one of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane.
Preferably, the silicon source III is selected from at least one of dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane.
Preferably, the CO is 2 The supercritical drying step comprises: discharging at least part of the alcohol solvent every 10-30min at the temperature of 35-45 ℃ and the pressure of 10-16 MPa until no alcohol solvent is discharged, and performing pressure relief treatment, wherein the pressure relief treatment conditions meet: the pressure is reduced to 0 in a time not exceeding 2 h. The inventors found that the preferred case has higher drying efficiency, and the prepared silicon-containing aerogel composite material has smaller shrinkage and better elastic property.
According to a preferred embodiment, the conditions of the first, second and third reactions are at least such that: the reaction temperature is 20-30 ℃ and the reaction time is 5-30min.
According to another preferred embodiment, the silicon source I and the solvent I, the acidic catalyst I and the surfactant I are used in a weight ratio of 1:3-15:14-16:0.1-0.3.
Preferably, the weight ratio of the silicon source II to the solvent II, the acidic catalyst II and the surfactant II is 1:0.7-15:2.0-12:0.05-0.3.
Preferably, the weight ratio of the silicon source III to the solvent III, the acidic catalyst III and the surfactant III is 1:1-30:2.5-15:0.05-0.6.
Preferably, the weight ratio of the silica sol I, the silica sol II, the silica sol III and the pore size controlling agent is 1:1-4:0.5-3:0.01-3. The inventors have found that the preferred case produces a silicon-containing aerogel composite having better processability and higher porosity.
Preferably, the pore size controlling agent is at least one selected from the group consisting of N, N-diethylformamide and N, N-dimethylformamide.
Preferably, the basic catalyst is selected from at least one of NaOH, naHCO3, and ammonia.
Preferably, the conditions of the fourth reaction at least satisfy: the reaction temperature is 20-30 ℃, and the reaction time is 10-60min.
Preferably, the fiber material is at least one selected from the group consisting of acetate fibers, lactate fibers, polyimide fibers, polypropylene fibers, and meltblown.
Preferably, the alcohol solvent is selected from at least one of methanol, ethanol, n-butanol, and isopropanol.
Preferably, the conditions of the impregnation mixing at least satisfy: the impregnation mixing temperature is 20-30 deg.C, and the impregnation mixing time is 10-60min.
Preferably, the aging condition at least satisfies: the aging temperature is 20-65 ℃, and the aging time is 16-48h.
As previously mentioned, a third aspect of the present invention provides the use of a silica-containing aerogel composite as described in the first aspect above in the manufacture of a cigarette filter.
The room temperature in the present invention means 25. + -. 5 ℃ unless otherwise specified.
The present invention will be described in detail below by way of examples. The starting materials in the following examples are all commercially available unless otherwise specified.
In the following examples, the test methods of the related partial characteristic parameters are as follows:
the test method of the powder falling rate comprises the following steps: weighing the mass m0 of the silica aerogel composite material sample of 10cm × 10cm, putting the silica aerogel composite material sample into a standard vibrating sieving machine (model BZS-200, changan group Co., ltd.), taking out the silica aerogel composite material sample after 2min, and weighing the mass m1 of the silica aerogel composite material sample after vibrating and sieving. Powder dropping rate = (m 0-m 1)/m 0 x 100%.
The density test method comprises the following steps: weighing a cuboid silicon-containing aerogel composite material sample to obtain the mass m of the sample, and respectively measuring the length, the width and the thickness of the sample to obtain the volume V of the sample, wherein the density rho = m/V.
Porosity test method: weighing the mass m0 of a silicon-containing aerogel composite material sample by using an analytical balance, soaking the silicon-containing aerogel composite material sample in a beaker containing absolute ethyl alcohol for 5min, weighing the total mass m1 of the beaker containing the absolute ethyl alcohol and the silicon-containing aerogel composite material sample, then placing the beaker in a vacuum drier and vacuumizing until no bubbles overflow in the beaker, taking out the silicon-containing aerogel composite material sample, and weighing the mass m2 of the vacuumized beaker, wherein the porosity is = (m 1-m2-m 0)/(m 1-m 2). Times.100%.
The method for testing the adsorption rate comprises the following steps: weighing the mass m0 of the silicon-containing aerogel composite material sample, then placing the silicon-containing aerogel composite material sample in white oil, soaking until the silicon-containing aerogel composite material sample reaches adsorption balance, taking out, and weighing the mass m1 of the soaked silicon-containing aerogel composite material sample. Adsorption capacity = (m 1-m 0)/m 0.
The test method of the elastic property comprises the following steps: and (3) vertically pressing the silicon-containing aerogel sample, and measuring the rebound rate of the silicon-containing aerogel sample when the pressure is removed, wherein the original height h0 of the silicon-containing aerogel sample and the height h1 recovered after the pressure is removed. Rebound resilience =1- (h 0-h 1)/h 0 × 100%.
The method for testing the processability comprises the following steps: and cutting the silicon-containing aerogel sample by using a cutter, and evaluating the processing performance of the silicon-containing aerogel sample according to the existence of fracture and breakage of the silicon-containing aerogel sample and the regularity of cut.
Method for testing total particulate matter: the method for testing the total particulate matter of the cigarettes is specified in the total particulate matter and the tar by a smoking machine according to the routine analysis of GB/T19609-2004 cigarettes.
The tar yield test method comprises the following steps: the method for testing the tar content of the cigarettes is specified in the total particulate matter and the tar by a smoking machine according to the routine analysis of GB/T19609-2004 cigarettes.
The method for testing the nicotine amount comprises the following steps: the method for testing the nicotine content of cigarette is specified in total particulate matter and tar by a smoking machine according to the routine analysis of GB/T19609-2004 cigarette.
Example 1
1g of methyl orthosilicate (i.e., silicon source I), 14.9g of glacial acetic acid (i.e., acidic catalyst I) and 0.27g of cetyltrimethylammonium bromide (i.e., surfactant I) were mixed in 7.85g of methanol (i.e., solvent I) at room temperature and stirred for 30min (i.e., first reaction) to obtain silica sol I;
4g of methyltrimethoxysilane (i.e. silicon source II) was mixed with 11.17g of glacial acetic acid (i.e. acidic catalyst II) and 0.27g of cetyltrimethylammonium bromide (i.e. surfactant II) in 7.85g of methanol (i.e. solvent II) at room temperature and stirred for 30min (i.e. second reaction) to give silica sol II;
2.6g of dimethyldiethoxysilane (i.e. silicon source III) was mixed with 7.45g of glacial acetic acid (i.e. acidic catalyst III) and 0.27g of cetyltrimethylammonium bromide (i.e. surfactant III) in 7.85g of methanol (i.e. solvent III) at room temperature and stirred for 30min (i.e. third reaction) to give silica sol III;
mixing 5g of the silica sol I, 10g of the silica sol II and 10g of the silica sol III with 5g of N, N-dimethylformamide (i.e., a pore size control agent) at room temperature and stirring for 10min (i.e., a fourth reaction), standing, and adjusting the pH value to 9.0 with 5.0mol/L of ammonia water (i.e., a basic catalyst) to obtain a first mixture;
soaking and mixing 5g of cellulose acetate and 20g of the first mixture at room temperature for 35min, adding ethanol to ensure that the cellulose acetate is not on the liquid surface, aging at 40 ℃ for 24h, then discharging the ethanol at 40 ℃ and 13MPa every 15min until no ethanol is discharged, and reducing the pressure to 0 within 2h to obtain the silicon-containing aerogel composite material C1.
Example 2
This example was carried out using a similar procedure to example 1, except that: and replacing the equal weight of the methyl orthosilicate with the ethyl orthosilicate to obtain the silicon-containing aerogel composite material C2.
Example 3
Mixing 1g of methyl polysilicate (i.e. silicon source I) with 15g of hydrochloric acid (i.e. acidic catalyst I) and 0.2g of cetyltrimethylammonium bromide (i.e. surfactant I) in 9g of methanol (i.e. solvent I) at room temperature and stirring for 25min (i.e. first reaction) to obtain silica sol I;
mixing 1g of methyltriethoxysilane (i.e., silicon source II), 7g of glacial acetic acid (i.e., acidic catalyst II) and 0.2g of poloxamer (i.e., surfactant II) in 8g of n-butanol (i.e., solvent II) at room temperature and stirring for 20min (i.e., second reaction) to obtain silica sol II;
mixing 1g of dimethyldiethoxysilane (i.e., silicon source III) with 9g of oxalic acid (i.e., acidic catalyst III) and 0.35g of cetyltrimethylammonium bromide (i.e., surfactant III) in 15g of isopropanol (i.e., solvent III) at room temperature and stirring for 25min (i.e., a third reaction) to obtain silica sol III;
mixing 5g of the silica sol I, 10g of the silica sol II and 10g of the silica sol III with 7.5g of N, N-diethylformamide (i.e., a pore size control agent) at room temperature and stirring for 35min (i.e., a fourth reaction), standing, and adjusting the pH value to 9.0 with 5.0mol/L of ammonia (i.e., a basic catalyst) to obtain a first mixture;
soaking and mixing 5g of cellulose acetate and 20g of the first mixture at room temperature for 35min, adding ethanol to ensure that the cellulose acetate is not on the liquid surface, aging at 40 ℃ for 32h, then discharging the ethanol at 40 ℃ and 13MPa every 15min until no ethanol is discharged, and reducing the pressure to 0 within 2h to obtain the silicon-containing aerogel composite material C3.
Example 4
Mixing 1g of poly butyl silicate (namely silicon source I), 15g of glacial acetic acid (namely acid catalyst I) and 0.2g of sodium dodecyl sulfate (namely surfactant I) in 6g of ethanol (namely solvent I) at room temperature, and stirring for 15min (namely a first reaction) to obtain silica sol I;
mixing 3g of methyltrimethoxysilane (i.e., silicon source II) with 10.5g of 1mol/L hydrochloric acid (i.e., acidic catalyst II) and 0.3g of cetyltrimethylammonium bromide (i.e., surfactant II) in 6g of ethanol (i.e., solvent II) at room temperature and stirring for 20min (i.e., second reaction) to obtain silica sol II;
mixing 2g of dimethyldiethoxysilane (i.e., silicon source III) with 8g of glacial acetic acid (i.e., acidic catalyst III) and 3g of cetyltrimethylammonium bromide (i.e., surfactant III) in 6g of methanol (i.e., solvent III) at room temperature and stirring for 15min (i.e., a third reaction) to obtain silica sol III;
mixing 5g of the silica sol I, 15g of the silica sol II and 7.5g of the silica sol III with 5g of N, N-dimethylformamide (i.e., a pore size controlling agent) at room temperature and stirring for 30min (i.e., a fourth reaction), standing, and adjusting the pH value to 9.0 with 6.5mol/L of ammonia (i.e., a basic catalyst) to obtain a first mixture;
soaking and mixing 5g of lactic acid fiber and 20g of the first mixture at room temperature for 50min, adding methanol to ensure that the liquid surface is submerged in the lactic acid fiber, aging at 40 ℃ for 32h, then discharging the methanol at 30 ℃ and 16MPa every 10min until no methanol is discharged, and reducing the pressure to 0 within 2h to obtain the silicon-containing aerogel composite material C4.
Example 5
Mixing 1g of polyethyl silicate (i.e., silicon source I) with 14g of hydrochloric acid (i.e., acidic catalyst I) and 0.1g of cetyltrimethylammonium bromide (i.e., surfactant I) in 4g of methanol (i.e., solvent I) at room temperature and stirring for 10min (i.e., first reaction) to obtain silica sol I;
mixing 2g of methyltrimethoxysilane (i.e., silicon source II) with 8g of glacial acetic acid (i.e., acidic catalyst II) and 0.1g of poloxamer (i.e., surfactant II) in 2g of n-butanol (i.e., solvent II) at room temperature and stirring for 20min (i.e., second reaction) to obtain silica sol II;
3g of diethyldiethoxysilane (i.e., silicon source III) was mixed with 7.5g of oxalic acid (i.e., acidic catalyst III) and 0.9g of cetyltrimethylammonium bromide (i.e., surfactant III) in 15g of isopropanol (i.e., solvent III) at room temperature and stirred for 15min (i.e., third reaction) to obtain silica sol III;
mixing 5g of the silica sol I, 5g of the silica sol II and 2.5g of the silica sol III with 0.5g of N, N-diethylformamide (i.e., a pore size control agent) at room temperature and stirring for 50min (i.e., a fourth reaction), standing, and adjusting the pH to 8.0 with 6.5mol/L of ammonia (i.e., a basic catalyst) to obtain a first mixture;
soaking and mixing 5g of polypropylene fibers and 15g of the first mixture at room temperature for 40min, adding ethanol to ensure that the surface of the polypropylene fibers is submerged, aging the polypropylene fibers at 20 ℃ for 48h, then discharging the ethanol at 45 ℃ and 10MPa every 20min until no ethanol is discharged, and reducing the pressure to 0 within 2h to obtain the silicon-containing aerogel composite material C5.
Example 6
Mixing 1g of methyl orthosilicate (i.e., silicon source I), 16g of glacial acetic acid (i.e., acidic catalyst I) and 0.3g of cetyltrimethylammonium bromide (i.e., surfactant I) in 9g of butanol (i.e., solvent I) at room temperature and stirring for 15min (i.e., first reaction) to obtain silica sol I;
mixing 2g of methyltrimethoxysilane (i.e. silicon source II), 4g of hydrofluoric acid (i.e. acidic catalyst II) and 0.4g of sodium dodecyl sulfate (i.e. surfactant II) in 6g of methanol (i.e. solvent II) at room temperature, and stirring for 10min (i.e. second reaction) to obtain silica sol II;
mixing 2g of dimethyldiethoxysilane (i.e., silicon source III) with 12g of glacial acetic acid (i.e., acidic catalyst III) and 0.1g of poloxamer (i.e., surfactant III) in 2g of ethanol (i.e., solvent III) at room temperature and stirring for 10min (i.e., third reaction) to obtain silica sol III;
mixing 5g of the silica sol I, 20g of the silica sol II and 15g of the silica sol III with 10g of N, N-diethylformamide (i.e., a pore size control agent) at room temperature and stirring for 60min (i.e., a fourth reaction), standing, and adjusting the pH value to 10.0 with 6.5mol/L of ammonia (i.e., a basic catalyst) to obtain a first mixture;
and soaking and mixing 5g of melt-blown fabric and 25g of the first mixture at room temperature for 60min, adding ethanol, ageing the melt-blown fabric at 65 ℃ for 16h under the condition that the liquid level of the ethanol is not higher than the liquid level of the melt-blown fabric, then discharging the ethanol at 35 ℃ and 10MPa every 30min until no ethanol is discharged, and reducing the pressure to 0 within 2h to obtain the silicon-containing aerogel composite material C6.
Comparative example 1
This comparative example was carried out using a procedure similar to that of example 1, except that: and replacing methyl orthosilicate and the like by methyltrimethoxysilane in weight to obtain the silicon-containing aerogel composite material DC1.
Comparative example 2
This comparative example was carried out using a procedure similar to that of example 1, except that: and replacing the same weight of the methyl orthosilicate with dimethyl diethoxysilane to obtain the silicon-containing aerogel composite material DC2.
Comparative example 3
This comparative example was carried out using a procedure similar to that of example 1, except that: the amount of methyl orthosilicate used was 0.5g, and a silicon-containing aerogel composite DC3 was obtained.
Comparative example 4
This comparative example was carried out using a procedure similar to that of example 1, except that the drying treatment was carried out in a different manner, specifically:
and (3) drying the product after dipping and mixing at normal pressure in a stepped heating way: drying at 30 ℃ for 3h; drying at 60 deg.C for 4h; drying at 80 deg.C for 6h; and drying at 120 ℃ for 2h to obtain the silicon-containing aerogel composite material DC4.
Test example 1
The silicon-containing aerogel composite materials prepared in the examples and the comparative examples were subjected to density, pore size, porosity, adsorption rate, dusting rate, elastic property and processability tests according to the methods described above, and the results are shown in table 1 below.
TABLE 1
As can be seen from the results in table 1, the silicon-containing aerogel materials provided by the present invention have low density, high adsorption rate, high porosity, and excellent elasticity and processability, and the materials provided by the present invention also have the advantage of no dusting, thereby causing no inhalation risk to smokers. The method for preparing the silicon-containing aerogel composite material has the advantages of simple process, short preparation period and wide industrial prospect.
Fig. 1 is a SEM of a silicon-containing aerogel sample according to preferred embodiment 1 of the present invention, wherein the left is a SEM of a silicon-containing aerogel sample at a magnification of 6.00K, and the right is a SEM of a silicon-containing aerogel sample at a magnification of 3.00K. It can be seen from figure 1 that the silicon-containing aerogel sample is formed by a uniform bead packing and the pore size distribution is between 500-1000 nm.
FIG. 2 is an exemplary illustration of a sample of a silicon-containing aerogel provided in accordance with preferred embodiment 1 of the present invention; the left figure is the silicon-containing aerogel sample before bending, and the right figure is the silicon-containing aerogel sample after bending. It can be seen from fig. 2 that the silicon-containing aerogel sample has no fracture and excellent elasticity after being bent.
Test example 2
The silicon-containing aerogel composite materials prepared in the examples and the comparative examples and tobacco are prepared into cigarettes to detect total particulate matters, tar content and nicotine content of main stream smoke of the cigarettes, and the results are shown in table 2. (the preparation method of the cigarette refers to the method described in embodiment 1 of CN107536101A, which specifically comprises the following steps:
1) Crushing 50g of tobacco leaves and 100g of tobacco stems purchased from tobacco industry Limited liability company in Yunnan into 100-120 meshes of tobacco powder at 40 ℃;
2) Mixing the tobacco powder with sodium bicarbonate, potassium citrate, 10% white latex solution for tobacco, propylene glycol, tobacco essence and the like according to the mass ratio of 100:1:0.5:5:0.2:0.05, granulating and drying in one step to obtain tobacco particles, and removing the particles smaller than 70 meshes by air separation;
3) Spraying polyethylene hot melt adhesive on the surfaces of the tobacco particles qualified by winnowing, pressing the tobacco particles into the tobacco particles from one end of a cylindrical die with the diameter of 7.5mm by using a continuous feeding device under the condition of heat preservation, solidifying and rapidly cooling the tobacco particles, and extruding the tobacco particles from the other end to obtain tobacco particle round bars with the density of 0.3 g/mL;
4) And wrapping the extruded tobacco round rod by using cigarette paper, cutting the tobacco round rod into 59mm, and connecting the tobacco round rod with a cigarette filter rod through a tipping paper to prepare the cigarette. )
Cigarettes prepared from the silicon-containing aerogel composite materials C1, C2, C3, C4, C5, C6, DC1, DC2, DC3 and DC4 are marked as CY1, CY2, CY3, CY4, CY5, CY6, DCY1, DCY2, DCY3 and DCY4 respectively.
TABLE 2
| Cigarette numbering | Total particulate matter (mg) | Amount of tar (mg) | Amount of nicotine (mg) |
| CY1 | 7.34 | 6.0 | 0.51 |
| CY2 | 9.06 | 7.4 | 0.61 |
| CY3 | 9.08 | 7.6 | 0.60 |
| CY4 | 9.12 | 7.8 | 0.62 |
| CY5 | 9.07 | 7.4 | 0.60 |
| CY6 | 9.05 | 7.3 | 0.61 |
| DCY1 | 10.2 | 7.8 | 0.63 |
| DCY2 | 10.1 | 7.7 | 0.65 |
| DCY3 | 10.6 | 8.2 | 0.76 |
| DCY4 | 10.7 | 8.7 | 0.77 |
| Standard sample | 12.43 | 10.4 | 0.94 |
The results in table 2 show that the cigarette filter prepared from the material obtained by preparing the silica-containing aerogel material provided by the invention has excellent adsorption effect on total particulate matters, tar and nicotine in smoke.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (9)
1. The silicon-containing aerogel composite material is characterized by being formed by compounding silicon-containing aerogel and fibers, wherein the content weight ratio of the silicon-containing aerogel to the fibers is 1:2-5, the density of the material is 48.9-70.1g/cm 3 The aperture is 500nm-1.0 μm, the porosity is 90-93%, the adsorption rate is 8.5-10.7g/g, and the silicon-containing aerogel composite material is used for preparing cigarette filter tipThe silicon-containing aerogel composite material does not fall off powder and has no inhalation risk to smokers.
2. A method of making the silicon-containing aerogel composite of claim 1, comprising:
in the presence of a solvent I, carrying out a first reaction on a silicon source I, an acidic catalyst I and a surfactant I to obtain silica sol I; in the presence of a solvent II, carrying out a second reaction on a silicon source II, an acid catalyst II and a surfactant II to obtain silica sol II; in the presence of a solvent III, carrying out a third reaction on a silicon source III, an acidic catalyst III and a surfactant III to obtain silica sol III;
carrying out a fourth reaction on the silica sol I, the silica sol II and the silica sol III with a pore size control agent, and adjusting the pH value to 8.0-10.0 by using an alkaline catalyst to obtain a first mixture;
dipping and mixing fibers and the first mixture to obtain a second mixture, and contacting the second mixture with an alcohol solvent to carry out aging and drying in sequence to obtain the silicon-containing aerogel composite material; the drying is CO2 supercritical drying;
wherein the silicon source I is at least one selected from silicate ester, the silicon source II is at least one selected from alkyl trialkoxysilane, and the silicon source III is at least one selected from dialkyl dialkoxysilane.
3. The process according to claim 2, wherein the solvent I, the solvent II and the solvent III are each independently selected from at least one of methanol, ethanol, n-butanol, isopropanol; the acidic catalyst I, the acidic catalyst II and the acidic catalyst III are respectively and independently selected from at least one of hydrochloric acid, oxalic acid, hydrofluoric acid and glacial acetic acid; the surfactant I, the surfactant II and the surfactant III are respectively and independently selected from at least one of anionic surfactant, cationic surfactant and amphoteric surfactant.
4. The method according to claim 2 or 3, wherein the silicon source I is selected from at least one of methyl orthosilicate, ethyl orthosilicate, butyl orthosilicate, methyl polysilicate, ethyl polysilicate, butyl polysilicate; the silicon source II is at least one selected from methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane and ethyltriethoxysilane; the silicon source III is at least one selected from dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane and diethyldiethoxysilane.
5. The method of claim 2, wherein the step of CO2 supercritical drying comprises: discharging at least part of the alcohol solvent every 10-30min at the temperature of 35-45 ℃ and the pressure of 10-16 MPa until no alcohol solvent is discharged, and performing pressure relief treatment, wherein the pressure relief treatment conditions meet: reducing the pressure to 0 over a period of no more than 2 hours; the conditions of the first reaction, the second reaction and the third reaction at least satisfy: the reaction temperature is 20-30 ℃ and the reaction time is 5-30min.
6. The process according to claim 2, wherein the silicon source I and the solvent I, the acidic catalyst I and the surfactant I are used in a weight ratio of 1:3-15:14-16:0.1-0.3; the weight ratio of the silicon source II to the solvent II, the acidic catalyst II and the surfactant II is 1:0.7-15:2.0-12:0.05 to 0.3; the weight ratio of the silicon source III to the solvent III, the acidic catalyst III and the surfactant III is 1:1-30:2.5-15:0.05-0.6.
7. The method of claim 2, wherein the silica sol I, the silica sol II, the silica sol III and the pore size controlling agent are used in a weight ratio of 1:1-4:0.5-3:0.01 to 3; the pore size control agent is selected from at least one of N, N-diethylformamide and N, N-dimethylformamide; the alkaline catalyst is selected from NaOH and NaHCO 3 And ammonia water.
8. The method of claim 2, wherein the fourth reaction is conditioned to at least: the reaction temperature is 20-30 ℃, and the reaction time is 10-60min; the fiber is selected from at least one of acetate fiber, lactic acid fiber, polyimide fiber, polypropylene fiber and melt-blown cloth; the alcohol solvent is at least one selected from methanol, ethanol, n-butanol and isopropanol.
9. The method of claim 2, wherein the conditions of the impregnation mixing at least satisfy: the dipping and mixing temperature is 20-30 ℃, and the dipping and mixing time is 10-60min; the aging condition at least satisfies: the aging temperature is 20-65 ℃, and the aging time is 16-48h.
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