CN107715852B - Vanillin modified chitosan-SiO2Composite aerogel material and preparation method and application thereof - Google Patents
Vanillin modified chitosan-SiO2Composite aerogel material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 106
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention provides vanillin modified chitosan-SiO2The preparation method of the composite aerogel material and the application of the composite aerogel material in cigarette smoke adsorption are characterized in that after chitosan is subjected to amino modification, a silicon source precursor is hydrolyzed and condensed in an acidic solution of the modified chitosan, the gel is kept stand, the gel is aged and subjected to solvent exchange and then dried to obtain a hydrophilic composite material, the gel is subjected to surface modification and drying to obtain a hydrophobic composite material, and the aerogel material obtained after drying is subjected to cigarette smoke harmful substance adsorption. The vanillin modified chitosan-SiO of the invention2The composite aerogel material has strong adsorption capacity and high selectivity on harmful substances in the cigarette smoke; the method has the advantages of simple manufacture, low production cost and high safety performance.
Description
Technical Field
The invention relates to a composite aerogel material, a preparation method and application thereof, in particular to vanillin modified chitosan-SiO2A composite aerogel material, a preparation method and an adsorption application thereof in cigarette smoke; belongs to the new field of composite aerogel material.
Background
With the addition of the international tobacco control framework convention in China, the components of tobacco products are limited, meanwhile, the living standard of people is continuously improved, the safety and environmental protection awareness of people on smoking is stronger and stronger, and tar and harm reduction is imperative, so that the research on harmful substances in cigarettes and tar and harm reduction technologies become hot spots of the research of people; the special filter tip using the additive becomes one of important technical means for reducing tar and harm of the cigarette; xilautian and the like (Xilautian, application research of nano adsorbent in tar reduction of cigarettes [ J ]. Yunnan chemical industry, 2002, (3),1-3) prepare nano powder with filtering and adsorbing properties on smoke tar, and the nano powder is coated on acetate fiber tows to prepare tar reduction filter tip rods, wherein the dosage is 16-18 mg/cigarette, and the tar reduction effect can reach 4.4 mg/cigarette. However, when the tar content of the cigarette is reduced to a certain level, the flavor of the smoke can be greatly influenced, so that the application of tar-reducing and harm-reducing technology in the actual production process is restricted.
The chitosan is obtained by deacetylating chitin, is a natural polymer with abundant natural content, has good biocompatibility and microbial degradability, and can be subjected to various chemical modifications due to the existence of hydroxyl and amino in molecules, so that a plurality of useful new substances are obtained. In the course of a large number of basic and application studies, chitosan has been applied in various fields such as textiles, cosmetics, printing and dyeing, medicines, foods, environmental protection and the like. The pure chitosan is a transparent flaky or powdery solid of white or off-white half-shell chitosan, is tasteless, odorless and nontoxic, and has slight pearl luster.
SiO2Aerogel is a low-density porous solid material with a nano structure, and is called as 'frozen smoke' abroad. The material has the properties of high porosity, high specific surface area, low density and the like, and has wide application prospect, such as being used as a catalyst carrier, an acoustic impedance coupling material, a transparent heat insulation material, an adsorption material and the like. At present, SiO2The aerogel is prepared by a supercritical method, the equipment is complex, the production cost is high, and the danger is high, so that the danger and the production cost can be reduced by drying the prepared aerogel material at normal pressure, and SiO is used for preparing the aerogel2The vanillin modified chitosan is added into the aerogel material, so that the adsorption performance of harmful substances in the mainstream smoke of the cigarettes can be improved, and the adsorption selectivity of the cigarette can also be enhanced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides vanillin modified chitosan-SiO2The invention discloses a composite aerogel material, a preparation method and application thereof, and discloses a vanillin modified chitosan-SiO2The composite aerogel material has strong adsorption capacity and high selectivity on harmful substances in the cigarette smoke; the method has the advantages of simple manufacture, low production cost and high safety performance.
The invention providesProvides a vanillin modified chitosan-SiO2The preparation method of the composite aerogel material and the application of the composite aerogel material in cigarette smoke adsorption are characterized in that after chitosan is subjected to amino modification, a silicon source precursor is hydrolyzed and condensed in an acidic solution of the modified chitosan, the gel is kept stand, the gel is aged and subjected to solvent exchange and then dried to obtain a hydrophilic composite material, the gel is subjected to surface modification and drying to obtain a hydrophobic composite material, and the aerogel material obtained after drying is subjected to cigarette smoke harmful substance adsorption capacity testing.
According to a first embodiment of the present invention, there is provided a vanillin-modified chitosan-SiO2Compounding aerogel materials.
Vanillin modified chitosan-SiO2The composite aerogel material is obtained by modifying chitosan through vanillin to obtain vanillin-modified chitosan and then dissolving a silicon source precursor in the vanillin-modified chitosan.
In the invention, the precursor of the silicon source is silicate ester, preferably methyl silicate, ethyl silicate, isopropyl orthosilicate and butyl orthosilicate; more preferably, tetraethoxysilane.
According to a second embodiment of the present invention, there is provided a method for preparing vanillin-modified chitosan-SiO2Methods of compounding aerogel materials.
Preparation of vanillin modified chitosan-SiO2A method of compounding an aerogel material, the method comprising the steps of:
1) adding chitosan into vanillin, heating and refluxing to obtain vanillin-modified chitosan;
2) adding a silicon source precursor into vanillin-modified chitosan, stirring, standing for gelation, and washing; obtaining vanillin modified chitosan-SiO2And (5) preparing a crude product of the composite aerogel material.
Preferably, the method further comprises:
3) the vanillin modification chitosan-SiO obtained in the step 2)2Soaking and washing a crude product of the composite aerogel material in a normal hexane solution containing trimethylchlorosilane; obtaining vanillin modified shellpolysaccharide-SiO2Compounding aerogel materials.
In the invention, the step 1) is specifically as follows: adding chitosan into an organic solvent, soaking at constant temperature, swelling, filtering and cleaning, adding the swollen chitosan into the organic solvent containing vanillin, heating and refluxing, carrying out suction filtration to obtain a product after reaction, washing and drying to obtain vanillin-modified chitosan.
In the invention, the step 2) is specifically as follows: dissolving vanillin-modified chitosan in hydrochloric acid solution, and stirring at room temperature; uniformly mixing ethyl orthosilicate and ethanol, adding the mixture into a vanillin-modified chitosan solution, and stirring; adding HF solution, stirring, standing for gelation, and aging; soaking and washing the aged gel in distilled water, soaking and washing in ethanol, soaking and washing with n-hexane, and drying to obtain vanillin modified chitosan-SiO2And (5) preparing a crude product of the composite aerogel material.
In the invention, the step 3) is specifically as follows: the furfural obtained in the step 2) is modified by chitosan-SiO2Soaking the crude product of the composite aerogel material in a normal hexane solution containing trimethylchlorosilane, soaking in the normal hexane solution for washing, and drying to obtain the vanillin modified chitosan-SiO2Compounding aerogel materials.
In the present invention, the organic solvent in step 1) is an alcohol solution, preferably one or both of methanol and ethanol. The mass ratio of the chitosan to the vanillin in the step 1) is 1:1-10, preferably 1:1.2-6, and more preferably 1: 1.5-4. The temperature of the constant-temperature soaking in the step 1) is 15-90 ℃, preferably 20-80 ℃, and more preferably 25-70 ℃. The soaking time at constant temperature is 0.5-48h, preferably 1-36h, more preferably 2-24 h. The cleaning in the step 1) is performed by using an alcoholic solution, preferably an alcoholic solution. The temperature of the addition reflux in step 1) is 55 to 100 ℃, preferably 60 to 90 ℃, more preferably 65 to 80 ℃. The washing in the step 1) is performed by using an alcoholic solution, and preferably by using an ethanol solution.
In the present invention, the concentration of the hydrochloric acid solution in the step 2) is 0.05 to 1.0mol/L, preferably 0.1 to 0.8mol/L, and more preferably 0.15 to 0.5 mol/L. Mixing ethyl orthosilicate and ethanol, wherein the mass ratio of the ethyl orthosilicate to the ethanol is 1-5:1, preferably 1.2-3:1, and more preferably 1.5-2: 1. The mass ratio of the vanillin-modified chitosan to the tetraethoxysilane is 1:15-100, preferably 1:20-90, and more preferably 1: 25-80. The stirring time is 2-48h, preferably 6-36h, more preferably 12-24 h. The HF solution is added in a mass concentration of 1 to 40%, preferably 3 to 20%, more preferably 5 to 10%. The mass ratio of the added HF solution to the tetraethoxysilane is 1:100-1000, preferably 1:200-800, and more preferably 1: 400-600. The soaking and washing time is 2-72h, preferably 6-48h, and more preferably 12-36 h.
In the invention, the volume concentration of the trimethylchlorosilane in the normal hexane solution containing the trimethylchlorosilane in the step 3) is 1-20%, preferably 3-15%, and more preferably 5-10%. The soaking and washing time is 2-72h, preferably 6-48h, and more preferably 12-36 h.
According to a third embodiment of the present invention, there is provided a vanillin-modified chitosan-SiO prepared by the above method2Vanillin modified chitosan-SiO obtained by compounding aerogel material2Compounding aerogel materials.
According to a fourth embodiment provided by the present invention, there is provided a vanillin-modified chitosan-SiO2Application of the composite aerogel material.
Vanillin modified chitosan-SiO2Use of a composite aerogel material prepared by modifying the vanillin-modified chitosan-SiO of the first embodiment2A composite aerogel material, or a vanillin-modified chitosan-SiO prepared by the method of the second embodiment2The composite aerogel material is used in cigarette filter sticks.
Preferably, the particle size of the material is 20 to 100 mesh, preferably 30 to 80 mesh, more preferably 40 to 60 mesh.
Preferably, the addition amount of the material added into each cigarette filter stick is 1-20mg, preferably 3-18mg, and more preferably 5-15 mg.
In the present invention, all the materials used are commercially available, and there is no particular requirement. Preferably, chitosan with viscosity of 14cps and deacetylation degree of 96.1%; or chitosan with viscosity of 37cps and deacetylation degree of 95.7%; or chitosan with viscosity of 59cps and deacetylation degree of 85.7%.
According to the invention, chitosan is modified by vanillin, so that the adsorption performance of chitosan is improved. The chitosan molecule contains a large amount of free-NH2and-OH, which is easy to carry out chemical reaction, and introduces other functional groups, thereby widening the application range. The invention uses free-NH in chitosan molecule2and-OH reacts with vanillin, and the compound obtained after the reaction can well adsorb harmful ingredients in the cigarette smoke.
In the invention, the chitosan is added into the organic solvent for soaking at constant temperature, so that the contact area of the reaction is increased, and the reaction is more sufficient.
In the invention, the vanillin modified chitosan is dissolved in the hydrochloric acid solution to be uniformly dispersed. The vanillin modified chitosan can be dissolved in an acidic aqueous solution, and meanwhile, the hydrochloric acid is a catalyst for hydrolyzing the tetraethoxysilane, so that the hydrolysis of the tetraethoxysilane is promoted. According to the invention, vanillin modified chitosan is dissolved in hydrochloric acid aqueous solution, after a mixed solution of ethyl orthosilicate and ethanol is added, the modified chitosan cannot be precipitated, and is uniformly mixed with the ethyl orthosilicate which starts to be hydrolyzed, and HF is added to form uniform gel.
In the invention, tetraethoxysilane and ethanol are uniformly mixed and added into a vanillin modified chitosan solution, and the tetraethoxysilane starts to hydrolyze to generate silicic acid sol.
In the invention, HF solution is added to accelerate polycondensation reaction and reduce gel time. F-Size and OH-Close to and capable of reacting with Si to form>4-coordinate complexes and HF as a catalyst produce gels with many similar characteristics.
In the invention, the aged gel is put into distilled water for soaking and washing to remove hydrochloric acid and HF in the gel; soaking in ethanol for washing, and displacing water in the gel; and then, soaking and washing by using normal hexane, replacing ethanol in the gel, and drying after the solvent in the gel is the normal hexane with low surface tension. Reduce the capillary action in the pore size of the gel and reduce the effect of pore size collapse during drying.
In the invention, the obtained vanillin modified chitosan-SiO2The crude product of the composite aerogel material is soaked in a normal hexane solution containing trimethylchlorosilane, and the trimethylchlorosilane is used as a modifier to carry out surface modification on the gel washed by the normal hexane. And soaking and washing the modified gel in a normal hexane solution, removing acid generated in the modification process, and drying to obtain the hydrophobic material. The adsorption performance of harmful substances in the mainstream smoke of the cigarettes is researched. the-Cl of trimethylchlorosilane replaces-H in-OH groups on the gel surface, causing the alcogel surface to become-Si-O-Si (CH)3)3Thereby achieving the surface modification effect.
In the invention, the dried composite material is crushed and sieved, and the material with the grain diameter of 40-60 meshes is selected and added into the cigarette filter tip to carry out the adsorption test of harmful substances of the cigarette.
The invention prepares vanillin modified chitosan-SiO2The composite aerogel material can be uniformly mixed with the cut tobacco, can be adhered to the surface of the cut tobacco, can enhance the tensile strength, the water resistance and the bursting strength, is not easy to break during processing, and is suitable for modern high-speed cigarette making machines; the tobacco additive can remarkably enhance the combustion performance of cigarettes, has the function of reducing the content of tar and nicotine in the cigarettes, reduces the miscellaneous gas of the cigarettes, reduces harmful substances in the smoke, improves the smoking taste and reveals the fragrance; can also effectively inhibit the tobacco leaves from mildewing and prolong the storage time of the tobacco.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1. the vanillin modified chitosan-SiO of the invention2The composite aerogel material has high specific surface area which can reach 735.75m2The crotonaldehyde reduction agent has the advantages that the crotonaldehyde reduction rate can reach 38.67 percent;
2. the preparation process is simple, and the requirements on experimental conditions are not high;
drawings
FIG. 1 is a vanillin-modified chitosan-SiO prepared in one embodiment 1 of the present invention2Aerogel infrared absorption spectroscopy;
FIG. 2 is an infrared absorption spectrum of a composite aerogel prepared in example 2 of the present invention;
fig. 3 is a scanning electron micrograph of the composite aerogel prepared in one embodiment 2 of the present invention.
Detailed Description
According to a first embodiment of the present invention, there is provided a vanillin-modified chitosan-SiO2Compounding aerogel materials.
Vanillin modified chitosan-SiO2The composite aerogel material is obtained by modifying chitosan through vanillin to obtain vanillin-modified chitosan and then dissolving a silicon source precursor in the vanillin-modified chitosan.
In the invention, the precursor of the silicon source is silicate ester, preferably methyl silicate, ethyl silicate, isopropyl orthosilicate and butyl orthosilicate; more preferably, tetraethoxysilane.
According to a second embodiment of the present invention, there is provided a method for preparing vanillin-modified chitosan-SiO2Methods of compounding aerogel materials.
Preparation of vanillin modified chitosan-SiO2A method of compounding an aerogel material, the method comprising the steps of:
1) adding chitosan into vanillin, heating and refluxing to obtain vanillin-modified chitosan;
2) adding a silicon source precursor into vanillin-modified chitosan, stirring, standing for gelation, and washing; obtaining vanillin modified chitosan-SiO2And (5) preparing a crude product of the composite aerogel material.
Preferably, the method further comprises:
3) the vanillin modification chitosan-SiO obtained in the step 2)2Soaking and washing a crude product of the composite aerogel material in a normal hexane solution containing trimethylchlorosilane; obtaining vanillin modified chitosan-SiO2Compounding aerogel materials.
In the invention, the step 1) is specifically as follows: adding chitosan into an organic solvent, soaking at constant temperature, swelling, filtering and cleaning, adding the swollen chitosan into the organic solvent containing vanillin, heating and refluxing, carrying out suction filtration to obtain a product after reaction, washing and drying to obtain vanillin-modified chitosan.
In the invention, the step 2) is specifically as follows: dissolving vanillin-modified chitosan in hydrochloric acid solution, and stirring at room temperature; uniformly mixing ethyl orthosilicate and ethanol, adding the mixture into a vanillin-modified chitosan solution, and stirring; adding HF solution, stirring, standing for gelation, and aging; soaking and washing the aged gel in distilled water, soaking and washing in ethanol, soaking and washing with n-hexane, and drying to obtain vanillin modified chitosan-SiO2And (5) preparing a crude product of the composite aerogel material.
In the invention, the step 3) is specifically as follows: the furfural obtained in the step 2) is modified by chitosan-SiO2Soaking the crude product of the composite aerogel material in a normal hexane solution containing trimethylchlorosilane, soaking in the normal hexane solution for washing, and drying to obtain the vanillin modified chitosan-SiO2Compounding aerogel materials.
In the present invention, the organic solvent in step 1) is an alcohol solution, preferably one or both of methanol and ethanol. The mass ratio of the chitosan to the vanillin in the step 1) is 1:1-10, preferably 1:1.2-6, and more preferably 1: 1.5-4. The temperature of the constant-temperature soaking in the step 1) is 15-90 ℃, preferably 20-80 ℃, and more preferably 25-70 ℃. The soaking time at constant temperature is 0.5-48h, preferably 1-36h, more preferably 2-24 h. The cleaning in the step 1) is performed by using an alcoholic solution, preferably an alcoholic solution. The temperature of the addition reflux in step 1) is 55 to 100 ℃, preferably 60 to 90 ℃, more preferably 65 to 80 ℃. The washing in the step 1) is performed by using an alcoholic solution, and preferably by using an ethanol solution.
In the present invention, the concentration of the hydrochloric acid solution in the step 2) is 0.05 to 1.0mol/L, preferably 0.1 to 0.8mol/L, and more preferably 0.15 to 0.5 mol/L. Mixing ethyl orthosilicate and ethanol, wherein the mass ratio of the ethyl orthosilicate to the ethanol is 1-5:1, preferably 1.2-3:1, and more preferably 1.5-2: 1. The mass ratio of the vanillin-modified chitosan to the tetraethoxysilane is 1:15-100, preferably 1:20-90, and more preferably 1: 25-80. The stirring time is 2-48h, preferably 6-36h, more preferably 12-24 h. The HF solution is added in a mass concentration of 1 to 40%, preferably 3 to 20%, more preferably 5 to 10%. The mass ratio of the added HF solution to the tetraethoxysilane is 1:100-1000, preferably 1:200-800, and more preferably 1: 400-600. The soaking and washing time is 2-72h, preferably 6-48h, and more preferably 12-36 h.
In the invention, the volume concentration of the trimethylchlorosilane in the normal hexane solution containing the trimethylchlorosilane in the step 3) is 1-20%, preferably 3-15%, and more preferably 5-10%. The soaking and washing time is 2-72h, preferably 6-48h, and more preferably 12-36 h.
According to a third embodiment provided by the present invention, there is provided a vanillin-modified chitosan-SiO2Application of the composite aerogel material.
Vanillin modified chitosan-SiO2Use of a composite aerogel material prepared by modifying the vanillin-modified chitosan-SiO of the first embodiment2A composite aerogel material, or a vanillin-modified chitosan-SiO prepared by the method of the second embodiment2The composite aerogel material is used in cigarette filter sticks.
Preferably, the particle size of the material is 20 to 100 mesh, preferably 30 to 80 mesh, more preferably 40 to 60 mesh.
Preferably, the addition amount of the material added into each cigarette filter stick is 1-20mg, preferably 3-18mg, and more preferably 5-15 mg.
Example 1
Preparation of Vanillin-modified Chitosan-SiO2A method of compounding an aerogel material, the method comprising the steps of:
1) soaking 3g of 14cps chitosan with deacetylation degree of 96.1% in ethanol, heating at 70 deg.C for swelling for 2h, filtering, washing, adding into 100ml ethanol, adding 6g vanillin, stirring, heating and refluxing for 12 h; filtering to obtain yellow product, washing, and drying at 50 deg.C under constant pressure and constant temperature to obtain vanillin modified chitosan;
2) dissolving 3g of the vanillin modified chitosan in 400ml of hydrochloric acid solution with the concentration of 0.15mol/L, and uniformly stirring to mark as solution A; uniformly mixing 126ml of ethyl orthosilicate and 100ml of absolute ethyl alcohol, and marking as a solution B; mixing the solution B and the solution A, stirring for 24 hours, marking as a solution C, gradually hydrolyzing ethyl orthosilicate in an acidic solution, and gradually mixing the two phases of the solution into a phase;
and dropwise adding 25ml of 1% HF solution into the solution C, stirring for 1h to uniformly mix the solution, standing for gelation, and aging for 24h to form stable gel. Soaking and washing the gel in distilled water twice, washing with ethanol three times, and washing with n-hexane three times, wherein the soaking time is 24h each time; and (5) drying.
Referring to the drawings, FIG. 1 shows vanillin-modified chitosan-SiO prepared in example 12Aerogel infrared absorption spectrum, 3436cm as seen from the figure-1Vicinities are-OH and-NH21647cm of telescopic vibration overlapped absorption peak-1Near the peak, C-N expansion and contraction vibration absorption peak, 1386cm-1The vicinity is-CH in chitosan3Symmetric deformation vibration absorption peak, 1084cm-1Nearby is C-O stretching vibration absorption peak of 965cm-1The vicinity thereof was a bending vibration absorption peak of Si-OH, 797cm-1And the Si-O bond symmetric stretching vibration absorption peak is nearby, which indicates that the material is successfully compounded.
The material is analyzed by nitrogen adsorption and desorption, and the specific surface area is 735.75m2(g) an average pore diameter of 3.23nm, an average particle diameter of 8.15nm and a pore volume of 0.59m3/g。
The obtained aerogel material is crushed, the material with the grain diameter of 40-60 meshes is selected and added into a cigarette filter, the addition amount of each cigarette is 12mg, and the result of a smoking test shows that the prepared adsorbing material can reduce the content of crotonaldehyde in mainstream smoke by 23.24 percent, and the result is shown in Table 1.
TABLE 1 test materials test results
The control sample is a cigarette without material additives, and is characterized in that the filter tip is processed into two sections of unitary filter tips, wherein the filter tip is 15mm close to the mouth end and 10mm close to the tobacco shred end; the experimental sample is a cigarette containing a material additive in a manner of being sandwiched between two sections of filter tips. Example 2
Preparation of Vanillin-modified Chitosan-SiO2A method of compounding an aerogel material, the method comprising the steps of:
1) soaking 6g of 14cps chitosan with deacetylation degree of 96.1% in ethanol, swelling at room temperature for 24h, filtering, washing, adding into 120ml ethanol, adding 18g vanillin, stirring, heating and refluxing for 12 h; filtering to obtain yellow product, washing, and drying at 50 deg.C under constant pressure and constant temperature to obtain vanillin modified chitosan;
2) dissolving 6g of the vanillin modified chitosan in 400ml of hydrochloric acid solution with the concentration of 0.15mol/L, and uniformly stirring to mark as solution A; uniformly mixing 126ml of ethyl orthosilicate and 100ml of absolute ethyl alcohol, and marking as a solution B; mixing the solution B and the solution A, stirring for 24 hours, marking as a solution C, gradually hydrolyzing ethyl orthosilicate in an acidic solution, and gradually mixing the two phases of the solution into a phase;
and dropwise adding 25ml of 1% HF solution into the solution C, stirring for 1h to uniformly mix the solution, standing for gelation, and aging for 24h to form stable gel. Soaking and washing the gel in distilled water twice, washing with ethanol three times, and washing with n-hexane three times, wherein the soaking time is 24h each time;
3) then, soaking the gel into a normal hexane solution containing 7.5% (v/v) of trimethylchlorosilane for surface modification, and repeating the steps for three times for 24 hours each time; soaking the modified gel into n-hexane solution for washing three times, and washing for 24 hours each time; and (5) drying.
Referring to the drawings, FIG. 2 is an infrared absorption spectrum, 3436cm, of the hydrophobic composite aerogel prepared in example 2-1Vicinities are-OH and NH22967cm superimposed absorption peak of stretching vibration-1The vicinity is C-H stretching vibration peak, 1628cm-1Near C ═ N stretching vibration absorption peak, 1513cm-1The vicinity is a characteristic peak of benzene ring, 1088cm-1Near C-O expansionThe enhancement of the shock absorption peak, C-H shock absorption peak, indicates that the hydrophobic treatment is effective. FIG. 3 is a scanning electron micrograph of the hydrophobic composite aerogel prepared in example 2, from which it can be seen that the material has a loose porous structure.
The material is analyzed by nitrogen adsorption and desorption, and the specific surface area is 718.56m2Per g, average pore diameter of 4.17nm, average particle diameter of 8.35nm, and pore volume of 0.75m3/g。
The obtained aerogel material is crushed, the material with the grain diameter of 40-60 meshes is selected and added into a cigarette filter, the addition amount of each cigarette is 12mg, and the result of a smoking test shows that the prepared adsorbing material can reduce the content of crotonaldehyde in mainstream smoke by 19.54 percent, and the result is shown in Table 2.
TABLE 2 test results of the test materials
The control sample is a cigarette without material additives, and is characterized in that the filter tip is processed into two sections of unitary filter tips, wherein the filter tip is 15mm close to the mouth end and 10mm close to the tobacco shred end; the experimental sample is a cigarette containing a material additive in a manner of being sandwiched between two sections of filter tips.
Example 3
Preparation of Vanillin-modified Chitosan-SiO2A method of compounding an aerogel material, the method comprising the steps of:
1) soaking 3g of chitosan with 37cps and deacetylation degree of 95.7% in ethanol, heating at 70 deg.C for swelling for 6h, filtering, washing, adding into 100ml ethanol, adding 6g vanillin, stirring, heating and refluxing for 12 h; filtering to obtain yellow product, washing, and drying at 50 deg.C under constant pressure and constant temperature to obtain vanillin modified chitosan;
2) dissolving 3g of the vanillin modified chitosan in 400ml of hydrochloric acid solution with the concentration of 0.15mol/L, and uniformly stirring to mark as solution A; uniformly mixing 126ml of ethyl orthosilicate and 100ml of absolute ethyl alcohol, and marking as a solution B; and mixing the solution B and the solution A, marking as solution C, stirring for 24h, gradually hydrolyzing the tetraethoxysilane in the acidic solution, and gradually mixing the two phases of the solution into one phase.
And dropwise adding 25ml of 1% HF solution into the solution C, stirring for 1h to uniformly mix the solution, standing for gelation, and aging for 24h to form stable gel. Soaking and washing the gel in distilled water twice, washing with ethanol three times, and washing with n-hexane three times, wherein the soaking time is 24h each time;
3) then, soaking the gel into a normal hexane solution containing 7.5% (v/v) of trimethylchlorosilane for surface modification, and repeating the steps for three times for 24 hours each time; soaking the modified gel into n-hexane solution for washing three times, and washing for 24 hours each time; and (5) drying.
The material is analyzed by nitrogen adsorption and desorption, and the specific surface area is 554.99m2(g) an average pore diameter of 3.21nm, an average particle diameter of 10.8nm and a pore volume of 0.45m3/g。
The obtained aerogel material is crushed, the material with the grain diameter of 40-60 meshes is selected and added into a cigarette filter, the addition amount of each cigarette is 12mg, and a smoking test result shows that the prepared adsorbing material can reduce the content of crotonaldehyde in mainstream smoke by 38.67 percent, and the result is shown in Table 3.
TABLE 3 test materials test results
The control sample is a cigarette without material additives, and is characterized in that the filter tip is processed into two sections of unitary filter tips, wherein the filter tip is 15mm close to the mouth end and 10mm close to the tobacco shred end; the experimental sample is a cigarette containing a material additive in a manner of being sandwiched between two sections of filter tips.
Example 4
Example 2 was repeated, except that the temperature of the soaking at constant temperature in step 1) was 50 ℃. The soaking time at constant temperature is 12 h. The temperature of the addition reflux in step 1) was 70 ℃.
Example 5
Example 3 was repeated except that the hydrochloric acid solution in step 2) had a concentration of 0.3 mol/L. Mixing ethyl orthosilicate and ethanol, wherein the mass ratio of the ethyl orthosilicate to the ethanol is 3: 1. The mass ratio of the vanillin-modified chitosan to the tetraethoxysilane is 1: 50. The stirring time was 18 h. The concentration of the added HF solution was 8%. The mass ratio of the added HF solution to the tetraethoxysilane is 1: 500. The time for soaking and washing is 30 h.
Example 6
Example 3 was repeated, except that the volume concentration of trimethylchlorosilane in the trimethylchlorosilane-containing n-hexane solution of step 3) was 8%. The time for soaking and washing is 30 h.
Claims (24)
1. Preparation of vanillin modified chitosan-SiO2A method of compounding an aerogel material, the method comprising the steps of:
1) adding chitosan into vanillin, heating and refluxing to obtain vanillin-modified chitosan;
2) dissolving vanillin-modified chitosan in hydrochloric acid solution, then uniformly mixing ethyl orthosilicate and ethanol, adding the mixture into the vanillin-modified chitosan solution, stirring, standing for gelation, and washing; obtaining vanillin modified chitosan-SiO2A composite aerogel material crude product;
3) the vanillin modification chitosan-SiO obtained in the step 2)2Soaking and washing a crude product of the composite aerogel material in a normal hexane solution containing trimethylchlorosilane; obtaining vanillin modified chitosan-SiO2Compounding aerogel materials.
2. The method of claim 1, wherein: the step 1) is specifically as follows: adding chitosan into an organic solvent, soaking at constant temperature, filtering and cleaning after swelling, adding the swollen chitosan into the organic solvent containing vanillin, heating and refluxing, performing suction filtration to obtain a product after reaction, washing and drying to obtain vanillin-modified chitosan; and/or
The step 2) is specifically as follows: dissolving vanillin-modified chitosan in hydrochloric acid solution, and stirring at room temperature; uniformly mixing ethyl orthosilicate and ethanol, adding the mixture into a vanillin-modified chitosan solution, and stirring; adding HF solution, stirring, standing for gelation, and aging; soaking and washing the aged gel in distilled waterWashing, soaking in ethanol for washing, soaking in n-hexane for washing, and drying to obtain vanillin modified chitosan-SiO2And (5) preparing a crude product of the composite aerogel material.
3. The method according to claim 1 or 2, characterized in that: the step 3) is specifically as follows: the vanillin modification chitosan-SiO obtained in the step 2)2Soaking the crude product of the composite aerogel material in a normal hexane solution containing trimethylchlorosilane, soaking in the normal hexane solution for washing, and drying to obtain the vanillin modified chitosan-SiO2Compounding aerogel materials.
4. The method of claim 2, wherein: the organic solvent in the step 1) is an alcoholic solution; in the step 1), the mass ratio of the chitosan to the vanillin is 1: 1-10; the temperature of the constant-temperature soaking in the step 1) is 15-90 ℃; soaking at constant temperature for 0.5-48 h; cleaning with an alcoholic solution in the step 1); the temperature of the heating reflux in the step 1) is 55-100 ℃; the washing in step 1) is performed by using an alcoholic solution.
5. The method of claim 3, wherein: the organic solvent in the step 1) is an alcoholic solution; in the step 1), the mass ratio of the chitosan to the vanillin is 1: 1-10; the temperature for soaking at constant temperature in the step 1) is 15-90 ℃; soaking at constant temperature for 0.5-48 h; cleaning with an alcoholic solution in the step 1); the temperature of the heating reflux in the step 1) is 55-100 ℃; the washing in step 1) is performed by using an alcoholic solution.
6. The method according to claim 4 or 5, characterized in that: the organic solvent in the step 1) is one or two of methanol and ethanol; in the step 1), the mass ratio of the chitosan to the vanillin is 1: 1.2-6; the temperature for soaking at constant temperature in the step 1) is 20-80 ℃; soaking at constant temperature for 1-36 h; cleaning with an ethanol solution in the step 1); the temperature of the heating reflux in the step 1) is 60-90 ℃; washing in the step 1) is carried out by adopting an ethanol solution.
7. The method of claim 6, wherein: in the step 1), the mass ratio of the chitosan to the vanillin is 1: 1.5-4; the temperature for soaking at constant temperature in the step 1) is 25-70 ℃; soaking at constant temperature for 2-24 h; the temperature of the heating reflux in the step 1) is 65-80 ℃.
8. The method according to any one of claims 2, 4-5, 7, wherein: the concentration of the hydrochloric acid solution in the step 2) is 0.05-1.0 mol/L; mixing ethyl orthosilicate and ethanol, wherein the mass ratio of the ethyl orthosilicate to the ethanol is 1-5: 1; the mass ratio of the vanillin-modified chitosan to the tetraethoxysilane is 1: 15-100; stirring for 2-48 h; the mass concentration of the added HF solution is 1-40%; the mass ratio of the added HF solution to the tetraethoxysilane is 1: 100-1000; the time for soaking and washing is 2-72 h.
9. The method of claim 3, wherein: the concentration of the hydrochloric acid solution in the step 2) is 0.05-1.0 mol/L; mixing ethyl orthosilicate and ethanol, wherein the mass ratio of the ethyl orthosilicate to the ethanol is 1-5: 1; the mass ratio of the vanillin-modified chitosan to the tetraethoxysilane is 1: 15-100; stirring for 2-48 h; the mass concentration of the added HF solution is 1-40%; the mass ratio of the added HF solution to the tetraethoxysilane is 1: 100-1000; the time for soaking and washing is 2-72 h.
10. The method of claim 8, wherein: the concentration of the hydrochloric acid solution in the step 2) is 0.1-0.8 mol/L; mixing ethyl orthosilicate and ethanol, wherein the mass ratio of the ethyl orthosilicate to the ethanol is 1.2-3: 1; the mass ratio of the vanillin-modified chitosan to the tetraethoxysilane is 1: 20-90; stirring for 6-36 h; the mass concentration of the added HF solution is 3-20%; the mass ratio of the added HF solution to the tetraethoxysilane is 1: 200-800; the time for soaking and washing is 6-48 h.
11. The method of claim 9, wherein: the concentration of the hydrochloric acid solution in the step 2) is 0.1-0.8 mol/L; mixing ethyl orthosilicate and ethanol, wherein the mass ratio of the ethyl orthosilicate to the ethanol is 1.2-3: 1; the mass ratio of the vanillin-modified chitosan to the tetraethoxysilane is 1: 20-90; stirring for 6-36 h; the mass concentration of the added HF solution is 3-20%; the mass ratio of the added HF solution to the tetraethoxysilane is 1: 200-800; the time for soaking and washing is 6-48 h.
12. The method according to claim 10 or 11, characterized in that: the concentration of the hydrochloric acid solution in the step 2) is 0.15-0.5 mol/L; mixing ethyl orthosilicate and ethanol, wherein the mass ratio of the ethyl orthosilicate to the ethanol is 1.5-2: 1; the mass ratio of the vanillin-modified chitosan to the tetraethoxysilane is 1: 25-80; stirring for 12-24 h; the mass concentration of the added HF solution is 5-10%; the mass ratio of the added HF solution to the tetraethoxysilane is 1: 400-600; the time for soaking and washing is 12-36 h.
13. The method according to any one of claims 5, 9, 11, wherein: in the step 3), the volume concentration of the trimethylchlorosilane in the normal hexane solution containing the trimethylchlorosilane is 1-20%; the time for soaking and washing is 2-72 h.
14. The method of claim 3, wherein: in the step 3), the volume concentration of the trimethylchlorosilane in the normal hexane solution containing the trimethylchlorosilane is 1-20%; the time for soaking and washing is 2-72 h.
15. The method of claim 13, wherein: in the step 3), the volume concentration of the trimethylchlorosilane in the normal hexane solution containing the trimethylchlorosilane is 3-15%; the time for soaking and washing is 6-48 h.
16. The method of claim 14, wherein: in the step 3), the volume concentration of the trimethylchlorosilane in the normal hexane solution containing the trimethylchlorosilane is 3-15%; the time for soaking and washing is 6-48 h.
17. The method according to claim 15 or 16, characterized in that: in the step 3), the volume concentration of the trimethylchlorosilane in the normal hexane solution containing the trimethylchlorosilane is 5-10 percent; the time for soaking and washing is 12-36 h.
18. The vanillin-modified chitosan-SiO prepared according to the method of any one of claims 1-172The composite aerogel material is characterized in that: the material is obtained by modifying chitosan through vanillin to obtain vanillin-modified chitosan and then dissolving a silicon source precursor in the vanillin-modified chitosan.
19. The material of claim 18, wherein: the precursor of the silicon source is silicate ester.
20. The material of claim 19, wherein: the precursor of the silicon source is methyl silicate, ethyl silicate, isopropyl orthosilicate and butyl orthosilicate.
21. The material of claim 20, wherein: the precursor of the silicon source is tetraethoxysilane.
22. The vanillin-modified chitosan-SiO prepared according to the method of any one of claims 1 to 172Use of a composite aerogel material, characterized in that: the vanillin-modified chitosan-SiO prepared according to the method of any one of claims 1 to 172The composite aerogel material is used in the cigarette filter stick; the particle size of the material is 20-100 meshes; the additive amount of the material added into each cigarette filter stick is 1-20 mg.
23. The vanillin-modified chitosan-SiO of claim 222Use of a composite aerogel material, characterized in that: granules of said materialThe diameter is 30-80 meshes; the additive amount of the material added into each cigarette filter stick is 3-18 mg.
24. The vanillin-modified chitosan-SiO of claim 232Use of a composite aerogel material, characterized in that: the particle size of the material is 40-60 meshes; the additive amount of the material added into each cigarette filter stick is 5-15 mg.
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| CN110961088B (en) * | 2019-12-16 | 2022-06-28 | 浙江中烟工业有限责任公司 | On-line trapping method for aldehydic acid substances in dried tobacco escaping substances |
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| CN114307967A (en) * | 2020-09-30 | 2022-04-12 | 湖南中烟工业有限责任公司 | Organic-inorganic composite aerogel for reducing phenolic ketone harmful substances in mainstream smoke and preparation and application thereof |
| CN114307953B (en) * | 2020-09-30 | 2024-03-08 | 湖南中烟工业有限责任公司 | Silica/carbon composite aerogel for reducing harmful substances in flue gas and preparation and application thereof |
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| CN112915103B (en) * | 2021-01-27 | 2023-03-24 | 仲恺农业工程学院 | Vanillin modified chitosan Schiff base chelated zinc sustained release agent as well as preparation method and application thereof |
| CN113735556B (en) * | 2021-08-13 | 2022-12-20 | 红塔烟草(集团)有限责任公司 | Silicon-containing aerogel composite material and preparation method and application thereof |
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| US20070154698A1 (en) * | 2005-12-30 | 2007-07-05 | Aspen Aerogels, Inc. | Highly flexible aerogel insulated textile-like blankets |
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| US7122122B2 (en) * | 2003-07-22 | 2006-10-17 | Kraft Foods Holdings, Inc. | Molecular imprinting of solute on cellulose/silica composite, and products and uses thereof |
| CN104140553A (en) * | 2014-07-18 | 2014-11-12 | 天津大学 | Hydrophobic chitosan-silicon dioxide composite aerogel and preparation method and oil absorption application thereof |
| CN104194066A (en) * | 2014-09-15 | 2014-12-10 | 中国科学院上海硅酸盐研究所 | Silicon oxide-chitosan composite aerogel and preparation method thereof |
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| "烟用改性壳聚糖的制备及其降苯酚效果";胡少东等;《食品与机械》;20170630;第33卷(第6期);摘要，第1.2.1节 * |
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