CN107715852A - Vanillic aldehyde modification of chitosan SiO2Aerogel composite and its production and use - Google Patents
Vanillic aldehyde modification of chitosan SiO2Aerogel composite and its production and use Download PDFInfo
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- CN107715852A CN107715852A CN201711065304.6A CN201711065304A CN107715852A CN 107715852 A CN107715852 A CN 107715852A CN 201711065304 A CN201711065304 A CN 201711065304A CN 107715852 A CN107715852 A CN 107715852A
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- chitosan
- vanillic aldehyde
- sio
- modification
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- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 230000004048 modification Effects 0.000 title claims abstract description 84
- 238000012986 modification Methods 0.000 title claims abstract description 84
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 239000004964 aerogel Substances 0.000 claims abstract description 63
- 239000000463 material Substances 0.000 claims abstract description 51
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 44
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 44
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 44
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 44
- 235000019504 cigarettes Nutrition 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 76
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 72
- 238000005406 washing Methods 0.000 claims description 36
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 238000002791 soaking Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 230000001476 alcoholic effect Effects 0.000 claims description 9
- 238000007654 immersion Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 230000008961 swelling Effects 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 241001502050 Acis Species 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 3
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 claims 1
- 239000000779 smoke Substances 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 5
- 230000002209 hydrophobic effect Effects 0.000 abstract description 4
- 230000001473 noxious effect Effects 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 66
- 235000019441 ethanol Nutrition 0.000 description 32
- 238000012360 testing method Methods 0.000 description 14
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 11
- 241000208125 Nicotiana Species 0.000 description 9
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 230000006196 deacetylation Effects 0.000 description 7
- 238000003381 deacetylation reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 4
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000004566 IR spectroscopy Methods 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000013068 control sample Substances 0.000 description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 229920002101 Chitin Polymers 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- IWICDTXLJDCAMR-UHFFFAOYSA-N trihydroxy(propan-2-yloxy)silane Chemical compound CC(C)O[Si](O)(O)O IWICDTXLJDCAMR-UHFFFAOYSA-N 0.000 description 2
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229960002715 nicotine Drugs 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- -1 printing and dyeing Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 235000019505 tobacco product Nutrition 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides a kind of vanillic aldehyde modification of chitosan SiO2The preparation method of aerogel composite and its cigarette smoke absorption in apply, by chitosan carry out it is amino modified after, silicon source presoma is hydrolyzed in the acid solution of modification of chitosan, is condensed, stand gel, gel is dried after aging, exchange of solvent, hydrophilic composite material is obtained, gel progress surface modification, obtains hydrophobic composites after drying, the aerogel material obtained after drying carries out cigarette smoke noxious substance.The vanillic aldehyde modification of chitosan SiO of the present invention2Aerogel composite is strong for the noxious substance ability in cigarette smoke, and selectivity is high；The method of the present invention makes simply, and production cost is low, and security performance is high.
Description
Technical field
The present invention relates to a kind of aerogel composite and its production and use, and in particular to a kind of vanillic aldehyde is modified
Chitosan-SiO2Aerogel composite and preparation method and its adsorption applications in cigarette smoke；Belong to composite aerogel
Material frontier.
Background technology
As China adds《The international Framework Convention on Tobacco Control》, tobacco product composition is limited, while people
Living standard improves constantly, and people are more and more stronger to the security and environmental protection consciousness of smoking, and reducing tar and reducing harm is imperative, because
Nuisance Quality Research and reducing tar and reducing harm technology turn into the focus of people's research in this cigarette；Apply the special filter of additive
Mouth, it has also become one of important technical of Tar；Xie Xiaotian etc. (is thanked and is laughed at day nano adsorbers in reducing cigarette tar and reducing
In application study [J] Yunnan chemicals, 2002, (3), 1-3) be prepared for there is filtering and absorption property to receive tarry matters in smoke
Ground rice end, is applied on acetate silk, tar-reducing filter rod is made, dosage is 16-18mg/ branch, and tar reduction effect can reach
4.4mg/ branch.But after the tar content of cigarette is reduced to certain level, the fragrance of flue gas can be greatly affected, thus
Constrain application of the reducing tar and reducing harm technology in actual production process.
Chitosan is to be obtained by chitin by deacetylation, and chitin is a kind of natural polymer, nature content
Abundant, and chitosan has good a biocompatibility and microbic resolvability, intramolecular is deposited due to hydroxyl and amino
A variety of chemical modifications can be being carried out, so as to obtain many useful novel substances.In the process of a large amount of basic and applied research
In, chitosan is applied in the multiple fields such as weaving, cosmetics, printing and dyeing, medicine, food, environmental protection.Pure chitosan is
The sheet or powdery solid of a kind of white or the chitosan transparent of canescence half, tasteless, odorless, non-toxic, pure chitosan is slightly precious
Pearly-lustre pool.
SiO2Aeroge is a kind of low density porous property solid material with nanostructured, and foreign countries are referred to as " frost smoke ".
Because it has the performances such as high porosity and high-specific surface area and low-density, have a extensive future, can such as be used as catalyst
Carrier, acoustic impedance coupling material, transparent heat-insulated material and sorbing material etc..SiO at present2The preparation of aeroge is frequently with overcritical
Method is dried, and its equipment is complicated, and production cost is high, dangerous high, therefore, aerogel material prepared by constant pressure and dry, can be dropped
Low dangerous and production cost, and in SiO2Vanillic aldehyde modification of chitosan is added in aerogel material, it can be improved and rolled up
The absorption property of harmful substance in cigarette main flume, can also strengthen its adsorptive selectivity.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of vanillic aldehyde modification of chitosan-SiO2Aerogel composite
And its production and use, vanillic aldehyde modification of chitosan-SiO of the invention2Aerogel composite is in cigarette smoke
Noxious substance ability it is strong, selectivity is high；The method of the present invention makes simply, and production cost is low, and security performance is high.
The invention provides a kind of vanillic aldehyde modification of chitosan-SiO2The preparation method of aerogel composite and its rolling up
Cigarette flue gas absorption in apply, by chitosan carry out it is amino modified after, acid solution reclaimed water of the silicon source presoma in modification of chitosan
Solution, condensation, stand gel, and gel is dried after aging, exchange of solvent, obtain hydrophilic composite material, and gel carries out table
Face modification, hydrophobic composites are obtained after drying, the aerogel material obtained after drying carries out cigarette smoke harmful substance suction
Attached aptitude tests.
According to the first embodiment provided by the invention, there is provided a kind of vanillic aldehyde modification of chitosan-SiO2Compound airsetting
Glue material.
A kind of vanillic aldehyde modification of chitosan-SiO2Aerogel composite, the material are that chitosan is carried out by vanillic aldehyde
It is modified, the chitosan that vanillic aldehyde is modified is obtained, then silicon source presoma is dissolved in the chitosan of vanillic aldehyde modification and obtained
's.
In the present invention, the silicon source presoma is esters of silicon acis, preferably methyl silicate, silester, positive silicic acid isopropyl
Ester, butyl silicate；More preferably tetraethyl orthosilicate.
According to second of embodiment provided by the invention, there is provided one kind prepares vanillic aldehyde modification of chitosan-SiO2It is compound
The method of aerogel material.
One kind prepares vanillic aldehyde modification of chitosan-SiO2The method of aerogel composite, this method comprise the following steps：
1) add chitosan into vanillic aldehyde, be heated to reflux, obtain the chitosan of vanillic aldehyde modification；
2) silicon source presoma is added in the chitosan that vanillic aldehyde is modified, stirring, stands gel, washing；Obtain vanillic aldehyde
Modification of chitosan-SiO2Aerogel composite crude product.
Preferably, this method also includes：
3) the vanillic aldehyde modification of chitosan-SiO for obtaining step 2)2Aerogel composite crude product is in chlorine containing trimethyl
Soak, wash in the hexane solution of silane；Obtain vanillic aldehyde modification of chitosan-SiO2Aerogel composite.
In the present invention, step 1) is specially：Add chitosan into constant temperature in organic solvent to soak, filtering is crossed after swelling
Wash, the chitosan of swelling is added in the organic solvent containing vanillic aldehyde, is heated to reflux, product is filtered out after reaction, wash,
The chitosan of vanillic aldehyde modification is obtained after drying.
In the present invention, step 2) is specially：The chitosan that vanillic aldehyde is modified is dissolved in hydrochloric acid solution, is stirred at room temperature
Uniformly；Tetraethyl orthosilicate and ethanol are well mixed, are added in the chitosan solution of vanillic aldehyde modification, stirring；It is molten to add HF
Liquid, stir, stand gel, aging；Gel after aging is put into washing by soaking in distilled water, then immerses in ethanol and soaks
Washing, then using n-hexane washing by soaking, dry, obtain vanillic aldehyde modification of chitosan-SiO2Aerogel composite is slightly produced
Product.
In the present invention, step 3) is specially：Oxalaldehyde modification of chitosan-the SiO that step 2) is obtained2Composite aerogel material
Material crude product is soaked in the hexane solution containing trim,ethylchlorosilane, then immerses washing by soaking in hexane solution, is dried, is obtained
Obtain vanillic aldehyde modification of chitosan-SiO2Aerogel composite.
In the present invention, the organic solvent described in step 1) is alcoholic solution, preferably one kind or two in methanol, ethanol
Kind.Chitosan and vanillic aldehyde mass ratio are 1 in step 1):1-10, preferably 1:1.2-6 more preferably 1:1.5-4.Step 1)
Described in constant temperature immersion temperature be 15-90 DEG C, preferably 20-80 DEG C, more preferably 25-70 DEG C.Constant temperature immersion time be
0.5-48h, preferably 1-36h, more preferably 2-24h.Cleaning is cleaned using alcoholic solution described in step 1), it is preferred to use ethanol
Solution cleans.The temperature that backflow is added described in step 1) is 55-100 DEG C, preferably 60-90 DEG C, more preferably 65-80 DEG C.
Washing is washed using alcoholic solution described in step 1), it is preferred to use ethanol solution cleans.
In the present invention, the concentration of hydrochloric acid solution described in step 2) is 0.05-1.0mol/L, preferably 0.1-
0.8mol/L, more preferably 0.15-0.5mol/L.The mass ratio of tetraethyl orthosilicate and ethanol mixing, tetraethyl orthosilicate and ethanol
For 1-5:1, preferably 1.2-3:1, more preferably 1.5-2:1.The chitosan and the mass ratio of tetraethyl orthosilicate that vanillic aldehyde is modified
For 1:15-100, preferably 1:20-90, more preferably 1:25-80.Mixing time is 2-48h, preferably 6-36h, more preferably
12-24h.The mass concentration of the HF solution of addition is 1-40%, preferably 3-20%, more preferably 5-10%.The HF of addition is molten
Liquid and tetraethyl orthosilicate mass ratio are 1:100-1000, preferably 1:200-800, more preferably 1:400-600.The immersion is washed
The time washed is 2-72h, preferably 6-48h, more preferably 12-36h.
In the present invention, in the hexane solution containing trim,ethylchlorosilane described in step 3), the volume of trim,ethylchlorosilane
Concentration is 1%-20%, preferably 3%-15%, more preferably 5%-10%.The time of the washing by soaking is 2-72h, preferably
For 6-48h, more preferably 12-36h.
According to the third embodiment provided by the invention, there is provided prepare vanillic aldehyde modification of chitosan-SiO by above-mentioned2
Vanillic aldehyde modification of chitosan-the SiO that the method for aerogel composite is obtained2Aerogel composite.
According to the 4th kind of embodiment provided by the invention, there is provided a kind of vanillic aldehyde modification of chitosan-SiO2Compound airsetting
The application of glue material.
A kind of vanillic aldehyde modification of chitosan-SiO2The purposes of aerogel composite, by described in the first embodiment
Vanillic aldehyde modification of chitosan-SiO2Aerogel composite, or vanillic aldehyde prepared by second of embodiment methods described
Modification of chitosan-SiO2Aerogel composite, in cigarette filter rod.
Preferably, the particle diameter of the material is 20-100 mesh, preferably 30-80 mesh, more preferably 40-60 mesh.
Preferably, the addition that the material is added in every cigarette filter rod is 1-20mg, preferably 3-18mg, it is more excellent
Elect 5-15mg as.
In the present invention, all materials used are commercially available, without special requirement.Preferably, chitosan uses
Viscosity is 14cps, deacetylation 96.1%；Or chitosan uses viscosity as 37cps, deacetylation 95.7%；Or chitosan
Viscosity is used as 59cps, the one of which in deacetylation 85.7%.
Chitosan is modified by the present invention by vanillic aldehyde, improves the absorption property of chitosan.Contain in chitosan molecule
There is largely free-NH2With-OH, it is easy to be chemically reacted, introduces other functional groups, its application can be widened.This hair
Bright-the NH by dissociating in chitosan molecule2Reacted with-OH and vanillic aldehyde, can be very by this reacted compound
Harmful components in good absorption cigarette smoke.
In the present invention, add chitosan into constant temperature in organic solvent to soak, increase reaction contact area, make reaction more
Add fully.
In the present invention, the chitosan that vanillic aldehyde is modified is dissolved in hydrochloric acid solution, it is uniformly dispersed.Vanillic aldehyde changes
Property chitosan is soluble in acidic aqueous solution, while hydrochloric acid is the catalyst of teos hydrolysis, promotes positive silicic acid second
Ester hydrolysis.The present invention is dissolved in aqueous hydrochloric acid solution by vanillic aldehyde modification of chitosan, adds tetraethyl orthosilicate and ethanol mixes
After closing liquid, modified chitosan will not be precipitated, and the tetraethyl orthosilicate for starting to hydrolyze is well mixed, and formation is uniform after adding HF
Gel.
In the present invention, tetraethyl orthosilicate and ethanol are well mixed, are added in the chitosan solution of vanillic aldehyde modification,
Tetraethyl orthosilicate starts to hydrolyze, and generates silica sol.
In the present invention, HF solution is added, accelerates polycondensation reaction, reduces gel time.F-Size and OH-It is close, Er Qieneng
Reacted with Si, generation>The complex compound of 4 coordinations, and the gel that HF is done obtained by catalyst has many similar characteristics.
In the present invention, the gel after aging is put into washing by soaking in distilled water, removes hydrochloric acid and HF in gel；Soak again
Enter washing by soaking in ethanol, displace the water in gel；Then n-hexane washing by soaking is used, ethanol in gel is replaced, makes to coagulate
Solvent is dry after the low n-hexane for showing tension force in glue.Reduce capillarity in gel aperture, reduce aperture when drying and cave in
Effect.
In the present invention, by the oxalaldehyde modification of chitosan-SiO of acquisition2Aerogel composite crude product is containing trimethyl
Soaked in the hexane solution of chlorosilane, be as modifying agent, to gel of the n-hexane after washed using trim,ethylchlorosilane
Carry out surface modification.Modified gel is immersed into washing by soaking in hexane solution again, removed caused by modifying process
Dried after acid, obtain hydrophobic material.Research is to noxious substance performance in cigarette mainstream flue gas.Trim,ethylchlorosilane-
- the H in-OH bases in Cl substitution gel surfaces so that alcogel surface becomes-Si-O-Si (CH3)3Hydrophobic group, so as to reach
To surface modification effect.
In the present invention, dried composite is crushed, sieved, and is selected the material that particle diameter is 40-60 mesh and is added
Into cigarette filter, harmful matter in cigarette adsorption test is carried out.
The present invention prepares vanillic aldehyde modification of chitosan-SiO2Aerogel composite, the product can uniformly mix with pipe tobacco,
And pipe tobacco surface can be adhered to, and it can strengthen tensile strength, water resistance, bursting strength, it is non-breakable during processing, suitable for Modern High-Speed
Cigarette machine；The tobacco additive agent can significantly increase the combustibility of cigarette, have the work for reducing tobacco tar and nicotine content
With mitigating the miscellaneous gas of cigarette, harmful substances from flue gases is reduced, and inhaling taste is improved, and fragrance appears；Also cigarette can effectively be suppressed
Leaf mold becomes, and extends the holding time of tobacco.
Compared with prior art, technical scheme has following advantageous effects：
1st, vanillic aldehyde modification of chitosan-SiO of the invention2Aerogel composite has high-specific surface area, reachable
735.75m2/ g, there is preferable absorption property to part harmful substance in cigarette mainstream flue gas, it is reachable to crotonaldehyde reduced rate
38.67%；
2nd, preparation technology of the present invention is simple, less demanding to experiment condition；
Brief description of the drawings
Fig. 1 is the vanillic aldehyde modification of chitosan-SiO prepared in one embodiment of the invention 12Aeroge infrared absorption light
Spectrum；
Fig. 2 is the infrared absorption spectroscopy of the composite aerogel prepared in one embodiment of the invention 2；
Fig. 3 is the scanning electron microscope (SEM) photograph of the composite aerogel prepared in one embodiment of the invention 2.
Embodiment
According to the first embodiment provided by the invention, there is provided a kind of vanillic aldehyde modification of chitosan-SiO2Compound airsetting
Glue material.
A kind of vanillic aldehyde modification of chitosan-SiO2Aerogel composite, the material are that chitosan is carried out by vanillic aldehyde
It is modified, the chitosan that vanillic aldehyde is modified is obtained, then silicon source presoma is dissolved in the chitosan of vanillic aldehyde modification and obtained
's.
In the present invention, the silicon source presoma is esters of silicon acis, preferably methyl silicate, silester, positive silicic acid isopropyl
Ester, butyl silicate；More preferably tetraethyl orthosilicate.
According to second of embodiment provided by the invention, there is provided one kind prepares vanillic aldehyde modification of chitosan-SiO2It is compound
The method of aerogel material.
One kind prepares vanillic aldehyde modification of chitosan-SiO2The method of aerogel composite, this method comprise the following steps：
1) add chitosan into vanillic aldehyde, be heated to reflux, obtain the chitosan of vanillic aldehyde modification；
2) silicon source presoma is added in the chitosan that vanillic aldehyde is modified, stirring, stands gel, washing；Obtain vanillic aldehyde
Modification of chitosan-SiO2Aerogel composite crude product.
Preferably, this method also includes：
3) the vanillic aldehyde modification of chitosan-SiO for obtaining step 2)2Aerogel composite crude product is in chlorine containing trimethyl
Soak, wash in the hexane solution of silane；Obtain vanillic aldehyde modification of chitosan-SiO2Aerogel composite.
In the present invention, step 1) is specially：Add chitosan into constant temperature in organic solvent to soak, filtering is crossed after swelling
Wash, the chitosan of swelling is added in the organic solvent containing vanillic aldehyde, is heated to reflux, product is filtered out after reaction, wash,
The chitosan of vanillic aldehyde modification is obtained after drying.
In the present invention, step 2) is specially：The chitosan that vanillic aldehyde is modified is dissolved in hydrochloric acid solution, is stirred at room temperature
Uniformly；Tetraethyl orthosilicate and ethanol are well mixed, are added in the chitosan solution of vanillic aldehyde modification, stirring；It is molten to add HF
Liquid, stir, stand gel, aging；Gel after aging is put into washing by soaking in distilled water, then immerses in ethanol and soaks
Washing, then using n-hexane washing by soaking, dry, obtain vanillic aldehyde modification of chitosan-SiO2Aerogel composite is slightly produced
Product.
In the present invention, step 3) is specially：Oxalaldehyde modification of chitosan-the SiO that step 2) is obtained2Composite aerogel material
Material crude product is soaked in the hexane solution containing trim,ethylchlorosilane, then immerses washing by soaking in hexane solution, is dried, is obtained
Obtain vanillic aldehyde modification of chitosan-SiO2Aerogel composite.
In the present invention, the organic solvent described in step 1) is alcoholic solution, preferably one kind or two in methanol, ethanol
Kind.Chitosan and vanillic aldehyde mass ratio are 1 in step 1):1-10, preferably 1:1.2-6 more preferably 1:1.5-4.Step 1)
Described in constant temperature immersion temperature be 15-90 DEG C, preferably 20-80 DEG C, more preferably 25-70 DEG C.Constant temperature immersion time be
0.5-48h, preferably 1-36h, more preferably 2-24h.Cleaning is cleaned using alcoholic solution described in step 1), it is preferred to use ethanol
Solution cleans.The temperature that backflow is added described in step 1) is 55-100 DEG C, preferably 60-90 DEG C, more preferably 65-80 DEG C.
Washing is washed using alcoholic solution described in step 1), it is preferred to use ethanol solution cleans.
In the present invention, the concentration of hydrochloric acid solution described in step 2) is 0.05-1.0mol/L, preferably 0.1-
0.8mol/L, more preferably 0.15-0.5mol/L.The mass ratio of tetraethyl orthosilicate and ethanol mixing, tetraethyl orthosilicate and ethanol
For 1-5:1, preferably 1.2-3:1, more preferably 1.5-2:1.The chitosan and the mass ratio of tetraethyl orthosilicate that vanillic aldehyde is modified
For 1:15-100, preferably 1:20-90, more preferably 1:25-80.Mixing time is 2-48h, preferably 6-36h, more preferably
12-24h.The mass concentration of the HF solution of addition is 1-40%, preferably 3-20%, more preferably 5-10%.The HF of addition is molten
Liquid and tetraethyl orthosilicate mass ratio are 1:100-1000, preferably 1:200-800, more preferably 1:400-600.The immersion is washed
The time washed is 2-72h, preferably 6-48h, more preferably 12-36h.
In the present invention, in the hexane solution containing trim,ethylchlorosilane described in step 3), the volume of trim,ethylchlorosilane
Concentration is 1%-20%, preferably 3%-15%, more preferably 5%-10%.The time of the washing by soaking is 2-72h, preferably
For 6-48h, more preferably 12-36h.
According to the third embodiment provided by the invention, there is provided a kind of vanillic aldehyde modification of chitosan-SiO2Compound airsetting
The application of glue material.
A kind of vanillic aldehyde modification of chitosan-SiO2The purposes of aerogel composite, by described in the first embodiment
Vanillic aldehyde modification of chitosan-SiO2Aerogel composite, or vanillic aldehyde prepared by second of embodiment methods described
Modification of chitosan-SiO2Aerogel composite, in cigarette filter rod.
Preferably, the particle diameter of the material is 20-100 mesh, preferably 30-80 mesh, more preferably 40-60 mesh.
Preferably, the addition that the material is added in every cigarette filter rod is 1-20mg, preferably 3-18mg, it is more excellent
Elect 5-15mg as.
Embodiment 1
Prepare vanillic aldehyde modification of chitosan-SiO2The method of aerogel composite, this method comprise the following steps：
1) by 3g14cps, the chitosan that deacetylation is 96.1% is immersed in 70 DEG C of heating swelling 2h in ethanol, filter,
It is added to after washing in 100ml ethanol, adds 6g vanillic aldehydes, agitating and heating backflow 12h；Yellow product is filtered out, is washed, 50
DEG C normal pressure freeze-day with constant temperature obtains vanillic aldehyde modification of chitosan；
2) the above-mentioned vanillic aldehyde modification of chitosan of 3g is taken to be dissolved in 400ml, concentration is in 0.15mol/L hydrochloric acid solution, is stirred
Mix uniformly, labeled as solution A；126ml tetraethyl orthosilicates and 100ml absolute ethyl alcohols are well mixed, labeled as solution B；Will be molten
Liquid B mixes with solution A, stirs 24h, labeled as solution C, tetraethyl orthosilicate gradually hydrolyzes in an acidic solution, and solution is by two-phase
Gradually it is mixed into a phase；
25ml 1%HF solution is added dropwise dropwise into solution C, stirring 1h is well mixed solution, stands gel, aging
24h, form stable gel.Gel is immersed to washing by soaking in distilled water successively, and twice, ethanol washs three times, n-hexane washing
Three times, each soak time is 24h；Dry.
Referring to accompanying drawing, Fig. 1 is vanillic aldehyde modification of chitosan-SiO made from embodiment 12Aeroge infrared absorption spectroscopy,
As can be seen that 3436cm from figure-1It is nearby-OH and-NH2Stretching vibration overlapping absorbance peak, 1647cm-1It is nearby that C=N stretches
Contracting vibration absorption peak, in 1386cm-1It is nearby-CH in chitosan3Symmetrical deformation vibration absworption peak, 1084cm-1It is nearby C-O
Stretching vibration absworption peak, 965cm-1It is nearby Si-OH flexural vibrations absworption peak, 797cm-1It is nearby that Si-O keys are symmetrically stretched
Contracting vibration absorption peak, illustrate Material cladding success.
Above-mentioned material is through nitrogen adsorption desorption analysis, specific surface area 735.75m2/ g, average pore size 3.23nm, it is average
Particle diameter is 8.15nm, pore volume 0.59m3/g。
The aerogel material of acquisition is crushed, the material that particle diameter is 40-60 mesh is selected and is added in cigarette filter, every
Cigarette addition is 12mg, and suction result of the test shows that the sorbing material prepared by the present invention can make crotonaldehyde in mainstream smoke
Content declines 23.24%, the results are shown in Table 1.
The test material test result of table 1.
Control sample is free from the cigarette of meterial additive, is characterized in that filter tip is processed into the unitary filter tip of two sections, nearly mouth end
15mm, nearly pipe tobacco end 10mm；It is the cigarette containing meterial additive to test sample, and material addition manner is clipped between two section filter tips.
Embodiment 2
Prepare vanillic aldehyde modification of chitosan-SiO2The method of aerogel composite, this method comprise the following steps：
1) by 6g14cps, the chitosan that deacetylation is 96.1% is immersed in room temperature swelling 24h in ethanol, filtering, washing
After be added in 120ml ethanol, add 18g vanillic aldehydes, agitating and heating backflow 12h；Yellow product is filtered out, is washed, 50 DEG C
Normal pressure freeze-day with constant temperature obtains vanillic aldehyde modification of chitosan；
2) the above-mentioned vanillic aldehyde modification of chitosan of 6g is taken to be dissolved in 400ml, concentration is in 0.15mol/L hydrochloric acid solution, is stirred
Mix uniformly, labeled as solution A；126ml tetraethyl orthosilicates and 100ml absolute ethyl alcohols are well mixed, labeled as solution B；Will be molten
Liquid B mixes with solution A, stirs 24h, labeled as solution C, tetraethyl orthosilicate gradually hydrolyzes in an acidic solution, and solution is by two-phase
Gradually it is mixed into a phase；
25ml 1%HF solution is added dropwise dropwise into solution C, stirring 1h is well mixed solution, stands gel, aging
24h, form stable gel.Gel is immersed to washing by soaking in distilled water successively, and twice, ethanol washs three times, n-hexane washing
Three times, each soak time is 24h；
3) gel is then immersed in progress surface modification in the hexane solution containing 7.5% (v/v) trim,ethylchlorosilane,
In triplicate, each 24h；Modified gel is immersed in hexane solution and washed three times, each 24h；Dry.
Referring to accompanying drawing, Fig. 2 is the infrared absorption spectroscopy of the hydrophobicity composite aerogel prepared in embodiment 2,3436cm-1It is attached
Closely it is-OH and NH2Stretching vibration overlapping absorbance peak, 2967cm-1It is nearby C-H stretching vibration peaks, 1628cm-1It is nearby C=N
Stretching vibration absworption peak, 1513cm-1It is nearby phenyl ring characteristic peak, 1088cm-1It is nearby C-O stretching vibration absworption peaks, C-H
The enhancing of vibration absorption peak illustrates that hydrophobic treatment is effective.Fig. 3 is the scanning electricity of the hydrophobicity composite aerogel prepared in embodiment 2
Mirror figure, it is seen that the material has loose and porous structure.
Above-mentioned material is through nitrogen adsorption desorption analysis, specific surface area 718.56m2/ g, average pore size 4.17nm, it is average
Particle diameter is 8.35nm, pore volume 0.75m3/g。
The aerogel material of acquisition is crushed, the material that particle diameter is 40-60 mesh is selected and is added in cigarette filter, every
Cigarette addition is 12mg, and suction result of the test shows that the sorbing material prepared by the present invention can make crotonaldehyde in mainstream smoke
Content declines 19.54%, the results are shown in Table 2.
The test material test result of table 2.
Control sample is free from the cigarette of meterial additive, is characterized in that filter tip is processed into the unitary filter tip of two sections, nearly mouth end
15mm, nearly pipe tobacco end 10mm；It is the cigarette containing meterial additive to test sample, and material addition manner is clipped between two section filter tips.
Embodiment 3
Prepare vanillic aldehyde modification of chitosan-SiO2The method of aerogel composite, this method comprise the following steps：
1) by 3g 37cps, the chitosan that deacetylation is 95.7% is immersed in 70 DEG C of heating swelling 6h, mistake in ethanol
It is added to after filter, washing in 100ml ethanol, adds 6g vanillic aldehydes, agitating and heating backflow 12h；Yellow product is filtered out, is washed
Wash, 50 DEG C of normal pressure freeze-day with constant temperature obtain vanillic aldehyde modification of chitosan；
2) the above-mentioned vanillic aldehyde modification of chitosan of 3g is taken to be dissolved in 400ml, concentration is in 0.15mol/L hydrochloric acid solution, is stirred
Mix uniformly, labeled as solution A；126ml tetraethyl orthosilicates and 100ml absolute ethyl alcohols are well mixed, labeled as solution B；Will be molten
Liquid B mixes with solution A, labeled as solution C, stirs 24h, tetraethyl orthosilicate gradually hydrolyzes in an acidic solution, and solution is by two-phase
Gradually it is mixed into a phase.
25ml 1%HF solution is added dropwise dropwise into solution C, stirring 1h is well mixed solution, stands gel, aging
24h, form stable gel.Gel is immersed to washing by soaking in distilled water successively, and twice, ethanol washs three times, n-hexane washing
Three times, each soak time is 24h；
3) gel is then immersed in progress surface modification in the hexane solution containing 7.5% (v/v) trim,ethylchlorosilane,
In triplicate, each 24h；Modified gel is immersed in hexane solution and washed three times, each 24h；Dry.
Above-mentioned material is through nitrogen adsorption desorption analysis, specific surface area 554.99m2/ g, average pore size 3.21nm, it is average
Particle diameter is 10.8nm, pore volume 0.45m3/g。
The aerogel material of acquisition is crushed, the material that particle diameter is 40-60 mesh is selected and is added in cigarette filter, every
Cigarette addition is 12mg, and suction result of the test shows that the sorbing material prepared by the present invention can make crotonaldehyde in mainstream smoke
Content declines 38.67%, the results are shown in Table 3.
The test material test result of table 3.
Control sample is free from the cigarette of meterial additive, is characterized in that filter tip is processed into the unitary filter tip of two sections, nearly mouth end
15mm, nearly pipe tobacco end 10mm；It is the cigarette containing meterial additive to test sample, and material addition manner is clipped between two section filter tips.
Embodiment 4
Embodiment 2 is repeated, the temperature that simply constant temperature soaks in step 1) is 50 DEG C.The time of constant temperature immersion is 12h.Step
1) temperature that backflow is added described in is 70 DEG C.
Embodiment 5
Embodiment 3 is repeated, simply the concentration of hydrochloric acid solution described in step 2) is 0.3mol/L.Tetraethyl orthosilicate and ethanol
The mass ratio of mixing, tetraethyl orthosilicate and ethanol is 3:1.The chitosan and the mass ratio of tetraethyl orthosilicate that vanillic aldehyde is modified are 1:
50.Mixing time is 18h.The concentration of the HF solution of addition is 8%.The HF solution and tetraethyl orthosilicate mass ratio of addition are 1:
500.The time of the washing by soaking is 30h.
Embodiment 6
Embodiment 3 is repeated, simply in the hexane solution containing trim,ethylchlorosilane described in step 3), trim,ethylchlorosilane
Volumetric concentration is 8%.The time of the washing by soaking is 30h.
Claims (10)
- A kind of 1. vanillic aldehyde modification of chitosan-SiO2Aerogel composite, the material are that chitosan is modified by vanillic aldehyde Afterwards, the chitosan that vanillic aldehyde is modified is obtained, silicon source presoma is then dissolved in what is obtained in the chitosan of vanillic aldehyde modification.
- 2. material according to claim 1, it is characterised in that：The silicon source presoma is esters of silicon acis, preferably silicic acid first Ester, silester, positive isopropyl silicate, butyl silicate；More preferably tetraethyl orthosilicate.
- 3. one kind prepares vanillic aldehyde modification of chitosan-SiO2The method of aerogel composite, this method comprise the following steps：1) add chitosan into vanillic aldehyde, be heated to reflux, obtain the chitosan of vanillic aldehyde modification；2) silicon source presoma is added in the chitosan that vanillic aldehyde is modified, stirring, stands gel, washing；Vanillic aldehyde is obtained to be modified Chitosan-SiO2Aerogel composite crude product.
- 4. according to the method for claim 3, it is characterised in that：This method also includes：3) the oxalaldehyde modification of chitosan-SiO for obtaining step 2)2Aerogel composite crude product is containing trim,ethylchlorosilane Soak, wash in hexane solution；Obtain vanillic aldehyde modification of chitosan-SiO2Aerogel composite.
- 5. the method according to claim 3 or 4, it is characterised in that：Step 1) is specially：Add chitosan into organic molten Constant temperature is soaked in agent, and cleaning is filtered after swelling, the chitosan of swelling is added in the organic solvent containing vanillic aldehyde, heated back Stream, product is filtered out after reaction, washing, the chitosan of vanillic aldehyde modification is obtained after drying；And/orStep 2) is specially：The chitosan that vanillic aldehyde is modified is dissolved in hydrochloric acid solution, is stirred at room temperature uniformly；By positive silicic acid second Ester and ethanol are well mixed, and are added in the chitosan solution of vanillic aldehyde modification, stirring；HF solution is added, is stirred, is stood Gel, aging；Gel after aging is put into washing by soaking in distilled water, then immerses washing by soaking in ethanol, then using just Hexane washing by soaking, dry, obtain vanillic aldehyde modification of chitosan-SiO2Aerogel composite crude product.
- 6. the method according to claim 4 or 5, it is characterised in that：Step 3) is specially：The oxalaldehyde that step 2) obtains is changed Property chitosan-SiO2Aerogel composite crude product is soaked in the hexane solution containing trim,ethylchlorosilane, then is immersed just Washing by soaking in hexane solution, dry, obtain vanillic aldehyde modification of chitosan-SiO2Aerogel composite.
- 7. the method according to claim 5 or 6, it is characterised in that：Organic solvent described in step 1) is alcoholic solution, excellent Elect one or both of methanol, ethanol as；Chitosan and vanillic aldehyde mass ratio are 1 in step 1):1-10, preferably 1:1.2- 6, more preferably 1:1.5-4；The temperature of the immersion of constant temperature described in step 1) is 15-90 DEG C, preferably 20-80 DEG C, is more preferably 25-70℃；The time of constant temperature immersion is 0.5-48h, preferably 1-36h, more preferably 2-24h；Cleaning is adopted described in step 1) Cleaned with alcoholic solution, it is preferred to use ethanol solution cleans；The temperature that backflow is added described in step 1) is 55-100 DEG C, is preferably 60-90 DEG C, more preferably 65-80 DEG C；Washing is washed using alcoholic solution described in step 1), it is preferred to use ethanol solution cleans.
- 8. according to the method any one of claim 5-7, it is characterised in that：The concentration of hydrochloric acid solution described in step 2) For 0.05-1.0mol/L, preferably 0.1-0.8mol/L, more preferably 0.15-0.5mol/L；Tetraethyl orthosilicate and ethanol mix Close, the mass ratio of tetraethyl orthosilicate and ethanol is 1-5:1, preferably 1.2-3:1, more preferably 1.5-2:1；What vanillic aldehyde was modified The mass ratio of chitosan and tetraethyl orthosilicate is 1:15-100, preferably 1:20-90, more preferably 1:25-80；Mixing time is 2-48h, preferably 6-36h, more preferably 12-24h；The mass concentration of the HF solution of addition is 1-40%, preferably 3-20%, More preferably 5-10%；The HF solution and tetraethyl orthosilicate mass ratio of addition are 1:100-1000, preferably 1:200-800, more Preferably 1:400-600；The time of the washing by soaking is 2-72h, preferably 6-48h, more preferably 12-36h.
- 9. according to the method any one of claim 5-8, it is characterised in that：Step 3) is described containing trim,ethylchlorosilane In hexane solution, the volumetric concentration of trim,ethylchlorosilane is 1%-20%, preferably 3%-15%, more preferably 5%- 10%；The time of the washing by soaking is 2-72h, preferably 6-48h, more preferably 12-36h.
- 10. vanillic aldehyde modification of chitosan-SiO2The purposes of aerogel composite or according to any one of claim 3-9 Vanillic aldehyde modification of chitosan-SiO prepared by method2The purposes of aerogel composite, wherein by described in claim 1 or 2 Vanillic aldehyde modification of chitosan-SiO2Aerogel composite, or method will be prepared according to any one of claim 3-9 Vanillic aldehyde modification of chitosan-SiO2Aerogel composite, in cigarette filter rod；Preferably, the particle diameter of the material For 20-100 mesh, preferably 30-80 mesh, more preferably 40-60 mesh；Preferably, the material is added in every cigarette filter rod Addition be 1-20mg, preferably 3-18mg, more preferably 5-15mg.
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