CN117659443B - High-barrier hydrogel and preparation method thereof - Google Patents
High-barrier hydrogel and preparation method thereof Download PDFInfo
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- CN117659443B CN117659443B CN202311606270.2A CN202311606270A CN117659443B CN 117659443 B CN117659443 B CN 117659443B CN 202311606270 A CN202311606270 A CN 202311606270A CN 117659443 B CN117659443 B CN 117659443B
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 131
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 69
- 229920001661 Chitosan Polymers 0.000 claims abstract description 60
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 238000004132 cross linking Methods 0.000 claims abstract description 28
- 239000007864 aqueous solution Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000019832 sodium triphosphate Nutrition 0.000 claims abstract description 23
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000021615 conjugation Effects 0.000 claims abstract description 5
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 26
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- UMFJAHHVKNCGLG-UHFFFAOYSA-N n-Nitrosodimethylamine Chemical compound CN(C)N=O UMFJAHHVKNCGLG-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- LIGACIXOYTUXAW-UHFFFAOYSA-N phenacyl bromide Chemical compound BrCC(=O)C1=CC=CC=C1 LIGACIXOYTUXAW-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 230000004888 barrier function Effects 0.000 claims description 4
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 3
- 125000003047 N-acetyl group Chemical group 0.000 claims description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 20
- 239000000779 smoke Substances 0.000 abstract description 15
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 239000004615 ingredient Substances 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 235000019504 cigarettes Nutrition 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000008213 purified water Substances 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- BMTZEAOGFDXDAD-UHFFFAOYSA-M 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholin-4-ium;chloride Chemical compound [Cl-].COC1=NC(OC)=NC([N+]2(C)CCOCC2)=N1 BMTZEAOGFDXDAD-UHFFFAOYSA-M 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000000391 smoking effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000013268 sustained release Methods 0.000 description 2
- 239000012730 sustained-release form Substances 0.000 description 2
- 239000001116 FEMA 4028 Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004885 tandem mass spectrometry Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D1/00—Cigars; Cigarettes
- A24D1/02—Cigars; Cigarettes with special covers
-
- 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
- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/16—Cyclodextrin; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/16—Cyclodextrin; Derivatives thereof
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- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention provides a high-barrier hydrogel and a preparation method thereof, wherein the method comprises the following steps: dissolving chitosan in acetic acid aqueous solution, and adding glutaraldehyde or tripolyphosphate to carry out a crosslinking reaction to obtain chitosan hydrogel; performing a crosslinking reaction on cyclodextrin and epichlorohydrin in water to obtain cyclodextrin hydrogel; conjugation is carried out on chitosan hydrogel and cyclodextrin hydrogel under the action of glutaraldehyde or 4- (4, 6-dimethoxy triazine-2-yl) -4-methylmorpholine hydrochloride to obtain high-barrier hydrogel; the high-barrier hydrogel prepared by the method has a good adsorption effect on harmful ingredients in main stream smoke, and can be subjected to solidification treatment after adsorption, so that the secondary release of the harmful substances is avoided.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a high-barrier hydrogel and a preparation method thereof.
Background
Tipping paper is a paper used for covering a cigarette filter, which is mainly used for providing a barrier to isolate lips of a smoker from a filter element of the cigarette, and is used for providing a better smoking experience, and simultaneously, in order to reduce the absorption of harmful components in smoke as much as possible, the surface of the tipping paper is usually perforated so as to provide an air channel while smoking, on the one hand, fresh air is provided, and on the other hand, the fresh air can be used for cooling the smoke so as to condense part of volatile harmful substances.
However, volatile harmful substances are easily leached out through the tipping paper after being deposited on the surface of the tipping paper, and are present on the outer surface of the tipping paper, so that the hands and lips of a smoker are extremely liable to come into contact with the harmful substances again and be absorbed by the skin.
In order to block harmful substances and prevent the harmful substances inside the filter tip from leaching out to directly contact with a human body, a hydrogel with good blocking effect is needed.
Disclosure of Invention
In view of the above, the invention provides a high-barrier hydrogel and a preparation method thereof, which aim to improve the barrier effect of tipping paper on harmful substances in cigarette smoke, in particular nitrosamine.
The technical scheme of the invention is realized as follows: the invention provides a preparation method of high-barrier hydrogel, which comprises the following steps:
Dissolving chitosan in acetic acid aqueous solution, and adding glutaraldehyde or tripolyphosphate to carry out a crosslinking reaction to obtain chitosan hydrogel;
Performing a crosslinking reaction on cyclodextrin and epichlorohydrin in water to obtain cyclodextrin hydrogel;
Conjugation is carried out on chitosan hydrogel and cyclodextrin hydrogel under the action of glutaraldehyde or 4- (4, 6-dimethoxy triazine-2-yl) -4-methylmorpholine hydrochloride to obtain high-barrier hydrogel;
The invention combines the chitosan hydrogel and the cyclodextrin hydrogel, so that the hydrogel has the characteristics of two hydrogels, and the hydrogel is used in cigarette tipping paper, so that the content of harmful substances in the sucked smoke can be greatly reduced, and the adsorption and fixation effects on the harmful substances in the cigarette are extremely strong, so that the secondary release of the harmful substances can be avoided.
In some embodiments, the chitosan: glutaraldehyde or tripolyphosphate: the weight ratio of the aqueous solution of acetic acid is (1-5): (5-10): 100, wherein the volume concentration of the acetic acid aqueous solution is 1-2%; cyclodextrin: epichlorohydrin: the weight ratio of water is (2-10): (5-20): 100; chitosan hydrogel: cyclodextrin hydrogel: glutaraldehyde or 4- (4, 6-dimethoxy triazine-2-yl) -4-methylmorpholine hydrochloride with a mass ratio of 1: (1-10): (1-3).
In some embodiments, when preparing the chitosan hydrogel, the temperature of the crosslinking reaction is 25-37 ℃ and the reaction time is 1-4 hours; when preparing cyclodextrin hydrogel, the temperature of the crosslinking reaction is 25-37 ℃ and the reaction time is 1-24h; when the high-barrier hydrogel is prepared, the temperature of the crosslinking reaction is 25-37 ℃ and the reaction time is 1-4h.
In some embodiments, the cyclodextrin is modified by a method comprising: mixing cyclodextrin aqueous solution with pH value of 9.5-10.5 and N-nitrosodimethylamine, stirring and reacting for 2-10h at 25-30 ℃, adding acetonitrile solution of 2-bromoacetophenone into the reaction solution after the reaction is finished, continuously stirring and reacting for 2-10h at 25-30 ℃, filtering and drying to obtain the modified cyclodextrin.
The cyclodextrin hydrogel has better encapsulation and sustained-release performance, and part of active sites are consumed in the process of conjugation with the chitosan hydrogel, so that the encapsulation and sustained-release performance of the cyclodextrin hydrogel is reduced to a certain extent, and in order to enable the cyclodextrin hydrogel to have better adsorption capacity for harmful substances in smoke, the surface modification is carried out by adopting nitrosamine, and meanwhile, the reactive functional group is introduced, so that the adsorption and combination capacity of the cyclodextrin hydrogel to the harmful substances in the smoke is improved.
In some embodiments, the cyclodextrin: n-nitrosodimethylamine: the mass ratio of the 2-bromoacetophenone is 100: (0.01-0.05): (1-10).
In some embodiments, the chitosan comprises: at least one of carboxymethyl chitosan, N-acetyl chitosan and quaternized chitosan.
On the other hand, the invention also provides the high-barrier hydrogel prepared by the preparation method.
In a third aspect, the invention also provides an application of the high-barrier hydrogel in tipping paper, and the high-barrier hydrogel is coated on the surface of the tipping paper, so that the fixed-line adsorption effect of the high-barrier hydrogel on part of harmful substances in smoke is improved.
The cyclodextrin is beta-cyclodextrin.
Compared with the prior art, the high-barrier hydrogel and the preparation method thereof have the following beneficial effects:
The invention provides a high-barrier hydrogel which can be used for tipping paper for cigarettes, and the conjugated hydrogel which is provided with chitosan hydrogel and cyclodextrin hydrogel at the same time is prepared in a conjugation mode, so that the hydrogel can adsorb and fix harmful substances on smoke passing through the surface of the tipping paper, and can effectively prevent the adsorbed harmful substances from being released again.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an external view of a high-barrier hydrogel prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the high-barrier hydrogel prepared in example 1 of the present invention;
FIG. 3 is a nuclear magnetic resonance spectrum of the modified cyclodextrin prepared in example 2 of the present invention;
FIG. 4 is an external view of the high-barrier hydrogel prepared in example 2 of the present invention;
FIG. 5 is a scanning electron microscope image of the high-barrier hydrogel prepared in example 2 of the present invention;
FIG. 6 is a nuclear magnetic resonance spectrum of the modified cyclodextrin prepared in example 3 of the present invention;
FIG. 7 is an external view of the high-barrier hydrogel prepared in example 3 of the present invention;
FIG. 8 is a scanning electron microscope image of the high-barrier hydrogel prepared in example 3 of the present invention;
FIG. 9 is a nuclear magnetic resonance spectrum of the high-barrier hydrogel prepared in example 4 of the present invention;
FIG. 10 is an external view of the high-barrier hydrogel prepared in example 4 of the present invention;
FIG. 11 is a scanning electron microscope image of the high-barrier hydrogel prepared in example 4 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the invention belong. If the definitions set forth in this section are contrary to or otherwise inconsistent with the definitions set forth in the patents, patent applications, published patent applications and other publications incorporated herein by reference, the definitions set forth in this section are preferentially set forth in the definitions set forth herein.
All starting materials used herein were from commercial sources unless otherwise defined.
Example 1
Preparing chitosan hydrogel:
1 part of chitosan, 100 parts of acetic acid aqueous solution with volume concentration of 2% and 5 parts of glutaraldehyde are weighed, the chitosan is dissolved in the acetic acid aqueous solution, and after glutaraldehyde is added, the chitosan hydrogel is obtained by crosslinking and stirring reaction for 1h at 25 ℃.
Preparing cyclodextrin hydrogel:
2 parts of cyclodextrin, 5 parts of sodium tripolyphosphate and 100 parts of water are weighed, cyclodextrin and sodium tripolyphosphate are added into water, and the cyclodextrin hydrogel is obtained after crosslinking and stirring reaction for 1 hour at 25 ℃;
Preparation of high-barrier hydrogels:
1 part of chitosan hydrogel, 1 part of cyclodextrin hydrogel and 1 part of glutaraldehyde are weighed, the chitosan hydrogel, the cyclodextrin hydrogel and the glutaraldehyde are mixed, and the mixture is subjected to crosslinking stirring reaction for 1 hour at 25 ℃ to obtain the high-barrier hydrogel.
The obtained high-barrier hydrogel electron microscope image is shown in fig. 2, has a porous microstructure, and can effectively adsorb harmful substances in smoke.
Example 2
Preparing chitosan hydrogel:
1 part of chitosan, 100 parts of acetic acid aqueous solution with volume concentration of 2% and 5 parts of glutaraldehyde are weighed, the chitosan is dissolved in the acetic acid aqueous solution, and after glutaraldehyde is added, the chitosan hydrogel is obtained by crosslinking and stirring reaction for 1-4 hours at 25 ℃.
Cyclodextrin modification treatment:
weighing 100 parts of cyclodextrin, mixing with water to obtain cyclodextrin aqueous solution, adding sodium hydroxide to adjust pH to prepare cyclodextrin aqueous solution with pH value of 10, adding 0.01 part of N-nitrosodimethylamine, stirring at 25 ℃ for reaction for 2 hours, adding 5 parts of acetonitrile solution containing 1 part of 2-bromoacetophenone after the reaction is finished, stirring at 25 ℃ for reaction for 2 hours, filtering and drying to obtain modified cyclodextrin.
Preparing cyclodextrin hydrogel:
2 parts of modified cyclodextrin, 5 parts of sodium tripolyphosphate and 100 parts of water are weighed, the modified cyclodextrin and the sodium tripolyphosphate are added into the water, and the mixture is subjected to crosslinking stirring reaction for 1 hour at 25 ℃ to obtain cyclodextrin hydrogel;
Preparation of high-barrier hydrogels:
1 part of chitosan hydrogel, 1 part of cyclodextrin hydrogel and 1 part of glutaraldehyde are weighed, the chitosan hydrogel, the cyclodextrin hydrogel and the glutaraldehyde are mixed, and the mixture is subjected to crosslinking stirring reaction for 1 hour at 25 ℃ to obtain the high-barrier hydrogel.
The obtained high-barrier hydrogel electron microscope image is shown in fig. 5, has a porous microstructure, has more uniform pore distribution compared with the embodiment 1, and can effectively adsorb harmful substances in smoke.
Example 3
Preparing chitosan hydrogel:
Weighing 5 parts of chitosan, 100 parts of acetic acid aqueous solution with volume concentration of 2% and 10 parts of glutaraldehyde, dissolving the chitosan in the acetic acid aqueous solution, adding the glutaraldehyde, and performing crosslinking and stirring reaction for 4 hours at 37 ℃ to obtain the chitosan hydrogel.
Preparing cyclodextrin hydrogel:
cyclodextrin modification treatment:
Weighing 100 parts of cyclodextrin, mixing with water to obtain cyclodextrin aqueous solution, adding sodium hydroxide to adjust pH to prepare cyclodextrin aqueous solution with pH value of 9.5, adding 0.05 part of N-nitrosodimethylamine, stirring at 30 ℃ for reaction for 10 hours, adding 40 parts of acetonitrile solution containing 10 parts of 2-bromoacetophenone after the reaction is finished, stirring at 30 ℃ for reaction for 10 hours, filtering and drying to obtain modified cyclodextrin.
10 Parts of modified cyclodextrin, 20 parts of sodium tripolyphosphate and 100 parts of water are weighed, the modified cyclodextrin and the sodium tripolyphosphate are added into the water, and the mixture is subjected to crosslinking stirring reaction for 24 hours at 37 ℃ to obtain cyclodextrin hydrogel;
Preparation of high-barrier hydrogels:
1 part of chitosan hydrogel, 10 parts of cyclodextrin hydrogel and 3 parts of DMTMM are weighed, the chitosan hydrogel and the cyclodextrin hydrogel are mixed with 4- (4, 6-dimethoxy triazine-2-yl) -4-methylmorpholine hydrochloride, and the mixture is subjected to crosslinking and stirring reaction for 4 hours at 37 ℃ to obtain the high-barrier hydrogel.
The high-barrier hydrogel electron microscope image is shown in fig. 8, has a porous microstructure, has irregular pore shape distribution compared with the embodiment 1 and 2, and can effectively adsorb harmful substances in smoke.
Example 4
Preparing chitosan hydrogel:
3 parts of carboxymethyl chitosan, 100 parts of acetic acid aqueous solution with volume concentration of 2% and 7 parts of sodium tripolyphosphate are weighed, chitosan is dissolved in the acetic acid aqueous solution, and after the sodium tripolyphosphate is added, the chitosan hydrogel is obtained through crosslinking and stirring reaction for 3 hours at 30 ℃.
Preparing cyclodextrin hydrogel:
cyclodextrin modification treatment:
Weighing 100 parts of cyclodextrin, mixing with water to obtain cyclodextrin aqueous solution, adding sodium hydroxide to adjust pH to prepare cyclodextrin aqueous solution with pH value of 10.5, adding 0.04 part of N-nitrosodimethylamine, stirring at 27 ℃ for reaction for 8 hours, adding 20 parts of acetonitrile solution containing 6 parts of 2-bromoacetophenone after the reaction is finished, stirring at 27 ℃ for reaction for 8 hours, filtering and drying to obtain modified cyclodextrin.
8 Parts of modified cyclodextrin, 16 parts of sodium tripolyphosphate and 100 parts of water are weighed, the modified cyclodextrin and the sodium tripolyphosphate are added into the water, and the mixture is subjected to crosslinking stirring reaction for 12 hours at 30 ℃ to obtain cyclodextrin hydrogel;
Preparation of high-barrier hydrogels:
1 part of chitosan hydrogel, 5 parts of cyclodextrin hydrogel and 2 parts of DMTMM are weighed, the chitosan hydrogel and the cyclodextrin hydrogel are mixed with 4- (4, 6-dimethoxy triazine-2-yl) -4-methylmorpholine hydrochloride, and the mixture is subjected to crosslinking and stirring reaction for 3 hours at 30 ℃ to obtain the high-barrier hydrogel.
The obtained high-barrier hydrogel electron microscope image is shown in fig. 11, has a porous microstructure, and meanwhile, has a complex surface structure, and can effectively adsorb harmful substances in smoke.
Comparative example 1
Preparing chitosan hydrogel:
Weighing 3 parts of chitosan, 100 parts of acetic acid aqueous solution with volume concentration of 2% and 7 parts of sodium tripolyphosphate, dissolving chitosan in the acetic acid aqueous solution, adding sodium tripolyphosphate, and performing crosslinking stirring reaction for 3 hours at 30 ℃ to obtain chitosan hydrogel.
Comparative example 2
Preparing cyclodextrin hydrogel:
8 parts of cyclodextrin, 16 parts of sodium tripolyphosphate and 100 parts of water are weighed, cyclodextrin and sodium tripolyphosphate are added into water, and the cyclodextrin hydrogel is obtained after crosslinking and stirring reaction for 12 hours at 30 ℃;
Comparative example 3
Preparing chitosan hydrogel:
Weighing 3 parts of chitosan, 100 parts of acetic acid aqueous solution with volume concentration of 2% and 7 parts of sodium tripolyphosphate, dissolving chitosan in the acetic acid aqueous solution, adding sodium tripolyphosphate, and performing crosslinking stirring reaction for 3 hours at 30 ℃ to obtain chitosan hydrogel.
Preparing cyclodextrin hydrogel:
8 parts of cyclodextrin, 16 parts of sodium tripolyphosphate and 100 parts of water are weighed, cyclodextrin and sodium tripolyphosphate are added into water, and the cyclodextrin hydrogel is obtained after crosslinking and stirring reaction for 12 hours at 30 ℃;
Mixing the hydrogel:
Weighing 1 part of chitosan hydrogel and 5 parts of cyclodextrin hydrogel, and mixing the chitosan hydrogel and the cyclodextrin hydrogel to obtain mixed hydrogel.
And (3) experimental verification:
Respectively spin-coating the prepared hydrogel on the surface of tipping paper, drying, and then using the tipping paper for tipping production of filter tips and cigarettes to prepare cigarettes with the perimeter of 23.4mm and the length of 84mm, measuring the release amount of nitrosamine in main stream smoke by adopting a high performance liquid chromatography tandem mass spectrometry, and respectively calculating the release amount reduction rate of nitrosamine by taking conventional untreated tipping paper as a blank example to obtain the following results:
The data result shows that the hydrogel spin-coating treatment tipping paper can obviously improve the release amount of nitrosamine in main stream smoke of cigarettes after being applied to cigarettes.
Removing the tipping paper subjected to the sucking treatment, soaking the tipping paper with 100ml of purified water, detecting the purified water after soaking, wherein the detected positions in the purified water soaked in the tipping paper of a blank example contain NAB17 ppm, NAT44 ppm, NNK40 ppm and NNN36 ppm, and the soaked purified water of the tipping paper obtained in examples 1-4 does not detect nitrosamine components, while in comparative example 1, NAB26ppm, NAT64 ppm, NNK58 ppm and NNN48 ppm; NAB31 ppm, NAT82 ppm, NNK60 ppm and NNN54 ppm were detected in comparative example 2, and NAB33 ppm, NAT79 ppm, NNK48 ppm and NNN57 ppm were detected in comparative example 3.
The comparison shows that the high-barrier hydrogel can improve the adsorption capacity of tipping paper on harmful substance nitrosamine, has good fixing effect after adsorption, and effectively avoids the harm of secondary release.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (7)
1. The preparation method of the high-barrier hydrogel is characterized by comprising the following steps of:
dissolving chitosan in acetic acid water solution, adding glutaraldehyde or tripolyphosphate for crosslinking reaction to obtain chitosan hydrogel, and obtaining chitosan: glutaraldehyde or tripolyphosphate: the weight ratio of the aqueous solution of acetic acid is (1-5): (5-10): 100, wherein the volume concentration of the acetic acid aqueous solution is 1-2%;
Performing a crosslinking reaction on cyclodextrin and epichlorohydrin in water to obtain cyclodextrin hydrogel, wherein the cyclodextrin hydrogel comprises: epichlorohydrin: the weight ratio of water is (2-10): (5-20): 100;
Conjugation is carried out on chitosan hydrogel and cyclodextrin hydrogel under the action of glutaraldehyde or 4- (4, 6-dimethoxy triazine-2-yl) -4-methylmorpholine hydrochloride to obtain high-barrier hydrogel, wherein the chitosan hydrogel is prepared by the following steps: cyclodextrin hydrogel: glutaraldehyde or 4- (4, 6-dimethoxy triazine-2-yl) -4-methylmorpholine hydrochloride with a mass ratio of 1: (1-10): (1-3).
2. The method for preparing the high-barrier hydrogel according to claim 1, wherein the temperature of the crosslinking reaction is 25-37 ℃ and the reaction time is 1-4 hours when the chitosan hydrogel is prepared; when preparing cyclodextrin hydrogel, the temperature of the crosslinking reaction is 25-37 ℃ and the reaction time is 1-24h; when the high-barrier hydrogel is prepared, the temperature of the crosslinking reaction is 25-37 ℃ and the reaction time is 1-4h.
3. The method for preparing the high-barrier hydrogel according to claim 1, wherein the cyclodextrin is modified by a method comprising: mixing cyclodextrin aqueous solution with pH value of 9.5-10.5 and N-nitrosodimethylamine, stirring and reacting for 2-10h at 25-30 ℃, adding acetonitrile solution of 2-bromoacetophenone into the reaction solution after the reaction is finished, continuously stirring and reacting for 2-10h at 25-30 ℃, filtering and drying to obtain the modified cyclodextrin.
4. A method of preparing a high barrier hydrogel according to claim 3, wherein the cyclodextrin: n-nitrosodimethylamine: the mass ratio of the 2-bromoacetophenone is 100: (0.01-0.05): (1-10).
5. The method of preparing a high-barrier hydrogel of claim 1, wherein the chitosan comprises: at least one of carboxymethyl chitosan, N-acetyl chitosan and quaternized chitosan.
6. A high-barrier hydrogel prepared by the method of any one of claims 1-5.
7. Use of the high barrier hydrogel of claim 6 in tipping paper.
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| CN112841717A (en) * | 2020-12-31 | 2021-05-28 | 江苏都梁矿业集团有限公司 | Aromatized attapulgite based cigarette filter tip additive material as well as preparation method and application thereof |
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| CN112841717A (en) * | 2020-12-31 | 2021-05-28 | 江苏都梁矿业集团有限公司 | Aromatized attapulgite based cigarette filter tip additive material as well as preparation method and application thereof |
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