CN114316349B - Preparation method of chitosan film and chitosan film - Google Patents
Preparation method of chitosan film and chitosan film Download PDFInfo
- Publication number
- CN114316349B CN114316349B CN202111623544.XA CN202111623544A CN114316349B CN 114316349 B CN114316349 B CN 114316349B CN 202111623544 A CN202111623544 A CN 202111623544A CN 114316349 B CN114316349 B CN 114316349B
- Authority
- CN
- China
- Prior art keywords
- chitosan
- solution
- casting solution
- acid
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 51
- 238000005266 casting Methods 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000011521 glass Substances 0.000 claims description 10
- 238000003381 deacetylation reaction Methods 0.000 claims description 8
- 230000006196 deacetylation Effects 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical group OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 239000004088 foaming agent Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 12
- 238000000605 extraction Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 82
- 230000004907 flux Effects 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 10
- 229940098773 bovine serum albumin Drugs 0.000 description 10
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- 229920000491 Polyphenylsulfone Polymers 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003361 porogen Substances 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- -1 poly (arylene ether Chemical class 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a preparation method of a chitosan film and the chitosan film prepared by the method, and the method comprises the following steps: s1: mixing chitosan, acid, monohydric alcohol of C1-C6, pore-forming agent and water to obtain a casting solution, wherein the mass content of the chitosan is 0.5% -2.5% based on the total mass of the casting solution; s2: placing the casting solution on a carrier to obtain a carrier loaded with a chitosan film; s3: and immersing the carrier loaded with the chitosan film into alkali liquor and water in sequence to separate the chitosan film from the carrier. The method of the invention is to pump in advance when the membrane is immersed in alkali liquor, no solvent residue exists in the membrane, the membrane structure is uniform, and the uniform extraction of the pore-forming agent and the smoothness of pore channels caused by the full regular arrangement of the pore-forming agent are ensured.
Description
Technical Field
The invention relates to the field of membrane materials, in particular to a preparation method of a chitosan membrane and the chitosan membrane.
Technical Field
Chitosan is obtained by deacetylation reaction of chitin, and is a natural polymer compound with the largest amino group reserves and annual biosynthesis in nature. Chitosan is nontoxic and easy to degrade, has low cost, and has been widely applied in various fields such as food, medicine, environmental protection, etc. The chitosan membrane is a membrane with separation function prepared from chitosan. In the prior art, the preparation is mostly carried out by adopting a phase inversion method, namely, a solution or a solid-liquid mixture is converted into a solid phase membrane in a coagulating bath. The method has the defects of different conversion speeds of different depths of the film, non-uniform microstructure of the finally formed film, more dead end structure content and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a chitosan film and the chitosan film prepared by the method. The invention prepares the chitosan membrane by adopting concentration and solvent extraction for the first time, and the membrane is immersed in alkali liquor for extraction in advance, so that no solvent residue exists in the membrane, the membrane structure is uniform, and the uniform extraction of the pore-forming agent and the smoothness of pore channels caused by the full and regular arrangement of the pore-forming agent are ensured.
The first aspect of the present invention provides a method for preparing a chitosan film, comprising the steps of:
s1: mixing chitosan, acid, monohydric alcohol of C1-C6, pore-forming agent and water to obtain a casting solution, wherein the mass content of the chitosan is 0.5% -2.5% based on the total mass of the casting solution;
s2: placing the casting solution on a carrier to obtain a carrier loaded with a chitosan film;
s3: and immersing the carrier loaded with the chitosan film into alkali liquor and water in sequence to separate the chitosan film from the carrier.
According to some embodiments of the invention, the method further comprises standing the casting solution to foam prior to placing the casting solution on the support. In some embodiments, the time of resting is 0.5h to 3h, such as 1h or 2h.
According to some embodiments of the invention, in S2, after the casting solution is placed on the carrier, a heating treatment is performed to volatilize the monohydric alcohol of C1-C6 and water in the casting solution, thereby obtaining the carrier loaded with the chitosan film.
According to some embodiments of the invention, the method further comprises washing the chitosan film obtained in S3, preferably with water, to neutrality.
According to some embodiments of the invention, the chitosan is present in an amount of 0.6%, 0.7%, 0.75%, 0.85%, 0.9%, 0.95%, 1.0%, 1.05%, 1.1%, 1.15%, 1.2%, 1.25%, 1.35%, 1.4%, 1.45%, 1.5%, 1.55%, 1.6%, 1.65%, 1.7%, 1.75%, 1.8%, 1.85%, 1.9%, 1.95%, 2.1%, 2.2%, 2.3%, 2.4% and any value therebetween, based on the total mass of the casting solution. In some embodiments, the chitosan is present in an amount of 0.8% to 2.0% by mass based on the total mass of the casting solution.
According to some embodiments of the invention, the acid is present in an amount of 0.5% -5% by mass of the total mass of the casting solution, such as 0.8%, 1.2%, 1.5%, 1.7%, 2.0%, 2.3%, 2.5%, 2.7%, 3.0%, 3.3%, 3.5%, 3.7%, 3.9%, 4.2%, 4.5%, 4.7% and any value therebetween. In some embodiments, the acid is present in an amount of 1% to 4% by mass based on the total mass of the casting solution.
According to some embodiments of the invention, the porogen is present in an amount of 0.5% to 10% by weight, e.g., 1.5%, 2.0%, 3.0%, 4.0%, 5.0%, 6.0%, 7.0%, 7.5%, 8.5%, 9.0% by weight, and any value therebetween, based on the total weight of the casting solution. In some embodiments, the porogen is present in an amount of 1% to 8% by mass based on the total mass of the casting solution.
According to some embodiments of the invention, the C1-C6 monohydric alcohol is present in an amount ranging from 10% to 50% by mass, such as 15%, 20%, 25%, 27%, 32%, 35%, 37%, 42%, 45% by mass, and any value therebetween, based on the total mass of the casting solution. In some embodiments, the C1-C6 monohydric alcohol is present in an amount of 30% to 40% by mass based on the total mass of the casting solution.
According to some embodiments of the invention, the water is present in an amount of 50% to 70% by weight of the total mass of the casting solution, such as 52%, 54%, 57%, 60%, 62%, 64%, 67%, 69% and any values therebetween, and in some embodiments, the water is present in an amount of 55% to 65% by weight of the total mass of the casting solution.
In some embodiments, the casting solution comprises 0.9wt% to 1.5wt% chitosan, 3wt% to 4wt% acid, 1wt% to 2wt% porogen, 30wt% to 40wt% C1-C6 monohydric alcohol, and 55wt% to 65wt% water. In some embodiments, the casting solution comprises 0.8wt% to 1.2wt% chitosan, 3.5wt% to 4.5wt% acid, 1.5wt% to 2.0wt% porogen, 30wt% to 34wt% C1-C6 monohydric alcohol, and 60wt% to 64wt% water.
According to some embodiments of the invention, in S1, the mixing is for a time of 4h-32h, e.g. 5h, 7h, 9h, 10h, 12h, 14h, 15h, 17h, 18h, 22h, 24h, 25h, 27h, 29h, 31h and any value in between. In some embodiments, the mixing is for a period of 8h to 20h.
According to some embodiments of the invention, the porogen is selected from one or more of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyvinyl alcohol, and polyvinylpyrrolidone. In some embodiments, the porogen is selected from polyethylene glycols. In some embodiments, the porogen is selected from polyethylene glycols having a molecular weight of 200-600, such as PEG200, PEG400, or PEG600.
According to some embodiments of the invention, the chitosan has a degree of deacetylation of not less than 55%, preferably more than 70%, for example 75%, 80%, 85%, 90%, 95% and any value in between. In some embodiments, the chitosan has a molecular weight of 1 x 10 5 -2×10 6 Preferably 3X 10 5 -7×10 5 。
According to some embodiments of the invention, in S1, the ratio of the volume of the casting solution to the surface area of the support is (5-30) mL:100cm 2 For example 7mL:100cm 2 、9mL:100cm 2 、12mL:100cm 2 、14mL:100cm 2 、17mL:100cm 2 、19mL:100cm 2 、21mL:100cm 2 、23mL:100cm 2 、27mL:100cm 2 Or any value therebetween. In some embodiments, the ratio of the volume of the casting solution to the surface area of the support is (7.5-25) mL 100cm 2 . In some embodiments, the ratio of the volume of the casting solution to the surface area of the support is (15-22.5) mL 100cm 2 。
According to some embodiments of the invention, the support is selected from one or more of a glass plate, a ceramic plate, or an organic polymer plate.
According to some embodiments of the invention, the acid is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, and trifluoroacetic acid.
According to some embodiments of the invention, the C1-C6 monohydric alcohol is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol.
According to some embodiments of the invention, the lye is one or more of sodium hydroxide solution, potassium carbonate solution, sodium carbonate solution, potassium phosphate solution and sodium phosphate solution. In some embodiments, the lye is present in a concentration of 0.1% to 10% by mass.
According to some embodiments of the invention, the preparation method of the chitosan film comprises the following specific steps:
(1) Mixing monohydric alcohol of C1-C6, acid, water, pore-forming agent and chitosan to obtain casting solution;
(2) Standing the casting solution in an ultrasonic instrument to remove foam;
(3) Pouring the defoamed casting film liquid on a carrier, enabling the casting film liquid to extend to be as large as the carrier, and then heating and drying the casting film liquid until all solvents volatilize completely, so as to obtain the carrier loaded with the chitosan film;
(4) Immersing the membrane in (3) in sodium hydroxide solution, preferably 10% sodium hydroxide solution, for 0.5-3 h, such as 1h or 2h, then immersing in distilled water, washing to neutrality, and preserving in wet state to obtain chitosan-based membrane.
In a second aspect, the present invention provides a chitosan film prepared by the preparation method of the first aspect.
According to some embodiments of the invention, the chitosan membrane has an average pore size of 0.005 μm to 5 μm.
The third aspect of the invention provides the chitosan film prepared by the preparation method according to the first aspect or the application of the chitosan film in the composite film material.
According to some embodiments of the invention, the chitosan film is used as a base film in a composite film material.
Detailed Description
The present invention will be further illustrated by the following specific examples, but the scope of the present invention is not limited thereto.The measurement of the Ubbelohde viscosity of the sulfonated poly (arylene ether) was performed according to the following procedure
(1) 500ml of N-methylpyrrolidone was measured in a volumetric flask, and 2.6215g of lithium bromide was added to prepare a solution.
(2) 20mL of a solution of N-methylpyrrolidone and lithium bromide was measured with a 20mL pipette to dissolve the sulfonated polyethersulfone polymer to be tested, the polymer mass was 0.2g, and filtered through a 0.45 μm filter.
(3) The temperature of the whole test system is set to 25 ℃, and the temperature is measured after being constant.
(4) 10mL of polymer solution is injected into a black-bone viscometer, the outflow time of the polymer solution is measured three times, and the average t1 is taken;
(5) Sequentially adding 5ml,5ml,10ml,10ml N-methylpyrrolidone and lithium bromide solution respectively, repeating the step (4), measuring the outflow time of the polymer solution for three times, and taking an average t2; t3; t4; and t5.
(6) The solution was poured out, and the Ubbelohde viscometer was washed three times with a solution of N-methylpyrrolidone and lithium bromide, and 10ml of the solution of N-methylpyrrolidone and lithium bromide was measured, and the outflow time t0 was measured.
(7) From t0; t1; t2; t3; t4; t5 look-up table, the intrinsic viscosity value of the polymer is obtained.
Membrane performance testing includes flux and rejection
(1) The water flux test method comprises the following steps:
the membrane was pre-pressed for 2h at a pressure of 0.1MPa, and then its water permeation rate was measured in an ultrafilter with a pressure of 0.2MPa, over 2% MgSO 4 The solution is the solution for measuring flux, and the solution is 2% MgSO (MgSO) which penetrates through unit membrane area in unit time 4 The volume of the solution is the water flux of the membrane.
F＝V/(At)
Wherein: f is water flux (mL/cm) 2 h) The method comprises the steps of carrying out a first treatment on the surface of the V is 2% MgSO filtered over time t 4 Solution volume (mL); a is the effective area (cm) of the membrane 2 ) The method comprises the steps of carrying out a first treatment on the surface of the t is time (h).
(2) 0.1% BSA solution flux test method:
the membrane was pre-pressed for 2h at a pressure of 0.1MPa and flux measurement was performed in an ultrafilter at a pressure range of 0.2-0.5 MPa. The volume of 0.1% BSA solution per unit effective membrane area per unit time calculated using 0.1% Bovine Serum Albumin (BSA) solution as medium was expressed as the flux of 0.1% BSA solution through the membrane.
(3) The interception rate testing method comprises the following steps:
rejection refers to the percentage of the total amount of solute in a solution that is retained by a membrane after the solution passes through the membrane. The medium was treated with 0.1% bovine serum albumin (BSA molecular weight 65000) or polyethylene glycol (molecular weight 100000) solution, and the optical density values of the stock solution and the filtrate were measured.
R＝(C 1 -C 2 )/C 1 ×100％
Wherein: r is the retention rate; c1 is the concentration of the solute in the stock solution; c2 is the concentration of the solute in the permeate.
(4) The anti-pollution capability test method comprises the following steps:
the index of membrane fouling was assessed by attenuation of permeate flux and rejection.
Flux decay test method: pre-pressing with pure water for more than 20min, replacing the medium solution with 1% bovine serum albumin solution, and measuring the flux of the bovine serum albumin solution three times continuously to obtain average value as first flux data. And then taking out the membrane, flushing with distilled water, and putting the membrane into a device for continuous measurement to obtain flux data. Stable values were obtained by repeating 3 times.
FR＝(J 0 -J w )/J 0
Wherein: FR is the degree of decrease in water flux before and after membrane use; j (J) 0 Pure water flux before membrane use; j (J) w Pure water flux after membrane use.
(5) The salt removal rate test method comprises the following steps:
salt removal rate= (1-C P /C F )×100％
Wherein: c (C) P Conductivity measured for the solution collected after 24h testing of the membrane; c (C) F 2000 mg.L -1 Conductivity measured for NaCl solution.
Examples 1 to 5, comparative examples 1 to 2
Mixing 95% ethanol with water, acetic acid, pore-forming agent PEG400 and chitosan (95% deacetylation degree) with different mass according to a certain proportion (see table 1), and stirring for 20h to obtain chitosan film solution, namely casting film solution. The solution was allowed to stand in an ultrasonic apparatus for one hour to perform defoaming, the drying platform was horizontally calibrated in advance, and a 20mL volume of casting solution was weighed and poured onto a clean glass plate (10X 10 cm) so as to be spread to the same size as the carrier. Drying in an infrared lamp box at 80 ℃ for 24 hours until all solvents (95% ethanol and water) are volatilized completely; immersing the membrane in 10% sodium hydroxide solution for 1h, immersing in distilled water, separating the membrane from the glass plate, washing to neutrality, and preserving in wet state to obtain chitosan membrane.
TABLE 1
Example 6 to example 10
34g of 95% ethanol volatile agent, 2g of acetic acid, 64g of water, 4g of PEG400 pore-forming agent and 1.0g of chitosan (95% deacetylation degree) are mixed and stirred for different times (specific stirring time is shown in Table 2) to obtain chitosan film solution, namely film casting solution. The solution was allowed to stand in an ultrasonic apparatus for one hour to perform defoaming, the drying platform was horizontally calibrated in advance, and a 20mL volume of casting solution was weighed and poured onto a clean glass plate (10X 10 cm) so as to be spread to the same size as the carrier. Drying in an infrared lamp box at 80 ℃ for 24 hours until all solvents (95% ethanol and water) are volatilized completely; immersing the membrane in 10% sodium hydroxide solution for 1h, immersing in distilled water, separating the membrane from the glass plate, washing to neutrality, and preserving in wet state to obtain chitosan membrane.
TABLE 2
Example 11-example 17
34g of 95% ethanol volatile agent, 2g of acetic acid, 64g of water, 4g of pore-forming agent (the species of the pore-forming agent is shown in Table 3) and 1g of chitosan (the degree of deacetylation of 95%) are mixed and stirred for 20 hours to obtain a chitosan film solution, namely a film casting solution. The solution was allowed to stand in an ultrasonic apparatus for one hour to perform defoaming, the drying platform was horizontally calibrated in advance, and a 20mL volume of casting solution was weighed and poured onto a clean glass plate (10X 10 cm) so as to be spread to the same size as the carrier. Drying in an infrared lamp box at 80 ℃ for 24 hours until all solvents (95% ethanol and water) are volatilized completely; immersing the membrane in 10% sodium hydroxide solution for 1h, immersing in distilled water, separating the membrane from the glass plate, washing to neutrality, and preserving in wet state to obtain chitosan membrane.
TABLE 3 Table 3
Example 18-example 25
34g of 95% ethanol volatile agent, 2g of acetic acid, 4g of PEG400 pore-forming agent, 64g of water and 2.0g of chitosan (with the degree of deacetylation of 95%) are mixed and stirred for 20 hours to obtain a chitosan film solution, namely a film casting solution. The solution was allowed to stand in an ultrasonic apparatus for defoaming for one hour, the drying platform was calibrated horizontally in advance, and casting solutions of different volumes (specific volumes are shown in Table 4) were measured and poured onto a clean glass plate (10X 10 cm) so as to be spread into the same size as the carrier. Drying in an infrared lamp box at 80 ℃ for 24 hours until all solvents (95% ethanol and water) are volatilized completely; immersing the membrane in 10% sodium hydroxide solution for 1h, immersing in distilled water, separating the membrane from the glass plate, washing to neutrality, and preserving in wet state to obtain chitosan membrane.
TABLE 4 Table 4
Example 26
The chitosan film prepared in example 20 was immersed in an aprotic solvent N, N-dimethylacetamide DMAc for dissolving sulfonated polyphenylsulfone, repeated 3 times, and then immersed in a 1% sulfonated polyphenylsulfone solution (solvent N, N-dimethylacetamide) having a degree of sulfonation of 50% for 20 hours. And taking out the membrane, immersing the membrane into the same solvent N, N-dimethylacetamide DMAc, repeating for 3 times, immersing the membrane into deionized water again, and repeating for 3 times to obtain the chitosan composite membrane which is stored in a wet state in water for subsequent testing.
The water flux of the composite membrane is 13.28mL cm -2 ·h -1 The rejection rate of the 0.1% BSA solution is 99.7%, the desalination rate is 34.7% and the anti-pollution is 0.52.
Wherein, 50% sulfonation degree sulfonated polyphenylsulfone is prepared as follows:
preparation of sulfonated polyphenylsulfone (salt form):
pretreating raw materials before starting reaction, drying DCDPS and BP in a vacuum oven at 55 ℃ for 12h, and K 2 CO 3 SDCDPS was dried in a vacuum oven at 120 ℃ for 12h. 24.56g of bis (4-chloro-3-sulfonated phenyl) sulfone (SDCDPS), 14.36g of 4,4' -dichlorodiphenyl sulfone (DCDPS) and 18.62g of Biphenol (BP) were charged under nitrogen (99.999%, flow rate: 10-15) to a 500mL straight three-necked flask equipped with a water separator, a serpentine condenser, an elbow, a stirrer and an air-guide tube, and 144mL of N, N-dimethylacetamide (DMAc), 72mL of toluene (Tol) and 15.89g of anhydrous potassium carbonate were then charged thereto. DMAc is used as a solvent, anhydrous potassium carbonate is used as an acid binding agent, toluene is used as a water splitting agent, after the mixture is completely dissolved, the temperature is increased to 165 ℃ (oil bath temperature), toluene is refluxed and split for 12 hours, after the water splitting is completed, toluene in the system is removed through the water splitting device, the temperature is increased to 186 ℃ (oil bath temperature) to continue the reaction, the reaction is continued for 4 hours at the temperature, a dark brown viscous solution is obtained, the reaction is stopped, and the reaction solution is slowly poured into 1000mL of deionized water to obtain a white strip polymer. Heating (heating plate temperature) at 105 ℃ for 12h, and boiling for 3-4 times to remove the solvent and inorganic salt contained in the polymer, and finally obtaining the pure white strip polymer with the yield of Y=98%. Intrinsic viscosity: 0.52dL/g.
Preparation of sulfonated polyphenylsulfone (acid form):
the preparation method comprises the steps of pre-treating raw materials before starting reaction, placing 50% sulfonated polyphenylsulfone in a vacuum oven at 80 ℃ for drying for 12 hours, weighing 5g of dried sulfonated polyphenylsulfone, dissolving in 10mL of DMAC solution, slowly pouring the mixed solution into 2% HCl aqueous solution uniformly, and acidifying for 24 hours to obtain the white filamentous polymer. The fine thread-like objects are filtered out and placed in 100mL of deionized water, heated (heating disc temperature) for 12h at 80 ℃ and boiled for 3-4 times so as to remove the solvent and Hl contained in the polymer, after the common oven is fully dried at 80 ℃, the solid is transferred to a vacuum drying oven at 50 ℃ for drying for 48h, and finally the yellowish polymer is obtained, and the yield Y=98%. Intrinsic viscosity: 0.52dL/g.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (10)
1. A method for preparing a chitosan film, comprising the steps of:
s1: mixing chitosan, acid, C1-C6 monohydric alcohol, pore-forming agent and water to obtain casting solution, wherein the mixing time is 8-20 h, the mass content of the chitosan is 0.8-1.7%, the mass content of the acid is 0.5-5%, the mass content of the pore-forming agent is 0.5-10%, and the mass content of the C1-C6 monohydric alcohol is 10-50% based on the total mass of the casting solution; the pore-forming agent is PEG400 or PEG200, and the monohydric alcohol of C1-C6 is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol;
s2: placing the casting solution on a carrier, and performing heating treatment to completely volatilize C1-C6 monohydric alcohol and water in the casting solution to obtain a carrier loaded with a chitosan film; wherein the ratio of the volume of the casting solution to the surface area of the carrier is (5-30) mL/100 cm 2 ；
S3: and immersing the carrier loaded with the chitosan film into alkali liquor and water in sequence to separate the chitosan film from the carrier.
2. The method according to claim 1, wherein the casting solution is mixed with the casting solution in a mixing state,
the mass content of the acid is 1% -4%; and/or
The mass content of the pore-foaming agent is 1% -8%; and/or
The mass content of the monohydric alcohol of C1-C6 is 30% -40%.
3. The method according to claim 1, wherein the ratio of the volume of the casting solution to the surface area of the support is (7.5-25) mL/100 cm 2 。
4. The method according to claim 1, wherein the ratio of the volume of the casting solution to the surface area of the support is (15-22.5) mL/100 cm 2 。
5. The method according to any one of claims 1 to 4, wherein the chitosan has a degree of deacetylation of not less than 55%, and the chitosan has a molecular weight of 1X 10 5 -2×10 6 。
6. The method according to claim 5, wherein the chitosan has a degree of deacetylation of more than 70%, and the chitosan has a molecular weight of 3X 10 5 -7×10 5 。
7. The method according to any one of claims 1 to 4, wherein the carrier is selected from a glass plate, a ceramic plate, or an organic polymer plate;
and/or the acid is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid and trifluoroacetic acid;
and/or the alkali liquor is one or more of sodium hydroxide solution, potassium carbonate solution, sodium carbonate solution, potassium phosphate solution and sodium phosphate solution.
8. A chitosan film prepared according to the preparation method of any one of claims 1 to 7.
9. The chitosan membrane according to claim 8, wherein the average pore size of the chitosan membrane is 0.005 μm to 5 μm.
10. Use of a chitosan film prepared by the preparation method according to any one of claims 1 to 7 or the chitosan film according to claim 8 or 9 in a composite film material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111623544.XA CN114316349B (en) | 2021-12-28 | 2021-12-28 | Preparation method of chitosan film and chitosan film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111623544.XA CN114316349B (en) | 2021-12-28 | 2021-12-28 | Preparation method of chitosan film and chitosan film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114316349A CN114316349A (en) | 2022-04-12 |
| CN114316349B true CN114316349B (en) | 2023-11-10 |
Family
ID=81015067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111623544.XA Active CN114316349B (en) | 2021-12-28 | 2021-12-28 | Preparation method of chitosan film and chitosan film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114316349B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5993661A (en) * | 1997-04-14 | 1999-11-30 | The Research Foundation Of State University Of New York | Macroporous or microporous filtration membrane, method of preparation and use |
| CN111467978A (en) * | 2020-03-03 | 2020-07-31 | 贵州省材料产业技术研究院(贵州省复合改性聚合物材料工程技术研究中心、国家复合改性聚合物材料工程技术研究中心) | Method for preparing chitosan crosslinked styrene maleic anhydride/polyether sulfone composite nanofiltration membrane |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050006302A1 (en) * | 2003-01-22 | 2005-01-13 | Council Of Scientific And Industrial Research | Process for the preparation of porous membrane |
-
2021
- 2021-12-28 CN CN202111623544.XA patent/CN114316349B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5993661A (en) * | 1997-04-14 | 1999-11-30 | The Research Foundation Of State University Of New York | Macroporous or microporous filtration membrane, method of preparation and use |
| CN111467978A (en) * | 2020-03-03 | 2020-07-31 | 贵州省材料产业技术研究院(贵州省复合改性聚合物材料工程技术研究中心、国家复合改性聚合物材料工程技术研究中心) | Method for preparing chitosan crosslinked styrene maleic anhydride/polyether sulfone composite nanofiltration membrane |
Non-Patent Citations (2)
| Title |
|---|
| 壳聚糖膜的制备及在废水处理上的应用;田淑杰;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20070515;全文 * |
| 壳聚糖超滤膜制备及其在水产品加工废水处理中的应用;刘强;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20090215;第4.2.3.1节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114316349A (en) | 2022-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4774132A (en) | Polyvinylidene difluoride structure | |
| CN104248918B (en) | A kind of method that semi-intercrossing network method prepares hydrophilic anti-pollution composite hyperfiltration membrane | |
| CN103087342B (en) | Graphene oxide/PVDF (polyvinylidene fluoride) blended cation exchange membrane and preparation method thereof | |
| Han et al. | Homogeneous polyethersulfone hybrid membranes prepared with in-suit synthesized magnesium hydroxide nanoparticles by phase inversion method | |
| Zhang et al. | UV-crosslinked chitosan/polyvinylpyrrolidone blended membranes for pervaporation | |
| CN107376673B (en) | Loaded with TiO2PES ultrafiltration membrane of nanotube and preparation method and application thereof | |
| CN103464006B (en) | Preparation of PDMS/PVDF (polydimethylsiloxane/polyvinylidene fluoride) blended microporous film | |
| Ying et al. | Recovery of acetone from aqueous solution by ZIF-7/PDMS mixed matrix membranes | |
| CN102430343B (en) | Preparation method of flat polyvinylidene fluoride micro-filtration membrane | |
| CN104667768A (en) | Preparation method for novel anti-pollution polysulfone flat plate ultrafiltration membrane | |
| CN102580581A (en) | Composite ultrafiltration film and preparation method thereof | |
| CN101069750A (en) | Virus-eliminating filtering film and preparing method | |
| CN103143273A (en) | Preparation method of aromatic polymer porous membrane | |
| CN102489178B (en) | Method for preparing molybdenum disulfide pervaporation membrane for separating alcohol-containing wastewater | |
| CN114316349B (en) | Preparation method of chitosan film and chitosan film | |
| CN101816897A (en) | ZSM-5 molecular sieve filled silicon rubber/cellulose acetate composite membrane and preparation method thereof | |
| CN112675714A (en) | Polyarylester composite nanofiltration membrane and preparation method thereof | |
| CN100431676C (en) | Processing technology of polyacrylic acid and cellulose acetate composite membrane | |
| CN102266729A (en) | Organic-inorganic hydrid film used for pervaporation separation of methanol/methyl acetate azeotropic system and preparation method thereof | |
| JPH0536092B2 (en) | ||
| JP2513460B2 (en) | Composite semipermeable membrane and manufacturing method thereof | |
| CN110563229A (en) | Purification treatment process of high-salinity wastewater | |
| Kuo et al. | A new method for cellulose membrane fabrication and the determination of its characteristics | |
| CN1124175C (en) | Preparation method of dry type polyacrylointrile ultrafiltration membrane | |
| CN110860220A (en) | Preparation method of solvent-resistant modified polyaryletherketone ultrafiltration membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |