CN114307669B - Water-soluble aldehyde starch-polyethyleneimine coating modified polymer film and preparation method thereof - Google Patents
Water-soluble aldehyde starch-polyethyleneimine coating modified polymer film and preparation method thereof Download PDFInfo
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- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract description 90
- 229920002873 Polyethylenimine Polymers 0.000 title claims abstract description 79
- 238000000576 coating method Methods 0.000 title claims abstract description 56
- 239000011248 coating agent Substances 0.000 title claims abstract description 52
- 229920006254 polymer film Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920002472 Starch Polymers 0.000 claims abstract description 72
- 235000019698 starch Nutrition 0.000 claims abstract description 72
- 239000008107 starch Substances 0.000 claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000007864 aqueous solution Substances 0.000 claims abstract description 36
- 239000008367 deionised water Substances 0.000 claims abstract description 27
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- 238000005507 spraying Methods 0.000 claims abstract description 20
- 238000004140 cleaning Methods 0.000 claims abstract description 10
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- 238000000034 method Methods 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 16
- 239000012065 filter cake Substances 0.000 claims description 10
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- 238000006243 chemical reaction Methods 0.000 claims description 6
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- 238000001556 precipitation Methods 0.000 claims description 6
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
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- 239000003960 organic solvent Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 2
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- 239000000463 material Substances 0.000 description 15
- 230000004048 modification Effects 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 239000007921 spray Substances 0.000 description 7
- 239000004677 Nylon Substances 0.000 description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 229920001778 nylon Polymers 0.000 description 6
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- 238000000926 separation method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000001471 micro-filtration Methods 0.000 description 5
- 229920005597 polymer membrane Polymers 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 4
- 229960003638 dopamine Drugs 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
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- 238000011084 recovery Methods 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
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- DUDCYUDPBRJVLG-UHFFFAOYSA-N ethoxyethane methyl 2-methylprop-2-enoate Chemical compound CCOCC.COC(=O)C(C)=C DUDCYUDPBRJVLG-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000036541 health Effects 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 239000012466 permeate Substances 0.000 description 1
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
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- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
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Abstract
The invention provides a preparation method of a water-soluble aldehyde starch-polyethyleneimine coating modified polymer film, which comprises the following steps: step 1: preparing water-soluble aldehyde starch by adopting soluble starch; step 2: respectively preparing water-soluble aldehyde starch aqueous solution and polyethyleneimine aqueous solution; step 3: and alternately spraying a water-soluble aldehyde starch aqueous solution and a polyethyleneimine aqueous solution on the surface of the polymer film, heating the sprayed polymer film in an oven, taking out, and cleaning the film with deionized water to obtain the multifunctional modified polymer film. The invention also provides a water-soluble aldehyde starch-polyethyleneimine coating modified polymer film. The preparation method of the polymer film is simple, and the preparation process does not adopt an organic solvent, so that the polymer film has the characteristic of environmental protection.
Description
Technical Field
The invention belongs to the fields of energy conservation, environmental protection and new materials, and particularly relates to a method for modifying a polymer film by using a water-soluble aldehyde starch-polyethylenimine coating.
Background
The surface coating technology is a very practical method for improving the surface hydrophilicity of the film material, hydrophilic groups can be fixed on the surface of a commodity polymer film through the coating technology, the anti-pollution performance of the polymer film can be obviously improved, and various properties such as heavy metal adsorption, dye adsorption or antibiosis and the like can be endowed to the polymer film even through introduced functional groups.
By using the existing coating technology, the coating components from various small molecules to polymer macromolecules can be easily coated on the surface of the film by direct spraying, dip coating, spin coating and other methods. However, the existing coating technology has two problems: firstly, coating component diluents are often used in the coating process, and basically all the diluents are organic solvents which are easy to volatilize into the air to cause environmental pollution and harm to human health, and can dissolve polymer film base materials to destroy the body structure of the polymer film; second, the coating components are coated on the surface of the polymer film by a simple coating method to be adsorbed on the surface of the polymer film by secondary physical interaction, and the single coating components are not connected through chemical bonds between molecules and are easy to fall off from the surface of the film. In order to solve the above problems, researchers have carried out membrane modification studies using various water-soluble components, and the most reported methods in literature and patents are to modify polymer membranes with dopamine and its derivatives to impart anti-fouling properties thereto (CN 201310171221.0, CN201610936876.6, CN201610114843.3, CN201610901039.X, CN201710885393.2, CN201610648526.X, CN201510147356.2, CN 201710324332.9). Polydopamine inspired by mussels is a widely focused strategy for membrane modification due to the universality and universality of the polydopamine, and the simple and mild coating process of the polydopamine has excellent adhesion and good secondary reaction activity. When in use, the membrane is immersed in alkaline dopamine solution, so that hydrophilic polydopamine layer can be induced on the surface of the membrane, and polydopamine can be further grafted and introduced into other organic or inorganic materials to carry out multiple modification on the surface of the membrane material due to rich functional groups on the surface of the polydopamine. However, the dopamine raw material is expensive, is unfavorable for mass production and use, and needs to find a cheap substitute. Therefore, researchers further develop cheap similar substitutes for application, and the university of Nanchang Wang Zhenxing and the like are inspired by the easy adsorption of protein by a hydrophobic separation membrane and tanning of leather, develop a method for modifying the surface of the hydrophobic membrane by superhydrophilization based on protein adsorption-tannic acid curing, realize the efficient modification of various hydrophobic materials by polyphenols (Journal of Materials Chemistry A,2018,6,13959), and perform a series of application attempts (Journal of Materials Chemistry A,2018,6,3391,Journal of Membrane Science,2018,564,317), but when tannic acid is used as a coating, the coating reaction needs a long time, and an alcohol solvent is still needed by an application system developed later; zhang Ganwei, et al, from the university of Suzhou science and technology, have used poly (styrene-co-maleic anhydride) (PSMA) and Polyethylenimine (PEI) in a simple and quick way to coat a variety of substrate materials, including polyvinylidene fluoride (PVDF) microfiltration membranes, cotton, nylon mesh and stainless steel mesh, to improve their oil-water separation properties. The substrate material was coated with PSMA followed by PEI to produce a crosslinked polymer coating, and the entire coating process could be completed within 30 min. The copolymer coating can obviously endow the substrate material with super-hydrophilic and underwater super-oleophobic properties and underwater dynamic oil pollution resistance. All coating base materials can be used for separating oil-water mixtures, wherein the coating PVDF micro-filtration membrane has excellent oil-water emulsion separation performance (Industrial & Engineering Chemistry Research,2019,58,19475), the coating system can realize rapid crosslinking reaction, a stable hydrophilic polymer coating layer is formed on the surface of a polymer membrane, but a small amount of organic solvent is still required for PSMA used in the process; the water-soluble polymer poly (glycidyl methacrylate-co-poly (ethylene glycol) methyl ether methacrylate) P (GMA-co-mPEGMA) is further prepared, and the PVDF micro-filtration membrane is coated with an aqueous solution of P (GMA-co-mPEGMA) and Polyethyleneimine (PEI) by a spraying method so as to ensure the surface hydrophilicity and the pollution resistance of the PVDF micro-filtration membrane. P (GMA-co-mPEGA) and PEI have a plurality of reaction sites consisting of amino groups and epoxy groups, so that the opportunity for crosslinking reaction is greatly increased, and the stability of the coating is improved. As the coating components can use water as a solvent, the pollution to the environment (CN 202011397479.9) is reduced to the greatest extent, but P (GMA-co-mPEGMA) needs to be prepared by an atom transfer radical method and still uses an organic solvent, which is unfavorable for large-scale production and cannot control the green and environment-friendly characteristics of the whole process from the source.
In view of the above, a modified polymer film having a stable coating layer without using an organic solvent and having a simple preparation process has been desired.
Disclosure of Invention
In view of the above-described drawbacks of the prior art, an object of the present invention is to provide a water-soluble aldehyde starch-polyethylenimine coating modified polymer film;
the invention also aims to provide a preparation method of the water-soluble aldehyde starch-polyethyleneimine coating modified polymer film.
To achieve the above and other related objects, the present invention provides a method for modifying a polymer film with a water-soluble aldehyde starch-polyethylenimine coating, comprising the steps of:
step 1: preparing water-soluble aldehyde starch by adopting soluble starch;
step 2: respectively preparing water-soluble aldehyde starch aqueous solution and polyethyleneimine aqueous solution;
step 3: and alternately spraying a water-soluble aldehyde starch aqueous solution and a polyethyleneimine aqueous solution on the surface of the polymer film, heating the sprayed polymer film in an oven, taking out, and cleaning the film with deionized water to obtain the multifunctional modified polymer film.
Preferably, the preparation method of the water-soluble aldehyde starch in the step 1 comprises the following steps: placing soluble starch powder into a round-bottom flask, adding deionized water at 35 ℃, placing the round-bottom flask into a water bath at 35 ℃, adding sodium periodate after starch is completely dissolved under the magnetic stirring condition, wrapping the round-bottom flask with tinfoil paper to avoid light, and continuing stirring reaction; then adding acetone, suction filtering, dissolving the filter cake in deionized water, precipitating with acetone, repeatedly precipitating and washing twice, and finally vacuum drying the filter cake obtained by suction filtering at normal temperature to obtain the water-soluble aldehyde starch.
Preferably, the preparation method of the water-soluble aldehyde starch in the step 1 comprises the following steps: placing 10.65g of soluble starch powder into a 250mL round-bottom flask, adding 200mL of deionized water at 35 ℃, placing the round-bottom flask into a water bath at 35 ℃, adding 3.71g of sodium periodate after starch is completely dissolved under the magnetic stirring condition, wrapping the round-bottom flask with tinfoil paper to avoid light, and continuing stirring to react for 2 hours; then 400mL of acetone is added, suction filtration is carried out, the filter cake is dissolved in deionized water, then acetone precipitation is carried out, the precipitation and washing are repeated for two times, and finally, the filter cake obtained by suction filtration is dried in vacuum at normal temperature, thus obtaining the water-soluble aldehyde starch.
Preferably, the polymer film sprayed in the step 3 is placed in an oven to be heated at a temperature of 30-100 ℃ for 0.1-10 hours.
Preferably, the mass percentage concentration of the aldehyde starch in the water-soluble aldehyde starch aqueous solution is 0.1-10% (wt%).
Preferably, the mass percentage concentration of the aldehyde starch in the water-soluble aldehyde starch aqueous solution is 1-3% (wt%).
Preferably, the mass percentage concentration of the polyethyleneimine in the polyethyleneimine water solution is 0.1-30% (wt%).
Preferably, the mass percentage concentration of the polyethyleneimine in the polyethyleneimine water solution is 3-10% (wt%); the weight average molecular weight of the polyethyleneimine is 600-60000 g/mol; the spraying times of the water-soluble aldehyde starch solution and the polyethyleneimine solution are 1-10 times.
Preferably, the polymer membrane is a polyvinylidene fluoride membrane, a nylon membrane, a polysulfone membrane, a polyethersulfone membrane or a polyacrylonitrile membrane.
A water-soluble aldehyde starch-polyethyleneimine coating modified polymer film prepared by the method.
The method for modifying the polymer film by using the water-soluble aldehyde starch-polyethyleneimine coating and the farm have the following beneficial effects:
1) The two coating components of aldehyde starch and polyethyleneimine can be dissolved in water, so that the pollution to the environment and the damage to a polymer film caused by a common coating organic solvent can be avoided;
2) The aldehyde starch raw material used in the invention is a natural polymer derivative, and has wide raw material sources and low cost;
3) The aldehyde group in the aldehyde starch used in the invention can react with ammonia in polyethyleneimine at normal temperature, so that a very stable cross-linked coating can be formed on the surface of the polymer film rapidly;
4) The coating modified polymer film prepared by the invention not only has excellent hydrophilicity and anti-pollution performance, but also has the characteristics of oil-water separation, heavy metal adsorption separation, dye adsorption separation, antibiosis and the like.
Detailed Description
Further advantages and effects of the present invention will become apparent to those skilled in the art from the disclosure of the present invention, which is described by the following specific examples.
Example 1:
placing 10.65g of soluble starch powder into a 250mL round-bottom flask, adding 200mL of deionized water at 35 ℃, placing the round-bottom flask into a water bath at 35 ℃, adding 3.71g of sodium periodate after starch is completely dissolved under the magnetic stirring condition, wrapping the round-bottom flask with tinfoil paper to avoid light, and continuing stirring to react for 2 hours; then 400mL of acetone is added, suction filtration is carried out, the filter cake is dissolved in deionized water, then acetone precipitation is carried out, the precipitation and washing are repeated for two times, and finally, the filter cake obtained by suction filtration is dried in vacuum at normal temperature, thus obtaining the water-soluble aldehyde starch.
Example 2:
a method of modifying a polyvinylidene fluoride film (PVDF) with a water soluble aldehyde starch-polyethylenimine coating comprising the steps of:
step 1, preparing water-soluble aldehyde starch by adopting the preparation method of the embodiment 1;
step 2, respectively dissolving the water-soluble aldehyde starch and the polyethyleneimine (with the weight average molecular weight of 25000 g/mol) in deionized water to respectively prepare water-soluble aldehyde starch water-soluble polyethyleneimine water solution with the mass percentage concentration of 1% (wt%);
(3) Spraying water-soluble aldehyde starch aqueous solution and polyethyleneimine aqueous solution on the surface of the PVDF film alternately by utilizing a sprayer (or a spray gun or various sprayers under the conditions of air, no air and other conditions by a manual or automatic mode) for 3 times respectively; and (3) heating the PVDF film subjected to spray coating modification in an oven at 70 ℃ for 3 hours, taking out, and cleaning the film with deionized water to obtain the water-soluble aldehyde starch-polyethyleneimine coating modified PVDF film.
Example 3:
a method for modifying polyacrylonitrile by using a water-soluble aldehyde starch-polyethyleneimine coating, which comprises the following steps:
step 1, preparing water-soluble aldehyde starch by adopting the preparation method of the embodiment 1;
step 2, respectively dissolving the water-soluble aldehyde starch and the polyethyleneimine (with the weight average molecular weight of 10000 g/mol) in deionized water to respectively prepare a water-soluble aldehyde starch aqueous solution with the mass percentage concentration of 1.5 percent (wt%) and a polyethyleneimine aqueous solution with the mass percentage concentration of 5 percent (wt%);
step 3, alternately spraying the water-soluble aldehyde starch aqueous solution and the polyethyleneimine aqueous solution on the surface of the polyacrylonitrile membrane by using a sprayer (or a spray gun or various atomizers under the conditions of air, no air and other conditions in a manual or automatic mode), wherein the spraying is carried out for 2 times; and (3) heating the spray-modified polyacrylonitrile membrane in an oven at 60 ℃ for 3 hours, taking out, and cleaning the membrane with deionized water to obtain the water-soluble aldehyde starch-polyethyleneimine coating modified polyacrylonitrile membrane.
Example 4:
a method for modifying a nylon membrane with a water-soluble aldehyde starch-polyethylenimine coating, comprising the steps of:
step 1, preparing water-soluble aldehyde starch by adopting the preparation method of the embodiment 1;
step 2, respectively dissolving the water-soluble aldehyde starch and the polyethyleneimine (with the weight average molecular weight of 1800 g/mol) in deionized water to respectively prepare a water-soluble aldehyde starch aqueous solution with the mass percentage concentration of 3% (wt%) and a polyethyleneimine aqueous solution with the mass percentage concentration of 5% (wt%);
(3) The water-soluble aldehyde starch aqueous solution and the polyethyleneimine aqueous solution are alternately sprayed on the surface of the nylon membrane by utilizing a sprayer (or a spray gun or various sprayers are manually or automatically carried out under the conditions of air, no air and other conditions), and the spraying is carried out for 3 times respectively; and (3) heating the nylon membrane subjected to spray coating modification in a baking oven at 50 ℃ for 5 hours, taking out, and cleaning the membrane with deionized water to obtain the water-soluble aldehyde starch-polyethyleneimine coating modified nylon membrane.
Example 5:
a method of modifying a polyvinylidene fluoride film (PVDF) with a water soluble aldehyde starch-polyethylenimine coating comprising the steps of:
step 1, preparing water-soluble aldehyde starch by adopting the preparation method of the embodiment 1;
step 2, respectively dissolving the water-soluble aldehyde starch and the polyethyleneimine (with the weight average molecular weight of 60000 g/mol) in deionized water to respectively prepare water-soluble aldehyde starch water-soluble polyethyleneimine water solution with the mass percentage concentration of 1% (wt%);
(3) Spraying water-soluble aldehyde starch aqueous solution and polyethyleneimine aqueous solution on the surface of the PVDF film alternately by utilizing a sprayer (or a spray gun or various sprayers under the conditions of air, no air and other conditions by a manual or automatic mode) for 5 times respectively; and (3) heating the PVDF film subjected to spray coating modification in an oven at 60 ℃ for 2 hours, taking out, and cleaning the film with deionized water to obtain the water-soluble aldehyde starch-polyethyleneimine coating modified PVDF film.
Example 6:
a method of modifying a polyvinylidene fluoride film (PVDF) with a water soluble aldehyde starch-polyethylenimine coating comprising the steps of:
step 1, preparing water-soluble aldehyde starch by adopting the preparation method of the embodiment 1;
step 2, respectively dissolving the water-soluble aldehyde starch and the polyethyleneimine (with the weight average molecular weight of 10000 g/mol) in deionized water to respectively prepare water-soluble aldehyde starch water-soluble polyethyleneimine water solution with the mass percentage concentration of 2% (wt%);
(3) Spraying water-soluble aldehyde starch aqueous solution and polyethyleneimine aqueous solution on the surface of the PVDF film alternately by utilizing a sprayer (or a spray gun or various sprayers under the conditions of air, no air and other conditions by a manual or automatic mode) for 3 times respectively; and (3) heating the PVDF film subjected to spray coating modification in an oven at 80 ℃ for 1h, taking out, and cleaning the film with deionized water to obtain the water-soluble aldehyde starch-polyethyleneimine coating modified PVDF film.
Example 7:
a method of modifying a polyvinylidene fluoride film (PVDF) with a water soluble aldehyde starch-polyethylenimine coating comprising the steps of:
step 1, preparing water-soluble aldehyde starch by adopting the preparation method of the embodiment 1;
step 2, respectively dissolving the water-soluble aldehyde starch and the polyethyleneimine (with the weight average molecular weight of 10000 g/mol) in deionized water to respectively prepare water-soluble aldehyde starch water-soluble polyethyleneimine water solution with the mass percentage concentration of 0.5% (wt%) and polyethyleneimine water solution with the mass percentage concentration of 3% (wt%);
(3) Spraying water-soluble aldehyde starch aqueous solution and polyethyleneimine aqueous solution on the surface of the PVDF film alternately by utilizing a sprayer (or a spray gun or various sprayers under the conditions of air, no air and other conditions by a manual or automatic mode) for 3 times respectively; and (3) heating the PVDF film subjected to spray coating modification in an oven at 80 ℃ for 1h, taking out, and cleaning the film with deionized water to obtain the water-soluble aldehyde starch-polyethyleneimine coating modified PVDF film.
Example 8:
a method for modifying a polysulfone membrane with a water-soluble aldehyde starch-polyethyleneimine coating, comprising the steps of:
step 1, preparing water-soluble aldehyde starch by adopting the preparation method of the embodiment 1;
step 2, respectively dissolving the water-soluble aldehyde starch and the polyethyleneimine (with the weight average molecular weight of 25000 g/mol) in deionized water to respectively prepare water-soluble aldehyde starch water-soluble polyethyleneimine water solution with the mass percentage concentration of 3% (wt%);
(3) Spraying water-soluble aldehyde starch aqueous solution and polyethyleneimine aqueous solution on the surface of the PVDF film alternately by utilizing a sprayer (or a spray gun or various sprayers under the conditions of air, no air and other conditions by a manual or automatic mode) for 2 times respectively; and (3) heating the sprayed modified polysulfone membrane in an oven at 60 ℃ for 5 hours, taking out, and cleaning the membrane with deionized water to obtain the water-soluble aldehyde starch-polyethyleneimine coating modified PVDF membrane.
The modified polymer membrane material prepared in the above example was tested for hydrophilicity and anti-fouling performance, the hydrophilicity was represented by a water contact angle, and the anti-fouling performance was represented by a membrane flux recovery rate after filtration of a BSA solution.
The specific test method is as follows:
water contact angle test:
the water contact angle was measured by the lying drop method, 10 points were taken on one film sample using a contact angle measuring instrument, and the average value was calculated as the water contact angle of the film surface.
Membrane flux recovery test:
the deionization was poured into a ultrafilter cup, pre-pressed for 30min under nitrogen pressure at 0.1mpa, and then the time taken for 100mL permeate was calculated to calculate membrane flux. 1000ppm of BSA solution was poured into a ultrafilter cup and pre-pressed under nitrogen at 0.1mpa for 30min until the flux was constant. And (3) after the membrane polluted by bovine serum albumin is washed by sodium hypochlorite, testing the membrane flux and calculating the recovery rate of the membrane flux.
The properties of the modified polymer film materials prepared in the examples are shown in the following table:
table 1: properties of the modified polymer film materials produced in the examples:
from the properties of the hydrophilically modified PVDF microfiltration membranes prepared in examples 1 to 7, it can be seen that the modified polymer membrane materials of the invention are superior to the unmodified membrane samples in both hydrophilicity and anti-fouling properties.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (7)
1. A method for modifying a polymer film with a water-soluble aldehyde starch-polyethylenimine coating, comprising the steps of:
step 1: preparing water-soluble aldehyde starch by adopting soluble starch;
step 2: respectively preparing water-soluble aldehyde starch aqueous solution and polyethyleneimine aqueous solution;
step 3: alternately spraying a water-soluble aldehyde starch aqueous solution and a polyethyleneimine aqueous solution on the surface of a polymer film, heating the sprayed polymer film in an oven, taking out, and cleaning the film with deionized water to obtain a multifunctional modified polymer film; wherein,
the polymer film sprayed in the step 3 is placed in an oven to be heated at the temperature of 30-100 ℃ for 0.1-10 h;
the mass percentage concentration of the aldehyde starch in the water-soluble aldehyde starch aqueous solution is 0.1-10%;
the mass percentage concentration of the polyethyleneimine in the polyethyleneimine water solution is 0.1-30%;
the weight average molecular weight of the polyethyleneimine is 600-60000 g/mol;
the spraying times of the water-soluble aldehyde starch solution and the polyethyleneimine solution are 1-10 times.
2. The method for modifying a polymer film with a water-soluble aldehyde starch-polyethyleneimine coating according to claim 1, wherein the method for preparing the water-soluble aldehyde starch in step 1: placing soluble starch powder into a round-bottom flask, adding deionized water at 35 ℃, placing the round-bottom flask into a water bath at 35 ℃, adding sodium periodate after starch is completely dissolved under the magnetic stirring condition, wrapping the round-bottom flask with tinfoil paper to avoid light, and continuing stirring reaction; then adding acetone, suction filtering, dissolving the filter cake in deionized water, precipitating with acetone, repeatedly precipitating and washing twice, and finally vacuum drying the filter cake obtained by suction filtering at normal temperature to obtain the water-soluble aldehyde starch.
3. The method for modifying a polymer film with a water-soluble aldehyde starch-polyethyleneimine coating according to claim 2, wherein the water-soluble aldehyde starch preparation method in step 1: placing 10.65g of soluble starch powder into a 250mL round-bottom flask, adding 200mL of deionized water at 35 ℃, placing the round-bottom flask into a water bath at 35 ℃, adding 3.71g of sodium periodate after starch is completely dissolved under the magnetic stirring condition, wrapping the round-bottom flask with tinfoil paper to avoid light, and continuing stirring to react for 2 hours; then 400mL of acetone is added, suction filtration is carried out, the filter cake is dissolved in deionized water, then acetone precipitation is carried out, the precipitation and washing are repeated for two times, and finally, the filter cake obtained by suction filtration is dried in vacuum at normal temperature, thus obtaining the water-soluble aldehyde starch.
4. The method for modifying a polymer film with a water-soluble aldehyde starch-polyethyleneimine coating according to claim 3, wherein the concentration of the aldehyde starch in the water-soluble aldehyde starch aqueous solution is 1 to 3% by mass.
5. The method for modifying a polymer film with a water-soluble aldehyde starch-polyethyleneimine coating according to claim 4, wherein the mass percentage concentration of polyethyleneimine in the polyethyleneimine aqueous solution is 3% -10%.
6. The method for modifying a polymer film with a water-soluble aldehyde starch-polyethylenimine coating according to claim 1, 2, 3, 4 or 5, wherein the polymer film is a polyvinylidene fluoride film, a nylon film, a polysulfone film, a polyethersulfone film or a polyacrylonitrile film.
7. A water-soluble aldehyde starch-polyethylenimine coating modified polymer film prepared by the method of claim 6.
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