CN114146571A - Preparation method of high-flux quaternary ammonium salt structure porous membrane material for oil-water separation - Google Patents
Preparation method of high-flux quaternary ammonium salt structure porous membrane material for oil-water separation Download PDFInfo
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- 150000003242 quaternary ammonium salts Chemical group 0.000 title claims abstract description 57
- 239000012528 membrane Substances 0.000 title claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000000926 separation method Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920001721 polyimide Polymers 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 29
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims abstract description 21
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 36
- 229920005575 poly(amic acid) Polymers 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 21
- 238000002791 soaking Methods 0.000 claims description 20
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 18
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 12
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 238000010907 mechanical stirring Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 11
- 150000004985 diamines Chemical class 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 125000001302 tertiary amino group Chemical group 0.000 abstract 2
- 239000002253 acid Substances 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000007888 film coating Substances 0.000 description 4
- 238000009501 film coating Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 230000004907 flux Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- -1 metallurgy Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- Manufacturing & Machinery (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
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Abstract
The invention discloses a preparation method of a high-flux quaternary ammonium salt structure porous membrane material for oil-water separation, and relates to a preparation method of a high-flux quaternary ammonium salt structure porous membrane material for oil-water separation. The invention aims to solve the problem that the quaternary ammonium salt structure is damaged by temperature in the imidization process of preparing the hydrophilic polyimide film with the quaternary ammonium salt structure in the prior art. The method comprises the following steps: firstly, adding a diamine monomer containing a tertiary amine group in the polymerization process for copolymerization; secondly, imidizing to prepare a polyimide film containing a tertiary amine group; and thirdly, performing quaternary ammonium salt reaction on the surface of the prepared polyimide film and propane sultone to finally obtain the hydrophilic polyimide film. The invention can well control the reaction temperature, ensure the mechanical property of the film, solve the problem that the temperature damages the quaternary ammonium salt structure in the imidization process in the past, and prepare the polyimide film material with good acid and alkali resistance and hydrophilic property. The invention is suitable for the membrane material used for water treatment.
Description
Technical Field
The invention relates to a preparation method of a high-flux quaternary ammonium salt structure porous membrane material for oil-water separation.
Background
The rapid development of industries such as oil exploitation, petrochemical industry, medicine, metallurgy, textile, food and the like generates a large amount of oily wastewater, and how to rapidly and efficiently treat the oily wastewater is a current research hotspot. The most effective method for treating the oily wastewater at present is a membrane separation technology, which is simple to operate, efficient and rapid, can be applied to large-scale industrialization and has no secondary pollution.
The membrane separation effect is influenced by the hydrophilicity and hydrophobicity of the membrane and the size of the interaction between surface properties and solutes. Hydrophobic membranes, which are composed of olefin-based polymers and which are effective in removing small amounts of water impurities from oils, have been studied more. However, when treating oily wastewater containing a small amount of oil, water is often forced to pass through the hydrophobic membrane to become a penetrating fluid, impurities such as oil are left on the surface of the membrane, so that 'concentration polarization' is generated quickly, the membrane is seriously polluted, and oil molecules are easy to agglomerate in pores of the hydrophobic membrane to block the water from passing through, so that the water flux is reduced sharply. Therefore, to prevent membrane fouling, the chemical nature of the membrane surface should be such that it is more accessible to water, which dictates the need for hydrophilic membrane materials.
At present, the research at home and abroad finds that the hydrophilic modification method of the membrane can be roughly summarized into the following three modes: surface coating, surface grafting by chemical method and blending modification. Three membrane hydrophilic modification methods have respective advantages and disadvantages. The surface coating method is the simplest method for improving the hydrophilic effect of the membrane surface, and a hydrophilic substance with a certain specific functional group is coated or precipitated on the membrane surface in a direct mode or an indirect mode, so that a hydrophilic layer is formed on the membrane surface, and the hydrophilic effect of the membrane is further improved. However, the hydrophilic coating layer formed on the membrane surface by the surface coating method is formed by physical adsorption, has a disadvantage of instability, and the hydrophilic layer is easily eluted during the operation and washing, loses the ability to work for a long time, and is not suitable for mass production, and in order to secure a high coating rate, a large amount of additives are required to increase the production cost, which is expensive. Grafting on the surface of the membrane can block pores on the surface of the membrane, and the water flux of the membrane is reduced to a certain extent; the operation process of surface grafting is complex, the forming preparation and the functional modification of the membrane material are carried out in two steps, the surface of the membrane is easy to be damaged mechanically, certain influence can be caused to the original mechanical strength of the membrane in the modification process, and the use effect of the membrane is reduced. The blending modification is a common method in batch production, the preparation and modification processes can be completed in one unit, any pretreatment and post-treatment are not needed, the preparation process is simple, the cost is low, and the method is a modification method which is most easy to realize industrial production. However, the most serious defects of the blending modification are poor durability, easy internal migration and poor stability.
The separation membrane can realize effective oil-water separation, diamine monomers containing sulfonic acid groups are introduced into a polymer main chain to prepare a film, and the polyimide film with the main chain containing hydrophilic sulfonic acid groups is synthesized by utilizing the characteristic reaction of quaternary ammonium salt of propane sultone.
The hydrophilic polyimide film containing the quaternary ammonium salt structure has excellent mechanical properties and chemical stability which are peculiar to the PI film, and due to the characteristic structure of the grafted quaternary ammonium salt, the surface of the prepared film has good hydrophilic properties and can give consideration to both mechanical properties and hydrophilicity. However, in the imidization process of the existing hydrophilic polyimide film with the quaternary ammonium salt structure, the quaternary ammonium salt structure is damaged due to the temperature, so that the hydrophilic polyimide film loses the advantages of the quaternary ammonium salt structure.
Disclosure of Invention
The invention provides a preparation method of a high-flux quaternary ammonium salt structure porous membrane material for oil-water separation, aiming at solving the problem that the temperature damages the quaternary ammonium salt structure in the imidization process of the existing preparation of a quaternary ammonium salt structure hydrophilic polyimide film.
The preparation method of the high-flux quaternary ammonium salt structure porous membrane material for oil-water separation is specifically carried out according to the following steps:
firstly, dissolving 4, 4' -diaminodiphenyl ether and N-methyl-2, 2-diaminodiethylamine in N, N-dimethylacetamide solvent under the condition of mechanical stirring, after completely dissolving, adding diphenyl ether tetracid dianhydride into the mixture in batches; stirring for 4-6 h at room temperature to obtain a polyamic acid solution; the solid content of the polyamic acid solution is 25%;
secondly, filtering the polyamic acid solution by using a filter screen, and coating the polyamic acid solution on a clean glass plate by using an automatic coating machine to obtain a film; the thickness of the film is controlled to be 10-30 mu m;
thirdly, placing the film obtained in the second step in a drying oven for heating and drying at the temperature of 130-350 ℃, wherein the heating time is 2-4 h, and naturally cooling to room temperature to obtain a polyamic acid film;
fourthly, soaking the polyamic acid film obtained in the third step in a solvent, and weighing 1, 3-propane sultone and adding the weighed 1, 3-propane sultone into the solvent; soaking the film in a clean water phase for 48 hours at room temperature to obtain a hydrophilic polyimide film containing a quaternary ammonium salt structure; the amount of the 1, 3-propane sultone and N-methyl-2, 2-diaminodiethylamine is the same.
The invention has the beneficial effects that:
the method has the advantages of simple and easy reaction, simple process and easy operation.
Secondly, the invention can well control the reaction temperature by the reaction of propane sultone and the characteristic quaternary ammonium salt of tertiary amine, ensure the mechanical property of the film and solve the problem that the temperature damages the quaternary ammonium salt structure in the imidization process in the past.
The molecular weight and the reaction temperature of the hydrophilic film polymer prepared by the invention are controllable, so that the mechanical property and the hydrophilic property of the material are considered, and the problem of low mechanical strength in the past is solved.
The invention is used for preparing the hydrophilic polyimide film with the quaternary ammonium salt structure.
Drawings
FIG. 1 is a photograph of a film obtained in step two of the example;
FIG. 2 is a graph showing the infrared contrast of the polyamic acid film obtained in the third step and the hydrophilic polyimide film containing a quaternary ammonium salt structure obtained in the fourth step of the example at different heating temperatures; wherein a is the polyamic acid film obtained in the third step, and b is the hydrophilic polyimide film containing the quaternary ammonium salt structure obtained in the fourth step;
FIG. 3 is a static contact angle image of a polyamic acid film obtained in step three of the example;
fig. 4 is a static contact angle image of the hydrophilic polyimide film containing a quaternary ammonium salt structure obtained in the fourth step of the example.
Detailed Description
The first embodiment is as follows: the preparation method of the high-flux quaternary ammonium salt structure porous membrane material for oil-water separation in the embodiment specifically comprises the following steps:
firstly, dissolving 4, 4' -diaminodiphenyl ether and N-methyl-2, 2-diaminodiethylamine in N, N-dimethylacetamide solvent under the condition of mechanical stirring, after completely dissolving, adding diphenyl ether tetracid dianhydride into the mixture in batches; stirring for 4-6 h at room temperature to obtain a polyamic acid solution; the solid content of the polyamic acid solution is 25%;
secondly, filtering the polyamic acid solution by using a filter screen, and coating the polyamic acid solution on a clean glass plate by using an automatic coating machine to obtain a film; the thickness of the film is controlled to be 10-30 mu m;
thirdly, placing the film obtained in the second step in a drying oven for heating and drying at the temperature of 130-350 ℃, wherein the heating time is 2-4 h, and naturally cooling to room temperature to obtain a polyamic acid film;
fourthly, soaking the polyamic acid film obtained in the third step in a solvent, and weighing 1, 3-propane sultone and adding the weighed 1, 3-propane sultone into the solvent; soaking the film in a clean water phase for 48 hours at room temperature to obtain a hydrophilic polyimide film containing a quaternary ammonium salt structure; the amount of the 1, 3-propane sultone and N-methyl-2, 2-diaminodiethylamine is the same. .
The polyamic acid solution obtained in step one of the present embodiment is yellow, viscous, clear and transparent.
The method has the advantages of simple and easy reaction, simple process and easy operation.
In the embodiment, a polyimide film material having hydrophilic properties is prepared by designing a molecular structure.
According to the hydrophilic film obtained by the embodiment, the reaction temperature can be well controlled through the reaction of propane sultone and the characteristic quaternary ammonium salt of tertiary amine, the mechanical property of the film is ensured, and the problem that the temperature damages the quaternary ammonium salt structure in the imidization process in the past is solved.
The polymer molecular weight and the reaction temperature of the hydrophilic film obtained by the embodiment are controllable, so that the mechanical property and the hydrophilic property of the material are both considered, the problem of low mechanical strength in the past is solved, and a technical and material basis is provided for preparing a porous film material with high flux and high separation efficiency.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: in the first step, the quantity ratio of the total quantity of the 4, 4' -diaminodiphenyl ether and N-methyl-2, 2-diaminodiethylamine to the diphenyl ether tetracarboxylic dianhydride substance is 1 (1-1.2). The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the quantity ratio of the total quantity of the 4, 4' -diaminodiphenyl ether and N-methyl-2, 2-diaminodiethylamine in the first step to the quantity of diphenyl ether tetracarboxylic dianhydride substance is 1: 1.1. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the quantity ratio of the total quantity of the 4, 4' -diaminodiphenyl ether and N-methyl-2, 2-diaminodiethylamine in the first step to the quantity of diphenyl ether tetracarboxylic dianhydride substance is 1: 1.05. The others are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the specific mode of adding the diphenyl ether tetracid dianhydride in batches in the first step is that the diphenyl ether tetracid dianhydride is added for 8 times in 4h, the adding amount of the first time is 1/2 of the total substance amount, the adding amount of the second time is 1/4 of the total substance amount, the adding amount of the third time is 1/8 of the total substance amount, the adding amount of the fourth time is 1/16 of the total substance amount, the adding amount of the fifth time is 1/32 of the total substance amount, the adding amount of the sixth time is 1/64 of the total substance amount, the adding amount of the seventh time is 1/128 of the total substance amount, and the adding amount of the eighth time is the residual diphenyl ether tetracid dianhydride. The other is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: and the thickness of the film in the second step is controlled to be 20 mu m. The other is the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and in the third step, the mixture is placed in an oven to be heated and dried under the condition that the temperature is 140 ℃. The other is the same as one of the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: and in the third step, the mixture is placed in an oven to be heated and dried under the condition that the temperature is 150 ℃. The other is the same as one of the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: and step three, placing the mixture in an oven to be heated and dried under the condition that the temperature is 200 ℃. The rest is the same as the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: the third step is carried out by heating and drying in an oven at a temperature of 300 ℃ as in any one of the first to ninth embodiments.
The beneficial effects of the present invention are demonstrated by the following examples:
the first embodiment is as follows: the preparation method of the high-flux quaternary ammonium salt structure porous membrane material for oil-water separation specifically comprises the following steps:
firstly, 63g of 4,4 '-diaminodiphenyl ether and 2.6g N-methyl-2, 2-diaminodiethylamine are weighed and dissolved in N, N-dimethylacetamide solvent under the condition of mechanical stirring, and after the 4, 4' -diaminodiphenyl ether and 2.6-methyl-2, 2-diaminodiethylamine are completely dissolved, 40g of diphenyl ether tetracarboxylic dianhydride is added in turn in batches. Stirring and reacting at room temperature, and continuously stirring for 4h after the feeding is finished to obtain yellow viscous clear transparent polyamic acid solution. The solid content of the polyamic acid solution is 25%;
secondly, filtering the PAA solution by a filter screen, and coating a film on a clean glass plate by an automatic film coating machine, wherein the thickness of the film can be controlled to be 10 mu m;
thirdly, heating the film in an oven at the temperature of 130 ℃ for 4 hours, and naturally cooling to room temperature;
fourthly, soaking the film in a solvent, weighing 2.7g of 1, 3-propane sultone with the same amount of the N-methyl-2, 2-diaminodiethylamine and adding the weighed 1, 3-propane sultone into the solvent. And soaking at room temperature for 48h, and then soaking in a clean water phase to obtain the hydrophilic polyimide film containing the quaternary ammonium salt structure.
Example one prepared hydrophilic polyimide film with a quaternary ammonium salt structure was light yellow in color.
Example two: the preparation method of the high-flux quaternary ammonium salt structure porous membrane material for oil-water separation specifically comprises the following steps:
firstly, 63g of 4,4 '-diaminodiphenyl ether and 2.6g N-methyl-2, 2-diaminodiethylamine are weighed and dissolved in N, N-dimethylacetamide solvent under the condition of mechanical stirring, and after the 4, 4' -diaminodiphenyl ether and 2.6-methyl-2, 2-diaminodiethylamine are completely dissolved, 40g of diphenyl ether tetracarboxylic dianhydride is added in turn in batches. Stirring and reacting at room temperature, and continuously stirring for 4h after the feeding is finished to obtain yellow viscous clear transparent polyamic acid solution. The solid content of the polyamic acid solution is 25%;
secondly, filtering the PAA solution by a filter screen, and coating a film on a clean glass plate by an automatic film coating machine, wherein the thickness of the film can be controlled to be 10 mu m;
thirdly, heating the film in an oven at the temperature of 140 ℃ for 4 hours, and naturally cooling to room temperature;
fourthly, soaking the film in a solvent, weighing 2.7g of 1, 3-propane sultone with the same amount of the N-methyl-2, 2-diaminodiethylamine and adding the weighed 1, 3-propane sultone into the solvent. And soaking at room temperature for 48h, and then soaking in a clean water phase to obtain the hydrophilic polyimide film containing the quaternary ammonium salt structure.
Example three: the preparation method of the high-flux quaternary ammonium salt structure porous membrane material for oil-water separation specifically comprises the following steps:
firstly, 63g of 4,4 '-diaminodiphenyl ether and 2.6g N-methyl-2, 2-diaminodiethylamine are weighed and dissolved in N, N-dimethylacetamide solvent under the condition of mechanical stirring, and after the 4, 4' -diaminodiphenyl ether and 2.6-methyl-2, 2-diaminodiethylamine are completely dissolved, 40g of diphenyl ether tetracarboxylic dianhydride is added in turn in batches. Stirring and reacting at room temperature, and continuously stirring for 4h after the feeding is finished to obtain yellow viscous clear transparent polyamic acid solution. The solid content of the polyamic acid solution is 25%;
secondly, filtering the PAA solution by a filter screen, and coating a film on a clean glass plate by an automatic film coating machine, wherein the thickness of the film can be controlled to be 20 mu m;
thirdly, heating the film in an oven at the temperature of 140 ℃ for 4 hours, and naturally cooling to room temperature;
fourthly, soaking the film in a solvent, weighing 2.7g of 1, 3-propane sultone with the same amount of the N-methyl-2, 2-diaminodiethylamine and adding the weighed 1, 3-propane sultone into the solvent. And soaking at room temperature for 48h, and then soaking in a clean water phase to obtain the hydrophilic polyimide film containing the quaternary ammonium salt structure.
Example four: the preparation method of the high-flux quaternary ammonium salt structure porous membrane material for oil-water separation specifically comprises the following steps:
firstly, 63g of 4,4 '-diaminodiphenyl ether and 2.6g N-methyl-2, 2-diaminodiethylamine are weighed and dissolved in N, N-dimethylacetamide solvent under the condition of mechanical stirring, and after the 4, 4' -diaminodiphenyl ether and 2.6-methyl-2, 2-diaminodiethylamine are completely dissolved, 40g of diphenyl ether tetracarboxylic dianhydride is added in turn in batches. Stirring and reacting at room temperature, and continuously stirring for 4h after the feeding is finished to obtain yellow viscous clear transparent polyamic acid solution. The solid content of the polyamic acid solution is 25%;
secondly, filtering the PAA solution by a filter screen, and coating a film on a clean glass plate by an automatic film coating machine, wherein the thickness of the film can be controlled to be 20 mu m;
thirdly, heating the film in an oven at the temperature of 280 ℃ for 4 hours, and naturally cooling to room temperature;
fourthly, soaking the film in a solvent, weighing 2.7g of 1, 3-propane sultone with the same amount of the N-methyl-2, 2-diaminodiethylamine and adding the weighed 1, 3-propane sultone into the solvent. And soaking at room temperature for 48h, and then soaking in a clean water phase to obtain the hydrophilic polyimide film containing the quaternary ammonium salt structure.
FIG. 1 is a photograph of a film obtained in step two of the example; FIG. 2 is a graph showing the infrared contrast of the polyamic acid film obtained in the third step and the hydrophilic polyimide film containing a quaternary ammonium salt structure obtained in the fourth step of the example at different heating temperatures; wherein a is the polyamic acid film obtained in the third step, and b is the hydrophilic polyimide film containing the quaternary ammonium salt structure obtained in the fourth step; FIG. 3 is a static contact angle image of a polyamic acid film obtained in step three of the example; fig. 4 is a static contact angle image of the hydrophilic polyimide film containing a quaternary ammonium salt structure obtained in the fourth step of the example. As can be seen from fig. 1, the polyimide film was uniformly smooth and pale yellow; as can be seen from the infrared image in FIG. 2, the polyimide film soaked with the lactone successfully completes the quaternary ammonium salt reaction to obtain a polyimide film containing a quaternary ammonium salt structure; as can be seen from the contact angle photograph in fig. 3, the contact angle of the polyimide film after soaking in lactone was lower than that of the film before soaking, demonstrating that the polyimide film containing the oil quaternary ammonium salt structure was hydrophilic.
Claims (10)
1. A preparation method of a high-flux quaternary ammonium salt structure porous membrane material for oil-water separation is characterized in that the preparation method of the high-flux quaternary ammonium salt structure porous membrane material for oil-water separation is specifically carried out according to the following steps:
firstly, dissolving 4, 4' -diaminodiphenyl ether and N-methyl-2, 2-diaminodiethylamine in N, N-dimethylacetamide solvent under the condition of mechanical stirring, after completely dissolving, adding diphenyl ether tetracid dianhydride into the mixture in batches; stirring for 4-6 h at room temperature to obtain a polyamic acid solution; the solid content of the polyamic acid solution is 25%;
secondly, filtering the polyamic acid solution by using a filter screen, and coating the polyamic acid solution on a clean glass plate by using an automatic coating machine to obtain a film; the thickness of the film is controlled to be 10-30 mu m;
thirdly, placing the film obtained in the second step in a drying oven for heating and drying at the temperature of 130-350 ℃, wherein the heating time is 2-4 h, and naturally cooling to room temperature to obtain a polyamic acid film;
fourthly, soaking the polyamic acid film obtained in the third step in a solvent, and weighing 1, 3-propane sultone and adding the weighed 1, 3-propane sultone into the solvent; soaking the film in a clean water phase for 48 hours at room temperature to obtain a hydrophilic polyimide film containing a quaternary ammonium salt structure; the amount of the 1, 3-propane sultone and N-methyl-2, 2-diaminodiethylamine is the same.
2. The method for preparing a high-flux quaternary ammonium salt structure porous membrane material for oil-water separation according to claim 1, wherein the ratio of the sum of the amounts of the 4, 4' -diaminodiphenyl ether and N-methyl-2, 2-diaminodiethylamine to the amount of diphenyl ether tetracarboxylic dianhydride in the first step is 1 (1-1.2).
3. The method for preparing a high-flux quaternary ammonium salt structure porous membrane material for oil-water separation according to claim 2, wherein the ratio of the sum of the amounts of the 4, 4' -diaminodiphenyl ether and N-methyl-2, 2-diaminodiethylamine to the amount of diphenyl ether tetracarboxylic dianhydride substance in step one is 1: 1.1.
4. The method for preparing a high-flux quaternary ammonium salt structure porous membrane material for oil-water separation according to claim 2, wherein the ratio of the sum of the amounts of the 4, 4' -diaminodiphenyl ether and N-methyl-2, 2-diaminodiethylamine to the amount of diphenyl ether tetracarboxylic dianhydride substance in step one is 1: 1.05.
5. The method for preparing a high-flux quaternary ammonium salt structure porous membrane material for oil-water separation according to claim 1, wherein the step one of feeding diphenyl ether tetracarboxylic dianhydride in batches is performed 8 times in 4 hours, the first feeding is 1/2 times of the total amount of substances, the second feeding is 1/4 times of the total amount of substances, the third feeding is 1/8 times of the total amount of substances, the fourth feeding is 1/16 times of the total amount of substances, the fifth feeding is 1/32 times of the total amount of substances, the sixth feeding is 1/64 times of the total amount of substances, the seventh feeding is 1/128 times of the total amount of substances, and the eighth feeding is the residual diphenyl ether tetracarboxylic dianhydride.
6. The method for preparing a high-flux quaternary ammonium salt structure porous membrane material for oil-water separation according to claim 1, wherein the thickness of the membrane in the second step is controlled to be 20 μm.
7. The method for preparing the porous membrane material with the high-flux quaternary ammonium salt structure for oil-water separation according to claim 1, wherein the porous membrane material is dried by heating in an oven at a temperature of 140 ℃ in the third step.
8. The method for preparing the porous membrane material with the high-flux quaternary ammonium salt structure for oil-water separation according to claim 1, wherein the drying is carried out in an oven at a temperature of 150 ℃ in the third step.
9. The method for preparing the porous membrane material with the high-flux quaternary ammonium salt structure for oil-water separation according to claim 1, wherein the drying is carried out in an oven at a temperature of 200 ℃ in the third step.
10. The method for preparing the porous membrane material with the high-flux quaternary ammonium salt structure for oil-water separation according to claim 1, wherein the drying is carried out in an oven at a temperature of 300 ℃ in the third step.
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| US20020010311A1 (en) * | 1999-11-24 | 2002-01-24 | Edman James Richard | Polyimide composition having improved peel strength when clad |
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