CN112808022A - Polyvinyl amine membrane with hydrophilic and hydrophobic functional groups and preparation method and application thereof - Google Patents
Polyvinyl amine membrane with hydrophilic and hydrophobic functional groups and preparation method and application thereof Download PDFInfo
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- B01D69/10—Supported membranes; Membrane supports
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B01D71/60—Polyamines
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Abstract
The invention provides a polyvinylamine membrane with hydrophilic and hydrophobic functional groups and a preparation method and application thereof, wherein the membrane comprises a separation layer and a supporting layer; wherein the separating layer is a product obtained by further grafting a hydrophobic side chain aldehyde group-containing compound on guanidyl-modified polyvinylamine; the supporting layer is a polyacrylonitrile ultrafiltration membrane. According to the invention, part of hydrophilic group amino groups in polyvinylamine are modified into more hydrophilic guanidyl by regulating and controlling a hydrophilic group structure and a microphase topological structure in a membrane, and meanwhile, part of amino groups are grafted with aldehyde compounds with hydrophobic side chains, and microphase separation is carried out in the membrane by utilizing the polarity difference of hydrophilic and hydrophobic groups on a polymer chain, so that a continuous hydrophilic channel is formed by induction, the water transfer is promoted, and the selectivity and the permeability of the membrane to water are improved at the same time.
Description
Technical Field
The invention relates to the technical field of membrane separation, in particular to a polyvinylamine membrane with hydrophilic and hydrophobic functional groups, and a preparation method and application thereof.
Background
Pervaporation, also known as pervaporation, is a novel membrane separation technology and is particularly suitable for separating near-boiling point and constant-boiling point organic mixture solution which is difficult to separate or cannot be separated by a distillation method; the membrane separation technology is widely used for removing organic solvent and water in a mixture, removing a small amount of volatile organic compounds in wastewater and recovering high value-added components in an aqueous solution. Compared with other traditional dehydration methods, the pervaporation technology has the advantages of simple operation, high product purity, small raw material loss, no pollution in the process, low energy consumption, easy coupling and the like, and has obvious technical and economic advantages in production.
The pervaporation technology is that vacuum is formed at the permeation side of the membrane, the chemical potential difference between the front side and the rear side of the membrane is taken as a driving force to accompany phase change, and separation is carried out by selective adsorption of the membrane and different permeation rates in the membrane; therefore, membrane materials are the core of pervaporation technology, and ideal pervaporation membranes must have both high permeability and high selectivity. The membrane material used in the prior art is mostly a polymer membrane and generally follows a dissolution diffusion mechanism, namely, the diffusion of the solvent and the solute in the membrane obeys Fick's law, and both the solvent and the solute can be dissolved on the surface of the membrane, so the permeability of the substance not only depends on the diffusion coefficient, but also depends on the solubility of the substance in the membrane, and the diffusion coefficient of the solute is much smaller than that of water molecules, so that the quantity of water molecules penetrating through the membrane is more than that of the solute penetrating through diffusion; therefore, if the solubility of the polymeric membrane can be increased to increase the selectivity of the membrane and the molecular chain spacing is increased to improve the permeability of the membrane, the problem of the mutual restriction between the permeability and the selectivity can be fundamentally solved, and the separation capacity of the pervaporation membrane can be improved.
Disclosure of Invention
The invention aims to provide a polyvinylamine membrane with hydrophilic and hydrophobic functional groups, and a preparation method and application thereof. Through regulating and controlling the hydrophilic group structure and the microphase topological structure in the membrane, part of hydrophilic group amino groups in the polyvinylamine are modified into more hydrophilic guanidyl to improve the solubility of the polymeric membrane, and meanwhile, part of amino groups are grafted with aldehyde compounds with hydrophobic side chains to increase the distance between the polymeric chains, thereby improving the permeability of the membrane; the polarity difference of hydrophilic and hydrophobic groups on a polymer chain is utilized to carry out microphase separation in the membrane, a continuous hydrophilic channel is formed by induction, and the transfer of water is promoted, so that the selectivity and the permeability of the membrane to water are improved.
One of the technical schemes of the invention is that the polyvinylamine membrane with hydrophilic and hydrophobic functional groups comprises a separation layer and a support layer; wherein the separation layer is a product obtained by further grafting a hydrophobic side chain aldehyde group-containing compound on guanidyl-modified polyvinylamine.
Further, the support layer is a polyacrylonitrile ultrafiltration membrane.
In the second technical scheme of the invention, the preparation method of the polyvinylamine membrane with hydrophilic and hydrophobic functional groups comprises the following steps:
(1) ion exchange is carried out on the polyvinylamine to prepare deionized polyvinylamine;
(2) modifying part of amido and cyanamide in deionized polyvinyl amine to obtain polyvinyl guanidine;
(3) carrying out mixed reaction on the polyethylene guanidine and a hydrophobic side chain aldehyde group-containing compound to prepare a polyethylene guanidine solution with part of amine grafted hydrophobic side chain aldehyde group-containing compound;
(4) crosslinking a polyethylene guanidine solution grafted with a part of amino and containing hydrophobic side chain aldehyde group compound with glutaraldehyde to obtain a crosslinked polyethylene guanidine solution containing hydrophobic side chains;
(5) and (3) coating the crosslinked polyethylene guanidine solution containing the hydrophobic side chain on a polyacrylonitrile base film, standing and carrying out microphase separation to obtain the polyethylene amine film with hydrophilic and hydrophobic functional groups.
Further, the preparation process of the polyvinylamine in the step (1) comprises the following steps:
n-vinylformamide, deionized water and an initiator are mixed according to the weight ratio of 1: (6-7): (0.008-0.009), mixing, introducing nitrogen gas for 2-5min, vacuumizing, reacting at 45-55 deg.C for 2-5h, adding acid solution, hydrolyzing for 1.5-2.5h, precipitating with alcohol, and drying to obtain polyvinylamine;
wherein the initiator is one of 2, 2-azobisisobutyronitrile, azodiisopropylimidazoline hydrochloride and azobisisoheptonitrile; the acid solution is one of hydrochloric acid, nitric acid and acetic acid, and the concentration of the acid solution is 1-2 mol/L.
Further, the deionization reaction of the polyvinylamine in the step (1) specifically comprises:
adding activated strong-base anion exchange resin into 3 wt% of polyvinylamine solution, carrying out ion exchange for 6-8 hours under the stirring condition, and filtering to obtain deionized polyvinylamine;
wherein the mass ratio of the strongly basic anion exchange resin to the polyvinylamine is 8:1-10: 1.
Further, the step (2) specifically includes the following steps:
putting the deionized polyvinylamine into an acetic acid solution containing cyanamide at the temperature of 70-90 ℃ for reacting for 3-6h to obtain the polyvinylguanidine;
wherein the mol ratio of the deionized polyvinylamine to the cyanamide to the acetic acid is 1 (0.1-0.2) to 0.05-0.2.
Further, the step (3) specifically includes the following steps:
dripping a mixed solution of acetic acid and tetrahydrofuran containing a hydrophobic side chain aldehyde compound into a polyvinyl guanidine solution at the temperature of 20-30 ℃, and reacting for 2-3h to obtain part of polyvinyl guanidine with amino grafted hydrophobic side chain aldehyde compound;
wherein, the mol ratio of the polyethylene guanidine, the hydrophobic side chain aldehyde compound and the acetic acid is 1 (0.04-0.1) to 0.01-0.08; the grafting range is 4-10%;
when the grafting amount is less than 4%, the content of a hydrophobic chain is low, the proportion of hydrophobic and hydrophilic groups is low, the polarity difference is small, the microphase separation is not obvious, when the grafting amount is more than 10%, the proportion of the hydrophobic and hydrophilic groups is increased, the microphase separation is obvious, a hydrophilic channel is formed, and when the grafting amount is higher, too many hydrophilic group amino groups are consumed, the hydrophilicity of the membrane is reduced, and the transfer and selection of water are not facilitated.
The mass ratio of the tetrahydrofuran to the polyethylene guanidine solution is 1 (10-20).
Further, the step (4) comprises the steps of:
heating a part of the polyethylene guanidine solution grafted with the hydrophobic side chain aldehyde group-containing compound to 30 ℃, dropwise adding 2 wt% glutaraldehyde solution, carrying out crosslinking reaction for 1h, defoaming, and standing to obtain the polyethylene guanidine solution containing the hydrophobic side chain;
wherein, the molar ratio of the polyethylene guanidine with part of amine group grafted hydrophobic side chain aldehyde group compound to the glutaraldehyde is 1 (0.005-0.02).
Further, the step (5) includes the steps of:
coating the hydrophobic side chain-containing polyguanidine solution on a supporting layer, standing for microphase separation to obtain a poly vinylamine membrane with hydrophilic and hydrophobic functional groups;
wherein the coating thickness is 1.0-1.5 μm.
According to the third technical scheme, the polyvinylamine membrane with hydrophilic and hydrophobic functional groups is used as a pervaporation membrane material in the separation of ethanol and water mixed solution.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, by regulating and controlling the structure of a hydrophilic group and a microphase topological structure in the membrane, weak basic amino in polyvinylamine is modified into strong basic guanidyl, meanwhile, part of amino is grafted with a hydrophobic chain, and a hydrophilic channel is formed by microphase separation and induction by utilizing the polarity difference of the hydrophilic and hydrophobic groups, so that the selectivity and permeability of the membrane to water are improved. The preparation process is simple, convenient and controllable, the raw materials are easy to obtain, the conditions are mild, the prepared hydrophobic comb side chain-containing polyvinyl guanidine composite membrane is used for separating an ethanol/water mixed solution, a microphase separation structure is generated in the membrane by utilizing the polarity difference of hydrophilic and hydrophobic groups on a polymer chain, an ordered nano hydrophilic channel is naturally formed, the selective transfer of water molecules in the channel is enhanced, the water flux is improved, and the composite membrane has higher flux and selectivity.
Drawings
FIG. 1 is an AFM surface view of a polyvinyguanidine-valeraldehyde film prepared in example 1 of the present invention;
FIG. 2 is an AFM surface view of a polyvinyguanidine-heptanal film prepared in example 2 of the present invention;
FIG. 3 is an AFM surface image of a pure polyvinylamine film prepared by comparative example 1 of the present invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
Step 1, preparing polyvinylamine by free radical polymerization-hydrolysis: adding 5g of N-vinylformamide, 30g of deionized water and 0.045g of 2.2-azobisisobutyronitrile into a 500ml three-neck flask, installing an experimental device, adding an anti-suck-back device, connecting the anti-suck-back device to the front of a bubbler, introducing nitrogen for 3 minutes after the device is connected, continuously vacuumizing for 2 minutes, stopping a vacuum pump, repeating the steps for 2 times to start reaction, starting timing when the reaction temperature reaches a specified temperature at 50 ℃, reacting for 3 hours, and quickly adding 100ml of HCl solution for hydrolysis; after two hours, the reaction temperature is increased to 60 ℃ when the dissolution is complete, timing is started when the temperature reaches 60 ℃, the reaction is carried out for two hours again, ethanol is used for precipitation after the reaction is finished, and the mixture is dried in vacuum for standby.
Step 2, deionizing polyvinyl amine: dissolving 3g of polyvinylamine in the step 1 in water to prepare a solution with the concentration of 3 wt%, then adding 30g of activated strong-base anion exchange resin into the polyvinylamine solution for ion exchange, removing H ions on amino groups in the polyvinylamine, stirring for 8 hours, and filtering to obtain deionized polyvinylamine, wherein the pH of the solution is 8 for later use;
step 3, modifying guanidyl by partial amino groups of polyvinylamine: adding 20g of the deionized polyvinylamine obtained in the step 2 into a three-neck flask, adding into 0.1113g of acetic acid solution containing 0.1558g of cyanamide at 80 ℃, reacting for 3h, and stopping the reaction to obtain the polyvinylguanidine for later use;
step 4, grafting a part of amino groups in the polyethylene guanidine with a hydrophobic side chain aldehyde group compound; taking the polyguanidine obtained in the step 3 as a solution A; 0.0798g of valeraldehyde is dissolved in 0.0278g of acetic acid and 1g of tetrahydrofuran solution to obtain a solution B, the solution B is slowly dropped into the solution A at 25 ℃, the reaction is carried out for 3 hours, and the reaction is stopped for standby application (the grafting amount of valeraldehyde is 5%);
step 5, crosslinking the hydrophobic side chain-containing polyethylene guanidine: heating the solution to 30 ℃, dropwise adding 0.927g of 2 wt% glutaraldehyde solution, crosslinking for 1 hour at room temperature, defoaming, and standing for later use;
step 6, preparing a modified polyethylene guanidine composite membrane; and (3) coating the prepared hydrophobic side chain-containing polyguanidine solution on a polyacrylonitrile-based membrane, wherein the thickness of a separation layer is 1.5 microns, and standing until the microphase separation is carried out to prepare the composite membrane.
The AFM surface diagram of the grafted hydrophobic side chain polyethylene-based guanidine composite membrane (polyethylene guanidine-valeraldehyde membrane) prepared by the preparation method is shown in figure 1, and the figure 1 obviously shows that the prepared composite membrane has microphase separation, and a channel beneficial to water transfer is constructed; it is used for separating mixed solution of ethanol and water with flux of 1.69kg/m2h, separation factor 351.
Example 2
Step 1, preparing polyvinylamine by free radical polymerization-hydrolysis: adding 5g of N-vinylformamide, 30g of deionized water and 0.045g of 2.2-azobisisobutyronitrile into a 500ml three-neck flask, installing an experimental device, adding an anti-suck-back device, connecting the anti-suck-back device to the front of a bubbler, introducing nitrogen for 3 minutes after the device is connected, continuously vacuumizing for 2 minutes, stopping a vacuum pump, repeating the steps for 2 times to start reaction, starting timing when the reaction temperature reaches a specified temperature at 50 ℃, reacting for 3 hours, and quickly adding 100ml of HCl solution for hydrolysis; after two hours, the reaction temperature is increased to 60 ℃ when the dissolution is complete, timing is started when the temperature reaches 60 ℃, the reaction is carried out for two hours again, ethanol is used for precipitation after the reaction is finished, and the mixture is dried in vacuum for standby.
Step 2, deionizing polyvinyl amine: preparing 3g of polyvinylamine in the step 1 into a solution with the weight percent of 3, then adding 24g of activated strong-base anion exchange resin into the polyvinylamine solution for ion exchange, removing H ions on amino groups in the polyvinylamine, stirring for 8 hours, and filtering to obtain deionized polyvinylamine, wherein the pH value of the solution is 8 for later use;
step 3, modifying guanidyl by partial amino groups of polyvinylamine: adding 20g of the deionized polyvinylamine obtained in the step 2 into a three-neck flask, adding 0.2226g of acetic acid solution containing 0.1169g of cyanamide at 75 ℃, reacting for 3h, and stopping the reaction to obtain the polyvinylguanidine for later use;
step 4, grafting a part of amino groups in the polyethylene guanidine with a hydrophobic side chain aldehyde group compound; taking the polyguanidine obtained in the step 3 as a solution A; 0.1058g of heptanal is dissolved in 0.0278g of acetic acid and 1g of tetrahydrofuran solution to obtain a solution B, the solution B is slowly dropped into the solution A at 25 ℃, the reaction is carried out for 3 hours, and the reaction is stopped for standby application (the grafting amount of the heptanal is 5%);
step 5, crosslinking the hydrophobic side chain-containing polyethylene guanidine: heating the solution to 30 ℃, dropwise adding 0.927g of 2 wt% glutaraldehyde solution, crosslinking for 1 hour at room temperature, defoaming, and standing for later use;
step 6, preparing a modified polyethylene guanidine composite membrane; and (3) coating the prepared hydrophobic side chain-containing polyguanidine solution on a polyacrylonitrile-based membrane, wherein the thickness of a separation layer is 1.5 microns, and standing until the microphase separation is carried out to prepare the composite membrane.
The AFM surface diagram of the polyvidone-heptaldehyde composite membrane (polyvidone-heptaldehyde membrane) prepared by the preparation method is shown in figure 2, and the figure 2 obviously shows that the prepared composite membrane meets the condition that microphase separation exists and a channel beneficial to water transfer is constructed; it is used for separating mixed solution of ethanol and water with flux of 1.82kg/m2h, separation factor 305.
Example 3
The same as example 2, except that the amount of heptaldehyde added in step 4 was 0.1694g, and the amount of heptaldehyde grafted in the hydrophobic side chain aldehyde group-containing compound in which part of the amine groups were grafted in the polyvinyl guanidine prepared was 8%.
It is used for separating mixed solution of ethanol and water with flux of 1.87kg/m2h, separation factor 305.
Comparative example 1
Step 1, preparing polyvinylamine by free radical polymerization-hydrolysis: adding 5g of N-vinylformamide, 30g of deionized water and 0.045g of 2.2-azobisisobutyronitrile into a 500ml three-neck flask, installing an experimental device, adding an anti-suck-back device, connecting the anti-suck-back device to the front of a bubbler, introducing nitrogen for 3 minutes after the device is connected, continuously vacuumizing for 2 minutes, stopping a vacuum pump, repeating the steps for 2 times to start reaction, starting timing when the reaction temperature reaches a specified temperature at 50 ℃, reacting for 3 hours, and quickly adding 100ml of HCl solution for hydrolysis; after two hours, the reaction temperature is increased to 60 ℃ when the dissolution is complete, timing is started when the temperature reaches 60 ℃, the reaction is carried out for two hours again, ethanol is used for precipitation after the reaction is finished, and the mixture is dried in vacuum for standby.
Step 2, preparing a polyvinylamine composite membrane; and (3) coating the prepared polyvinylamine solution on a polyacrylonitrile-based membrane, standing to prepare the composite membrane, wherein the thickness of a separation layer is 1.5 microns.
AFM surface diagram of pure polyvinylamine composite membrane prepared by the above preparation method is shown in FIG. 3, and the pure polyvinylamine composite membrane is used for separating mixed solution of ethanol and water, and has flux of 1.5kg/m2h, separation factor 241.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A polyvinyl amine membrane with hydrophilic and hydrophobic functional groups is characterized by comprising a separation layer and a support layer; wherein the separation layer is a product obtained by further grafting a hydrophobic side chain aldehyde group-containing compound on guanidyl-modified polyvinylamine.
2. The polyvinylamine membrane with hydrophilic and hydrophobic functional groups according to claim 1, wherein the support layer is a polyacrylonitrile ultrafiltration membrane.
3. A method for preparing the polyvinylamine membrane with hydrophilic and hydrophobic functional groups according to any one of claims 1 to 2, which comprises the steps of:
(1) ion exchange is carried out on the polyvinylamine to prepare deionized polyvinylamine;
(2) modifying part of amido and cyanamide in deionized polyvinyl amine to obtain polyvinyl guanidine;
(3) carrying out mixed reaction on the polyethylene guanidine and a hydrophobic side chain aldehyde group-containing compound to prepare a polyethylene guanidine solution with part of amine grafted hydrophobic side chain aldehyde group-containing compound;
(4) crosslinking a polyethylene guanidine solution grafted with a part of amino and containing hydrophobic side chain aldehyde group compound with glutaraldehyde to obtain a crosslinked polyethylene guanidine solution containing hydrophobic side chains;
(5) and (3) coating the crosslinked polyethylene guanidine solution containing the hydrophobic side chain on a polyacrylonitrile base film, standing and carrying out microphase separation to obtain the polyethylene amine film with hydrophilic and hydrophobic functional groups.
4. The method for preparing a polyvinylamine membrane having hydrophilic and hydrophobic functional groups according to claim 3, wherein the preparation process of polyvinylamine in the step (1) comprises the following steps:
n-vinylformamide, deionized water and an initiator are mixed according to the weight ratio of 1: (6-7): (0.008-0.009), mixing, introducing nitrogen gas for 2-5min, vacuumizing, reacting at 45-55 deg.C for 2-5h, adding acid solution, hydrolyzing for 1.5-2.5h, precipitating with alcohol, and drying to obtain polyvinylamine;
wherein the initiator is one of 2, 2-azobisisobutyronitrile, azodiisopropylimidazoline hydrochloride and azobisisoheptonitrile; the acid solution is one of hydrochloric acid, nitric acid and acetic acid, and the concentration of the acid solution is 1-2 mol/L.
5. The method for preparing a polyvinylamine membrane having hydrophilic and hydrophobic functional groups according to claim 3, wherein the deionization reaction of polyvinylamine in the step (1) specifically comprises:
adding activated strong-base anion exchange resin into 3 wt% of polyvinylamine solution, carrying out ion exchange for 6-8 hours under the stirring condition, and filtering to obtain deionized polyvinylamine;
wherein the mass ratio of the strongly basic anion exchange resin to the polyvinylamine is 8:1-10: 1.
6. The method for preparing a polyvinylamine membrane having hydrophilic and hydrophobic functional groups according to claim 3, wherein the step (2) specifically comprises the steps of:
putting the deionized polyvinylamine into an acetic acid solution containing cyanamide at the temperature of 70-90 ℃ for reacting for 3-6h to obtain the polyvinylguanidine;
wherein the mol ratio of the deionized polyvinylamine to the cyanamide to the acetic acid is 1 (0.1-0.2) to 0.05-0.2.
7. The method for preparing a polyvinylamine membrane having hydrophilic and hydrophobic functional groups according to claim 3, wherein the step (3) specifically comprises the steps of:
dripping a mixed solution of acetic acid and tetrahydrofuran containing a hydrophobic side chain aldehyde compound into a polyvinyl guanidine solution at the temperature of 20-30 ℃, and reacting for 2-3h to obtain part of polyvinyl guanidine with amino grafted hydrophobic side chain aldehyde compound;
wherein the molar ratio of the polyvinyl guanidine to the hydrophobic side chain aldehyde compound to the acetic acid is 1 (0.04-0.1) to 0.01-0.08, and the mass ratio of the tetrahydrofuran to the polyvinyl guanidine solution is 1 (10-20).
8. The method for preparing a polyvinylamine membrane having hydrophilic and hydrophobic functional groups according to claim 3, wherein the step (4) comprises the steps of:
heating a part of the polyethylene guanidine solution grafted with the hydrophobic side chain aldehyde group-containing compound to 30 ℃, dropwise adding 2 wt% glutaraldehyde solution, carrying out crosslinking reaction for 1h, defoaming, and standing to obtain the polyethylene guanidine solution containing the hydrophobic side chain;
wherein, the molar ratio of the polyethylene guanidine with part of amine group grafted hydrophobic side chain aldehyde group compound to the glutaraldehyde is 1 (0.005-0.02).
9. The method for preparing a polyvinylamine membrane having hydrophilic and hydrophobic functional groups according to claim 3, wherein the step (5) comprises the steps of:
coating the hydrophobic side chain-containing polyguanidine solution on a supporting layer, standing for microphase separation to obtain a poly vinylamine membrane with hydrophilic and hydrophobic functional groups;
wherein the coating thickness is 1.0-1.5 μm.
10. Use of the polyvinylamine membrane with hydrophilic and hydrophobic functional groups according to any one of claims 1 to 2 as a pervaporation membrane material in the separation of ethanol and water mixed solution.
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| CN114805645A (en) * | 2022-04-13 | 2022-07-29 | 晋能控股煤业集团有限公司 | Preparation method and application of biguanidinated polyvinylamine |
| CN115228305A (en) * | 2022-06-20 | 2022-10-25 | 深圳高性能医疗器械国家研究院有限公司 | Janus film and preparation method thereof |
| CN115663203A (en) * | 2022-11-04 | 2023-01-31 | 河北科技大学 | Weak base group reinforced cyclic quaternary ammonium salt type electrode binder for fuel cell and preparation method thereof |
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| CN115663203A (en) * | 2022-11-04 | 2023-01-31 | 河北科技大学 | Weak base group reinforced cyclic quaternary ammonium salt type electrode binder for fuel cell and preparation method thereof |
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