CN116333216A - Imidazolyl zwitterionic polymer, PVDF membrane modified by imidazolyl zwitterionic polymer and modification method of imidazolyl zwitterionic polymer - Google Patents
Imidazolyl zwitterionic polymer, PVDF membrane modified by imidazolyl zwitterionic polymer and modification method of imidazolyl zwitterionic polymer Download PDFInfo
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- 238000002715 modification method Methods 0.000 title description 8
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-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
-
- 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
-
- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides an imidazolyl zwitterionic polymer, which is synthesized by taking 1-vinylimidazole and vinyltrimethoxysilane as raw materials and AIBN as an initiator; then the sulfonate is introduced by using 1, 3-propane sultone to prepare the catalyst. Based on the imidazolyl zwitterionic polymer, sulfonate is introduced, and a two-step method is adopted to carry out hydrophilic modification on the surface and pore canal of the PVDF membrane, so that the modified PVDF membrane shows excellent super-hydrophilicity/underwater super-oleophobicity, has excellent antibacterial and protein adhesion resistance, and can realize high-efficiency oil-water emulsion separation under various severe environments. The invention also provides an imidazole-based zwitterionic polymer modified PVDF membrane prepared by the method.
Description
Technical Field
The invention relates to the technical field of separation membrane materials, in particular to an imidazolyl zwitterionic polymer, a PVDF membrane modified by the imidazolyl zwitterionic polymer and a modification method.
Background
With the continuous development of industrialization and city, the production of oily wastewater is explosively increased. During transportation and use, the oil and water mixture often forms emulsions due to vibration, agitation, and shearing. Therefore, under the current large background of pursuing green environmental protection, the oil-water emulsion separation by using the membrane technology, and particularly the oil-containing wastewater treatment by using the surface with special wettability has great significance and value.
At present, the surface super-hydrophilic/underwater super-oleophobic modified polyvinylidene fluoride (PVDF) membrane can be used for realizing oil-water separation and emulsion separation.
In the prior art, hydrophilic modification of a PVDF membrane by dopamine and diethylenetriamine and oil-water separation performance (functional materials, 2022,53 (10): 10222-10228, authors: du Guoyong, yuan Qiao) are carried out, and hydrophobic PVDF membrane is immersed in a mixed solution of dopamine hydrochloride (DA)/Diethylenetriamine (DETA) in a certain mass ratio, so that the super-hydrophilic-underwater super-oleophobic PVDF/polydopamine/diethylenetriamine (PVDF/PDA/DETA) membrane is prepared. Although the membrane can realize the separation of oil-water mixture, the membrane still has the defect in the separation performance of oil-water emulsion. For this reason, studies have shown that the introduction of micro-nano structures on super-hydrophilic surfaces can effectively achieve emulsion separation. For example, chinese patent No. CN109499393B prepares super-hydrophilic PVDF film through constructing surface micro-nano structure and amino polymer, and realizes the efficient separation of oil-water mixture and emulsified oil. In addition, preparation of the underwater super oleophobic PVDF film and research on the oil-water separation performance of the emulsion thereof (Chongqing university, 2020.004121, asAnd (2) the following: wang Deyong, etc.) to prepare tannic acid/polyvinylpyrrolidone/SiO 2 The PVDF film modified by the composite coating is used for realizing the separation of oil-in-water emulsion and has better oil stain resistance. Indeed, the above-mentioned studies and patent inventions show some oil-resistant adhesion while emulsion separation, but in practical applications, adhesion of microorganisms (bacteria, algae) and proteins is still an important cause of serious decrease in the separated water flux.
Zwitterionic polymers (zwitterionic polymers) are a class of materials having a pair of opposite charges on the repeat unit that can undergo hydration by ionic solvation and are stronger than the hydration effects of conventional nonionic hydrophilic materials by hydrogen bonding, generally exhibiting excellent anti-bioadhesion properties, including anti-nonspecific protein adsorption, anti-cell adhesion, anti-bacterial adhesion, biofilm formation, and the like. Therefore, the amphoteric ion polymer has better hydrophilicity on one hand, and can construct the super-hydrophilic/underwater super-oleophobic surface for super-efficient oil-water separation performance; on the other hand, excellent bioadhesive properties can be achieved by the formation of the hydration layer. However, the zwitterionic polymer material still faces the problems of complex preparation process, higher cost, insufficient antibacterial performance and the like when being applied to the oil-water separation membrane. For example, chinese patent No. CN114405287B first grafts a hydrophilic monomer containing hydroxyl groups onto the PVDF membrane surface to form a hydrophilic polymer gel layer, and then successfully grafts the zwitterionic monomer 3- (methacrylamido) propyl-dimethyl (3-thiopropyl) ammonium hydroxide inner salt (MPDSAH) onto the membrane surface by a surface initiated-atom transfer radical polymerization (SI-ATRP) reaction. Although the method enhances the hydrophilicity of the PVDF film and improves the anti-pollution capability, the hydrophilic film does not have sterilization performance and is difficult to maintain a long-acting anti-bioadhesion function, and in addition, the preparation process is long and the cost is high.
Therefore, how to prepare the amphoteric ion polymer with good hydrophilicity, antibacterial property and bioadhesion resistance, and modify the surface of the PVDF substrate by a simple and efficient method becomes a problem to be solved urgently.
Disclosure of Invention
The invention provides an imidazolyl zwitterionic polymer, which is modified by a PVDF membrane, has excellent super-hydrophilicity/underwater super-oleophobicity, has excellent antibacterial and protein adhesion resistance, and can realize high-efficiency oil-water emulsion separation in various severe environments.
The technical scheme of the invention is as follows:
an imidazolyl zwitterionic polymer having the structural formula:
the synthesis method of the imidazolyl zwitterionic polymer comprises the following steps:
1-vinylimidazole and vinyltrimethoxysilane are taken as raw materials, AIBN is taken as an initiator to synthesize an imidazole-based copolymer;
and then introducing sulfonate by using 1, 3-propane sultone to prepare the imidazolyl zwitterionic polymer.
The invention also provides a method for modifying the PVDF film by the imidazolyl zwitterionic polymer, which comprises the following steps:
s1, synthesizing an imidazolyl copolymer by taking 1-vinylimidazole and vinyltrimethoxysilane as raw materials and AIBN as an initiator;
s2, immersing the PVDF substrate in a Tris-HCl-ethanol solution of dopamine to enable dopamine monomers to be covered in a substrate pore channel;
step S3, immersing the PVDF substrate modified in the step S2 into Tris-HCl solution of dopamine hydrochloride monomer and ethanol solution of TEOS-imidazolyl copolymer for codeposition reaction, and then drying and curing the fully immersed PVDF substrate;
step S4, immersing the PVDF substrate of the step S3 in Fe 3+ In the aqueous solution of (2), the polymer on the surface of the PVDF substrate is reacted with Fe 3+ Crosslinking, taking out and drying;
s5, soaking the PVDF substrate in the step S4 in a methanol solution containing 1, 3-propane sultone, reacting for 6-8 hours at 60-80 ℃, taking out the PVDF substrate, cleaning and drying to prepare the imidazole-based zwitterionic polymer modified PVDF film; specifically, the reaction temperature may be 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, or may be other temperature values within the range; the reaction time may be 6h, 7h or 8h, or may be other values within this range.
Further, the specific process for synthesizing the imidazolyl copolymer in the step S1 is as follows:
mixing isopropanol, 1-vinyl imidazole and vinyl trimethoxy silane, adding azo-diisobutyronitrile for initiation, bubbling in a nitrogen atmosphere, heating in an oil bath for a period of time, transferring the reaction solution into diethyl ether for coagulation, and performing suction filtration and drying to obtain an imidazole-based copolymer;
wherein the mol ratio of the 1-vinylimidazole to the vinyltrimethoxysilane is 8-12:1; the addition amount of the initiator is 0.1-0.5% of the mass of the monomer; the volume ratio of the diethyl ether to the polymer reaction solution is 8-10:1. Specifically, the molar ratio of 1-vinylimidazole to vinyltrimethoxysilane may be 8: 1. 9: 1. 10:1, 11:1 or 12:1, other ratios within this range are also possible; the initiator may be added in an amount of 0.1%, 0.2%, 0.3%, 0.4% or 0.5% by mass of the monomer, or may be added in other amounts within the range; the volume ratio of diethyl ether to the polymer reaction solution may be 8:1, 9:1 or 10:1, or may be other values within this range.
Further, in the step S1, the temperature of the oil bath is 60-80 ℃, and the heating time of the oil bath is 8-16h. Specifically, the temperature of the oil bath may be 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, or may be other temperature values within the range; the oil bath heating time may be 8h, 10h, 12h, 14h or 16h, or may be other values within this range.
Further, in the step S2, the dopamine concentration is 2-5mg/mL, and the volume ratio of Tris-HCl to ethanol is 1:1, the soaking time is 1-10min. Specifically, the dopamine concentration may be 2mg/mL, 3mg/mL, 4mg/mL or 5mg/mL, or may be other values within this range.
Further, in the step S3, the concentration of the dopamine hydrochloride monomer in the Tris-HCl solution of the dopamine hydrochloride monomer is 2-5mg/mL, the concentration of the ethanol solution of the TEOS-imidazolyl copolymer is 30-40mg/mL, and the volume ratio of the Tris-HCl solution of the dopamine hydrochloride monomer to the ethanol solution of the TEOS-imidazolyl copolymer is 1:1-2:3. Specifically, the concentration of the dopamine hydrochloride monomer can be 2mg/mL, 3mg/mL, 4mg/mL or 5mg/mL, and can also be other values within the range; the ethanol solution concentration of the TEOS-imidazolyl copolymer can be 30mg/mL, 32mg/mL, 35mg/mL or 40mg/mL, and can also be other values within the range; the volume ratio of Tris HCl solution of dopamine hydrochloride monomer to ethanol solution of TEOS-imidazolyl copolymer may be 1: 1. 2:3. 3:4 or 4:5, other values within this range are also possible.
Further, in the step S3, the codeposition reaction is carried out on a shaker at room temperature for 8-15 hours. The reaction time is 8h, 10h, 12h or 15h, and may be any other value within the above range. Experiments show that the reaction time is shorter, the amount of the imidazolyl copolymer on the surface is smaller below 6 hours, and the thickness of the formed coating cannot lead the PVDF film to achieve super-hydrophilic performance; when the reaction time reaches a certain degree, the optimal time is 8-15h, the thickness of the coating is basically unchanged, and the PVDF film can reach a super-hydrophilic and underwater super-oleophobic state.
Further, in step S4, fe is contained 3+ The iron salt used in the aqueous solution of (2) is FeCl 3 Or Fe (Fe) 2 (SO 4 ) 3 ，Fe 3+ The concentration is 0.2-0.4mol/L, the infiltration time is 10-20min, and the drying temperature is 30-35 ℃. Specifically, fe 3+ The concentration may be 0.2mol/L, 0.3mol/L or 0.4mol/L, or other values within the range; the soaking time can be 10min, 15min or 20min, or can be other values in the range; the drying temperature is 30 ℃, 32 ℃ or 35 ℃, and other temperature values within the range can be adopted.
Further, in the step S5, the concentration of the 1, 3-propane sultone is 30-120mg/mL, and the drying temperature is 30-35 ℃. Specifically, the concentration of 1, 3-propane sultone may be 30mg/mL, 40mg/mL, 50mg/mL, 60mg/mL, 70mg/mL, 80mg/mL, 90mg/mL, 100mg/mL, 110mg/mL or 120mg/mL, or other values within the range; the drying temperature may be 30 ℃, 32 ℃ or 35 ℃, or may be other temperature values within the range.
The invention also provides an imidazole based zwitterionic polymer modified PVDF film prepared by the method.
Compared with the prior art, the imidazolyl zwitterionic polymer, the PVDF membrane modified by the imidazolyl zwitterionic polymer and the modification method have the beneficial effects that:
1. according to the PVDF membrane modified by the imidazolyl zwitterionic polymer and the modification method, the surface and the pore canal of the PVDF membrane are subjected to hydrophilic modification by adopting a two-step method, and the membrane pore canal is mainly made to contain dopamine hydrochloride monomers by utilizing a pre-soaking method so as to ensure the adsorption grafting of the imidazolyl copolymer in the pore canal in the later step. Wherein the interaction force between the substances comprises: adhesion of Polydopamine (PDA) to PVDF substrate surface and pore channels; PDA phenolic hydroxyl and toe silicon hydroxyl react with the chemical bond of trimethoxysilane in the copolymer; the interaction of the PDA and the imidazole ring, namely the cation-II interaction, the hydrogen bond interaction and the like. Finally, a hydrophilic coating with a micro-nano structure is formed on the surface of the substrate, so that the modified PVDF film shows excellent super-hydrophilicity/underwater super-oleophobicity, wherein the contact angle of water is below 10 degrees, and the contact angle of underwater oil is above 150 degrees.
2. According to the imidazolyl zwitterionic polymer modified PVDF membrane and the modification method, the modified polymer main chain has the characteristic functions of zwitterions due to the fact that the imidazole ring with positive charges and the sulfonic acid group with negative charges are simultaneously arranged in the modified polymer main chain. At the same time, compared with other common zwitterions, the positive charge on imidazole ring can effectively neutralize the negative charge of bacteria to inactivate the bacteria, and has excellent sterilization effect (the number of bacteria is 10 8 Down to 6X 10 3 CFU/mL); after sulfonate anions are introduced into the gel to become zwitterions, the gel reacts with water molecules to form a compact hydration layer, so that the gel has excellent antibacterial and protein adhesion resisting functions; in particular, the introduction of silane groups allows the polymer to better react with phenolic hydroxyl groups in the Polydopamine (PDA) groups, bind more firmly to the surface of the membrane, and react with Fe in polydopamine and in the presence of Fe 3+ Under the crosslinking action, the long-acting stability of the modified polyurethane can be obviously enhancedThe modified PVDF membrane can be subjected to efficient emulsion separation under various severe environments (pH: 1-13 and high-salt solution), and the separation efficiency is up to more than 99%.
3. The PVDF membrane modified by the imidazolyl zwitterionic polymer and the modification method thereof reduce the roughness of the membrane surface by introducing sulfonate anions, greatly enhance the anti-adhesion effect, and greatly improve the water flux of the membrane (reaching 4000Lm by enhancing the hydrophilicity of the membrane -2 h -1 bar -1 ) The flux of the emulsion reaches 1700Lm -2 h -1 bar -1 The filtration rate is increased, and the recovery rate after multiple cycles is more than 94%.
4. The PVDF membrane and the modification method for the modification of the oxazolyl zwitterionic polymer adopt a two-step method to carry out hydrophilic modification on the surface and pore canal of the PVDF membrane, wherein the zwitterionic polymer is prepared by coupling 1-vinylimidazole and vinyltrimethoxysilane with lower cost, an initiator AIBN is used as a raw material to synthesize an imidazole copolymer, and then 1, 3-propane sultone is used to introduce negative ion sulfonate, so that the multifunctional imidazolyl zwitterionic polymer is finally obtained.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared test chart of the imidazolyl zwitterionic polymer poly (VI-co-VTS) of the present invention;
FIG. 2 is a flow chart of an imidazolyl zwitterionic polymer modified PVDF membrane of the present invention;
FIG. 3 is an SEM image of an imidazolyl zwitterionic polymer modified PVDF membrane of the present invention with a PVDF membrane prior to modification;
FIG. 4 is an AFM image of an imidazolyl zwitterionic polymer modified PVDF film of the present invention with a PVDF film prior to modification;
FIG. 5 is a graph showing the comparison of water flux before and after modification of PVDF membrane pore passages;
FIG. 6 shows the presence or absence of Fe 3+ A PVDF membrane contact angle change comparison chart under the crosslinking modification condition;
FIG. 7 is a graph of water permeation of PVDF membrane dyed with methylene blue under different treatment conditions;
FIG. 8 is a schematic view of the submerged self-cleaning of an imidazolyl zwitterionic polymer modified PVDF film of the present invention;
FIG. 9 is an image of an antimicrobial experiment of PVDF film under different processing conditions;
FIG. 10 is an image of anti-adhesion fluorescence under different processing conditions;
FIG. 11 is a graph showing the emulsion separation effect of the modified PVDF film of example 2.
Detailed Description
In order to better understand the technical solution in the embodiments of the present invention and make the above objects, features and advantages of the present invention more obvious and understandable, the following detailed description of the present invention will be further described.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and should be considered as specifically disclosed herein.
Example 1
An imidazolyl zwitterionic polymer having the structural formula:
the synthesis method of the imidazolyl zwitterionic polymer comprises the following steps:
mixing isopropanol, 1-vinyl imidazole and vinyl trimethoxy silane, adding azo-diisobutyronitrile for initiating, bubbling in nitrogen atmosphere, heating in an oil bath for a period of time, transferring the reaction solution into diethyl ether for coagulation, and carrying out suction filtration and drying to obtain an imidazole-based copolymer poly (VI-co-VTS), wherein an infrared test chart is shown in figure 1;
wherein, the mol ratio of the 1-vinylimidazole to the vinyltrimethoxysilane is 10:1; the addition amount of the initiator is 0.2% of the mass of the monomer; the volume ratio of the diethyl ether to the polymer reaction solution is 10:1;
the oil bath temperature is 65 ℃ and the oil bath time is 10 hours.
Example 2
A method for modifying PVDF membrane by imidazolyl zwitterionic polymer comprises the following steps:
referring to fig. 2, a flowchart of the modified PVDF membrane of the invention is shown, and the specific process includes the following steps:
membrane pore canal modification: repeatedly cleaning the PVDF substrate in ethanol and deionized water for 30min by using an ultrasonic cleaner; then soaking the membrane in a dopamine Tris-HCl-ethanol solution (the concentration of the dopamine is 2mg/mL, the volume ratio of the dopamine to the ethanol is 1:1), completely soaking the membrane in the dopamine solution for 5min, and repeating the operation for 3-4 times to ensure that the membrane pore canal is covered with dopamine monomers;
modification of imidazolyl polymers: the membrane pore modified PVDF substrate was completely immersed in 20mL of an equal volume of Tris-HCl solution of dopamine hydrochloride monomer (dopamine concentration of 2 mg/mL) and TEOS/poly (VI-co-VTS) in ethanol (TEOS concentration of 24mg/mL, poly (VI-co-VTS) concentration of 12 mg/mL) for co-deposition and reacted on a shaker at room temperature (25 ℃) for 10h. Placing the fully soaked PVDF substrate in a baking oven at 30 ℃ for curing for 15min;
Fe 3+ crosslinking treatment: impregnating the surface of PVDF substrate modified by imidazole-based polymer into FeCl of 0.2mol/L 3 Placing in solution for 15min, taking out, and oven drying at 30deg.CDrying for 5min;
introducing sulfonate anions: fe is added to 3+ The PVDF substrate after the crosslinking treatment is soaked in a solution containing 100mg/mL of 1, 3-propane sultone-methanol, and the reaction is carried out for 7 hours at the temperature of 65 ℃. And taking out the PVDF substrate, washing with deionized water, and then placing the PVDF substrate in a 30 ℃ oven for drying for 1min to obtain the imidazole-based zwitterionic polymer modified PVDF film capable of being used for emulsion separation.
Referring to fig. 3 and 4, fig. 3 is an SEM image of an imidazole-based zwitterionic polymer modified PVDF film of the invention and a PVDF film before modification, fig. 3 (a) shows an SEM image of a normal PVDF film, and fig. 3 (b) shows an SEM image of a modified PVDF film; fig. 4 is an AFM image of an imidazole-based zwitterionic polymer-modified PVDF film of the invention and a PVDF film before modification, fig. 4 (a) shows an AFM image of a normal PVDF film, and fig. 4 (b) shows an AFM image of a modified PVDF film. As can be seen from fig. 3 and fig. 4, the modified PVDF membrane pore channel forms a nano-structure of the polyimidazole zwitterionic polymer, so that it has good hydrophilicity and underwater super oleophobic ability.
Example 3
The process of the imidazole-based zwitterionic polymer modified PVDF film differs from example 2 in that: and the step of modifying the PVDF membrane pore canal by soaking the PVDF membrane pore canal with the dopamine Tris-HCl-ethanol solution is omitted. Referring to fig. 4, a comparison graph of water flux before and after modification of PVDF membrane channels is shown in fig. 5, and it can be seen from fig. 5 that the membrane channels are modified by using dopamine Tris-HCl-ethanol solution infiltration, so that the water flux is greatly increased.
Example 4
The process of the imidazole-based zwitterionic polymer modified PVDF film differs from example 2 in that: cancel Fe 3+ And a crosslinking treatment step. After the film was left for about 2 weeks, contact angle measurements were performed again, see FIG. 6, for the presence or absence of Fe 3+ Comparison of change in contact angle of PVDF film under crosslinking modification conditions, wherein 6 (a) represents that Fe was not used in the present example 3+ Change in PVDF film contact angle under crosslinking conditions, fig. 6 (b) shows a graph of change in PVDF film contact angle of example 2; as can be seen from FIG. 6, fe is used 3+ Oil/water connection of crosslinked PVDF membranesThe antenna is not changed obviously, and Fe is not used 3+ The cross-linked film water contact angle increases and the underwater oil contact angle decreases.
Example 5
Contact angle test
The water contact angle of the imidazolyl zwitterionic polymer modified PVDF film of example 2 in air was tested, and the instantaneous contact angle was less than 30℃and gradually decreased to 0℃in 5-10 seconds. The contact angle of the underwater oil can be greater than 150 degrees; the contact angle of the oil is tested by adopting different oils, and the test shows that the contact angle of the oil is larger than 150 degrees and the oil is super oleophobic whether the oil is light oil such as toluene, cyclohexane or heavy oil such as carbon tetrachloride; the modified PVDF film after repeated recycling can still achieve the super-oleophobic performance of multiple oils.
Meanwhile, the modified PVDF film has excellent hydrophilic capacity and underwater self-cleaning performance, the hydrophilic performance and the underwater self-cleaning performance are shown in figures 7 and 8, wherein figure 7 is a water permeation diagram of the PVDF film dyed with methylene blue under different treatment conditions, figure 7 (a) shows a water permeation diagram of the common PVDF film dyed with methylene blue, and figure 7 (b) shows a water permeation diagram of the modified PVDF film dyed with methylene blue; fig. 8 is a schematic view of underwater self-cleaning of an imidazole-based zwitterionic polymer-modified PVDF film of the invention, fig. 8 (a) showing heavy oil underwater self-cleaning ability, and fig. 8 (b) showing light oil underwater self-cleaning ability. As can be seen from fig. 7 and 8, the common PVDF film is hydrophobic, the modified PVDF film has excellent hydrophilic ability, and the modified PVDF film has efficient self-cleaning ability in heavy oil and light oil environments.
Example 6
Antibacterial test
Taking CFU as 10 8 100 microliters of staphylococcus aureus (MRSA) of (2) are respectively covered on a common PVDF membrane and a PVDF membrane modified in the example 2, the bacteria on the membrane are washed by quantitative PBS, the bacteria on the membrane are ultrasonically washed, and after the bacteria are coated on a suspension bacteria liquid for 24 hours, the growth conditions of the bacteria on the two membranes are recorded, so that the antibacterial effect of the membrane is observed.
Referring to fig. 9, an image of an antibacterial test of a PVDF film under different process conditions is shown, wherein fig. 9 (a) shows an antibacterial test of a general PVDF film, and fig. 9 (b) shows an antibacterial test of a modified PVDF film. As can be seen from FIG. 9, the modified PVDF membrane has obviously reduced bacterial cells compared with the common PVDF membrane, and has good antibacterial performance.
Example 7
Anti-adhesion test
Taking CFU as 10 8 20 microliter of staphylococcus aureus (MRSA) and adding 1980 microliter of LB medium, immersing PVDF membrane and modified membrane in bacterial solution, incubating for about 24 hours, then washing the bacteria on the membrane 3 times with quantitative PBS, then putting the membrane into quantitative PBS solution for ultrasonic oscillation, and recording the growth of bacteria on the two membranes after 24 hours by plating the suspension bacterial solution. Referring to fig. 10, the anti-adhesion fluorescence image under different processing conditions is shown in fig. 10 (a), and fig. 10 (b) shows the modified PVDF anti-bacterial anti-adhesion fluorescence image, and as can be seen from fig. 10, the modified PVDF film has good anti-adhesion performance.
Example 8
Emulsion separation test
1mL of light oil (toluene, cyclohexane, n-hexane and the like) is taken and dissolved in 99mL of water, 50-100ppm of Sodium Dodecyl Sulfate (SDS) surfactant is added, a cell breaker is used, ultrasonic treatment is carried out for 20-30min, so that an oil-water emulsion is obtained, the oil-water emulsion is subjected to suction filtration by using the PVDF film modified in the embodiment 2 under the condition of 1bar, clear water is obtained, the water flux is calculated, and TOC in the water is tested, so that the oil-water emulsion separation efficiency is obtained. Referring to fig. 11, an emulsion separation effect diagram of the modified PVDF membrane of example 2 is shown in fig. 11 (a), where fig. 11 (a) shows water and emulsion flux of the oil-water separation experiment after multiple cycles, and fig. 11 (b) shows water flux and separation efficiency of the oil-water separation experiment of different oils, and as can be seen from fig. 11, the modified PVDF membrane has higher stable water flux and separation efficiency in different emulsion environments.
The cost of the single membrane of the PVDF membrane modified by the imidazolyl zwitterionic polymer is calculated as follows:
in conclusion, the process for modifying the PVDF membrane by the imidazolyl zwitterionic polymer has the advantages of low cost, simple preparation method, low cost and good industrial application prospect.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention.
Claims (10)
1. An imidazolyl zwitterionic polymer characterized by the structural formula:
the synthesis method of the imidazolyl zwitterionic polymer comprises the following steps:
1-vinylimidazole and vinyltrimethoxysilane are taken as raw materials, AIBN is taken as an initiator to synthesize an imidazole-based copolymer;
and then introducing sulfonate by using 1, 3-propane sultone to prepare the imidazolyl zwitterionic polymer.
2. A method for modifying a PVDF membrane with an imidazolyl zwitterionic polymer, comprising the steps of:
s1, synthesizing an imidazolyl copolymer by taking 1-vinylimidazole and vinyltrimethoxysilane as raw materials and AIBN as an initiator;
s2, immersing the PVDF substrate in a Tris-HCl-ethanol solution of dopamine to enable dopamine monomers to be covered in a substrate pore channel;
step S3, immersing the PVDF substrate modified in the step S2 into Tris-HCl solution of dopamine hydrochloride monomer and ethanol solution of TEOS-imidazolyl copolymer for codeposition reaction, and then drying and curing the fully immersed PVDF substrate;
step S4, immersing the PVDF substrate of the step S3 in Fe 3+ In the aqueous solution of (2), the polymer on the surface of the PVDF substrate is reacted with Fe 3+ Crosslinking, taking out and drying;
and S5, soaking the PVDF substrate in the step S4 in a methanol solution containing 1, 3-propane sultone, reacting for 6-8 hours at 60-80 ℃, taking out the PVDF substrate, cleaning and drying to prepare the imidazole-based zwitterionic polymer modified PVDF film.
3. The method for modifying a PVDF membrane by an imidazole-based zwitterionic polymer according to claim 2, wherein the specific process for synthesizing the imidazole-based copolymer in step S1 is as follows:
mixing isopropanol, 1-vinyl imidazole and vinyl trimethoxy silane, adding azo-diisobutyronitrile for initiation, bubbling in a nitrogen atmosphere, heating in an oil bath for a period of time, transferring the reaction solution into diethyl ether for coagulation, and performing suction filtration and drying to obtain an imidazole-based copolymer;
wherein the mol ratio of the 1-vinylimidazole to the vinyltrimethoxysilane is 8-12:1; the addition amount of the initiator is 0.1-0.5% of the mass of the monomer; the volume ratio of the diethyl ether to the polymer reaction solution is 8-10:1.
4. The method for modifying a PVDF film with an imidazolyl zwitterionic polymer according to claim 3, wherein in step S1, the oil bath temperature is 60-80℃and the oil bath heating time is 8-16h.
5. The method for modifying a PVDF membrane according to claim 2, wherein in step S2, the dopamine concentration is 2-5mg/mL, the volume ratio of Tris/HCl to ethanol is 1:1, the soaking time is 1-10min.
6. The method for modifying a PVDF membrane by an imidazolyl zwitterionic polymer according to claim 2, wherein in step S3, the concentration of dopamine hydrochloride monomer in Tris-HCl solution of dopamine hydrochloride monomer is 2-5mg/mL, the concentration of ethanol solution of TEOS-imidazolyl copolymer is 30-40mg/mL, and the volume ratio of Tris-HCl solution of dopamine hydrochloride monomer to ethanol solution of TEOS-imidazolyl copolymer is 1:1-2:3.
7. The method for modifying a PVDF film according to claim 2, wherein in step S3, the co-deposition reaction is carried out on a shaker at room temperature for 8 to 15 hours.
8. The method for modifying a PVDF film according to claim 2, wherein in step S4, fe is contained 3+ The iron salt used in the aqueous solution of (2) is FeCl 3 Or Fe (Fe) 2 (SO 4 ) 3 ，Fe 3+ The concentration is 0.2-0.4mol/L, the infiltration time is 10-20min, and the drying temperature is 30-35 ℃.
9. The method for modifying a PVDF film according to claim 2, wherein the concentration of 1, 3-propane sultone in step S5 is 30-120mg/mL and the drying temperature is 30-35 ℃.
10. An imidazolyl zwitterionic polymer modified PVDF membrane, prepared by the method of any of claims 2-9.
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| CN118105538A (en) * | 2024-03-07 | 2024-05-31 | 常州集硕医疗器械有限公司 | Modified fiber reinforced PEEK bone scaffold material and preparation method thereof |
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| CN116836605A (en) * | 2023-08-11 | 2023-10-03 | 四川大学 | Antibacterial and antifouling self-healing material, coating and preparation method thereof |
| CN116836605B (en) * | 2023-08-11 | 2024-04-26 | 四川大学 | Antibacterial and antifouling self-healing material, coating and preparation method thereof |
| CN118105538A (en) * | 2024-03-07 | 2024-05-31 | 常州集硕医疗器械有限公司 | Modified fiber reinforced PEEK bone scaffold material and preparation method thereof |
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