CN112121646A - Antibacterial polyamide water treatment membrane with quaternary phosphonium salt and preparation method thereof - Google Patents
Antibacterial polyamide water treatment membrane with quaternary phosphonium salt and preparation method thereof Download PDFInfo
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Abstract
The invention provides a quaternary phosphonium salt antibacterial polyamide water treatment membrane which comprises a porous support membrane, a separation functional layer and a coating which are sequentially arranged from bottom to top; the separation function layer and the coating layer are supported by the porous support membrane; the preparation method of the water treatment membrane is also provided, the S1 porous support membrane is formed, the S2 separation functional layer is aminated, the S3 separation functional layer is halogenated, the S4 coating is formed, the S5 is dried and post-treated, the quaternary phosphonium salt is one of the latest research achievements in the research field of antibacterial agents, experiments prove that the antibacterial effect of the quaternary ammonium salt is nearly two orders of magnitude of the antibacterial effect of the quaternary ammonium salt, and the antibacterial performance of the polyamide water treatment membrane is greatly improved after the quaternary phosphonium salt coating is modified.
Description
Technical Field
The invention relates to the technical field of sewage treatment filter membranes, and particularly relates to a quaternary phosphonium salt antibacterial polyamide water treatment membrane and a preparation method thereof.
Background
In the field of sewage treatment filter membrane technology, the filter membrane water treatment is a solid-liquid separation technology, and is characterized by that it uses membrane pores to filter water and retain impurities in water, and uses said membrane to mainly remove colloid and plankton, remove insoluble iron and manganese and remove fungi. However, the sterilization process cannot be omitted in order to avoid the bacteria from being regenerated in the clean water tank. In the raw water directly connected to the plate-and-frame type and spiral type membranes, suspended matter in the raw water should be removed before flowing into the membranes so that the membrane pores are not closed.
Different from the filtering membrane separation technology, the membrane separation technology is adopted to provide necessary operation pressure for raw water supply only, the filtering membrane is flushed only after a long time of operation, other procedures are omitted, the membrane device is operated under the condition that the membrane device is easy to automate, unmanned management is achieved, and automation of conventional treatment is not easy. In particular, a composite membrane type reverse osmosis membrane and a nanofiltration membrane which use polyamide materials as separation layers are easy to adsorb and accumulate substances such as bacteria and the like due to strong hydrophobicity of the polyamide materials, so that the permeability of the membrane is influenced by pollution blockage of the membrane. For example, after quaternary ammonium salt antibacterial agents are researched earlier and widely used, although the filtration efficiency can be greatly improved, a large number of microorganisms are easy to adsorb, grow and propagate on the surface of the membrane to cause bacterial pollution, bacterial fungi and the like gradually generate certain drug resistance, and residues after use have certain toxicity to cause the pollution and blockage of the membrane to cause the reduction of the membrane performance. Therefore, the invention provides a quaternary phosphonium salt antibacterial polyamide water treatment membrane and a preparation method thereof, aims to solve the problems of poor antibacterial effect, easy pollution blockage and low water production flux of the water treatment membrane, and improves the antibacterial effect on the polyamide water treatment membrane so as to prolong the service life of the polyamide water treatment membrane.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a quaternary phosphonium salt antibacterial polyamide water treatment membrane and a preparation method thereof.
In order to achieve the above object, the present invention provides a method for preparing a quaternary phosphonium salt antibacterial polyamide water treatment membrane, comprising the steps of:
s1 porous support membrane formation, preparing a porous support membrane 20 as a support, the porous support membrane 20 is not particularly limited as long as it is a membrane capable of forming a separation function layer on the surface thereof, the porous support membrane 20 is an ultrafiltration membrane in which a microporous layer having an average pore diameter of 0.02 to 0.4 μm is formed on a nonwoven fabric, examples of a material for forming the microporous layer include polyaryl ether sulfone such as polysulfone and polyethersulfone, polyimide, polyvinylidene fluoride, etc., polysulfone or polyaryl ether sulfone may be used from the viewpoints of chemical stability, mechanical stability and thermal stability, a self-supporting porous support membrane made of thermosetting resin such as epoxy resin having the above average pore diameter may be used, the thickness of the porous support membrane 20 is not particularly limited, and may be in the range of 10 to 200 μm, or in the range of 20 to 65 μm;
s2 separation functional layer amination, contacting a first solution containing a raw material of the separation functional layer 30, typically an aqueous solution containing a polyfunctional amine as a raw material of the separation functional layer 30 (hereinafter referred to as "aqueous amine solution"), with the porous support membrane 20; forming an amine-containing layer on the surface of the porous support film 20 by bringing an amine aqueous solution into contact with the porous support film 20; the aqueous amine solution may contain a polar solvent other than water, such as alcohol, in addition to water; a polar solvent such as alcohol other than water may be used in place of water;
the polyfunctional amine is an amine having a plurality of reactive amino groups; examples of the polyfunctional amine include aromatic polyfunctional amines, aliphatic polyfunctional amines, and alicyclic polyfunctional amines;
s3 separating the functional layer from acyl halide, and contacting the second solution with the amine-containing layer; the second solution is a solution containing other raw materials of the separation functional layer 30; in detail, the second solution is a solution containing polyfunctional acyl halide as other raw material of the separation functional layer 30 (hereinafter, referred to as "acyl halide solution"); when the acyl halide solution is contacted with the amine-containing layer, the polymerization reaction of amine and acyl halide is carried out at the interface of the amine-containing layer and the acyl halide solution layer; thereby forming a separation function layer 30; contacting and reacting a solution containing the material of the coating layer 40 with the separating function layer 30; heating and drying the separation function layer 30 together with the porous support membrane 20; by performing heat treatment on the separation functional layer 30, the mechanical strength, heat resistance, and the like of the separation functional layer 30 can be improved; the heating temperature is, for example, 70 ℃ to 200 ℃ or 80 ℃ to 130 ℃; the heating time is, for example, 30 seconds to 10 minutes or 40 seconds to 7 minutes;
the polyfunctional acyl halide is an acyl halide having a plurality of reactive carbonyl groups; as the polyfunctional acid halide, aromatic polyfunctional acid halide, aliphatic polyfunctional acid halide and alicyclic polyfunctional acid halide;
s4 coating layer formation, the polymer-containing layer is formed by contacting the aqueous solution containing the polymer with the separating function layer 30, and then the polymer-containing layer is dried. The method of contacting the aqueous solution with the separation functional layer 30 is not particularly limited. The separation functional layer 30 may be immersed in an aqueous solution together with the porous support membrane 20, or an aqueous solution may be applied to the surface of the separation functional layer 30. The contact time of the separation functional layer 30 with the aqueous solution is, for example, 10 seconds to 10 minutes, and the mechanical strength, heat resistance, and the like of the coating layer 40 can be improved by heat treatment of the polymer-containing layer; the heating temperature is, for example, 50 ℃ to 80 ℃; the heating time is, for example, 30 seconds to 300 seconds. After the separation functional layer 30 is brought into contact with the aqueous solution, a cleaning step of removing excess aqueous solution from the separation functional layer 30 may be performed. The solvent of the aqueous solution may contain a polar solvent such as alcohol other than water in addition to water. A polar solvent other than water, such as alcohol, may be used instead of water.
S5 drying and post-treating, heating and drying the polymer-containing layer; by heat-treating the polymer-containing layer, the mechanical strength, heat resistance, and the like of the coating layer 40 can be improved; the heating temperature is, for example, 50 ℃ to 80 ℃; the heating time is, for example, 30 seconds to 300 seconds.
After the drying step is performed at room temperature, a further drying step may be performed at an atmospheric temperature higher than room temperature using a dryer; by performing the above steps, a water treatment membrane 10 having a porous support membrane 20, a separation functional layer 30, and a coating layer 40 can be obtained; the thickness of the coating layer 40 is not particularly limited, and is, for example, 10nm to 900 nm; the presence of the coating 40 can be confirmed using transmission electron microscopy; the composition analysis of the polymer contained in the coating layer 40 can be performed, for example, by fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), or time-of-flight secondary ion mass spectrometry (TOF-SIMS).
Preferred examples of the aromatic polyfunctional amine in step S2 include m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1, 3, 5-triaminobenzene, 1, 2, 4-triaminobenzene, 3, 5-diaminobenzoic acid, 2, 4-diaminotoluene, 2, 6-diaminotoluene, N' -dimethyl-m-phenylenediamine, 2, 4-diaminoanisole, amoebol, and xylylenediamine.
Examples of the aliphatic polyfunctional amine include ethylenediamine, propylenediamine, tris (2-aminoethyl) amine, and N-phenylethylenediamine.
Examples of the alicyclic polyfunctional amine include 1, 3-diaminocyclohexane, 1, 2-diaminocyclohexane, 1, 4-diaminocyclohexane, piperazine derivatives, and the like.
Preferably, only one selected from these polyfunctional amines may be used, or two or more selected from these polyfunctional amines may be used in combination. The polyfunctional amine may be at least one selected from the group consisting of piperazine and piperazine derivatives. In other words, the separation functional layer 30 may also be composed of a polyamide containing at least one selected from the group consisting of piperazine and piperazine derivatives as a monomer unit. Such polyamides exhibit excellent divalent ion selective separation performance.
Preferably, the piperazine derivative is a compound obtained by substituting at least one of hydrogen atoms bonded to a carbon atom or a nitrogen atom of piperazine with a substituent. Examples of the substituent include an alkyl group, an amino group, and a hydroxyl group. Examples of the piperazine derivative include 2, 5-dimethylpiperazine, 2-methylpiperazine, 2, 6-dimethylpiperazine, 2, 3, 5-trimethylpiperazine, 2, 5-diethylpiperazine, 2, 3, 5-triethylpiperazine, 2-n-propylpiperazine, 2, 5-di-n-butylpiperazine, and 4-aminomethylpiperazine.
Preferably, the polyfunctional amine may be used alone or in combination of two or more selected from piperazine and the piperazine derivatives.
In order to facilitate the formation of the amine-containing layer and to improve the performance of the separation functional layer 30, a polymer such as polyvinyl alcohol, polyvinyl pyrrolidone, or polyacrylic acid, or a polyol such as sorbitol or glycerin may be added to the amine aqueous solution.
The concentration of the amine component in the amine aqueous solution may be in the range of 0.1 to 15% by weight, or 1 to 10% by weight. By appropriately adjusting the concentration of the amine component, generation of defects such as pinholes in the separation functional layer 30 can be suppressed. In addition, the separation functional layer 30 having excellent salt trapping performance can be formed. Further, if the concentration of the amine component is appropriately adjusted, the thickness of the separation functional layer 30 is also appropriately adjusted, whereby the water treatment membrane 10 capable of achieving a sufficient permeation flux can be obtained.
The method of contacting the aqueous amine solution with the porous support membrane 20 is not particularly limited. A method of immersing the porous support membrane 20 in an aqueous amine solution, a method of coating an aqueous amine solution on the porous support membrane 20, a method of spraying an aqueous amine solution on the porous support membrane 20, or the like may be suitably employed. After the step of bringing the amine aqueous solution into contact with the porous support membrane 20, a step of removing an excess amine aqueous solution from the porous support membrane 20 may be performed. For example, by extending the amine-containing layer with a rubber roller, excess amine aqueous solution can be removed from the porous support film 20. By removing the excess amine aqueous solution, the separation functional layer 30 can be formed to an appropriate thickness.
Preferably, in step S3, examples of the aromatic polyfunctional acyl halide include trimesoyl chloride, terephthaloyl chloride, isophthaloyl chloride, biphenyldicarbonyl chloride, naphthalenedicarbonyl chloride, benzenetrisulfonyl chloride, benzenedisulfonyl chloride, and chlorosulfonyl chloride.
Examples of the aliphatic polyfunctional acid halide include propane dicarboxylic acid dichloride, butane dicarboxylic acid dichloride, pentane dicarboxylic acid dichloride, propane tricarboxylic acid dichloride, butane tricarboxylic acid dichloride, pentane tricarboxylic acid dichloride, glutaryl halide, and adipoyl halide.
Examples of the alicyclic polyfunctional acid halide include cyclopropane trimethyl chloride, cyclobutane tetracarboxylic acid chloride, cyclopentane trimethyl chloride, cyclopentane tetracarboxylic acid chloride, cyclohexane trimethyl acid chloride, tetrahydrofuran tetracarboxylic acid chloride, cyclopentane dicarboxylic acid chloride, cyclobutane dicarboxylic acid chloride, cyclohexane dicarboxylic acid chloride, tetrahydrofuran dicarboxylic acid chloride, and the like.
Only one kind selected from these polyfunctional acid halides may be used, or two or more kinds may be used in combination. In order to obtain the separation functional layer 30 having excellent salt-trapping property, aromatic polyfunctional acyl halide may also be used. In addition, a three-or more-membered polyfunctional acid halide may be used as at least a part of the polyfunctional acid halide component to form a crosslinked structure.
As the solvent of the acid halide solution, an organic solvent, particularly a nonpolar organic solvent, can be used. The organic solvent is not particularly limited as long as it has low solubility in water, does not deteriorate the porous support membrane 20, and can dissolve the polyfunctional acyl halide component. Examples of the organic solvent include saturated hydrocarbons such as cyclohexane, heptane, octane, and nonane; and halogenated hydrocarbons such as 1, 1, 2-trichlorotrifluoroethane. Saturated hydrocarbons having a boiling point of 300 ℃ or lower or 200 ℃ or lower may also be used.
The concentration of the acid halide component in the acid halide solution may be in the range of 0.01 to 5% by weight, or may be in the range of 0.05 to 3% by weight; by appropriately adjusting the concentration of the acid halide component, the unreacted amine component and the acid halide component can be reduced. In addition, generation of defects such as pinholes in the separation functional layer 30 can be suppressed, whereby the water treatment membrane 10 having excellent salt rejection performance; further, if the concentration of the acid halide component is appropriately adjusted, the thickness of the separation functional layer 30 is also appropriately adjusted, whereby the water treatment membrane 10 capable of achieving a sufficient permeation flux can be provided.
The method of contacting the acid halide solution with the amine-containing layer is not particularly limited. The amine-containing layer may be immersed in the acid halide solution together with the porous support membrane 20, or the surface of the amine-containing layer may be coated with the acid halide solution. The contact time of the amine-containing layer with the acid halide solution is, for example, 10 seconds to 5 minutes or 30 seconds to 1 minute. After the amine-containing layer is contacted with the acid halide solution, a step of removing an excess acid halide solution from the amine-containing layer may be performed.
Further, step S3 heats and dries the separation function layer 30 together with the porous support film 20. By performing the heat treatment on the separation functional layer 30, the mechanical strength, heat resistance, and the like of the separation functional layer 30 can be improved. The heating temperature is, for example, 70 ℃ to 200 ℃ or 80 ℃ to 130 ℃. The heating time is, for example, 30 seconds to 10 minutes or 40 seconds to 7 minutes. After the drying step is performed at room temperature, a further drying step may be performed at an atmospheric temperature higher than room temperature using a dryer.
The conditions for carrying out the interfacial polymerization method are described in, for example, Japanese patent application laid-open Nos. 58-24303 and 1-1. In the method of the present embodiment, these known techniques can be appropriately employed.
In the amine aqueous solution and/or the acid halide solution, various additives may be added to facilitate the formation of the separation functional layer 30 or to improve the performance of the water treatment membrane 10 to be obtained. Examples of additives include: surfactants such as sodium dodecylbenzenesulfonate, sodium dodecylsulfate and sodium lauryl sulfate, basic compounds such as sodium hydroxide, trisodium phosphate and triethylamine, which are effective in removing hydrogen halide produced by polymerization, and acylation catalysts.
By performing the above steps, a membrane having the porous support membrane 20 and the separation functional layer 30 can be obtained. The thickness of the separation functional layer 30 is not particularly limited, and may be, for example, 0.05 μm to 2 μm, or 0.1 μm to 1 μm.
In the present specification, a method of directly forming the separation functional layer 30 on the surface of the porous support film 20 by an interfacial polymerization method is described. However, it is also possible to form the separation functional layer 30 on a support other than the porous support membrane 20, and then transfer the resulting separation functional layer 30 onto the porous support membrane 20 and integrate it. In other words, the separation function layer 30 may be transferred from another support to the porous support film 20.
Preferably, the material of the coating layer 40 described in step S3 may be a polymer having a repeating unit represented by the following formula (1).
An antibacterial polymer having a quaternary phosphonium salt-based branched chain structure of the formula (1):
wherein: the vertical wavy line is a polymer skeleton which is a skeleton of natural polymer and derivatives thereof, a skeleton of synthetic polymer and derivatives thereof and/or a semisynthetic polymer skeleton;
the natural polymer and the derivative thereof in the skeleton of the natural polymer and the derivative thereof are specifically as follows: one or more of guar gum, xanthan gum, starch, chitosan, cellulose, hyaluronic acid, pectin, gelatin, gum arabic, casein, chitin, fibroin, albumin, casein, hyaluronic acid, glycogen, lipopolysaccharide, mucin, sericin, gellan gum, dextran, chitosan oligosaccharide, inulin, polyfructose, dextran, mannooligosaccharide, mannan, fungal polysaccharide, galactan, glucosaminoglycan, glycoprotein, glycolipid, proteoglycan, cellulose, dextran, chondroitin sulfate, dermatan sulfate, sulfuric acid, heparin, heparan sulfate, agar or pullulan, or further, and/or one or more of derivatives of the above substances;
the synthetic polymer and the derivative thereof in the skeleton of the synthetic polymer and the derivative thereof are one or more of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polyethylene, polypropylene, polyvinyl acetate, polylactic acid, polyglycolic acid, polyether-ether-ketone, polyacrylic acid, polyacrylamide, polytetrahydrofuran, polybutylene oxide, polyurethane, polymaleic anhydride, polyurea, polyhydroxyethyl methyl acrylate, polypropylene glycol, polycaprolactone or polyhydroxyalkanoate, or further one or more of the derivatives of the substances; the semisynthetic polymer skeleton is a polymer skeleton obtained by chemical reaction of at least one natural polymer or a derivative thereof and at least one synthetic polymer or a derivative thereof;
in formula (1), P + is a phosphorus atom constituting the quaternary phosphine cation. X is Cl-、Br-、I-、ClO4 -、ClO3 -、NO3 -、SO3 2-、 HSO3 -、OH-、R4COO-、CO3 2-、SO4 2-Or CF3COO-；
Y is O, S, S-S, OC (O), OC (O) O, C (O) O, NR5R6、CONR6Substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heterocyclyl;
R1、R2、R3、R4、R5、R6each independently selected from: H. substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, and substituted or unsubstituted heterocyclic group;
m or n is independently selected from an integer of 0 to 1000.
The quaternary phosphine cation may be a copolymer of a polymer containing the cation of formula (1) as a first monomer and a polymer of a second monomer, and the second monomer may be one or more selected from 3-chloro-2-hydroxypropyldiallylamine hydrochloride, allylamine, and acrylamide.
The copolymer may be a random copolymer or a block copolymer.
The ratio of the first monomer to the second monomer is not particularly limited. For example, the ratio of the first monomer to the second monomer is 5: 95 to 95: 5, or 30: 70 to 70: 30. The weight average molecular weight of the polymer or copolymer is not particularly limited, and is, for example, 10000 to 100000. The preferred ratio is 99: 1, preferably the copolymerization molecular weight is 70000.
The polymer containing haloamine functionality and the polymer containing quaternary phosphonium salt functionality may constitute a copolymer.
Or the polymer containing the haloamine functional group and the polymer containing the quaternary phosphonium salt functional group are independent polymers respectively, and are crosslinked by physical acting force;
and the polymer containing the halogen amine functional group and the polymer containing the quaternary phosphonium salt functional group are crosslinked with the separation functional layer through chemical bonds or physical force.
Further, the coating layer 40 may be formed by: the polymer-containing layer is formed by contacting an aqueous solution containing a polymer with the separation functional layer 30, and then the polymer-containing layer is dried. The method of contacting the aqueous solution with the separation functional layer 30 is not particularly limited. The separation functional layer 30 may be immersed in an aqueous solution together with the porous support membrane 20, or an aqueous solution may be applied to the surface of the separation functional layer 30. The contact time of the separation functional layer 30 with the aqueous solution is, for example, 10 seconds to 10 minutes. After the separation functional layer 30 is brought into contact with the aqueous solution, a cleaning step of removing excess aqueous solution from the separation functional layer 30 may be performed. The solvent of the aqueous solution may contain a polar solvent such as alcohol other than water in addition to water. A polar solvent other than water, such as alcohol, may be used instead of water.
In addition, the invention also provides a quaternary phosphonium salt antibacterial polyamide water treatment membrane,
the water treatment membrane 10 is provided with a porous support membrane 20, a separation functional layer 30 and a coating 40 in sequence from bottom to top; the separation function layer 30 and the coating layer 40 are supported by the porous support membrane 20; the separation function layer 30 is disposed on the porous support membrane 20; the coating 40 is disposed on the separating functional layer 30; said coating 40 is in direct contact with the separating functional layer 30; the water treatment membrane 10 may be a composite semipermeable membrane;
the separating function layer 30 is made of polyamide, and the coating 40 can kill and/or inhibit bacterial substances on the surface of the water treatment membrane.
By performing the above steps, the water treatment membrane 10 having the porous support membrane 20, the separation functional layer 30, and the coating layer 40 can be obtained. The thickness of the coating layer 40 is not particularly limited, and is, for example, 10nm to 900 nm. The presence of the coating 40 can be confirmed using transmission electron microscopy. The composition analysis of the polymer contained in the coating layer 40 can be performed, for example, by fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), or time-of-flight secondary ion mass spectrometry (TOF-SIMS).
The "average pore diameter" refers to a value calculated by the following method; first, observing the surface or cross section of the film or layer with an electron microscope (e.g., a scanning electron microscope), and measuring the diameters of a plurality of observed holes (e.g., any 10 holes); the average of the measured values of the diameters of the pores is defined as "average pore diameter"; the "diameter of the hole" refers to the major diameter of the hole, and more specifically, refers to the diameter of the smallest circle that can surround the hole.
Compared with the prior art, the invention has the following beneficial effects:
1. the quaternary phosphonium salt is one of the latest research achievements in the field of antibacterial agent research, experiments prove that the antibacterial effect of the quaternary phosphonium salt is nearly two orders of magnitude of the antibacterial effect of the quaternary ammonium salt, and the antibacterial performance of the polyamide water treatment membrane adopting the quaternary phosphonium salt antibacterial coating is greatly improved;
2. in addition, the surface layer of the polyamide membrane is hydrophobic, and the polyamide membrane is modified by a hydrophilic quaternary phosphonium salt coating, so that the pollution resistance is improved.
Drawings
FIG. 1 is a schematic structural diagram of a quaternary phosphonium salt antibacterial polyamide water treatment membrane;
reference numerals: 10-water treatment membrane, 20-porous support membrane, 30-separation functional layer and 40-coating.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to specific embodiments below so that those skilled in the art can fully understand the technical contents of the present invention. It should be noted that the specific embodiments described herein are merely illustrative of the concepts of the invention and are not intended to limit the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
As shown in fig. 1, a quaternary phosphonium salt antibacterial polyamide water treatment membrane 10 of the present invention comprises, from bottom to top, a porous support membrane 20, a separation functional layer 30 and a coating layer 40; the separation function layer 30 and the coating layer 40 are supported by the porous support membrane 20; the separation function layer 30 is disposed on the porous support film 20; the coating layer 40 is disposed on the separation function layer 30; the coating layer 40 is in direct contact with the separating functional layer 30; the water treatment membrane 10 may be a composite semipermeable membrane; the separation functional layer 30 is made of polyamide; the coating 40 may kill and/or inhibit bacterial matter on the surface of the water treatment membrane.
The preparation method of the quaternary phosphonium salt antibacterial polyamide water treatment membrane comprises the following steps,
example 1 (sample 1):
the contact angle is a reflection of the hydrophilicity and hydrophobicity of the membrane surface. Before testing, the film samples were dried overnight in a vacuum oven at 40 ℃. The fixed drop method (Sessile drop method) was used in this experiment. First, a rectangular membrane or a modified membrane is cut and fixed on a glass slide. The surface of the separating functional layer was immersed in an aqueous solution containing 0.5% by weight of polymer 4 for 5 minutes after dropping a drop of deionized water onto the film using a micropipette. Then, the separation functional layer was air-dried for 30 seconds and further kept in a hot air dryer at 120 ℃ for 2 minutes, thereby forming a coating layer on the separation functional layer. In this manner, a separation membrane of sample 1 was obtained. The polymer 4 is a polymer represented by formula (3).
Example 2 (sample 2):
the difference from example 1 was that a separation membrane was obtained in the same manner as in sample 1, except that the concentration of polymer 4 in the aqueous solution was changed to 0.03 wt%.
Example 3 (sample 3):
the difference from example 1 was that a separation membrane was obtained by the same method as sample 1, except that the concentration of polymer 4 in the aqueous solution was changed to 0.01 wt%.
Example 4 (sample 4):
a separation membrane was obtained in the same manner as in example 1, except that the polymer 4 was changed to the polymer 5 and the concentration of the polymer 5 in the aqueous solution was changed to 0.05 wt%. The polymer 5 is a copolymer represented by formula (4).
Evaluation of antibacterial effect performance:
the evaluation of antibacterial performance is made with reference to test method 100-2004 of the American Association of textile chemical stainers (AATCC). Coli (e.coli) was selected as a representative cell, and the antibacterial performance of the modified membrane was evaluated.
Table 1: evaluation table of antibacterial performance of quaternary phosphonium salt antibacterial polyamide water treatment membrane
| Class of quaternary phosphonium salt polymers | Polymer concentration (%) | Bacteriostatic ratio (%) | |
| Sample 1 | Polymer 4 | 0.5 | 99.3 |
| Sample 2 | Polymer 4 | 0.03 | 82.8 |
| Sample 3 | Polymer 4 | 0.01 | 85.1 |
| Sample No. 4 | Polymer 5 | 0.05 | 99.4 |
It should be noted that the above-mentioned preferred embodiments are merely illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A quaternary phosphonium salt antibacterial polyamide water treatment membrane which is characterized in that,
the water treatment membrane (10) comprises a porous support membrane (20), a polyamide separation functional layer (30) and a coating (40) which are arranged from bottom to top in sequence; the polyamide separation functional layer (30) and the coating layer (40) are supported by a porous support membrane (20); the material of the coating (40) is composed of a polymer of a repeating unit represented by the following formula (1);
wherein P + in formula (1) is a phosphorus atom constituting a quaternary phosphine cation, and X is Cl-、Br-、I-、ClO4 -、ClO3 -、NO3 -、SO3 2-、HSO3 -、OH-、R4COO-、C03 2-、SO4 2-Or CF3COO-(ii) a The vertical wavy line is a macromolecular skeleton;
y is O, S, S-S, OC (O), OC (O) O, C (O) O, NR5R6、CONR6Substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heterocyclyl; the R is1、R2、R3、R4、R5、R6Each independently selected from: H. substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, and substituted or unsubstituted heterocyclic group; m or n is independently selected from an integer of 0 to 1000.
2. The quaternary phosphonium salt antibacterial polyamide water treatment membrane according to claim 1,
the polymer skeleton is a natural polymer and a derivative skeleton thereof, a synthetic polymer and a derivative skeleton thereof and/or a semisynthetic polymer skeleton.
3. The quaternary phosphonium salt antibacterial polyamide water treatment membrane according to claim 2,
the natural polymer and its derivatives in the skeleton are one or more of guar gum, xanthan gum, starch, chitosan, cellulose, hyaluronic acid, pectin, gelatin, acacia, casein, chitin, silk fibroin, albumin, casein, hyaluronic acid, glycogen, lipopolysaccharide, mucoprotein, sericin, gellan gum, dextran, chitosan oligosaccharide, inulin, polyfructose, dextran, mannooligosaccharide, mannan, fungal polysaccharide, galactan, glucosaminoglycan, glycoprotein, glycolipid, proteoglycan, cellulose, dextran, chondroitin sulfate, dermatan sulfate, sulfuric acid, heparin, heparan sulfate, agar and pullulan.
4. The quaternary phosphonium salt antibacterial polyamide water treatment membrane according to claim 2 or 3,
the synthetic polymer and the derivative thereof with the skeleton are one or a mixture of more of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polyethylene, polypropylene, polyvinyl acetate, polylactic acid, polyglycolic acid, polyether-ether-ketone, polyacrylic acid, polyacrylamide, polytetrahydrofuran, polybutylene oxide, polyurethane, polymaleic anhydride, polyurea, polyhydroxyethyl methyl acrylate, polypropylene glycol, polycaprolactone or polyhydroxyalkanoate.
5. The quaternary phosphonium salt antibacterial polyamide water treatment membrane according to claim 2,
the semisynthetic polymer skeleton is obtained by chemical reaction of at least one natural polymer or its derivative and at least one synthetic polymer or its derivative.
6. The quaternary phosphonium salt antibacterial polyamide water-treatment membrane as set forth in claim 1, wherein the water-treatment membrane (10) further has a support body supporting the separation function layer.
7. The quaternary phosphonium salt antibacterial polyamide water treatment membrane as claimed in claim 1, wherein the quaternary phosphonium cation is a copolymer composed of a polymer containing the cation of formula (1) as a first monomer and a polymer of a second monomer.
8. The membrane of claim 7, wherein the second monomer is one or more of 3-chloro-2-hydroxypropyl diallyl amine hydrochloride, allyl amine and acrylamide.
9. The membrane of claim 7, wherein the copolymer is a random copolymer or a block copolymer.
10. A preparation method of a quaternary phosphonium salt antibacterial polyamide water treatment membrane is characterized by comprising the following steps:
s1 forming a porous support membrane, preparing a porous support membrane (20) as a support, wherein the porous support membrane (20) is an ultrafiltration membrane formed by a microporous layer with an average pore diameter of 0.02-0.4 μm on non-woven fabric;
s2 amination of the separation functional layer, bringing a first solution containing a raw material of the separation functional layer (30) into contact with the porous support membrane (20), the first solution containing an aqueous solution of a polyfunctional amine as a raw material of the separation functional layer (30); forming an amine-containing layer on a surface of a porous support membrane (20) by contacting an amine aqueous solution with the porous support membrane (20);
s3 separating acyl halide of the functional layer, contacting the amine-containing layer with a second solution of a solution containing other raw materials of the separating functional layer (30), and performing polymerization reaction of amine and acyl halide at the interface of the amine-containing layer and acyl halide solution layer to form the separating functional layer (30); bringing a solution containing the material of the coating (40) into contact reaction with the separating functional layer (30); heating and drying the separation function layer (30) together with the porous support membrane (20); the mechanical strength and the heat resistance of the separation functional layer (30) are improved by performing heat treatment on the separation functional layer (30); the heating temperature is 70-200 ℃; the heating time is 30 seconds to 10 minutes;
s4 coating formation, namely, contacting an aqueous solution containing a polymer with a separation functional layer (30) to form a polymer-containing layer, and then drying the polymer-containing layer, wherein the contact time of the separation functional layer (30) and the aqueous solution is 10 seconds to 10 minutes, and the heating temperature is 50 ℃ to 80 ℃; heating for 30 to 300 seconds, and removing excess aqueous solution from the separation functional layer (30) after the separation functional layer (30) is brought into contact with the aqueous solution;
s5 drying and post-treating, heating and drying the polymer-containing layer; the mechanical strength and heat resistance of the coating layer 40 are improved by heat treatment of the polymer-containing layer; the heating temperature is 50-80 ℃; the heating time is 30-300 seconds.
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| CN202010809395.5A CN112121646A (en) | 2020-08-12 | 2020-08-12 | Antibacterial polyamide water treatment membrane with quaternary phosphonium salt and preparation method thereof |
| CN202110923413.7A CN113600029A (en) | 2020-08-12 | 2021-08-12 | Antibacterial polyamide water treatment membrane with quaternary phosphonium salt and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112978987A (en) * | 2021-02-19 | 2021-06-18 | 北京九泉科技有限公司 | Novel water purification unit made of environment-friendly materials |
| CN113546522A (en) * | 2021-08-10 | 2021-10-26 | 大连理工大学盘锦产业技术研究院 | Preparation method of reinforced Pebax mixed matrix membrane |
| CN116078179A (en) * | 2021-11-05 | 2023-05-09 | 日东电工株式会社 | Composite semipermeable membrane, spiral membrane element, water treatment system and water treatment method |
-
2020
- 2020-08-12 CN CN202010809395.5A patent/CN112121646A/en active Pending
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112978987A (en) * | 2021-02-19 | 2021-06-18 | 北京九泉科技有限公司 | Novel water purification unit made of environment-friendly materials |
| CN113546522A (en) * | 2021-08-10 | 2021-10-26 | 大连理工大学盘锦产业技术研究院 | Preparation method of reinforced Pebax mixed matrix membrane |
| CN113546522B (en) * | 2021-08-10 | 2022-07-26 | 大连理工大学盘锦产业技术研究院 | Preparation method of reinforced Pebax mixed matrix membrane |
| CN116078179A (en) * | 2021-11-05 | 2023-05-09 | 日东电工株式会社 | Composite semipermeable membrane, spiral membrane element, water treatment system and water treatment method |
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