CN113600017A - Antibacterial ultrafiltration membrane of quaternary phosphonium salt and preparation method thereof - Google Patents
Antibacterial ultrafiltration membrane of quaternary phosphonium salt and preparation method thereof Download PDFInfo
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- CN113600017A CN113600017A CN202110922384.2A CN202110922384A CN113600017A CN 113600017 A CN113600017 A CN 113600017A CN 202110922384 A CN202110922384 A CN 202110922384A CN 113600017 A CN113600017 A CN 113600017A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D61/145—Ultrafiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/22—Thermal or heat-resistance properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
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Abstract
The invention provides a quaternary phosphonium salt antibacterial ultrafiltration membrane which sequentially comprises a porous mechanical support membrane, an ultrafiltration separation functional layer and a polymer layer from bottom to top, and also provides a preparation method of the ultrafiltration membrane, wherein the step S1 is to form a porous support membrane, the step S2 is to prepare the polymer layer, and the steps are to carry out drying and post-treatment on the polymer layer S3. The quaternary phosphonium salt is one of the latest research results in the field of antibacterial agent research, and 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, so that the antibacterial performance of the ultrafiltration membrane can be greatly improved; secondly, after a separation contact layer of the ultrafiltration membrane is coated with a hydrophilic quaternary phosphonium salt antibacterial polymer by using a traditional hydrophobic material, the hydrophilicity is improved, so that the pollution resistance is good and the water production flux is high; in addition, the positively charged P + ions of the quaternary phosphonium salt polymer layer can impart ion rejection properties to the ultrafiltration membrane, particularly for positively charged ionic species.
Description
Technical Field
The invention relates to the technical field of sewage treatment filter membranes, and particularly relates to a quaternary phosphonium salt antibacterial ultrafiltration 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. The ultrafiltration membrane developed at present is made of organic polymer materials, such as quaternary ammonium salt antibacterial agents, and is earlier researched and widely used, although the filtration efficiency can be greatly improved, a large number of microorganisms are easy to adsorb, grow and reproduce 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 of the membrane to block the membrane to cause the performance reduction of the membrane. Therefore, the invention provides a quaternary phosphonium salt antibacterial ultrafiltration membrane and a preparation method thereof, which aim to solve the problems of poor antibacterial effect, easy pollution blockage and low water production flux of a water treatment membrane, improve the antibacterial effect on the water treatment membrane and prolong the service life of the ultrafiltration membrane.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a quaternary phosphonium salt antibacterial ultrafiltration 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 ultrafiltration membrane, comprising the steps of:
s1 porous support membrane, 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 an ultrafiltration separation functional layer on the surface thereof, and the porous support membrane 20 is an ultrafiltration membrane, generally a polyester nonwoven fabric, capable of forming a microporous ultrafiltration separation functional layer having an average pore diameter of 0.001 to 0.4 μm on the porous support layer; examples of the membrane-forming material for the microporous ultrafiltration separation functional layer include polyaryl ether sulfones such as polysulfone and polyethersulfone, polyimides, polyvinylidene fluoride, and the like; from the viewpoint of chemical stability, mechanical stability and thermal stability, polysulfone, polyarylethersulfone or polyimide may be used; in addition, a self-supporting porous support membrane made of a thermosetting resin such as an epoxy resin having the above average pore diameter; the thickness of the porous support membrane 20 is not particularly limited, and may be, for example, in the range of 10 μm to 200 μm, or in the range of 20 μm to 65 μm;
s2 polymer layer preparation, contacting an aqueous solution containing a polymer with the separation functional layer 30 to form a polymer-containing layer, and then drying the polymer-containing layer; the method of bringing the aqueous solution into contact with the separation functional layer 30 is not particularly limited, and the separation functional layer 30 and the porous support membrane 20 may be immersed in the aqueous solution, or the aqueous solution may be applied to the surface of the separation functional layer 30, and the contact time of the separation functional layer 30 and the aqueous solution is, for example, 10 seconds to 10 minutes, and after the separation functional layer 30 is brought into contact with the aqueous solution, a washing step of removing excess aqueous solution from the separation functional layer 30 may be performed, and the solvent of the aqueous solution may contain a polar solvent other than water, such as alcohol, in addition to water, or may contain a polar solvent other than water, such as alcohol, instead of water;
the polymer is a copolymer consisting of a polymer with quaternary phosphine cations as a first monomer and a polymer with a second monomer, the second monomer can use only one or more selected from 3-chloro-2-hydroxypropyl diallyl amine hydrochloride, allylamine and acrylamide, and the copolymer can be a random copolymer or a block copolymer;
s3 drying and post-treatment, followed by heating and drying the polymer-containing layer, and heat treatment of the polymer-containing layer, the mechanical strength, heat resistance, and the like of the polymer layer 40 can be improved, and the heating temperature is, for example, 50 to 80 ℃, and the heating time is, for example, 30 to 300 seconds.
By performing the above steps, a separation membrane having the porous support membrane 20, the separation function layer 30, and the polymer layer 40 can be obtained; the thickness of the polymer layer 40 is not particularly limited, and is, for example, 10nm to 900 nm; the presence of the polymer layer 40 can be confirmed using transmission electron microscopy; the composition analysis of the polymer contained in the polymer layer 40 can be performed by, for example, fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), or time-of-flight secondary ion mass spectroscopy (TOF-SIMS).
Preferably, the quaternary phosphine cation of step S3 has the structural formula,
in the formula (1), P + is a phosphorus atom constituting a quaternary phosphine cation, R1、R2And R3Each independently is a substituent containing a carbon atom bonded to a nitrogen atom; in formula (1), the counter ion of P + is not particularly limited; the counterion of P + is a monovalent anion, for example F-、Cl-、Br-、I-A plasma of halogen ions;
in the formula (1), R1、R2And R3May be an alkyl group; examples of the alkyl group include a methyl group, an ethyl group, and a propyl group; in detail, R1, R2 and R3 may beIs methyl; when R1, R2, and R3 are alkyl groups such as methyl groups, the polymer layer 40 is more hydrophilic, which improves the water flux of the separation membrane 10;
preferably, the copolymer is a copolymer of a polymer containing the cation of the 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;
preferably, the copolymer can be a random copolymer or a block copolymer;
preferably, the ratio of the first monomer to the second monomer is not particularly limited;
preferably, 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.
In addition, the invention also provides a quaternary phosphonium salt antibacterial ultrafiltration membrane,
the ultrafiltration membrane 10 comprises a porous support membrane 20, an ultrafiltration separation functional layer 30 and a polymer layer 40 which are arranged from bottom to top in sequence; the ultrafiltration separation functional layer 30 and the polymer layer 40 are supported by the porous support membrane 20; the ultrafiltration separation functional layer 30 is disposed on the porous support membrane 20; the polymer layer 40 is disposed on the ultrafiltration separation functional layer 30; the polymer layer 40 is in direct contact with the ultrafiltration separation functional layer 30; the ultrafiltration separation functional layer 30 is composed of a microporous layer with an average pore diameter of 0.001 to 0.4 μm; the polymer layer 40 may kill and/or inhibit bacterial species on the surface of the separation membrane.
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.
Preferably, the preparation method of the porous support film 20 directly forming the separation function layer 30 is according to steps S1 to S3; however, the porous support membrane 20 serves only as a mechanical support, and therefore, when the separation function layer 30 itself can be formed to have sufficient mechanical properties, the porous support membrane 20 may be omitted, that is, a part or the whole of the structure of the separation function layer 30 itself constitutes the porous support membrane 20.
Next, a solution containing the material of the polymer layer 40 is brought into contact with the separation function layer 30; the material of the polymer layer 40 may be a polymer having a repeating unit represented by the above formula (1).
Compared with the prior art, the invention has the following beneficial effects:
1. the quaternary phosphonium salt is one of the latest research results in the field of antibacterial agent research, and 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.
2. In addition, the quaternary phosphonium salt coating covers the hydrophobic material on the separation surface layer of the original ultrafiltration membrane, so that the hydrophilicity of the surface layer of the antibacterial ultrafiltration membrane is greatly improved, the pollution resistance is better, and the water yield is high.
3. The positively charged P + ions of the quaternary phosphonium salt polymer layer can impart ion rejection properties to the ultrafiltration membrane, particularly for positively charged ionic species.
Drawings
FIG. 1 is a schematic structural diagram of a quaternary phosphonium salt antibacterial ultrafiltration membrane;
reference numerals: 10-ultrafiltration membrane, 20-porous support membrane, 30-ultrafiltration separation functional layer and 40-polymer layer.
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, an ultrafiltration membrane 10 of a quaternary phosphonium salt antibacterial ultrafiltration membrane of the present invention comprises a porous support membrane 20, an ultrafiltration separation functional layer 30 and a polymer layer 40 in sequence from bottom to top; the ultrafiltration separation functional layer 30 and the polymer layer 40 are supported by the porous support membrane 20; the ultrafiltration separation functional layer 30 is disposed on the porous support membrane 20; the polymer layer 40 is disposed on the ultrafiltration separation functional layer 30; the polymer layer 40 is in direct contact with the ultrafiltration separation functional layer 30; the ultrafiltration separation functional layer 30 is composed of a microporous layer having an average pore diameter of 0.001 to 0.4 μm; the polymer layer 40 may kill and/or inhibit bacterial species on the surface of the separation membrane.
The preparation method of the quaternary phosphonium salt antibacterial ultrafiltration membrane of the invention is as follows,
comparative example (sample 1):
mixing 16 wt% of polysulfone membrane material, 2.0 wt% of PEG20000 and an organic solvent N, N-dimethylacetamide (DMAc), heating to 80 ℃, stirring for 24 hours, cooling to 25 ℃, standing and defoaming for 8 hours to obtain a membrane casting solution A; and coating the casting solution A on a polyester non-woven fabric mechanical support body in a blade mode, and preparing the flat ultrafiltration membrane separation functional layer 30 by using pure water at 35 ℃ as a coagulating bath through a phase inversion method.
Example 1 (sample 2):
the surface of the separating functional layer of sample 1 was soaked in an aqueous solution containing 0.5 wt% of polymer 4 for 5 minutes; 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 polymer layer on the separation functional layer; the separation membrane of sample 1 was obtained in this manner; the polymer 4 is a polymer represented by the formula (2), the counter ion thereof is a chloride ion, and each of R1, R2 and R3 is a methyl group, and the weight average molecular weight thereof is 20000 Da.
Example 2 (sample 3):
the difference from example 2 is that a separation membrane was obtained in the same manner as in sample 1 except that the concentration of the polymer 4 in the aqueous solution was changed to 0.03 wt%.
Example 3 (sample 4):
the difference from example 2 is 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 0.01 wt%.
Example 4 (sample 5)
A difference from example 2 in that a separation membrane was obtained in the same manner as in sample 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 was a chemically crosslinked block copolymer represented by the formula (3) having a weight average molecular weight of 70000 Da. The first monomer for forming the copolymer is a quaternary phosphonium salt polymer, the counter ion of the quaternary phosphonium salt polymer is chloride ion, and R1, R2 and R3 are all methyl; the second monomer composing the copolymer is acrylamide; the mass ratio of the first monomer quaternary phosphonium salt polymer to the second monomer acrylamide polymer is 1: 5.
Evaluation of antibacterial property: 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.
Evaluation of film properties: MgCl at 500ppm2The aqueous solution was tested for desalting and permeation performance at an operating temperature of 25 ℃ and an operating pressure of 4 bar.
Table 1: antibacterial performance evaluation table of quaternary phosphonium salt antibacterial ultrafiltration membrane
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. The antibacterial quaternary phosphonium salt ultrafiltration membrane is characterized in that the ultrafiltration membrane (10) comprises a porous mechanical support membrane (20), an ultrafiltration separation functional layer (30) and a polymer layer (40) which are sequentially arranged from bottom to top; the ultrafiltration membrane (10) is treated with an aqueous solution of a polymer; the polymer contains a repeating unit represented by the following formula (1),
in formula (1), P+To form the phosphorus atom of the quaternary phosphonium cation, R1、R2And R3Each independently is a substituent containing a carbon atom bonded to the phosphorus atom.
2. The quaternary phosphonium salt antibacterial ultrafiltration membrane of claim 1, wherein: the R is1、R2And R3Is alkyl, or methyl, or hydroxy-or 3-chloro-2-hydroxypropyl, or 2, 3-epoxypropyl.
3. The quaternary phosphonium salt antibacterial ultrafiltration membrane of claim 1 or 2, wherein: the polymer is a copolymer of a first monomer and a second monomer constituting the repeating unit, and the second monomer has a reactive substituent capable of chemically bonding with the separation functional layer.
4. The quaternary phosphonium salt antibacterial ultrafiltration membrane of claim 3, wherein: the reactive substituent is an epoxy group, a hydroxyl group, an amino group or an amido group.
5. The quaternary phosphonium salt antibacterial ultrafiltration membrane of claim 4, wherein: the second monomer is 3-chloro-2-hydroxypropyl diallyl amine hydrochloride, or allylamine, or acrylamide.
6. The quaternary phosphonium salt antibacterial ultrafiltration membrane of claim 1, wherein: the porous mechanical support membrane (20) supports the separation functional layer (30).
7. The quaternary phosphonium salt antibacterial ultrafiltration membrane of claim 1 or 6, wherein: the porous mechanical support membrane (20) is a PVDF ultrafiltration membrane, or a polysulfone ultrafiltration membrane or a polyethersulfone ultrafiltration membrane.
8. The quaternary phosphonium salt antibacterial ultrafiltration membrane of claim 7, wherein: the porous mechanical support membrane (20) is subjected to an electrical charging treatment.
9. A preparation method of a quaternary phosphonium salt antibacterial ultrafiltration membrane is characterized by comprising the following steps:
s1 forming a porous support membrane, preparing a porous support (20) as a support, wherein an ultrafiltration membrane of a microporous ultrafiltration separation functional layer with an average pore diameter of 0.001-0.4 μm is formed on the porous support, and the support is a polyester non-woven fabric; the material for forming the microporous ultrafiltration separation functional layer is one or a mixture of more of polyaryl ether sulfone such as polysulfone, polyether sulfone and the like, polyimide and polyvinylidene fluoride;
s2 preparation of a polymer layer (40) by contacting an aqueous solution containing a polymer with a separating functional layer (30) to form a polymer-containing layer, comprising the steps of: immersing the separation functional layer (30) in an aqueous solution together with a porous support membrane (20), the contact time of the separation functional layer (30) with the aqueous solution being 10 seconds to 10 minutes, and after contacting the separation functional layer (30) with the aqueous solution, washing for removing an excess aqueous solution from the separation functional layer (30);
s3 drying and post-treatment, and then heating and drying the polymer-containing layer, and heating the polymer-containing layer at a heating temperature of 50 to 80 ℃ for a heating time of 30 to 300 seconds can improve the mechanical strength, heat resistance, and the like of the polymer layer (40).
10. The method for preparing the quaternary phosphonium salt antibacterial ultrafiltration membrane according to claim 9, wherein the method comprises the following steps: the polymer is a copolymer consisting of a polymer with quaternary phosphine cation as a first monomer and a polymer with a second monomer, and the second monomer can use only one or more selected from 3-chloro-2-hydroxypropyl diallyl amine hydrochloride, allylamine and acrylamide for mixing, and the copolymer is a random copolymer or a block copolymer.
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