CN112516812A - Copper-containing antibacterial thin-layer composite film and preparation method and application thereof - Google Patents
Copper-containing antibacterial thin-layer composite film and preparation method and application thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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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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Abstract
The invention discloses a copper-containing antibacterial thin-layer composite membrane and a preparation method and application thereof. The composite membrane comprises a reinforcing layer, a supporting layer and a separating layer, wherein the separating layer is located on one surface of the supporting layer, the reinforcing layer is located on the other surface of the supporting layer, the supporting layer is a polymer porous membrane, the separating layer is a polyamide separating layer loaded with copper hydroxide, and the mass content of copper element in the separating layer is 0.5-10 wt%. Firstly, preparing a polyamine solution and a polyacyl chloride solution of copper hydroxide; then the supporting layer is contacted with the polyamine solution and the polyacyl chloride solution of the copper hydroxide in sequence and then is subjected to heat treatment to obtain the copper-based alloy. The copper-containing antibacterial thin-layer composite membrane prepared according to the invention has the advantages of lasting antibacterial performance, simple preparation process, suitability for mass production and the like.
Description
Technical Field
The invention relates to the field of separation membranes, in particular to a copper-containing antibacterial thin-layer composite membrane and a preparation method and application thereof.
Background
Thin-layer composite membranes used as nanofiltration membranes and reverse osmosis membranes are widely applied to various fields, but the problem of membrane pollution is one of the obstacles restricting the development of the thin-layer composite membranes and is also an important problem which needs to be solved urgently. Especially, in the use process, microorganisms are easy to grow, reproduce and migrate on the surface of the membrane to cause biological pollution, the performance of the membrane is directly influenced, the quality and the quantity of produced water are reduced, the effective operation pressure is reduced, and the operation cost is increased.
Research shows that the introduction of an antibacterial agent on the surface of the membrane, which endows the membrane with the contact sterilization property, is an effective method for improving the anti-biological pollution capability of the membrane. Compared with organic antibacterial agents (including quaternary ammonium salts, polyguanidine, organic amine and the like) and natural antibacterial agents (including chitin, chitosan and the like), the inorganic antibacterial agents (including titanium dioxide, silver, copper and the like) have the advantages of heat resistance, durability, continuity, safety and the like. KR2003005931A discloses a reverse osmosis membrane having excellent antibacterial effect and activity of decomposing organic pollutants and a method for producing the same, which comprises adding titanium compound into acidic aqueous solution to hydrolyze to obtain titanium dioxide nanoparticles, treating with acid solution having pH of 1-6 or alkali solution having pH of 9-13 to obtain stable titanium dioxide nanoparticles, and immersing the reverse osmosis membrane into the solution containing titanium dioxide nanoparticles to bond titanium dioxide with a film. CN109046038A discloses a preparation method of a high-strength antibacterial reverse osmosis membrane, which comprises the steps of taking reed leaves as a raw material, reacting the reed leaves with citric acid, malic acid and maleic anhydride to prepare a reaction product, mixing the reaction product with a silver nitrate solution to obtain a filter cake, finally soaking a polysulfone membrane in a solid-liquid mixture, and drying to obtain the high-strength antibacterial reverse osmosis membrane. CN103480284A discloses a pollution-resistant polyamide composite membrane and a preparation method thereof, in the method, a nano silver, copper or titanium compound is mixed with a PVA solution and then coated on the surface of a polyamide reverse osmosis membrane to obtain the pollution-resistant polyamide composite membrane.
Therefore, in the prior art, although the antibacterial performance of the membrane surface is improved by immersing the reverse osmosis membrane into a solution containing antibacterial metal or coating the surface of the reverse osmosis membrane with an antibacterial functional layer, on one hand, antibacterial metal particles attached to the membrane surface are quickly lost along with the use of the membrane, so that the durability of the antibacterial performance of the membrane surface is poor, on the other hand, the preparation steps are added, the post-treatment time is long, and the production cost is increased.
Therefore, there is a need to develop a thin composite film with good antibacterial durability and simple preparation process and a method for preparing the same.
Disclosure of Invention
The technical problem to be solved by the invention is to provide an antibacterial thin-layer composite film which has lasting antibacterial performance and simple preparation process and is suitable for mass production and a preparation method thereof aiming at the defects of the prior art.
The inventors of the present invention have conducted extensive studies and found that copper hydroxide is hardly soluble in water but can form a solution by complexing with amines such as ethylenediamine and triethylenetetramine at an appropriate ratio. In the process of interfacial polymerization of the solution and a polyacyl chloride solution, as amine monomers react with acyl chloride monomers to generate polyamide, copper hydroxide is separated out and fixed on a polyamide layer while amine is consumed, and on the other hand, residual carboxylic acid groups in the polyamide layer are complexed with copper ions to play a role in fixing copper ions. In the course of use of the film, copper ions are slowly dissolved in water, thereby achieving a long-term bactericidal action and increasing the lasting antibacterial ability of the film, and thus the present invention has been completed.
One of the purposes of the invention is to provide a copper-containing antibacterial thin-layer composite membrane, which comprises a reinforcing layer, a support layer and a separation layer, wherein the separation layer is positioned on one surface of the support layer, the reinforcing layer is positioned on the other surface of the support layer, the support layer is a polymer porous membrane, and the separation layer is a polyamide separation layer loaded with copper hydroxide.
According to the present invention, the support layer is not particularly limited, and it is preferable that the polymer porous membrane of the support layer is a membrane of one or more of polysulfone, polyethersulfone and polyacrylonitrile.
In the present invention, the source of the support layer is not particularly limited and may be conventionally selected in the art, for example, may be commercially available, and in a preferred case, may be self-made by a phase inversion method. The phase inversion method is well known to those skilled in the art, and may be, for example, a gas phase gel method, a solvent evaporation gel method, a thermal gel method, or an immersion gel method, and preferably an immersion gel method. In a preferred embodiment, a primary membrane is formed by coating a coating solution containing polysulfone on a reinforcing layer, and then the primary membrane is converted into a support layer using a phase inversion method to obtain a polysulfone porous support layer.
According to the invention, the thickness of the support layer can be changed in a larger range, preferably the average thickness of the support layer is 20-80 μm, so that the support layer and the polyamide separation layer can achieve better synergistic matching, the obtained composite membrane has better ion interception performance and higher water flux, and more preferably the average thickness of the support layer is 30-60 μm.
The reinforced layer is positioned on one surface of the supporting layer, so that the supporting layer is more favorably formed, and the composite film has better mechanical property. In addition, the reinforcing layer is not particularly limited in the present invention, and may be selected conventionally in the art, for example, one or more of a polyester layer, a polyethylene layer, or a polypropylene layer, preferably a polyester layer, and more preferably a polyester nonwoven fabric support layer. The source of the enhancement layer is not particularly limited and may be a conventional choice in the art, for example, commercially available.
The thickness of the reinforcing layer is not particularly limited and may be conventionally selected in the art, and in a preferred case, the average thickness of the reinforcing layer is 40 to 100 μm, and more preferably 50 to 90 μm.
In the present invention, the copper hydroxide-supporting polyamide separation layer is preferably obtained by interfacial polymerization of a polyamine solution of copper hydroxide and a polybasic acid chloride solution.
According to the invention, the mass content of the copper element in the polyamide separation layer is preferably 0.5-10 wt%, and more preferably 1-5 wt%.
According to the present invention, the polyamide separation layer is a polyamide film having a crosslinked polyamide structure and formed on the surface of the support layer so as to be bonded to the support layer. The average thickness of the copper hydroxide-loaded polyamide separation layer is 50-300 nm, and preferably 100-200 nm.
According to the invention, the thin-layer composite membrane comprises a composite nanofiltration membrane and/or a composite reverse osmosis membrane.
The second aspect of the present invention provides a method for preparing the copper-containing antibacterial thin-layer composite film, comprising the following steps:
(1) preparing the support layer on one surface of the reinforcing layer;
(2) a copper hydroxide-loaded polyamide separation layer was prepared on the other surface of the support layer.
Wherein, the method of step (1) can be selected conventionally in the field, and preferably adopts a phase inversion method, and a supporting layer polymer solution can be coated on one surface of the reinforcing layer, and the supporting layer with the surface adhesion reinforcing layer can be obtained through phase inversion.
The phase inversion method may specifically be: dissolving the polymer of the support layer in a solvent to obtain a polymer solution with the concentration of 10-20 wt%, and defoaming at normal temperature; and then coating the polymer solution on the enhancement layer to obtain an initial film, and soaking the initial film in water at the temperature of 10-30 ℃ for 1-60 min, so that the polymer layer on the surface of the enhancement layer is subjected to phase conversion into the support layer polymer porous film.
Among them, the solvent may be N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, or the like.
According to the method of the present invention, as a method for forming a polyamide separation layer on the other surface of the support layer in step (2), it is preferable to obtain by interfacial polymerization of a polyamine solution of copper hydroxide and a polybasic acid chloride solution. According to the present invention, it is more preferable that the other surface of the support layer is contacted with a solution of a polyamine of copper hydroxide and a solution of a polybasic acid chloride in this order, and then subjected to heat treatment.
In the present invention, the term "interfacial polymerization" means: polymerization reaction at the interface of two solutions (or the interface organic phase side) in which two monomers are dissolved, respectively, and which are not soluble in each other.
According to the invention, the polyamine comprises a main polyamine or comprises a main polyamine and a secondary polyamine, wherein the main polyamine is selected from at least one of ethylenediamine, 1, 3-propanediamine, triethylene tetramine or polyethylene polyamine; the accessory polyamine is selected from one or more of m-phenylenediamine, p-phenylenediamine, piperazine and polyethyleneimine.
When the polyamine comprises main polyamine and auxiliary polyamine, the mass percent of the main polyamine in the polyamine is 50-100%.
In the interfacial polymerization, the polyamine of copper hydroxide is preferably used in the form of a solution, and the solvent for dissolving the polyamine may be a solvent which is incompatible with a solvent for dissolving a polybasic acid chloride described later and is inert to the polyamine. As such a solvent, for example, one or more of water, methanol and acetonitrile; preferably water.
The concentration of the polyamine in the polyamine solution of copper hydroxide is not particularly limited and may be selected conventionally in the art. For example, the concentration of the polyamine in the polyamine solution may be 0.01 to 10% by weight, preferably 0.1 to 2.5% by weight.
In the present invention, the type of the polybasic acid chloride is not particularly limited, and may be any acid chloride compound commonly used in the art for producing polyamides. Preferably, the polybasic acyl chloride is one or more of trimesoyl chloride, isophthaloyl chloride and terephthaloyl chloride; more preferably trimesoyl chloride.
In the interfacial polymerization, the polybasic acid chloride is preferably used in the form of a solution, and the solvent for dissolving the polybasic acid chloride may be a solvent which is incompatible with the solvent for dissolving the polyamine and inert to the polybasic acid chloride. Such a solvent may be, for example, an organic solvent, and the organic solvent is preferably one or more of n-hexane, dodecane, n-heptane, and paraffinic solvent oils (Isopar E, Isopar G, Isopar H, Isopar L, and Isopar M).
The concentration of the polybasic acid chloride in the polybasic acid chloride solution is not particularly limited and may be conventionally selected in the art. For example, the concentration of the polybasic acid chloride in the polybasic acid chloride solution may be 0.01 to 1% by weight, preferably 0.05 to 0.5% by weight.
The amount of the polyamine and the polybasic acid chloride can be changed within a wide range, and the mass concentration ratio of the polyamine to the polybasic acid chloride is preferably (1-50): 1, and more preferably (10-30): 1.
According to the invention, the mass ratio of the copper hydroxide to the polyamine in the polyamine solution of the copper hydroxide is (0.01-2): 1, preferably (0.05-1): 1.
The method for obtaining the polyamide separation layer of the present invention by interfacial polymerization of the above-mentioned polyamine solution of copper hydroxide and the polyacyl chloride solution is not particularly limited, and various conventional contact methods used in the art for interfacial polymerization of polyamine and polyacyl chloride can be used. Preferably, the contact time of the other surface of the support layer and the polyamine solution of copper hydroxide is 10-120 s, preferably 15-60 s; the contact time with the polyacyl chloride solution is 10-120 s, preferably 15-60 s; the temperature during the contact is 10-40 ℃.
According to the invention, when the heat treatment is carried out, the heat treatment temperature is 20-100 ℃, and the time is 1-10 min; preferably, the heat treatment temperature is 25-80 ℃ and the time is 2-5 min.
Specifically, the step of preparing the copper hydroxide-loaded polyamide separation layer on the other surface of the support layer according to the present invention may include: firstly, preparing a polyamine solution of copper hydroxide and preparing a polyacyl chloride solution; then, the other surface of the polymer layer is sequentially contacted with a polyamine solution of copper hydroxide and a polyacyl chloride solution, and then subjected to heat treatment.
The invention also aims to provide the application of the copper-containing antibacterial thin-layer composite membrane in the water treatment process.
The copper-containing antibacterial thin-layer composite membrane comprises a reinforcing layer, a supporting layer and a polyamide separation layer loaded with copper hydroxide, wherein the separation layer is obtained by carrying out interfacial polymerization on a polyamine solution and a polyacyl chloride solution of the copper hydroxide; in the interfacial polymerization process, the amine monomer reacts with the acyl chloride monomer to generate polyamide, and simultaneously copper hydroxide is separated out and fixed on the polyamide layer, and on the other hand, the residual carboxylic acid group in the polyamide layer is complexed with copper ions to play a role in fixing the copper ions. During the use process of the membrane, copper ions can be slowly dissolved in water, so that the long-term sterilization effect is achieved, and the lasting antibacterial capacity of the membrane is improved.
The copper-containing antibacterial thin-layer composite film and the preparation method thereof provided by the invention have the following advantages:
(1) the preparation method of the copper-containing antibacterial thin-layer composite film provided by the invention is simple and low in production cost.
(2) The copper-containing antibacterial thin-layer composite film provided by the invention has strong antibacterial durability, and the introduction of a copper compound does not cause the performance of the thin-layer composite film to be obviously reduced or even improved.
(3) The preparation process of the copper-containing antibacterial thin-layer composite membrane provided by the invention is similar to the conventional preparation process, does not need to introduce additional reaction steps, and can be realized on the existing equipment, so that the copper-containing antibacterial thin-layer composite membrane has a good industrial production prospect.
Detailed Description
In order that the invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the invention thereto.
The performance evaluation and evaluation method of the copper-containing antibacterial thin-layer composite film comprises the following steps:
(1) the water flux is defined as: the volume of water per membrane area per unit time that permeates under certain operating conditions is expressed in L/(m)2·h)。
(2) The salt cut-off R is defined as: under certain operating pressure conditions, the salt concentration C of the feeding liquidfWith the salt concentration C in the permeatePThe difference is divided by the feed solution salt concentration. Namely: r ═ CP-Cf)/CP×100％。
The test operation conditions adopted by the composite reverse osmosis membrane are as follows: the feed was 2000ppm aqueous sodium chloride, operating pressure was 225psi and operating temperature was 25 ℃.
The test operation conditions adopted by the composite nanofiltration membrane are as follows: the feed was a 500ppm aqueous solution of magnesium sulfate, operating pressure was 80psi and operating temperature was 25 ℃.
(3) And (3) testing antibacterial performance: shearing the antibacterial thin-layer composite membrane into a sample of 40mm multiplied by 40mm, contacting the sample with 100 mu L of escherichia coli bacterial liquid, culturing for 18h in a constant-temperature incubator at 37 ℃, counting viable bacteria by using an inverted plate method, and simultaneously carrying out a comparative test on a common composite membrane (not containing antibacterial copper compounds). The calculation formula of the antibacterial rate is as follows:
the antibacterial ratio (%) (1-B/A). times.100%
In the formula, A is the viable count of a common composite membrane sample; b is the viable count of the antibacterial composite membrane sample.
In the following examples, copper hydroxide, ethylenediamine and polyethylenepolyamine were obtained from Shanghai Aladdin Biotechnology Ltd, and triethylenetetramine, trimesoyl chloride and terephthaloyl chloride were obtained from carbofuran technology Ltd; polyethyleneimine is available from alfa aesar; isopar E is available from Shilange chemical Co., Ltd; other chemicals were purchased from the national pharmaceutical group chemicals, ltd.
The preparation of the supporting layer on the surface of the reinforcing layer is prepared by adopting a phase inversion method, and the preparation method comprises the following specific steps:
dissolving a certain amount of polysulfone (the number average molecular weight is 80000) in N, N-dimethylformamide to prepare a polysulfone solution with the concentration of 18 weight percent, and defoaming for 2 hours at normal temperature; then, the polysulfone solution was coated on a polyester nonwoven fabric (75 μm thick) with a doctor blade to obtain an initial film, which was then immersed in water at a temperature of 25 ℃ for 60min to obtain a polysulfone support layer. The polysulfone support layer has an average thickness of 50 μm.
Example 1
1g of ethylenediamine and 100mL of deionized water were added to 0.812g of copper hydroxide in this order, followed by stirring to obtain an ethylenediamine solution of copper hydroxide, and 100mL of Isopar E was added to 0.1g of trimesoyl chloride, followed by stirring to obtain a trimesoyl chloride solution. Contacting the upper surface of the polysulfone supporting layer with an ethylenediamine solution containing copper hydroxide, and discharging liquid after contacting for 60s at 25 ℃; then, the upper surface of the supporting layer is contacted with trimesoyl chloride solution again, and liquid is discharged after the contact for 30s at 25 ℃; then, the film was placed in an oven and heated at 70 ℃ for 2min to obtain a composite film CuR 1. X-ray photoelectron spectroscopy tests show that the mass content of the copper element on the surface of the composite film is 8.2 wt%. Wherein the polyamide separating layer has an average thickness of 185 nm.
The resulting composite membrane CuR1 was soaked in water for 24 hours and then tested for its salt rejection capacity against 2000ppm aqueous sodium chloride solution at a test pressure of 225psi and a temperature of 25 deg.C, with the results shown in Table 1. In addition, the antibacterial activity was examined by the microbial count method, and the results are shown in table 1.
Example 2
0.5g of ethylenediamine and 100mL of deionized water are sequentially added to 0.487g of copper hydroxide and stirred to obtain an ethylenediamine solution of copper hydroxide, and 100mL of Isopar E is added to 0.1g of trimesoyl chloride and stirred to obtain a trimesoyl chloride solution. Contacting the upper surface of the polysulfone supporting layer with an ethylenediamine solution containing copper hydroxide, and discharging liquid after contacting for 30s at 25 ℃; then, the upper surface of the supporting layer is contacted with trimesoyl chloride solution again, and liquid is discharged after the contact for 30s at 25 ℃; then, the film was placed in an oven and heated at 80 ℃ for 3min to obtain a composite film CuR 2. X-ray photoelectron spectroscopy tests show that the mass content of the copper element on the surface of the composite film is 5.1 wt%. Wherein the polyamide separating layer had an average thickness of 153 nm.
The resulting composite membrane CuR2 was soaked in water for 24 hours and then tested for its salt rejection capacity against 2000ppm aqueous sodium chloride solution at a test pressure of 225psi and a temperature of 25 deg.C, with the results shown in Table 1. In addition, the antibacterial activity was examined by the microbial count method, and the results are shown in table 1.
Example 3
0.1G of ethylenediamine and 100mL of deionized water were added to 0.065G of copper hydroxide in this order, followed by stirring to obtain an ethylenediamine solution of copper hydroxide, and 100mL of Isopar G was added to 0.05G of trimesoyl chloride, followed by stirring to obtain a trimesoyl chloride solution. Contacting the upper surface of the polysulfone supporting layer with an ethylenediamine solution containing copper hydroxide, and discharging liquid after contacting for 60s at 25 ℃; then, the upper surface of the supporting layer is contacted with trimesoyl chloride solution again, and liquid is discharged after the contact for 60s at 25 ℃; then, the film was placed in an oven and heated at 90 ℃ for 5min to obtain a composite film CuR 3. X-ray photoelectron spectroscopy tests show that the mass content of the copper element on the surface of the composite film is 1.8 wt%. Wherein the polyamide separating layer has an average thickness of 139 nm.
The resulting composite membrane CuR3 was soaked in water for 24 hours and then tested for its salt rejection capacity against 2000ppm aqueous sodium chloride solution at a test pressure of 225psi and a temperature of 25 deg.C, with the results shown in Table 1. In addition, the antibacterial activity was examined by the microbial count method, and the results are shown in table 1.
Example 4
To 0.1G of copper hydroxide, 1.4G of triethylene tetramine, 0.1G of m-phenylenediamine, and 100mL of deionized water were sequentially added and stirred to obtain a mixed amine solution of copper hydroxide, and to 0.05G of trimesoyl chloride, 100mL of Isopar G was added and stirred to obtain a trimesoyl chloride solution. Contacting the upper surface of the polysulfone supporting layer with a mixed amine solution containing copper hydroxide, and discharging liquid after contacting for 30s at 25 ℃; then, the upper surface of the supporting layer is contacted with trimesoyl chloride solution again, and liquid is discharged after the contact for 60s at 25 ℃; then, the film was placed in an oven and heated at 90 ℃ for 5min to obtain a composite film CuR 4. X-ray photoelectron spectroscopy tests show that the mass content of the copper element on the surface of the composite film is 2.5 wt%. Wherein the polyamide separating layer has an average thickness of 139 nm.
The resulting composite membrane CuR4 was soaked in water for 24 hours and then tested for its salt rejection capacity against 2000ppm aqueous sodium chloride solution at a test pressure of 225psi and a temperature of 25 deg.C, with the results shown in Table 1. In addition, the antibacterial activity was examined by the microbial count method, and the results are shown in table 1.
Example 5
0.5g of triethylene tetramine and 100mL of deionized water are sequentially added into 0.167g of copper hydroxide and stirred to obtain a triethylene tetramine solution of the copper hydroxide, and 100mL of Isopar E is added into 0.1g of trimesoyl chloride and stirred to obtain a trimesoyl chloride solution. Contacting the upper surface of the polysulfone supporting layer with a triethylene tetramine solution containing copper hydroxide, and discharging liquid after contacting for 90s at 25 ℃; then, the upper surface of the supporting layer is contacted with trimesoyl chloride solution again, and liquid is discharged after the contact for 60s at 25 ℃; then, the film was placed in an oven and heated at 50 ℃ for 5min to obtain a composite film CuN 1. X-ray photoelectron spectroscopy tests show that the mass content of the copper element on the surface of the composite film is 1.5 wt%. Wherein the polyamide separating layer has an average thickness of 208 nm.
The resulting composite membrane CuN1 was soaked in water for 24 hours and then tested for salt rejection to a 500ppm aqueous solution of magnesium sulfate at a test pressure of 80psi and a temperature of 25 deg.C, with the results shown in Table 1. In addition, the antibacterial activity was examined by the microbial count method, and the results are shown in table 1.
Example 6
1.5g of triethylene tetramine and 100mL of deionized water are sequentially added into 0.25g of copper hydroxide and stirred to obtain a triethylene tetramine solution of the copper hydroxide, and 100mL of Isopar E is added into a mixture of 0.1g of trimesoyl chloride and 0.1g of terephthaloyl chloride and stirred to obtain a polyacyl chloride solution. Contacting the upper surface of the polysulfone supporting layer with a triethylene tetramine solution containing copper hydroxide, and discharging liquid after contacting for 60s at 25 ℃; then, the upper surface of the supporting layer is contacted with a polybasic acyl chloride solution again, and the liquid is discharged after the contact for 60s at 25 ℃; then, the film was placed in an oven and heated at 60 ℃ for 3min to obtain composite film CuN 2. X-ray photoelectron spectroscopy tests show that the mass content of the copper element on the surface of the composite film is 2.1 wt%. Wherein the polyamide separating layer has an average thickness of 225 nm.
The resulting composite membrane CuN2 was soaked in water for 24 hours and then tested for salt rejection to a 500ppm aqueous solution of magnesium sulfate at a test pressure of 80psi and a temperature of 25 deg.C, with the results shown in Table 1. In addition, the antibacterial activity was examined by the microbial count method, and the results are shown in table 1.
Example 7
1g of triethylene tetramine, 1g of polyethylene polyamine and 100mL of deionized water are sequentially added into 0.1g of copper hydroxide and stirred to obtain a polyamine solution of the copper hydroxide, and 100mL of Isopar E is added into 0.1g of trimesoyl chloride and stirred to obtain a trimesoyl chloride solution. Contacting the upper surface of the polysulfone supporting layer with a polyamine solution containing copper hydroxide, and discharging liquid after contacting for 90s at 25 ℃; then, the upper surface of the supporting layer is contacted with trimesoyl chloride solution again, and liquid is discharged after the contact for 60s at 25 ℃; then, the film was placed in an oven and heated at 50 ℃ for 5min to obtain a composite film CuN 3. X-ray photoelectron spectroscopy tests show that the mass content of the copper element on the surface of the composite film is 1.2 wt%. Wherein the polyamide separating layer has an average thickness of 234 nm.
The resulting composite membrane CuN3 was soaked in water for 24 hours and then tested for salt rejection to a 500ppm aqueous solution of magnesium sulfate at a test pressure of 80psi and a temperature of 25 deg.C, with the results shown in Table 1. In addition, the antibacterial activity was examined by the microbial count method, and the results are shown in table 1.
Example 8
1g of polyethylene polyamine, 0.5g of polyethyleneimine and 100mL of deionized water are sequentially added to 0.08g of copper hydroxide, and stirred to obtain a polyamine solution of copper hydroxide, and 100mL of Isopar E is added to 0.1g of trimesoyl chloride and stirred to obtain a trimesoyl chloride solution. Contacting the upper surface of the polysulfone supporting layer with a polyamine solution containing copper hydroxide, and discharging liquid after contacting for 90s at 25 ℃; then, the upper surface of the supporting layer is contacted with trimesoyl chloride solution again, and liquid is discharged after the contact for 60s at 25 ℃; then, the film was placed in an oven and heated at 50 ℃ for 5min to obtain a composite film CuN 4. X-ray photoelectron spectroscopy tests show that the mass content of the copper element on the surface of the composite film is 1.3 wt%. Wherein the polyamide separating layer has an average thickness of 184 nm.
The resulting composite membrane CuN4 was soaked in water for 24 hours and then tested for salt rejection to a 500ppm aqueous solution of magnesium sulfate at a test pressure of 80psi and a temperature of 25 deg.C, with the results shown in Table 1. In addition, the antibacterial activity was examined by the microbial count method, and the results are shown in table 1.
Comparative example 1
A composite membrane was prepared as in example 1, except that copper hydroxide was not added to the ethylenediamine solution, and interfacial polymerization was performed with the acid chloride solution to obtain composite membrane R1. Wherein the polyamide separating layer has an average thickness of 217 nm.
The resulting composite membrane R1 was soaked in water for 24 hours and then tested for its salt rejection capacity against 2000ppm aqueous sodium chloride solution at a test pressure of 225psi and a temperature of 25 deg.C, with the results shown in Table 1. In addition, the antibacterial activity was examined by the microbial count method, and the results are shown in table 1.
Comparative example 2
The process for preparing a composite membrane was carried out as in example 5, except that copper hydroxide was not added to the triethylenetetramine solution, and interfacial polymerization was carried out with the acid chloride solution to obtain composite membrane N1. Wherein the polyamide separating layer has an average thickness of 226 nm.
The resulting composite film, N1, was soaked in water for 24 hours and then tested for salt rejection to a 500ppm aqueous solution of magnesium sulfate at a test pressure of 80psi and a temperature of 25 deg.C, with the results shown in Table 1. In addition, the antibacterial activity was examined by the microbial count method, and the results are shown in table 1.
TABLE 1 comparison of the Performance of the examples with that of the comparative examples
Comparing CuR1 and R1, and CuN1 and N1 in Table 1, it can be seen that the flux and salt rejection rate of the antibacterial thin-layer composite membrane prepared by the method are not obviously reduced compared with those of the antibacterial thin-layer composite membrane prepared by the comparative example, but the sterilization rate is as high as more than 80-90%. The separation layer in the antibacterial thin-layer composite membrane provided by the invention is obtained by interfacial polymerization of a polyamine solution of copper hydroxide and a polybasic acyl chloride solution, and in the polymerization process, an amine monomer reacts with an acyl chloride monomer to generate polyamide, and simultaneously copper hydroxide is separated out and fixed on a polyamide layer, and on the other hand, residual carboxylic acid groups in the polyamide layer are complexed with copper ions to play a role in fixing copper ions. Therefore, during the use process of the membrane, copper ions can be slowly dissolved in water, so that the long-term sterilization effect is achieved, and the lasting antibacterial capacity of the membrane is improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (16)
1. The copper-containing antibacterial thin-layer composite membrane is characterized by comprising a reinforcing layer, a supporting layer and a separating layer, wherein the separating layer is positioned on one surface of the supporting layer, the reinforcing layer is positioned on the other surface of the supporting layer, the supporting layer is a polymer porous membrane, and the separating layer is a polyamide separating layer loaded with copper hydroxide.
2. The copper-containing antibacterial thin-layer composite film according to claim 1, characterized in that:
the polymer porous membrane of the support layer is one or more of polysulfone, polyethersulfone and polyacrylonitrile.
3. The copper-containing antibacterial thin-layer composite film according to claim 1, characterized in that:
the enhancement layer is one or more of a polyester layer, a polyethylene layer or a polypropylene layer.
4. The copper-containing antibacterial thin-layer composite film according to claim 1, characterized in that:
the content of copper element in the copper hydroxide-loaded polyamide separation layer is 0.5-10 wt%, and preferably 1-5 wt%.
5. The copper-containing antibacterial thin-layer composite film according to claim 1, characterized in that:
the polyamide separation layer loaded with the copper hydroxide is obtained by carrying out interfacial polymerization on a polyamine solution of the copper hydroxide and a polyacyl chloride solution.
6. The copper-containing antibacterial thin-layer composite film according to claim 1, characterized in that:
the average thickness of the enhancement layer is 40-100 μm, preferably 50-90 μm;
the average thickness of the supporting layer is 20-80 μm, and preferably 30-60 μm;
the average thickness of the polyamide separation layer is 50-300 nm, and preferably 100-200 nm.
7. A method for preparing the copper-containing antibacterial thin-layer composite film according to any one of claims 1 to 6, comprising the steps of:
(1) preparing the support layer on one surface of the reinforcing layer;
(2) a copper hydroxide-loaded polyamide separation layer was prepared on the other surface of the support layer.
8. The method for preparing the copper-containing antibacterial thin-layer composite film according to claim 7, characterized in that:
in the step (1), a supporting layer polymer solution is coated on one surface of the reinforcing layer, and the supporting layer with the surface attached with the reinforcing layer is obtained through phase inversion.
9. The method for preparing the copper-containing antibacterial thin-layer composite film according to claim 7, characterized in that:
in the step (2), the other surface of the support layer is sequentially contacted with a polyamine solution of copper hydroxide and a solution of polyacyl chloride, and then heat treatment is performed.
10. The method for preparing the copper-containing antibacterial thin-layer composite film according to claim 9, characterized in that:
the polyamine comprises a main polyamine or a main polyamine and a secondary polyamine, and the main polyamine is selected from at least one of ethylenediamine, 1, 3-propanediamine, triethylene tetramine or polyethylene polyamine; the accessory polyamine is selected from at least one of m-phenylenediamine, p-phenylenediamine, piperazine and polyethyleneimine;
the polybasic acyl chloride is selected from at least one of trimesoyl chloride, isophthaloyl dichloride or terephthaloyl dichloride.
11. The method for preparing the copper-containing antibacterial thin-layer composite film according to claim 10, characterized in that:
the mass concentration ratio of the polyamine to the polybasic acyl chloride is (1-50): 1, preferably (10-30): 1.
12. The method for preparing the copper-containing antibacterial thin-layer composite film according to claim 10, characterized in that:
when the polyamine comprises main polyamine and accessory polyamine, the mass percent of the main polyamine is 50-100%.
13. The method for preparing the copper-containing antibacterial thin-layer composite film according to claim 9, characterized in that:
the mass ratio of the copper hydroxide to the polyamine in the polyamine solution of the copper hydroxide is (0.01-2): 1, preferably (0.05-1): 1.
14. The method for preparing the copper-containing antibacterial thin-layer composite film according to claim 9, characterized in that:
and the contact time of the other surface of the support layer and a polyamine solution of copper hydroxide is 10-120 s, and the contact time of the other surface of the support layer and a polyacyl chloride solution is 10-120 s.
15. The method for preparing the copper-containing antibacterial thin-layer composite film according to claim 9, characterized in that:
the heat treatment temperature is 20-100 ℃, and the heat treatment time is 1-10 min.
16. Use of a copper-containing antimicrobial thin-layer composite membrane according to any one of claims 1 to 6 in a water treatment process.
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