CN109384955B - Method for producing microorganism-inhibiting filter membrane - Google Patents
Method for producing microorganism-inhibiting filter membrane Download PDFInfo
- Publication number
- CN109384955B CN109384955B CN201710679930.8A CN201710679930A CN109384955B CN 109384955 B CN109384955 B CN 109384955B CN 201710679930 A CN201710679930 A CN 201710679930A CN 109384955 B CN109384955 B CN 109384955B
- Authority
- CN
- China
- Prior art keywords
- nano zinc
- particles
- zinc particles
- nano
- master batch
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/06—Flat membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- 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
- B01D71/02—Inorganic material
- B01D71/022—Metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/38—Graft polymerization
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
- C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
Abstract
The invention provides a method for manufacturing a filter membrane for inhibiting microorganisms, which comprises the following steps: obtaining a nano zinc precursor and dissolving the nano zinc precursor in water; adding at least one reducing agent and at least one interface agent into water dissolved with nano zinc precursor to reduce zinc ions of the nano zinc precursor into zinc particles so as to form liquid with nano zinc particles; respectively placing the liquid with the nano zinc particles and a polymer into plastic master batch process equipment, respectively processing the liquid with the nano zinc particles and the polymer into a volatile state by the plastic master batch process equipment, then carrying out air extraction mixing by the plastic master batch process equipment, and adding at least one grafting agent to carry out mixed grafting linking, so that the nano zinc particles can be stably linked with the polymer, and thus, a plastic master batch with the nano zinc particles is completed; finally, the plastic master batch with the nano zinc particles is made into a filter membrane with the nano zinc particles by a membrane making device, and the filter membrane has the functions of resisting bacteria and inhibiting bacterial growth.
Description
Technical Field
The present invention relates to a method for producing a filter membrane, and more particularly to a method for producing a filter membrane capable of inhibiting microorganisms, which has antibacterial and bacterial growth inhibiting functions.
Background
Zinc is a powerful antimicrobial nutrient, which is a trace nutrient. The main antibacterial mechanism is as follows: zinc is an antioxidant component of human body, contains four zinc atoms, can protect cell membranes and tissues from being damaged by hydroxyl radicals, and has detoxification function and antibacterial effect completely due to the relationship of zinc. Zinc can change the metabolism of bacterial sources, so that the probability of reviving bacterial load is reduced; thus, the production of many bacteria can be prevented by zinc.
Therefore, zinc has been proved to promote apoptosis of bacterial cells, so that the person skilled in the art has developed to combine zinc into an article, thereby achieving the function of combining zinc into the article, and having antibacterial and bacteriostatic functions.
Taking zinc element and plastic as an example, the existing zinc element and plastic combination process is mainly characterized in that plastic master batches are firstly added into an organic solvent to enable the plastic master batches to be dissolved in the organic solvent so as to form a plastic solution, then zinc element is added into the plastic solution for mixing, and finally the plastic granules with zinc element are prepared in plastic granulating equipment.
And then the finished plastic granules with zinc element are used for manufacturing various articles (such as textiles, containers and the like) to obtain the articles made of the plastic solution with zinc element, so as to have the functions of resisting and inhibiting bacteria.
However, in the existing zinc element and plastic combination process method, because the plastic solution after the plastic master batch is dissolved is thick liquid, when the zinc element is added into the plastic solution, the problem that the zinc element cannot be uniformly mixed with the plastic solution can be generated; in addition, the existing zinc element is in a zinc ion state, so that the existing zinc element cannot form a stable chain with the plastic solution, and an object (such as a textile) made of the existing plastic solution with the zinc element is extremely easy to gradually flow away the zinc element through water washing, so that the antibacterial or bacteriostatic function of the object made of the existing plastic solution with the zinc element is gradually reduced, and even the antibacterial or bacteriostatic capability is lost. For example: although the filter membrane with zinc element can reach the standard that the unit particle exceeds 600ppm in the initial stage, the zinc element gradually flows off along with long-time water flushing, so that the filter membrane with zinc element does not reach the standard that the unit particle exceeds 600 ppm.
Also, as disclosed in China with publication No. CN102205209B, an antibacterial polymer ultrafiltration membrane and a preparation method thereof are disclosed, wherein polymer membrane preparation liquid is prepared firstly; adding antibacterial agent particles with long-term slow-release effect, which are compounded by inorganic carriers (such as zeolite) and antibacterial agents (such as zinc metal ions), into the polymer film-forming liquid, wherein the antibacterial agent particles with long-term slow-release effect, which are compounded by the inorganic carriers and the antibacterial agents, account for 0.01-0.1% of the weight of the polymers in the polymer film-forming liquid by weight, and the particle size of the antibacterial agent particles is 0.01-10 mu m; preparing the antibacterial polymer ultrafiltration membrane by adopting a dry-wet method or a wet spinning technology through a non-solvent induced phase separation method (NIPS) or a thermal induced phase separation method (TIPS); the ultrafiltration membrane prepared by the method can be used for filtering and purifying water, and has long-term antibacterial effect. Can be widely applied to drinking water treatment, household water purifiers, and filtration purification of foods and medicines.
However, the above patent mainly uses inorganic antibacterial agent with zeolite powder as carrier, during mixing into film-forming solvent, silver, copper, zinc and other antibacterial agent can dissolve out to form ion state, and is lost greatly in phase transition water bath stage, so that proper equivalent of filter membrane containing antibacterial agent can not be controlled accurately; in the patent, inorganic antibacterial agents taking zeolite and other powder as carriers are added into homogeneous casting solution, and powder precipitation phenomenon can occur in the standing and defoaming process, so that the homogeneity of the casting solution is affected, and the uniformity of the equivalent of the antibacterial agents contained in the filter membrane is lacked; meanwhile, the dispersibility of the fine powder is difficult to ensure, and under the condition of powder agglomeration, the physical properties and the filtering precision of the filter membrane are changed, so that the use benefit is influenced.
Disclosure of Invention
In order to solve the problems and defects in the prior art, the invention discloses a method for manufacturing a filter membrane for inhibiting microorganisms, which comprises the following steps: obtaining a nano zinc precursor and dissolving the nano zinc precursor in water; adding at least one reducing agent and at least one interface agent into water dissolved with nano zinc precursor to reduce zinc ions of the nano zinc precursor into zinc particles so as to form liquid with nano zinc particles; respectively placing the liquid with the nano zinc particles and a polymer into plastic master batch process equipment, respectively processing the liquid with the nano zinc particles and the polymer into volatile state by the plastic master batch process equipment, and then carrying out air extraction and mixing by the plastic master batch process equipment, so that the liquid with the nano zinc particles and the polymer with the volatile state are mixed in the air extraction process, and at least one grafting agent is added for carrying out mixed grafting chain so as to complete the plastic master batch with the nano zinc particles; finally, the plastic master batch with the nano zinc particles is passed through a membrane making device to prepare a filter membrane with the nano zinc particles.
The technical scheme of the invention is as follows: firstly reducing a nano zinc precursor and obtaining nano zinc particles, reducing the nano zinc ions into nano zinc particles by using a reducing agent, and then combining the nano zinc particles with the nano zinc particles by using an interface agent in a modified grafting (chemical grafting) mode, so that the reduced nano zinc particles cannot be combined with other particles (namely, secondary agglomeration between the nano zinc particles is prevented), thereby reducing the stable nano zinc particles; then forming plastic master batch with nano zinc particles by using an air extraction mixing mode, wherein the plastic master batch process equipment respectively processes liquid with nano zinc particles and high polymer substances until the liquid and the high polymer substances are in a volatile state and then mixes the liquid and the high polymer substances in the air extraction process, so that the nano zinc particles and the high polymer substances can be uniformly and stably linked to finish the plastic master batch with nano zinc particles; finally, the plastic master batch with the nano zinc particles is passed through a membrane making device to prepare a filter membrane with the nano zinc particles.
Wherein the nano zinc precursor is one of zinc chloride, zinc gluconate, zinc acetate, zinc sulfate and zinc carbonate, and can be dissolved in water.
Wherein the reducing agent is diamine compound (hydroazenec)The components include, but are not limited to, lipounds), gluconic acid (dextrose), sodium ascorbate (sodium ascorbate), ascorbic acid (sodium carboxymethylcellulose (Sodium carboxymethyl cellulose, CMC), sulfur dioxide (SO) 2 ) Strong reducing agent (NaBH) 4 ) One or more of them.
Wherein, the interface agent is selected from: cationic surfactant (Cetyl trimethylammonium bromide, CTAB), sodium dodecyl sulfate (Sodium Dodecyl Sulfate, SDS), polyvinyl pyrrolidone (PVP), 3- (trimethoxysilyl) propyl acrylate (3- (trimethoxyysilyl) propyl methacrylate), methanesulfonic acid (MSMA, sodium hydrogen sulfate), L- (-) -Dibenzoyl tartaric acid (DBTA), aminopropyl trimethoxysilane (3-aminopropyl-silane, APTMS), 3-Mercaptopropyl) trimethoxysilane (3-Mercaptopropyl) trimethoxysilane, MPTMS.
Wherein the polymer is one of PET, PA6 and PP, PE, ABS, PC, PVDF, PS, PES, PVC, PAN.
In the step c, the melt grafting mode is performed in plastic master batch processing equipment, the plastic master batch processing equipment is provided with a double-screw air suction mechanism and at least six air suction holes, the double-screw air suction mechanism is in a vacuum state, the liquid with nano zinc particles and the polymer are respectively placed in the plastic master batch processing equipment, the weight ratio of the liquid with nano zinc particles to the polymer is between 1:10 and 1:1, and after the plastic master batch processing equipment is used for respectively processing the liquid with nano zinc particles and the polymer to a volatile state, the liquid with nano zinc particles and the polymer to the volatile state are mixed and linked through the double-screw air suction mechanism and the six air suction holes, and the grafting agent is added at the moment to perform mixed grafting linking so as to complete the plastic master batch with nano zinc particles.
Wherein in the step b, the zinc ions of the nano zinc precursor are reduced into nano zinc particles by: will Z 2+ The concentration is 1×10 -5 mole～1×10 -3 Putting zinc ions between the moles into a glass bottle, adding deionized water (DI), setting the concentration of Sodium Dodecyl Sulfate (SDS) to be 1 mM-10000 mM, setting the concentration of cationic interface active agent (CTAB) to be 1 Mm-10000 mM, setting the concentration of sodium carboxymethylcellulose (CMC) to be 1-20wt%, uniformly stirring by a heating stirrer, and adding a reducing agent sodium metabisulfite Na 2 S 2 O 5 1 to 5 g of strong reducing agent (NaBH) 4 ) Then 0.01-10M solution is added with reducing agent respectively in the stirring process, when the reducing agent is at high PH value, 0.1-40 mu l of concentrated hydrochloric acid is added dropwise, at this time, the PH value of the solution is regulated to about 1-5, the solution is continuously stirred and placed into 50-90 DEG hot water bath, and then the solution is heated and stirred by a magnetite electric heating stirrer, namely nano zinc ions are reduced into nano zinc particles.
Wherein, in the step b, the mode of reducing the zinc ions of the nano zinc precursor into the nano zinc particles is sonochemistry method: the nano zinc precursor is placed into a reaction bottle, the reaction bottle is placed into an ultrasonic tank to generate a reduction free radical and a reduction metal ion by ultrasonic oscillation so as to generate nano zinc metal particles, then a metal salt aqueous solution is placed into the reaction bottle, the interface agent is added to stabilize the nano zinc metal particles, the reaction bottle is placed into an ultrasonic oscillator to oscillate, and the reaction is completed after 8-15 minutes, namely the nano zinc ions are reduced into nano zinc particles.
In the step b, the mode of reducing the zinc ions of the nano zinc precursor into the nano zinc particles is an electrochemical method, the electrochemical method is to generate metal nano particles by using an electrochemical method, and the particle size is adjusted by controlling the current of an electrolysis device, so that the zinc ions of the nano zinc precursor are reduced into the nano zinc particles by using the electrochemical method.
Wherein the grafting agent is one of maleic anhydride, acetic anhydride, glycidyl methacrylate, acrylamide and acrylic acid.
Wherein the filter membrane with nano zinc particles is in the form of a hollow fiber filter membrane, a flat plate filter membrane or other filter membranes.
Thus, the filter membrane with nano zinc particles, which is prepared from plastic master batches with nano zinc particles, can be used for filtering liquid or gas, and has antibacterial and bacteriostatic effects by utilizing the zinc particles, so that the filter membrane with nano zinc particles has the functions of resisting bacteria and inhibiting bacterial growth; meanwhile, the nano zinc particles and the high polymer can be stably linked, so that the filter membrane with the nano zinc particles is not easy to lose the nano zinc particles due to solvent or phase transition or water bath, and the effect of lasting and effective maintenance of the antibacterial and bacteriostatic ability of the article is achieved.
Drawings
Fig. 1: a flowchart of the method for producing a microorganism-inhibiting filter membrane of the present invention;
fig. 2: the chemical formula state diagram of the polyethylene karst-idone (PVP) and the nano zinc particles after the grafting process;
fig. 3: the chemical formula state diagram of the Sodium Dodecyl Sulfate (SDS) and nano zinc particles after the grafting process;
fig. 4: one embodiment of a process for reducing zinc ions of a nano zinc precursor to nano zinc particles is shown in the present invention;
fig. 5: the nano zinc particles of the invention are added with a grafting chemical formula state diagram of a maleic anhydride grafting agent and PVDF;
fig. 6: the nano zinc particles of the invention are added with a grafting chemical formula state diagram of maleic anhydride grafting agent and PES;
fig. 7: the nano zinc particles of the invention are added with a grafting chemical formula state diagram of a maleic anhydride grafting agent and PAN;
fig. 8: the state diagram of the grafting chemical formula of the maleic anhydride grafting agent and PVC is added to the nano zinc particles;
fig. 9: a first detection report of the method for producing a microorganism-inhibiting filter membrane of the present invention;
fig. 10: a second test report of the method for producing a microorganism-inhibiting filter membrane of the present invention;
fig. 11: a third test report of the method for producing a microorganism-inhibiting filter membrane of the present invention;
fig. 12: fourth test report of the method for producing a microorganism-inhibiting filter membrane of the present invention.
Detailed Description
The features and advantages of the present invention will now be described in detail with reference to the accompanying drawings, and the following examples are provided to illustrate the invention in further detail, but are not intended to limit the scope of the invention in any way.
Referring to fig. 1, the invention discloses a method for manufacturing a filter membrane for inhibiting microorganisms, which comprises the following steps:
step 100: obtaining a nano zinc precursor, wherein the nano zinc precursor is soluble in water, and the nano zinc precursor is soluble in water. The nano zinc precursor can be one of zinc chloride, zinc gluconate, zinc acetate, zinc sulfate, zinc carbonate and the like, and is dissolved in water. For example, zinc dioxide is dissolved in water: zn (zinc) 2+ (s)+2e - →Zn(aq)。
Step 110: adding at least one reducing agent and at least one interface agent into water dissolved with the nano zinc precursor, so as to reduce zinc ions of the nano zinc precursor into nano zinc particles, thereby forming a liquid with nano zinc particles; namely, reducing nano zinc ions into nano zinc particles by using a reducing agent, and then combining the nano zinc particles with the interface agent in a modified grafting (chemical grafting) mode, so that the reduced nano zinc particles can not be combined with other particles (namely, secondary agglomeration between the nano zinc particles is prevented), thereby reducing stable nano zinc particles. The reducing agent can be selected from the following components: diamine compounds (glycoses), sodium ascorbates (ascorbates), sodium carboxymethylcellulose (Sodium carboxymethyl cellulose, CMC), sulfur dioxide (SO) 2 ) One or more of a strong reducing agent (NaBH 4).
The interface agent can be selected from the following components: one or more of cationic surfactant (Cetyl trimethylammonium bromide, abbreviated as CTAB), sodium dodecyl sulfate (Sodium Dodecyl Sulfate, abbreviated as SDS), polyvinyl pyrrolidone (PVP), 3- (trimethoxysilyl) propyl acrylate (3- (trimethoxyysilyl) propyl methacrylate), methanesulfonic acid (MSMA, sodium hydrogen sulfate), L- (-) -Dibenzoyl tartaric acid (DBTA), aminopropyl trimethoxysilane (3-aminopropyl-silane, abbreviated as APTMS), and 3-Mercaptopropyl) trimethoxysilane (3-Mercaptopropyl) trimethoxysilane, abbreviated as (MPTMS).
Step 120: respectively placing the liquid with nano zinc particles and a polymer in plastic master batch process equipment in a melt grafting mode, processing the liquid with nano zinc particles and the polymer to be volatile by the plastic master batch process equipment, and then carrying out air suction mixing by the plastic master batch process equipment, so that the liquid with nano zinc particles and the polymer to be volatile are subjected to air suction, and at least one grafting agent is added to carry out mixed grafting linking to complete the plastic master batch with nano zinc particles. The polymer may be a polymer of other plastics such as PET (polyethylene terephthalate), PA6 (polyamide (NYLON), PP (polypropylene), PE (polyethylene), ABS (acrylonitrile-butadiene-styrene copolymer), PC (polycarbonate), PVDF (polyvinylidene fluoride), PS (polystyrene), PEs (polyethersulfone), PVC (polyvinylchloride), PAN (polyacrylonitrile), and the like.
Step 130: and (3) passing the plastic master batch with the nano zinc particles through a membrane making device to prepare a filter membrane with the nano zinc particles.
In the step 110, the process of combining the nano-zinc particles with the interface agent is a modification process by grafting the nano-zinc particles with the interface agent by means of modified grafting (chemical grafting), so that the nano-zinc particles cannot be combined with other particles, and when the nano-zinc particles and the interface agent pass through the grafting process, the nano-zinc particles form a composite material. For example: the chemical formula of the polyvinyl pyrrolidone (PVP) and nano zinc particles is shown in figure 2 after the grafting process. Also for example: the chemical formula of the polymer is shown in figure 3 after the grafting process of Sodium Dodecyl Sulfate (SDS) and nano zinc particles.
In the step 110, when the interface agent is sodium carboxymethyl cellulose (CMC), the sodium carboxymethyl cellulose (CMC) is soluble in the aqueous solution, so that the aqueous solution is viscous, and the movement rate of the nano zinc particles in the viscous aqueous solution is slowed down, so as to reduce the chance of collision and aggregation, thereby achieving a stable effect. Meanwhile, the temperature can be changed, the concentration of the reducing agent can be adjusted and other reaction conditions are used for changing the particle size distribution of the nano zinc particles, so that the purpose of controlling the particle size is achieved.
The present invention further describes a specific example of reducing zinc ions of the nano-zinc precursor to nano-zinc particles in step 110. Wherein Z is 2+ The concentration is 1×10 -5 mole～1×10 -3 Putting zinc ions between the moles into a glass bottle, adding deionized water (DI), setting the concentration of Sodium Dodecyl Sulfate (SDS) to be 1 mM-10000 mM, setting the concentration of cationic interface active agent (CTAB) to be 1 Mm-10000 mM, setting the concentration of sodium carboxymethylcellulose (CMC) to be 1-20wt%, uniformly stirring by a heating stirrer, and adding a reducing agent sodium metabisulfite Na 2 S 2 O 5 1 to 5 g of strong reducing agent (NaBH) 4 ) Then 0.01 to 10M solution. During the stirring process, reducing agents are respectively added; at this time, if the reducing agent is high in pH value, 0.1-40 μl of concentrated hydrochloric acid is added dropwise, the pH value of the solution is adjusted to about 1-5, and then the solution is stirred and placed in a hot water bath with 50-90 degrees, and then heated and stirred by a magneto electric heating stirrer, so as to obtain nano zinc ions for reduction into nano zinc particles, and the process is shown in FIG. 4.
The second embodiment is further described in the step 110, which is a specific description of reducing zinc ions of the nano-zinc precursor to nano-zinc particles. Wherein, a sonochemistry method (namely utilizing ultrasonic to promote reduction) is utilized to put a nano zinc precursor into a reaction bottle, and the reaction bottle is placed into an ultrasonic tank to generate a reduction free radical and a reduction metal ion by ultrasonic oscillation so as to generate nano zinc metal particles; then the metal salt aqueous solution is put into a reaction bottle and added withThe interface active agent stabilizes nano zinc metal particles, the reaction bottle is placed in an ultrasonic oscillator to oscillate, and the reaction is completed after 8-15 minutes, so as to obtain nano zinc particles; the reaction mechanism is as follows: h 2 O.fwdarw.H+. OH (sonolysis),. OH (. H) +RH.fwdarw.R (reducing species) +H 2 O(H 2 ) RH →.R (reducing species, reduction product) +.H (sonolysis),. R (reducing species, reduction product) +Zn (M-1) ++ H++ R+. The driving force of the reaction mechanism comes from cavitation generated by vibration waves or OH or H generated between the cavitation and the solution, and carbon chain molecules are reduced to generate R free radicals; or RH between interfaces is oscillated to form R free radical, which reacts with metal ion in oxidation-reduction reaction to reduce the metal ion into zero-valence metal nanometer particle.
The driving force of the reaction mechanism comes from cavitation generated by vibration waves or OH or H generated between the cavitation and the solution, and carbon chain molecules are reduced to generate R free radicals; or RH between interfaces is oscillated to form R free radical, which reacts with metal ion in oxidation-reduction reaction to reduce the metal ion into zero-valence metal nanometer particle.
The present invention further provides a third embodiment for describing a specific example of reducing zinc ions of the nano-zinc precursor to nano-zinc particles in the step 110. Wherein, an electrochemical method is adopted, which is Reetz, M.T. and Helbig in 1994, and W. the electrochemical method is adopted to generate metal nano particles, and the particle size can be adjusted by controlling the current of an electrolysis device; therefore, the invention can reduce zinc ions of the nano zinc precursor into nano zinc particles by an electrochemical method, and the process is as follows:
anode: metal block material → metal ion + ne -
And (3) cathode: metal ion +ne - +interfacial agent → nano metal ion/interfacial agent
Total reaction: metal block + interfacial agent → nano metal particles/interfacial agent
In the step 120, the melt grafting method is to respectively place the liquid with nano zinc particles and a polymer into a plastic master batch process device, wherein the plastic master batch process device is provided with a double-screw air suction mechanism and at least six air suction holes, and the double-screw air suction mechanism is in a vacuum state; respectively placing the liquid with the nano zinc particles and a polymer into plastic master batch process equipment, wherein the weight ratio of the liquid with the nano zinc particles to the polymer can be between 1:10 and 1:1; after the liquid with nano zinc particles and the polymer in the volatile state are processed to be in the volatile state by plastic master batch processing equipment, the liquid with nano zinc particles in the volatile state and the polymer in the volatile state are mixed and linked in the air extraction process through a double-screw air extraction mechanism and six air extraction holes, and at the moment, at least one grafting agent is added to carry out mixed grafting and linking so as to finish the plastic master batch with nano zinc particles; the blending addition amount of the grafting agent is between 0.1 and 5 percent relative to the weight percentage concentration of the polymer.
The grafting agent may be Maleic anhydride (MAA), and its molecular formula is C 4 H 2 O 3 The chemical formula is as follows:
the grafting agent can be Acetic Anhydride (AA) with a molecular formula of (CH) 3 CO) 2 O, its chemical formula is:
the grafting agent can be glycidyl methacrylate (Glycidyl methacrylate; GMA for short), and its molecular formula is C 7 H 10 O 3 The chemical formula is as follows:
the grafting agent can be Acrylamide (AM), and its molecular formula is CH 2 ＝CHCONH 2 The chemical formula is as follows:
the grafting agent can be acrylic acid (AAM for short), and the molecular formula is C 3 H 4 O 2 The chemical formula is as follows:
the present invention is directed to an example illustrating the grafting chemistry of the inventive nano-zinc particles with PVDF, PES, PAN, PVC; wherein: as shown in fig. 5, the grafting chemical formula of the nano zinc particle-added maleic anhydride (MAA) grafting agent and PVDF of the present invention is illustrated; as shown in fig. 6, the grafting chemical formula of the nano zinc particle-added maleic anhydride (MAA) grafting agent and PES of the present invention is illustrated; as shown in fig. 7, the grafting chemical formula of the nano zinc particle-added maleic anhydride (MAA) grafting agent and PAN of the present invention is illustrated; as shown in FIG. 8, the grafting chemical formula of the nano zinc particle-added maleic anhydride (MAA) grafting agent and PVC according to the present invention is illustrated.
Therefore, the technical scheme of the invention is as follows: firstly reducing a nano zinc precursor to obtain nano zinc particles, reducing the nano zinc ions into nano zinc particles by using a reducing agent, and then combining the nano zinc particles with the nano zinc particles by using an interface agent in a modified grafting (chemical grafting) mode, so that the reduced nano zinc particles cannot be combined with other particles (namely, secondary agglomeration between the nano zinc particles is prevented), thereby reducing the stable nano zinc particles; then, a molten grafting mode is utilized and at least one grafting agent is added to carry out mixed grafting and linking to form plastic master batch with nano zinc particles, after liquid with nano zinc particles and high polymer are respectively processed to be in a volatile state by plastic master batch process equipment, and the liquid and the high polymer are mixed in the air extraction process, so that the nano zinc particles can be uniformly and stably linked with the high polymer to complete the plastic master batch with nano zinc particles; finally, the plastic master batch with the nano zinc particles is passed through a membrane making device to prepare a filter membrane with the nano zinc particles. The filter membrane with the nano zinc particles can be in the form of a hollow fiber filter membrane, a flat plate filter membrane or other forms of filter membranes.
It is worth noting that the melting grafting mode can be utilized to make the nano zinc particles and the high polymer generate the joint, and at the same time, the mechanical property of the high polymer is not affected, and even the plastic can obtain excellent physical properties, such as the improvement of ductility and toughness; thus, the invention can avoid the defects generated by the traditional manufacturing method of adding any form of organic or inorganic antibacterial agent into the casting solution; according to the invention, before film preparation, nano zinc particles are grafted on a high polymer, so that after the high polymer is dissolved in a film-making solvent such as DMF/DMAC/NMP and the like, a homogeneous casting solution can be formed, and the problems of uneven dispersion or serious agglomeration of an antibacterial agent are effectively avoided; meanwhile, the leaching amount of zinc particles can be effectively reduced in the water bath process of phase transition of the casting solution, the zinc equivalent of the filter membrane product is ensured, and the concentration of the microorganisms is inhibited. For example: the filter membrane of the nano zinc particles prepared by the invention can reach the standard that the unit particles exceed 600 ppm.
The present invention tries to illustrate a first test description (as shown in fig. 9), which is tested by SGS international test technology corporation, the test date is 2015, 2, 9, and is known from the test result: the plastic master batch prepared from the zinc-containing plastic solvent prepared by the method can reach 12700ppm of zinc per unit.
The present invention tries to take a second test description (as shown in fig. 10), which is tested by SGS international test technology company, the test date is 2015, 4, 27 days, and the test result is that: the zinc content of the hollow fiber membrane prepared from the plastic master batch with the nano zinc particles can reach 851ppm.
The present invention tries to illustrate a third test (as shown in fig. 11), which is performed by SGS international test technology corporation, the test date is 2016, 9, 30, and the test result is that: the zinc-containing particles of the PS hollow fiber membrane prepared from the plastic master batch with the nano zinc particles can reach 845ppm.
Thus, the conclusion of the first, second and third detection descriptions can be found: the filter membrane manufacturing method of the invention can still obtain similar or similar results under the same construction method, the same formula, different time and different equipment conditions, namely, the plastic master batch with the nano zinc particles is proved to be repeatable, and the plastic master batch has the advantage.
The invention tries to take a fourth detection description (shown in figure 12), which is carried out by SGS International inspection science and technology company, the detection date is 2016, 9 and 30 days, and the detection result shows that the zinc element eluted by the plastic master batch with nano zinc particles in the casting mould liquid phase transition water bath process is only 3ppm, namely, after the product of the invention detects white liquid by an ICP-AES (inductively coupled plasma atomic emission spectrometry analysis) method, the eluted zinc ion is 3ppm per unit, and the lowest value of the adopted detection mode is that if the eluted zinc element is lower than 2ppm, the instrument cannot detect; thus, the present invention was shown to test this data, and it was concluded that plastic master batches with nano zinc particles, which are not easily eluted with zinc, remained mostly in the fiber membrane filaments, and the measured 3ppm level of eluted, proved to be quite low.
The filter membrane with the nano zinc particles can be used for filtering liquid or gas, and the filter membrane with the nano zinc particles has the functions of decomposing bacteria and inhibiting the growth of the bacteria by utilizing the antibacterial effect of the zinc particles; meanwhile, the nano zinc particles and the high polymer can be stably linked, so that the filter membrane with the nano zinc particles is not easy to gradually lose the nano zinc particles through washing, and the antibacterial capability of the article is effectively maintained.
It is noted that the filter membrane with nano zinc particles of the present invention can inhibit the growth of bacteria, and uses nano zinc oxide to constantly have an electric energy gap of 3.3eV, and when the filter membrane contacts with microorganism bacteria or ammonia gas molecules, the electric energy gap can promote the bond breaking of extracellular layer molecules or ammonia gas molecules, such as: the metabolism, nutrition and other mechanisms of the outer membrane of the bacteria are lost, so that the death of cells is promoted, and the functions of decomposing bacteria and inhibiting the growth of the bacteria are achieved.
In addition, when the filter membrane with nano zinc particles is applied to filtering ammonia gas molecules, the electric energy gap can be emptyWater molecules H in the gas 2 O is free, the reaction requires H 2 O participates in forming-OH radicals which react with NH 3 The reaction deprives the H therein to gradually form NH 2 Finally N is combined with other N to form stable N 2 Molecules, whole NH 3 The molecular decomposition formula is as follows:
NH (m-1) +-OH→NH m - +H 2 O
finally, the free nitrogen atom will bond with the nitrogen atom: N+N.fwdarw.N 2 Becomes nitrogen.
Claims (10)
1. A method for producing a microorganism-inhibiting filter membrane, comprising:
a, obtaining a nano zinc precursor, and dissolving the nano zinc precursor in water;
b, adding at least one reducing agent and at least one interface agent into water dissolved with the nano zinc precursor, so as to reduce zinc ions of the nano zinc precursor into nano zinc particles, thereby forming a liquid with nano zinc particles;
c, respectively placing the liquid with the nano zinc particles and a polymer in plastic master batch process equipment in a melt grafting mode, processing the liquid with the nano zinc particles and the polymer to a volatile state by the plastic master batch process equipment, and then carrying out air suction mixing by the plastic master batch process equipment, so that the liquid with the nano zinc particles and the polymer in the volatile state are subjected to air suction, and at least one grafting agent is added to carry out mixed grafting chain so as to complete a plastic master batch with the nano zinc particles;
the polymer is selected from plastics, and the plastic material is one of PET, PA6 and PP, PE, ABS, PC, PVDF, PS, PES, PVC, PAN;
and d, passing the plastic master batch with the nano zinc particles through a membrane preparation device to prepare a filter membrane with the nano zinc particles.
2. The method for producing a microbial-inhibiting filter membrane according to claim 1, wherein the nano zinc precursor is one of zinc chloride, zinc gluconate, zinc acetate, zinc sulfate and zinc carbonate, and is soluble in water.
3. The method for producing a microbial-inhibiting filter membrane according to claim 1, wherein the reducing agent is selected from the group consisting of diamines, gluconic acid, sodium ascorbate, ascorbic acid, sodium carboxymethylcellulose, sulfur dioxide, naBH 4 One or more of them.
4. The method for producing a microbial-inhibiting filter membrane according to claim 1, wherein the interface agent is selected from the group consisting of: sodium dodecyl sulfate, polyvinylpyrrolidone, 3- (trimethoxysilyl) propyl acrylate, methanesulfonic acid, DBTA, aminopropyl trimethoxysilane, and (3-mercaptopropyl) trimethoxysilane.
5. The method of claim 1, wherein in the step c, the melt grafting is performed in a plastic master batch process device, the plastic master batch process device has a double screw pump mechanism and at least six pump holes, the double screw pump mechanism is in a vacuum state, the liquid with nano zinc particles and the polymer are respectively placed in the plastic master batch process device, the weight ratio of the liquid with nano zinc particles to the polymer is between 1:10 and 1:1, and the plastic master batch process device respectively processes the liquid with nano zinc particles and the polymer to a volatile state, then the liquid with nano zinc particles and the polymer in a volatile state are mixed and linked in the pump process by the double screw pump mechanism and the six pump holes, and the grafting agent is added at the moment to perform mixed grafting linking, so as to complete the plastic master batch with nano zinc particles.
6. The method for producing a microorganism-inhibiting filtration membrane according to claim 1The method is characterized in that in the step b, the mode of reducing the zinc ions of the nano zinc precursor into the nano zinc particles is as follows: will Z 2+ The concentration is 1×10 -5 mole ~ 1×10 -3 Putting zinc ions between moles into a glass bottle, adding deionized water, setting the concentration of sodium dodecyl sulfate to be 1 mM-10000 mM, setting the concentration of cationic interface active agent to be 1Mm mM-10000 mM, setting the concentration of sodium carboxymethyl cellulose to be 1-20 wt%, uniformly stirring by a heating stirrer, and adding a reducing agent sodium metabisulfite Na 2 S 2 O 5 1-5 g of NaBH 4 And 0.01-10M solution, and respectively adding a reducing agent in the stirring process, and when the reducing agent is at a high pH value, dripping 0.1-40 mu l of concentrated hydrochloric acid, adjusting the pH value of the solution to 1-5 at the moment, continuously stirring, placing into a 50-90-DEG hot water bath, and heating and stirring by using a magnetite electric heating stirrer, namely reducing the nano zinc ions into nano zinc particles.
7. The method of claim 1, wherein in the step b, the zinc ions of the nano zinc precursor are reduced to nano zinc particles by sonochemical method: the nano zinc precursor is placed into a reaction bottle, the reaction bottle is placed into an ultrasonic tank, reduced free radicals and reduced metal ions are generated by ultrasonic oscillation to generate nano zinc metal particles, then a metal salt aqueous solution is placed into the reaction bottle, the interface agent is added to stabilize the nano zinc metal particles, the reaction bottle is placed into an ultrasonic oscillator to oscillate, and the reaction is completed after 8-15 minutes, namely the nano zinc ions are reduced into nano zinc particles.
8. The method of claim 1, wherein in the step b, the zinc ions of the nano zinc precursor are reduced to nano zinc particles by electrochemical method, wherein the electrochemical method is to generate metal nano particles by electrochemical method, and the particle size is adjusted by controlling the current of an electrolysis device, thereby reducing the zinc ions of the nano zinc precursor to nano zinc particles by the electrochemical method.
9. The method for producing a microorganism-inhibiting filtration membrane according to claim 1, wherein the grafting agent is one of maleic anhydride, acetic anhydride, glycidyl methacrylate, acrylamide and acrylic acid.
10. The method for producing a microbial-inhibiting filter according to claim 1, wherein the filter having nano zinc particles is a hollow fiber filter, a flat plate filter or other filter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710679930.8A CN109384955B (en) | 2017-08-10 | 2017-08-10 | Method for producing microorganism-inhibiting filter membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710679930.8A CN109384955B (en) | 2017-08-10 | 2017-08-10 | Method for producing microorganism-inhibiting filter membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109384955A CN109384955A (en) | 2019-02-26 |
| CN109384955B true CN109384955B (en) | 2023-08-04 |
Family
ID=65414998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710679930.8A Active CN109384955B (en) | 2017-08-10 | 2017-08-10 | Method for producing microorganism-inhibiting filter membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109384955B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113045707A (en) * | 2021-02-26 | 2021-06-29 | 李文静 | Antibacterial synthetic resin and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2160945A1 (en) * | 2008-09-09 | 2010-03-10 | Polymers CRC Limited | Antimicrobial Article |
| CN104017308A (en) * | 2014-06-19 | 2014-09-03 | 江苏凯尚节能科技有限公司 | Novel antibacterial plastic |
| CN105694438A (en) * | 2016-02-18 | 2016-06-22 | 惠州市环美盛新材料有限公司 | Nano inorganic antibacterial fiber masterbatch and preparation method thereof |
| CN106589764A (en) * | 2015-10-19 | 2017-04-26 | 吴翊廷 | Manufacturing method of antibacterial plastic master batches and application method of product thereof |
-
2017
- 2017-08-10 CN CN201710679930.8A patent/CN109384955B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2160945A1 (en) * | 2008-09-09 | 2010-03-10 | Polymers CRC Limited | Antimicrobial Article |
| CN104017308A (en) * | 2014-06-19 | 2014-09-03 | 江苏凯尚节能科技有限公司 | Novel antibacterial plastic |
| CN106589764A (en) * | 2015-10-19 | 2017-04-26 | 吴翊廷 | Manufacturing method of antibacterial plastic master batches and application method of product thereof |
| CN105694438A (en) * | 2016-02-18 | 2016-06-22 | 惠州市环美盛新材料有限公司 | Nano inorganic antibacterial fiber masterbatch and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109384955A (en) | 2019-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10421827B2 (en) | Method for manufacturing filter membrane for inhibiting microorganisms | |
| CN106977751B (en) | A kind of composite antibacterial deodorization functions master batch, the preparation method of fiber | |
| CN103361885B (en) | A kind of preparation method of antibacterial fibroin fiber film | |
| CN101812801B (en) | Antibacterial functional fibers | |
| CN108456331B (en) | A kind of metal-organic framework materials are the preparation method of the vulcanizing activator of carrier | |
| CN111909454A (en) | Antibacterial masterbatch and application thereof | |
| CN102000832A (en) | Preparation method and purification process of nano silver | |
| TW200413120A (en) | Process for producing metal fine powder | |
| CN106283241B (en) | The method for preparing nano silver blending native cellulose fibre | |
| CN109384955B (en) | Method for producing microorganism-inhibiting filter membrane | |
| CN102295308A (en) | Method for preparing zinc oxide by using zinc-containing waste liquid as raw material | |
| TWI337892B (en) | ||
| JP6405013B1 (en) | Manufacturing method of membrane filter for suppressing microorganisms | |
| CN114875521A (en) | Preparation method of efficient antibacterial and antiviral fiber | |
| KR100890632B1 (en) | Preparation of silver colloid from impure silver salt | |
| EP3446774A1 (en) | Method for manufacturing filter membrane for inhibiting microorganisms | |
| CN106853538A (en) | A kind of quick method for preparing particle diameter and the copper nano-particle of morphology controllable | |
| CN105597578A (en) | Antibacterial separating membrane with directionally induced and loaded nano-silver and preparation method of antibacterial separating membrane | |
| KR101931663B1 (en) | Method for Manufacturing Filter Membrane for Inhibiting Microorganisms | |
| CN102978414B (en) | Method for precipitating gold from cyanogen-containing gold-plated waste liquid | |
| TWI671118B (en) | Method for manufacturing filter membrane for inhibiting microorganism | |
| CN107520459A (en) | The preparation method and antibiotic plastic of copper nano particles | |
| CN108744995B (en) | A kind of antibacterial composite hollow fiber membrane and preparation method thereof | |
| CN112143025A (en) | Compound antibacterial agent and preparation method and application thereof | |
| CN112831068B (en) | Preparation method of novel antibacterial composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |