CN114806045A - Modified master batch for preparing antibacterial polyvinylidene fluoride porous membrane and preparation method thereof - Google Patents
Modified master batch for preparing antibacterial polyvinylidene fluoride porous membrane and preparation method thereof Download PDFInfo
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/223—Packed additives
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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
- B01D69/08—Hollow fibre membranes
- B01D69/087—Details relating to the spinning process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
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- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- 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
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
- C08K5/31—Guanidine; Derivatives thereof
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention relates to a modified master batch for preparing a bacteriostatic polyvinylidene fluoride porous membrane and a preparation method thereof, wherein the modified master batch comprises the following raw materials in percentage by weight: 10-15% of polyvinylidene fluoride; 50-60% of inorganic powder; 20-30% of a high-molecular bacteriostatic agent liquid preparation; 1-5% of a modified additive; the preparation method comprises the steps of S1-S3: adding a modified additive into the inorganic powder, and pretreating under a high-speed mixing and shearing condition; after pretreatment, uniformly mixing the pretreated mixture with a high-molecular bacteriostatic agent liquid preparation under the condition of high-speed stirring and simultaneously carrying out ultrasonic dispersion to prepare a mixed dispersion system; and (3) uniformly stirring and mixing the mixed dispersion system and the polyvinylidene fluoride by using a high-speed mixer, melting and mixing by using a double-screw extruder, exhausting micromolecule volatile matters by adopting a multi-section vacuumizing mode, and extruding, cooling and granulating through a columnar die. The invention makes it possible to efficiently prepare the long-acting bacteriostatic polyvinylidene fluoride porous membrane with excellent indexes based on the thermally induced phase separation method.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a modified master batch for preparing a bacteriostatic polyvinylidene fluoride porous membrane and a preparation method thereof.
Background
The membrane separation technology belongs to one of the high-efficiency, energy-saving and environment-friendly technologies in the separation technology in the field of water treatment, and is widely applied to various aspects such as sewage deep treatment, battery diaphragms, medical materials and the like due to strong controllability of separation precision and good and stable separation effect.
The polyvinylidene fluoride has the characteristics of outstanding chemical resistance, high temperature resistance and stable property, and provides various choices for processing modes of the polyvinylidene fluoride, so that the polyvinylidene fluoride is a main raw material of the ultramicro filter membrane. The microbial pollution is a main pollution source of the ultramicro filter membrane in the actual use process, particularly in a membrane bioreactor system, so that the bacteriostatic modification of the membrane is an effective way for preventing the microbial pollution of the membrane and improving the operation efficiency and the efficiency.
In the prior art, the polyvinylidene fluoride porous membrane mainly has two preparation technology systems:
one method is based on the principle of non-solvent induced phase separation, and the method needs simple equipment, has lower processing temperature, is convenient for adding various modification aids, but requires the aids to have better compatibility with a casting solution system, so the selection range and the dosage of the aids are limited to a certain extent; meanwhile, the low-temperature strong solvent required by the method often has certain microbial toxicity, and the solvent is difficult to separate and recycle after being dissolved in a non-solvent in the forming process, so that the solvent wastewater in the film making process becomes a difficult problem; secondly, the film prepared by the method is often low in strength, thin in functional skin layer, easy to damage and short in service life.
The other method is a thermally induced phase separation method, the method utilizes the characteristics of high-temperature compatibility and low-temperature phase separation of resin and a diluent to prepare a homogeneous porous membrane, and the membrane prepared by the method has the characteristics of high strength, good chemical resistance, uniform pore diameter and the like, so that the service life of the membrane is greatly prolonged, and the thermally induced phase separation method gradually becomes a leading preparation technology of a new generation of PVDF porous membrane. However, because the thermal phase separation method has a high processing temperature, the selection of the corresponding modifier needs to fully consider the problems of heat resistance of the modified raw material, compatibility and dispersibility in a system, high-temperature volatility, durability in a matrix during use and the like, and therefore, the technology of directly blending and modifying the thermal phase PVDF porous membrane also has some defects which are difficult to overcome.
When the micromolecule bacteriostatic agent is added into the porous membrane for use, the micromolecule bacteriostatic agent is easy to elute, so the time efficiency is short, and the actual use value in the porous membrane is low; the high molecular bacteriostatic agent has lower toxicity, and simultaneously can form a three-dimensional network cross interpenetrating structure with matrix resin when being added into the membrane due to large molecular weight, so that the high molecular bacteriostatic agent can exist in the membrane for a long time and keep longer timeliness. However, the addition amount of the bacteriostatic agent is generally low in the whole formula, and the compatibility with the body is difficult to ensure, so that when the porous membrane containing the high-molecular antibacterial agent is prepared by using a thermally induced phase separation method, the pure bacteriostatic agent is difficult to directly and well disperse in a porous membrane preparation system when in use; the liquid high molecular bacteriostatic agent is generally an aqueous solution containing active ingredients with certain mass concentration, and is difficult to be directly added into a film-making system.
The method for preparing the polyvinylidene fluoride porous membrane with long-acting bacteriostasis and excellent other indexes by the thermally induced phase separation method has the defects of the prior bacteriostasis modification method, so that the development of a high-efficiency mode based on the thermally induced phase separation method for preparing the polyvinylidene fluoride porous membrane with long-acting bacteriostasis is urgently needed.
Disclosure of Invention
Aiming at the difficulty of preparing the antibacterial modified polyvinylidene fluoride porous membrane by a thermally induced phase separation method in the prior art, the invention firstly provides the modified master batch for preparing the antibacterial polyvinylidene fluoride porous membrane and the preparation method thereof, so that the preparation method is favorable for preparing the antibacterial polyvinylidene fluoride porous membrane with high efficiency.
Therefore, according to the first aspect of the invention, a modified master batch for preparing a bacteriostatic polyvinylidene fluoride porous membrane is provided, which comprises the following raw materials in percentage by weight:
polyvinylidene fluoride (PVDF): 10-15%;
inorganic powder: 50-60%;
the polymer bacteriostatic agent liquid preparation comprises the following components: 20-30%;
and (3) modifying additives: 1 to 5 percent.
The antibacterial polyvinylidene fluoride porous membrane is prepared by using the modified master batch, wherein the content of polyvinylidene fluoride in the modified master batch is 10-15%, and the content of polyvinylidene fluoride in the modified master batch exceeds the lower limit and the upper limit, so that the strength, the pore diameter and the flux of the membrane are not optimized; when the content of the inorganic powder is 50-60%, the pore size, the number and the arrangement uniformity of a subsequently prepared antibacterial polyvinylidene fluoride porous membrane can be ensured, the pore size arrangement is not uniform when the pore size, the number and the arrangement uniformity exceed the upper limit and the lower limit, and the flux of the antibacterial polyvinylidene fluoride porous membrane is influenced by the change of the number of the pore sizes; the content of the modified additive is set to be 1-5%, so that internal crosslinking and membrane yarn spinnability in the subsequent antibacterial polyvinylidene fluoride porous membrane spinning process can be ensured.
Furthermore, the polyvinylidene fluoride is high molecular weight polyvinylidene fluoride, and the melt flow rate of the polyvinylidene fluoride is 1-4 g/10min under the condition of 230 ℃/21.6 kg.
Still further, the high molecular weight polyvinylidene fluoride is a vinylidene fluoride homopolymer.
In addition, the inorganic powder is nano inorganic powder, and the nano inorganic powder is one of nano calcium carbonate, nano silicon dioxide and nano titanium dioxide.
Still further, the nano calcium carbonate is a cubic-like nano calcium carbonate having an average particle diameter of 20 to 150 nm.
In addition, the polymeric bacteriostatic agent liquid preparation contains 25 to 50 weight percent of active ingredients, namely the polymeric bacteriostatic agent. It should be noted that, by setting the content of the polymeric bacteriostatic agent at 25 to 50%, the bacteriostatic effect of the subsequently produced bacteriostatic polyvinylidene fluoride porous membrane can be ensured to the maximum, and when the content is lower than the lower limit, the bacteriostatic effect is reduced and when the content is higher than the upper limit, the bacteriostatic effect is increased but unnecessary waste is caused.
Still further, the polymeric bacteriostatic agent is one or more of polyhexamethylene guanidine (PHMG), polyhexamethylene biguanide (PHMB), chitosan and their derivatives with weight average molecular weight of 20000.
Further, the modifying additive is a high temperature resistant surfactant, preferably an organic fluorine type surfactant, such as perfluorosulfonate or perfluorocarboxylic acid.
According to a second aspect of the present invention, a preparation method of a modified master batch for preparing a bacteriostatic polyvinylidene fluoride porous membrane is provided, which comprises the following steps:
s1: pretreating inorganic powder under the conditions of high-speed mixing and shearing to eliminate soft agglomeration and partial hard agglomeration, and adding a modifying additive into the inorganic powder for treatment at the same time of pretreatment;
s2: uniformly mixing the pretreated inorganic powder and a high-molecular bacteriostatic agent liquid preparation under the condition of high-speed stirring, and simultaneously dispersing by ultrasonic waves to prepare a mixed dispersion system taking the inorganic powder as a carrier;
s3: and (2) uniformly stirring and mixing the mixed dispersion system and polyvinylidene fluoride by using a high-speed mixer, melting and mixing the mixture by using a double-screw extruder, simultaneously discharging small molecular volatile matters (such as water vapor and low-boiling-point substances) by adopting a multi-section vacuumizing mode, extruding through a columnar die, cooling and granulating to prepare the modified master batch.
Further, in step S1, the inorganic powder is stirred in a high speed mixer, and the improving additive is added to the inorganic powder while stirring, and the mixture is stirred at a high speed for 10 min.
Further, in step S2, the pretreated inorganic powder and the polymeric bacteriostatic agent liquid preparation are mixed in an ultrasonic processor with high-speed stirring to obtain a mixed dispersion system, wherein the frequency of the ultrasonic wave is set to 30KHZ, and the stirring time is 0.5 to 1 hour.
Further, in step S3, the temperature of melt kneading the mixture in the twin-screw extruder is 180 to 200 ℃.
Further, in step S3, the cooling dicing refers to water cooling dicing or air cooling dicing, the water cooling temperature during the water cooling dicing is controlled at 15 to 35 ℃, and the air cooling temperature during the air cooling dicing is normal temperature, wherein the water cooling particles after the water cooling dicing are dried at 80 ℃ to remove surface floating water.
According to a third aspect of the present invention, there is provided a bacteriostatic porous polyvinylidene fluoride membrane, which is composed of the following raw materials:
preparing a modified master batch for the antibacterial polyvinylidene fluoride porous membrane;
polyvinylidene fluoride; and
an organic liquid;
wherein the weight percentage of the modified master batch, the polyvinylidene fluoride and the organic liquid is controlled within the range of 1:1: 1-1: 1: 2.
Further, the polyvinylidene fluoride is a vinylidene fluoride homopolymer.
Further, the organic liquid is one or more of synthetic vegetable esters, citric acid esters, adipates and soybean oil.
According to a fourth aspect of the present invention, there is provided a method for preparing the above bacteriostatic polyvinylidene fluoride porous membrane, which comprises the following steps:
1) preparing the modified master batch according to the preparation method of the modified master batch for preparing the antibacterial polyvinylidene fluoride porous membrane;
2) adding the modified master batch, polyvinylidene fluoride and organic liquid into a double-screw extruder in a weight ratio of 1:1: 1-1: 1:2 by using a continuous weighing feeding mode to perform heating, melting, mixing and extruding;
3) homogenizing the melt at 180-230 ℃, and then spraying out through a metering pump and a mouth mold;
4) after cooling and forming, carrying out acid-base reaction on the organic liquid and the inorganic powder to extract the organic liquid and the inorganic powder, and finishing the preparation of the antibacterial polyvinylidene fluoride porous membrane;
wherein, in the step 2), the modified master batch and the polyvinylidene fluoride are added at one feed inlet of the double-screw extruder, and the organic liquid is added at the downstream position of the feed inlet.
Further, in the step 3), the neck mold is an annular neck mold, so that the antibacterial polyvinylidene fluoride porous membrane prepared in the step 3) is an antibacterial polyvinylidene fluoride hollow fiber membrane.
Further, in the step 4), after cooling and forming, stretching and shaping are carried out according to the requirement of aperture adjustment, and then the organic liquid and the inorganic powder are extracted through acid-base reaction.
Further, in the step 2), the weight percentage of the modified master batch, the polyvinylidene fluoride and the organic liquid is controlled to be 1:1: 1.5.
Further, the polyvinylidene fluoride is a vinylidene fluoride homopolymer.
Further, the organic liquid is one or more of synthetic vegetable esters, citric acid esters, adipates and soybean oil.
Compared with the prior art, the invention has the following advantages:
1) compared with the traditional thermally induced phase separation method, the invention adds the bacteriostatic agent, so that the polyvinylidene fluoride porous membrane has the bacteriostatic function, and the antimicrobial (especially bacteria, fungi and the like) pollution characteristics of the membrane product in practical application are improved, thereby improving the energy efficiency of the membrane in the process of sewage treatment and tap water purification with surface water as a water source;
2) according to the invention, inorganic nano calcium carbonate with high specific surface area is used as a carrier, so that a liquid preparation bacteriostatic agent (namely a bacteriostatic agent liquid preparation) is easy to adsorb on the carrier, and then the carrier and polyvinylidene fluoride are fully mixed, thus the purpose that the liquid preparation bacteriostatic agent is uniformly dispersed into a mixed system is achieved, the compatibility requirement of resin and the liquid preparation bacteriostatic agent is reduced, the selection range of the liquid preparation bacteriostatic agent is widened, and the preparation of the bacteriostatic polyvinylidene fluoride porous membrane based on a thermally induced phase separation method is easier to industrialize;
3) according to the invention, the master batch is added in the preparation process of the polyvinylidene fluoride porous membrane by utilizing the space occupying effect of nano materials (namely nano calcium carbonate), so that the growth and the increase of each component in the crystallization process can be limited, the formation of stacked spherulites can be prevented, the dispersion effect of the bacteriostatic agent in the porous membrane is further enhanced, the nano calcium carbonate is extracted by reaction by utilizing acid after curing and forming, and the high molecular bacteriostatic agent is highly dispersed in the membrane, so that long-acting bacteriostasis can be realized;
4) the modified master batch for preparing the antibacterial polyvinylidene fluoride porous membrane is a high dispersion with inorganic powder such as nano calcium carbonate as a carrier, and is directly added into a double-screw extruder in proportion and continuously weighed with matrix polyvinylidene fluoride and organic liquid in a using mode, and the antibacterial polyvinylidene fluoride porous membrane is prepared by a thermally induced phase separation method, so that compared with the traditional directly blended thermally induced phase separation method for preparing the porous membrane, the antibacterial polyvinylidene fluoride porous membrane has stronger membrane preparation continuity and is more convenient for large-scale amplification; meanwhile, substances (such as bacteriostatic agents) which cannot be directly added into a blending system can be selected from a final film preparation formula, so that the selectivity of the components of the formula is greatly expanded, and the diversity of the modification direction of the porous film prepared by a thermally induced phase separation method is expanded;
5) the high molecular weight polyvinylidene fluoride selected by the invention is used as the master batch forming support matrix resin, and when the high molecular weight polyvinylidene fluoride is added into the polyvinylidene fluoride which is suitable for the traditional thermally induced phase separation method to prepare the membrane for mixing and membrane preparation, the modified master batch and the polyvinylidene fluoride can be well compatible, so that the uniform dispersion of the bacteriostatic agent is realized, and the strength of the porous membrane can be improved without influencing the pore-forming performance.
These and other aspects of the invention are apparent from and will be elucidated with reference to the embodiments described hereinafter.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Firstly), preparing a modified master batch for preparing a bacteriostatic polyvinylidene fluoride nano porous membrane: grinding the nano calcium carbonate to penetrate through a 325-mesh screen, adding the ground and sieved powder into a high-speed mixer, adding a perfluorinated sulfonate solution serving as a modified additive into the nano calcium carbonate in a spraying mode while stirring, and stirring at a high speed for 10 min; then transferring the pretreated powder into an ultrasonic processor with high-speed stirring, adding a PHMG (PH) water agent (namely, phosphoric acid polyhexamethylene guanidine, a derivative of polyhexamethylene guanidine), stirring for 20min under the ultrasonic condition of 30KHZ, adding high molecular weight polyvinylidene fluoride powder with MFR of 2.0g/10min (230 ℃, 21.6 kg), and uniformly stirring; and then introducing the mixture into a double-screw extruder, mixing at 200 ℃, and simultaneously vacuumizing for multiple sections to discharge micromolecule volatiles, wherein the vacuum degree is-0.3 to-0.7 bar.
The prepared modified master batch comprises the following components in percentage by weight:
nano calcium carbonate: 60 percent of
Aqueous phmg (ph): 27 percent of
High molecular weight polyvinylidene fluoride: 10 percent of
Perfluorosulfonate solution: 3 percent of
II) preparing a bacteriostatic polyvinylidene fluoride hollow fiber membrane: adding the modified master batch, PVDF and triethyl citrate in the first) part into a double-screw extruder in a weight-measuring feeding mode according to the proportion of 1:1:1.5 by using a system of serially connecting a double-screw extruder with a metering pump, mixing at 195 ℃, extruding and cooling through an annular neck mold to form a hollow fiber membrane, stretching by 2 times, extracting the organic solvent and the nano calcium carbonate in the hollow fiber membrane by using ethanol and hydrochloric acid, and obtaining the antibacterial polyvinylidene fluoride hollow fiber membrane.
Thirdly), performance detection: the prepared antibacterial polyvinylidene fluoride hollow fiber membrane has the pure water flux of 1000L per square meter per hour at 25 ℃ and 0.1Mpa, the tensile breaking strength of 16Mpa and the breaking elongation of 100 percent, and the maximum aperture is 0.2um and the porosity is 77 percent by using a bubble pressure method.
Comparative example 1
Uniformly stirring polyvinylidene fluoride powder, calcium carbonate and triethyl citrate according to the proportion of 1:0.2:1.5 by using a high-speed mixer, adding the mixture into a double-screw extruder, mixing at 195 ℃, extruding and cooling by using a metering pump and an annular die to form a hollow fiber membrane, stretching by 2 times, extracting organic solvent and nano calcium carbonate in the hollow fiber membrane by using liquids such as ethanol, hydrochloric acid and the like, and preparing the polyvinylidene fluoride hollow fiber membrane without the master batch. The pure water flux under 0.1Mpa is 400L/(. square meter. multidot.h), the tensile breaking strength is 10Mpa, the breaking elongation is 40%, the maximum aperture is 0.4um and the porosity is 66% by using a foam-compression method.
Example 2
One) preparing a bacteriostatic polyvinylidene fluoride porous membrane by using a modified master batch: grinding the nano calcium carbonate to penetrate through a 325-mesh screen, adding the ground and sieved powder into a high-speed mixer, adding a perfluorocarboxylic acid solution into the nano calcium carbonate in a spraying mode while stirring, and stirring at a high speed for 10 min; then transferring the pretreated powder into an ultrasonic processor with high-speed stirring, adding a carboxymethyl chitosan-containing aqueous solution, stirring for 20min under the condition of 30KHZ, adding high-molecular-weight polyvinylidene fluoride powder with MFR of 2.0g/10min (230 ℃, 21.6 kg), and uniformly stirring; and then introducing the mixture into a double-screw extruder, mixing at 190 ℃, and simultaneously vacuumizing for multiple sections to discharge micromolecule volatiles, wherein the vacuum degree is-0.4 to-0.7 bar.
The prepared modified master batch comprises the following components in percentage by weight:
nano calcium carbonate: 50 percent of
Carboxymethyl chitosan aqua: 30 percent of
High molecular weight polyvinylidene fluoride: 15 percent of
Perfluorocarboxylic acid solution: 5 percent of
II) preparing a bacteriostatic polyvinylidene fluoride hollow fiber membrane: adding the modified master batch in the first) part, polyvinylidene fluoride powder and trioctyl acetylcitrate into a double-screw extruder in a weight-measuring feeding mode according to the proportion of 1:1:1.5 by using a system of serially connecting a double-screw extruder with a metering pump, mixing at 220 ℃, extruding through an annular neck die, cooling to form a hollow fiber membrane, stretching by 2 times, extracting the organic solvent and the nano calcium carbonate in the hollow fiber membrane by using ethanol and hydrochloric acid, and obtaining the antibacterial polyvinylidene fluoride hollow fiber membrane.
Thirdly), performance detection: the prepared antibacterial polyvinylidene fluoride hollow fiber membrane has the pure water flux of 1200L/square meter at 25 ℃ and 0.1Mpa, the tensile breaking strength of 20Mpa and the elongation at break of 130 percent, the maximum aperture is 0.3um and the porosity is 70 percent measured by a bubble pressure method.
Example 3
Firstly), preparing bacteriostatic nano calcium carbonate master batches: grinding the nano calcium carbonate to penetrate through a 325-mesh screen, adding the ground and sieved powder into a high-speed mixer, adding a perfluorocarboxylic acid solution into the nano calcium carbonate in a spraying manner while stirring, and stirring at a high speed for 10 min; then transferring the pretreated powder into an ultrasonic processor with high-speed stirring, adding a PHMG (GL) (namely polyhexamethylene guanidine gluconate, polyhexamethylene guanidine derivative) aqueous solution, stirring for 20min under the condition of 30KHZ, adding a high molecular weight polyvinylidene fluoride powder material with MFR of 2.0g/10min (230 ℃, 21.6 kg), and uniformly stirring; and then introducing the mixture into a double-screw extruder, mixing at 200 ℃, and simultaneously vacuumizing for multiple sections to discharge micromolecule volatiles, wherein the vacuum degree is-0.5 to-0.8 bar.
The prepared modified master batch comprises the following components in percentage by weight:
nano calcium carbonate: 55 percent of
PHMG (GL) water agent: 25 percent
High molecular weight polyvinylidene fluoride: 15 percent of
Perfluorocarboxylic acid solution: 5 percent of
II) preparing a bacteriostatic polyvinylidene fluoride hollow fiber membrane: and (2) adding the modified master batch, polyvinylidene fluoride powder, dioctyl adipate and triethyl citrate mixed solution (the weight ratio of the two components is 1: 1) in the first part (1: 1) into a double-screw extruder in a gravimetric feeding mode according to the weight ratio of 1:1:1.5, mixing at 220 ℃, extruding through a metering pump and an annular die, cooling to form a hollow fiber membrane, stretching by 2 times, and extracting the organic solvent and the nano calcium carbonate in the hollow fiber membrane by using ethanol and hydrochloric acid to obtain the antibacterial polyvinylidene fluoride hollow fiber membrane.
Thirdly), performance detection: the prepared antibacterial polyvinylidene fluoride hollow fiber membrane has the pure water flux of 1300L/((square meter) h) at 25 ℃ and 0.1Mpa, the tensile breaking strength of 18Mpa and the breaking elongation of 100 percent, and the maximum aperture is 0.25um and the porosity is 73 percent measured by using a bubble pressure method.
Example 4
One) preparing a bacteriostatic polyvinylidene fluoride porous membrane by using a modified master batch: grinding the nano calcium carbonate to penetrate through a 325-mesh screen, adding the ground and sieved powder into a high-speed mixer, adding a perfluorinated sulfonate solution into the nano calcium carbonate in a spraying mode while stirring, and stirring at a high speed for 10 min; then transferring the pretreated powder into an ultrasonic processor with high-speed stirring, adding a carboxymethyl chitosan-containing aqueous solution, stirring for 20min under the condition of 30KHZ, adding high-molecular-weight polyvinylidene fluoride powder with MFR of 2.0g/10min (230 ℃, 21.6 kg), and uniformly stirring; and then introducing the mixture into a double-screw extruder, mixing at 190 ℃, and simultaneously vacuumizing for multiple sections to discharge micromolecule volatiles, wherein the vacuum degree is-0.4 to-0.7 bar.
The prepared modified master batch comprises the following components in percentage by weight:
nano calcium carbonate: 60 percent of
Carboxymethyl chitosan aqua: 20 percent of
High molecular weight polyvinylidene fluoride: 15 percent of
Perfluorosulfonate solution: 5 percent of
II) preparing a bacteriostatic polyvinylidene fluoride hollow fiber membrane: adding the modified master batch in the first) part, polyvinylidene fluoride powder and trioctyl acetylcitrate into a double-screw extruder in a weight-measuring feeding mode according to the proportion of 1:1:1.5 by using a system of serially connecting a double-screw extruder with a metering pump, mixing at 220 ℃, extruding through an annular neck die, cooling to form a hollow fiber membrane, stretching by 2 times, extracting the organic solvent and the nano calcium carbonate in the hollow fiber membrane by using ethanol and hydrochloric acid, and obtaining the antibacterial polyvinylidene fluoride hollow fiber membrane.
Thirdly), performance detection: the prepared antibacterial polyvinylidene fluoride hollow fiber membrane has the pure water flux of 1000L per square meter per hour at 25 ℃ and 0.1Mpa, the tensile breaking strength of 22Mpa and the breaking elongation of 110 percent, and the maximum aperture is 0.2um and the porosity is 70 percent measured by a bubble pressure method.
Example 5
Firstly), preparing bacteriostatic nano calcium carbonate master batches: grinding the nano calcium carbonate to penetrate through a 325-mesh screen, adding the ground and sieved powder into a high-speed mixer, adding a perfluorocarboxylic acid solution into the nano calcium carbonate in a spraying mode while stirring, and stirring at a high speed for 10 min; then transferring the pretreated powder into an ultrasonic processor with high-speed stirring, adding a PHMG (polyhexamethylene guanidine) aqueous solution, stirring for 20min under the condition of 30KHZ, adding high molecular weight polyvinylidene fluoride powder with MFR of 2.0g/10min (230 ℃, 21.6 kg), and uniformly stirring; and then introducing the mixture into a double-screw extruder, mixing at 200 ℃, and simultaneously vacuumizing for multiple sections to discharge micromolecule volatiles, wherein the vacuum degree is-0.5 to-0.8 bar.
The prepared modified master batch comprises the following components in percentage by weight:
nano calcium carbonate: 60 percent of
PHMG aqueous solution: 26 percent of
High molecular weight polyvinylidene fluoride: 13 percent of
Perfluorocarboxylic acid solution: 1 percent of
II) preparing a bacteriostatic polyvinylidene fluoride hollow fiber membrane: and (2) adding the modified master batch, polyvinylidene fluoride powder, dioctyl adipate and triethyl citrate mixed solution (the weight ratio of the two components is 1: 1) in the first part (1: 1) into a double-screw extruder in a gravimetric feeding mode according to the weight ratio of 1:1:1.5, mixing at 220 ℃, extruding through a metering pump and an annular die, cooling to form a hollow fiber membrane, stretching by 2 times, and extracting the organic solvent and the nano calcium carbonate in the hollow fiber membrane by using ethanol and hydrochloric acid to obtain the antibacterial polyvinylidene fluoride hollow fiber membrane.
Thirdly), performance detection: the prepared antibacterial polyvinylidene fluoride hollow fiber membrane has the pure water flux of 1150L/square meter at 25 ℃ and 0.1Mpa, the tensile breaking strength of 20Mpa and the breaking elongation of 105 percent, the maximum aperture is 0.21 mu m and the porosity is 71 percent measured by a bubble pressure method.
The following describes the bacteriostatic properties of the above examples 1 to 5 and comparative examples:
the detection method refers to GB/T37206-2018, wherein the experiment of 'long-acting' in example 1 in Table 1 refers to the preparation of samples after the samples prepared in example 1 are cleaned for 24 hours through sterile ultrapure water, and the average antibacterial rate results after the experiment are shown in the following table 1:
TABLE 1 bacteriostatic effect of the examples
Obviously, as can be seen from table 1, the antibacterial rate of the antibacterial polyvinylidene fluoride hollow fiber membrane prepared by the invention is greatly improved compared with that of the comparative example, and the antibacterial effect is obvious.
While the invention has been described with respect to the foregoing technical disclosure and technical features, it will be understood that various changes and modifications in the above-described components and steps, including combinations of features disclosed herein either individually or as claimed, and obviously including other combinations of such features, may be made by those skilled in the art within the spirit of the invention. Such variations and/or combinations are within the skill of the art to which the invention pertains and are within the scope of the following claims.
Claims (13)
1. A modified master batch for preparing a bacteriostatic polyvinylidene fluoride porous membrane is characterized by comprising the following raw materials in percentage by weight:
polyvinylidene fluoride: 10-15%;
inorganic powder: 50-60%;
the polymer bacteriostatic agent liquid preparation comprises the following components: 20-30%;
and (3) modifying additives: 1 to 5 percent.
2. The modified master batch for preparing the antibacterial polyvinylidene fluoride porous membrane according to claim 1, wherein the polyvinylidene fluoride is high molecular weight polyvinylidene fluoride, and the melt flow rate of the polyvinylidene fluoride is 1-4 g/10min under the condition of 230 ℃/21.6 kg.
3. The modified master batch for preparing the bacteriostatic polyvinylidene fluoride porous membrane according to claim 2, wherein the high molecular weight polyvinylidene fluoride is a vinylidene fluoride homopolymer.
4. The modified master batch for preparing the antibacterial polyvinylidene fluoride porous membrane according to claim 1, wherein the inorganic powder is nano inorganic powder, and the nano inorganic powder is one of nano calcium carbonate, nano silicon dioxide and nano titanium dioxide.
5. The modified master batch for preparing the antibacterial polyvinylidene fluoride porous membrane according to claim 4, wherein the nano calcium carbonate is a cubic nano calcium carbonate with the average particle size of 20-150 nm.
6. The modified master batch for preparing the bacteriostatic polyvinylidene fluoride porous membrane according to claim 1, wherein the polymer bacteriostatic agent liquid preparation contains 25-50 wt% of the polymer bacteriostatic agent.
7. The modified master batch for preparing the antibacterial polyvinylidene fluoride porous membrane according to claim 6, wherein the polymeric bacteriostatic agent is one or more of polyhexamethylene guanidine, polyhexamethylene biguanide, chitosan and derivatives thereof with the weight average molecular weight of 20000.
8. The modified master batch for preparing the bacteriostatic polyvinylidene fluoride porous membrane according to claim 1, wherein the modified additive is an organic fluorine surfactant.
9. The preparation method of the modified master batch for preparing the bacteriostatic polyvinylidene fluoride porous membrane according to any one of claims 1 to 8 comprises the following steps:
s1: pretreating the inorganic powder under the conditions of high-speed mixing and shearing to eliminate soft agglomeration and partial hard agglomeration, and adding the modified additive into the inorganic powder for treatment at the same time of pretreatment;
s2: uniformly mixing the pretreated inorganic powder and the macromolecular bacteriostatic agent liquid preparation under the condition of high-speed stirring, and simultaneously dispersing by ultrasonic waves to prepare a mixed dispersion system taking the inorganic powder as a carrier;
s3: and uniformly stirring and mixing the mixed dispersion system and the polyvinylidene fluoride by using a high-speed mixer, melting and mixing the mixture by using a double-screw extruder, simultaneously discharging small molecule volatile matters by adopting a multi-section vacuumizing mode, extruding through a columnar die, cooling and granulating to prepare the modified master batch.
10. The method of claim 9, wherein in step S1, the inorganic powder is stirred in a high-speed mixer, and the modified additive is added to the inorganic powder while stirring, and the mixture is stirred at a high speed for 10 min.
11. The method for preparing the modified masterbatch for preparing the antibacterial polyvinylidene fluoride porous membrane according to claim 9, wherein in step S2, the pretreated inorganic powder and the liquid polymer antibacterial agent are prepared in an ultrasonic processor with high-speed stirring, and the mixed dispersion system is prepared, wherein the frequency of the ultrasonic wave is set to 30KHZ, and the stirring time is 0.5-1 h.
12. The method for preparing the modified masterbatch for preparing the antibacterial polyvinylidene fluoride porous membrane according to claim 9, wherein in the step S3, the temperature for melting and mixing the mixture in the twin-screw extruder is 180-200 ℃.
13. The method for preparing the modified master batch for preparing the antibacterial polyvinylidene fluoride porous membrane according to claim 12, wherein in the step S3, the cooling granulation is water cooling granulation or air cooling granulation, the water cooling temperature during the water cooling granulation is controlled to be 15-35 ℃, the air cooling temperature during the air cooling granulation is normal temperature, and the water cooling particles after the water cooling granulation are dried at 80 ℃ to remove surface floating water.
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