CN114806045B - 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 PDF

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CN114806045B
CN114806045B CN202210526499.4A CN202210526499A CN114806045B CN 114806045 B CN114806045 B CN 114806045B CN 202210526499 A CN202210526499 A CN 202210526499A CN 114806045 B CN114806045 B CN 114806045B
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polyvinylidene fluoride
master batch
modified master
inorganic powder
antibacterial
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CN114806045A (en
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张伟政
徐志成
王旭梅
万思青
李文国
王志勇
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SHANDONG ZHAOJIN MOTIAN CO Ltd
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SHANDONG ZHAOJIN MOTIAN CO Ltd
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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 bacteriostat liquid preparation; 1-5% of a modifying additive; the preparation method comprises the steps of S1-S3: the inorganic powder is added with a modifying additive and is pretreated under the condition of high-speed mixing and shearing; after pretreatment, the pretreated water and the macromolecular bacteriostatic agent liquid preparation are uniformly mixed under the high-speed stirring condition and simultaneously dispersed together by ultrasonic waves to prepare a mixed dispersion system; and (3) uniformly stirring and mixing the mixed dispersion system and polyvinylidene fluoride by a high-speed mixer, melting and mixing by a double-screw extruder, discharging small molecular volatile matters by adopting a multi-stage vacuumizing mode, and extruding, cooling and granulating by a columnar die. The invention makes it possible to prepare long-acting antibacterial polyvinylidene fluoride porous film with excellent indexes based on thermal phase separation method.

Description

Modified master batch for preparing antibacterial polyvinylidene fluoride porous membrane and preparation method thereof
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 technologies of high efficiency, energy conservation and environmental protection in the current water treatment field, and meanwhile, the separation precision is strong in controllability, the separation effect is good and stable, and the membrane separation technology is widely applied to various aspects of sewage deep treatment, battery diaphragms, medical materials and the like.
The polyvinylidene fluoride has the characteristics of outstanding chemical resistance, high temperature resistance and stable property, and provides various choices for the processing mode, so that the polyvinylidene fluoride is a main raw material of the ultra-micro filter membrane. Microbial contamination is a main pollution source of the ultra-micro filtration membrane in the actual use process, especially in a membrane bioreactor system, so that the bacteriostasis modification of the membrane is a more effective way for preventing the microbial contamination of the membrane and improving the operation efficiency and efficiency.
In the prior art, polyvinylidene fluoride porous membranes mainly have two preparation technical systems:
a method based on the non-solvent induced phase separation principle is characterized by simple equipment, low processing temperature and convenient addition of various modification aids, but better compatibility between the aid and the casting solution system, so that the selection range and the dosage of the aid are limited to a certain extent; meanwhile, the method is difficult to separate and recycle because the required low-temperature strong solvent often has certain microbial toxicity, and the solvent is dissolved in the non-solvent in the forming process, so that the solvent wastewater treatment in the film-making process becomes a difficult problem; secondly, the membrane prepared by the method is low in strength, thin in functional cortex, easy to damage and short in service life.
The other is a thermally induced phase separation method, which utilizes the characteristics of high-temperature compatibility and low-temperature phase separation of resin and 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 the leading preparation technology of a new generation of PVDF porous membrane. However, because the processing temperature of the thermally induced phase separation method is higher, the selection of the corresponding modifier needs to fully consider the problems of heat resistance of the modified raw materials, compatibility and dispersibility in a system, high-temperature volatility, durability in a matrix in use and the like, so that the technology of directly blending the modified thermally induced phase PVDF porous membrane also has some defects which are difficult to overcome.
The micromolecular bacteriostatic agent is easy to elute when being added into the porous membrane for use, so that the aging is shorter, and the actual use value in the porous membrane is lower; the high molecular bacteriostat has lower toxicity, and 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 bacteriostat can exist in the membrane for a long time, and the long timeliness is maintained. However, the general addition amount of the bacteriostatic agent is very 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 thermal phase separation method, the pure bacteriostatic agent is difficult to be directly and well dispersed in a porous membrane preparation system when in use; the liquid macromolecular bacteriostatic agent is generally an aqueous solution containing active ingredients with certain mass concentration, and is difficult to directly add into a film-making system.
The thermal phase separation method for preparing hollow products has excellent physical and chemical properties, but the existing antibacterial modification method has defects, so that development of a polyvinylidene fluoride porous membrane with long-acting antibacterial effect and excellent other indexes is urgently needed to be developed in a high-efficiency mode based on the thermal phase separation method.
Disclosure of Invention
Aiming at the difficulty in preparing the antibacterial modified polyvinylidene fluoride porous membrane by the thermally induced phase separation method in the prior art, the invention firstly provides a modified master batch for preparing the antibacterial polyvinylidene fluoride porous membrane and a preparation method thereof, which are beneficial to preparing the antibacterial polyvinylidene fluoride porous membrane efficiently.
To this end, according to a first aspect of the present invention, there is provided a modified master batch for preparing a bacteriostatic polyvinylidene fluoride porous film, which is composed of the following raw materials in weight percentage:
polyvinylidene fluoride (PVDF): 10-15%;
inorganic powder: 50-60%;
high molecular bacteriostatic agent liquid preparation: 20-30%;
modification additive: 1-5%.
In order to ensure that the subsequent efficient preparation of the antibacterial polyvinylidene fluoride porous membrane is carried out, the polyvinylidene fluoride content in the modified master batch is more proper at 10-15%, and the polyvinylidene fluoride content exceeding the lower limit and the upper limit is not beneficial to the optimization selection of membrane wire strength, pore diameter and flux; when the content of the inorganic powder is 50-60%, the pore size, the number and the arrangement uniformity of the antibacterial polyvinylidene fluoride porous membrane manufactured in the follow-up process can be ensured, the pore size arrangement is uneven when the pore size exceeds the upper limit and the lower limit, and the flux of the antibacterial polyvinylidene fluoride porous membrane is influenced by the change of the pore size and the number; the content of the modified additive is set to be 1-5% so as to ensure the internal crosslinking and the spinnability of the membrane filaments in the subsequent spinning process of the antibacterial polyvinylidene fluoride porous membrane.
Further, the polyvinylidene fluoride is high molecular weight polyvinylidene fluoride, and the melt flow rate 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 liquid preparation of the high-molecular bacteriostatic agent comprises 25-50% by weight of active ingredients, namely the high-molecular bacteriostatic agent. The content of the macromolecular bacteriostatic agent is set to 25-50%, the bacteriostatic effect of the subsequently produced bacteriostatic polyvinylidene fluoride porous membrane can be guaranteed to the maximum extent, the bacteriostatic effect is lower than the lower limit, the bacteriostatic effect is reduced and higher than the upper limit, and the bacteriostatic effect is increased but unnecessary waste is caused.
Still further, the polymeric bacteriostat is one or a mixture of more than one of polyhexamethylene guanidine (PHMG), polyhexamethylene biguanide (PHMB), chitosan and derivatives thereof with weight average molecular weight more than 20000.
Still further, the modifying additive is a high temperature resistant surfactant, preferably an organofluorine type surfactant, such as a perfluorosulfonate or perfluorocarboxylic acid.
According to a second aspect of the present invention, there is provided a method for preparing a modified master batch for preparing a bacteriostatic porous polyvinylidene fluoride membrane, comprising the steps of:
s1: pretreating inorganic powder under the condition of high-speed mixing and shearing to eliminate soft agglomeration and partial hard agglomeration, and adding a modification additive into the inorganic powder for simultaneous treatment while pretreating;
s2: uniformly mixing the pretreated inorganic powder and the macromolecular bacteriostatic agent liquid preparation under the high-speed stirring condition, and simultaneously dispersing by ultrasonic waves to prepare a mixed dispersion system taking the inorganic powder as a carrier;
s3: the mixed dispersion system and polyvinylidene fluoride are stirred and mixed uniformly by a high-speed mixer, the mixture is melted and mixed by a double-screw extruder, simultaneously small molecular volatile matters (such as water vapor and low boiling point matters) are discharged by adopting a multi-stage vacuumizing mode, and then the modified master batch is prepared by extruding through a columnar die and cooling and granulating.
Further, in step S1, the inorganic powder is stirred in a high-speed mixer, and the improvement additive is added to the inorganic powder while stirring, and the mixture is stirred at a high speed for 10 minutes.
In step S2, the pretreated inorganic powder and the macromolecular bacteriostatic agent liquid preparation are prepared into a mixed dispersion system in an ultrasonic processor with high-speed stirring, wherein the frequency of ultrasonic waves is set to be 30KHZ, and the stirring time is 0.5-1 h.
In step S3, the temperature of the mixture in the twin-screw extruder for melt kneading is 180-200 ℃.
In step S3, the cooling and granulating step is to control the water cooling temperature to 15-35 ℃ during the water cooling and granulating or to control the air cooling temperature to normal temperature during the air cooling and granulating, wherein the water cooling and granulating step is to dry the water cooling granules at 80 ℃ to remove surface floating water.
According to a third aspect of the present invention, there is provided a bacteriostatic polyvinylidene fluoride porous membrane, which is composed of the following raw materials:
the modified master batch for preparing the antibacterial polyvinylidene fluoride porous membrane;
polyvinylidene fluoride; and
an organic liquid;
wherein the weight percentages of the modified master batch, the polyvinylidene fluoride and the organic liquid are 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, adipic acid esters and soybean oil.
According to a fourth aspect of the present invention, there is provided a method for preparing the above antibacterial polyvinylidene fluoride porous film, comprising the steps of:
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 according to the weight percentage of 1:1:1-1:1:2 by using a continuous weighing feeding mode to carry out heating, melting, mixing and extrusion;
3) Homogenizing the melt at 180-230 ℃, and then spraying the melt through a metering pump and a die;
4) After cooling and forming, the organic liquid and inorganic powder are subjected to acid-base reaction and extracted, so that the preparation of the antibacterial polyvinylidene fluoride porous membrane is completed;
wherein, in the step 2), the modified master batch and polyvinylidene fluoride are added at one feed port of the twin-screw extruder, and the organic liquid is added at a position downstream of the one feed port.
Further, in the step 3), the die is an annular die, so that the antibacterial polyvinylidene fluoride porous membrane prepared in the step 3) is an antibacterial polyvinylidene fluoride hollow fiber membrane.
In step 4), the organic liquid and the inorganic powder are subjected to acid-base reaction and extraction after the cooling and molding are performed according to the aperture adjustment requirement.
Further, in step 2), the weight percentages of the modified master batch, polyvinylidene fluoride and organic liquid are 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, adipic acid esters 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 increases the addition of the bacteriostat, so that the polyvinylidene fluoride porous membrane can have the bacteriostasis 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 tap water purification process of sewage treatment and surface water as a water source;
2) According to the invention, the inorganic nano calcium carbonate with high specific surface area is used as the carrier, so that the liquid preparation type bacteriostat (namely the bacteriostat liquid preparation) is easy to adsorb on the carrier, and then the carrier and the polyvinylidene fluoride are fully mixed, so that the liquid preparation type bacteriostat is uniformly dispersed into a mixed system, the compatibility requirement of resin and the liquid preparation type bacteriostat is reduced, the selection range of the liquid preparation type bacteriostat is widened, and the preparation method of the bacteriostasis type polyvinylidene fluoride porous membrane based on the thermally induced phase separation method is easier to industrialize;
3) The invention utilizes the occupying effect of nano materials (namely nano calcium carbonate), so that the addition of the master batch in the preparation process of the polyvinylidene fluoride porous membrane can limit the growth and the increase of each component in the crystallization process, thereby preventing the formation of stacked spherulites, further enhancing the dispersing effect of the bacteriostatic agent in the porous membrane, extracting the nano calcium carbonate by utilizing acid after solidification and molding, and highly dispersing the macromolecular bacteriostatic agent in the membrane, thereby realizing long-term bacteriostasis;
4) The modified master batch for preparing the antibacterial polyvinylidene fluoride porous membrane is a high dispersion taking inorganic powder such as nano calcium carbonate as a carrier, and is prepared by directly adding the inorganic powder such as nano calcium carbonate and the matrix polyvinylidene fluoride and the organic liquid into a double-screw extruder according to a proportion and continuously weighing, and preparing the antibacterial polyvinylidene fluoride porous membrane by a thermally induced phase separation method; meanwhile, substances (such as a bacteriostatic agent) which cannot be directly added into a blending system can be selected in the final film-making formula, so that the selectivity of formula components is greatly expanded, and meanwhile, the diversity of modification directions 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 master batch molding support matrix resin, and when the high molecular weight polyvinylidene fluoride is added into the polyvinylidene fluoride which is conventionally suitable for preparing films by a thermally induced phase separation method for mixing and preparing films, the modified master batch and the polyvinylidene fluoride can be well compatible, so that the uniform dispersion of the bacteriostat is realized, and meanwhile, the strength of the porous film can be improved without influencing the pore-forming performance.
These and other aspects of the invention will be apparent from and elucidated with reference to the embodiments described hereinafter.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Preparation of modified master batch for preparing antibacterial polyvinylidene fluoride nano porous film: grinding nano calcium carbonate, passing through a 325-mesh screen, adding the ground and sieved powder into a high-speed mixer, stirring, adding the perfluorosulfonate solution serving as a modification additive into the nano calcium carbonate in a spray form, and stirring at a high speed for 10min; then transferring the pretreated powder to an ultrasonic processor with high-speed stirring, adding PHMG (PH) water agent (namely polyhexamethylene guanidine phosphate, 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 the mixture is led into a double-screw extruder, mixed at 200 ℃, and simultaneously the small molecular volatile matters are discharged through multistage vacuumizing, wherein the vacuum degree is-0.3 to-0.7 bar.
The weight percentages of the components of the prepared modified master batch are as follows:
nano calcium carbonate: 60 percent of
PHMG (PH) aqua: 27 percent of
High molecular weight polyvinylidene fluoride: 10 percent of
Perfluorosulfonate solution: 3%
Secondly), preparing a bacteriostatic polyvinylidene fluoride hollow fiber membrane: and (3) adding the modified master batch in the first part, PVDF and triethyl citrate into a double-screw extruder in a weight feeding mode according to the proportion of 1:1:1.5 by using a system of a double-screw extruder serial metering pump, mixing at 195 ℃, extruding and cooling through an annular mouth die to form a hollow fiber membrane, stretching for 2 times, and extracting an organic solvent and nano calcium carbonate from the hollow fiber membrane by using ethanol and hydrochloric acid to obtain the antibacterial polyvinylidene fluoride hollow fiber membrane.
Third), performance detection: the prepared antibacterial polyvinylidene fluoride hollow fiber membrane has pure water flux of 1000L/(. Square.m.h) at 25 ℃ and 0.1Mpa, tensile breaking strength of 16Mpa, elongation at break of 100%, maximum pore diameter of 0.2um measured by a bubble pressure method and porosity of 77%.
Comparative example 1
Uniformly stirring polyvinylidene fluoride powder, calcium carbonate and triethyl citrate according to the proportion of 1:0.2:1.5 by a high-speed mixer, adding the mixture into a double-screw extruder, mixing the mixture at 195 ℃, extruding and cooling the mixture through a metering pump and an annular mouth die to form a hollow fiber membrane, stretching the hollow fiber membrane by 2 times, and extracting an organic solvent and nano calcium carbonate in the hollow fiber membrane by using ethanol, hydrochloric acid and other liquids to prepare the polyvinylidene fluoride hollow fiber membrane without master batch. The pure water flux at 0.1Mpa was measured to be 400L/(. Square.m.h), the tensile strength at break was 10Mpa, the elongation at break was 40%, the maximum pore size was 0.4um, and the porosity was 66%.
Example 2
A) modified master batch for preparing antibacterial polyvinylidene fluoride porous membrane: grinding nano calcium carbonate, passing through a 325-mesh screen, adding the ground and sieved powder into a high-speed mixer, stirring, adding the perfluorocarboxylic acid solution into the nano calcium carbonate in a spray mode, and stirring at a high speed for 10min; then transferring the pretreated powder to an ultrasonic processor with high-speed stirring, adding a carboxymethyl chitosan water agent, stirring for 20min under the condition of 30KHZ, adding high-molecular weight polyvinylidene fluoride powder with MFR of 2.0g/10min (230 ℃ and 21.6 kg), and uniformly stirring; and then the mixture is led into a double-screw extruder, mixed at 190 ℃, and simultaneously the small molecular volatile matters are discharged through multistage vacuumizing, wherein the vacuum degree is-0.4 to-0.7 bar.
The weight percentages of the components of the prepared modified master batch are as follows:
nano calcium carbonate: 50 percent of
Carboxymethyl chitosan aqua: 30%
High molecular weight polyvinylidene fluoride: 15%
Perfluorocarboxylic acid solution: 5%
Secondly), preparing a bacteriostatic polyvinylidene fluoride hollow fiber membrane: and (3) adding the modified master batch in the first part, polyvinylidene fluoride powder and acetyl trioctyl citrate into a double-screw extruder in a weighing feeding mode according to the proportion of 1:1:1.5 by using a system of a double-screw extruder serial metering pump, mixing at 220 ℃, extruding through an annular die, cooling to form a hollow fiber membrane, stretching for 2 times, and extracting an organic solvent and nano calcium carbonate in the hollow fiber membrane by using ethanol and hydrochloric acid to obtain the antibacterial polyvinylidene fluoride hollow fiber membrane.
Third), performance detection: the prepared antibacterial polyvinylidene fluoride hollow fiber membrane has pure water flux of 1200L/(. Square.m.h) at 25 ℃ and 0.1Mpa, tensile breaking strength of 20Mpa, elongation at break of 130%, maximum pore diameter of 0.3um measured by a bubble pressure method and porosity of 70%.
Example 3
Preparing antibacterial nano calcium carbonate master batch: grinding nano calcium carbonate, passing through a 325-mesh screen, adding the ground and sieved powder into a high-speed mixer, stirring, adding the perfluorocarboxylic acid solution into the nano calcium carbonate in a spray mode, and stirring at a high speed for 10min; then transferring the pretreated powder to an ultrasonic processor with high-speed stirring, adding PHMG (GL) (namely, polyhexamethylene guanidine gluconate, derivatives of polyhexamethylene guanidine) aqua, stirring for 20min at 30KHZ, adding high molecular weight polyvinylidene fluoride powder with MFR of 2.0g/10min (230 ℃ C., 21.6 kg), and stirring uniformly; and then the mixture is led into a double-screw extruder, mixed at 200 ℃, and simultaneously the small molecular volatile matters are discharged through multistage vacuumizing, wherein the vacuum degree is-0.5 to-0.8 bar.
The weight percentages of the components of the prepared modified master batch are as follows:
nano calcium carbonate: 55%
PHMG (GL) aqua: 25 percent of
High molecular weight polyvinylidene fluoride: 15%
Perfluorocarboxylic acid solution: 5%
Secondly), preparing a bacteriostatic polyvinylidene fluoride hollow fiber membrane: and (3) adding the modified master batch in the first part, polyvinylidene fluoride powder, adipic acid dioctyl ester and triethyl citrate mixed solution (the weight ratio of the two components is 1:1) into a double-screw extruder in a weighing feeding manner according to the weight ratio of the two components of 1:1:1.5 by using a system of a double-screw extruder serial metering pump, mixing at 220 ℃, extruding through the metering pump and an annular mouth die, cooling to form a hollow fiber membrane, stretching for 2 times, and extracting an organic solvent and nano calcium carbonate in the hollow fiber membrane by using ethanol and hydrochloric acid to obtain the antibacterial polyvinylidene fluoride hollow fiber membrane.
Third), performance detection: the prepared antibacterial polyvinylidene fluoride hollow fiber membrane has pure water flux of 1300L/(. Square.m.h) at 25 ℃ and 0.1Mpa, tensile breaking strength of 18Mpa, elongation at break of 100%, maximum pore diameter of 0.25um measured by a bubble pressure method and porosity of 73%.
Example 4
A) modified master batch for preparing antibacterial polyvinylidene fluoride porous membrane: grinding nano calcium carbonate, passing through a 325-mesh screen, adding the ground and sieved powder into a high-speed mixer, stirring, adding the perfluorosulfonate solution into the nano calcium carbonate in a spray form, and stirring at a high speed for 10min; then transferring the pretreated powder to an ultrasonic processor with high-speed stirring, adding a carboxymethyl chitosan water agent, stirring for 20min under the condition of 30KHZ, adding high-molecular weight polyvinylidene fluoride powder with MFR of 2.0g/10min (230 ℃ and 21.6 kg), and uniformly stirring; and then the mixture is led into a double-screw extruder, mixed at 190 ℃, and simultaneously the small molecular volatile matters are discharged through multistage vacuumizing, wherein the vacuum degree is-0.4 to-0.7 bar.
The weight percentages of the components of the prepared modified master batch are as follows:
nano calcium carbonate: 60 percent of
Carboxymethyl chitosan aqua: 20 percent of
High molecular weight polyvinylidene fluoride: 15%
Perfluorosulfonate solution: 5%
Secondly), preparing a bacteriostatic polyvinylidene fluoride hollow fiber membrane: and (3) adding the modified master batch in the first part, polyvinylidene fluoride powder and acetyl trioctyl citrate into a double-screw extruder in a weighing feeding mode according to the proportion of 1:1:1.5 by using a system of a double-screw extruder serial metering pump, mixing at 220 ℃, extruding through an annular die, cooling to form a hollow fiber membrane, stretching for 2 times, and extracting an organic solvent and nano calcium carbonate in the hollow fiber membrane by using ethanol and hydrochloric acid to obtain the antibacterial polyvinylidene fluoride hollow fiber membrane.
Third), performance detection: the prepared antibacterial polyvinylidene fluoride hollow fiber membrane has pure water flux of 1000L/(. Square.m.h) at 25 ℃ and 0.1Mpa, tensile breaking strength of 22Mpa, elongation at break of 110%, maximum pore diameter of 0.2um measured by a bubble pressure method and porosity of 70%.
Example 5
Preparing antibacterial nano calcium carbonate master batch: grinding nano calcium carbonate, passing through a 325-mesh screen, adding the ground and sieved powder into a high-speed mixer, stirring, adding the perfluorocarboxylic acid solution into the nano calcium carbonate in a spray mode, and stirring at a high speed for 10min; then transferring the pretreated powder to an ultrasonic processor with high-speed stirring, adding PHMG (polyhexamethylene guanidine) aqua, stirring for 20min under the condition of 30KHZ, adding high molecular weight polyvinylidene fluoride powder with MFR of 2.0g/10min (230 ℃ and 21.6 kg), and uniformly stirring; and then the mixture is led into a double-screw extruder, mixed at 200 ℃, and simultaneously the small molecular volatile matters are discharged through multistage vacuumizing, wherein the vacuum degree is-0.5 to-0.8 bar.
The weight percentages of the components of the prepared modified master batch are as follows:
nano calcium carbonate: 60 percent of
PHMG aqua: 26%
High molecular weight polyvinylidene fluoride: 13%
Perfluorocarboxylic acid solution: 1%
Secondly), preparing a bacteriostatic polyvinylidene fluoride hollow fiber membrane: and (3) adding the modified master batch in the first part, polyvinylidene fluoride powder, adipic acid dioctyl ester and triethyl citrate mixed solution (the weight ratio of the two components is 1:1) into a double-screw extruder in a weighing feeding manner according to the weight ratio of the two components of 1:1:1.5 by using a system of a double-screw extruder serial metering pump, mixing at 220 ℃, extruding through the metering pump and an annular mouth die, cooling to form a hollow fiber membrane, stretching for 2 times, and extracting an organic solvent and nano calcium carbonate in the hollow fiber membrane by using ethanol and hydrochloric acid to obtain the antibacterial polyvinylidene fluoride hollow fiber membrane.
Third), performance detection: the prepared antibacterial polyvinylidene fluoride hollow fiber membrane has pure water flux of 1150L/(. Square.m.h) at 25 ℃ and 0.1Mpa, tensile breaking strength of 20Mpa, elongation at break of 105%, maximum pore diameter of 0.21um measured by a bubble pressure method and porosity of 71%.
The following describes the antibacterial performance test of the above examples 1 to 5 and comparative examples:
the test method refers to GB/T37206-2018, wherein the long-acting test of the example 1 in the table 1 refers to that the sample prepared in the example 1 is prepared after being subjected to sterile ultra-pure water transmembrane cleaning for 24 hours, and the average antibacterial rate results after the test are shown in the following table 1:
table 1 antibacterial effect of each example
Figure DEST_PATH_IMAGE002
Obviously, as shown in table 1, the antibacterial rate of the antibacterial polyvinylidene fluoride hollow fiber membrane prepared by the invention is obviously and greatly improved compared with the comparative example, and the antibacterial effect is obvious.
While the present disclosure and features have been described above, it will be understood that variations and modifications in the above-described components and steps, including combinations of features individually disclosed or claimed herein, as well as other combinations of features that are apparent to persons skilled in the art, may be made under the inventive concepts of the present disclosure. Such variations and/or combinations fall within the technical field to which the invention relates and fall within the scope of the claims of the invention.

Claims (10)

1. The antibacterial polyvinylidene fluoride porous membrane thermal phase separation method for preparing modified master batch is characterized by comprising the following raw materials in percentage by weight:
high molecular weight polyvinylidene fluoride: 10-15%;
nano inorganic powder: 50-60%;
high molecular bacteriostatic agent liquid preparation: 20-30%;
modification additive: 1-5%,
wherein the nano inorganic powder is nano calcium carbonate, the polymer bacteriostat liquid preparation comprises 25-50% of polymer bacteriostat by weight percentage, the modifying additive is organic fluorine surfactant,
and wherein the preparation method of the modified master batch comprises the following steps:
s1: pretreating the nano inorganic powder under the condition of high-speed mixing and shearing to eliminate soft agglomeration and partial hard agglomeration, and adding the modification additive into the nano inorganic powder for simultaneous treatment while pretreating;
s2: uniformly mixing the pretreated nano inorganic powder and the macromolecular bacteriostatic agent liquid preparation under the high-speed stirring condition, and simultaneously dispersing by ultrasonic waves to prepare a mixed dispersion system taking the nano inorganic powder as a carrier;
s3: and (3) uniformly stirring and mixing the mixed dispersion system and the high-molecular weight polyvinylidene fluoride by using a high-speed mixer, melting and mixing the mixture by using a double-screw extruder, simultaneously exhausting small molecular volatile matters by adopting a multi-stage vacuumizing mode, extruding by using a columnar die, and cooling and granulating to prepare the modified master batch.
2. The antibacterial polyvinylidene fluoride porous membrane thermal phase separation method for preparing modified master batch according to claim 1, wherein the high molecular weight polyvinylidene fluoride has a melt flow rate of 1-4 g/10min under the condition of 230 ℃/21.6 kg.
3. The method for preparing modified master batch by using the antibacterial polyvinylidene fluoride porous membrane thermal phase separation method according to claim 2, wherein the high molecular weight polyvinylidene fluoride is a vinylidene fluoride homopolymer.
4. The method for preparing modified master batch by using the antibacterial polyvinylidene fluoride porous membrane thermal phase separation method according to claim 1, wherein the nano calcium carbonate is cubic nano calcium carbonate with an average particle size of 20-150 nanometers.
5. The method for preparing modified master batch by using the antibacterial polyvinylidene fluoride porous membrane thermal phase separation method according to claim 1, wherein the macromolecular antibacterial agent is one or more of polyhexamethylene guanidine, polyhexamethylene biguanide, chitosan and derivatives thereof with weight average molecular weight more than 20000.
6. The method for preparing the modified master batch by the bacteriostatic polyvinylidene fluoride porous membrane thermal phase separation method according to any one of claims 1 to 5, comprising the following steps:
s1: pretreating the nano inorganic powder under the condition of high-speed mixing and shearing to eliminate soft agglomeration and partial hard agglomeration, and adding the modification additive into the nano inorganic powder for simultaneous treatment while pretreating;
s2: uniformly mixing the pretreated nano inorganic powder and the macromolecular bacteriostatic agent liquid preparation under the high-speed stirring condition, and simultaneously dispersing by ultrasonic waves to prepare a mixed dispersion system taking the nano inorganic powder as a carrier;
s3: and (3) uniformly stirring and mixing the mixed dispersion system and the high-molecular weight polyvinylidene fluoride by using a high-speed mixer, melting and mixing the mixture by using a double-screw extruder, simultaneously exhausting small molecular volatile matters by adopting a multi-stage vacuumizing mode, extruding by using a columnar die, and cooling and granulating to prepare the modified master batch.
7. The method for preparing modified master batch by thermal phase separation method of antibacterial polyvinylidene fluoride porous membrane according to claim 6, wherein in step S1, the nano inorganic powder is stirred in a high-speed mixer, and the modified additive is added into the nano inorganic powder while stirring, and stirring is carried out at high speed for 10min.
8. The method for preparing modified master batch by using a bacteriostatic porous polyvinylidene fluoride membrane thermal phase separation method according to claim 6, wherein in the step S2, the pretreated nano inorganic powder and the macromolecular bacteriostatic liquid preparation are prepared into the mixed dispersion system in an ultrasonic processor with high-speed stirring, wherein the frequency of ultrasonic waves is set to be 30KHZ, and the stirring time is 0.5-1 h.
9. The method for preparing the modified master batch by the bacteriostatic porous polyvinylidene fluoride membrane thermal phase separation method according to claim 6, wherein in the step S3, the temperature of the mixture in a double-screw extruder for melting and mixing is 180-200 ℃.
10. The method for preparing modified master batch by using the antibacterial polyvinylidene fluoride porous membrane thermal phase separation method according to claim 9, wherein in the step S3, the cooling and granulating means water-cooling and granulating or air-cooling and granulating, the water-cooling temperature is controlled to be 15-35 ℃ during water-cooling and granulating, the air-cooling temperature is normal temperature during air-cooling and granulating, and the water-cooling and granulating water-cooling particles are dried at 80 ℃ to remove surface floating water.
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