CN109395590B - Preparation method of PVDF (polyvinylidene fluoride) antibacterial film - Google Patents

Preparation method of PVDF (polyvinylidene fluoride) antibacterial film Download PDF

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CN109395590B
CN109395590B CN201811086400.3A CN201811086400A CN109395590B CN 109395590 B CN109395590 B CN 109395590B CN 201811086400 A CN201811086400 A CN 201811086400A CN 109395590 B CN109395590 B CN 109395590B
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唐圆圆
王子铱
梁琨
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Southwest University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
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    • C08J2327/00—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
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    • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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Abstract

The invention provides a preparation method of a PVDF antibacterial film, which adopts nano CuAl2O4The spinel is used as an antibacterial agent in the antibacterial film, and the preparation method comprises the following steps: mixing nano CuAl2O4Ultrasonically dispersing spinel in solution of polyethylene glycol and polyvinyl alcohol for 10-15 hr to form casting solution, standing for defoaming, and vacuum filtering to obtain CuAl doped solution2O4And depositing the spinel film casting solution on the surface of the original film, and drying the film. The nano CuAl2O4The mass ratio of the spinel to the polyvinyl alcohol to the polyethylene glycol is 1-2: 4-6: 100. the invention adopts a surface coating method to prepare nano CuAl2O4The spinel modified PVDF antibacterial film has the advantages of simple process, low preparation cost, excellent antibacterial property and heavy metal stability, low leaching rate of heavy metal copper ions, higher mechanical strength and toughness, high wear resistance and high permeability resistance to gas and liquid.

Description

Preparation method of PVDF (polyvinylidene fluoride) antibacterial film
Technical Field
The invention belongs to the technical field of seawater desalination and sewage treatment, and particularly relates to a preparation method of a PVDF antibacterial film.
Background
The seawater desalination can realize the expansion and application of water resources, can increase the total amount of fresh water, is not influenced by time, space and climate in the increasingly aggravated situation of water resource crisis, and provides a source for drinking water for agriculture, industry or residents.
The membrane technology is a new technology in the fields of seawater desalination and sewage treatment, and the PVDF membrane has the characteristics of good chemical stability, heat resistance, pollution resistance, excellent mechanical property, wide processing temperature range, easiness in membrane formation and the like, and is widely applied to the field of membrane preparation. But the PVDF film inevitably has the problem of microbial contamination in the application process, and the addition of an antibacterial agent is an effective means for solving the problem. Copper-containing nanoparticles are a commonly used antibacterial agent, but the addition of the copper-containing nanoparticles inevitably has the problem of copper leaching, and when the content of copper ions is higher than a certain level, the copper-containing nanoparticles can cause harm to the environment and human bodies, so that the preparation of an antibacterial film by using the copper-containing nanoparticles with low leaching rate as the antibacterial agent is very necessary.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a nano CuAl2O4The spinel is a PVDF antibacterial film of an antibacterial agent.
The invention provides a preparation method of a PVDF antibacterial film, which adopts nano CuAl2O4The spinel is used as an antibacterial agent in the antibacterial film, and the preparation method comprises the following steps:
mixing nano CuAl2O4Ultrasonically dispersing spinel in solution of polyethylene glycol and polyvinyl alcohol for 10-15 hr to form casting solution, standing for defoaming, and vacuum filtering to obtain Cu-Al doped solution2O4And depositing the spinel casting solution on the surface of the film, and drying the film.
In the preparation method of the PVDF antibacterial film, the nano CuAl2O4The mass ratio of the spinel to the polyvinyl alcohol to the polyethylene glycol is 1-2: 4-6: 100.
in the preparation method of the PVDF antibacterial film, the nano CuAl2O4The spinel is prepared by the following steps:
s1 adding Cu (NO)3)2·3H2O and Al (NO)3)3·9H2Preparing O into a solution according to a molar ratio of Cu to Al of 1: 1.5-2.5;
s2, titrating the solution prepared in the S1 step by using 1mol/L NaOH to gradually generate blue precipitate;
s3, heating the mixed solution containing the blue precipitate after the dropwise addition, and gradually changing the precipitate from blue to brown;
s4, filtering and drying the brown precipitate obtained in the step S3, and finally calcining the brown precipitate in a muffle furnace at high temperature to obtain the nano CuAl2O4Spinel powder.
The nano CuAl2O4In the step S2 for spinel preparation, the NaOH was gradually added dropwise to the mixed solution at a rate of 4 to 6 mL/min.
The nano CuAl2O4In the step S3 of preparing spinel, the mixed liquid containing blue precipitate after the dropwise addition is heated at 80-100 ℃ for 1-2 hours.
The nano CuAl2O4In the step S4 for preparing spinel, the brown precipitate is filtered and dried, and then is placed in a muffle furnace for high-temperature calcination at the temperature of 1000 ℃ and 1100 ℃ for 1-4 hours.
The nano CuAl2O4In the step S4 of spinel preparation, the prepared nano CuAl2O4The leaching rate of copper ions in the spinel is 4.51 mg/L.
The PVDF antibacterial film prepared by the invention has simple process and low preparation cost, and adopts the nano CuAl2O4Spinel has excellent antibacterial property, and simultaneously, the leaching rate of heavy metal copper ions is far lower than CuO, so that the spinel has high heavy metal stability, high mechanical strength and toughness, high wear resistance, and high permeability resistance to gas and liquid, can effectively remove impurities such as macromolecules, bacteria, silt and the like, cannot precipitate heavy metal in the using process, cannot influence human bodies and environments, and has wide application in the field of sewage treatment and seawater desalination treatment.
Drawings
FIG. 1 shows the nano CuAl prepared in example 1 of the present invention2O4SEM photograph of spinel;
FIG. 2 shows the nano CuAl prepared in example 1 of the present invention2O4TEM photograph of spinel;
FIG. 3 is a SEM image of the surface of a PVDF raw film;
FIG. 4 is a surface SEM image of a PVDF antibacterial film prepared by the invention;
FIG. 5 is an SEM image of a raw film cross-section;
FIG. 6 is a SEM image of the cross section of a PVDF antibacterial film prepared by the invention;
FIG. 7 is a graph of the surface roughness of the original film;
FIG. 8 is a surface roughness chart of a PVDF antibacterial film prepared by the present invention;
FIG. 9 is a graph of contact angles of the surface of the original film;
FIG. 10 is a surface contact angle diagram of a PVDF antibacterial film prepared by the present invention;
FIG. 11 is a graph showing the results of the primary membrane antibacterial test;
FIG. 12 is a graph showing the results of the antibacterial property test of the PVDF antibacterial film prepared by the present invention;
fig. 13 is a graph comparing copper ion leaching rate with CuO for nano spinel prepared by the present invention.
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The preparation method of the PVDF antibacterial film provided by the invention adopts nano CuAl2O4The spinel is used as an antibacterial agent in the antibacterial film, and the preparation method comprises the following steps: mixing nano CuAl2O4Ultrasonically dispersing spinel in polyethylene glycol (PEG-10000) and polyvinyl alcohol (PVA-1750) solution for 10-15 hours to form a casting solution, standing for defoaming for 1-2 hours, and performing vacuum filtration to mix the solution with CuAl2O4Depositing the spinel casting solution on the surface of the PVDF original membrane in a surface coating mode, and preparing the PVDF original membraneAnd washing the modified membrane with water twice, and naturally drying.
In the preparation method of the PVDF antibacterial film, the nano CuAl2O4The mass ratio of the spinel to the polyvinyl alcohol to the polyethylene glycol is 1-2: 4-6: 100.
wherein polyvinyl alcohol is binder capable of making nano CuAl2O4The spinel and the polyvinyl alcohol can be fully mixed; polyethylene glycol is used as dispersant to make the nano CuAl2O4The spinel is uniformly dispersed in the polyvinyl alcohol.
In the step, too much polyvinyl alcohol is selected to cause particle agglomeration, and too much polyethylene glycol causes too thin antibacterial components in the film.
In the preparation method of the invention, the nano CuAl2O4The spinel is prepared by the following steps:
s1 adding Cu (NO)3)2·3H2O and Al (NO)3)3·9H2And preparing a mixed solution of O and Cu and Al according to a molar ratio of 1: 1.5-2.5.
S2 was gradually added dropwise to the mixed solution prepared in step S1 with 1mol/L NaOH at a rate of 4-6mL/min, and a blue precipitate was gradually formed.
In this step, NaOH is added to form a blue precipitate of copper hydroxide and aluminum hydroxide. The chemical reaction formula of the step is as follows:
Cu2++2OH-→Cu(OH)2↓ (1)
Al3++3OH-→Al(OH)3↓ (2)
s3 the mixed solution containing the blue precipitate added dropwise was heated to gradually change the precipitate from blue to brown.
In the step, the blue precipitate is heated at 80-100 ℃ for 1-2 hours, so that the copper hydroxide and the aluminum hydroxide are gradually decomposed, and the brown solution is obtained after the precipitate is decomposed.
The chemical reaction formula of the step is as follows:
Figure BDA0001803249430000041
Figure BDA0001803249430000042
s4, filtering and drying the brown precipitate obtained in the step S3, and finally calcining the precipitate at high temperature in a muffle furnace, wherein the temperature of the high-temperature calcination in the muffle furnace is 1000-1100 ℃ for 1-4 hours. Obtaining the nano CuAl2O4Spinel powder.
Figure BDA0001803249430000051
Figure BDA0001803249430000052
Figure BDA0001803249430000053
When the calcination temperature is 700 ℃, only a small amount of CuAl is available2O4The particle size of the particles is continuously increased along with the increase of the calcining temperature and the extension of the reaction time, and CuAl is generated2O4The yield of (A) is gradually increased, and pure CuAl can be obtained when the temperature is 1000 DEG C2O4。
However, when the temperature exceeds 1100 ℃, other side reactions occur, and CuAl in the product is generated2O4Can generate changes to influence CuAl2O4Purity of spinel.
The following reaction scheme:
2CuAl2O4→2CuAlO2+Al2O3+0.5O2 (8)
CuAl2O4→CuO+Al2O3 (9)
2CuO→Cu2O+0.5O2 (10)
CuO+Al2O3→2CuAlO2 (11)
only a small amount of CuAl is generated when the calcination time is less than 1h2O4The particle diameter of the particles is continuously increased along with the extension of the calcination time, and CuAl is generated2O4The yield of (2) is gradually increased, and when the calcination time is 3-4 h, pure CuAl can be obtained2O4When the calcination time reaches 5h, CuAlO is present2And (4) generating.
Pure CuAl can be obtained when the heating rate is 5 ℃/min and 10 ℃/min2O4The particle size of the particles is continuously reduced along with the increase of the temperature rise rate, but the particles prepared under the condition of 4-6 ℃/min are all below 100 nanometers, and are nano spinel. When the temperature exceeds 6 ℃/min, CuAlO begins to exist2And yield gradually increased.
The PVDF antibacterial film prepared by the steps of the invention adopts nano CuAl2O4Spinel as antibacterial agent in antibacterial film and nano CuAl2O4The spinel has excellent antibacterial property and extremely low leaching rate of copper ions, and the nano CuAl is prepared on the basis of a PVDF (polyvinylidene fluoride) primary film by a surface coating method2O4The spinel modified PVDF antibacterial film has the advantages of simple whole process, low cost, higher antibacterial property, and simultaneously, the leaching rate of heavy metal copper ions is far lower than CuO, so that the spinel modified PVDF antibacterial film has excellent heavy metal stability, and no heavy metal is separated out in the use process, thereby achieving the purposes of permeation, filtration, removal of impurities such as macromolecules, bacteria, silt and the like, simultaneously avoiding the influence on human bodies and the environment, and having better application effect in the field of sewage treatment and seawater desalination treatment.
The present invention will be described in further detail with reference to examples.
Example 1:
mono-nano CuAl2O4Preparation of spinel:
s1 weighing copper nitrate [ Cu (NO) according to the Cu to Al molar ratio of 1:23)2·3H2O]24.16g of aluminum nitrate [ Al (NO)3)3·9H2O]75.02g, placing inAdding deionized water into the container, and stirring and mixing to form a mixed solution;
s2, dropwise adding 1mol/L NaOH 1L into the mixed solution prepared in the step, wherein the dropwise adding speed is 6ml/min, and gradually generating blue precipitates;
s3, heating the mixed solution containing the blue precipitate after the dropwise addition, gradually raising the temperature of the container to 90 ℃ within 2 hours, and stopping heating when the precipitate gradually changes from blue to brown;
s4 pouring out the clear liquid in the container, filtering the residual brown precipitate with Buchner funnel, drying in oven for 2 hr, and calcining at 1100 deg.C for 3 hr in muffle furnace to obtain nano CuAl2O4Spinel powder.
Referring to FIGS. 1 and 2, it can be seen from the SEM and TEM results that the CuAl prepared in this example2O4Spinel is polyhedral and has reached nanometer level.
Secondly, preparing a PVDF film:
s5 preparing the obtained nano CuAl2O4Mixing 0.2g of spinel powder, 1g of polyethylene glycol (PEG-10000) and 4g of polyvinyl alcohol (PVA-1750), and performing ultrasonic dispersion for 10 hours to form a membrane casting solution;
s6, standing the casting solution for 1 hour to defoam, and doping the casting solution with CuAl through a vacuum suction filter2O4Depositing the spinel film casting liquid on the surface of an original film, and drying the film.
Comparing fig. 3 and 4, and fig. 5 and 6, after the casting solution is coated on the original film, nano CuAl2O4The spinel can be well adhered to the surface of the original film.
Referring to fig. 7-10, will have nano CuAl2O4The PVDF film prepared by coating the spinel casting film liquid on the original film has the advantages of increased roughness and reduced contact angle.
Referring to FIGS. 11 and 12, the amount of Escherichia coli in the PVDF antibacterial film prepared by the inventive example was greatly reduced to 4.9X 107And 8.7X 107The PVDF antibacterial film is proved to have excellent antibacterial property and can effectively inhibit bacteriaAttachment and growth of (3).
Copper-containing nanoparticles inevitably have the problem of leaching of copper ions, and when the content of copper ions exceeds a certain limit, the copper-containing nanoparticles cause harm to the environment and human bodies. The PVDF antibacterial film prepared in the embodiment of the present invention was subjected to a leaching experiment test for copper ions for 24 hours, and compared with CuO.
Through determination, the copper ion leaching rates of the PVDF antibacterial film CuO prepared by the embodiment of the invention are respectively 4.51mg/L and 64.73mg/L, and the surface areas are respectively 51.08m2G and 0.17m2(ii) in terms of/g. The normalization calculation follows the following equation:
Figure BDA0001803249430000071
wherein C is the leaching rate (mg/L) of heavy metals, Vleachate is the volume (L) of the leaching solution, n is the mole number (mol) of copper ions, W is the mass (g) of the sample, and S is the surface area (m) of the sample per unit mass2/g)。
By calculation, MCuO,normalized＝1.20×103mg/(mol·m2)，MCuAl2O4,normalized＝0.65mg/(mol·m2). Thus, it can be seen that the nano CuAl2O4The standardized leaching rate of spinel is 1850 times lower than that of CuO. (see FIG. 13). As can be seen from the results shown in FIG. 13, nano CuAl2O4The spinel has a copper ion leaching rate far lower than that of CuO, and has a good copper ion stabilizing effect.
Therefore, the PVDF antibacterial film has better antibacterial property and heavy metal stability.
Example 2:
mono-nano CuAl2O4Preparation of spinel:
s1 weighing copper nitrate [ Cu (NO) according to Cu to Al molar ratio of 1:1.53)2·3H2O]24.16g of aluminum nitrate [ Al (NO)3)3·9H2O]56.27g, placing the mixture into a container, adding deionized water, and stirring and mixing to form a mixed solution;
s2, dropwise adding 1mol/L NaOH 1L into the mixed solution prepared in the step, wherein the dropwise adding speed is 5ml/min, and gradually generating blue precipitates;
s3, heating the mixed solution containing the blue precipitate after the dropwise addition, gradually raising the temperature of the container to 100 ℃ within 2 hours, and stopping heating when the precipitate gradually changes from blue to brown;
s4 pouring out the clear liquid in the container, filtering the residual brown precipitate with Buchner funnel, drying in oven for 1.5 hr, and calcining in muffle furnace at 1000 deg.C for 4 hr to obtain nanometer CuAl2O4Spinel powder.
Secondly, preparing a PVDF film:
s5 preparing the obtained nano CuAl2O4Mixing 0.4g of spinel powder, 1g of polyethylene glycol (PEG-10000) and 4g of polyvinyl alcohol (PVA-1750), and performing ultrasonic dispersion for 12 hours to form a membrane casting solution;
s6, standing the casting solution for 1.5 hours for defoaming, and filtering the casting solution doped with CuAl through a vacuum filter2O4Depositing the spinel film casting liquid on the surface of an original film, and drying the film.
Example 3:
mono-nano CuAl2O4Preparation of spinel:
s1 weighing copper nitrate [ Cu (NO) according to the Cu to Al molar ratio of 1:2.53)2·3H2O]24.16g of aluminum nitrate [ Al (NO)3)3·9H2O]93.78g, placing in a container, adding deionized water, stirring and mixing to form a mixed solution;
s2, dropwise adding 1mol/L NaOH 1L into the mixed solution prepared in the step, wherein the dropwise adding speed is 4ml/min, and gradually generating blue precipitates;
s3, heating the mixed solution containing the blue precipitate after the dropwise addition, gradually raising the temperature of the container to 80 ℃ within 1.5 hours, and stopping heating when the precipitate gradually changes from blue to brown;
s4, pouring out the clear liquid in the container, filtering the residual brown precipitate with a Buchner funnel, drying in an oven for 1 hour, finally putting in a muffle furnace, calcining at 1100 ℃ for 3 hours,obtaining the nano CuAl2O4Spinel powder.
Secondly, preparing a PVDF film:
s5 preparing the obtained nano CuAl2O4Mixing 0.2g of spinel powder, 1.2g of polyethylene glycol (PEG-10000) and 4g of polyvinyl alcohol (PVA-1750), and performing ultrasonic dispersion for 15 hours to form a membrane casting solution;
s6, standing the casting solution for 2 hours for defoaming, and filtering the casting solution doped with CuAl through a vacuum filter2O4Depositing the spinel film casting liquid on the surface of an original film, and drying the film.
The above-mentioned embodiments of the present invention and the accompanying drawings are only part of the preferred embodiments of the present invention, and are not intended to limit the present invention, and those skilled in the art may make modifications, equivalents and improvements without departing from the spirit of the present invention.

Claims (6)

1. The preparation method of the PVDF antibacterial film is characterized in that nano CuAl is adopted2O4The spinel is used as an antibacterial agent in the antibacterial film, and the preparation method comprises the following steps:
mixing nano CuAl2O4Ultrasonically dispersing spinel in solution of polyethylene glycol and polyvinyl alcohol for 10-15 hr to form casting solution, standing for defoaming, and vacuum filtering to obtain Cu-Al doped solution2O4Depositing the spinel film casting solution on the surface of the original film, and drying the film to obtain the nano CuAl2O4The mass ratio of the spinel to the polyvinyl alcohol to the polyethylene glycol is 1-2: 4-6: 100.
2. the method for preparing PVDF antibacterial film as defined in claim 1, wherein said nano CuAl is added2O4The spinel is prepared by the following steps:
s1 adding Cu (NO)3)2·3H2O and Al (NO)3)3·9H2Preparing O into a mixed solution according to a molar ratio of Cu to Al of 1: 1.5-2.5;
s2, titrating the solution prepared in the S1 step by using 1mol/L NaOH to gradually generate blue precipitate;
s3, heating the mixed solution containing the blue precipitate after the dropwise addition, and gradually changing the precipitate from blue to brown;
s4, filtering and drying the brown precipitate obtained in the step S3, and finally calcining the brown precipitate in a muffle furnace at high temperature to obtain the nano CuAl2O4Spinel powder.
3. The method for preparing PVDF antibacterial film as claimed in claim 2, wherein in the step S2, the NaOH is gradually added dropwise into the mixed solution at a rate of 4-6 mL/min.
4. The method for preparing PVDF antibacterial film as claimed in claim 2, wherein in the step S3, the mixed solution containing blue precipitate after the dropwise addition is heated at 80-100 ℃ for 1-2 hours.
5. The method for preparing PVDF antibacterial membrane as claimed in claim 2, wherein in the step S4, after the brown precipitate is filtered and dried, the temperature of high temperature calcination in a muffle furnace is 1000-1100 ℃ for 1-4 hours.
6. The method for preparing PVDF antibacterial film as defined in claim 2, wherein said prepared nano CuAl2O4The leaching rate of copper ions in the spinel is 4.51 mg/L.
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