CN111644077A - Hydrophilic polyvinylidene fluoride nanofiltration membrane and preparation method thereof - Google Patents

Hydrophilic polyvinylidene fluoride nanofiltration membrane and preparation method thereof Download PDF

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CN111644077A
CN111644077A CN202010544044.6A CN202010544044A CN111644077A CN 111644077 A CN111644077 A CN 111644077A CN 202010544044 A CN202010544044 A CN 202010544044A CN 111644077 A CN111644077 A CN 111644077A
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polyvinylidene fluoride
ecip
nanofiltration membrane
hydrophilic
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CN111644077B (en
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齐松松
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Shanghai Xunjiang Technology Co ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • 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
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2325/36—Hydrophilic membranes

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Abstract

The invention provides a hydrophilic polyvinylidene fluoride nanofiltration membrane, which comprises a polyvinylidene fluoride-based membrane body and a hydrophilic polymer polymerized on the polyvinylidene fluoride-based membrane body, and the structure of the hydrophilic polyvinylidene fluoride nanofiltration membrane is shown as a formula (I). The invention also provides a preparation method, which comprises the following steps: step 1: firstly, placing a polyvinyl alcohol solution in a water bath kettle, and then dropwise adding Epoxy Chloroalkane (ECIP) one by one to prepare ECIP modified PVA; step 2: keeping the reaction temperature at 100 ℃, adding aniline into the system, and reacting for 4 hours. Then placing the system in an ice-water bath to obtain a modified ECIP/PVA/PANI dispersion liquid; and step 3: and (3) placing the modified ECIP/PVA/PANI dispersion liquid into an ice-water bath, and vertically placing a PVDF substrate cleaned by deionized water into a beaker to obtain the hydrophilic polyvinylidene fluoride nanofiltration membrane. The invention researches that the polyvinylidene fluoride membrane is combined with the hydrophilic polymer, so that the property of the polyvinylidene fluoride membrane is improved to improve the cleaning efficiency of the membrane and reduce the pollution of the nanofiltration membrane.

Description

Hydrophilic polyvinylidene fluoride nanofiltration membrane and preparation method thereof
Technical Field
The invention belongs to the technical field of environment-friendly materials, and particularly relates to a hydrophilic polyvinylidene fluoride nanofiltration membrane and a preparation method thereof.
Background
With the increasing demand of water treatment, membrane separation technology has been widely used in the water treatment industry. Membrane separation is a method of separating, classifying, purifying and enriching each component in a mixture under the push of external energy or chemical potential difference by utilizing the selective permeation action of a membrane. The nanofiltration membrane is one of the most common membrane separation treatments, and is usually synthesized from PVDF (polyvinylidene fluoride), which is a good acid-resistant, corrosion-resistant, and oxidation-resistant membrane material, but the membrane is inevitably polluted by particles, micelles, and some solute molecules during the use process, so that the water flux of the membrane is reduced, the energy consumption is increased, the service life of the membrane is shortened, the membrane is polluted, the flux is unrecoverable, and irreversible membrane pollution is formed.
At present, the membrane pollution is avoided mainly by a cleaning device or a physical method in China, for example, CN110038457A introduces an anti-pollution photocatalytic self-cleaning nanofiltration membrane and a preparation method thereof, and after the nanofiltration membrane is modified by a carbon quantum dot with photocatalytic activity, the nanofiltration membrane has self-cleaning performance under visible light. However, the method can only be applied under visible light conditions, and has a narrow application range and low practicability. Chinese patent CN209507812U introduced a nanofiltration membrane device for increasing water recovery rate and reducing energy consumption, wherein water flows to the outside through a right opening, a third connecting hopper and a third water pipe in sequence after flowing out of the inner cavity on the right side of the right sealing plate through a plurality of groups of nanofiltration tubes. The device installation is loaded down with trivial details, and water just can go on accomplishing clean process through multiple device for the clean inefficiency of nanofiltration membrane.
Therefore, the existing nanofiltration membrane has low cleaning efficiency, narrow application range and low practicability, and becomes a technical problem to be solved urgently by the technical personnel in the field.
Disclosure of Invention
In order to solve the defects of the prior art, the hydrophilic polyvinylidene fluoride nanofiltration membrane and the preparation method thereof are different from the existing physical cleaning mode, and the research of the invention improves the property of the polyvinylidene fluoride membrane by combining the polyvinylidene fluoride membrane with a hydrophilic polymer to improve the membrane cleaning efficiency and reduce the nanofiltration membrane pollution.
The invention aims to provide a hydrophilic polyvinylidene fluoride nanofiltration membrane.
The invention also aims to provide the hydrophilic polyvinylidene fluoride nanofiltration membrane and a preparation method thereof.
The above purpose of the invention is realized by the following technical scheme:
the invention provides a hydrophilic polyvinylidene fluoride nanofiltration membrane, which comprises a polyvinylidene fluoride-based membrane body and a hydrophilic polymer polymerized on the polyvinylidene fluoride-based membrane body; the structural formula of the hydrophilic polymer is shown as the formula (I):
Figure BDA0002540055650000021
wherein n is 300-.
The invention also provides a preparation method of the hydrophilic polyvinylidene fluoride nanofiltration membrane, which comprises the following steps:
step 1: firstly, placing a polyvinyl alcohol solution in a water bath kettle, and stirring at the rotation speed of 300-; then adding a potassium hydroxide solution into the polyvinyl alcohol solution, dropwise adding epoxy chloroalkane, keeping the temperature at 100-102 ℃, reacting for 2-3h after the pH value is stabilized to 10-11, and adjusting the pH value of the system to 7 by using a hydrochloric acid solution to prepare ECIP modified PVA with the mass fraction of 20-40%;
step 2: adding aniline into the ECIP modified PVA to perform a crosslinking reaction for 4-5h at the temperature of 100-105 ℃, wherein the solid content ratio of the ECIP modified PVA to the aniline is (1:2) - (2:1), the structural formula of the hydrophilic polymer in the modified ECIP/PVA/PANI dispersion liquid is shown as the formula (I),
and step 3: after the reaction is finished, placing the reactant in an ice-water bath at 0 ℃, adding a hydrochloric acid solution to adjust the pH value of the reactant to 3-4, then dropwise adding ammonium persulfate to react for 24 hours to obtain a dispersion liquid, filling the dispersion liquid into a dialysis bag, dialyzing with distilled water to remove inorganic salts and low molecular compounds to obtain the modified ECIP/PVA/PANI dispersion liquid, wherein,
and 4, step 4: putting the modified ECIP/PVA/PANI dispersion liquid into a beaker, putting the beaker into an ice water bath, vertically putting a cleaned substrate fixed with a polyvinylidene fluoride base film into the beaker, and stirring while adding an ammonium persulfate solution after the temperature is constant at 0 ℃;
and 5: and after the reaction is finished, washing away the reaction solution and the polymer particles adhered to the surface of the polyvinylidene fluoride base membrane, and airing to obtain the hydrophilic polyvinylidene fluoride nanofiltration membrane.
Preferably, the mass fraction of the ECIP-modified PVA is 25%.
Preferably, the molar ratio of the ECIP modified PVA to the aniline is 1: 1.5.
Preferably, the reaction temperature in step 1 is 100 ℃.
Preferably, the reaction time of step 1 is 2 h.
Preferably, the temperature of the crosslinking reaction in step 2 is 100 ℃.
Preferably, the time of the crosslinking reaction in step 2 is 4 h.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention takes nucleophilic substitution reaction as a mechanism, firstly takes epoxy chloropropane as a modifier, successfully introduces epoxy groups on the surface of PVA (polyvinyl alcohol), and increases the reactivity of PVA. And a large amount of active hydroxyl groups are arranged on a molecular chain of the PVA, and the hydroxyl groups are replaced by epoxy groups when the hydroxyl groups and aniline are subjected to chemical reaction, so that a large amount of oxygen groups and hydroxyl groups are gathered on the surface of aniline (PANI) molecules in the finally synthesized ECIP/PVA/PANI dispersion liquid, and the hydrophilicity of PANI is improved.
After the contact angle test, the prepared hydrophilic PVDF nanofiltration membrane shows that the contact angles of the hydrophilic polymer are smaller than 90 degrees due to the deposition on the surface of the PVDF substrate, and the hydrophilicity is greatly improved, so that the pollution of the PVDF nanofiltration membrane is reduced. In addition, as the hydroxyl is replaced by the epoxy group, aniline molecules can react with the epoxy group on an active site, so that polymerization among the aniline molecules is prevented, the stability inside the ECIP/PVA/PANI dispersion liquid is ensured, and the durability of hydrophilic modification can be further improved when the ECIP/PVA/PANI is polymerized on a polyvinylidene fluoride nanofiltration membrane.
Drawings
FIG. 1 is an infrared spectrum of a hydrophilic polymer prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
Step 1: firstly, polyvinyl alcohol solution with the solid content of 20 percent is added into a 250ml three-neck flask and placed into a water bath kettle with the controllable temperature, the temperature is set to be 100 ℃, and the stirring is carried out at the rotating speed of 300 r/min. Then adding a potassium hydroxide (KOH) solution into the reaction system, adjusting the pH of the system to 10, dropwise adding Epoxy Chloroalkane (ECIP) (10mmol, 1g), detecting that the pH is kept constant at 10, reacting for 2 hours after the pH is stabilized, adjusting the pH of the system to 7 by using a diluted hydrochloric acid solution, and preparing the ECIP modified PVA with the mass fraction of 20%, wherein the chemical equation of the reaction is as follows:
Figure BDA0002540055650000051
wherein n is 100-.
Step 2: keeping the reaction temperature at 100 ℃, adding aniline with the solid content of 40% into the system, and reacting for 4 hours. Then placing the system in an ice-water bath at 0 ℃, adding a hydrochloric acid solution to adjust the pH value of the system to 3-4, then dropwise adding an Ammonium Persulfate (APS) solution (DMSO is used as a solvent), reacting for 24 hours, then finishing, filling the obtained dispersion into a dialysis bag, dialyzing for 12 hours with distilled water, and removing inorganic salts and low-molecular compounds to obtain the modified ECIP/PVA/PANI dispersion, wherein the chemical equation of the reaction is as follows:
Figure BDA0002540055650000052
wherein n is 300-.
And step 3: and putting the beaker containing the ECIP/PVA/PANI dispersion liquid into an ice water bath, and vertically putting the substrate which is cleaned by deionized water and fixed with the polyvinylidene fluoride basal membrane into the beaker. The magnetic stirrer was started at a constant temperature of about 0 ℃ and the addition of ammonium persulfate solution was started. And after the reaction is finished, washing away the reaction solution and the polymer particles adhered to the surface of the polyvinylidene fluoride base membrane by using deionized water. And (3) soaking the washed composite membrane in 2mol/L hydrochloric acid for a period of time to ensure that the composite membrane is completely doped, and airing to obtain the ECIP/PVA/PANI-PVDF composite nanofiltration membrane.
In this example, the mass fraction of the ECIP-modified PVA was 20%, and the content ratio of the ECIP-modified PVA to the aniline was 1: 2.
Example 2
The present example is different from example 1 in that the ECIP-modified PVA was 25% by mass.
Example 3
The present example is different from example 1 in that the ECIP-modified PVA was 30% by mass.
Example 4
The present example is different from example 1 in that the ECIP-modified PVA was 40% by mass.
Example 5
The difference between this example and example 1 is that the ECIP modified PVA to aniline content ratio is 1: 1.5.
Example 6
This example differs from example 1 in that the ECIP modified PVA to aniline content ratio was 1:1.
Example 7
This example differs from example 1 in that the ratio of ECIP modified PVA to aniline content is 2: 1.
Comparative example 1
Step 1: adding a polyvinyl alcohol solution with the solid content of 20% into a 250ml three-neck flask, placing the three-neck flask into a temperature-controllable water bath, keeping the reaction temperature at 100 ℃, adding aniline with the solid content of 40% into the system, and reacting for 4 hours. And then placing the system in an ice-water bath at 0 ℃, adding a hydrochloric acid solution to adjust the pH value of the system to 3-4, then dropwise adding Ammonium Persulfate (APS), reacting for 24 hours, completing the reaction, filling the obtained dispersion into a dialysis bag, dialyzing for 12 hours by using distilled water, and removing inorganic salts and low-molecular compounds to obtain the PVA/PANI mixed solution.
Step 2: putting a beaker filled with PVA/PANI mixed solution into an ice water bath, vertically putting a substrate which is cleaned by deionized water and is fixed with a polyvinylidene fluoride basal membrane into the beaker, and stirring while adding ammonium persulfate solution after the temperature is constant at 0 ℃. And after the reaction is finished, washing away the reaction solution adhered to the surface of the polyvinylidene fluoride base membrane by using deionized water, putting the washed composite membrane into 2mol/L hydrochloric acid for soaking for a period of time to ensure that the composite membrane is completely doped, and airing to obtain the PVA/PANI-PVDF composite nanofiltration membrane.
Comparative example 2
Adding a hydrochloric acid solution into aniline with a solid content of 40% to adjust the pH value of a reaction system to 3-4, then placing the system in an ice-water bath at 0 ℃, dropwise adding Ammonium Persulfate (APS), reacting for 24 hours, then completing, filling the obtained dispersion liquid into a dialysis bag, dialyzing for 12 hours with distilled water, and removing inorganic salts and low-molecular compounds to obtain the PANI mixed solution.
Step 2: and (3) putting the beaker filled with the PANI mixed solution into an ice water bath, vertically putting the substrate which is cleaned by deionized water and is fixed with the polyvinylidene fluoride basal membrane into the beaker, and stirring while adding ammonium persulfate solution after the temperature is constant at 0 ℃. And after the reaction is finished, washing away the reaction solution adhered to the surface of the polyvinylidene fluoride base membrane by using deionized water, putting the washed composite membrane into 2mol/L hydrochloric acid for soaking for a period of time to ensure that the composite membrane is completely doped, and airing to obtain the PANI-PVDF composite nanofiltration membrane.
In summary, FIG. 1 is a graph of the infrared spectrum of the ECIP/ECIP/PANI polymer of the present invention at about 1644cm as shown in FIG. 1-1And 1579cm－1The peak at (A) is a stretching vibration peak of C ═ O bond in PVA. Another characteristic peak of PVA is 976cm-1Left and right, due to the C-O bond. At 3352cm－1The broad peaks at the left and right are due to stretching vibration of-O-H bond and N-H in ECIP/PVA/PANI film2The superposition of the stretching vibrations of the keys. It can be seen that PANI was successfully attached to the ECIP molecular chain via ECIP.
The particle size data of the dispersions of inventive examples 1 to 4 and comparative example 1 are shown in table 1:
TABLE 1 results of particle size comparison of dispersions of examples 1 to 4 and comparative example 1
Figure BDA0002540055650000071
As can be seen from table 1, when no ECIP is added, comparative example 1 only reacts polyvinyl alcohol with aniline, but does not react epoxy group with aniline, resulting in a large reduction of reactive active sites, and a large amount of aniline polymerizes on limited active sites, resulting in an uneven particle size distribution of the dispersion, which further destabilizes the dispersion system, and reduces the durability of hydrophilic modification of the polyvinylidene fluoride nanofiltration membrane.
And in the embodiments 1-4, because the ECIP is added, the ECIP firstly forms a polymer with a large number of epoxy groups with the PVA, and the aniline further reacts with the epoxy groups with a large number of active sites, so that the self-polymerization frequency of the aniline is reduced, the formed ECIP/PVA/PANI dispersion liquid is more and more stable, and the durability of the ECIP/PVA/PANI-PVDF nanofiltration membrane hydrophilic modification is effectively improved. Wherein, when the mass fraction of the ECIP modified PVA is 25%, the particle size of the dispersion liquid is the smallest, which represents that the dispersion liquid system is the most stable.
Wherein, the contact angle test data of inventive example 1, examples 5-7 and comparative example 2 are shown in table 2:
table 2 contact angle test results of example 1, examples 5 to 7 and comparative example 2
Figure BDA0002540055650000081
As can be seen from Table 2, the ECIP/ECIP/PANI polymers of examples 1 and 5-7 of the present invention have contact angles less than 90 degrees and good hydrophilicity. When the solid content ratio of the polymer ECIP/PVA to the aniline is 1:1.5, the contact angle is at least 43.5 degrees, which shows that the hydrophilic effect of the polyvinylidene fluoride nanofiltration membrane is optimal. And in the comparative example 2, the contact angle is larger than 90 degrees when no ECIP/PVA is added, which represents that the prepared polyvinylidene fluoride nanofiltration membrane has hydrophobicity.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. A hydrophilic polyvinylidene fluoride nanofiltration membrane is characterized by comprising a polyvinylidene fluoride-based membrane body and a hydrophilic polymer polymerized on the polyvinylidene fluoride-based membrane body; the structural formula of the hydrophilic polymer is shown as the formula (I):
Figure FDA0002540055640000011
wherein n is 300-.
2. The preparation method of the hydrophilic polyvinylidene fluoride nanofiltration membrane is characterized by comprising the following steps:
step 1: firstly, polyvinyl alcohol is placed in a water bath kettle and stirred at the rotating speed of 300-; then adding a potassium hydroxide solution into the polyvinyl alcohol solution, dropwise adding epoxy chloroalkane, keeping the temperature at 100-102 ℃, reacting for 2-3h after the pH value is stabilized to 10-11, and adjusting the pH value of the system to 7 by using a hydrochloric acid solution to prepare ECIP modified PVA with the mass fraction of 20-40%;
step 2: adding aniline into the ECIP modified PVA to perform a crosslinking reaction for 4-5h at the temperature of 100-105 ℃, wherein the solid content ratio of the ECIP modified PVA to the aniline is (1:2) - (2:1), the structural formula of the hydrophilic polymer in the modified ECIP/PVA/PANI dispersion liquid is shown as the formula (I),
and step 3: after the reaction is finished, placing the reactant in an ice-water bath at 0 ℃, adding a hydrochloric acid solution to adjust the pH value of the reactant to 3-4, then dropwise adding ammonium persulfate to react for 24 hours to obtain a dispersion liquid, filling the dispersion liquid into a dialysis bag, dialyzing with distilled water to remove inorganic salts and low molecular compounds to obtain the modified ECIP/PVA/PANI dispersion liquid, wherein,
and 4, step 4: putting the modified ECIP/PVA/PANI dispersion liquid into a beaker, putting the beaker into an ice water bath, vertically putting a cleaned substrate fixed with a polyvinylidene fluoride base film into the beaker, and stirring while adding an ammonium persulfate solution after the temperature is constant at 0 ℃;
and 5: and after the reaction is finished, washing away the reaction solution and the polymer particles adhered to the surface of the polyvinylidene fluoride base membrane, and airing to obtain the hydrophilic polyvinylidene fluoride nanofiltration membrane.
3. The method for preparing the hydrophilic polyvinylidene fluoride nanofiltration membrane of claim 2, wherein the ECIP modified PVA is 25% by mass.
4. The preparation method of the hydrophilic polyvinylidene fluoride nanofiltration membrane of claim 2, wherein the molar ratio of the ECIP modified PVA to the aniline is 1: 1.5.
5. The method for preparing the hydrophilic polyvinylidene fluoride nanofiltration membrane according to claim 2, wherein the reaction temperature in the step 1 is 100 ℃.
6. The preparation method of the hydrophilic polyvinylidene fluoride nanofiltration membrane as claimed in claim 2, wherein the reaction time in the step 1 is 2 hours.
7. The method for preparing the hydrophilic polyvinylidene fluoride nanofiltration membrane according to claim 2, wherein the temperature of the crosslinking reaction in the step 2 is 100 ℃.
8. The method for preparing the hydrophilic polyvinylidene fluoride nanofiltration membrane according to claim 2, wherein the time of the crosslinking reaction in the step 2 is 4 hours.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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