CN115414801B - Method for preparing durable hydrophilic polytetrafluoroethylene separation membrane by one-step method - Google Patents

Method for preparing durable hydrophilic polytetrafluoroethylene separation membrane by one-step method Download PDF

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CN115414801B
CN115414801B CN202211062509.XA CN202211062509A CN115414801B CN 115414801 B CN115414801 B CN 115414801B CN 202211062509 A CN202211062509 A CN 202211062509A CN 115414801 B CN115414801 B CN 115414801B
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separation membrane
preparing
polytetrafluoroethylene
mixed solution
polytetrafluoroethylene separation
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CN115414801A (en
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朱利平
张梦晓
王建宇
方传杰
王霄鹤
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Shaoxing Research Institute Of Zhejiang University
Zhejiang University ZJU
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Shaoxing Research Institute Of Zhejiang University
Zhejiang University ZJU
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/30Polyalkenyl halides
    • B01D71/32Polyalkenyl halides containing fluorine atoms
    • B01D71/36Polytetrafluoroethene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079Manufacture of membranes comprising organic and inorganic components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02Inorganic material
    • B01D71/024Oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/36Hydrophilic membranes

Abstract

The invention provides a preparation method of a hydrophilic polytetrafluoroethylene separation membrane, which belongs to the technical field of membranes and comprises the following steps: (1) preparing an organic molecular solution in a reactor; (2) Adding inorganic particles into the organic molecule solution to form a mixed solution; (3) Soaking a polytetrafluoroethylene separation membrane in the mixed solution, and uniformly distributing the mixed solution on the surface of the polymer membrane and the pore canal of the polymer membrane by adopting ultrasonic, vibration or stirring modes; (4) Taking out the soaked polytetrafluoroethylene separation membrane from the mixed solution, and drying the polytetrafluoroethylene separation membrane; (5) And (3) sintering the dried polytetrafluoroethylene separation membrane at a high temperature. The method can be applied to preparing the durable hydrophilic polytetrafluoroethylene separation membrane, the water contact angle of the separation membrane prepared by the method can be reduced to 0 ℃ in 10 seconds, the flux of the separation membrane can be increased to 5-40 times of that of the original membrane, and the porosity is increased by not more than 10%. And the reaction conditions are simple and easy to control, are easy to amplify, are suitable for large-scale production, and have good application prospects.

Description

Method for preparing durable hydrophilic polytetrafluoroethylene separation membrane by one-step method
Technical Field
The invention relates to the technical field of hydrophilization modification of polytetrafluoroethylene separation membranes, in particular to a method for preparing a durable hydrophilic polytetrafluoroethylene separation membrane by a one-step method.
Background
The membrane separation technology has the advantages of low energy consumption, convenient operation and the like, and is widely applied to chemical industry, medicine, environment and the like in which material separation is required. The polytetrafluoroethylene separation membrane has been spotlighted because of its extremely stable chemical properties, corrosion resistance, tensile strength and the like, and has been widely applied to the field of sewage treatment in extreme working condition environments such as landfill leachate, quilting, weaving, electroplating and the like. But the surface presents extremely strong hydrophobicity due to extremely small specific surface energy, so that the separation power consumption in the using process is increased and a certain application scene is limited.
Therefore, the preparation of the polytetrafluoroethylene separation membrane which has high strength, high chemical resistance and hydrophilicity has important practical significance, and the current preparation of the hydrophilic separation membrane mainly comprises the steps of using hydrophilic organic polymers in the early stage, blending hydrophilic oxide particles with polytetrafluoroethylene resin, stretching, sintering, coating with a later surfactant and the like. In the two methods, the former process is too long and cannot greatly reduce the surface water contact angle due to the influence of the doping amount; the latter has the disadvantage that the coated surfactant is easily detached. In view of the above problems, a solution is proposed below.
Disclosure of Invention
The invention aims to provide a method for preparing a durable hydrophilic polytetrafluoroethylene separation membrane by a one-step method, which has the advantages of shorter process flow and durable hydrophilic polytetrafluoroethylene separation membrane process, so as to meet the requirements of the current separation field and the expansion of applicability, thereby saving the separation power consumption and creating greater social benefits.
The invention provides a method for preparing a durable hydrophilic polytetrafluoroethylene separation membrane by a one-step method. The method mainly utilizes the good chemical resistance and hydrophilicity of inorganic particles and the difference of molecular acting force among organic molecules, inorganic particles and polytetrafluoroethylene separation membranes, so that the organic molecules and inorganic particles in organic-inorganic mixed solution are deposited on the surface of the polytetrafluoroethylene separation membranes and inside the pore channels in an order of 'before and after', and meanwhile, the combination between the organic molecules and the inorganic particles is more stable through heat treatment at a certain temperature in the reaction process. The polytetrafluoroethylene separation membrane prepared by the method has excellent hydrophilic performance, and the water permeability flux can be improved by 5-40 times. The method is simple in preparation and easy to amplify, and has great popularization value
The technical aim of the invention is realized by the following technical scheme:
a method for preparing a durable hydrophilic polytetrafluoroethylene separation membrane by a one-step method, comprising the following steps:
step (1): preparing organic molecule solution in a reactor by using solvent and organic molecules,
step (2): adding inorganic particles into the organic molecule solution to form a mixed solution, and uniformly stirring the mixed solution;
step (3): soaking a polytetrafluoroethylene separation membrane in the mixed solution, uniformly distributing the mixed solution on the surface of the polymer membrane and in the pore canal of the polymer membrane in an ultrasonic, oscillating or stirring mode, wherein the soaking temperature is 0-99 ℃ and the soaking time is 0-48 hours;
step (4): taking out the soaked polytetrafluoroethylene separating membrane from the mixed solution, drying the polytetrafluoroethylene separating membrane at the drying temperature of 30-100 ℃,
step (5): and (3) sintering the dried polytetrafluoroethylene separation membrane at a high temperature of 200-310 ℃ to obtain the durable hydrophilic polytetrafluoroethylene separation membrane.
The solvent in the step (1) is acetone, diethyl ether, tetrahydrofuran, ethanol or a mixture of a plurality of solvents;
the organic molecules in the step (1) are perfluoro octyl silane coupling agent, perfluoro polyacrylic acid, tween 80, sodium carboxymethyl cellulose or a mixture of the perfluoro octyl silane coupling agent, the perfluoro polyacrylic acid, tween 80 and sodium carboxymethyl cellulose, and the mass percentage concentration of the organic molecules in the organic molecule solution is 0.001-10%. Preferably 0.1-8%, more preferably 1-5%, most preferably 2-4%;
the inorganic particles in the step (2) are alumina particles, titanium dioxide particles and silicon dioxide particles, and the particle size of the particles is 1-50 nanometers; the mass percentage concentration of the inorganic particles in the mixed solution is 0.05-10%, preferably 0.1-8%, more preferably 0.5-2%;
the polytetrafluoroethylene separation membrane in the step (3) is a polytetrafluoroethylene flat membrane or a polytetrafluoroethylene hollow fiber membrane, and the pore diameter of the membrane is 0.1um-2um. The soaking temperature is 0-99 ℃ and the soaking time is 0-48 hours; preferably 20-70 deg.c, and soaking time is 10-30 hr.
The method for preparing the durable hydrophilic polytetrafluoroethylene separation membrane by the one-step method is characterized in that the drying temperature in the step (4) is 30-100 ℃; preferably 30-60 ℃ and the drying time is 5-60 minutes.
The method for preparing the durable hydrophilic polytetrafluoroethylene separation membrane by the one-step method is characterized in that the sintering temperature in the step (5) is 200-310 ℃, preferably 200-270 ℃ and the sintering time is 0.5-30 minutes
The beneficial effects of the invention are as follows: in the invention, the concentration of organic molecules and inorganic particles in the organic-inorganic mixed solution, the soaking temperature, the soaking time and the drying temperature have direct influence on the final performance of the polytetrafluoroethylene separation membrane. The invention mainly uses the difference of adsorption energy among organic molecules, inorganic suspension and polytetrafluoroethylene separation membranes, so that the structure of the prepared hydrophilic separation membrane is subject to the adsorption sequence of separation membrane fibers, organic molecules and inorganic particles, and meanwhile, the organic molecules also carry active sites capable of depositing inorganic particles, and the interaction force between the organic molecules and the inorganic particles is enhanced. Therefore, the concentration, soaking temperature and soaking time of the organic molecules and inorganic particles directly influence the statistical distribution relation of the components on the surface of the membrane, and the statistical distribution influences the hydrophilicity of the prepared separation membrane. The drying temperature directly influences the acting force mode and firmness between the organic molecules and the inorganic particles, and meanwhile, the inorganic particles also determine the hydrophilicity and firmness of the prepared separation membrane.
The method for preparing the durable hydrophilic polytetrafluoroethylene separation membrane by the one-step method is used for the polytetrafluoroethylene separation membrane. The hydrophilic angle of the separation membrane prepared by the method can be reduced to 0 degree within 10 seconds, the water flux is improved by 5-40 times, and the method is simple in process, easy to amplify and has great popularization value.
Drawings
FIG. 1 is a schematic illustration of the preparation of a flat sheet membrane according to the present invention;
FIG. 2 is a schematic diagram showing the adsorption sequence of the fiber-organic molecule-inorganic particle of the fiber separation membrane of the present invention;
FIG. 3 is a comparison of the front and back flux of an example of the present invention for preparing a hydrophilic polytetrafluoroethylene separation membrane;
FIG. 4 is a comparison of water contact angles before and after the preparation of hydrophilic polytetrafluoroethylene separation membranes in accordance with examples of the present invention.
Detailed Description
The present invention will now be described in detail and fully with reference to the following specific embodiments, it being apparent that the embodiments described are only some, but not all, of the embodiments of the invention. Given the examples of the present invention, all other embodiments that a person of ordinary skill in the art could achieve without the inventive effort are within the scope of the present invention.
Example 1
(1) Preparing a mixed solution of 2% of perfluorinated polyacrylic acid, 48% of acetone and 48% of water in percentage by mass;
(2) Dropwise adding 2% titanium dioxide suspended particles into the mixed solution, and uniformly stirring;
(3) Soaking the polytetrafluoroethylene separation membrane in the mixed solution in the step (2) for 24 hours at 30 ℃;
(4) Taking out the polytetrafluoroethylene separation membrane, and drying for 10 minutes at 60 ℃;
(5) And sintering the dried polytetrafluoroethylene separation membrane at 250 ℃ for 3 minutes. Thus obtaining the hydrophilic polytetrafluoroethylene separation membrane.
Example 2
(1) Preparing a mixed solution of 1% of perfluorooctyl silane coupling agent, 1% of perfluoropolyacrylic acid, 49% of ethanol and 49% of water in percentage by mass;
(2) Dropwise adding 2% silicon dioxide suspended particles into the mixed solution, and uniformly stirring;
(3) Soaking the polytetrafluoroethylene separation membrane in the mixed solution in the step (2) for 24 hours at 30 ℃;
(4) Taking out the polytetrafluoroethylene separation membrane, and drying for 3 minutes at 60 ℃;
(5) And sintering the dried polytetrafluoroethylene separation membrane at 250 ℃ for 5 minutes. Thus obtaining the hydrophilic polytetrafluoroethylene separation membrane.
Example 3
(1) Preparing a mixed solution of 1% of perfluorooctyl silane coupling agent, 1% of Tween 80, 60% of acetone and 38% of water in percentage by mass;
(2) Dropwise adding 2% titanium dioxide suspended particles into the mixed solution, and uniformly stirring;
(3) Soaking the polytetrafluoroethylene separation membrane in the mixed solution in the step (2) for 24 hours at 30 ℃;
(4) Taking out the polytetrafluoroethylene separation membrane, and drying for 10 minutes at 40 ℃;
(5) And sintering the dried polytetrafluoroethylene separation membrane at 270 ℃ for 1.5 minutes. Thus obtaining the hydrophilic polytetrafluoroethylene separation membrane.
Example 4
(1) Preparing a mixed solution of 1% of perfluorooctyl silane coupling agent, 1% of sodium carboxymethyl cellulose, 48% of ethanol and 48% of water in percentage by mass;
(2) Dropwise adding 2% titanium dioxide suspended particles into the mixed solution, and uniformly stirring;
(3) Soaking the polytetrafluoroethylene separation membrane in the mixed solution in the step (2) for 24 hours at 30 ℃;
(4) Taking out the polytetrafluoroethylene separation membrane, and drying for 5 minutes at 60 ℃;
(5) And sintering the dried polytetrafluoroethylene separation membrane at 250 ℃ for 3 minutes. Thus obtaining the hydrophilic polytetrafluoroethylene separation membrane.
The following film performance tests were performed on the above examples, and the test results showed that:
the hydrophilic polytetrafluoroethylene separation membranes prepared in examples 1-4 have excellent hydrophilic performance, and the water flux can be improved by 5-40 times. Taking polytetrafluoroethylene hollow fiber membranes as an example, water flux data and contact angle data before and after modification are shown in fig. 3 and 4, respectively. In FIG. 3, the water flux of the polytetrafluoroethylene hollow fiber membrane before modification is 135L/(m) 2 hbar), modificationThe post-water flux is 3750L/(m) 2 hbar) is 27.8 times before modification, the water contact angle of the polytetrafluoroethylene hollow fiber separation membrane before modification is about 120 degrees, and the water contact angle can reach 0 degrees within 8 seconds after modification, which shows that the modification effect is obvious.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (10)

1. A method for preparing a durable hydrophilic polytetrafluoroethylene separation membrane by a one-step method, which is characterized by comprising the following steps:
step (1): preparing organic molecule solution in a reactor by using solvent and organic molecules,
step (2): adding inorganic particles into the organic molecule solution to form a mixed solution, and uniformly stirring the mixed solution;
step (3): soaking a polytetrafluoroethylene separation membrane in the mixed solution, uniformly distributing the mixed solution on the surface of the polymer membrane and in the pore canal of the polymer membrane in an ultrasonic, oscillating or stirring mode, wherein the soaking temperature is 0-99 ℃ and the soaking time is 0-48 hours;
step (4): taking out the soaked polytetrafluoroethylene separation membrane from the mixed solution, and drying the polytetrafluoroethylene separation membrane at the drying temperature of 30-100 ℃;
step (5): sintering the dried polytetrafluoroethylene separation membrane at a high temperature of 200-310 ℃ to obtain a durable hydrophilic polytetrafluoroethylene separation membrane;
the solvent in the step (1) is acetone, diethyl ether, tetrahydrofuran, ethanol or a mixture of a plurality of solvents;
the organic molecules in the step (1) are perfluorooctyl silane coupling agent, perfluoropolyacrylic acid, tween 80, sodium carboxymethyl cellulose or a mixture of the above, and the mass percentage concentration of the organic molecules in the organic molecule solution is 0.001-10%;
the inorganic particles in the step (2) are alumina particles, titanium dioxide particles and silicon dioxide particles, and the particle size of the particles is 1-50 nanometers; the mass percentage concentration of the inorganic particles in the mixed solution is 0.05-10%;
the polytetrafluoroethylene separation membrane in the step (3) is a polytetrafluoroethylene flat membrane or a polytetrafluoroethylene hollow fiber membrane, the pore diameter of the membrane is 0.1um-2um, the soaking temperature is 0-99 ℃, and the soaking time is 0-48 hours.
2. The method for preparing a durable hydrophilic polytetrafluoroethylene separation membrane according to claim 1, wherein the drying temperature in step (4) is 30-100 degrees celsius and the drying time is 5-60 minutes.
3. The method for preparing a durable hydrophilic polytetrafluoroethylene separation membrane according to claim 2, wherein the drying temperature in step (4) is preferably 30-60 degrees celsius, and the drying time is 5-60 minutes.
4. The method for preparing a durable hydrophilic polytetrafluoroethylene separation membrane according to claim 1, wherein the sintering temperature in step (5) is 200-310 degrees celsius and the sintering time is 0.5-30 minutes.
5. The method for preparing a durable hydrophilic polytetrafluoroethylene separation membrane according to claim 4, wherein the sintering temperature in step (5) is preferably 200-270 degrees celsius, and the sintering time is 0.5-30 minutes.
6. The method for preparing a durable hydrophilic polytetrafluoroethylene separation membrane according to claim 1, wherein the mass percentage concentration of organic molecules in said organic molecule solution in step (1) is preferably 1 to 5%.
7. The method for preparing a durable hydrophilic polytetrafluoroethylene separation membrane according to claim 6, wherein the concentration of organic molecules in said organic molecule solution in step (1) is more preferably 2 to 4% by mass.
8. The method for preparing a durable hydrophilic polytetrafluoroethylene separation membrane according to claim 1, wherein the mass percentage concentration of said inorganic particles in the mixed solution in step (2) is preferably 0.1 to 8%.
9. The method for preparing a durable hydrophilic polytetrafluoroethylene separation membrane according to claim 8, wherein the mass percentage concentration of said inorganic particles in the mixed solution in step (2) is more preferably 0.5 to 2%.
10. The method for preparing a durable hydrophilic polytetrafluoroethylene separation membrane according to claim 1, wherein the soaking temperature in step (3) is preferably 20-70 degrees celsius, and the soaking time is preferably 10-30 hours.
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CN115779768B (en) * 2023-02-01 2023-05-16 天津艾尔森生物科技有限公司 Filtering and stirring integrated essence production equipment
CN115779697B (en) * 2023-02-13 2023-06-06 天津海派特环保科技有限公司 Hydrophilic modification method of hollow fiber separation membrane

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140008113A (en) * 2012-07-10 2014-01-21 웅진케미칼 주식회사 Multilayer ptfe hollow fiber membrane having hydrophilicity and manufacturing method thereof
CN104001433A (en) * 2014-05-14 2014-08-27 浙江舒普氟材科技有限公司 Production process of hydrophilic polytetrafluoroethylene microporous film
CN104096489A (en) * 2013-12-24 2014-10-15 广州中国科学院先进技术研究所 Preparation method of inorganic-organic functional polytetrafluoroethylene microporous membrane
CN110523299A (en) * 2019-09-16 2019-12-03 德蓝水技术股份有限公司 A kind of preparation method of hydrophilic polyfluortetraethylemicroporous hollow-fibre membrane

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140008113A (en) * 2012-07-10 2014-01-21 웅진케미칼 주식회사 Multilayer ptfe hollow fiber membrane having hydrophilicity and manufacturing method thereof
CN104096489A (en) * 2013-12-24 2014-10-15 广州中国科学院先进技术研究所 Preparation method of inorganic-organic functional polytetrafluoroethylene microporous membrane
CN104001433A (en) * 2014-05-14 2014-08-27 浙江舒普氟材科技有限公司 Production process of hydrophilic polytetrafluoroethylene microporous film
CN110523299A (en) * 2019-09-16 2019-12-03 德蓝水技术股份有限公司 A kind of preparation method of hydrophilic polyfluortetraethylemicroporous hollow-fibre membrane

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PVA and CS cross-linking combined with in situ chimeric SiO2 nanoparticle adhesion to enhance the hydrophilicity and antibacterial properties of PTFE flat membranes;Chengcai Li et.al;RSC Advances(第9期);19205–19216 *

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