CN106268370A - Poly tetrafluoroethylene low temperature plasma hydrophilic modifying and timeliness modification processing method - Google Patents
Poly tetrafluoroethylene low temperature plasma hydrophilic modifying and timeliness modification processing method Download PDFInfo
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- CN106268370A CN106268370A CN201610753382.4A CN201610753382A CN106268370A CN 106268370 A CN106268370 A CN 106268370A CN 201610753382 A CN201610753382 A CN 201610753382A CN 106268370 A CN106268370 A CN 106268370A
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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
- B01D71/36—Polytetrafluoroethene
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- 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
- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
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- 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
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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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
- 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
- C08J2327/02—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
- C08J2327/12—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
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
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Abstract
The invention provides a kind of poly tetrafluoroethylene low temperature plasma hydrophilic modifying and timeliness modification processing method, the method comprises the following steps: pretreatment cleaning poly tetrafluoroethylene, and adds organic molecule using as hydrophilic group donor；Low-temperature plasma method etching poly tetrafluoroethylene grafting hydrophilic group.The method also includes: with modified Teflon film hydrophilic group as site, and graft polymers protection hydrophilic group also further enhances hydrophilic.
Description
Technical field
The invention belongs to PTFE (politef) membrane modifying field, be specifically related to the low-temperature plasma modified place of PTFE film
Reason and polymer grafting method.
Background technology
Membrance separation is widely used in water treatment field, has that energy consumption is low, automaticity is high, non-secondary pollution, can reclaim
The advantages such as recycling material.PTFE film is sufficiently stable, has good antiacid alkali, resistance to corrosion, but PTFE film has very
Strong hydrophobicity, the most permeable under conditions of pressurization 1MPa, therefore by suitable modification, improve the parent of PTFE film
Aqueous, is significant.
PTFE tradition method of modifying has: wet-chemical treatment method, i.e. naphthalene-sodium, ammonia-sodium solution facture, and this method is to utilize corruption
Erosion liquid removes the fluorine atom on PTFE surface and improves material surface activity, but this method has the disadvantage that: PTFE after (1) process
Surface is the most dimmed, blackening, affects material appearance；(2) after processing, the PTFE surface resistivity when high temperature declines, and exposes for a long time
In the sun, material adhesive property can seriously reduce；(3) processing procedure can produce substantial amounts of harmful waste liquid, serious environment pollution.
High-energy radiation graft modification is that gamma-rays, high-power electron beam and the ultraviolet light etc. produced by ionizing radiation irradiate polymer,
Producing active site at polymer surfaces, the graft copolymerization of trigger monomer, this method of modifying is the highest due to emittance, easily
Membrane structure is caused to destroy.
Plasma modification method utilizes the non-polymerization gases such as Ar more, and the free radical of generation is sent out with the oxygen in air or water
Raw reaction forms peroxide, can crosslink with function monomer such as acrylic acid further and be polymerized, and obtains hydrophilic surface.This
Method, the free radical of plasma exciatiaon is limited, and reacts formation peroxide with object and be divided into two stages and carry out, efficiency
Relatively low, and this method of modifying is mainly surface modification, limited to the modified effect in the middle of film layer.Although film surface can be improved
Hydrophilicity, but less to the water permeability improvement result of film.
Therefore, this area is in the urgent need to developing a kind of novel politef overcoming above-mentioned prior art defect
Membrane modifying method.
Summary of the invention
The invention provides poly tetrafluoroethylene low temperature plasma hydrophilic modifying and the timeliness modification of a kind of novelty
Method, thus solve problems of the prior art.
The invention provides a kind of poly tetrafluoroethylene low temperature plasma hydrophilic modifying and timeliness modification processing method, should
Method comprises the following steps:
Pretreatment cleaning poly tetrafluoroethylene, and add organic molecule using as hydrophilic group donor, including:
(1) poly tetrafluoroethylene is soaked in butanone supersound process, be dried under vacuum to butanone and thoroughly volatilize；
(2) treated poly tetrafluoroethylene is soaked in organic solvent and supersound process, then dry so that film table
Face is dried, so that organic solvent molecule is fully dispersed in poly tetrafluoroethylene surface and film layer, makees in subsequent treatment
For hydrophilic group donor；And
Low-temperature plasma method etching poly tetrafluoroethylene grafting hydrophilic group, including:
(3) pretreated poly tetrafluoroethylene is carried out Low Temperature Plasma Treating, wherein, process power be 1～
600W, the time is 0.1～3000s, and plasma air pressure is 1～1000 millitorrs, and temperature is 20-500 DEG C, and low temperature plasma etches
Politef strand produces active atoms of carbon, excites organic solvent molecule to produce hydrophilic active group simultaneously, thus poly-
It is grafted hydrophilic group, it is achieved poly tetrafluoroethylene surface and the hydrophilic modifying of film layer on tetrafluoroethene strand.
In one preferred embodiment, the method also includes: with modified Teflon film hydrophilic group as site,
Graft polymers protection hydrophilic group also further enhances hydrophilic, including:
(4) modified Teflon film is immersed in the aqueous solution treating grafted monomers, heating in water bath, and it is anti-to carry out grafting
Should；And
(5) washing except non-grafted organic monomer, vacuum drying preserves.
Another preferred embodiment in, in step (1), the power of supersound process is 0～200W, and temperature is 0
～50 DEG C, the time is 0.1-3 hour.
Another preferred embodiment in, in step (2), the time soaked in organic solvent is that 1-48 is little
Time；The power of supersound process is 0～200W, and temperature is 0～50 DEG C, and the time is 0-3 hour；Dry temperature and be 1-101 DEG C, dry
Time is 1-10 minute.
Another preferred embodiment in, in step (2), described organic solvent includes: methanol, formaldehyde, formic acid,
Ethanol, ethylene glycol, acetaldehyde, acetic acid, ethanedioic acid, propanol, isopropanol, propionic aldehyde, isopropyl aldehyde, propanoic acid, isopropyl acid and acrylic acid.
Another preferred embodiment in, in step (3), use reaction of low temperature plasma device carry out low temperature etc.
Gas ions processes, and processes sample and is close to pole plate, and polar plate spacing is 2.54～15.24cm.
Another preferred embodiment in, in step (3), use purity be 99.99% argon, nitrogen or
Combinations thereof gas produces plasma gas stream.
Another preferred embodiment in, in step (4), heating in water bath keep 10～100 DEG C, nitrogen protect
Under the conditions of carry out graft reaction 0.1～50 hours.
Another preferred embodiment in, in step (4), described in polymer monomer to be grafted include: acrylic acid,
Propenyl, butenoic acid, butenol, amylene, hexene, allene, butadiene, isoprene, hexatriene, butine, pentyne, hexin,
Heptyne, octyne, n-heptylacetylene, decine and undecyne.
Another preferred embodiment in, in step (5), use successively deionized water, NaOH solution and go from
Sub-water washes except non-grafted organic monomer.
Accompanying drawing explanation
Fig. 1 shows the PTFE film scanning electron microscope (SEM) photograph after the Low Temperature Plasma Treating according to the embodiment of the present application 1.
Fig. 2 shows PTFE former film water droplet contact angle test result.Figure it is seen that former film water droplet contact angle is bigger.
Fig. 3 shows the most preprocessed water droplet contact angle test result directly carrying out Low Temperature Plasma Treating sample.
From figure 3, it can be seen that even if former film is the most preprocessed, after Low Temperature Plasma Treating, water droplet contact angle is also obviously reduced.
Fig. 4 shows that PTFE film is after the inventive method pretreatment, through low temperature plasma according to the embodiment of the present application 2
Water droplet contact angle test result after process.
Fig. 5 shows water droplet contact angle test result after the graft polymers monomer according to the embodiment of the present application 3.
Fig. 6 shows that PTFE film is after the inventive method pretreatment, through low temperature plasma according to the embodiment of the present application 4
Infrared Characterization result after process.
Fig. 7 shows that (1# film is former film to membrane flux test result；2# film not pretreatment, direct Low Temperature Plasma Treating；
3# film pretreatment adds Low Temperature Plasma Treating；4# film is again through acrylic acid-grafted process after 3# film the same terms processes).From figure
7 it can be seen that former film (unmodified membrane) flux is minimum (being " 0 "), and modified flux significantly increases.Wherein, PTFE film is through pre-place
After reason, then film (3# film) flux carrying out Low Temperature Plasma Treating is maximum.
Fig. 8 shows according to the embodiment of the present application 5, and film surface contact angle is with the change of resting period, and wherein 1# film is pre-
Process adds Low Temperature Plasma Treating；2# film is after 1# film the same terms processes, then through acrylic acid-grafted process.The result of Fig. 8
Showing, after graft acrylic acid, the hydrophilic of PTFE Modified Membrane further enhances, and hydrophilic nmature keeps stable.
Detailed description of the invention
Present inventor is through extensively in-depth study, for the hydrophobicity that PTFE film in prior art is extremely strong,
And traditional plasma method of modifying can only be to the defect of PTFE film surface modification, it is proposed that a kind of organic solvent pretreatment
PTFE film low-temperature plasma method of modifying, by the preprocess method of the present invention, can be before any plasma treatment on film surface
With film layer loads organic molecule, in low temperature plasma atmosphere, these organic molecules are excited generation active group, with etc.
The free radical direct reaction produced in gas ions engages, and reaches the purpose of grafting active group in the middle of film surface with film layer；So
Afterwards by graft polymers monomer, form hydrophilic polymer protective layer on surface, improve modified stable.
The invention provides a kind of poly tetrafluoroethylene low temperature plasma hydrophilic modifying and timeliness modification processing method, should
Method comprises the following steps:
The first step: butanone soaks supersound process PTFE film, is dried under vacuum to butanone and thoroughly volatilizees, removes membrane removal surface and film layer
In impurity；
Second step: with organic solvent soak, supersound process PTFE film, and dry, make film surface substantially dry；By pre-place
Reason, makes that organic solvent molecule is fully dispersed, loads to PTFE film surface with film layer, supply as hydrophilic group in subsequent treatment
Body；
3rd step: adjust suitable power, plasma gas flow amount, polar plate spacing, process time, by pretreated
PTFE film is placed in reaction of low temperature plasma device process, and low temperature plasma etching PTFE strand produces active atoms of carbon,
Excite organic solvent molecule to produce hydrophilic active group simultaneously, thus on PTFE strand, be grafted hydrophilic group, it is achieved
PTFE film surface and film layer hydrophilic modifying；
4th step: modified PTFE film is immersed in the certain density aqueous solution treating grafted monomers, heating in water bath,
Under nitrogen protective condition, with hydrophilic group as site, it is grafted organic polymer；
5th step: remove non-grafted organic monomer, vacuum drying, the sample after preservation process.
In the method for the invention, in the first step, the power of supersound process is 0～200W, and temperature is 0～50 DEG C, time
Between be 0.1-3 hour, preferably 2 hours.
In the method for the invention, in second step, described organic solvent is methanol (CH4O), formaldehyde (CH3O), formic acid
(CH2O2), ethanol (C2H6O), ethylene glycol (C2H6O2), acetaldehyde (C2H5O), acetic acid (C2H4O2), ethanedioic acid (C2H2O4), propanol
(C3H8O), isopropanol, propionic aldehyde (C3H6O), isopropyl aldehyde, propanoic acid (C3H6O2), isopropyl acid, various alcohols, aldehydes and the acid such as acrylic acid
Class I liquid I, or their mixing liquid.
In the method for the invention, in second step, the time soaked in organic solvent is 1-48 hour, and preferably 24 is little
Time；The power of supersound process is 0～200W, and temperature is 0～50 DEG C, and the time is 0-3 hour；Dry temperature and be 1-101 DEG C, preferably
30 DEG C, drying time is 1-10 minute.
In the method for the invention, in the third step, the plasma discharge power of employing is 1～600W, plasma (orifice) gas
Body flow is 1～1000 millitorrs, and the process time is 0.1～3000s, and temperature is 20-500 DEG C, polar plate spacing be 2.54～
15.24cm。
In the method for the invention, in the third step, argon, nitrogen or their group using purity to be 99.99%
Close gas and produce plasma atmosphere.
In the method for the invention, in the 4th step, described in polymer monomer to be grafted be acrylic acid (C3H4O2), propylene
Alcohol (C3H5O), butenoic acid (C4H6O2), butenol (C4H7O), amylene (C5H10), hexene (C6H12), allene (C3H4), butadiene
(C4H6), isoprene (C5H8), hexatriene (C6H8), butine (C4H6), pentyne (C5H8), hexin (C6H10), heptyne (C7H12)、
Octyne (C8H14), n-heptylacetylene (C9H16), decine (C10H18), undecyne (C11H20) etc. various alkene, alkene alcohol, alkene aldehyde, alkene
Acid, alkynes, alkynes alcohol, alkynes aldehyde and alkynes acid solution body, or their mixing liquid.
In the method for the invention, in the 4th step, heating in water bath keeps 10～100 DEG C, and graft reaction 0.1～50 is little
Time.
In the method for the invention, in the 5th step, remove with deionized water, NaOH solution, deionized water rinsing successively
Non-grafted organic monomer.
Main advantages of the present invention are:
The present invention, compared with tradition grafting method, has the advantage that
1, technological process is simple, and controllability is strong, environmental friendliness；
2, Cement Composite Treated by Plasma generation free radical produces with active group and grafting is carried out simultaneously, and graft reaction efficiency is high；
3, active group all can be grafted in film surface with film layer, improves film surface and the hydrophilic in film layer, improves thoroughly
Aqueous energy；
4, after graft polymers monomer, hydrophilic modifying effect improves and more stable further.
Embodiment
The present invention is expanded on further below in conjunction with specific embodiment.It should be appreciated, however, that these embodiments are only used for
The bright present invention and be not meant to limit the scope of the invention.The test method of unreceipted actual conditions in the following example, generally
According to normal condition, or according to the condition proposed by manufacturer.Except as otherwise noted, all of percentage ratio and number are by weight
Meter.
Embodiment 1:
Processing step:
Former for PTFE membrane sample soaks in butanone ultrasonic (power 100W, temperature 30 DEG C) process 2 hours, be dried under vacuum to
Acetone thoroughly volatilizees, then immersion treatment 24 hours in methanol solution, and ultrasonic (power 100W, temperature 30 DEG C) processes 2 hours,
Under the conditions of 30 DEG C, dry 6min, make film surface substantially dry.Arranging reaction of low temperature plasma device polar plate spacing is 5.08cm,
Discharge power is 150W, N2Plasma flow is 100 millitorrs, processes sample 300s.
Experimental result:
The electron scanning micrograph of treated sample is as shown in Figure 1.It will be seen from figure 1 that Cement Composite Treated by Plasma
After, PTFE fiber becomes loose, and fiber aspect interlocks, and membrane aperture slightly increases, and has relatively multifilament side chain to produce.
Embodiment 2:
Processing step:
Former for PTFE membrane sample soaks in butanone ultrasonic (power 170W, temperature 40 DEG C) process 1 hour, be dried under vacuum to
Acetone thoroughly volatilizees, then immersion treatment 30 hours in methanol solution, and ultrasonic (power 150W, temperature 30 DEG C) processes 2 hours,
Under the conditions of 30 DEG C, dry 5min, make film surface substantially dry.Arranging reaction of low temperature plasma device polar plate spacing is 5.08cm,
Discharge power is 100W, N2Plasma flow is 100 millitorrs, processes sample 700s.
Experimental result:
The water droplet contact angle angle, surface of treated sample is tested as shown in Figure 4.From fig. 4, it can be seen that according to the present invention
After PTFE film is modified by method, contact angle is obviously reduced.
Embodiment 3:
Processing step:
Former for PTFE membrane sample soaks in butanone ultrasonic (power 100W, temperature 30 DEG C) process 2.5 hours, vacuum drying
Thoroughly volatilizing to acetone, then immersion treatment 10 hours in methanol solution, ultrasonic (power 100W, temperature 30 DEG C) processes 2.5
Hour, under the conditions of 60 DEG C, dry 5min, make film surface substantially dry.Arranging reaction of low temperature plasma device polar plate spacing is
5.08cm, discharge power is 750W, N2Plasma flow is 400 millitorrs, processes sample 800s.Again sample is put into 60%
In (volume ratio) acrylic acid aqueous solution, under nitrogen protective condition, heating in water bath to 70 DEG C, reacts 2 hours.
Experimental result:
The surface water droplet contact angle test result of treated sample is as shown in Figure 5.From fig. 5, it can be seen that embodiment 3 changes
The water droplet contact angle of the PTFE film of property, less compared with the water droplet contact angle of the PTFE film of embodiment 2 modification, i.e. hydrophilic is more preferable.
Embodiment 4:
Processing step:
Former for PTFE membrane sample soaks in butanone ultrasonic (power 150W, temperature 30 DEG C) process 1.5 hours, vacuum drying
Thoroughly volatilizing to acetone, then immersion treatment 18 hours in methanol solution, it is little that ultrasonic (power 100W, temperature 30 DEG C) processes 2
Time, under the conditions of 40 DEG C, dry 5.5min, make film surface substantially dry.Arranging reaction of low temperature plasma device polar plate spacing is
5.08cm, discharge power is 750W, N2Plasma flow is 200 millitorrs, processes sample 1200s.Again sample is put into 60%
In (volume ratio) acrylic acid aqueous solution, under nitrogen protective condition, heating in water bath to 50 DEG C, reacts 4 hours.
Experimental result: Fourier's infrared analysis result of modified ptfe film is as shown in Figure 6.From fig. 6, it can be seen that it is modified
PTFE film occurs in that C=O, C-O, C=N, C-N stretching vibration, the successfully hydrophilic group at film surface grafting is described.
Embodiment 5:
Processing step:
Former for PTFE membrane sample soaks in butanone ultrasonic (power 100W, temperature 30 DEG C) process 2 hours, be dried under vacuum to
Acetone thoroughly volatilizees, then immersion treatment 28 hours in having methanol solution, and it is little that ultrasonic (power 180W, temperature 40 DEG C) processes 1
Time, under the conditions of 60 DEG C, dry 10min, make film surface substantially dry.Arranging reaction of low temperature plasma device polar plate spacing is
5.08cm, discharge power is 950W, N2Plasma flow is 700 millitorrs, processes the sample 1600s (table of treated sample
Face water droplet contact angle changes over as shown in Fig. 8 (1#)).Again sample is put in 55% (volume ratio) acrylic acid aqueous solution,
Under nitrogen protective condition, heating in water bath to 70 DEG C, (the surface water droplet contact angle of treated sample is in time to react 12 hours
Change is as shown in Fig. 8 (2#)).
Experimental result:
Comparison diagram 8 (1#) and Fig. 8 (2#) understand, and after graft acrylic acid, PTFE Modified Membrane hydrophilic further enhances, and parent
Aqueous nature can keep stable, the most ageing good.
Above-mentioned listed embodiment is only presently preferred embodiments of the present invention, is not used for limiting the enforcement model of the present invention
Enclose.The most all equivalence changes made according to the content of scope of the present invention patent and modification, all should be the technology model of the present invention
Farmland.
The all documents mentioned in the present invention are incorporated as reference the most in this application, just as each document by individually
It is incorporated as with reference to like that.In addition, it is to be understood that after the above-mentioned teachings having read the present invention, those skilled in the art can
To make various changes or modifications the present invention, these equivalent form of values fall within the model that the application appended claims is limited equally
Enclose.
Claims (10)
1. poly tetrafluoroethylene low temperature plasma hydrophilic modifying and a timeliness modification processing method, the method includes following step
Rapid:
Pretreatment cleaning poly tetrafluoroethylene, and add organic molecule using as hydrophilic group donor, including:
(1) poly tetrafluoroethylene is soaked in butanone supersound process, be dried under vacuum to butanone and thoroughly volatilize；
(2) treated poly tetrafluoroethylene is soaked in organic solvent also supersound process, then dries so that film surface is done
Dry, so that organic solvent molecule is fully dispersed in poly tetrafluoroethylene surface and film layer, as parent in subsequent treatment
Water group donor；And
Low-temperature plasma method etching poly tetrafluoroethylene grafting hydrophilic group, including:
(3) pretreated poly tetrafluoroethylene carrying out Low Temperature Plasma Treating, wherein, processing power is 1～600W, time
Between be 0.1～3000s, plasma air pressure is 1～1000 millitorrs, and temperature is 20-500 DEG C, low temperature plasma etching polytetrafluoro
Ethylene molecule chain produces active atoms of carbon, excites organic solvent molecule to produce hydrophilic active group simultaneously, thus at polytetrafluoroethyl-ne
It is grafted hydrophilic group, it is achieved poly tetrafluoroethylene surface and the hydrophilic modifying of film layer on alkene strand.
2. the method for claim 1, it is characterised in that the method also includes: with modified Teflon film hydrophilic group
Group is site, and graft polymers protection hydrophilic group also further enhances hydrophilic, including:
(4) modified Teflon film is immersed in the aqueous solution treating grafted monomers, heating in water bath, and carries out graft reaction；
And
(5) washing except non-grafted organic monomer, vacuum drying preserves.
3. method as claimed in claim 1 or 2, it is characterised in that in step (1), the power of supersound process be 0～
200W, temperature is 0～50 DEG C, and the time is 0.1-3 hour.
4. method as claimed in claim 1 or 2, it is characterised in that in step (2), the time soaked in organic solvent
For 1-48 hour；The power of supersound process is 0～200W, and temperature is 0～50 DEG C, and the time is 0-3 hour；Drying temperature is 1-
101 DEG C, drying time is 1-10 minute.
5. method as claimed in claim 1 or 2, it is characterised in that in step (2), described organic solvent includes: methanol,
Formaldehyde, formic acid, ethanol, ethylene glycol, acetaldehyde, acetic acid, ethanedioic acid, propanol, isopropanol, propionic aldehyde, isopropyl aldehyde, propanoic acid, isopropyl acid and
Acrylic acid.
6. method as claimed in claim 1 or 2, it is characterised in that in step (3), use reaction of low temperature plasma device
Carrying out Low Temperature Plasma Treating, process sample and be close to pole plate, polar plate spacing is 2.54～15.24cm.
7. method as claimed in claim 1 or 2, it is characterised in that in step (3), using purity is the argon of 99.99%
Gas, nitrogen or combinations thereof gas produce plasma gas stream.
8. method as claimed in claim 2, it is characterised in that in step (4), heating in water bath keeps 10～100 DEG C, at nitrogen
Graft reaction 0.1～50 hours are carried out under the conditions of gas shielded.
9. method as claimed in claim 2, it is characterised in that in step (4), described in polymer monomer to be grafted include:
Acrylic acid, propenyl, butenoic acid, butenol, amylene, hexene, allene, butadiene, isoprene, hexatriene, butine, penta
Alkynes, hexin, heptyne, octyne, n-heptylacetylene, decine and undecyne.
10. method as claimed in claim 2, it is characterised in that in step (5), use deionized water, NaOH solution successively
Non-grafted organic monomer is removed with deionized water rinsing.
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| CN107540864A (en) * | 2017-09-26 | 2018-01-05 | 中国工程物理研究院化工材料研究所 | The method of modifying of the single hydroxyl functional group of fluorine resin |
| CN108854573A (en) * | 2018-07-18 | 2018-11-23 | 威海清尔特环境科技有限公司 | A kind of hydrophilic modification method of seperation film |
| CN109092085A (en) * | 2018-08-24 | 2018-12-28 | 刘宁生 | A kind of photoinduction polytetrafluoroethylene (PTFE) hydrophilic modification method |
| CN109248569A (en) * | 2018-10-19 | 2019-01-22 | 上海恩捷新材料科技有限公司 | A kind of seperation film and preparation method thereof |
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| CN110038445A (en) * | 2019-04-08 | 2019-07-23 | 同济大学 | A kind of hydrophobic membrane hydrophilic modification method |
| CN110038445B (en) * | 2019-04-08 | 2022-09-16 | 同济大学 | Hydrophilic modification method for hydrophobic membrane |
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| WO2021139012A1 (en) * | 2020-01-07 | 2021-07-15 | 南京大学 | Method for activating polytetrafluoroethylene and application |
| CN111320778A (en) * | 2020-02-25 | 2020-06-23 | 深圳赛兰仕科创有限公司 | PTFE membrane surface treatment method and PTFE membrane surface treatment system |
| CN112980039A (en) * | 2021-03-12 | 2021-06-18 | 浙江科赛新材料科技有限公司 | High-adhesion polytetrafluoroethylene film and preparation method and application thereof |
| CN115042460A (en) * | 2022-07-20 | 2022-09-13 | 上海翊科聚合物科技有限公司 | Continuous etching method of PTFE (polytetrafluoroethylene) tube |
| CN115347244A (en) * | 2022-09-13 | 2022-11-15 | 重庆太蓝新能源有限公司 | Lithium ion battery and preparation method thereof |
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