CN106268370B - Polytetrafluoroethylene film low temperature plasma hydrophilic modifying and timeliness modification processing method - Google Patents
Polytetrafluoroethylene film low temperature plasma hydrophilic modifying and timeliness modification processing method Download PDFInfo
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- CN106268370B CN106268370B CN201610753382.4A CN201610753382A CN106268370B CN 106268370 B CN106268370 B CN 106268370B CN 201610753382 A CN201610753382 A CN 201610753382A CN 106268370 B CN106268370 B CN 106268370B
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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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- 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
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- 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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- 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 present invention provides a kind of polytetrafluoroethylene film low temperature plasma hydrophilic modifying and timeliness modification processing method, method includes the following steps: pretreatment cleaning polytetrafluoroethylene film, and organic molecule is added using as hydrophilic radical donor；Low-temperature plasma method etches polytetrafluoroethylene film and grafting hydrophilic group.This method further include: using modified Teflon film hydrophilic radical as site, graft polymers protection hydrophilic radical simultaneously further enhances hydrophily.
Description
Technical field
The invention belongs to PTFE (polytetrafluoroethylene (PTFE)) membrane modifying fields, and in particular to the low-temperature plasma modified place of PTFE film
Reason and polymer grafting method.
Background technique
UF membrane is widely used in water treatment field, have low energy consumption, high degree of automation, it is without secondary pollution, can recycle
The advantages that recycling substance.PTFE film is sufficiently stable, has good antiacid alkali, resistance to corrosion, but PTFE film has very
Strong hydrophobicity, it is almost waterproof under conditions of pressurizeing 1MPa, therefore by modification appropriate, improve the parent of PTFE film
It is aqueous, it is of great significance.
PTFE tradition method of modifying has: wet-chemical treatment method, i.e. naphthalene-sodium, ammonia-sodium solution facture, which is to utilize corruption
Erosion liquid removes the fluorine atom on the surface PTFE to improve material surface activity, but this method has the disadvantage that: (1) PTFE after handling
The obvious dimmed, blackening in surface, influences material appearance；(2) the surface resistivity decline of PTFE at high temperature, long-term exposure after handling
In the sun, material adhesive property can be reduced seriously；(3) treatment process can generate a large amount of harmful waste liquid, seriously pollute environment.
High-energy radiation graft modification is the irradiation polymer such as gamma-rays, high-power electron beam and ultraviolet light generated by ionising radiation,
Active site is generated in polymer surfaces, causes the graft copolymerization of monomer, this method of modifying is since radiation energy is very high, easily
Membrane structure is caused to destroy.
Plasma modification method utilizes the non-polymerizations gas such as Ar more, oxygen or water hair in the free radical and air of generation
Raw reaction forms peroxide, can further crosslink and polymerize with function monomer such as acrylic acid, obtains hydrophilic surface.It is this
The free radical of method, plasma exciatiaon is limited, and reacts with object to form peroxide and be divided into two stages and carry out, efficiency
It is lower, and this method of modifying is mainly that surface is modified, it is limited to the modified effect among film layer.Although film surface can be improved
Hydrophilicity, but it is smaller to the water permeability improvement result of film.
Therefore, there is an urgent need in the art to develop a kind of novel polytetrafluoroethylene (PTFE) for overcoming above-mentioned prior art defect
Membrane modifying method.
Summary of the invention
The present invention provides a kind of novel polytetrafluoroethylene film low temperature plasma hydrophilic modifying and timeliness modifications
Method, to solve problems of the prior art.
The present invention provides a kind of polytetrafluoroethylene film low temperature plasma hydrophilic modifying and timeliness modification processing methods, should
Method the following steps are included:
Pretreatment cleaning polytetrafluoroethylene film, and organic molecule is added using as hydrophilic radical donor, comprising:
(1) polytetrafluoroethylene film is impregnated to ultrasonic treatment in butanone, butanone is dried under vacuum to and thoroughly volatilizees；
(2) processed polytetrafluoroethylene film is impregnated and is ultrasonically treated in organic solvent, then drying is so that film table
Face is dry, so that organic solvent molecule is fully dispersed into polytetrafluoroethylene (PTFE) film surface and film layer, makees in subsequent processing
For hydrophilic radical donor；And
Low-temperature plasma method etches polytetrafluoroethylene film and grafting hydrophilic group, comprising:
(3) by pretreated polytetrafluoroethylene film carry out Low Temperature Plasma Treating, wherein processing power be 1~
600W, time are 0.1~3000s, and plasma air pressure is 1~1000 millitorr, and temperature is 20-500 DEG C, low temperature plasma etching
Polytetrafluoroethylene (PTFE) strand generates active atoms of carbon, while organic solvent molecule being excited to generate hydrophilic active group, thus poly-
It is grafted upper hydrophilic radical on tetrafluoroethene strand, realizes the hydrophilic modifying of polytetrafluoroethylene (PTFE) film surface and film layer.
In one preferred embodiment, this method further include: using modified Teflon film hydrophilic radical as site,
Graft polymers protection hydrophilic radical simultaneously further enhances hydrophily, comprising:
(4) modified Teflon film is immersed in the aqueous solution to grafted monomers, heating water bath, and be grafted anti-
It answers；And
(5) non-grafted organic monomer is washed off, vacuum drying saves.
In another preferred embodiment, in step (1), the power of ultrasonic treatment is 0~200W, temperature 0
~50 DEG C, the time is 0.1-3 hours.
In another preferred embodiment, in step (2), the time impregnated in organic solvent is that 1-48 is small
When；The power of ultrasonic treatment is 0~200W, and temperature is 0~50 DEG C, and the time is 0-3 hours；Drying temperature is 1-101 DEG C, drying
Time is 1-10 minutes.
In another preferred embodiment, in step (2), the organic solvent include: methanol, formaldehyde, formic acid,
Ethyl alcohol, ethylene glycol, acetaldehyde, acetic acid, ethanedioic acid, propyl alcohol, isopropanol, propionic aldehyde, isopropyl aldehyde, propionic acid, isopropyl acid and acrylic acid.
In another preferred embodiment, in step (3), low temperature etc. is carried out using reaction of low temperature plasma device
Gas ions processing, processing sample are close to pole plate, and pole plate spacing is 2.54~15.24cm.
In another preferred embodiment, in step (3), use purity for 99.99% argon gas, nitrogen or
Their combination gas generates plasma gas stream.
In another preferred embodiment, in step (4), heating water bath is kept for 10~100 DEG C, in nitrogen protection
Under the conditions of carry out graft reaction 0.1~50 hour.
In another preferred embodiment, in step (4), the 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.
In another preferred embodiment, in step (5), successively using deionized water, NaOH solution and go from
Sub- water washes off non-grafted organic monomer.
Detailed description of the invention
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 original film waters to drip contact angle test result.Figure it is seen that former film water droplet contact angle is larger.
Fig. 3 shows the not preprocessed direct water droplet contact angle test result for carrying out Low Temperature Plasma Treating sample.
From figure 3, it can be seen that water droplet contact angle is also obviously reduced after Low Temperature Plasma Treating even if former film is not preprocessed.
Fig. 4 is shown according to the embodiment of the present application 2, and PTFE film is after the method for the present invention pre-processes, through low temperature plasma
Water droplet contact angle test result after processing.
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 is shown according to the embodiment of the present application 4, and PTFE film is after the method for the present invention pre-processes, through low temperature plasma
IR Characterization result after processing.
Fig. 7 shows membrane flux test result, and (1# film is former film；2# film does not pre-process, direct Low Temperature Plasma Treating；
The pretreatment of 3# film plus Low Temperature Plasma Treating；4# film is after 3# film the same terms are handled again through acrylic acid-grafted processing).From figure
7 as can be seen that former film (unmodified membrane) flux is minimum (for " 0 "), and modified flux significantly increases.Wherein, PTFE film is located in advance
After reason, then carry out film (3# film) flux maximum of Low Temperature Plasma Treating.
Fig. 8 is shown according to the embodiment of the present application 5, and film surface contact angle is with the variation of resting period, and wherein 1# film is pre-
Processing plus Low Temperature Plasma Treating；After 2# film is the processing of 1# film the same terms, then through acrylic acid-grafted processing.The result of Fig. 8
After showing grafted propylene acid, the hydrophily of PTFE Modified Membrane is further enhanced, and hydrophilic nmature keeps stablizing.
Specific embodiment
Present inventor after extensive and in-depth study, for the extremely strong hydrophobicity of PTFE film in the prior art,
And traditional plasma method of modifying can only be modified to PTFE film surface defect, propose a kind of organic solvent pretreatment
PTFE film low-temperature plasma method of modifying, preprocess method through the invention can be before any plasma treatment in film surface
With organic molecule is loaded in film layer, in low temperature plasma atmosphere, these organic molecules, which are excited, generates active group, with etc.
The free radical generated in gas ions directly reacts engagement, achievees the purpose that be grafted active group among film surface and film layer；So
Afterwards by graft polymers monomer, hydrophilic polymer protective layer is formed on surface, improves modified stable.
The present invention provides a kind of polytetrafluoroethylene film low temperature plasma hydrophilic modifying and timeliness modification processing methods, should
Method the following steps are included:
Step 1: butanone impregnates ultrasonic treatment PTFE film, it is dried under vacuum to butanone and thoroughly volatilizees, removes film surface and film layer
In impurity；
Step 2: being impregnated with organic solvent, ultrasonic treatment PTFE film, and dry, makes film surface substantially dry；By locating in advance
Reason, makes that organic solvent molecule is fully dispersed, loads in PTFE film surface and film layer, in subsequent processing as hydrophilic radical confession
Body；
Step 3: suitable power, plasma gas flow amount, pole plate spacing, processing time are adjusted, it will be pretreated
PTFE film is placed in reaction of low temperature plasma device and handles, and low temperature plasma etches PTFE strand and generates active atoms of carbon,
It excites organic solvent molecule to generate hydrophilic active group simultaneously, to be grafted upper hydrophilic radical on PTFE strand, realizes
PTFE film surface and film layer hydrophilic modifying；
Step 4: modified PTFE film is immersed in the certain density aqueous solution to grafted monomers, heating water bath,
Under the conditions of nitrogen protection, using hydrophilic radical as site, it is grafted organic polymer；
Step 5: the non-grafted organic monomer of removal, vacuum drying, the sample that saves that treated.
In the method for the invention, in the first step, the power of ultrasonic treatment is 0~200W, and temperature is 0~50 DEG C, when
Between be 0.1-3 hours, preferably 2 hours.
In the method for the invention, in second step, the organic solvent is methanol (CH4O), formaldehyde (CH3O), formic acid
(CH2O2), ethyl alcohol (C2H6O), ethylene glycol (C2H6O2), acetaldehyde (C2H5O), acetic acid (C2H4O2), ethanedioic acid (C2H2O4), propyl alcohol
(C3H8O), isopropanol, propionic aldehyde (C3H6O), isopropyl aldehyde, propionic 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 impregnated in organic solvent is 1-48 hours, and preferably 24 is small
When；The power of ultrasonic treatment is 0~200W, and temperature is 0~50 DEG C, and the time is 0-3 hours；Drying temperature is 1-101 DEG C, preferably
30 DEG C, drying time is 1-10 minutes.
In the method for the invention, in the third step, the plasma discharge power used is 1~600W, plasma (orifice) gas
Body flow is 1~1000 millitorr, and the processing time is 0.1~3000s, and temperature is 20-500 DEG C, pole plate spacing for 2.54~
15.24cm。
In the method for the invention, in the third step, use purity for 99.99% argon gas, nitrogen or their group
It closes gas and generates plasma atmosphere.
In the method for the invention, in the 4th step, the polymer monomer to be grafted is 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 water bath is kept for 10~100 DEG C, and graft reaction 0.1~50 is small
When.
In the method for the invention, it in the 5th step, is successively washed off with deionized water, NaOH solution, deionized water
Non-grafted organic monomer.
Main advantages of the present invention are:
The present invention has the advantage that compared with traditional grafting method
1, process flow is simple, and controllability is strong, environmental-friendly；
2, corona treatment is generated free radicals to generate and be grafted with active group and be carried out simultaneously, and graft reaction is high-efficient；
3, active group can be grafted in film surface and film layer, improve the hydrophily in film surface and film layer, be improved saturating
Aqueous energy；
4, after graft polymers monomer, hydrophilic modifying effect is further increased and more stable.
Embodiment
Below with reference to specific embodiment, the present invention is further explained.It should be appreciated, however, that these embodiments are only used for
It is bright the present invention and be not meant to limit the scope of the invention.The test method of actual conditions is not specified in the following example, usually
According to normal conditions, or according to the normal condition proposed by manufacturer.Unless otherwise indicated, all percentage and number be by weight
Meter.
Embodiment 1:
Processing step:
PTFE original membrane sample is impregnated ultrasonic (power 100W, 30 DEG C of temperature) to handle 2 hours in butanone, is dried under vacuum to
Butanone thoroughly volatilizees, then immersion treatment 24 hours in methanol solution, and ultrasonic (power 100W, 30 DEG C of temperature) is handled 2 hours,
6min is dried under the conditions of 30 DEG C, makes film surface substantially dry.Setting reaction of low temperature plasma device pole plate spacing is 5.08cm,
Discharge power is 150W, N2Plasma flow is 100 millitorrs, handles sample 300s.
Experimental result:
The electron scanning micrograph of processed sample is as shown in Figure 1.It will be seen from figure 1 that corona treatment
Afterwards, PTFE fiber becomes loosely, and fiber aspect interlocks, and membrane aperture slightly increases, and has and generates compared with multifilament branch.
Embodiment 2:
Processing step:
PTFE original membrane sample is impregnated ultrasonic (power 170W, 40 DEG C of temperature) to handle 1 hour in butanone, is dried under vacuum to
Butanone thoroughly volatilizees, then immersion treatment 30 hours in methanol solution, and ultrasonic (power 150W, 30 DEG C of temperature) is handled 2 hours,
5min is dried under the conditions of 30 DEG C, makes film surface substantially dry.Setting reaction of low temperature plasma device pole plate spacing is 5.08cm,
Discharge power is 100W, N2Plasma flow is 100 millitorrs, handles sample 700s.
Experimental result:
The surface water droplet contact angle angle test of processed sample is as shown in Figure 4.From fig. 4, it can be seen that according to the present invention
After method is modified PTFE film, contact angle is obviously reduced.
Embodiment 3:
Processing step:
PTFE original membrane sample is impregnated ultrasonic (power 100W, 30 DEG C of temperature) to handle 2.5 hours in butanone, vacuum drying
It thoroughly volatilizees to butanone, then immersion treatment 10 hours in methanol solution, ultrasonic (power 100W, 30 DEG C of temperature) processing 2.5
Hour, 5min is dried under the conditions of 60 DEG C, makes film surface substantially dry.Reaction of low temperature plasma device pole plate spacing, which is arranged, is
5.08cm, discharge power 750W, N2Plasma flow is 400 millitorrs, handles sample 800s.Sample is put into 60% again
In (volume ratio) acrylic acid aqueous solution, under the conditions of nitrogen protection, heating water bath reacts 2 hours to 70 DEG C.
Experimental result:
Test results are shown in figure 5 for the surface water droplet contact angle of processed sample.From fig. 5, it can be seen that embodiment 3 changes
Property PTFE film water droplet contact angle, the water droplet contact angle of the PTFE film modified compared with embodiment 2 is smaller, i.e., hydrophily is more preferable.
Embodiment 4:
Processing step:
PTFE original membrane sample is impregnated ultrasonic (power 150W, 30 DEG C of temperature) to handle 1.5 hours in butanone, vacuum drying
It thoroughly volatilizees to butanone, then immersion treatment 18 hours in methanol solution, ultrasonic (power 100W, 30 DEG C of temperature) processing 2 is small
When, 5.5min is dried under the conditions of 40 DEG C, makes film surface substantially dry.Reaction of low temperature plasma device pole plate spacing, which is arranged, is
5.08cm, discharge power 750W, N2Plasma flow is 200 millitorrs, handles sample 1200s.Sample is put into 60% again
In (volume ratio) acrylic acid aqueous solution, under the conditions of nitrogen protection, heating water bath reacts 4 hours to 50 DEG C.
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 modified
Occur C=O, C-O, C=N, C-N stretching vibration in PTFE film, illustrates successfully in film surface grafting hydrophilic radical.
Embodiment 5:
Processing step:
PTFE original membrane sample is impregnated ultrasonic (power 100W, 30 DEG C of temperature) to handle 2 hours in butanone, is dried under vacuum to
Butanone thoroughly volatilizees, then immersion treatment 28 hours in having methanol solution, and ultrasonic (power 180W, 40 DEG C of temperature) processing 1 is small
When, 10min is dried under the conditions of 60 DEG C, makes film surface substantially dry.Reaction of low temperature plasma device pole plate spacing, which is arranged, is
5.08cm, discharge power 950W, N2Plasma flow is 700 millitorrs, handles the sample 1600s (table of processed sample
Face water droplet contact angle is changed over time as shown in Fig. 8 (1#)).Sample is put into 55% (volume ratio) acrylic acid aqueous solution again,
Under the conditions of nitrogen protection, heating water bath is to 70 DEG C, and (the surface water droplet contact angle of processed sample is at any time within 12 hours for reaction
Variation is as shown in Fig. 8 (2#)).
Experimental result:
After comparing Fig. 8 (1#) and Fig. 8 (2#) it is found that grafted propylene is sour, PTFE Modified Membrane hydrophily is further enhanced, and parent
Aqueous nature can keep stable, i.e., timeliness is good.
Above-mentioned listed embodiment is only presently preferred embodiments of the present invention, implementation model not for the purpose of limiting the invention
It encloses.Equivalence changes and modification made by the content of i.e. all claims according to the present invention, all should be technology model of the invention
Farmland.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can be with
The present invention is made various changes or modifications, these equivalent forms also fall within the scope of the appended claims of the present application.
Claims (9)
1. a kind of polytetrafluoroethylene film low temperature plasma hydrophilic modifying and timeliness modification processing method, this method includes following step
It is rapid:
Pretreatment cleaning polytetrafluoroethylene film, and organic molecule is added using as hydrophilic radical donor, comprising:
(1) polytetrafluoroethylene film is impregnated to ultrasonic treatment in butanone, butanone is dried under vacuum to and thoroughly volatilizees；
(2) processed polytetrafluoroethylene film is impregnated and is ultrasonically treated in organic solvent, then dried so that film surface is dry
It is dry, so that organic solvent molecule is fully dispersed into polytetrafluoroethylene (PTFE) film surface and film layer, in subsequent processing as parent
Water group donor；And
Low-temperature plasma method etches polytetrafluoroethylene film and grafting hydrophilic group, comprising:
(3) pretreated polytetrafluoroethylene film being subjected to Low Temperature Plasma Treating, wherein processing power is 1~600W, when
Between be 0.1~3000s, plasma air pressure be 1~1000 millitorr, temperature be 20-500 DEG C, low temperature plasma etch polytetrafluoro
Ethylene molecule chain generates active atoms of carbon, while organic solvent molecule being excited to generate hydrophilic active group, thus in polytetrafluoroethyl-ne
It is grafted upper hydrophilic radical on alkene strand, realizes the hydrophilic modifying of polytetrafluoroethylene (PTFE) film surface and film layer,
Wherein, this method further include: using modified Teflon film hydrophilic radical as site, graft polymers protects hydrophilic radical
And further enhance hydrophily, comprising:
(4) modified Teflon film is immersed in the aqueous solution to grafted monomers, heating water bath, and carries out graft reaction；
And
(5) non-grafted organic monomer is washed off, vacuum drying saves.
2. the method as described in claim 1, which is characterized in that in step (1), the power of ultrasonic treatment is 100~200W,
Temperature is 0~50 DEG C, and the time is 0.1-3 hours.
3. the method as described in claim 1, which is characterized in that in step (2), the time impregnated in organic solvent is 1-
48 hours；The power of ultrasonic treatment is 100~200W, and temperature is 0~50 DEG C, and the time is 1-3 hours；Drying temperature is 30-101
DEG C, drying time is 1-10 minutes.
4. the method as described in claim 1, which is characterized in that in step (2), the organic solvent includes: methanol, first
Aldehyde, formic acid, ethyl alcohol, ethylene glycol, acetaldehyde, acetic acid, ethanedioic acid, propyl alcohol, isopropanol, propionic aldehyde, isopropyl aldehyde, propionic acid, isopropyl acid and third
Olefin(e) acid.
5. the method as described in claim 1, which is characterized in that in step (3), carried out using reaction of low temperature plasma device
Low Temperature Plasma Treating, processing sample are close to pole plate, and pole plate spacing is 2.54~15.24cm.
6. the method as described in claim 1, which is characterized in that in step (3), use argon gas, nitrogen of the purity for 99.99%
Gas or their combination gas generate plasma gas stream.
7. the method as described in claim 1, which is characterized in that in step (4), heating water bath is kept for 10~100 DEG C, in nitrogen
It is carried out graft reaction 0.1~50 hour under the conditions of gas shielded.
8. the method as described in claim 1, which is characterized in that in step (4), the polymer monomer to be grafted includes:
Acrylic acid, propenyl, butenoic acid, butenol, amylene, hexene, allene, butadiene, isoprene, hexatriene, butine, penta
Alkynes, hexin, heptyne, octyne, n-heptylacetylene, decine and undecyne.
9. the method as described in claim 1, which is characterized in that in step (5), successively use deionized water, NaOH solution
Non-grafted organic monomer is washed off with deionized water.
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| CN110433881A (en) * | 2019-09-02 | 2019-11-12 | 丹娜（天津）生物科技有限公司 | A kind of hydrophilic modification method of micro-fluidic chip microchannel material |
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| CN107540864B (en) * | 2017-09-26 | 2020-07-07 | 中国工程物理研究院化工材料研究所 | Modification method for single hydroxyl functionalization of fluorine-containing resin |
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| CN110433881A (en) * | 2019-09-02 | 2019-11-12 | 丹娜（天津）生物科技有限公司 | A kind of hydrophilic modification method of micro-fluidic chip microchannel material |
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