CN106237872A - A kind of hydrophilic modification method of microporous teflon membran - Google Patents
A kind of hydrophilic modification method of microporous teflon membran Download PDFInfo
- Publication number
- CN106237872A CN106237872A CN201610746328.7A CN201610746328A CN106237872A CN 106237872 A CN106237872 A CN 106237872A CN 201610746328 A CN201610746328 A CN 201610746328A CN 106237872 A CN106237872 A CN 106237872A
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- Prior art keywords
- teflon membran
- microporous teflon
- ethylene glycol
- acrylic acid
- modification method
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
-
- 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides the hydrophilic modification method of a kind of microporous teflon membran, it can solve the existing chemically or physically method of existing employing and carry out that preparing of microporous teflon membran hydrophilic modification method existence be numerous and diverse, the hydraulic performance decline of material own, the problem of modified hydrophilic poor stability.It comprises the following steps successively, and microporous teflon membran is fully infiltrated in acetum by (1)；(2) microporous teflon membran through step (1) fully infiltration is put into acrylic acid solution and crosslink copolyreaction with acrylic acid solution, thus introduce COOH group on microporous teflon membran surface；(3) microporous teflon membran after step (2) crosslinks copolyreaction with acrylic acid put into together with amphipathic copolymer ethylene glycol ε caprolactone diol ethylene glycol in thionyl chloride and react 4 hours～5 hours under the temperature conditions of 70 DEG C～80 DEG C.
Description
Technical field
The present invention relates to the manufacture field of high molecule microfilter membrane material, especially relate to the processing of microporous teflon membran
Field, the hydrophilic modification method of a kind of microporous teflon membran.
Background technology
Polytetrafluoroethylene (PTFE) because of its have that chemical stability is good, high/low temperature adaptability and chemical resistance and effect
The advantages such as little surface tension and coefficient of friction and be widely used in multiple technical fields such as filtration, clothing, biology, medicine,
, surface wettability official post less yet with the surface tension of PTFE film obtains it and has stronger hydrophobicity, also makes PTFE film
In sewage disposal process, easily produce serious fouling membrane, cause it to be difficult in water treatment procedure play useful effect；Cause
This, can the hydrophilic effectively improving PTFE film surface have become it extensively, for a long time and stably use with antifouling property
Key in various useless water purifications Yu process.Polytetrafluoroethylmicroporous microporous membrane hydrophilic modification is always membrance separation area research
Focus and difficult point, at present, domestic and international research worker mainly use including including sodium-naphthalene chemical treatment etc. chemically and physically side
Method carries out hydrophilic modifying to PTFE microporous membrane, although achieve certain effect, but these method of modifying yet suffer from following lacking
Point: existing chemical treatment method preparation process is numerous and diverse, and it is easily caused the change of this body structure of material, cause this fever of the body of material
Decline with chemical stability；Although single physical method is simple to operate, but modified hydrophilic less stable, its hydrophilic effect
Fruit can weaken along with the prolongation of the time of use.
Summary of the invention
For the problems referred to above, the invention provides the hydrophilic modification method of a kind of microporous teflon membran, it can solve
What the existing chemically or physically method of existing employing carried out microporous teflon membran hydrophilic modification method existence prepares numerous and diverse, material
The hydraulic performance decline of material own, the problem of modified hydrophilic poor stability.
A kind of hydrophilic modification method of microporous teflon membran, it is characterised in that: it comprises the following steps successively,
(1) microporous teflon membran is fully infiltrated in acetum；
(2) hand over putting into acrylic acid solution through step (1) the fully microporous teflon membran of infiltration with acrylic acid solution
Connection copolyreaction, thus at microporous teflon membran surface introducing-COOH group；
(3) will be through the microporous teflon membran after step (2) and acrylic acid crosslink copolyreaction and amphipathic copolymer second
Glycol-6-caprolactone glycol-ethylene glycol is put in thionyl chloride together and to react 4 under the temperature conditions of 70 DEG C～80 DEG C little
Time～5 hours,
。
Further, described amphipathic copolymer ethylene glycol-6-caprolactone glycol-ethylene glycol is by Polyethylene Glycol and 6-caprolactone
In molar ratio (1+x): 17.5 are prepared from, wherein x is constant ,-0.1≤x≤0.1.
Further, in described step (1), microporous teflon membran infiltrates 2 hours in acetum.
Further, the concrete steps of described step (2) are that the poly tetrafluoroethylene fully infiltrated by acetum is put into
Heating in water bath magnetic agitation in acrylic acid solution, reaction temperature 40 DEG C～50 DEG C, 2 hours response time～3 hours.
The hydrophilic modification method of the microporous teflon membran of the present invention, its utilize amphipathic copolymer ethylene glycol-ε-oneself in
Esterdiol-ethylene glycol carries out hydrophilic modifying to microporous teflon membran, and method is simple, modified politef micropore
The hydrophilic good stability of film.
Detailed description of the invention
Embodiment one:
A kind of hydrophilic modification method of microporous teflon membran, it comprises the following steps successively:
A. by 36g Polyethylene Glycol (PEG) that molecular weight is 2000 with 40g 6-caprolactone (CL) (with molar ratio computing PEG:CL=
0.9:17.5) it is warming up to 120 DEG C, is dehydrated 30min, pours the 250ml tri-mouthfuls burning equipped with thermometer, reflux condensing tube and agitator into
In Ping, 50 DEG C of insulations, then nitrogen atmosphere is warming up to 130 DEG C, adds octoate catalyst stannous Sn that mass ratio is 0.3%
(Oct) 2, after being polymerized 24 hours, product to be poured into while hot in normal hexane and precipitate, gained white solid puts into vacuum drying oven, 30 DEG C
Under be dried to constant weight, obtain ethylene glycol-6-caprolactone glycol-ethylene glycol (PEG-PCL-PEG) amphipathic copolymer；
B. take 5g microporous teflon membran (PTFE film) infiltration in acetum 2 hours, make microporous teflon membran
Complete wetting；
C. the PTFE film of complete wetting is put into and acrylic acid solution crosslinks copolyreaction, heating in water bath magnetic agitation,
React 2 hours at 50 DEG C, thus at PTFE film surface introducing-COOH group；
D. by above-mentioned having been introduced on surface-PTFE film and the ethylene glycol-6-caprolactone glycol-ethylene glycol (PEG-of COOH group
PCL-PEG) amphipathic copolymer puts into thionyl chloride (SOCl together2React 5 hours in) and under the temperature conditions of 70 DEG C, second
The hydroxyl of glycol-6-caprolactone glycol-ethylene glycol (PEG-PCL-PEG) reacts with C-Cl group.
Embodiment two:
A kind of hydrophilic modification method of microporous teflon membran, it comprises the following steps successively:
A. by 40g Polyethylene Glycol (PEG) that molecular weight is 2000 and 40g 6-caprolactone (CL) (with molar ratio computing, PEG:CL=
1:17.5) it is warming up to 120 DEG C, is dehydrated 30min, pours the 250ml there-necked flask equipped with thermometer, reflux condensing tube and agitator into
In, 50 DEG C of insulations, then nitrogen atmosphere is warming up to 130 DEG C, adds octoate catalyst stannous Sn (Oct) that mass ratio is 0.3%
2, after being polymerized 24 hours, product to be poured into while hot in normal hexane and precipitate, gained white solid puts into vacuum drying oven, dry at 30 DEG C
Dry to constant weight, i.e. obtain ethylene glycol-6-caprolactone glycol-ethylene glycol (PEG-PCL-PEG) amphipathic copolymer；
B. take 5g microporous teflon membran (PTFE film) infiltration in acetum 2 hours, make microporous teflon membran
Complete wetting；
C. the PTFE film of complete wetting being put in acrylic acid solution and crosslink copolyreaction with acrylic acid, heating in water bath is also
Magnetic agitation, reaction 2.5h at 45 DEG C, thus introducing-COOH group in PTFE film；
D. by above-mentioned having been introduced on surface-PTFE film and the ethylene glycol-6-caprolactone glycol-ethylene glycol (PEG-of COOH group
PCL-PEG) amphipathic copolymer puts into thionyl chloride (SOCl together24.5h, ethylene glycol-6-caprolactone is reacted in) and at 75 DEG C
The hydroxyl of glycol-ethylene glycol (PEG-PCL-PEG) reacts with C-Cl group.
Embodiment three:
A kind of hydrophilic modification method of microporous teflon membran, it comprises the following steps successively:
A. by 44g Polyethylene Glycol (PEG) that molecular weight is 2000 and 40g 6-caprolactone (CL) (with molar ratio computing, PEG:CL=
1.1:17.5) it is warming up to 120 DEG C, is dehydrated 30min, pours the 250ml tri-mouthfuls burning equipped with thermometer, reflux condensing tube and agitator into
In Ping, 50 DEG C of insulations, then nitrogen atmosphere is warming up to 130 DEG C, adds octoate catalyst stannous Sn that mass ratio is 0.3%
(Oct) 2, after being polymerized 24 h, product to be poured into while hot in normal hexane and precipitate, gained white solid puts into vacuum drying oven, at 30 DEG C
It is dried to constant weight, i.e. obtains ethylene glycol-6-caprolactone glycol-ethylene glycol (PEG-PCL-PEG) amphipathic copolymer；
B. take 5g microporous teflon membran (PTFE film) infiltration in acetum 2 hours, make microporous teflon membran complete
Full moistening；
C. the PTFE film of complete wetting being put in acrylic acid solution and crosslink copolyreaction with acrylic acid, heating in water bath is also
Magnetic agitation, after reacting 3 hours at 40 DEG C, thus introducing-COOH group in PTFE film；
D. by above-mentioned having been introduced on surface-PTFE film and the ethylene glycol-6-caprolactone glycol-ethylene glycol (PEG-of COOH group
PCL-PEG) amphipathic copolymer puts into thionyl chloride (SOCl together2React 4 hours in) and at 80 DEG C, ethylene glycol-ε-own interior
The hydroxyl of esterdiol-ethylene glycol (PEG-PCL-PEG) reacts with C-Cl group.
In above three embodiment, mass ratio be 0.3% octoate catalyst stannous Sn (Oct) 2 to specifically refer to catalyst pungent
Acid stannous accounts for the mass percent of Polyethylene Glycol, 6-caprolactone and stannous octoate gross mass.
Hydrophilic modifying process latter 1 hour, the politef micropore of 1 month is completed respectively to according to above three embodiment
Film carries out the detection of water contact angle respectively, and testing result contacts with the water of the microporous teflon membran processed without hydrophilic modifying
The contrast at angle see table:
As can be seen from the above table, the water of the microporous teflon membran after above three embodiment carries out hydrophilic modifying process connects
Significantly reduce before the more unmodified process of feeler, i.e. show the poly tetrafluoroethylene after the hydrophilic modification method of the present invention processes
The hydrophilic of the poly tetrafluoroethylene that the more non-hydrophilic modifying of hydrophilic processes is greatly improved；And it is little to process 1 at hydrophilic modifying
Water contact angle time after is less with the water contact angle change after hydrophilic modifying processes 1 month, also indicates that the parent through the present invention
The hydrophilic good stability of the poly tetrafluoroethylene after the process of water method of modifying.
The inventive method make use of amphipathic copolymer ethylene glycol-6-caprolactone glycol-ethylene glycol to come politef micro-
Pore membrane carries out hydrophilic modifying, and this amphipathic copolymer is to be prepared from 6-caprolactone by ethylene glycol, owing to polycaprolactone has
There are good biocompatibility, hypotoxicity, hydrophobicity, and Polyethylene Glycol be a kind of hypotoxic water-soluble linear polymer,
Urine conjunction property can be formed on membrane material surface, organic and colloid absorption is had the resistance of excellence, thus by Polyethylene Glycol
The amphipathic copolymer prepared with polycaprolactone carries out hydrophilic modifying to microporous teflon membran and can be greatly improved polytetrafluoroethyl-ne
The hydrophilic of alkene microporous membrane and contamination resistance, and its hydrophilic stability can be improved, it is recognized as safety non-toxic simultaneously, therefore
Microporous teflon membran after utilizing this amphipathic copolymer to carry out hydrophilic treated can be applied in drinking water treatment equipment, really
Protect drinking water safety.
Claims (4)
1. the hydrophilic modification method of a microporous teflon membran, it is characterised in that: it comprises the following steps successively,
(1) microporous teflon membran is fully infiltrated in acetum；
(2) hand over putting into acrylic acid solution through step (1) the fully microporous teflon membran of infiltration with acrylic acid solution
Connection copolyreaction, thus at microporous teflon membran surface introducing-COOH group；
(3) will be through the microporous teflon membran after step (2) and acrylic acid crosslink copolyreaction and amphipathic copolymer second
Glycol-6-caprolactone glycol-ethylene glycol is put in thionyl chloride together and to react 4 under the temperature conditions of 70 DEG C～80 DEG C little
Time～5 hours,
。
The hydrophilic modification method of a kind of microporous teflon membran the most according to claim 1, it is characterised in that: described two
Parent's copolymer ethylene glycol-6-caprolactone glycol-ethylene glycol is by ethylene glycol and 6-caprolactone (1+x) in molar ratio: 17.5 preparations and
Becoming, wherein x is constant ,-0.1≤x≤0.1.
The hydrophilic modification method of a kind of microporous teflon membran the most according to claim 1 and 2, it is characterised in that: institute
State microporous teflon membran in step (1) to infiltrate in acetum 2 hours.
The hydrophilic modification method of a kind of microporous teflon membran the most according to claim 1 and 2, it is characterised in that: institute
The concrete steps stating step (2) are that the poly tetrafluoroethylene fully infiltrated by acetum puts into heating in water bath in acrylic acid solution
And magnetic agitation, reaction temperature 40 DEG C～50 DEG C, 2 hours response time～3 hours.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610746328.7A CN106237872A (en) | 2016-08-29 | 2016-08-29 | A kind of hydrophilic modification method of microporous teflon membran |
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| CN201610746328.7A CN106237872A (en) | 2016-08-29 | 2016-08-29 | A kind of hydrophilic modification method of microporous teflon membran |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108479403A (en) * | 2018-04-13 | 2018-09-04 | 苏州凯虹高分子科技有限公司 | Super super hydrophilic tube microfiltration membrane of one kind and preparation method thereof |
| CN115400595A (en) * | 2022-08-24 | 2022-11-29 | 哈尔滨工业大学 | Method for self-assembling ultrathin hydrogel organic microfiltration membrane |
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| CN101062981A (en) * | 2006-04-26 | 2007-10-31 | 汕头大学 | Novel block macromolecular material and preparation method thereof |
| CN101108313A (en) * | 2007-04-28 | 2008-01-23 | 浙江大学 | Method of amphipathic nature fluorine-contained copolymer modifying surface of polytetrafluoroethylene porous membrane |
| JP2012236178A (en) * | 2011-05-13 | 2012-12-06 | Nok Corp | Method for producing vinylidene fluoride resin porous membrane |
| CN104479157A (en) * | 2015-01-06 | 2015-04-01 | 山东理工大学 | Method for improving hydrophilia and flexibility of polypeptide membrane through polycaprolactone and polyethylene glycol |
| US20150168841A1 (en) * | 2013-12-13 | 2015-06-18 | Kabushiki Kaisha Toshiba | Pattern forming method |
-
2016
- 2016-08-29 CN CN201610746328.7A patent/CN106237872A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1425706A (en) * | 2003-01-14 | 2003-06-25 | 天津大学 | Polyglycol block modified polyhexanolactone and its preparing method |
| CN101062981A (en) * | 2006-04-26 | 2007-10-31 | 汕头大学 | Novel block macromolecular material and preparation method thereof |
| CN101108313A (en) * | 2007-04-28 | 2008-01-23 | 浙江大学 | Method of amphipathic nature fluorine-contained copolymer modifying surface of polytetrafluoroethylene porous membrane |
| JP2012236178A (en) * | 2011-05-13 | 2012-12-06 | Nok Corp | Method for producing vinylidene fluoride resin porous membrane |
| US20150168841A1 (en) * | 2013-12-13 | 2015-06-18 | Kabushiki Kaisha Toshiba | Pattern forming method |
| CN104479157A (en) * | 2015-01-06 | 2015-04-01 | 山东理工大学 | Method for improving hydrophilia and flexibility of polypeptide membrane through polycaprolactone and polyethylene glycol |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108479403A (en) * | 2018-04-13 | 2018-09-04 | 苏州凯虹高分子科技有限公司 | Super super hydrophilic tube microfiltration membrane of one kind and preparation method thereof |
| CN115400595A (en) * | 2022-08-24 | 2022-11-29 | 哈尔滨工业大学 | Method for self-assembling ultrathin hydrogel organic microfiltration membrane |
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