CN115245743A - Polytetrafluoroethylene microporous membrane and hydrophilic modification method thereof - Google Patents
Polytetrafluoroethylene microporous membrane and hydrophilic modification method thereof Download PDFInfo
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- CN115245743A CN115245743A CN202210917215.4A CN202210917215A CN115245743A CN 115245743 A CN115245743 A CN 115245743A CN 202210917215 A CN202210917215 A CN 202210917215A CN 115245743 A CN115245743 A CN 115245743A
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- microporous membrane
- sulfonyl fluoride
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- polytetrafluoroethylene
- hydrophilic modification
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 61
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 61
- -1 Polytetrafluoroethylene Polymers 0.000 title claims abstract description 51
- 239000012982 microporous membrane Substances 0.000 title claims abstract description 32
- 238000002715 modification method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 13
- 229920000570 polyether Polymers 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000004873 anchoring Methods 0.000 claims abstract description 10
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims abstract description 9
- 229940124530 sulfonamide Drugs 0.000 claims abstract description 9
- 150000003456 sulfonamides Chemical group 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005917 acylation reaction Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000003760 magnetic stirring Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 7
- IWBOPFCKHIJFMS-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl) ether Chemical compound NCCOCCOCCN IWBOPFCKHIJFMS-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 claims description 4
- RAFNCPHFRHZCPS-UHFFFAOYSA-N di(imidazol-1-yl)methanethione Chemical compound C1=CN=CN1C(=S)N1C=CN=C1 RAFNCPHFRHZCPS-UHFFFAOYSA-N 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 150000003141 primary amines Chemical class 0.000 claims description 4
- 150000003335 secondary amines Chemical class 0.000 claims description 4
- HFBHOAHFRNLZGN-LURJTMIESA-N (2s)-2-formamido-4-methylpentanoic acid Chemical compound CC(C)C[C@@H](C(O)=O)NC=O HFBHOAHFRNLZGN-LURJTMIESA-N 0.000 claims description 3
- QBJWTPSWRBFJOL-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-2-sulfonyl fluoride Chemical compound C(C(C(C(C(F)(F)F)(F)S(=O)(=O)F)(F)F)(F)F)(C(C(C(F)(F)F)(F)F)(F)F)(F)F QBJWTPSWRBFJOL-UHFFFAOYSA-N 0.000 claims description 3
- ZLKNPIVTWNMMMH-UHFFFAOYSA-N 1-imidazol-1-ylsulfonylimidazole Chemical compound C1=CN=CN1S(=O)(=O)N1C=CN=C1 ZLKNPIVTWNMMMH-UHFFFAOYSA-N 0.000 claims description 3
- JCEZOHLWDIONSP-UHFFFAOYSA-N 3-[2-[2-(3-aminopropoxy)ethoxy]ethoxy]propan-1-amine Chemical compound NCCCOCCOCCOCCCN JCEZOHLWDIONSP-UHFFFAOYSA-N 0.000 claims description 3
- YOOSAIJKYCBPFW-UHFFFAOYSA-N 3-[4-(3-aminopropoxy)butoxy]propan-1-amine Chemical compound NCCCOCCCCOCCCN YOOSAIJKYCBPFW-UHFFFAOYSA-N 0.000 claims description 3
- BHFJBHMTEDLICO-UHFFFAOYSA-N Perfluorooctylsulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O BHFJBHMTEDLICO-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- LLRMJSJSADDGPK-UHFFFAOYSA-N n'-(3-methoxypropyl)propane-1,3-diamine Chemical compound COCCCNCCCN LLRMJSJSADDGPK-UHFFFAOYSA-N 0.000 claims description 3
- LUYQYZLEHLTPBH-UHFFFAOYSA-N perfluorobutanesulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O LUYQYZLEHLTPBH-UHFFFAOYSA-N 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 abstract description 3
- 239000004202 carbamide Substances 0.000 abstract description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005694 sulfonylation reaction Methods 0.000 abstract description 2
- 239000012510 hollow fiber Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- HSDJWNJDPDJOEV-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O HSDJWNJDPDJOEV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- JHOUEDHRTBPBDG-UHFFFAOYSA-N 5-fluoro-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=C1C=CC=C2F JHOUEDHRTBPBDG-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910006095 SO2F Inorganic materials 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
Classifications
-
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a polytetrafluoroethylene microporous membrane and a hydrophilic modification method thereof, which comprises the steps of adding DMF solution, triethylamine and PU into a reaction vessel, fully stirring to prepare PU solution, transferring a PTFE membrane anchoring perfluoroalkyl sulfonyl fluoride into the PU solution, carrying out vacuum for 5-30 minutes under-0.06-0.1 MPa, and standing for 2-10 hours; taking out the PTFE microporous membrane, drying in an oven at 50-80 deg.C for 1-4h, subjecting sulfonyl fluoride and primary and secondary amine of PU to acylation reaction to generate topological structure, anchoring on polytetrafluoroethylene, and introducing hydrophilic sulfonamide, ether bond and amino structure. Because the fluorocarbon chain surface energy of the Rf-structure is lower, the Rf-structure is well combined with PTFE, and sulfonamide, ether bond and amino structure are introduced on the PTFE to improve the acid-base resistance of the hydrophilic coating through the sulfonylation reaction of sulfonyl fluoride and primary and secondary amino groups on the polyether urea structural material.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of polytetrafluoroethylene water treatment, and particularly relates to a hydrophilic modification technology of a polytetrafluoroethylene microporous membrane.
[ background of the invention ]
Membrane separation techniques have been extensively studied for their environmental friendliness, low energy consumption, high separation efficiency, good flexibility, and space savings. Microporous Polytetrafluoroethylene (PTFE) membranes have excellent chemical resistance, thermal stability, low surface friction, strong hydrophobicity, and self-cleaning properties. These properties make it a durable membrane for sewage treatment, however the strong hydrophobic nature of PTFE membranes has hindered its use in water treatment. It is therefore highly desirable to modify PTFE to obtain hydrophilic microporous membranes, particularly hydrophilic polytetrafluoroethylene membranes that are resistant to chemical cleaning.
[ summary of the invention ]
Aiming at the defects in the prior art, the invention aims to provide a polytetrafluoroethylene microporous membrane and a hydrophilic modification method of a sulfonated polyether urea structure thereof, so as to improve the hydrophilicity of the polytetrafluoroethylene microporous membrane and the acid-base resistance of a hydrophilic coating.
In order to solve the technical problems, the invention adopts the following technical scheme:
on one hand, the invention provides a hydrophilic modification method of a sulfonated polyether urea structure on a polytetrafluoroethylene microporous membrane, which comprises the following steps:
1) Cleaning a PTFE microporous membrane with absolute ethyl alcohol and then drying;
2) Adding perfluoroalkyl sulfonyl fluoride and absolute ethanol into a reaction container for mixing, wherein the mass fraction of the perfluoroalkyl sulfonyl fluoride is 0.6-5.0%;
3) Placing the cleaned and dried PTFE microporous membrane in a reaction container, defoaming for 10-30min by means of an ultrasonic and vacuum auxiliary system, standing for 1-6h, and enabling the perfluoroalkyl sulfonyl fluoride to be closely arranged and deposited on the PTFE fiber by virtue of intermolecular acting force;
4) Adding DMF solution, triethylamine and PU into a reaction container, fully stirring to prepare PU solution, transferring the PTFE membrane anchoring perfluoroalkyl sulfonyl fluoride into the PU solution, and standing for 2-10h after 5-30 minutes of vacuum at-0.06-0.1 MPa;
5) Taking out the PTFE microporous membrane, drying in an oven at 50-80 deg.C for 1-4h, subjecting sulfonyl fluoride and primary and secondary amine of PU to acylation reaction to generate topological structure, anchoring on polytetrafluoroethylene, and introducing hydrophilic sulfonamide, ether bond and amino structure.
Preferably, the preparation method of PU comprises the following steps: adding a diimidazole and DMF solution into a reaction container, removing oxygen under the protection of nitrogen gas, controlling the temperature to be less than 1 ℃, slowly dripping an ether diamine structure material under magnetic stirring, increasing the water bath value to 40-60 ℃ after dripping to ensure that two ends of PU are capped by amino groups and the mass of the ether diamine structure is more than that of the diimidazole, continuing the magnetic stirring for 6-12 hours, and finally distilling the reactant to obtain the PU structure.
Preferably, the reaction vessel is placed in a bath of ice and water, the temperature being controlled to less than 1 ℃.
Preferably, the mass ratio of the diimidazole to the DMF solution is 0.1-0.4.
Preferably, the structural material of the ether diamine type comprises 1,2-bis (2-aminoethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, N1- (3-methoxypropyl) -1,3-propanediamine, 1,4-butanediol bis (3-aminopropyl) ether, ethylene glycol bis (3-aminopropyl) ether and diethylene glycol bis (3-aminopropyl) ether.
Preferably, the diimidazoles include 1,1-carbonyldiimidazole, 1,1-thiocarbonyldiimidazole, 1,1' -sulfonyldiimidazole, bis (1H-imidazolyl) imine.
Preferably, the perfluoroalkanesulfonyl fluoride is one or a mixture of two or more of perfluorobutanesulfonyl fluoride, perfluorohexanesulfonyl fluoride and perfluorooctanesulfonyl fluoride.
In addition, on the other hand, the polytetrafluoroethylene microporous membrane is also provided and is prepared by adopting the hydrophilic modification method.
By adopting the technical scheme, the invention has the following beneficial effects:
perfluoroalkyl sulfonyl fluorides (represented by RfSO2F, such as n-C4F9SO2F, n-C6F13SO2F, n-C8F17SO 2F) are a group of hydroxyl activating agents with excellent performance. RfSO2F can activate the hydroxyl of an alcohol and is widely applied to the construction of C-F, C-O, C-N and C-S bonds, and can be used as an excellent condensation reagent for activating the hydroxyl of an organic carboxylic acid to perform esterification, amidation and anhydrization reactions.
Because the fluorocarbon chain surface energy of the Rf-structure is lower, the Rf-structure is well combined with PTFE, and sulfonamide, ether bond and amino structure are introduced on the PTFE to improve the acid-base resistance of the hydrophilic coating through the sulfonylation reaction of sulfonyl fluoride and primary and secondary amino groups on the polyether urea structural material.
Because the sulfonyl group of Rf-SO2F is a stronger electron-withdrawing group, the hydrogen atom on the sulfonamide nitrogen atom generated by primary amine on PU is influenced by the sulfonyl group to have certain acidity, and can react with sodium hydroxide solution to generate sodium salt dissolved in water; the sulfonamide generated from the secondary amine on PU cannot react with alkali because the nitrogen atom has no hydrogen atom, so that the sulfonamide is insoluble in alkali water, and therefore, a hydrophilic structure generated from the PU structure has good chemical resistance.
These features and advantages of the present invention will be disclosed in more detail in the following detailed description of the invention.
[ detailed description ] A
The technical solutions of the embodiments of the present invention are explained and illustrated below, but the following embodiments are only preferred embodiments of the present invention, and not all of them. Based on the embodiments in the implementation, other embodiments obtained by those skilled in the art without any creative effort belong to the protection scope of the present invention.
A hydrophilic modification method of a sulfonated polyether urea structure on a polytetrafluoroethylene microporous membrane comprises the following steps:
1) Cleaning a PTFE microporous membrane with absolute ethyl alcohol and then drying;
2) Adding perfluoroalkyl sulfonyl fluoride and absolute ethanol into a reaction container for mixing, wherein the concentration of the perfluoroalkyl sulfonyl fluoride is 0.6-5.0%;
3) Placing the cleaned and dried PTFE microporous membrane in a reaction container, defoaming for 10-30min by means of an ultrasonic and vacuum auxiliary system, standing for 1-6h, and enabling the perfluoroalkyl sulfonyl fluoride to be closely arranged and deposited on the PTFE fiber by virtue of intermolecular acting force;
4) Adding DMF solution, triethylamine and PU into a reaction container, fully stirring to prepare PU solution, transferring the PTFE film anchoring the perfluoroalkyl sulfonyl fluoride into the PU solution, and standing for 2-10h after vacuum for 5-30 min under-0.06-0.1 MPa;
5) Taking out the PTFE microporous membrane, drying in an oven at 50-80 ℃ for 1-4h, carrying out acylation reaction on sulfonyl fluoride and primary and secondary amine with a PU structure in the process to generate a topological cross-linked structure, and anchoring on polytetrafluoroethylene to introduce hydrophilic sulfonamide, ether bond and amino structure.
The preparation method of the PU structure comprises the following steps: adding a diimidazole and DMF solution into a reaction container, removing oxygen under the protection of nitrogen gas, controlling the temperature to be less than 1 ℃, slowly dropwise adding ether diamine under magnetic stirring, raising the water bath value to 40-60 ℃ after dropwise adding in order to ensure that two ends of PU are capped by amino groups and the molar weight of the ether diamine is more than that of the diimidazole, continuing magnetic stirring for 6-12h, and finally distilling the reactant to obtain the PU structure.
The reaction vessel may be placed in a bath of ice and water with the temperature controlled to less than 1 ℃.
The mass ratio of the diimidazole to the DMF solution is from 0.1 to 0.4, e.g. 0.3.
The structure of the ether diamine is NH2-R-O-R-NH2, and comprises 1,2-bis (2-aminoethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, N1- (3-methoxypropyl) -1,3-propanediamine, 1,4-butanediol bis (3-aminopropyl) ether, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether and the like. One or more of them may be added in combination.
The diimidazole includes 1,1-carbonyldiimidazole, 1,1-thiocarbonyldiimidazole, 1,1' -sulfonyldiimidazole and bis (1H-imidazolyl) imide, and specifically one of them may be added.
The perfluoroalkyl sulfonyl fluoride comprises one of perfluorobutyl sulfonyl fluoride, perfluorohexyl ethyl sulfonyl fluoride and perfluorooctyl sulfonyl fluoride which are specifically added.
Example one
Synthesis of polyether Thiourea (PU-TCDI)
(1) 2.0g of 1,1-thiocarbonyldiimidazole and 10.0ML of DMF solution are added into a 250ML three-neck flask, oxygen is removed under the protection of nitrogen gas, the device is placed in an ice-water mixed bath, the temperature is controlled to be lower than 1 ℃, 2.3g of 1,2-bis (2-aminoethoxy) ethane is slowly dripped under the magnetic stirring, after dripping is finished, the water bath is heated to 60 ℃, and the magnetic stirring is continued for 12 hours. And finally, distilling the reactant to obtain the Zongzi-yellow purified viscous liquid PU-TCDI.
Hydrophilic modification of PTFE
(2) Cleaning polytetrafluoroethylene hollow fiber membrane with aperture of 0.2-0.3 μm with anhydrous ethanol, removing surface impurities, and drying in oven at 40 deg.C for 10 min.
(3) Anhydrous ethanol and perfluorohexylsulfonyl fluoride were added to a three-necked reaction flask in a concentration of 1.2%.
(4) And (3) placing the cleaned polytetrafluoroethylene hollow fiber membrane into a three-mouth reaction bottle, defoaming for 10min by virtue of an ultrasonic and vacuum auxiliary system, and standing for 6h.
(5) A three-necked reaction flask was charged with 38.7g of DMF solution, 2.1g of PU-TCDI and 1.2g of triethylamine, the mass fraction of PU-TCDI was 5.0%, and after stirring sufficiently, the above-mentioned PTFE membrane anchoring perfluorohexylsulfonyl fluoride was transferred to a PTU solution, and the solution was evacuated at-0.092 MPa for 20min and then allowed to stand for 6 hours.
(6) And taking out the PTFE microporous membrane, and drying in an oven at 80 ℃ for 2h.
Example two
Synthesis of Polyetherureas (PU-CDI)
(1) 2.3g of 1,1-carbonyldiimidazole and 10.0ML of DMF solution are added into a 250ML three-neck flask, oxygen is removed under the protection of nitrogen, the device is placed in an ice-water mixed bath, the temperature is controlled to be less than 1 ℃, 3.2g of 1,2-bis (2-aminoethyl) ethane is slowly dripped under the magnetic stirring, after dripping is finished, the water bath is heated to 60 ℃, and the magnetic stirring is continued for 12 hours. And finally, distilling the reactant to obtain white purified viscous liquid PU.
Hydrophilic modification of PTFE
(2) Cleaning polytetrafluoroethylene hollow fiber membrane with aperture of 0.2-0.3 μm with anhydrous ethanol, removing surface impurities, and drying in oven at 40 deg.C for 10 min.
(3) Anhydrous ethanol and perfluorohexylethanesulfonyl fluoride were added to the three-necked flask at a concentration of 1.8%. And (3) placing the cleaned polytetrafluoroethylene hollow fiber membrane into a three-mouth reaction bottle, defoaming for 20min by virtue of an ultrasonic and vacuum auxiliary system, and standing for 8h.
(4) 38.7g of DMF solution, 2.1g of PU-CDI and 1.2g of triethylamine were put into a three-necked flask, and the mass fraction of PU-CDI was 5.0%, and after stirring sufficiently, the above-mentioned PTFE film anchoring perfluorohexylsulfonyl fluoride was transferred into the PU-CDI solution, and the mixture was evacuated at-0.092 MPa for 30 minutes and then allowed to stand for 12 hours.
And taking out the PTFE microporous membrane, and drying in an oven at 85 ℃ for 1.5h.
In the above two examples, after hydrophilic modification of the polytetrafluoroethylene microporous membrane, a hydrophilic polytetrafluoroethylene microporous membrane was obtained, which is shown in table 1 in comparison with the ratio before modification.
TABLE 1
While the invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that the invention is not limited thereto, but rather, may be embodied in many different forms and varied. Any modification which does not depart from the functional and structural principles of the invention is intended to be included within the scope of the claims.
Claims (8)
1. A hydrophilic modification method of a polytetrafluoroethylene microporous membrane by a sulfonated polyether urea structure is characterized by comprising the following steps:
1) Cleaning a PTFE microporous membrane with absolute ethyl alcohol and then drying;
2) Adding perfluoroalkyl sulfonyl fluoride and absolute ethanol into a reaction container for mixing, wherein the mass fraction of the perfluoroalkyl sulfonyl fluoride is 0.6-5.0%;
3) Placing the cleaned and dried PTFE microporous membrane in a reaction container, defoaming for 10-30min by means of an ultrasonic and vacuum auxiliary system, standing for 1-6h, and enabling the perfluoroalkyl sulfonyl fluoride to be closely arranged and deposited on the PTFE fiber by virtue of intermolecular acting force;
4) Adding DMF solution, triethylamine and PU into a reaction container, fully stirring to prepare PU solution, transferring the PTFE membrane anchoring perfluoroalkyl sulfonyl fluoride into the PU solution, and standing for 2-10h after 5-30 minutes of vacuum at-0.06-0.1 MPa;
5) Taking out the PTFE microporous membrane, drying in an oven at 50-80 deg.C for 1-4h, subjecting sulfonyl fluoride and primary and secondary amine of PU to acylation reaction to generate topological structure, anchoring on polytetrafluoroethylene, and introducing hydrophilic sulfonamide, ether bond and amino structure.
2. The method for hydrophilic modification of polytetrafluoroethylene microporous membrane by sulfonated polyether urea structure according to claim 1, wherein PU is prepared by the following steps: adding a diimidazole and DMF solution into a reaction container, removing oxygen under the protection of nitrogen gas, controlling the temperature to be less than 1 ℃, slowly dripping an ether diamine structure material under magnetic stirring, increasing the water bath value to 40-60 ℃ after dripping to ensure that two ends of PU are capped by amino groups and the mass of the ether diamine structure is more than that of the diimidazole, continuing the magnetic stirring for 6-12 hours, and finally distilling the reactant to obtain the PU structure.
3. The method for hydrophilic modification of a polytetrafluoroethylene microporous membrane by a sulfonated polyether urea structure according to claim 2, wherein the reaction vessel is placed in an ice-water mixed bath, and the temperature is controlled to be less than 1 ℃.
4. The method for hydrophilic modification of a polytetrafluoroethylene microporous membrane by a sulfonated polyether urea structure according to claim 2, wherein the mass ratio of the diimidazole to the DMF solution is 0.1-0.4.
5. The hydrophilic modification method of the sulfonated polyether urea structure on the polytetrafluoroethylene microporous membrane, as recited in claim 2, wherein the ether diamine structure material comprises 1,2-bis (2-aminoethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, N1- (3-methoxypropyl) -1,3-propanediamine, 1,4-butanediol bis (3-aminopropyl) ether, ethylene glycol bis (3-aminopropyl) ether, and diethylene glycol bis (3-aminopropyl) ether.
6. The method for hydrophilic modification of polytetrafluoroethylene microporous membrane by sulfonated polyether urea structures according to claim 2, wherein the diimidazoles include 1,1-carbonyldiimidazole, 1,1-thiocarbonyldiimidazole, 1,1' -sulfonyldiimidazole and bis (1 hydro-imidazolyl) imide.
7. The method for hydrophilic modification of polytetrafluoroethylene microporous membrane by sulfonated polyether urea structures according to claim 1, wherein the perfluoroalkyl sulfonyl fluoride is one or a mixture of two or more of perfluorobutyl sulfonyl fluoride, perfluorohexyl ethyl sulfonyl fluoride and perfluorooctyl sulfonyl fluoride.
8. A polytetrafluoroethylene microporous membrane, characterized in that the polytetrafluoroethylene microporous membrane is modified by the hydrophilic modification method of any one of claims 1 to 7.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1768912A (en) * | 2005-10-13 | 2006-05-10 | 中材科技股份有限公司 | High temperature resistant P.T.F.E. coated filter material |
| CN103483618A (en) * | 2013-10-11 | 2014-01-01 | 苏州汇龙膜技术发展有限公司 | Hydrophilic modification method of polytetrafluoroethylene porous membrane |
| JP2016074830A (en) * | 2014-10-07 | 2016-05-12 | 三菱マテリアル株式会社 | Hydrophilic oil repellent solution, surface coating material, coating film, resin composition, oil and water separation filter medium and porous body |
| CN106574165A (en) * | 2014-07-30 | 2017-04-19 | 三菱综合材料株式会社 | Hydrophilic oil repellent agent and method for manufacturing same, and surface covering material, coating film, resin composition, oil-water separation filter medium, and porous body |
| CN109867892A (en) * | 2019-03-26 | 2019-06-11 | 段瑶瑶 | A kind of preparation method with using the strongly adherent tetrafluoroethylene resin of polyurethane |
| CN110330782A (en) * | 2019-06-26 | 2019-10-15 | 江苏理工学院 | A kind of preparation method of modified graphene oxide/polyurethane heat resistant composite material |
| CN110878133A (en) * | 2019-11-08 | 2020-03-13 | 常熟三爱富中昊化工新材料有限公司 | Hydrophilic polytetrafluoroethylene microporous membrane and preparation method thereof |
| CN112848572A (en) * | 2021-02-07 | 2021-05-28 | 际华集团股份有限公司系统工程中心 | Superstrong waterproof multifunctional composite fabric and manufacturing method thereof |
| CN113322001A (en) * | 2021-05-25 | 2021-08-31 | 安徽名士达新材料有限公司 | High-wear-resistance light-cured UV paint and production process thereof |
-
2022
- 2022-08-01 CN CN202210917215.4A patent/CN115245743B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1768912A (en) * | 2005-10-13 | 2006-05-10 | 中材科技股份有限公司 | High temperature resistant P.T.F.E. coated filter material |
| CN103483618A (en) * | 2013-10-11 | 2014-01-01 | 苏州汇龙膜技术发展有限公司 | Hydrophilic modification method of polytetrafluoroethylene porous membrane |
| CN106574165A (en) * | 2014-07-30 | 2017-04-19 | 三菱综合材料株式会社 | Hydrophilic oil repellent agent and method for manufacturing same, and surface covering material, coating film, resin composition, oil-water separation filter medium, and porous body |
| JP2016074830A (en) * | 2014-10-07 | 2016-05-12 | 三菱マテリアル株式会社 | Hydrophilic oil repellent solution, surface coating material, coating film, resin composition, oil and water separation filter medium and porous body |
| CN109867892A (en) * | 2019-03-26 | 2019-06-11 | 段瑶瑶 | A kind of preparation method with using the strongly adherent tetrafluoroethylene resin of polyurethane |
| CN110330782A (en) * | 2019-06-26 | 2019-10-15 | 江苏理工学院 | A kind of preparation method of modified graphene oxide/polyurethane heat resistant composite material |
| CN110878133A (en) * | 2019-11-08 | 2020-03-13 | 常熟三爱富中昊化工新材料有限公司 | Hydrophilic polytetrafluoroethylene microporous membrane and preparation method thereof |
| CN112848572A (en) * | 2021-02-07 | 2021-05-28 | 际华集团股份有限公司系统工程中心 | Superstrong waterproof multifunctional composite fabric and manufacturing method thereof |
| CN113322001A (en) * | 2021-05-25 | 2021-08-31 | 安徽名士达新材料有限公司 | High-wear-resistance light-cured UV paint and production process thereof |
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