CN114797504A - Sulfonated polyamide/hydrophobic polymer composite membrane and preparation method and application thereof - Google Patents
Sulfonated polyamide/hydrophobic polymer composite membrane and preparation method and application thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 103
- 229920001600 hydrophobic polymer Polymers 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 229920006159 sulfonated polyamide Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 155
- 239000000243 solution Substances 0.000 claims abstract description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000012696 Interfacial polycondensation Methods 0.000 claims abstract description 24
- 229920000768 polyamine Polymers 0.000 claims abstract description 21
- 239000004952 Polyamide Substances 0.000 claims abstract description 20
- 229920002647 polyamide Polymers 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 239000008346 aqueous phase Substances 0.000 claims description 48
- 239000000178 monomer Substances 0.000 claims description 48
- 239000012074 organic phase Substances 0.000 claims description 44
- 239000002904 solvent Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 18
- 238000011049 filling Methods 0.000 claims description 17
- 229920005597 polymer membrane Polymers 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical group ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 12
- 230000007480 spreading Effects 0.000 claims description 12
- 238000003892 spreading Methods 0.000 claims description 12
- JVMSQRAXNZPDHF-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C(N)=C1 JVMSQRAXNZPDHF-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 150000001263 acyl chlorides Chemical class 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- VOPSFYWMOIKYEM-UHFFFAOYSA-N 2,5-diaminobenzene-1,4-disulfonic acid Chemical compound NC1=CC(S(O)(=O)=O)=C(N)C=C1S(O)(=O)=O VOPSFYWMOIKYEM-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000012466 permeate Substances 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 238000001471 micro-filtration Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 238000000108 ultra-filtration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000006053 organic reaction Methods 0.000 claims 1
- 230000000149 penetrating effect Effects 0.000 claims 1
- 239000003495 polar organic solvent Substances 0.000 claims 1
- 238000009736 wetting Methods 0.000 claims 1
- 229920006254 polymer film Polymers 0.000 abstract description 6
- 230000035699 permeability Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 91
- 210000004379 membrane Anatomy 0.000 description 75
- -1 polyethylene Polymers 0.000 description 14
- 230000005540 biological transmission Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000004698 Polyethylene Substances 0.000 description 9
- 229920000573 polyethylene Polymers 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- HEAHMJLHQCESBZ-UHFFFAOYSA-N 2,5-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(N)C(S(O)(=O)=O)=C1 HEAHMJLHQCESBZ-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 210000002469 basement membrane Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000009292 forward osmosis Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 230000010399 physical interaction Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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Classifications
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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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
-
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/36—Introduction of specific chemical groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
- B01D2325/023—Dense layer within the membrane
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a sulfonated polyamide/hydrophobic polymer composite membrane and a preparation method and application thereof. And (2) fully infiltrating the polymer film with polyacyl chloride organic solution, diffusing the polyacyl chloride organic solution to the other side of the polymer film, contacting with polyamine aqueous solution to form an immiscible interface layer, and carrying out interfacial polycondensation on the polyamine and the polyacyl chloride at the interface layer to generate an aromatic crosslinked polyamide compact thin layer so as to obtain the polyamide-hydrophobic polymer composite film. The invention solves the problem that polyamine aqueous solution can not be soaked and spread on the surface of a hydrophobic polymer film by a reverse interfacial polycondensation method, limits a reaction area at the skin layer of a polymer film substrate, improves the composite stability between a polyamide compact layer and a polymer microporous film, introduces sulfonic acid groups, and improves the hydrophilicity and the adsorption permeability to water vapor.
Description
The technical field is as follows:
the invention relates to the technical field of membrane materials, in particular to a sulfonated polyamide/hydrophobic polymer composite membrane prepared based on a reverse interfacial polycondensation method, and a preparation method and application thereof.
Background art:
the homogeneous polymer membrane obtained by the traditional membrane preparation method is difficult to simultaneously have a compact separation layer and a porous support layer, and is difficult to realize the simultaneous improvement of the component transmittance and the retention rate, so that the polymer composite membrane is developed, namely, a thin compact layer is compounded on the surface of the polymer porous membrane support layer in the modes of coating, spraying, interfacial polycondensation and the like, and the membrane pore structures, the wettability, the chemical components and the like of the porous support layer and the compact selection layer can be respectively regulated and controlled, so that the separation performance of the separation membrane is improved, and the selectivity of the separation membrane material is widened. The method is a common method for preparing a reverse osmosis membrane, a nanofiltration membrane and a forward osmosis membrane at present, wherein a polyamide layer with a nanometer-level thickness is grown on the surface of a microporous membrane such as polysulfone, polyvinylidene fluoride, polyacrylonitrile, cellulose acetate and the like through the interfacial polycondensation of polyamine and polyacyl chloride, and the method is deeply researched and widely applied.
However, the traditional interfacial polycondensation method is implemented by fully soaking polyamine aqueous solution on the surface of a supporting layer, removing the redundant reaction solution after soaking for a period of time, spreading polyacyl chloride organic solution on the surface of the film enriched with polyamine monomers, and performing polycondensation crosslinking reaction at an immiscible water-organic solvent interface. The polyamide functional layer obtained by this method has the following problems: (1) the method is characterized in that a polymer supporting layer with poor hydrophilicity is directly adopted, a compact polyamide layer is difficult to form on the surface of the polymer supporting layer, and a supporting layer base film is required to have good hydrophilicity so as to realize the sufficient infiltration and enrichment of aqueous phase reaction liquid on the surface of the film, so that the material of the supporting layer is limited to a hydrophilic polymer, and the hydrophilic modification is usually carried out on the polymer with poor hydrophilicity; (2) the interfacial polycondensation reaction occurs in an organic phase layer, a water phase monomer needs to diffuse into the organic phase for reaction, and the organic phase layer is isolated from a supporting layer by a water phase layer, so that the generated polyamide layer has the problem of connection stability with the supporting layer, the polyamide layer is peeled from the supporting layer after being used for a long time, and a certain chemical or physical interaction needs to be given to the polyamide layer and the supporting layer for improving the stability of the polyamide layer. In view of the above problems, the present invention provides a novel interfacial polycondensation method, i.e., a reverse interfacial polycondensation implementation method.
The invention content is as follows:
the invention aims to disclose a method for preparing a moisture-permeable and gas-barrier polymer film by a reverse interfacial polycondensation method and a prepared composite film, and solve the problem that a compact polyamide layer cannot be formed on the surface of a hydrophobic polymer supporting layer by the traditional method. A compact separation layer with a small thickness can be effectively constructed on the surface of a polymer membrane supporting layer through interfacial polycondensation of polyamine and polyacyl chloride at a membrane skin layer, the hydrophilicity of the membrane is improved by introducing sulfonic acid groups, and the problem that interfacial polycondensation cannot be carried out on the surface of a hydrophobic polymer membrane supporting layer due to the fact that the surface of the hydrophobic polymer membrane supporting layer is difficult to be infiltrated by aqueous phase reaction liquid can be solved through a reverse interfacial polycondensation method. The prepared sulfonated polyamide/hydrophobic polymer composite membrane has higher moisture and gas barrier properties, can be used in the field of total heat exchange, and has economic and efficient preparation process.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of sulfonated polyamide/hydrophobic polymer composite membrane comprises the steps of spreading a hydrophobic polymer supporting layer above an aqueous phase reaction solution, enabling the lower surface of the polymer supporting layer to be in full contact with the aqueous phase reaction solution but not to be soaked, enabling an organic phase reaction solution arranged on the upper surface of the hydrophobic polymer supporting layer to permeate through the polymer supporting layer, forming an immiscible interface with the aqueous phase reaction solution at the lower surface of the polymer supporting layer, and enabling an aqueous phase monomer to diffuse into the polymer supporting layer to be subjected to condensation polymerization and crosslinking with the organic phase monomer existing in and on the polymer supporting layer to generate a compact sulfonated polyamide layer. The reverse interfacial polycondensation method can solve the problem that the traditional interfacial polycondensation reaction can not be performed on the surface of a hydrophobic polymer film, and the polyamide layer generated by the reaction is embedded with the film hole structure, so that the connection stability of the polyamide layer and the film hole structure is also improved. The hydrophobic polymer support layer is a hydrophobic polymer porous membrane, and the contact angle is 90-130 degrees.
Specifically, the aqueous phase monomer is polyamine containing sulfonic acid groups, the aqueous phase reaction solution is an aqueous solution of polyamine containing sulfonic acid groups, the organic phase monomer is polybasic acid chloride, and the organic phase reaction solution is an organic solution of polybasic acid chloride.
Specifically, the preparation method of the sulfonated polyamide/hydrophobic polymer composite membrane comprises the following steps:
1) respectively preparing polyamine aqueous solution and polyacyl chloride organic solution:
deionized water is used as a solvent, a polyamine monomer containing sulfonic acid groups is added, and after stirring and dissolving, an aqueous phase reaction solution with the mass fraction of 0.5-3.5% is prepared, wherein the concentration of the aqueous phase reaction solution is preferably 0.6-2.1%; the preparation method comprises the steps of taking a nonpolar organic solvent as a solvent, adding a polybasic acyl chloride monomer, stirring and dissolving to prepare an organic phase reaction solution with the mass fraction of 0.2-1.8%, wherein the concentration of the organic phase reaction solution is preferably 0.3-1.5%.
The polyamine monomer containing the sulfonic acid group is any one of 2, 4-diaminobenzene sulfonic acid, 2, 5-diaminobenzene sulfonic acid and 2, 5-diamino-1, 4-benzene disulfonic acid, or a mixed solution of any one and piperazine;
the polybasic acyl chloride is trimesoyl chloride;
the nonpolar organic solvent is any one of n-hexane, toluene, xylene, n-octane and cyclohexane.
2) The polyamine aqueous solution and the polyacyl chloride organic solution have interfacial polycondensation reaction at the skin layer of the hydrophobic polymer film:
and (2) filling an aqueous phase reaction solution into a lower layer reaction container, slowly spreading a hydrophobic polymer porous membrane on the surface of the aqueous phase reaction solution, removing bubbles which may be generated, fixing the hydrophobic polymer porous membrane between an upper layer reaction container and a lower layer reaction container, injecting an organic phase reaction solution into the upper layer reaction container, allowing the organic phase reaction solution to downwards permeate into the hydrophobic polymer porous membrane, allowing the aqueous phase reaction solution and the organic phase reaction solution to react at the surface skin layer of the lower surface of the hydrophobic polymer porous membrane for 1-12 min to generate a compact polyamide layer, wherein the reaction time is preferably 2-10 min, transferring the membrane into a 60 ℃ oven, keeping for 30min, continuously completing the reaction, fully cleaning the surface of the membrane, and drying.
The hydrophobic polymer porous membrane is a hydrophobic microfiltration membrane or an ultrafiltration membrane, such as any one of a polyethylene porous membrane, a polypropylene porous membrane, a polyvinylidene fluoride porous membrane, a polytetrafluoroethylene porous membrane and a polydimethylsiloxane porous membrane.
The sulfonated polyamide layer is a compact layer, has the thickness of 50-400 nm, is partially filled in a porous skin layer of the polymer film, has good connection stability with a hydrophobic polymer film, has good moisture and gas barrier properties, and can be used in the field of total heat exchange and also can be used for separating organic solvents.
The invention has the beneficial effects that:
(1) a compact polyamide layer is synthesized on the surface of the hydrophobic polymer porous membrane by a reverse interfacial polycondensation method, so that the problem that the surface of the hydrophobic polymer porous membrane is difficult to be wetted by aqueous solution is solved;
(2) the introduction of sulfonic acid groups can improve the hydrophilicity of the surface of the composite membrane and improve the adsorption and diffusion capacity to water vapor;
(3) the preparation process is simple, economic and efficient, and the polymer support layer basement membrane does not need to be pre-modified.
Drawings
FIG. 1 is an apparatus for preparing a sulfonated polyamide/hydrophobic polymer composite membrane according to the present invention;
FIG. 2 is a scanning electron microscope image of the surface topography of the sulfonated polyamide/hydrophobic polymer composite membranes prepared in examples 3 and 5;
FIG. 3 is a scanning electron microscope image of the cross-sectional morphology of the sulfonated polyamide/hydrophobic polymer composite membrane prepared in example 3 or 5;
FIG. 4 is a surface contact angle chart of sulfonated polyamide/hydrophobic polymer composite membranes prepared in example 1, example 3 and example 5;
FIG. 5 shows the water vapor transmission and CO transmission of the sulfonated polyamide/hydrophobic polymer composite membranes prepared in examples 1, 3 and 5 2 Barrier performance is plotted against time.
FIG. 6 is a scanning electron microscope photograph of the surface morphology of the sulfonated polyamide/hydrophobic polymer composite membrane prepared by the conventional interfacial polycondensation method in control group 1
Detailed Description
The invention will be further described with reference to the drawings and the embodiments, but the scope of the invention is not limited thereto.
Example 1:
as shown in fig. 1, the apparatus for preparing moisture and gas permeable polymer film by reverse interfacial polycondensation according to this embodiment includes a lower reaction vessel 1, an upper reaction vessel 2 and a fixing clip 3, wherein the lower reaction vessel 1 is open at the upper end, the edge of the upper end opening extends outward to form a fixing lug, the upper reaction vessel 2 is open at the lower end, the edge of the lower end opening of the upper reaction vessel extends outward to form a fixing lug, an injection port is disposed at the upper end of the upper reaction vessel, and the upper end opening of the lower reaction vessel 1 corresponds to the lower end opening of the upper reaction vessel 2. When the reactor is used, an aqueous phase reaction solution is filled in the lower layer reaction container, the hydrophobic polymer porous membrane is placed on the surface of the aqueous phase reaction solution, the upper end opening and the fixing lug of the lower layer reaction container 1 are respectively aligned with the lower end opening and the fixing lug of the upper layer reaction container 2, and the hydrophobic polymer porous membrane is placed at the openings of the lower layer reaction container 1 and the upper layer reaction container 2 and is fixed by the fixing lugs at the left end and the right end which are clamped by the fixing clamp 3.
The preparation method of the polyamide/hydrophobic polymer composite membrane material comprises the following specific steps:
adding piperazine monomer into deionized water serving as a solvent, stirring and dissolving to prepare an aqueous phase reaction solution with the mass fraction of 1.2%; adding trimesoyl chloride monomer into n-hexane as a solvent, stirring and dissolving to prepare an organic phase reaction solution with the mass fraction of 1.0%;
filling an aqueous phase reaction solution into a lower layer reaction container at room temperature, slowly spreading a polyethylene porous membrane on the surface of the aqueous phase reaction solution, removing bubbles which may be generated, fixing the membrane between an upper layer reaction container and a lower layer reaction container, filling an organic phase reaction solution into the upper layer reaction container, taking out a polymer membrane after the aqueous phase reaction solution and the organic phase reaction solution react for 2min at an interface, transferring the polymer membrane into a 60 ℃ oven for holding for 30min, continuing to finish the reaction, then fully cleaning the surface of the membrane, and drying;
the water contact angle of the prepared film is 63 degrees, and the water vapor transmission rate is 4530 g/(m) 2 ·24h)，CO 2 Transmittance of 4.3X 10 3 cm 3 /(m 2 ·24h·0.1MPa)。
Example 2:
the preparation method of the sulfonated polyamide/hydrophobic polymer composite membrane material comprises the following specific steps:
adding a piperazine/2, 4-diaminobenzene sulfonic acid mixed monomer with the mass ratio of 7:3 into deionized water serving as a solvent, and stirring and dissolving to prepare an aqueous phase reaction solution with the total monomer mass fraction of 1.2%; adding trimesoyl chloride monomer into n-hexane as a solvent, stirring and dissolving to prepare an organic phase reaction solution with the mass fraction of 1.0%;
filling an aqueous phase reaction solution into a lower layer reaction container at room temperature, slowly spreading a polyethylene porous membrane on the surface of the reaction solution, removing bubbles which may be generated, fixing the membrane between an upper layer reaction container and a lower layer reaction container, filling an organic phase reaction solution into an upper layer reaction container, taking out a polymer membrane after the aqueous phase reaction solution and the organic phase reaction solution react for 2min at an interface, transferring the polymer membrane into a 60 ℃ oven for holding for 30min, continuing to finish the reaction, then fully cleaning the surface of the membrane, and drying;
the water contact angle of the prepared film is 57 degrees, and the water vapor transmission rate is 5624 g/(m) 2 ·24h)，CO 2 Transmittance of 8.2X 10 3 cm 3 /(m 2 ·24h·0.1MPa)。
Example 3:
the preparation method of the sulfonated polyamide/hydrophobic polymer composite membrane material comprises the following specific steps:
adding a piperazine/2, 4-diaminobenzene sulfonic acid mixed monomer with the mass ratio of 3:7 into deionized water serving as a solvent, and stirring and dissolving to prepare an aqueous phase reaction solution with the total monomer mass fraction of 1.5%; adding trimesoyl chloride monomer into n-hexane as a solvent, stirring and dissolving to prepare an organic phase reaction solution with the mass fraction of 1.2%;
filling an aqueous phase reaction solution into a lower layer reaction container at room temperature, slowly spreading a polyethylene porous membrane on the surface of the reaction solution, removing bubbles which may be generated, fixing the membrane between an upper layer reaction container and a lower layer reaction container, filling an organic phase reaction solution into an upper layer reaction container, taking out a polymer membrane after the aqueous phase reaction solution and the organic phase reaction solution react for 2min at an interface, transferring the polymer membrane into a 60 ℃ oven for holding for 30min, continuing to finish the reaction, then fully cleaning the surface of the membrane, and drying;
the water contact angle of the prepared film is 52 degrees, and the water vapor transmission rate is 5824 g/(m) 2 ·24h)，CO 2 The permeation rate was 1.3X 10 4 cm 3 /(m 2 24 h.0.1 MPa). Compared with the example 1 and the example 2, after 70 percent of piperazine monomer is replaced by 2, 4-diaminobenzene sulfonic acid monomer, the hydrophilicity of the surface of the composite membrane is further improved, the water vapor transmission rate is further improved, but the CO is further improved 2 The permeability is also significantly increased, probably because the film-forming properties of the 2, 4-diaminobenzenesulphonic acid monomer in interfacial polycondensation with trimesoyl chloride are not as good as those of piperazine in interfacial polycondensation with trimesoyl chloride, i.e. the latter is more compact.
Example 4:
the preparation method of the sulfonated polyamide/hydrophobic polymer composite membrane material comprises the following specific steps:
adding a 2, 4-diaminobenzene sulfonic acid monomer by taking deionized water as a solvent, stirring and dissolving to prepare an aqueous phase reaction solution with the total monomer mass fraction of 0.75%; adding a trimesoyl chloride monomer into xylene serving as a solvent, stirring and dissolving to prepare an organic phase reaction solution with the mass fraction of 0.5%;
filling an aqueous phase reaction solution into a lower layer reaction container at room temperature, slowly spreading a polyvinylidene fluoride porous membrane on the surface of the reaction solution, removing bubbles which may be generated, fixing the membrane between an upper layer reaction container and a lower layer reaction container, filling an organic phase reaction solution into the upper layer reaction container, taking out a polymer membrane after the aqueous phase reaction solution and the organic phase reaction solution react at an interface for 4min, transferring the polymer membrane into a 60 ℃ oven for holding for 30min, continuing to finish the reaction, then fully cleaning the surface of the membrane, and drying;
the water contact angle of the prepared film is 46 degrees, and the water vapor transmission rate is 6015 g/(m) 2 ·24h)，CO 2 The permeation rate is 1.8X 10 4 cm 3 /(m 2 ·24h·0.1MPa)。
Example 5:
the preparation method of the sulfonated polyamide/hydrophobic polymer composite membrane material comprises the following specific steps:
adding a 2, 4-diaminobenzene sulfonic acid monomer by taking deionized water as a solvent, stirring and dissolving to prepare an aqueous phase reaction solution with the total monomer mass fraction of 1.75%; cyclohexane is taken as a solvent, a trimesoyl chloride monomer is added, and an organic phase reaction solution with the mass fraction of 1.2 percent is prepared after stirring and dissolving;
filling an aqueous phase reaction solution into a lower layer reaction container at room temperature, slowly spreading a polyethylene porous membrane on the surface of the reaction solution, removing bubbles which may be generated, fixing the membrane between an upper layer reaction container and a lower layer reaction container, filling an organic phase reaction solution into an upper layer reaction container, taking out a polymer membrane after the aqueous phase reaction solution and the organic phase reaction solution react for 4min at an interface, transferring the polymer membrane into a 60 ℃ oven for keeping for 30min, continuing to finish the reaction, then fully cleaning the surface of the membrane, and drying;
water connection of prepared membraneThe feeler angle is 47 degrees, and the water vapor transmission rate is 5328 g/(m) 2 ·24h)，CO 2 Transmittance of 1.4X 10 3 cm 3 /(m 2 24 h.0.1 MPa). Compared with the examples 1 and 4, after piperazine monomer is completely replaced by 2, 4-diaminobenzene sulfonic acid monomer, the concentration of the monomer is increased and the reaction time is prolonged, and the composite membrane can simultaneously have higher water vapor transmission rate and lower CO 2 The permeability is due to the high surface hydrophilicity and high solubility to water vapor, but the thickness of the dense selective layer increases with increasing monomer concentration and reaction time, resulting in CO 2 The transmittance is reduced.
Example 6:
the preparation method of the sulfonated polyamide/hydrophobic polymer composite membrane material comprises the following specific steps:
adding a 2, 5-diaminobenzene sulfonic acid monomer by taking deionized water as a solvent, stirring and dissolving to prepare an aqueous phase reaction solution with the total monomer mass fraction of 2.1%; toluene is taken as a solvent, a trimesoyl chloride monomer is added, and an organic phase reaction solution with the mass fraction of 1.5 percent is prepared after stirring and dissolving;
filling an aqueous phase reaction solution into a lower layer reaction container at room temperature, slowly spreading a polytetrafluoroethylene porous membrane on the surface of the reaction solution, removing bubbles which may be generated, fixing the membrane between an upper layer reaction container and a lower layer reaction container, filling an organic phase reaction solution into an upper layer reaction container, taking out a polymer membrane after the aqueous phase reaction solution and the organic phase reaction solution react for 10min at an interface, transferring the polymer membrane into a 60 ℃ oven for keeping for 30min, continuing to finish the reaction, then fully cleaning the surface of the membrane, and drying;
the water contact angle of the prepared film is 46 degrees, and the water vapor transmission rate is 5460 g/(m) 2 ·24h)，CO 2 The permeation rate was 9.5X 10 2 cm 3 /(m 2 ·24h·0.1MPa)。
Example 7:
the preparation method of the sulfonated polyamide/hydrophobic polymer composite membrane material comprises the following specific steps:
deionized water is used as a solvent, 2, 5-diamino-1, 4-benzene disulfonic acid monomers are added, and water phase reaction solution with the total mass fraction of the monomers of 1.75 percent is prepared after stirring and dissolving; adding trimesoyl chloride monomer into n-hexane as a solvent, stirring and dissolving to prepare an organic phase reaction solution with the mass fraction of 1.25%;
filling an aqueous phase reaction solution into a lower layer reaction container at room temperature, slowly spreading a polypropylene porous membrane on the surface of the reaction solution, removing bubbles which may be generated, fixing the membrane between an upper layer reaction container and a lower layer reaction container, filling an organic phase reaction solution into an upper layer reaction container, taking out a polymer membrane after the aqueous phase reaction solution and the organic phase reaction solution react for 6min at an interface, transferring the polymer membrane into a 60 ℃ oven for holding for 30min, continuing to finish the reaction, then fully cleaning the surface of the membrane, and drying;
the water contact angle of the prepared film is 41 degrees, and the water vapor transmission rate is 5784 g/(m) 2 ·24h)，CO 2 Transmittance of 4.5X 10 3 cm 3 /(m 2 24 h.0.1 MPa). When each polyamine monomer contains two sulfonic acid groups, the hydrophilicity is further improved and the water vapor transmission rate is further improved, but the density of the polyamide separation layer is reduced, resulting in CO 2 The transmittance is improved to a certain degree.
Comparative example 1
The sulfonated polyamide/hydrophobic polymer composite membrane material is prepared by a traditional interfacial polycondensation method, and the method comprises the following specific steps:
adding a piperazine/2, 4-diaminobenzene sulfonic acid mixed monomer with the mass ratio of 5:5 into deionized water serving as a solvent, and stirring and dissolving to prepare an aqueous phase reaction solution with the total monomer mass fraction of 1.5%; adding trimesoyl chloride monomer into n-hexane as a solvent, stirring and dissolving to prepare an organic phase reaction solution with the mass fraction of 0.75%;
fixing the polyethylene porous membrane at room temperature, firstly pouring the aqueous phase reaction solution on the surface of the polyethylene porous membrane to enable the aqueous phase reaction solution to be fully contacted with the surface of the polyethylene porous membrane for 5min, then pouring the excess aqueous phase reaction solution, and then pouring the organic phase reaction solution on the surface of the polyethylene porous membrane for 3 min. Then, the excess organic phase reaction solution was removed, and the film was transferred to a 60 ℃ oven for 30min to continue to complete the reaction. The membrane surface was then thoroughly cleaned and dried.
As can be seen from the film surface topography shown in the attached figure 6, because the water phase reaction solution is not infiltrated on the surface of the hydrophobic polymer film, and the polyamine monomer cannot be enriched on the surface of the film, a compact polyamide or sulfonated polyamide separation layer cannot be obtained on the hydrophobic polymer film by adopting the traditional interfacial polycondensation method, the surface of the film still has a porous structure, and the CO separation layer has a porous structure 2 Gases do not have barrier properties and therefore cannot be used in total heat exchange membranes.
Claims (9)
1. A process for preparing the sulfonated polyamide/hydrophobic polymer composite membrane includes spreading the hydrophobic polymer supporting layer over the aqueous phase reaction solution, fully contacting but not wetting the lower surface of said polymer supporting layer, penetrating the organic phase reaction liquid on the upper surface of said hydrophobic polymer supporting layer through said polymer supporting layer, forming an immiscible interface with the aqueous phase reaction solution at the lower surface of the polymer supporting layer, diffusing the aqueous phase monomer into the polymer supporting layer to perform polycondensation and crosslinking with the organic phase monomer in and on the polymer supporting layer to generate a compact sulfonated polyamide layer, wherein the aqueous phase monomer is polyamine containing sulfonic acid groups, the aqueous phase reaction solution is an aqueous solution of polyamine containing sulfonic acid groups, the organic phase monomer is polybasic acyl chloride, and the organic phase reaction liquid is an organic solution of the polybasic acyl chloride.
2. The preparation method of the sulfonated polyamide/hydrophobic polymer composite membrane according to claim 1, wherein the sulfonated polyamide layer has a thickness of 50 to 400nm, is partially filled in a porous skin layer of the polymer membrane, has good connection stability with the hydrophobic polymer membrane, and has good moisture and gas barrier properties.
3. The method for preparing a sulfonated polyamide/hydrophobic polymer composite membrane according to claim 1, comprising the steps of:
1) respectively preparing polyamine aqueous solution and polyacyl chloride organic solution:
deionized water is used as a solvent, a polyamine monomer containing sulfonic acid groups is added, and after stirring and dissolving, a water phase reaction solution with the mass fraction of 0.5-3.5% is prepared; adding a polybasic acyl chloride monomer into a nonpolar organic solvent serving as a solvent, stirring and dissolving the mixture to prepare an organic phase reaction solution with the mass fraction of 0.2-1.8%,
2) the polyamine aqueous solution and the polyacyl chloride organic solution have interfacial polycondensation reaction at the skin layer of the hydrophobic polymer film:
and (2) filling an aqueous phase reaction solution into a lower layer reaction container, slowly spreading a hydrophobic polymer porous membrane on the surface of the aqueous phase reaction solution, removing bubbles which may be generated, fixing the hydrophobic polymer porous membrane between an upper layer reaction container and a lower layer reaction container, filling an organic phase reaction solution into the upper layer reaction container, allowing the organic phase reaction solution to downwards permeate into the hydrophobic polymer porous membrane, allowing the aqueous phase reaction solution and the organic phase reaction solution to react at the surface skin layer of the lower surface of the hydrophobic polymer porous membrane for 1-12 min to generate a compact polyamide layer, transferring the membrane into a 60 ℃ oven to keep for 30min, continuously completing the reaction, fully cleaning the surface of the membrane, and drying.
4. The method for preparing a sulfonated polyamide/hydrophobic polymer composite membrane according to claim 3, wherein the polyamine monomer having a sulfonic acid group is any one of 2, 4-diaminobenzenesulfonic acid, 2, 5-diamino-1, 4-benzenedisulfonic acid, or a mixed solution of any one with piperazine; the polybasic acyl chloride is trimesoyl chloride.
5. The method for preparing a sulfonated polyamide/hydrophobic polymer composite membrane according to claim 3, wherein the non-polar organic solvent is any one of n-hexane, toluene, xylene, n-octane, and cyclohexane.
6. The method for preparing the sulfonated polyamide/hydrophobic polymer composite membrane according to claim 3, wherein the concentration of the aqueous reaction solution in the step (1) is 0.6 to 2.1%, the concentration of the organic reaction solution is 0.3 to 1.5%, and the reaction time is 2 to 10 min.
7. The method for preparing sulfonated polyamide/hydrophobic polymer composite membrane according to claim 3, wherein the hydrophobic polymer porous membrane is a hydrophobic microfiltration membrane or an ultrafiltration membrane.
8. A polyamide/hydrophobic polymer composite membrane prepared by the method of any one of claims 2 to 7.
9. The polyamide/hydrophobic polymer composite membrane prepared by the method of any one of claims 2 to 7 is used for the separation of organic solvents and total heat exchange processes.
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