CN115178098A - Hydrophobic separation and filtration membrane and preparation method and application thereof - Google Patents
Hydrophobic separation and filtration membrane and preparation method and application thereof Download PDFInfo
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- 238000001914 filtration Methods 0.000 title claims description 54
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Classifications
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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
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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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
- B01D69/10—Supported membranes; Membrane supports
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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
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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
- B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/447—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by membrane distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The hydrophobic separation filter membrane comprises a support layer and a hydrophobic layer formed on the support layer, wherein the hydrophobic layer is a porous structure layer formed by stacking spherical or sphere-like silicon-based nano particles, the silicon-based nano particles are made of a three-dimensional reticular organic silicon polymer, and the three-dimensional reticular organic silicon polymer is mainly formed by a chemical crosslinking reaction of a first linear hydrophobic organic silicon polymer and a second linear hydrophobic organic silicon polymer. According to the invention, by constructing the three-dimensional network organic silicon polymer and adjusting the entanglement state of polymer chains by using the electrostatic spraying process, organic and rigid silicon-based nano particles which are regular in shape and uniformly distributed can be formed by spraying, and the anti-wettability and the separation stability of the membrane are improved.
Description
Technical Field
The invention relates to the technical field of membrane separation, in particular to a hydrophobic separation filtering membrane and a preparation method and application thereof.
Background
Water shortage has become a worldwide problem and is further exacerbated as populations grow and water pollution becomes more prevalent. Obtaining fresh water resources by desalination of sea water is an important method for solving the shortage of water resources at present. Among various seawater desalination technologies, the Membrane Distillation (MD) process is an ideal membrane separation technology due to its high desalination rate and mild operating conditions. In the MD process, non-volatile components and water vapor are separated by the superhydrophobic membrane pores of the superhydrophobic separation filtration membrane. However, when the super-hydrophobic separation filter membrane is wetted with water, the membrane pores will lose the separation function. Therefore, the anti-wettability of the superhydrophobic separation filtration membrane determines its separation stability.
Generally, the super-hydrophobicity of the membrane surface is realized by adopting a low surface energy material and combining a method for regulating a micro-nano structure of surface layering, and representatively, the micro-nano structure of the membrane surface is regulated and controlled by introducing rigid inorganic nanoparticles (such as silicon dioxide and the like) in electrostatic spinning or electrostatic spraying so as to improve the hydrophobicity and the anti-wettability, however, the solubility and the dispersibility of the rigid inorganic nanoparticles in a polymer solution of electrostatic spinning or electrostatic spraying are poor, the uniform distribution of the rigid inorganic nanoparticles on the membrane surface is seriously influenced, and the anti-wettability and the separation stability of the membrane are influenced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a hydrophobic separation and filtration membrane and a preparation method and application thereof.
In order to realize the purpose, the technical scheme of the invention is as follows:
a hydrophobic separation and filtration membrane comprises a support layer and a hydrophobic layer formed on the support layer, wherein the hydrophobic layer is a porous structure layer formed by stacking spherical or sphere-like silicon-based nanoparticles, the silicon-based nanoparticles are made of a three-dimensional reticular organic silicon polymer, and the three-dimensional reticular organic silicon polymer is mainly formed by a chemical crosslinking reaction of a first linear hydrophobic organic silicon polymer and a second linear hydrophobic organic silicon polymer.
The invention also provides a preparation method of the hydrophobic separation and filtration membrane, which comprises the following steps:
carrying out chemical crosslinking reaction on the first linear hydrophobic organosilicon polymer and the second linear hydrophobic organosilicon polymer to obtain a three-dimensional reticular organosilicon polymer solution;
placing the three-dimensional reticular organic silicon polymer solution in an electrostatic injector, laying a supporting layer on a collector, rotating the collector around a shaft, injecting the three-dimensional reticular organic silicon polymer solution by the electrostatic injector to form silicon-based nano particles, depositing the silicon-based nano particles on the supporting layer, curing the silicon-based nano particles to form a hydrophobic layer, and obtaining the separation filtering membrane.
The embodiment of the invention has the following beneficial effects:
according to the embodiment of the invention, the three-dimensional network organic silicon polymer is constructed to provide a tighter polymer entanglement state, the three-dimensional network organic silicon polymer can form spherical or spheroidal organic silicon-based nanoparticles with regular shapes, the organic silicon-based nanoparticles are uniformly distributed, the anti-wettability and the separation stability of the membrane are improved, and the compatibility of the organic silicon-based nanoparticles and the supporting layer is higher, so that the anti-wettability and the separation stability of the membrane are also improved.
According to the embodiment of the invention, the three-dimensional reticular organic silicon polymer solution is electrostatically sprayed by using an electrostatic spraying process, and the entanglement state of the polymer is further tightened through the electrostatic spraying process, so that organic and rigid silicon-based nano particles which are spherical or spheroidal and are regularly and uniformly distributed can be sprayed, and the anti-wettability and the separation stability of the membrane are improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Wherein:
fig. 1 is SEM images of separation filtration membranes obtained in comparative example 1 and examples 1 to 6, wherein the first row of each picture is an SEM picture of the PVDF support layer of comparative example 1, the second row to seventh row of each picture are SEM pictures of the hydrophobic separation filtration membranes obtained in examples 1 to 6, respectively, the first column of each picture is a low-magnification surface SEM picture of each membrane, the second column of each picture is a high-magnification surface SEM picture of each membrane, respectively, and the third column of each picture is a cross-sectional SEM picture of each membrane, respectively.
Fig. 2 is a schematic view of the static water contact angle of each of the hydrophobic separation filtration membranes prepared in comparative example 1 and examples 1 to 6.
FIG. 3 is a graph showing the relationship among distillation time, flux and rejection rate in a membrane distillation test of a hydrophobic separation filtration membrane, wherein (a) is membrane distillation data of a PVDF support layer of comparative example 1, and (b) is membrane distillation data of a hydrophobic separation filtration membrane obtained in example 4.
FIG. 4 is a graph showing the relationship between flux, salt rejection and time in membrane distillation using the hydrophobic separation filtration membrane obtained in example 4.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention discloses a hydrophobic separation filter membrane, which comprises a support layer and a hydrophobic layer formed on the support layer, wherein the hydrophobic layer is a porous structure layer formed by stacking spherical or sphere-like silicon-based nano particles, the silicon-based nano particles are made of a three-dimensional reticular organic silicon polymer, and the three-dimensional reticular organic silicon polymer is mainly formed by a chemical crosslinking reaction of a first linear hydrophobic organic silicon polymer and a second linear hydrophobic organic silicon polymer.
According to the invention, a three-dimensional network organic silicon polymer is constructed, so that a tighter entanglement state can be provided, the rigidity of silicon-based nanoparticles formed by the three-dimensional network organic silicon polymer is stronger, spherical or spheroidal regular shape can be formed, the rigid silicon-based nanoparticles are uniformly distributed, the anti-wettability and the separation stability of the membrane are improved, and the silicon-based nanoparticles are organic polymers, have higher compatibility with a supporting layer, and are also beneficial to improving the anti-wettability and the separation stability of the membrane.
In some embodiments, the end-capping of the first linear hydrophobic silicone polymer comprises C = C bonds, the second linear hydrophobic silicone polymer comprises Si-H bonds, and the Si-H bonds and the C = C bonds undergo a hydrosilylation reaction that crosslinks the first linear hydrophobic silicone polymer and the second linear hydrophobic silicone polymer to form a three-dimensional network silicone polymer. In the above technical scheme, the second linear hydrophobic organosilicon polymer is grafted to the first linear hydrophobic organosilicon polymer by a hydroalkylation reaction, so as to improve the branching degree of the first linear hydrophobic organosilicon polymer.
In other embodiments, the first linear hydrophobic silicone polymer and the second linear hydrophobic silicone polymer may also be cross-linked by other chemical cross-linking reactions to form a three-dimensional network silicone polymer, for example, the first linear hydrophobic silicone polymer includes unsaturated groups such as C = C bonds or C ≡ C bonds, and the second linear hydrophobic silicone polymer also includes unsaturated groups such as C = C bonds or C ≡ C bonds, and the first linear hydrophobic silicone polymer and the second linear hydrophobic silicone polymer are chemically cross-linked by a polymerization reaction. In this embodiment, the first and second linear hydrophobic silicone polymers may include at least one of a divinyl-terminated PDMS polymer, a monovinyl-terminated PDMS polymer, and a divinyl-terminated poly (dimethylsiloxane-co-diphenylsiloxane), respectively.
Further, in some embodiments, when crosslinking occurs by a hydroalkylation reaction, the first linear hydrophobic silicone polymer may include at least one of a divinyl-terminated PDMS polymer, a monovinyl-terminated PDMS polymer, and a divinyl-terminated poly (dimethylsiloxane-co-diphenylsiloxane). The first linear hydrophobic silicone polymer may have an average molecular weight of 10000 to 30000.
The second linear hydrophobic silicone polymer may comprise a trimethylsilyl terminated polydimethylsiloxane/polymethylhydrogensiloxane copolymer. The second linear hydrophobic organosilicon polymer may have an average molecular weight of 950 to 13000.
The mass ratio of the first linear hydrophobic silicone polymer to the second linear hydrophobic silicone polymer may be 8 to 12.
In some embodiments, the starting materials for forming the three-dimensional network silicone polymer may include, in addition to the first linear hydrophobic silicone polymer and the second linear hydrophobic silicone polymer described above, POSS that contain unsaturated groups that are capable of chemically crosslinking with the first linear hydrophobic silicone polymer and/or the second linear hydrophobic silicone polymer. The chemical structural formula of POSS is
The POSS containing unsaturated groups means that R groups connected with eight vertex angle Si atoms of a silicon-oxygen polyhedral nucleus contain unsaturated groups, the unsaturated groups can be C = C bonds or C ≡ C bonds, and the like, so that the POSS and the first linear hydrophobic organic compound are connectedThe silicon polymer and/or the second linear hydrophobic organic silicon polymer are chemically crosslinked, and the POSS is grafted into a three-dimensional network organic silicon polymer grid formed by crosslinking the first linear hydrophobic organic silicon polymer and the second linear hydrophobic organic silicon polymer through chemical combination, so that the dispersion uniformity of the POSS can be enhanced. Because POSS has an inorganic inner core with a polyhedral structure, the rigidity of the silicon-based nano particles can be further improved by adding POSS. In addition, referring to C-2, D-2, E-2, F-2 and G-2 in FIG. 1, when POSS is doped, the surface of the spherical silicon-based nanoparticles generates protrusions to form cauliflower-like spherical particles, and the protrusions can increase the roughness of the spherical particles, thereby improving the hydrophobicity of the particle surface. Because POSS is chemically combined into the three-dimensional reticular organic silicon polymer grids, the three-dimensional reticular organic silicon polymer modifies the inorganic core of POSS, the binding force between POSS and the supporting layer is enhanced, the structural stability of the hydrophobic layer is improved, and the long-term stability of anti-wetting is improved.
When the first linear hydrophobic silicone polymer and the second linear hydrophobic silicone polymer undergo hydroalkylation reactions, the POSS may include at least one of vinyl-POSS (i.e., the R groups to which the eight apical Si atoms of the silicone polyhedral core of the POSS are bonded are partially or entirely vinyl), allyl-POSS (i.e., the R groups to which the eight apical Si atoms of the silicone polyhedral core of the POSS are bonded are partially or entirely allyl), and vinyl siloxy-POSS (i.e., the R groups to which the eight apical Si atoms of the silicone polyhedral core of the POSS are bonded are partially or entirely vinyl siloxy), C = C bonds in the foregoing POSS also undergoing hydrosilylation addition reactions with Si-H bonds in the second linear hydrophobic silicone polymer, causing the POSS to also be grafted by chemical bonding into the three-dimensional network silicone polymer network formed by crosslinking the first linear hydrophobic silicone polymer and the second linear hydrophobic silicone polymer.
Further, in some embodiments, the mass ratio of the first linear hydrophobic silicone polymer to the second linear hydrophobic silicone polymer is from 8 to 12:1; the mass ratio of the first linear hydrophobic organosilicon polymer to the POSS is 6/1 to 6/5.
In some embodiments, the starting materials for forming the three-dimensional network silicone polymer may include the POSS described above and the support layer-forming polymer in addition to the first linear hydrophobic silicone polymer and the second linear hydrophobic silicone polymer described above. The polymer forming the support layer is doped, so that the compatibility between the silicon-based nanoparticles and the support layer can be further enhanced, and the structural stability and the long-term stability of wetting resistance of the hydrophobic layer are improved.
Further, in some embodiments, the mass ratio of the first linear hydrophobic silicone polymer to the second linear hydrophobic silicone polymer is from 8 to 12:1; the mass ratio of the first linear hydrophobic organic silicon polymer to the POSS is 6/1-6/5; the mass ratio of the first linear hydrophobic organosilicon polymer to the polymer forming the support layer is 3/2 to 1/1.
In some embodiments, the starting materials forming the three-dimensional network silicone polymer may include, in addition to the first linear hydrophobic silicone polymer and the second linear hydrophobic silicone polymer described above, a polymer forming a support layer.
Further, in some embodiments, the mass ratio of the first linear hydrophobic silicone polymer to the second linear hydrophobic silicone polymer is from 8 to 12:1; the mass ratio of the first linear hydrophobic organosilicon polymer to the polymer forming the support layer is 3/2 to 1/1.
In some embodiments, the polymer forming the support layer comprises at least one of Polysulfone (PSU), polyethersulfone (PES), cellulose Acetate (CA), polyvinyl chloride (PVC), polyacrylonitrile (PAN), polyvinyl alcohol (PVA), polyetheretherketone (PEEK), polyamide (PA), and the like, as well as derivatives of the above materials.
In some embodiments, the material of the support layer comprises at least one of Polysulfone (PSU), polyethersulfone (PES), cellulose Acetate (CA), polyvinyl chloride (PVC), polyacrylonitrile (PAN), polyvinyl alcohol (PVA), polyetheretherketone (PEEK), polyamide (PA), and the like, as well as derivatives thereof.
In some embodiments, the silicon-based nanoparticles have an average particle size of 1nm to 3nm.
In some embodiments, the hydrophobic layer has a porosity of 60% to 70%.
In some embodiments, the hydrophobic layer has an average pore size of 0.4 μm to 0.5 μm.
In some embodiments, the hydrophobic layer has a static water contact angle of 145 ° to 166 °.
In some embodiments, the hydrophobic layer has a surface energy of 4.25mN/m to 7.5mN/m.
In some embodiments, the hydrophobic layer has a thickness of 10 μm to 20 μm.
In some embodiments, the hydrophobic separation filtration membrane has a flux of 20LMH to 25LMH for a 3.5wt.% NaCl solution.
In some embodiments, the hydrophobic separation filtration membrane has a rejection rate of greater than 99.9% for a 3.5wt.% NaCl solution.
In some embodiments, the support layer has a thickness of 50 μm to 150 μm.
In some embodiments, the support layer has an average pore size of 0.22 μm to 0.65 μm.
In some embodiments, the static water contact angle of the support layer is from 110 ° to 120 °.
The invention also discloses a preparation method of the hydrophobic separation and filtration membrane, which comprises the following steps:
s1: and carrying out chemical crosslinking reaction on the first linear hydrophobic organic silicon polymer and the second linear hydrophobic organic silicon polymer to obtain a three-dimensional reticular organic silicon polymer solution.
In the above technical solutions, the first linear hydrophobic organosilicon polymer and the second linear hydrophobic organosilicon polymer are as described above and are not described herein again. As noted above, the chemically cross-linking reaction may also include POSS containing unsaturated groups and/or support layer forming polymers, which are not described in detail herein.
In the above technical solution, when the end-capping of the first linear hydrophobic organosilicon polymer includes a C = C bond, the second linear hydrophobic organosilicon polymer includes a Si — H bond, the first linear hydrophobic organosilicon polymer and the second linear hydrophobic organosilicon polymer are chemically cross-linked by an addition reaction of hydrosilylation, specifically, the temperature of the polymerization reaction may be 50 ℃ to 80 ℃, and the catalyst used includes at least one of Pt, pd, and Rh.
In the above technical solution, in some embodiments, the mass concentration of the three-dimensional network silicone polymer in the three-dimensional network silicone polymer solution is 3.0wt.% to 5.5wt.%.
S2: the method comprises the following steps of placing a three-dimensional reticular organic silicon polymer solution in an electrostatic injector, laying a supporting layer on a collector, rotating the collector around a shaft, injecting the three-dimensional reticular organic silicon polymer solution by the electrostatic injector to form silicon-based nano particles, depositing the silicon-based nano particles on the supporting layer, and curing the silicon-based nano particles to form a hydrophobic layer to obtain the separation filtering membrane.
In the technical scheme, in some embodiments, the feeding rate of the three-dimensional reticular organic silicon polymer solution in the electrostatic injector is 0.8-2.0 mL/h, the inner diameter of a needle head of the electrostatic injector is 0.4-0.72 mm, the voltage between the electrostatic injector and the collector is 12-20 kV, the distance between the tip of the electrostatic injector and the collector is 7-14 cm, and the rotating speed of the collector around a shaft is 50-140 r/min.
The hydrophobic separation and filtration membrane can be applied to seawater desalination. Of course, other technical fields including microfiltration, ultrafiltration, nanofiltration or reverse osmosis processes are also applicable.
The following are specific examples.
Example 1
The hydrophobic separation filter membrane comprises a PVDF (polyvinylidene fluoride) support layer and a hydrophobic layer formed on the PVDF support layer, wherein the hydrophobic layer is a porous structure layer formed by stacking spherical silicon-based nanoparticles, and a polymer forming the silicon-based nanoparticles is formed by chemically crosslinking vinyl-terminated PDMS (polydimethylsiloxane) and trimethylsilyl-terminated polydimethylsiloxane/polymethylhydrosiloxane copolymer. Specifically, the preparation method comprises the following steps:
1) Dissolving 2.7 parts by weight of divinyl-terminated PDMS (average molecular weight 25000) in a mixed solvent of 47.5 parts by weight of DMF and 47.5 parts by weight of THF, adding 0.3 part by weight of trimethylsilyl-terminated polydimethylsiloxane/polymethylhydrosiloxane copolymer (average molecular weight 13000) and a small amount of catalyst Pt to obtain a mixture, continuously stirring the mixture at 65 ℃ for 6 hours to complete the hydrosilylation reaction, adding 2.0 parts by weight of PVDF after the reaction is completed, stirring for 4 hours, and ultrasonically dispersing for 10 minutes to obtain a uniform three-dimensional reticular organosilicon polymer solution, wherein the mass concentration of the three-dimensional reticular organosilicon polymer in the three-dimensional reticular organosilicon polymer solution is 3.0wt.%.
2) Placing 5mL of the three-dimensional reticular organic silicon polymer solution prepared in the step 1) in an electrostatic injection injector, laying a PVDF (polyvinylidene fluoride) support layer (the thickness is 125 mu m) on a collector, enabling the electrostatic injection injector to be positioned above the collector, enabling the electrostatic injection injector to be electrically connected with a high-voltage output positive electrode, enabling the collector to be electrically connected with a negative electrode (a grounding end), setting the voltage between the high-voltage output positive electrode and the negative electrode (namely the voltage between the electrostatic injection injector and the collector) to be 18kV, enabling the speed of the collector to rotate around a shaft to be 140r/min, enabling the feeding rate of the three-dimensional reticular organic silicon polymer solution in the electrostatic injection injector to be 1.2mL/h, enabling the inner diameter of a needle head of the electrostatic injection injector to be 0.4mm, enabling the distance between the tip of the electrostatic injection injector and the collector to be 8cm, opening the high-voltage output positive electrode to perform electrostatic injection until the electrostatic injection solution is used up, depositing a silicon-based electrostatic nano particle obtained by electrostatic injection on the PVDF support layer, immediately taking an uncured membrane from the collector down, placing the collector in a vacuum drying box, evaporating the residual solvent for 24 hours at 85 ℃ to obtain a final hydrophobic separation layer, wherein the hydrophobic nano particle has the thickness of 20 mu m.
Examples 2 to 6
Examples 2 to 6 are different from example 1 in that the three-dimensional network polymer constituting the silicon-based nanoparticles is formed by chemically crosslinking vinyl-terminated PDMS (polydimethylsiloxane), trimethylsilyl-terminated polydimethylsiloxane/polymethylhydrosiloxane copolymer, and vinyl POSS in the amounts of 0.5, 1.0, 1.5, 2.0, and 2.5 parts by weight, respectively, and the other processes and parameters are the same. Specifically, the preparation method comprises the following steps:
1) Dissolving vinyl-terminated PDMS and vinyl POSS in a mixed solvent of DMF and THF, stirring to form a uniform solution, adding trimethylsilyl-terminated polydimethylsiloxane/polymethylhydrosiloxane copolymer and a catalyst Pt to obtain a mixture, continuously stirring the mixture at 65 ℃ for 6 hours to complete a hydrosilylation reaction, adding PVDF after the reaction is completed, stirring for 4 hours, and ultrasonically dispersing for 10 minutes to obtain a uniform three-dimensional network organic silicon polymer solution.
2) Placing the three-dimensional reticular organic silicon polymer solution prepared in the step 1) in an electrostatic injection injector, laying a PVDF (polyvinylidene fluoride) support layer on a collector, enabling the electrostatic injection injector to be located above the collector, enabling the electrostatic injection injector to be electrically connected with a high-voltage output positive electrode, enabling the collector to be electrically connected with a negative electrode (a grounding end), setting the voltage between the high-voltage output positive electrode and the negative electrode (namely the voltage between the electrostatic injection injector and the collector) to be 16kV, enabling the speed of the collector to rotate around a shaft to be 140r/min, enabling the feeding rate of the three-dimensional reticular organic silicon polymer solution in the electrostatic injection injector to be 2mL/h, enabling the inner diameter of a needle head of the electrostatic injection injector to be 0.72mm, enabling the distance between the tip of the electrostatic injection injector and the collector to be 8cm, opening the high-voltage output positive electrode to perform electrostatic injection for 6h, depositing silicon-based nano particles obtained through the electrostatic injection on the PVDF support layer, immediately taking off an uncured film from the collector after the electrostatic injection is finished, placing the electrostatic injection in a vacuum drying box, and evaporating residual solvent for 24 hours at 80 ℃ to obtain the final hydrophobic separation membrane.
The proportions of the respective raw materials used in examples 1 to 6 are shown in Table 1.
Table 1: ratios of raw materials used in examples 1 to 6
Comparative example 1
Comparative example 1 is a PVDF support layer used in examples 1-6.
Comparative example 2
Comparative example 2 differs from example 4 only in that: no chemical crosslinking reaction occurred, the solution used for electrostatic spraying was a mixed polymer solution comprising vinyl terminated PDMS, vinyl POSS and trimethylsilyl terminated polydimethylsiloxane/polymethylhydrosiloxane copolymer, and the rest of the procedure and parameters were the same as in example 4.
In the comparative example 2, the particles sprayed by the electrostatic spraying method were non-spherical, irregular in shape, trailing, and non-uniformly distributed on the collector, and the resulting pores were not uniform, and it can be judged from the morphology that the hydrophobic layer prepared in the comparative example 2 did not have good hydrophobicity.
The hydrophobic separation filtration membranes of the above examples and comparative examples were tested.
The surface morphology and the cross-sectional morphology of the hydrophobic separation filtration membranes prepared in examples 1 to 6 and comparative example 1 were characterized by SEM, as shown in fig. 1, wherein each picture in the first row is a picture of the PVDF support layer of comparative example 1, each picture in the second row to the seventh row is a picture of the hydrophobic separation filtration membrane prepared in examples 1 to 6, each picture in the first column is a low-magnification surface SEM picture of each membrane, each picture in the second column is a high-magnification surface SEM picture of each membrane, each picture in the third column is a cross-sectional SEM picture of each membrane, as can be seen from fig. 1: 1) Referring to the pictures of the second row to the seventh row, the silicon-based nanoparticles prepared by the method are spherical or spheroidal, have regular shapes and uniform particle size distribution, and have the particle size range of 1 nm-3 nm; 2) Comparing the third row to the seventh row with the second row, it can be seen that the silicon-based nanoparticles obtained by undoped vinyl POSS are spherical particles with smooth surfaces, when the vinyl POSS is doped, the surfaces of the silicon-based nanoparticles are raised, the number of the raised particles is increased with the increase of the doping amount of the vinyl POSS, so that the spherical-like particles similar to cauliflowers are formed, and excessive vinyl POSS easily causes the formation of larger clusters; 3) Referring to the pictures in the second row to the seventh row, it can be seen that the silicon-based nanoparticles can be uniformly distributed; 4) Referring to the third column of pictures, no obvious boundary is found between the support layer and the hydrophobic layer, which indicates that the silicon-based nanoparticles and the support layer have better compatibility and stronger bonding force; 5) Referring to the third column of pictures, it can be seen that the porous structure of the hydrophobic layer is looser than that of the support layer, and has a larger pore size than that of the support layer, and it can be seen that the deposition of the silicon-based nanoparticles does not block the pores of the original PVDF support layer, and does not have a bad effect on the original PVDF support layer.
When hydrophobicity tests are performed on each of the hydrophobic separation filtration membranes prepared in comparative example 1 and examples 1 to 6, and the static Water Contact Angle (WCA) of each membrane is as shown in fig. 2, it can be seen that 1) the WCA angle of the PVDF support layer of comparative example 1 is less than 120 °, and the WCA angles of each of the hydrophobic separation filtration membranes prepared in examples 1 to 6 of the present invention are 147 °, 150 °, 153 °, 166 °, 156 ° and 150 °, respectively, and it can be seen that the hydrophobic layer prepared in the present invention has excellent hydrophobic properties; 2) When the vinyl POSS content was 1.5wt.%, the resulting hydrophobic layer exhibited the greatest WCA angle, exhibiting superhydrophobicity.
Based on the surface morphology and WCA angle results of the respective membranes, the hydrophobic separation filtration membrane obtained in example 4 has the strongest anti-hydrophobicity, and the hydrophobic separation filtration membrane obtained in example 4 was subjected to a membrane distillation test using the PVDF support layer of comparative example 1 as comparative data, according to the following experimental procedures: a seawater solution was simulated using 3.5wt.% NaCl solution, and the liquid tension of surfactant SDS seasoning solution was introduced, the NaCl solution was circulated in front of the separation filtration membrane, the filtered liquid was continuously collected in the rear side of the membrane, 0.1mM surfactant SDS was introduced at the beginning of filtration, the concentration of SDS was maintained at 0.1mM during 1 hour of filtration, and the concentration of SDS was increased by 0.1mM per 1 hour of filtration, and the salt rejection and flux of the separation filtration membrane were observed, and the results are shown in FIG. 3. It can be seen that the flux of the separation filtration membrane prepared in example 4 maintained a stable flux, about 22LMH to 25LMH, during the desalting process, and a constant desalting rate of more than 99.9% was obtained.
The hydrophobic separation filtration membrane prepared in example 4 was subjected to a long-term membrane distillation experiment, which was carried out as follows: the seawater solution was simulated using 3.5wt.% NaCl feed solution, the NaCl feed solution was circulated at the front side of the separation filtration membrane, the filtered liquid was continuously collected at the rear side of the membrane, and the filtration was continued for 200h, the result is shown in fig. 4. As can be seen from fig. 4: the hydrophobic separation and filtration membrane prepared in example 4 maintains a stable flux of 20LMH to 25LMH and a stable salt rejection rate of more than 99.9% during filtration for 200 h.
The hydrophobic separation filtration membranes prepared in examples 1 to 6 were subjected to porosity measurement by a gravimetric method, first, the mass W of the dry film was measured 2 Then, the sample was completely soaked with ethanol, and the mass W of the wet film was measured 1 The porosity epsilon of the membrane is calculated by the following formula:
wherein D is e Is the density of ethanol and has the unit of g/m 3 ，D p The density of the polymer for preparing the film is given in g/m 3 See table 2 for results.
Table 2: performance index of the hydrophobic separation filtration membranes of examples 1 to 6 and comparative example 1
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the claims. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The hydrophobic separation and filtration membrane is characterized by comprising a support layer and a hydrophobic layer formed on the support layer, wherein the hydrophobic layer is a porous structure layer formed by stacking spherical or quasi-spherical silicon-based nanoparticles, the silicon-based nanoparticles are made of a three-dimensional reticular organic silicon polymer, and the three-dimensional reticular organic silicon polymer is mainly formed by a chemical crosslinking reaction of a first linear hydrophobic organic silicon polymer and a second linear hydrophobic organic silicon polymer.
2. The hydrophobic separation filtration membrane of claim 1, wherein the end-caps of the first linear hydrophobic silicone polymer comprise C = C bonds, the second linear hydrophobic silicone polymer comprises Si-H bonds, and the Si-H bonds and the C = C bonds undergo a hydrosilylation reaction to crosslink the first linear hydrophobic silicone polymer and the second linear hydrophobic silicone polymer to form the three-dimensional network silicone polymer.
3. Hydrophobic separation and filtration membrane according to claim 2, characterized in that it satisfies at least one of the following characteristics a to e:
a. the first linear hydrophobic silicone polymer comprises at least one of a divinyl-terminated PDMS polymer, a monovinyl-terminated PDMS polymer, and a divinyl-terminated poly (dimethylsiloxane-co-diphenylsiloxane);
b. the second linear hydrophobic organosilicon polymer comprises a trimethylsilyl-terminated polydimethylsiloxane/polymethylhydrogensiloxane copolymer;
c. the mass ratio of the first linear hydrophobic organic silicon polymer to the second linear hydrophobic organic silicon polymer is 8-12: 1;
d. the average molecular weight of the first linear hydrophobic organic silicon polymer is 10000-30000;
e. the average molecular weight of the second linear hydrophobic organic silicon polymer is 950-13000.
4. A hydrophobic separation filtration membrane according to any one of claims 1 to 3, characterized in that the raw material forming the three-dimensional network silicone polymer further comprises POSS containing unsaturated groups capable of undergoing a chemical crosslinking reaction with the first linear hydrophobic silicone polymer and/or the second linear hydrophobic silicone polymer and/or a polymer forming the support layer.
5. Hydrophobic separation and filtration membrane according to claim 4, characterized in that it satisfies at least one of the following characteristics a to e:
a. the mass ratio of the first linear hydrophobic organic silicon polymer to the second linear hydrophobic organic silicon polymer is 8-12: 1; the mass ratio of the first linear hydrophobic organic silicon polymer to the POSS is 6/1-6/5;
b. the mass ratio of the first linear hydrophobic organic silicon polymer to the second linear hydrophobic organic silicon polymer is 8-12: 1; the mass ratio of the first linear hydrophobic organosilicon polymer to the polymer forming the support layer is 3/2-1/1;
c. the mass ratio of the first linear hydrophobic organic silicon polymer to the second linear hydrophobic organic silicon polymer is 8-12: 1; the mass ratio of the first linear hydrophobic organic silicon polymer to the POSS is 6/1-6/5; the mass ratio of the first linear hydrophobic organosilicon polymer to the polymer forming the support layer is 3/2-1/1;
d. the polymer forming the supporting layer comprises at least one of polysulfone, polyethersulfone, cellulose acetate, polyvinyl chloride, polyacrylonitrile, polyvinyl alcohol, polyetheretherketone, polyamide and derivatives of the above materials;
e. the POSS includes at least one of vinyl-POSS, allyl-POSS, and vinylsiloxy-POSS.
6. Hydrophobic separation and filtration membrane according to claim 1, characterized in that it satisfies at least one of the following characteristics a to l:
a. the average grain diameter of the silicon-based nano particles is 1 nm-3 nm;
b. the porosity of the hydrophobic layer is 60% -70%;
c. the average pore diameter of the hydrophobic layer is 0.4-0.5 μm;
d. the static water contact angle of the hydrophobic layer is 145-166 degrees;
e. the surface energy of the hydrophobic layer is 4.25 mN/m-7.5 mN/m;
f. the thickness of the hydrophobic layer is 10-20 μm;
g. the flux of the hydrophobic separation and filtration membrane to 3.5wt.% of NaCl solution is 20 LMH-25 LMH;
h. the hydrophobic separation filtration membrane has a rejection rate of greater than 99.9% for a 3.5wt.% NaCl solution;
i. the thickness of the supporting layer is 50-150 μm;
j. the average pore diameter of the supporting layer is 0.22-0.65 μm;
k. the static water contact angle of the supporting layer is 110-120 degrees;
the material of the support layer comprises at least one of polysulfone, polyethersulfone, cellulose acetate, polyvinyl chloride, polyacrylonitrile, polyvinyl alcohol, polyetheretherketone, polyamide and derivatives of the above materials.
7. A method for preparing a hydrophobic separation filtration membrane, comprising the steps of:
carrying out chemical crosslinking reaction on the first linear hydrophobic organic silicon polymer and the second linear hydrophobic organic silicon polymer to obtain a three-dimensional reticular organic silicon polymer solution;
placing the three-dimensional reticular organic silicon polymer solution in an electrostatic injection injector, laying a supporting layer on a collector, rotating the collector around a shaft, injecting the three-dimensional reticular organic silicon polymer solution by the electrostatic injection injector to form silicon-based nano particles, depositing the silicon-based nano particles on the supporting layer, and curing the silicon-based nano particles to form a hydrophobic layer to obtain the separation filtering membrane.
8. The process for the preparation of a hydrophobic separation and filtration membrane according to claim 7, characterized in that it satisfies at least one of the following characteristics a to c:
a. the mass concentration of the three-dimensional reticular organic silicon polymer in the three-dimensional reticular organic silicon polymer solution is 3.0-5.5 wt.%;
b. the feeding rate of the three-dimensional reticular organic silicon polymer solution in the electrostatic injector is 0.8 mL/h-2.0 mL/h;
c. the inner diameter of a needle head of the electrostatic injector is 0.4-0.72 mm;
d. the voltage between the electrostatic injector and the collector is 12 kV-20 kV;
e. the distance between the tip of the electrostatic injector and the collector is 7-14 cm;
f. the rotating speed of the collector around the shaft is 50 r/min-140 r/min.
9. The method of preparing a hydrophobic separation filtration membrane according to claim 7 wherein the end-capping of the first linear hydrophobic organosilicon polymer comprises C = C bonds, the second linear hydrophobic organosilicon polymer comprises Si-H bonds, and the Si-H bonds and the C = C bonds undergo a hydrosilylation reaction to crosslink the first linear hydrophobic organosilicon polymer and the second linear hydrophobic organosilicon polymer to form the three-dimensional network organosilicon polymer, the temperature of the polymerization reaction being from 50 ℃ to 80 ℃, and the catalyst of the polymerization reaction comprising at least one of Pt, pd, and Rh.
10. Use of a hydrophobic separation filtration membrane according to any one of claims 1 to 6 or a hydrophobic separation filtration membrane produced by the production method according to any one of claims 7 to 9 for desalination of sea water.
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