WO2017012152A1 - 一种快速环保制备致密分离膜的方法 - Google Patents

一种快速环保制备致密分离膜的方法 Download PDF

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WO2017012152A1
WO2017012152A1 PCT/CN2015/086468 CN2015086468W WO2017012152A1 WO 2017012152 A1 WO2017012152 A1 WO 2017012152A1 CN 2015086468 W CN2015086468 W CN 2015086468W WO 2017012152 A1 WO2017012152 A1 WO 2017012152A1
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base film
membrane
spraying
psf
porous base
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French (fr)
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张国俊
范红玮
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Beijing University of Technology
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Beijing University of Technology
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules

Definitions

  • the invention belongs to the technical field of membrane separation, and particularly relates to a method for preparing a dense separation membrane quickly and environmentally.
  • membrane technology has become one of the common technologies to solve major problems in the fields of water resources, energy, environment and traditional industrial transformation.
  • organic polymer membrane materials based on dense, defect-free separation layers can efficiently screen and separate specific ions and molecules, and have great application potential in gas separation, material separation and water treatment.
  • the conventional method generally uses a solid or high viscosity polymer as a dense separation layer.
  • Cross-linking the main body, and dissolving the polymer in an organic solvent is the key to obtaining a dense separation layer, and therefore these toxic and harmful solvents Excessive use and volatilization can cause serious secondary pollution to the environment and cause serious harm to the health of film-making workers.
  • Spraying technology is a method of spraying a material onto a surface of a support body by a mechanical atomization at a certain speed to form a coating.
  • the method can uniformly distribute the liquid on the surface of the support body, and can control the thickness of the coating by adjusting the number of spraying, which is one of the important components of the surface process technology.
  • Spraying techniques can also be used for the preparation of dense separation membranes. For example, Zhang Guojun et al. (CN102698613A, CN102512980A, CN102698612A, CN103182251B) invented various dense separation membrane automatic spraying devices and methods by means of spraying technology, and successfully prepared a series of dense membranes with different selective separation layers.
  • the technical problem to be solved by the embodiments of the present invention is to provide a method for rapidly preparing a dense separation membrane.
  • the specific technical solutions are as follows:
  • a rapid and environmentally friendly method for preparing a dense separation membrane comprising:
  • Step a Fixing the porous base film on the rotating carrier film stage, and setting the film surface temperature of the porous base film to 60-200 °C.
  • Step b spraying the liquid oligomer and the curing agent solution on the surface of the porous base film in an atomized manner, respectively, causing the liquid oligomer to undergo in-situ cross-linking reaction on the surface of the porous base film to obtain dense separation. membrane.
  • the curing agent solution is used to cause the in situ crosslinking reaction to occur in the liquid oligomer.
  • the curing agent solution is a mixture of a crosslinking agent, a crosslinking agent and a catalyst for causing the liquid oligomer to undergo the in-situ crosslinking reaction or for initiating the liquid oligomer.
  • the method further comprises: before the step a, performing a plugging pretreatment on the porous base film, filling the inner pores of the porous base film with deionized water, and maintaining the surface in a dry state.
  • the porous base film is selected from an organic polymer film, an inorganic film or an organic/inorganic hybrid film, and has an average pore diameter of 0.001 to 100 ⁇ m.
  • the rotation speed of the carrier film stage is 60 rpm or more.
  • the liquid oligomer is selected from at least one of silicone oil, epoxy resin, unsaturated polyester, low molecular weight polyether, polyurea, polycarbonate, polyamide, polyester polyol, and styrene.
  • the crosslinking agent is selected from the group consisting of ethyl orthosilicate, propyl orthosilicate, butyl silicate, diethoxysilane, hydrogen-containing polysiloxane, dimethylsilane, and hexa At least one of methyl diisocyanates;
  • the catalyst is selected from at least one of dibutyltin dilaurate, monobutyltin oxide, dibutyltin oxide, tripropyltin oxide, dipropyltin oxide, and chloroplatinic acid;
  • the initiator is selected from the group consisting of benzoyl peroxide and/or methyl ethyl ketone peroxide.
  • the curing agent solution uses an environmentally friendly solvent selected from the group consisting of deionized water and/or ethanol;
  • the crosslinking agent and the catalyst have a mass concentration of 1% to 30% and 0.1% to 5%, respectively.
  • the liquid oligomer and the curing agent solution are respectively sprayed on the surface of the porous base film by using a pressure spray gun;
  • the viscosity of the liquid oligomer is less than 500 mPa ⁇ s at normal temperature.
  • the nozzle of the pressure lance is disposed corresponding to the center of the porous base film; and the distance between the nozzle and the center of the porous base film is controlled to be 20-80 cm.
  • the liquid oligomer and the curing agent solution are sprayed in a number of 1-10
  • the spraying time is 1-10s each time; the spraying time interval is 0-120s per cycle.
  • the spraying speed is controlled to be 2-3 ml/s, and the spraying pressure is 0.2 to 0.4 MPa.
  • the method for preparing a dense separation membrane quickly and environmentally-provided by the embodiment of the invention by spraying the liquid oligomer and the curing agent solution which is cross-linked and solidified on the surface of the porous base film at 60-200 ° C, so that the two are in situ In the reaction, a dense separation layer closely bonded to the surface of the porous base film is formed, thereby obtaining a dense separation membrane which is desired to be dense and defect-free and excellent in separation performance.
  • the inventive cross-linking reaction is carried out at a temperature of 60-200 ° C by spraying, thereby effectively shortening the preparation time of the dense separation membrane, shortening it to 8-350 s, and improving the dense separation membrane. Preparation efficiency.
  • the embodiment of the invention prepares the dense separation membrane by directly using the liquid oligomer, thereby avoiding the use of toxic and harmful solvents, reducing environmental pollution, and being safer and more environmentally friendly.
  • the method provided by the embodiment of the present invention further comprises: before the step a, performing a plugging pretreatment on the porous base film, so that the inner pore of the porous base film is filled with deionized water, and the surface is kept dry.
  • a plugging pretreatment on the porous base film, so that the inner pore of the porous base film is filled with deionized water, and the surface is kept dry.
  • Figure 1 Scanning electron micrograph (1-1) and cross-sectional scanning electron micrograph (1-2) of a hydroxyl-terminated PDMS/PSf dense separation membrane prepared in Example 3 of the present invention; scanning electron micrograph of a porous PSf base film surface (1) -3) and sectional scanning electron micrograph (1-4);
  • Example 2 is a scanning electron micrograph (2-1) and a sectional scanning electron micrograph (2-2) of a vinyl-terminated PDMS-PMHS/PSf dense separation membrane prepared in Example 7 of the present invention
  • FIG. 3 Scanning electron micrograph (3-1) and sectional scanning electron micrograph (3-2) of the PU/PSf dense separation membrane prepared in Example 14 of the present invention
  • Fig. 4 is a scanning electron micrograph (4-1) and a sectional scanning electron micrograph (4-2) of a UPR/PSf dense separation membrane prepared in Example 15 of the present invention.
  • the embodiment of the invention provides a method for preparing a dense separation membrane quickly and environmentally, comprising the following steps:
  • Step a Fixing the porous base film on the rotating carrier film stage, and setting the film surface temperature of the porous base film to 60-200 °C.
  • Step b spraying the liquid oligomer and the curing agent solution on the surface of the porous base film by atomization, respectively, so that the liquid oligomer is in-situ cross-linked on the surface of the porous base film to obtain a dense separation membrane without defects.
  • the curing agent solution used is used to cause the liquid oligomer to undergo an in-situ crosslinking reaction.
  • the method for preparing a dense separation membrane quickly and environmentally-provided by the embodiment of the invention by spraying the liquid oligomer and the curing agent solution which is cross-linked and solidified on the surface of the porous base film at 60-200 ° C, so that the two are in situ In the reaction, a dense separation layer closely bonded to the surface of the porous base film is formed, thereby obtaining a dense separation membrane which is desired to be dense and defect-free and excellent in separation performance.
  • the inventive cross-linking reaction is carried out at a temperature of 60-200 ° C by spraying, thereby effectively shortening the preparation time of the dense separation membrane, shortening it to 8-350 s, and improving the dense separation membrane. Preparation efficiency.
  • the embodiment of the invention prepares the dense separation membrane by directly using the liquid oligomer, thereby avoiding the use of toxic and harmful solvents, reducing environmental pollution, and being safer and more environmentally friendly.
  • the curing agent solution used in the examples of the present invention has a function of enabling the liquid oligomer to undergo an in-situ crosslinking reaction.
  • the curing agent solutions used will also vary depending on the liquid oligomer used.
  • the curing agent solution may be a crosslinking agent for in situ crosslinking reaction of the liquid oligomer, or may further be a mixture of the crosslinking agent and a catalyst capable of catalyzing an in-situ crosslinking reaction, or It may also be an initiator for initiating an in-situ crosslinking reaction of a liquid oligomer.
  • an environmentally friendly solvent is employed in the curing agent solution to increase the dispersion of the curing agent solution.
  • the environmentally friendly solvent is selected from the group consisting of deionized water and/or ethanol.
  • the concentration of the crosslinking agent and the catalyst contained therein are preferably from 1% to 30% and from 0.1% to 5%, respectively, so that the liquid oligomer and the liquid oligomer can be The cross-linking reaction of the cross-linking agent is more complete, and the prepared separation membrane is more dense.
  • the above crosslinking agent may be selected from the group consisting of ethyl orthosilicate, propyl orthosilicate, butyl silicate, diethoxysilane, hydrogen-containing polysiloxane, dimethylsilane, hexamethylene At least one of isocyanates;
  • the above catalyst may be selected from at least one of dibutyltin dilaurate, monobutyltin oxide, dibutyltin oxide, tripropyltin oxide, dipropyltin oxide, chloroplatinic acid
  • the above initiator may be at least one selected from the group consisting of benzoyl peroxide and methyl ethyl ketone peroxide.
  • the liquid oligomer used in the examples of the present invention is an organic polymer which is conventional in the art and which is in a liquid state at normal temperature and pressure.
  • the liquid oligomer may be selected from the group consisting of silicone oil, epoxy resin, unsaturated polyester, low molecular weight polyether, polyurea, polycarbonate, polyamide, polyester polyol, At least one of styrene.
  • the types of the above liquid oligomers are all common chemical materials in the art and are commercially available.
  • the silicone oil can be a terminal hydroxyl silicone oil, a terminal vinyl silicone oil, a methyl silicone oil, or any combination of the three.
  • the type of the curing agent solution varies depending on the kind of the liquid oligomer.
  • a cross-linking agent hexamethylene diisocyanate can be used as a curing agent solution
  • a cross-linking agent ortho-silicon can be used.
  • a mixture of acid ethyl ester and a catalyst of dibutyltin dilaurate is used as a curing agent solution
  • an initiator methyl ethyl ketone peroxide can be used as a curing agent solution.
  • the method provided by the embodiment of the present invention further comprises: before performing step 101, performing a plugging pretreatment on the porous base film, so that the inner pore of the porous base film is filled with deionized water, and the surface is kept dry.
  • a plugging pretreatment on the porous base film, so that the inner pore of the porous base film is filled with deionized water, and the surface is kept dry.
  • the specific operation steps of the plugging pretreatment performed on the porous base film are as follows: first, the porous base film is immersed in an ethanol solvent for 1-3 hours, and then placed in a suction bottle filled with deionized water. After vacuum filtration for 5-10 hours, it was taken out and placed in the air to completely evaporate the surface of the porous base film.
  • the porous base film used is selected from an organic polymer film having an average pore diameter of 0.001 to 100 ⁇ m, an inorganic film or an organic/inorganic hybrid film.
  • the organic polymer film may be a polysulfone film, a polycarbonate film, a polyethylene film, a polyethersulfone film, a polytetrafluoroethylene film, a polyvinylidene fluoride film, a polyhexafluoropropylene film, or a chitosan.
  • the inorganic film may be a zirconium oxide film, a zinc oxide film, an aluminum oxide film, or the like
  • the organic/inorganic hybrid film may be a polysulfone/SiO 2 film, a polysulfone/MOF (metal organic skeleton) film, or a polysulfone. / molecular sieve membrane, polyvinylidene fluoride / SiO 2 membrane, and the like.
  • the step b it is preferred to use a liquid oligomer having a viscosity of less than 500 mPa ⁇ s.
  • This arrangement not only ensures smooth implementation of the spraying process, but also has a good atomization effect of spraying, and is advantageous for forming a dense and defect-free separation film.
  • the viscosity of the liquid oligomer may be 0-50 mPa ⁇ s, 50-100 mPa ⁇ s, 100-500 mPa ⁇ s, or 150-300 mPa ⁇ s, or 200-400 mPa ⁇ s or the like.
  • the viscosity may be 50 mPa ⁇ s, 100 mPa ⁇ s, 150 mPa ⁇ s, 200 mPa ⁇ s, 250 mPa ⁇ s, 300 mPa ⁇ s, 350 mPa ⁇ s, 400 mPa ⁇ s, 450 mPa ⁇ s or 500 mPa ⁇ s.
  • the porous base film is placed on the rotating carrier table so that the sprayed liquid oligomer and the curing agent solution can be uniformly distributed on the surface of the porous base film.
  • the porous base film is preferably in the form of a disk having a diameter of 15 to 20 cm based on the shape of a film-loading stage commonly used in the art to avoid unnecessary waste of the porous base film.
  • the rotation speed of the carrier stage is preferably 60 rpm or more.
  • the rotational speed can be 60 rpm, 100 rpm, 150 rpm, 200 rpm, 250 rpm, 300 rpm, 350 rpm, 400 rpm, 450 rpm, 500 rpm, 550 rpm, 600 rpm, and the like.
  • the porous base film has a film surface temperature of 60 ° C to 200 ° C, and may be, for example, 60 ° C, 80 ° C, 100 ° C, 120 ° C, 140 ° C, 160 ° C, 180 ° C, 200 ° C, or the like.
  • the sprayed liquid oligomer can be rapidly cross-linked with the curing agent solution, and a dense separation layer can be formed not only on the surface of the porous base film but also shortened.
  • the film formation time increases the film forming efficiency. If the surface temperature of the porous base film is lower than 60 ° C, the crosslinking reaction proceeds slowly, and above 200 ° C, the dense separation layer just formed is destroyed.
  • the film surface temperature of the above porous base film can be achieved by various means, for example, irradiation with a high temperature baking lamp selected from at least one of a Yuba heating lamp, an infrared baking lamp or an ultraviolet baking lamp.
  • a high temperature baking lamp selected from at least one of a Yuba heating lamp, an infrared baking lamp or an ultraviolet baking lamp.
  • step b in order to facilitate the spraying process on the porous base film, the liquid oligomer and the curing agent solution are sprayed on the surface of the porous base film by atomization by using a pressure spray gun.
  • the pressure lance includes a spray gun for spraying liquid oligomers and a spray gun for spraying a curing agent solution.
  • the specific embodiment of the above spraying may be spraying the liquid oligomer and the curing agent solution at the same time, or alternately spraying the liquid oligomer and the curing agent solution (that is, spraying the liquid oligomer once, and then spraying the curing agent solution once, Then alternately spray in sequence).
  • step b should be carried out under conditions of an ambient humidity of 60% or less.
  • the ambient humidity may be 10% to 60%, 30% to 50%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 55%, 58%, and the like.
  • the nozzle of the pressure spray gun is disposed corresponding to the center of the porous base film, and the distance between the control nozzle and the center of the porous base film is 20-80 cm, so that the sprayed liquid can be made low.
  • the atomization effect of the polymer is optimal and the distribution on the surface of the porous base film is more uniform.
  • the number of times of spraying of the liquid oligomer and the curing agent solution, the spraying time of each time, and the interval time per cycle are completely controlled automatically by a logic controller (Programmable Logic Controller, PLC).
  • the liquid oligomer and the curing agent solution are sprayed 1-10 times, so that the separation layer of the separation membrane has a thin thickness, reduces the resistance, increases the permeation flux, and ensures the separation membrane.
  • the density of the separation layer; each spraying time is 1-10s, the spraying time is too long not only wastes the raw materials, but also does not achieve the atomization effect of spraying.
  • the interval between each spraying process is 0-120 s, during which time the last time is guaranteed.
  • the sprayed liquid oligomer and the curing agent solution reacted completely.
  • the above “spraying process per cycle” refers to spraying the liquid oligomer and the curing agent solution separately as a cycle process.
  • the spraying speed of the liquid oligomer and the curing agent solution is 2-3 ml/s, and the spraying pressure is 0.2-0.4 MPa. This limitation optimizes the atomization of the spray liquid oligomer and the curing agent solution.
  • the porous base membrane is a polysulfone (PSf) plate type ultrafiltration membrane with a molecular weight cut off of 20,000.
  • PSf polysulfone
  • the selected liquid oligomer is a hydroxyl group-containing PDMS (viscosity is 100 mPa ⁇ s), and the selected crosslinking agent and catalyst are respectively positive silicon.
  • Ethyl acetate and dibutyltin dilaurate is ethanol
  • the selected high-temperature baking lamp is the Yuba heating lamp.
  • liquid terminal hydroxyl group PDMS is directly placed in a container for use; a mass concentration of 10% tetraethyl orthosilicate and a mass concentration of 1% dibutyltin dilaurate are mixed and dissolved in a small amount of ethanol solvent. ,stand-by;
  • the pretreated PSf base film was cut into a 20 cm diameter disc and fixed on a vertically placed carrier film stage, and rotated at a constant speed of 100 rpm, while the PSf base film was always baked at a high temperature baking lamp. under;
  • the prepared terminal hydroxyl group PDMS/PSf dense separation membrane is subjected to pervaporation, preferably by pervaporation performance test.
  • the test conditions were as follows: a 10 wt.% ethanol/water system having a feed temperature of 60 ° C, a membrane effective area of 50.24 cm 2 , and a membrane downstream pressure of 200 Pa.
  • pervaporation membrane properties were measured as follows: permeate flux 711 g/m 2 h, permeate liquid ethanol content 33.3 wt.%, separation factor 4.5.
  • the prepared terminal hydroxyl group PDMS/PSf dense separation membrane was used for gas separation performance test to concentrate oxygen in the air.
  • the test conditions were as follows: the feed gas was a 25 ° C oxygen/nitrogen mixture (20.9% oxygen) supplied by an air compressor with an effective area of 50.24 cm 2 and a pressure difference of 200 kPa on both sides of the membrane.
  • the gas separation and separation performance measured was: gas permeation flux of 28.57 L/min m 2 and permeate side oxygen concentration of 22.9%.
  • the porous base membrane is a polysulfone (PSf) plate type ultrafiltration membrane with a molecular weight cut off of 20,000.
  • PSf polysulfone
  • the selected liquid oligomer is a hydroxyl group-containing PDMS (viscosity is 100 mPa ⁇ s), and the selected crosslinking agent and catalyst are respectively positive silicon.
  • Ethyl acetate and dibutyltin dilaurate is ethanol
  • the selected high-temperature baking lamp is the Yuba heating lamp.
  • liquid terminal hydroxyl group PDMS is directly placed in a container for use; a mass concentration of 10% tetraethyl orthosilicate and a mass concentration of 1% dibutyltin dilaurate are mixed and dissolved in a small amount of ethanol solvent. ,stand-by;
  • the pretreated PSf base film was cut into a 20 cm diameter disc and fixed on a vertically placed carrier film stage, and rotated at a constant speed of 100 rpm, while the PSf base film was always baked at a high temperature baking lamp. under;
  • the surface of the PSf base film is rotated at a constant speed; the distance between the spray gun and the base film is 50 cm, the PDMS time of spraying the liquid terminal hydroxyl group is 3 s, and the time of spraying the ethanol mixture of tetraethyl orthosilicate/dibutyltin dilaurate is 5s, spraying area is more than 150cm 2 , the number of circulating spraying is 3 times, the interval between each cycle is 30s, the spray speed of all spray guns is 2-3ml/s, the pressure is 0.3MPa.
  • the liquid terminal hydroxyl group PDMS on the surface of PSf base film undergoes in-situ chemical crosslinking reaction under the baking of 80 °C Yuba heating lamp.
  • the crosslinking time is the spraying time (84s), which forms dense hydroxyl groups. PDMS/PSf separation membrane.
  • the prepared terminal hydroxyl group PDMS/PSf dense separation membrane is subjected to pervaporation, preferably by pervaporation performance test.
  • the test conditions were as follows: a 10 wt.% ethanol/water system having a feed temperature of 60 ° C, a membrane effective area of 50.24 cm 2 , and a membrane downstream pressure of 200 Pa.
  • pervaporation membrane properties were measured as follows: permeate flux 556 g/m 2 h, permeate liquid ethanol content 44.4 wt.%, separation factor 7.2.
  • the prepared terminal hydroxyl group PDMS/PSf dense separation membrane was used for gas separation performance test to concentrate oxygen in the air.
  • the test conditions were as follows: the feed gas was a 25 ° C oxygen/nitrogen mixture (20.9% oxygen) supplied by an air compressor with an effective area of 50.24 cm 2 and a pressure difference of 200 kPa on both sides of the membrane.
  • the gas separation and separation performance measured was: gas permeation flux of 21.38 L/min m 2 and permeate side oxygen concentration of 24%.
  • the porous base membrane is a polysulfone (PSf) plate type ultrafiltration membrane with a molecular weight cut off of 20,000.
  • PSf polysulfone
  • the selected liquid oligomer is a hydroxyl group-containing PDMS (viscosity is 100 mPa ⁇ s), and the selected crosslinking agent and catalyst are respectively positive silicon.
  • Ethyl acetate and dibutyltin dilaurate is ethanol
  • the selected high-temperature baking lamp is the Yuba heating lamp.
  • liquid terminal hydroxyl group PDMS is directly placed in a container for use; a mass concentration of 10% tetraethyl orthosilicate and a mass concentration of 1% dibutyltin dilaurate are mixed and dissolved in a small amount of ethanol solvent. ,stand-by;
  • the pretreated PSf base film was cut into a 20 cm diameter disc and fixed on a vertically placed carrier film stage, and rotated at a constant speed of 100 rpm, while the PSf base film was always baked at a high temperature baking lamp. under;
  • the surface of the PSf base film is rotated at a constant speed; the distance between the spray gun and the base film is 50 cm, the PDMS time of spraying the liquid terminal hydroxyl group is 3 s, and the time of spraying the ethanol mixture of tetraethyl orthosilicate/dibutyltin dilaurate is 5s, spraying area is more than 150cm 2 , the number of circulating spraying is 5 times, the interval between each cycle is 30s, the spray speed of all spray guns is 2-3ml/s, the pressure is 0.3MPa.
  • the SEM photograph shows (Fig. 1) that the porous structure of the surface of the PSf base film is compared (Fig. 1-3), the PDMS separation layer of the terminal hydroxyl group is dense and defect-free (Fig. 1-1); the cross-sectional structure of the PSf base film is compared (Fig. 1) 4), the terminal hydroxyl group PDMS separation layer thickness is 8 ⁇ m ( Figure 1-2)
  • the prepared terminal hydroxyl group PDMS/PSf dense separation membrane was subjected to pervaporation performance test to recover small molecule organic matter in the aqueous solution.
  • the test conditions were: 3 wt.% ethanol/water system with a feed temperature of 60 ° C, 10 wt.% ethanol/water system, 3 wt.% n-propanol/water system, 3 wt.% isopropanol/water system, 3 wt.
  • % n-butanol/water system 3wt.% isobutanol/water system, 3wt.% acetone/water system, 3wt.% ethyl acetate/water system, membrane effective area is 50.24cm 2 , membrane downstream pressure is 200Pa .
  • the permeation vaporization membrane properties were as follows: 3wt.% ethanol/water system permeation flux was 320.33g/m 2 h, permeate ethanol content 31.2wt.%, separation factor 14.66; 10wt.% ethanol/water system permeation The amount is 521.00 g/m 2 h, the ethanol content in the permeate is 50.30 wt.%, the separation factor is 9.11; the permeation flux of the 3 wt.% n-propanol/water system is 416.67 g/m 2 h, and the n-propanol in the permeate The content is 40.7wt.%, the separation factor is 22.19; the permeation flux of 3wt.% isopropanol/water system is 325.76g/m 2 h, the isopropanol content in the permeate is 36.95wt.%, the separation factor is 18.95; 3wt.% The permeation flux of n-but
  • the prepared terminal hydroxyl group PDMS/PSf dense separation membrane was used for gas separation performance test to concentrate oxygen in the air.
  • the test conditions were as follows: the feed gas was a 25 ° C oxygen/nitrogen mixture (20.9% oxygen) supplied by an air compressor with an effective area of 50.24 cm 2 and a pressure difference of 200 kPa on both sides of the membrane.
  • gas permeation flux was 14.78 L/min m 2
  • permeate side oxygen concentration was 26.2%.
  • the porous base membrane is a polysulfone (PSf) plate type ultrafiltration membrane with a molecular weight cut off of 20,000.
  • PSf polysulfone
  • the selected liquid oligomer is a hydroxyl group-containing PDMS (viscosity is 100 mPa ⁇ s), and the selected crosslinking agent and catalyst are respectively positive silicon.
  • Ethyl acetate and dibutyltin dilaurate is ethanol
  • the selected high temperature baking lamp is the Yuba heating lamp.
  • liquid terminal hydroxyl group PDMS is directly placed in a container for use; a mass concentration of 10% tetraethyl orthosilicate and a mass concentration of 1% dibutyltin dilaurate are mixed and dissolved in a small amount of ethanol solvent. ,stand-by;
  • the pretreated PSf base film was cut into a 20 cm diameter disc and fixed on a vertically placed carrier film stage, and rotated at a constant speed of 100 rpm, while the PSf base film was always baked in the Yuba heating lamp. under;
  • the surface of the PSf base film is rotated at a constant speed; the distance between the spray gun and the base film is 50 cm, the PDMS time of spraying the liquid terminal hydroxyl group is 3 s, and the time of spraying the ethanol mixture of tetraethyl orthosilicate/dibutyltin dilaurate is 5s, spraying area is more than 150cm 2 , the number of circulating spraying is 10 times, the interval between each cycle is 30s, the spray speed of all spray guns is 2-3ml/s, the pressure is 0.3MPa.
  • the liquid terminal hydroxyl group PDMS on the surface of PSf base film undergoes in-situ chemical crosslinking reaction under the baking of 80 °C Yuba heating lamp, and the crosslinking time is the spraying time (350s), which forms dense Hydroxyl-terminated PDMS/PSf separation membrane.
  • the prepared terminal hydroxyl group PDMS/PSf dense separation membrane is subjected to pervaporation, preferably by pervaporation performance test.
  • the test conditions were as follows: a 10 wt.% ethanol/water system having a feed temperature of 60 ° C, a membrane effective area of 50.24 cm 2 , and a membrane downstream pressure of 200 Pa.
  • pervaporation membrane properties were measured as follows: permeate flux 420 g/m 2 h, permeate liquid ethanol content 48.6 wt.%, separation factor 8.5.
  • the prepared terminal hydroxyl group PDMS/PSf dense separation membrane was used for gas separation performance test to concentrate oxygen in the air.
  • the test conditions were as follows: the feed gas was a 25 ° C oxygen/nitrogen mixture (20.9% oxygen) supplied by an air compressor with an effective area of 50.24 cm 2 and a pressure difference of 200 kPa on both sides of the membrane.
  • gas permeation flux was 6.13 L/min m 2
  • permeate side oxygen concentration was 27.3%.
  • the porous base membrane is a polysulfone (PSf) plate type ultrafiltration membrane with a molecular weight cut off of 20,000.
  • PSf polysulfone
  • the selected liquid oligomer is a hydroxyl group-containing PDMS (viscosity is 100 mPa ⁇ s), and the selected crosslinking agent and catalyst are respectively positive silicon.
  • Ethyl acetate and dibutyltin dilaurate is an ethanol/water mixture (mass ratio 1:1)
  • the selected high-temperature baking lamp is a Yuba heating lamp.
  • liquid terminal hydroxyl group PDMS is directly placed in the container for use;
  • the tetraethyl orthosilicate having a mass concentration of 10% and the dibutyl tin dilaurate having a mass concentration of 1% are mixed and dissolved in a mass ratio of 1: 1 in an ethanol/water mixed solvent, ready for use;
  • the pretreated PSf base film was cut into a 20 cm diameter disc and fixed on a vertically placed carrier film stage, and rotated at a uniform speed of 100 rpm, while the PSf base film was always baked in the Yuba heating lamp. Bake under
  • the spray gun and the base film is 50 cm
  • the PDMS time of spraying the liquid terminal hydroxyl group is 3 s
  • spraying the ethanol/water mixture of ethyl orthosilicate/dibutyltin dilaurate The time of the solution is 5s
  • the spraying area is more than 150cm 2
  • the number of circulating spraying is 5 times
  • the interval between each cycle is 30s
  • the spray speed of all spray guns is 2-3ml/s
  • the pressure is 0.3MPa.
  • the prepared terminal hydroxyl group PDMS/PSf dense separation membrane is subjected to pervaporation, preferably by pervaporation performance test.
  • the test conditions were as follows: a 10 wt.% ethanol/water system having a feed temperature of 60 ° C, a membrane effective area of 50.24 cm 2 , and a membrane downstream pressure of 200 Pa.
  • pervaporation membrane properties were measured as follows: permeate flux 640 g/m 2 h, ethanol content in permeate 34.7 wt.%, separation factor 4.78.
  • the porous base membrane is a polysulfone (PSf) plate type ultrafiltration membrane with a molecular weight cut off of 20,000.
  • the selected liquid oligomer is a hydroxyl group-containing PDMS (viscosity is 100 mPa ⁇ s), and the selected crosslinking agent and catalyst are respectively positive silicon.
  • Ethyl acetate and dibutyltin dilaurate, the selected high-temperature baking lamp is the Yuba heating lamp.
  • liquid terminal hydroxyl group PDMS is directly placed in a container for use;
  • the tetraethyl orthosilicate and dibutyltin dilaurate are mixed at a mass ratio of 10:1, and are used without any solvent;
  • the pretreated PSf base film was cut into a 20 cm diameter disc and fixed on a vertically placed carrier film stage, and rotated at a constant speed of 100 rpm, while the PSf base film was always baked in the Yuba heating lamp. under;
  • the surface of the PSf base film; the distance between the spray gun and the base film is 50 cm, the PDMS time for spraying the liquid terminal hydroxyl group is 3 s, and the time for spraying the mixture of tetraethyl orthosilicate/dibutyltin dilaurate is 5 s, and the spray area is larger than 150cm 2 , the number of cycles of spraying is 5 times, the interval between each cycle is 30s, the spray speed of all spray guns is 2-3ml / s, the pressure is 0.3MPa.
  • the prepared terminal hydroxyl group PDMS/PSf dense separation membrane is subjected to pervaporation, preferably by pervaporation performance test.
  • the test conditions were as follows: a 10 wt.% ethanol/water system having a feed temperature of 60 ° C, a membrane effective area of 50.24 cm 2 , and a membrane downstream pressure of 200 Pa.
  • pervaporation membrane properties were measured as follows: permeation flux 75 g/m 2 h, ethanol content in the permeate was 29.2 wt.%, and separation factor was 3.71.
  • the porous base membrane is a polysulfone (PSf) plate type ultrafiltration membrane with a molecular weight cut off of 20,000.
  • the selected liquid oligomer is a terminal vinyl group PDMS (viscosity: 300 mPa ⁇ s), and the selected crosslinking agent and catalyst are respectively PMHS.
  • chloroplatinic acid, the environmentally friendly solvent is ethanol, and the selected high-temperature baking lamp is the Yuba heating lamp.
  • the pretreated PSf base film was cut into a 20 cm diameter disc and fixed on a vertically placed carrier film stage, and rotated at a constant speed of 100 rpm, while the PSf base film was always baked in the Yuba heating lamp. under;
  • the liquid terminal vinyl PDMS on the surface of PSf base film is in situ chemical cross-linking reaction with PMHS under the baking of 80 °C Yuba heating lamp, and the crosslinking time is spraying time (160s), which forms dense The terminal vinyl PDMS-PMHS/PSf separation membrane.
  • the SEM photograph shows (Fig. 2) that the terminal vinyl-based PDMS-PMHS separation layer is dense and defect-free (Fig. 2-1); the terminal vinyl PDMS-PMHS separation layer has a thickness of 5 ⁇ m (Fig. 2-2)
  • the prepared terminal vinyl PDMS-PMHS/PSf dense separation membrane was subjected to pervaporation performance test to recover small molecule organic matter in the aqueous solution.
  • the test conditions were: 3 wt.% ethanol/water system with a feed temperature of 60 ° C, 10 wt.% ethanol/water system, 3 wt.% n-propanol/water system, 3 wt.% isopropanol/water system, 3 wt.
  • % n-butanol/water system 3wt.% isobutanol/water system, 3wt.% acetone/water system, 3wt.% ethyl acetate/water system, membrane effective area is 50.24cm 2 , membrane downstream pressure is 200Pa .
  • the pervaporation membrane performance was measured as follows: 3wt.% ethanol/water system permeation flux was 1079.55g/m 2 h, permeate ethanol content 31.03wt.%, separation factor 14.55; 10wt.% ethanol/water system permeation The amount is 1729.55g/m 2 h, the ethanol content in the permeate is 51.64wt.%, the separation factor is 9.61; the permeation flux of 3wt.% n-propanol/water system is 1353.79g/m 2 h, n-propanol in the permeate The content is 40.46wt.%, the separation factor is 22.2; the permeation flux of 3wt.% isopropanol/water system is 1292.42g/m 2 h, the isopropanol content in the permeate is 37.43wt.%, the separation factor is 19.34; 3wt.% The permeation flux of n-butanol/water system is
  • the prepared terminal vinyl PDMS-PMHS/PSf dense separation membrane was used for gas separation performance test to concentrate oxygen in the air.
  • the test conditions were as follows: the feed gas was a 25 ° C oxygen/nitrogen mixture (20.9% oxygen) supplied by an air compressor with an effective area of 50.24 cm 2 and a pressure difference of 200 kPa on both sides of the membrane.
  • gas permeation flux was 19.81 L/min m 2
  • permeate side oxygen concentration was 26.6%.
  • the porous base membrane is a polysulfone (PSf) plate type ultrafiltration membrane with a molecular weight cut off of 20,000.
  • the selected liquid oligomer is a terminal vinyl group PDMS (viscosity: 300 mPa ⁇ s), and the selected crosslinking agent and catalyst are respectively PMHS.
  • chloroplatinic acid, the environmentally friendly solvent is ethanol, and the selected high-temperature baking lamp is the Yuba heating lamp.
  • the pretreated PSf base film was cut into a 20 cm diameter disc and fixed on a vertically placed carrier film stage, and rotated at a constant speed of 100 rpm, while the PSf base film was always baked in the Yuba heating lamp. under;
  • the liquid end vinyl PDMS on the surface of PSf base film is in situ chemical cross-linking reaction with PMHS under the baking of 80 °C Yuba heating lamp.
  • the crosslinking time is the spraying time (350s), which forms dense.
  • the terminal vinyl PDMS-PMHS/PSf separation membrane is the spraying time (350s), which forms dense.
  • the prepared terminal vinyl PDMS/PSf dense separation membrane is subjected to pervaporation, preferably pervaporation performance test.
  • the test conditions were as follows: a 10 wt.% ethanol/water system having a feed temperature of 60 ° C, a membrane effective area of 50.24 cm 2 , and a membrane downstream pressure of 200 Pa.
  • pervaporation membrane properties were measured as follows: permeation flux 181.06 g/m 2 h, permeate liquid ethanol content 50.34 wt.%, separation factor 9.12.
  • the prepared terminal hydroxyl group PDMS/PSf dense separation membrane was used for gas separation performance test to concentrate oxygen in the air.
  • the test conditions were as follows: the feed gas was a 25 ° C oxygen/nitrogen mixture (20.9% oxygen) supplied by an air compressor with an effective area of 50.24 cm 2 and a pressure difference of 200 kPa on both sides of the membrane.
  • the gas separation and separation performance measured was: gas permeation flux of 8.61 L/min m 2 and permeate side oxygen concentration of 28.1%.
  • the porous base membrane is a polysulfone (PSf) plate type ultrafiltration membrane with a molecular weight cut off of 20,000.
  • PSf polysulfone
  • the selected liquid oligomer is a terminal vinyl group PDMS (viscosity: 300 mPa ⁇ s), and the selected crosslinking agent and catalyst are respectively PMHS.
  • chloroplatinic acid, the environmentally friendly solvent is ethanol, and the high temperature baking lamp selects the Yuba heating lamp.
  • the pretreated PSf base film was cut into a 20 cm diameter disc and fixed on a vertically placed carrier film stage, and rotated at a constant speed of 100 rpm, while the PSf base film was always baked in the Yuba heating lamp. under;
  • the liquid terminal vinyl PDMS on the surface of PSf base film is in situ chemical cross-linking reaction with PMHS under the baking of 80 °C Yuba heating lamp.
  • the crosslinking time is the spraying time (8s), which forms dense The terminal vinyl PDMS-PMHS/PSf separation membrane.
  • the prepared terminal vinyl PDMS/PSf dense separation membrane is subjected to pervaporation, preferably pervaporation performance test.
  • the test conditions were as follows: a 10 wt.% ethanol/water system having a feed temperature of 60 ° C, a membrane effective area of 50.24 cm 2 , and a membrane downstream pressure of 200 Pa.
  • pervaporation membrane properties were measured as follows: permeation flux 3642.42 g/m 2 h, permeate liquid ethanol content 42.26 wt.%, separation factor 6.59.
  • the prepared terminal hydroxyl group PDMS/PSf dense separation membrane was used for gas separation performance test to concentrate oxygen in the air.
  • the test conditions were as follows: the feed gas was a 25 ° C oxygen/nitrogen mixture (20.9% oxygen) supplied by an air compressor with an effective area of 50.24 cm 2 and a pressure difference of 200 kPa on both sides of the membrane.
  • the gas separation and separation performance measured was: gas permeation flux of 38.36 L/min m 2 and permeate side oxygen concentration of 23%.
  • the porous base membrane is a polysulfone (PSf) plate type ultrafiltration membrane with a molecular weight cut off of 20,000.
  • PSf polysulfone
  • the selected liquid oligomer is a terminal vinyl group PDMS (viscosity: 300 mPa ⁇ s), and the selected crosslinking agent and catalyst are respectively PMHS.
  • chloroplatinic acid, the environmentally friendly solvent is ethanol, and the high temperature baking lamp selects the Yuba heating lamp.
  • liquid vinyl PDMS is placed directly in the container for use without adding any organic solvent; the mass concentration of 1% PMHS and the mass concentration of 0.1% chloroplatinic acid are mixed and dissolved in a small amount of ethanol solvent. ,stand-by;
  • the pretreated PSf base film was cut into a 20 cm diameter disc and fixed on a vertically placed carrier film stage, and rotated at a constant speed of 100 rpm, while the PSf base film was always baked in the Yuba heating lamp. under;
  • the liquid terminal vinyl PDMS on the surface of PSf base film is in situ chemical cross-linking reaction with PMHS under the baking of 80 °C Yuba heating lamp, and the crosslinking time is spraying time (160s), which forms dense The terminal vinyl PDMS-PMHS/PSf separation membrane.
  • the prepared terminal vinyl PDMS/PSf dense separation membrane is subjected to pervaporation, preferably pervaporation performance test.
  • the test conditions were as follows: a 10 wt.% ethanol/water system having a feed temperature of 60 ° C, a membrane effective area of 50.24 cm 2 , and a membrane downstream pressure of 200 Pa.
  • pervaporation membrane properties were measured as follows: permeation flux 1275g/m 2 h, permeate liquid ethanol content 50.74wt.%, separation factor 9.27.
  • the porous base membrane is a polysulfone (PSf) plate type ultrafiltration membrane with a molecular weight cut off of 20,000.
  • the selected liquid oligomer is a terminal vinyl group PDMS (viscosity: 300 mPa ⁇ s), and the selected crosslinking agent and catalyst are respectively PMHS.
  • chloroplatinic acid, the environmentally friendly solvent is ethanol, and the heater is heated at high temperature to select the heater.
  • the pretreated PSf base film was cut into a 20 cm diameter disc and fixed on a vertically placed carrier film stage, and rotated at a constant speed of 100 rpm, while the PSf base film was always baked in the Yuba heating lamp. under;
  • the liquid terminal vinyl PDMS on the surface of PSf base film is in situ chemical cross-linking reaction with PMHS under the baking of 80 °C Yuba heating lamp, and the crosslinking time is spraying time (160s), which forms dense The terminal vinyl PDMS-PMHS/PSf separation membrane.
  • the prepared terminal vinyl PDMS/PSf dense separation membrane is subjected to pervaporation, preferably pervaporation performance test.
  • the test conditions were as follows: a 10 wt.% ethanol/water system having a feed temperature of 60 ° C, a membrane effective area of 50.24 cm 2 , and a membrane downstream pressure of 200 Pa.
  • pervaporation membrane properties were measured as follows: permeation flux 1426.52 g/m 2 h, ethanol content in permeate was 51.19 wt.%, and separation factor was 9.44.
  • the porous base membrane is a polysulfone (PSf) plate type ultrafiltration membrane with a molecular weight cut off of 20,000.
  • PSf polysulfone
  • the selected liquid oligomer is a terminal vinyl group PDMS (viscosity: 300 mPa ⁇ s), and the selected crosslinking agent and catalyst are respectively PMHS.
  • chloroplatinic acid, the environmentally friendly solvent is ethanol, and the high temperature baking lamp selects the Yuba heating lamp.
  • liquid vinyl PDMS is placed directly in the container for use without adding any organic solvent; the mass concentration of 20% PMHS and the mass concentration of 0.1% chloroplatinic acid are mixed and dissolved in a small amount of ethanol solvent. ,stand-by;
  • the pretreated PSf base film was cut into a 20 cm diameter disc and fixed on a vertically placed carrier film stage, and rotated at a constant speed of 100 rpm, while the PSf base film was always baked in the Yuba heating lamp. under;
  • the liquid terminal vinyl PDMS on the surface of PSf base film is in situ chemical cross-linking reaction with PMHS under the baking of 80 °C Yuba heating lamp, and the crosslinking time is spraying time (160s), which forms dense The terminal vinyl PDMS-PMHS/PSf separation membrane.
  • the prepared terminal vinyl PDMS/PSf dense separation membrane is subjected to pervaporation, preferably pervaporation performance test.
  • the test conditions were as follows: a 10 wt.% ethanol/water system having a feed temperature of 60 ° C, a membrane effective area of 50.24 cm 2 , and a membrane downstream pressure of 200 Pa.
  • pervaporation membrane properties were measured as follows: permeate flux 711.36 g/m 2 h, permeate liquid ethanol content 47.63 wt.%, separation factor 8.18.
  • the porous base membrane is a polysulfone (PSf) plate type ultrafiltration membrane with a molecular weight cut off of 20,000.
  • PSf polysulfone
  • the selected liquid oligomer is a terminal vinyl group PDMS (viscosity: 300 mPa ⁇ s), and the selected crosslinking agent and catalyst are respectively PMHS.
  • chloroplatinic acid, the environmentally friendly solvent is ethanol, and the high temperature baking lamp selects the Yuba heating lamp.
  • the pretreated PSf base film was cut into a 20 cm diameter disc and fixed on a vertically placed carrier film stage, and rotated at a constant speed of 100 rpm, while the PSf base film was always baked in the Yuba heating lamp. under;
  • the liquid terminal vinyl PDMS on the surface of PSf base film is in situ chemical cross-linking reaction with PMHS under the baking of 80 °C Yuba heating lamp, and the crosslinking time is spraying time (160s), which forms dense The terminal vinyl PDMS-PMHS/PSf separation membrane.
  • the prepared terminal vinyl PDMS/PSf dense separation membrane is subjected to pervaporation, preferably pervaporation performance test.
  • the test conditions were as follows: a 10 wt.% ethanol/water system having a feed temperature of 60 ° C, a membrane effective area of 50.24 cm 2 , and a membrane downstream pressure of 200 Pa.
  • pervaporation membrane properties were measured as follows: permeate flux 266.13 g/m 2 h, permeate liquid ethanol content 42.44 wt.%, separation factor 6.64.
  • the porous base membrane is a polysulfone (PSf) flat ultrafiltration membrane with a molecular weight cutoff of 20,000.
  • the selected liquid oligomer is a polyester polyol (viscosity of 300 mPa ⁇ s), and the selected crosslinking agent is hexamethylene. Isocyanate, high temperature baking lamp selects Yuba heating lamp.
  • liquid polyester polyol is directly placed in a container for use without adding any organic solvent; the hexamethylene diisocyanate is directly placed in another container for use without any solvent dissolution;
  • the pretreated PSf base film was cut into a 20 cm diameter disc and fixed on a vertically placed carrier film stage, and rotated at a constant speed of 100 rpm, while the PSf base film was always baked in the Yuba heating lamp. under;
  • the liquid polyester polyol and hexamethylene diisocyanate are alternately sprayed in a highly atomized manner to the surface of the uniformly rotating PSf base film by two pressure spray guns;
  • the distance between the base films is 50cm
  • the time for spraying the liquid polyester polyol is 2s
  • the time for spraying hexamethylene diisocyanate is 5s
  • the spray area is more than 150cm 2
  • the number of cycles of spraying is 2 times.
  • the interval is 30 s
  • the spray speed of all spray guns is 2-3 ml/s and the pressure is 0.3 MPa.
  • the liquid terminal vinyl PDMS on the surface of PSf base film is in situ chemical cross-linking reaction with PMHS under the baking of 80 °C Yuba heating lamp.
  • the crosslinking time is the spraying time (44s), which forms dense Polyurethane (PU) / PSf separation membrane.
  • the SEM photograph shows (Fig. 3) that the terminal vinyl-based PDMS-PMHS separation layer is dense and defect-free (Fig. 3-1); the terminal vinyl PDMS-PMHS separation layer has a thickness of 5 ⁇ m (Fig. 3-2)
  • the prepared terminal vinyl PU/PSf dense separation membrane was subjected to pervaporation performance test to recover small molecule organic matter in the aqueous solution.
  • the test conditions were: 3 wt.% ethanol/water system with a feed temperature of 60 ° C, 3 wt.% n-butanol/water system, 3 wt.% isobutanol/water system, 3 wt.% ethyl acetate/water system,
  • the effective area of the membrane was 50.24 cm 2 and the pressure on the downstream side of the membrane was 200 Pa.
  • the pervaporation membrane properties were measured as follows: 3wt.% ethanol/water system permeation flux was 944.7g/m 2 h, permeate ethanol content 21.20wt.%, separation factor 8.70; 3wt.% n-butanol/water system
  • the permeate flux is 1267.42g/m 2 h, the n-butanol content in the permeate is 38.91wt.%, the separation factor is 2059;
  • the permeation flux of 3wt.% isobutanol/water system is 1607.58g/m 2 h, permeate
  • the isobutanol content is 44.04 wt.%, the separation factor is 25.45;
  • the 3 wt.% ethyl acetate/water system permeation flux is 1100 g/m 2 h, the permeate liquid ethyl acetate content is 53.50 wt.%, and the separation factor is 37.20;
  • the porous base membrane is a polysulfone (PSf) flat ultrafiltration membrane with a molecular weight cutoff of 20,000.
  • the selected liquid oligomer is an unsaturated polyester (viscosity of 300 mPa ⁇ s).
  • the selected curing agent is methyl ethyl ketone peroxide and high temperature baking.
  • the lamp is a heater for the Yuba.
  • the pretreated PSf base film was cut into a 20 cm diameter disc and fixed on a vertically placed carrier film stage, and rotated at a constant speed of 100 rpm, while the PSf base film was always baked in the Yuba heating lamp. under;
  • the liquid unsaturated polyester and methyl ethyl ketone peroxide are sprayed alternately to the surface of the uniformly rotating PSf base film by two atomizing spray guns; between the spray gun and the base film
  • the distance is 50cm
  • the time of spraying the liquid unsaturated polyester is 2s
  • the time of spraying methyl ethyl ketone once is 5s
  • the spraying area is more than 150cm 2
  • the number of circulating spraying is 2 times
  • the interval between each cycle is 30s
  • all The spray speed of the spray gun is 2-3 ml/s and the pressure is 0.3 MPa.
  • the SEM photograph shows (Fig. 4) that the UPR separation layer is dense and defect-free (Fig. 4-1); the UPR separation layer has a thickness of 4 ⁇ m (Fig. 4-2)
  • the prepared UPR/PSf dense separation membrane was subjected to a pervaporation performance test to separate a toluene/n-heptane mixture.
  • the test conditions were as follows: a 50 wt.% benzene/n-heptane system having a feed temperature of 40 ° C, a membrane effective area of 50.24 cm 2 , and a membrane downstream pressure of 200 Pa.
  • pervaporation membrane properties were measured as follows: permeate flux 106.06 g/m 2 h, permeate liquid toluene content 80.53 wt.%, separation factor 4.14.
  • the porous base membrane is a polysulfone (PSf) flat ultrafiltration membrane with a molecular weight cut off of 20,000.
  • the selected liquid oligomer is an unsaturated polyester (viscosity of 300 mPa ⁇ s), and the selected curing agent is methyl ethyl ketone peroxide.
  • the high temperature baking lamp is a heater for the Yuba.
  • the pretreated PSf base film was cut into a 20 cm diameter disc and fixed on a vertically placed carrier film stage, and rotated at a constant speed of 100 rpm, while the PSf base film was always baked in the Yuba heating lamp. under;
  • the prepared UPR/PSf dense separation membrane was subjected to a pervaporation performance test to separate a toluene/n-heptane mixture.
  • the test conditions were as follows: a 50 wt.% benzene/n-heptane system having a feed temperature of 40 ° C, a membrane effective area of 50.24 cm 2 , and a membrane downstream pressure of 200 Pa.
  • pervaporation membrane properties were measured as follows: permeation flux 151.52 g/m 2 h, permeate liquid toluene content 75.33 wt.%, separation factor 3.05.
  • the porous base membrane is a polysulfone (PSf) flat ultrafiltration membrane with a molecular weight cutoff of 20,000.
  • the selected liquid oligomer is an unsaturated polyester (viscosity of 300 mPa ⁇ s).
  • the selected curing agent is methyl ethyl ketone peroxide and high temperature baking.
  • the lamp is selected to be a heater.
  • the pretreated PSf base film was cut into a 20 cm diameter disc and fixed on a vertically placed carrier film stage, and rotated at a constant speed of 100 rpm, while the PSf base film was always baked in the Yuba heating lamp. under;
  • the liquid unsaturated polyester and methyl ethyl ketone peroxide are sprayed alternately to the surface of the uniformly rotating PSf base film by two atomizing spray guns; between the spray gun and the base film
  • the distance is 50cm
  • the time of spraying the liquid unsaturated polyester is 2s
  • the time of spraying methyl ethyl ketone once is 5s
  • the spraying area is more than 150cm 2
  • the number of circulating spraying is 3 times
  • the interval between each cycle is 30s
  • all The spray speed of the spray gun is 2-3 ml/s and the pressure is 0.3 MPa.
  • the liquid unsaturated polyester on the surface of PSf base film undergoes in-situ chemical crosslinking reaction under the baking of 80 °C Yuba heating lamp.
  • the crosslinking time is the spraying time (81s), which forms a dense one.
  • Saturated polyester resin (UPR) / PSf separation membrane is the spraying time (81s), which forms a dense one.
  • the prepared UPR/PSf dense separation membrane was subjected to a pervaporation performance test to separate a toluene/n-heptane mixture.
  • the test conditions were as follows: a 50 wt.% benzene/n-heptane system having a feed temperature of 40 ° C, a membrane effective area of 50.24 cm 2 , and a membrane downstream pressure of 200 Pa.
  • pervaporation membrane properties were measured as follows: permeate flux 75.76 g/m 2 h, permeate liquid toluene content 81 wt.%, separation factor 4.26.

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Abstract

一种快速环保制备致密分离膜的方法，包括：将多孔基膜固定于旋转的载膜台上，并使多孔基膜的膜面温度为60-200℃；分别将液态低聚物和固化剂溶液以雾化方式喷涂在多孔基膜表面，使液态低聚物在多孔基膜表面发生原位交联反应，得到致密、无缺陷的分离膜。该方法操作简便、极大地缩短了成膜时间，提高了制膜效率；且绿色、环保，具有普适性，适于膜的规模化制备。

Description

一种快速环保制备致密分离膜的方法 技术领域
本发明属于膜分离技术领域，特别涉及一种快速环保制备致密分离膜的方法。
背景技术
当前，膜技术已成为解决人类面临的水资源、能源、环境和传统产业改造等领域重大问题的共性技术之一。尤其是基于致密、无缺陷分离层的有机聚合物膜材料，可以对特定的离子和分子进行高效的筛分和分离，在气体分离、物料分离和水处理等多领域具有巨大的应用潜力。此外，由于其取材广泛、单位面积制造成本低廉、组件装填密度大等优点，更易于工业放大和商业化的应用。
目前，绝大多数的有机聚合物致密分离膜材料都是由传统的刮膜法、浸渍法制备。在制膜过程中，需要经聚合物的溶解和脱泡(铸膜液的配制)、铸膜液在多孔基膜上的刮涂过程、溶剂的挥发、后处理等多步操作才能完成，过程极其复杂；且整个过程需要持续几小时到十几个小时，甚至几天才能制得致密分离膜，耗时多，成膜效率极低；在膜液的刮涂过程中也存在人为因素，由此可导致基膜表面形成的分离层厚度不均，易产生缺陷，所制备的膜结构和性能不稳定，重复性差；此外，传统方法一般采用固态或高黏度的高聚物作为致密分离层的交联主体，且高聚物在有机溶剂(如正庚烷、甲苯、三氯甲烷、四氢呋喃、二甲基甲酰胺、吡咯烷酮等)中溶解是获得致密分离层的关键，因此这些有毒有害溶剂的大量使用和挥发会对环境造成严重的二次污染，并对制膜工人的健康造成严重危害。
喷涂技术，是将料液通过机械雾化作用以一定速度喷射沉积到支撑体表面形成涂层的方法。该方法可使料液均匀地分布于支撑体表面，通过调节喷涂的次数可控制涂层的厚度，是表面过程技术的重要组成部分之一。喷涂技术也可用于致密分离膜的制备。例如，张国俊等(CN102698613A，CN102512980A，CN102698612A，CN103182251B)借助喷涂技术发明了多种致密分离膜自动喷涂装置和方法，并成功制备出系列具有不同选择性分离层的致密膜。但发明人发现，这些发明装置虽然在一定程度上简化了制膜过程，但仍然需要高聚物的溶解步骤和后处理，因此，要形成致密分离层仍需较长时间(几个小时)，且聚合物的溶解也要用到大量有机溶剂；为此，张国俊等(CN201310654128)又发明了一种环境友好优先透醇复合膜的制备装置及方法，在该方法中，虽然使用液态低聚物成膜可减少有机溶剂的环境污染，但聚合物的后交联时间长达6～20h，制膜效率需进一步提升。
发明内容
本发明实施例所要解决的技术问题在于，提供了一种快速环保制备致密分离膜的方法。具体技术方案如下：
一种快速环保制备致密分离膜的方法，包括：
步骤a、将多孔基膜固定于旋转的载膜台上，并使所述多孔基膜的膜面温度为60-200℃。
步骤b、分别将液态低聚物和固化剂溶液以雾化方式喷涂在所述多孔基膜表面，使所述液态低聚物在所述多孔基膜表面发生原位交联反应，得到致密分离膜。
所述固化剂溶液用于使所述液态低聚物发生所述原位交联反应。
具体地，所述固化剂溶液为用于使所述液态低聚物发生所述原位交联反应的交联剂、交联剂与催化剂的混合物或用于引发所述液态低聚物进行所述原位交联反应的引发剂。
进一步地，所述方法还包括：在进行所述步骤a之前，对所述多孔基膜进行堵孔预处理，使所述多孔基膜的内部孔道充满去离子水，且表面保持干燥状态。
具体地，所述多孔基膜选自有机聚合物膜、无机膜或有机/无机杂化膜，且平均孔径为0.001-100μm。
具体地，作为优选，所述载膜台的旋转速度大于等于60rpm。
具体地，所述液态低聚物选自硅油、环氧树脂、不饱和聚酯、低分子量聚醚、聚脲、聚碳酸酯、聚酰胺、聚酯多元醇、苯乙烯中的至少一种。
具体地，作为优选，所述交联剂选自正硅酸乙酯、正硅酸丙酯、硅酸丁酯、二乙氧基硅烷、含氢聚硅氧烷、二甲基硅烷、六亚甲基二异氰酸酯中的至少一种；
所述催化剂选自二月桂酸二丁基锡、单丁基氧化锡、二丁基氧化锡、三丙基氧化锡、二丙基氧化锡、氯铂酸中的至少一种；
所述引发剂选自过氧化苯酰和/或过氧化甲乙酮。
作为优选，所述固化剂溶液采用环境友好型溶剂，所述环境友好型溶剂选自去离子水和/或乙醇；
所述固化剂溶液中，所述交联剂和所述催化剂质量浓度分别为1％-30％和0.1％-5％。
具体地，作为优选，所述步骤b中，在相对湿度低于60％的环境中，通过采用压力喷枪分别将所述液态低聚物和所述固化剂溶液喷涂在所述多孔基膜表面；
所述液态低聚物的黏度为常温下低于500mPa·s。
具体地，作为优选，所述压力喷枪的喷嘴与所述多孔基膜的中心对应设置；控制所述喷嘴与所述多孔基膜中心之间的距离为20-80cm。
具体地，作为优选，所述液态低聚物和所述固化剂溶液的喷涂次数均为1-10 次；每次的喷涂时间均为1-10s；每循环一次喷涂过程的时间间隔为0-120s。
具体地，作为优选，控制喷涂速度为2-3ml/s，喷涂压力为0.2-0.4MPa。
本发明实施例提供的技术方案带来的有益效果是：
本发明实施例提供的快速环保制备致密分离膜的方法，通过将液态低聚物和使其交联固化的固化剂溶液喷涂在60-200℃的多孔基膜表面，使两者发生原位交联反应，在多孔基膜表面形成一层与其紧密结合的致密分离层，从而得到本发明期望的致密无缺陷且分离性能优异的致密分离膜。一方面，本发明实施例通过采用喷涂方式在60-200℃的温度下进行原位交联反应，有效缩短了致密分离膜的制备时间，使其缩短至8-350s，提高了致密分离膜的制备效率。另一方面，本发明实施例通过直接采用液态低聚物制备致密分离膜，避免了使用有毒有害溶剂，减少了环境污染，更加安全环保。
进一步，本发明实施例提供的方法还包括：在进行步骤a之前，对多孔基膜进行堵孔预处理，使多孔基膜的内部孔道充满去离子水，且表面保持干燥状态。通过对多孔基膜进行堵孔预处理，不仅使该多孔基膜的膜孔内的有机污染物溶解出来，还可防止所喷涂的液态低聚物渗入膜孔(在喷涂加热过程中，膜孔内的水会蒸发形成压力阻止喷涂的高压材料进入孔道)，保证多孔基膜表面形成的分离层具有较薄的厚度，提高所制备的致密分离膜的膜通量。
附图说明
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1：本发明实施例3所制备的羟基封端的PDMS/PSf致密分离膜表面扫描电镜图(1-1)及断面扫描电镜图(1-2)；多孔PSf基膜表面扫描电镜图(1-3)及断面扫描电镜图(1-4)；
图2：本发明实施例7所制备的乙烯基封端的PDMS-PMHS/PSf致密分离膜表面扫描电镜图(2-1)及断面扫描电镜图(2-2)；
图3：本发明实施例14所制备的PU/PSf致密分离膜表面扫描电镜图(3-1)及断面扫描电镜图(3-2)；
图4：本发明实施例15所制备的UPR/PSf致密分离膜表面扫描电镜图(4-1)及断面扫描电镜图(4-2)。
扫描电镜图采用Hitachi S-4300型扫描电子显微镜(SEM)观察和测定。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合附图对本发明实 施方式作进一步地详细描述。
本发明实施例提供了一种快速环保制备致密分离膜的方法，包括以下步骤：
步骤a、将多孔基膜固定于旋转的载膜台上，并使多孔基膜的膜面温度为60-200℃。
步骤b、分别将液态低聚物和固化剂溶液以雾化方式喷涂在多孔基膜表面，使液态低聚物在多孔基膜表面发生原位交联反应，得到无缺陷的致密分离膜。其中，所使用的固化剂溶液用于使液态低聚物发生原位交联反应。
本发明实施例提供的快速环保制备致密分离膜的方法，通过将液态低聚物和使其交联固化的固化剂溶液喷涂在60-200℃的多孔基膜表面，使两者发生原位交联反应，在多孔基膜表面形成一层与其紧密结合的致密分离层，从而得到本发明期望的致密无缺陷且分离性能优异的致密分离膜。一方面，本发明实施例通过采用喷涂方式在60-200℃的温度下进行原位交联反应，有效缩短了致密分离膜的制备时间，使其缩短至8-350s，提高了致密分离膜的制备效率。另一方面，本发明实施例通过直接采用液态低聚物制备致密分离膜，避免了使用有毒有害溶剂，减少了环境污染，更加安全环保。
本领域技术人员可以理解的是，本发明实施例所用固化剂溶液具有能够使液态低聚物进行原位交联反应的功能。根据所使用的液态低聚物的不同，所使用的固化剂溶液也相应不同。举例来说，该固化剂溶液可以为用于使液态低聚物发生原位交联反应的交联剂，或者进一步可以为该交联剂与能够催化原位交联反应的催化剂的混合物，或者还可以为用于引发液态低聚物进行原位交联反应的引发剂。
作为优选，该固化剂溶液中采用环境友好型溶剂，以提高固化剂溶液的分散度。具体地，该环境友好型溶剂选自去离子水和/或乙醇。进一步地，当固化剂溶液中含有环境友好型溶剂时，其中所含交联剂和催化剂质量浓度分别优选为1％-30％和0.1％-5％，如此设置，可使液态低聚物和交联剂交联反应更加完全，所制备的分离膜更致密。
具体地，上述交联剂可以选自正硅酸乙酯、正硅酸丙酯、硅酸丁酯、二乙氧基硅烷、含氢聚硅氧烷、二甲基硅烷、六亚甲基二异氰酸酯中的至少一种；上述催化剂可以选自二月桂酸二丁基锡、单丁基氧化锡、二丁基氧化锡、三丙基氧化锡、二丙基氧化锡、氯铂酸中的至少一种；上述引发剂可以选自过氧化苯酰、过氧化甲乙酮中的至少一种。
此外，本发明实施例所用的液态低聚物为本领域常见的，在常温常压下为液体状态的有机聚合物。作为优选，本发明实施例中，液态低聚物可以为选自硅油、环氧树脂、不饱和聚酯、低分子量聚醚、聚脲、聚碳酸酯、聚酰胺、聚酯多元醇、 苯乙烯中的至少一种。上述液态低聚物的类型均为本领域常见的化工原料，可以通过市购得到。例如，硅油可以为端羟基硅油、端乙烯基硅油、甲基硅油、或者三者的任意组合。
根据前述，当固化剂溶液的类型随着液态低聚物的种类而变化。举例来说，当液态低聚物为聚酯多元醇时，可以使用交联剂六亚甲基二异氰酸酯作为固化剂溶液；当液态低聚物为端羟基硅油时，可以使用交联剂正硅酸乙酯以及催化剂二月桂酸二丁基锡的混合物作为固化剂溶液；当液态低聚物为不饱和聚酯时，可以使用引发剂过氧化甲乙酮作为固化剂溶液。
以下将对本发明实施例的具体操作步骤进行具体描述及优选：
进一步，本发明实施例提供的方法还包括：在进行步骤101之前，对多孔基膜进行堵孔预处理，使多孔基膜的内部孔道充满去离子水，且表面保持干燥状态。通过对多孔基膜进行堵孔预处理，不仅使该多孔基膜的膜孔内的有机污染物溶解出来，还可防止所喷涂的液态低聚物渗入膜孔，保证多孔基膜表面形成的分离层具有较薄的厚度，提高所制备的致密分离膜的膜通量。
具体地，对该多孔基膜所进行的堵孔预处理具体操作步骤如下：首先将多孔基膜浸渍于乙醇溶剂中1-3小时，然后将其放入充满去离子水的抽滤瓶中，真空抽滤5-10小时后取出放置于空气中，使多孔基膜表面水挥发完全。
其中，本发明实施例中，所用多孔基膜选自平均孔径为0.001-100μm的有机聚合物膜、无机膜或有机/无机杂化膜。举例来说，该有机聚合物膜可以为聚砜膜、聚碳酸酯膜、聚乙烯膜、聚醚砜膜、聚四氟乙烯膜、聚偏氟乙烯膜、聚六氟丙烯膜、壳聚糖膜等；该无机膜可以为氧化锆膜、氧化锌膜、氧化铝膜等；该有机/无机杂化膜可以为聚砜/SiO2膜、聚砜/MOF(金属有机骨架)膜、聚砜/分子筛膜、聚偏氟乙烯/SiO2膜等。本领域技术人员可以理解的是，本领域常见的其他纳滤膜、超滤膜、微滤膜等也可作为本发明实施例期望的多孔基膜。
具体地，步骤b中，优选使用黏度低于500mPa·s的液态低聚物，如此设置，不仅可保证喷涂过程顺利实施，且喷涂的雾化效果好，利于形成致密无缺陷的分离膜。举例来说，该液态低聚物的黏度可以为0-50mPa·s，50-100mPa·s，100-500mPa·s，或者150-300mPa·s，或者200-400mPa·s等。进一步举例来说，该黏度可以为50mPa·s，100mPa·s，150mPa·s，200mPa·s，250mPa·s，300mPa·s，350mPa·s，400mPa·s，450mPa·s或者500mPa·s。
此外，步骤a中，通过将多孔基膜放置在旋转的载膜台上，以便于所喷涂的液态低聚物和固化剂溶液能够在多孔基膜表面均匀分配。首先，基于本领域常用的载膜台的形状，该多孔基膜优选为直径15-20cm的圆片状，以避免多孔基膜不必要的浪费。其次，为了使所喷涂的液态低聚物在多孔基膜表面分布更加均匀， 以形成致密无缺陷的分离膜，且避免过多的能耗产生，该载膜台的旋转速度优选大于等于60rpm。例如，其可以为60-100rpm、60-200rpm、60-300rpm、60-400rpm、60-500rpm、60-600rpm。进一步举例来说，该旋转速度可以为60rpm、100rpm、150rpm、200rpm、250rpm、300rpm、350rpm、400rpm、450rpm、500rpm、550rpm、600rpm等。
进一步地，该多孔基膜的膜面温度为60℃-200℃，举例来说，其可以为60℃、80℃、100℃、120℃、140℃、160℃、180℃、200℃等。通过对多孔基膜表面的膜面温度进行如上限定，可使所喷涂的液态低聚物与其固化剂溶液快速地发生交联反应，不仅可在多孔基膜表面形成致密的分离层，还可缩短成膜时间，提高制膜效率。若多孔基膜表面温度低于60℃，交联反应进行缓慢，高于200℃则会破坏刚形成的致密的分离层。
进一步地，上述多孔基膜的膜面温度可通过多种方式来实现，例如可以选用高温烤灯照射，该高温烤灯选自浴霸取暖灯、红外线烤灯或紫外线烤灯中的至少一种。
步骤b中，为了便于在多孔基膜上实施喷涂过程，通过采用压力喷枪分别将液态低聚物和固化剂溶液以雾化方式喷涂在多孔基膜表面。可以理解的是，该压力喷枪包括用于喷涂液态低聚物的喷枪和用于喷涂固化剂溶液的喷枪。相应地，上述喷涂的具体实施方式可以为同时喷涂液态低聚物和固化剂溶液，或者交替喷涂液态低聚物和固化剂溶液(即喷涂一次液态低聚物，随后再喷涂一次固化剂溶液，然后再依次交替喷涂即可)。
为了形成致密且无大孔缺陷的分离层，步骤b应在环境湿度小于等于60％的条件下实施。例如，该环境湿度可以为10％-60％、30％-50％、15％、20％、25％、30％、35％、40％、45％、55％、58％等。
当采用压力喷枪进行上述喷涂时，该压力喷枪的喷嘴与多孔基膜的中心对应设置，且控制喷嘴与多孔基膜中心之间的距离为20-80cm，如此设置，可使所喷涂的液态低聚物雾化效果达到最佳，且在多孔基膜表面分布更均匀。
其中，液态低聚物和固化剂溶液的喷涂次数、每次的喷涂时间及每循环一次的间隔时间完全由逻辑控制器(Programmable Logic Controller，PLC)实现自动控制。
具体地，作为优选，液态低聚物和固化剂溶液的喷涂次数均为1-10次，从而使分离膜的分离层具有较薄的厚度，减小阻力，提高渗透通量，同时保证分离膜的分离层的致密性；每次喷涂时间均为1-10s，喷涂时间过长不仅浪费原料，还起不到喷涂的雾化效果。
每循环一次喷涂过程的时间间隔为0-120s，在该时间间隔内，可保证上一次 喷涂的液态低聚物和固化剂溶液反应完全。其中，上述“每循环一次喷涂过程”指的时分别喷涂一次液态低聚物和固化剂溶液作为一个循环过程。
具体地，作为优选，液体低聚物和固化剂溶液的喷涂速度为2-3ml/s，喷涂压力为0.2-0.4MPa。对此限定可使喷涂液体低聚物和固化剂溶液的雾化效果达到最佳。
以下将通过具体实施例进一步地描述本发明。
在以下具体实施例中，所涉及的操作未注明条件者，均按照常规条件或者制造商建议的条件进行。所用原料未注明生产厂商及规格者均为可以通过市购获得的常规产品。
实施例1
采用多孔基膜为聚砜(PSf)平板式超滤膜，截留分子量20000，选用的液态低聚物为端羟基的PDMS(黏度为100mPa·s)，选取的交联剂和催化剂分别为正硅酸乙酯和二月桂酸二丁基锡，环境友好型溶剂为乙醇，选取的高温烤灯为浴霸取暖灯。
制备方法及步骤：
1)将液态的端羟基的PDMS直接置于容器中待用；将质量浓度为10％的正硅酸乙酯和质量浓度为1％的二月桂酸二丁基锡混合后溶于少量的乙醇溶剂中，待用；
2)将预处理后的PSf基膜剪成直径为20cm的圆片后固定于垂直放置的载膜台上，并以100rpm的速度匀速旋转，同时使PSf基膜始终处于高温烤灯的烘烤下；
3)在环境湿度为20％条件下，用两个压力喷枪分别将液态的端羟基PDMS及其正硅酸乙酯/二月桂酸二丁基锡的乙醇混合溶液以高度雾化的方式交替喷涂至匀速旋转的PSf基膜表面；喷枪与基膜间的距离为50cm，喷涂一次液态的端羟基PDMS时间为3s，喷涂一次正硅酸乙酯/二月桂酸二丁基锡的乙醇混合溶液的时间为5s，喷涂面积大于150cm2，循环喷涂次数为1次，所有喷枪的喷速均为2-3ml/s，压力0.3MPa。
4)在喷涂的同时，PSf基膜表面的液态端羟基PDMS在80℃的浴霸取暖灯烘烤下发生原位化学交联反应，交联时间即喷涂时间(8s)，进而形成致密的端羟基PDMS/PSf分离膜。
将所制备的端羟基PDMS/PSf致密分离膜进行渗透汽化优选透醇性能测试。测试条件为：进料温度为60℃的10wt.％乙醇/水体系，膜有效面积为50.24cm2，膜下游压力为200Pa。
测得渗透汽化膜性能为：渗透通量711g/m2h，透过液中乙醇含量33.3wt.％， 分离因子4.5。
将所制备的端羟基PDMS/PSf致密分离膜用于气体分离性能测试，浓缩空气中的氧气。测试条件为：进料气体为25℃氧气/氮气混合物(氧气为20.9％)，由空气压缩机提供，膜有效面积为50.24cm2，膜两侧压差为200kPa。
测得的气体分离分离性能为：气体渗透通量为28.57L/min m2，透过侧氧气浓度为22.9％。
实施例2
采用多孔基膜为聚砜(PSf)平板式超滤膜，截留分子量20000，选用的液态低聚物为端羟基的PDMS(黏度为100mPa·s)，选取的交联剂和催化剂分别为正硅酸乙酯和二月桂酸二丁基锡，环境友好型溶剂为乙醇，选取的高温烤灯为浴霸取暖灯。
制备方法及步骤：
1)将液态的端羟基的PDMS直接置于容器中待用；将质量浓度为10％的正硅酸乙酯和质量浓度为1％的二月桂酸二丁基锡混合后溶于少量的乙醇溶剂中，待用；
2)将预处理后的PSf基膜剪成直径为20cm的圆片后固定于垂直放置的载膜台上，并以100rpm的速度匀速旋转，同时使PSf基膜始终处于高温烤灯的烘烤下；
3)在环境湿度为20％条件下，用两个压力喷枪分别将液态的端羟基的PDMS及其正硅酸乙酯/二月桂酸二丁基锡的乙醇混合溶液以高度雾化的方式交替喷涂至匀速旋转的PSf基膜表面；喷枪与基膜间的距离为50cm，喷涂一次液态的端羟基的PDMS时间为3s，喷涂一次正硅酸乙酯/二月桂酸二丁基锡的乙醇混合溶液的时间为5s，喷涂面积大于150cm2，循环喷涂次数为3次，每循环一次中间间隔时间为30s，所有喷枪的喷速均为2-3ml/s，压力0.3MPa。
4)在喷涂的同时，PSf基膜表面的液态端羟基PDMS在80℃的浴霸取暖灯烘烤下发生原位化学交联反应，交联时间即喷涂时间(84s)，进而形成致密的端羟基PDMS/PSf分离膜。
将所制备的端羟基PDMS/PSf致密分离膜进行渗透汽化优选透醇性能测试。测试条件为：进料温度为60℃的10wt.％乙醇/水体系，膜有效面积为50.24cm2，膜下游压力200Pa。
测得渗透汽化膜性能为：渗透通量556g/m2h，透过液中乙醇含量44.4wt.％，分离因子7.2。
将所制备的端羟基PDMS/PSf致密分离膜用于气体分离性能测试，浓缩空气中的氧气。测试条件为：进料气体为25℃氧气/氮气混合物(氧气为20.9％)，由 空气压缩机提供，膜有效面积为50.24cm2，膜两侧压差为200kPa。
测得的气体分离分离性能为：气体渗透通量为21.38L/min m2，透过侧氧气浓度为24％。
实施例3
采用多孔基膜为聚砜(PSf)平板式超滤膜，截留分子量20000，选用的液态低聚物为端羟基的PDMS(黏度为100mPa·s)，选取的交联剂和催化剂分别为正硅酸乙酯和二月桂酸二丁基锡，环境友好型溶剂为乙醇，选取的高温烤灯为浴霸取暖灯。
制备方法及步骤：
1)将液态的端羟基的PDMS直接置于容器中待用；将质量浓度为10％的正硅酸乙酯和质量浓度为1％的二月桂酸二丁基锡混合后溶于少量的乙醇溶剂中，待用；
2)将预处理后的PSf基膜剪成直径为20cm的圆片后固定于垂直放置的载膜台上，并以100rpm的速度匀速旋转，同时使PSf基膜始终处于高温烤灯的烘烤下；
3)在环境湿度为20％条件下，用两个压力喷枪分别将液态的端羟基的PDMS及其正硅酸乙酯/二月桂酸二丁基锡的乙醇混合溶液以高度雾化的方式交替喷涂至匀速旋转的PSf基膜表面；喷枪与基膜间的距离为50cm，喷涂一次液态的端羟基的PDMS时间为3s，喷涂一次正硅酸乙酯/二月桂酸二丁基锡的乙醇混合溶液的时间为5s，喷涂面积大于150cm2，循环喷涂次数为5次，每循环一次中间间隔时间为30s，所有喷枪的喷速均为2-3ml/s，压力0.3MPa。
4)在喷涂的同时，PSf基膜表面的液态端羟基PDMS在80℃的浴霸取暖灯烘烤下发生原位化学交联反应，交联时间即喷涂时间(160s)，进而形成致密的端羟基PDMS/PSf分离膜。
SEM照片显示(图1)，对比PSf基膜表面的多孔结构(图1-3)，端羟基的PDMS分离层致密无缺陷(图1-1)；对比PSf基膜的断面结构(图1-4)，端羟基的PDMS分离层厚度为8μm(图1-2)
将所制备的端羟基PDMS/PSf致密分离膜进行渗透汽化性能测试，回收水溶液中小分子有机物。测试条件为：进料温度分别为60℃的3wt.％乙醇/水体系、10wt.％乙醇/水体系、3wt.％正丙醇/水体系、3wt.％异丙醇/水体系、3wt.％正丁醇/水体系、3wt.％异丁醇/水体系、3wt.％丙酮/水体系、3wt.％乙酸乙酯/水体系，膜有效面积为50.24cm2，膜下游侧压力为200Pa。
测得渗透汽化膜性能为：3wt.％乙醇/水体系渗透通量为320.33g/m2h，透过液中乙醇含量31.2wt.％，分离因子14.66；10wt.％乙醇/水体系渗透通量为521.00 g/m2h，透过液中乙醇含量50.30wt.％，分离因子9.11；3wt.％正丙醇/水体系渗透通量为416.67g/m2h，透过液中正丙醇含量40.7wt.％，分离因子22.19；3wt.％异丙醇/水体系渗透通量为325.76g/m2h，透过液中异丙醇含量36.95wt.％，分离因子18.95；3wt.％正丁醇/水体系渗透通量为526.52g/m2h，透过液中正丁醇含量45.3wt.％，分离因子26.78；3wt.％异丁醇/水体系渗透通量为589.39g/m2h，透过液中异丁醇含量49.9wt.％，分离因子32.20；3wt.％丙酮/水体系渗透通量为409.85g/m2h，透过液中丙酮含量53.24wt.％，分离因子36.81；3wt.％乙酸乙酯/水体系渗透通量为569.70g/m2h，透过液中乙酸乙酯含量63.27wt.％，分离因子55.70；
将所制备的端羟基PDMS/PSf致密分离膜用于气体分离性能测试，浓缩空气中的氧气。测试条件为：进料气体为25℃氧气/氮气混合物(氧气为20.9％)，由空气压缩机提供，膜有效面积为50.24cm2，膜两侧压差为200kPa。
测得的气体分离分离性能为：气体渗透通量为14.78L/min m2，透过侧氧气浓度为26.2％。
实施例4
采用多孔基膜为聚砜(PSf)平板式超滤膜，截留分子量20000，选用的液态低聚物为端羟基的PDMS(黏度为100mPa·s)，选取的交联剂和催化剂分别为正硅酸乙酯和二月桂酸二丁基锡，环境友好型溶剂为乙醇，选取的高温烤灯为浴霸取暖灯
制备方法及步骤：
1)将液态的端羟基的PDMS直接置于容器中待用；将质量浓度为10％的正硅酸乙酯和质量浓度为1％的二月桂酸二丁基锡混合后溶于少量的乙醇溶剂中，待用；
2)将预处理后的PSf基膜剪成直径为20cm的圆片后固定于垂直放置的载膜台上，并以100rpm的速度匀速旋转，同时使PSf基膜始终处于浴霸取暖灯的烘烤下；
3)在环境湿度为20％条件下，用两个压力喷枪分别将液态的端羟基的PDMS及其正硅酸乙酯/二月桂酸二丁基锡的乙醇混合溶液以高度雾化的方式交替喷涂至匀速旋转的PSf基膜表面；喷枪与基膜间的距离为50cm，喷涂一次液态的端羟基的PDMS时间为3s，喷涂一次正硅酸乙酯/二月桂酸二丁基锡的乙醇混合溶液的时间为5s，喷涂面积大于150cm2，循环喷涂次数为10次，每循环一次中间间隔时间为30s，所有喷枪的喷速均为2-3ml/s，压力0.3MPa。
4)在喷涂的同时，PSf基膜表面的液态端羟基PDMS在80℃的浴霸取暖灯烘烤下发生原位化学交联反应，交联时间即喷涂时间(350s)，进而形成致密的 端羟基PDMS/PSf分离膜。
将所制备的端羟基PDMS/PSf致密分离膜进行渗透汽化优选透醇性能测试。测试条件为：进料温度为60℃的10wt.％乙醇/水体系，膜有效面积为50.24cm2，膜下游压力200Pa。
测得渗透汽化膜性能为：渗透通量420g/m2h，透过液中乙醇含量48.6wt.％，分离因子8.5。
将所制备的端羟基PDMS/PSf致密分离膜用于气体分离性能测试，浓缩空气中的氧气。测试条件为：进料气体为25℃氧气/氮气混合物(氧气为20.9％)，由空气压缩机提供，膜有效面积为50.24cm2，膜两侧压差为200kPa。
测得的气体分离分离性能为：气体渗透通量为6.13L/min m2，透过侧氧气浓度为27.3％。
实施例5
采用多孔基膜为聚砜(PSf)平板式超滤膜，截留分子量20000，选用的液态低聚物为端羟基的PDMS(黏度为100mPa·s)，选取的交联剂和催化剂分别为正硅酸乙酯和二月桂酸二丁基锡，环境友好型溶剂为乙醇/水混合物(质量比为1：1)，选取的高温烤灯为浴霸取暖灯。
制备方法及步骤：
1)将液态的端羟基的PDMS直接置于容器中待用；将质量浓度为10％的正硅酸乙酯和质量浓度为1％的二月桂酸二丁基锡混合后溶于质量比为1:1的乙醇/水混合溶剂中，待用；
2)将预处理后的PSf基膜剪成直径为20cm的圆片后固定于垂直放置的载膜台上，并以100rpm的速度匀速旋转，同时使PSf基膜始终处于浴霸取暖烤灯的烘烤下；
3)在环境湿度为20％条件下，用两个压力喷枪分别将液态的端羟基的PDMS及其正硅酸乙酯/二月桂酸二丁基锡的乙醇/水混合溶液以高度雾化的方式交替喷涂至匀速旋转的PSf基膜表面；喷枪与基膜间的距离为50cm，喷涂一次液态的端羟基的PDMS时间为3s，喷涂一次正硅酸乙酯/二月桂酸二丁基锡的乙醇/水混合溶液的时间为5s，喷涂面积大于150cm2，循环喷涂次数为5次，每循环一次中间间隔时间为30s，所有喷枪的喷速均为2-3ml/s，压力0.3MPa。
4)在喷涂的同时，PSf基膜表面的液态端羟基PDMS在80℃的浴霸取暖灯烘烤下发生原位化学交联反应，交联时间即喷涂时间(160s)，进而形成致密的端羟基PDMS/PSf分离膜。
将所制备的端羟基PDMS/PSf致密分离膜进行渗透汽化优选透醇性能测试。测试条件为：进料温度为60℃的10wt.％乙醇/水体系，膜有效面积为50.24cm2， 膜下游压力200Pa。
测得渗透汽化膜性能为：渗透通量640g/m2h，透过液中乙醇含量34.7wt.％，分离因子4.78。
实施例6
采用多孔基膜为聚砜(PSf)平板式超滤膜，截留分子量20000，选用的液态低聚物为端羟基的PDMS(黏度为100mPa·s)，选取的交联剂和催化剂分别为正硅酸乙酯和二月桂酸二丁基锡，选取的高温烤灯为浴霸取暖灯。
制备方法及步骤：
1)将液态的端羟基的PDMS直接置于容器中待用；将正硅酸乙酯和二月桂酸二丁基锡按质量比10:1混合后待用，不用任何溶剂溶解；
2)将预处理后的PSf基膜剪成直径为20cm的圆片后固定于垂直放置的载膜台上，并以100rpm的速度匀速旋转，同时使PSf基膜始终处于浴霸取暖灯的烘烤下；
3)在环境湿度为20％条件下，用两个压力喷枪分别将液态的端羟基的PDMS及其正硅酸乙酯/二月桂酸二丁基锡的混合物以高度雾化的方式交替喷涂至匀速旋转的PSf基膜表面；喷枪与基膜间的距离为50cm，喷涂一次液态的端羟基的PDMS时间为3s，喷涂一次正硅酸乙酯/二月桂酸二丁基锡混合物的时间为5s，喷涂面积大于150cm2，循环喷涂次数为5次，每循环一次中间间隔时间为30s，所有喷枪的喷速均为2-3ml/s，压力0.3MPa。
4)在喷涂的同时，PSf基膜表面的液态端羟基PDMS在80℃的浴霸取暖灯烘烤下发生原位化学交联反应，交联时间即喷涂时间(160s)，进而形成致密的端羟基PDMS/PSf分离膜。
将所制备的端羟基PDMS/PSf致密分离膜进行渗透汽化优选透醇性能测试。测试条件为：进料温度为60℃的10wt.％乙醇/水体系，膜有效面积为50.24cm2，膜下游压力200Pa。
测得渗透汽化膜性能为：渗透通量75g/m2h，透过液中乙醇含量29.2wt.％，分离因子3.71。
实施例7
采用多孔基膜为聚砜(PSf)平板式超滤膜，截留分子量20000，选用的液态低聚物为端乙烯基的PDMS(黏度为300mPa·s)，选取的交联剂和催化剂分别为PMHS和氯铂酸，环境友好型溶剂为乙醇，选取的高温烤灯为浴霸取暖灯。
制备方法及步骤：
1)将液态的乙烯基的PDMS直接置于容器中待用，不添加任何有机溶剂；将质量浓度为10％的PMHS和质量浓度为0.1％的氯铂酸混合后溶于少量的乙醇溶剂中，待用；
2)将预处理后的PSf基膜剪成直径为20cm的圆片后固定于垂直放置的载膜台上，并以100rpm的速度匀速旋转，同时使PSf基膜始终处于浴霸取暖灯的烘烤下；
3)在环境湿度为20％条件下，用两个压力喷枪分别将液态的端乙烯基的PDMS及PMHS/氯铂酸的乙醇混合溶液以高度雾化的方式交替喷涂至匀速旋转的PSf基膜表面；喷枪与基膜间的距离为50cm，喷涂一次液态的端乙烯基的PDMS时间为3s，喷涂一次PMHS/氯铂酸的乙醇混合溶液的时间为5s，喷涂面积大于150cm2，循环喷涂次数为5次，每循环一次中间间隔时间为30s，所有喷枪的喷速均为2-3ml/s，压力0.3MPa。
4)在喷涂的同时，PSf基膜表面的液态端乙烯基PDMS在80℃的浴霸取暖灯烘烤下与PMHS发生原位化学交联反应，交联时间即喷涂时间(160s)，进而形成致密的端乙烯基PDMS-PMHS/PSf分离膜。
SEM照片显示(图2)，端乙烯基的PDMS-PMHS分离层致密无缺陷(图2-1)；端乙烯基的PDMS-PMHS分离层厚度为5μm(图2-2)
将所制备的端乙烯基的PDMS-PMHS/PSf致密分离膜进行渗透汽化性能测试，回收水溶液中小分子有机物。测试条件为：进料温度分别为60℃的3wt.％乙醇/水体系、10wt.％乙醇/水体系、3wt.％正丙醇/水体系、3wt.％异丙醇/水体系、3wt.％正丁醇/水体系、3wt.％异丁醇/水体系、3wt.％丙酮/水体系、3wt.％乙酸乙酯/水体系，膜有效面积为50.24cm2，膜下游侧压力为200Pa。
测得渗透汽化膜性能为：3wt.％乙醇/水体系渗透通量为1079.55g/m2h，透过液中乙醇含量31.03wt.％，分离因子14.55；10wt.％乙醇/水体系渗透通量为1729.55g/m2h，透过液中乙醇含量51.64wt.％，分离因子9.61；3wt.％正丙醇/水体系渗透通量为1353.79g/m2h，透过液中正丙醇含量40.46wt.％，分离因子22.2；3wt.％异丙醇/水体系渗透通量为1292.42g/m2h，透过液中异丙醇含量37.43wt.％，分离因子19.34；3wt.％正丁醇/水体系渗透通量为1599.24g/m2h，透过液中正丁醇含量49.53wt.％，分离因子31.73；3wt.％异丁醇/水体系渗透通量为1956.82g/m2h，透过液中异丁醇含量52.99wt.％，分离因子36.45；3wt.％丙酮/水体系渗透通量为1798.48g/m2h，透过液中丙酮含量59.65wt.％，分离因子47.80；3wt.％乙酸乙酯/水体系渗透通量为1646.97g/m2h，透过液中乙酸乙酯含量65.18wt.％，分离因子60.53；
将所制备的端乙烯基PDMS-PMHS/PSf致密分离膜用于气体分离性能测试， 浓缩空气中的氧气。测试条件为：进料气体为25℃氧气/氮气混合物(氧气为20.9％)，由空气压缩机提供，膜有效面积为50.24cm2，膜两侧压差为200kPa。
测得的气体分离分离性能为：气体渗透通量为19.81L/min m2，透过侧氧气浓度为26.6％。
实施例8
采用多孔基膜为聚砜(PSf)平板式超滤膜，截留分子量20000，选用的液态低聚物为端乙烯基的PDMS(黏度为300mPa·s)，选取的交联剂和催化剂分别为PMHS和氯铂酸，环境友好型溶剂为乙醇，选取的高温烤灯为浴霸取暖灯。
制备方法及步骤：
1)将液态的乙烯基的PDMS直接置于容器中待用，不添加任何有机溶剂；将质量浓度为10％的PMHS和质量浓度为0.1％的氯铂酸混合后溶于少量的乙醇溶剂中，待用；
2)将预处理后的PSf基膜剪成直径为20cm的圆片后固定于垂直放置的载膜台上，并以100rpm的速度匀速旋转，同时使PSf基膜始终处于浴霸取暖灯的烘烤下；
3)在环境湿度为20％条件下，用两个压力喷枪分别将液态的端乙烯基的PDMS及PMHS/氯铂酸的乙醇混合溶液以高度雾化的方式交替喷涂至匀速旋转的PSf基膜表面；喷枪与基膜间的距离为50cm，喷涂一次液态的端乙烯基的PDMS时间为3s，喷涂一次PMHS/氯铂酸的乙醇混合溶液的时间为5s，喷涂面积大于150cm2，循环喷涂次数为10次，每循环一次中间间隔时间为30s，所有喷枪的喷速均为2-3ml/s，压力0.3MPa。
4)在喷涂的同时，PSf基膜表面的液态端乙烯基PDMS在80℃的浴霸取暖灯烘烤下与PMHS发生原位化学交联反应，交联时间即喷涂时间(350s)，进而形成致密的端乙烯基PDMS-PMHS/PSf分离膜。
将所制备的端乙烯基的PDMS/PSf致密分离膜进行渗透汽化优选透醇性能测试。测试条件为：进料温度为60℃的10wt.％乙醇/水体系，膜有效面积为50.24cm2，膜下游压力200Pa。
测得渗透汽化膜性能为：渗透通量181.06g/m2h，透过液中乙醇含量50.34wt.％，分离因子9.12。
将所制备的端羟基PDMS/PSf致密分离膜用于气体分离性能测试，浓缩空气中的氧气。测试条件为：进料气体为25℃氧气/氮气混合物(氧气为20.9％)，由空气压缩机提供，膜有效面积为50.24cm2，膜两侧压差为200kPa。
测得的气体分离分离性能为：气体渗透通量为8.61L/min m2，透过侧氧气浓度为28.1％。
实施例9
采用多孔基膜为聚砜(PSf)平板式超滤膜，截留分子量20000，选用的液态低聚物为端乙烯基的PDMS(黏度为300mPa·s)，选取的交联剂和催化剂分别为PMHS和氯铂酸，环境友好型溶剂为乙醇，高温烤灯选取浴霸取暖灯。
制备方法及步骤：
1)将液态的乙烯基的PDMS直接置于容器中待用，不添加任何有机溶剂；将质量浓度为10％的PMHS和质量浓度为0.1％的氯铂酸混合后溶于少量的乙醇溶剂中，待用；
2)将预处理后的PSf基膜剪成直径为20cm的圆片后固定于垂直放置的载膜台上，并以100rpm的速度匀速旋转，同时使PSf基膜始终处于浴霸取暖灯的烘烤下；
3)在环境湿度为20％条件下，用两个压力喷枪分别将液态的端乙烯基的PDMS及PMHS/氯铂酸的乙醇混合溶液以高度雾化的方式交替喷涂至匀速旋转的PSf基膜表面；喷枪与基膜间的距离为50cm，喷涂一次液态的端乙烯基的PDMS时间为3s，喷涂一次PMHS/氯铂酸的乙醇混合溶液的时间为5s，喷涂面积大于150cm2，循环喷涂次数为1次，所有喷枪的喷速均为2-3ml/s，压力0.3MPa。
4)在喷涂的同时，PSf基膜表面的液态端乙烯基PDMS在80℃的浴霸取暖灯烘烤下与PMHS发生原位化学交联反应，交联时间即喷涂时间(8s)，进而形成致密的端乙烯基PDMS-PMHS/PSf分离膜。
将所制备的端乙烯基的PDMS/PSf致密分离膜进行渗透汽化优选透醇性能测试。测试条件为：进料温度为60℃的10wt.％乙醇/水体系，膜有效面积为50.24cm2，膜下游压力200Pa。
测得渗透汽化膜性能为：渗透通量3642.42g/m2h，透过液中乙醇含量42.26wt.％，分离因子6.59。
将所制备的端羟基PDMS/PSf致密分离膜用于气体分离性能测试，浓缩空气中的氧气。测试条件为：进料气体为25℃氧气/氮气混合物(氧气为20.9％)，由空气压缩机提供，膜有效面积为50.24cm2，膜两侧压差为200kPa。
测得的气体分离分离性能为：气体渗透通量为38.36L/min m2，透过侧氧气浓度为23％。
实施例10
采用多孔基膜为聚砜(PSf)平板式超滤膜，截留分子量20000，选用的液态低聚物为端乙烯基的PDMS(黏度为300mPa·s)，选取的交联剂和催化剂分别为PMHS和氯铂酸，环境友好型溶剂为乙醇，高温烤灯选取浴霸取暖灯。
制备方法及步骤：
1)将液态的乙烯基的PDMS直接置于容器中待用，不添加任何有机溶剂；将质量浓度为1％的PMHS和质量浓度为0.1％的氯铂酸混合后溶于少量的乙醇溶剂中，待用；
2)将预处理后的PSf基膜剪成直径为20cm的圆片后固定于垂直放置的载膜台上，并以100rpm的速度匀速旋转，同时使PSf基膜始终处于浴霸取暖灯的烘烤下；
3)在环境湿度为20％条件下，用两个压力喷枪分别将液态的端乙烯基的PDMS及PMHS/氯铂酸的乙醇混合溶液以高度雾化的方式交替喷涂至匀速旋转的PSf基膜表面；喷枪与基膜间的距离为50cm，喷涂一次液态的端乙烯基的PDMS时间为3s，喷涂一次PMHS/氯铂酸的乙醇混合溶液的时间为5s，喷涂面积大于150cm2，循环喷涂次数为5次，每循环一次中间间隔时间为30s，所有喷枪的喷速均为2-3ml/s，压力0.3MPa。
4)在喷涂的同时，PSf基膜表面的液态端乙烯基PDMS在80℃的浴霸取暖灯烘烤下与PMHS发生原位化学交联反应，交联时间即喷涂时间(160s)，进而形成致密的端乙烯基PDMS-PMHS/PSf分离膜。
将所制备的端乙烯基的PDMS/PSf致密分离膜进行渗透汽化优选透醇性能测试。测试条件为：进料温度为60℃的10wt.％乙醇/水体系，膜有效面积为50.24cm2，膜下游压力200Pa。
测得渗透汽化膜性能为：渗透通量1275g/m2h，透过液中乙醇含量50.74wt.％，分离因子9.27。
实施例11
采用多孔基膜为聚砜(PSf)平板式超滤膜，截留分子量20000，选用的液态低聚物为端乙烯基的PDMS(黏度为300mPa·s)，选取的交联剂和催化剂分别为PMHS和氯铂酸，环境友好型溶剂为乙醇，高温开灯选取浴霸取暖灯。
制备方法及步骤：
1)将液态的乙烯基的PDMS直接置于容器中待用，不添加任何有机溶剂；将质量浓度为5％的PMHS和质量浓度为0.1％的氯铂酸混合后溶于少量的乙醇溶剂中，待用；
2)将预处理后的PSf基膜剪成直径为20cm的圆片后固定于垂直放置的载膜台上，并以100rpm的速度匀速旋转，同时使PSf基膜始终处于浴霸取暖灯的烘烤下；
3)在环境湿度为20％条件下，用两个压力喷枪分别将液态的端乙烯基的PDMS及PMHS/氯铂酸的乙醇混合溶液以高度雾化的方式交替喷涂至匀速旋转的PSf基膜表面；喷枪与基膜间的距离为50cm，喷涂一次液态的端乙烯基的 PDMS时间为3s，喷涂一次PMHS/氯铂酸的乙醇混合溶液的时间为5s，喷涂面积大于150cm2，循环喷涂次数为5次，每循环一次中间间隔时间为30s，所有喷枪的喷速均为2-3ml/s，压力0.3MPa。
4)在喷涂的同时，PSf基膜表面的液态端乙烯基PDMS在80℃的浴霸取暖灯烘烤下与PMHS发生原位化学交联反应，交联时间即喷涂时间(160s)，进而形成致密的端乙烯基PDMS-PMHS/PSf分离膜。
将所制备的端乙烯基的PDMS/PSf致密分离膜进行渗透汽化优选透醇性能测试。测试条件为：进料温度为60℃的10wt.％乙醇/水体系，膜有效面积为50.24cm2，膜下游压力200Pa。
测得渗透汽化膜性能为：渗透通量1426.52g/m2h，透过液中乙醇含量51.19wt.％，分离因子9.44。
实施例12
采用多孔基膜为聚砜(PSf)平板式超滤膜，截留分子量20000，选用的液态低聚物为端乙烯基的PDMS(黏度为300mPa·s)，选取的交联剂和催化剂分别为PMHS和氯铂酸，环境友好型溶剂为乙醇，高温烤灯选取浴霸取暖灯。
制备方法及步骤：
1)将液态的乙烯基的PDMS直接置于容器中待用，不添加任何有机溶剂；将质量浓度为20％的PMHS和质量浓度为0.1％的氯铂酸混合后溶于少量的乙醇溶剂中，待用；
2)将预处理后的PSf基膜剪成直径为20cm的圆片后固定于垂直放置的载膜台上，并以100rpm的速度匀速旋转，同时使PSf基膜始终处于浴霸取暖灯的烘烤下；
3)在环境湿度为20％条件下，用两个压力喷枪分别将液态的端乙烯基的PDMS及PMHS/氯铂酸的乙醇混合溶液以高度雾化的方式交替喷涂至匀速旋转的PSf基膜表面；喷枪与基膜间的距离为50cm，喷涂一次液态的端乙烯基的PDMS时间为3s，喷涂一次PMHS/氯铂酸的乙醇混合溶液的时间为5s，喷涂面积大于150cm2，循环喷涂次数为5次，每循环一次中间间隔时间为30s，所有喷枪的喷速均为2-3ml/s，压力0.3MPa。
4)在喷涂的同时，PSf基膜表面的液态端乙烯基PDMS在80℃的浴霸取暖灯烘烤下与PMHS发生原位化学交联反应，交联时间即喷涂时间(160s)，进而形成致密的端乙烯基PDMS-PMHS/PSf分离膜。
将所制备的端乙烯基的PDMS/PSf致密分离膜进行渗透汽化优选透醇性能测试。测试条件为：进料温度为60℃的10wt.％乙醇/水体系，膜有效面积为50.24cm2，膜下游压力200Pa。
测得渗透汽化膜性能为：渗透通量711.36g/m2h，透过液中乙醇含量47.63wt.％，分离因子8.18。
实施例13
采用多孔基膜为聚砜(PSf)平板式超滤膜，截留分子量20000，选用的液态低聚物为端乙烯基的PDMS(黏度为300mPa·s)，选取的交联剂和催化剂分别为PMHS和氯铂酸，环境友好型溶剂为乙醇，高温烤灯选取浴霸取暖灯。
制备方法及步骤：
1)将液态的乙烯基的PDMS直接置于容器中待用，不添加任何有机溶剂；将质量浓度为30％的PMHS和质量浓度为0.1％的氯铂酸混合后溶于少量的乙醇溶剂中，待用；
2)将预处理后的PSf基膜剪成直径为20cm的圆片后固定于垂直放置的载膜台上，并以100rpm的速度匀速旋转，同时使PSf基膜始终处于浴霸取暖灯的烘烤下；
3)在环境湿度为20％条件下，用两个压力喷枪分别将液态的端乙烯基的PDMS及PMHS/氯铂酸的乙醇混合溶液以高度雾化的方式交替喷涂至匀速旋转的PSf基膜表面；喷枪与基膜间的距离为50cm，喷涂一次液态的端乙烯基的PDMS时间为3s，喷涂一次PMHS/氯铂酸的乙醇混合溶液的时间为5s，喷涂面积大于150cm2，循环喷涂次数为5次，每循环一次中间间隔时间为30s，所有喷枪的喷速均为2-3ml/s，压力0.3MPa。
4)在喷涂的同时，PSf基膜表面的液态端乙烯基PDMS在80℃的浴霸取暖灯烘烤下与PMHS发生原位化学交联反应，交联时间即喷涂时间(160s)，进而形成致密的端乙烯基PDMS-PMHS/PSf分离膜。
将所制备的端乙烯基的PDMS/PSf致密分离膜进行渗透汽化优选透醇性能测试。测试条件为：进料温度为60℃的10wt.％乙醇/水体系，膜有效面积为50.24cm2，膜下游压力200Pa。
测得渗透汽化膜性能为：渗透通量266.13g/m2h，透过液中乙醇含量42.44wt.％，分离因子6.64。
实施例14
采用多孔基膜为聚砜(PSf)平板式超滤膜，截留分子量20000，选用的液态低聚物为聚酯多元醇(黏度为300mPa·s)，选取的交联剂为六亚甲基二异氰酸酯，高温烤灯选取浴霸取暖灯。
制备方法及步骤：
1)将液态的聚酯多元醇直接置于容器中待用，不添加任何有机溶剂；将六亚甲基二异氰酸酯直接置于另一容器中待用，不用任何溶剂溶解；
2)将预处理后的PSf基膜剪成直径为20cm的圆片后固定于垂直放置的载膜台上，并以100rpm的速度匀速旋转，同时使PSf基膜始终处于浴霸取暖灯的烘烤下；
3)在环境湿度为20％条件下，用两个压力喷枪分别将液态的聚酯多元醇及六亚甲基二异氰酸酯以高度雾化的方式交替喷涂至匀速旋转的PSf基膜表面；喷枪与基膜间的距离为50cm，喷涂一次液态的聚酯多元醇时间为2s，喷涂一次六亚甲基二异氰酸酯的时间为5s，喷涂面积大于150cm2，循环喷涂次数为2次，每循环一次中间间隔时间为30s，所有喷枪的喷速均为2-3ml/s，压力0.3MPa。
4)在喷涂的同时，PSf基膜表面的液态端乙烯基PDMS在80℃的浴霸取暖灯烘烤下与PMHS发生原位化学交联反应，交联时间即喷涂时间(44s)，进而形成致密的聚氨酯(PU)/PSf分离膜。
SEM照片显示(图3)，端乙烯基的PDMS-PMHS分离层致密无缺陷(图3-1)；端乙烯基的PDMS-PMHS分离层厚度为5μm(图3-2)
将所制备的端乙烯基的PU/PSf致密分离膜进行渗透汽化性能测试，回收水溶液中小分子有机物。测试条件为：进料温度分别为60℃的3wt.％乙醇/水体系、3wt.％正丁醇/水体系、3wt.％异丁醇/水体系、3wt.％乙酸乙酯/水体系，膜有效面积为50.24cm2，膜下游侧压力为200Pa。
测得渗透汽化膜性能为：3wt.％乙醇/水体系渗透通量为944.7g/m2h，透过液中乙醇含量21.20wt.％，分离因子8.70；3wt.％正丁醇/水体系渗透通量为1267.42g/m2h，透过液中正丁醇含量38.91wt.％，分离因子2059；3wt.％异丁醇/水体系渗透通量为1607.58g/m2h，透过液中异丁醇含量44.04wt.％，分离因子25.45；3wt.％乙酸乙酯/水体系渗透通量为1100g/m2h，透过液中乙酸乙酯含量53.50wt.％，分离因子37.20；
实施例15
采用多孔基膜为聚砜(PSf)平板式超滤膜，截留分子量20000，选用的液态低聚物为不饱和聚酯(黏度为300mPa·s)，选取的固化剂为过氧化甲乙酮，高温烤灯为浴霸取暖灯。
制备方法及步骤：
1)将液态的不饱和聚酯直接置于容器中待用，不添加任何有机溶剂；将过氧化甲乙酮直接置于另一容器中待用，不用任何溶剂溶解；
2)将预处理后的PSf基膜剪成直径为20cm的圆片后固定于垂直放置的载膜台上，并以100rpm的速度匀速旋转，同时使PSf基膜始终处于浴霸取暖灯的烘烤下；
3)在环境湿度为20％条件下，用两个压力喷枪分别将液态的不饱和聚酯和 过氧化甲乙酮以高度雾化的方式交替喷涂至匀速旋转的PSf基膜表面；喷枪与基膜间的距离为50cm，喷涂一次液态的不饱和聚酯时间为2s，喷涂一次过氧化甲乙酮的时间为5s，喷涂面积大于150cm2，循环喷涂次数为2次，每循环一次中间间隔时间为30s，所有喷枪的喷速均为2-3ml/s，压力0.3MPa。
4)在喷涂的同时，PSf基膜表面的液态不饱和聚氨酯在80℃的浴霸取暖灯烘烤下发生原位化学交联反应，交联时间即喷涂时间(44s)，进而形成致密的不饱和聚酯树脂(UPR)/PSf分离膜。
SEM照片显示(图4)，UPR分离层致密无缺陷(图4-1)；UPR分离层厚度为4μm(图4-2)
将所制备的UPR/PSf致密分离膜进行渗透汽化性能测试，分离甲苯/正庚烷混合物。测试条件为：进料温度为40℃的50wt.％苯/正庚烷体系，膜有效面积为50.24cm2，膜下游侧压力为200Pa。
测得渗透汽化膜性能为：渗透通量106.06g/m2h，透过液中甲苯含量80.53wt.％，分离因子4.14。
实施例16
采用多孔基膜为聚砜(PSf)平板式超滤膜，截留分子量20000，选用的液态低聚物为不饱和聚酯(黏度为300mPa·s)，选取的固化剂为过氧化甲乙酮，选取的高温烤灯为浴霸取暖灯。
制备方法及步骤：
1)将液态的不饱和聚酯直接置于容器中待用，不添加任何有机溶剂；将过氧化甲乙酮直接置于另一容器中待用，不用任何溶剂溶解；
2)将预处理后的PSf基膜剪成直径为20cm的圆片后固定于垂直放置的载膜台上，并以100rpm的速度匀速旋转，同时使PSf基膜始终处于浴霸取暖灯的烘烤下；
3)在环境湿度为20％条件下，用两个压力喷枪分别将液态的不饱和聚酯和过氧化甲乙酮以高度雾化的方式交替喷涂至匀速旋转的PSf基膜表面；喷枪与基膜间的距离为50cm，喷涂一次液态的不饱和聚酯时间为2s，喷涂一次过氧化甲乙酮的时间为5s，喷涂面积大于150cm2，循环喷涂次数为1次，所有喷枪的喷速均为2-3ml/s，压力0.3MPa。
4)在喷涂的同时，PSf基膜表面的液态不饱和聚酯在80℃的浴霸取暖灯烘烤下发生原位化学交联反应，交联时间即喷涂时间(7s)，进而形成致密的不饱和聚酯树脂(UPR)/PSf分离膜。
将所制备的UPR/PSf致密分离膜进行渗透汽化性能测试，分离甲苯/正庚烷 混合物。测试条件为：进料温度为40℃的50wt.％苯/正庚烷体系，膜有效面积为50.24cm2，膜下游侧压力为200Pa。
测得渗透汽化膜性能为：渗透通量151.52g/m2h，透过液中甲苯含量75.33wt.％，分离因子3.05。
实施例17
采用多孔基膜为聚砜(PSf)平板式超滤膜，截留分子量20000，选用的液态低聚物为不饱和聚酯(黏度为300mPa·s)，选取的固化剂为过氧化甲乙酮，高温烤灯选取浴霸取暖灯。
制备方法及步骤：
1)将液态的不饱和聚酯直接置于容器中待用；将过氧化甲乙酮直接置于另一容器中待用，不用任何溶剂溶解；
2)将预处理后的PSf基膜剪成直径为20cm的圆片后固定于垂直放置的载膜台上，并以100rpm的速度匀速旋转，同时使PSf基膜始终处于浴霸取暖灯的烘烤下；
3)在环境湿度为20％条件下，用两个压力喷枪分别将液态的不饱和聚酯和过氧化甲乙酮以高度雾化的方式交替喷涂至匀速旋转的PSf基膜表面；喷枪与基膜间的距离为50cm，喷涂一次液态的不饱和聚酯时间为2s，喷涂一次过氧化甲乙酮的时间为5s，喷涂面积大于150cm2，循环喷涂次数为3次，每循环一次中间间隔时间为30s，所有喷枪的喷速均为2-3ml/s，压力0.3MPa。
4)在喷涂的同时，PSf基膜表面的液态不饱和聚酯在80℃的浴霸取暖灯烘烤下发生原位化学交联反应，交联时间即喷涂时间(81s)，进而形成致密的不饱和聚酯树脂(UPR)/PSf分离膜。
将所制备的UPR/PSf致密分离膜进行渗透汽化性能测试，分离甲苯/正庚烷混合物。测试条件为：进料温度为40℃的50wt.％苯/正庚烷体系，膜有效面积为50.24cm2，膜下游侧压力为200Pa。
测得渗透汽化膜性能为：渗透通量75.76g/m2h，透过液中甲苯含量81wt.％，分离因子4.26。
以上所述仅为本发明的较佳实施例，并不用以限制本发明的保护范围，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种快速环保制备致密分离膜的方法，其特征在于，包括以下步骤：
    步骤a、将多孔基膜固定于旋转的载膜台上，并使所述多孔基膜的膜面温度为60-200℃。
    步骤b、分别将液态低聚物和固化剂溶液以雾化方式喷涂在所述多孔基膜表面，使所述液态低聚物在所述多孔基膜表面发生原位交联反应，得到致密分离膜；
    所述固化剂溶液用于使所述液态低聚物发生所述原位交联反应。
  2. 根据权利要求1所述的方法，其特征在于，所述固化剂溶液为用于使所述液态低聚物发生所述原位交联反应的交联剂、交联剂与催化剂的混合物或用于引发所述液态低聚物进行所述原位交联反应的引发剂；所述固化剂溶液中，所述交联剂和所述催化剂质量浓度分别为1％-30％和0.1％-5％。
  3. 根据权利要求2所述的方法，其特征在于，所述交联剂选自正硅酸乙酯、正硅酸丙酯、硅酸丁酯、二乙氧基硅烷、含氢聚硅氧烷、二甲基硅烷、六亚甲基二异氰酸酯中的至少一种；
    所述催化剂选自二月桂酸二丁基锡、单丁基氧化锡、二丁基氧化锡、三丙基氧化锡、二丙基氧化锡、氯铂酸中的至少一种；
    所述引发剂选自过氧化苯酰和/或过氧化甲乙酮。
  4. 根据权利要求1所述的方法，其特征在于，所述方法还包括：在进行所述步骤a之前，对所述多孔基膜进行堵孔预处理，使所述多孔基膜的内部孔道充满去离子水，且表面保持干燥状态。
  5. 根据权利要求1所述的方法，其特征在于，所述多孔基膜选自有机聚合物膜、无机膜或有机/无机杂化膜，且平均孔径为0.001-100μm。
  6. 根据权利要求1所述的方法，其特征在于，所述液态低聚物选自硅油、环氧树脂、不饱和聚酯、低分子量聚醚、聚脲、聚碳酸酯、聚酰胺、聚酯多元醇、苯乙烯中的至少一种。
  7. 根据权利要求1所述的方法，其特征在于，所述固化剂溶液采用环境友好型溶剂，所述环境友好型溶剂选自去离子水和/或乙醇。
  8. 根据权利要求1所述的方法，其特征在于，所述步骤b中，在相对湿度低于60％的环境中，通过采用压力喷枪分别将所述液态低聚物和所述固化剂溶液喷涂在所述多孔基膜表面；
    所述液态低聚物的常温黏度低于500mPa·s。
  9. 根据权利要求1所述的方法，其特征在于，控制喷涂速度为2-3ml/s，喷涂压力为0.2-0.4MPa。
  10. 根据权利要求1所述的方法，其特征在于，所述液态低聚物和所述固化剂溶液的喷涂次数均为1-10次；每次的喷涂时间均为1-10s；每循环一次喷涂过程的时间间隔为0-120s；
    所述压力喷枪的喷嘴与所述多孔基膜的中心对应设置；控制所述喷嘴与所述多孔基膜中心之间的距离为20-80cm；
    所述载膜台的旋转速度大于等于60rpm。
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