CN105435655B - A kind of solvent resistant separation membrane material and preparation method thereof - Google Patents
A kind of solvent resistant separation membrane material and preparation method thereof Download PDFInfo
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- CN105435655B CN105435655B CN201410418407.6A CN201410418407A CN105435655B CN 105435655 B CN105435655 B CN 105435655B CN 201410418407 A CN201410418407 A CN 201410418407A CN 105435655 B CN105435655 B CN 105435655B
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Abstract
The invention discloses a kind of low cost, solvent resistant separation membrane material and preparation method thereof, the structure of the membrane material is two layers of dense layer surface and porous support layer or three layers of dense layer surface, porous support layer and dense layer surface；Suitable for alkanes, esters, alcohols solvent system filtering and isolate and purify.The solvent resistant separation membrane material is the composite material that two kinds of different high molecular polymers obtain after the entanglement of strand level, one of which high molecular polymer is selected from polysulfones, polyether sulfone, makrolon, polyvinyl chloride, polyvinyl alcohol, polyarylene sulfide, and another high molecular polymer is selected from polyacrylonitrile, polyimides, polyetherimide, polyamide.The present invention uses common macromolecule member material for primary raw material, changes the solvent resistance of membrane material by post-processing, to substantially reduce the cost of solvent resistant membrane material, promotes the extensive use of solvent resistant membrane material.
Description
Technical field
The invention belongs to macromolecule member material fields, and in particular to a kind of solvent resistant membrane material and preparation method thereof.
Background technology
It is a large amount of use organic solvent as reaction dissolution medium in industrial circle production process, or as diluting medium,
Equipment cleaning solvent, lubricant etc..These solvents include alkanes, such as butane, pentane, hexane, heptane, octane, decane, the moon
Osmanthus alkane etc.；Alcohols, such as methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol etc.；Lubricating base oil：Such as straight chain, branch, multibranched paraffin,
Monocycle, bicyclic, polycyclic ring alkane etc.；Esters, such as methyl formate, ethyl acetate, higher fatty acids and glycerine, glycerophosphatide class
Deng.Above-mentioned dicyandiamide solution encompasses industrial circle such as chemical industry, petrochemical industry, coal chemical industry, food engineering etc..These in production process are molten
The reuse of agent, the separation for dissolving substance are required for accurate separating medium to realize, membrane material is a kind of ideal low energy
The isolation technics of consumption.
Membrane technology has been one of the mostly important technology of relative maturity in water process and environmental protection.However it can
For the membrane material of long-term tolerance solvent also in the budding stage, basic reason is membrane material based on common macromolecule to molten
Agent tolerance is not high.Inorganic material film has extraordinary tolerance to organic solvent, technically fully meets requirement.But nothing
Machine membrane material pore size distribution is wider, and molecular weight cut off is difficult to control, from the pollution angle of separating effect and film for be not optimal；
And inorganic material film cost wants much higher relative to organic film material, using by larger limitation.Therefore, it is suitable to search out
Macromolecule member material, it is crucial to obtain solvent-proof membrane material by physics and the chemical modification of material.
Currently used macromolecule member material includes polysulfones, polyether sulfone, makrolon, polyvinyl chloride, polyvinyl alcohol, poly- virtue
Base thioether, polyacrylonitrile, polyimides, polyetherimide, polyamide etc..Since the macromolecule of these types is in alkanes, alcohol
There is different degrees of swelling in class, esters and fats solvent, leads to macromolecule member material intensity and reduced performance, cannot be satisfied
The basic demand used steadily in the long term.Chinese invention patent 100363094C discloses polyimides solvent resistant sodium filter membrane preparation side
Method is prepared for the membrane material of resistance to lubricating oil using high-temperature cross-linking.U.S. patent Nos US5264166 discloses high-temperature cross-linking method and obtains
To the polyimide film material of tolerance ketones solvent, however since such high molecular material is of high cost, such material is limited
Application range.U.S. patent Nos US5205934 discloses the preparation method of solvent resistant polypropylene cyanogen membrane material, will be made poly- third
Alkene nitrile film is contacted with the ethanol solution of sodium ethoxide, then heat cross-linking at a temperature of 115 DEG C, obtain resistance to DMF, NMF and
The membrane material of DMSO.U.S. patent Nos 6113794 are disclosed using polypropylene cyanogen as basement membrane, and surface coats chitosan class hydrophile
Matter, then prepare solvent resistant sodium filter membrane material using glutaraldehyde chemical crosslinking means.
In the range of molecular cut-off rate is more than 5000Da, in addition to polypropylene cyanogen membrane material, there are no it is more it is low at
This high performance solvent resistant polymeric membrane is available.
Invention content
The object of the present invention is to provide a kind of low costs, solvent resistant separation membrane material and preparation method thereof, mainly solve
The seldom technical problem of the solvent resistant polymeric membrane of alternative low-cost and high-performance in the prior art.
Used technical solution is as follows to solve above-mentioned technical problem by the present invention：
A kind of solvent resistant separation membrane material, the membrane material are two or more different high molecular polymer in molecule
The composite material obtained after entanglement on level；In the different high molecular polymers of two or more in the membrane material at least
There is a kind of high molecular polymer to be selected from polysulfones, polyether sulfone, makrolon, polyvinyl chloride, polyvinyl alcohol, polyarylene sulfide, at least
There is another high molecular polymer to be selected from polyacrylonitrile, polyimides, polyetherimide, polyamide.Two kinds in the membrane material
Or two or more different high molecular polymers, any of which high molecular polymer account for membrane material macromolecule total amount 10~
90%.Wherein, it is to select two kinds or two or more high molecular materials, the method post-processed with the type and membrane material of material
It is related.
The structure of the solvent resistant separation membrane material is divided into dense layer surface, two class of porous support layer.Specifically, membrane material
Structure can be dense layer surface/two layers of porous support layer or dense layer surface/three layers of porous support layer/dense layer surface.These
Structure type can be adjusted according to the demand to membrane structure.The membrane material skin thickness of the present invention is porous at 5-50000 nanometers
The thickness of supporting layer is then at 10-3000 microns.Porous support layer can be finger-like pore structure or spongelike structure.These terms
It is the basic terms of field of membrane material, any personnel for having membrane material basic knowledge can understand the culvert of above-mentioned term
Justice.
Preferably, the membrane material is the composite material obtained after two kinds of different high molecular polymers tangle, one of which
High molecular polymer be selected from polysulfones, polyether sulfone, polyvinyl chloride, another high molecular polymer be selected from polyacrylonitrile, polyimides,
Polyetherimide, polyamide.
The type of the solvent resistant separation membrane material tolerance solvent includes alkanes, esters, alcohols solvent, specifically includes carbon
4-20 alkane, the fat of carbon 2-30, carbon 1-20 alcohol.
Another molecular cut off for being noteworthy characterized by fine and close hole of the solvent resistant separation membrane material is 5000-
1000000Da. or aperture are between 1 nanometer and 1 micron.
Solvent resistant separation membrane material swelling ratio in different types of dicyandiamide solution is all different, however alkanes,
Volume sweell(ing) rate in esters, alcohols solvent is not higher than 80%, and linear swelling ratio is not higher than 40%.Higher than this swelling range, film
The mechanical strength and component stability of material will substantially reduce, to influence the service life of membrane material.In addition, the pore structure of membrane material
Significant changes, reduced performance may occur in use.
The present invention also provides a kind of preparation methods of solvent resistant separation membrane material, and this method comprises the following steps：
Step 1, two kinds or more of high molecular polymer and additive, solvent are mixed into homogeneous solution, it is described uniform
Solution passes through one-step forming at the beginning of nozzle extrusion or scraper；At least one kind is selected from described two or more high molecular polymers
Polysulfones, polyether sulfone, makrolon, polyvinyl chloride, polyvinyl alcohol, polyarylene sulfide, it is at least another to be selected from polyacrylonitrile, gather
Acid imide, polyetherimide, polyamide；Step 2, aforementioned material immersion precipitation after molding is bathed, solidification, then rinsing removal
Additive and solvent；Step 3, it is finally post-processed, the post-processing approach is that high temperature is carried out in 60~350 DEG C of temperature ranges
Heating, or infiltration obtain the solvent resistant separation membrane material to heat cross-linking in the solution containing crosslinking agent after the completion of processing
Material.
The preparation method of solvent resistant separation membrane material is simple and ripe in the present invention, and using immersion precipitation, feature exists
Macromolecule and additive and solvent are mixed into homogeneous solution in first, then first one-step forming, then immersion precipitation bath solidification, then floated
It washes away and removes additive and solvent, membrane material is post-processed.
In order to realize the hydrophilic and hydrophobic of different membrane structures and membrane material, need to add in film preparation solution non-molten
Agent, the additive are selected from methanol, ethyl alcohol, propyl alcohol, ethylene glycol, polyvinyl alcohol, sodium chloride, calcium chloride, lithium chloride, chlorination
Magnesium.Used additive amount is determined according to the neighbouring of solution than α value.The specific additive amount of additive is poor according to different systems
It is different larger, but the additive amount of specific additive can be determined according to defined above.According to system gel phasor, we define height
The characteristic value β value of copolymer solution is defined as the ratio of the amount and solvent of the small molecule additive in solution.According to definition,
The β value of gel point, high polymeric solution is maximum.If β value is more than the value in any solution composition, solution is always at gel
State.It is molten to be defined as high polymer adjacent to than α value for another characterisitic parameter that we can define macromolecule preparation liquid as a result,
The β value ratio of the β value of liquid and the system in gel point.
The neighbouring of solution than α value is the numerical value for weighing the non-solvent type amount of substance added in Polymer Solution.
In general, without adding any non-solvent type substance in a solution, the neighbouring of solution than α value is 0；In the turbid of solution
Point, the neighbouring of solution than α value is 1.So any homogeneous solution it is neighbouring than α value between 0 and 1.To any one solution body
System, the constituent of the non-solvent and Polymer Solution system that are added when solution is adjacent to than α value by 1, the ginsengs such as solution temperature
Number is directly related, and it for the professional person that membrane material is had gained some understanding is a basic conception that this concept, which is any one, therefore
This patent refers to that solution is neighbouring than α value, the concrete composition without referring to solution.The α values of macromolecule preparation liquid are up to 1, number
The absolute size of value quantitatively provides degree of the Polymer Solution apart from gel phase separation point.Therefore, signified in the present invention to add
Add the amount of agent by the α values (i.e. by the neighbouring than α value of raw material and the mixed homogeneous solution of solvent) of macromolecule preparation liquid to indicate,
General α values are between 0.1~0.9, and preferably 0.2~0.9.
The solvent is selected from N-methyl pyrrolidone, dimethylformamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), third
One or more of ketone, gamma-butyrolacton, trimethyl phosphate or triethyl phosphate.Solvent employed in the present invention is polarity
There is organic solvent the characteristic dissolved each other with water, solvent to select can realize to mixing high molecular highly dissoluble as standard.
It is that film forming speed is very fast using the advantage for the solvent that can be dissolved each other with water, production efficiency is high, while used organic solvent is equal
For can rapid degradation material, environment will not be adversely affected.
In the present invention, by the Polymer Solution configured (i.e. homogeneous solution), squeezed out by nozzle or scraper tentatively at
After type, the air section that can be all controlled by one section of temperature and humidity, 10~90 DEG C of temperature range during air section, preferably 15
~60 DEG C；Relative humidity is 20~100%, preferably 50~95%.Nozzle referred herein squeezes out or scraper is molded according to right
Model state needs to prepare doughnut or plate film material, is not the innovative point of the present invention, any system to membrane material
The personnel for having basic understanding can prepare hollow fibre according to method provided by the invention in conjunction with ready-made film preparation equipment
Dimension or tablet membrane material.
The medium of coagulation bath temperature coagulation bath is water, the mixture of water and polar solvent, alcohols or is alcohol in the present invention
The mixture of class and water；Coagulation bath temperature is 4~100 DEG C, preferably 10~80 DEG C.Any preparation to membrane material has basic understanding
Personnel can determine other corresponding films as needed in conjunction with ready-made film preparation equipment according to method provided by the invention
Preparation parameter.General rule is：The high aperture of coagulation bath temperature is larger, and nonaqueous solvents content is high in coagulation bath, and aperture is bigger.
The membrane material post-processing approach of the present invention includes two classes：One kind is by high-temperature heating, by high molecular crosslink；It is a kind of
It is to use crosslinking agent, finally obtains stable membrane material.Hot crosslinked temperature range is between 100-300 degree.Chemical crosslinking
Method then passes through：(1) membrane material is infiltrated into the aqueous solution containing crosslinking agent glutaraldehyde or maleic anhydride, crosslinking agent therein
Concentration range 0.1~10%, preferably 0.5~5%, infiltrating time 10-60 minutes, preferably 15-30 minutes；(2) it then takes out
It is put into after membrane material and is dried in temperature controlled baking oven and promote to be chemically crosslinked, at 10-120 minutes, temperature controlled crosslinking time
At 40~150 DEG C, preferably 60~100 DEG C, final membrane material is obtained.
Technology path disclosed in this invention and method are suitable for preparing doughnut, tablet and tubular type, self-supporting or
Additional support type membrane material, it is any to have the personnel of basic common sense be according to method system provided by the present invention film preparation
Standby any form and membrane material.Method disclosed by the invention is suitable for ultrafiltration, the preparation of micro-filtration membrane material, due to being suitable for this hair
The pore diameter range of bright membrane material, the molecular weight that shuts off that can prepare membrane material are more than 5000Da, and maximum diameter of hole is up to 1 micron.Specifically
Implementation method can pass through effective control of formula and film preparation parameter to preparation liquid.
Compared with prior art, beneficial effects of the present invention are as follows：For the not perfect of current technology, the invention discloses
A kind of novel solvent resistant supermicro filtration membrane material based on conventional macromolecule member material changes the resistance to of membrane material by post-processing
Solvent nature can substantially reduce the cost of solvent filter separation, to promoting membrane material to be filtered and separation field in solvent resistant
Development is of great significance.
Description of the drawings
Fig. 1 is polysulfones/polyetherimide hollow-fibre membrane cross section structure figure that embodiment 1 obtains, and membrane structure is caused by inside
Close cortex and external dense layer surface and porous support layer are constituted.
Specific implementation mode
Embodiment 1
18 grams of polyether sulfone, 5 grams of polyetherimide are dissolved in 75 grams of dimethylacetylamides and 8 at 100 DEG C and under being sufficiently stirred
Gram ethylene glycol in the mixed solvent, the neighbouring of solution than α value is 0.35.After macromolecule is completely dissolved, by 40 micron pore sizes
After stainless steel wire net filtration, merging temperature control standing and defoaming in 50 DEG C of doughnut batch can.Film preparation parameter is：Spinneret
Head 0.8/1.3mm, air section height 45mm, temperature and humidity is respectively 30 DEG C/80%, spinning speed 12m/min, and coagulation bath is
30 DEG C of water.Film cleans up after solidification, is soaked into 1% glutaraldehyde water solution, 30 minutes time.Drip-dry is then taken out, is put
Enter and is crosslinked in the baking oven of 75 DEG C of temperature, time 25min.The pure water flux for measuring film is 357Lm-2·hr-1·bar-1；Using
Ethanol test transmitance is 2250Lm-2·hr-1·bar-1；Using hexane test transmitance 1360Lm-2·hr-1·bar-1.The membrane material of above-mentioned preparation infiltrates 24 hours in decane, and linear swelling ratio is less than 5%；It infiltrates 24 hours in hexane, line
Property swelling ratio be less than 3%；It is infiltrated 24 hours in ethyl acetate, linear swelling ratio is less than 5%；24 are infiltrated in triglyceride
Hour, linear swelling ratio is less than 2%.Scanning electron microscope structure observation finds membrane structure by interior solid cortex and external dense layer surface
And porous support layer is constituted.The molecular interception rate of membrane material is tested using different molecular weight protein, obtaining interception capacity is
42000Da。
Comparing embodiment 2
18 grams of polyether sulfone is dissolved in 75 grams of dimethylacetylamides and the (addition of 8 grams of ethylene glycol at 100 DEG C and under being sufficiently stirred
Agent) in the mixed solvent.After macromolecule is completely dissolved, after the stainless steel wire net filtration by 40 micron pore sizes, it is placed in temperature control
Make the standing and defoaming in 50 DEG C of doughnut batch can.Film preparation parameter is：Spinning head 0.8/1.3mm, air section height 45mm,
Temperature and humidity is respectively 30 DEG C/80%, spinning speed 12m/min, and coagulation bath is 30 DEG C of water.Measure film pure water flux be
560L·m-2·hr-1·bar-1.Prepared material infiltrates 24 hours in decane, and linear swelling ratio is 35%；In hexane
Infiltration 24 hours, linear swelling ratio are 29%；It is infiltrated 24 hours in ethyl acetate, linear swelling ratio is 45%；In glycerine three
It is infiltrated 24 hours in sour fat, linear swelling ratio is 25%.Test doughnut film-strength is substantially reduced.
Embodiment 3
18 grams of polyether sulfone, 15 grams of polyimides, be dissolved at 120 DEG C and under being sufficiently stirred 65 grams of N-methyl pyrrolidones and
25 grams of PEG400 in the mixed solvents, the neighbouring of solution than α value is 0.5.After macromolecule is completely dissolved, by 40 micron pore sizes
Standing and defoaming after stainless steel wire net filtration.The use of thickness is 300 microns of stainless steel spatulas, Polymer Solution is coated to glass plate
On, it is placed in air (22 DEG C, relative humidity 55%) and immerses split-phase solidification in 30 DEG C of water after stopping about 2 seconds.Wait for membrane material
After being fully cured, takes out membrane material and further clean.After cleaning up, it is soaked into 1% glutaraldehyde water solution, 30 minutes time.
Drip-dry is then taken out, is put into the baking oven of 65 DEG C of temperature and is crosslinked, time 60min.The pure water flux for measuring film is 207Lm-2·
hr-1·bar-1；Use ethanol test transmitance for 1340Lm-2·hr-1·bar-1；Using hexane test transmitance 780L
m-2·hr-1·bar-1.The membrane material of above-mentioned preparation infiltrates 24 hours in decane, and linear swelling ratio is less than 1%；In hexane
Infiltration 24 hours, linear swelling ratio are less than 1%；It is infiltrated 24 hours in ethyl acetate, linear swelling ratio is less than 2%；In glycerine
It is infiltrated 24 hours in three sour fat, linear swelling ratio is less than 2%.Scanning electron microscope structure observation finds membrane structure by a dense layer surface
It is constituted with porous support layer.The molecular interception rate of membrane material is tested using different molecular weight protein, obtaining interception capacity is
20000Da。
Embodiment 4
12 grams of polyvinyl chloride, 5 grams of polyamide are dissolved in 65 grams of N-methyl pyrrolidones and 8 at 60 DEG C and under being sufficiently stirred
In gram propanol solvent mixture, the neighbouring of solution than α value is 0.8.After macromolecule is completely dissolved, by the stainless of 40 micron pore sizes
Standing and defoaming after steel wire net filtration.The use of thickness is 300 microns of stainless steel spatulas, Polymer Solution is coated on glass plate,
It is placed in air (25 DEG C, relative humidity 80%) and immerses split-phase solidification in 70 DEG C of water after stopping about 2 seconds.Wait for membrane material complete
After all solidstate, takes out membrane material and further clean.After cleaning up, it is soaked into 1% maleic anhydride aqueous solution, 20 minutes time.
Drip-dry is then taken out, is put into the baking oven of 100 DEG C of temperature and is crosslinked, time 30min.The pure water flux for measuring film is 2500Lm-2·hr-1·bar-1.Use ethanol test transmitance for 15000Lm-2·hr-1·bar-1Transmitance is tested using hexane
8000L·m-2·hr-1·bar-1.The membrane material of above-mentioned preparation infiltrates 24 hours in decane, and linear swelling ratio is less than 4%；
It is infiltrated 24 hours in hexane, linear swelling ratio is less than 5%；It is infiltrated 24 hours in ethyl acetate, linear swelling ratio is less than 4%；
It is infiltrated 24 hours in triglyceride, linear swelling ratio is less than 5%.It tests to obtain membrane material using different pore size analyzer
0.16 micron of maximum diameter of hole.
Embodiment 5
13 grams of polysulfones, 5 grams of polypropylene cyanogen, 65 grams of dimethylformamides are dissolved at 60 DEG C and under being sufficiently stirred and 15 grams poly-
Ethylene glycol 400 mixes, solution it is neighbouring than being 0.3.After macromolecule is completely dissolved, by the stainless steel cloth of 40 micron pore sizes
Standing and defoaming after filtering.The use of thickness is 250 microns of stainless steel spatulas, Polymer Solution is coated on glass plate, immerses 80
Split-phase cures in DEG C water.After waiting for membrane material to be fully cured, takes out membrane material and further clean.After cleaning up, it is put into temperature
It is crosslinked in 120 DEG C of baking oven, time 45min.The pure water flux for measuring film is 3400Lm-2·hr-1·bar-1.Using ethyl alcohol
Test transmitance is 15800Lm-2·hr-1·bar-1Using hexane test transmitance 6200Lm-2·hr-1·bar-1.On
The membrane material for stating preparation infiltrates 24 hours in decane, and linear swelling ratio is less than 1%；It infiltrates 24 hours in hexane, it is linear molten
Swollen rate is less than 1%；It is infiltrated 24 hours in ethyl acetate, linear swelling ratio is less than 1%；Infiltration 24 is small in triglyceride
When, linear swelling ratio is less than 1%.It tests to obtain 0.25 micron of the maximum diameter of hole of membrane material using different pore size analyzer.
Comparing embodiment 6
13 grams of polysulfones, 77 grams of dimethylformamides are dissolved at 60 DEG C and under being sufficiently stirred and 15 grams of polyethylene glycol 400s are mixed
It closes.The PS membrane of acquisition is soaked into and is infiltrated 24 hours in decane, linear swelling ratio is with reference to embodiment 5 by membrane preparation method
25%；It infiltrates 24 hours in hexane, linear swelling ratio is 31%；It is infiltrated 24 hours in ethyl acetate, linear swelling ratio is
39%；It is infiltrated 24 hours in triglyceride, linear swelling ratio is 28%.Membrane material apparently strength reduction.
The part preferred embodiment of the present invention is above are only, the present invention is not limited in the content of embodiment.For ability
For technical staff in domain, can there is various change and change within the scope of the method for the present invention, made by it is any variation and more
Change, within the scope of the present invention.
Claims (8)
1. a kind of solvent resistant separation membrane material, the structure of the membrane material is two layers of dense layer surface and porous support layer, or fine and close
Three layers of cortex, porous support layer and dense layer surface, it is characterised in that：The membrane material is that two kinds of different high molecular polymers are dividing
The composite material obtained after the entanglement of subchain level；What the membrane material obtained after tangling for two kinds of different high molecular polymers answers
Condensation material, one of which high molecular polymer are selected from polysulfones, polyether sulfone, polyvinyl chloride, and another high molecular polymer is selected from poly-
Acrylonitrile, polyimides, polyetherimide, polyamide；The solvent resistant separation membrane material is 5000- for molecular cut off
The compound of 1000000Da.
2. a kind of solvent resistant separation membrane material as described in claim 1, it is characterised in that：Two kinds of differences in the membrane material
High molecular polymer, any of which high molecular polymer account for the 10~90% of membrane material macromolecule total amount.
3. a kind of solvent resistant separation membrane material as described in claim 1, it is characterised in that：The solvent resistant separation membrane material is used
In being separated by filtration for alkanes, esters or alcohols solvent.
4. a kind of solvent resistant separation membrane material as claimed in claim 3, it is characterised in that：The solvent resistant separation membrane material exists
Linear swelling ratio in the alkanes, esters or alcohols solvent is not higher than 20%.
5. a kind of preparation method of solvent resistant separation membrane material described in claim 1, this method comprises the following steps：
Step 1, two kinds of high molecular polymers and additive, solvent are mixed into homogeneous solution, the homogeneous solution passes through nozzle
Extrusion or the first one-step forming of scraper；In described two high molecular polymers, one of which high molecular polymer is selected from polysulfones, polyethers
Sulfone, polyvinyl chloride, another high molecular polymer are selected from polyacrylonitrile, polyimides, polyetherimide, polyamide；
Step 2, aforementioned material immersion precipitation after molding is bathed, solidification, then rinsing removal additive and solvent；
Step 3, finally post-processed, the post-processing approach be 60~350 DEG C of temperature ranges in be heated at high temperature, or
Heat cross-linking in the solution containing crosslinking agent is infiltrated, the solvent resistant separation membrane material is obtained after the completion of processing.
6. a kind of preparation method of solvent resistant separation membrane material as claimed in claim 5, it is characterised in that：The additive
Selected from methanol, ethyl alcohol, propyl alcohol, ethylene glycol, polyvinyl alcohol, sodium chloride, calcium chloride, lithium chloride, magnesium chloride；The solvent is selected from
N-methyl pyrrolidone, dimethylformamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), acetone, gamma-butyrolacton, trimethyl phosphate
Or one or more of triethyl phosphate.
7. a kind of preparation method of solvent resistant separation membrane material as claimed in claim 5, it is characterised in that：The coagulation bath
One kind in water or alcohol of medium or its mixing, the temperature of coagulation bath is 4~100 DEG C.
8. a kind of preparation method of solvent resistant separation membrane material as claimed in claim 5, it is characterised in that：The crosslinking agent
For glutaraldehyde or maleic anhydride, crosslinker concentration range 0.1~10%, 40-150 DEG C of crosslinking temperature range.
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| CN106178969A (en) * | 2016-07-28 | 2016-12-07 | 湖南沁森环保高科技有限公司 | The preparation method of a kind of high-performance complex reverse osmosis membrane and prepared reverse osmosis membrane thereof |
| CN107188819B (en) * | 2017-06-19 | 2019-04-12 | 浙江迪萧环保科技有限公司 | A kind of separating and recovering method of N,N-dimethylformamide and polyvinyl alcohol |
| CN112915807B (en) * | 2021-01-29 | 2022-08-02 | 华中科技大学 | Polar aprotic solvent-resistant polyacrylonitrile separation membrane and preparation method and application thereof |
| CN114191991A (en) * | 2021-12-22 | 2022-03-18 | 中国科学院苏州纳米技术与纳米仿生研究所 | Metal ion coordination cross-linked polyimide solvent-resistant nanofiltration membrane, preparation method and application |
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| CN101462024A (en) * | 2008-12-24 | 2009-06-24 | 北京时代沃顿科技有限公司 | Composite reverse osmosis membrane with high-intensity anti-pollution layer and preparation method thereof |
| CN101773789A (en) * | 2010-03-23 | 2010-07-14 | 何涛 | Hydrophilic film material and preparation method thereof |
| CN103846013A (en) * | 2012-12-05 | 2014-06-11 | 中国科学院大连化学物理研究所 | Porous material-polymer gas separation composite membrane |
| CN103877868A (en) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | Separation membrane preparation method and high-flux and high-strength separation membrane |
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