CN107362703A - Non- MPD types high stability reverse osmosis membrane, preparation method and its usage - Google Patents
Non- MPD types high stability reverse osmosis membrane, preparation method and its usage Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention discloses non-MPD types high stability reverse osmosis membrane, preparation method and its usage; by protecting sulfonation method to synthesize a series of multiple functionalized sulfonated diamine monomers; and prepare sulfonated polyamide complex reverse osmosis membrane by these monomers; pass through the test to its performance and configuration of surface, it was demonstrated that passing through reverse osmosis membrane prepared by the method for interfacial polymerization by multifunction sulfonated diamine monomer has a business exploitativeness.The present invention can break through traditional commerce complex reverse osmosis membrane using m-phenylene diamine (MPD) and its preparation mode of derivative, while the high salt-stopping rate of conventional reverse osmosis film is kept, further improve the water permeability of membrane material.
Description
Technical field
The present invention relates to a kind of reverse osmosis membrane, preparation method and applications, particularly a kind of compound reverse osmosis of sulfonated polyamide
Permeable membrane, preparation method and its usage, belong to complex reverse osmosis membrane preparation field.
Background technology
Reverse osmosis technology is water is permeated by a side of higher concentration with hydraulic pressure (or pump pressurization) using pellicle (RO films)
To a side of low concentration, using aperture be only 1/10000um RO films (equivalent to the 1/60000 of Escherichia coli size, virus
1/3000), present social industrial pollutants and heavy metal, bacterium, virus etc. are largely mixed into impurity in water and all removed；
So as to reach defined physical and chemical index and sanitary standard, produce to clear to pure water, be the optimal choosing that human body supplements moisture content in time
Select.
Most commercialization polyamide reverse osmose membrane (such as Dow, Toray company etc.) all uses interface polymerization reaction at present
It is prepared, they all have higher salt rejection rate and water flux.In preparation process, almost all of aqueous phase monomers are adopted
With m-phenylene diamine (MPD) (MPD) and its derivative, and foreign patent has carried out very strict protection to this.
Research outside Current Domestic is also mostly carried out around MPD, such as is codissolved in aqueous phase by sericin and with MPD
Reverse osmosis membrane (Journal of Membrane Science, 2017,523,282-290) is prepared, or it is molten in MPD aqueous phase
Doped portion inorganic nano-particle or graphite alkenes material (Desalination, 2017,411,89-100) are improving in liquid
The water flux or resistance tocrocking of film.The performance of these films has part lifting, but searches to the bottom, and it is peculiar still can not to break away from MPD
Chemical constitution constraint.Problem is, if abandoning MPD completely, the performance of most telolemma is mostly unable to reach counter-infiltration requirement
Equipment with high desalinization requirement.
Work before us is prepared for a kind of compound RO films (CN201511027626.2) of sulfonated polyamide, this RO films
NaCl is dammed with higher, desalinization can be used for, but its flux is relatively low, result in actual mechanical process is power consumption
Higher, commercial viability is not high.
The content of the invention
It is an object of the invention to provide a kind of sulfonated polyamide complex reverse osmosis membrane, preparation method and applications.
Realizing the technical solution of the object of the invention is：
Sulfonated polyamide complex reverse osmosis membrane of the present invention, including supporting layer and aramid layer, described polyamide
The structure of layer is as follows：
Wherein, the structure of "-X- " is as follows：
Further, described supporting layer is micro-filtration or ultrafiltration Flat Membrane or hollow-fibre membrane, material PVDF, PAN,
Any one in PSf and PES.
A kind of multiple functionalized sulfonated diamine monomer of said structure aramid layer is prepared, its structure is as follows：
Wherein, the structure of "-X- " is as follows：
The preparation method of above-mentioned multiple functionalized sulfonated diamine monomer is as follows：
(a) BTA, aniline, certain dialdehyde are reacted in ethanol solution, obtains white precipitate after being stirred at room temperature, take out
Washing and drying after filter, white solid A is obtained, wherein, BTA, aniline, the mol ratio of certain dialdehyde are 1:1:1.5-1:
1.5:4；
(b) solid A is added in tetrahydrofuran, adds sodium borohydride, reacted at 20-90 DEG C, reaction is evaporated after terminating
Solvent, add water to adjust pH to neutrality, then white solid B is obtained through filtering drying, wherein, the mol ratio of A and sodium borohydride is 1:
1-1:10；
(c) solid B is dissolved in tetrahydrofuran, TFAA is added dropwise, is separated out after reaction in water, filter drying
After obtain solid C, wherein, the mol ratio of B and TFAA is 1:2-1:5；
(d) it is added dropwise sulfonated reagent in C, to entering in deionized water after being reacted at 0-100 DEG C, adjusts to neutrality, rotation
Turn to add ethanol extraction organic matter after being evaporated, rotary evaporation separates out product D after filtering, and is washed repeatedly with acetone, wherein C with
The mol ratio of sulfonated reagent is 1:2-1:10；
(e) D is added in deionized water, is added dropwise hydrazine hydrate, heating stirring at 30-100 DEG C, adjusted pH to 1-5, obtain
To the sulfonated diamine monomer, wherein, the mol ratio of D and hydrazine hydrate is 1:2-1:50.
Further, in step (a), it is 1-24h that the time, which is stirred at room temperature, and certain dialdehyde is：Terephthalaldehyde, Isosorbide-5-Nitrae-benzene diethyl
Aldehyde, the propionic aldehyde of Isosorbide-5-Nitrae-benzene two, the acetaldehyde of 1,2- benzene two；In step (b), reaction time 1-24h；In step (c), reaction time 1-
10h；In step (d), reaction time 1-24h, the oleum that sulfonated reagent is the concentrated sulfuric acid or concentration is 10-50wt%；Step
Suddenly in (e), reaction time 1-24h.
The preparation method of above-mentioned sulfonated polyamide complex reverse osmosis membrane, comprises the following steps：
(1) take sulfonated diamine monomer to be dissolved in water and aqueous phase solution is made, use alkaline matter to adjust pH as 9~11, will
Aqueous phase solution contacts with support layer surface, and after support layer surface is infiltrated completely by aqueous phase solution, it is unnecessary to remove support layer surface
Aqueous phase solution；
(2) product of step (1) and the organic phase solution containing pyromellitic trimethylsilyl chloride are completely attached to, it is had completely
After machine phase solution impregnation, remove the organic phase solution of membrane removal excess surface and evaporate into dry；
(3) membrane material that step (2) obtains is cleaned with organic solvent, after volatilization with deionized water clean to film surface without
Reaction residue.
Preferably, in step (1), the concentration of aqueous phase solution is 0.1-3wt%；Alkaline matter be sodium hydroxide, sodium carbonate,
One or more in potassium carbonate, triethylamine；Aqueous phase solution infiltrating time is more than 1min.
Preferably, in step (2), the concentration of organic phase solution pyromellitic trimethylsilyl chloride is 0.01-0.5wt%；Organic solvent
For one kind in petroleum ether, n-hexane, hexamethylene, normal heptane, positive flow silane, n-dodecane, toluene, dimethylbenzene, isopropanol or more
Kind mixed solution；Infiltrating time is more than 10s.
Preferably, in step (3), organic solvent is petroleum ether, n-hexane, hexamethylene, normal heptane, positive flow silane, positive 12
One or more mixed solutions in alkane, toluene, dimethylbenzene, isopropanol.
Compared with prior art, its advantage is the present invention：
(1) MPD use is abandoned completely, what novel sulfonated polyamide composite reverse osmosis membrane was prepared with traditional MPD/TMC
The separating property of membrane material is suitable, and long-time durability is extremely excellent, without being kept in dark place；
(2) synthesis technique of polynary sulfonated diamine monomer is simple, and raw material is cheap and easily-available, without using organo-metallic catalyst
Or high-temperature and high-pressure conditions, and the efficiency of pcr product of each step unit operation is all higher than 80% so that industrially it is easier to be promoted.
Brief description of the drawings
Fig. 1 is that the performance test of reverse osmosis membrane made from embodiment 5,6,7,8,9 is compared.(test pressure 1.2MPa,
NaCl solution concentration is 2.0g/L, 25 DEG C)
Fig. 2 is the performance degradation figure after reverse osmosis membrane long-time illumination in 31 days made from embodiment 5,6,7,8,9.(test
Pressure is 1.2MPa, and NaCl solution concentration is 2.0g/L, 25 DEG C)
Fig. 3 is the ESEM surface (a) of reverse osmosis membrane made from embodiment 5 and sectional drawing (b).
Fig. 4 is the ESEM surface (a) of reverse osmosis membrane made from embodiment 6 and sectional drawing (b).
Fig. 5 is the ESEM surface (a) of reverse osmosis membrane made from embodiment 7 and sectional drawing (b).
Fig. 6 is the ESEM surface (a) of reverse osmosis membrane made from embodiment 8 and sectional drawing (b).
Fig. 7 is the ESEM surface (a) of reverse osmosis membrane made from embodiment 9 and sectional drawing (b).
Embodiment
The synthetic route of multiple functionalized sulfonated diamine monomer includes following steps：
Wherein, the structure of "-X- " is as follows：
Embodiment 14,4'- ((Isosorbide-5-Nitrae-phenylene is double (methylene)) double (azanyls)) DAADBSA, 4,4'- ((Isosorbide-5-Nitrae-
Phenylenebis (methylene)) bis (azanediyl)) dibenzenesulfonic acid (PMABSA) synthesis,
Its structural formula is：
(1) M1 synthesis
6.3952g BTA white flock powder and 250mL ethanol are placed in 500mL round-bottomed flask, slowly
5g aniline solutions and 3.6g terephthalaldehyde solution are added, fixes, is stirred at room temperature in iron stand, white precipitate is obtained after 8h, take out
Washed after filter with ethanol, obtain white solid M1 12.36g (yield is about 87.45%).
(2) M2 synthesis
10g M1 are placed in 100mL round-bottomed flasks, 200mL tetrahydrofuran solutions is added, is slow added into 2.8735g boron
Sodium hydride, bottleneck dress reflux condensing tube, is placed in oil bath pan 60 DEG C and is stirred at reflux, viscous fluid is obtained after 12h, hangs after steaming plus water,
Add watery hydrochloric acid to adjust pH to 3-7, powder filters after separating out and obtains white solid M2 5.1g (yield is about 93.13%).
(3) M3 synthesis
4.5g M2 are added into 38mL tetrahydrofurans, 10.815mL TFAAs are added dropwise under condition of ice bath, are returned
Stream reaction 5h, solvent evaporated.Solid adds deionized water and is washed till neutrality, and suction filtration obtains M3 9.8g (yield is about 93.38%).
(4) M4 synthesis
7.2g M3 are added in 100mL round-bottomed flasks, 20% oleum is added dropwise under condition of ice bath, react 5h.Will
Reaction solution is added dropwise in 200mL deionized waters, is added NaCl and is salted out product.Washed repeatedly with acetone, obtain solid M4 9.2g
(yield is about 95.89%).
(5) M5 synthesis
9gM4 and 50mL deionized waters are added in 150mL round-bottomed flasks, add 12.05g hydrazine hydrate solutions, 50 DEG C add
PH to 2-5 is adjusted after thermal agitation 3h, product is filtered and dries, obtain M5 6.1g (yield is about 96.85%).
PMABSA structural characterization is as follows：FTIR(KBr):ν2920(C-H),1690,3400(N-H),1093(C-N),
1477 (C=C), 1176,1031cm-1(S=O) .LC-MSMS [M-H]-=448.1.
Embodiment 24,4'- ((Isosorbide-5-Nitrae-phenylene is double (ethane -2,1- diyl)) double (azanyls)) DAADBSA, 4,4'-
((1,4-phenylenebis(ethane-2,1-diyl))bis(azanediyl))dibenzenesulfonic acid(p-
PEABSA synthesis), its structural formula are：
(1) M1 synthesis
28.6g BTA white flock powder and 250mL ethanol are placed in 500mL round-bottomed flask, slowly added
Enter 22.5g aniline solutions and 22mL Isosorbide-5-Nitraes-acetaldehyde of benzene two, fix, be stirred at room temperature in iron stand, white precipitate is obtained after 8h, take out
Washed after filter with ethanol, obtain white solid M1 42.8g (yield is about 78%).
(2) M2 synthesis
32.1g M1 are placed in 500mL round-bottomed flasks, 200mL tetrahydrofuran solutions is added, is slow added into 11.0g boron
Sodium hydride, bottleneck dress reflux condensing tube, is placed in oil bath pan 60 DEG C and is stirred at reflux, viscous fluid is obtained after 12h, hangs after steaming plus water,
Add watery hydrochloric acid to adjust pH to 3-7, powder filters after separating out and obtains white solid M2 11.2g (yield is about 86%).
(3) M3 synthesis
4.1g M2 are added into 37.5mL tetrahydrofurans, 11.0mL TFAAs are added dropwise under condition of ice bath, are returned
Stream reaction 5h, solvent evaporated.Solid adds deionized water and is washed till neutrality, and suction filtration obtains M3 7.4g (yield is about 95%).
(4) M4 synthesis
7.4g M3 are added in 100mL round-bottomed flasks, 10% oleum is added dropwise under condition of ice bath, react 5h.Will
Reaction solution is added dropwise in 200mL deionized waters, is added NaCl and is salted out product.Washed repeatedly with acetone, obtain solid M4
10.8g (yield is about 96%).
(5) M5 synthesis
10.6g M4 and 50mL deionized waters are added in 150mL round-bottomed flasks, add 15g hydrazine hydrate solutions, 50 DEG C
PH to 2-5 is adjusted after heating stirring 3h, product is filtered and dries, obtain M5 7.2g (yield is about 97%).
P-PEABSA structural characterization is as follows：FTIR(KBr):ν2920(C-H),1690,3400(N-H),1093(C-N),
1477 (C=C), 1176,1031cm-1(S=O) .LC-MSMS [M-H]-=476.6.
Embodiment 34,4'- ((Isosorbide-5-Nitrae-phenylene is double (propane -3,1- diyl)) double (azanyls)) DAADBSA, 4,4'-
((1,4-phenylenebis(propane-3,1-diyl))bis(azanediyl))dibenzenesulfonic acid
(PPABSA) synthesis, its structural formula are：
(1) M1 synthesis
28.6g BTA white flock powder and 250mL ethanol are placed in 500mL round-bottomed flask, slowly added
Enter 22.5g aniline solutions and the propionic aldehyde of 17mL1,4- benzene two, fix, be stirred at room temperature in iron stand, white precipitate is obtained after 8h, filter
Washed afterwards with ethanol, obtain white solid M1 46.3g (yield is about 82%).
(2) M2 synthesis
33.8g M1 are placed in 500mL round-bottomed flasks, 200mL tetrahydrofuran solutions is added, is slow added into 11.0g boron
Sodium hydride, bottleneck dress reflux condensing tube, is placed in oil bath pan 60 DEG C and is stirred at reflux, viscous fluid is obtained after 12h, hangs after steaming plus water,
Add watery hydrochloric acid to adjust pH to 3-7, powder filters after separating out and obtains white solid M2 11.5g (yield is about 87%).
(3) M3 synthesis
4.6g M2 are added into 37.5mL tetrahydrofurans, 11.0mL TFAAs are added dropwise under condition of ice bath, are returned
Stream reaction 5h, solvent evaporated.Solid adds deionized water and is washed till neutrality, and suction filtration obtains M3 6.8g (yield is about 92%).
(4) M4 synthesis
6.8g M3 are added in 100mL round-bottomed flasks, 20% oleum is added dropwise under condition of ice bath, react 5h.Will
Reaction solution is added dropwise in 200mL deionized waters, is added NaCl and is salted out product.Washed repeatedly with acetone, obtain solid M4 9.7g
(yield is about 96%).
(5) M5 synthesis
9.7g M4 and 50mL deionized waters are added in 150mL round-bottomed flasks, add 15g hydrazine hydrate solutions, 50 DEG C add
PH to 2-5 is adjusted after thermal agitation 3h, product is filtered and dries, obtain M5 6.1g (yield is about 98%).PPABSA structure table
Sign is as follows：FTIR(KBr):ν 2920 (C-H), 1690,3400 (N-H), 1093 (C-N), 1477 (C=C), 1176,1031cm-1
(S=O) .LC-MSMS [M-H]-=476.5.
The 4,4'- of embodiment 4 ((1,2- phenylenes are double (ethane -2,1- diyls)) double (azanyls)) DAADBSA 4,4'-
((1,2-phenylenebis(ethane-2,1-diyl))bis(azanediyl))dibenzenesulfonic acid(o-
PEABSA synthesis), its structural formula are：
(1) M1 synthesis
28.6g BTA white flock powder and 250mL ethanol are placed in 500mL round-bottomed flask, slowly added
Enter 22.5g aniline solutions and the acetaldehyde of 16mL1,2- benzene two, fix, be stirred at room temperature in iron stand, white precipitate is obtained after 8h, filter
Washed afterwards with ethanol, obtain white solid M1 46.3g (yield is about 82%).
(2) M2 synthesis
35g M1 are placed in 500mL round-bottomed flasks, 200mL tetrahydrofuran solutions is added, is slow added into 12.0g boron hydrogen
Change sodium, bottleneck dress reflux condensing tube, be placed in oil bath pan 60 DEG C and be stirred at reflux, viscous fluid is obtained after 12h, hang after steaming plus water, add
Watery hydrochloric acid adjusts pH to 3-7, and powder filters after separating out and obtains white solid M2 13.3g (yield is about 84%).
(3) M3 synthesis
4.6g M2 are added into 37.5mL tetrahydrofurans, 11.0mL TFAAs are added dropwise under condition of ice bath, are returned
Stream reaction 5h, solvent evaporated.Solid adds deionized water and is washed till neutrality, and suction filtration obtains M3 6.9g (yield is about 92%).
(4) M4 synthesis
6.9g M3 are added in 100mL round-bottomed flasks, 20% oleum is added dropwise under condition of ice bath, is heated to 60
DEG C reaction 5h.Reaction solution is added dropwise in 200mL deionized waters, NaCl is added and salts out product.Washed, obtained repeatedly with acetone
Solid M4 13.5g (yield is about 99%).
(5) M5 synthesis
13.5g M4 and 50mL deionized waters are added in 150mL round-bottomed flasks, add 15g hydrazine hydrate solutions, 50 DEG C
PH to 2-5 is adjusted after heating stirring 3h, product is filtered and dries, obtain M5 9.7g (yield is about 97%).
O-PEABSA structural characterization is as follows：FTIR(KBr):ν2920(C-H),1690,3400(N-H),1093(C-N),
1477 (C=C), 1176,1031cm-1(S=O) .LC-MSMS [M-H]-=636.7.
The preparation of the PMABSA/TMC reverse osmosis membranes of embodiment 5
(1) aqueous phase solution A preparation：PMABSA 0.5g are dissolved in 100mL deionized waters, after being completely dissolved, utilize hydrogen
Sodium oxide molybdena regulation pH produces aqueous phase solution after being 11.
(2) organic phase solution B preparation：Pyromellitic trimethylsilyl chloride 0.5g is dissolved in 100mL petroleum ethers, after stirring and dissolving i.e.
Obtain organic phase solution.
(3) aqueous phase solution prepared is poured over polyether sulfone support layer surface, it is molten to pour out unnecessary aqueous phase after immersion 10min
Liquid.Organic phase solution is poured into support layer surface again, contacts and unnecessary organic phase solution and clear with hexamethylene is poured out after 10s
Wash, clean its surface to reactionless residue with deionized water after solvent volatilization completely, sulfonated aromatic polyamide reverse osmosis is made
Permeable membrane PMABSA/TMC, it is stored in standby in deionized water.
The preparation of the p-PEABSA/TMC reverse osmosis membranes of embodiment 6
(1) aqueous phase solution A preparation：P-PEABSA 1g are dissolved in 100mL deionized waters, after being completely dissolved, utilize three
Ethamine regulation pH produces aqueous phase solution after being 10.
(2) organic phase solution B preparation：Pyromellitic trimethylsilyl chloride 0.15g is dissolved in 100mL n-hexanes, after stirring and dissolving
Produce organic phase solution.
(3) aqueous phase solution prepared is poured over polyether sulfone support layer surface, it is molten to pour out unnecessary aqueous phase after immersion 5min
Liquid.Organic phase solution is poured into support layer surface again, contacts and unnecessary organic phase solution and clear with n-hexane is poured out after 60s
Wash, clean its surface to reactionless residue with deionized water after solvent volatilization completely, sulfonated aromatic polyamide reverse osmosis is made
Permeable membrane p-PEABSA/TMC, it is stored in standby in deionized water.
The preparation of the PPABSA/TMC reverse osmosis membranes of embodiment 7
(1) aqueous phase solution A preparation：PPABSA 3g are dissolved in 100mL deionized waters, after being completely dissolved, utilize carbonic acid
Potassium regulation pH produces aqueous phase solution after being 9.
(2) organic phase solution B preparation：Pyromellitic trimethylsilyl chloride 0.01g is dissolved in 100mL n-hexanes, after stirring and dissolving
Produce organic phase solution.
(3) aqueous phase solution prepared is poured over polyether sulfone support layer surface, it is molten to pour out unnecessary aqueous phase after immersion 1min
Liquid.Organic phase solution is poured into support layer surface again, contacts and unnecessary organic phase solution and clear with n-hexane is poured out after 120s
Wash, clean its surface to reactionless residue with deionized water after solvent volatilization completely, sulfonated aromatic polyamide reverse osmosis is made
Permeable membrane PPABSA/TMC, it is stored in standby in deionized water.
The preparation of the o-PEABSA/TMC reverse osmosis membranes of embodiment 8
(1) aqueous phase solution A preparation：O-PEABSA 1g are dissolved in 100mL deionized waters, after being completely dissolved, utilize carbon
Sour sodium regulation pH produces aqueous phase solution after being 10.
(2) organic phase solution B preparation：Pyromellitic trimethylsilyl chloride 0.2g is dissolved in 100mL n-dodecanes, after stirring and dissolving
Produce organic phase solution.
(3) aqueous phase solution prepared is poured over polyether sulfone support layer surface, it is molten to pour out unnecessary aqueous phase after immersion 10min
Liquid.Organic phase solution is poured into support layer surface again, contacts and unnecessary organic phase solution and clear with n-hexane is poured out after 60s
Wash, clean its surface to reactionless residue with deionized water after solvent volatilization completely, sulfonated aromatic polyamide reverse osmosis is made
Permeable membrane o-PEABSA/TMC, it is stored in standby in deionized water.
The preparation of the laboratory MPD/TMC reverse osmosis membranes of embodiment 9
(1) aqueous phase solution A preparation：M-phenylene diamine (MPD) 1g is dissolved in 100mL deionized waters, after being completely dissolved, utilizes three second
Amine regulation pH produces aqueous phase solution after being 10.
(2) organic phase solution B preparation：Pyromellitic trimethylsilyl chloride 0.15g is dissolved in 100mL n-hexanes, after stirring and dissolving
Produce organic phase solution.
(3) aqueous phase solution prepared is poured over polyether sulfone support layer surface, it is molten to pour out unnecessary aqueous phase after immersion 10min
Liquid.Organic phase solution is poured into support layer surface again, contacts and unnecessary organic phase solution and clear with normal heptane is poured out after 60s
Wash, clean its surface to reactionless residue with deionized water after solvent volatilization completely, sulfonated aromatic polyamide reverse osmosis is made
Permeable membrane MPD/TMC, it is stored in standby in deionized water.
The test of the reverse osmosis membrane performance of embodiment 10
The characterizing method of reverse osmosis membrane performance is that reverse osmosis membrane is put into the counter-infiltration testing mould of standard,
Under the conditions of 2000ppm NaCl, temperature are 25 DEG C, pH value 6.5-7.5, pressure are 1.2MPa, the flow of direct measurement penetrating fluid
P (unit L), and water flux J (L m are calculated according to formula J=P/ (S*T)-2h-1), wherein S is that (unit is effective membrane area
m2), T is the time (hour) of measurement；And according to formula R (%)=(1-CP/Cf) * 100 calculating salt rejection rates, wherein R is desalination hundred
Divide rate, CpIt is the solute concentration of penetrating fluid, CfIt is the solute concentration of test fluid.By the reverse osmosis membrane being prepared in above-mentioned standard
Film properties characterize under the conditions of test, test result is as shown in Figure 1.It can be seen that optimized under laboratory condition
Reverse osmosis membrane is suitable with the MPD/TMC reverse osmosis membrane performances optimized under laboratory condition, or even is slightly better than laboratory system
MPD/TMC films.At present, industrial reverse osmosis membrane is substantially reacted using MPD and TMC, if abandoning MPD completely, most telolemma
Performance be mostly unable to reach RO requirement equipment with high desalinization requirement.Therefore, the new diamine monomer that this patent is developed, is used for
MPD is substituted completely, will be the important breakthrough of domestic and international reverse osmosis membrane research.
Performance test after the reverse osmosis membrane of embodiment 11 is deposited for a long time
The characterizing method of reverse osmosis membrane performance is that reverse osmosis membrane is put into the counter-infiltration testing mould of standard,
Under the conditions of 2000ppm NaCl, temperature are 25 DEG C, pH value 6.5-7.5, pressure are 1.2MPa, the flow of direct measurement penetrating fluid
P (unit L), and water flux J (L m are calculated according to formula J=P/ (S*T)-2h-1), wherein S is that (unit is effective membrane area
m2), T is the time (hour) of measurement；And according to formula R (%)=(1-CP/Cf) * 100 calculating salt rejection rates, wherein R is desalination hundred
Divide rate, CpIt is the solute concentration of penetrating fluid, CfIt is the solute concentration of test fluid.This experiment will be anti-made from embodiment 5,6,7,8,9
Permeable membrane is placed in deionized water and stored, and its separating property is tested after 31 days, and test result is as shown in Figure 2.Can be with from result
To find out, the water flux of all RO films has been decayed, but reverse osmosis membrane made from this experiment is weak compared with MPD/TMC attenuations, and
Rejection effect increases, and illustrates that film made from this laboratory is easier to industrially deposit, and taken again after depositing for a long time
Separating effect is than traditional industry film MPD/TMC excellents.
The reverse osmosis membrane pattern test of embodiment 12
Reverse osmosis membrane characterizes its shape characteristic using field emission scanning electron microscope.Fig. 3,4,5,6,7 be respectively embodiment 5,6,
7th, the surface of obtained reverse osmosis membrane, section electron microscope in 8,9.We have observed that film rough surface, section have many small from figure
Projection, be advantageous to increase the surface area of film, improve water flux, the aramid layer of the reverse osmosis membrane is relatively thin, about 100nm, meets
The shape characteristic of conventional reverse osmosis film.
Claims (10)
1. non-MPD types high stability reverse osmosis membrane, including supporting layer and aramid layer, it is characterised in that described aramid layer
Structure it is as follows：
Wherein, the structure of "-X- " is as follows：
2. reverse osmosis membrane as claimed in claim 1, it is characterised in that described supporting layer be micro-filtration or ultrafiltration Flat Membrane or in
Empty fiber membrane, any one in material PVDF, PAN, PSf and PES.
3. preparing the multiple functionalized sulfonated diamine monomer of reverse osmosis membrane as claimed in claim 1, its characteristic is that its structure is such as
Under：
Wherein, the structure of "-X- " is as follows：
4. the preparation method of reverse osmosis membrane as claimed in claim 1, it is characterised in that comprise the following steps：(1) take multifunctional
Change sulfonated diamine monomer, which is dissolved in water, is made aqueous phase solution, and regulation pH value is 9~11, and aqueous phase solution and support layer surface are connect
Touch, after support layer surface is infiltrated completely by aqueous phase solution, remove the unnecessary aqueous phase solution of support layer surface；
(2) product of step (1) and the organic phase solution containing pyromellitic trimethylsilyl chloride are completely attached to, makes it completely by organic phase
After solution impregnation, remove the organic phase solution of membrane removal excess surface and evaporate into dry；
(3) membrane material that step (2) obtains is cleaned with organic solvent, cleaned after volatilization with deionized water reactionless to film surface
Residue.
5. preparation method as claimed in claim 4, it is characterised in that in step (1), the concentration of aqueous phase solution is 0.1-
3wt%；PH value is adjusted using the one or more in sodium hydroxide, sodium carbonate, potassium carbonate, triethylamine；When aqueous phase solution infiltrates
Between be more than 1min.
6. preparation method as claimed in claim 4, it is characterised in that in step (2), pyromellitic trimethylsilyl chloride in organic phase solution
Concentration be 0.01-0.5wt%；The organic solvent of organic phase solution is petroleum ether, n-hexane, hexamethylene, normal heptane, positive certain herbaceous plants with big flowers
One or more mixed solutions in alkane, n-dodecane, toluene, dimethylbenzene, isopropanol；Infiltrating time is more than 10s.
7. preparation method as claimed in claim 4, it is characterised in that in step (3), organic solvent be petroleum ether, n-hexane,
One or more mixed solutions in hexamethylene, normal heptane, positive flow silane, n-dodecane, toluene, dimethylbenzene, isopropanol.
8. the preparation method of multiple functionalized sulfonated diamine monomer, it is characterised in that comprise the following steps：
(a) BTA, aniline, certain dialdehyde are reacted in ethanol solution, be stirred at room temperature, filter after washing and drying, obtain
Solid A, wherein, BTA, aniline, the mol ratio of certain dialdehyde are 1:1:1.5‐1:1.5:4；
(b) solid A being added in tetrahydrofuran, adds sodium borohydride, reacted at 20-90 DEG C, reaction terminates rear solvent evaporated,
Add water to adjust pH to neutrality, then solid B is obtained through filtering drying, wherein, the mol ratio of A and sodium borohydride is 1:1‐1:10；
(c) solid B is dissolved in tetrahydrofuran, TFAA is added dropwise, is separated out after reaction in water, filtering and drying to obtain
To solid C, wherein, the mol ratio of B and TFAA is 1:2‐1:5；
(d) it is added dropwise sulfonated reagent in C, to entering in deionized water after being reacted at 0-100 DEG C, adjusts to neutrality, rotation and steam
Ethanol extraction organic matter is added after distributing, rotary evaporation separates out product D after filtering, and is washed repeatedly with acetone, wherein C and sulfonation
The mol ratio of reagent is 1:2‐1:10；
(e) D is added in deionized water, is added dropwise hydrazine hydrate, heating stirring at 30-100 DEG C, adjusted pH to 1-5, obtain institute
Sulfonated diamine monomer is stated, wherein, the mol ratio of D and hydrazine hydrate is 1:2‐1:50.
9. preparation method as claimed in claim 8, it is characterised in that in step (a), it is 1-24h that the time, which is stirred at room temperature, and certain two
Aldehyde is any one in terephthalaldehyde, the acetaldehyde of 1,4- benzene two, the propionic aldehyde of 1,4- benzene two and the acetaldehyde of 1,2- benzene two；In step (b), instead
It is 1-24h between seasonable；In step (c), reaction time 1-10h；In step (d), reaction time 1-24h, sulfonated reagent is
The concentrated sulfuric acid or the oleum that concentration is 10-50wt%；In step (e), reaction time 1-24h.
10. reverse osmosis membrane according to claim 1 or 2 is in advanced treatment of wastewater, Treated sewage reusing, desalinization and high-quality drink
Purposes in being prepared with water.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110787651A (en) * | 2018-08-01 | 2020-02-14 | 孝感市思远新材料科技有限公司 | Covalent organic framework film material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110284457A1 (en) * | 2010-05-24 | 2011-11-24 | Mickols William E | Composite membrane with coating comprising polyalkylene oxide and oxy-substituted phenyl compounds |
| CN103140553A (en) * | 2010-07-29 | 2013-06-05 | 科莱恩金融(Bvi)有限公司 | Acid dyes |
| CN105642137A (en) * | 2015-12-31 | 2016-06-08 | 南京理工大学 | Reverse osmosis membrane and preparation method and application thereof |
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2017
- 2017-08-22 CN CN201710728251.5A patent/CN107362703A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110284457A1 (en) * | 2010-05-24 | 2011-11-24 | Mickols William E | Composite membrane with coating comprising polyalkylene oxide and oxy-substituted phenyl compounds |
| CN103140553A (en) * | 2010-07-29 | 2013-06-05 | 科莱恩金融(Bvi)有限公司 | Acid dyes |
| CN105642137A (en) * | 2015-12-31 | 2016-06-08 | 南京理工大学 | Reverse osmosis membrane and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110787651A (en) * | 2018-08-01 | 2020-02-14 | 孝感市思远新材料科技有限公司 | Covalent organic framework film material and preparation method thereof |
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