CN102658027A - High-flux reverse osmosis composite membrane and preparation method thereof - Google Patents
High-flux reverse osmosis composite membrane and preparation method thereof Download PDFInfo
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Abstract
The invention provides a compound shown as a formula I. The invention further provides a reverse osmosis membrane. The reverse osmosis membrane comprises a supporting layer and an active separating layer, wherein the active separating layer is positioned on the surface of the supporting layer and is formed by polymerizing aromatic polyacyl chloride and aromatic polyamine through interface; and the aromatic polyamine comprises the compound shown as the formula I and m-phenylenediamine. The composite membrane provided by the invention has high desalination rate and high water flux.
Description
Technical field
The present invention relates to the membrane separation technique field, be specifically related to a kind of reverse osmosis composite membrane and preparation method thereof.
Background technology
Reverse osmosis membrane is a family macromolecule material preparation, can realize the artificial pellicle of reverse osmosis membrane separation operation.Its action principle is through being motive force with the pressure differential, from solution, isolates solvent.Because reverse osmosis membrane should have efficient salt rejection rate under high flow rate, have higher mechanical strength and service life, can be than bringing into play function under the low operating pressure; Can tolerate the influence of chemistry or biochemical action, receive factor affecting such as pH value, temperature less, system pleurodiaphragmatic in terspace material source easily; Process easy; Advantage such as with low cost, so reverse osmosis membrane has been widely used in chemical industry, water treatment, desalinization, medicine and other fields.
Reverse osmosis membrane mainly is divided into two big types: one type is the CAM with unsymmetric structure; Another kind of is the aromatic polyamide composite membrane.Wherein CAM is because its pH narrow application range, and facile hydrolysis, operating pressure require higher and reason such as water flux is lower, and its development is restricted.Advantages such as the aromatic polyamide reverse osmosis composite membrane then has salt rejection rate high, and water flux is big, and application pH wide ranges and chemical stability are better extensively are used.The aromatic polyamide reverse osmosis composite membrane of having realized at present industrialization is prepared through the interfacial polymerization technology on porous support layer by polyamine and polynary acyl chlorides; Resulting poly aromatic acid amides separating layer thickness is approximately 200nm; Played main desalination centrifugation, porous support layer then provides necessary mechanical strength and pressure tightness.
At present, commercial reverse osmosis composite membrane is to be prepared by m-phenylene diamine (MPD) and the trimesoyl chloride method through interfacial polymerization.Except the polymerisation that amido and acid chloride groups take place, also be accompanied by the hydrolysis (changing into carboxyl) of acyl chlorides thus the hydrophily of composite membrane is increased (for example Chinese patent CN 1724130A, CN 1370796A etc.).In reverse osmosis composite membrane, the key of control composite membrane separating property is the polyamide ultrathin separating layer of the composite membrane the superiors, and water flux, salt is held back is two important parameters estimating the reverse osmosis composite membrane performance.High water flux mainly is because there is high hydrophily (hydrophily comes from the hydrolysis of unreacted acyl chlorides) on aromatic polyamides composite membrane surface.In order to increase the hydrophily of composite membrane, people are incorporated into sulfonic acid group, hydroxy-acid group or hydrophilic polymer (like polyvinyl alcohol, polyvinyl phenol etc.) in the aromatic polyamides again.Though these methods make the water flux of composite membrane that increase to a certain degree arranged, salt rejection rate but descends obviously.Therefore, promptly will reach high water flux, keep good salt to hold back again simultaneously, thin active aramid layer and highly cross-linked structure are the prerequisite conditions of composite membrane.
Summary of the invention
The technical problem that the present invention will solve is to provide a kind of high desalination rate that promptly has, and has reverse osmosis composite membrane of high water flux and preparation method thereof again.
In order to solve above technical problem, the invention provides the compound shown in a kind of formula I:
Preferably, said compound has the structure shown in the formula Ia:
Preferably, said compound has the structure shown in the formula Ib:
The present invention also provides a kind of reverse osmosis composite membrane, comprising:
Supporting layer;
Active separating layer is positioned at said support layer surface;
Wherein said active separating layer is formed through interfacial polymerization by aromatic polycarboxylic acyl chlorides and aromatic polycarboxylic amine; Said aromatic polycarboxylic amine comprises described compound of claim 1 and m-phenylene diamine (MPD).
Preferably, said polynary fragrant acyl chlorides is: trimesoyl chloride, 3,4 ', 5-biphenyl three acyl chlorides, 3,3 ', 5,5 '-biphenyl tetracid, 2,2 ', 5,5 '-biphenyl four acyl chlorides and 2,2 ', 4,4 '-in biphenyl four acyl chlorides one or more.
Preferably, said supporting layer comprises:
Polyester non-woven fabric;
The polysulfone material layer is positioned at said polyester non-woven fabric surface;
Said active separating layer is formed at said polysulfone material laminar surface.
The present invention also provides a kind of preparation method of said reverse osmosis composite membrane, comprising:
A) aqueous solution with aromatic polycarboxylic amine is poured over support layer surface, covers said support layer surface;
B) again the organic solution of aromatic polycarboxylic acyl chlorides is poured over the liquid film surface that said aromatic polycarboxylic amine aqueous solution forms, covers said liquid film and obtain having active separating layer prefabricated component;
C) with obtaining reverse osmosis membrane after the said prefabricated component drying.
Preferably, the mass and size concentration of aromatic polycarboxylic amine is 1.5%～3% in the said aromatic polycarboxylic amine aqueous solution; The mass and size concentration of aromatic polycarboxylic acyl chlorides described in the organic solution of said aromatic polycarboxylic acyl chlorides is 0.05%～0.2%.
Preferably, in the aqueous solution of said aromatic polycarboxylic amine, (Ia, the mass ratio that compound shown in Ib) and m-phenylene diamine (MPD) are pressed is (0.05～0.30) to formula I: (1.45～2.95).
Preferably, said step a) is specially:
A1) polysulfones, perforating agent and surfactant are mixed in organic solvent;
A2) said mixed solution is coated with scrapes on polyester non-woven fabric, then it is immersed the inversion of phases layer that is supported takes place in water;
A3) aqueous solution with said aromatic polycarboxylic amine is poured on the polysulfone material layer of support layer surface, covers said polysulfone material layer.
The invention provides the compound shown in a kind of formula I, it is characterized in that aromatic polyamine compound connects with the amido link key, prepare reverse osmosis composite membrane through interfacial polymerization after, the hydrophily of reverse osmosis membrane has increased, and then water flux has increased.The test result of composite membrane surface current electrokinetic potential shows; Increase along with DABA concentration; The streaming potential on film surface reduces gradually, explain that the hydroxy-acid group content on film surface increases and increases along with the compound concentration shown in the formula I, and the salt rejection rate of the reverse osmosis membrane of its salt rejection rate and prior art for preparing remains basically stable; So with the reverse osmosis membrane of the compound shown in the formula I provided by the invention when guaranteeing the high desalination rate; Can improve water flux, effectively reduce the operation energy consumption of membrane component, increase work efficiency.
The present invention also provides a kind of preparation method of reverse osmosis membrane; This method uses interfacial polymerization to make different monomers in water and the organic facies in interfacial polymerization; Form stable cross-linked structure fast, on said supporting layer, form active separating layer, the preparation condition of whole reverse osmosis membrane is gentle; The preparation process is easy to control, and is fit to large-scale industrial production.
Description of drawings
The reverse osmosis membrane surface current electrokinetic potential resolution chart of Fig. 1 comparative example 1 of the present invention and embodiment 1～5 preparation;
The surperficial SEM figure of the composite membrane that Fig. 2 comparative example 1 provides;
The section SEM figure of the composite membrane that Fig. 3 comparative example 1 provides;
The surperficial SEM figure of the composite membrane that Fig. 4 embodiment 1 provides;
The section SEM figure of the composite membrane that Fig. 5 embodiment 1 provides;
The surperficial SEM figure of the composite membrane that Fig. 6 embodiment 2 provides;
The section SEM figure of the composite membrane that Fig. 7 embodiment 2 provides;
The surperficial SEM figure of the composite membrane that Fig. 8 embodiment 3 provides;
The section SEM figure of the composite membrane that Fig. 9 embodiment 3 provides;
The surperficial SEM figure of the composite membrane that Figure 10 embodiment 4 provides;
The section SEM figure of the composite membrane that Figure 11 embodiment 4 provides;
The surperficial SEM figure of the composite membrane that Figure 12 embodiment 5 provides;
The section SEM figure of the composite membrane that Figure 13 embodiment 5 provides.
The specific embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiments of the invention are described, but should be appreciated that these just restriction for further specifying feature and advantage of the present invention rather than patent of the present invention being required is described.
The invention provides the compound shown in a kind of formula I,
Wherein, the amido on the phenyl ring of said right side is preferably placed at ortho position, a position or the contraposition of amido link, more preferably between the position and contraposition, promptly said compound has the structure shown in formula Ia or the formula Ib:
According to the present invention, the compound shown in the said formula I has 3 amidos and amido link all can obtain baroque polyamide structure obtaining having with acyl chloride reaction, and unreacted acid chloride groups is hydrolyzed into carboxyl.Compound shown in the formula I is Duoed an amido than m-phenylene diamine (MPD), the composite membrane that therefore obtains by the compound shown in the formula I of high-load, and the degree of cross linking is higher.Because interfacial polymerization is a process that the oneself suppresses, high-crosslinking-degree hinders amine monomers and further spreads to organic facies.Amine monomers is diffused in the organic facies relatively low, causes unreacted acid chloride groups to increase, and the increase of composite membrane surface hydroxy-acid group has improved the hydrophily of composite membrane.Owing to contain amido link in the compound shown in the formula I, so the polarity of monomer is strong, be difficult for to the organic facies diffusion, the polyamide molecular weight and the number that cause generating reduce, thereby make compound separating layer thickness reduce.
According to above-mentioned theory, the invention provides a kind of use the compound shown in the formula I as monomer and aromatic polycarboxylic acyl chlorides through the reverse osmosis membrane that interfacial polymerization on supporting layer obtains, comprising:
Supporting layer;
Active separating layer is positioned at said support layer surface;
Wherein said active separating layer is formed through interfacial polymerization by aromatic polycarboxylic acyl chlorides and aromatic polycarboxylic amine; Said aromatic polycarboxylic amine comprises described compound of formula I and m-phenylene diamine (MPD).
According to the present invention, said polynary fragrant acyl chlorides is preferably: trimesoyl chloride, 3,4 ', 5-biphenyl three acyl chlorides, 3,3 ', 5,5 '-biphenyl tetracid, 2,2 ', 5,5 '-biphenyl four acyl chlorides and 2,2 ', 4,4 '-in biphenyl four acyl chlorides one or more.Said aromatic polycarboxylic amine is preferably formula Ia or formula Ib.In order further to increase being connected between monomer and the supporting layer, in the reverse osmosis composite membrane provided by the invention, said supporting layer also preferably includes: polyester non-woven fabric; The polysulfone material layer is positioned at said polyester non-woven fabric surface; Said active separating layer is formed at said polysulfone material laminar surface.Because polysulfone material has crosslinkable site, and has high strength, thus on polyester non-woven fabric blade coating one deck polysulfone material, can either improve the firmness of active separating layer and supporting layer, can improve film strength again.
The present invention also provides a kind of preparation method of reverse osmosis composite membrane, comprising:
A) aqueous solution with aromatic polycarboxylic amine is poured on support layer surface, covers said support layer surface;
B) again the organic solution of aromatic polycarboxylic acyl chlorides is poured on the liquid film surface that said aromatic polycarboxylic amine aqueous solution forms, covers said liquid film and obtain having active separating layer prefabricated component;
C) with obtaining reverse osmosis membrane after the said prefabricated component drying.
According to the present invention, the compound shown in the said formula I is to be prepared voluntarily by the inventor, and the preparation principle equation is following:
With the compound shown in the formula Ia is example; By dinitro formyl chloride and paranitroanilinum stirring reaction in solvent, obtain N-(4-nitrobenzophenone)-3 ', 5 '-the dinitro benzene acid amides; Then under the effect of Pd/C composite catalyst; Nitro is reduced to amido, obtains N-(4-aminocarbonyl phenyl)-3 ', and 5 '-two amido benzamides are the compound shown in the formula Ia.According to the present invention, the preparation method of the compound shown in the said formula I is specially:
, churned mechanically 100mL three-necked bottle adds 3 in being housed, and the 5-dinitrobenzoyl chloride (12.1g, 52.5mmol) and N, N-dimethylacetylamide (50mL).Under the stirring at room, drip paranitroanilinum (6.9g, N 50mmol), N-dimethylacetylamide (10mL) solution.After dripping end, system continues to stir 1～6h.At last reactant liquor is sunk in the saturated sodium carbonate solution, finish reaction.Fully stir, the solid matter of separating out is filtered, wash three times, collect yellow solid and be N-(4-nitroaniline)-3 ', 5 '-dinitro benzene acid amides, yield: 90%.
1H?NMR(DMSO-d
6，300MHz)，δppm：9.48(s，1H)，7.29-7.34(dd，2H)，6.46-6.49(dd，2H)，6.22(dd，2H?J＝1.4Hz)，5.92(s，1H)，4.82-4.86(dd，6H).
N-(4-aminocarbonyl phenyl)-3 ', the preparation of 5 '-two amido benzamides 6 (DABA)
The mixed solvent (1: 1 that in the hydrogenation still of 300mL, adds ethanol and dioxane; 150mL), and then adding N-(4-nitroaniline)-3 ', 5 '-dinitro benzene acid amides (13.3g; 40mmol), nitrogen protection adds the 10%Pd/C (665mg) of catalytic amount down.Be warming up to alcohol reflux reaction 8h.Reaction removes by filter Pd/C after finishing, and solvent evaporated obtains white solid.Yield: 96%.
1H?NMR(DMSO-d
6，300MHz)，δppm：9.48(s，1H)，7.29-7.34(dd，2H)，6.46-6.49(dd，2H)，6.22(dd，2H?J＝1.4Hz)，5.92(s，1H)，4.82-4.86(dd，6H).
N-(3-nitrobenzophenone)-3,5-dinitro benzene acid amides 5 use compound 1 and compound 3 to prepare yield: 92% according to the method for compound 4.
1H?NMR(DMSO-d
6，300MHz)，δppm：11.20(s，1H)，9.16(s，2H)，8.99(s，1H)，8.72(s，1H)，8.19(dd，J＝6.0Hz，1H)，8.00(dd，J＝6.0Hz，1H)，7.68(t，J＝9.0Hz，1H)。
N-(3-aminocarbonyl phenyl)-3,5-two amido benzamides 7 use the preparation of compound 5 hydrogenating reductions, yield: 95% according to the method for compound 6.
1H?NMR(DMSO-d
6，300MHz)，δppm：9.56(s，1H)，7.06(d，J＝9.0Hz，1H)，6.87(t，J＝9.0Hz，1H)，6.75(d，J＝9.0Hz?1H)，6.24-6.28(m，3H)，5.93(s，1H)，4.92(s，6H).
After having prepared the compound shown in the formula I, said compound is mixed with m-phenylene diamine (MPD), as mix monomer, then with said mix monomer and aromatic polycarboxylic acyl chloride reaction.According to the compound shown in the formula I according to the invention and m-phenylene diamine (MPD) by weight being (0.05～0.30): (1.45～2.95).Preferably, the mass and size concentration of aromatic polycarboxylic amine is 1.5%～3% in the said aromatic polycarboxylic amine aqueous solution; According to the present invention, the mass and size concentration of aromatic polycarboxylic acyl chlorides described in the organic solution of said aromatic polycarboxylic acyl chlorides is 0.05%～0.2%.According to the present invention, the solvent of said organic solution is preferably cyclohexane, ISOPAR.
According to the present invention, said aromatic polycarboxylic acyl chlorides can be through Chinese patent CN 1935338A and Chinese patent CN 101332415A preparation.
In order to improve the firmness of active separating layer and supporting layer, can improve film strength again simultaneously, according to the present invention, earlier at the surperficial blade coating polysulfone material of polyester non-woven fabric layer.
Said polysulfone material layer mixes polysulfones, perforating agent and surfactant in organic solvent; Then, said mixed solution is coated with scrapes on polyester non-woven fabric, then it is immersed the inversion of phases layer that is supported takes place in water; The aqueous solution with said aromatic polycarboxylic amine is poured on the polysulfone material layer of support layer surface at last, covers said polysulfone material layer.Or according to one Chinese patent application: the condition preparation in " the aromatic polyamides reverse osmosis composite membrane of biphenyl contenting structure " (number of patent application 2006100172037).
Use contains hydroaropic substances such as sulfonic acid, hydroxy-acid group amine monomers in the prior art increases the composite membrane surface hydrophilicity, and then increases the water flux of composite membrane, but salt rejection rate but descends obviously.And need the concentration of amine higher, thereby cause the waste of amine raw material.And the present invention has only used three amine monomers (DABA) of amine gross mass 0.25wt%, makes the water flux of composite membrane improve 50%, has practiced thrift the cost of raw material greatly.
Below be the embodiment of the invention, set forth the present invention program in detail.
Comparative example 1
At first dispose the aqueous solution of polyamine: mass and size concentration is 2.0% m-phenylene diamine (MPD), and mass and size concentration is 1.0% triethylamine, and mass and size concentration is 0.05% dodecyl sodium sulfate, and camphorsulfonic acid is regulated the pH value; Prepare organic phase solution then: mass and size concentration is 0.10% trimesoyl chloride cyclohexane solution.Earlier the aqueous solution of amine is poured into the surface of polysulfone supporting layer, soak 3min, remove superfluous water solution then, dry 3min under the room temperature condition in the air.Again cyclohexane solution is poured into polysulfone supporting layer surface coverage 20s, remove the unnecessary organic solution in surface after, 60 ℃ of heat treatment 3min in the baking oven that the film that obtains is put into further carry out polymerisation.At last the reverse osmosis membrane that obtains is used deionized water rinsing 20min, be kept in 1.0% solution of sodium bisulfite for use.
(3) performance test
Film at first will carefully be checked under fluorescent lamp to avoid obvious defects before test, and film need be stablized 4 hours with pure water under the pressure of 2.0Mpa.
The test condition that adopts in the embodiment of the invention is: the sodium-chloride water solution of 2000ppm, operating pressure are 2.0Mpa, and operating temperature is 25 ℃, the about 19cm of effective film area
2
Water flux (L/m
2.h) volume by the water through film in the certain hour calculates, and formula is:
Wherein V is the volume that passes through the water of film in the unit interval, and A is the area of film, and t is the time.
Salt rejection rate is calculated through the electrical conductivity of material liquid and penetrating fluid, and formula is:
λ wherein
pBe the electrical conductivity of penetrating fluid, λ
fElectrical conductivity for material liquid.
All membrane samples are all got three parallel samples, and each sample surveys twice, averages then.
Embodiment 1
Adopt m-phenylene diamine (MPD) and N-(4-aminocarbonyl phenyl)-3 ', the mixture of 5 '-two amido benzamides (DABA), the mass and size concentration (g/mL) of total aromatic polyamine is 2%, and material rate is as shown in table 1, and all the other conditions are with comparing embodiment 1.
Embodiment 2～5
Method according to embodiment 1 prepares N-(4-aminocarbonyl phenyl)-3 ', and the mass and size concentration (g/mL) of the aromatic polyamine that the mixture of 5 '-two amido benzamides is total is 2%, and material rate is as shown in table 1, and all the other conditions are with comparing embodiment 1.
Table 1 composite membrane counter-infiltration The performance test results
The counter-infiltration The performance test results shows that along with the increase of DABA concentration in amine aqueous solution, the salt rejection rate of composite membrane has some reduction (comparing with simple use m-phenylene diamine (MPD)), from 98.4% to 98.1%, and the salt rejection rate standard deviation is 0.14%, but water flux is from 37.5L/m
2H is increased to 55.4L/m
2H can significantly improve the water flux (the highest lifting 50%) of composite membrane.We have carried out following sign to the reverse osmosis composite membrane active layer in order to explain this phenomenon
(1) through the chemical composition of x-ray photoelectron power spectrum (XPS) analysis polyamide composite film active layer, test result is listed in the table 2.Test result shows that along with the increase of DABA content in the polyamine aqueous solution, the ratio of composite membrane surface O/N is also increasing, and explains that the ratio of composite membrane surface hydroxy-acid group and amido link content increases.
Table 2 composite membrane surface-element is formed
(2) through the surperficial hydrophily of measurement of contact angle illustrative composite membrane.Along with the increase of DABA concentration in amine aqueous solution, the contact angle on composite membrane surface reduces to 60.2 from 75.5, and the hydrophily of film is greatly improved, and sees table 3.
The test result of table 3 film surface contact angle
In the active layer of polyamide composite film, hydroxy-acid group and amido link have material impact to the hydrophily on composite membrane surface.And the hydrophily of carboxylic acid will be higher than amido link.The analysis result of comprehensive XPS, the content of film surface hydroxy-acid group has increased, so the hydrophily on film surface increases.The increase of composite membrane surface hydrophilicity helps hydrone and diffuses into the film from water, has increased the concentration of hydrone in film, is favourable to the water flux of composite membrane.
(3) test result of composite membrane surface current electrokinetic potential (calculating through the Fairbrother-Mastin method) has shown; Increase along with DABA concentration; The streaming potential on film surface reduces gradually, explains that the hydroxy-acid group content on film surface increases and increases along with DABA concentration, sees accompanying drawing 1.
(4) utilize SEM (SEM) that the surface and the section of composite membrane are characterized, studied the influence of DABA concentration to the composite membrane configuration of surface, the result sees accompanying drawing 2～13.Can find out that by figure along with the increase of DABA monomer concentration, it is more and more level and smooth that the composite membrane surface becomes, and the thickness of polyamide active layer is also more and more thinner.The picture analyzing result shows that DABA concentration is 0,0.05,0.10,0.15,0.20,0.25w/v%, and corresponding composite membrane active layer thickness is respectively 554 ± 50, and 438 ± 50,389 ± 50,292 ± 50,238 ± 50,198 ± 50nm.
Accompanying drawing 1: composite membrane SEM photo a, b, c, d, e, f correspond respectively to the concentration of DABA: 0,0.05,0.10,0.15,0.20,0.25w/v% and polysulfones support membrane.
The composite membrane surface chemistry is formed and the result of study of configuration of surface shows, introduces the hydrophily that this type three amine monomers have increased the composite membrane surface, has reduced the thickness of polyamide active layer.Explained the reason that this type reverse osmosis composite membrane water flux increases considerably theoretically.
Adopt m-phenylene diamine (MPD) and N-(3-aminocarbonyl phenyl)-3 '; The mixture of 5 '-two amido benzamides; The mass and size concentration (g/mL) of total aromatic polyamine is 2%, and its weight ratio is that m-phenylene diamine (MPD): N-(3-aminocarbonyl phenyl)-3 ', 5 '-two amido benzamides are 7: 1.All the other conditions are with comparing embodiment 1.Test result is: flux: 51.3L/m
2H; Salt rejection rate: 97.6%
Adopt m-phenylene diamine (MPD) and N-(4-aminocarbonyl phenyl)-3 '; The mixture of 5 '-two amido benzamides; The mass and size concentration (g/mL) of total aromatic polyamine is 2%, and its weight ratio is that m-phenylene diamine (MPD): N-(4-aminocarbonyl phenyl)-3 ', 5 '-two amido benzamides are 7: 1.The mass and size concentration (g/mL) of total polynary acyl chlorides of aromatic series is 0.10%, its weight ratio 3,4 ', and 5-biphenyl three acyl chlorides: trimesoyl chloride is 4: 1, all the other conditions are with comparing embodiment 1.Test result is: flux: 45.6L/m
2H; Salt rejection rate: 97.5%
Adopt m-phenylene diamine (MPD) and N-(4-aminocarbonyl phenyl)-3 '; The mixture of 5 '-two amido benzamides; The mass and size concentration (g/mL) of total aromatic polyamine is 2%, and its weight ratio is that m-phenylene diamine (MPD): N-(4-aminocarbonyl phenyl)-3 ', 5 '-two amido benzamides are 7: 1.The mass and size concentration (g/mL) of total polynary acyl chlorides of aromatic series is 0.10%, its weight ratio 3,4 ', and 5-biphenyl three acyl chlorides: trimesoyl chloride is 1: 1, all the other conditions are with comparing embodiment 1.
Test result is: flux: 52.3L/m
2H; Salt rejection rate: 97.0%
Adopt m-phenylene diamine (MPD) and N-(4-aminocarbonyl phenyl)-3 '; The mixture of 5 '-two amido benzamides; The mass and size concentration (g/mL) of total aromatic polyamine is 2%, and its weight ratio is that m-phenylene diamine (MPD): N-(4-aminocarbonyl phenyl)-3 ', 5 '-two amido benzamides are 7: 1.The mass and size concentration (g/mL) of total polynary acyl chlorides of aromatic series is 0.10%, its weight ratio 3,4 ', and 5-biphenyl three acyl chlorides: trimesoyl chloride is 1: 2, all the other conditions are with comparing embodiment 1.
Test result is: flux: 50.4L/m
2H; Salt rejection rate: 97.6%
Adopt m-phenylene diamine (MPD) and N-(4-aminocarbonyl phenyl)-3 '; The mixture of 5 '-two amido benzamides; The mass and size concentration (g/mL) of total aromatic polyamine is 2%, and its weight ratio is that m-phenylene diamine (MPD): N-(4-aminocarbonyl phenyl)-3 ', 5 '-two amido benzamides are 7: 1.The mass and size concentration (g/mL) of total polynary acyl chlorides of aromatic series is 0.10%, its weight ratio 3,3 ', 5, and 5 '-biphenyl, four acyl chlorides: trimesoyl chloride is 4: 1, all the other conditions are with comparing embodiment 1.Test result is: flux: 49.9L/m
2H; Salt rejection rate: 98.6%
Embodiment 11
Adopt m-phenylene diamine (MPD) and N-(4-aminocarbonyl phenyl)-3 '; The mixture of 5 '-two amido benzamides; The mass and size concentration (g/mL) of total aromatic polyamine is 2%, and its weight ratio is that m-phenylene diamine (MPD): N-(4-aminocarbonyl phenyl)-3 ', 5 '-two amido benzamides are 7: 1.The mass and size concentration (g/mL) of total polynary acyl chlorides of aromatic series is 0.10%, its weight ratio 3,3 ', 5, and 5 '-biphenyl, four acyl chlorides: trimesoyl chloride is 1: 1, all the other conditions are with comparing embodiment 1.Test result is: flux: 56.9L/m
2H; Salt rejection rate: 97.5%
Embodiment 12
Adopt m-phenylene diamine (MPD) and N-(4-aminocarbonyl phenyl)-3 '; The mixture of 5 '-two amido benzamides; The mass and size concentration (g/mL) of total aromatic polyamine is 2%, and its weight ratio is that m-phenylene diamine (MPD): N-(4-aminocarbonyl phenyl)-3 ', 5 '-two amido benzamides are 7: 1.The mass and size concentration (g/mL) of total polynary acyl chlorides of aromatic series is 0.10%, its weight ratio 3,3 ', 5, and 5 '-biphenyl, four acyl chlorides: trimesoyl chloride is 1: 2, all the other conditions are with comparing embodiment 1.Test result is: flux: 52.8L/m
2H; Salt rejection rate: 97.1%
Embodiment 13
Adopt m-phenylene diamine (MPD) and N-(4-aminocarbonyl phenyl)-3 '; The mixture of 5 '-two amido benzamides; The mass and size concentration (g/mL) of total aromatic polyamine is 2%, and its weight ratio is that m-phenylene diamine (MPD): N-(4-aminocarbonyl phenyl)-3 ', 5 '-two amido benzamides are 7: 1.The mass and size concentration (g/mL) of total polynary acyl chlorides of aromatic series is 0.10%, its weight ratio 2,2 ', 4, and 4 '-biphenyl, four acyl chlorides: trimesoyl chloride is 4: 1, all the other conditions are with comparing embodiment 1.Test result is: flux: 40.4L/m
2H; Salt rejection rate: 98.8%
Embodiment 14
Adopt m-phenylene diamine (MPD) and N-(4-aminocarbonyl phenyl)-3 '; The mixture of 5 '-two amido benzamides; The mass and size concentration (g/mL) of total aromatic polyamine is 2%, and its weight ratio is that m-phenylene diamine (MPD): N-(4-aminocarbonyl phenyl)-3 ', 5 '-two amido benzamides are 7: 1.The mass and size concentration (g/mL) of total polynary acyl chlorides of aromatic series is 0.10%, its weight ratio 2,2 ', 4, and 4 '-biphenyl, four acyl chlorides: trimesoyl chloride is 1: 1, all the other conditions are with comparing embodiment 1.Test result is: flux: 46.4L/m
2H; Salt rejection rate: 98.3%
Embodiment 15
Adopt m-phenylene diamine (MPD) and N-(4-aminocarbonyl phenyl)-3 '; The mixture of 5 '-two amido benzamides; The mass and size concentration (g/mL) of total aromatic polyamine is 2%, and its weight ratio is that m-phenylene diamine (MPD): N-(4-aminocarbonyl phenyl)-3 ', 5 '-two amido benzamides are 7: 1.The mass and size concentration (g/mL) of total polynary acyl chlorides of aromatic series is 0.10%, its weight ratio 2,2 ', 4, and 4 '-biphenyl, four acyl chlorides: trimesoyl chloride is 1: 2, all the other conditions are with comparing embodiment 1.Test result is: flux: 46.0L/m
2H; Salt rejection rate: 97.7%
Embodiment 16
Adopt m-phenylene diamine (MPD) and N-(4-aminocarbonyl phenyl)-3 '; The mixture of 5 '-two amido benzamides; The mass and size concentration (g/mL) of total aromatic polyamine is 2%, and its weight ratio is that m-phenylene diamine (MPD): N-(4-aminocarbonyl phenyl)-3 ', 5 '-two amido benzamides are 7: 1.The mass and size concentration (g/mL) of total polynary acyl chlorides of aromatic series is 0.10%, its weight ratio 2,2 ', 5, and 5 '-biphenyl, four acyl chlorides: trimesoyl chloride is 4: 1, all the other conditions are with comparing embodiment 1.Test result is: flux: 43.7L/m
2H; Salt rejection rate: 96.0%
Embodiment 17
Adopt m-phenylene diamine (MPD) and N-(4-aminocarbonyl phenyl)-3 '; The mixture of 5 '-two amido benzamides; The mass and size concentration (g/mL) of total aromatic polyamine is 2%, and its weight ratio is that m-phenylene diamine (MPD): N-(4-aminocarbonyl phenyl)-3 ', 5 '-two amido benzamides are 7: 1.The mass and size concentration (g/mL) of total polynary acyl chlorides of aromatic series is 0.10%, its weight ratio 2,2 ', 5, and 5 '-biphenyl, four acyl chlorides: trimesoyl chloride is 1: 1, all the other conditions are with comparing embodiment 1.Test result is: flux: 44.6L/m
2H; Salt rejection rate: 95.1%
Embodiment 18
Adopt m-phenylene diamine (MPD) and N-(4-aminocarbonyl phenyl)-3 '; The mixture of 5 '-two amido benzamides; The mass and size concentration (g/mL) of total aromatic polyamine is 2%, and its weight ratio is that m-phenylene diamine (MPD): N-(4-aminocarbonyl phenyl)-3 ', 5 '-two amido benzamides are 7: 1.The mass and size concentration (g/mL) of total polynary acyl chlorides of aromatic series is 0.10%, its weight ratio 2,2 ', 5, and 5 '-biphenyl, four acyl chlorides: trimesoyl chloride is 1: 2, all the other conditions are with comparing embodiment 1.Test result is: flux: 43.0L/m
2H; Salt rejection rate: 95.6%
More than a kind of reverse osmosis composite membrane provided by the invention and preparation method thereof has been carried out detailed introduction; Having used concrete example among this paper sets forth principle of the present invention and embodiment; The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. the compound shown in the formula I:
2. compound according to claim 1 is characterized in that, has the structure shown in the formula Ia:
3. compound according to claim 1 is characterized in that, has the structure shown in the formula Ib:
4. a reverse osmosis composite membrane is characterized in that, comprising:
Supporting layer;
Active separating layer is positioned at said support layer surface;
Wherein said active separating layer is formed through interfacial polymerization by aromatic polycarboxylic acyl chlorides and aromatic polycarboxylic amine; Said aromatic polycarboxylic amine comprises described compound of claim 1 and m-phenylene diamine (MPD).
5. according to the composite membrane shown in the claim 4, it is characterized in that said polynary fragrant acyl chlorides is: trimesoyl chloride, 3,4 ', 5-biphenyl three acyl chlorides, 3; 3 ', 5,5 '-biphenyl tetracid, 2,2 ', 5; 5 '-biphenyl four acyl chlorides and 2,2 ', 4,4 '-in biphenyl four acyl chlorides one or more.
6. reverse osmosis membrane according to claim 4 is characterized in that, said supporting layer comprises:
Polyester non-woven fabric;
The polysulfone material layer is positioned at said polyester non-woven fabric surface;
Said active separating layer is formed at said polysulfone material laminar surface.
7. the preparation method of the described reverse osmosis composite membrane of claim 4 is characterized in that, comprising:
A) aqueous solution with aromatic polycarboxylic amine is poured over support layer surface;
B) again the organic solution of aromatic polycarboxylic acyl chlorides is poured over the liquid film surface that said aromatic polycarboxylic amine aqueous solution forms, obtains having active separating layer prefabricated component;
C) with obtaining reverse osmosis membrane after the said prefabricated component drying.
8. preparation method according to claim 7 is characterized in that, the mass and size concentration of aromatic polycarboxylic amine is 1.5%～3% in the said aromatic polycarboxylic amine aqueous solution; The mass and size concentration of aromatic polycarboxylic acyl chlorides described in the organic solution of said aromatic polycarboxylic acyl chlorides is 0.05%～0.2%.
9. according to claim 7 or 8 described preparation methods, it is characterized in that in the aqueous solution of said aromatic polycarboxylic amine, the mass ratio that compound shown in formula Ia, the formula Ib and m-phenylene diamine (MPD) are pressed is (0.05～0.30): (1.45～2.95).
10. according to claim 7 or 8 described preparation methods, it is characterized in that said step a) is specially:
A1) polysulfones, perforating agent and surfactant are mixed in organic solvent;
A2) said mixed solution is coated with scrapes on polyester non-woven fabric, then it is immersed the inversion of phases layer that is supported takes place in water;
A3) aqueous solution with said aromatic polycarboxylic amine is poured on the polysulfone material layer of support layer surface.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103272498A (en) * | 2013-05-14 | 2013-09-04 | 天津大学 | Surface grafting modified aromatic polyamide composite reverse osmosis membrane and preparation method thereof |
| CN104548967A (en) * | 2014-12-24 | 2015-04-29 | 哈尔滨工业大学 | In-situ preparation method for high-selectivity forward osmosis polyamide composite membrane |
| CN105435660A (en) * | 2015-12-24 | 2016-03-30 | 中国科学院烟台海岸带研究所 | Anti-pollution composite multi-layer polymer separation membrane and preparation method thereof |
Citations (1)
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| CN101462025A (en) * | 2008-08-13 | 2009-06-24 | 贵阳时代汇通膜科技有限公司 | Double-layer polyamide surface layer composite reverse osmosis membrane and preparation method thereof |
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- 2012-04-20 CN CN2012101187694A patent/CN102658027A/en active Pending
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| CN101462025A (en) * | 2008-08-13 | 2009-06-24 | 贵阳时代汇通膜科技有限公司 | Double-layer polyamide surface layer composite reverse osmosis membrane and preparation method thereof |
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| HAIFENG WANG ET AL.: "Polyamide thin-film composite membranes prepared from a novel triamine 3,5-diamino-N-(4-aminophenyl)-benzamide monomer and m-phenylenediamine", 《JOURNAL OF MEMBRANE SCIENCE》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103272498A (en) * | 2013-05-14 | 2013-09-04 | 天津大学 | Surface grafting modified aromatic polyamide composite reverse osmosis membrane and preparation method thereof |
| CN103272498B (en) * | 2013-05-14 | 2015-01-21 | 天津大学 | Surface grafting modified aromatic polyamide composite reverse osmosis membrane and preparation method thereof |
| CN104548967A (en) * | 2014-12-24 | 2015-04-29 | 哈尔滨工业大学 | In-situ preparation method for high-selectivity forward osmosis polyamide composite membrane |
| CN104548967B (en) * | 2014-12-24 | 2017-01-11 | 哈尔滨工业大学 | In-situ preparation method for high-selectivity forward osmosis polyamide composite membrane |
| CN105435660A (en) * | 2015-12-24 | 2016-03-30 | 中国科学院烟台海岸带研究所 | Anti-pollution composite multi-layer polymer separation membrane and preparation method thereof |
| CN105435660B (en) * | 2015-12-24 | 2018-09-14 | 中国科学院烟台海岸带研究所 | A kind of antipollution composite multi-layer polymer separation film and preparation method thereof |
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