CN104548976B - Reverse osmosis membrane as well as preparation method and application thereof - Google Patents
Reverse osmosis membrane as well as preparation method and application thereof Download PDFInfo
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- CN104548976B CN104548976B CN201310500524.2A CN201310500524A CN104548976B CN 104548976 B CN104548976 B CN 104548976B CN 201310500524 A CN201310500524 A CN 201310500524A CN 104548976 B CN104548976 B CN 104548976B
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- 0 C**(cc1)ccc1S(C(C=C1)=CCC1Oc1ccc(C(C2C=CC=CC22)(c(cc3)ccc3[U]*)NI2(=C)=[U])cc1*)(=N)=O Chemical compound C**(cc1)ccc1S(C(C=C1)=CCC1Oc1ccc(C(C2C=CC=CC22)(c(cc3)ccc3[U]*)NI2(=C)=[U])cc1*)(=N)=O 0.000 description 3
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a reverse osmosis membrane, a preparation method of the reverse osmosis membrane and application of the reverse osmosis membrane to the field of water treatment. The reverse osmosis membrane comprises a support layer and a separation layer which is positioned on the surface of the support layer, wherein the separation layer comprises polyhedral oligomeric silsesquioxane and sulfonated poly ether sulfone which has a structure as shown in any one of formula (I) to formula (III). The reverse osmosis membrane provided by the invention has excellent chlorine resistance and relatively high water flux and desalination ratio at the same time.
Description
Technical field
The present invention relates to a kind of reverse osmosis membrane, a kind of preparation method of reverse osmosis membrane, the reverse osmosis being prepared by the method
The application in water treatment field of permeable membrane and described reverse osmosis membrane.
Background technology
Reverse osmosis membrane is because having the good separation performance to organic molecule and inorganic ion, safe and environment-friendly, easy to operate
The advantages of and become one of key technology of water process.So far, being mainly used in sea water and bitter of reverse osmosis membrane
The fields such as desalination, water softening, middle Water Sproading, Industrial Wastewater Treatment and ultra-pure water preparation.At present, on market 90% reverse osmosis
Permeable membrane is composite membrane, i.e. be made up of stratum disjunctum and supporting layer.Wherein, the preparation method of composite membrane mainly has: weak solution coating
Method, interfacial polymerization and Plasma Polymerization etc..The composite membrane being currently widely used in water treatment field mainly takes boundary
The mode of face polymerization, for example, it is possible to polyamide film is compound to micropore support counterdie surface.However, the chemistry knot of polyamide
Structure makes the chlorine-resistant property of such composite membrane very weak, and all commercialization polyamide composite films are almost nil to the permission of free chlorine, from
And increased film pretreatment cost and reduce its service life.Therefore, the chlorine-resistant property improving film is that current reverse osmosis membrane grinds
One of vital task studied carefully.
Sulfonated polyether sulphone has preferable acid resistance, alkaline resistance properties and chlorine-resistant property, has preferably in film field
Application prospect.Us4818387 discloses a kind of sulfonated polyether sulphone composite membrane (shown in structure such as formula ()) and preparation method thereof.
Test result shows, the sulfonated polyether sulphone composite membrane using dip coating preparation has extraordinary chlorine-resistant property and oxidative resistance
Energy.Cn101721926a discloses a kind of sulfonation copolymerization containing naphthyridine ketone structure aryl ether sulfone composite membrane (structure such as formula () institute
Show) and preparation method thereof, such composite membrane has good separation property, water penetration and chlorine resistance.Additionally, research it is also shown that
Although sulfonated polyether sulphone has excellent acid resistance, alkaline resistance properties and chlorine-resistant property, multiple with the polyamide of commercialization
Close film to compare, its salt rejection rate and water penetration are still poor, and this also counteracts that the process of its industrialization.
Content of the invention
The invention aims to overcoming the salt rejection rate of existing sulfonated polyether sulphone reverse osmosis film and water penetration relatively
The defect of difference, and a kind of reverse osmosis membrane with excellent salt rejection rate, water penetration and chlorine resistance, a kind of reverse osmosis membrane are provided
Preparation method, the application in water treatment field of the reverse osmosis membrane being prepared by the method and described reverse osmosis membrane.
The invention provides a kind of reverse osmosis membrane, wherein, described reverse osmosis membrane includes supporting layer and is located at described supporting layer
Stratum disjunctum on surface, described stratum disjunctum contains polyhedral oligomeric silsesquioxane and has any one in formula ()-formula ()
The sulfonated polyether sulphone of shown structure；
Wherein, in formula (), r1-r15Identical or different, and it is each independently h or c1-c5Alkyl, m >=2；
In formula (), r1'-r22' identical or different, and it is each independently hydrogen or c1-c5Alkyl, r23' it is chemical bond
Or it is c1-c5Alkylidene, p:q=0-10:1；
In formula (), r1''-r17' ' identical or different, and it is each independently hydrogen or c1-c5Alkyl, n >=2.
Present invention also offers a kind of preparation method of reverse osmosis membrane, wherein, the method includes to contain polyhedral oligomeric
Silsesquioxane, have the sulfonated polyether sulphone of structure and solvent shown in any one in formula ()-formula () casting solution coating
On supporting layer formed primary membrane, and by described primary membrane solvent remove, be supported layer and be located at described supporting layer table
The reverse osmosis membrane of the stratum disjunctum on face；
Wherein, in formula (), r1-r15Identical or different, and it is each independently h or c1-c5Alkyl, m >=2；
In formula (), r1'-r22' identical or different, and it is each independently hydrogen or c1-c5Alkyl, r23' it is chemical bond
Or it is c1-c5Alkylidene, p:q=0-10:1；
In formula (), r1''-r17' ' identical or different, and it is each independently hydrogen or c1-c5Alkyl, n >=2.
The invention provides the reverse osmosis membrane being prepared by said method.
Additionally, present invention also offers application in water treatment field for the described reverse osmosis membrane.
The present inventor finds after further investigation, and the stratum disjunctum in the reverse osmosis membrane that the present invention provides contains many
Face body oligomeric silsesquioxane and the sulfonated polyether sulphone with structure shown in any one in formula ()-formula (), on the one hand,
Described sulfonated polyether sulphone has very excellent chlorine-resistant property；On the other hand, the introducing of polyhedral oligomeric silsesquioxane is not
The salt rejection rate of reverse osmosis membrane and water flux only can be improved additionally it is possible to improve the stability of described reverse osmosis membrane, so that described
Reverse osmosis membrane can have excellent salt rejection rate, water penetration and chlorine resistance, great prospects for commercial application concurrently.
A preferred embodiment of the invention, when described polyhedral oligomeric silsesquioxane is for having formula () institute
Show structure mono amino propyl group seven isobutyl group silsesquioxane when, because described mono amino propyl group seven isobutyl group silsesquioxane contains
There is amino, hydrogen bond can be formed with the sulfonic group in sulfonated polyether sulphone, both improve compatible with described sulfonated polyether sulphone
Property, Hydrophilic ionic cluster region being reduced again, thus inhibiting the swelling of described reverse osmosis membrane, and so that reverse osmosis membrane is more caused
Close, improve its salt rejection rate.Further, since the formation of hydrogen bond, mono amino propyl group seven isobutyl group silsesquioxane is in the form of hydrogen bond
It is fixed on described sulfonated polyether sulphone side chain, increases the free volume of strand, thus further increasing described reverse osmosis
The water flux of permeable membrane.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The reverse osmosis membrane that the present invention provides includes supporting layer and the stratum disjunctum being located in described support layer surface, described separation
Layer is containing polyhedral oligomeric silsesquioxane and the sulfonated polyether sulphone with structure shown in any one in formula ()-formula ()；
Wherein, in formula (), r1-r15Identical or different, and it is each independently h or c1-c5Alkyl, m >=2；
In formula (), r1'-r22' identical or different, and it is each independently hydrogen or c1-c5Alkyl, r23' it is chemical bond
Or it is c1-c5Alkylidene, p:q=0-10:1；
In formula (), r1''-r17' ' identical or different, and it is each independently hydrogen or c1-c5Alkyl, n >=2.
Described c1-c5The instantiation of alkyl can include but is not limited to: methyl, ethyl, n-pro-pyl, isopropyl, positive fourth
Base, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl and neopentyl.Described c1-c5Alkylidene concrete reality
Example can include but is not limited to: methylene, ethylidene, sub- n-pro-pyl, isopropylidene, sub- normal-butyl, sub- sec-butyl, sub- isobutyl
Base, the sub- tert-butyl group, sub- n-pentyl, isoamylidene, sub- tertiary pentyl and sub- neopentyl.
The present invention does not have spy to the content of the polyhedral oligomeric silsesquioxane in described stratum disjunctum and sulfonated polyether sulphone
Do not limit, but so that both can play more preferable mating reaction, the described sulfonated polyether sulphone with 100 weight portions is
Benchmark, the content of described polyhedral oligomeric silsesquioxane is preferably 0.1-20 weight portion, more preferably 0.5-10 weight portion.
According to the present invention particularly preferably, in formula (), r1-r15For h, 2≤m≤100, now, corresponding sulfonation gathers virtue
Ether sulfone has the structure shown in formula (), abbreviation c-spaes；
In formula (), r1'、r3'、r6'、r8' it is methyl, r2'、r4'、r5'、r7'、r9'-r22' it is h, r23' it is chemical bond, p
For 0-90, q is 10-100, and now, corresponding sulfonated polyether sulphone has the structure shown in formula (), abbreviation p-spaes；Or
Person,
r1'-r22' it is h, r23' it is chemical bond, p is 0-90, and q is 10-100, and now, corresponding sulfonated polyether sulphone has
Structure shown in formula (), abbreviation spaes；
In formula (), r1''-r15' ' it is hydrogen, r16' ' and r17' ' it is methyl, 2≤n≤100, now, corresponding sulfonation gathers
Aryl ether sulfone has the structure shown in formula (), abbreviation spsu.
According to the present invention, the ion exchange capacity of described sulfonated polyether sulphone is preferably 0.5-2.5mmol/g, more preferably
1-2mmol/g, the reverse osmosis membrane so enabling to has higher water flux and salt rejection rate.Wherein, described sulfonation gathers virtue
The ion exchange capacity of ether sulfone refers to sulfonic molal quantity in 1g sulfonated polyether sulphone, and it can be entered using acid base titration method
Row measures.Additionally, described sulfonated polyether sulphone can be commercially available it is also possible to according to various method systems well known in the art
Standby obtain, here will not be described in great detail.
Described polyhedral oligomeric silsesquioxane is the oligosiloxane with nano-scale cage structure, is also called cube
Silane, its Full Name in English is polyhedral oligomeric silsesquioxane, abbreviation poss.Poss has caged knot
Structure, the skeleton of cage is elementary composition by silica, and silica element ratio is 1:1.5, and the outside of cage is then covered by organic substituents
Lid.The molecular diameter of whole poss is generally 1-3nm.Caged surface by poss is made up of organic substituents, and this makes
Obtain it, with sulfonated polyether sulphone, there is the good compatibility.
Wherein, the mono amino propyl group seven isobutyl group silsesquioxane with structure shown in formula () is a kind of amido modified mistake
Poss, amino be in alkalescence, can with sulfonated polyether sulphone sulfonic group formed hydrogen bond, both increased itself and sulfonated polyether sulphone
The compatibility, Hydrophilic ionic cluster region can be reduced again such that it is able to suppression film swelling in water, improve its separating property.Cause
This particularly preferably, described polyhedral oligomeric silsesquioxane is to have mono amino propyl group seven isobutyl of structure shown in formula ()
Base silsesquioxane:
The present invention is not particularly limited to the thickness of described supporting layer and stratum disjunctum, can be the conventional choosing of this area
Select, but so that this two-layer can play more preferable coordinated effect, thus enabling the reverse osmosis membrane obtaining preferably
Have excellent chlorine-resistant property, higher water flux and salt rejection rate concurrently it is preferable that the thickness of described supporting layer is 90-150 micron,
The thickness of described stratum disjunctum is 0.1-0.5 micron.
According to the present invention, described supporting layer various can be had certain intensity and can be used in reverse osmosis membrane by existing
Material make, generally can be by one or more of phenolphthalein type non-sulfonated polyether sulphone, polyether sulfone, Bisphenol A Type polysulfones etc.
Make, all being known, here will not be described in great detail to this those skilled in the art.
The present invention provide reverse osmosis membrane preparation method include by containing polyhedral oligomeric silsesquioxane, there is formula
In ()-formula (), the sulfonated polyether sulphone of structure shown in any one and the casting solution of solvent are coated in and are formed just on supporting layer
Filming, and by described primary membrane solvent remove, be supported layer and be located at described support layer surface on stratum disjunctum anti-
Permeable membrane；
Wherein, in formula (), r1-r15Identical or different, and it is each independently h or c1-c5Alkyl, m >=2；
In formula (), r1'-r22' identical or different, and it is each independently hydrogen or c1-c5Alkyl, r23' it is chemical bond
Or it is c1-c5Alkylidene, p:q=0-10:1；
In formula (), r1''-r17' ' identical or different, and it is each independently hydrogen or c1-c5Alkyl, n >=2.
The present invention is not particularly limited to the consumption of described casting solution, but so that the reverse osmosis membrane arriving can be more preferable
Have excellent chlorine-resistant property, higher water flux and salt rejection rate concurrently it is preferable that the consumption of described casting solution makes described separation
The thickness of layer is 0.1-0.5 micron.Additionally, the thickness of supporting layer can also be the conventional selection of this area, for example, it is possible to be
90-150 micron.
The present invention does not have to the consumption of the polyhedral oligomeric silsesquioxane in described casting solution, sulfonated polyether sulphone and solvent
Have and especially limit, as long as the reverse osmosis membrane enabling to can have excellent chlorine-resistant property, higher water flux concurrently and take off
Salt rate, for example, on the basis of the described sulfonated polyether sulphone of 100 weight portions, described polyhedral oligomeric silsesquioxane
Consumption can be 0.1-20 weight portion, preferably 0.5-10 weight portion；The consumption of described solvent can be 100-20000 weight
Part, preferably 500-10000 weight portion.
According to the present invention particularly preferably, in formula (), r1-r15For h, 2≤m≤100, now, corresponding sulfonation gathers virtue
Ether sulfone has the structure shown in formula (), abbreviation c-spaes；
In formula (), r1'、r3'、r6'、r8' it is methyl, r2'、r4'、r5'、r7'、r9'-r22' it is h, r23' it is chemical bond, p
For 0-90, q is 10-100, and now, corresponding sulfonated polyether sulphone has the structure shown in formula (), abbreviation p-spaes；Or
Person,
r1'-r22' it is h, r23' it is chemical bond, p is 0-90, and q is 10-100, and now, corresponding sulfonated polyether sulphone has
Structure shown in formula (), abbreviation spaes；
In formula (), r1''-r15' ' it is hydrogen, r16' ' and r17' ' it is methyl, 2≤n≤100, now, corresponding sulfonation gathers
Aryl ether sulfone has the structure shown in formula (), abbreviation spsu.
According to the present invention, the ion exchange capacity of described sulfonated polyether sulphone is preferably 0.5-2.5mmol/g, more preferably
1-2mmol/g, the reverse osmosis membrane so enabling to has higher water flux and salt rejection rate.Additionally, described sulfonation gathers virtue
Ether sulfone can be commercially available it is also possible to prepare according to various methods well known in the art, here will not be described in great detail.
According to the present invention particularly preferably, described polyhedral oligomeric silsesquioxane be there is structure shown in formula ()
Mono amino propyl group seven isobutyl group silsesquioxane, the reverse osmosis membrane so enabling to has higher water flux and desalination
Rate；
The present invention is not particularly limited to the species of described solvent, as long as described polyhedral oligomeric silicon sesquialter can be dissolved
Oxygen alkane and sulfonated polyether sulphone, for example, it is possible to in formic acid, acetic acid, methanol, ethanol, acetone, glycol monoethyl ether and water
One or more.Under preferable case, described solvent is the mixed solvent of formic acid, glycol monoethyl ether and water, and described formic acid,
Glycol monoethyl ether can be 1-50:1-30:1, preferably 1-25:1-20:1 with the weight ratio of water, using this mixed solvent more
Be conducive to the dissolving of above-mentioned substance.
As a rule, existing reverse osmosis membrane generally includes stratum disjunctum and supporting layer.Described supporting layer can be existing
Various have certain intensity and can act as the material of reverse osmosis membrane and make, generally can be by phenolphthalein type polyarylether sulfone, poly- virtue
One or more of ether sulfone, Bisphenol A Type polysulfones etc. are made.And the layer being formed after removing the solvent in described primary membrane is
Stratum disjunctum.Additionally, so that the reverse osmosis membrane arriving more smooth it is preferable that the present invention provide reverse osmosis membrane preparation side
Method is additionally included in before casting solution is coated on supporting layer, and described supporting layer is fixed on a glass.
According to the present invention it is possible to the solvent in described primary membrane be removed according to existing various methods, for example, it is possible to will
The supporting layer being coated with described primary membrane heats 10-36 hour at 25-70 DEG C.It should be noted that in the present invention, will be described
Solvent removes and does not refer to utterly remove, and refers to the amount of acceptable solvent in film product as commonly understood in the art, to this
Those skilled in the art can know, here will not be described in great detail.
Present invention also offers the reverse osmosis membrane being prepared by said method.
Additionally, present invention also offers application in water treatment field for the described reverse osmosis membrane.
Theing improvement is that of the present invention provides a kind of new reverse osmosis membrane, and the method for described water process and condition are equal
Can be same as the prior art or similar, here will not be described in great detail.
Hereinafter will be described the present invention by embodiment.
In the following Examples and Comparative Examples:
(1) ion exchange capacity of sulfonated polyether sulphone refers to sulfonic molal quantity in 1g sulfonated polyether sulphone, and it is adopted
It is measured with acid base titration method；
(2) water flux of reverse osmosis membrane records by the following method: reverse osmosis membrane is loaded in membrane cisterna, pre- under 1.2mpa
Pressure is after 0.5 hour, under pressure is for 2.0mpa, temperature record the water transit dose of described reverse osmosis membrane in 1h under the conditions of being 25 DEG C,
And water flux is calculated by below equation:
J=q/(a t), wherein, j is water flux, and q is water transit dose (l), and a is effective membrane area (m of reverse osmosis membrane2),
T is the time (h)；
(3) salt rejection rate of reverse osmosis membrane records by the following method: reverse osmosis membrane is loaded in membrane cisterna, pre- under 1.2mpa
After pressure 0.5h, under pressure is for 2.0mpa, temperature records the sodium chloride that initial concentration in 1h is 2000ppm under the conditions of being 25 DEG C former
The concentration change of sodium chloride in aqueous solution and permeate, and salt rejection rate is calculated by below equation:
R=(cp-cf)/cp× 100%, wherein, r is salt rejection rate, cpFor the concentration of sodium chloride in stock solution, cfFor chlorine in permeate
Change the concentration of sodium.
Embodiment 1
This embodiment is used for reverse osmosis membrane that the present invention provides and preparation method thereof is described.
The mono amino propyl group seven isobutyl group silsesquioxane that 0.01g is had structure shown in formula () is added to 100g by first
(the weight ratio of formic acid, glycol monoethyl ether and deionized water is the mixed solvent of acid, glycol monoethyl ether and deionized water composition
70:25:5, similarly hereinafter) in, make homogeneous weak solution after ultrasonic disperse.It is subsequently adding the dried c-spaes(of 1.0g and be purchased from Tianjin
Yan Jin Science and Technology Ltd., has the structure shown in formula (), r1-r15For h, m is 60, and ion exchange capacity is 1.49mmol/
G), casting solution is obtained after stirring and dissolving.By Bisphenol A Type polysulphones hyperfiltration membrane (purchased from DOW Chemical, thickness is 125 microns, similarly hereinafter)
Fix on a glass, and the casting solution preparing equably is brushed in ultrafiltration membrane surface, then heat treatment 30 at 70 DEG C
Minute, obtain the reverse osmosis membrane m1 including supporting layer and the stratum disjunctum being located in described support layer surface, wherein, described supporting layer
Thickness be 125 microns, the thickness of described stratum disjunctum is 0.2 micron.
After reverse osmosis membrane m1 is soaked 24 hours in water, precompressed 0.5 hour under 1.2mpa, then in pressure be
2.0mpa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and result is as shown in table 1.Additionally, this reverse osmosis membrane m1 is existed
After soaking 24 hours in the aqueous sodium hypochlorite solution of 2000ppm, precompressed 0.5 hour under 1.2mpa, then in pressure be
2.0mpa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and result is as shown in table 1.
Embodiment 2
This embodiment is used for reverse osmosis membrane that the present invention provides and preparation method thereof is described.
The mono amino propyl group seven isobutyl group silsesquioxane that 0.02g is had structure shown in formula () is added to 100g by first
In the mixed solvent of acid, glycol monoethyl ether and deionized water composition, after ultrasonic disperse, make homogeneous weak solution.It is subsequently adding
The dried c-spaes(of 1.0g is purchased from Yan Jin Technology Co., Ltd., has the structure shown in formula (), r1-r15For h, m
For 80, ion exchange capacity is 1.37mmol/g), casting solution is obtained after stirring and dissolving.Bisphenol A Type polysulphones hyperfiltration membrane is fixed on
On glass plate, and the casting solution preparing equably is brushed in ultrafiltration membrane surface, then heat treatment 30 minutes at 70 DEG C, obtain
To the reverse osmosis membrane m2 including supporting layer and the stratum disjunctum being located in described support layer surface, wherein, the thickness of described supporting layer
For 125 microns, the thickness of described stratum disjunctum is 0.2 micron.
After reverse osmosis membrane m2 is soaked 24 hours in water, precompressed 0.5 hour under 1.2mpa, then in pressure be
2.0mpa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and result is as shown in table 1.Additionally, this reverse osmosis membrane m2 is existed
After soaking 24 hours in the aqueous sodium hypochlorite solution of 2000ppm, precompressed 0.5 hour under 1.2mpa, then in pressure be
2.0mpa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and result is as shown in table 1.
Embodiment 3
This embodiment is used for reverse osmosis membrane that the present invention provides and preparation method thereof is described.
The mono amino propyl group seven isobutyl group silsesquioxane that 0.03g is had structure shown in formula () is added to 100g by first
In the mixed solvent of acid, glycol monoethyl ether and deionized water composition, after ultrasonic disperse, make homogeneous weak solution.It is subsequently adding
The dried c-spaes(of 1.0g is purchased from Yan Jin Technology Co., Ltd., has the structure shown in formula (), r1-r15For h, m
For 5, ion exchange capacity is 1.49mmol/g), casting solution is obtained after stirring and dissolving.Bisphenol A Type polysulphones hyperfiltration membrane is fixed on
On glass plate, and the casting solution preparing equably is brushed in ultrafiltration membrane surface, then heat treatment 30 minutes at 70 DEG C, obtain
To the reverse osmosis membrane m3 including supporting layer and the stratum disjunctum being located in described support layer surface, wherein, the thickness of described supporting layer
For 125 microns, the thickness of described stratum disjunctum is 0.2 micron.
After reverse osmosis membrane m3 is soaked 24 hours in water, precompressed 0.5 hour under 1.2mpa, then in pressure be
2.0mpa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and result is as shown in table 1.Additionally, this reverse osmosis membrane m3 is existed
After soaking 24 hours in the aqueous sodium hypochlorite solution of 2000ppm, precompressed 0.5 hour under 1.2mpa, then in pressure be
2.0mpa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and result is as shown in table 1.
Embodiment 4
This embodiment is used for reverse osmosis membrane that the present invention provides and preparation method thereof is described.
The mono amino propyl group seven isobutyl group silsesquioxane that 0.05g is had structure shown in formula () is added to 100g by first
In the mixed solvent of acid, glycol monoethyl ether and deionized water composition, after ultrasonic disperse, make homogeneous weak solution.It is subsequently adding
The dried c-spaes(of 1.0g is purchased from Yan Jin Technology Co., Ltd., has the structure shown in formula (), r1-r15For h, m
For 60, ion exchange capacity is 1.49mmol/g), casting solution is obtained after stirring and dissolving.Bisphenol A Type polysulphones hyperfiltration membrane is fixed on
On glass plate, and the casting solution preparing equably is brushed in ultrafiltration membrane surface, then heat treatment 30 minutes at 70 DEG C, obtain
To the reverse osmosis membrane m4 including supporting layer and the stratum disjunctum being located in described support layer surface, wherein, the thickness of described supporting layer
For 125 microns, the thickness of described stratum disjunctum is 0.2 micron.
After reverse osmosis membrane m4 is soaked 24 hours in water, precompressed 0.5 hour under 1.2mpa, then in pressure be
2.0mpa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and result is as shown in table 1.Additionally, this reverse osmosis membrane m4 is existed
After soaking 24 hours in the aqueous sodium hypochlorite solution of 2000ppm, precompressed 0.5 hour under 1.2mpa, then in pressure be
2.0mpa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and result is as shown in table 1.
Embodiment 5
This embodiment is used for reverse osmosis membrane that the present invention provides and preparation method thereof is described.
The mono amino propyl group seven isobutyl group silsesquioxane that 0.01g is had structure shown in formula () is added to 100g by first
In the mixed solvent of acid, glycol monoethyl ether and deionized water composition, after ultrasonic disperse, make homogeneous weak solution.It is subsequently adding
The dried p-spaes(of 1.0g is purchased from Yan Jin Technology Co., Ltd., has the structure shown in formula (), r1'、r3'、r6'、
r8' it is methyl, r2'、r4'、r5'、r7'、r9'-r22' it is h, r23' it is chemical bond, p is 50, q is 50, and ion exchange capacity is
1.51mmol/g), casting solution is obtained after stirring and dissolving.Bisphenol A Type polysulphones hyperfiltration membrane is fixed on a glass, and will prepare
Casting solution equably brush in ultrafiltration membrane surface, then heat treatment 30 minutes at 70 DEG C, obtain including supporting layer and are located at
The reverse osmosis membrane m5 of the stratum disjunctum in described support layer surface, wherein, the thickness of described supporting layer is 125 microns, described separation
The thickness of layer is 0.2 micron.
After reverse osmosis membrane m5 is soaked 24 hours in water, precompressed 0.5 hour under 1.2mpa, then in pressure be
2.0mpa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and result is as shown in table 1.Additionally, this reverse osmosis membrane m5 is existed
After soaking 24 hours in the aqueous sodium hypochlorite solution of 2000ppm, precompressed 0.5 hour under 1.2mpa, then in pressure be
2.0mpa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and result is as shown in table 1.
Embodiment 6
This embodiment is used for reverse osmosis membrane that the present invention provides and preparation method thereof is described.
The mono amino propyl group seven isobutyl group silsesquioxane that 0.01g is had structure shown in formula () is added to 100g by first
In the mixed solvent of acid, glycol monoethyl ether and deionized water composition, after ultrasonic disperse, make homogeneous weak solution.It is subsequently adding
The dried spaes(of 1.0g is purchased from Yan Jin Technology Co., Ltd., has the structure shown in formula (), r1'-r22' it is h,
r23' it is chemical bond, p is 50, q is 50, and ion exchange capacity is 1.59mmol/g), casting solution is obtained after stirring and dissolving.By bis-phenol
A type polysulphones hyperfiltration membrane is fixing on a glass, and the casting solution preparing equably is brushed in ultrafiltration membrane surface, then in 70
Heat treatment 30 minutes at DEG C, obtain the reverse osmosis membrane m6 including supporting layer and the stratum disjunctum being located in described support layer surface, its
In, the thickness of described supporting layer is 125 microns, and the thickness of described stratum disjunctum is 0.2 micron.
After reverse osmosis membrane m6 is soaked 24 hours in water, precompressed 0.5 hour under 1.2mpa, then in pressure be
2.0mpa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and result is as shown in table 1.Additionally, this reverse osmosis membrane m6 is existed
After soaking 24 hours in the aqueous sodium hypochlorite solution of 2000ppm, precompressed 0.5 hour under 1.2mpa, then in pressure be
2.0mpa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and result is as shown in table 1.
Embodiment 7
This embodiment is used for reverse osmosis membrane that the present invention provides and preparation method thereof is described.
The mono amino propyl group seven isobutyl group silsesquioxane that 0.01g is had structure shown in formula () is added to 100g by first
In the mixed solvent of acid, glycol monoethyl ether and deionized water composition, after ultrasonic disperse, make homogeneous weak solution.It is subsequently adding
The dried spsu(of 1.0g is purchased from Yan Jin Technology Co., Ltd., has the structure shown in formula (), r1''-r15' ' it is hydrogen,
r16' ' and r17' ' it is methyl, n is 80, and ion exchange capacity is 1.40mmol/g) 1.0g, casting solution is obtained after stirring and dissolving.Will
Bisphenol A Type polysulphones hyperfiltration membrane is fixing on a glass, and the casting solution preparing equably is brushed in ultrafiltration membrane surface, then
Heat treatment 30 minutes at 70 DEG C, obtain the reverse osmosis membrane including supporting layer and the stratum disjunctum being located in described support layer surface
M7, wherein, the thickness of described supporting layer is 125 microns, and the thickness of described stratum disjunctum is 0.2 micron.
After reverse osmosis membrane m7 is soaked 24 hours in water, precompressed 0.5 hour under 1.2mpa, then in pressure be
2.0mpa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and result is as shown in table 1.Additionally, this reverse osmosis membrane m7 is existed
After soaking 24 hours in the aqueous sodium hypochlorite solution of 2000ppm, precompressed 0.5 hour under 1.2mpa, then in pressure be
2.0mpa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and result is as shown in table 1.
Embodiment 8
This embodiment is used for reverse osmosis membrane that the present invention provides and preparation method thereof is described.
Method according to embodiment 1 prepares reverse osmosis membrane, except for the difference that, has the mono amino propyl group of structure shown in formula ()
Seven isobutyl group silsesquioxanes are substituted with prestox eight silsesquioxane of identical weight part, obtain including supporting layer and are located at institute
State the reverse osmosis membrane m8 of the stratum disjunctum in support layer surface, wherein, the thickness of described supporting layer is 125 microns, described stratum disjunctum
Thickness be 0.2 micron.
After reverse osmosis membrane m8 is soaked 24 hours in water, precompressed 0.5 hour under 1.2mpa, then in pressure be
2.0mpa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and result is as shown in table 1.Additionally, this reverse osmosis membrane m8 is existed
After soaking 24 hours in the aqueous sodium hypochlorite solution of 2000ppm, precompressed 0.5 hour under 1.2mpa, then in pressure be
2.0mpa, temperature measure water flux and salt rejection rate under the conditions of being 25 DEG C, and result is as shown in table 1.
Comparative example 1
This comparative example is used for reference reverse osmosis membrane and preparation method thereof is described.
Method according to embodiment 1 prepares reverse osmosis membrane, except for the difference that, has the mono amino propyl group of structure shown in formula ()
Seven isobutyl group silsesquioxanes are substituted with the c-spaes of identical weight part, obtain including supporting layer and are located at described supporting layer table
The reference reverse osmosis membrane dm1 of the stratum disjunctum on face, wherein, the thickness of described supporting layer is 125 microns, the thickness of described stratum disjunctum
For 0.2 micron.
After reference reverse osmosis membrane dm1 is soaked 24 hours in water, precompressed 0.5 hour under 1.2mpa, then in pressure
Water flux and salt rejection rate is measured, result is as shown in table 1 under the conditions of being 25 DEG C for 2.0mpa, temperature.Additionally, by this reference reverse osmosis
After film dm1 soaks 24 hours in the aqueous sodium hypochlorite solution of 2000ppm, precompressed 0.5 hour under 1.2mpa, then in pressure
Water flux and salt rejection rate is measured, result is as shown in table 1 under the conditions of being 25 DEG C for 2.0mpa, temperature.
Table 1
As can be seen from the above results, the reverse osmosis membrane that the present invention provides not only has more excellent water flux and desalination
Rate, and it is soaked in the aqueous sodium hypochlorite solution of 2000ppm 24 hours afterwards, still there is higher water flux and desalination
Rate it can be seen that, it has stronger chlorine-resistant property.That is, the reverse osmosis membrane that the present invention provides can have concurrently excellent well
Chlorine-resistant property, higher water flux and salt rejection rate, great prospects for commercial application.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to various can
The compound mode of energy no longer separately illustrates.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.
Claims (14)
1. a kind of reverse osmosis membrane is it is characterised in that described reverse osmosis membrane includes supporting layer and is located in described support layer surface
Stratum disjunctum, described stratum disjunctum contains polyhedral oligomeric silsesquioxane and has structure shown in any one in formula ()-formula ()
Sulfonated polyether sulphone；
Wherein, in formula (), r1-r15Identical or different, and it is each independently h or c1-c5Alkyl, m >=2；
In formula (), r1'-r22' identical or different, and it is each independently hydrogen or c1-c5Alkyl, r23' for chemical bond or be
c1-c5Alkylidene, p:q=0-10:1；
In formula (), r1”-r17" identical or different, and it is each independently hydrogen or c1-c5Alkyl, n >=2；
The ion exchange capacity of described sulfonated polyether sulphone is 0.5-2.5mmol/g.
2. reverse osmosis membrane according to claim 1, wherein, on the basis of the described sulfonated polyether sulphone of 100 weight portions, institute
The content stating polyhedral oligomeric silsesquioxane is 0.1-20 weight portion.
3. reverse osmosis membrane according to claim 1 and 2, wherein,
In formula (), r1-r15For h, 2≤m≤100；
In formula (), r1'、r3'、r6'、r8' it is methyl, r2'、r4'、r5'、r7'、r9'-r22' it is h, r23' it is chemical bond, p is 0-
90, q is 10-100；Or, r1'-r22' it is h, r23' it is chemical bond, p is 0-90, and q is 10-100；
In formula (), r1”-r15" it is hydrogen, r16" and r17" it is methyl, 2≤n≤100.
4. reverse osmosis membrane according to claim 1, wherein, the ion exchange capacity of described sulfonated polyether sulphone is 1-
2mmol/g.
5. reverse osmosis membrane according to claim 1 and 2, wherein, described polyhedral oligomeric silsesquioxane is to have formula
The mono amino propyl group seven isobutyl group silsesquioxane of structure shown in ():
6. reverse osmosis membrane according to claim 1 and 2, wherein, the thickness of described supporting layer is 90-150 micron, described point
The thickness of absciss layer is 0.1-0.5 micron.
7. a kind of preparation method of reverse osmosis membrane it is characterised in that the method include by containing polyhedral oligomeric silsesquioxane,
There is the sulfonated polyether sulphone of structure shown in any one and the casting solution of solvent in formula ()-formula () be coated on supporting layer
Form primary membrane, and the solvent in described primary membrane is removed, be supported layer and the separation being located in described support layer surface
The reverse osmosis membrane of layer；
Wherein, in formula (), r1-r15Identical or different, and it is each independently h or c1-c5Alkyl, m >=2；
In formula (), r1'-r22' identical or different, and it is each independently hydrogen or c1-c5Alkyl, r23' for chemical bond or be
c1-c5Alkylidene, p:q=0-10:1；
In formula (), r1”-r17" identical or different, and it is each independently hydrogen or c1-c5Alkyl, n >=2；
The ion exchange capacity of described sulfonated polyether sulphone is 0.5-2.5mmol/g.
8. preparation method according to claim 7, wherein, on the basis of the described sulfonated polyether sulphone of 100 weight portions, institute
The consumption stating polyhedral oligomeric silsesquioxane is 0.1-20 weight portion, and the consumption of described solvent is 100-20000 weight portion.
9. the preparation method according to claim 7 or 8, wherein,
In formula (), r1-r15For h, 2≤m≤100；
In formula (), r1'、r3'、r6'、r8' it is methyl, r2'、r4'、r5'、r7'、r9'-r22' be, r23' it is chemical bond, p is 0-
90, q is 10-100；Or, r1'-r22' it is h, r23' it is chemical bond, p is 0-90, and q is 10-100；
In formula (), r1”-r15" it is hydrogen, r16" and r17" it is methyl, 2≤n≤100.
10. preparation method according to claim 9, wherein, the ion exchange capacity of described sulfonated polyether sulphone is 1-
2mmol/g.
11. preparation methoies according to claim 7 or 8, wherein, described polyhedral oligomeric silsesquioxane is to have formula
The mono amino propyl group seven isobutyl group silsesquioxane of structure shown in ():
12. preparation methoies according to claim 7 or 8, wherein, the thickness of described supporting layer is 90-150 micron, described
It is 0.1-0.5 micron that the consumption of casting solution makes the thickness of the stratum disjunctum obtaining.
The reverse osmosis membrane that 13. methods described in any one in claim 7-12 prepare.
Application in water treatment field for the reverse osmosis membrane described in any one in 14. claim 1-6 and 13.
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| CN109692582B (en) * | 2017-10-20 | 2021-08-03 | 中国石油化工股份有限公司 | Reverse osmosis membrane and preparation method and application thereof |
| CN114086423A (en) * | 2020-08-25 | 2022-02-25 | 中国制浆造纸研究院有限公司 | Sulfonated modified anhydrous humidifying device and preparation method and application thereof |
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