CN109692579A - Reverse osmosis membrane and its preparation method and application - Google Patents
Reverse osmosis membrane and its preparation method and application Download PDFInfo
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- CN109692579A CN109692579A CN201710981617.XA CN201710981617A CN109692579A CN 109692579 A CN109692579 A CN 109692579A CN 201710981617 A CN201710981617 A CN 201710981617A CN 109692579 A CN109692579 A CN 109692579A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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Abstract
The present invention relates to seperation film field, a kind of application of the preparation method and the reverse osmosis membrane of reverse osmosis membrane, the reverse osmosis membrane in water treatment procedure is disclosed.The reverse osmosis membrane includes supporting layer and polyamide separating layer, wherein, one surface of the polyamide separating layer is bonded with the supporting layer, and the polyamide separating layer is by carrying out interfacial polymerization with polynary acyl chlorides for polyamine, the ammonium salt containing epoxy group and obtaining in the presence of curing accelerator.Reverse osmosis membrane provided by the invention improves the hydrophily of film, makes film surface with positive charge, improve film to the contamination resistance of cationic surfactant or other positive charge pollutants by the way that ammonium salt groups are fixed in polyamide separating layer；Also, it is crosslinked by the epoxy group in the ammonium salt containing epoxy group with polyamide, increases the crosslink density of reverse osmosis membrane separation layer, further improve the salt-stopping rate of film.
Description
Technical field
The present invention relates to seperation film fields, and in particular to a kind of reverse osmosis membrane, the reverse osmosis membrane preparation method and should
Application of the reverse osmosis membrane in water treatment procedure.
Background technique
Membrane separation technique is in appearance early 20th century, and the new skill of a kind of separation to emerge rapidly after the 1960s
Art.Since membrane separation technique had not only had the function of separation, concentration, purifying and purification, but also there are efficient, energy-saving and environmental protection, molecular level
Filtering, filter process be simple, therefore the characteristics such as easily controllable are widely used in food, medicine, biology, environmental protection, chemical industry, smelting
The fields such as gold, the energy, petroleum, water process, electronics, bionical, produce huge economic benefit and social benefit, it has also become current
One of most important means in separation science.
The core of membrane separation technique is exactly seperation film.Microfiltration membranes, ultrafiltration membrane, nanofiltration can be divided into according to the size of membrane aperture
Film and reverse osmosis membrane.Wherein, reverse osmosis membrane is again because having the good separation performance to small organic molecule and inorganic ion, peace
Entirely, environmental protection, it is easy to operate the advantages that and become one of the key technology of water treatment field.So far, reverse osmosis membrane is mainly applied
In the fields such as seawater and brackish water desalination, water softening, the recycling of middle water, Industrial Wastewater Treatment and ultrapure water preparation.Currently, city
The main product of field is the mode for taking interfacial polymerization, and polyamide film is combined to micropore support counterdie surface.Common work
Skill process, is discussed in detail in US4277344.Such reverse osmosis membrane product not only salt-stopping rate with higher also has saturating
The advantages such as aqueous good, resistance to pH range wide (2-12) and operating pressure are low.However, fouling membrane is always to influence film properties, drop
An important factor for its low service life.Fouling membrane refer in the feed liquid contacted with film particle, colloidal particle or solute transportation with
Film occurs physics, chemical action or because concentration polarization makes certain solutes in the concentration of film surface more than its solubility and mechanism
Caused by film surface or fenestra adsorb, deposit, cause membrane aperture to become smaller or block, make membrane flux and stalling characteristic it is obvious under
The irreversible change phenomenon of drop.Flux decline caused by absorption of the polluter in film surface and fenestra and UF membrane energy
The reduction of power, especially protein absorption are the main reason for causing the decline of membrane flux.The method solved at present is to prevent fouling membrane
It is post-processed with to fouling membrane.Relative to post-processing, the reverse osmosis composite membrane material with anti-fouling performance is developed and developed
It is the most basic and most direct approach for solving the problems, such as this.
In order to improve the contamination resistance of polyamide composite film, does a lot of work both at home and abroad, be concentrated mainly on surface and change
Property processing and surface covering.
The method of membrane surface modification processing is numerous, and the hydrophily for increasing film surface is such as handled by surfactant
(Desalination, 1998,115:15-32)；The processing of United States Patent (USP) US5028453 using plasma is introduced in film surface
Hydrophilic radical, to improve the resistance tocrocking of composite membrane, corona treatment is limited to technical conditions and cost and cannot at present
Realize large-scale production；United States Patent (USP) US5151183 carries out fluorination treatment to film surface to improve the antipollution of film using fluorine gas
Property, while fluorine gas processing is easily broken film surface polyamide molecule chain, to affect the separating property and service life of film.
The reverse osmosis membrane simple and with excellent stain resistance therefore, it is necessary to a kind of preparation method.
Summary of the invention
The purpose of the invention is to overcome the defect of existing reverse osmosis membrane low contamination resistance, and provide a kind of side of preparation
Method is simple and has the reverse osmosis membrane of excellent stain resistance and preparation method thereof and the reverse osmosis membrane answering in water treatment procedure
With.
The present inventor has found by in-depth study, due in interfacial polymerization process, the ammonium containing epoxy group
Under the action of curing accelerator, the amide group that epoxy group is formed with amino and interfacial polymerization reacts salt, will
Ammonium salt groups are fixed in polyamide separating layer, improve the hydrophily of film, and make film surface with positive charge, improve film pair
The contamination resistance of cationic surfactant or other positive charge pollutants；Also, epoxy group is in the work of curing accelerator
Under, it may occur that the ring-opening polymerization of epoxy increases the compactness extent of reverse osmosis membrane separation layer, further improves film
Salt-stopping rate has thus completed the present invention.
That is, one aspect of the present invention provides a kind of reverse osmosis membrane, which includes supporting layer and polyamide separating layer,
Wherein, a surface of the polyamide separating layer is bonded with the supporting layer, and the polyamide separating layer in solidification by promoting
Into in the presence of agent, polyamine, the ammonium salt containing epoxy group are subjected to interfacial polymerization with polynary acyl chlorides and obtained.
Second aspect of the present invention provides a kind of preparation method of reverse osmosis membrane, this method comprises: depositing in curing accelerator
Under, supporting layer is contacted with polyamine, the ammonium salt containing epoxy group with polynary acyl chlorides and carries out interfacial polymerization formation separating layer, and
The epoxy group in the ammonium salt containing epoxy group is crosslinked with polyamide to react.
The present invention also provides reverse osmosis membranes prepared by the above method.
In addition, the application the present invention also provides the reverse osmosis membrane in water treatment procedure.
Reverse osmosis membrane according to the present invention, due in interfacial polymerization process, on the one hand, in interfacial polymerization process, contain
The ammonium salt of epoxy group is under the action of curing accelerator, the amide group of epoxy group and amino and interfacial polymerization formation
It reacts, quaternary ammonium salt group is fixed in polyamide separating layer, the hydrophily of film is improved, and make film surface with positive electricity
Lotus improves film to the contamination resistance of cationic surfactant or other positive charge pollutants；Also, epoxy group is solid
Under the action of change promotor, it may occur that the ring-opening polymerization of epoxy increases the compactness extent of reverse osmosis membrane separation layer, into one
Step improves the salt-stopping rate of film.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of reverse osmosis membrane, which includes supporting layer and polyamide separating layer, wherein described
One surface of polyamide separating layer is bonded with the supporting layer, and the polyamide separating layer passes through the presence in curing accelerator
Under, polyamine, the ammonium salt containing epoxy group are subjected to interfacial polymerization with polynary acyl chlorides and obtained.
In the present invention, term " interfacial polymerization " refers to: it is immiscible at two kinds, it is dissolved with the solution of different monomers respectively
Interface on (or interface organic phase side) polymerization reaction for carrying out.
In the present invention, by the presence of curing accelerator, by polyamine, the ammonium salt containing epoxy group and polynary acyl
Chlorine carries out interfacial polymerization and obtains the polyamide separating layer, and the surface and inside that can make the polyamide separating layer are by containing
The ammonium salt of epoxy group is modified, that is to say, that epoxy group in the ammonium salt containing epoxy group not only with the polyamide
The polyamide crosslinking of layer surface is separated, and is crosslinked with the polyamide inside the polyamide separating layer.
In the present invention, by making the separating layer be crosslinked with the ammonium salt containing epoxy group, the hydrophily of film is improved, and
Make film surface with positive charge, improves film to the contamination resistance of cationic surfactant or other positive charge pollutants；
Also, epoxy group is under the action of curing accelerator, it may occur that the ring-opening polymerization of epoxy increases reverse osmosis membrane separation
The compactness extent of layer, further improves the salt-stopping rate of film.In the present invention, the salt-stopping rate as reverse osmosis membrane of the invention is excellent
Be selected as 99% or more, more preferably 99.1% or more, more preferably 99.3% or more, 99.5% or more, 99.7% or more or
99.9% or more.
In addition, the water flux of the reverse osmosis membrane is preferably 40L/m in the case where meeting above-mentioned salt rejection rate2H or more,
More preferably 45L/m2H or more, preferably 60L/m2H is hereinafter, more preferably 50L/m2H or less.Water flux as reverse osmosis membrane
It can specifically enumerate: 40L/m2h、41L/m2h、42L/m2h、43L/m2h、44L/m2h、45L/m2h、46L/m2h、47L/m2h、
48L/m2h、49L/m2h、50L/m2h、55L/m2h、58L/m2H or 60L/m2H etc..
In the present invention, in order to enable to reverse osmosis membrane can preferably have both excellent anti-fouling performance, higher
Water flux and salt rejection rate, the preferably described polyamide separating layer with a thickness of 0.05-0.3 μm, more preferably 0.1-0.2 μm.As
The thickness of separating layer can specifically enumerate 0.005 μm, 0.01 μm, 0.02 μm, 0.03 μm, 0.04 μm, 0.05 μm, 0.06 μm, 0.07
μm, 0.08 μm, 0.09 μm, 0.1 μm, 0.2 μm or 0.3 μm etc..
In the present invention, the polyamide separating layer is modified by the ammonium salt surface containing epoxy group, so that described contain ring
Epoxy group in the ammonium salt of oxygen groups is crosslinked with polyamide.As long as can be to poly- as the ammonium salt containing epoxy group
The surface of amide separating layer is modified, so that the epoxy group in the ammonium salt containing epoxy group is crosslinked with polyamide
?.Epoxy group in the ammonium salt containing epoxy group can be 1 or 2 or more, preferably 1 or 2, more preferably
It is 1.
The above-mentioned ammonium salt containing epoxy group is preferably ammonium halide salt, more preferable ammonium halide salt, such as chlorination ammonium salt, ammonium bromide
Salt or iodate ammonium salt, further preferably chlorination ammonium salt.2,3- can be for example selected from as such ammonium salt containing epoxy group
Epoxypropyltrimethylchloride chloride, 2,3- Epoxypropyl triethyl ammonium chloride, 1,2- glycidyl dimethyl dodecyl base chlorination
Ammonium, diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium chloride, 3- epoxy ammonium bromide,
2,3- glycidyl triethylammonium bromide, 1,2- glycidyl dimethyl dodecyl base ammonium bromide, diethyl -2,3- epoxy third
Base-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium bromide, 3- epoxy ammonium iodide, 2,3- glycidyl triethiodide
Change ammonium, 1,2- glycidyl dimethyl dodecyl base ammonium iodide and diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygroup)]
One or more of silicon propyl ammonium iodide.Preferably, the ammonium salt containing epoxy group is selected from 2,3- glycidyl three
Ammonio methacrylate, 2,3- Epoxypropyl triethyl ammonium chloride, 1,2- glycidyl dimethyl dodecyl ammonium chlorides, diethyl-
2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium chloride, 3- epoxy ammonium bromide, 2,3- epoxy third
Base triethylammonium bromide, 1,2- glycidyl dimethyl dodecyl base ammonium bromide, diethyl -2,3- glycidyl-[3- (methyl
One or more of dimethoxy)] silicon propyl ammonium bromide.It is highly preferred that the ammonium salt containing epoxy group be selected from 2,
3- epoxypropyltrimethylchloride chloride, 2,3- Epoxypropyl triethyl ammonium chloride, 1,2- glycidyl dimethyl dodecyl base chlorine
Change one or more of ammonium and diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium chloride.
In the present invention, for the type of the polyamine, there is no particular limitation, can be for commonly used in the art for systems
Amine compounds used in standby polyamide.For example, can be m-phenylene diamine (MPD), p-phenylenediamine, o-phenylenediamine, piperazine and equal benzene triamine
One of or it is a variety of；Preferably m-phenylene diamine (MPD).In addition, the preferably described polyamine is in the form of a solution when carrying out interfacial polymerization
It uses, can be incompatible with the solvent of the aftermentioned polynary acyl chlorides of dissolution and to described more as the solvent for dissolving the polyamine
First inert solvent of amine.It for example can be one of water, methanol and acetonitrile or a variety of as such solvent；Preferably water.
In addition, for the concentration of the polyamine, there is no particular limitation, can be the conventional selection of this field.For example,
The content of the polyamine in the water phase containing polyamine, the ammonium salt containing epoxy group and curing accelerator can be 0.5-
10 weight %, preferably 1-5 weight %.The content of polyamine is specifically as follows 0.5 weight %, 1 weight in the polynary amine aqueous solution
Measure %, 2 weight %, 3 weight %, 4 weight %, 5 weight %, 6 weight %, 7 weight %, 8 weight %, 9 weight % or 10 weights
Measure % etc..
In the present invention, for the type of the polynary acyl chlorides, also there is no particular limitation, can usually use for this field
In preparing chloride compounds used in polyamide.For example, can be pyromellitic trimethylsilyl chloride, m-phthaloyl chloride and terephthaldehyde
One of acyl chlorides is a variety of；Preferably pyromellitic trimethylsilyl chloride.
In addition, the preferably described polynary acyl chlorides uses in the form of a solution when carrying out interfacial polymerization, it is described polynary as dissolving
The solvent of acyl chlorides can be incompatible with the solvent of above-mentioned dissolution polyamine and to the polynary inert solvent of acyl chlorides.As
Such solvent for example can be organic solvent, as the organic solvent be preferably n-hexane, dodecane, normal heptane,
One of Isopar E, Isopar G, Isopar H, Isopar L and Isopar M or a variety of.
In addition, for the concentration of polynary acyl chlorides in the polynary solution of acid chloride, there is no particular limitation, can be this field
Conventional selection.For example, the content of polynary acyl chlorides can be 0.025-1 weight % in the polynary solution of acid chloride, preferably
0.05-0.5 weight %.The content of polynary acyl chlorides can specifically enumerate 0.025 weight %, 0.05 weight in the polynary solution of acid chloride
Measure %, 0.1 weight %, 0.2 weight %, 0.3 weight %, 0.4 weight %, 0.5 weight %, 0.6 weight %, 0.7 weight %,
0.8 weight %, 0.9 weight % or 1 weight % etc..
According to the present invention, to the curing accelerator, there is no particular limitation, can be commonly used in the art various
Curing accelerator.It such as can be phenolic cure accelerator or amine-type cure accelerator, preferably phenolic cure accelerator.As
The curing accelerator for example can be 2,4,6- tri- (dimethylamino methyl) phenol, phenol, o-cresol, metacresol, isophthalic two
Phenol, nonyl phenol, bisphenol-A, salicylic acid, benzyl dimethylamine, triethanolamine, bicyclic amidine, triethylamine, pyridine, N- 2-glycidyl benzene
Amine, N- 2-glycidyl para-totuidine, N- ethyl-N glycidol aniline, N- ethyl-N glycidol ortho-aminotoluene, tetraethyl
Ammonium bromide, tetrabutylammonium bromide, diethylenetriamine, triethylene tetramine, polyethylene polyamine, benzyl alcohol, 2,4- imidazoles, 1- benzyl-
One of 2- ethyl imidazol(e), 2-methylimidazole and 1- amino-ethyl 2-methylimidazole are a variety of；Preferably tri- (diformazan of 2,4,6-
Amino methyl) one of phenol, phenol, metacresol and resorcinol or a variety of.
In addition, for the concentration of curing accelerator, there is no particular limitation, can be the conventional selection of this field.For example,
The concentration of the curing accelerator described in the water phase containing polyamine, the ammonium salt containing epoxy group and curing accelerator can be
0.005-10 weight %, preferably 0.01-1 weight %.The concentration of the curing accelerator be specifically as follows 0.01 weight %,
0.03 weight %, 0.05 weight %, 0.1 weight %, 0.2 weight %, 0.3 weight %, 0.4 weight %, 0.5 weight %, 0.6 weight
Measure %, 0.7 weight %, 0.8 weight %, 0.9 weight %, 1 weight %, 2 weight %, 3 weight %, 4 weight %, 5 weight %, 6
Weight %, 7 weight %, 8 weight %, 9 weight % or 10 weight % etc..
According to the present invention, in the water phase containing polyamine, the ammonium salt containing epoxy group and curing accelerator, contain epoxy
The ammonium salt of group, the weight ratio of the dosage of curing accelerator and polyamine are 0.01-10:0.001-5:1, preferably 0.05-
5:0.01-1:1.It, can be with by using such water phase containing polyamine, the ammonium salt containing epoxy group and curing accelerator
The complex reverse osmosis membrane enable preferably has both excellent salt-stopping rate and higher water flux.
Dosage as the polyamine and the polynary acyl chlorides can change in a larger range, it is preferable that
The mass concentration ratio of the polyamine and the polynary acyl chlorides is 1-100:1, more preferably 5-50:1, further preferably 10-
40:1 is still more preferably 15-35:1, is still more preferably 18-25:1.As the polyamine and the polynary acyl chlorides
Mass concentration ratio can specifically enumerate: 15:1,16:1,17:1,18:1,19:1,20:1,21:1,22:1,23:1,24:1,
25:1 or 30:1 etc..
Polyamide separating layer of the invention is obtained as the polyamine and the polynary acyl chlorides are carried out interfacial polymerization
There is no particular limitation for mode, the various routines that polyamine can be made to use with the progress interfacial polymerization of polynary acyl chlorides for this field
The way of contact.In the present invention, it is preferred to which supporting layer is successively promoted with containing polyamine, the ammonium salt containing epoxy group and solidification
It is in contact into the water phase of agent and containing the organic of polynary acyl chlorides, is then heat-treated.
According to the present invention, to the condition of the interface polymerization reaction, there is no particular limitation, can be conventional for this field
Selection, for example, by supporting layer successively with the water phase containing polyamine, the ammonium salt containing epoxy group and curing accelerator and contain
In the case where having the solution of polynary acyl chlorides to be contacted, the time that supporting layer is contacted with the solution containing polyamine is 5-100s,
Preferably 10-60s (such as can be 10s, 20s, 30s, 40s, 50s or 60s)；Supporting layer connects with the solution containing polynary acyl chlorides
The time of touching is 5-100s, preferably 10-60s (such as can be 10s, 20s, 30s, 40s, 50s or 60s).When above-mentioned contact
Temperature can be 10-40 DEG C (such as can be 25 DEG C).
In addition, the condition of the heat treatment includes: that heat treatment temperature is 40-150 DEG C, at heat when carrying out above-mentioned heat treatment
The reason time is 0.5-20min；Preferably, it is 50-120 DEG C that the condition of the heat treatment, which includes: heat treatment temperature, heat treatment time
For 1-10min.Here, heat treatment temperature for example can be 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C or 120
℃.The time of heat treatment for example can be 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min.
According to the present invention, for the supporting layer, there is no particular limitation, can be by existing various with centainly strong
It spends and the material that can be used in reverse osmosis membrane is made, it usually can be by polyester, polyacrylonitrile, Kynoar, the non-sulphur of phenolphthalein type
Change one of polyether sulphone, polyether sulfone and polysulfones or a variety of is made.In addition, the supporting layer can be single hole or porous knot
Structure.The supporting layer is preferably polysulfone porous supporting layer.
In the present invention, there is no particular limitation in source of the present invention to the polysulfone porous supporting layer, for example, can lead to
Commercially available acquisition is crossed, in situations where it is preferred, can also obtain using phase inversion self-control.Wherein, the phase inversion is ability
Known to field technique personnel, for example, gel method, thermal gels method can be evaporated for gas phase gel method, solvent or immerse gel method,
Preferably immerse gel method.In a preferred embodiment, by the way that the coating liquid containing polysulfones is coated in polysulfones counterdie
Then upper formation primary membrane converts supporting layer for the primary membrane using phase inversion, to obtain polysulfone porous supporting layer.
According to the present invention, the thickness of the supporting layer is not particularly limited, can is the usually used of this field
Thickness, but in order to enable each layer can play the role of better coordinated, the complex reverse osmosis membrane enable is more preferable
Have both excellent salt-stopping rate and higher water flux, in situations where it is preferred, the supporting layer with a thickness of 30-60 μm, more
Preferably 35-45 μm.As the thickness of supporting layer, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm or 60 μm etc. can be enumerated.
A preferred embodiment according to the present invention, which further includes enhancement layer, the enhancement layer and institute
State another surface fitting of supporting layer.By forming the enhancement layer, it is not only more advantageous to the formation of supporting layer, and can also
Enough so that complex reverse osmosis membrane has better mechanical property.There is no particular limitation to the enhancement layer by the present invention, Ke Yiwei
The selection of this field routine preferably gathers for example, can be one of polyester layer, polyethylene layer and polypropylene layer or a variety of
Ester layer, more preferably non-woven polyester layer of cloth.From the point of view of capable of playing the role of better coordinated from each layer, it is preferable that
The enhancement layer with a thickness of 50-100 μm, more preferably 60-80 μm.As the thickness of enhancement layer, can specifically enumerate: 50 μm,
55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm or 95 μm etc..
The present invention also provides the preparation methods of above-mentioned reverse osmosis membrane, this method comprises: in the presence of curing accelerator,
Supporting layer is contacted with polyamine, the ammonium salt containing epoxy group with polynary acyl chlorides and carries out interfacial polymerization formation separating layer, and makes institute
It states the epoxy group in the ammonium salt containing epoxy group and is crosslinked with polyamide and reacted.
Preparation method through the invention, can while forming separating layer so that the polyamide of separating layer with contain ring
Epoxy groups cross-link in the ammonium salt of oxygen groups ultimately forms modified separating layer.
The step of preferred embodiment according to the present invention, the interfacial polymerization and the cross-linking reaction includes:
First the supporting layer is contacted with the water phase containing polyamine, the ammonium salt containing epoxy group and curing accelerator, then with contain
There is the organic of polynary acyl chlorides to be in contact.
In the present invention, as long as can change to the surface of polyamide separating layer as the ammonium salt containing epoxy group
Property, so that the epoxy group and polyamide in the ammonium salt containing epoxy group crosslink.It is described containing epoxy group
Epoxy group in ammonium salt can be 1 or 2 or more, preferably 1 or 2, more preferably 1.
The above-mentioned ammonium salt containing epoxy group is preferably ammonium halide salt, more preferable ammonium halide salt, such as chlorination ammonium salt, ammonium bromide
Salt or iodate ammonium salt, further preferably chlorination ammonium salt.2,3- can be for example selected from as such ammonium salt containing epoxy group
Epoxypropyltrimethylchloride chloride, 2,3- Epoxypropyl triethyl ammonium chloride, 1,2- glycidyl dimethyl dodecyl base chlorination
Ammonium, diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium chloride, 3- epoxy ammonium bromide,
2,3- glycidyl triethylammonium bromide, 1,2- glycidyl dimethyl dodecyl base ammonium bromide, diethyl -2,3- epoxy third
Base-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium bromide, 3- epoxy ammonium iodide, 2,3- glycidyl triethiodide
Change ammonium, 1,2- glycidyl dimethyl dodecyl base ammonium iodide and diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygroup)]
One or more of silicon propyl ammonium iodide.Preferably, the ammonium salt containing epoxy group is selected from 2,3- glycidyl three
Ammonio methacrylate, 2,3- Epoxypropyl triethyl ammonium chloride, 1,2- glycidyl dimethyl dodecyl ammonium chlorides, diethyl-
2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium chloride, 3- epoxy ammonium bromide, 2,3- epoxy third
Base triethylammonium bromide, 1,2- glycidyl dimethyl dodecyl base ammonium bromide, diethyl -2,3- glycidyl-[3- (methyl
One or more of dimethoxy)] silicon propyl ammonium bromide.It is highly preferred that the ammonium salt containing epoxy group be selected from 2,
3- epoxypropyltrimethylchloride chloride, 2,3- Epoxypropyl triethyl ammonium chloride, 1,2- glycidyl dimethyl dodecyl base chlorine
Change one or more of ammonium and diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium chloride.
In the present invention, for the type of the polyamine, there is no particular limitation, can be for commonly used in the art for systems
Amine compounds used in standby polyamide.For example, can be m-phenylene diamine (MPD), p-phenylenediamine, o-phenylenediamine, piperazine and equal benzene triamine
One of or it is a variety of；Preferably m-phenylene diamine (MPD).In addition, the preferably described polyamine is in the form of a solution when carrying out interfacial polymerization
It uses, can be incompatible with the solvent of the aftermentioned polynary acyl chlorides of dissolution and to described more as the solvent for dissolving the polyamine
First inert solvent of amine.It for example can be one of water, methanol and acetonitrile or a variety of as such solvent；Preferably water.
In addition, for the concentration of the polyamine, there is no particular limitation, can be the conventional selection of this field.For example,
The content of the polyamine in the water phase containing polyamine, the ammonium salt containing epoxy group and curing accelerator can be 0.5-
10 weight %, preferably 1-5 weight %.The content of polyamine is specifically as follows 0.5 weight %, 1 weight in the polynary amine aqueous solution
Measure %, 2 weight %, 3 weight %, 4 weight %, 5 weight %, 6 weight %, 7 weight %, 8 weight %, 9 weight % or 10 weights
Measure % etc..
In the present invention, for the type of the polynary acyl chlorides, also there is no particular limitation, can usually use for this field
In preparing chloride compounds used in polyamide.For example, can be pyromellitic trimethylsilyl chloride, m-phthaloyl chloride and terephthaldehyde
One of acyl chlorides is a variety of；Preferably pyromellitic trimethylsilyl chloride.
In addition, the preferably described polynary acyl chlorides uses in the form of a solution when carrying out interfacial polymerization, it is described polynary as dissolving
The solvent of acyl chlorides can be incompatible with the solvent of above-mentioned dissolution polyamine and to the polynary inert solvent of acyl chlorides.As
Such solvent for example can be organic solvent, as the organic solvent be preferably n-hexane, dodecane, normal heptane,
One of Isopar E, Isopar G, Isopar H, Isopar L and Isopar M or a variety of.
In addition, for the concentration of polynary acyl chlorides in the polynary solution of acid chloride, there is no particular limitation, can be this field
Conventional selection.For example, the content of polynary acyl chlorides can be 0.025-1 weight % in the polynary solution of acid chloride, preferably
0.05-0.5 weight %.The content of polynary acyl chlorides can specifically enumerate 0.025 weight %, 0.05 weight in the polynary solution of acid chloride
Measure %, 0.1 weight %, 0.2 weight %, 0.3 weight %, 0.4 weight %, 0.5 weight %, 0.6 weight %, 0.7 weight %,
0.8 weight %, 0.9 weight % or 1 weight % etc..
According to the present invention, to the curing accelerator, there is no particular limitation, can be commonly used in the art various
Curing accelerator.It such as can be phenolic cure accelerator or amine-type cure accelerator, preferably phenolic cure accelerator.As
The curing accelerator for example can be 2,4,6- tri- (dimethylamino methyl) phenol, phenol, o-cresol, metacresol, isophthalic two
Phenol, nonyl phenol, bisphenol-A, salicylic acid, benzyl dimethylamine, triethanolamine, bicyclic amidine, triethylamine, pyridine, N- 2-glycidyl benzene
Amine, N- 2-glycidyl para-totuidine, N- ethyl-N glycidol aniline, N- ethyl-N glycidol ortho-aminotoluene, tetraethyl
Ammonium bromide, tetrabutylammonium bromide, diethylenetriamine, triethylene tetramine, polyethylene polyamine, benzyl alcohol, 2,4- imidazoles, 1- benzyl-
One of 2- ethyl imidazol(e), 2-methylimidazole and 1- amino-ethyl 2-methylimidazole are a variety of；Preferably tri- (diformazan of 2,4,6-
Amino methyl) one of phenol, phenol, metacresol and resorcinol or a variety of.
In addition, for the concentration of curing accelerator, there is no particular limitation, can be the conventional selection of this field.For example,
The concentration of the curing accelerator described in the water phase containing polyamine, the ammonium salt containing epoxy group and curing accelerator can be
0.005-10 weight %, preferably 0.01-1 weight %.The concentration of the curing accelerator be specifically as follows 0.01 weight %,
0.03 weight %, 0.05 weight %, 0.1 weight %, 0.2 weight %, 0.3 weight %, 0.4 weight %, 0.5 weight %, 0.6 weight
Measure %, 0.7 weight %, 0.8 weight %, 0.9 weight %, 1 weight %, 2 weight %, 3 weight %, 4 weight %, 5 weight %, 6
Weight %, 7 weight %, 8 weight %, 9 weight % or 10 weight % etc..
According to the present invention, in the water phase containing polyamine, the ammonium salt containing epoxy group and curing accelerator, contain epoxy
The ammonium salt of group, the weight ratio of the dosage of curing accelerator and polyamine are 0.01-10:0.001-5:1, preferably 0.05-
5:0.01-1:1.It, can be with by using such water phase containing polyamine, the ammonium salt containing epoxy group and curing accelerator
The complex reverse osmosis membrane enable preferably has both excellent salt-stopping rate and higher water flux.
Dosage as the polyamine and the polynary acyl chlorides can change in a larger range, it is preferable that
The mass concentration ratio of the polyamine and the polynary acyl chlorides is 1-100:1, more preferably 5-50:1, further preferably 10-
40:1 is still more preferably 15-35:1, is still more preferably 18-25:1.As the polyamine and the polynary acyl chlorides
Mass concentration ratio can specifically enumerate: 15:1,16:1,17:1,18:1,19:1,20:1,21:1,22:1,23:1,24:1,
25:1 or 30:1 etc..
According to the present invention, to the condition of the interface polymerization reaction, there is no particular limitation, can be conventional for this field
Selection, for example, by supporting layer successively with the water phase containing polyamine, the ammonium salt containing epoxy group and curing accelerator and contain
In the case where having the solution of polynary acyl chlorides to be contacted, the time that supporting layer is contacted with the solution containing polyamine is 5-100s,
Preferably 10-60s (such as can be 10s, 20s, 30s, 40s, 50s or 60s)；Supporting layer connects with the solution containing polynary acyl chlorides
The time of touching is 5-100s, preferably 10-60s (such as can be 10s, 20s, 30s, 40s, 50s or 60s).When above-mentioned contact
Temperature can be 10-40 DEG C (such as can be 25 DEG C).
In the present invention, in order to enable to reverse osmosis membrane can preferably have both excellent anti-fouling performance, higher
Water flux and salt rejection rate, the preferably described polyamide separating layer with a thickness of 0.05-0.3 μm, more preferably 0.1-0.2 μm.As
The thickness of separating layer can specifically enumerate 0.005 μm, 0.01 μm, 0.02 μm, 0.03 μm, 0.04 μm, 0.05 μm, 0.06 μm, 0.07
μm, 0.08 μm, 0.09 μm, 0.1 μm, 0.2 μm or 0.3 μm etc..
A preferred embodiment according to the present invention, this method further include carrying out after taking out obtained reverse osmosis membrane
Heat treatment.
As the method for above-mentioned formation separating layer, it can specifically include following steps:
(1) supporting layer is contacted with the water phase containing polyamine, the ammonium salt containing epoxy group and curing accelerator, is arranged
Liquid；
(2) film that step (1) obtains is mixed with the organic phase containing polynary acyl chlorides, drain obtains compound reverse osmosis
Permeable membrane；
(3) complex reverse osmosis membrane is heat-treated.
In addition, the condition of the heat treatment includes: that heat treatment temperature is 40-150 DEG C, at heat when carrying out above-mentioned heat treatment
The reason time is 0.5-20min；Preferably, it is 50-120 DEG C that the condition of the heat treatment, which includes: heat treatment temperature, heat treatment time
For 1-10min.Here, heat treatment temperature for example can be 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C or 120
℃.The time of heat treatment for example can be 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min.
According to the present invention, for the supporting layer, there is no particular limitation, can be by existing various with centainly strong
It spends and the material that can be used in reverse osmosis membrane is made, it usually can be by polyester, polyacrylonitrile, Kynoar, the non-sulphur of phenolphthalein type
Change one of polyether sulphone, polyether sulfone and polysulfones or a variety of is made.In addition, the supporting layer can be single hole or porous knot
Structure.The supporting layer is preferably polysulfone porous supporting layer.
In the present invention, there is no particular limitation in source of the present invention to the polysulfone porous supporting layer, for example, can lead to
Commercially available acquisition is crossed, in situations where it is preferred, can also obtain using phase inversion self-control.Wherein, the phase inversion is ability
Known to field technique personnel, for example, gel method, thermal gels method can be evaporated for gas phase gel method, solvent or immerse gel method,
Preferably immerse gel method.In a preferred embodiment, by the way that the coating liquid containing polysulfones is coated in polysulfones counterdie
Then upper formation primary membrane converts supporting layer for the primary membrane using phase inversion, to obtain polysulfone porous supporting layer.
According to the present invention, the thickness of the supporting layer is not particularly limited, can is the usually used of this field
Thickness, but in order to enable each layer can play the role of better coordinated, the complex reverse osmosis membrane enable is more preferable
Have both excellent salt-stopping rate and higher water flux, in situations where it is preferred, the supporting layer with a thickness of 30-60 μm, more
Preferably 35-45 μm.As the thickness of supporting layer, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm or 60 μm etc. can be enumerated.
A preferred embodiment according to the present invention, this method further include another surface shape in the supporting layer
At enhancement layer.By forming the enhancement layer, it is not only more advantageous to the formation of supporting layer, and can also make compound reverse osmosis
Film has better mechanical property.There is no particular limitation to the enhancement layer by the present invention, can be the selection of this field routine,
For example, can be one of polyester layer, polyethylene layer and polypropylene layer or a variety of, preferably polyester layer, more preferably polyester
Nonwoven layer.From the point of view of capable of playing the role of better coordinated from each layer, it is preferable that the enhancement layer with a thickness of
50-100 μm, more preferably 60-80 μm.It as the thickness of enhancement layer, can specifically enumerate: 50 μm, 55 μm, 60 μm, 65 μm, 70 μ
M, 75 μm, 80 μm, 85 μm, 90 μm or 95 μm etc..
The present invention also provides the complex reverse osmosis membranes being prepared by preparation method provided by the present invention.
The present invention also provides by complex reverse osmosis membrane provided by the present invention and by preparation side provided by the present invention
Application of the complex reverse osmosis membrane of method preparation in water treatment field.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples:
(1) water flux of complex reverse osmosis membrane is tested obtain by the following method: complex reverse osmosis membrane is fitted into membrane cisterna,
It is described compound anti-in 1h being measured under pressure is 1.55MPa, under the conditions of temperature is 25 DEG C at 1.2MPa after precompressed 0.5 hour
The water transit dose of permeable membrane, and be calculated by the following formula to obtain:
J=Q/ (At), wherein J is water flux, and Q is water transit dose (L), and A is effective membrane area of complex reverse osmosis membrane
(m2), t is the time (h)；
(2) salt rejection rate of complex reverse osmosis membrane tests obtain by the following method: complex reverse osmosis membrane is fitted into membrane cisterna,
At 1.2MPa after precompressed 0.5h, under pressure is 1.55MPa, measure initial concentration in 1h under the conditions of temperature is 25 DEG C and be
The concentration of sodium chloride changes in the sodium chloride raw water solution and permeate of 2000ppm, and is calculated by the following formula to obtain:
R=(Cp-Cf)/Cp× 100%, wherein R is salt rejection rate, CpFor the concentration of sodium chloride in stoste, CfFor in permeate
The concentration of sodium chloride；
(3) the stain resistance test of reverse osmosis membrane:
The stain resistance of reverse osmosis membrane is tested as follows: reverse osmosis membrane being fitted into membrane cisterna, in 1.2MPa
After lower precompressed 0.5h, the water transit dose of reverse osmosis membrane in 1h is measured under the conditions of pressure is 1.55MPa, temperature is 25 DEG C, and lead to
It crosses following formula and water flux is calculated: Q1=J/ (At), wherein J is water transit dose (L), Q1For water flux (L/m2H), A
For effective membrane area (m of reverse osmosis membrane2), t is the time (h).It is to contain NaCl and cetyl three by loop test fluid exchange
(wherein the concentration of NaCl is 2000ppm to the mixed aqueous solution of methyl bromide ammonium, and the concentration of cetyl trimethylammonium bromide is
1000ppm), after running 6h under the conditions of pressure is 1.55MPa, temperature is 25 DEG C, pressure is 1.55MPa, temperature is 25 DEG C
Under the conditions of measure the water flux Q of reverse osmosis membrane2；It then, is 1.55MPa, temperature in pressure after rinsing reverse osmosis membrane 0.5h with clear water
Under the conditions of degree is 25 DEG C, water flux Q when circulation fluid is 2000ppmNaCl aqueous solution is measured3；The water flux of reverse osmosis membrane declines
Rate D is calculated by the following formula to obtain: D=(Q1-Q2)/Q1× 100%；Flux recovery rate H passes through reverse osmosis membrane after washing
Following formula is calculated: H=Q3/Q1× 100%.Wherein, water flux rate of descent is lower, flux recovery rate is higher, then shows
The anti-fouling performance of reverse osmosis membrane is better.
(4) thickness measurement: using the cross-section morphology of scanning electron microscope (model S4800) test diaphragm, and then film layer is obtained
Thickness.
In addition, in following embodiment and preparation example, 2,3- epoxypropyltrimethylchloride chlorides, 2,3- glycidyl, three second
Ammonium chloride, 1,2- glycidyl dimethyl dodecyl ammonium chlorides, diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygen
Base)] silicon propyl ammonium chloride, m-phenylene diamine (MPD), pyromellitic trimethylsilyl chloride, cetyl trimethylammonium bromide is purchased from lark prestige science and technology has
Limit company；Isopar E is purchased from Xi Long Chemical Co., Ltd.；Other chemical reagent are purchased from the limited public affairs of Chinese medicines group chemical reagent
Department.
Polysulfone porous supporting layer is made using phase inversion, the specific steps are as follows: by polysulfones (number-average molecular weight 80000)
It is dissolved in n,N-Dimethylformamide, the polysulfones solution that obtained concentration is 18 weight %, the standing and defoaming 120min at 25 DEG C, so
Afterwards, polysulfones solution is coated in using scraper with a thickness of initial film is obtained on 75 μm of polyester non-woven fabric, with i.e. by it in temperature
To impregnate 60min in 25 DEG C of water so that the polysulfones layer on polyester non-woven fabric surface through inversion of phases at perforated membrane, most afterwards through 3 water
It washes to obtain the polysulfone porous membrane that overall thickness is 115 μm (supporting layer is with a thickness of 40 μm).
Embodiment 1
The embodiment is for illustrating reverse osmosis membrane provided by the invention and preparation method thereof.
Polysulfone porous membrane upper surface (polysulfones layer surface, similarly hereinafter) is contacted into the m-phenylene diamine (MPD) aqueous solution containing 2 weight %, 1
2,4,6- tri- (dimethylamino methyl) phenol of 2, the 3- epoxypropyltrimethylchloride chloride of weight % and 0.1 weight %, 25
Drain after contact 10s at DEG C；Then, polysulfone porous membrane upper surface is contacted again containing 0.1 weight % pyromellitic trimethylsilyl chloride
Isopar E solution contacts drain after 10s at 25 DEG C；Then, film is put into baking oven, heats 5min at 70 DEG C, is answered
Close reverse osmosis membrane M1, wherein separating layer with a thickness of 115nm.
Embodiment 2
The embodiment is for illustrating complex reverse osmosis membrane provided by the invention and preparation method thereof.
Polysulfone porous membrane upper surface is contacted to the 2,3- epoxy third of the m-phenylene diamine (MPD) aqueous solution containing 2 weight %, 5 weight %
2,4,6- tri- (dimethylamino methyl) phenol of triethylammonium chloride and 0.5 weight % contact drain after 10s at 25 DEG C；
Then, polysulfone porous membrane upper surface is contacted into the Isopar E solution containing 0.1 weight % pyromellitic trimethylsilyl chloride again, is connect at 25 DEG C
Drain after touching 10s；Then, film is put into baking oven, heats 3min at 100 DEG C, obtain complex reverse osmosis membrane M2, wherein point
Absciss layer with a thickness of 118nm.
Embodiment 3
The embodiment is for illustrating complex reverse osmosis membrane provided by the invention and preparation method thereof.
Polysulfone porous membrane upper surface is contacted to the 1,2- epoxy of the m-phenylene diamine (MPD) aqueous solution containing 2 weight %, 0.5 weight %
2,4,6- tri- (dimethylamino methyl) phenol of propyl-dimethyl lauryl ammonium chloride and 0.05 weight % contact at 25 DEG C
Drain after 10s；Then, that polysulfone porous membrane upper surface is contacted the Isopar E containing 0.1 weight % pyromellitic trimethylsilyl chloride again is molten
Liquid contacts drain after 10s at 25 DEG C；Then, film is put into baking oven, heats 2min at 120 DEG C, obtains complex reverse osmosis membrane
M3, wherein separating layer with a thickness of 108nm.
Embodiment 4
The embodiment is for illustrating complex reverse osmosis membrane provided by the invention and preparation method thereof.
Prepare complex reverse osmosis membrane M4 according to the method for embodiment 1, institute the difference is that, with diethyl -2,3- epoxy
Propyl-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium chloride replaces 2,3- epoxypropyltrimethylchloride chloride, the thickness of separating layer
For 120nm.
Embodiment 5
The embodiment is for illustrating complex reverse osmosis membrane provided by the invention and preparation method thereof.
Prepare complex reverse osmosis membrane M5 according to the method for embodiment 1, institute the difference is that, with resorcinol replacement 2,4,
6- tri- (dimethylamino methyl) phenol.
Embodiment 6
The embodiment is for illustrating complex reverse osmosis membrane provided by the invention and preparation method thereof.
Prepare complex reverse osmosis membrane M6 according to the method for embodiment 1, institute the difference is that, with phenol replacement 2,4,6- tri-
(dimethylamino methyl) phenol.
Embodiment 7
The embodiment is for illustrating complex reverse osmosis membrane provided by the invention and preparation method thereof.
Prepare complex reverse osmosis membrane M7 according to the method for embodiment 1, institute the difference is that, with metacresol replacement 2,4,6-
Three (dimethylamino methyl) phenol.
Comparative example 1
Prepare complex reverse osmosis membrane DM1 according to the method for embodiment 1, institute the difference is that, without containing epoxy in water phase
The ammonium salt and curing accelerator of group, separating layer with a thickness of 110nm.
Comparative example 2
Prepare complex reverse osmosis membrane DM2 according to the method for embodiment 1, institute the difference is that, promote in water phase without solidification
Into agent, separating layer with a thickness of 113nm.
Test case
After reverse osmosis membrane obtained in above-described embodiment and comparative example is impregnated for 24 hours in water, pressure be 1.55MPa,
Temperature measures water flux Q under the conditions of being 25 DEG C1With the salt rejection rate to NaCl (2000ppm), the results are shown in Table 1.And same
Under the conditions of temperature and pressure, its stain resistance is tested, which is containing 2000ppmNaCl and 1000ppm cetyl ammonium bromide
Mixed aqueous solution in run 6h after measure its water flux Q2And water flux Q after washing3, it is reverse osmosis thus to calculate this
The water flux rate of descent and flux recovery rate of film, the results are shown in Table 1.
Table 1
It can be seen that reverse osmosis membrane provided by the invention water flux with higher by the result of above embodiments 1-7
And salt-stopping rate, also, there is stronger resistance tocrocking to ionic surfactant.In addition, preparation method provided by the invention
Simply, great prospects for commercial application.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (16)
1. a kind of reverse osmosis membrane, which includes supporting layer and polyamide separating layer, which is characterized in that the polyamide point
One surface of absciss layer is bonded with the supporting layer, and the polyamide separating layer, will be more by the presence of curing accelerator
First amine, the ammonium salt containing epoxy group carry out interfacial polymerization with polynary acyl chlorides and obtain.
2. reverse osmosis membrane according to claim 1, wherein the salt-stopping rate of the reverse osmosis membrane is 99% or more.
3. reverse osmosis membrane according to claim 1 or 2, wherein the polyamide separating layer with a thickness of 0.05-0.3 μm,
More preferably 0.1-0.2 μm；
Preferably, the supporting layer is polysulfone porous supporting layer；
Preferably, the supporting layer with a thickness of 30-60 μm, more preferably 35-45 μm.
4. reverse osmosis membrane according to claim 1 or 2, wherein the ammonium salt containing epoxy group is ammonium halide salt；
Preferably, the ammonium salt containing epoxy group is selected from 2,3- epoxypropyltrimethylchloride chloride, 2,3- glycidyl three
Ethyl ammonium chloride, 1,2- glycidyl dimethyl dodecyl ammonium chlorides, diethyl -2,3- glycidyl-[3- (methyl dimethoxy
Oxygroup)] silicon propyl ammonium chloride, 3- epoxy ammonium bromide, 2,3- glycidyl triethylammonium bromide, 1,2- epoxy third
Base dimethyl dodecyl base ammonium bromide, diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium bromide, 3-
Epoxy ammonium iodide, 2,3- glycidyl triethyl group ammonium iodide, 1,2- glycidyl dimethyl dodecyl base iodate
One or more of ammonium and diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium iodide；
Preferably, the ammonium salt containing epoxy group is selected from 2,3- epoxypropyltrimethylchloride chloride, 2,3- glycidyl three
Ethyl ammonium chloride, 1,2- glycidyl dimethyl dodecyl ammonium chlorides, diethyl -2,3- glycidyl-[3- (methyl dimethoxy
Oxygroup)] silicon propyl ammonium chloride, 3- epoxy ammonium bromide, 2,3- glycidyl triethylammonium bromide, 1,2- epoxy third
In base dimethyl dodecyl base ammonium bromide, diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium bromide
It is one or more kinds of；
It is highly preferred that the ammonium salt containing epoxy group is selected from 2,3- epoxypropyltrimethylchloride chloride, 2,3- glycidyl
Triethyl ammonium chloride, 1,2- glycidyl dimethyl dodecyl ammonium chlorides and diethyl -2,3- glycidyl-[3- (methyl two
One or more of methoxyl group)] silicon propyl ammonium chloride.
5. reverse osmosis membrane according to claim 1 or 2, wherein ammonium salt, curing accelerator containing epoxy group and polynary
The weight ratio of the dosage of amine is 0.01-10:0.001-5:1；
Preferably, the weight ratio of the dosage of polyamine and polynary acyl chlorides is 1-100:1；
Preferably, the polyamine is one of m-phenylene diamine (MPD), p-phenylenediamine, o-phenylenediamine, piperazine and equal benzene triamine or more
Kind, the polynary acyl chlorides is one of pyromellitic trimethylsilyl chloride, m-phthaloyl chloride and paraphthaloyl chloride or a variety of；
Preferably, the curing accelerator be selected from 2,4,6- tri- (dimethylamino methyl) phenol, phenol, o-cresol, metacresol,
Resorcinol, nonyl phenol, bisphenol-A, salicylic acid, benzyl dimethylamine, triethanolamine, bicyclic amidine, triethylamine, pyridine, N- bis- shrink
Glycerol aniline, N- 2-glycidyl para-totuidine, N- ethyl-N glycidol aniline, N- ethyl-N glycidol ortho-aminotoluene,
Tetraethylammonium bromide, tetrabutylammonium bromide, diethylenetriamine, triethylene tetramine, polyethylene polyamine, benzyl alcohol, 2,4- imidazoles, 1-
One of benzyl -2- ethyl imidazol(e), 2-methylimidazole and 1- amino-ethyl 2-methylimidazole are a variety of；2 are more preferably selected from,
One of 4,6- tri- (dimethylamino methyl) phenol, phenol, metacresol and resorcinol are a variety of.
6. reverse osmosis membrane according to claim 1 or 2, wherein the reverse osmosis membrane further includes enhancement layer, the enhancement layer with
Another surface of the supporting layer is bonded；
Preferably, the enhancement layer is one of polyester layer, polyethylene layer and polypropylene layer or a variety of, preferably polyester layer,
More preferably non-woven polyester layer of cloth；
Preferably, the enhancement layer with a thickness of 50-100 μm, more preferably 60-80 μm.
7. a kind of preparation method of reverse osmosis membrane, this method comprises: in the presence of curing accelerator, by supporting layer with it is polynary
Amine, the ammonium salt containing epoxy group are contacted with polynary acyl chlorides carries out interfacial polymerization formation separating layer, and makes described containing epoxy group
Epoxy group in ammonium salt is crosslinked with polyamide reacts.
8. preparation method according to claim 7, wherein the step of interfacial polymerization and the cross-linking reaction includes:
First the supporting layer is contacted with the water phase containing polyamine, the ammonium salt containing epoxy group and curing accelerator, then with contain
There is the organic of polynary acyl chlorides to be in contact.
9. preparation method according to claim 7, wherein containing polyamine, the ammonium salt containing epoxy group and solidification
In the water phase of promotor, the content of the polyamine is 0.5-10 weight %, preferably 1-5 weight %；
Preferably, the content of the ammonium salt containing epoxy group is 0.05-10 weight %, preferably 0.1-5 weight %；
Preferably, the content of the curing accelerator is 0.005-10 weight %, preferably 0.01-1 weight %；
Preferably, the weight ratio of the dosage of the ammonium salt containing epoxy group, curing accelerator and polyamine is 0.01-10:
0.001-5:1；
Preferably, in the organic phase containing polynary acyl chlorides, the content of the polynary acyl chlorides can be 0.025-1 weight %, excellent
It is selected as 0.05-0.5 weight %；
Preferably, the weight ratio of the dosage of polyamine and polynary acyl chlorides is 1-100:1.
10. the method according to any one of claim 7-9, wherein the ammonium salt containing epoxy group is ammonium halide
Salt；
Preferably, the ammonium salt containing epoxy group is selected from 2,3- epoxypropyltrimethylchloride chloride, 2,3- glycidyl three
Ethyl ammonium chloride, 1,2- glycidyl dimethyl dodecyl ammonium chlorides, diethyl -2,3- glycidyl-[3- (methyl dimethoxy
Oxygroup)] silicon propyl ammonium chloride, 3- epoxy ammonium bromide, 2,3- glycidyl triethylammonium bromide, 1,2- epoxy third
Base dimethyl dodecyl base ammonium bromide, diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium bromide, 3-
Epoxy ammonium iodide, 2,3- glycidyl triethyl group ammonium iodide, 1,2- glycidyl dimethyl dodecyl base iodate
One or more of ammonium and diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium iodide；
Preferably, the ammonium salt containing epoxy group is selected from 2,3- epoxypropyltrimethylchloride chloride, 2,3- glycidyl three
Ethyl ammonium chloride, 1,2- glycidyl dimethyl dodecyl ammonium chlorides, diethyl -2,3- glycidyl-[3- (methyl dimethoxy
Oxygroup)] silicon propyl ammonium chloride, 3- epoxy ammonium bromide, 2,3- glycidyl triethylammonium bromide, 1,2- epoxy third
In base dimethyl dodecyl base ammonium bromide, diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium bromide
It is one or more kinds of；
It is highly preferred that the ammonium salt containing epoxy group is selected from 2,3- epoxypropyltrimethylchloride chloride, 2,3- glycidyl
Triethyl ammonium chloride, 1,2- glycidyl dimethyl dodecyl ammonium chlorides and diethyl -2,3- glycidyl-[3- (methyl two
One or more of methoxyl group)] silicon propyl ammonium chloride.
11. the method according to any one of claim 7-9, wherein the curing accelerator promotees selected from phenolic cure
Into agent and/or amine-type cure accelerator；
Preferably, the curing accelerator be selected from 2,4,6- tri- (dimethylamino methyl) phenol, phenol, o-cresol, metacresol,
Benzenediol, nonyl phenol, bisphenol-A, salicylic acid, benzyl dimethylamine, triethanolamine, bicyclic amidine, triethylamine, pyridine, N- bis- shrink sweet
Oily aniline, N- 2-glycidyl para-totuidine, N- ethyl-N glycidol aniline, N- ethyl-N glycidol ortho-aminotoluene, four
Ethyl phosphonium bromide ammonium, tetrabutylammonium bromide, diethylenetriamine, triethylene tetramine, polyethylene polyamine, benzyl alcohol, 2,4- imidazoles, 1- benzyl
One of base -2- ethyl imidazol(e), 2-methylimidazole and 1- amino-ethyl 2-methylimidazole are a variety of.
12. the method according to any one of claim 7-9, wherein this method includes that the reverse osmosis membrane that will be obtained takes
It is heat-treated after out；
Preferably, it is 40-150 DEG C, preferably 50-120 DEG C that the condition of the heat treatment, which includes: temperature,；
Preferably, the condition of the heat treatment include: the time be 0.5-20min, preferably 1-10min.
13. the method according to any one of claim 7-9, wherein the supporting layer is by polyester, polyacrylonitrile, poly-
One of the non-sulfonated polyether sulphone of vinylidene, phenolphthalein type, polyether sulfone and polysulfones a variety of are made.
14. the method according to any one of claim 7-9, wherein this method further includes in the another of the supporting layer
One surface forms enhancement layer；
Preferably, the enhancement layer is one of polyester layer, polyethylene layer and polypropylene layer or a variety of, preferably polyester layer,
More preferably non-woven polyester layer of cloth；
Preferably, the enhancement layer with a thickness of 50-100 μm, more preferably 60-80 μm.
15. the reverse osmosis membrane that the method as described in any one of claim 7-14 is prepared.
16. application of the reverse osmosis membrane in water treatment procedure described in any one of claim 1-6 and 15.
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| CN112844079A (en) * | 2020-12-29 | 2021-05-28 | 宁波日新恒力科技有限公司 | Modified polysulfone porous supporting layer for reverse osmosis composite membrane, preparation method of modified polysulfone porous supporting layer and quaternized polysulfone modified reverse osmosis composite membrane |
| CN115445458A (en) * | 2022-09-16 | 2022-12-09 | 北京碧水源膜科技有限公司 | Nanofiltration membrane for magnesium-lithium separation and preparation method thereof |
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