CN105709619B - A kind of positively charged nanofiltration membranes and preparation method thereof - Google Patents
A kind of positively charged nanofiltration membranes and preparation method thereof Download PDFInfo
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- CN105709619B CN105709619B CN201410730312.8A CN201410730312A CN105709619B CN 105709619 B CN105709619 B CN 105709619B CN 201410730312 A CN201410730312 A CN 201410730312A CN 105709619 B CN105709619 B CN 105709619B
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Abstract
The invention discloses a kind of positively charged nanofiltration membranes and preparation method thereof.The main component of the positively charged nanofiltration membranes is the selfing co-product of tertiary amine-type chlorine-containing copolymer A or the product of chlorine-containing polymer B and tertiary amine-type polymer C blended cross linking.The positively charged nanofiltration membranes the preparation method comprises the following steps: (1) by tertiary amine-type chlorine-containing copolymer A, or chlorine-containing polymer B, tertiary amine-type polymer C are dissolved in casting solution, quaternized inhibitor is added, it is uniformly mixed and preparation liquid is made, solidified from coagulating bath by solution phase inversion, is prepared into active precursor film；(2) active precursor film obtained is heat-treated, obtains positively charged nanofiltration membranes.Plate membrane or hollow-fibre membrane can be made in the present invention, and Membrane properties and structure controllability is strong in preparation process, simple process, and manufacturing cost is low, cleanly production can be achieved, and has good industrial prospect.
Description
Technical field
The invention belongs to technical field of membrane separation, in particular to a kind of preparation method of positively charged nanofiltration membranes.
Background technique
Membrane separation technique have many advantages, such as high-efficient, equipment be simple and convenient to operate, energy conservation and environmental protection, shown in industrial circle
Great application potential out, application range have expanded to the neck such as biology, medicine, environmental protection, the energy, sea water desalination, wastewater treatment
Domain.Nanofiltration (Nanofiltration, abbreviation NF) is a kind of membrane separation technique between reverse osmosis (RO) and ultrafiltration (UF),
It is one of the hot spot of current world's water treatment field research.Typical nanofiltration membrane has feature below: (1) nanofiltration membrane is generally all
It is composite membrane, is made of supporting layer and dense functional layer, the cutoff performance and flux of nanofiltration membrane depends on dense functional layer.(2)
For the relative molecular weight (200~2000) of retention substance between reverse osmosis between ultrafiltration, membrane aperture is about 1nm.(3) retention of film
Performance is had different rejections to the ion of different valence state, usually to list by aperture sieve effect and electric charging effect joint effect
Valence ion (NO3 -、Cl-、Na+、K+) rejection it is lower (30-50%), to high valence ion (PO4 3-、SO4 2-、Mg2+、Ca2+) cut
Stay rate higher (90% or so).(4) operating pressure is lower than reverse osmosis required pressure, general operating pressure 0.8~
Between 2.0MPa.It is in food industry, chemical and medicine industry industry, Drinking Water Industry, before there is wide application in the fields such as wastewater treatment
Scape.
The preparation method of commercialization nanofiltration membrane is to be with sulfonated polysulfone (SPS), sulfonated polyether sulfone (SPES) ultrafiltration membrane at present
Supporting layer (basement membrane), being formed by interfacial polymerization on surface layer has polyamide (PA) dense functional layer in nanofiltration aperture to obtain
Nanofiltration membrane with double-layer structure.Interfacial polymerization is first to coat the aqueous solution of one layer of polyamine in support film surface, is then applied again
The organic solution for covering one layer of polynary acyl chlorides prepares polyamide dense functional layer with reacting for polynary acyl chlorides using polyamine.It is existing
There is technology using the method that interfacial polymerization method, surface coat to prepare nanofiltration membrane, nanofiltration membrane obtained is divided into supporting layer and cause
The double-layer structure of close functional layer uses different polyamines for water if Chinese patent CN102423643B and CN101254419B
Mutually coating basement membrane, the basement membrane are supporting layer；It then is that oil mutually carries out being cross-linked to form dense functional layer with polynary acyl chlorides.Its deficiency
Be in: first under higher operating pressure, existing monofilm, which is unable to reach, has both preferable cutoff performance and high throughput
Requirement, the monofilm of existing good mechanical property is unable to satisfy the cutoff performance of nanofiltration membrane；The good list of existing cutoff performance
Tunic, is unable to satisfy the requirement of nanofiltration membrane mechanical performance, and film is easy to the deformation that is crushed, membrane structure is caused to be destroyed.In order to maintain
The stability of membrane structure and meet cutoff performance simultaneously, it has to using the two layer composite structure of supporting layer and dense functional layer
Film, to meet the requirement of nanofiltration membrane mechanical performance and cutoff performance, to greatly improve manufacturing cost.And existing ultrafiltration
Film and microfiltration membranes can use monofilm, be since both films do not need to retain ion, it is only necessary to retain macromolecule
The substance (molecular weight > 10,000) of amount, cutoff performance require well below nanofiltration membrane cutoff performance, and its aperture it is larger (>
10nm), (usually 0.01-0.1MPa) is just able to satisfy high-throughput requirement under very low operating pressure, so need not specially adopt
With supporting layer come the mechanical performance of reinforced film.
The prior art is also resided in using the shortcoming of interfacial polymerization method preparation nanofiltration membrane, polynary using water phase when molding
Amine and oily phase acyl chlorides successively coat, and carry out cross-linking reaction to provide fine and close dense functional layer, complex steps, and react gained
To there was only physisorption, not no high forces of chemical bond, in conjunction with unstable, film knot between dense functional layer and supporting layer
Structure is very easy to be destroyed when cleaning.Finally, meeting thicker by the dense functional layer that interfacial polymerization or surface cladding process construct
The flux for reducing nanofiltration membrane, will obtain higher flux, must just improve using pressure, necessarily will increase operating cost.In addition,
Polyamide dense functional layer type prepared by existing commercialization nanofiltration membrane is single, and majority prepares plate membrane, operation
Shi Caiyong rolled membrane module, not easy cleaning after pollution.Therefore, it set off in search and is realized in terms of material selection and film build method two
The preparation of low cost, high-performance nanofiltration membrane is the main outlet of Nanofiltration-membrane technique development.
Summary of the invention
In view of the deficiencies of the prior art, technical problem to be solved by the invention is to provide a kind of positively charged nanofiltration membranes and its
Preparation method.Provided positively charged nanofiltration membranes, can under very low operating pressure (0.3MPa), can efficiently remove divalent from
Son (MgSO4Rejection > 98%) and solute of the molecular weight higher than 200, and to monovalent ion (NaCl) and low molecular weight substance
Retention be higher than 50%, while being also able to maintain very high flux (> 40L/m2/h).Positively charged nanofiltration membranes provided by the present invention
Preparation method, be film-made using being first blended, then the method for carrying out quaternized crosslinking.The quaternary ammonium chloride generated after quaternized crosslinking
Group not only provides charge, also good hydrophily and excellent mechanical performance is provided for film, completely without tradition
Interfacial polymerization nanofiltration membrane double-layer structure design, it is only necessary to monofilm has just reached excellent service performance.Due to preparing work
The unicity of skill simplicity and membrane structure greatly increases the stability of the positively charged nanofiltration membrane structure and performance, thus
Using survivable with wash phase, the service life is longer, is suitable for a variety of embrane method water treatment facilities and engineering.
Different from the prior art, positively charged nanofiltration membranes provided by the invention, improving, nanofiltration membrane is high performance simultaneously, solves
Some problems of the existing technology:
(1) method of the prior art is needed such as polymer nano filter membrane prepared by interfacial polymerization using double membrane structure,
Only has physisorption between middle supporting layer and dense functional layer, without stronger active force, membrane structure is easily destroyed, to property
It can cause unstability；And positively charged nanofiltration membranes of the present invention are only made of a kind of cross-linked polymer, are single-layer membrane structure,
Preferable cutoff performance and high-throughput requirement are had both, can satisfy the needs of nanofiltration process.Thus, there is no existing nanofiltration membranes
Supporting layer and dense functional layer stripping problem, guarantee that the performance of film is stablized in use process, there is longer service life.It will
Polymer nano filter membrane of the invention is placed in 60 DEG C of deionized waters isothermal vibration 20 days, and flux and cutoff performance remain unchanged.
(2) method of the prior art, such as polymer nano filter membrane prepared by interfacial polymerization, dense functional layer is excessively fine and close, film
Hydrophily is poor, causes the flux of nanofiltration membrane lower, it is necessary to when with just application is able to satisfy under high operating pressure (0.8~2MPa)
Throughput requirements, this is also that it must be using supporting layer come the reason of enhancing crushing resistance, and higher operating pressure then can be very big
Ground improves operating cost；And single layer positively charged nanofiltration membranes of the present invention and it is existing include supporting layer and dense functional layer
Nanofiltration membrane cutoff performance having the same provide excellent hydrophilic and due to containing quaternary ammonium chloride and tertiary amine group
Performance, so that positively charged nanofiltration membranes of the present invention can reach very high infiltration at lower pressure (such as 0.3MPa)
Flux (> 40L/m2H), much higher than the nanofiltration membrane of conventional method preparation, separative efficiency is improved, operating cost is reduced.
(3) method of the prior art, such as polymer nano filter membrane prepared by interfacial polymerization, the polyamine and acyl chlorides of use are carried out
It is cross-linked to form dense functional layer, this cross-linking reaction functions only as the effect of dense functional layer, there was only physical absorption work with support membrane
With, and the crosslinking of the selfing co-product of positively charged nanofiltration membranes of the present invention or tertiary amine and chlorine in blended cross linking product is then simultaneously
Have the function of three aspects, is to convert chemical crosslinking effect for physical entanglement effect between macromolecular first, to assign film
Excellent mechanical performance generates quaternary ammonium chloride salt groups during being followed by crosslinked, this group has positive charge, assigns film
Charge improves the cutoff performance and antifouling property of film, finally, crosslinking generate quaternary ammonium chloride also provided for film it is good
Good hydrophily, makes film possess higher flux under compared with ow operating pressure (such as 0.3MPa).
(4) method of the prior art, the supporting layer such as polymer nano filter membrane prepared by interfacial polymerization, in double membrane structure
Mainly with sulfonated polysulfone (SPS), sulfonated polyether sulfone (SPES) ultrafiltration membrane, such material price is high, increases the raw material of film itself
Cost.And positively charged nanofiltration membranes of the present invention use single-layer membrane structure, do not need supporting layer, receiving compared with the prior art
Cost is reduced 60% by filter membrane.
The present invention adopts the following technical scheme that:
A kind of positively charged nanofiltration membranes, the material of the nanofiltration membrane are the selfing co-product or chlorine-containing polymer of copolymer A
The product of B and tertiary amine-type polymer C blended cross linking, the crosslinked group in cross-linking products are quaternary ammonium chloride salt groups, wherein
The structural formula of the copolymer A is as follows:
In formula: m+n=800~5000, preferably m+n=1000~3000；
M/n=10/1~1/1；
R1=H or Cl；
R2=H or CH3；
R3=contain tertiary amine group；
The structural formula of the chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=800~5000, preferably x=1000~3000；
The structural formula of the tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=contain tertiary amine group；
Y=800~5000, preferably y=1000~3000.
Two kinds of cross-linked polymers provided by the invention are all to carry out quaternization reaction realization by tertiary amine group and chlorine, for
While nanofiltration membrane provides lotus positive electricity performance, cross-linked network is also constructed.This enhances the charge of nanofiltration membrane simultaneously
Repelling effect and aperture sieving actoion.
The positively charged nanofiltration membranes can be copolymer A self-crosslinking and be formed, cross-linking process schematic diagram such as Fig. 1.It is described
Copolymer A contain-Cl and tertiary amine Liang Zhong functional group simultaneously, self-crosslinking reaction twines the physics of copolymer chain molecule of the same race
Knot effect is converted into netted chemical cross-linked structure, and excellent mechanical performance is provided for nanofiltration membrane, is provided in film use process
The close performance of resistance to compression.Also, the self-crosslinking reaction is also quaternization reaction, forms quaternary ammonium chloride salt groups and is provided for positive electricity
Lotus assigns film charge, improves the cutoff performance and antifouling property of film, finally, it is also film that crosslinking, which generates quaternary ammonium chloride,
Good hydrophily is provided, film is made to possess higher flux under compared with ow operating pressure (such as 0.3MPa).
The positively charged nanofiltration membranes are also possible to the crosslinked action of two kinds of polymer interchain, and cross-linking process schematic diagram is such as
Fig. 2.Wherein tertiary amine-type polymer C provides tertiary amine group and excellent hydrophilicity, and containing using polyvinyl chloride as representative
Chlorine polymer B is cheap, and chemical stability is good, acid and alkali-resistance, chemical attack, has excellent mechanical strength, in Shui Chu
The multiple fields such as reason, biological medicine are widely used.Pass through quaternized cross-linking reaction after both polymer chains are blended
The cross-linked polymer of generation not only has excellent hydrophilicity but also chemical stability is good, acid and alkali-resistance, resistant to chemical etching, has
Excellent mechanical strength, and the crosslinking of tertiary amine and chlorine is to convert chemical crosslinking for physical entanglement effect between macromolecular first
Effect generates quaternary ammonium chloride salt groups during being followed by crosslinked, this group band to assign film excellent mechanical performance
There is positive charge, assign film charge, improve the cutoff performance and antifouling property of film, finally, crosslinking generates quaternary ammonium chloride
Good hydrophily also is provided for film, film is made to possess higher flux under compared with ow operating pressure (such as 0.3MPa).
Preferably, chlorine-containing polymer B of the present invention is the product of vinyl-type fluorochemical monomer polymerization, the tertiary amine-type
Polymer C is the product of vinyl-type tertiary amine monomers polymerization, and the copolymer A is vinyl-type fluorochemical monomer and vinyl-type uncle
The product of amine monomers copolymerization.
Preferably, any one of vinyl-type fluorochemical monomer of the present invention in vinyl chloride, vinylidene chloride
Or it is any a variety of, the vinyl-type tertiary amine monomers are selected from dimethylaminoethyl methacrylate, methacrylic acid diethylamino
Base ethyl ester, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylamino
Propylacrylamide, 4-vinylpridine, 2- vinylpyridine, any one in vinyl imidazole.
Preferably, the quaternary ammonium chloride salt groups are selected from following structural formula:
In formula: R=CH3Or CH2CH3。
Preferably, the mass percentage of the quaternary ammonium chloride salt groups is 2%~10%.
The present invention also provides a kind of preparation method of positively charged nanofiltration membranes, positively charged nanofiltration membranes made from this method are altogether
The selfing co-product of polymers A, includes the following steps:
(1) copolymer A is dissolved in casting solution, quaternized inhibitor is added, be uniformly mixed and preparation liquid is made, pass through
Solution phase inversion solidifies from coagulating bath, is prepared into active precursor film；
(2) active precursor film made from step (1) is heat-treated, obtains positively charged nanofiltration membranes；
The structural formula of the copolymer A is as follows:
In formula: m+n=800~5000, preferably m+n=1000~3000；
M/n=10/1~1/1；
R1=H or Cl；
R2=H or CH3；
R3=contain tertiary amine group.
Preferably, copolymer A described in step (1) is copolymerized by vinyl-type fluorochemical monomer and vinyl-type tertiary amine monomers
Product.It is furthermore preferred that the vinyl-type fluorochemical monomer in vinyl chloride, vinylidene chloride any one or it is any
It is a variety of, the vinyl-type tertiary amine monomers be selected from dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate,
Dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylamino-propyl propylene
Amide, 4-vinylpridine, 2- vinylpyridine, any one in vinyl imidazole.
Preferably, quaternized inhibitor described in step (1) be selected from diethyl ether, methylene chloride, acetone, methanol, ethyl alcohol,
In pentane, pentamethylene any one or it is any a variety of, the concentration of the quaternized inhibitor be mass percentage 0~
10wt%.
Preferably, be made described in step (1) preparation liquid temperature be 5~50 DEG C, the coagulation bath temperature be 5~
50℃。
Preferably, heat treatment temperature described in step (2) is 50~120 DEG C, and heat treatment time is 1~24 hour.
Preferably, heat treatment method described in step (2) is that dry film is directly heat-treated or by film through Glycerine-Aqueous Solution
Or glycerol-ethylene glycol solution it is processed after one of be heat-treated again.
Preferably, the quaternary ammonium chloride salt groups are selected from following structural formula:
In formula: R=CH3Or CH2CH3。
Preferably, the mass percentage of the quaternary ammonium chloride salt groups is 2%~10%.
The present invention also provides a kind of preparation method of positively charged nanofiltration membranes, positively charged nanofiltration membranes made from this method are to contain
The product of chlorine polymer B and tertiary amine-type polymer C blended cross linking, includes the following steps:
(1) chlorine-containing polymer B and tertiary amine-type polymer C are dissolved in casting solution, quaternized inhibitor is added, mixed
Preparation liquid uniformly is made, is solidified from coagulating bath by solution phase inversion, is prepared into active precursor film；
(2) active precursor film made from step (1) is heat-treated, obtains positively charged nanofiltration membranes；
The structural formula of the chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=800~5000, preferably x=1000~3000；
The structural formula of the tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=contain tertiary amine group；
Y=800~5000, preferably y=1000~3000.
Preferably, chlorine-containing polymer B described in step (1) is the product being polymerize by vinyl-type fluorochemical monomer, the uncle
Amine type polymer C is the product being polymerize by vinyl-type tertiary amine monomers.It is furthermore preferred that vinyl-type list containing chlorine of the present invention
Body in vinyl chloride, vinylidene chloride any one or it is any a variety of, the vinyl-type tertiary amine monomers are selected from methyl
Dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, acrylic acid lignocaine second
Ester, dimethylaminopropyl methacrylamide, dimethylamino propyl acrylamide, 4-vinylpridine, 2- vinylpyridine, ethylene
Any one in base imidazoles.
Preferably, quaternized inhibitor described in step (1) be selected from diethyl ether, methylene chloride, acetone, methanol, ethyl alcohol,
In pentane, pentamethylene any one or it is any a variety of, the concentration of the quaternized inhibitor be mass percentage 0~
10wt%.
Preferably, be made described in step (1) preparation liquid temperature be 5~50 DEG C, the coagulation bath temperature be 5~
50℃。
Preferably, heat treatment temperature described in step (2) is 50~120 DEG C, and heat treatment time is 1~24 hour.
Preferably, heat treatment method described in step (2) is that dry film is directly heat-treated or by film through Glycerine-Aqueous Solution
Or glycerol-ethylene glycol solution it is processed after one of be heat-treated again.
Preferably, the quaternary ammonium chloride salt groups are selected from following structural formula:
In formula: R=CH3Or CH2CH3。
Preferably, the mass percentage of the quaternary ammonium chloride salt groups is 2%~10%.
Crosslinked polymer is in a kind of effective ways for improving polymer strength.Pass through cross-linking reaction, polymer macromolecule
Chemistry occurs between chain to tangle, keeps polymer insoluble, does not melt, can raising polymer in various degree mechanical property,
Heat-resistant stability, wearability, solvent resistance and creep resistance etc..Therefore, polymer film is mentioned using the method for crosslinked polymer
High filtration film dynamic performance is a kind of effective method.It is worth noting that, crosslinked polymer process can only occur in filter membrane
After molding.But if crosslinked polymer occurs in film-forming process, it will affect the preparation of filter membrane.Mistake primarily now
Filter membrane preparation method includes fusion drawn method, non-solvent induction phase separation method, thermally induced phase separation etc..No matter which kind of method,
Have a liquid condition during forming solid-state filter membrane: fusion drawn method is melt, and both rear is solution.Obviously,
Cross-linked polymer can not form uniform melt or solution, thus can not prepare filter membrane.Therefore, how in film-forming process
Polymer does not crosslink, and film forming post-consumer polymer crosslink be one prepare crosslinking polymer film need solve
Problem.Preparation method of the present invention is during configuring preparation liquid in response to this problem, in order to prevent tertiary amine group and chlorine
Quaternized cross-linking reaction occurs in configuration preparation liquid and film-forming process, quaternized inhibitor is added.And quaternized inhibitor
Addition depend on preparation liquid configure temperature, preparation liquid temperature or film temperature be higher than 25 DEG C when, need that 0.5- is added
The quaternized inhibitor of 10wt%.
Positively charged nanofiltration membranes of the present invention can be made various forms of films, including plate membrane, hollow-fibre membrane.
The method of solution inversion of phases preparation plate membrane may is that preparation liquid in stainless steel carrier, glass carrier or nonwoven
Liquid film, and film-forming in the coagulating bath of 5~50 DEG C of immersion are spread on cloth.Solution inversion of phases prepares the method for hollow-fibre membrane such as
Under: preparation liquid is squeezed out from spinning head with the pressure of 0.1~0.3Mpa, while 5~50 DEG C of core liquid is with 10~50ml/min
Flow velocity flowed out from the central tube of spinning head, liquid film immerses behind 0~20 centimetre of the air gap in 5~50 DEG C of coagulating bath
Film-forming.
During solution inversion of phases, due to the effect of hydrophilic component so that tertiary amine group copolymerization component or polymer to
Film surface (coagulating bath one end) migration, so that enrichment phenomenon occurs in the surface in film.According to the detailed process of solution inversion of phases,
This enrichment phenomenon can also occur on the hole wall in membrane body.Due to the appearance of this enrichment phenomenon, make active precursor film
Surface and internal channel surfaces all contain more tertiary amine group, provide for the nanofiltration film surface lotus positive electricity after quaternization reaction
Possibility.
The beneficial effect of the present invention compared with prior art has:
Only a kind of cross-linked polymer composition of positively charged nanofiltration membranes disclosed by the invention, creative uses monofilm knot
Structure guarantees that the performance of film is stablized, there is longer use there is no the stripping problem of supporting layer and dense functional layer in use process
Service life.
Positively charged nanofiltration membranes disclosed by the invention, entanglement and further quaternized crosslinking due to polymer chain itself are made
With, chemical crosslinking effect is converted by physical entanglement effect between macromolecular, thus assign film excellent mechanical performance, guarantee film
Composition, stable structure, assign the longer service life of film.
Positively charged nanofiltration membranes disclosed by the invention and general polymer nano filter membrane separating property having the same, and by
In containing quaternary ammonium chloride and tertiary amine group, excellent hydrophilicity is provided, so that positively charged nanofiltration membranes of the present invention
Very high permeation flux (> 40L/m can be reached at lower pressure (such as 0.3MPa)2H), it is much higher than conventional method system
Standby nanofiltration membrane, improves separative efficiency, reduces operating cost.
Positively charged nanofiltration membranes disclosed by the invention generate quaternary ammonium chloride salt groups during crosslinking, this group has
Positive charge assigns film charge, improves the cutoff performance and antifouling property of film.
The preparation method of positively charged nanofiltration membranes disclosed by the invention, the method that film forming uses disposable solution inversion of phases, at
Quaternized crosslinking is carried out after film, this makes in preparation process, and Membrane properties and structure controllability is strong, simple process, and manufacturing cost is low, can
Realize cleanly production.
Detailed description of the invention
Fig. 1 is the quaternized schematic diagram of polymer A self-crosslinking of embodiment 1；
Fig. 2 is that the chlorine-containing polymer B and tertiary amine-type polymer C of embodiment 2 are crosslinked quaternized schematic diagram；
Fig. 3 is active precursor film made from embodiment 1 and receives further across plate obtained after heat treatment cross-linking reaction
The upper surface of filter membrane, lower surface, section electron microscope；
Fig. 4 be active precursor film made from embodiment 2 and further across heat treatment cross-linking reaction after hollow fibre obtained
The section of wiener filter membrane, inner surface, outer surface electron microscope.
Specific embodiment
Below with specific embodiment the present invention will be described in detail positively charged nanofiltration membrane preparation method.The implementation of all embodiments walks
Rapid identical as implementation steps described in summary of the invention, parameter is every implementation condition and obtains membrane structure and performance in table.
It should be noted that the embodiment is not construed as limiting the invention, those skilled in the art can be from public affairs of the invention
All deformations that the content opened directly is exported or associated, are considered as protection scope of the present invention.
Synthetic example 1
Copolymer A series (A1-A9) synthesis:
By taking copolymer A 1 as an example, 10g dimethylaminoethyl methacrylate and 100g vinyl chloride are mixed, 1.03g is added
Initiator azodiisobutyronitrile (AIBN), reacted 7 hours at 85 DEG C, obtain the following dimethylaminoethyl acrylate methyl ammonia of structural formula
The copolymer (A1) of base ethyl ester and vinyl chloride:
In formula: m+n=800
M/n=10/1
R1=H
R2=CH3
R3=COOCH2CH2N(CH3)2
Other A2-A9 are obtained using identical synthesis process, formula and technique such as table H1-1, in obtained polymer formulae
Parameter such as table H1-2.
Table H1-1
Table H1-2:
Synthetic example 2
Polymer C serial (C1-C9) synthesis:
By taking polymer C1 as an example, 100g dimethylaminoethyl methacrylate is dissolved in 500g water, the initiation of 1.03g is added
Agent ammonium persulfate reacts 5 hours at 70 DEG C, obtains the following dimethylaminoethyl methacrylate polymer of structural formula
(C2):
In formula:
R2=CH3
R3=COOCH2CH2N(CH3)2
Y=800
Other polymers C2-C9 is obtained using identical synthesis process, formula and technique such as table H1-1, obtained polymer knot
Parameter such as table H1-2 in structure formula.
Table H1-1
Table H1-2:
The characterizing method of positively charged nanofiltration membrane structure and performance:
The structure and pattern of film: with scanning electron microscope (JSM-5510LV, Japan) observation film microscopic appearance.
The measurement of water flux, cutoff performance and stability:
1, water flux: using pure water as feeding liquid, measuring the osmotic water flux of nanofiltration membrane, logical according to unit time unit area
The volume for crossing film calculates the flux of film；
2, cutoff performance: with the NaCl of 1g/L, MgSO4,Congo red solution is feeding liquid, passes through measurement feeding liquid and exudation
The conductivity or ultraviolet spectra of liquid release related concentrations, and the rejection of film is calculated according to feeding liquid and diffusate concentration proportion.It surveys
Strip part are as follows: 25 DEG C of temperature, pressure 0.3MPa；
3, stability: film is placed in 60 DEG C of deionized waters isothermal vibration 20 days, retest flux and cutoff performance.
Embodiment 1
By mass percentage be 20% A1 and mass percentage be 1% acetone be dissolved in DMAC N,N' dimethyl acetamide
It is mixed and made into preparation liquid, preparation liquid is spread into liquid film, and film-forming in the water of 10 DEG C of immersion, obtained plate membrane are impregnated through water
Cleaning, obtains active precursor film.It is heat-treated 10 hours at 80 DEG C after the active precursor film of preparation is dried, obtains lotus positive level
Plate nanofiltration membrane.
It is film-made formula of liquid, preparation condition and membrane structure and performance is as shown in table 1.
Table 1
Attached drawing 3 is for active precursor film made from the present embodiment and further across plate obtained after heat treatment cross-linking reaction
The upper surface of nanofiltration membrane, lower surface, section electron microscope.There are a large amount of micropores for being greater than 100nm in the upper surface of active precursor film.And it passes through
The aperture of nanofiltration membrane upper surface obtained is reduced to 1nm after Overheating Treatment cross-linking reaction, and surface texture is still finer and close, uniform, reaches
To nanofiltration rank.And in terms of the section structure of film, there is no apparent cross-linked structure as active precursor film, and after Overheating Treatment
Nanofiltration membrane obtained has apparent cross-linked structure, assigns the function of the excellent mechanical performance of film and high retention.
Plate nanofiltration membrane made from the present embodiment is under 25 DEG C, the test condition of 0.3MPa, pure water flux 44.4L/
m2H, the NaCl solution rejection to 1g/L is 51.2%, to the MgSO of 1g/L4Solution rejection is 99.1%, to the rigid of 1g/L
Arnotto rejection is 99.9%, film is placed in 60 DEG C of deionized waters isothermal vibration 20 days, flux and cutoff performance are kept substantially
It is constant.
Comparative example 1
By mass percentage be 20% A1 and mass percentage be 1% acetone be dissolved in DMAC N,N' dimethyl acetamide
It is mixed and made into preparation liquid, preparation liquid is spread into liquid film, and film-forming in the water of 10 DEG C of immersion, obtained plate membrane are impregnated through water
Cleaning, obtains active precursor film.Plate membrane is obtained after the active precursor film of preparation is dried.Be film-made formula of liquid, preparation condition and
Membrane structure and performance are as shown in table 1-1.
Table 1-1
Comparing embodiment 1 and comparative example 1, since comparative example is not heat-treated, so nothing in membrane structure
Cross-linked state, cutoff performance can not reach the performance requirement of nanofiltration membrane, there was only 10.2% rejection to monovalent salt NaCl, to two
Valence salt MgSO4Also there was only 34.1% rejection.And after shaking 20 days, cutoff performance further declines, and due to not handing over
Connection causes mechanical performance bad, and the decaying of flux is also very big.Thus the necessity it can be concluded that heat treatment step is compared, and
Cross-linking reaction plays very crucial effect to film properties.
Comparative example 2
The m-phenylene diamine (MPD) aqueous solution that mass percentage is 2% is applied on polyether sulfone flat support film, after draining, leaching
Enter in 0.5% pyromellitic trimethylsilyl chloride hexane solution, takes out and dry after placement 1min, in 70 DEG C of heat treatment 15min, obtain bilayer
The plate nanofiltration membrane of structure.
Film properties are as shown in table 1-2.Wherein water flux and rejection are tested, and are carried out in the case where 1.2MPa has pressure.
Table 1-2
Comparing embodiment 1 and comparative example 2, comparative example 2 prepare double-layer structure using traditional interfacial polymerization
Plate nanofiltration membrane, when the operating pressure for needing 1.2MPa, can be only achieved flux is 38.4L/m2H, in the operation pressure of 0.3MPa
Flux very little under power is not able to satisfy the operation requirement of nanofiltration.In addition, being decreased obviously to the rejection of salt, explanation after concussion 20 days
Dense functional layer and support Coating combination are insecure, lead to the unstable of cutoff performance.And plate nanofiltration prepared by the present invention
Film operating pressure only needs 0.3MPa, and film is placed in 60 DEG C of deionized waters isothermal vibration 20 days, flux and cutoff performance
It is held essentially constant, stability is good.
Embodiment 2
C1, the copolymer that mass percentage is 20% vinyl chloride and quality percentage that mass percentage is 15% are contained
Amount is dissolved in n,N-Dimethylformamide and is mixed and made into preparation liquid for 2% diethyl ether, with the pressure of 0.1Mpa by preparation liquid from spray
It is squeezed out in silk head, while 35 DEG C of core liquid is flowed out from the central tube of spinning head, liquid film immerses 35 behind 1 centimetre of the air gap
DEG C coagulating bath in film-forming, obtained hollow-fibre membrane obtains active precursor film through water soaking and washing.By the activity of preparation
Precursor film dries after impregnating 10h with 20% glycerine water solution, is heat-treated 5 hours at 95 DEG C, obtains lotus positive electricity doughnut and receive
Filter membrane.
It is film-made formula of liquid, preparation condition and membrane structure and performance is as shown in table 2.
Table 2
Attached drawing 4 is for active precursor film made from the present embodiment and further across obtained hollow after heat treatment cross-linking reaction
The section of fiber nano filtering film, inner surface, outer surface electron microscope.The surfaces externally and internally of active precursor film has a large amount of micro- greater than 100nm
Hole.And the aperture of nanofiltration membrane surfaces externally and internally obtained is reduced to 1nm after Overheating Treatment cross-linking reaction, surface texture still relatively causes
It is close, uniform, reach nanofiltration rank.
Embodiment 3
The preparation step and structure of positively charged nanofiltration membranes and the characterizing method of performance are shown in embodiment 1:
It is film-made formula of liquid, film preparation condition and membrane structure and performance is as shown in table 3.
Table 3
Embodiment 4
The preparation step and structure of positively charged nanofiltration membranes and the characterizing method of performance are shown in embodiment 2:
It is film-made formula of liquid, film preparation condition and membrane structure and performance is as shown in table 4.
Table 4
Embodiment 5
The preparation step and structure of positively charged nanofiltration membranes and the characterizing method of performance are shown in embodiment 1:
It is film-made formula of liquid, film preparation condition and membrane structure and performance is as shown in table 5.
Table 5
Embodiment 6
The preparation step and structure of positively charged nanofiltration membranes and the characterizing method of performance are shown in embodiment 2:
It is film-made formula of liquid, film preparation condition and membrane structure and performance is as shown in table 6.
Table 6
Embodiment 7
The preparation step and structure of positively charged nanofiltration membranes and the characterizing method of performance are shown in embodiment 1:
It is film-made formula of liquid, film preparation condition and membrane structure and performance is as shown in table 7.
Table 7
Embodiment 8
The preparation step and structure of positively charged nanofiltration membranes and the characterizing method of performance are shown in embodiment 1:
It is film-made formula of liquid, film preparation condition and membrane structure and performance is as shown in table 8.
Table 8
Embodiment 9
The preparation step and structure of positively charged nanofiltration membranes and the characterizing method of performance are shown in embodiment 1:
It is film-made formula of liquid, film preparation condition and membrane structure and performance is as shown in table 9.
Table 9
Embodiment 10
The preparation step and structure of positively charged nanofiltration membranes and the characterizing method of performance are shown in embodiment 1:
It is film-made formula of liquid, film preparation condition and membrane structure and performance is as shown in table 10.
Table 10
Embodiment 11
The preparation step and structure of positively charged nanofiltration membranes and the characterizing method of performance are shown in embodiment 2:
It is film-made formula of liquid, film preparation condition and membrane structure and performance is as shown in table 11.
Table 11
Embodiment 12
The preparation step and structure of positively charged nanofiltration membranes and the characterizing method of performance are shown in embodiment 2:
It is film-made formula of liquid, film preparation condition and membrane structure and performance is as shown in table 12.
Table 12
Embodiment 13
The preparation step and structure of positively charged nanofiltration membranes and the characterizing method of performance are shown in embodiment 2:
It is film-made formula of liquid, film preparation condition and membrane structure and performance is as shown in table 13.
Table 13
Embodiment 14
The preparation step and structure of positively charged nanofiltration membranes and the characterizing method of performance are shown in embodiment 2:
It is film-made formula of liquid, film preparation condition and membrane structure and performance is as shown in table 14.
Table 14
Embodiment 15
The preparation step and structure of positively charged nanofiltration membranes and the characterizing method of performance are shown in embodiment 2:
It is film-made formula of liquid, film preparation condition and membrane structure and performance is as shown in Table 15.
Table 15
Embodiment 16
The preparation step and structure of positively charged nanofiltration membranes and the characterizing method of performance are shown in embodiment 2:
It is film-made formula of liquid, film preparation condition and membrane structure and performance is as shown in table 16.
Table 16
Embodiment 17
The preparation step and structure of positively charged nanofiltration membranes and the characterizing method of performance are shown in embodiment 2:
It is film-made formula of liquid, film preparation condition and membrane structure and performance is as shown in table 17.
Table 17
Embodiment 18
The preparation step and structure of positively charged nanofiltration membranes and the characterizing method of performance are shown in embodiment 2:
It is film-made formula of liquid, film preparation condition and membrane structure and performance is as shown in table 18.
Table 18
The nanofiltration film properties made from all embodiments can be seen that under 25 DEG C, the test condition of 0.3MPa, and pure water is logical
Amount is above 40L/m2H is above 50% to the NaCl solution rejection of 1g/L, to the MgSO of 1g/L4Solution rejection is above
98%, the Congo red rejection to 1g/L is 99.9%, and film is placed in 60 DEG C of deionized waters isothermal vibration 20 days, flux and
Cutoff performance is held essentially constant, and illustrates that the structure of film and performance are highly stable.
Claims (15)
1. a kind of positively charged nanofiltration membranes, it is characterised in that: the material of the nanofiltration membrane is the selfing co-product of copolymer A, or
The product of chlorine-containing polymer B and tertiary amine-type polymer C blended cross linking, the crosslinked group in cross-linking products are quaternary ammonium chloride alkali
Group, wherein
The structural formula of the copolymer A is as follows:
In formula: m+n=800~5000；
M/n=10/1~1/1；
R1=H or Cl；
R2=H or CH3；
R3=contain tertiary amine group；
The structural formula of the chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=800~5000；
The structural formula of the tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=contain tertiary amine group；
Y=800~5000；
The preparation method of the positively charged nanofiltration membranes is selected from any one of following methods:
Method 1: the preparation method of the positively charged nanofiltration membranes includes the following steps:
(1) copolymer A is dissolved in casting solution, quaternized inhibitor is added, be uniformly mixed and preparation liquid is made, pass through solution
Phase inversion solidifies from coagulating bath, is prepared into active precursor film；
(2) active precursor film made from step (1) is heat-treated, obtains positively charged nanofiltration membranes；
The structural formula of the copolymer A is as follows:
In formula: m+n=800~5000；
M/n=10/1~1/1；
R1=H or Cl；
R2=H or CH3；
R3=contain tertiary amine group；
Method 2: the preparation method of the positively charged nanofiltration membranes includes the following steps:
(1) chlorine-containing polymer B and tertiary amine-type polymer C are dissolved in casting solution, quaternized inhibitor is added, be uniformly mixed
Preparation liquid is made, is solidified from coagulating bath by solution phase inversion, is prepared into active precursor film；
(2) active precursor film made from step (1) is heat-treated, obtains positively charged nanofiltration membranes；
The structural formula of the chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=800~5000；
The structural formula of the tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=contain tertiary amine group；
Y=800~5000.
2. a kind of positively charged nanofiltration membranes, it is characterised in that: the material of the nanofiltration membrane is the selfing co-product of copolymer A, or
The product of chlorine-containing polymer B and tertiary amine-type polymer C blended cross linking, the crosslinked group in cross-linking products are quaternary ammonium chloride alkali
Group, wherein
The structural formula of the copolymer A is as follows:
In formula: m+n=800~5000；
M/n=10/1~1/1；
R1=H or Cl；
R2=H or CH3；
R3=contain tertiary amine group；
The structural formula of the chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=800~5000；
The structural formula of the tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=contain tertiary amine group；
Y=1000~3000；
The preparation method of the positively charged nanofiltration membranes is selected from any one of following methods:
Method 1: the preparation method of the positively charged nanofiltration membranes includes the following steps:
(1) copolymer A is dissolved in casting solution, quaternized inhibitor is added, be uniformly mixed and preparation liquid is made, pass through solution
Phase inversion solidifies from coagulating bath, is prepared into active precursor film；
(2) active precursor film made from step (1) is heat-treated, obtains positively charged nanofiltration membranes；
The structural formula of the copolymer A is as follows:
In formula: m+n=800~5000；
M/n=10/1~1/1；
R1=H or Cl；
R2=H or CH3；
R3=contain tertiary amine group；
Method 2: the preparation method of the positively charged nanofiltration membranes includes the following steps:
(1) chlorine-containing polymer B and tertiary amine-type polymer C are dissolved in casting solution, quaternized inhibitor is added, be uniformly mixed
Preparation liquid is made, is solidified from coagulating bath by solution phase inversion, is prepared into active precursor film；
(2) active precursor film made from step (1) is heat-treated, obtains positively charged nanofiltration membranes；
The structural formula of the chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=800~5000；
The structural formula of the tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=contain tertiary amine group；
Y=1000~3000.
3. a kind of positively charged nanofiltration membranes, it is characterised in that: the material of the nanofiltration membrane is the selfing co-product of copolymer A, or
The product of chlorine-containing polymer B and tertiary amine-type polymer C blended cross linking, the crosslinked group in cross-linking products are quaternary ammonium chloride alkali
Group, wherein
The structural formula of the copolymer A is as follows:
In formula: m+n=800~5000；
M/n=10/1~1/1；
R1=H or Cl；
R2=H or CH3；
R3=contain tertiary amine group；
The structural formula of the chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=1000~3000；
The structural formula of the tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=contain tertiary amine group；
Y=800~5000；
The preparation method of the positively charged nanofiltration membranes is selected from any one of following methods:
Method 1: the preparation method of the positively charged nanofiltration membranes includes the following steps:
(1) copolymer A is dissolved in casting solution, quaternized inhibitor is added, be uniformly mixed and preparation liquid is made, pass through solution
Phase inversion solidifies from coagulating bath, is prepared into active precursor film；
(2) active precursor film made from step (1) is heat-treated, obtains positively charged nanofiltration membranes；
The structural formula of the copolymer A is as follows:
In formula: m+n=800~5000；
M/n=10/1~1/1；
R1=H or Cl；
R2=H or CH3；
R3=contain tertiary amine group；
Method 2: the preparation method of the positively charged nanofiltration membranes includes the following steps:
(1) chlorine-containing polymer B and tertiary amine-type polymer C are dissolved in casting solution, quaternized inhibitor is added, be uniformly mixed
Preparation liquid is made, is solidified from coagulating bath by solution phase inversion, is prepared into active precursor film；
(2) active precursor film made from step (1) is heat-treated, obtains positively charged nanofiltration membranes；
The structural formula of the chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=1000~3000；
The structural formula of the tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=contain tertiary amine group；
Y=800~5000.
4. a kind of positively charged nanofiltration membranes, it is characterised in that: the material of the nanofiltration membrane is the selfing co-product of copolymer A, or
The product of chlorine-containing polymer B and tertiary amine-type polymer C blended cross linking, the crosslinked group in cross-linking products are quaternary ammonium chloride alkali
Group, wherein
The structural formula of the copolymer A is as follows:
In formula: m+n=800~5000；
M/n=10/1~1/1；
R1=H or Cl；
R2=H or CH3；
R3=contain tertiary amine group；
The structural formula of the chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=1000~3000；
The structural formula of the tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=contain tertiary amine group；
Y=1000~3000；
The preparation method of the positively charged nanofiltration membranes is selected from any one of following methods:
Method 1: the preparation method of the positively charged nanofiltration membranes includes the following steps:
(1) copolymer A is dissolved in casting solution, quaternized inhibitor is added, be uniformly mixed and preparation liquid is made, pass through solution
Phase inversion solidifies from coagulating bath, is prepared into active precursor film；
(2) active precursor film made from step (1) is heat-treated, obtains positively charged nanofiltration membranes；
The structural formula of the copolymer A is as follows:
In formula: m+n=800~5000；
M/n=10/1~1/1；
R1=H or Cl；
R2=H or CH3；
R3=contain tertiary amine group；
Method 2: the preparation method of the positively charged nanofiltration membranes includes the following steps:
(1) chlorine-containing polymer B and tertiary amine-type polymer C are dissolved in casting solution, quaternized inhibitor is added, be uniformly mixed
Preparation liquid is made, is solidified from coagulating bath by solution phase inversion, is prepared into active precursor film；
(2) active precursor film made from step (1) is heat-treated, obtains positively charged nanofiltration membranes；
The structural formula of the chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=1000~3000；
The structural formula of the tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=contain tertiary amine group；
Y=1000~3000.
5. a kind of positively charged nanofiltration membranes, it is characterised in that: the material of the nanofiltration membrane is the selfing co-product of copolymer A, or
The product of chlorine-containing polymer B and tertiary amine-type polymer C blended cross linking, the crosslinked group in cross-linking products are quaternary ammonium chloride alkali
Group, wherein
The structural formula of the copolymer A is as follows:
In formula: m+n=1000~3000；
M/n=10/1~1/1；
R1=H or Cl；
R2=H or CH3；
R3=contain tertiary amine group；
The structural formula of the chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=800~5000；
The structural formula of the tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=contain tertiary amine group；
Y=800~5000；
The preparation method of the positively charged nanofiltration membranes is selected from any one of following methods:
Method 1: the preparation method of the positively charged nanofiltration membranes includes the following steps:
(1) copolymer A is dissolved in casting solution, quaternized inhibitor is added, be uniformly mixed and preparation liquid is made, pass through solution
Phase inversion solidifies from coagulating bath, is prepared into active precursor film；
(2) active precursor film made from step (1) is heat-treated, obtains positively charged nanofiltration membranes；
The structural formula of the copolymer A is as follows:
In formula: m+n=1000~3000；
M/n=10/1~1/1；
R1=H or Cl；
R2=H or CH3；
R3=contain tertiary amine group；
Method 2: the preparation method of the positively charged nanofiltration membranes includes the following steps:
(1) chlorine-containing polymer B and tertiary amine-type polymer C are dissolved in casting solution, quaternized inhibitor is added, be uniformly mixed
Preparation liquid is made, is solidified from coagulating bath by solution phase inversion, is prepared into active precursor film；
(2) active precursor film made from step (1) is heat-treated, obtains positively charged nanofiltration membranes；
The structural formula of the chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=800~5000；
The structural formula of the tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=contain tertiary amine group；
Y=800~5000.
6. a kind of positively charged nanofiltration membranes, it is characterised in that: the material of the nanofiltration membrane is the selfing co-product of copolymer A, or
The product of chlorine-containing polymer B and tertiary amine-type polymer C blended cross linking, the crosslinked group in cross-linking products are quaternary ammonium chloride alkali
Group, wherein
The structural formula of the copolymer A is as follows:
In formula: m+n=1000~3000；
M/n=10/1~1/1；
R1=H or Cl；
R2=H or CH3；
R3=contain tertiary amine group；
The structural formula of the chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=800~5000；
The structural formula of the tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=contain tertiary amine group；
Y=1000~3000；
The preparation method of the positively charged nanofiltration membranes is selected from any one of following methods:
Method 1: the preparation method of the positively charged nanofiltration membranes includes the following steps:
(1) copolymer A is dissolved in casting solution, quaternized inhibitor is added, be uniformly mixed and preparation liquid is made, pass through solution
Phase inversion solidifies from coagulating bath, is prepared into active precursor film；
(2) active precursor film made from step (1) is heat-treated, obtains positively charged nanofiltration membranes；
The structural formula of the copolymer A is as follows:
In formula: m+n=1000~3000；
M/n=10/1~1/1；
R1=H or Cl；
R2=H or CH3；
R3=contain tertiary amine group；
Method 2: the preparation method of the positively charged nanofiltration membranes includes the following steps:
(1) chlorine-containing polymer B and tertiary amine-type polymer C are dissolved in casting solution, quaternized inhibitor is added, be uniformly mixed
Preparation liquid is made, is solidified from coagulating bath by solution phase inversion, is prepared into active precursor film；
(2) active precursor film made from step (1) is heat-treated, obtains positively charged nanofiltration membranes；
The structural formula of the chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=800~5000；
The structural formula of the tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=contain tertiary amine group；
Y=1000~3000.
7. a kind of positively charged nanofiltration membranes, it is characterised in that: the material of the nanofiltration membrane is the selfing co-product of copolymer A, or
The product of chlorine-containing polymer B and tertiary amine-type polymer C blended cross linking, the crosslinked group in cross-linking products are quaternary ammonium chloride alkali
Group, wherein
The structural formula of the copolymer A is as follows:
In formula: m+n=1000~3000；
M/n=10/1~1/1；
R1=H or Cl；
R2=H or CH3；
R3=contain tertiary amine group；
The structural formula of the chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=1000~3000；
The structural formula of the tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=contain tertiary amine group；
Y=800~5000；
The preparation method of the positively charged nanofiltration membranes is selected from any one of following methods:
Method 1: the preparation method of the positively charged nanofiltration membranes includes the following steps:
(1) copolymer A is dissolved in casting solution, quaternized inhibitor is added, be uniformly mixed and preparation liquid is made, pass through solution
Phase inversion solidifies from coagulating bath, is prepared into active precursor film；
(2) active precursor film made from step (1) is heat-treated, obtains positively charged nanofiltration membranes；
The structural formula of the copolymer A is as follows:
In formula: m+n=1000~3000；
M/n=10/1~1/1；
R1=H or Cl；
R2=H or CH3；
R3=contain tertiary amine group；
Method 2: the preparation method of the positively charged nanofiltration membranes includes the following steps:
(1) chlorine-containing polymer B and tertiary amine-type polymer C are dissolved in casting solution, quaternized inhibitor is added, be uniformly mixed
Preparation liquid is made, is solidified from coagulating bath by solution phase inversion, is prepared into active precursor film；
(2) active precursor film made from step (1) is heat-treated, obtains positively charged nanofiltration membranes；
The structural formula of the chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=1000~3000；
The structural formula of the tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=contain tertiary amine group；
Y=800~5000.
8. a kind of positively charged nanofiltration membranes, it is characterised in that: the material of the nanofiltration membrane is the selfing co-product of copolymer A, or
The product of chlorine-containing polymer B and tertiary amine-type polymer C blended cross linking, the crosslinked group in cross-linking products are quaternary ammonium chloride alkali
Group, wherein
The structural formula of the copolymer A is as follows:
In formula: m+n=1000~3000；
M/n=10/1~1/1；
R1=H or Cl；
R2=H or CH3；
R3=contain tertiary amine group；
The structural formula of the chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=1000~3000；
The structural formula of the tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=contain tertiary amine group；
Y=1000~3000；
The preparation method of the positively charged nanofiltration membranes is selected from any one of following methods:
Method 1: the preparation method of the positively charged nanofiltration membranes includes the following steps:
(1) copolymer A is dissolved in casting solution, quaternized inhibitor is added, be uniformly mixed and preparation liquid is made, pass through solution
Phase inversion solidifies from coagulating bath, is prepared into active precursor film；
(2) active precursor film made from step (1) is heat-treated, obtains positively charged nanofiltration membranes；
The structural formula of the copolymer A is as follows:
In formula: m+n=1000~3000；
M/n=10/1~1/1；
R1=H or Cl；
R2=H or CH3；
R3=contain tertiary amine group；
Method 2: the preparation method of the positively charged nanofiltration membranes includes the following steps:
(1) chlorine-containing polymer B and tertiary amine-type polymer C are dissolved in casting solution, quaternized inhibitor is added, be uniformly mixed
Preparation liquid is made, is solidified from coagulating bath by solution phase inversion, is prepared into active precursor film；
(2) active precursor film made from step (1) is heat-treated, obtains positively charged nanofiltration membranes；
The structural formula of the chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=1000~3000；
The structural formula of the tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=contain tertiary amine group；
Y=1000~3000.
9. positively charged nanofiltration membranes according to claim 1-8, which is characterized in that the chlorine-containing polymer B is second
The product of alkenyl type fluorochemical monomer polymerization, the tertiary amine-type polymer C is the product of vinyl-type tertiary amine monomers polymerization, described total
Polymers A is the product of vinyl-type fluorochemical monomer and the copolymerization of vinyl-type tertiary amine monomers.
10. positively charged nanofiltration membranes according to claim 9, which is characterized in that the vinyl-type fluorochemical monomer is selected from
In vinyl chloride, vinylidene chloride any one or it is any a variety of, the vinyl-type tertiary amine monomers are selected from methacrylic acid
Dimethylaminoethyl, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, two
First aminopropyl methacrylamide, dimethylamino propyl acrylamide, 4-vinylpridine, 2- vinylpyridine, vinyl miaow
Any one in azoles.
11. positively charged nanofiltration membranes according to claim 1-8, which is characterized in that the quaternary ammonium chloride salt groups
Selected from following structural formula:
In formula: R=CH3Or CH2CH3。
12. positively charged nanofiltration membranes according to claim 1-8, which is characterized in that quaternary ammonium described in step (1)
Change inhibitor in diethyl ether, methylene chloride, acetone, methanol, ethyl alcohol, pentane, pentamethylene any one or it is any a variety of.
13. positively charged nanofiltration membranes according to claim 1-8, which is characterized in that step is made described in (1)
The temperature of preparation liquid is 5~50 DEG C, and the coagulation bath temperature is 5~50 DEG C；Heat treatment temperature described in step (2) be 50~
120 DEG C, heat treatment time is 1~24 hour.
14. positively charged nanofiltration membranes according to claim 1-8, which is characterized in that the copolymer A is by ethylene
The product of fundamental mode fluorochemical monomer and the copolymerization of vinyl-type tertiary amine monomers.
15. positively charged nanofiltration membranes according to claim 1-8, which is characterized in that the chlorine-containing polymer B be by
The product of vinyl-type fluorochemical monomer polymerization, the tertiary amine-type polymer C is the product being polymerize by vinyl-type tertiary amine monomers.
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| CN201410437650.2A CN104190265A (en) | 2014-08-31 | 2014-08-31 | Low-pressure high-flux chlorine-containing polymer nanofiltration membrane with stable separation layer and preparation method thereof |
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| CN201410733614.0A Active CN105363359B (en) | 2014-08-31 | 2014-12-04 | A kind of cross-linking type lotus positive electricity chlorine-containing polymer filter membrane and preparation method thereof |
| CN201410730313.2A Active CN105363350B (en) | 2014-08-31 | 2014-12-04 | A kind of charged type hollow fiber filtering membrane of asymmetrical chlorine-containing polymer base and preparation method thereof |
| CN201410733611.7A Active CN105363353B (en) | 2014-08-31 | 2014-12-04 | A kind of charged type chlorine-containing polymer NF membrane and preparation method thereof |
| CN201410730312.8A Active CN105709619B (en) | 2014-08-31 | 2014-12-04 | A kind of positively charged nanofiltration membranes and preparation method thereof |
| CN201410734459.4A Active CN105709608B (en) | 2014-08-31 | 2014-12-04 | A kind of chlorine-containing polymer base hollow fiber filtering membrane and preparation method thereof with high resistance tocrocking |
| CN202011363839.3A Pending CN112403286A (en) | 2014-08-31 | 2014-12-04 | Positively charged nanofiltration membrane based on tertiary amine type amphiphilic copolymer and preparation method thereof |
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| CN201410730313.2A Active CN105363350B (en) | 2014-08-31 | 2014-12-04 | A kind of charged type hollow fiber filtering membrane of asymmetrical chlorine-containing polymer base and preparation method thereof |
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| CN202011363839.3A Pending CN112403286A (en) | 2014-08-31 | 2014-12-04 | Positively charged nanofiltration membrane based on tertiary amine type amphiphilic copolymer and preparation method thereof |
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| CN112403286A (en) | 2021-02-26 |
| CN105363353B (en) | 2018-03-20 |
| CN105642129A (en) | 2016-06-08 |
| CN105363353A (en) | 2016-03-02 |
| CN105709619A (en) | 2016-06-29 |
| CN105363350A (en) | 2016-03-02 |
| CN105363359A (en) | 2016-03-02 |
| CN105363359B (en) | 2017-06-30 |
| CN105363350B (en) | 2018-01-30 |
| CN105709608A (en) | 2016-06-29 |
| CN105709608B (en) | 2019-04-26 |
| CN104190265A (en) | 2014-12-10 |
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