CN105709619A - Positively charged nanofiltration membrane and preparation method thereof - Google Patents
Positively charged nanofiltration membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a positively charged nanofiltration membrane and a preparation method thereof. The positively charged nanofiltration membrane comprises the main component of a self-crosslinked product of a tertiary amine chlorine-containing copolymer A, or a blended crosslinked product of a chlorine-containing polymer B and a tertiary amine polymer C. The preparation method of the positively charged nanofiltration membrane comprises the steps: (1) dissolving the tertiary amine chlorine-containing copolymer A, or the chlorine-containing polymer B and the tertiary amine polymer C in a membrane preparation solvent, adding a quaternization inhibitor, mixing uniformly to prepare a membrane preparation liquid, and curing from a coagulation bath by a solution phase conversion method to prepare an active precursor membrane; and (2) carrying out heat treatment on the prepared active precursor membrane, to obtain the positively charged nanofiltration membrane. The positively charged nanofiltration membrane can be made into a flat membrane or a hollow fiber membrane; in the preparation process, controllability of the membrane structure and properties are strong, the process is simple, the production cost is low, cleaning production can be realized, and the membrane has good industrialized prospect.
Description
Technical field
The invention belongs to technical field of membrane separation, particularly to the preparation method of a kind of positively charged nanofiltration membranes.
Background technology
Membrane separation technique has the advantage such as efficiency height, simple, easy to operate, the energy-conserving and environment-protective of equipment, demonstrates great application potential at industrial circle, and its range of application has expanded to the fields such as biology, medicine, environmental protection, the energy, desalinization, wastewater treatment.Nanofiltration (Nanofiltration, be called for short NF) is a kind of membrane separation technique between reverse osmosis (RO) and ultrafiltration (UF), is one of the focus of current World Water process field research.Typical NF membrane has following feature: (1) NF membrane is typically all composite membrane, is made up of supporting layer and dense functional layer, and cutoff performance and the flux of NF membrane depend on dense functional layer.(2) retaining the relative molecular weight (200～2000) of material between reverse osmosis and ultrafiltration, membrane aperture is about 1nm.(3) cutoff performance of film is subject to aperture sieve effect and electric charging effect joint effect, the ion of different valence state is had different rejection, generally to monovalention (NO3 -、Cl-、Na+、K+) rejection relatively low (30-50%), to high valence ion (PO4 3-、SO4 2-、Mg2+、Ca2+) rejection higher (about 90%).(4) pressure needed for operation pressure ratio reverse osmosis is low, and general operation pressure is between 0.8～2.0MPa.It is at food industry, chemical and medicine industry industry, Drinking Water Industry, and the field such as wastewater treatment has broad application prospects.
The preparation method of current commercialization NF membrane is with SPSF (SPS), sulfonated polyether sulfone (SPES) ultrafilter membrane for supporting layer (basement membrane), and by interfacial polymerization, on top layer, formation has polyamide (PA) dense functional layer in nanofiltration aperture thus obtaining having double-deck NF membrane.Interfacial polymerization is first at the aqueous solution of one layer of polyamine of support membrane surface-coated, is then coated with the organic solution of one layer of polynary acyl chlorides, utilizes the reaction of polyamine and polynary acyl chlorides to prepare polyamide dense functional layer.Prior art adopts interfacial polymerization method, the method for surface-coated prepares NF membrane, the NF membrane prepared is divided into the double-layer structure of supporting layer and dense functional layer, as Chinese patent CN102423643B and CN101254419B just adopts different polyamines to be aqueous phase coating basement membrane, this basement membrane is supporting layer；Then it is that oil phase carries out being cross-linked to form dense functional layer with polynary acyl chlorides.It is disadvantageous in that: first under higher operating pressure, and existing monofilm is unable to reach and has good cutoff performance and high-throughout requirement concurrently, and the monofilm of existing good mechanical property cannot meet the cutoff performance of NF membrane；The monofilm that existing cutoff performance is good, it is impossible to meet the requirement of NF membrane mechanical performance, film is easy to the deformation that is crushed, and causes that membrane structure is destroyed.In order to maintain the stability of membrane structure and meet cutoff performance simultaneously, it has to adopting the two layer composite structure film of supporting layer and dense functional layer, meeting the requirement of NF membrane mechanical performance and cutoff performance, thus drastically increasing manufacturing cost.And existing ultrafilter membrane and micro-filtration membrane can adopt monofilm, it is owing to ion need not be retained by both films, have only to retain the material (molecular weight > 10,000) of high molecular, its cutoff performance requires the cutoff performance well below NF membrane, and relatively big (> 10nm in its aperture), supporting layer under very low operating pressure, (it is generally 0.01-0.1MPa) just can meet high flux requirement, so need not be adopted specially to carry out the mechanical performance of reinforced film.
Prior art adopts the weak point that interfacial polymerization method prepares NF membrane to also reside in, aqueous phase polyamine and oil phase acyl chlorides is adopted to be coated with successively during molding, carry out the dense functional layer that cross-linking reaction provides fine and close, complex steps, and react and between obtained dense functional layer and supporting layer, only have physisorption, there is no the high forces of chemical bond, in conjunction with unstable, be very easy to destroyed when membrane structure is cleaned.Finally, the dense functional layer constructed by interfacial polymerization or surface-coated method is thicker, can reduce the flux of NF membrane, will obtain higher flux, is necessary for improving use pressure, will necessarily increase operating cost.It addition, the polyamide dense functional layer kind prepared by existing commercialization NF membrane is single, and majority prepares Flat Membrane, adopts rolled membrane module, not easy cleaning after pollution during operation.Therefore, select and film build method two aspect set off in search the main outlet being prepared by Nanofiltration-membrane technique development realizing low cost, high-performance NF membrane from material.
Summary of the invention
For the deficiencies in the prior art, the technical problem to be solved is to provide a kind of positively charged nanofiltration membranes and preparation method thereof.The positively charged nanofiltration membranes provided, under very low operation pressure (0.3MPa), can remove divalent ion (MgSO efficiently4Rejection > 98%) and the molecular weight solute higher than 200, and monovalent ion (NaCl) and low molecular weight substance retained higher than 50%, while can also keep very high flux (> 40L/m2/ h).The preparation method of positively charged nanofiltration membranes provided by the present invention, adopts first blended masking then the method carrying out quaternized crosslinking.The quaternary ammonium chloride salt groups generated after quaternized crosslinking not only provides charge, good hydrophilic and excellent mechanical performance is also provided for film, completely without traditional double-deck design of interfacial polymerization NF membrane, it is only necessary to monofilm has just reached excellent serviceability.Due to the easy unicity with membrane structure of preparation technology, the stability of described positively charged nanofiltration membrane structure and performance is made to be greatly increased, thus survivable with wash phase using, longer service life, it is suitable for multiple embrane method water treatment facilities and engineering.
It is different from prior art, positively charged nanofiltration membranes provided by the invention, raising NF membrane is high performance while, solves some problems that prior art exists:
(1) method of prior art, such as polymer nano filter membrane prepared by interfacial polymerization, it is necessary to adopt double membrane structure, wherein only have physisorption between supporting layer and dense functional layer, not having higher active force, membrane structure is easily destroyed, and performance is caused unstability；And positively charged nanofiltration membranes of the present invention is only made up of a kind of cross linked polymer, for single-layer membrane structure, have good cutoff performance and high-throughout requirement concurrently, it is possible to meet the needs of nanofiltration process.Therefore, it is absent from the supporting layer of existing NF membrane and the stripping problem of dense functional layer, use procedure ensures the stable performance of film, has longer service life.Being placed in 60 DEG C of deionized waters by the polymer nano filter membrane of the present invention isothermal vibration 20 days, flux and cutoff performance remain unchanged.
(2) method of prior art, such as polymer nano filter membrane prepared by interfacial polymerization, dense functional layer is excessively fine and close, film hydrophilic is poor, cause that the flux of NF membrane is relatively low, must with high operating pressure (0.8～2MPa) under could meet application time throughput requirements, this is also that it must adopt supporting layer to strengthen the reason of crushing resistance, and higher operating pressure then can drastically increase operating cost；And monolayer positively charged nanofiltration membranes of the present invention and the existing NF membrane comprising supporting layer and dense functional layer have identical cutoff performance, and due to containing quaternary ammonium chloride and tertiary amine group, provide the hydrophilicity of excellence so that positively charged nanofiltration membranes of the present invention just can reach significantly high permeation flux (> 40L/m under relatively low pressure (such as 0.3MPa)2H), far above NF membrane prepared by traditional method, improve separation efficiency, reduce operating cost.
(3) method of prior art, such as polymer nano filter membrane prepared by interfacial polymerization, the polyamine and the acyl chlorides that adopt carry out being cross-linked to form dense functional layer, this cross-linking reaction functions only as the effect of dense functional layer, physisorption is only had with support membrane, the crosslinking of the tertiary amine in the self-crosslinking product of positively charged nanofiltration membranes of the present invention or blended cross linking product and chlorine then has the effect of three aspects simultaneously, first it is that physical entanglement effect between macromole is converted into chemical crosslinking effect, thus giving the mechanical performance that film is excellent, next to that the process of crosslinking generates quaternary ammonium chloride salt groups, this group is with positive charge, give film charge, improve cutoff performance and the antifouling property of film, finally, the quaternary ammonium chloride that crosslinking generates also provides good hydrophilic for film, film is made to have higher flux under relatively low operating pressure (such as 0.3MPa).
(4) method of prior art, such as polymer nano filter membrane prepared by interfacial polymerization, supporting layer in its double membrane structure mainly with SPSF (SPS), sulfonated polyether sulfone (SPES) ultrafilter membrane, this kind of material price height, adds the cost of material of film itself.And positively charged nanofiltration membranes of the present invention adopts single-layer membrane structure, it is not necessary to supporting layer, compared to the NF membrane of prior art, cost is reduced 60%.
The present invention adopts the following technical scheme that:
A kind of positively charged nanofiltration membranes, the material of described NF membrane is the self-crosslinking product of copolymer A, or the product of chlorine-containing polymer B and tertiary amine-type polymer C blended cross linking, and the crosslinked group in cross-linking products is quaternary ammonium chloride salt groups, wherein,
The structural formula of described copolymer A is as follows:
In formula: m+n=800～5000, it is preferable that m+n=1000～3000；
M/n=10/1～1/1；
R1=H or Cl；
R2=H or CH3；
R3=containing tertiary amine group；
The structural formula of described chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=800～5000, it is preferable that x=1000～3000；
The structural formula of described tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=containing tertiary amine group；
Y=800～5000, it is preferable that y=1000～3000.
Two kinds of cross linked polymers provided by the invention are all carried out quaterisation realization by tertiary amine group and chlorine, while providing lotus positive electricity performance for NF membrane, also construct cross-linked network.This electrical charge rejection effect simultaneously enhancing nanofiltration membrane and aperture sieving actoion.
Described positively charged nanofiltration membranes can be that copolymer A self-crosslinking is formed, its cross-linking process schematic diagram such as Fig. 1.Described copolymer A contains-Cl and tertiary amine Liang Zhong functional group simultaneously, self-crosslinking reaction makes the physical entanglement effect of copolymer chain molecule of the same race be converted into netted chemistry cross-linked structure, the mechanical performance of excellence is provided, it is provided that the close performance of resistance to compression in film use procedure for NF membrane.And, this self-crosslinking reaction is also quaterisation, form quaternary ammonium chloride salt groups for which providing positive charge, give film charge, improve cutoff performance and the antifouling property of film, finally, crosslinking generates quaternary ammonium chloride and also provides good hydrophilic for film, makes film have higher flux under relatively low operating pressure (such as 0.3MPa).
Described positively charged nanofiltration membranes can also be the crosslinked action between two kinds of polymer chains, its cross-linking process schematic diagram such as Fig. 2.Wherein tertiary amine-type polymer C provides the hydrophilicity of tertiary amine group and excellence, and with polrvinyl chloride be representative chlorine-containing polymer B cheap, chemical stability is good, acid and alkali-resistance, chemical attack, there is the mechanical strength of excellence, be widely used in multiple fields such as water process, biological medicines.The cross linked polymer generated by quaternized cross-linking reaction after blended for both polymer chains not only had excellent hydrophilicity but also chemical stability is good, acid and alkali-resistance, resistance to chemical attack, there is the mechanical strength of excellence, and first the crosslinking of tertiary amine and chlorine is that physical entanglement effect between macromole is converted into chemical crosslinking effect, thus giving the mechanical performance that film is excellent, next to that the process of crosslinking generates quaternary ammonium chloride salt groups, this group is with positive charge, give film charge, improve cutoff performance and the antifouling property of film, finally, crosslinking generates quaternary ammonium chloride and also provides good hydrophilic for film, film is made to have higher flux under relatively low operating pressure (such as 0.3MPa).
Preferably, chlorine-containing polymer B of the present invention is the product of the chloride monomer polymerization of vinyl-type, described tertiary amine-type polymer C is the product of vinyl-type tertiary amine monomers polymerization, and described copolymer A is the product of the chloride monomer of vinyl-type and vinyl-type tertiary amine monomers copolymerization.
Preferably, the chloride monomer of vinyl-type of the present invention in vinyl chloride, the vinylidene chloride any one or arbitrarily multiple, any one in dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylamino propyl acrylamide, 4-vinylpridine, 2-vinylpyridine, vinyl imidazole of described vinyl-type tertiary amine monomers.
Preferably, described quaternary ammonium chloride salt groups is selected from structural formula:
In formula: R=CH3Or CH2CH3。
Preferably, the weight/mass percentage composition of described quaternary ammonium chloride salt groups is 2%～10%.
The preparation method that present invention also offers a kind of positively charged nanofiltration membranes, the positively charged nanofiltration membranes that the method prepares is the self-crosslinking product of copolymer A, comprises the steps:
(1) being dissolved in casting solution by copolymer A, add quaternized inhibitor, mix homogeneously makes preparation liquid, is solidified from coagulating bath by solution phase inversion, prepares Viability precursor film；
(2) active precursor film heat treatment step (1) prepared, obtains positively charged nanofiltration membranes；
The structural formula of described copolymer A is as follows:
In formula: m+n=800～5000, it is preferable that m+n=1000～3000；
M/n=10/1～1/1；
R1=H or Cl；
R2=H or CH3；
R3=containing tertiary amine group.
Preferably, copolymer A described in step (1) is by the product of the chloride monomer of vinyl-type Yu vinyl-type tertiary amine monomers copolymerization.Preferred, the chloride monomer of described vinyl-type in vinyl chloride, the vinylidene chloride any one or arbitrarily multiple, any one in dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylamino propyl acrylamide, 4-vinylpridine, 2-vinylpyridine, vinyl imidazole of described vinyl-type tertiary amine monomers.
Preferably, quaternized inhibitor described in step (1) in diethyl ether, dichloromethane, acetone, methanol, ethanol, pentane, the Pentamethylene. any one or arbitrarily multiple, the concentration of described quaternized inhibitor is weight/mass percentage composition 0～10wt%.
Preferably, the temperature making preparation liquid described in step (1) is 5～50 DEG C, and described coagulation bath temperature is 5～50 DEG C.
Preferably, the heat treatment temperature described in step (2) is 50～120 DEG C, and heat treatment time is 1～24 hour.
Preferably, the heat treatment method described in step (2) be the direct heat treatment of dry film or by film through the one in heat treatment again after Glycerine-Aqueous Solution or glycerol-ethylene glycol solution processes.
Preferably, described quaternary ammonium chloride salt groups is selected from structural formula:
In formula: R=CH3Or CH2CH3。
Preferably, the weight/mass percentage composition of described quaternary ammonium chloride salt groups is 2%～10%.
The preparation method that present invention also offers a kind of positively charged nanofiltration membranes, the positively charged nanofiltration membranes that the method prepares is the product of chlorine-containing polymer B and tertiary amine-type polymer C blended cross linking, comprises the steps:
(1) being dissolved in casting solution by chlorine-containing polymer B and tertiary amine-type polymer C, add quaternized inhibitor, mix homogeneously makes preparation liquid, is solidified from coagulating bath by solution phase inversion, prepares Viability precursor film；
(2) active precursor film heat treatment step (1) prepared, obtains positively charged nanofiltration membranes；
The structural formula of described chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=800～5000, it is preferable that x=1000～3000；
The structural formula of described tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=containing tertiary amine group；
Y=800～5000, it is preferable that y=1000～3000.
Preferably, chlorine-containing polymer B described in step (1) is that described tertiary amine-type polymer C is the product being polymerized by vinyl-type tertiary amine monomers by the product of the chloride monomer polymerization of vinyl-type.Preferred, the chloride monomer of vinyl-type of the present invention in vinyl chloride, the vinylidene chloride any one or arbitrarily multiple, any one in dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylamino propyl acrylamide, 4-vinylpridine, 2-vinylpyridine, vinyl imidazole of described vinyl-type tertiary amine monomers.
Preferably, quaternized inhibitor described in step (1) in diethyl ether, dichloromethane, acetone, methanol, ethanol, pentane, the Pentamethylene. any one or arbitrarily multiple, the concentration of described quaternized inhibitor is weight/mass percentage composition 0～10wt%.
Preferably, the temperature making preparation liquid described in step (1) is 5～50 DEG C, and described coagulation bath temperature is 5～50 DEG C.
Preferably, the heat treatment temperature described in step (2) is 50～120 DEG C, and heat treatment time is 1～24 hour.
Preferably, the heat treatment method described in step (2) be the direct heat treatment of dry film or by film through the one in heat treatment again after Glycerine-Aqueous Solution or glycerol-ethylene glycol solution processes.
Preferably, described quaternary ammonium chloride salt groups is selected from structural formula:
In formula: R=CH3Or CH2CH3。
Preferably, the weight/mass percentage composition of described quaternary ammonium chloride salt groups is 2%～10%.
Crosslinked polymer is at a kind of effective ways improving polymer strength.By cross-linking reaction, occur chemistry to tangle between polymer macromolecule chain, make polymer insoluble, do not melt, it is possible to the mechanical property improving polymer in various degree, heat-resistant stability, wearability, solvent resistance and creep resistance etc..Therefore, it is a kind of effective method that polymeric film adopts the method for crosslinked polymer improve filter membrane mechanical property.After it should be noted that crosslinked polymer process can only occur in filter membrane molding.If but crosslinked polymer occurs in film-forming process, then can affect the preparation of filter membrane.Filter membrane preparation method primarily now includes fusion drawn method, non-solvent induction phase separation method, thermally induced phase separation etc..No matter which kind of method, has a liquid condition: fusion drawn method is melt in the process forming solid-state filter membrane, rear both be solution.Obviously, cross linked polymer cannot form uniform melt or solution, thus cannot prepare filter membrane.Therefore, how in film-forming process, polymer does not cross-link, and cross-links in film forming post-consumer polymer that to be one prepare the problem that crosslinking polymer film needs solve.For this problem preparation method of the present invention in the process of configuration preparation liquid, in order to prevent tertiary amine group and chlorine from configuration preparation liquid and film-forming process, quaternized cross-linking reaction occurring, add quaternized inhibitor.And preparation liquid configuration temperature is depended in the addition of quaternized inhibitor, when preparation liquid temperature or masking temperature are higher than 25 DEG C, it is necessary to add the quaternized inhibitor of 0.5-10wt%.
Positively charged nanofiltration membranes of the present invention can make various forms of film, including Flat Membrane, hollow-fibre membrane.
Solution inversion of phases is prepared the method for Flat Membrane and be may is that preparation liquid spreads to liquid film on stainless steel carrier, glass carrier or non-woven fabrics, and immerses film-forming in the coagulating bath of 5～50 DEG C.The method that solution inversion of phases prepares hollow-fibre membrane is as follows: extruded from spinning head by preparation liquid with the pressure of 0.1～0.3Mpa, simultaneously the core liquid of 5～50 DEG C flows out from the central canal of spinning head with the flow velocity of 10～50ml/min, and liquid film immerses film-forming in the coagulating bath of 5～50 DEG C behind the air gap of 0～20 centimetre.
In solution inversion of phases process, due to the effect of hydrophilic component so that tertiary amine group copolymerization component or polymer migrate to film surface (coagulating bath one end), thus occurring in that enrichment phenomenon on the surface of film.Detailed process according to solution inversion of phases, this enrichment phenomenon also can occur on the hole wall in membrane body.Due to the appearance of this enrichment phenomenon, make the surface of active precursor film and internal channel surfaces all contain more tertiary amine group, provide probability for the NF membrane surface lotus positive electricity after quaterisation.
Present invention beneficial effect compared with prior art has:
Only a kind of cross linked polymer composition of positively charged nanofiltration membranes disclosed by the invention, creationary use single-layer membrane structure, it is absent from the stripping problem of supporting layer and dense functional layer, use procedure ensures the stable performance of film, have longer service life.
Positively charged nanofiltration membranes disclosed by the invention, entanglement and further quaternized crosslinked action due to polymer chain itself, physical entanglement effect between macromole is converted into chemical crosslinking effect, thus giving the mechanical performance that film is excellent, ensure the composition of film, Stability Analysis of Structures, give the service life that film is longer.
Positively charged nanofiltration membranes disclosed by the invention and general polymer nano filter membrane have identical separating property, and due to containing quaternary ammonium chloride and tertiary amine group, provide the hydrophilicity of excellence so that positively charged nanofiltration membranes of the present invention just can reach significantly high permeation flux (> 40L/m under relatively low pressure (such as 0.3MPa)2H), far above NF membrane prepared by traditional method, improve separation efficiency, reduce operating cost.
Positively charged nanofiltration membranes disclosed by the invention, generates quaternary ammonium chloride salt groups in the process of crosslinking, this group, with positive charge, gives film charge, improves cutoff performance and the antifouling property of film.
The preparation method of positively charged nanofiltration membranes disclosed by the invention, film forming adopts the method for disposable solution inversion of phases, carrying out quaternized crosslinking after film forming, this makes, and Membrane properties and structure controllability in preparation process is strong, technique simple, low cost of manufacture, can realize cleanly production.
Accompanying drawing explanation
Fig. 1 is the quaternized schematic diagram of polymer A self-crosslinking of embodiment 1；
Chlorine-containing polymer B and tertiary amine-type polymer C that Fig. 2 is embodiment 2 cross-link quaternized schematic diagram；
Fig. 3 is the active precursor film for preparing of embodiment 1 and further across the upper surface of flat board NF membrane prepared after heat treatment cross-linking reaction, lower surface, section Electronic Speculum figure；
Fig. 4 is the active precursor film for preparing of embodiment 2 and further across the section of hollow fiber nanofiltration membrane prepared after heat treatment cross-linking reaction, inner surface, outer surface Electronic Speculum figure.
Detailed description of the invention
Positively charged nanofiltration membrane preparation method of the present invention is described in detail below with specific embodiment.The enforcement step of all embodiments is all identical with the enforcement step described in summary of the invention, and in table, parameter is every implementation condition and obtains membrane structure and performance.It should be noted that described embodiment is not construed as limiting the invention, all deformation that those of ordinary skill in the art can directly derive from present disclosure or associate, all it is considered as protection scope of the present invention.
Synthetic example 1
Copolymer A series (A1-A9) synthesis:
For copolymer A 1,10g dimethylaminoethyl methacrylate and 100g vinyl chloride are mixed, add the initiator azodiisobutyronitrile (AIBN) of 1.03g, react 7 hours at 85 DEG C, obtain the copolymer (A1) of the following dimethylaminoethyl methacrylate of structural formula and vinyl chloride:
In formula: m+n=800
M/n=10/1
R1=H
R2=CH3
R3=COOCH2CH2N(CH3)2
Other A2-A9 adopt identical building-up process to obtain, formula and technique such as table H1-1, parameter such as table H1-2 in the polymer formulae obtained.
Table H1-1
Table H1-2:
Synthetic example 2
Polymer C series (C1-C9) synthesis:
For polymer C1,100g dimethylaminoethyl methacrylate is dissolved in 500g water, adds the initiator ammonium persulfate of 1.03g, react 5 hours at 70 DEG C, obtain the dimethylaminoethyl methacrylate polymer (C2) that structural formula is following:
In formula:
R2=CH3
R3=COOCH2CH2N(CH3)2
Y=800
Other polymer C2-C9 adopts identical building-up process to obtain, formula and technique such as table H1-1, parameter such as table H1-2 in the polymer formulae obtained.
Table H1-1
Table H1-2:
The characterizing method of positively charged nanofiltration membrane structure and performance:
The structure of film and pattern: observe film microscopic appearance by scanning electron microscope (JSM-5510LV, Japan).
The mensuration of water flux, cutoff performance and stability:
1, water flux: with pure water for feeding liquid, measures the osmotic water flux of NF membrane, passes through the flux of the volume computing film of film according to unit interval unit are；
2, cutoff performance: with NaCl, the MgSO of 1g/L4, Congo red solution is feeding liquid, releases related concentrations by the electrical conductivity or ultraviolet spectra measuring feeding liquid and transudate, calculates the rejection of film according to feeding liquid and transudate concentration proportion.Test condition is: temperature 25 DEG C, 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
A1 and the acetone that weight/mass percentage composition is 1% that weight/mass percentage composition is 20% are dissolved in N, N-dimethyl acetylamide is mixed and made into preparation liquid, preparation liquid spreads to liquid film, and immerses film-forming in the water of 10 DEG C, the Flat Membrane obtained is cleaned through water soaking, obtains active precursor film.After the active precursor film of preparation is dried at 80 DEG C heat treatment 10 hours, obtain lotus positive electricity flat board NF membrane.
Preparation liquid formula, preparation condition and membrane structure and performance are as shown in table 1.
Table 1
Accompanying drawing 3 for the present embodiment prepare active precursor film and further across after heat treatment cross-linking reaction prepare the upper surface of flat board NF membrane, lower surface, section Electronic Speculum figure.The upper surface of active precursor film has a large amount of micropore more than 100nm.And the aperture of the NF membrane upper surface prepared after Overheating Treatment cross-linking reaction is reduced to 1nm, surface texture is still finer and close, homogeneous, reaches nanofiltration rank.And from the section structure of film, there is no obvious cross-linked structure as active precursor film, and the NF membrane prepared after Overheating Treatment has had obvious cross-linked structure, gives the excellent mechanical performance of film and the high function retained.
The flat board NF membrane that the present embodiment prepares is at 25 DEG C, and under the test condition of 0.3MPa, pure water flux is 44.4L/m2H, the NaCl solution rejection to 1g/L is 51.2%, the MgSO to 1g/L4Solution rejection is 99.1%, and 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, and flux and cutoff performance are held essentially constant.
Comparative example 1
A1 and the acetone that weight/mass percentage composition is 1% that weight/mass percentage composition is 20% are dissolved in N, N-dimethyl acetylamide is mixed and made into preparation liquid, preparation liquid spreads to liquid film, and immerses film-forming in the water of 10 DEG C, the Flat Membrane obtained is cleaned through water soaking, obtains active precursor film.Flat Membrane is obtained after being dried by the active precursor film of preparation.Preparation liquid formula, preparation condition and membrane structure and performance are such as shown in table 1-1.
Table 1-1
Comparing embodiment 1 and comparative example 1, do not carry out heat treatment, so without cross-linked state in membrane structure, cutoff performance cannot arrive the performance requirement of NF membrane, monovalent salt NaCl only have the rejection of 10.2%, to divalent salts MgSO due to comparative example4Also only has the rejection of 34.1%.And after shaking 20 days, cutoff performance declines further, and causing that mechanical performance is bad due to uncrosslinked, the decay of flux is also very big.Thus contrast can draw the necessity of heat treatment step, and film properties is played very crucial effect by cross-linking reaction.
Comparative example 2
The m-diaminobenzene. aqueous solution that weight/mass percentage composition is 2% is applied on polyether sulfone flat support film, after draining, immerse in 0.5% pyromellitic trimethylsilyl chloride hexane solution, take out after placing 1min and dry, in 70 DEG C of heat treatment 15min, obtain double-deck flat board NF membrane.
Film properties is such as shown in table 1-2.Wherein water flux and rejection test, all carry out under 1.2MPa has pressure.
Table 1-2
Comparing embodiment 1 and comparative example 2, comparative example 2 adopts traditional interfacial polymerization to prepare double-deck flat board NF membrane, and when the operating pressure needing 1.2MPa, can be only achieved flux is 38.4L/m2H, under the operating pressure of 0.3MPa, flux is only small, it is impossible to meet the operation requirement of nanofiltration.It addition, after shaking 20 days, the rejection of salt is decreased obviously, illustrates that dense functional layer is insecure with support Coating combination, cause the instability of cutoff performance.And the flat board NF membrane operating pressure prepared by the present invention has only to 0.3MPa, and film being placed in 60 DEG C of deionized waters isothermal vibration 20 days, flux and cutoff performance are held essentially constant, and stability is good.
Embodiment 2
Copolymer and the diethyl ether that weight/mass percentage composition is 2% that C1 that weight/mass percentage composition is 15%, weight/mass percentage composition are 20% vinyl chloride are dissolved in N, dinethylformamide is mixed and made into preparation liquid, with the pressure of 0.1Mpa, preparation liquid is extruded from spinning head, the core liquid of 35 DEG C flows out from the central canal of spinning head simultaneously, liquid film immerses film-forming in the coagulating bath of 35 DEG C behind the air gap of 1 centimetre, the hollow-fibre membrane obtained cleans through water soaking, obtains active precursor film.Dry after the active precursor film of preparation is soaked 10h with 20% glycerine water solution, heat treatment 5 hours at 95 DEG C, obtain lotus positive electricity hollow fiber nanofiltration membrane.
Preparation liquid formula, preparation condition and membrane structure and performance are as shown in table 2.
Table 2
Accompanying drawing 4 for the present embodiment prepare active precursor film and further across after heat treatment cross-linking reaction prepare the section of hollow fiber nanofiltration membrane, inner surface, outer surface Electronic Speculum figure.The surfaces externally and internally of active precursor film has a large amount of micropore more than 100nm.And the aperture of the NF membrane surfaces externally and internally prepared after Overheating Treatment cross-linking reaction is reduced to 1nm, surface texture is still finer and close, homogeneous, reaches nanofiltration rank.
Embodiment 3
The characterizing method of the preparation process of positively charged nanofiltration membranes and structure and performance is shown in embodiment 1:
Preparation liquid formula, film preparation condition and membrane structure and performance are as shown in table 3.
Table 3
Embodiment 4
The characterizing method of the preparation process of positively charged nanofiltration membranes and structure and performance is shown in embodiment 2:
Preparation liquid formula, film preparation condition and membrane structure and performance are as shown in table 4.
Table 4
Embodiment 5
The characterizing method of the preparation process of positively charged nanofiltration membranes and structure and performance is shown in embodiment 1:
Preparation liquid formula, film preparation condition and membrane structure and performance are as shown in table 5.
Table 5
Embodiment 6
The characterizing method of the preparation process of positively charged nanofiltration membranes and structure and performance is shown in embodiment 2:
Preparation liquid formula, film preparation condition and membrane structure and performance are as shown in table 6.
Table 6
Embodiment 7
The characterizing method of the preparation process of positively charged nanofiltration membranes and structure and performance is shown in embodiment 1:
Preparation liquid formula, film preparation condition and membrane structure and performance are as shown in table 7.
Table 7
Embodiment 8
The characterizing method of the preparation process of positively charged nanofiltration membranes and structure and performance is shown in embodiment 1:
Preparation liquid formula, film preparation condition and membrane structure and performance are as shown in table 8.
Table 8
Embodiment 9
The characterizing method of the preparation process of positively charged nanofiltration membranes and structure and performance is shown in embodiment 1:
Preparation liquid formula, film preparation condition and membrane structure and performance are as shown in table 9.
Table 9
Embodiment 10
The characterizing method of the preparation process of positively charged nanofiltration membranes and structure and performance is shown in embodiment 1:
Preparation liquid formula, film preparation condition and membrane structure and performance are as shown in table 10.
Table 10
Embodiment 11
The characterizing method of the preparation process of positively charged nanofiltration membranes and structure and performance is shown in embodiment 2:
Preparation liquid formula, film preparation condition and membrane structure and performance are as shown in table 11.
Table 11
Embodiment 12
The characterizing method of the preparation process of positively charged nanofiltration membranes and structure and performance is shown in embodiment 2:
Preparation liquid formula, film preparation condition and membrane structure and performance are as shown in table 12.
Table 12
Embodiment 13
The characterizing method of the preparation process of positively charged nanofiltration membranes and structure and performance is shown in embodiment 2:
Preparation liquid formula, film preparation condition and membrane structure and performance are as shown in table 13.
Table 13
Embodiment 14
The characterizing method of the preparation process of positively charged nanofiltration membranes and structure and performance is shown in embodiment 2:
Preparation liquid formula, film preparation condition and membrane structure and performance are as shown in table 14.
Table 14
Embodiment 15
The characterizing method of the preparation process of positively charged nanofiltration membranes and structure and performance is shown in embodiment 2:
Preparation liquid formula, film preparation condition and membrane structure and performance are as shown in Table 15.
Table 15
Embodiment 16
The characterizing method of the preparation process of positively charged nanofiltration membranes and structure and performance is shown in embodiment 2:
Preparation liquid formula, film preparation condition and membrane structure and performance are as shown in table 16.
Table 16
Embodiment 17
The characterizing method of the preparation process of positively charged nanofiltration membranes and structure and performance is shown in embodiment 2:
Preparation liquid formula, film preparation condition and membrane structure and performance are as shown in table 17.
Table 17
Embodiment 18
The characterizing method of the preparation process of positively charged nanofiltration membranes and structure and performance is shown in embodiment 2:
Preparation liquid formula, film preparation condition and membrane structure and performance are as shown in table 18.
Table 18
From all embodiments prepare NF membrane performance it can be seen that at 25 DEG C, under the test condition of 0.3MPa, pure water flux is above 40L/m2H, is above 50% to the NaCl solution rejection of 1g/L, the MgSO to 1g/L4Solution rejection is above 98%, and the Congo red rejection of 1g/L is 99.9%, and film is placed in 60 DEG C of deionized waters isothermal vibration 20 days, and flux and cutoff performance are held essentially constant, and illustrates that the structure of film and performance are highly stable.
Claims (10)
1. a positively charged nanofiltration membranes, it is characterised in that: the material of described NF membrane is the self-crosslinking product of copolymer A, or the product of chlorine-containing polymer B and tertiary amine-type polymer C blended cross linking, and the crosslinked group in cross-linking products is quaternary ammonium chloride salt groups, wherein,
The structural formula of described copolymer A is as follows:
In formula: m+n=800～5000, it is preferable that m+n=1000～3000；
M/n=10/1～1/1；
R1=H or Cl；
R2=H or CH3；
R3=containing tertiary amine group；
The structural formula of described chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=800～5000, it is preferable that x=1000～3000；
The structural formula of described tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=containing tertiary amine group；
Y=800～5000, it is preferable that y=1000～3000.
2. positively charged nanofiltration membranes according to claim 1, it is characterized in that, described chlorine-containing polymer B is the product of the chloride monomer polymerization of vinyl-type, described tertiary amine-type polymer C is the product of vinyl-type tertiary amine monomers polymerization, and described copolymer A is the product of the chloride monomer of vinyl-type and vinyl-type tertiary amine monomers copolymerization.
3. positively charged nanofiltration membranes according to claim 2, it is characterized in that, the chloride monomer of described vinyl-type in vinyl chloride, the vinylidene chloride any one or arbitrarily multiple, any one in dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylamino propyl acrylamide, 4-vinylpridine, 2-vinylpyridine, vinyl imidazole of described vinyl-type tertiary amine monomers.
4. the positively charged nanofiltration membranes according to any one of claim 1-3, it is characterised in that described quaternary ammonium chloride salt groups is selected from structural formula:
、、Or
In formula: R=CH3Or CH2CH3。
5. the preparation method of a positively charged nanofiltration membranes, it is characterised in that comprise the steps:
(1) being dissolved in casting solution by copolymer A, add quaternized inhibitor, mix homogeneously makes preparation liquid, is solidified from coagulating bath by solution phase inversion, prepares Viability precursor film；
(2) active precursor film heat treatment step (1) prepared, obtains positively charged nanofiltration membranes；
The structural formula of described copolymer A is as follows:
In formula: m+n=800～5000, it is preferable that m+n=1000～3000；
M/n=10/1～1/1；
R1=H or Cl；
R2=H or CH3；
R3=containing tertiary amine group.
6. the preparation method of a positively charged nanofiltration membranes, it is characterised in that comprise the steps:
(1) being dissolved in casting solution by chlorine-containing polymer B and tertiary amine-type polymer C, add quaternized inhibitor, mix homogeneously makes preparation liquid, is solidified from coagulating bath by solution phase inversion, prepares Viability precursor film；
(2) active precursor film heat treatment step (1) prepared, obtains positively charged nanofiltration membranes；
The structural formula of described chlorine-containing polymer B is as follows:
In formula:
R1=H or Cl；
X=800～5000, it is preferable that x=1000～3000；
The structural formula of described tertiary amine-type polymer C is as follows:
In formula:
R2=H or CH3；
R3=containing tertiary amine group；
Y=800～5000, it is preferable that y=1000～3000.
7. the preparation method of a kind of positively charged nanofiltration membranes according to claim 5 or 6, it is characterized in that, the quaternized inhibitor described in step (1) in diethyl ether, dichloromethane, acetone, methanol, ethanol, pentane, the Pentamethylene. any one or arbitrarily multiple.
8. the preparation method of a kind of positively charged nanofiltration membranes according to claim 5 or 6, it is characterised in that the temperature making preparation liquid described in step (1) is 5～50 DEG C, described coagulation bath temperature is 5～50 DEG C；Heat treatment temperature described in step (2) is 50～120 DEG C, and heat treatment time is 1～24 hour.
9. the preparation method of a kind of positively charged nanofiltration membranes according to claim 5, it is characterised in that described copolymer A is by the product of the chloride monomer of vinyl-type Yu vinyl-type tertiary amine monomers copolymerization.
10. the preparation method of a kind of positively charged nanofiltration membranes according to claim 6, it is characterised in that described chlorine-containing polymer B is that described tertiary amine-type polymer C is the product being polymerized by vinyl-type tertiary amine monomers by the product of the chloride monomer polymerization of vinyl-type.
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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 |
| 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 |
| 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 |
| CN201410734310.6A Pending CN105642129A (en) | 2014-08-31 | 2014-12-04 | Positively charged nano-filtration membrane based on tertiary amine type amphiphilic copolymer 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 |
| 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 |
| 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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Also Published As
| Publication number | Publication date |
|---|---|
| CN105363359A (en) | 2016-03-02 |
| CN105363353B (en) | 2018-03-20 |
| CN105642129A (en) | 2016-06-08 |
| CN105363350B (en) | 2018-01-30 |
| CN105709608B (en) | 2019-04-26 |
| CN112403286A (en) | 2021-02-26 |
| CN105709619B (en) | 2019-04-30 |
| CN105363359B (en) | 2017-06-30 |
| CN105363350A (en) | 2016-03-02 |
| CN105709608A (en) | 2016-06-29 |
| CN104190265A (en) | 2014-12-10 |
| CN105363353A (en) | 2016-03-02 |
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