CN110314561A

CN110314561A - A kind of polymeric film material and preparation method thereof

Info

Publication number: CN110314561A
Application number: CN201810272464.6A
Authority: CN
Inventors: 何春菊; 邱中勇; 王建秀; 刘子媛; 曲智华; 曲智清
Original assignee: Donghua University
Current assignee: Donghua University; National Dong Hwa University
Priority date: 2018-03-29
Filing date: 2018-03-29
Publication date: 2019-10-11

Abstract

The present invention provides a kind of polymeric film materials and preparation method thereof.Polymer film is prepared by being first dissolved in the amphipathic polymer with tertiary amine groups in organic solvent with the polymer for being used to prepare seperation film in the present invention, then polymer film is put into quaternizing agent solution and carries out quaternization reaction, obtain bisexual ion purification polymeric film material, since zwitterionic polymer exists in the form of blend with the polymer for being used to prepare seperation film, and zwitterionic polymer includes hydrophobic segment, therefore polymeric film material provided by the invention has permanent hydrophilic antifouling property, and due to the strong hydrophily of amphoteric ion, the speed that hydrophilic segment is migrated to film surface is fast, the hydrophilic segment coverage rate of film surface is high, antifouling property is excellent.

Description

A kind of polymeric film material and preparation method thereof

Technical field

The present invention relates to technical field of polymer materials more particularly to a kind of polymeric film material and preparation method thereof.

Background technique

In membrane filtration processes, the polymer separation film of common nanofiltration or ultrafiltration due to membrane material itself hydrophobicity, It is easily absorbing the pollutants such as protein in liquid to be treated, colloidal particle in use, leads to Pore Blocking, causes film dirty Dye is irreversibly remarkably decreased and persistently increases with the pressure difference of film two sides so as to cause the flux of film in use process, separates Effect is poor, shortens the service life of film.

Cause fouling membrane most basic reason be material hydrophobicity, a large amount of research work proves, film surface hydrophily Promotion be conducive to improve the antifouling property of membrane material, therefore polymer porous film is modified, assigns film surface hydrophily It is one of the important way for improving hydrophobic film pollution resistance.Common method be coat hydrophilic polymer coating in film surface, but It is that coating is easy to fall off in use, while will cause Pore Blocking in coating procedure, reducing its functionality.And it is grafted and changes Property, modification by copolymerization method then process is complicated, it is more difficult to accomplish scale production.The method of blending and modifying is relatively easy, and easily In industrialization, this kind of method adds water-soluble polymer and nanoparticle in preparation liquid, to carry out the hydrophilic modifying of film.But It is faint with water solubility or with basal body binding force due to additive, it can gradually be lost in use, the hydrophilic of film is caused to change Property effect cannot be lasting.Therefore, developing practicable method of modifying is just particularly important.

In recent years studies have shown that can using amphipathic polymer as blending and modifying additive.Due in amphipathic polymer Hydrophilic chain and membrane body material between thermodynamics it is incompatible, hydrophilic segment will be moved spontaneously to film surface in film forming procedure Enrichment is moved, hydrophilic laminate is formed in film surface, to significantly improve the surface hydrophilicity and antifouling property of film.Meanwhile two Hydrophobic chain in close polymer molecule can prevent amphipathic polymer from film matrix because having good compatibility with membrane body material It is lost.But since the speed that hydrophilic segment is migrated to film surface is slow, the hydrophilic segment coverage rate of film surface is low, modified effect It is subject to certain restrictions.

It is also disclosed in the prior art using the surface progress that there is amphoteric ion to the polymer on polymer film of group It is modified.But since amphoteric polymer cannot dissolve in organic solvent, so in the prior art such as bibliography 1 (CN102580585A) its in carries out interface by polyvinyl alcohol graft copolymerized amphoteric ion copolymer and polyamine, polynary acyl chlorides monomer Polymerization forms the composite nanometer filtering film of the polyamide functional layer containing amphoteric ion group on polyacrylonitrile porous support membrane.This Kind double-layer structure equally exists amphoteric ion can gradually be lost radical polymerisation object in use, lead to the hydrophilic modifying of film The unendurable problem of effect.In addition, also disclosing a kind of polymerization of group containing arone in bibliography 2 (CN104069753A) The antipollution method of modifying of object film.This method using UV graft polymerization (methyl) acrylic acid epoxy Arrcostab in super (micro-) filter or Nanofiltration film surface, further reaction generates alkyl halide, under the conditions of existing for certain catalyst, ligand or the reducing agent and acrylic acid The reaction of betaines compound obtains super (micro-) filter or nanofiltration membrane with excellent hydrophilic and antifouling property.Although using Radiation grafting can be improved the persistence of hydrophilic modifying, but higher cost, it is difficult to obtain in the processing of polymer film sufficiently It answers.Therefore it provides a kind of polymeric film material with permanent hydrophilic antifouling property and preparation method thereof becomes this field urgently It solves the problems, such as.

Summary of the invention

The technical problem to be solved in the present invention is to provide a kind of polymeric film material with permanent hydrophilic antifouling property and Preparation method.By being first dissolved in the amphipathic polymer with tertiary amine groups with the polymer for being used to prepare seperation film in the present invention It is prepared into polymer film in organic solvent, then polymer film is put into quaternizing agent solution and carries out quaternization reaction, is obtained To bisexual ion purification polymeric film material, due to zwitterionic polymer and the polymer of seperation film is used to prepare with blend Form exist, and zwitterionic polymer includes hydrophobic segment, therefore polymeric film material provided by the invention has and holds Long hydrophilic antifouling property；Further, the hydrophily strong due to amphoteric ion, the speed that hydrophilic segment is migrated to film surface is fast, The hydrophilic segment coverage rate of film surface is high, and antifouling property is excellent.

In order to solve the above technical problems, having comprising (a) zwitterionic the present invention provides a kind of polymeric film material Polymer and (b) are used to prepare the polymer of seperation film, and wherein amphoteric ion includes quaternary ammonium group.

Further, there is zwitterionic polymer to be made by the amphipathic polymer containing tertiary amine groups is quaternized, amphiphilic The monomer of polymer includes the function monomer containing carbon-carbon double bond and tertiary amine groups simultaneously.

Further, function monomer is selected from (methyl) dimethylaminoethyl acrylate, (methyl) acrylic acid lignocaine second One or more of ester, N- (3- dimethylamino-propyl) Methacrylamide.

Further, amphipathic polymer is ABA block copolymer, and B block is the hydrophobic chain comprising dimethyl silicone polymer Section, A block are by the function monomer homopolymerization simultaneously containing carbon-carbon double bond and tertiary amine groups or to be copolymerized obtained hydrophilic segment.

Further, the weight ratio of amphipathic polymer and the polymer for being used to prepare seperation film is 0.1-30:1-30.

Further, the molecular weight distributing index containing zwitterionic polymer is 1~1.3.

Further, the polymer for being used to prepare seperation film is selected from fluoropolymer, polysulfones and its derivative, polypropylene One of nitrile, polymethyl methacrylate, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, cellulose and its derivates are several Kind.

Further, polymeric film material is plate membrane or hollow-fibre membrane.

Further, the present invention also provides a kind of preparation methods of polymeric film material, comprising the following steps:

1) polymer, the second solvent, pore-foaming agent and the amphipathic polymer that are used to prepare seperation film are blended and prepare casting solution, Then polymer film is made using filming technology, the monomer of amphipathic polymer includes the function containing tertiary amine groups and carbon-carbon double bond simultaneously It can property monomer；

2) polymer film obtained in step 1) is put into quaternizing agent solution and carries out quaternization reaction, obtain both sexes Ionomeric polymer membrane material.

Further, amphipathic polymer is prepared by atom transition free radical polymerization reaction.

Further, prepare amphipathic polymer the following steps are included:

Macromole evocating agent end halogen dimethyl polysiloxane is added in the reaction vessel, complexing agent, contains tertiary amine groups simultaneously With the functional monomer, catalyst cuprous halide and solvent of carbon-carbon double bond, wherein cuprous halide should add under inert gas protection Enter, monomer, end halogen dimethyl siloxane, cuprous halide and complexing agent molar ratio be 1~10000:1:0.1~10:0.1~ 10, it is warming up to 30~120 DEG C under inert gas protection, reacts 1~72 hour；

Further, quaternization reaction is to carry out reaction 1~72 hour at a temperature of 10~70 DEG C.

Further, the functional monomer simultaneously containing tertiary amine groups and carbon-carbon double bond is selected from (methyl) acrylate One or more of ethyl ester, (methyl) diethylaminoethyl acrylate, N- (3- dimethylamino-propyl) Methacrylamide.

Further, casting solution includes in terms of quality percentage: being used to prepare the polymer 10~30% of seperation film, pore Agent 1~10%, amphipathic polymer 0.1~30%, the second solvent 30~87.8%, the preparation method of casting solution are that will be used to make Polymer, pore-foaming agent, the second solvent and the amphipathic polymer of standby seperation film are put into homogenizing apparatus, carry out the dissolution that homogenizes, Then vacuum or discontinuous degassing.

Further, quaternary ammonium reagent is selected from one or more of sultones, halosulfonic acid, bromine carboxylic acid, alkylhalide group ether.

Further, the polymeric film material as made from aforementioned preparation process that the present invention also provides one kind.

In conclusion polymeric film material provided by the invention has excellent and lasting antifouling property.

Detailed description of the invention

The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments:

Fig. 1 is Br-PDMS-Br macromole evocating agent prepared by embodiment 1¹HNMR；

Fig. 2 is PDMAEMA-b-PDMS-b-PDMAEMA's prepared by embodiment 1¹HNMR；

Fig. 3 is the surface scan electron microscope of polymer flat plate film prepared by embodiment 1；

Fig. 4 is the surface A FM figure of polymer flat plate film prepared by embodiment 1；

Fig. 5 is the surface water contact angle photo of polymer flat plate film prepared by embodiment 1.

Specific embodiment

Presently in connection with attached drawing, better embodiment of the invention is discussed in detail.Although description of the invention will combine each Embodiment is introduced together, but this feature for not representing the invention is only limitted to the several embodiments.On the contrary, combining real It is to be possible to the other selections extended to cover based on claim of the invention that the mode of applying, which makees the purpose that invention is introduced, Or transformation.In order to provide to depth understanding of the invention, be described below in will include many concrete details.The present invention can also be with Implement without using these details.In addition, in order to avoid confusion or obscuring emphasis of the invention, some details will in the de-scription It is omitted.

Many for water process polymer films due to the chemical composition of itself be it is fixed, itself do not have hydrophily. Then inventor envisions that by being modified to polymer film, its hydrophily is assigned.

The present invention by the hydrophily of amphipathic polymer and its organic solvent dissolubility and amphoteric ion functional group boundary Face characteristic combines, and is blended by amphipathic polymer with the polymer for being used to prepare seperation film, obtains blend film, then with season Quaternization reaction occurs for ammonium reagent, lures that the hydrophilic segment of amphipathic polymer is migrated toward film surface or fenestra into, and by tertiary amine Group becomes amphoteric ion quaternary ammonium group, increases the hydrophily of film surface, is promoted using the excellent antifouling property of amphoteric ion poly- The stain resistance of compound film.The polymeric film material in the present invention is finally obtained, it includes (a) to have zwitterionic polymerization Object and (b) are used to prepare the polymer of seperation film, and wherein amphoteric ion includes quaternary ammonium group.

Further, there is zwitterionic polymer to be used to prepare seperation film by the amphipathic polymer containing tertiary amine groups Polymer in the presence of it is quaternized be made, the monomer of amphipathic polymer includes the function containing carbon-carbon double bond and tertiary amine groups simultaneously Monomer, it is preferable that function monomer is selected from (methyl) dimethylaminoethyl acrylate, (methyl) diethylaminoethyl acrylate, N- One or more of (3- dimethylamino-propyl) Methacrylamide.

Further, it is total that the random copolymer that amphipathic polymer can be hydrophilic monomer and hydrophobic monomer is also possible to block Polymers.Preferred amphipathic polymer is ABA block copolymer in the present invention, and B block is the hydrophobic chain comprising dimethyl silicone polymer Section, A block are by the function monomer homopolymerization simultaneously containing carbon-carbon double bond and tertiary amine groups or to be copolymerized obtained hydrophilic segment.Block is total Polymers is relative to random copolymer, and hydrophilic segment is easier to move to polymer film surface, and antifouling property is more preferable.

Preferably, the molecular weight distributing index containing zwitterionic polymer is 1~1.3.By accurately controlling two The molecular weight distribution of the polymer of property ion, it is ensured that the length of hydrophilic segment is uniform, is further ensured that polymer film surface Hydrophilic layer thickness it is uniform, polymer film surface antifouling property is uniform.

Further, amphipathic polymer relative to 10-30 mass parts is used to prepare seperation film in polymeric film material Polymer, the lower limit of amphipathic polymer content is 0.1 parts by weight, preferably 1.0,1.2,1.5,1.8,2.0,2.2,2.5, 2.8,3.0,3.2 or 3.5 parts by weight；It is limited to 30 parts by weight, the parts by weight of preferably 30,25,20,15,10 or 5 thereon.Relative to The polymer for being used to prepare seperation film of 10-30 mass parts, if the content of amphipathic polymer less than 0.1 parts by weight, finally Polymeric film material hydrophily it is insufficient, the defect that film antifouling property can not be overcome poor；On the other hand, if amphiphilic polymerize The content of object is greater than 30 parts by weight, then the production cost of final polymeric film material is excessively high, and obtained casting film fluid viscosity It is too small, it also will affect the filming performance of film, so that expected balance, and film is not achieved in the pollution resistance of most telolemma and production cost Flexibility and mechanical strength have downward trend.

Further, the polymer for being used to prepare seperation film is selected from fluoropolymer, polysulfones and its derivative, polypropylene One of nitrile, polymethyl methacrylate, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, cellulose and its derivates are several Kind.Wherein, fluoropolymer is preferably Kynoar, ethylene-tetrafluoroethylene copolymer etc.；Polysulfones and its derivative include poly- Sulfone, sulfonated polysulfone, polyether sulfone, sulfonated polyether sulfone, polyarylsulfone (PAS), aromatic polysulfonamides etc..

Further, polymeric film material is plate membrane or hollow-fibre membrane.

Further, the second solvent is selected from dimethylformamide (DMF), dimethyl acetamide (DMAC), N- methylpyrrole One or more of alkanone (NMP), dimethyl sulfoxide (DMSO), ketone, esters.

Further, filming technology above-mentioned is the filming technology of conventional preparation plate membrane or hollow-fibre membrane, packet Include phase separation method (Nonsolvent Induce Phase Separation, NIPS) or thermally induced phase separation (Thermally Induced Phase Separation, TIPS).

Functional monomer simultaneously containing tertiary amine groups and carbon-carbon double bond is because having the vinyl and activity of polymerism in its molecule Higher tertiary amine groups, can carry out homopolymerization, copolymerization and it is quaternized based on various chemical reactions.Studies have shown that atom transfer is certainly The polymerization that can be used for the functional monomer simultaneously containing tertiary amine groups and carbon-carbon double bond by base polymerization (ATRP), obtained polymer tool There are anti-pollution, bacteria resistance energy.ATRP becomes conjunction due to its excellent polymerization Modulatory character as novel living polymerisation process At the prefered method of amphipathic polymer.ATRP method is flat by establishing reactive species and the reversible dynamic of suspend mode kind in the polymerization Weighing apparatus makes the concentration of the free free radical in reaction system be in extremely low always by alternate " promoting work-inactivation " reversible reaction State, force irreversible termination reaction to be reduced to minimum level, so that " activity "/controllable free-radical polymerisation is realized, to polymerization Reaction carries out Effective Regulation.

For realize foregoing invention thought, the present invention first by ATRP method synthesize amphipathic polymer, then be used to prepare The polymer of seperation film is blended, and polymer blend membrane is made, and by subsequent quaternization reaction, realizes polymer film surface Bisexual ion purification.

It further, is ABA block copolymer by the amphipathic polymer that aforementioned ATRP method synthesizes, B block is comprising poly- The hydrophobic segment of dimethyl siloxane, A block are by the function monomer homopolymerization or copolymerization simultaneously containing carbon-carbon double bond and tertiary amine groups Obtained hydrophilic segment.

Further, prepare amphipathic polymer the following steps are included:

Macromole evocating agent end halogen dimethyl polysiloxane is added in the reaction vessel, complexing agent, contains tertiary amine groups simultaneously With the functional monomer, catalyst cuprous halide and the first solvent of carbon-carbon double bond, wherein cuprous halide should be in inert gas shielding Lower addition, monomer, the molar ratio for holding halogen dimethyl siloxane, cuprous halide and complexing agent are 1~10000:1:0.1~10:0.1 ~10, it is warming up to 30~120 DEG C under inert gas protection, reacts 1~72 hour；Obtain amphipathic polymer.Wherein, halogenation is sub- Copper is cuprous bromide or stannous chloride；Complexing agent is bipyridyl, PMDETA, Me₆TREM, cymene；First solvent is Toluene, butanone, normal propyl alcohol, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethyl acetamide (DMAC), methyl pyrrole One of pyrrolidone (NMP), isopropanol, or mixed by wherein several.

Further, initiator end halogen dimethyl silicone polymer above-mentioned is made by following steps: being added in a reservoir One of silicone oil containing active hydrogen, triethylamine and tetrahydrofuran, methylene chloride, toluene, butanone substance or several substances Mixture, be placed in -10~10 DEG C；Lead to inert gas to exclude air；2- bromo isobutyl carboxylic acid halides is slowly added dropwise, continues at room temperature React 1~72h；Insoluble ammonium salt is removed, by liquid separation, is dried to obtain macromole evocating agent end halogen dimethyl siloxane, wherein The molar ratio of silicone oil, triethylamine and 2- bromo isobutyl carboxylic acid halides containing active hydrogen is 50:1~6:1~6, and 2- bromo isobutyl carboxylic acid halides is 2- bromine isobutyl acylbromide or 2- bromine isobutyryl chloride, end halogen dimethyl silicone polymer are end bromine dimethyl silicone polymer or are end chlorine poly- two Methylsiloxane.

Further, quaternization reaction is to carry out reaction 1~72 hour at a temperature of 10~70 DEG C.Wherein, quaternary ammoniated examination Agent is selected from one or more of sultones, halosulfonic acid, bromine carboxylic acid, alkylhalide group ether.

Further, casting solution includes in terms of quality percentage: being used to prepare the polymer 10~30% of seperation film, pore Agent 1~10%, amphipathic polymer 0.1~30%, the second solvent 30~87.8%, the preparation method of casting solution are that will be used to make Polymer, pore-foaming agent, the second solvent and the amphipathic polymer of standby seperation film are put into homogenizing apparatus, carry out the dissolution that homogenizes, Then vacuum or discontinuous degassing.Wherein, pore-foaming agent be one of polyvinylpyrrolidone, polyethylene glycol, polyethylene glycol oxide or It is several.

Further, the present invention also provides one kind polymeric film materials as made from aforementioned any preparation method.

It is tested through practical application, polymer film prepared by the embodiment of the present invention possesses very high pollution resistance, and is discharged water The indices of matter have all reached urban reclaimed water water standard " urban sewage reutilization urban reclaimed water water standard " (GB/T18920-2002) and industrial reuse standard " urban sewage reutilization water quality standard for industries " (GB/ T19923-2005).Therefore, polymer film of the invention is suitable for municipal sewage such as sanitary wastewater and industrial wastewater ratio Such as the processing of Leather Factory's waste water, practical application value height.

Test method and standard:

The test assessment of following technical indicator is carried out to the polymer film that following each embodiments and comparative example obtain.

Polymer film surface and section micromorphology: dry film is broken in liquid nitrogen or directly after sputtered platinum, with Japan JSM-5600LV type scanning electron microscope test；

The water flux test method of film: being 12cm by area²Film is placed in homemade flux measuring device, in 0.15MPa After lower precompressed 30min, membrane flux tends towards stability, and pressure is down to 0.1MPa, pure water flux is the water body penetrated in the unit time Product.Amount of flux is the volume that per membrane area penetrates water in the unit time, and flux J=V/ (A × t), wherein V is the water body penetrated Product (L), A is membrane area (m²), t is time of penetration (h), J unit L/m²h。

Rejection: routinely detection method is tested, for example can refer to method described in following documents: Li Nana etc., The research of PVDF/PVA blend film." functional material ", 2007 volume 38 the 12nd 1975-1980 pages of the phase.

Film surface contact angle test: film is developed on the glass sheet, is placed in contact angle measurement (model OCA40Micro) Platform on, 3 microlitres of pure water are dripped to every time by film surface by the syringe in device, utilize contact angle imaging software, calculate water Drip the angle in film surface.Each sample measures 5 times, calculates average value.

The test of the secondary water flux response rate of film: film is placed in filter device, successively filters pure water 2h, and it is logical to obtain stablizing water Measure J₁, then feed liquid is changed to the BSA solution of 1g/L, refilter 2h to flux stabilized, obtain stable albumen flux J_BSA, After take the film out and put back in testing mould with after pure water rinsing, then measure pure water stabilized flux 2h, obtain stablizing water flux J₂.The The ratio of secondary water flux and first time water flux is secondary flux recovery rate (FRR value), and FRR value is higher, antifouling property Better.J_BSAWith J₁Ratio and 1 difference be anti-protein-contamination parameter flux rate of descent be RFR (%), RFR value is smaller, Antifouling property is better.

Chemical reagent used in the following example and comparative example is as follows:

1. hydroxy silicon oil, amido silicon oil: Jinan Guo Bang Chemical Co., Ltd..

2. polymer:

Kynoar (PVDF): three Ai Fu new material limited liability companies；

Polyether sulfone (PES): add brightness chemical products Co., Ltd；

Polysulfones (PS): add brightness chemical products Co., Ltd；

Ethylene-tetrafluoroethylene copolymer (ETFE): Yancheng Yong Hui plastics Co., Ltd；

Polyacrylonitrile (PAN): the energy saving Science and Technology Ltd. of Nanjing strength；

Polymethyl methacrylate (PMMA): Li Yang Co., Ltd, Mitsubishi；

Polyvinyl alcohol (PVA): Shanxi three-dimensional group Co., Ltd；

Ethylene-vinyl alcohol copolymer (EVOH): Kuraray Co., Ltd；

Cellulose esters: Yi Shiman Co., Ltd；

Polyethylene glycol (PEG), polyethylene glycol oxide (PEO), polyethylene pyrrole network alkanone (PVP) are purchased from Chinese Medicine (group) Solution on Chemical Reagents in Shanghai company.

3. other reagents are all that analysis is pure, it is purchased from China Medicine (Group) Shanghai Chemical Reagent Co.,.

Embodiment 1

1. preparing amphipathic polymer 1

(1) in the reaction vessel be added 30g hydroxypropyl silicone oil (molecular weight 4000), 1.6g (15.5mmol) triethylamine and 40ml toluene leads to 10min N₂Gas.The mixture of 3.5g 2- bromo isobutyl acylbromide and 20ml tetrahydrofuran is added dropwise at -10 DEG C, It is added in about 1h.The reaction was continued at room temperature 72h.After completion of the reaction, after being filtered to remove insoluble ammonium salt, n-hexane dissolution is added, It is washed with deionized 3 times, anhydrous magnesium sulfate drying 24 hours is added, colourless transparent solution is obtained by filtration, after removing solvent, obtains To macromolecular ATRP initiator B r-PDMS-Br.

(2) first that monomer DMAEMA parlkaline aluminium oxide pillar removing polymerization inhibitor is spare.Successively add in the reaction vessel Enter macromole evocating agent (0.5mmol, 2g), monomer DMAEMA (25mmol, 3.93g), toluene 12g obtained in step (1), so Lead to nitrogen half an hour afterwards, then CuBr (1mmol, 0.1435g) is added under nitrogen protection, is eventually adding complexing agent pentamethyl two Ethylene triamine (PMDETA, 1mmol, 0.1733g).80 DEG C are reacted 24 hours, sudden cold and be passed through air.It is poly- with tetrahydrofuran dilution Polymer solution, filtering remove most of solvent, and concentrate precipitates in n-hexane, then heavy through tetrahydrofuran dissolution, n-hexane Forming sediment, rear filter paper filters for several times for purifying, and by product, drying for 24 hours, obtains colloidal solid under the conditions of 50 DEG C in vacuum drying oven.

(3) Fig. 1 is the nuclear-magnetism figure of Br-PDMS-Br macromole evocating agent.Br-PDMS-Br nuclear magnetic spectrum after terminal groups modification It is consistent substantially with the chemical shift of chemDraw software prediction, wherein 7.26ppm is CDCl₃Solvent peak, so by¹H-NMR It is found that a and e is integrated obtain S respectively in figure_e/S_a=30,Macromole evocating agent It synthesizes successfully.

(4) Fig. 2 is PDMAEMA-b-PDMS-b-PDMAEMA's¹H-NMR, wherein displacement is 2.29,2.57,4.05 difference For in PDMAEMA-N (CH₃)₂、—CH₂- N-and-O-CH₂- proton peak, as shown in a, b, c in figure.It is silicon at 0.1 - CH in oil₃Proton peak, as shown in d in figure.Calculating three block molecular weight by integral gained is 1.4 ten thousand.Prove amphipathic polymer It synthesizes successfully.

2. preparing plate membrane

Obtained amphipathic polymer 0.07g is dissolved into the DMAc of 56.43g, the pore of the PVDF and 3g of 10.5g is added Agent PVP K30, pre-swollen 1 hour, is redissolved 3 hours under mechanical stirring, and casting solution is made；Casting solution is true by 12 hours After empty deaeration processing, topple on a glass using 200 microns of scraper knifing, after be immediately placed in water coagulating bath, curing molding, Obtain blend flat sheet membrane.

3. film surface bisexual ion purification is blended

Blend flat sheet membrane is placed in 3- bromo-butyric acid/butanol solution of 0.1g/ml, shakes 1 hour at 70 DEG C, then uses Deionized water and alcohol alternately rinse, and obtain surface bisexual ion purification plate membrane.Then various tests are carried out.

Comparative example 1-1

It is outside the pale of civilization that surface amphoteric ion carried out to blend flat sheet membrane except not, is prepared and is blended using method same as Example 1 Plate membrane.

Comparative example 1-2

Except by the solvent of amphipathic polymer solution phase homogenous quantities substitution in addition to, other substances are constant, using with comparative example 1-1 Identical method, preparation are not added with the pure film of amphipathic polymer.

The blend flat sheet membrane performance test of embodiment 1, comparative example 1-1 and comparative example 1-2:

In the BSA aqueous solution dynamic Contamination measurement of 1g/L, the secondary water flux recovery of surface bisexual ion purification plate membrane Rate reaches 80%, and blend flat sheet membrane reaches 67%, and the flux recovery rate of pure film only has 50%；Surface bisexual ion purification plate membrane Retention rate of proteins be 72%, blend flat sheet membrane 65% is more much higher than pure film 33%；Surface bisexual ion purification plate membrane resists Protein contamination parameter flux rate of descent is RFR (%) 55%, blend flat sheet membrane RFR76%, and pure film is 89%.

Fig. 3 is that the surface SEM of blend flat sheet membrane schemes.Fig. 3 (a) is that the surface SEM of pure film schemes, and Fig. 3 (b) is blend flat sheet membrane Surface SEM figure, Fig. 3 (c) be surface bisexual ion purification plate membrane surface SEM scheme.It can be seen that.Pure film surface is more smooth, Blend flat sheet membrane, surface bisexual ion purification plate membrane surface there is vermicular texture, this is because amphipathic copolymer and its two Property ionization self assembly cause, which helps to improve the antifouling property of film.

Fig. 4 is that the surface A FM of blend flat sheet membrane schemes.Fig. 4 (a) is that the surface A FM of pure film schemes, and Fig. 4 (b) is blend flat sheet membrane Surface A FM figure, Fig. 4 (c) be surface bisexual ion purification plate membrane surface A FM scheme.It can be seen that blend flat sheet membrane, surface The surface roughness of bisexual ion purification plate membrane is above pure film, and the trend of increase is presented.Such hydrophilic, coarse structure has Help improve the pollution resistance of film.

Fig. 5 is the surface water contact angle experiment photo of plate membrane.Fig. 5 (a) is the upper surface contact angle schematic diagram of pure film, figure 5 (b) be the upper surface contact angle schematic diagram of blend flat sheet membrane, and Fig. 5 (c) is that the upper surface of surface bisexual ion purification plate membrane contacts Angle schematic diagram.It can be seen that the initial contact angle of surface bisexual ion purification plate membrane is 81 °, contact angle is reduced in 2 minutes 24 °, the initial contact angle of blend flat sheet membrane is 86 °, and contact angle is reduced to 64 ° in 2 minutes, and the initial contact angle of pure film is 94 °, and be held essentially constant at any time.

Embodiment 2

1. preparing amphipathic polymer 2

(5) 30g ethoxy silicone oil (molecular weight 2300) is added in the reaction vessel, 0.6g triethylamine and 230ml toluene lead to 10min N₂Gas.The mixture of 3.5g 2- bromo isobutyl acylbromide and 20ml tetrahydrofuran is added dropwise at -5 DEG C, is added in about 1h. The reaction was continued at room temperature 72h.After completion of the reaction, after being filtered to remove insoluble ammonium salt, n-hexane dissolution is added, is washed with deionized water It washs 3 times, anhydrous magnesium sulfate drying 24 hours is added, colourless transparent solution is obtained by filtration, after removing solvent, obtains macromolecular ATRP Initiator.

(6) first that monomer DMAEMA parlkaline aluminium oxide pillar removing polymerization inhibitor is spare.Successively add in the reaction vessel Enter macromole evocating agent (2g), monomer DMAEMA (39.3g) obtained in step (1), isopropanol 6g, dimethylformamide 6g, Then lead to nitrogen half an hour, then CuBr (0.1435g) is added under nitrogen protection, be eventually adding complexing agent pentamethyl divinyl Triamine (PMDETA, 0.1733g).80 degree are reacted 24 hours, sudden cold and be passed through air.With tetrahydrofuran dilute polymer solution, Filtering removes most of solvent, and concentrate precipitates in n-hexane, then through tetrahydrofuran dissolution, n-hexane deposition and purification number Filter paper filtering after secondary, by product, drying for 24 hours, obtains product under the conditions of 50 DEG C in vacuum drying oven.

2. preparing blend hollow fiber membrane

Obtained amphipathic polymer 0.7g is dissolved into the DMSO of 61.6g, PMMA the and 0.7g molecular weight that 7g is added is 1000000 polyethylene glycol oxide, the ultrasound swelling of power 100W 1 hour, is redissolved 10 hours, casting solution is made；Solution through filtering, After deaeration, under conditions of metering pump is with 10r/min revolving speed, spinning pressure 0.5Mpa, from the spinneret being made of two concentric tubes Head squeezes out；After 100mm dry-spinning path, in the aqueous solution that solvent content is 10%, temperature is 15 DEG C, solution internal circulating load is 20L/h Middle solidification, tetra- or more spun filament Zai Jing two-way (axially and radially) is stretched and appropriateness retraction, 5 washings, 20% propylene glycol second After alcoholic solution processing, wound with the speed of 20m/min to get blend hollow fiber membrane.

3. blend hollow fiber membrane surface bisexual ion purification

Blend hollow fiber membrane is placed in propane sultone/butanol solution of 1.0g/ml, it is small that 72 are shaken at 10 DEG C When, it is then alternately rinsed with deionized water and alcohol, obtains surface bisexual ion purification hollow-fibre membrane.Then various surveys are carried out Examination.

Comparative example 2-1

It is outside the pale of civilization that surface amphoteric ion carried out to blend hollow fiber membrane except not, is prepared using method same as Example 2 Blend hollow fiber membrane.

The blend hollow fiber membrane performance test of embodiment 2 and embodiment 2-1:

In hydrophily test, the surface contact angle of surface bisexual ion purification hollow-fibre membrane is 30 °, and doughnut is blended The surface contact angle of film is 50 °, in the BSA aqueous solution dynamic Contamination measurement of 1g/L, surface bisexual ion purification hollow-fibre membrane Secondary flux recovery rate is 89%, blend hollow fiber membrane 72%.

Embodiment 3

1. preparing amphipathic polymer 3

(1) 3000g methylol silicone oil (molecular weight 6000g/mol) is added in the reaction vessel, 320g triethylamine and 40ml Butanone leads to 60min argon gas to exclude air.The 2- bromo isobutyl acylbromide and 4000ml tetrahydro furan of 700g are slowly added dropwise at -5 DEG C The mixture muttered adds in about 1h.It continues the reaction at room temperature for 24 hours.After completion of the reaction, after removing insoluble ammonium salt, be added just oneself Alkane dissolution, is washed with deionized 3 times, and anhydrous magnesium sulfate drying 24 hours is added, colourless transparent solution is obtained by filtration, removes molten After agent, macromolecular ATRP initiator is obtained.

(2) first that monomer DMAEMA parlkaline aluminium oxide pillar removing polymerization inhibitor is spare.Successively add in the reaction vessel Enter macromole evocating agent (40g), monomer DMAEMA (5.2g), normal propyl alcohol 1970g, then leads to nitrogen half an hour, then in argon gas Protection is lower to be added CuBr (14.35g), pentamethyl-diethylenetriamine (PMDETA, 17.33g).30 degree react 72 hours, it is sudden it is cold simultaneously Being passed through air stops reaction, after tetrahydrofuran dilute polymer solution, removes mantoquita and complexing agent, gained filtrate removes big After the tetrahydrofuran of part, concentrate precipitates in n-hexane, then filters after for several times through tetrahydrofuran dissolution, n-hexane deposition and purification Paper filtering, by product, drying for 24 hours, obtains product under the conditions of 50 DEG C in vacuum drying oven.

2. preparing plate membrane

Obtained amphipathic polymer 10g is dissolved into the triacetyl glycerine of 40g, PVDF, 23g of 20g is added PEG400 and 7g K30 pre-swollen 1 hour under mechanical stirring, is redissolved 12 hours, casting solution is made；Casting solution passes through 12 hours Vacuum defoamation processing after, topple on a glass using 200 microns of scraper knifing, after be immediately placed in water coagulating bath, solidify Molding, obtains blend flat sheet membrane.

3. film surface bisexual ion purification is blended

Bromo-decane/THF solution of 5.0g/ml is prepared, is impregnated 36 hours at 30 DEG C of blend flat sheet membrane, then uses deionized water It is alternately rinsed with alcohol, obtains surface bisexual ion purification plate membrane.Then various tests are carried out.

Comparative example 3-1

It is outside the pale of civilization that surface amphoteric ion carried out to blend flat sheet membrane except not, is prepared and is blended using method same as Example 3 Plate membrane.

Comparative example 3-2

Except the solvents of amphipathic polymer solution phase homogenous quantities is substituted, other substances are constant, using with comparative example 3-1 phase Same method, preparation are not added with the pure film of amphipathic polymer.

The blend flat sheet membrane performance test of embodiment 3, comparative example 3-1 and comparative example 3-2:

In hydrophily test, the initial contact angle of surface bisexual ion purification plate membrane is 71 °, is contacted in 2 minutes Angle falls to 6 °, and the initial contact angle of blend flat sheet membrane is 84 °, and the initial contact angle of pure film is 94 °；In the BSA water of 1g/L In solution dynamic Contamination measurement, the secondary flux recovery rate of surface bisexual ion purification plate membrane reaches 85%, blend flat sheet membrane Reach 70%, and the flux recovery rate of pure film only has 50%；The retention rate of proteins of surface bisexual ion purification plate membrane is 90%, altogether Mixed plate membrane is 71%, more much higher than pure film 33%；Under the anti-protein-contamination parameter flux of surface bisexual ion purification plate membrane Drop rate be RFR (%) 51%, blend flat sheet membrane 76%, and pure film be 89%.

Embodiment 4

1. preparing amphipathic polymer 4

(1) 30g hydroxyl butyl silicone oil (molecular weight 1000g/mol) is added in the reaction vessel, 3.2g triethylamine and 40ml THF, 20ml methylene chloride lead to 20min nitrogen into flask.The 2- bromo isobutyl acylbromide of 7g is slowly added dropwise at 0 DEG C, in about 1h It adds.The reaction was continued at room temperature 48h.After completion of the reaction, insoluble ammonium salt, excess of solvent are removed, is washed with deionized 3 times, It is 12 hours dry that dead plaster is added, colourless transparent solution is obtained after filtering；Obtain macromolecular ATRP initiator.

(2) first that monomer DMAEMA parlkaline aluminium oxide pillar removing polymerization inhibitor is spare.Successively add in the reaction vessel Enter macromole evocating agent (2g), monomer DMAEMA (1572g), DEAM (1852g), butanone 13540g, it is half small then to lead to nitrogen When, then CuCl (0.02g), bipyridyl (0.03g) are added under nitrogen protection, it is reacted 65 hours at 40 DEG C.It is sudden cold and be passed through sky Gas stops reaction.After tetrahydrofuran dilute polymer solution, it is concentrated after removing mantoquita and complexing agent, concentrate is just Precipitated in hexane, then through tetrahydrofuran dissolution, n-hexane deposition and purification for several times after filter paper filter, by product in vacuum drying oven Drying for 24 hours, obtains product under the conditions of 50 DEG C.

2. preparing plate membrane

Obtained amphipathic polymer 30g is dissolved into the in the mixed solvent of the NMP and 10g repefral of 25g, K12,1gPEG200 of ETFE, 4g of 30g is added, under mechanical stirring pre-swollen 1 hour, is redissolved 24 hours, casting film is made Liquid；Casting solution is toppled over after vacuum defoamation processing in 24 hours on a glass using 200 microns of scraper knifing, rear rapid It is placed in water coagulating bath, curing molding obtains blend flat sheet membrane.

3. film surface bisexual ion purification is blended

Blend flat sheet membrane is placed in 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride/butanol solution of 0.5g/ml, at 40 DEG C It impregnates 24 hours, is then alternately rinsed with deionized water and alcohol, obtain surface bisexual ion purification plate membrane.Then it carries out various Test.

Comparative example 4-1

It is outside the pale of civilization that surface amphoteric ion carried out to blend flat sheet membrane except not, is prepared and is blended using method same as Example 4 Plate membrane.

Comparative example 4-2

Except by the solvent of amphipathic polymer solution phase homogenous quantities substitution in addition to, other substances are constant, using with comparative example 4-1 Identical method, preparation are not added with the pure film of amphipathic polymer.

The blend flat sheet membrane performance test of embodiment 4, comparative example 4-1 and comparative example 4-2:

In hydrophily test, the initial contact angle of surface bisexual ion purification plate membrane is 81 °, the contact angle in 2 minutes 14 ° are fallen to, the initial interface contacts angle of blend flat sheet membrane is 85 °, and the initial contact angle of pure film is 114 °；1g/L's In BSA aqueous solution dynamic Contamination measurement, the secondary flux recovery rate of surface bisexual ion purification plate membrane reaches 85%, is blended flat Plate film reaches 66%, and pure film only has 50%；The retention rate of proteins of surface bisexual ion purification plate membrane is 90%, blend flat sheet membrane It is 71%, it is more much higher than pure film 33%；The anti-protein-contamination parameter flux rate of descent of surface bisexual ion purification plate membrane is RFR (%) 2.5%, blend flat sheet membrane 60%, and pure film is 89%.

Embodiment 5

1. preparing amphipathic polymer 5

(1) 20g aminopropyl silicone oil (molecular weight 500g/mol) is added in the reaction vessel, 3.2g triethylamine and 140ml fourth Ketone leads to 20min nitrogen into flask, the 2- bromo isobutyryl chloride of 7g is slowly added dropwise at 5 DEG C, adds in about 1h.At room temperature after Continuous reaction 1h.After completion of the reaction, insoluble ammonium salt, excess of solvent are removed, is washed with deionized 3 times, anhydrous magnesium sulfate is added It is 12 hours dry, obtain macromolecular ATRP initiator.

(2) macromole evocating agent (20g), monomer DEAM (92.6g), dimethylformamide are sequentially added in the reaction vessel Then 225g leads to argon gas half an hour, then CuBr (1.435g), three (2- dimethylaminoethyl) amine are added under protection of argon gas (Me6TREM, 2.3).60 DEG C react 48 hours, it is sudden cold and be passed through air make reaction stop, with tetrahydrofuran diluted polymer After solution, after removing mantoquita and pentamethyl-diethylenetriamine (PMDETA, 1.733g), the most of solvent of removing is vacuumized, is obtained Concentrate precipitated in n-hexane, then through tetrahydrofuran dissolution, n-hexane deposition and purification for several times after filter paper filter, by product Dry 12h under the conditions of 50 DEG C, obtains product in vacuum drying oven.

2. preparing plate membrane

Obtained amphipathic polymer 15g is dissolved into the in the mixed solvent of 30gNMP and 15g dibutyl phthalate, is added Enter 25gETFE and 15gK30, pre-swollen 1 hour under mechanical stirring is redissolved 24 hours, and casting solution is made；Casting solution passes through 24 Hour vacuum defoamation processing after, topple on a glass using 200 microns of scraper knifing, after be immediately placed in water coagulating bath, Curing molding obtains blend flat sheet membrane.

3. film surface bisexual ion purification is blended

Blend flat sheet membrane is placed on 1.0g/ml glycidyl ethyl-trimethyl salmiac ether/THF solution, in solution, 40 DEG C It is lower to impregnate 24 hours, it is then alternately rinsed with deionized water and alcohol, obtains surface bisexual ion purification plate membrane.Then it carries out each Kind test.

Comparative example 5-1

It is outside the pale of civilization that surface amphoteric ion carried out to blend flat sheet membrane except not, is prepared and is blended using method same as Example 5 Plate membrane.

Comparative example 5-2

Except by the solvent of amphipathic polymer solution phase homogenous quantities substitution in addition to, other substances are constant, using with comparative example 5-1 Identical method, preparation are not added with the pure film of amphipathic polymer.

The blend flat sheet membrane performance test of embodiment 5, comparative example 5-1 and comparative example 5-2:

Embodiment 6

1. preparing amphipathic polymer 6

(1) 30g aminomethyl silicone oil (molecular weight 100g/mol) is added in the reaction vessel, 3.2g triethylamine and 40ml dichloro Methane, 30ml tetrahydrofuran lead to 60min nitrogen into flask to exclude air.The 2- bromo that 7g is slowly added dropwise at 10 DEG C is different Butyl chloride adds in about 1h.The reaction was continued at room temperature 12h.After completion of the reaction, insoluble ammonium salt is removed, is washed with deionized 3 It is secondary, anhydrous magnesium sulfate drying 24 hours is added, obtains macromolecular ATRP initiator.

(2) macromole evocating agent (1g), monomer DMAPMA (170.3g), solvent DMSO are sequentially added in the reaction vessel (38.05g) then leads to argon gas half an hour, then CuBr (0.14g), cymene are added under protection of argon gas (PMDETA, 0.134g), 120 DEG C react 1 hour, it is sudden cold and be passed through air make reaction stop, with tetrahydrofuran dilute polymerize After object solution, neutral alumina pillar is crossed to remove mantoquita and complexing agent, gained filtrate removes most of solvent through rotary evaporation Afterwards, concentrate precipitates in n-hexane, then through tetrahydrofuran dissolution, n-hexane deposition and purification for several times after filter paper filter, will produce Drying for 24 hours, obtains product to object under the conditions of 60 DEG C in vacuum drying oven.

2. preparing plate membrane

Obtained amphipathic polymer 5g is dissolved into DMSO the and 35g gamma-butyrolacton of 30g, 20gPS and 10g is added and causes Agent PEG2W in hole pre-swollen 1 hour under mechanical stirring, is redissolved 12 hours, casting solution is made；Casting solution is true by 24 hours After empty deaeration processing, topple on a glass using 200 microns of scraper knifing, after be immediately placed in water coagulating bath, curing molding, Obtain blend flat sheet membrane.

3. film surface bisexual ion purification is blended

Blend flat sheet membrane is placed in chloromethyl octyl ether/butanol solution of 0.5g/ml, impregnates 48 hours at 40 DEG C, then It is alternately rinsed with deionized water and alcohol, obtains surface bisexual ion purification plate membrane.Then various tests are carried out.

Comparative example 6-1

It is outside the pale of civilization that surface amphoteric ion carried out to blend flat sheet membrane except not, is prepared and is blended using method same as Example 6 Plate membrane.

Comparative example 6-2

Except by the solvent of amphipathic polymer solution phase homogenous quantities substitution in addition to, other substances are constant, using with comparative example 6-1 Identical method, preparation are not added with the pure film of amphipathic polymer.

The blend flat sheet membrane performance test of embodiment 6, comparative example 6-1 and comparative example 6-2:

In hydrophily test, the initial contact angle of surface bisexual ion purification plate membrane is 71 °, is contacted in 2 minutes Angle falls to 14 °, and the initial interface contacts angle of blend flat sheet membrane is 81 °, and the initial contact angle of pure film is 94 °；1g/L's In BSA aqueous solution dynamic Contamination measurement, the secondary flux recovery rate of surface bisexual ion purification plate membrane reaches 98%, is blended flat Plate film reaches 85%, and pure film only has 65%；The retention rate of proteins of surface bisexual ion purification plate membrane is 99%, blend flat sheet membrane It is 98%, pure film is 95%；The anti-protein-contamination parameter flux rate of descent of surface bisexual ion purification plate membrane is RFR (%) 2.5%, blend flat sheet membrane 30%, and pure film is 45%.

Embodiment 7

1. preparing amphipathic polymer 7

(1) 20g aminoethyl silicone oil (molecular weight 20000g/mol) is added in the reaction vessel, 3.2g triethylamine and 40ml tetra- Hydrogen furans leads to 20min nitrogen, the 2- bromo isobutyryl chloride of 7g is slowly added dropwise at 4 DEG C, the reaction was continued at room temperature 1h.It has reacted Bi Hou removes insoluble ammonium salt, is washed with deionized 3 times, and anhydrous magnesium sulfate drying 12 hours is added, obtains macromolecular ATRP Initiator.

(2) macromole evocating agent (20g), monomer DEAM (92.6g), dimethyl acetamide are sequentially added in the reaction vessel Then 225g leads to argon gas half an hour, CuBr (1.435g), pentamethyl-diethylenetriamine (PMDETA, 1.733g) is added.50 It is DEG C reaction 60 hours, sudden cold and be passed through air.

2. preparing plate membrane

Obtained amphipathic polymer solution 20g is dissolved into the DMF of 65g, the pore-foaming agent of the PES and 3g of 12g is added PEO20W pre-swollen 1 hour under mechanical stirring, is redissolved 6 hours, casting solution is made；Casting solution is de- by 12 hours vacuum After bubble processing, topple on a glass using 200 microns of scraper knifing, after be immediately placed in water coagulating bath, curing molding obtains Blend flat sheet membrane.

3. film surface bisexual ion purification is blended

1.5g/ml glycidyl ethyl-trimethyl salmiac ether/ethanol solution is prepared, will be blended at 50 DEG C of plate blend film It impregnates 24 hours, is then alternately rinsed with deionized water and alcohol, obtain surface bisexual ion purification plate membrane.Then it carries out various Test.

Comparative example 7-1

It is outside the pale of civilization that surface amphoteric ion carried out to blend flat sheet membrane except not, is prepared and is blended using method same as Example 7 Plate membrane.

Comparative example 7-2

Except by the solvent of amphipathic polymer solution phase homogenous quantities substitution in addition to, other substances are constant, using with comparative example 7-1 Identical method, preparation are not added with the pure film of amphipathic polymer.

The blend flat sheet membrane performance test of embodiment 7, comparative example 7-1 and comparative example 7-2:

In hydrophily test, the initial interface contacts angle of surface bisexual ion purification plate membrane is 79 °, inscribed at 2 minutes Feeler falls to 35 °, and the initial interface contacts angle of blend flat sheet membrane is 85 °, and the initial contact angle of pure film is 104 °；In 1g/L BSA aqueous solution dynamic Contamination measurement in, the secondary flux recovery rate of surface bisexual ion purification plate membrane reaches 85%, is blended Plate membrane is 76%, and the flux recovery rate of pure film only has 60%；The anti-protein-contamination of surface bisexual ion purification plate membrane is joined Number flux rates of descent be RFR (%) 23%, blend flat sheet membrane 40%, and pure film be 89%.

Embodiment 8

1. preparing amphipathic polymer 8

(1) 30g ammonia butyl silicone oil (molecular weight 200g/mol) is added in the reaction vessel, 3.2g triethylamine and 40ml fourth Ketone, 20ml toluene lead to 60min nitrogen.The 2- bromo isobutyryl chloride of 7g is slowly added dropwise at -2 DEG C, the reaction was continued at room temperature 36h. After completion of the reaction, insoluble ammonium salt, excess of solvent are removed, n-hexane dissolution is then added, is washed with deionized 3 times, is added Anhydrous magnesium sulfate is 24 hours dry, and colourless transparent solution is obtained after filtering, after removing solvent, obtains macromolecular ATRP initiator.

(2) macromole evocating agent (2g), monomer DMAPMA (170.3g), methacrylic acid are sequentially added in the reaction vessel Lignocaine ethyl ester (43g), NMP (2985g), isopropanol (350g), then helium injection gas half an hour, be added CuBr (0.07g), Cymene (PMDETA, 0.07g) reacts 5 hours at 110 DEG C, sudden cold and be passed through air.

2. preparing plate membrane

Obtained amphipathic polymer solution 17g is dissolved into the mixing of the diethyl phthalate of the DMF and 25g of 50g In solvent, the pore-foaming agent PEG400 of the PAN and 4g of 20g is added, pre-swollen 1 hour under mechanical stirring is redissolved 4 hours, is made Casting solution；Casting solution is toppled over after vacuum defoamation processing in 4 hours on a glass using 200 microns of scraper knifing, rear fast Speed is placed in water coagulating bath, and curing molding obtains blend flat sheet membrane.

3. film surface bisexual ion purification is blended

The bromine sulfonic acid ethanol as solvent for preparing 2.0g/ml, blend flat sheet membrane is impregnated 10 hours at 60 DEG C, is then used Deionized water and alcohol alternately rinse, and obtain surface bisexual ion purification plate membrane.Then various tests are carried out.

Comparative example 8-1

It is outside the pale of civilization that surface amphoteric ion carried out to blend flat sheet membrane except not, is prepared and is blended using method same as Example 8 Plate membrane.

Comparative example 8-2

Except by the solvent of amphipathic polymer solution phase homogenous quantities substitution in addition to, other substances are constant, using with comparative example 8-1 Identical method, preparation are not added with the pure film of amphipathic polymer.

The blend flat sheet membrane performance test of embodiment 8, comparative example 8-1 and comparative example 8-2:

In hydrophily test, the initial interface contacts angle of surface bisexual ion purification plate membrane is 80 °, inscribed at 2 minutes Feeler falls to 29 °, and the initial interface contacts angle of blend flat sheet membrane is 75 °, and be not added with amphipathic polymer pure film it is initial Contact angle is 100 °；In the BSA aqueous solution dynamic Contamination measurement of 1g/L, the secondary water flux of surface bisexual ion purification plate membrane Recovery rate reaches 95%, blend flat sheet membrane 80%, and the flux recovery rate of pure film only has 62%；Surface bisexual ion purification plate The retention rate of proteins of film is 99%, plate membrane 96%, and pure film is 90%；The anti-protein of surface bisexual ion purification plate membrane is dirty Dye parameter flux rate of descent be RFR (%) 12%, blend flat sheet membrane 45%, and pure film be 76%.

Embodiment 9

1. preparing amphipathic polymer 9

(1) 20g hydroxyl amyl silicone oil (molecular weight 3000g/mol) is added in the reaction vessel, 3.2g triethylamine and 40ml bis- Chloromethanes leads to 20min nitrogen, the 2- bromo isobutyryl chloride of 7g is slowly added dropwise at 8 DEG C, the reaction was continued at room temperature 60h.It has reacted Bi Hou removes insoluble ammonium salt, is washed with deionized 3 times, and anhydrous magnesium sulfate drying 12 hours is added, obtains macromolecular ATRP Initiator.

(2) macromole evocating agent (3g), monomer DEAM (785g) DMAEMA (120g) are sequentially added in the reaction vessel, just Then propyl alcohol 2000g, isopropanol 1300g lead to argon gas half an hour, CuBr (0.5g), pentamethyl-diethylenetriamine is added (PMDETA, 0.34g).It is reacted 36 hours at 70 DEG C, it is sudden cold and be passed through air.

2. preparing plate membrane

Obtained amphipathic polymer solution 3g is dissolved into the DMSO of 40g, the pore-foaming agent of the PVA and 3g of 10g is added PEG2000 agitated under sonication pre-swollen 1 hour, is redissolved 1 hour, casting solution is made；Solution is measuring after filtering, deaeration Under conditions of pump is with 20r/min revolving speed, spinning pressure 0.4Mpa, squeezed out from the spinning head being made of two concentric tubes；Through 800mm After dry-spinning path, solidified in the aqueous solution that solvent content is 50%, temperature is 40 DEG C, solution internal circulating load is 10L/h, spun filament is again Four or more two-way (axially and radially) were stretched and appropriateness bounces back, 6 wash, after ethanol solution processing, with the speed of 10m/min Degree winding is to get blend hollow fiber membrane.

3. blend hollow fiber membrane surface bisexual ion purification

Blend hollow fiber membrane is placed in chlorosulfonic acid/butanol solution of 0.5g/ml, impregnates 10 hours at 60 DEG C, then It is alternately rinsed with deionized water and alcohol, obtains surface bisexual ion purification hollow-fibre membrane.Then various tests are carried out.

Comparative example 9-1

It is outside the pale of civilization that surface amphoteric ion carried out to blend hollow fiber membrane except not, is prepared using method same as Example 9 Blend hollow fiber membrane.

The blend hollow fiber membrane performance test of embodiment 9 and embodiment 9-1:

In hydrophily test, the surface contact angle of surface bisexual ion purification hollow-fibre membrane is 30 °, and doughnut is blended The surface contact angle of film is 50 °, in the BSA aqueous solution dynamic Contamination measurement of 1g/L, surface bisexual ion purification hollow-fibre membrane Secondary flux recovery rate is 92%, blend hollow fiber membrane 72%.

Embodiment 10

1. preparing amphipathic polymer 10

(1) 20g ammonia amyl silicone oil (molecular weight 5000g/mol) is added in the reaction vessel, 3.2g triethylamine and 40ml bis- Chloromethanes leads to 20min nitrogen, the 2- bromo isobutyryl chloride of 7g is slowly added dropwise at -7 DEG C, the reaction was continued at room temperature 1h.It has reacted Bi Hou removes insoluble ammonium salt, is washed with deionized 3 times, and anhydrous magnesium sulfate drying 12 hours is added, obtains macromolecular ATRP Initiator.

(2) macromole evocating agent (1g), monomer DEAM (9.26g), methyl pyrrolidone are sequentially added in the reaction vessel Then 150g leads to argon gas half an hour, CuBr (0.1435g), pentamethyl-diethylenetriamine (PMDETA, 0.1733g) is added.? 90 DEG C are reacted 25 hours, sudden cold and be passed through air.

2. preparing plate membrane

Obtained amphipathic polymer solution 15g is dissolved into the butanone of 67g, the cellulose acetate and 3g of 20g is added Pore-foaming agent PEO120W, ultrasonic pre-swollen 1 hour are redissolved 12 hours, and casting solution is made；Solution is being counted after filtering, deaeration Under conditions of amount pump is with 5r/min revolving speed, spinning pressure 0.6Mpa, squeezed out from the spinning head being made of two concentric tubes；Through 20mm It after dry-spinning path, is solidified in the aqueous solution that temperature is 5 DEG C, solution internal circulating load is 10L/h, tetra- or more spun filament Zai Jing is two-way (axially and radially) it stretches and appropriateness bounces back, 4 wash, after the processing of 15% glycerite, wound with the speed of 10m/min, i.e., Obtain blend hollow fiber membrane.

3. blend hollow fiber membrane surface bisexual ion purification

Blend hollow fiber membrane is placed in propane sultone/butanol solution of 1.0g/ml, is impregnated 65 hours at 50 DEG C, Then it is alternately rinsed with deionized water and alcohol, obtains surface bisexual ion purification hollow-fibre membrane.Then various tests are carried out.

Comparative example 10-1

It is outside the pale of civilization that surface amphoteric ion carried out to blend hollow fiber membrane except not, is prepared using method same as in Example 10 Blend hollow fiber membrane.

The blend hollow fiber membrane performance test of embodiment 10 and embodiment 10-1:

In hydrophily test, the surface contact angle of surface bisexual ion purification hollow-fibre membrane is 20 °, and doughnut is blended The surface contact angle of film is 40 °, in the BSA aqueous solution dynamic Contamination measurement of 1g/L, surface bisexual ion purification hollow-fibre membrane Secondary flux recovery rate is 98%, blend hollow fiber membrane 92%.

Embodiment 11

1. preparing amphipathic polymer 11

(1) 20g hydroxypropyl silicone oil (molecular weight 7000g/mol) is added in the reaction vessel, 3.2g triethylamine and 40ml bis- Chloromethanes leads to 20min nitrogen, the 2- bromo isobutyryl chloride of 7g is slowly added dropwise at 4 DEG C, the reaction was continued at room temperature 1h.It has reacted Bi Hou removes insoluble ammonium salt, is washed with deionized 3 times, and anhydrous magnesium sulfate drying 12 hours is added, obtains macromolecular ATRP Initiator.

(2) macromole evocating agent (20g), monomer DEAM (9.26g), toluene 15g, butanone are sequentially added in the reaction vessel Then 35g leads to argon gas half an hour, CuBr (0.1435g), pentamethyl-diethylenetriamine (PMDETA, 0.1733g) is added.? 100 DEG C are reacted 10 hours, sudden cold and be passed through air.

2. preparing plate membrane

Obtained amphipathic polymer solution 5g is dissolved into NMP the and 50g gamma-butyrolacton of 20g, is added 10.5g's EVOH and 3g K90 pre-swollen 1 hour under mechanical stirring, is redissolved 8 hours, casting solution is made；Casting solution was by 24 hours After vacuum defoamation processing, topple on a glass using 200 microns of scraper knifing, after be immediately placed in water coagulating bath, be solidified into Type obtains blend flat sheet membrane.

3. film surface bisexual ion purification is blended

Blend flat sheet membrane is placed in 3- bromo-butyric acid/butanol solution of 0.2g/ml, impregnates 56 hours at 20 DEG C, then It is alternately rinsed with deionized water and alcohol, obtains surface bisexual ion purification plate membrane.Then various tests are carried out.

Comparative example 11-1

Except not to blend flat sheet membrane carry out surface amphoteric ion it is outside the pale of civilization, using with the identical method of embodiment 11 preparation be blended Plate membrane.

Comparative example 11-2

Except by the solvent of amphipathic polymer solution phase homogenous quantities substitution in addition to, other substances are constant, using with comparative example 11- 1 identical method, preparation are not added with the pure film of amphipathic polymer.

The blend flat sheet membrane performance test of embodiment 11, comparative example 11-1 and comparative example 11-2:

In hydrophily test, the initial interface contacts angle of surface bisexual ion purification plate membrane is 35 °, inscribed at 2 minutes Feeler falls to 2 °, and the initial interface contacts angle of blend flat sheet membrane is 55 °, and the initial contact angle of pure film is 76 °；1g/L's In BSA aqueous solution dynamic Contamination measurement, the secondary flux recovery rate of surface bisexual ion purification plate membrane reaches 97%, is blended flat Plate film is 85%, and the flux recovery rate of pure film only has 60%；The retention rate of proteins of surface bisexual ion purification plate membrane is 99%, Blend flat sheet membrane is 95%, higher than pure film 88%；The anti-protein-contamination parameter flux of surface bisexual ion purification plate membrane declines Rate be RFR (%) 5%, blend flat sheet membrane 21%, and pure film be 67%.

Embodiment 12

1. preparing amphipathic polymer 12

(1) 20g hydroxypropyl silicone oil (molecular weight 10000g/mol) is added in the reaction vessel, 3.2g triethylamine and 40ml bis- Chloromethanes leads to 20min nitrogen, the 2- bromo isobutyryl chloride of 7g is slowly added dropwise at 9 DEG C, the reaction was continued at room temperature 1h.It has reacted Bi Hou removes insoluble ammonium salt, is washed with deionized 3 times, and anhydrous magnesium sulfate drying 12 hours is added, obtains macromolecular ATRP Initiator.

(2) macromole evocating agent (20g), monomer DEAM (92.6g) are sequentially added in the reaction vessel, DMF215g, Then NMP100g leads to argon gas half an hour, CuBr (1.435g), pentamethyl-diethylenetriamine (PMDETA, 1.733g) is added. It is reacted 60 hours at 50 DEG C, it is sudden cold and be passed through air.

2. preparing plate membrane

Obtained amphipathic polymer 10g is dissolved into the DMF of 54g, the pore-foaming agent PEO20W of the PES and 3g of 12g is added, Pre-swollen 1 hour under mechanical stirring is redissolved 6 hours, and casting solution is made；Casting solution was handled by vacuum defoamation in 12 hours Afterwards, topple on a glass using 200 microns of scraper knifing, after be immediately placed in water coagulating bath, curing molding obtains being blended flat Plate film.

3. film surface bisexual ion purification is blended

3-BPA (3- bromo-propionic acid) ethanol as solvent for preparing 2.1g/ml will be blended at 50 DEG C of plate blend film and impregnate 24 Hour, it is then alternately rinsed with deionized water and alcohol, obtains surface bisexual ion purification plate membrane.Then various tests are carried out.

Comparative example 12-1

Except not to blend flat sheet membrane carry out surface amphoteric ion it is outside the pale of civilization, using with the identical method of embodiment 12 preparation be blended Plate membrane.

Comparative example 12-2

Except by the solvent of amphipathic polymer solution phase homogenous quantities substitution in addition to, other substances are constant, using with comparative example 12- 1 identical method, preparation are not added with the pure film of amphipathic polymer.

The blend flat sheet membrane performance test of embodiment 12, comparative example 12-1 and comparative example 12-2:

Understand for the ease of reading, counted the initiator of polymer 1-12 and the type of monomer and dosage in table 1, In, the unit of dosage is g.

The initiator of amphipathic polymer 1-12 and the type of monomer and dosage in table 1

The film properties of all embodiments and comparative example in 3 present invention of table

Table 3 is the performance of the polymer film of the preparation of all embodiments and comparative example in the present invention, in conjunction with the embodiments 1 to reality Applying example 12 can be seen that under design of the invention, using a variety of variety classes, the macromole evocating agent of different amounts, function Monomer, the polymer for being used to prepare seperation film and quaternizing agent can be prepared with permanent hydrophilic antifouling property and pollution resistance The excellent polymeric film material of energy.Further, the embodiment and comparative example all in conjunction with the present invention, specifically with 1 He of embodiment Comparative example 1-1 and comparative example 1-2 can be seen that the secondary water flux recovery of the surface bisexual ion purification plate membrane in embodiment 1 Rate reaches 80%, and the blend flat sheet membrane in comparative example 1-1 reaches 67%, and the flux recovery rate of pure film only has in comparative example 1-2 50%；The retention rate of proteins of surface bisexual ion purification plate membrane is 72%, and blend flat sheet membrane 65% is higher very than pure film 33% It is more；The anti-protein-contamination parameter flux rate of descent of surface bisexual ion purification plate membrane is RFR (%) 55%, and blend flat sheet membrane is RFR76%, and pure film is 89%, i.e., the plate membrane antifouling property after bisexual ion purification is obtained relative to blend flat sheet membrane and pure film Great promotion.In addition, in film surface contact angle test, surface bisexual ion purification plate membrane in embodiment 1 it is initial Contact angle is 81 °, and contact angle is reduced to 24 ° in 2 minutes, and the initial contact angle of the blend flat sheet membrane in comparative example 1-1 is 86 °, Contact angle is reduced to 64 ° in 2 minutes, and the initial contact angle of the pure film in comparative example 1-2 is 94 °, and basic holding at any time It is constant.It can also prove that the hydrophilicity of bisexual ion purification film in surface provided by the invention is better than non-surface bisexual ion purification and obtains The blend film arrived and pure film.

Above-mentioned explanation is the embodiment of specific embodiment in the present invention, for being illustrated more clearly that invention of the invention Design, but it is for the restriction to scope of the presently claimed invention that it, which is not,.Inventive concept according to the present invention, this field skill Art personnel can be easy variants and modifications the above embodiments, and the variants and modifications that these belong in inventive concept of the invention are equal Including within the scope of the claims of the invention.

Claims

1. a kind of polymeric film material, which is characterized in that comprising (a) there is zwitterionic polymer and (b) to be used to prepare point Polymer from film, wherein the amphoteric ion includes quaternary ammonium group.

2. polymeric film material according to claim 1, which is characterized in that described to have zwitterionic polymer by containing There is the amphipathic polymer of tertiary amine groups is quaternized to be made, the monomer of the amphipathic polymer includes containing carbon-carbon double bond and tertiary amine simultaneously The function monomer of base.

3. polymeric film material according to claim 2, which is characterized in that the function monomer is selected from (methyl) acrylic acid One of dimethylaminoethyl, (methyl) diethylaminoethyl acrylate, N- (3- dimethylamino-propyl) Methacrylamide Or it is several.

4. polymeric film material according to claim 2, which is characterized in that the amphipathic polymer is ABA block copolymerization Object, the B block are the hydrophobic segment comprising dimethyl silicone polymer, and the A block is by containing carbon-carbon double bond and uncle simultaneously The hydrophilic segment that the function monomer homopolymerization or copolymerization of amido obtain.

5. polymeric film material according to claim 2, which is characterized in that the amphipathic polymer is used to prepare with described The weight ratio of the polymer of seperation film is 0.1-30:10-30.

6. polymeric film material according to claim 1, which is characterized in that point containing zwitterionic polymer Son amount profile exponent is 1~1.3.

7. polymeric film material according to claim 1, which is characterized in that the polymer choosing for being used to prepare seperation film It is total from fluoropolymer, polysulfones and its derivative, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, ethylene-vinyl alcohol One or more of polymers, cellulose and its derivates.

8. polymeric film material according to claim 1, which is characterized in that the polymeric film material be plate membrane or in Empty fiber membrane.

9. a kind of preparation method of polymeric film material, which comprises the following steps:

1) polymer, the second solvent, pore-foaming agent and the amphipathic polymer that are used to prepare seperation film are blended and prepare casting solution, then Polymer film is made using filming technology, and the monomer of the amphipathic polymer includes the function containing tertiary amine groups and carbon-carbon double bond simultaneously It can property monomer；

2) polymer film obtained in step 1) is put into quaternizing agent solution and carries out quaternization reaction, obtain amphoteric ion Fluidized polymer membrane material.

10. preparation method according to claim 9, which is characterized in that the amphipathic polymer is by atom transferred free radical Polymerization reaction preparation.

11. preparation method according to claim 10, which is characterized in that the amphipathic polymer is ABA block copolymer, The B block is the hydrophobic segment comprising dimethyl silicone polymer, and the A block is by containing carbon-carbon double bond and tertiary amine groups simultaneously Function monomer homopolymerization or the obtained hydrophilic segment of copolymerization.

12. preparation method according to claim 11, which is characterized in that preparing the amphipathic polymer includes following step It is rapid:

Macromole evocating agent end halogen dimethyl polysiloxane is added in the reaction vessel, complexing agent, contains tertiary amine groups and carbon simultaneously Functional monomer, catalyst cuprous halide and the first solvent of carbon double bond, wherein cuprous halide should add under inert gas protection Enter, monomer, end halogen dimethyl siloxane, cuprous halide and complexing agent molar ratio be 1~10000:1:0.1~10:0.1~ 10, it is warming up to 30~120 DEG C under inert gas protection, reacts 1~72 hour.

13. preparation method according to claim 9, which is characterized in that the quaternization reaction is in 10~70 DEG C of temperature Under carry out reaction 1~72 hour.

14. preparation method according to claim 9, which is characterized in that described simultaneously containing tertiary amine groups and carbon-carbon double bond Functional monomer is selected from (methyl) dimethylaminoethyl acrylate, (methyl) diethylaminoethyl acrylate, N- (3- dimethylamino One or more of propyl) Methacrylamide.

15. preparation method according to claim 9, which is characterized in that the casting solution includes in terms of quality percentage: using In the polymer 10~30% of preparative separation film, pore-foaming agent 1~10%, amphipathic polymer 0.1~30%, the second solvent 30~ 87.8%, the preparation method of the casting solution is that will be used to prepare polymer, pore-foaming agent, the second solvent and the amphiphilic of seperation film Polymer is put into homogenizing apparatus, carries out the dissolution that homogenizes, then vacuum or discontinuous degassing.

16. preparation method according to claim 9, which is characterized in that the quaternary ammonium reagent is selected from sultones, halogen sulphur One or more of acid, bromine carboxylic acid, alkylhalide group ether.

17. polymeric film material made from a kind of preparation method as described in any one of claim 9-16.