CN105585659A - Multifunctional amphiphilic terpolymer as well as preparation method and application thereof - Google Patents

Multifunctional amphiphilic terpolymer as well as preparation method and application thereof Download PDF

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CN105585659A
CN105585659A CN201610090858.0A CN201610090858A CN105585659A CN 105585659 A CN105585659 A CN 105585659A CN 201610090858 A CN201610090858 A CN 201610090858A CN 105585659 A CN105585659 A CN 105585659A
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solvent
casting solution
preparation
terpolymer
functional
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何旭敏
刘建
李振峰
夏海平
孙洪贵
兰秀娟
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XIAMEN STARMEM FILM TECHNOLOGY Co Ltd
Xiamen University
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XIAMEN STARMEM FILM TECHNOLOGY Co Ltd
Xiamen University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0013—Casting processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/38—Hydrophobic membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/26—Use as polymer for film forming

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Abstract

The invention discloses a multifunctional amphiphilic terpolymer as well as a preparation method and application thereof, and relates to the technical fields of high polymer chemistry and separation membrane. The multifunctional amphiphilic terpolymer is a random copolymer and consists of three parts: a hydrophobic chain segment methyl methacrylate, a chain segment 4-vinyl pyridine with a pH response group and a hydrophilic chain segment polyethylene glycol monomethyl ether methacrylate. The preparation method comprises the following steps: dissolving three monomers MMA, 4-VPy and PEGMA in a solvent; adding an initiator and stirring; introducing a gas, bubbling and removing oxygen; sealing the reaction bottle and putting in an oil bath for reaction; precipitating the reaction liquid in a precipitating agent; performing suction filtration and washing to remove unreacted monomer, initiator and solvent; and drying to obtain the multifunctional amphiphilic terpolymer. The multifunctional amphiphilic terpolymer can be used for preparing an anti-pollution pH-response polyether sulfone ultrafiltration membrane. The structure is novel, the synthesis method is simple, and the structure can be selectively controlled through the synthesis conditions.

Description

A kind of multi-functional amphipathic terpolymer and its preparation method and application
Technical field
The present invention relates to polymer chemistry and diffusion barrier technical field, especially relate to a kind of multi-functional amphipathic ternary altogetherPolymers and its preparation method and application.
Background technology
Milipore filter is a class pressure differential type diffusion barrier, has the spies such as operating pressure is little, energy consumption is low, technical process is simplePoint, is widely used in the fields such as tap water purifying, desalinization, Industrial Wastewater Treatment, albumen be concentrated. Polyether sulfone (PES) isA milipore filter filmogen for excellent performance, has splendid antioxygenic property and heat endurance, and mechanical strength is high, creep resistantPerformance is good, acidproof, alkaline-resisting, corrosion-resistant, is not subject to the impact (J.Membr.Sci.2004,233,101-111) of general chemical reagent.But PES milipore filter, because hydrophobicity is stronger, can produce serious film and pollute in the process using, and this can make membrane flux significantlyDecline, and have a strong impact on separating property and the service life (J.Membr.Sci.2008,318,405-412) of film. Research shows,Use amphipathic copolymer PES milipore filter to be carried out modification and can significantly be promoted the antifouling property of film(Prog.Mater.Sci.2013,58,76-150). Amphipathic copolymer is in a class formation, to contain hydrophobic segment and parent simultaneouslyThe polymer of water segment, in the process of inversion of phases film forming, it can be enriched in film surface under the effect of surface segregation effect, fromAnd hydrophily and the antifouling property of raising film.
Meanwhile, if amphipathic copolymer is carried out to appropriate MOLECULE DESIGN, introduce corresponding functional group, can also make polyethersSulfone milipore filter obtains special performance, as pH response performance. PH response film is a kind of stimulation-response type diffusion barrier, its infiltrationCharacter (flux, rejection etc.) can change with the variation of pH value, and this specific character has effectively been expanded the application of diffusion barrier(J.Membr.Sci.2011,378,369-381). What give film pH response performance is pH response group, common pH response baseThere is carboxyl in group, pyridine radicals etc., and its pH Response Mechanism is relevant with the conformation transition of strand.
In sum, if can synthesize a kind of multi-functional amphipathic copolymer by MOLECULE DESIGN, make to contain in its structure simultaneouslyThere are hydrophobic grouping, pH response group and hydrophilic radical, and with it, PES milipore filter carried out to modification, can be possessed simultaneouslyThe PES milipore filter of look antifouling property and pH response performance.
Summary of the invention
In order to solve the membrane pollution problem of PES milipore filter and to give film outstanding pH response performance, object of the present invention existsIn a kind of multi-functional amphipathic terpolymer and preparation method thereof is provided.
Another object of the present invention is to provide described multi-functional amphipathic terpolymer preparing antipollution and pH soundAnswer the application in polyether sulfone (PES) milipore filter.
The chemical structural formula of described multi-functional amphipathic terpolymer is as follows:
Wherein, m is any one value in 3,8,18,30, and x is any one integer in 330～620, y is 210～Any one integer in 540, z is any one integer in 15～80.
Described multi-functional amphipathic terpolymer is a kind of random copolymer, and this copolymer is by hydrophobic segment metering systemAcid methyl esters (MMA), segment 4-vinylpridine (4-VPy) and hydrophilic segment methoxypolyethylene glycol methyl-prop with pH response groupOlefin(e) acid ester (PEGMA) three part compositions.
The preparation method's of described multi-functional amphipathic terpolymer concrete steps are as follows:
MMA, 4-VPy, tri-kinds of monomers of PEGMA are dissolved in solvent, then add initator, after stirring, ventilate after bubbling deoxygenationBy reaction bulb sealing, be placed in oil bath and react, then reactant liquor is precipitated in precipitating reagent, suction filtration, washing, unreacted to removeMonomer, initator and solvent, obtain multi-functional amphipathic terpolymer after being dried.
The molecular weight of described PEGMA monomerCan be in 300g/mol, 500g/mol, 950g/mol, 1500g/molAny one, preferably 500g/mol;
Described solvent can be selected from DMF (DMF), DMA (DMAc), N-methylpyrroleAt least one in alkane ketone (NMP), methyl-sulfoxide (DMSO), Isosorbide-5-Nitrae-dioxane etc.; Preferably one in DMF, DMAc, DMSO etc.Kind;
The mass percent of described MMA, 4-VPy, PEGMA and solvent can be: (5%～15%): (6%～20%):(4%～10%): (55%～85%), total amount is 100%; Preferably (8%～15%): (12%～20%): (7%～10%)∶(55％～73％)；
Described initator can be selected from azodiisobutyronitrile (AIBN) or dibenzoyl peroxide (BPO), preferably AIBN; DescribedThe addition of initator can be 3%～7% of three kinds of monomer gross masses, and preferably 3%～5%;
The gas that described bubbling is used can be nitrogen or argon gas, preferably argon gas; The time of described bubbling can be 15～30min,Preferably 20～30min;
The temperature of reacting in described oil bath can be 60～80 DEG C, and the time of reacting in oil bath can be 24～48h; Anti-in oil bathPreferably 65～75 DEG C of the temperature of answering, preferably 24～32h of the time of reacting in oil bath;
Described precipitating reagent can be selected from least one in methyl alcohol, ethanol, ether etc.; In particular methanol, ether etc. at leastA kind of.
Described being dried can adopt vacuum drying, and dry temperature can be 60～80 DEG C, and the dry time can be 24～48h,Preferably 60～70 DEG C of dry temperature, preferably 24～32h of dry time.
Described multi-functional amphipathic terpolymer can be prepare should in antipollution and pH response polyether sulfone (PES) milipore filterWith. The concrete grammar of described application is as follows:
1) preparation casting solution: polyether sulfone (PES), multi-functional amphipathic terpolymer, pore-foaming agent are dissolved in solvent,The mixed liquor arriving obtains casting solution after stirring;
In step 1) in, described pore-foaming agent is optional from polyethylene glycol (PEG) or polyvinylpyrrolidone (PVP) etc., wherein poly-second twoThe molecular weight of alcohol (PEG)The molecular weight of polyvinylpyrrolidone (PVP) M n ‾ = 10000 ~ 150000 g / m o l ; Preferred: the molecular weight of PEG M n ‾ = 400 ~ 2000 g / m o l , The molecular weight of PVPDescribedSolvent can be selected from the one in DMF, DMAc, NMP etc., preferably DMF or NMP; In described casting solution, the quality percentage of each component containsAmount is respectively: polyether sulfone (PES)=16%～22%, and multi-functional amphipathic terpolymer=0.5%～4%, pore-foaming agent=5%～15%, solvent=59%～78.5%; In described casting solution, the quality percentage composition of each component is preferably respectively: polyethersSulfone (PES)=16%～20%, multi-functional amphipathic terpolymer=1.5%～3%, pore-foaming agent=5%～10%, solvent=67%～77.5%; The temperature of described stirring can be 50～70 DEG C, and the time of stirring can be 12～24h, and the temperature of stirring is excellentSelect 60～70 DEG C, preferably 15～20h of the time of stirring.
2) standing and defoaming: casting solution is left standstill, until the bubble in casting solution removes completely;
In step 2) in, described dwell temperature is 25～60 DEG C, time of repose is 12～24h, dwell temperature preferably 50～60 DEG C, time of repose is 18～24h preferably.
3) knifing: substrate is placed on knifing machine, gets the casting solution curtain coating that is cooled to room temperature in substrate one end, start knifingMachine knifing;
4) forming film with phase transformation method: by the coagulating bath of putting into 0～40 DEG C after placing with the substrate of liquid film, through solvent-After non-solvent exchange, liquid film is converted into solid film, after solvent-nonsolvent exchange completely, solid-state diaphragm is taken out, be placed in fromMore than preserving 24h in sub-water, to remove solvent residual in solid-state diaphragm.
In step 4) in, the time of described placement can be 0～60s, preferably 0～15s; The temperature of described coagulating bath can be 0～40 DEG C, preferably 15～30 DEG C; Described coagulating bath is at least one in deionized water, methyl alcohol, ethanol etc., preferably deionizationWater.
Multi-functional amphipathic terpolymer provided by the invention contains several functions group, and (hydrophobic grouping, pH respond baseGroup and hydrophilic radical), novel structure, synthetic method is simple, and its structure can be carried out selective regulation by synthesis condition; Meanwhile,Multi-functional amphipathic terpolymer provided by the invention can be directly used in the modification of PES milipore filter, the PES milipore filter after modificationPossess outstanding antifouling property and pH response performance. The lifting of PES milipore filter antifouling property can significantly reduce film deviceOperating cost also extends service life of film, and giving of pH response performance will effectively be expanded the application of PES milipore filter. ThisThe bright preparation for antipollution and pH response PES milipore filter provides brand-new approach.
Brief description of the drawings
Fig. 1 is the multi-functional amphipathic terpolymer of preparation in embodiment 11HNMR figure;
Fig. 2 is the DSC figure of the multi-functional amphipathic terpolymer of preparation in embodiment 1;
Fig. 3 is the GPC figure of the multi-functional amphipathic terpolymer of preparation in embodiment 1;
Fig. 4 is the antifouling property test result of the modified PES milipore filter of preparation in embodiment 11;
Fig. 5 is the pH response performance test result of the modified PES milipore filter of preparation in embodiment 11.
Detailed description of the invention
For the performance of PES milipore filter before and after modification is contrasted, the present invention is using multi-functional amphipathic ternary altogetherWhen preparing modified PES milipore filter, also under identical condition, prepares polymers unmodified PES milipore filter. Test resultShow, the flux of unmodified PES milipore filter is at 178.4-191.8L/ (h.m2.bar) between, to cutting of bovine serum albumin (BSA)Stay rate between 84.0%～90.2%, flux response rate is between 50.1%～55.7%, and antifouling property is very poor; In addition,The flux of unmodified PES milipore filter can not change with the variation of material liquid pH value, does not possess pH respective performances.
Embodiment 1
The present embodiment is in order to prepare multi-functional amphipathic terpolymer provided by the invention.
By 2.0mlMMA (purchased from Shanghai Aladdin biochemical technology limited company), 2.8ml4-VPy (purchased fromSigma-Aldrich company), 5.3mlPEGMA (m=8,Purchased from Sigma-Aldrich company) be dissolved inIn 25.0mlDMF, then in mixed liquor, add 51.9mgAIBN (purchased from the limited public affairs of Shanghai Aladdin biochemical technology shareDepartment), logical argon gas bubbling 30min (deoxygenation) after stirring, by reaction bulb good seal, is placed in 75 DEG C of oil baths instead after bubblingAnswer 24h. Then reactant liquor is precipitated in ether, suction filtration, washing, to remove unreacted monomer, initator and solvent. ProductVacuum drying 24h at 70 DEG C, finally obtains 8.5g solid, and productive rate is 84.2%.
According to described product1HNMR test result, this product δ=3.572ppm, δ=4.030ppm, δ=There is absworption peak at 6.927ppm, δ=8.422ppm place.
According to the DSC test result of described product, this product only has a Tg, and Tg=81 DEG C.
According to the GPC test result of described product, the molecular weight of this product is:
The multi-functional amphipathic terpolymer of preparing in embodiment 11HNMR figure is referring to Fig. 1, multi-functional two of preparationThe DSC figure of parent's property terpolymer is referring to Fig. 2, and the GPC figure of the multi-functional amphipathic terpolymer of preparation is referring to Fig. 3.
Embodiment 2
The present embodiment is in order to prepare multi-functional amphipathic terpolymer provided by the invention.
By 2mlMMA (purchased from Shanghai Aladdin biochemical technology limited company), 4.8ml4-VPy (purchased from Sigma-Aldrich company), 4.4mlPEGMA (m=8,Purchased from Sigma-Aldrich company) be dissolved in 30mlIn DMAc, then in mixed liquor, add 49.6mgAIBN (purchased from Shanghai Aladdin biochemical technology limited company), stirEvenly, logical argon gas bubbling 20min (deoxygenation), by reaction bulb good seal, is placed in 65 DEG C of oil baths and reacts 32h after bubbling. ConnectReactant liquor is precipitated in methyl alcohol, suction filtration, washing, to remove unreacted monomer, initator and solvent. Product is at 60 DEG CVacuum drying 32h, finally obtains 9.3g solid, and productive rate is 83%.
According to described product1HNMR test result, this product δ=3.570ppm, δ=4.031ppm, δ=There is absworption peak at 6.930ppm, δ=8.424ppm place.
According to the DSC test result of described product, this product only has a Tg, and Tg=85 DEG C.
According to the GPC test result of described product, the molecular weight of this product is:
Embodiment 3
The present embodiment is in order to prepare multi-functional amphipathic terpolymer provided by the invention.
By 3.5mlMMA (purchased from Shanghai Aladdin biochemical technology limited company), 2ml4-VPy (purchased from Sigma-Aldrich company), 6.8mlPEGMA (m=8,Purchased from Sigma-Aldrich company) be dissolved in 35mlIn DMSO, then in mixed liquor, add 31.2mgAIBN (purchased from Shanghai Aladdin biochemical technology limited company), stirEvenly, logical argon gas bubbling 25min (deoxygenation), by reaction bulb good seal, is placed in 70 DEG C of oil baths and reacts 28h after bubbling. ConnectReactant liquor is precipitated in ether, suction filtration, washing, to remove unreacted monomer, initator and solvent. Product is at 65 DEG CVacuum drying 28h, finally obtains 10.6g solid, and productive rate is 86.2%.
According to described product1HNMR test result, this product δ=3.568ppm, δ=4.027ppm, δ=There is absworption peak at 6.925ppm, δ=8.431ppm place.
According to the DSC test result of described product, this product only has a Tg, and Tg=71 DEG C.
According to the GPC test result of described product, the molecular weight of this product is:
Embodiment 4
The present embodiment is in order to prepare multi-functional amphipathic terpolymer provided by the invention.
By 3mlMMA (purchased from Shanghai Aladdin biochemical technology limited company), 3ml4-VPy (purchased from Sigma-Aldrich company), 4.8mlPEGMA (m=8,Purchased from Sigma-Aldrich company) be dissolved in 22mlIn DMF, then in mixed liquor, add 44mgBPO (purchased from Shanghai Aladdin biochemical technology limited company), stirRear logical nitrogen bubble 15min (deoxygenation), by reaction bulb good seal, is placed in 75 DEG C of oil baths and reacts 26h after bubbling. Then willReactant liquor precipitates in methyl alcohol, suction filtration, and washing, to remove unreacted monomer, initator and solvent. Product is vacuum at 60 DEG CDry 25h, finally obtains 8.7g solid, and productive rate is 80.6%.
According to described product1HNMR test result, this product δ=3.578ppm, δ=4.056ppm, δ=There is absworption peak at 6.987ppm, δ=8.465ppm place.
According to the DSC test result of described product, this product only has a Tg, and Tg=79 DEG C.
According to the GPC test result of described product, the molecular weight of this product is:
Embodiment 5
The present embodiment is in order to prepare multi-functional amphipathic terpolymer provided by the invention.
By 2.5mlMMA (purchased from Shanghai Aladdin biochemical technology limited company), 3.5ml4-VPy (purchased fromSigma-Aldrich company), 4.2mlPEGMA (m=3,Purchased from Sigma-Aldrich company) be dissolved inIn 28mlDMAc, then in mixed liquor, add 38.6mgAIBN (purchased from the limited public affairs of Shanghai Aladdin biochemical technology shareDepartment), logical argon gas bubbling 22min (deoxygenation) after stirring, by reaction bulb good seal, is placed in 73 DEG C of oil baths instead after bubblingAnswer 29h. Then reactant liquor is precipitated in ethanol, suction filtration, washing, to remove unreacted monomer, initator and solvent. ProductVacuum drying 30h at 68 DEG C, finally obtains 8.1g solid, and productive rate is 79.4%.
According to described product1HNMR test result, this product δ=3.597ppm, δ=4.076ppm, δ=There is absworption peak at 6.998ppm, δ=8.479ppm place.
According to the DSC test result of described product, this product only has a Tg, and Tg=84 DEG C.
According to the GPC test result of described product, the molecular weight of this product is:
Embodiment 6
The present embodiment is in order to prepare multi-functional amphipathic terpolymer provided by the invention.
By 2mlMMA (purchased from Shanghai Aladdin biochemical technology limited company), 4ml4-VPy (purchased from Sigma-Aldrich company), 3.5mlPEGMA (m=3,Purchased from Sigma-Aldrich company) be dissolved in 25mlIn DMSO, then in mixed liquor, add 45.0mgBPO (purchased from Shanghai Aladdin biochemical technology limited company), stirEvenly, logical argon gas bubbling 24min (deoxygenation), by reaction bulb good seal, is placed in 72 DEG C of oil baths and reacts 40h after bubbling. ConnectReactant liquor is precipitated in methanol/ethanol=1:1 (volume ratio), suction filtration, washing, to remove unreacted monomer, initatorAnd solvent. Product is vacuum drying 31h at 63 DEG C, finally obtains 7.8g solid, and productive rate is 82.1%.
According to described product1HNMR test result, this product δ=3.554ppm, δ=4.057ppm, δ=There is absworption peak at 6.987ppm, δ=8.454ppm place.
According to the DSC test result of described product, this product only has a Tg, and Tg=86 DEG C.
According to the GPC test result of described product, the molecular weight of this product is:
Embodiment 7
The present embodiment is in order to prepare multi-functional amphipathic terpolymer provided by the invention.
By 4mlMMA (purchased from Shanghai Aladdin biochemical technology limited company), 3ml4-VPy (purchased from Sigma-Aldrich company), 5.5mlPEGMA (m=18,Purchased from Sigma-Aldrich company) be dissolved in 32mlIn Isosorbide-5-Nitrae-dioxane, then in mixed liquor, add 41.6mgBPO (purchased from the limited public affairs of Shanghai Aladdin biochemical technology shareDepartment), logical nitrogen bubble 25min (deoxygenation) after stirring, by reaction bulb good seal, is placed in 78 DEG C of oil baths instead after bubblingAnswer 36h. Then reactant liquor is precipitated in ether, suction filtration, washing, to remove unreacted monomer, initator and solvent. ProductVacuum drying 30h at 66 DEG C, finally obtains 9.8g solid, and productive rate is 78.4%.
According to described product1HNMR test result, this product δ=3.583ppm, δ=4.028ppm, δ=There is absworption peak at 6.984ppm, δ=8.456ppm place.
According to the DSC test result of described product, this product only has a Tg, and Tg=73 DEG C.
According to the GPC test result of described product, the molecular weight of this product is:
Embodiment 8
The present embodiment is in order to prepare multi-functional amphipathic terpolymer provided by the invention.
By 1.5mlMMA (purchased from Shanghai Aladdin biochemical technology limited company), 4.5ml4-VPy (purchased fromSigma-Aldrich company), 6.6mlPEGMA (m=18,Purchased from Sigma-Aldrich company) be dissolved inIn 40mlDMF, then in mixed liquor, add 50.3mgAIBN (purchased from Shanghai Aladdin biochemical technology limited company),After stirring, logical argon gas bubbling 30min (deoxygenation), by reaction bulb good seal, is placed in 69 DEG C of oil baths and reacts after bubbling27h. Then reactant liquor is precipitated in ethanol, suction filtration, washing, to remove unreacted monomer, initator and solvent. Product inVacuum drying 25h at 67 DEG C, finally obtains 10.4g solid, and productive rate is 82.5%.
According to described product1HNMR test result, this product δ=3.586ppm, δ=4.057ppm, δ=There is absworption peak at 6.965ppm, δ=8.487ppm place.
According to the DSC test result of described product, this product only has a Tg, and Tg=67 DEG C.
According to the GPC test result of described product, the molecular weight of this product is:
Embodiment 9
The present embodiment is in order to prepare multi-functional amphipathic terpolymer provided by the invention.
By 3.5mlMMA (purchased from Shanghai Aladdin biochemical technology limited company), 3ml4-VPy (purchased from Sigma-Aldrich company), 4.2mlPEGMA (m=30,Purchased from Sigma-Aldrich company) be dissolved in 38mlIn DMSO, then in mixed liquor, add 47.8mgAIBN (purchased from Shanghai Aladdin biochemical technology limited company), stirEvenly, logical nitrogen bubble 22min (deoxygenation), by reaction bulb good seal, is placed in 60 DEG C of oil baths and reacts 48h after bubbling. ConnectReactant liquor is precipitated in ether/methyl alcohol=1:1 (volume ratio), suction filtration, washing, to remove unreacted monomer, initatorAnd solvent. Product is vacuum drying 24h at 65 DEG C, finally obtains 8.1g solid, and productive rate is 79.4%.
According to described product1HNMR test result, this product δ=3.545ppm, δ=4.054ppm, δ=There is absworption peak at 6.956ppm, δ=8.486ppm place.
According to the DSC test result of described product, this product only has a Tg, and Tg=64 DEG C.
According to the GPC test result of described product, the molecular weight of this product is:
Embodiment 10
The present embodiment is in order to prepare multi-functional amphipathic terpolymer provided by the invention.
By 3mlMMA (purchased from Shanghai Aladdin biochemical technology limited company), 4ml4-VPy (purchased from Sigma-Aldrich company), 5.5mlPEGMA (m=30,Purchased from Sigma-Aldrich company) be dissolved in 28mlIn DMF, then in mixed liquor, add 38.6mgBPO (purchased from Shanghai Aladdin biochemical technology limited company), stir allEven rear logical argon gas bubbling 30min (deoxygenation), by reaction bulb good seal, is placed in 80 DEG C of oil baths and reacts 32h after bubbling. ThenReactant liquor is precipitated in ether/ethanol=1:4 (volume ratio), suction filtration, washing, with remove unreacted monomer, initator andSolvent. Product is vacuum drying 28h at 69 DEG C, finally obtains 10.5g solid, and productive rate is 84%.
According to described product1HNMR test result, this product δ=3.564ppm, δ=4.028ppm, δ=There is absworption peak at 6.991ppm, δ=8.447ppm place.
According to the DSC test result of described product, this product only has a Tg, and Tg=66 DEG C.
According to the GPC test result of described product, the molecular weight of this product is:
Embodiment 11
The present embodiment is being prepared antipollution and pH sound in order to multi-functional amphipathic terpolymer provided by the invention to be describedAnswer the application in PES milipore filter, this application comprises following step:
Step (1) preparation casting solution: by the multi-functional amphipathic ternary polymerization of preparation in 4gPES, 0.75g embodiment 1Thing, 2gPEGBe dissolved in 18.7mlDMF, the mixed liquor obtaining stirs 15h at 70 DEG C, finally obtainsObtain the casting solution of homogeneous.
Step (2) standing and defoaming: stop stirring, casting solution is left standstill at 45 DEG C to 20h, until the bubble in casting solution is completeEntirely remove.
Step (3) knifing: clean smooth glass plate is placed on knifing machine, get the casting solution curtain coating that is cooled to room temperature inGlass plate one end, starts knifing machine knifing.
Step (4) forming film with phase transformation method: steadily put into 25 DEG C after at room temperature placing 15s with the glass plate of liquid filmDeionized water in, after solvent-nonsolvent exchange, liquid film can be converted into solid film, after solvent-nonsolvent exchange completelyDiaphragm is taken out, be placed in more than deionized water preserves 24h, to remove solvent residual in diaphragm.
In embodiment 11, the antifouling property test result of the modified PES milipore filter of preparation is referring to Fig. 4; The modification of preparationThe pH response performance test result of PES milipore filter is referring to Fig. 5.
Test result shows, the flux of the prepared PES milipore filter of the present embodiment is 236.6L/ (h.m2.bar), to BSA'sRejection is 95.2%, and flux response rate is 98.6%; In addition, the flux of the prepared PES milipore filter of the present embodiment is with material liquid pHValue increase and significantly rise, its flux that is 6 o'clock in material liquid pH value is that pH is 2 o'clock 31.7 times.
Embodiment 12
The present embodiment is being prepared antipollution and pH sound in order to multi-functional amphipathic terpolymer provided by the invention to be describedAnswer the application in PES milipore filter, this application comprises following step:
Step (1) preparation casting solution: by the multi-functional amphipathic terpolymer of preparation in 5gPES, 0.5g embodiment 1,2.5gPEGBe dissolved in 17.4mlNMP, the mixed liquor obtaining stirs 20h at 60 DEG C, finally obtainsThe casting solution of homogeneous.
Step (2) standing and defoaming: stop stirring, casting solution is left standstill at 60 DEG C to 18h, until the bubble in casting solution is completeEntirely remove.
Step (3) knifing: clean smooth glass plate is placed on knifing machine, get the casting solution curtain coating that is cooled to room temperature inGlass plate one end, starts knifing machine knifing.
Step (4) forming film with phase transformation method: steadily put into 30 DEG C after at room temperature placing 10s with the glass plate of liquid filmDeionized water in, after solvent-nonsolvent exchange, liquid film can be converted into solid film, after solvent-nonsolvent exchange completelyDiaphragm is taken out, be placed in more than deionized water preserves 24h, to remove solvent residual in diaphragm.
Test result shows, the flux of the prepared PES milipore filter of the present embodiment is 247.8L/ (h.m2.bar), to BSA'sRejection is 97.2%, and flux response rate is 95.8%; In addition, the flux of the prepared PES milipore filter of the present embodiment is with material liquid pHValue increase and significantly rise, its flux that is 6 o'clock in material liquid pH value is that pH is 2 o'clock 19.6 times.
Embodiment 13
The present embodiment is being prepared antipollution and pH sound in order to multi-functional amphipathic terpolymer provided by the invention to be describedAnswer the application in PES milipore filter, this application comprises following step:
Step (1) preparation casting solution: by the multi-functional amphipathic ternary of preparation in 4.5gPES, 0.375g embodiment 1 altogetherPolymers, 1.25gPVPBe dissolved in 19.4mlDMF, the mixed liquor obtaining stirs 18h at 65 DEG C,The final casting solution that obtains homogeneous.
Step (2) standing and defoaming: stop stirring, casting solution is left standstill at 50 DEG C to 24h, until the bubble in casting solution is completeEntirely remove.
Step (3) knifing: clean smooth glass plate is placed on knifing machine, get the casting solution curtain coating that is cooled to room temperature inGlass plate one end, starts knifing machine knifing.
Step (4) forming film with phase transformation method: steadily put into 15 DEG C after at room temperature placing 0s with the glass plate of liquid filmDeionized water in, after solvent-nonsolvent exchange, liquid film can be converted into solid film, after solvent-nonsolvent exchange completelyDiaphragm is taken out, be placed in more than deionized water preserves 24h, to remove solvent residual in diaphragm.
Test result shows, the flux of the prepared PES milipore filter of the present embodiment is 228.4L/ (h.m2.bar), to BSA'sRejection is 94.6%, and flux response rate is 94.7%; In addition, the flux of the prepared PES milipore filter of the present embodiment is with material liquid pHValue increase and significantly rise, its flux that is 6 o'clock in material liquid pH value is that pH is 2 o'clock 12.7 times.
Embodiment 14
The present embodiment is being prepared antipollution and pH sound in order to multi-functional amphipathic terpolymer provided by the invention to be describedAnswer the application in PES milipore filter, this application comprises following step:
Step (1) preparation casting solution: by the multi-functional amphipathic ternary polymerization of preparation in 4.25gPES, 1g embodiment 2Thing, 2gPVPBe dissolved in 18.2mlDMF, the mixed liquor obtaining stirs 20h at 66 DEG C, finalObtain the casting solution of homogeneous.
Step (2) standing and defoaming: stop stirring, casting solution is left standstill at 45 DEG C to 20h, until the bubble in casting solution is completeEntirely remove.
Step (3) knifing: clean smooth glass plate is placed on knifing machine, get the casting solution curtain coating that is cooled to room temperature inGlass plate one end, starts knifing machine knifing.
Step (4) forming film with phase transformation method: steadily put into 20 DEG C after at room temperature placing 5s with the glass plate of liquid filmDeionized water/ethanol=4: in 1 (volume ratio), after solvent-nonsolvent exchange, liquid film can be converted into solid film, treats moltenAfter agent-non-solvent exchange completely, diaphragm is taken out, be placed in more than deionized water preserves 24h, residual molten to remove in diaphragmAgent.
Test result shows, the flux of the prepared PES milipore filter of the present embodiment is 253.9L/ (h.m2.bar), to BSA'sRejection is 98.3%, and flux response rate is 96.3%; In addition, the flux of the prepared PES milipore filter of the present embodiment is with material liquid pHValue increase and significantly rise, its flux that is 6 o'clock in material liquid pH value is that pH is 2 o'clock 18.4 times.
Embodiment 15
The present embodiment is being prepared antipollution and pH sound in order to multi-functional amphipathic terpolymer provided by the invention to be describedAnswer the application in PES milipore filter, this application comprises following step:
Step (1) preparation casting solution: by the multi-functional amphipathic ternary of preparation in 4.75gPES, 0.55g embodiment 3 altogetherPolymers, 1.75gPEGBe dissolved in 18.5mlNMP, the mixed liquor obtaining stirs 12h at 62 DEG C,Obtain eventually the casting solution of homogeneous.
Step (2) standing and defoaming: stop stirring, casting solution is left standstill at 50 DEG C to 16h, until the bubble in casting solution is completeEntirely remove.
Step (3) knifing: clean smooth glass plate is placed on knifing machine, get the casting solution curtain coating that is cooled to room temperature inGlass plate one end, starts knifing machine knifing.
Step (4) forming film with phase transformation method: steadily put into 30 DEG C after at room temperature placing 40s with the glass plate of liquid filmDeionized water in, after solvent-nonsolvent exchange, liquid film can be converted into solid film, after solvent-nonsolvent exchange completelyDiaphragm is taken out, be placed in more than deionized water preserves 24h, to remove solvent residual in diaphragm.
Test result shows, the flux of the prepared PES milipore filter of the present embodiment is 236.4L/ (h.m2.bar), to BSA'sRejection is 96.8%, and flux response rate is 93.3%; In addition, the flux of the prepared PES milipore filter of the present embodiment is with material liquid pHValue increase and significantly rise, its flux that is 6 o'clock in material liquid pH value is that pH is 2 o'clock 14.7 times.
Embodiment 16
The present embodiment is being prepared antipollution and pH sound in order to multi-functional amphipathic terpolymer provided by the invention to be describedAnswer the application in PES milipore filter, this application comprises following step:
Step (1) preparation casting solution: by the multi-functional amphipathic ternary of preparation in 5.5gPES, 0.625g embodiment 4 altogetherPolymers, 1.8gPEGBe dissolved in 17.5mlNMP, the mixed liquor obtaining stirs 18h at 50 DEG C, finalObtain the casting solution of homogeneous.
Step (2) standing and defoaming: stop stirring, casting solution is left standstill at 30 DEG C to 20h, until the bubble in casting solution is completeEntirely remove.
Step (3) knifing: clean smooth glass plate is placed on knifing machine, get the casting solution curtain coating that is cooled to room temperature inGlass plate one end, starts knifing machine knifing.
Step (4) forming film with phase transformation method: steadily put into 25 DEG C after at room temperature placing 20s with the glass plate of liquid filmDeionized water/methyl alcohol=2: in 1 (volume ratio), after solvent-nonsolvent exchange, liquid film can be converted into solid film, treats moltenAfter agent-non-solvent exchange completely, diaphragm is taken out, be placed in more than deionized water preserves 24h, residual molten to remove in diaphragmAgent.
Test result shows, the flux of the prepared PES milipore filter of the present embodiment is 259.5L/ (h.m2.bar), to BSA'sRejection is 97.2%, and flux response rate is 90.5%; In addition, the flux of the prepared PES milipore filter of the present embodiment is with material liquid pHValue increase and significantly rise, its flux that is 6 o'clock in material liquid pH value is that pH is 2 o'clock 10.7 times.
Embodiment 17
The present embodiment is being prepared antipollution and pH sound in order to multi-functional amphipathic terpolymer provided by the invention to be describedAnswer the application in PES milipore filter, this application comprises following step:
Step (1) preparation casting solution: by the multi-functional amphipathic ternary of preparation in 5.25gPES, 0.875g embodiment 5 altogetherPolymers, 1.75gPEGBe dissolved in 17.6mlDMF, the mixed liquor obtaining stirs 18h at 50 DEG C,The final casting solution that obtains homogeneous.
Step (2) standing and defoaming: stop stirring, casting solution is left standstill at 35 DEG C to 15h, until the bubble in casting solution is completeEntirely remove.
Step (3) knifing: clean smooth glass plate is placed on knifing machine, get the casting solution curtain coating that is cooled to room temperature inGlass plate one end, starts knifing machine knifing.
Step (4) forming film with phase transformation method: steadily put into 20 DEG C after at room temperature placing 25s with the glass plate of liquid filmEthanol in, after solvent-nonsolvent exchange, liquid film can be converted into solid film, after solvent-nonsolvent exchange completely by filmSheet takes out, and is placed in more than deionized water preserves 24h, to remove solvent residual in diaphragm.
Test result shows, the flux of the prepared PES milipore filter of the present embodiment is 245.6L/ (h.m2.bar), to BSA'sRejection is 93.9%, and flux response rate is 95.5%; In addition, the flux of the prepared PES milipore filter of the present embodiment is with material liquid pHValue increase and significantly rise, its flux that is 6 o'clock in material liquid pH value is that pH is 2 o'clock 22.8 times.
Embodiment 18
The present embodiment is being prepared antipollution and pH sound in order to multi-functional amphipathic terpolymer provided by the invention to be describedAnswer the application in PES milipore filter, this application comprises following step:
Step (1) preparation casting solution: by the multi-functional amphipathic ternary polymerization of preparation in 4.9gPES, 0.4g embodiment 6Thing, 2.25gPVPBe dissolved in 17.8mlNMP, the mixed liquor obtaining stirs 20h at 58 DEG C,Obtain eventually the casting solution of homogeneous.
Step (2) standing and defoaming: stop stirring, casting solution is left standstill at 30 DEG C to 20h, until the bubble in casting solution is completeEntirely remove.
Step (3) knifing: clean smooth glass plate is placed on knifing machine, get the casting solution curtain coating that is cooled to room temperature inGlass plate one end, starts knifing machine knifing.
Step (4) forming film with phase transformation method: steadily put into 22 DEG C after at room temperature placing 5s with the glass plate of liquid filmDeionization/methyl alcohol=5: in 1 (volume ratio), after solvent-nonsolvent exchange, liquid film can be converted into solid film, treat solvent-After non-solvent exchange completely, diaphragm is taken out, be placed in more than deionized water preserves 24h, to remove solvent residual in diaphragm.
Test result shows, the flux of the prepared PES milipore filter of the present embodiment is 261.1L/ (h.m2.bar), to BSA'sRejection is 93.4%, and flux response rate is 91.5%; In addition, the flux of the prepared PES milipore filter of the present embodiment is with material liquid pHValue increase and significantly rise, its flux that is 6 o'clock in material liquid pH value is that pH is 2 o'clock 9.8 times.
Embodiment 19
The present embodiment is being prepared antipollution and pH sound in order to multi-functional amphipathic terpolymer provided by the invention to be describedAnswer the application in PES milipore filter, this application comprises following step:
Step (1) preparation casting solution: by the multi-functional amphipathic ternary polymerization of preparation in 4.2gPES, 0.25g embodiment 7Thing, 2.5gPVPBe dissolved in 18.8mlDMF, the mixed liquor obtaining stirs 14h at 50 DEG C, finalObtain the casting solution of homogeneous.
Step (2) standing and defoaming: stop stirring, casting solution is left standstill at 38 DEG C to 22h, until the bubble in casting solution is completeEntirely remove.
Step (3) knifing: clean smooth glass plate is placed on knifing machine, get the casting solution curtain coating that is cooled to room temperature inGlass plate one end, starts knifing machine knifing.
Step (4) forming film with phase transformation method: steadily put into 10 DEG C after at room temperature placing 35s with the glass plate of liquid filmDeionization/ethanol=1: in 1 (volume ratio), after solvent-nonsolvent exchange, liquid film can be converted into solid film, treat solvent-After non-solvent exchange completely, diaphragm is taken out, be placed in more than deionized water preserves 24h, to remove solvent residual in diaphragm.
Test result shows, the flux of the prepared PES milipore filter of the present embodiment is 227.6L/ (h.m2.bar), to BSA'sRejection is 94.3%, and flux response rate is 85.2%; In addition, the flux of the prepared PES milipore filter of the present embodiment is with material liquid pHValue increase and significantly rise, its flux that is 6 o'clock in material liquid pH value is that pH is 2 o'clock 6.5 times.
Embodiment 20
The present embodiment is being prepared antipollution and pH sound in order to multi-functional amphipathic terpolymer provided by the invention to be describedAnswer the application in PES milipore filter, this application comprises following step:
Step (1) preparation casting solution: by the multi-functional amphipathic ternary polymerization of preparation in 5gPES, 0.125g embodiment 8Thing, 3gPEGBe dissolved in 16.9mlDMAc, the mixed liquor obtaining stirs 20h at 55 DEG C, finally obtainsObtain the casting solution of homogeneous.
Step (2) standing and defoaming: stop stirring, casting solution is left standstill at 55 DEG C to 18h, until the bubble in casting solution is completeEntirely remove.
Step (3) knifing: clean smooth glass plate is placed on knifing machine, get the casting solution curtain coating that is cooled to room temperature inGlass plate one end, starts knifing machine knifing.
Step (4) forming film with phase transformation method: steadily put into 15 DEG C after at room temperature placing 45s with the glass plate of liquid filmMethyl alcohol in, after solvent-nonsolvent exchange, liquid film can be converted into solid film, after solvent-nonsolvent exchange completely by filmSheet takes out, and is placed in more than deionized water preserves 24h, to remove solvent residual in diaphragm.
Test result shows, the flux of the prepared PES milipore filter of the present embodiment is 258.5L/ (h.m2.bar), to BSA'sRejection is 96.8%, and flux response rate is 81.9%; In addition, the flux of the prepared PES milipore filter of the present embodiment is with material liquid pHValue increase and significantly rise, its flux that is 6 o'clock in material liquid pH value is that pH is 2 o'clock 5.4 times.
Embodiment 21
The present embodiment is being prepared antipollution and pH sound in order to multi-functional amphipathic terpolymer provided by the invention to be describedAnswer the application in PES milipore filter, this application comprises following step:
Step (1) preparation casting solution: by the multi-functional amphipathic ternary polymerization of preparation in 5.3gPES, 0.15g embodiment 9Thing, 3.75gPEGBe dissolved in 16mlDMAc, the mixed liquor obtaining stirs 14h at 65 DEG C, finalObtain the casting solution of homogeneous.
Step (2) standing and defoaming: stop stirring, casting solution is left standstill at 60 DEG C to 13h, until the bubble in casting solution is completeEntirely remove.
Step (3) knifing: clean smooth glass plate is placed on knifing machine, get the casting solution curtain coating that is cooled to room temperature inGlass plate one end, starts knifing machine knifing.
Step (4) forming film with phase transformation method: steadily put into 10 DEG C after at room temperature placing 50s with the glass plate of liquid filmDeionized water in, after solvent-nonsolvent exchange, liquid film can be converted into solid film, after solvent-nonsolvent exchange completelyDiaphragm is taken out, be placed in more than deionized water preserves 24h, to remove solvent residual in diaphragm.
Test result shows, the flux of the prepared PES milipore filter of the present embodiment is 241.7L/ (h.m2.bar), to BSA'sRejection is 97.6%, and flux response rate is 80.5%; In addition, the flux of the prepared PES milipore filter of the present embodiment is with material liquid pHValue increase and significantly rise, its flux that is 6 o'clock in material liquid pH value is that pH is 2 o'clock 4.7 times.
Embodiment 22
The present embodiment is being prepared antipollution and pH sound in order to multi-functional amphipathic terpolymer provided by the invention to be describedAnswer the application in PES milipore filter, this application comprises following step:
Step (1) preparation casting solution: by the multi-functional amphipathic ternary of preparation in 5.6gPES, 0.28g embodiment 10 altogetherPolymers, 1.7gPVPBe dissolved in 17.8mlDMAc, the mixed liquor obtaining stirs 12h at 70 DEG C,The final casting solution that obtains homogeneous.
Step (2) standing and defoaming: stop stirring, casting solution is left standstill at 58 DEG C to 16h, until the bubble in casting solution is completeEntirely remove.
Step (3) knifing: clean smooth glass plate is placed on knifing machine, get the casting solution curtain coating that is cooled to room temperature inGlass plate one end, starts knifing machine knifing.
Step (4) forming film with phase transformation method: steadily put into 0 DEG C after at room temperature placing 60s with the glass plate of liquid filmDeionized water in, after solvent-nonsolvent exchange, liquid film can be converted into solid film, after solvent-nonsolvent exchange completelyDiaphragm is taken out, be placed in more than deionized water preserves 24h, to remove solvent residual in diaphragm.
Test result shows, the flux of the prepared PES milipore filter of the present embodiment is 240.9L/ (h.m2.bar), to BSA'sRejection is 96.2%, and flux response rate is 78.5%; In addition, the flux of the prepared PES milipore filter of the present embodiment is with material liquid pHValue increase and significantly rise, its flux that is 6 o'clock in material liquid pH value is that pH is 2 4.2 times.

Claims (10)

1. a multi-functional amphipathic terpolymer, is characterized in that its chemical structural formula is as follows:
Wherein, m is any one value in 3,8,18,30, and x is any one integer in 330～620, and y is in 210～540Any one integer, z is any one integer in 15～80.
2. a kind of multi-functional amphipathic terpolymer as claimed in claim 1, it is characterized in that a kind of random copolymer, shouldCopolymer is by hydrophobic segment methyl methacrylate, segment 4-vinylpridine and the poly-second two of hydrophilic segment with pH response groupAlcohol methyl ether methacrylate three part compositions.
3. a kind of preparation method of multi-functional amphipathic terpolymer as claimed in claim 1, is characterized in that it specifically walksRapid as follows:
MMA, 4-VPy, tri-kinds of monomers of PEGMA are dissolved in solvent, then add initator, will be anti-after the deoxygenation of ventilation bubbling after stirringShould seal by bottle, be placed in oil bath and react, then reactant liquor is precipitated in precipitating reagent, suction filtration, washing, to remove unreacted listBody, initator and solvent, obtain multi-functional amphipathic terpolymer after being dried.
4. a kind of preparation method of multi-functional amphipathic terpolymer as claimed in claim 3, is characterized in that described PEGMAThe molecular weight of monomerFor any one in 300g/mol, 500g/mol, 950g/mol, 1500g/mol, preferably 500g/mol；
Described solvent can be selected from DMF, DMA, 1-METHYLPYRROLIDONE, methyl-sulfoxide,At least one in Isosorbide-5-Nitrae-dioxane; The preferably one in DMF, DMAc, DMSO.
5. a kind of preparation method of multi-functional amphipathic terpolymer as claimed in claim 3, it is characterized in that described MMA,The mass percent of 4-VPy, PEGMA and solvent is: (5%～15%): (6%～20%): (4%～10%): (55%～85%), total amount is 100%; Preferably (8%～15%): (12%～20%): (7%～10%): (55%～73%).
6. a kind of preparation method of multi-functional amphipathic terpolymer as claimed in claim 3, is characterized in that described initiationAgent is selected from azodiisobutyronitrile or dibenzoyl peroxide, preferably azodiisobutyronitrile; The addition of described initator can be three3%～7% of kind of monomer gross mass, preferably 3%～5%;
The gas that described bubbling is used can be nitrogen or argon gas, preferably argon gas; The time of described bubbling can be 15～30min, preferably20～30min。
7. a kind of preparation method of multi-functional amphipathic terpolymer as claimed in claim 3, is characterized in that described oil bathThe temperature of middle reaction is 60～80 DEG C, and the time of reacting in oil bath is 24～48h; The temperature of reacting in oil bath preferably 65～75DEG C, preferably 24～32h of the time of reacting in oil bath;
Described precipitating reagent can be selected from least one in methyl alcohol, ethanol, ether; At least one in particular methanol, ether;
Described being dried can adopt vacuum drying, and dry temperature can be 60～80 DEG C, and the dry time can be 24～48h, dryPreferably 60～70 DEG C of temperature, preferably 24～32h of dry time.
As claimed in claim 1 multi-functional amphipathic terpolymer preparing in antipollution and pH response poly (ether-sulfone) ultrafiltration membraneApplication.
9. application as claimed in claim 8, is characterized in that its concrete grammar is as follows:
1) preparation casting solution: polyether sulfone, multi-functional amphipathic terpolymer, pore-foaming agent are dissolved in solvent to the mixing obtainingLiquid obtains casting solution after stirring;
2) standing and defoaming: casting solution is left standstill, until the bubble in casting solution removes completely;
3) knifing: substrate is placed on knifing machine, gets the casting solution curtain coating that is cooled to room temperature in substrate one end, start knifing machine and scrapeFilm;
4) forming film with phase transformation method: after being placed, puts into by the substrate with liquid film the coagulating bath of 0～40 DEG C, and molten through solvent-non-After agent exchange, liquid film is converted into solid film, after solvent-nonsolvent exchange completely, solid-state diaphragm is taken out, and is placed in deionized waterMiddle preservation is more than 24h, to remove solvent residual in solid-state diaphragm.
10. application as claimed in claim 9, is characterized in that in step 1) in, described pore-foaming agent is selected from polyethylene glycol or poly-secondAlkene pyrrolidone, the wherein molecular weight of polyethylene glycolThe molecular weight of polyvinylpyrrolidonePreferred: the molecular weight of polyethylene glycolPolyvinylpyrrolidineThe molecular weight of ketoneDescribed solvent can be selected from the one in DMF, DMAc, NMP, preferably DMFOr NMP; In described casting solution, the quality percentage composition of each component is respectively: polyether sulfone=16%～22%, and multi-functional amphipathicTerpolymer=0.5%～4%, pore-foaming agent=5%～15%, solvent=59%～78.5%; In described casting solution each groupThe quality percentage composition dividing is preferably respectively: polyether sulfone=16%～20%, and multi-functional amphipathic terpolymer=1.5%～3%, pore-foaming agent=5%～10%, solvent=67%～77.5%; The temperature of described stirring can be 50～70 DEG C, stirring timeBetween can be 12～24h, preferably 60～70 DEG C of the temperature of stirring, preferably 15～20h of the time of stirring;
In step 2) in, described dwell temperature is 25～60 DEG C, time of repose is 12～24h, and preferably 50～60 DEG C of dwell temperature,Time of repose is 18～24h preferably;
In step 4) in, the time of described placement can be 0～60s, preferably 0～15s; The temperature of described coagulating bath can be 0～40DEG C, preferably 15～30 DEG C; Described coagulating bath is at least one in deionized water, methyl alcohol, ethanol, preferably deionized water.
CN201610090858.0A 2016-02-18 2016-02-18 Multifunctional amphiphilic terpolymer as well as preparation method and application thereof Pending CN105585659A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109382002A (en) * 2017-08-02 2019-02-26 浙江工业大学 A kind of intelligent switch film and preparation method thereof based on nanogel
CN112108015A (en) * 2020-10-10 2020-12-22 天津工业大学 Preparation method of structurally controllable amphiphilic hyperbranched polymer in-situ modified ultrafiltration membrane

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140083931A1 (en) * 2012-03-05 2014-03-27 Chung Yuan Christian University Anti-biofouling Membrane for Water-Treatment
CN104174297A (en) * 2014-08-13 2014-12-03 浙江大学 Method for preparing self-healing polymer separation film

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140083931A1 (en) * 2012-03-05 2014-03-27 Chung Yuan Christian University Anti-biofouling Membrane for Water-Treatment
CN104174297A (en) * 2014-08-13 2014-12-03 浙江大学 Method for preparing self-healing polymer separation film

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
FU LIU，等: ""Preparation of hydrophilic and fouling resistant poly(vinyllidene fluoride) hollow fiber membranes"", 《JOURNAL OF MEMBRANE SCIENCE》 *
RUI WANG，等: ""Preparation and characterization of pH-sensitive polyethersulfone hollow fiber membranes modified by poly(methyl methylacrylate-co-4-vinyl pyridine) copolymer"", 《JOURNAL OF MEMBRANE SCIENCE》 *
徐又一，等: "《高分子膜材料》", 30 April 2005, 化学工业出版社 *
王建宇: ""两亲性共聚物的分子设计、合成及其共混改性疏水聚合物多孔膜的研究"", 《中国博士学位论文全文数据库 工程科技I辑》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109382002A (en) * 2017-08-02 2019-02-26 浙江工业大学 A kind of intelligent switch film and preparation method thereof based on nanogel
CN109382002B (en) * 2017-08-02 2021-06-04 浙江工业大学 Intelligent switch membrane based on nanogel and preparation method thereof
CN112108015A (en) * 2020-10-10 2020-12-22 天津工业大学 Preparation method of structurally controllable amphiphilic hyperbranched polymer in-situ modified ultrafiltration membrane

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