CN103736408B - A kind of polysulfone porous membrane to temperature, acidity response and preparation method thereof and application - Google Patents
A kind of polysulfone porous membrane to temperature, acidity response and preparation method thereof and application Download PDFInfo
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Abstract
The invention belongs to film preparation and technical field of modification, particularly a kind of polysulfone porous membrane to temperature, acidity response and preparation method and application.The present invention utilizes the principle of " click chemistry ", by the environment-responsive polymer of alkynyl end, be grafted to PS membrane surface by the reactive chemistry between alkynyl and nitrine, thus obtain the PS membrane that surface grafting has environment-responsive polymer chain, reach the object of modified polysulfone membrane environment response.The fenestra of the polysulfone porous membrane to temperature, acidity response that the method prepares can change with the change of pH and temperature, and has invertibity, and the physical and chemical performance of film substrate simultaneously does not change substantially.
Description
Technical field
The invention belongs to film preparation and technical field of modification, particularly a kind of polysulfone porous membrane to temperature, acidity response and preparation method and application.
Background technology
Polysulfones is slightly amber armorphous transparent or semitransparent polymer, excellent in mechanical performance, and rigidity is large, wear-resisting, high strength, heat endurance is high, hydrolysis, good stability of the dimension, molding shrinkage is little, nontoxic, radiation hardness, resistance to combustion, has the property put out, chemical stability is good, except red fuming nitric acid (RFNA), the concentrated sulfuric acid, halogenated hydrocarbons, and the general acid of ability, alkali, salt, at ketone, swelling in ester.The perforated membrane prepared based on polysulfones has the superiority the same with polysulfones substrate, and it is all widely used in electric, food and commodity, automobile, aviation, the department such as medical treatment and general industry.
Because PS membrane itself has hydrophobic speciality, because which limit its application in a lot of field, its contact angle is generally greater than 70 °, and tradition is only limitted to environment-responsive modification to the modification of PS membrane.Hydrophilic modifying is carried out to PS membrane, effectively can reduce the absorption of environment-responsive material on PS membrane surface in filtrate, but the use along with film there will be the decline of membrane flux, this is because: the fine particle thing that (1) is insoluble in water is adsorbed on film surface, blocking fenestra passage; (2) use repeatedly under certain pressure intensity, causes fenestra deformation, and membrane structure is damaged.
(1) usual means needed of dealing with problems are that film is carried out backwash, namely by oppositely pressurization, allow the particle of script incarceration in fenestra separate out from former road.But relative to perseverance to exerting pressure, break-in exert pressure operate comparatively loaded down with trivial details.Reach the requirement of problem (2), need the functional polymer not adding other as much as possible, ensure that the physical and chemical performance of polysulfones substrate does not change.
How to prepare and permanent just can go out the granular absorption thing on PS membrane surface to exerting pressure, while can keep again the film of the physical and chemical performance of polysulfones substrate, be the main purpose of this patent.
If the size of fenestra can be made to change increase controlled under external condition, and can reply again, then can deal with problems (1) by permanent to exerting pressure.When particle incarceration is in polysulfones fenestra, by changing external condition, PS membrane hole dimension is increased, then particle just can be broken through polysulfones fenestra by hydraulic pressure thus be removed.Change external condition more afterwards, allow polysulfones fenestra be returned to original size, reuse.And temperature and pH are the means that most easy to reach can change.For reaching this object, design and synthesis prepare fenestra have temperature or pH response PS membrane be very significant.
Conventional blending modification method modified polysulfone film, be about to additive containing specific hydrophilic or hydrophobic units and polysulfones with the blended film forming of certain proportion, with comparing class of the present invention like patent be CN101721023A, the basilar memebrane of this invention is Kynoar, reaches the effect required for problem (1) by grafting stimulating responsive polymer side chain.But the physical and chemical performance of this method on film substrate has impact, film forming can be caused to be deteriorated, fenestra heterogeneity, membrane structure is unstable, is unfavorable for deal with problems (2).The patent of patent CN1962040A have employed composite algorithm, polymer by Thermo-sensitive covers the effect that basement membrane surface reaches problem (1), but the limitation of the method is the filming performance extreme difference of temperature sensing polymer, and and the combination of basilar memebrane only belong to physical bond, the standby membrane stability of this legal system has much room for improvement.
In recent years, cause by surface the PS membrane preparing temperature or pH response and have many sections of similar documents and patent report.Patent CN102875195A and CN103123958A, document JournalofMembraneScience352(2010) 22 – 31 and JournalofMembraneScience442(2013) 206 – 215 report the film of external environment response prepared by the method.The superiority of this method is, polymer modification is only carried out on film surface, does not have impact to the physical and chemical performance of film substrate.The requirement required for problem (2) can be met.But the limitation of the method also clearly, surperficial Inducing Graft Polymerization thing, needs to carry out specially treated to basilar memebrane, thus provides the surface functional group of available initiation.Such as plasma resonance, ultraviolet irradiation, soda acid process etc., these methods operate with high costs a bit, cannot large-scale production, and some condition is comparatively harsh, harmful effect can be produced to basilar memebrane itself, surface initiation polymerization requires also higher to operating condition simultaneously, needs strict anaerobic, otherwise polymerization efficiency and polymerization controllability will be had a greatly reduced quality.Therefore for modified polysulfone film, more gentle simple means are needed.
Click chemistry as a kind of in recent years in field of polymer technology by the method for extensive concern and use, there is reaction condition and simply easily operate, the outstanding feature that mild condition is not harsh.
This patent, in conjunction with the advantage of click chemistry, has carried out the improvement of preparation method for problem described before, has first been undertaken blended by Azide polysulfones and polysulfones substrate.Introducing in polysulfones substrate can for the nitrine functional group of reaction, and because Azide polysulfones physical and chemical performance is very similar with polysulfones substrate, therefore this blended performance impact to polysulfones substrate is minimum, avoids the defect described in problem (2).Secondly, the temperature sensing polymer previously prepared good end being contained alkynyl by click chemistry reaction temperature and be grafted to polysulfones/Azide polysulfones blend film surface and fenestra inner wall surface, reach the target of dealing with problems required for (1).
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, primary and foremost purpose of the present invention is to provide a kind of polysulfone porous membrane to temperature, acidity response.
Another order of the present invention is the preparation method providing the above-mentioned polysulfone porous membrane to temperature, acidity response.
Another object of the present invention is the application providing the above-mentioned polysulfone porous membrane to temperature, acidity response.
Object of the present invention is achieved through the following technical solutions:
To a preparation method for the polysulfone porous membrane of temperature, acidity response, comprise following steps:
(1) polysulfones industrial goods and Azide polysulfones blended: the technical grade polysulfones raw material of 1 ~ 14 mass parts, the Azide polysulfones of 1 ~ 14 mass parts, the pore-foaming agent of 1 mass parts are joined in the organic solvent A of 40 mass parts, stirring at room temperature, to transparent clarification, obtains the casting solution of polysulfones industrial goods and Azide polysulfones blend film;
(2) polysulfones/Azide polysulfone blends prepares perforated membrane: the polysulfones industrial goods prepare step (1) and the casting solution of Azide polysulfones blend film are poured onto on blade applicator substrate, adjust blade height, blade coating film forming, immerses substrate in coagulating bath solvent at 25 ~ 50 DEG C; After film is separated with substrate, film is taken out and dries, prepare polysulfones/Azide polysulfone porous membrane;
(3) to the modifying surface of polysulfones/Azide polysulfone porous membrane: polysulfones/Azide polysulfone porous membrane step (2) prepared is immersed in the solvent B of 400 mass parts; Add the environment-responsive polymer C of 10 ~ 50 mass parts, the copper sulphate of 1 mass parts, the sodium ascorbate of 1 mass parts again, reactor is sealed, then passes into bubbling inert gas 20 ~ 50min, most oxygen in removing reactor; Reactor is placed in water bath with thermostatic control, is 15 ~ 50 DEG C in temperature, and pH is 6.0 ~ 9.0 times, reaction 12 ~ 72h; After reaction terminates, film is taken out and wash 1 ~ 5 time with water, dry again after removing unreacted environment-responsive polymer C on perforated membrane and other impurity; Obtain the polysulfone porous membrane to temperature, acidity response;
Technical grade polysulfones raw material described in step (1) be polysulfones S3010(Germany BASF), its structural formula as shown in Equation 1:
The structural formula of the Azide polysulfones described in step (1) is as shown in Equation 2:
The synthesized reference document of Azide polysulfones: H.Toiserkani, G.Yilmaz, Y.Yagci, L.Torun, Macromol.Chem.Phys.211 (2010);
Pore-foaming agent described in step (1) is polyethylene glycol, and molecular weight is 2000Da;
Organic solvent A described in step (1) is the one in methyl pyrrolidone, dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), oxolane, carrene, chloroform, carbon tetrachloride;
Blade applicator blade height described in step (2) is 150um;
Coagulating bath solvent described in step (2) is one or more mixtures in water, ethanol, methyl alcohol, isopropyl alcohol;
The aperture of the polysulfones described in step (2)/Azide polysulfone porous membrane is 5 ~ 10um, and porosity is 63%;
Solvent B described in step (3) is one or more mixtures in water, ethanol, methyl alcohol, isopropyl alcohol;
The environment-responsive polymer of to be end the be alkynyl of the environment-responsive polymer C described in step (3); Be preferably alkynyl end polyacrylic acid (PAA-C ≡ CH), alkynyl end polymethylacrylic acid (PMAA-C ≡ CH), alkynyl end PNIPAM and acrylic acid copolymer (P(NIPAAm-co-AA)-C ≡ CH) or copolymer (the P(NIPAAm-co-MAA)-C ≡ CH of alkynyl end PNIPAM and methacrylic acid) in any one polymer;
The synthetic method of described alkynyl end polyacrylic acid (PAA-C ≡ CH) comprises following steps: get 2 of the bromo acid propynyl ester initator of 1 mass parts, the acrylic acid (AA) of 150 mass parts, the methyl alcohol of 100 mass parts, the CuCl of 1 mass parts and 1 mass parts, 2'-bipyridyl, 50 DEG C are carried out ATRP (ATRP) reaction under nitrogen protection, obtain the PAA-C ≡ CH that the degree of polymerization (DP) is 85;
The synthetic method of described alkynyl end polymethylacrylic acid (PMAA-C ≡ CH) comprises following steps: get 2 of the bromo acid propynyl ester initator of 1 mass parts, the methacrylic acid (MAA) of 150 mass parts, the methyl alcohol of 100 mass parts, the CuCl of 1 mass parts and 1 mass parts, 2'-bipyridyl, 50 DEG C are carried out ATRP (ATRP) reaction under nitrogen protection, obtain the PMAA-C ≡ CH that the degree of polymerization (DP) is 85;
Described alkynyl end PNIPAM and acrylic acid copolymer (P(NIPAAm-co-AA)-C ≡ CH) synthetic method comprise following steps: the bromo acid propynyl ester initator getting 1 mass parts, the N-isopropylacrylamide (NIPAAm) of 100 mass parts, the acrylic acid (AA) of 50 mass parts, the methyl alcohol of 100 mass parts, the CuCl of 1 mass parts and the PMDETA of 1 mass parts, 40 DEG C are carried out ATRP (ATRP) reaction under nitrogen protection, obtaining the degree of polymerization (DP) is the P(NIPAAm-co-AA of 108)-C ≡ CH,
Copolymer (the P(NIPAAm-co-MAA)-C ≡ CH of described alkynyl end PNIPAM and methacrylic acid) synthetic method comprise following steps: the bromo acid propynyl ester initator getting 1 mass parts, the N-isopropylacrylamide (NIPAAm) of 100 mass parts, the methacrylic acid (MAA) of 50 mass parts, the methyl alcohol of 100 mass parts, the CuCl of 1 mass parts and the PMDETA of 1 mass parts, 40 DEG C are carried out ATRP (ATRP) reaction response under nitrogen protection, obtaining the degree of polymerization (DP) is the P(NIPAAm-co-MAA of 109)-C ≡ CH.
The wherein synthesized reference document of bromo acid propynyl ester: TernaryGraftCopolymersandTheirUseinNanocapsulePreparatio n.Macromolecules(2013) 46; 2646 ~ 2657;
The fenestra of the polysulfone porous membrane to temperature, acidity response that the present invention prepares can change with the change of pH and temperature, and has invertibity, and the physical and chemical performance of film substrate simultaneously does not change substantially, can be widely used in film preparation and technical field of modification.
Principle of the present invention:
By Azide polysulfones and the blended masking of polysulfones, thus introduce nitrine functional group on PS membrane surface and fenestra inner wall surface, utilize the principle of " click chemistry " afterwards, by the environment-responsive polymer of alkynyl end, PS membrane surface is grafted to by the reactive chemistry between alkynyl and nitrine, thus obtain the PS membrane that surface grafting has environment-responsive polymer chain, reach preparation base performance and polysulfones basic simlarity, membrane pore size has the PS membrane (as shown in Figure 1) of environment-responsive simultaneously.
The present invention has following advantage and effect relative to prior art:
(1) Azide polysulfones is easily prepared, with low cost, and easily industrialization;
(2) Azide polysulfones and polysulfones blended after, providing on film surface can for the nitrine functional group of reaction, simultaneously on the physical and chemical performance of polysulfones substantially without affecting.And simple to operate, cost is low, and object easily reaches;
(3) structure being grafted to the environment-responsive polymerization on film surface is strictly controlled, and its ratio and the degree of polymerization can regulate arbitrarily according to the aperture of polysulfones basilar memebrane.
Accompanying drawing explanation
Fig. 1 is the polysulfone porous membrane principle schematic to temperature, acidity response.
Fig. 2 be to temperature, acidity response polysulfone porous membrane under high temperature (60 DEG C) and low temperature (5 DEG C), pH=2.2 time and pH=9.0 time flux.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, further detailed description is done to the present invention.But embodiments of the present invention are not limited thereto.
The raw material used in embodiment is as follows:
The wherein synthesized reference document of bromo acid propynyl ester: TernaryGraftCopolymersandTheirUseinNanocapsulePreparatio n.Macromolecules(2013) 46; 2646 ~ 2657;
The synthesized reference document of Azide polysulfones: H.Toiserkani, G.Yilmaz, Y.Yagci, L.Torun, Macromol.Chem.Phys.211 (2010);
Number involved in following examples is all mass fractions.
Embodiment 1
(1) polysulfones industrial goods and Azide polysulfones blended: 1 part of polysulfones S3010,14 parts of Azide polysulfones, 1 part of polyethylene glycol (Mw=2000Da) are joined in 40 parts of methyl pyrrolidones, 25 DEG C are stirred to transparent clarification, obtain the casting solution of polysulfones industrial goods and Azide polysulfones blend film;
(2) polysulfones/Azide polysulfone blends prepares perforated membrane: the polysulfones industrial goods prepare step (1) and the casting solution of Azide polysulfones blend film are poured onto on coating device substrate, adjust blade height to 150um, blade coating film forming, is immersed in the water substrate at 25 DEG C; After film is separated with substrate, taken out by film and dry, prepare polysulfones/Azide polysulfone porous membrane, its aperture is 5 ~ 10um, and porosity is 63%;
(3) to the modifying surface of polysulfones/Azide polysulfone porous membrane:
Get the bromo acid propynyl ester initator of 1 part, the methacrylic acid of 150 parts, the methyl alcohol of 100 parts, 1 part CuCl and 1 part 2,2'-bipyridyl, 50 DEG C are carried out ATRP (ATRP) reaction under nitrogen protection, obtain the PMAA-C ≡ CH that the degree of polymerization (DP) is 85;
Polysulfones/Azide polysulfone porous membrane step (2) prepared is immersed in 400 parts of water; Add 10 parts of environment-responsive polymer P MAA-C ≡ CH again, 1 part of copper sulphate, 1 part of sodium ascorbate, seals reactor; Then bubbling inert gas 20min is passed into, most oxygen in removing reactor; Reactor is placed in water bath with thermostatic control, is 15 DEG C in temperature, and pH is 7.0 times, reaction 12h; After reaction terminates, film is taken out and wash 1 time with water, remove the unreacted environment-responsive polymer P MAA-C ≡ CH on perforated membrane, and dry again after other impurity; Obtain the polysulfone porous membrane to temperature, acidity response;
Be 16.85 × 10 to the hot strength of polysulfone porous membrane of temperature, acidity response
-3mPa, under high temperature (60 DEG C) and low temperature (5 DEG C), pH=2.2 time and pH=9.0 time flux as shown in Figure 2.
Embodiment 2
(1) polysulfones industrial goods and Azide polysulfones blended: 3 parts of polysulfones S3010,12 parts of Azide polysulfones, 1 part of polyethylene glycol (Mw=2000Da) are joined in 40 parts of dimethylacetylamides, 25 DEG C are stirred to transparent clarification, obtain the casting solution of polysulfones industrial goods and Azide polysulfones blend film;
(2) polysulfones/Azide polysulfone blends prepares perforated membrane: the polysulfones industrial goods prepare step (1) and the casting solution of Azide polysulfones blend film are poured onto on coating device substrate, adjust blade height to 150um, blade coating film forming, substrate immerses in ethanol by 25 DEG C; After film is separated with substrate, taken out by film and dry, prepare polysulfones/Azide polysulfone porous membrane, its aperture is 5 ~ 10um, and porosity is 63%;
(3) to the modifying surface of polysulfones/Azide polysulfone porous membrane:
Get the bromo acid propynyl ester initator of 1 part, the acrylic acid (AA) of 150 parts, the methyl alcohol of 100 parts, 1 part CuCl and 1 part 2,2'-bipyridyl, 50 DEG C are carried out ATRP (ATRP) reaction under nitrogen protection, obtain the PAA-C ≡ CH that the degree of polymerization (DP) is 85;
Polysulfones step (2) prepared/Azide polysulfones blend film is immersed in 400 parts of methyl alcohol; Add 15 parts of environment-responsive polymer P AA-C ≡ CH again, 1 part of copper sulphate, 1 part of sodium ascorbate, seals reactor; Then bubbling inert gas 25min is passed into, most oxygen in removing reactor; Reactor is placed in water-bath, is 25 DEG C in temperature, and pH is 6.0 times, reaction 18h; After reaction terminates, film is taken out and wash 3 times with water, remove the unreacted environment-responsive polymer on perforated membrane, and dry again after other impurity; Obtain the polysulfone porous membrane to temperature, acidity response;
Be 17.25 × 10 to the hot strength of polysulfone porous membrane of temperature, acidity response
-3mPa, under high temperature (60 DEG C) and low temperature (5 DEG C), pH=2.2 time and pH=9.0 time flux as shown in Figure 2.
Embodiment 3
(1) polysulfones industrial goods and Azide polysulfones blended: 5 parts of polysulfones S3010,10 parts of Azide polysulfones, 1 part of polyethylene glycol (Mw=2000Da) are joined in 40 parts of dimethyl formamides, 25 DEG C are stirred to transparent clarification, obtain the casting solution of polysulfones industrial goods and Azide polysulfones blend film;
(2) polysulfones/Azide polysulfone blends prepares perforated membrane: the polysulfones industrial goods prepare step (1) and the casting solution of Azide polysulfones blend film are poured onto on coating device substrate, adjust blade height to 150um, blade coating film forming, substrate immerses in methyl alcohol by 25 DEG C; After film is separated with substrate, taken out by film and dry, prepare polysulfones/Azide polysulfone porous membrane, its aperture is 5 ~ 10um, and porosity is 63%;
(3) to the modifying surface of polysulfones/Azide polysulfone porous membrane:
Get the bromo acid propynyl ester initator of 1 part, the methacrylic acid of 150 parts, the methyl alcohol of 100 parts, 1 part CuCl and 1 part 2,2'-bipyridyl, 50 DEG C are carried out ATRP (ATRP) reaction under nitrogen protection, obtain the PMAA-C ≡ CH that the degree of polymerization (DP) is 85;
Polysulfones step (2) prepared/Azide polysulfones blend film is immersed in 400 parts of ethanol; Add 20 parts of environment-responsive polymer P MAA-C ≡ CH again, 1 part of copper sulphate, 1 part of sodium ascorbate, seals reactor; Then bubbling inert gas 30min is passed into, most oxygen in removing reactor; Reactor is placed in water bath with thermostatic control, is 35 DEG C in temperature, and pH is 7.0 times, reaction 24h; After reaction terminates, film is taken out and wash 3 times with water, remove the unreacted environment-responsive polymer on perforated membrane, and dry again after other impurity, obtain the polysulfone porous membrane to temperature, acidity response;
Be 17.54 × 10 to the hot strength of polysulfone porous membrane of temperature, acidity response
-3mPa, under high temperature (60 DEG C) and low temperature (5 DEG C), pH=2.2 time and pH=9.0 time flux as shown in Figure 2.
Embodiment 4
(1) polysulfones industrial goods and Azide polysulfones blended: 7 parts of polysulfones S3010,8 parts of Azide polysulfones, 1 part of polyethylene glycol (Mw=2000Da) are joined in 40 parts of dimethyl sulfoxide (DMSO)s, 25 DEG C are stirred to transparent clarification, obtain the casting solution of polysulfones industrial goods and Azide polysulfones blend film;
(2) polysulfones/Azide polysulfone blends prepares perforated membrane: be poured onto on coating device substrate by the casting solution of the polysulfones industrial goods of above-mentioned preparation and Azide polysulfones blend film, adjust blade height to 150um, blade coating film forming, substrate immerses in isopropyl alcohol by 25 DEG C; After film is separated with substrate, taken out by film and dry, prepare polysulfones/Azide polysulfone porous membrane, its aperture is 5 ~ 10um, and porosity is 63%;
(3) to the modifying surface of polysulfones/Azide polysulfone porous membrane:
Get the bromo acid propynyl ester initator of 1 part, the N-isopropylacrylamide (NIPAAm) of 100 parts, the methacrylic acid (MAA) of 50 parts, the PMDETA of the methyl alcohol of 100 parts, the CuCl and 1 of 1 part part, 40 DEG C are carried out ATRP (ATRP) reaction response under nitrogen protection, and obtaining the degree of polymerization (DP) is the P(NIPAAm-co-MAA of 109)-C ≡ CH;
Polysulfones step (2) prepared/Azide polysulfones blend film is immersed in 400 parts of isopropyl alcohols; Add 30 parts of environment-responsive polymer P (NIPAAm-co-MAA)-C ≡ CH again, 1 part of copper sulphate, 1 part of sodium ascorbate, seals reactor; Then bubbling inert gas 35min is passed into, most oxygen in removing reactor; Reactor is placed in water bath with thermostatic control, is 45 DEG C in temperature, and pH is 9.0 times, reaction 30h; After reaction terminates, film is taken out and wash 3 times with water, remove the unreacted environment-responsive polymer on perforated membrane, and dry again after other impurity, obtain the polysulfone porous membrane to temperature, acidity response;
Be 18.21 × 10 to the hot strength of polysulfone porous membrane of temperature, acidity response
-3mPa, under high temperature (60 DEG C) and low temperature (5 DEG C), pH=2.2 time and pH=9.0 time flux as shown in Figure 2.
Embodiment 5
(1) polysulfones industrial goods and Azide polysulfones blended: 9 parts of polysulfones S3010,6 parts of Azide polysulfones, 1 part of polyethylene glycol (Mw=2000Da) to be joined in 40 parts of oxolanes 25 DEG C and are stirred to the casting solution that transparent clarification obtains polysulfones industrial goods and Azide polysulfones blend film;
(2) polysulfones/Azide polysulfone blends prepares perforated membrane: be poured onto on coating device substrate by the casting solution of the polysulfones industrial goods of above-mentioned preparation and Azide polysulfones blend film, adjust blade height to 150um, blade coating film forming, substrate is immersed in the water by 25 DEG C; After film is separated with substrate, taken out by film and dry, prepare polysulfones/Azide polysulfone porous membrane, its aperture is 5 ~ 10um, and porosity is 63%;
(3) to the modifying surface of polysulfones/Azide polysulfone porous membrane:
Get the bromo acid propynyl ester initator of 1 part, the N-isopropylacrylamide (NIPAAm) of 100 parts, the acrylic acid (AA) of 50 parts, the PMDETA of the methyl alcohol of 100 mass parts, the CuCl and 1 of 1 part part, 40 DEG C are carried out ATRP (ATRP) reaction under nitrogen protection, and obtaining the degree of polymerization (DP) is the P(NIPAAm-co-AA of 108)-C ≡ CH;
Polysulfones step (2) prepared/Azide polysulfones blend film is immersed in 400 parts of water, then adds 35 parts of environment-responsive polymer P (NIPAAm-co-AA)-C ≡ CH, 1 part of copper sulphate, and 1 part of sodium ascorbate, seals reactor; Then bubbling inert gas 40min is passed into, most oxygen in removing reactor; Reactor is placed in water bath with thermostatic control, is 50 DEG C in temperature, and pH is 9 times, reaction 36h; After reaction terminates, film is taken out and wash 3 times with water, remove the unreacted environment-responsive polymer on perforated membrane, and dry again after other impurity, obtain the polysulfone porous membrane to temperature, acidity response;
Be 18.14 × 10 to the hot strength of polysulfone porous membrane of temperature, acidity response
-3mPa, under high temperature (60 DEG C) and low temperature (5 DEG C), pH=2.2 time and pH=9.0 time flux as shown in Figure 2.
Embodiment 6
(1) polysulfones industrial goods and Azide polysulfones blended: 11 parts of polysulfones S3010,4 parts of Azide polysulfones, 1 part of polyethylene glycol (Mw=2000Da) to be joined in 40 parts of carrene 25 DEG C and stir, obtain the casting solution of polysulfones industrial goods and Azide polysulfones blend film to transparent clarification;
(2) polysulfones/Azide polysulfone blends prepares perforated membrane: be poured onto on coating device substrate by the casting solution of the polysulfones industrial goods of above-mentioned preparation and Azide polysulfones blend film, adjust blade height to 150um, blade coating film forming, substrate immerses in ethanol by 25 DEG C; After film is separated with substrate, taken out by film and dry, prepare polysulfones/Azide polysulfone porous membrane, its aperture is 5 ~ 10um, and porosity is 63%;
(3) to the modifying surface of polysulfones/Azide polysulfone porous membrane:
Get the bromo acid propynyl ester initator of 1 part, the acrylic acid (AA) of 150 parts, the methyl alcohol of 100 parts, 1 part CuCl and 1 part 2,2'-bipyridyl, 50 DEG C are carried out ATRP (ATRP) reaction under nitrogen protection, obtain the PAA-C ≡ CH that the degree of polymerization (DP) is 85;
Polysulfones step (2) prepared/Azide polysulfones blend film is immersed in 400 parts of methyl alcohol, then adds 40 parts of environment-responsive polymer P AA-C ≡ CH, 1 part of copper sulphate, and 1 part of sodium ascorbate, seals reactor; Then bubbling inert gas 45min is passed into, most oxygen in removing reactor; Reactor is placed in water bath with thermostatic control, is 50 DEG C in temperature, and pH is 8.0 times, reaction 54h; After reaction terminates, film is taken out and wash 3 times with water, remove the unreacted environment-responsive polymer on perforated membrane, and dry again after other impurity, obtain the polysulfone porous membrane to temperature, acidity response;
Be 18.36 × 10 to the hot strength of polysulfone porous membrane of temperature, acidity response
-3mPa, under high temperature (60 DEG C) and low temperature (5 DEG C), pH=2.2 time and pH=9.0 time flux as shown in Figure 2.
Embodiment 7
(1) polysulfones industrial goods are blended with Azide polysulfones: be stirred to joining in 40 parts of chloroforms 25 DEG C together with 14 parts of polysulfones S3010,1 part of Azide polysulfones, 1 part of polyethylene glycol (Mw=2000Da) casting solution that transparent clarification obtains polysulfones industrial goods and Azide polysulfones blend film;
(2) polysulfones/Azide polysulfone blends prepares perforated membrane: be poured onto on coating device substrate by the casting solution of above-mentioned preparation, adjusts blade height to 150um, blade coating film forming, and substrate immerses in methyl alcohol by 25 DEG C; After film is separated with substrate, taken out by film and dry, prepare polysulfones/Azide polysulfone porous membrane, its aperture is 5 ~ 10um, and porosity is 63%;
(3) to the modifying surface of polysulfones/Azide polysulfone porous membrane:
Get the bromo acid propynyl ester initator of 1 part, the N-isopropylacrylamide (NIPAAm) of 100 parts, the methacrylic acid (MAA) of 50 parts, the PMDETA of the methyl alcohol of 100 parts, the CuCl and 1 of 1 part part, 40 DEG C are carried out ATRP (ATRP) reaction response under nitrogen protection, and obtaining the degree of polymerization (DP) is the P(NIPAAm-co-MAA of 109)-C ≡ CH;
The polysulfones upper step prepared/Azide polysulfones blend film is immersed in 400 parts of ethanol; Add 50 parts of environment-responsive polymer P (NIPAAm-co-MAA)-C ≡ CH again, 1 part of copper sulphate, 1 part of sodium ascorbate, seals reactor; Then bubbling inert gas 50min is passed into, most oxygen in removing reactor; Reactor is placed in water bath with thermostatic control, is 15 DEG C in temperature, and pH is 7.0 times, reaction 72h; After reaction terminates, film is taken out and wash 5 times with water, remove the unreacted environment-responsive polymer on perforated membrane, and dry again after other impurity, obtain the polysulfone porous membrane to temperature, acidity response;
Be 18.54 × 10-3MPa to the hot strength of polysulfone porous membrane of temperature, acidity response, under high temperature (60 DEG C) and low temperature (5 DEG C), pH=2.2 time and pH=9.0 time flux as shown in Figure 2.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1., to a preparation method for the polysulfone porous membrane of temperature, acidity response, it is characterized in that comprising following steps:
(1) polysulfones industrial goods and Azide polysulfones blended: the technical grade polysulfones raw material of 1 ~ 14 mass parts, the Azide polysulfones of 1 ~ 14 mass parts, the pore-foaming agent of 1 mass parts are joined in the organic solvent A of 40 mass parts, stirring at room temperature, to transparent clarification, obtains the casting solution of polysulfones industrial goods and Azide polysulfones blend film;
(2) polysulfones/Azide polysulfone blends prepares perforated membrane: the polysulfones industrial goods prepare step (1) and the casting solution of Azide polysulfones blend film are poured onto on blade applicator substrate, adjust blade height, blade coating film forming, immerses substrate in coagulating bath solvent at 25 ~ 50 DEG C; After film is separated with substrate, film is taken out and dries, prepare polysulfones/Azide polysulfone porous membrane;
(3) to the modifying surface of polysulfones/Azide polysulfone porous membrane: polysulfones/Azide polysulfone porous membrane step (2) prepared is immersed in the solvent B of 400 mass parts; Add the environment-responsive polymer C of 10 ~ 50 mass parts, the copper sulphate of 1 mass parts, the sodium ascorbate of 1 mass parts again, reactor is sealed, then passes into bubbling inert gas 20 ~ 50min; Reactor is placed in water bath with thermostatic control, is 15 ~ 50 DEG C in temperature, and pH is 6.0 ~ 9.0 times, reaction 12 ~ 72h; After reaction terminates, film is taken out and wash 1 ~ 5 time with water, remove the unreacted environment-responsive polymer C on perforated membrane, and dry again after other impurity; Obtain the polysulfone porous membrane to temperature, acidity response;
The environment-responsive polymer of to be end the be alkynyl of the environment-responsive polymer C described in step (3).
2. the preparation method of a kind of polysulfone porous membrane to temperature, acidity response according to claim 1, is characterized in that:
Technical grade polysulfones raw material described in step (1) is polysulfones S3010, its structural formula as shown in Equation 1:
3. the preparation method of a kind of polysulfone porous membrane to temperature, acidity response according to claim 1, is characterized in that:
The structural formula of the Azide polysulfones described in step (1) is as shown in Equation 2:
4. the preparation method of a kind of polysulfone porous membrane to temperature, acidity response according to claim 1, is characterized in that:
The aperture of the polysulfones described in step (2)/Azide polysulfone porous membrane is 5 ~ 10um, and porosity is 63%.
5. the preparation method of a kind of polysulfone porous membrane to temperature, acidity response according to claim 1, is characterized in that:
Pore-foaming agent described in step (1) is polyethylene glycol, and molecular weight is 2000Da;
Organic solvent A described in step (1) is the one in methyl pyrrolidone, dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), oxolane, carrene, chloroform, carbon tetrachloride;
Blade applicator blade height described in step (2) is 150um;
Coagulating bath solvent described in step (2) is one or more mixtures in water, ethanol, methyl alcohol, isopropyl alcohol;
Solvent B described in step (3) is one or more mixtures in water, ethanol, methyl alcohol, isopropyl alcohol.
6. the preparation method of a kind of polysulfone porous membrane to temperature, acidity response according to claim 1, is characterized in that:
Described end any one polymer that to be the environment-responsive polymer of alkynyl be in PAA-C ≡ CH, PMAA-C ≡ CH, (P (NIPAAm-co-AA)-C ≡ CH) or P (NIPAAm-co-MAA)-C ≡ CH.
7. the preparation method of a kind of polysulfone porous membrane to temperature, acidity response according to claim 6, is characterized in that:
The synthetic method of described PAA-C ≡ CH comprises following steps: get 2 of the bromo acid propynyl ester initator of 1 mass parts, the acrylic acid of 150 mass parts, the methyl alcohol of 100 mass parts, the CuCl of 1 mass parts and 1 mass parts, 2'-bipyridyl, 50 DEG C are carried out atom transition free radical polymerization reaction under nitrogen protection, obtain the PAA-C ≡ CH that the degree of polymerization is 85;
The synthetic method of described PMAA-C ≡ CH comprises following steps: get 2 of the bromo acid propynyl ester initator of 1 mass parts, the methacrylic acid of 150 mass parts, the methyl alcohol of 100 mass parts, the CuCl of 1 mass parts and 1 mass parts, 2'-bipyridyl, 50 DEG C are carried out atom transition free radical polymerization reaction under nitrogen protection, obtain the PMAA-C ≡ CH that the degree of polymerization is 85;
The synthetic method of described P (NIPAAm-co-AA)-C ≡ CH comprises following steps: the PMDETA getting the bromo acid propynyl ester initator of 1 mass parts, the N-isopropylacrylamide of 100 mass parts, the acrylic acid of 50 mass parts, the methyl alcohol of 100 mass parts, the CuCl of 1 mass parts and 1 mass parts, 40 DEG C are carried out atom transition free radical polymerization reaction under nitrogen protection, obtain P (the NIPAAm-co-AA)-C ≡ CH that the degree of polymerization is 108;
The synthetic method of described P (NIPAAm-co-MAA)-C ≡ CH comprises following steps: the PMDETA getting the bromo acid propynyl ester initator of 1 mass parts, the N-isopropylacrylamide of 100 mass parts, the methacrylic acid of 50 mass parts, the methyl alcohol of 100 mass parts, the CuCl of 1 mass parts and 1 mass parts; 40 DEG C are carried out atom transition free radical polymerization reaction reaction under nitrogen protection, obtain P (the NIPAAm-co-MAA)-C ≡ CH that the degree of polymerization is 109.
8. to a polysulfone porous membrane for temperature, acidity response, it is characterized in that: adopt method according to any one of claim 1 ~ 7 to prepare.
9. the application of polysulfone porous membrane in film preparation and technical field of modification to temperature, acidity response according to claim 8.
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