CN104841293A - Oil water separation nanofiber membrane with CO2 stimulus response as well as preparation method and application thereof - Google Patents
Oil water separation nanofiber membrane with CO2 stimulus response as well as preparation method and application thereof Download PDFInfo
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- CN104841293A CN104841293A CN201510242944.4A CN201510242944A CN104841293A CN 104841293 A CN104841293 A CN 104841293A CN 201510242944 A CN201510242944 A CN 201510242944A CN 104841293 A CN104841293 A CN 104841293A
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Abstract
The invention discloses an oil water separation nanofiber membrane with CO2 stimulus response as well as a preparation method and application thereof. The preparation method comprises the following steps: (1) mixing a random copolymer and a solvent to obtain spinning solution, wherein the random copolymer is polymethyl methacrylate-2-Diethylaminoethyl Methacrylate; (2) performing electrostatic spinning on the spinning solution to obtain nanofibers, and interweaving and arranging the nanofibers to obtain the nanofiber membrane. The oil water separation nanofiber membrane is applied to oil water separation. The nanofiber membrane prepared by utilizing an electrostatic spinning technology has a CO2 stimulus response function, can selectively perform oil water separation, is low in cost, simple and convenient to operate, clean and environment-friendly, and has better separation effects for various oil-water mixed systems.
Description
Technical field
The present invention relates to one and there is CO
2water-oil separating nano fibrous membrane of stimuli responsive and preparation method thereof and application, belong to oily water separation technique field.
Background technology
In recent years, along with the continuous increase of oil-polluted water and oil field leakage accident, water-oil separating becomes the challenge of whole world facing.Exploitation has special infiltrating boundary material and will contribute to process and the recovery of oil-polluted water, promotes the sustainable development of industrial society.Along with the development of nanometer technology, surface chemistry and polymer science, there is " intelligence " boundary material of special wetability to be increasingly developed out to oil and glassware for drinking water, and then for two-way water-oil separating, namely optionally oil and water are separated from oil water mixture.
Until now, be employed successfully in based on the stimulus responsive polymers such as temperature, pH and constructed function interface material.Document Wang B.; The function surface that Guo Z.-G.Chem.Commun., 2013,49,9416-9418 utilize pH to respond, by regulating the Acidity of Aikalinity of solution system, achieves the selective water-oil separating of pH regulation and control.Although this material list reveals good oil-water separation, when practical operation, add alkali regulation system pH by acid adding, not only can cause the accumulation of salt, also can dilute solution, affect the cyclic reversibility of system.Therefore, need to utilize gentleer stimulus, the boundary material of development environment friendly is for regulating and controlling selective water-oil separating.CO
2wide material sources, environment-protecting clean is a kind of " green " stimulus, can telomerized polymer physicochemical property, for constructing function surface, has significant application value in the field such as efficient process gentle solution environment greenhouse effects of oil-polluted water.
Summary of the invention
The object of this invention is to provide one and there is CO
2water-oil separating nano fibrous membrane of stimuli responsive and preparation method thereof and application, the nano fibrous membrane that the present invention utilizes electrostatic spinning technique to prepare, has CO
2stimuli responsive function, selectively can carry out water-oil separating; It is with low cost, easy and simple to handle, clean environment firendly, all has higher separating effect to different types of oil mixing with water system.
The preparation method of water-oil separating nano fibrous membrane provided by the invention, comprises the steps: 1) random copolymer is mixed with solvent, obtain spinning solution;
Described random copolymer is polymethyl methacrylate-polymethylacrylic acid lignocaine ethyl ester;
The structure of described polymethyl methacrylate-polymethylacrylic acid lignocaine ethyl ester such as formula shown in I, in formula I, m:n=x:(1-x), m is the integer of 1 ~ 5000000, and x is 0 ~ 1, but x does not comprise 0 and 1;
2) described spinning solution electrostatic spinning is obtained nanofiber, described nanofiber interleaved arrangement, namely obtains described nano fibrous membrane.
In the present invention, x:(1-x in described polymethyl methacrylate-its structural formula I of polymethylacrylic acid lignocaine ethyl ester) represent the ratio of monomer component in polymer, what m and n represented is the degree of polymerization, and the polymethyl methacrylate in its molecule and polymethylacrylic acid lignocaine ethyl ester are irregular arrangement.
Above-mentioned method, described solvent can be at least one in oxolane, dimethyl formamide and carrene, specifically can be the mixed solvent that oxolane and dimethyl formamide form with volume ratio 7 ~ 3:1 with the mixed solvent of volume ratio 7:3 or 1:1 composition or oxolane and dimethyl formamide;
The mass percentage concentration of described spinning solution can be 5wt% ~ 30wt%, specifically can be 10wt%, 15wt%, 20wt%, 25wt% or 10wt% ~ 25wt%;
Step 1) in, the temperature of described mixing can be 20 ~ 50 DEG C, specifically can be 25 DEG C, and the time of described mixing can be 2 ~ 12h, specifically can be 5h;
Described polymethyl methacrylate-polymethylacrylic acid lignocaine ethyl ester is prepared as follows, its step is as follows: be dissolved in organic solvent by methyl methacrylate, diethylaminoethyl methacrylate and initator, oxygen in removing system, in blanket of nitrogen, namely reaction obtains described polymethyl methacrylate-polymethylacrylic acid lignocaine ethyl ester;
The number-average molecular weight of described polymethyl methacrylate-polymethylacrylic acid lignocaine ethyl ester can be 100 ~ 140kDa.
In the present invention, time prepared by described polymethyl methacrylate-polymethylacrylic acid lignocaine ethyl ester, the detailed process of described deoxygenation can be carries out at least 1 time " chilled nitrogen-bleed-inflated with nitrogen " process to system, bleed 15 minutes at every turn, specifically can be and carry out 3 times " chilled nitrogen-bleed-inflated with nitrogen " process, can oxygen in removing system;
After reaction terminates, reaction bulb is placed in liquid nitrogen, Exhaust Gas communicates with air, cessation reaction, the process of post processing, for removing desolventizing, is dissolved with carrene, add the n-hexane precipitation of octuple volume again, collecting precipitation, then carry out the process of dissolving-precipitating, namely obtain described polymethyl methacrylate-polymethylacrylic acid lignocaine ethyl ester.
Above-mentioned method, in the preparation of described polymethyl methacrylate-polymethylacrylic acid lignocaine ethyl ester (being called for short PMMA-co-PDEAEMA), the mol ratio of described methyl methacrylate, described diethylaminoethyl methacrylate and described initator can be 10 ~ 1000:10 ~ 1000:1, specifically can be 200:300:1,20:60:0.07 or 200 ~ 286:300 ~ 857:1;
Described organic solvent can be dioxane, oxolane, dimethylacetylamide or methyl phenyl ethers anisole; The mass percentage concentration of described methyl methacrylate in described organic solvent can be 5wt% ~ 17wt%;
Described initator can be azo-initiator or peroxide type initiators, described azo-initiator can be azodiisobutyronitrile or ABVN, and described peroxide type initiators can be dibenzoyl peroxide, dilauroyl peroxide or peroxidating di tert butyl carbonate;
The temperature of reaction can be 50 ~ 100 DEG C, and specifically can be 70 DEG C, the time can be 6 ~ 48h, specifically can be 24h, and oil bath pan can be adopted during reaction to heat.
Above-mentioned method, step 2) in, described electrostatic spinning adopts the syringe spinning with spinning head;
The diameter of described nanofiber can be 500 ~ 1000nm;
The temperature of described nanofiber interleaved arrangement can be 20 ~ 45 DEG C, and specifically can be 35 DEG C, humidity can be 30% ~ 80%, specifically can be 54%, and the time can be 8 ~ 15h, specifically can be 10h, 12h;
Step 2) also comprise dry step afterwards, the temperature of described drying can be 30 ~ 100 DEG C, and specifically can be 50 DEG C, the time can be 12 ~ 36h, specifically can be 24h, and described drying adopts vacuum drying oven to carry out.
Above-mentioned method, step 2) in, the condition of described electrostatic spinning is: the distance between the cylinder receiver of described spinning head and described syringe can be 10 ~ 30cm, specifically can be 12cm, 15cm, 20cm or 12 ~ 20cm, and the described syringe speed of injecting can be 0.2 ~ 2mL h
-1, specifically can be 0.8mL h
-1, 1mL h
-1or 0.8 ~ 1mL h
-1, voltage can be 7 ~ 20kV, specifically can be 15kV, 18kV, 20kV or 15 ~ 20kV.
Present invention also offers water-oil separating nano fibrous membrane prepared by above-mentioned method.
Above-mentioned nano fibrous membrane, the thickness of described water-oil separating nano fibrous membrane can be 50 ~ 150 μm, specifically can be 100 μm, 110 μm or 100 ~ 110 μm.
Water-oil separating nano fibrous membrane of the present invention is applied in water-oil separating.
When water-oil separating nano fibrous membrane of the present invention is applied in water-oil separating, oil is by described water-oil separating nano fibrous membrane, and water is blocked in outside it;
When described water-oil separating nano fibrous membrane is in water, pass into CO wherein
2after stimulation, then water is by described water-oil separating nano fibrous membrane, and oil is blocked in outside it;
Work as CO
2when post-stimulatory described water-oil separating nano fibrous membrane is in water, pass into N wherein
2by CO
2discharge, then described water-oil separating nano fibrous membrane reverts to oil and is blocked in outside it by, water.
When water-oil separating nano fibrous membrane of the present invention is applied in water-oil separating, every cm per minute
2described water-oil separating nano fibrous membrane pass into described CO
2amount be 1 ~ 100mL;
Every cm per minute
2described water-oil separating nano fibrous membrane pass into described N
2amount be 1 ~ 100mL.
In the present invention, polymethylacrylic acid lignocaine ethyl ester in described polymethyl methacrylate-polymethylacrylic acid lignocaine ethyl ester (being called for short PDEAEMA) can with CO
2effect so protonated, PDEAEMA polymer chain becomes unfolds, and stretches out material surface, shows stronger affinity to water droplet, has hydrophilic oleophobic property; Pass into N
2discharge CO
2, polymer deprotonation, returns to initial collapsed state, has very strong repulsive force, therefore have hydrophobic oleophilic oil to water droplet.The water contact angle of described water-oil separating nano fibrous membrane in air ambient is about 140 °; Described water-oil separating nano fibrous membrane is placed in water environment, passes into CO
2gas, subsequently at CO
2dry up in air-flow, surface water contact angle is reduced to 35 ° gradually, surface from hydrophobic become hydrophilic.Again tunica fibrosa is placed in water environment, passes into the N of 15 minutes
2, subsequently at N
2dry up in air-flow, find that water contact angle returns to original level, become hydrophobic surface again.Described water-oil separating nano fibrous membrane is placed in water, and its surface exhibits goes out stronger lipophile; Same, Xiang Shuizhong leads to the CO of 15 minutes
2gas, finds that oily contact angle increases to 155 °, changes oleophobic into by oleophylic.
The present invention has the following advantages:
1, water-oil separating nano fibrous membrane of the present invention achieves and utilizes CO
2the selective water-oil separating of gas regulating, namely at CO
2when not existing, material surface is as one " passage ", and to oily open to the outside world, to water " closedown ", i.e. lipophilic-hydrophobic property, separates oil from oil water mixture; At CO
2when existing, material surface is protonated, has hydrophilic oleophobic property, as one " passage ", to water open to the outside world, oil is presented to the state of " closedown ", water can be separated from oil water mixture.
2, the present invention can according to actual needs for the water-oil separating of oil-polluted water (as containing n-hexane, normal heptane, benzinum etc.).
3, CO provided by the invention
2the selective water-oil separating nano fibrous membrane of regulation and control is easy and simple to handle, cheap, preparation technology is efficient.
4, nano fibrous membrane of the present invention utilizes CO
2regulate and control selective water-oil separating as stimulus, clean environment firendly is pollution-free, and to system without destruction.
5, nano fibrous membrane good stability of the present invention, keeps higher circulation to oil and water, can reuse, and be applicable to multiple oil mixing with water system.
Accompanying drawing explanation
Fig. 1 is nanofiber film preparation schematic diagram of the present invention.Wherein Fig. 1 (a) is PMMA-co-PDEAEMA synthesis step, and Fig. 1 (b) is electrostatic spinning schematic diagram.
Fig. 2 is the polymer P MMA-co-PDEAEMA hydrogen nuclear magnetic resonance spectrogram of preparation in the embodiment of the present invention 1.
Fig. 3 is the surface topography stereoscan photograph of the water-oil separating nano fibrous membrane of preparation in the embodiment of the present invention 1.
Fig. 4 is that the nano fibrous membrane of preparation in the embodiment of the present invention 1 is at CO
2the change of (a) and rear (b) surface water contact angle of stimulation before stimulation.
Fig. 5 is that the nano fibrous membrane of preparation in the embodiment of the present invention 1 is at CO
2the change of (a) and rear (b) surface oil contact angle of stimulation before stimulation.
Fig. 6 is CO
2the water-oil separating schematic diagram of regulation and control.
Fig. 7 is the circulation of oil phase (n-hexane) and aqueous phase in the embodiment of the present invention 1.
Fig. 8 is the water content of n-hexane, benzinum and normal heptane in the embodiment of the present invention 1 ~ 4.
Detailed description of the invention
The experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
The preparation of embodiment 1, water-oil separating nano fibrous membrane
(1) random copolymer PMMA-co-PDEAEMA is synthesized
Synthesize according to the synthesis step such as shown in Fig. 1 (a): in 100mL round-bottomed flask, monomers methyl methacrylate (is called for short MMA, 4.0g, 40mmol), DEAEMA (11g, 60mmol) (be called for short AIBN with initator azodiisobutyronitrile, 33mg, 0.2mmol) be dissolved in 50mL dioxane, magnetic agitation half an hour.Subsequently, to reaction solution liquid nitrogen frozen--inflated with nitrogen process of bleeding, bleed 15 minutes at every turn, circulate three times.After removing the oxygen in reaction system completely, under nitrogen protection.Reaction bulb is placed in 75 DEG C of oil bath pans, magneton stirs, and reacts 24 hours.After reaction terminates, reaction bulb is placed in liquid nitrogen rapidly, and Exhaust Gas communicates with air, cessation reaction.The system for the treatment of is cooled to room temperature, revolves and steams removing dioxane, adds a small amount of carrene and dissolves, precipitate in the n-hexane of octuple volume, filter.And then dissolving-precipitation, in 35 DEG C of vacuum drying ovens, drying 24 hours, collects and obtains white solid PMMA-co-PDEAEMA 8.34g, productive rate 55.6%.The number-average molecular weight M of PMMA-co-PDEAEMA
n, GPC=129kDa, the structure of the molecular weight distribution PDI=1.56 of polymer, PMMA-co-PDEAEMA is such as formula shown in I, and wherein m:n=x:1-x is 0.6:0.4), be illustrated in figure 2 the hydrogen spectrogram of PMMA-co-PDEAEMA.
(2) PMMA-co-PDEAEMA spinning solution is prepared
The PMMA-co-PDEAEMA taking certain mass is dissolved in the mixed solvent of THF/DMF (volume ratio is 70/30), compound concentration is the polymer solution of 10wt%, 15wt%, 20wt% and 25wt% respectively, stirring at room temperature 5 hours, obtains uniform solution.
(3) PMMA-co-PDEAEMA nano fibrous membrane is prepared
As shown in Fig. 1 (b), the spinning solution that step (2) obtains is placed in the 2mL syringe containing Metallic Nozzle At The Ingot (specification is 16), the distance between shower nozzle and cylinder receiver is 15cm, and the speed of injecting is set to 1mL h
-1, voltage is set to 18kv.During nanofiber interleaved arrangement, ambient temperature is 35 DEG C, humidity is 54%, time is 12h, obtain nano fibrous membrane in 50 DEG C of vacuum drying ovens dry 24 hours, namely obtain water-oil separating nano fibrous membrane, the thickness of water-oil separating nano fibrous membrane that wherein polymer solution of 25wt% prepares is 100 μm.
The present invention prepares the polymer solution of the preferred 25wt% of water-oil separating nano fibrous membrane, the water-oil separating nano fibrous membrane that following application test adopts the polymer solution electrostatic spinning of 25wt% to prepare.
Water-oil separating nano fibrous membrane of the present invention is used for selective water-oil separating:
As shown in Figure 6, be clipped in the middle of fixture by water-oil separating nano fibrous membrane of the present invention, upper end taps into material glass tube, and lower end picks out material glass tube, and whole device is seated at above 250mL beaker.Nano fibrous membrane is fixed on as diffusion barrier between upper and lower two glass tubes, and 20mL water and 20mL n-hexane (volume ratio is 1:1) are as oil water mixture.CO
2during stimulation, nano fibrous membrane is placed in airtight water environment, passes into 15 minutes CO
2the amount of gas is 750mL, i.e. every cm per minute
2water-oil separating nano fibrous membrane pass into CO
2amount be 50mL; During reversible experiment, pass into 15 minutes N
2amount be 750mL discharge CO
2, i.e. every cm per minute
2water-oil separating nano fibrous membrane pass into N
2amount be 50mL.At the end of each circulation experiment, nano fibrous membrane is cleaned up, dry in drying box.
As shown in Figure 3, the nanofiber diameter in water-oil separating nano fibrous membrane film of the present invention, within the scope of 500 ~ 1000nm, meanwhile, can observe a large amount of micropores between nanofiber, and they play an important role alleviating in liquid mass transfer resistance.And continuous print nanofiber, with unordered shape interleaved arrangement, further increases tunica fibrosa surface roughness.
Nano fibrous membrane hydrophobic oleophilic oil prepared by the present embodiment; As shown in Figures 4 and 5, when carrying out CO
2after stimulation, tunica fibrosa surface becomes again hydrophilic oleophobic.By CO under water
2/ N
2alternately stimulate, tunica fibrosa is changed mutually between oleophylic-oleophobic-oleophylic, and has good cyclic reversibility.Electrospun nano-fibers film prepared by the present embodiment is through 5 CO
2/ N
2after alternately stimulating, stress and strain during fracture is respectively 1.22Mpa and 42%, does not find the reduction of obvious mechanical performance, has stable mechanical property, has good repeatability in actual applications.
Experimental provision is utilized to carry out water-oil separating experiment.In the mixed system by volume ratio being the oil that forms of the water of 1:1 and n-hexane and water, n-hexane can be collected by nano fibrous membrane very soon, and water is trapped within tunica fibrosa upper strata; Pass into the CO of 15 minutes
2be that to pour intermediate course into be in the glass container of nano fibrous membrane for the mixed system of the water of 1:1 and n-hexane composition again by above-mentioned identical volume ratio, can find that aqueous phase immerses tunica fibrosa gradually and is collected, and n-hexane rests in the glass tube of surperficial upper strata, not by nano fibrous membrane.Pass through CO
2the regulation and control of gas, Electrospun nano-fibers film prepared by the present embodiment can well be used for selective water-oil separating, and has higher circulation (as shown in Figure 7).
Oil sample (n-hexane) after being separated is carried out water content test, and water content is no more than 30ppm, shows that nano fibrous membrane has higher separative efficiency (as shown in Figure 8) in selective water-oil separating.
The preparation of embodiment 2, water-oil separating nano fibrous membrane
(1) random copolymer PMMA-co-PDEAEMA is synthesized
Synthesize according to the synthesis step such as shown in Fig. 1 (a): in 100mL round-bottomed flask, by monomer M MA (2.0g, 20mmol) with DEAEMA (11g, 60mmol), initiator A IBN (11mg, 0.07mmol) be dissolved in 40mL dioxane, magnetic agitation half an hour.Subsequently, to reaction solution liquid nitrogen frozen--inflated with nitrogen process of bleeding, bleed 15 minutes at every turn, circulate three times.After removing the oxygen in reaction system completely, under nitrogen protection.Reaction bulb is placed in 75 DEG C of oil bath pans, magneton stirs, and reacts 20 hours.After reaction terminates, reaction bulb is placed in liquid nitrogen rapidly, and Exhaust Gas communicates with air, cessation reaction.The system for the treatment of is cooled to room temperature, revolves and steams removing dioxane, adds a small amount of carrene and dissolves, precipitate in the n-hexane of octuple volume, filter.And then dissolving-precipitation, in 35 DEG C of vacuum drying ovens, drying 24 hours, collects and obtains white solid PMMA-co-PDEAEMA6.27g, productive rate 66.1%.M
n, GPC=112kDa, PDI=1.48, in formula I, m:n=x:1-x is 05:05.
(2) PMMA-co-PDEAEMA spinning solution is prepared
The PMMA-co-PDEAEMA taking certain mass is dissolved in the mixed solvent of THF/DMF (50/50 volume ratio), and compound concentration is the polymer solution of 25wt%, and stirring at room temperature 5 hours, obtains uniform solution.
(3) PMMA-co-PDEAEMA nano fibrous membrane is prepared
The spinning solution that step (2) obtains is placed in the 2mL syringe containing Metallic Nozzle At The Ingot (specification is 16), the distance between shower nozzle and cylinder receiver is 12cm, and the speed of injecting is set to 0.8mL h
-1, voltage is set to 15kV.During nanofiber interleaved arrangement, ambient temperature is 35 DEG C, and humidity is 54%, and the time is 10h, and obtain nano fibrous membrane in 50 DEG C of vacuum drying ovens dry 24 hours, namely obtain water-oil separating nano fibrous membrane, its thickness is 100 μm.
Water-oil separating nano fibrous membrane of the present invention is used for selective water-oil separating:
As shown in Figure 6, be clipped in the middle of fixture by water-oil separating nano fibrous membrane of the present invention, upper end taps into material glass tube, and lower end picks out material glass tube, and whole device is seated at above 250mL beaker.Nano fibrous membrane is fixed on as diffusion barrier between upper and lower two glass tubes, and 20mL water and 40mL n-hexane (volume ratio is 1:2) are as oil water mixture.CO
2during stimulation, nano fibrous membrane is placed in airtight water environment, passes into 15 minutes CO
2gas 750mL, i.e. every cm per minute
2water-oil separating nano fibrous membrane pass into CO
2amount be 50mL; During reversible experiment, pass into 15 minutes N
2750mL discharges CO
2, i.e. every cm per minute
2water-oil separating nano fibrous membrane pass into N
2amount be 50mL.At the end of each circulation experiment, nano fibrous membrane is cleaned up, dry in drying box.
Nanofiber diameter in water-oil separating nano fibrous membrane film of the present invention, within the scope of 600 ~ 800nm, meanwhile, can observe a large amount of micropores between nanofiber, and they play an important role alleviating in liquid mass transfer resistance.And continuous print nanofiber, with unordered shape interleaved arrangement, further increases tunica fibrosa surface roughness.
Nano fibrous membrane hydrophobic oleophilic oil prepared by the present embodiment; When carrying out CO
2after stimulation, tunica fibrosa surface becomes again hydrophilic oleophobic.By CO under water
2/ N
2alternately stimulate, tunica fibrosa is changed mutually between oleophylic-oleophobic-oleophylic, and has good cyclic reversibility.Electrospun nano-fibers film prepared by the present embodiment is through 8 CO
2/ N
2after alternately stimulating, stress and strain during fracture is respectively 1.22Mpa and 42%, does not find the reduction of obvious mechanical performance, has stable mechanical property, has good repeatability in actual applications.
Experimental provision is utilized to carry out water-oil separating experiment.In the mixed system by volume ratio being the oil that forms of the water of 1:1 and n-hexane and water, n-hexane can be collected by nano fibrous membrane very soon, and water is trapped within tunica fibrosa upper strata; Pass into the CO of 15 minutes
2be that to pour intermediate course into be in the glass container of nano fibrous membrane for the oil of the water of 1:1 and n-hexane composition and the mixed system of water again by above-mentioned identical volume ratio, can find that aqueous phase immerses tunica fibrosa gradually and is collected, and n-hexane rests in the glass tube of surperficial upper strata, not by nano fibrous membrane.Pass through CO
2the regulation and control of gas, Electrospun nano-fibers film prepared by the present embodiment can well be used for selective water-oil separating, and has higher circulation.
Oil sample (n-hexane) after being separated is carried out water content test, and water content is no more than 30ppm, shows that nano fibrous membrane has higher separative efficiency in selective water-oil separating.
The preparation of embodiment 3, water-oil separating nano fibrous membrane
(1) random copolymer PMMA-co-PDEAEMA is synthesized
Preparation method is with embodiment 1.
(2) PMMA-co-PDEAEMA spinning solution is prepared
Preparation method is with embodiment 2.
(3) PMMA-co-PDEAEMA nano fibrous membrane is prepared
As shown in Fig. 1 (b), the spinning solution that step (2) obtains is placed in the 2mL syringe containing Metallic Nozzle At The Ingot (specification is 16), the distance between shower nozzle and cylinder receiver is 20cm, and the speed of injecting is set to 1mL h
-1, voltage is set to 20kV.During nanofiber interleaved arrangement, ambient temperature is 35 DEG C, and humidity is 54%, and the time is 12h, and obtain nano fibrous membrane in 50 DEG C of vacuum drying ovens dry 24 hours, namely obtain water-oil separating nano fibrous membrane, its thickness is 110 μm.
Water-oil separating nano fibrous membrane of the present invention is used for selective water-oil separating:
As shown in Figure 6, be clipped in the middle of fixture by water-oil separating nano fibrous membrane of the present invention, upper end taps into material glass tube, and lower end picks out material glass tube, and whole device is seated at above 250mL beaker.Nano fibrous membrane is fixed on as diffusion barrier between upper and lower two glass tubes, and 20mL water and 20mL benzinum (volume ratio is 1:1) are as oil water mixture.CO
2during stimulation, nano fibrous membrane is placed in airtight water environment, passes into 15 minutes CO
2gas; During reversible experiment, pass into 15 minutes N
2discharge CO
2.At the end of each circulation experiment, nano fibrous membrane is cleaned up, dry in drying box.
Electrospun nano-fibers film diameter prepared by the present embodiment is within the scope of 600 ~ 800nm, and continuous print nanofiber, with unordered shape interleaved arrangement, further increases tunica fibrosa surface roughness.
Electrospun nano-fibers film hydrophobic oleophilic oil prepared by the present embodiment; When carrying out CO
2after stimulation, tunica fibrosa surface becomes again hydrophilic oleophobic.By CO under water
2/ N
2alternately stimulate, tunica fibrosa is changed mutually between oleophylic-oleophobic-oleophylic, and has good cyclic reversibility.Electrospun nano-fibers film prepared by the present embodiment is through 5 CO
2/ N
2after alternately stimulating, stress and strain during fracture is respectively 1.22Mpa and 42%, does not find the reduction of obvious mechanical performance, has stable mechanical property, has good repeatability in actual applications.
Experimental provision is utilized to carry out water-oil separating experiment.In the mixed system by volume ratio being the oil that forms of the water of 1:1 and benzinum and water, benzinum can be collected by nano fibrous membrane of the present invention very soon, and water is trapped within tunica fibrosa upper strata; Pass into the CO of 15 minutes
2be that to pour intermediate course into be in the glass container of nano fibrous membrane for the oil of the water of 1:1 and benzinum composition and the mixed system of water again by above-mentioned identical volume ratio, can find that aqueous phase immerses tunica fibrosa gradually and is collected, and benzinum rests in the glass tube of surperficial upper strata, not by nano fibrous membrane.Pass through CO
2the regulation and control of gas, nano fibrous membrane prepared by the present invention can well be used for selective water-oil separating.
Oil sample (benzinum) after being separated is carried out water content test, and water content is no more than 50ppm, shows that nano fibrous membrane has higher separative efficiency (as shown in Figure 8) in selective water-oil separating.
The preparation of embodiment 4, water-oil separating nano fibrous membrane
(1) random copolymer PMMA-co-PDEAEMA is synthesized
Preparation method is with embodiment 1.
(2) PMMA-co-PDEAEMA spinning solution is prepared
Preparation method is with embodiment 1.
(3) PMMA-co-PDEAEMA nano fibrous membrane is prepared
Preparation method is with embodiment 1.
Water-oil separating nano fibrous membrane of the present invention is used for selective water-oil separating:
As shown in Figure 6, be clipped in the middle of fixture by water-oil separating nano fibrous membrane of the present invention, upper end taps into material glass tube, and lower end picks out material glass tube, and whole device is seated at above 250mL beaker.Nano fibrous membrane is fixed on as diffusion barrier between upper and lower two glass tubes, and 20mL water and 20mL normal heptane (volume ratio is 1:1) are as oil water mixture.CO
2during stimulation, nano fibrous membrane is placed in airtight water environment, passes into 15 minutes CO
2gas; During reversible experiment, pass into 15 minutes N
2discharge CO
2.At the end of each circulation experiment, nano fibrous membrane is cleaned up, dry in drying box.
Electrospun nano-fibers film diameter prepared by the present embodiment, within the scope of 600-800nm, meanwhile, can observe a large amount of micropores between nanofiber, and they play an important role alleviating in liquid mass transfer resistance.And continuous print nanofiber, with unordered shape interleaved arrangement, further increases tunica fibrosa surface roughness.
Electrospun nano-fibers film hydrophobic oleophilic oil prepared by the present embodiment; When carrying out CO
2after stimulation, tunica fibrosa surface becomes again hydrophilic oleophobic.By CO under water
2/ N
2alternately stimulate, tunica fibrosa is changed mutually between oleophylic-oleophobic-oleophylic, and has good cyclic reversibility.Electrospun nano-fibers film prepared by the present embodiment is through 8 CO
2/ N
2after alternately stimulating, stress and strain during fracture is respectively 1.22Mpa and 42%, does not find the reduction of obvious mechanical performance, has stable mechanical property, has good repeatability in actual applications.
Experimental provision is utilized to carry out water-oil separating experiment.In the mixed system by volume ratio being the oil that forms of the water of 1:1 and normal heptane and water oil and neutral water, normal heptane can be collected by nano fibrous membrane very soon, and water is trapped within tunica fibrosa upper strata; Pass into the CO of 15 minutes
2be that to pour intermediate course into be in the glass container of nano fibrous membrane for the oil of the water of 1:1 and normal heptane composition and the mixed system of water again by above-mentioned identical volume ratio, can find that aqueous phase immerses tunica fibrosa gradually and is collected, and normal heptane rests in the glass tube of surperficial upper strata, not by nano fibrous membrane.Pass through CO
2the regulation and control of gas, Electrospun nano-fibers film prepared by the present embodiment can well be used for selective water-oil separating.
Oil sample (normal heptane) after being separated is carried out water content test, and water content is no more than 60ppm, shows that nano fibrous membrane has higher separative efficiency (as shown in Figure 8) in selective water-oil separating.
Claims (10)
1. a preparation method for water-oil separating nano fibrous membrane, comprises the steps: 1) random copolymer is mixed with solvent, obtain spinning solution;
Described random copolymer is polymethyl methacrylate-polymethylacrylic acid lignocaine ethyl ester;
The structure of described polymethyl methacrylate-polymethylacrylic acid lignocaine ethyl ester such as formula shown in I, in formula I, m:n=x:(1-x), m is the integer of 1 ~ 5000000, and x is 0 ~ 1, but x does not comprise 0 and 1;
2) described spinning solution electrostatic spinning is obtained nanofiber, described nanofiber interleaved arrangement, namely obtains described nano fibrous membrane.
2. method according to claim 1, is characterized in that: described solvent is at least one in oxolane, dimethyl formamide and carrene;
The mass percentage concentration of described spinning solution is 5wt% ~ 30wt%;
Step 1) in, the temperature of described mixing is 20 ~ 50 DEG C, and the time of described mixing is 2 ~ 12h;
Described polymethyl methacrylate-polymethylacrylic acid lignocaine ethyl ester is prepared as follows, its step is as follows: be dissolved in organic solvent by methyl methacrylate, diethylaminoethyl methacrylate and initator, oxygen in removing system, in blanket of nitrogen, namely reaction obtains described polymethyl methacrylate-polymethylacrylic acid lignocaine ethyl ester;
The number-average molecular weight of described polymethyl methacrylate-polymethylacrylic acid lignocaine ethyl ester can be 100 ~ 140kDa.
3. method according to claim 2, it is characterized in that: in the preparation of described polymethyl methacrylate-polymethylacrylic acid lignocaine ethyl ester, the mol ratio of described methyl methacrylate, described diethylaminoethyl methacrylate and described initator is 10 ~ 1000:10 ~ 1000:1;
Described organic solvent is dioxane, oxolane, dimethylacetylamide or methyl phenyl ethers anisole; The mass percentage concentration of described methyl methacrylate in described organic solvent is 5wt% ~ 17wt%;
Described initator is azo-initiator or peroxide type initiators, and described azo-initiator is azodiisobutyronitrile or ABVN, and described peroxide type initiators is dibenzoyl peroxide, dilauroyl peroxide or peroxidating di tert butyl carbonate;
The temperature of reaction is 50 ~ 100 DEG C, and the time is 6 ~ 48h.
4. the method according to any one of claim 1-3, is characterized in that: step 2) in, described electrostatic spinning adopts the syringe spinning with spinning head;
The diameter of described nanofiber is 500 ~ 1000nm;
The temperature of described nanofiber interleaved arrangement is 20 ~ 45 DEG C, and humidity is 30% ~ 80%, and the time is 8 ~ 15h;
Step 2) also comprise dry step afterwards, the temperature of described drying is 30 ~ 100 DEG C, and the time is 12 ~ 36h, and described drying adopts baking oven to carry out.
5. method according to claim 4, is characterized in that: step 2) in, the condition of described electrostatic spinning is: the distance between the cylinder receiver of described spinning head and described syringe is 10 ~ 30cm, and the described syringe speed of injecting is 0.2 ~ 2mL h
-1, voltage is 7 ~ 20kv.
6. water-oil separating nano fibrous membrane prepared by the method according to any one of claim 1-5.
7. nano fibrous membrane according to claim 6, is characterized in that: the thickness of described water-oil separating nano fibrous membrane is 50 ~ 150 μm.
8. the application of water-oil separating nano fibrous membrane in water-oil separating described in claim 6 or 7.
9. application according to claim 8, is characterized in that: when water-oil separating, and oil is by described water-oil separating nano fibrous membrane, and water is blocked in outside it;
When described water-oil separating nano fibrous membrane is in water, pass into CO wherein
2after stimulation, then water is by described water-oil separating nano fibrous membrane, and oil is blocked in outside it;
Work as CO
2when post-stimulatory described water-oil separating nano fibrous membrane is in water, pass into N wherein
2by CO
2discharge, then described water-oil separating nano fibrous membrane reverts to oil and is blocked in outside it by, water.
10. application according to claim 9, is characterized in that: every cm per minute
2described water-oil separating nano fibrous membrane pass into described CO
2amount be 1 ~ 100mL;
Every cm per minute
2described water-oil separating nano fibrous membrane pass into described N
2amount be 1 ~ 100mL.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105194907A (en) * | 2015-10-26 | 2015-12-30 | 东北林业大学 | Preparation method of pH-responsive oil-water separation copper wire mesh |
| CN106110899A (en) * | 2016-07-08 | 2016-11-16 | 浙江工业大学 | Method for preparing carbon dioxide responsive membrane |
| CN106178988A (en) * | 2016-08-01 | 2016-12-07 | 台州学院 | A kind of polyvinylidene fluoride blending film of photosynthesis-carbon dioxide response and preparation method thereof |
| CN107326652A (en) * | 2016-04-28 | 2017-11-07 | 南京林业大学 | A kind of preparation method of the nanofiber water-oil separationg film of pH responses |
| CN108355379A (en) * | 2018-03-23 | 2018-08-03 | 哈尔滨工业大学 | A kind of CO2The preparation method of the intelligent hydrophobe conversion copper mesh of response |
| CN108442100A (en) * | 2018-02-09 | 2018-08-24 | 江苏奥净嘉环保科技有限公司 | A kind of load nano-TiO2And the preparation method of the net cloth or fabric with photo-catalysis capability |
| CN111285433A (en) * | 2020-03-06 | 2020-06-16 | 中国科学院生态环境研究中心 | CO (carbon monoxide)2Method for treating emulsified oil wastewater by atmosphere response material |
| CN114259889A (en) * | 2021-12-16 | 2022-04-01 | 江南大学 | Emulsion separation membrane and preparation method and use method thereof |
| CN116407962A (en) * | 2023-05-22 | 2023-07-11 | 江南大学 | CO (carbon monoxide) 2 Photo-thermal dual-response type nanoemulsion separation membrane and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004188378A (en) * | 2002-12-13 | 2004-07-08 | Sanei Kogyo Kk | Filter for cleaning drain water, production method therefor, and setting and taking out methods |
| CN102794113A (en) * | 2012-08-24 | 2012-11-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Super hydrophobic-supper lipophilic polymer porous film, preparation method and application thereof |
| CN103263856A (en) * | 2013-05-28 | 2013-08-28 | 东华大学 | Preparation method of electrostatic spinning hydrophobic nanofiber porous membrane for membrane distillation |
-
2015
- 2015-05-13 CN CN201510242944.4A patent/CN104841293B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004188378A (en) * | 2002-12-13 | 2004-07-08 | Sanei Kogyo Kk | Filter for cleaning drain water, production method therefor, and setting and taking out methods |
| CN102794113A (en) * | 2012-08-24 | 2012-11-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Super hydrophobic-supper lipophilic polymer porous film, preparation method and application thereof |
| CN103263856A (en) * | 2013-05-28 | 2013-08-28 | 东华大学 | Preparation method of electrostatic spinning hydrophobic nanofiber porous membrane for membrane distillation |
Non-Patent Citations (1)
| Title |
|---|
| 车海龙等: "二氧化碳气体调控聚合物材料表面润湿性", 《2014年全国高分子材料科学与工程研讨会学术论文集（下册）》 * |
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| CN108355379A (en) * | 2018-03-23 | 2018-08-03 | 哈尔滨工业大学 | A kind of CO2The preparation method of the intelligent hydrophobe conversion copper mesh of response |
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