CN107326652A - A kind of preparation method of the nanofiber water-oil separationg film of pH responses - Google Patents
A kind of preparation method of the nanofiber water-oil separationg film of pH responses Download PDFInfo
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- CN107326652A CN107326652A CN201610288502.8A CN201610288502A CN107326652A CN 107326652 A CN107326652 A CN 107326652A CN 201610288502 A CN201610288502 A CN 201610288502A CN 107326652 A CN107326652 A CN 107326652A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002121 nanofiber Substances 0.000 title claims abstract description 16
- 239000003921 oil Substances 0.000 claims abstract description 54
- 229920001721 polyimide Polymers 0.000 claims abstract description 49
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000012528 membrane Substances 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001523 electrospinning Methods 0.000 claims abstract description 13
- 238000002474 experimental method Methods 0.000 claims abstract description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 239000000835 fiber Substances 0.000 claims abstract description 5
- 150000002466 imines Chemical class 0.000 claims abstract description 5
- 239000004952 Polyamide Substances 0.000 claims abstract description 4
- 230000004048 modification Effects 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims abstract description 4
- 229920002647 polyamide Polymers 0.000 claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- 239000004642 Polyimide Substances 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000005259 measurement Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 4
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 4
- 238000010186 staining Methods 0.000 claims description 4
- 238000001764 infiltration Methods 0.000 claims description 3
- 230000008595 infiltration Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 2
- LLDLZZVYXXUTJN-UHFFFAOYSA-N bromobenzene hydrate Chemical compound O.Brc1ccccc1 LLDLZZVYXXUTJN-UHFFFAOYSA-N 0.000 claims description 2
- FIMJSWFMQJGVAM-UHFFFAOYSA-N chloroform;hydrate Chemical compound O.ClC(Cl)Cl FIMJSWFMQJGVAM-UHFFFAOYSA-N 0.000 claims description 2
- YDVNLQGCLLPHAH-UHFFFAOYSA-N dichloromethane;hydrate Chemical compound O.ClCCl YDVNLQGCLLPHAH-UHFFFAOYSA-N 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims description 2
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229920005575 poly(amic acid) Polymers 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 2
- PRDUHXPVDHDGKN-UHFFFAOYSA-N tetrachloromethane;hydrate Chemical compound O.ClC(Cl)(Cl)Cl PRDUHXPVDHDGKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000005686 electrostatic field Effects 0.000 claims 1
- 239000012466 permeate Substances 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 239000010865 sewage Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 230000008859 change Effects 0.000 description 5
- 230000004936 stimulating effect Effects 0.000 description 3
- 230000003075 superhydrophobic effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention is a kind of preparation method of the nanofiber water-oil separationg film of pH responses, including：Synthesizing polyamides acid (PAA)；Electrospinning PAA nano fibrous membranes and imines turn to polyimide film (PI)；Prepare Nano particles of silicon dioxide (SNPs)/DA TiO of pH responses2Colloidal sol；SNPs/DA‑TiO2Modified PI nano fibrous membranes；Contact angle experiments characterize SNPs/DA TiO2The pH responses of/PI nano fibrous membranes；Water-oil separating is tested.Advantage：By to fiber membrane surface modification, obtaining with biodegradability, PI nano fibrous membranes with low cost, nontoxic, with pH responses；This high performance membrane material has broad application prospects in the leakage of water-oil separating, sewage disposal and deep-sea oil.
Description
Technical field
The present invention relates to the preparation method of the nanofiber water-oil separationg film of pH responses, it is particularly
It is a kind of to be used for the system that gravity drives the nanofiber water-oil separationg film that there is pH to respond of water-oil separating
Preparation Method.
Background technology
Recently it has been reported that gone out many has wetability under water with stimulating responsive.Some outside thorns
Swash such as, pH value, temperature, and the change of illumination can change under water by super-oleophilic to superoleophobic
The change of property.Therefore, a kind of material can according to the change of external condition allow oil by or allow
Water passes through, and very big flexibility can be provided in oil water separation process.It is this that there is stimulating responsive
The characteristics of, it is allowed to the oil water separation process of remote operation or automatic emergency.But most of big portion
The aqueous super oleophylic of the stimulating responsive of report or the acquirement on superoleophobic surface is divided on the one hand to pass through
The preparation process of the relatively valuable material such as gold, silver or complexity goes to build the micro nano structure being layered,
On the other hand it is modified by the poisonous fluorine-containing material of low-surface-energy and obtains special surface chemistry energy.So
And these preparation process have preparation process complexity, pollution, intensity difference, cost height are produced to environment
Shortcoming.Seriously limit their applications in practice.
The content of the invention
Proposed by the present invention is a kind of preparation method of the nanofiber water-oil separationg film of pH responses, its mesh
The drawbacks described above for being intended to overcome prior art to have, use PAA for raw material, it is quiet by high pressure
Electrospinning obtains PAA nano fibrous membranes, then PAA progress imidizations are obtained by temperature programming
To with biodegradability, with low cost, significantly separation flux, separative efficiency and mechanical strength
PI nano fibrous membranes；By to tunica fibrosa surface modification, obtaining functional fiber film material；
Moreover, this efficient super-hydrophobic super-oleophylic membrane material is in water-oil separating, sewage disposal and deep-sea stone
Had broad application prospects in oil leakage.
The technical solution of the present invention：A kind of preparation of the nanofiber water-oil separationg film of pH responses
Method, is comprised the technical steps that：
(1) synthesizing polyamides are sour (PAA)；
(2) electrospinning PAA nano fibrous membranes and imines turn to polyimides (PI) film；
(3) Nano particles of silicon dioxide (SNPs)/DA-TiO of pH responses is prepared2Colloidal sol；
(4)SNPs/DA-TiO2Modified PI nano fibrous membranes；
(5) contact angle experiments characterize SNPs/DA-TiO2The pH responses of/PI nano fibrous membranes；
(6) water-oil separating is tested.
The positive effect of the present invention
A. there is high separation flow and separative efficiency, flow reaches 6452.094Lm-2·h-1, point
More than 99% is reached from efficiency, 200 times are improved compared to the water-oil separationg film flow that in the market is bought,
Also there is higher separative efficiency.
A. there is high intensity, tensile strength reaches more than 400MPa, compared to conventional CA Nanowires
The tensile strength 6.65MPa of film is tieed up, more than 60 times is improved；
C. DA-TiO is only passed through2Modified PI nano fibrous membranes and the Maximum Contact angle of water can only achieve
125 °, and the property without super-hydrophobic and super oleophylic；And pass through SNPs/DA-TiO2Modified PI
The Maximum Contact angle of nano fibrous membrane and water is up to 154 °, and oily contact angle can reach 0 °, with super
The property of hydrophobic and super oleophylic, available for oil water separation process.
D. there is resistant to elevated temperatures property, be still able to keep super-hydrophobic property at a high temperature of difference.
E. have can lasting usability, after depositing 60 days, contact angle descends below 5%, by 20 times
Recycle, flow is still able to reach 5532.6L m-2h-1Left and right, separative efficiency reaches 98.5%.
Brief description of the drawings
Fig. 1 is the structural representation of electrospinning PAA nanofiber film devices.
Fig. 2 is the process schematic of the water-oil separating in the presence of ammonia.
Embodiment
The preparation method of the nanofiber water-oil separationg film of pH responses, is comprised the technical steps that：
(1) PAA is synthesized；
Added in the drying four-hole boiling flask that pipe is exported equipped with mechanical agitator, thermometer, nitrogen
2.9422 and 1.0814g of bibenzene tetracarboxylic dianhydride (BPDA) and p-phenylenediamine (PDA) difference (mole
Than 1: 1) be well mixed；Under strong mechanical agitation, 40ml DMAc are added, at -15 DEG C -5 DEG C
After lower reaction 24h hours, then terminate reaction, obtain PAA.
(2) electrospinning PAA nano fibrous membranes and imines turn to polyimides (PI) film：
With 1-5% (wt) PAA DMAc solution, in the high-pressure electrostatic that voltage is 30Kv (+20, -10KV)
Spinning in, the reception distance of syringe needle point to flywheel is 10-15cm, and the rotating speed of flywheel is
1000-2000 turns/min, and the speed of electrospinning is 0.5-1ml/h, is spun to polyamic acid (PAA) nanometer
Tunica fibrosa, as shown in Figure 1.By the good PAA nano fibrous membranes of electrospinning according to temperature programming
150 DEG C/1h, 200 DEG C/1h, 250 DEG C/1h, 300 DEG C/1h, 350 DEG C/30mim method is in tubular type
Imidization is carried out in stove and obtains PI films；The universal testing machine newly thought carefully with Shenzhen afterwards
(CMT-8500 types) is tested the stress-strain of PI films at room temperature, test its stress-should
Become.
(3) Nano particles of silicon dioxide (SNPs)/DA-TiO of pH responses is prepared2Colloidal sol：
0.3g tetraethyl titanates Ti (OBu)4Be dissolved in 2.5ml ethanol, then by this solution be added to containing
In the 10ml ethanol solutions of 0.18g capric acid, it is stirred vigorously.20 μ L0.1ml/L are added into mixed liquor
The HCL aqueous solution and 150 μ L water.10-30min is vigorously mixed at room temperature for, dioxy is obtained
Change titanium colloidal sol, to TiO2The ethanol that the Nano particles of silicon dioxide containing 1wt% is added in colloidal sol is molten
Liquid, stirs 30min, obtains the SNPs/DA-TiO of pH responses2Colloidal sol.
(4)SNPs/DA-TiO2Modified PI nano fibrous membranes：
PI nano fibrous membranes are dipped into SNPs/DA-TiO25min in solution, taking-up is dried at room temperature for
2h, afterwards further in 60 DEG C of dry 10min, then 120 DEG C solidify 3h.Obtain
SNPs/DA-TiO2/ PI films.
(5) contact angle experiments characterize SNPs/DA-TiO2The pH responses of/PI nano fibrous membranes：
PH=6.5 is taken respectively, and pH=12 water, n-hexane and dichloromethane utilize contact angle measurement water
In SNPs/DA-TiO2The contact angle of/PI films surface and under water n-hexane and dichloromethane.
(6) water-oil separating is tested：
1) 10ml dichloromethane and pH=6.5 water are measured respectively,
Water methylene blue staining, oily (dichloromethane) is dyed with oil red, is mixed.
SNPs/DA-TiO2/ PI functional fibre films are fixed between two glass tubes.Then, it will mix molten
Liquid is poured into glass tube above, carries out water-oil separating.The rapidly infiltration of red oil
SNPs/DA-TiO2/ PI tunica fibrosas, are flowed in following beaker, and the water of blueness still remains in upper strata
Glass tube in, and record the profit completely isolated time, and water before measurement separation and after separation
Volume.
2) 10ml hexane and pH=12 water are measured respectively,
Water methylene blue staining, oily (hexane) is dyed with oil red, is mixed.SNPs/DA-TiO2/PI
Functional fibre film is fixed between two glass tubes.Then, mixed solution is poured into glass above
In pipe, water-oil separating is carried out.The infiltration SNPs/DA-TiO of the water of blueness slowly2/ PI tunica fibrosas, stream
Into following beaker, and red oil is still remained in the glass tube on upper strata, and it is complete to record profit
With the volume of water after separation before the time separated, and measurement separation.
3) select respectively different You Heshui (pH=6.5) mixture (dichloromethane-water, bromobenzene-
Water, carbon tetrachloride-water, chloroform-water and 1,2- dichloroethanes-water) 20ml (1/1 (V/V)),
According to 1) progress water-oil separating experiment.
4) different You Heshui (pH=12) mixtures (petroleum ether-water, hexane-water) are selected respectively
20ml (1/1 (V/V)), according to 2) progress water-oil separating experiment.
5) the PAA films of electrospinning different-thickness and imidization obtain PI films respectively, then pass through
SNPs/DA-TiO2Solution modification obtains different-thickness SNPs/DA-TiO2/ PI tunica fibrosas.And by 1,
2) water-oil separating experiment is carried out.
4) SNPs/DA-TiO is selected2/ PI tunica fibrosas, and by 1,2) the multiple water-oil separating of progress
Of the invention to be exactly mainly electrospinning and obtain PI nano fibrous membranes by high temperature imidization, strain reaches
To more than 400MPa.And can high temperature resistant, use for recyclable 20 times, in actual water-oil separating
Application in, the time of water-oil separating can be greatlyd save, it is cost-effective.Overcome existing electricity
Film poor mechanical property in actual water-oil separating application is spun, it is not durable in use, in the mistake of recycling
The shortcoming corroded by high temperature harsh conditions is particularly easy in journey.Add existing water-oil separationg film can
Access times, have saved financial cost.
Claims (7)
- The preparation method of the nanofiber water-oil separationg film of 1.pH responses, it is characterized in that including following technique step Suddenly：(1) synthesizing polyamides are sour (PAA)；(2) electrospinning PAA nano fibrous membranes and imines turn to polyimides (PI) film；(3) Nano particles of silicon dioxide (SNPs)/DA-TiO of pH responses is prepared2Colloidal sol；(4)SNPs/DA-TiO2Modified PI nano fibrous membranes；(5) contact angle experiments characterize SNPs/DA-TiO2The pH responses of/PI nano fibrous membranes；(6) water-oil separating is tested.
- 2. the preparation method of the nanofiber water-oil separationg film of pH responses according to claim 1, its It is characterized in that described step (1) synthesizing polyamides are sour (PAA)；Equipped with mechanical agitator, thermometer, Nitrogen exports in the drying four-hole boiling flask of pipe and adds bibenzene tetracarboxylic dianhydride (BPDA) and p-phenylenediamine (PDA) 2.9422 and 1.0814g of difference (mol ratio 1: 1), is well mixed；Stirred in strong machinery Mix down, add DMAc 40ml, after being reacted 24h hours at -15 DEG C -5 DEG C, then terminate reaction, Obtain polyamic acid.
- 3. the preparation method of the nanofiber water-oil separationg film of pH responses according to claim 1, its It is characterized in that the preparation of described step (2) PAA nano fibrous membranes and imines turn to polyimides (PI) Film：With 1-5% (wt) PAA DMAc solution, in the high pressure that voltage is 30Kv (+20, -10KV) Spinning in electrostatic field, the reception distance of syringe needle point to flywheel is 10-15cm, and the rotating speed of flywheel is 1000-2000 turns/min, and the speed of electrospinning is 0.5-1ml/h, is spun to PAA nano fibrous membranes.Will The good PAA nano fibrous membranes of electrospinning are according to 150 DEG C/1h of temperature programming, 200 DEG C/1h, 250 DEG C/1h, 300 DEG C/1h, 350 DEG C/30min method carries out imidization in tube furnace and obtains PI films；Afterwards with deep The universal testing machine (CMT-8500 types) that ditch between fields is newly thought carefully to the stress-strains of PI films at room temperature Tested.
- 4. the preparation method of the nanofiber water-oil separationg film of pH responses according to claim 1, its It is characterized in Nano particles of silicon dioxide (SNPs)/DA-TiO that described step (3) prepares pH responses2 Colloidal sol：0.3g tetraethyl titanates Ti (OBu)4It is dissolved in 2.5ml ethanol, is then added to this solution In 10ml ethanol solutions containing 0.18g capric acid, it is stirred vigorously.20 μ L0.1ml/L are added into mixed liquor The HCL aqueous solution and 150 μ L water.10-30min is vigorously mixed at room temperature for, titanium dioxide is obtained Colloidal sol, to TiO2The ethanol solution of the Nano particles of silicon dioxide containing 1wt% is added in colloidal sol, is stirred 30min, obtains the SNPs/DA-TiO of pH responses2Colloidal sol.
- 5. the preparation method of the nanofiber water-oil separationg film of pH responses according to claim 1, its It is characterized in described step (4) SNPs/DA-TiO2The preparation method of modified PI nano fibrous membranes is： PI nano fibrous membranes are dipped into SNPs/DA-TiO25min in solution, taking-up is dried at room temperature for 2h, Afterwards further in 60 DEG C of dry 10min, then 120 DEG C solidify 3h.Obtain SNPs/DA-TiO2/PI Film.
- 6. the preparation method of the nanofiber water-oil separationg film of pH responses according to claim 1, its It is characterized in that described step (5) contact angle experiments characterize SNPs/DA-TiO2The pH of/PI nano fibrous membranes Response：PH=6.5 is taken respectively, and pH=12 water, n-hexane and dichloromethane utilize Contact-angle measurement Instrument water is in SNPs/DA-TiO2The contact angle of/PI films surface and under water n-hexane and dichloromethane.
- 7. the preparation method of the nanofiber water-oil separationg film of pH responses according to claim 1, its It is characterized in described step (6) water-oil separating experiment：1) 10ml dichloromethane and pH=6.5 water are measured respectively, Water methylene blue staining, oily (dichloromethane) is dyed with oil red, is mixed.SNPs/DA-TiO2/PI Functional fibre film is fixed between two glass tubes.Then, mixed solution is poured into glass tube above It is interior, carry out water-oil separating.Red oil rapidly permeates SNPs/DA-TiO2/ PI tunica fibrosas, are flowed to following Beaker in, and the water of blueness is still remained in the glass tube on upper strata, and it is completely isolated to record profit With the volume of water after separation before time, and measurement separation.2) 10ml hexane and pH=12 water are measured respectively, Water methylene blue staining, oily (hexane) is dyed with oil red, is mixed.SNPs/DA-TiO2/ PI work( Energy tunica fibrosa is fixed between two glass tubes.Then, mixed solution is poured into glass tube above, Carry out water-oil separating.The infiltration SNPs/DA-TiO of the water of blueness slowly2/ PI tunica fibrosas, are flowed to following In beaker, and red oil is still remained in the glass tube on upper strata, and record profit it is completely isolated when Between, and the volume before measurement separation with water after separation.3) select respectively different You Heshui (pH=6.5) mixture (dichloromethane-water, bromobenzene-water, Carbon tetrachloride-water, chloroform-water and 1,2- dichloroethanes-water) 20ml (1/1 (V/V)), according to 1) Carry out water-oil separating experiment.4) different You Heshui (pH=12) mixtures (petroleum ether-water, hexane-water) are selected respectively 20ml (1/1 (V/V)), according to 2) progress water-oil separating experiment.5) the PAA films of electrospinning different-thickness and imidization obtain PI films respectively, then pass through SNPs/DA-TiO2Solution modification obtains different-thickness SNPs/DA-TiO2/ PI tunica fibrosas.And by 1,2) Carry out water-oil separating experiment.4) SNPs/DA-TiO is selected2/ PI tunica fibrosas, and by 1,2) the multiple water-oil separating of progress.
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| CN111330457A (en) * | 2020-02-21 | 2020-06-26 | 平顶山学院 | Preparation and application of pH-responsive natural plant oil-water separation filter membrane |
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