CN103406030A - Preparation method of gas-phase crosslinking modified polyetherimide nanofiltration membrane - Google Patents
Preparation method of gas-phase crosslinking modified polyetherimide nanofiltration membrane Download PDFInfo
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- CN103406030A CN103406030A CN2013103702459A CN201310370245A CN103406030A CN 103406030 A CN103406030 A CN 103406030A CN 2013103702459 A CN2013103702459 A CN 2013103702459A CN 201310370245 A CN201310370245 A CN 201310370245A CN 103406030 A CN103406030 A CN 103406030A
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Abstract
The invention relates to a preparation method of a nanofiltration membrane, particularly a preparation method of a gas-phase crosslinking modified polyetherimide nanofiltration membrane. The invention aims to solve the problems of complex technique, high membrane preparation cost, high energy consumption, waste of solvent, environment pollution, poor solvent resistance of the prepared membrane, and incapability of wide application when the existing method is used for enhancing the solvent resistance and stability of the membrane in a non-aqueous solution system. The preparation method comprises the following steps: 1. preparing a polyetherimide film casting solution; 2. preparing a polyetherimide nanofiltration membrane by an immersion-precipitation process; 3. preparing a gas-phase crosslinking device; and 4. crosslinking the membrane in the crosslinking device to obtain the polyetherimide nanofiltration membrane. The method provided by the invention is simple to operate and low in cost, lowers the energy consumption and waste of solvent, and reduces the environmental pollution; and the obtained gas-phase crosslinking modified polyetherimide nanofiltration membrane has high solvent resistance and higher stability, and prevents over-expansion. The invention is used in the field of separation and purification of active components in the mixture in an organic solution.
Description
Technical field
The present invention relates to a kind of preparation method of NF membrane.
Background technology
NF membrane is used widely in each industrial circle and scientific research.NF membrane has many advantages, without phase transformation, little etc. without the impact of additive, temperature, makes it in the non-aqueous solution system in the fields such as petrochemical industry, medicine and food, have great potential using value as separation process.But at present traditional NF membrane mainly is applicable to water solution system, and is difficult to widen in the non-aqueous solution system and uses, and the actual industrial flow process relates to organic solvent system, therefore, further the anti-solvent NF membrane of research and development, just seem particularly important for the application of widening nanofiltration process.
Existing chemically-resistant solvent NF membrane solvent resistance in the gentle organic solvent of minority is good, but for most organic solvents, as chlorinated solvent and aprotic solvent, chemically-resistant solvent NF membrane stability is low, easily cause the film excessive expansion, dissolve, can't be for organic separation, therefore can't extensive use.Currently reported, by the cross-linking modified NF membrane of liquid phase anti-dissolubility and having good stability in organic solvent, but in the liquid phase cross-linking method, crosslinked solvent has toxicity, and to environment, and energy resource consumption is large, and the solvent waste, cause the masking cost high.
Summary of the invention
The objective of the invention is in order to solve aspect the solvent resistance of existing method when improving film and use in the non-aqueous solution system, stability, have that complex process, masking cost are high, energy resource consumption large, solvent waste, contaminated environment and the film poor solvent resistance of preparing, can't extensive use problem, and the preparation method of the cross-linking modified PEI NF membrane of a kind of gas phase provided.
The preparation method of the cross-linking modified PEI NF membrane of a kind of gas phase of the present invention carries out according to the following steps:
Step 2, submergence-precipitation method prepare the PEI NF membrane: the above-mentioned casting solution prepared is poured on glass plate, with blade applicator by the casting solution blade coating on glass plate, at room temperature glass plate is immersed in deionized water afterwards, after casting solution solidifies, on glass plate, obtain a skim, the gained film, more than deionized water submergence 24h, is changed to the water deionized water one time every 12h, take out stand-by.
Step 3, preparation gas phase crosslinking apparatus: as reforming apparatus, in reforming apparatus, add modifier by sealed glass jars; Wherein, the modifier volume added accounts for the 1/10-3/20 of sealed glass jars volume;
Step 4, the PEI NF membrane of above-mentioned preparation is suspended in crosslinking apparatus on the modifier liquid level, carry out crosslinked 1-1.5h, after crosslinked, be immersed in 48h in deionized water, change deionized water one time every 12h, namely obtain the NF membrane of the cross-linking modified polyetheramides of gas phase.
The present invention comprises following beneficial effect:
In the present invention, utilize ethylenediamine gas-phase modification PEI NF membrane, make it generate the cross-linked polymer chain.The NF membrane solvent resistance of the cross-linking modified polyetheramides of gas phase of preparation is strong, and the rejection of RB is reached to 99.8%, and solvent flux reaches 0.5L/ (m
2.h bar), and prevented film excessive expansion, dissolving (as shown in Figure 2), membrane stability is strengthened, and the preparation method is simple to operate, with low cost, the gas-phase modification agent has reduced the waste of energy resource consumption and solvent, reduce environmental pollution, can be widely used in organic separation.Gained ethylenediamine gas-phase modification PEI NF membrane, in the separation of the organic solution mixture that high energy is arranged, increases the yield of active ingredients aspect and has using value.
The accompanying drawing explanation
Fig. 1 is the cross-linking modified PEI NF membrane of ethylenediamine of preparation in embodiment mono-and the infrared spectrogram of the PEI NF membrane that non-modified is processed; Wherein, 1 means the cross-linking modified PEI NF membrane of ethylenediamine, and 2 mean the PEI NF membrane that non-modified is processed;
Fig. 2 be the cross-linking modified PEI NF membrane of ethylenediamine of preparation in embodiment mono-respectively at NMP, THF, DMSO, soak the photo of 72h rear stability in five kinds of organic solvents of acetone and DMAC; Wherein, the order of soaking from left to right organic solvent is NMP, THF, DMSO, acetone and DMAC;
Fig. 3 be PEI NF membrane that in embodiment mono-, non-modified is processed respectively at NMP, THF, DMSO, soak the photo of 72h rear stability in five kinds of organic solvents of acetone and DMAC; Wherein, the order of soaking from left to right organic solvent is NMP, THF, DMSO, acetone and DMAC.
The specific embodiment
The specific embodiment one: the preparation method of the cross-linking modified PEI NF membrane of a kind of gas phase of present embodiment, carry out according to the following steps:
Step 2, submergence-precipitation method prepare the PEI NF membrane: the above-mentioned casting solution prepared is poured on glass plate, with blade applicator by the casting solution blade coating on glass plate, at room temperature glass plate is immersed in deionized water afterwards, after casting solution solidifies, on glass plate, obtain a skim, the gained film, more than deionized water submergence 24h, is changed to water one time every 12h, take out stand-by.
Step 3, preparation gas phase crosslinking apparatus: as reforming apparatus, in reforming apparatus, add modifier by sealed glass jars; Wherein, the modifier volume added accounts for the 1/10-3/20 of sealed glass jars volume.
Step 4, the PEI NF membrane of above-mentioned preparation is suspended in crosslinking apparatus on the modifier liquid level, carry out crosslinked 1-1.5h, after crosslinked, be immersed in 48h in deionized water, change deionized water one time every 12h, namely obtain the NF membrane of the cross-linking modified polyetheramides of gas phase.
The specific embodiment two: what present embodiment was different from the specific embodiment one is: the time of repose described in step 1 is 24h.Other is identical with the specific embodiment one.
The specific embodiment three: what present embodiment was different from the specific embodiment one or two is: in the PEI casting solution described in step 1, the quality percentage composition of PEI is 20%, 23% or 25%.Other is identical with the specific embodiment one or two.
The specific embodiment four: what present embodiment was different from one of specific embodiment one to three is: it is characterized in that the modifier added in step 3 volume is to account for 3/20 of sealed glass jars volume.Other is identical with one of specific embodiment one to three.
The specific embodiment five: what present embodiment was different from one of specific embodiment one to four is: the modifier used in step 3 is ethylenediamine liquid.Other is identical with one of specific embodiment one to four.
The specific embodiment six: what present embodiment was different from one of specific embodiment one to five is: in step 4, control cross-linking modified time 1h.Other is identical with one of specific embodiment party one to five.
The preparation method of the cross-linking modified PEI NF membrane of a kind of gas phase of the present embodiment, carry out according to the following steps:
One, the NMP of the PEI of 25g and 75g is mixed to PEI casting solution processed, the casting solution of preparation is removed to bubble at the standing 24h of room temperature.
Two, submergence-precipitation method prepare the PEI NF membrane: the above-mentioned casting solution prepared is poured on glass plate, with blade applicator by the casting solution blade coating on glass plate, at room temperature this glass plate is immersed in deionized water afterwards, after solidifying, casting solution forms a skim, by standing under gained film room temperature, be immersed in 24h in deionized water, every 12h, change water one time, take out stand-by.
Three, preparation gas phase crosslinking apparatus: use the sealed glass jars of 1000mL as reforming apparatus, add modifier ethylenediamine 150mL.
Four, the above-mentioned PEI NF membrane made is suspended on and in crosslinking apparatus, carries out crosslinkedly, crosslinking time 1h, namely obtain vapor phase crosslinked polyethers acid imide NF membrane.
The preparation method of the cross-linking modified PEI NF membrane of the gas phase of preparation is carried out to test, the gel content determining of infrared spectrum.Test result by 1 figure infrared spectrum is as can be known, and the uncrosslinked typical functional group of PEI PEI is at 1779cm
-1, 1722cm
-1(C=O) carbonylic stretching vibration peak, 1360cm
-1(C-N) imido carbonnitrogen bond vibration peak; And PEI crosslinked after, at 1650cm
-1(C=O), 1540cm
-1(N-H) vibration peak appears, i.e. typical amido link, and original imido characteristic peak remitted its fury.The imide ring fracture is described, the cross-linking modified reaction of ethylenediamine occurs.In addition, the gel content determining result is that gel content reaches more than 92%, illustrates crosslinked abundant.
The cross-linking modified PEI NF membrane of the gas phase of preparation is carried out to stability test in organic solvent.The cross-linking modified PEI nanometer filtering film water of the gas phase of preparation wash clean is dried and is cut into small pieces, be immersed in respectively NMP, THF, DMSO, in five kinds of organic solvents of acetone and DMAC, Immersion time is 72h, the stability of the crosslinked rear polyimide film of test.As seen from Figure 2, crosslinking time 1h, film do not change in each solvent, do not occur to dissolve damaged; As seen from Figure 3, undressed film dissolves.The solvent resistance that the cross-linking modified PEI NF membrane of gas phase prepared is described is strong, and stability is strong.
The cross-linking modified PEI NF membrane of the gas phase of preparation is carried out to the RB amount of damming and flux test.Result shows, the rejection of RB reaches 99.8%, and solvent flux reaches 0.5L/ (m
2.h bar).Illustrate that rejection is high, the polyetherimde films after cross-linking modified is at NMP, THF, DMSO, good stability in acetone and DMAC solvent.
From the above results, the NF membrane solvent resistance of the cross-linking modified polyetheramides of gas phase of preparation is strong, rejection is high, and has prevented the film excessive expansion, dissolves, membrane stability is strengthened, and the preparation method is simple to operate, with low cost, the agent of ethylenediamine gas-phase modification has reduced the waste of energy resource consumption and solvent, reduce environmental pollution, can be widely used in organic separation.The separation of gained mixture in the organic solution of high energy is arranged, increase the yield of active ingredients aspect and have using value.In the separation of the organic solution mixture that high energy is arranged and increase aspect yield of active ingredients and have using value.
Claims (6)
1. the preparation method of the cross-linking modified PEI NF membrane of gas phase is characterized in that it is to carry out according to the following steps:
Step 1, the preparation casting solution, by the preparation casting solution at the standing 24-36h of room temperature; Wherein, casting solution is by PEI and solvent composition, and in casting solution, the quality percentage composition of PEI is 15%～28%, and the quality percentage composition of solvent is 85%-72%, and described solvent is NMP, DMF or THF;
Step 2, submergence-precipitation method prepare the PEI NF membrane: the above-mentioned casting solution prepared is poured on glass plate, with blade applicator by the casting solution blade coating on glass plate, at room temperature glass plate is immersed in deionized water afterwards, after casting solution solidifies, on glass plate, obtain a skim, the gained film more than submergence 24h, is changed to the water deionized water one time every 12h in deionized water, take out stand-by;
Step 3, preparation gas phase crosslinking apparatus: as reforming apparatus, in reforming apparatus, add modifier by sealed glass jars; Wherein, the modifier volume added accounts for the 1/10-3/20 of sealed glass jars volume;
Step 4, the PEI NF membrane of above-mentioned preparation is suspended in crosslinking apparatus on the modifier liquid level, carry out crosslinked 1-1.5h, after crosslinked, be immersed in 48h in deionized water, change deionized water one time every 12h, namely obtain the NF membrane of the cross-linking modified polyetheramides of gas phase.
2. the preparation method of the cross-linking modified PEI NF membrane of a kind of gas phase according to claim 1, is characterized in that the time of repose described in step 1 is 24h.
3. the preparation method of the cross-linking modified PEI NF membrane of a kind of gas phase according to claim 1, the quality percentage composition that it is characterized in that the PEI described in step 1 is 20%, 23% or 25%.
4. the preparation method of the cross-linking modified PEI NF membrane of a kind of gas phase according to claim 1, is characterized in that the modifier volume added described in step 3 is to account for 3/20 of sealed glass jars volume.
5. the preparation method of the cross-linking modified PEI NF membrane of a kind of gas phase according to claim 1, is characterized in that the modifier used in step 3 is ethylenediamine.
6. the preparation method of the cross-linking modified PEI NF membrane of a kind of gas phase according to claim 1, is characterized in that the cross-linking modified time 1h described in step 4.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105617888A (en) * | 2014-11-05 | 2016-06-01 | 天津大学 | High-throughput high-retention rate composite nanofiltration membrane preparation method |
| CN105970487A (en) * | 2016-07-13 | 2016-09-28 | 北京化工大学常州先进材料研究院 | Method for preparing polyimide-silicon dioxide composite nanofiber membrane with crosslinking morphology |
| CN106268374A (en) * | 2015-05-27 | 2017-01-04 | 天津大学 | A kind of solvent-resistant compound nanofiltration membrane and preparation method |
| CN106310964A (en) * | 2016-10-20 | 2017-01-11 | 合肥创想能源环境科技有限公司 | Treatment technology of modified polyetherimide nanofiltration membrane |
| CN106366335A (en) * | 2016-09-28 | 2017-02-01 | 华中科技大学 | Preparation method of cross-linked polyimide (PI) film, product of preparation method and application of product |
| CN107213796A (en) * | 2017-08-07 | 2017-09-29 | 北京林业大学 | A kind of preparation method of the novel polyetherimide NF membrane containing modified graphene oxide |
| CN110139888A (en) * | 2016-03-25 | 2019-08-16 | 沙特基础工业全球技术有限公司 | The composite article obtained by reactive precursor material |
| CN115382408A (en) * | 2022-08-12 | 2022-11-25 | 暨南大学 | Chemical vapor amination modified porous polymer film and preparation method and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105617888A (en) * | 2014-11-05 | 2016-06-01 | 天津大学 | High-throughput high-retention rate composite nanofiltration membrane preparation method |
| CN105617888B (en) * | 2014-11-05 | 2018-11-06 | 天津大学 | A kind of preparation method of high flux and high retention ratio composite nanometer filtering film |
| CN106268374A (en) * | 2015-05-27 | 2017-01-04 | 天津大学 | A kind of solvent-resistant compound nanofiltration membrane and preparation method |
| CN106268374B (en) * | 2015-05-27 | 2018-11-09 | 天津大学 | A kind of solvent-resistant compound nanofiltration membrane and preparation method |
| CN110139888A (en) * | 2016-03-25 | 2019-08-16 | 沙特基础工业全球技术有限公司 | The composite article obtained by reactive precursor material |
| CN105970487A (en) * | 2016-07-13 | 2016-09-28 | 北京化工大学常州先进材料研究院 | Method for preparing polyimide-silicon dioxide composite nanofiber membrane with crosslinking morphology |
| CN105970487B (en) * | 2016-07-13 | 2018-05-22 | 北京化工大学常州先进材料研究院 | A kind of method for preparing the polyimide/silicon dioxide composite nano-fiber membrane with crosslinking pattern |
| CN106366335A (en) * | 2016-09-28 | 2017-02-01 | 华中科技大学 | Preparation method of cross-linked polyimide (PI) film, product of preparation method and application of product |
| CN106366335B (en) * | 2016-09-28 | 2019-01-29 | 华中科技大学 | The preparation method and its product of cross-linked polyimide membranes and application |
| CN106310964A (en) * | 2016-10-20 | 2017-01-11 | 合肥创想能源环境科技有限公司 | Treatment technology of modified polyetherimide nanofiltration membrane |
| CN107213796A (en) * | 2017-08-07 | 2017-09-29 | 北京林业大学 | A kind of preparation method of the novel polyetherimide NF membrane containing modified graphene oxide |
| CN115382408A (en) * | 2022-08-12 | 2022-11-25 | 暨南大学 | Chemical vapor amination modified porous polymer film and preparation method and application thereof |
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Application publication date: 20131127 |