CN104474924B - A kind of preparation method of polyvinyl alcohol milipore filter - Google Patents
A kind of preparation method of polyvinyl alcohol milipore filter Download PDFInfo
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- CN104474924B CN104474924B CN201410794527.6A CN201410794527A CN104474924B CN 104474924 B CN104474924 B CN 104474924B CN 201410794527 A CN201410794527 A CN 201410794527A CN 104474924 B CN104474924 B CN 104474924B
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Abstract
The invention discloses a kind of preparation method of polymer material film, specifically refer to a kind of water flux high, to the preparation method of the higher milipore filter of small organic molecule rejection. The present invention is by polysulfones counterdie aqueous phase solution is processed to 1-3min, dry in the shade, then the oil-phase solution that is 0.2%-0.8% by mass fraction is coated on the film drying in the shade and processes 1-3min, again the film of gained is placed to 5-30min in 50-100 DEG C of baking oven, can obtain polyvinyl alcohol milipore filter; Advantage of the present invention is that preparation method is simply novel, and milipore filter has higher small organic molecule rejection and higher water flux.
Description
Technical field
The present invention relates to a kind of preparation method of polymer material film, specifically refer to a kind of water flux high, to littleThe preparation method of the milipore filter that molecule rejection to organics rate is higher.
Background technology
Pure PVA basement membrane easy swelling, wet film intensity difference, not withstand voltage in water, has limited to a great extentIts industrial applications. so obtain the PVA milipore filter that intensity is good, water-swellable is low must carry out itModification. Common method of modifying be introduce the second component, can with PVA molecule inHydroxyl form covalent bond or hydrogen bond, make it change into water-fast group, and then improve the water resistance of film,Obtain high-intensity PVA milipore filter.
China is the big producing country of polyvinyl alcohol plastics, and polyvinyl alcohol is one, to prepare preparation of anti-fouling ultrafiltration membrane potentialGood base material, the research of PVA milipore filter in recent years receives much concern. Ma Cailian etc. are to PVA ultrafiltrationThe progress of film has been carried out preliminary introduction, and (Yu Yuan, waits grinding of .PVA basement membrane for Ma Cailian, Song RenyuanStudy carefully and apply present situation [J]. application chemical industry, 2009,38 (3): 435-438.)On PVA strand, contain great amount of hydroxy group, there is very strong reactivity, prepare the ultra-thin top layer of composite membraneExcellent material, the existence on the ultra-thin top layer of PVA, can improve the hydrophilicity of film to a great extent, carriesHigh its anti-pollution ability.
Polyvinyl alcohol can be cross-linked with aldehyde, acid, isocyanates, acyl chlorides etc. Shang etc. are different with toluene twoCyanate (TDI), as crosslinking agent, reacts and prepares milipore filter with PVA, carries out the separation (Shang of water-oil emulsionY，PengYL.UFmembraneofPVAmodifiedwithTDI[J].Desalination，2008，221：324-330.)。
In general, milipore filter is that the rejection of the bovine serum albumin of 6-7 ten thousand can reach more than 99% to molecular weight. ButAll lower to the rejection of the organic molecule below 10000. This patent is for this deficiency of milipore filter, superThe crosslinked cortex of compound one deck pyromellitic trimethylsilyl chloride and polyvinyl alcohol on filter membrane, has strengthened milipore filter to organic little pointHolding back of son. Meanwhile, in polyvinyl alcohol, introduce ammonium alcohol polyvinyl phosphate, because ammonium alcohol polyvinyl phosphate is oneKind of white macromolecular compound is soluble in water, and it has phosphate groups, is a kind of strong electrolyte, soIn increasing rejection, also increase the water flux of milipore filter. Can make by simple mechanical blendingPolyvinyl alcohol occurs under the effect of catalyst with pyromellitic trimethylsilyl chloride after mixing with ammonium alcohol polyvinyl phosphate instead againShould. Acid chloride groups makes polyvinyl alcohol and pyromellitic trimethylsilyl chloride occur to be cross-linked with reacting of hydroxyl, has greatly increasedThe mechanical strength on film surface. Ammonium alcohol polyvinyl phosphate can be entrained in the cross-linked network of polyvinyl alcohol, also mayThere are small part and pyromellitic trimethylsilyl chloride to occur crosslinked. On ammonium alcohol polyvinyl phosphate, contain easily ionizable group, increasingWhen large water flux, also increase the selection permeability to ion.
Summary of the invention
For deficiency of the prior art, the present invention proposes a kind of preparation side of novel polyethylene alcohol milipore filterMethod. Polysulfones counterdie is used to the polyvinyl alcohol of the 1%-5% that has added suitable catalyst, ammonium alcohol polyvinyl phosphate concentrationFor the mixed solution of 0.1%-1% is processed 1-3min, then use the pyromellitic trimethylsilyl chloride oil solution processing of 0.2%-0.8%1-3min places 5-30min by prepared composite membrane in 50-100 DEG C of baking oven, and rinsing obtains milipore filter.
Concrete scheme of the present invention is as follows:
A preparation method for polyvinyl alcohol milipore filter, is characterized in that comprising the following steps:
Polysulfones counterdie being processed to 1-3min with aqueous phase solution, dry in the shade, is then 0.2%-0.8% by mass fractionOil-phase solution be coated on the film drying in the shade and process 1-3min, then by the film of gained at 50-100 DEG C of baking ovenMiddle placement 5-30min, can obtain polyvinyl alcohol milipore filter;
Wherein aqueous phase solution refers to that the mass content of polyvinyl alcohol is that the quality of 1%-5%, ammonium alcohol polyvinyl phosphate containsAmount is the mixed aqueous solution of 0.1%-1%; Oil-phase solution refers to that mass content is equal benzene three formyls of 0.2%-0.8%Fluorocarbon oil solution; The molecular cut off of polysulfones counterdie is 5-6 ten thousand.
As preferably, in the preparation method of above-mentioned a kind of polyvinyl alcohol milipore filter, hydrolyzed pva degree is 85-89%,Molecular weight is 100000-150000.
As preferably, the aqueous phase solution described in the preparation method of above-mentioned a kind of polyvinyl alcohol milipore filter is through vacuumDeaeration process after again with dealing with polysulfones counterdie.
As preferably, the ammonium alcohol polyvinyl phosphate described in the preparation method of above-mentioned a kind of polyvinyl alcohol milipore filter isPurity is 99.9% the pure raw material of analysis.
As preferably, described in the preparation method of above-mentioned a kind of polyvinyl alcohol milipore filter, in aqueous phase solution, add friendshipConnection agent, crosslinking agent is wherein dilute sulfuric acid or watery hydrochloric acid. Best results when crosslinking agent is wherein watery hydrochloric acid.In this process, perhaps chlorion has played certain effect.
Beneficial effect: the preparation method in the present invention is simply novel, and milipore filter has higher small organic molecule to cutStay rate and higher water flux.
Detailed description of the invention
Below in conjunction with example, the present invention will be further described, but protection scope of the present invention is not limited to this.
Embodiment 1
The polyvinyl alcohol of preparation 3%, the mixed solution that ammonium alcohol polyvinyl phosphate concentration is 0.2%, and add appropriateWatery hydrochloric acid, deaeration is for subsequent use. Preparation quality mark is 0.2% pyromellitic trimethylsilyl chloride oil solution, for subsequent use. To gather3% polyvinyl alcohol for sulfone counterdie, the mixed solution that ammonium alcohol polyvinyl phosphate concentration is 0.2% is processed 2min, the moonDry, the pyromellitic trimethylsilyl chloride solution that is then 0.2% by mass fraction is coated on the film drying in the shade processes 1min,The film of gained is placed to 15min in 80 DEG C of baking ovens again, make polyvinyl alcohol, ammonium alcohol polyvinyl phosphate and equal benzene threeFormyl chloride occurs crosslinked. Novel polyethylene alcohol milipore filter is 79% to the rejection of Macrogol 2000, water fluxFor 293LMH, to polyethylene glycol, 10000 rejection is 85%, and water flux is 222LMH.
Embodiment 2
The polyvinyl alcohol of preparation 3%, the mixed solution that ammonium alcohol polyvinyl phosphate concentration is 0, and add appropriate rare saltAcid, deaeration is for subsequent use. Preparation quality mark is 0.2% pyromellitic trimethylsilyl chloride oil solution, for subsequent use. At the bottom of polysulfones3% polyvinyl alcohol for film, the mixed solution that ammonium alcohol polyvinyl phosphate concentration is 0.4% is processed 2min, dries in the shade,Then the pyromellitic trimethylsilyl chloride solution that is 0.2% by mass fraction is coated on the film drying in the shade processes 1min, by instituteThe film obtaining is placed 15min in 80 DEG C of baking ovens again, makes polyvinyl alcohol, ammonium alcohol polyvinyl phosphate and equal benzene three formylsChlorine occurs crosslinked. Novel polyethylene alcohol milipore filter is 77% to the rejection of Macrogol 2000, and water flux is140LMH, to polyethylene glycol, 10000 rejection is 89%, water flux is 125LMH.
Embodiment 3
The polyvinyl alcohol of preparation 5%, the mixed solution that ammonium alcohol polyvinyl phosphate concentration is 0.2%, and add appropriateWatery hydrochloric acid, deaeration is for subsequent use. Preparation quality mark is 0.2% pyromellitic trimethylsilyl chloride oil solution, for subsequent use. To gather5% polyvinyl alcohol for sulfone counterdie, the mixed solution that ammonium alcohol polyvinyl phosphate concentration is 0.2% is processed 2min, the moonDry, the pyromellitic trimethylsilyl chloride solution that is then 0.2% by mass fraction is coated on the film drying in the shade processes 1min,The film of gained is placed to 15min in 80 DEG C of baking ovens again, make polyvinyl alcohol, ammonium alcohol polyvinyl phosphate and equal benzene threeFormyl chloride occurs crosslinked. Novel polyethylene alcohol milipore filter is 75% to the rejection of Macrogol 2000, water fluxFor 298LMH, to polyethylene glycol, 10000 rejection is 86%, and water flux is 218LMH.
Embodiment 4
The polyvinyl alcohol of preparation 4%, the mixed solution that ammonium alcohol polyvinyl phosphate concentration is 0.2%, and add appropriateWatery hydrochloric acid, deaeration is for subsequent use. Preparation quality mark is 0.2% pyromellitic trimethylsilyl chloride oil solution, for subsequent use. To gather4% polyvinyl alcohol for sulfone counterdie, the mixed solution that ammonium alcohol polyvinyl phosphate concentration is 0.2% is processed 2min, the moonDry, the pyromellitic trimethylsilyl chloride solution that is then 0.2% by mass fraction is coated on the film drying in the shade processes 1min,The film of gained is placed to 15min in 80 DEG C of baking ovens again, make polyvinyl alcohol, ammonium alcohol polyvinyl phosphate and equal benzene threeFormyl chloride occurs crosslinked. Novel polyethylene alcohol milipore filter is 83% to the rejection of Macrogol 2000, water fluxFor 290LMH, to polyethylene glycol, 10000 rejection is 92%, and water flux is 215LMH.
Embodiment 5
The polyvinyl alcohol of preparation 5%, the mixed solution that ammonium alcohol polyvinyl phosphate concentration is 0.2%, and add appropriateWatery hydrochloric acid, deaeration is for subsequent use. Preparation quality mark is 0.6% pyromellitic trimethylsilyl chloride oil solution, for subsequent use. To gather5% polyvinyl alcohol for sulfone counterdie, the mixed solution that ammonium alcohol polyvinyl phosphate concentration is 0.2% is processed 2min, the moonDry, the pyromellitic trimethylsilyl chloride solution that is then 0.6% by mass fraction is coated on the film drying in the shade processes 1min,The film of gained is placed to 15min in 80 DEG C of baking ovens again, make polyvinyl alcohol, ammonium alcohol polyvinyl phosphate and equal benzene threeFormyl chloride occurs crosslinked. Novel polyethylene alcohol milipore filter is 87% to the rejection of Macrogol 2000, water fluxFor 300LMH, to polyethylene glycol, 10000 rejection is 95%, and water flux is 229LMH.
Embodiment 6
The polyvinyl alcohol of preparation 5%, the mixed solution that ammonium alcohol polyvinyl phosphate concentration is 0.2%, and add appropriateWatery hydrochloric acid, deaeration is for subsequent use. Preparation quality mark is 0.8% pyromellitic trimethylsilyl chloride oil solution, for subsequent use. To gather5% polyvinyl alcohol for sulfone counterdie, the mixed solution that ammonium alcohol polyvinyl phosphate concentration is 0.2% is processed 2min, the moonDry, the pyromellitic trimethylsilyl chloride solution that is then 0.8% by mass fraction is coated on the film drying in the shade processes 1min,The film of gained is placed to 15min in 80 DEG C of baking ovens again, make polyvinyl alcohol, ammonium alcohol polyvinyl phosphate and equal benzene threeFormyl chloride occurs crosslinked. Novel polyethylene alcohol milipore filter is 86% to the rejection of Macrogol 2000, water fluxFor 288LMH, to polyethylene glycol, 10000 rejection is 97%, and water flux is 206LMH.
Claims (6)
1. a preparation method for polyvinyl alcohol milipore filter, is characterized in that comprising the following steps:
Polysulfones counterdie is processed to 1-3min with aqueous phase solution, dry in the shade, the oil phase that is then 0.2%-0.8% by mass fraction is moltenLiquid is coated on the film drying in the shade and processes 1-3min, then the film of gained is placed to 5-30min in 50-100 DEG C of baking oven,Obtain polyvinyl alcohol milipore filter;
Wherein aqueous phase solution refers to that the mass content of polyvinyl alcohol is that the mass content of 1%-5%, ammonium alcohol polyvinyl phosphate is 0.1%-1% mixed aqueous solution; Oil-phase solution refers to that mass content is the pyromellitic trimethylsilyl chloride oil solution of 0.2%-0.8%; Polysulfones counterdieMolecular cut off is 5-6 ten thousand.
2. the preparation method of a kind of polyvinyl alcohol milipore filter according to claim 1, is characterized in that hydrolyzed pvaDegree is 85-89%, and molecular weight is 100000-150000.
3. the preparation method of a kind of polyvinyl alcohol milipore filter according to claim 1, is characterized in that described water is moltenLiquid is again with dealing with polysulfones counterdie after vacuum defoamation is processed.
4. the preparation method of a kind of polyvinyl alcohol milipore filter according to claim 1, is characterized in that described polyethyleneAlcohol ammonium phosphate is that purity is 99.9% the pure raw material of analysis.
5. the preparation method of a kind of polyvinyl alcohol milipore filter according to claim 1, is characterized in that in aqueous phase solutionAdd crosslinking agent, crosslinking agent is wherein dilute sulfuric acid or watery hydrochloric acid.
6. the preparation method of a kind of polyvinyl alcohol milipore filter according to claim 5, is characterized in that described crosslinking agentFor watery hydrochloric acid.
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| CN105597572A (en) * | 2015-12-24 | 2016-05-25 | 北京碧水源膜科技有限公司 | Method for preparing nanofiltration membrane with high desalination selectivity and high flux |
| CN107837689B (en) * | 2017-09-25 | 2020-10-27 | 浙江理工大学 | Preparation method of composite nanofiltration membrane with ultrathin separation layer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2527423A1 (en) * | 2011-05-27 | 2012-11-28 | Roche Diagniostics GmbH | Dialysis fermenter - biorector with dialysis device |
| CN102911384A (en) * | 2012-10-23 | 2013-02-06 | 杭州水处理技术研究开发中心有限公司 | Preparation method of polyvinyl alcohol composite membrane modified by antibacterial phenol-derived aldehyde |
| CN103521099A (en) * | 2013-10-15 | 2014-01-22 | 杭州水处理技术研究开发中心有限公司 | Preparation method of cationic polyacrylamide polyvinyl alcohol nanofiltration membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2527423A1 (en) * | 2011-05-27 | 2012-11-28 | Roche Diagniostics GmbH | Dialysis fermenter - biorector with dialysis device |
| CN102911384A (en) * | 2012-10-23 | 2013-02-06 | 杭州水处理技术研究开发中心有限公司 | Preparation method of polyvinyl alcohol composite membrane modified by antibacterial phenol-derived aldehyde |
| CN103521099A (en) * | 2013-10-15 | 2014-01-22 | 杭州水处理技术研究开发中心有限公司 | Preparation method of cationic polyacrylamide polyvinyl alcohol nanofiltration membrane |
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