CN104474924A - Preparation method of polyvinyl alcohol ultra-filtration membrane - Google Patents
Preparation method of polyvinyl alcohol ultra-filtration membrane Download PDFInfo
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- CN104474924A CN104474924A CN201410794527.6A CN201410794527A CN104474924A CN 104474924 A CN104474924 A CN 104474924A CN 201410794527 A CN201410794527 A CN 201410794527A CN 104474924 A CN104474924 A CN 104474924A
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- polyvinyl alcohol
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Abstract
The invention discloses a preparation method of a high-molecular material membrane and in particular relates to a preparation method of an ultra-filtration membrane which is high in water flux and high in low-molecular-weight organic matter retention rate. The preparation method comprises the following steps: treating a polysulfone base membrane by using a water-phase solution for 1-3 minutes, and drying the membrane in the shade; then coating the membrane which is dried in the shade with an oil-phase solution, treating for 1-3 minutes, and then placing the obtained membrane in a drying oven for 5-30 minutes to obtain a polyvinyl alcohol ultra-filtration membrane, wherein the mass fraction of the oil-phase solution is 0.2-0.8 percent, and the temperature of the drying oven is 50-100 DEG C. The preparation method has the advantages that the preparation method is simple and novel; the ultra-filtration membrane is high in low-molecular-weight organic matter retention rate and high in 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 the preparation method of the higher milipore filter of small organic molecule rejection.
Background technology
Pure PVA basement membrane easy swelling, wet film intensity difference, not withstand voltage in water, greatly limit its industrial applications. so the PVA milipore filter that intensity is good, water-swellable is low will be obtained must carry out modification to it.Common method of modifying is introducing second component, can form covalent bond or hydrogen bond with the hydroxyl in PVA molecule, makes it change into water-fast group, and then improves the water resistance of film, obtains the PVA milipore filter of high strength.
China is the big producing country of polyvinyl alcohol plastics, and polyvinyl alcohol is a kind of potential excellent base material of preparation of anti-fouling ultrafiltration membrane of preparing, the research of PVA milipore filter in recent years receives much concern. and Ma Cailian etc. have carried out preliminary introduction (Ma Cailian to the progress of PVA milipore filter, Song Renyuan, Yu Yuan, Deng the Study and appliance present situation [J] of .PVA basement membrane. application chemical industry, 2009, 38 (3): 435-438.) PVA strand contains great amount of hydroxy group, there is very strong reactivity, it is the excellent material preparing the ultra-thin top layer of composite membrane, the existence on the ultra-thin top layer of PVA, the hydrophilicity of film can be improved to a great extent, improve its anti-pollution ability.
Polyvinyl alcohol can be cross-linked with aldehyde, acid, isocyanates, acyl chlorides etc.Shang etc. use toluene di-isocyanate(TDI) (TDI) as crosslinking agent, react with PVA and prepare milipore filter, carry out the separation (ShangY of water-oil emulsion, Peng Y L.UF membrane of PVA modified with TDI [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.But the rejection of the organic molecule to less than 10000 is all lower.This patent is not enough for this of milipore filter, and on milipore filter, the crosslinked cortex of compound one deck pyromellitic trimethylsilyl chloride and polyvinyl alcohol, enhances milipore filter retaining organic molecule.Meanwhile, in polyvinyl alcohol, introduce ammonium alcohol polyvinyl phosphate, because ammonium alcohol polyvinyl phosphate is that a kind of white macromolecular compound is soluble in water, and it has phosphate groups, a kind of strong electrolyte, so while increase rejection, also increase the water flux of milipore filter.React under the effect of catalyst with pyromellitic trimethylsilyl chloride again after polyvinyl alcohol can being made to mix with ammonium alcohol polyvinyl phosphate by simple mechanical blending.The reaction of acid chloride groups and hydroxyl makes polyvinyl alcohol and pyromellitic trimethylsilyl chloride occur to be cross-linked, and considerably increases the mechanical strength on film surface.Ammonium alcohol polyvinyl phosphate can be entrained in the cross-linked network of polyvinyl alcohol, small part and pyromellitic trimethylsilyl chloride also may be had to occur crosslinked.Containing easily ionizable group on ammonium alcohol polyvinyl phosphate, while increase water flux, too increase the selective penetrated property to ion.
Summary of the invention
For deficiency of the prior art, the present invention proposes a kind of preparation method of Novel polyvinyl alcohol milipore filter.By the polysulfones counterdie polyvinyl alcohol of 1%-5% that with the addition of suitable catalyst, ammonium alcohol polyvinyl phosphate concentration is the mixed solution process 1-3min of 0.1%-1%, use the pyromellitic trimethylsilyl chloride oil solution process 1-3min of 0.2%-0.8% again, prepared composite membrane is placed 5-30min 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 aqueous phase solution is carried out process 1-3min, dry in the shade, then be that the oil-phase solution of 0.2%-0.8% is coated in the enterprising row relax 1-3min of the film dried in the shade by mass fraction, then the film of gained is placed 5-30min in 50-100 DEG C of baking oven, polyvinyl alcohol milipore filter can be obtained;
Wherein aqueous phase solution refers to that the mass content of polyvinyl alcohol is 1%-5%, the mass content of ammonium alcohol polyvinyl phosphate is the mixed aqueous solution of 0.1%-1%; Oil-phase solution refers to that mass content is the pyromellitic trimethylsilyl chloride oil solution of 0.2%-0.8%; 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%, and molecular weight is 100000-150000.
As preferably, the aqueous phase solution described in preparation method of above-mentioned a kind of polyvinyl alcohol milipore filter for after vacuum defoamation process again with dealing with polysulfones counterdie.
As preferably, the ammonium alcohol polyvinyl phosphate described in preparation method of above-mentioned a kind of polyvinyl alcohol milipore filter to be purity be 99.9% the pure raw material of analysis.
As preferably, in aqueous phase solution, add crosslinking agent described in the preparation method of above-mentioned a kind of polyvinyl alcohol milipore filter, 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 serves certain effect.
Beneficial effect: the preparation method in the present invention is simply novel, milipore filter has higher small organic molecule rejection 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%, ammonium alcohol polyvinyl phosphate concentration is the mixed solution of 0.2%, and adds appropriate watery hydrochloric acid, and deaeration is for subsequent use.Preparation quality mark is the pyromellitic trimethylsilyl chloride oil solution of 0.2%, for subsequent use.By polysulfones counterdie with 3% polyvinyl alcohol, ammonium alcohol polyvinyl phosphate concentration is the mixed solution process 2min of 0.2%, dry in the shade, then by mass fraction be 0.2% pyromellitic trimethylsilyl chloride solution be coated on the film that dries in the shade and process 1min, place 15min by the film of gained again 80 DEG C of baking ovens, polyvinyl alcohol, ammonium alcohol polyvinyl phosphate and pyromellitic trimethylsilyl chloride are occurred crosslinked.Novel polyvinyl alcohol milipore filter is 79% to the rejection of Macrogol 2000, and water flux is 293LMH, and to polyethylene glycol, the rejection of 10000 is 85%, and water flux is 222LMH.
Embodiment 2
The polyvinyl alcohol of preparation 3%, ammonium alcohol polyvinyl phosphate concentration is the mixed solution of 0, and adds appropriate watery hydrochloric acid, and deaeration is for subsequent use.Preparation quality mark is the pyromellitic trimethylsilyl chloride oil solution of 0.2%, for subsequent use.By polysulfones counterdie with 3% polyvinyl alcohol, ammonium alcohol polyvinyl phosphate concentration is the mixed solution process 2min of 0.4%, dry in the shade, then by mass fraction be 0.2% pyromellitic trimethylsilyl chloride solution be coated on the film that dries in the shade and process 1min, place 15min by the film of gained again 80 DEG C of baking ovens, polyvinyl alcohol, ammonium alcohol polyvinyl phosphate and pyromellitic trimethylsilyl chloride are occurred crosslinked.Novel polyvinyl alcohol milipore filter is 77% to the rejection of Macrogol 2000, and water flux is 140LMH, and to polyethylene glycol, the rejection of 10000 is 89%, and water flux is 125LMH.
Embodiment 3
The polyvinyl alcohol of preparation 5%, ammonium alcohol polyvinyl phosphate concentration is the mixed solution of 0.2%, and adds appropriate watery hydrochloric acid, and deaeration is for subsequent use.Preparation quality mark is the pyromellitic trimethylsilyl chloride oil solution of 0.2%, for subsequent use.By polysulfones counterdie with 5% polyvinyl alcohol, ammonium alcohol polyvinyl phosphate concentration is the mixed solution process 2min of 0.2%, dry in the shade, then by mass fraction be 0.2% pyromellitic trimethylsilyl chloride solution be coated on the film that dries in the shade and process 1min, place 15min by the film of gained again 80 DEG C of baking ovens, polyvinyl alcohol, ammonium alcohol polyvinyl phosphate and pyromellitic trimethylsilyl chloride are occurred crosslinked.Novel polyvinyl alcohol milipore filter is 75% to the rejection of Macrogol 2000, and water flux is 298LMH, and to polyethylene glycol, the rejection of 10000 is 86%, and water flux is 218LMH.
Embodiment 4
The polyvinyl alcohol of preparation 4%, ammonium alcohol polyvinyl phosphate concentration is the mixed solution of 0.2%, and adds appropriate watery hydrochloric acid, and deaeration is for subsequent use.Preparation quality mark is the pyromellitic trimethylsilyl chloride oil solution of 0.2%, for subsequent use.By polysulfones counterdie with 4% polyvinyl alcohol, ammonium alcohol polyvinyl phosphate concentration is the mixed solution process 2min of 0.2%, dry in the shade, then by mass fraction be 0.2% pyromellitic trimethylsilyl chloride solution be coated on the film that dries in the shade and process 1min, place 15min by the film of gained again 80 DEG C of baking ovens, polyvinyl alcohol, ammonium alcohol polyvinyl phosphate and pyromellitic trimethylsilyl chloride are occurred crosslinked.Novel polyvinyl alcohol milipore filter is 83% to the rejection of Macrogol 2000, and water flux is 290LMH, and to polyethylene glycol, the rejection of 10000 is 92%, and water flux is 215LMH.
Embodiment 5
The polyvinyl alcohol of preparation 5%, ammonium alcohol polyvinyl phosphate concentration is the mixed solution of 0.2%, and adds appropriate watery hydrochloric acid, and deaeration is for subsequent use.Preparation quality mark is the pyromellitic trimethylsilyl chloride oil solution of 0.6%, for subsequent use.By polysulfones counterdie with 5% polyvinyl alcohol, ammonium alcohol polyvinyl phosphate concentration is the mixed solution process 2min of 0.2%, dry in the shade, then by mass fraction be 0.6% pyromellitic trimethylsilyl chloride solution be coated on the film that dries in the shade and process 1min, place 15min by the film of gained again 80 DEG C of baking ovens, polyvinyl alcohol, ammonium alcohol polyvinyl phosphate and pyromellitic trimethylsilyl chloride are occurred crosslinked.Novel polyvinyl alcohol milipore filter is 87% to the rejection of Macrogol 2000, and water flux is 300LMH, and to polyethylene glycol, the rejection of 10000 is 95%, and water flux is 229LMH.
Embodiment 6
The polyvinyl alcohol of preparation 5%, ammonium alcohol polyvinyl phosphate concentration is the mixed solution of 0.2%, and adds appropriate watery hydrochloric acid, and deaeration is for subsequent use.Preparation quality mark is the pyromellitic trimethylsilyl chloride oil solution of 0.8%, for subsequent use.By polysulfones counterdie with 5% polyvinyl alcohol, ammonium alcohol polyvinyl phosphate concentration is the mixed solution process 2min of 0.2%, dry in the shade, then by mass fraction be 0.8% pyromellitic trimethylsilyl chloride solution be coated on the film that dries in the shade and process 1min, place 15min by the film of gained again 80 DEG C of baking ovens, polyvinyl alcohol, ammonium alcohol polyvinyl phosphate and pyromellitic trimethylsilyl chloride are occurred crosslinked.Novel polyvinyl alcohol milipore filter is 86% to the rejection of Macrogol 2000, and water flux is 288LMH, and to polyethylene glycol, the rejection of 10000 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 aqueous phase solution is carried out process 1-3min, dry in the shade, then be that the oil-phase solution of 0.2%-0.8% is coated in the enterprising row relax 1-3min of the film dried in the shade by mass fraction, then the film of gained is placed 5-30min in 50-100 DEG C of baking oven, polyvinyl alcohol milipore filter can be obtained;
Wherein aqueous phase solution refers to that the mass content of polyvinyl alcohol is 1%-5%, the mass content of ammonium alcohol polyvinyl phosphate is the mixed aqueous solution of 0.1%-1%; Oil-phase solution refers to that mass content is the pyromellitic trimethylsilyl chloride oil solution of 0.2%-0.8%; The molecular cut off of polysulfones counterdie is 5-6 ten thousand.
2. the preparation method of a kind of polyvinyl alcohol milipore filter according to claim 1, it is characterized in that hydrolyzed pva degree is 85-89%, 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 aqueous phase solution is again with dealing with polysulfones counterdie after vacuum defoamation process.
4. the preparation method of a kind of polyvinyl alcohol milipore filter according to claim 1, is characterized in that described ammonium alcohol polyvinyl phosphate to be purity is the pure raw material of analysis of 99.9%.
5. the preparation method of a kind of polyvinyl alcohol milipore filter according to claim 1, in aqueous phase solution, add crosslinking agent described in it is characterized in that, 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 agent is watery hydrochloric acid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107837689A (en) * | 2017-09-25 | 2018-03-27 | 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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Patent 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107837689A (en) * | 2017-09-25 | 2018-03-27 | 浙江理工大学 | Preparation method of composite nanofiltration membrane with ultrathin separation layer |
| CN107837689B (en) * | 2017-09-25 | 2020-10-27 | 浙江理工大学 | Preparation method of composite nanofiltration membrane with ultrathin separation layer |
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