CN1087287A - The preparation of charged small-porosity series ultrafiltration membrane - Google Patents
The preparation of charged small-porosity series ultrafiltration membrane Download PDFInfo
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- CN1087287A CN1087287A CN 92111887 CN92111887A CN1087287A CN 1087287 A CN1087287 A CN 1087287A CN 92111887 CN92111887 CN 92111887 CN 92111887 A CN92111887 A CN 92111887A CN 1087287 A CN1087287 A CN 1087287A
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Abstract
A kind of preparation method of charged small-porosity milipore filter is that polyether sulphone is become sulfonated polyether sulphone with concentrated sulfuric acid Direct Sulfonation is that solvent and additives such as low boiling point organic solvent such as butanone, dioxane are modulated into casting solution and adopt forming film with phase transformation method as raw material and N-methyl pyrrolidone or dimethylacetylamide.Adopt this method can prepare the small-porosity series ultrafiltration membrane that molecular cut off is 1000～30,000 function admirable, can be applied in multiple fields such as chemical industry, environmental protection, food industry widely.
Description
The invention provides the preparation method and the application thereof of small-porosity series ultrafiltration membrane.Obtained milipore filter molecular cut off is 1000～30, between 000.
Modern polymeric membrane isolation technics has the history of three more than ten years.Nearly 20 come, membrane separating since power consumption less and the efficient height has become one of major fields of international scientific technical development.
Recently increasingly mature along with milipore filter and reverse osmosis membrane, exploitation to have chemical stability good, heat-resisting, charged with the little milipore filter of molecular cut off with in the millimicro filter membrane (claiming loose reverse osmosis membrane again) of low desalination degree become the interested problem of people.Because the membrane property of this class filter membrane between counter-infiltration and ultrafiltration, make it removing to low-molecular-weight organic solute in some and low concentration inorganic salts, the superiority of aspects such as the selection of multivalent ion sees through and holds back, compare with general counter-infiltration, this class film has the low and big characteristics for the treatment of capacity of operating pressure, thereby is a very potential class filter membrane.At present, polysulfones is carried out a large amount of sulfonation modifying work both at home and abroad, introduced hydrophilic radical-SO
3Or SO
3Hydrophily and the antifouling property of Na to improve material, and be used for preparing SPSF reverse osmosis membrane and milipore filter.But is the material preparation charged small-porosity series ultrafiltration membrane with this sulphur that has the phenolphthalein side chain through polyether sulphone, and molecular cut off is not seen bibliographical information both at home and abroad as yet at 1000-30 between 000.
The purpose of this invention is to provide a kind of sulfonated polyether sulphone of band phenolphthalein side chain that utilizes and be raw material, the method for preparing charged small-porosity series ultrafiltration membrane, this milipore filter molecular cut off between 000, can be widely used in fields such as chemical industry, environmental protection, food industry 1000～30.
Utilize polyether sulphone (PES-C) to be the method for feedstock production milipore filter, it generally is the membrane material (SPES-C) that earlier the polyether sulphone sulfonation is made certain sulfonation degree, again with membrane material and solvent with in casting solution, work the pore-foaming agent additive of reconciling the aperture and be mixed with out casting solution in proportion, utilize forming film with phase transformation method at last, promptly under uniform temperature, humidity, casting solution is poured on the glass plate, scrape certain thickness film with scraper, through behind the certain hour, change in the coagulation bath, the dipping film forming, treat that exchange of solvent fully after, rinsing obtains the finished product milipore filter.The preparation method of charged small-porosity series ultrafiltration membrane of the present invention, still adopt the preparation technology of above-mentioned milipore filter, earlier with the sulfonation of raw material polyether sulphone, be modulated into casting solution and utilize forming film with phase transformation method with solvent and additive again, it is characterized in that used solvent is N-methyl pyrrolidone (NMP) or dimethylacetylamide (DMAC), additive adopts low boiling point organic solvent, forms as one or more mixed solvents in ring ethanol, phenmethylol, EGME, dioxane, oxolane, butanone, ring ethyl ketone and the alditol.These low boiling point organic solvents that the present invention adopts can evaporate the purpose that reaches the adjustment hole warp rapidly in film forming procedure.Milipore filter preparation technology specifically provided by the invention is by following step:
1, polyether sulphone sulfonation and preparation membrane material
Selecting inherent viscosity for use is polyether sulphone (PES-C) between 0.68～0.72, and through concentrated sulfuric acid Direct Sulfonation, the neutralization of hydro-oxidation sodium obtains sulfonated polyether sulphone (SPES-C) then.The sulfonating reaction temperature is at 60～70 ℃, and the reaction time is 2～5hr, logical nitrogen protection.The SPES-C that gets certain sulfonation degree mixes by different proportion with PES-C, and obtaining sulfonation degree like this is that 0.1～0.3 polyether sulphone is as membrane material.
2, casting solution modulation
With above-mentioned membrane material and solvent, additive by a certain percentage mixed dissolution, leave standstill, exhaust bubble is modulated into casting solution, membrane material is a gross weight 15～25% in the casting solution of the present invention, the amount of additive is 2～20%, all the other are solvent.
3, forming film with phase transformation method
The present invention adopts into embrane method, and its casting solution is casting film-forming on the polished glass plate, is to evaporate film forming down for 70～90 ℃ at higher temperature, and the evaporation film formation time was advisable with 1～5 minute.Below by example technology of the present invention is given to illustrate further.
The preparation 1 of example 1 charged small-porosity milipore filter
Be that 0.3 SPES-C mixes by different proportion with PES-C with sulfonation degree, can obtain the membrane material between the sulfonation degree 0～0.3 like this.Be hybridly prepared into casting solution with such membrane material and solvent and additive, under the situation of relative humidity＜60%, become the thick film of 300Hm with scraper curtain coating on glass plate, evaporating temperature is 70～90 ℃, and evaporation time directly entered gel system film in 20 ℃ of water in 1～5 minute after the film forming.
As stated above, get sulfonation degree X
5=0.15SPES-C is a membrane material with PES-C mixing high polymer, and DMAC is a solvent, selects for use different low boiling organic additives to prepare milipore filter.Film properties after its additive and the film forming (with pure water flux and the interception capacity of various solutes is represented) as table 1.
Different organic additive film forming of table 1 and performance
NO additive types pure water flux (ml/cm
2Hatm) to PEG
6000Rejection (%)
1 acetone 8.1 97
2 butanone 8.0 97
3 dioxies unit ring 9.6 94
4 EGMEs 21.9 85
5 additive-free 40.0 70
(all the other are solvent, operating pressure 0.1MPa for additive concentration 17%, polymer concentration 20%)
The preparation 2 of example 2 milipore filters
Previous materials is mixed by a certain percentage with NMP, butanone, press preceding method system film, gained the results are shown in Table 2
Table 2 milipore filter and performance
NO high polymer (g) NMP (ml) butanone (ml) pure water flux is to PEG
3000
(ml/cm
2H) rejection (%)
1 10 25 10 3.4 99
2 10 27 8 5.7 92
3 10 29 6 7.5 50
4 10 31 4 7.8 53
5 10 33 2 7.2 20
The preparation 3 of example 3 milipore filters
With X
5=0.15 membrane material mixes by a certain percentage with NMP, butanone, spreads to thickness and be about the thick film of 160 μ m on glass plate.In 80 ℃ of baking ovens, evaporate certain hour, then gel film forming in 4 ℃ of water.Gained the results are shown in Table 3 and table 4.
Table 3 SPES-C, PES-C/NMP/SGH butanone system milipore filter and performance
NO evaporation time (min) pure water flux is to PEG
3000To PEG
1000
(ml/cm
2H) rejection (%) rejection (%)
1 0 5.2 95
1 6.6 99
2 6.0 99
2 0 1.4 90
1 2.8 93
2 2.6 94
(sequence number be 1 film according to high polymer 10g, NMP30ml butanone 10ml ratio is formulated).
Sequence number be 2 films according to high polymer 10g, NMP26ml, butanone 10ml ratio is formulated.Operating pressure 3qtm).
Table 4 SPES-C, PES-C/NMP-butanone system milipore filter and performance
NO high polymer NMP butanone pure water flux rejection
(g) (ml) (ml) ml/cm
2·h PEG
2000PEG
1000
1 10 30 10 7.5 63 50
2 10 26 10 4.2 90 74
3 10 25 10 3.6 97 85
4 10 22 10 0.85 98 96
5 10 20 10 0.5 98 96
6 10 26 10 2.6 94
7 10 25 10 2.0 95
8 10 22 10 0.7 98
9 10 20 10 0.5 98
(sequence number is 6 later membrane material X
5=0.3.80 ℃ of evaporating temperatures, evaporation time 2mln, operating pressure 3atm).
Example 4 milipore filters preparation 4
With SPES-C, NMP, dioxane, butanone mix by a certain percentage, make homogeneous solution, make film on glass plate, and 80～90 ℃ down behind the evaporation certain hours, gel film forming in 4 ℃ of water, gained the results are shown in Table 5 and table 6.
Table 5 SPES-C/NMP/ dioxane/butanone system milipore filter and performance
NO SPES-C NMP butanone dioxane pure water flux PEG
1000PEG
2000
(g) (ml) (ml) (ml) (ml/cm
2·h) R(%) R(%)
1 10 25 10 1 3.0 92 97
2 10 24 10 2 4.5 88 95
3 10 23 10 3 4.9 85 92
4 10 22 10 4 5.4 80 90
(operating pressure 0.3MPa, 80 ℃ of evaporating temperatures).
Utilize in the table 52 prescription, under different evaporating temperatures and evaporation time, make film and list in table 6.
Table 6 SPES-C/NMP/ dioxane/butanone system milipore filter and performance
Evaporating temperature (℃) evaporation time (min) pure water flux (ml/cmh) PEG
1000R%
80 2 4.9 92
90 1 4.6 85
2 3.2 95
3.5 1.8 97
5 1.2 92
The preparation 5 of example 5 milipore filters
Get sulfonation degree and be 0.15SPES-C membrane material and nmp solvent and butanone additive and be mixed with casting solution, press example 1 described method 80 ℃ of evaporation film forming (membrane material content 17%, all the other are solvent for additive 7.4%) down.Be used for alkali protease and separate (its molecular weight is 27,000～30,000), when operating pressure 0.1MPa, pure water flux (ml/cm
2H) be 23.4%, can reach more than 88% the alkali protease rejection.
By above-mentioned example, adopt technology provided by the invention can prepare the small-porosity series ultrafiltration membrane of function admirable, its molecular cut off can be 1000～30, and 000.This series membranes is applied to chemical industry, environmental protection, food industry, as making with extra care of dyestuff, caramel colorant and dairy products, uses in the multiple industrial production such as the purification of waste water, vinegar clarification filtration or soy sauce degerming.
Claims (4)
1, a kind of preparation method of charged small-porosity milipore filter, comprise the sulfonation of raw material polyether sulphone, be modulated into casting solution and use the forming film with phase transformation method operation with solvent and additive, it is characterized in that used solvent is N-methyl pyrrolidone (NMP) or dimethylacetylamide (DMAC), additive adopts low boiling point organic solvent, forms as one or more mixed solvents in ring ethanol, phenmethylol, EGME, dioxane, oxolane, butanone, ring ethyl ketone, the alditol.
2, in accordance with the method for claim 1; it is characterized in that described sulfonating reaction is that to select inherent viscosity for use be polyether sulphone (PES-C) between 0.68～0.72; through concentrated sulfuric acid Direct Sulfonation; the neutralization of hydro-oxidation sodium obtains sulfonated polyether sulphone (SPES-C) then; the sulfonating reaction temperature is at 60～70 ℃; reaction time is 2～5 hours, logical nitrogen protection.
3, according to the described preparation method of claim 1, it is characterized in that membrane material and solvent, additive by a certain percentage hybrid modulation become casting solution, wherein membrane material accounts for gross weight 15～25%, additive accounts for 2～20% of gross weight, all the other are solvent.
4,, it is characterized in that the forming film with phase transformation method process evaporates film forming under 70～90 ℃ of higher temperatures according to the described preparation method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92111887 CN1087287A (en) | 1992-11-24 | 1992-11-24 | The preparation of charged small-porosity series ultrafiltration membrane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92111887 CN1087287A (en) | 1992-11-24 | 1992-11-24 | The preparation of charged small-porosity series ultrafiltration membrane |
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| CN1087287A true CN1087287A (en) | 1994-06-01 |
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| CN 92111887 Withdrawn CN1087287A (en) | 1992-11-24 | 1992-11-24 | The preparation of charged small-porosity series ultrafiltration membrane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312198C (en) * | 2005-06-02 | 2007-04-25 | 上海交通大学 | Sulphonated poly(aryl ether ketone) block polybutadiene copolymer and process for preparing same |
| CN104759213A (en) * | 2014-09-25 | 2015-07-08 | 张一琛 | Preparation method of polymer charged porous membrane |
| CN109731480A (en) * | 2018-12-27 | 2019-05-10 | 上海唯赛勃环保科技股份有限公司 | A kind of preparation method of novel sulfonated polyether sulphone nanofiltration film composite material |
| CN110433670A (en) * | 2019-08-15 | 2019-11-12 | 温州大学 | High water flux sulfonated polyether sulfone-polyamide composite film and preparation method thereof |
-
1992
- 1992-11-24 CN CN 92111887 patent/CN1087287A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312198C (en) * | 2005-06-02 | 2007-04-25 | 上海交通大学 | Sulphonated poly(aryl ether ketone) block polybutadiene copolymer and process for preparing same |
| CN104759213A (en) * | 2014-09-25 | 2015-07-08 | 张一琛 | Preparation method of polymer charged porous membrane |
| CN109731480A (en) * | 2018-12-27 | 2019-05-10 | 上海唯赛勃环保科技股份有限公司 | A kind of preparation method of novel sulfonated polyether sulphone nanofiltration film composite material |
| CN110433670A (en) * | 2019-08-15 | 2019-11-12 | 温州大学 | High water flux sulfonated polyether sulfone-polyamide composite film and preparation method thereof |
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