CN102512994A - Method for preparing negatively charged membrane through ultraviolet radiation grafting - Google Patents
Method for preparing negatively charged membrane through ultraviolet radiation grafting Download PDFInfo
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- CN102512994A CN102512994A CN2011103988673A CN201110398867A CN102512994A CN 102512994 A CN102512994 A CN 102512994A CN 2011103988673 A CN2011103988673 A CN 2011103988673A CN 201110398867 A CN201110398867 A CN 201110398867A CN 102512994 A CN102512994 A CN 102512994A
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- charger
- bear electrolemma
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Abstract
The invention discloses a method for preparing a negatively charged membrane through ultraviolet radiation grafting. The method for preparing the negatively charged membrane through the ultraviolet radiation grafting comprises the following steps of: selecting a high molecular polymer membrane with carbonyl or sulfonyl at a main chain or a side chain as a basic membrane and a fluorine-containing negative ion with a structural formula of XCnF2nOCmF2mSO3-G<+> (wherein X is a halogen ion, G is hydrogen ion or metallic ion, and n and m are integers within 1 and 40 and including 1 and 40), as a functional charging agent, and grafting the functional charge agent onto the surface of the basic membrane by utilizing an ultraviolet radiation grafting method to obtain a negatively charged membrane so as to improve performances of the basic membrane. Compared with the prior art, the method for preparing the negatively charged membrane through the ultraviolet radiation grafting, disclosed by the invention, does not utilize an optical initiator so as not to exist a problem of environment pollution caused by residual radicals of the optical initiator; and simultaneously, the method for preparing the negatively charged membrane through the ultraviolet radiation grafting, disclosed by the invention, has the advantages of simple process, convenience for operation, fast processing speed and good treatment effect, thereby being a low-cost, high-efficiency, green and environment-friendly method, and having a wider industrial application prospect.
Description
Technical field
The invention belongs to membrane material modified technical field, be specifically related to the method that a kind of ultraviolet irradiation grafting prepares the bear electrolemma.
Background technology
In recent years, charged membrane more and more came into one's own owing to its unique stalling characteristic, had obtained development rapidly.Charged membrane is to be matrix with the stable synthetic material of physicochemical properties, introduces alkalescence or acid active group therein, processes the film that ion is had higher selection permeability.The stability of alkalescence active group is general not as acid active group, so the bear electrolemma is more stable than Positively charged membrane usually.Therefore the bear electrolemma can be used as milipore filter, NF membrane or reverse osmosis membrane because cation is had very high selection permeability, improves the selectivity and the flux of film, the contamination resistance of reinforcing membrane.
At present, utilize the bear electron ion exchange membrane of distinct methods, commercial application is arranged at aspects such as chlorine industry, electrochemical appliances with the preparation of engineering plastics such as polyether sulfone, polyether-ether-ketone, polybenzimidazoles.
Publication number is that the one Chinese patent application " aromatic polymer, its production method and purposes " of CN1446828 has proposed aromatic polymer that contains in a kind of side chain the super acids group and preparation method thereof; Publication number has proposed sulfonated polyether ketone type polymer for the Japanese patent application of the flat 11-502249 of special table; Publication number has proposed sulfonated polyether sulfone type polymer for the special Japanese patent application of opening flat 10-45913.These patent applications all are in polymer, to introduce sulfonic acid group through charger, and its shortcoming is that polymerization technique is complicated, is not easy to operation.
Therefore select the new charger with special nature for use, the ultraviolet irradiation graft modification technology that adopting process is simple, be convenient to operate, be easy to control, equipment investment is few has profound significance to bear electrolemma industrialization development.
The film surface is being carried out in the method and technology of modification, the ultraviolet radiation graft technology more and more receives everybody favor with its outstanding advantage.After diffusion barrier is processed, modification is carried out on its surface, both can improve the surface property of film; As improve selection permeability, stain resistance, physical and chemical stability and heat endurance of film or the like, can keep bulk properties unaffected again, and technology is simple; Be convenient to operation, be easy to control, equipment investment is few; Be to be expected to realize industrialized modification technology, thereby have bigger researching value and development potentiality.
Summary of the invention
Technical purpose of the present invention is the deficiency to existing preparation bear electrolemma; Provide a kind of ultraviolet irradiation grafting to prepare the method for bear electrolemma, this method is selected the new charger with special nature for use, under the ultraviolet light irradiation effect; Make the agent of bear electricity be grafted to basement membrane, improve the performance of basement membrane.
The present invention realizes that the technical scheme that above-mentioned technical purpose adopts is: a kind of ultraviolet irradiation grafting prepares the method for bear electrolemma, comprises the steps:
Step 1: the preparation weight concentration is 5%～60% charger solution in solvent;
Described solvent is one or more in acetone, N-methyl pyrrolidone, methyl alcohol, water, the ethanol;
Described charger is a fluo anion, and its structural formula is XC
nF
2nOC
mF
2mSO
3 -G
+, X is a halide ion, and G is hydrogen ion or metal ion, and n, m are 1 to 40 integers, comprise 1 and 40;
Step 2: the membrane surface that main chain or side chain is had carbonyl or sulfonyl evenly covers the charger solution that one deck step 1 obtains; Be placed on then under the ultraviolet irradiation light source; In air, nitrogen or inert gas atmosphere, carry out irradiation grafting, make charger be grafted to basement membrane;
Step 3: after graft reaction was accomplished, membrane surface unreacted residual charger and homopolymers were removed in washing, obtain the bear electrolemma.
Described basement membrane includes but not limited to polyether sulfone, polysulfones, polyarylsulfone (PAS), polyether-ketone and derivative thereof.
Described ultraviolet irradiation light source comprises high-pressure sodium lamp or low pressure mercury lamp, and its power is preferably 200W～800W.
During described ultraviolet irradiation light source irradiation basement membrane, be preferably 0.5cm～50cm with the distance of basement membrane.
The exposure time of described ultraviolet irradiation light source is preferably within 0.5min～30min;
In the described step 2, the method that membrane surface evenly covers one deck charger solution includes but not limited to one or more in infusion process, spin-coating method, the knife coating etc.
After graft reaction was accomplished, the method that membrane surface unreacted residual charger and homopolymers are removed in washing included but not limited to methods such as solvent extraction, supersound washing, flushing.
In sum, the present invention selects for use has photoactive polymer membrane, and promptly main chain or side chain have the basement membrane of carbonyl or sulfonyl, select structural formula XC for use
nF
2nOC
mF
2mSO
3 -G
+Fluo anion (wherein, X is a halide ion, and G is hydrogen ion or metal ion; N, m are 1 to 40 integers, comprise 1 and 40) be functional charger, utilize the method for ultraviolet light irradiation grafting; Functional charger is grafted to membrane surface, obtains the bear electrolemma, to improve the performance of basement membrane.Compared with prior art, the preparation method of bear electrolemma provided by the invention does not use light trigger, thereby the problem of environmental pollution that does not exist initiator residue to cause; Simultaneously, this preparation method has the advantage that technology is simple, easy to operate, process velocity is fast, treatment effect is good, is the method for a kind of low cost, high efficiency, environmental protection therefore, has extensive industrialized application prospect.
Description of drawings
Fig. 1 is PS membrane grafting I (CF in the embodiment of the invention 1
2)
2O (CF
2)
2SO
3XPS figure before and after the K.
The specific embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1:
In the present embodiment, be basement membrane with polysulfones (PSF) film, with I (CF
2)
2O (CF
2)
2SO
3K is a charger, and it is the uviol lamp of 400W that the ultraviolet irradiation light source is selected power for use, and it is following to utilize the ultraviolet irradiation grafting to prepare the concrete steps of bear electrolemma:
Step 1: as solvent, the preparation weight concentration is 10% I (CF with acetone
2)
2O (CF
2)
2SO
3K solution.
Step 2: adopt infusion process, PS membrane is immersed in the I (CF that step 1 configures
2)
2O (CF
2)
2SO
3In the K solution, take out behind the immersion 8h, this PS membrane surface evenly covers one deck I (CF
2)
2O (CF
2)
2SO
3K solution; Then, under air atmosphere, use uv light irradiation this surface coverage I (CF of power as 400W
2)
2O (CF
2)
2SO
3The PS membrane of K solution, irradiation distance are 12cm, and exposure time is 30min, make I (CF
2)
2O (CF
2)
2SO
3The K radiation grafting is to the PS membrane surface.
Step 3: after graft reaction is accomplished, with the PS membrane 24h after acetone solvent extraction steps 2 reaction treatment, to remove PS membrane surface unreacted residual I (CF
2)
2O (CF
2)
2SO
3K charger and homopolymers obtain the bear electrolemma.
Through above-mentioned ultraviolet irradiation grafting method, make charger I (CF
2)
2O (CF
2)
2SO
3K XPS is grafted to the PS membrane surface, obtains the bear electrolemma.Characterize the pure PS membrane that does not carry out above-mentioned reaction through XPS, and carry out the grafting PS membrane (being the bear electrolemma) behind the above-mentioned ultraviolet irradiation graft reaction, obtain the XPS figure of grafting front and back shown in Figure 1.
Can see intuitively from Fig. 1, compare with pure PS membrane, through behind the above-mentioned ultraviolet irradiation grafting method, charger I (CF
2)
2O (CF
2)
2SO
3K XPS successfully is grafted to the PS membrane surface.
The metabisulfite solution rejection of the bear electrolemma of present embodiment preparation is 92%.
Embodiment 2:
In the present embodiment, be basement membrane with the poly (ether sulfone) film, with Br (CF
2)
2O (CF
2)
2SO
3K is a charger, and it is the uviol lamp of 400W that the ultraviolet irradiation light source is selected power for use, and it is following to utilize the ultraviolet irradiation grafting to prepare the concrete steps of bear electrolemma:
Step 1: as solvent, the preparation weight concentration is 10% Br (CF with acetone
2)
2O (CF
2)
2SO
3K solution.
Step 2: adopt infusion process, poly (ether sulfone) film is immersed in the Br (CF that step 1 configures
2)
2O (CF
2)
2SO
3In the K charger solution, take out behind the immersion 12h, this poly (ether sulfone) film surface evenly covers one deck Br (CF
2)
2O (CF
2)
2SO
3K solution; Then, under argon atmosphere, use uv light irradiation this surface coverage Br (CF of power as 400W
2)
2O (CF
2)
2SO
3The poly (ether sulfone) film of K solution, irradiation distance are 12cm, and exposure time is 15min, make Br (CF
2)
2O (CF
2)
2SO
3The K radiation grafting is to the poly (ether sulfone) film surface.
Step 3: after graft reaction is accomplished, with the poly (ether sulfone) film 24h after acetone solvent extraction steps 2 reaction treatment, to remove poly (ether sulfone) film surface unreacted residual Br (CF
2)
2O (CF
2)
2SO
3K charger and homopolymers obtain the bear electrolemma.
Characterize the pure poly (ether sulfone) film that does not carry out above-mentioned reaction through XPS, and carry out the graft polyether sulfone film (being the bear electrolemma) behind the above-mentioned ultraviolet irradiation graft reaction, similar shown in Figure 1, can obtain Br (CF
2)
2O (CF
2)
2SO
3The K charger successfully grafts to the poly (ether sulfone) film surface.
The metabisulfite solution rejection of the bear electrolemma of present embodiment preparation is 94%.
Embodiment 3:
In the present embodiment, be basement membrane with the poly (ether sulfone) film, with I (CF
2)
2O (CF
2)
2SO
3K is a charger, and it is the uviol lamp of 400W that the ultraviolet irradiation light source is selected power for use, and it is following to utilize the ultraviolet irradiation grafting to prepare the concrete steps of bear electrolemma:
Step 1: as solvent, the preparation weight concentration is 15% I (CF with acetone
2)
4O (CF
2)
3SO
3K solution;
Step 2: adopt spin-coating method, the I (CF that step 1 is configured
2)
2O (CF
2)
2SO
3K solution evenly is spin-coated on the polyether sulfone membrane surface; Then, under nitrogen atmosphere, use uv light irradiation this surface coverage I (CF of power as 400W
2)
2O (CF
2)
2SO
3The poly (ether sulfone) film of K solution, irradiation distance are 12cm, and exposure time is 10min, make I (CF
2)
2O (CF
2)
2SO
3The K radiation grafting is to the poly (ether sulfone) film surface.
Step 3: after graft reaction is accomplished, with the poly (ether sulfone) film 24h after acetone solvent extraction steps 2 reaction treatment, to remove poly (ether sulfone) film surface unreacted residual I (CF
2)
2O (CF
2)
2SO
3K charger and homopolymers obtain the bear electrolemma.
Characterize the pure poly (ether sulfone) film that does not carry out above-mentioned reaction through XPS, and carry out the graft polyether sulfone film (being the bear electrolemma) behind the above-mentioned ultraviolet irradiation graft reaction, similar shown in Figure 1, can obtain I (CF
2)
2O (CF
2)
2SO
3The K charger successfully grafts to the poly (ether sulfone) film surface.
The metabisulfite solution rejection of the bear electrolemma of present embodiment preparation is 93%.
Embodiment 4:
In the present embodiment, be basement membrane with the polyether-ketone film, with Cl (CF
2)
3O (CF
2)
2SO
3Na is a charger, and it is the uviol lamp of 500W that the ultraviolet irradiation light source is selected power for use, and it is following to utilize the ultraviolet irradiation grafting to prepare the concrete steps of bear electrolemma:
Step 1: as solvent, the preparation weight concentration is 15% Cl (CF with ethanol
2)
3O (CF
2)
2SO
3Na solution;
Step 2: adopt infusion process, the polyether-ketone film is immersed in the Cl (CF that step 1 configures
2)
3O (CF
2)
2SO
3In the Na charger solution, take out behind the immersion 9h, this polyether-ketone film surface evenly covers one deck Cl (CF
2)
3O (CF
2)
2SO
3Na solution; Then, under air atmosphere, use uv light irradiation this surface coverage Cl (CF of power as 500W
2)
3O (CF
2)
2SO
3The polyether-ketone film of Na solution, irradiation distance are 10cm, and exposure time is 20min, make Cl (CF
2)
3O (CF
2)
2SO
3The Na radiation grafting is to polyether-ketone film surface.
Step 3: after graft reaction is accomplished, with the polyether-ketone film 24h after acetone solvent extraction steps 2 reaction treatment, to remove striping surface unreacted residual Cl (CF
2)
3O (CF
2)
2SO
3Na charger and homopolymers obtain the bear electrolemma.
Do not carry out the pure polyether-ketone film of above-mentioned reaction through the XPS sign, and carry out the graft polyether ketone film (being the bear electrolemma) behind the above-mentioned ultraviolet irradiation graft reaction, similar shown in Figure 1, can obtain Cl (CF
2)
3O (CF
2)
2SO
3The Na charger successfully grafts to polyether-ketone film surface.
The metabisulfite solution rejection of the bear electrolemma of present embodiment preparation is 95%.
Embodiment 5:
In the present embodiment, be basement membrane with the PS membrane, with I (CF
2)
2O (CF
2)
2SO
3K is a charger, and it is the uviol lamp of 600W that the ultraviolet irradiation light source is selected power for use, and it is following to utilize the ultraviolet irradiation grafting to prepare the concrete steps of bear electrolemma:
Step 1: as solvent, the preparation weight concentration is 15% I (CF with acetone
2)
2O (CF
2)
2SO
3K solution;
Step 2: adopt knife coating, the I (CF that step 1 is configured
2)
2O (CF
2)
2SO
3The even blade coating of K charger solution is on the PS membrane surface; Then, use uv light irradiation this surface coverage I (CF of power as 600W
2)
2O (CF
2)
2SO
3The PS membrane of K, irradiation distance are 15cm, and exposure time is 15min, make I (CF
2)
2O (CF
2)
2SO
3The K radiation grafting is to the PS membrane surface.
Step 3: after graft reaction is accomplished, with the PS membrane 24h after acetone solvent extraction steps 2 reaction treatment, to remove PS membrane surface unreacted residual I (CF
2)
2O (CF
2)
2SO
3K charger and homopolymers obtain the bear electrolemma.
Characterize the pure PS membrane that does not carry out above-mentioned reaction through XPS, and carry out the grafting PS membrane (being the bear electrolemma) behind the above-mentioned ultraviolet irradiation graft reaction, similar shown in Figure 1, can obtain I (CF
2)
2O (CF
2)
2SO
3The K charger successfully grafts to the PS membrane surface.
The metabisulfite solution rejection of the bear electrolemma of present embodiment preparation is 92%.
Embodiment 6:
In the present embodiment, be basement membrane with the polyarylsulfone (PAS) film, with Cl (CF
2)
5O (CF
2)
4SO
3K is a charger, and it is the uviol lamp of 400W that the ultraviolet irradiation light source is selected power for use, and it is following to utilize the ultraviolet irradiation grafting to prepare the concrete steps of bear electrolemma:
Step 1: as solvent, the preparation weight concentration is 15% Cl (CF with acetone
2)
5O (CF
2)
4SO
3K solution;
Step 2: adopt infusion process, the polyarylsulfone (PAS) film is immersed in the Cl (CF that step 1 configures
2)
5O (CF
2)
4SO
3In the K solution, take out behind the immersion 9h, this PS membrane surface evenly covers one deck Cl (CF
2)
5O (CF
2)
4SO
3K; Under argon atmosphere, use uv light irradiation this surface coverage Cl (CF of power as 400W
2)
5O (CF
2)
4SO
3The polyarylsulfone (PAS) film of K solution, irradiation distance are 10cm, and exposure time is 20min, make Cl (CF
2)
5O (CF
2)
4SO
3The K radiation grafting is to the polyarylsulfone (PAS) film.
Step 3: after graft reaction is accomplished, with the polyarylsulfone (PAS) film 24h after acetone solvent extraction steps 2 reaction treatment, to remove striping surface unreacted residual Cl (CF
2)
5O (CF
2)
4SO
3K charger and homopolymers obtain the bear electrolemma.
Do not carry out the pure polyarylsulfone (PAS) film of above-mentioned reaction through the XPS sign, and carry out the grafting polyarylsulfone (PAS) film (being the bear electrolemma) behind the above-mentioned ultraviolet irradiation graft reaction, similar shown in Figure 1, can obtain Cl (CF
2)
5O (CF
2)
4SO
3The K charger successfully grafts to polyarylsulfone (PAS) film surface.
The metabisulfite solution rejection of the bear electrolemma of present embodiment preparation is 93%.
Embodiment 7:
In the present embodiment, be basement membrane with the PS membrane, with I (CF
2)
2O (CF
2)
4SO
3K is a charger, and it is the uviol lamp of 300W that the ultraviolet irradiation light source is selected power for use, and it is following to utilize the ultraviolet irradiation grafting to prepare the concrete steps of bear electrolemma:
Step 1: as solvent, the preparation weight concentration is 30% I (CF with acetone
2)
2O (CF
2)
4SO
3K solution;
Step 2: adopt spin-coating method, the I (CF that step 1 is configured
2)
2O (CF
2)
2SO
3K solution evenly is spin-coated on the polysulfones membrane surface; Then, under nitrogen atmosphere, use uv light irradiation this surface coverage I (CF of power as 300W
2)
2O (CF
2)
2SO
3The PS membrane of K solution, irradiation distance are 10cm, and exposure time is 20min, make I (CF
2)
2O (CF
2)
2SO
3The K radiation grafting is to the PS membrane surface.
Step 3: after graft reaction is accomplished, with the PS membrane 24h after acetone solvent extraction steps 2 reaction treatment, to remove PS membrane surface unreacted residual I (CF
2)
2O (CF
2)
2SO
3K charger and homopolymers obtain the bear electrolemma.
Characterize the pure PS membrane that does not carry out above-mentioned reaction through XPS, and carry out the grafting PS membrane (being the bear electrolemma) behind the above-mentioned ultraviolet irradiation graft reaction, similar shown in Figure 1, can obtain I (CF
2)
2O (CF
2)
2SO
3The K charger successfully grafts to the PS membrane surface.
The metabisulfite solution rejection of the bear electrolemma of present embodiment preparation is 95%.
Above-described embodiment specifies technical scheme of the present invention; Be understood that the above is merely specific embodiment of the present invention; Be not limited to the present invention; All any modifications of in principle scope of the present invention, being made, replenish or be equal to alternatively etc., all should be included within protection scope of the present invention.
Claims (7)
1. a ultraviolet irradiation grafting prepares the method for bear electrolemma, it is characterized in that: comprise the steps:
Step 1: the preparation weight concentration is 5%～60% charger solution in solvent;
Described solvent is one or more in acetone, N-methyl pyrrolidone, methyl alcohol, water, the ethanol; Described charger is a fluo anion, and its structural formula is XC
nF
2nOC
mF
2mSO
3 -G
+, X is a halide ion, and G is hydrogen ion or metal ion, and n, m are 1 to 40 integers, comprise 1 and 40;
Step 2: the membrane surface that main chain or side chain is had carbonyl or sulfonyl evenly covers the charger solution that one deck step 1 obtains; Be placed on then under the ultraviolet irradiation light source; In air, nitrogen or inert gas atmosphere, carry out irradiation grafting, make charger be grafted to basement membrane;
Step 3: after graft reaction was accomplished, membrane surface unreacted residual charger and homopolymers were removed in washing, obtain the bear electrolemma.
2. ultraviolet irradiation grafting according to claim 1 prepares the method for bear electrolemma, it is characterized in that: described basement membrane comprises polyether sulfone, polysulfones, polyarylsulfone (PAS), polyether-ketone and derivative thereof.
3. ultraviolet irradiation grafting according to claim 1 and 2 prepares the method for bear electrolemma, it is characterized in that: the power of described ultraviolet irradiation light source is 200W～800W.
4. ultraviolet irradiation grafting according to claim 1 and 2 prepares the method for bear electrolemma, it is characterized in that: the irradiation distance of described ultraviolet irradiation light source is 0.5cm～50cm.
5. ultraviolet irradiation grafting according to claim 1 and 2 prepares the method for bear electrolemma, it is characterized in that: the exposure time of described ultraviolet irradiation light source is 0.5min～30min.
6. ultraviolet irradiation grafting according to claim 1 and 2 prepares the method for bear electrolemma, it is characterized in that: in the described step 2, the method that membrane surface evenly covers one deck charger solution comprises one or more in infusion process, spin-coating method, the knife coating.
7. ultraviolet irradiation grafting according to claim 1 and 2 prepares the method for bear electrolemma; It is characterized in that: in the described step 2; After graft reaction was accomplished, the method that membrane surface unreacted residual charger and homopolymers are removed in washing comprised solvent extraction process, supersound washing method and douche.
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|---|---|---|---|
| CN2011103988673A CN102512994A (en) | 2011-12-05 | 2011-12-05 | Method for preparing negatively charged membrane through ultraviolet radiation grafting |
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|---|---|---|---|
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6642319B2 (en) * | 2000-01-19 | 2003-11-04 | E. I. Du Pont De Nemours And Company | Process for making graft copolymers |
| CN1803265A (en) * | 2005-12-15 | 2006-07-19 | 复旦大学 | Method for preparing nanometer filter membrane using irradiating surface and copolymerized grafting technology |
| CN101444687A (en) * | 2008-08-28 | 2009-06-03 | 中国石油大学(华东) | Method for producing oil repellence filter element for filtering oily sewage of oil field |
-
2011
- 2011-12-05 CN CN2011103988673A patent/CN102512994A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6642319B2 (en) * | 2000-01-19 | 2003-11-04 | E. I. Du Pont De Nemours And Company | Process for making graft copolymers |
| CN1803265A (en) * | 2005-12-15 | 2006-07-19 | 复旦大学 | Method for preparing nanometer filter membrane using irradiating surface and copolymerized grafting technology |
| CN101444687A (en) * | 2008-08-28 | 2009-06-03 | 中国石油大学(华东) | Method for producing oil repellence filter element for filtering oily sewage of oil field |
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Application publication date: 20120627 |