CN100560191C - In-situ polymerization prepares the method for polyaniline composite hyperfiltration membrane - Google Patents
In-situ polymerization prepares the method for polyaniline composite hyperfiltration membrane Download PDFInfo
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- CN100560191C CN100560191C CNB2007100601380A CN200710060138A CN100560191C CN 100560191 C CN100560191 C CN 100560191C CN B2007100601380 A CNB2007100601380 A CN B2007100601380A CN 200710060138 A CN200710060138 A CN 200710060138A CN 100560191 C CN100560191 C CN 100560191C
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- hyperfiltration membrane
- composite hyperfiltration
- deionized water
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Abstract
The invention discloses the method that a kind of in-situ polymerization prepares polyaniline composite hyperfiltration membrane, belong to the technology of preparing of ultrafiltration composite membrane.This procedure comprises: under 20～25 ℃, add aniline again add citric acid, camphorsulfonic acid or salt acid for adjusting pH value in neopelex solution after, add PS membrane behind the mixing; Stirred 4～6 hours down at 20～25 ℃, continue to stir 2 hours down at 0～5 ℃ then; Again to the aqueous solution that wherein adds a certain amount of ammonium persulfate, under 0～5 ℃, finish reaction after the stirred for several minute.The polyaniline composite hyperfiltration membrane that makes had both obtained the finished product polyaniline composite hyperfiltration membrane through a series of cleanings.The inventive method is simple, easy operating, closely and uniformly be covered with nanometer fibrous polyaniline on the polyaniline composite hyperfiltration membrane surface that makes, cutoff performance and hydrophilicity improve a lot than basement membrane and can regulate cutoff performance and hydrophilicity by the control system film reaction time.
Description
Technical field
The present invention relates to a kind ofly prepare the method for polyaniline composite hyperfiltration membrane, belong to the technology of preparing of composite hyperfiltration membrane with in-situ polymerization.
Background technology
Domesticly begin the research and development of milipore filter and membrane process, at present more than 100 families nearly of manufacturer from eighties of last century the seventies.High-end field in the domestic milipore filter market (purposes such as used in electronic industry ultra-pure water, electrophoretic paint recovery, pharmacy, enzyme preparation) is controlled by overseas enterprise at present substantially.One of its reason, the milipore filter molecular cut off that is exactly domestic technique production is relatively large, focuses mostly on more than 50,000, does not reach the interception capacity of some application need.And present domestic milipore filter study on the modification focuses mostly on raising hydrophily and contamination resistance, as anti-protein-contamination branched block polymer ultrafiltration membrane of polyethersulfone preparation method (application number 200610016186.5, publication number CN 1962041A) and nano antiseptic material-polysulphone composite microporous filter film and preparation method thereof (application number 200510051363.9, publication number CN 1683061C).The domestic market presses for a kind of milipore filter technology of preparing, fills up molecular cut off space huge between present milipore filter and the NF membrane.
Polyaniline (PANI) has good heat-resisting, acid-proof alkaline because of it, and unique protonic acid doping characteristic etc. are widely used as the membrane material of processes such as gas separation, pervaporation and electrodialysis.The polyaniline of nanofiber pattern not only has inorganic nano material Al
2O
3, TiO
2Deng the high-ratio surface energy but also have the strong hydrophilicity characteristic, and a large amount of nanofiber is stacked and constitutes new separating layer the cutoff performance that improves milipore filter is contributed (K.Yoon, Polymer 47 (2006) 2434-2441) to some extent.Polysulfones (PS) has characteristics such as better chemical stability, mechanical performance, heat-resisting, acid-proof alkaline and is the basal lamina material of comparatively ripe composite membrane.And situ aggregation method is a kind of method of simple, the practical ultra-thin composite membrane of preparation, and this method at first is adsorbed on monomer on the base material, by the monomer polymerization on the initiating radical surface, thereby obtains the functional composite material of polymer overmold substrate surface.Situ aggregation method has does not need advantages such as special installation, simple to operate, controllable film thickness, and both compound efficient separating layer has kept the complete structure of basement membrane again.In view of this, we combine the polyaniline composite hyperfiltration membrane of using situ aggregation method exploitation low catching molecular with polyaniline and polysulfones.
Summary of the invention
The object of the present invention is to provide a kind of in-situ polymerization to prepare the method for polyaniline composite hyperfiltration membrane.This inventive method process is simple, easy operating, and cost is low, and the polyaniline composite hyperfiltration membrane that makes has higher and controlled cutoff performance and hydrophilicity.
The present invention is realized that by following technical proposals a kind of in-situ polymerization prepares the method for polyaniline composite hyperfiltration membrane.It is characterized in that comprising following process:
1) under 20～25 ℃ of temperature, with the neopelex solution of concentration 0.005～0.025M, be 2～3 with citric acid, camphorsulfonic acid or salt acid for adjusting pH value, place vial, add aniline again, make the solution that contains aniline 0.03M～0.2M.
2) PS membrane is moved in the solution that is made by step 1), under 100rpm, stirred 4～6 hours, continue to stir 2 hours down at 0～5 ℃ afterwards.Add ammonium persulfate in solution, the concentration of ammonium persulfate is 0.03M～0.1M and equates with the molar concentration of aniline, continues to stir 1～10 minute, reacts 0.5～24 hour under 0～5 ℃ of temperature then.
3) with step 2) in the polyaniline composite hyperfiltration membrane that makes, behind the impurity with the absorption of deionized water flush away surface, clean through absolute methanol again, the hydrochloric acid of mass concentration 36% cleans, and cleans with deionized water at last and obtains the finished product polyaniline composite hyperfiltration membrane.
The inventive method is simple, easy operating, cost is low, filming performance is good, and nanometer fibrous polyaniline closely and uniformly covers on the polysulfones basement membrane, forms new separating layer, the cutoff performance and the hydrophilicity of polysulfones basement membrane have been improved greatly, and can regulate the cutoff performance and the hydrophilicity of polyaniline composite hyperfiltration membrane by control the reaction time: along with the growth in reaction time, the cutoff performance and the hydrophilicity of polyaniline composite hyperfiltration membrane are all strengthened, and pure water flux descends simultaneously.Recording polysulfones basement membrane pure water flux under 0.16MPa is 200L/m
2H, the rejection of PEG 35K is 1.7%, the contact angle that records polysulfones basement membrane and deionized water in addition is 67 °; The pure water flux of each polyaniline composite hyperfiltration membrane that obtains to 24h at 0.16MPa test reaction 0.5h is for by 130L/m
2H is reduced to 30L/m
2H, the rejection of PEG 35K is for bringing up to 88.3% by 12.6%, and the contact angle that records each polyaniline composite hyperfiltration membrane and deionized water in addition is reduced to 40 ° by 65 °.
Description of drawings
Fig. 1 is the stereoscan photograph of embodiment 1 prepared polyaniline composite hyperfiltration membrane surface texture.
Fig. 2 is the stereoscan photograph of embodiment 1 prepared polyaniline composite hyperfiltration membrane section structure.
The specific embodiment
Embodiment 1
When temperature is 25 ℃, take by weighing 0.35g surfactant neopelex, place the deionized water of 200mL and, measure 1.7mL aniline again, join in the above-mentioned solution,, add 16 * 8cm with the 100rpm stirring and dissolving with lemon acid for adjusting pH to 2.3
2PS membrane, stirred 4 hours, continue down to stir 2 hours at 5 ℃ afterwards.Take by weighing the 4.25g ammonium persulfate again, be dissolved in the small amount of deionized water, it is joined in the above-mentioned solution that is equipped with PS membrane, stirred 10 minutes, reaction 24 hours under 0～5 ℃ of temperature again.Take out polyaniline composite hyperfiltration membrane after reaction is finished, through absolute methanol, the hydrochloric acid of mass concentration 36% and deionized water make the finished product polyaniline composite hyperfiltration membrane after cleaning and cleaning.Under 0.16MPa prepared polyaniline composite hyperfiltration membrane is tested, pure water flux is 27L/m
2H can reach 88.3% to the PEG35K aqueous solution rejection of 50ppm; Employing is lain in addition, and the method for dripping records this polyaniline composite hyperfiltration membrane and the deionized water contact angle is 40 °, and the electromicroscopic photograph on the surface of this polyaniline composite hyperfiltration membrane and the electromicroscopic photograph of section are seen accompanying drawing of the present invention.
Embodiment 2
When temperature is 25 ℃, take by weighing 0.7g surfactant neopelex, place the deionized water of 200mL and, measure 3.4mL aniline again, join in the above-mentioned solution,, add 16 * 8cm with the 100rpm stirring and dissolving with lemon acid for adjusting pH to 2.3
2PS membrane, stirred 4 hours, continue down to stir 2 hours at 5 ℃ afterwards.Take by weighing the 8.50g ammonium persulfate again, be dissolved in the small amount of deionized water, it is joined in the above-mentioned solution that is equipped with PS membrane, stirred 10 minutes, reaction 24 hours under 0～5 ℃ of temperature again.Take out polyaniline composite hyperfiltration membrane after reaction is finished, through absolute methanol, the hydrochloric acid of mass concentration 36% and deionized water make the finished product polyaniline composite hyperfiltration membrane after cleaning and cleaning.Under 0.16MPa prepared polyaniline composite hyperfiltration membrane is tested, pure water flux is 17L/m
2H can reach 59.2% to the PEG35K aqueous solution rejection of 50ppm; Employing is lain in addition, and the method for dripping records this polyaniline composite hyperfiltration membrane and the deionized water contact angle is 58 °.
Embodiment 3
When temperature is 25 ℃, take by weighing 0.12g surfactant neopelex, place the deionized water of 200mL and, measure 0.6mL aniline again, join in the above-mentioned solution,, add 16 * 8cm with the 100rpm stirring and dissolving with lemon acid for adjusting pH to 2.3
2PS membrane, stirred 4 hours, continue down to stir 2 hours at 5 ℃ afterwards.Take by weighing the 1.42g ammonium persulfate again, be dissolved in the small amount of deionized water, it is joined in the above-mentioned solution that is equipped with PS membrane, stirred 10 minutes, reaction 24 hours under 0～5 ℃ of temperature again.Take out polyaniline composite hyperfiltration membrane after reaction is finished, through absolute methanol, the hydrochloric acid of mass concentration 36% and deionized water make the finished product polyaniline composite hyperfiltration membrane after cleaning and cleaning.Under 0.16MPa prepared polyaniline composite hyperfiltration membrane is tested, pure water flux is 46L/m
2H can reach 50.6% to the PEG35K aqueous solution rejection of 50ppm; Employing is lain in addition, and the method for dripping records this polyaniline composite hyperfiltration membrane and the deionized water contact angle is 65 °.
Embodiment 4
When temperature is 25 ℃, take by weighing 0.35g surfactant neopelex, place the deionized water of 200mL and regulate pH to 2.3, measure 1.7mL aniline again, join in the above-mentioned solution,, add 16 * 8cm with the 100rpm stirring and dissolving with camphorsulfonic acid
2PS membrane, stirred 4 hours, continue down to stir 2 hours at 5 ℃ afterwards.Take by weighing the 4.25g ammonium persulfate again, be dissolved in the small amount of deionized water, it is joined in the above-mentioned solution that is equipped with PS membrane, stirred 10 minutes, reaction 24 hours under 0～5 ℃ of temperature again.Take out polyaniline composite hyperfiltration membrane after reaction is finished, through absolute methanol, the hydrochloric acid of mass concentration 36% and deionized water make the finished product polyaniline composite hyperfiltration membrane after cleaning and cleaning.Under 0.16MPa prepared polyaniline composite hyperfiltration membrane is tested, pure water flux is 47L/m
2H can reach 60.0% to the PEG35K aqueous solution rejection of 50ppm; Employing is lain in addition, and the method for dripping records this polyaniline composite hyperfiltration membrane and the deionized water contact angle is 60 °.
Embodiment 5
When temperature is 25 ℃, take by weighing 0.35g surfactant neopelex, place the deionized water of 200mL and regulate pH to 2.3, measure 1.7mL aniline again, join in the above-mentioned solution,, add 16 * 8cm with the 100rpm stirring and dissolving with hydrochloric acid
2PS membrane, stirred 4 hours, continue down to stir 2 hours at 5 ℃ afterwards.Take by weighing the 4.25g ammonium persulfate again, be dissolved in the small amount of deionized water, it is joined in the above-mentioned solution that is equipped with PS membrane, stirred 10 minutes, reaction 24 hours under 0～5 ℃ of temperature again.Take out polyaniline composite hyperfiltration membrane after reaction is finished, through absolute methanol, the hydrochloric acid of mass concentration 36% and deionized water make the finished product polyaniline composite hyperfiltration membrane after cleaning and cleaning.Under 0.16MPa prepared polyaniline composite hyperfiltration membrane is tested, pure water flux is 40L/m
2H can reach 71.0% to the PEG35K aqueous solution rejection of 50ppm; Employing is lain in addition, and the method for dripping records this polyaniline composite hyperfiltration membrane and the deionized water contact angle is 65 °.
Embodiment 6
When temperature is 25 ℃, take by weighing 0.35g surfactant neopelex, place the deionized water of 200mL and, measure 1.7mL aniline again, join in the above-mentioned solution,, add 16 * 8cm with the 100rpm stirring and dissolving with lemon acid for adjusting pH to 2.3
2PS membrane, stirred 4 hours, continue down to stir 2 hours at 5 ℃ afterwards.Take by weighing the 4.25g ammonium persulfate again, be dissolved in the small amount of deionized water, it is joined in the above-mentioned solution that is equipped with PS membrane, stirred 10 minutes, reaction 0.5 hour under 0～5 ℃ of temperature again.Take out polyaniline composite hyperfiltration membrane after reaction is finished, through absolute methanol, the hydrochloric acid of mass concentration 36% and deionized water make the finished product polyaniline composite hyperfiltration membrane after cleaning and cleaning.Under 0.16MPa prepared polyaniline composite hyperfiltration membrane is tested: pure water flux is 130L/m
2H can reach 12.6% to the PEG35K aqueous solution rejection of 50ppm; Employing is lain in addition, and the method for dripping records this polyaniline composite hyperfiltration membrane and the deionized water contact angle is 65 °.
Embodiment 7
When temperature is 25 ℃, take by weighing 0.35g surfactant neopelex, place the deionized water of 200mL and, measure 1.7mL aniline again, join in the above-mentioned solution,, add 16 * 8cm with the 100rpm stirring and dissolving with lemon acid for adjusting pH to 2.3
2PS membrane, stirred 4 hours, continue down to stir 2 hours at 5 ℃ afterwards.Take by weighing the 4.25g ammonium persulfate again, be dissolved in the small amount of deionized water, it is joined in the above-mentioned solution that is equipped with PS membrane, stirred 10 minutes, reaction 2.5 hours under 0～5 ℃ of temperature again.Take out polyaniline composite hyperfiltration membrane after reaction is finished, through absolute methanol, the hydrochloric acid of mass concentration 36% and deionized water make the finished product polyaniline composite hyperfiltration membrane after cleaning and cleaning.Under 0.16MPa prepared polyaniline composite hyperfiltration membrane is tested: pure water flux is 37L/m
2H can reach 69.8% to the PEG35K aqueous solution rejection of 50ppm; Employing is lain in addition, and the method for dripping records this polyaniline composite hyperfiltration membrane and the deionized water contact angle is 55 °.
Claims (1)
1, a kind of in-situ polymerization prepares the method for polyaniline composite hyperfiltration membrane, it is characterized in that comprising following process:
1) under 20～25 ℃ of temperature, with the neopelex solution of concentration 0.005～0.025M, be 2～3 with citric acid, camphorsulfonic acid or salt acid for adjusting pH value, place vial, add aniline again, make the solution that contains aniline 0.03M～0.2M;
2) PS membrane is moved in the aniline solution that makes by step 1), under 100rpm stirs 4～6 hours, continue down to stir 2 hours at 0～5 ℃ afterwards; Add ammonium persulfate in solution, the concentration of ammonium persulfate is 0.03M～0.1M and equates with the molar concentration of aniline, continues to stir 1～10 minute, reacts 0.5～24 hour under 0～5 ℃ of temperature then;
3) with step 2) in the polyaniline composite hyperfiltration membrane that makes, behind the impurity with the absorption of deionized water flush away surface, clean through absolute methanol again, the hydrochloric acid of mass concentration 36% cleans, and cleans with deionized water at last and obtains the finished product polyaniline composite hyperfiltration membrane.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2802630C1 (en) * | 2022-11-28 | 2023-08-30 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Кубанский государственный университет" (ФГБОУ ВО "КубГУ") | Method for producing a composite anion exchange membrane |
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| HUE040532T2 (en) * | 2008-12-11 | 2019-03-28 | Univ California | Filtration membrane |
| CN102343225A (en) * | 2011-09-28 | 2012-02-08 | 天津大学 | Preparation method of polyaniline (PANI) composite ultrafiltration membrane |
| CN102389722B (en) * | 2011-09-28 | 2013-12-04 | 天津大学 | Method for preparing nano composite ultrafiltration membrane by using polyaniline nano material |
| CN102553462B (en) * | 2012-01-11 | 2014-04-16 | 上海理工大学 | Carbon nano tube/polyaniline/polysulfone composite ultra-filtration membrane and preparing method thereof |
| US10265662B2 (en) | 2012-10-12 | 2019-04-23 | The Regents Of The University Of California | Polyaniline membranes, uses, and methods thereto |
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| CN105148619A (en) * | 2015-08-19 | 2015-12-16 | 中国科学院兰州化学物理研究所 | Method for preparing polyaniline modified porous material |
| CN105148747A (en) * | 2015-09-10 | 2015-12-16 | 哈尔滨工业大学宜兴环保研究院 | Preparation method of solvent resistant composite nanofiltration membrane |
| CN112316749B (en) * | 2020-10-20 | 2022-09-06 | 浙江长兴求是膜技术有限公司 | Chemical-hydrophilicity-resistant reversible PTFE microporous membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2802630C1 (en) * | 2022-11-28 | 2023-08-30 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Кубанский государственный университет" (ФГБОУ ВО "КубГУ") | Method for producing a composite anion exchange membrane |
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