CN101259386A - Phospholipid modified poly (ether-sulfone) ultrafiltration membrane capable of resisting protein pollution and preparation - Google Patents
Phospholipid modified poly (ether-sulfone) ultrafiltration membrane capable of resisting protein pollution and preparation Download PDFInfo
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- CN101259386A CN101259386A CNA2007100603653A CN200710060365A CN101259386A CN 101259386 A CN101259386 A CN 101259386A CN A2007100603653 A CNA2007100603653 A CN A2007100603653A CN 200710060365 A CN200710060365 A CN 200710060365A CN 101259386 A CN101259386 A CN 101259386A
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Abstract
The invention relates to a phospholipid modification polyether sulfone ultrafiltration membrane which resists protein pollution and a preparation method thereof. The invention takes phospholipid copolymer (MPC-BMA), the polyether sulfone (PES) and polyethyleneglycol (PEG2000) as the raw materials and prepares the materials according to the mass fraction of 0 to 4.8 percent of the phospholipid copolymer, 18 percent of the polyether sulfone and 15 percent of the polyethyleneglycol (PEG2000). The preparation method includes: the polyethyleneglycol and the phospholipid copolymer (MPC-BMA) are added in the N, N-dimethylformamide of the polyether sulfone (PES); the mixture is stirred for 4 to 6 hours under a temperature of 50 to 60 DEG C; the prepared uniform-phase casting solution stands for being defoamed for 2 to 4 hours under a temperature of 50 to 60 DEG C, is poured on a glass plate for membrane scraping after being cooled, and then is put into a water bath for being concreted and shaped into membrane after standing; the membrane is dipped in water for 24 to 36 hours to obtain the phospholipid modification polyether sulfone ultrafiltration membrane. The invention has simple process and gentle conditions; the obtained modification ultrafiltration membrane has excellent anti-pollution performance and can be applied to the separation of biological products, etc.
Description
Technical field
The present invention relates to the phospholipid modified poly (ether-sulfone) ultrafiltration membrane capable and the preparation method of milipore filter technology of preparing, particularly a kind of anti-protein-contamination.
Background technology
Ultrafiltration is the liquid phase sieve aperture separation process of carrying out under the effect of differential static pressure motive force.Utilize the molecular weight difference of separated material that it is separated, small-molecule substance sees through film, and macromolecular substances is trapped, the purpose of reach purification, separating and concentrating.Hyperfiltration technique is mainly used in and separates macromolecular compound (protein, nucleic acid polymers, enzyme etc.), colloidal dispersion (clay, pigment, mineral material etc.), emulsion (lubricating grease, washing agent, oil hydrosol etc.) from liquid phase substance.Compare with separating technologies such as traditional rectifying, absorption, extractions, it has, and equipment volume is little, investment cost is low, technological process is simple, low power consumption and other advantages.In view of above-mentioned advantage, ultrafiltration all has application to a certain degree in food and dairy industry, pharmaceuticals industry, textile industry, chemical industry, metallurgical industry, paper industry, leather industry.
The main reason of restriction hyperfiltration technique extensive use is that the big molecule of particulate, colloidal particle or solute in the system for handling is at film surface absorption, deposition or plug-hole, cause film to pollute, increase the operating cost of hyperfiltration technique, but had a strong impact on the property row of hyperfiltration technique.Studies show that the phospholipid molecule in the cell membrane has good antifouling property, solute molecules such as protein are had repulsive force, can effectively reduce the suction-operated of solute molecule on the film surface.
Up to the present, in the middle of the membrane material commonly used, polyether sulfone (PES) has excellent physics and chemical stability, the mechanical strength height, and advantage such as filming performance is good has obtained application widely.But the polyether sulfone hydrophobicity is stronger, causes absorption or the deposition on the film surface such as protein easily, causes serious film to pollute, and causes that flux descends, and separative efficiency reduces.Several different methods in the document (chemical treatment modification method, low-temperature plasma modified method etc.) is applied to membrane surface modification, strengthens the antifouling property on film surface, but most method of modifying complicated operation, condition harshness.Discover and utilize bionic principle, the phospholipid molecule in the similar cell membrane is incorporated in the membrane material with the surface segregation method, can improve the hydrophily on film surface, and can effectively resist absorption of proteins.
Summary of the invention
The object of the present invention is to provide a kind of phospholipid modified poly (ether-sulfone) ultrafiltration membrane capable and preparation method of anti-protein-contamination.This milipore filter has good contamination resistance to protein molecule, and preparation method's process is simple.
The phospholipid modified poly (ether-sulfone) ultrafiltration membrane capable of a kind of anti-protein-contamination provided by the invention is to be raw material with phospholipid copolymers (MPC-BMA), polyether sulfone (PES) and polyethylene glycol (PEG2000), press mass fraction, phospholipid copolymers 0～4.8%, polyether sulfone 18%, prepare burden with polyethylene glycol 15%, its preparation method may further comprise the steps:
1) at the N of polyether sulfone (PES), in the dinethylformamide, the polyethylene glycol of adding adds phospholipid copolymers (MPC-BMA) then, stirs 4～6 hours down at 50～60 ℃, is mixed with the homogeneous phase casting solution;
2) casting solution was 50～60 ℃ of following discontinuous degassings 2～4 hours, after being cooled to room temperature casting solution is poured on knifing on the glass plate, place 10～30 seconds in the air after, put into 25 ℃ of water-bath freezing films again, spend water logging bubble 24～36 hours, obtain phospholipid modified milipore filter.
The preparation method of the phospholipid modified poly (ether-sulfone) ultrafiltration membrane capable of a kind of anti-protein-contamination provided by the invention may further comprise the steps:
1) polyether sulfone (PES) was dissolved in N, in the dinethylformamide after under 110 ℃～150 ℃ dry 10～15 hours, the adding molecular weight is 2000 polyethylene glycol, add phospholipid copolymers (MPC-BMA) then, stirred 5 hours down, be mixed with the homogeneous phase casting solution at 50-60 ℃;
2) casting solution that step 1) is made was 50-60 ℃ of following discontinuous degassing 2～4 hours, after being cooled to room temperature casting solution is poured on knifing on the glass plate, after in air, placing 10～30 seconds, put into 25 ℃ of water-bath freezing films again, soaked 24～36 hours with deionized water, obtain phospholipid modified milipore filter.
Described phospholipid copolymers (MPC-BMA) structural formula is suc as formula shown in (I)
(I) preparation method of compound is with 2-phosphatid ylcholine hydroxy-ethyl acrylate (MPC) and n-BMA (BMA) 3: 7 in molar ratio, be dissolved in the ethanol, pour the four-hole boiling flask that is equipped with agitator, condenser into, after feeding the interior oxygen of nitrogen discharger, add initator-azodiisobutyronitrile (AIBN), stirred 20 hours down at 60 ℃.After 20 hours liquid cools to room temperature poured into and obtain precipitation in the water, washing, the phospholipid copolymers that obtains (MPC-BMA) is standby through vacuum drying.Monomer concentration and AIBN concentration are respectively 0.5mol/l and 5.0mmol/l.
The invention has the advantages that: the film preparation process is simple, mild condition.Introduce the phosphatide group in the poly (ether sulfone) film material after, when the hydrophily of film strengthened, the contamination resistance of film increased substantially.
The specific embodiment
Embodiment 1
With 2 monophosphatide phatidylcholine hydroxy-ethyl acrylates (MPC) and n-BMA (BMA) 3: 7 in molar ratio, be dissolved in the ethanol, pour the four-hole boiling flask that is equipped with agitator, condenser into, after feeding the interior oxygen of nitrogen discharger, add initator---azodiisobutyronitrile (AIBN), stirred 20 hours down at 60 ℃.After 20 hours liquid cools to room temperature poured into and obtain precipitation in the water, cyclic washing, the phospholipid copolymers that obtains (MPC-BMA) is standby through vacuum drying.Monomer concentration and AIBN concentration are respectively 0.5mol/l and 5.0mmol/l.Take by weighing the 5.00g polyether sulfone, 4.17g polyethylene glycol, phospholipid copolymers (MPC-BMA) 0.32g and 18.55gN, dinethylformamide is put in the there-necked flask, put into 60 ℃ water bath with thermostatic control and heat, stir mixed in 4 hours after, 60 ℃ of following standing and defoaming 2～4 hours.After being cooled to room temperature casting solution is poured on knifing on the glass plate, in air, place 10～30 seconds after, put into the water-bath freezing film again, soaked 24～36 hours with deionized water, obtain the milipore filter of the required phospholipid polyalcohol modification of this experiment.
The milipore filter process scanning electron microscope analysis of prepared phospholipid polyalcohol modification, contact angle analysis and X-ray diffraction analysis, this film pore-forming performance is good, and fenestra is evenly distributed, and the phosphatide group is in film surface enrichment, good hydrophilic property.Be used to separate 1g/L bovine serum albumin(BSA) cushioning liquid, flux can maintain 228.3L/ (m
2H), rejection is 96%.After washed with de-ionized water, have 73% flux response rate, and flux still is in higher level after circular flow repeatedly.
Embodiment 2
With 2-phosphatid ylcholine hydroxy-ethyl acrylate (MPC) and n-BMA (BMA) 3: 7 in molar ratio, be dissolved in the ethanol, pour the four-hole boiling flask that is equipped with agitator, condenser into, after feeding the interior oxygen of nitrogen discharger, add initator---azodiisobutyronitrile (AIBN), stirred 20 hours down at 60 ℃.After 20 hours liquid cools to room temperature poured into and obtain precipitation in the water, cyclic washing, the phospholipid copolymers that obtains (MPC-BMA) is standby through vacuum drying.Monomer concentration and AIBN concentration are respectively 0.5mol/l and 5.0mmol/l.Take by weighing the 5.12g polyether sulfone, 4.27g polyethylene glycol, phospholipid copolymers (MPC-BMA) 0.64g and 18.91gN, dinethylformamide is put in the there-necked flask, put into 60 ℃ water bath with thermostatic control and heat, stir mixed in 4 hours after, 60 ℃ of following standing and defoaming 2～4 hours.After being cooled to room temperature casting solution is poured on knifing on the glass plate, in air, place 10～30 seconds after, put into the water-bath freezing film again, soaked 24～36 hours with deionized water, obtain the milipore filter of the required phospholipid polyalcohol modification of this experiment.
The milipore filter process scanning electron microscope analysis of prepared phospholipid polyalcohol modification, contact angle analysis and X-ray diffraction analysis, this film pore-forming performance is good, and fenestra is evenly distributed, and the phosphatide group is in film surface enrichment, good hydrophilic property.Be used to separate 1g/L bovine serum albumin(BSA) cushioning liquid, flux can maintain 238.0L/ (m
2H), rejection is 74%.After washed with de-ionized water, have 67% flux response rate, and flux still is in higher level after circular flow repeatedly.
Embodiment 3
With 2-phosphatid ylcholine hydroxy-ethyl acrylate (MPC) and n-BMA (BMA) 3: 7 in molar ratio, be dissolved in the ethanol, pour the four-hole boiling flask that is equipped with agitator, condenser into, after feeding the interior oxygen of nitrogen discharger, add initator---azodiisobutyronitrile (AIBN), stirred 20 hours down at 60 ℃.After 20 hours liquid cools to room temperature poured into and obtain precipitation in the water, cyclic washing, the phospholipid copolymers that obtains (MPC-BMA) is standby through vacuum drying.Monomer concentration and AIBN concentration are respectively 0.5mol/l and 5.0mmol/l.Take by weighing the 5.31g polyether sulfone, 4.42g polyethylene glycol, phospholipid copolymers (MPC-BMA) 0.96g and 19.47gN, dinethylformamide is put in the there-necked flask, put into 60 ℃ water bath with thermostatic control and heat, stir mixed in 4 hours after, 60 ℃ of following standing and defoaming 2～4 hours.After being cooled to room temperature casting solution is poured on knifing on the glass plate, in air, place 10～30 seconds after, put into the water-bath freezing film again, soaked 24～36 hours with deionized water, obtain the milipore filter of the required phospholipid polyalcohol modification of this experiment.
The milipore filter process scanning electron microscope analysis of prepared phospholipid polyalcohol modification, contact angle analysis and X-ray diffraction analysis, this film pore-forming performance is good, and fenestra is evenly distributed, and the phosphatide group is in film surface enrichment, good hydrophilic property.Be used to separate 1g/L bovine serum albumin(BSA) cushioning liquid, flux can maintain 245.0L/ (m
2H), rejection is 70%.After washed with de-ionized water, have 76% flux response rate, and flux still is in higher level after circular flow repeatedly.
Embodiment 4
With 2-phosphatid ylcholine hydroxy-ethyl acrylate (MPC) and n-BMA (BMA) 3: 7 in molar ratio, be dissolved in the ethanol, pour the four-hole boiling flask that is equipped with agitator, condenser into, after feeding the interior oxygen of nitrogen discharger, add initator---azodiisobutyronitrile (AIBN), stirred 20 hours down at 60 ℃.After 20 hours liquid cools to room temperature poured into and obtain precipitation in the water, cyclic washing, the phospholipid copolymers that obtains (MPC-BMA) is standby through vacuum drying.Monomer concentration and AIBN concentration are respectively 0.5mol/l and 5.0mmol/l.Take by weighing the 5.38g polyether sulfone, 4.49g polyethylene glycol, phospholipid copolymers (MPC-BMA) 1.5g and 19.57gN, dinethylformamide is put in the there-necked flask, put into 60 ℃ water bath with thermostatic control and heat, stir mixed in 4 hours after, 60 ℃ of following standing and defoaming 2～4 hours.After being cooled to room temperature casting solution is poured on knifing on the glass plate, in air, place 10～30 seconds after, put into the water-bath freezing film again, soaked 24～36 hours with deionized water, obtain the milipore filter of the required phospholipid polyalcohol modification of this experiment.
The milipore filter process scanning electron microscope analysis of prepared phospholipid polyalcohol modification, contact angle analysis and X-ray diffraction analysis, this film pore-forming performance is good, and fenestra is evenly distributed, and the phosphatide group is in film surface enrichment, good hydrophilic property.Be used to separate 1g/L bovine serum albumin(BSA) cushioning liquid, flux can maintain 255.5L/ (m
2H), rejection is 59%.After washed with de-ionized water, have 91% flux response rate, and flux still is in higher level after circular flow repeatedly.
Comparative Examples 1
Take by weighing the 5.00g polyether sulfone, 4.17g polyethylene glycol and 18.61g N, dinethylformamide is put in the there-necked flask, puts into 60 ℃ water bath with thermostatic control and heats, stir mixed in 4 hours after, 60 ℃ of following standing and defoaming 2～4 hours.After being cooled to room temperature casting solution is poured on knifing on the glass plate, in air, place 10～30 seconds after, put into the water-bath freezing film again, soaked 24～36 hours with deionized water, obtain the required poly (ether-sulfone) ultrafiltration membrane of this experiment.Be used to separate 1g/L bovine serum albumin(BSA) cushioning liquid, flux is 203.3L/ (m
2H), rejection is 99%.After washed with de-ionized water, has 57% flux response rate.
Table 1 is depicted as the prepared film 1 of embodiment, film 2, and film 3, the ultra-filtration and separation of film 4 and Comparative Examples 1 prepared film 5 concentrates the stalling characteristic of 1g/L bovine serum albumin(BSA) cushioning liquid.
Table 1
Claims (4)
1, a kind of phospholipid modified poly (ether-sulfone) ultrafiltration membrane capable of anti-protein-contamination is characterized in that may further comprise the steps:
A kind of phospholipid modified poly (ether-sulfone) ultrafiltration membrane capable of anti-protein-contamination is to be raw material with phospholipid copolymers, polyether sulfone and polyethylene glycol, press mass fraction, phospholipid copolymers 0～4.8%, polyether sulfone 18%, prepare burden with polyethylene glycol 15%, its preparation method may further comprise the steps:
1) at the N of polyether sulfone, in the dinethylformamide, the polyethylene glycol of adding adds phospholipid copolymers then, stirs 5 hours down at 50～60 ℃, is mixed with the homogeneous phase casting solution;
2) casting solution was 50～60 ℃ of following discontinuous degassings 2～4 hours, after being cooled to room temperature casting solution is poured on knifing on the glass plate, place 10～30 seconds in the air after, put into 25 ℃ of water-bath freezing films again, spend water logging bubble 24～36 hours, obtain phospholipid modified milipore filter.
2, the preparation method of the phospholipid modified poly (ether-sulfone) ultrafiltration membrane capable of the described anti-protein-contamination of claim 1 is characterized in that may further comprise the steps:
1) polyether sulfone was dissolved in N after under 110 ℃～150 ℃ dry 12 hours, and in the dinethylformamide, the adding molecular weight is 2000 polyethylene glycol, adds phospholipid copolymers then, stirs 4～6 hours down at 50～60 ℃, is mixed with the homogeneous phase casting solution;
2) casting solution that step 1) is made was 50～60 ℃ of following discontinuous degassings 2～4 hours, after being cooled to room temperature casting solution is poured on knifing on the glass plate, after in air, placing 10～30 seconds, put into 25 ℃ of water-bath freezing films again, soaked 24～36 hours with deionized water, obtain the thick phospholipid modified milipore filter of 240 μ m.
3, according to the described preparation method of claim 2, the preparation method who it is characterized in that described phospholipid copolymers was: with 2-phosphatid ylcholine hydroxy-ethyl acrylate and n-BMA comonomer 3: 7 in molar ratio, be dissolved in the ethanol, pour the four-hole boiling flask that is equipped with agitator, condenser into, after feeding the interior oxygen of nitrogen discharger, add initator-azodiisobutyronitrile, after 60 ℃ are down stirred 20 hours, liquid cools to room temperature poured into and obtain precipitation in the water, washing, the phospholipid copolymers that obtains.Standby through vacuum drying.
4,, it is characterized in that described monomer concentration and AIBN concentration are respectively 0.5mol/l and 5.0mmol/l according to the described preparation method of claim 3.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102258947A (en) * | 2011-05-23 | 2011-11-30 | 苏州市新能膜材料科技有限公司 | Lecithin self-assembly cross-linking bionic modified polymer membrane material and preparation method thereof |
| CN104209014A (en) * | 2013-06-04 | 2014-12-17 | 中国石油天然气股份有限公司 | Biological pollution resistant porous membrane and preparation method thereof |
| CN106861437A (en) * | 2017-03-28 | 2017-06-20 | 天津大学 | A kind of preparation method of stabilization high-flux ultra-filtration membrane |
| CN109055294A (en) * | 2018-09-16 | 2018-12-21 | 苏州怡彼得生物技术有限公司 | A kind of cell culture artificial cell membrane's coating microcarrier and preparation method thereof |
| CN109351194A (en) * | 2018-11-02 | 2019-02-19 | 苏州立升净水科技有限公司 | The method of the membrane flux of ultrafiltration membrane preservative agent and raising ultrafiltration membrane |
| CN115920676A (en) * | 2022-12-07 | 2023-04-07 | 中复新水源科技有限公司 | Preparation method of polyimide composite nanofiltration membrane |
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- 2007-12-19 CN CNA2007100603653A patent/CN101259386A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102258947A (en) * | 2011-05-23 | 2011-11-30 | 苏州市新能膜材料科技有限公司 | Lecithin self-assembly cross-linking bionic modified polymer membrane material and preparation method thereof |
| CN104209014A (en) * | 2013-06-04 | 2014-12-17 | 中国石油天然气股份有限公司 | Biological pollution resistant porous membrane and preparation method thereof |
| CN106861437A (en) * | 2017-03-28 | 2017-06-20 | 天津大学 | A kind of preparation method of stabilization high-flux ultra-filtration membrane |
| CN106861437B (en) * | 2017-03-28 | 2019-12-20 | 天津大学 | Preparation method of stable high-flux ultrafiltration membrane |
| CN109055294A (en) * | 2018-09-16 | 2018-12-21 | 苏州怡彼得生物技术有限公司 | A kind of cell culture artificial cell membrane's coating microcarrier and preparation method thereof |
| CN109351194A (en) * | 2018-11-02 | 2019-02-19 | 苏州立升净水科技有限公司 | The method of the membrane flux of ultrafiltration membrane preservative agent and raising ultrafiltration membrane |
| CN109351194B (en) * | 2018-11-02 | 2021-08-06 | 苏州立升净水科技有限公司 | Ultrafiltration membrane preservative and method for improving membrane flux of ultrafiltration membrane |
| CN115920676A (en) * | 2022-12-07 | 2023-04-07 | 中复新水源科技有限公司 | Preparation method of polyimide composite nanofiltration membrane |
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