CN108939949B - Polyimide affinity membrane with high adsorption performance on bilirubin and preparation method thereof - Google Patents
Polyimide affinity membrane with high adsorption performance on bilirubin and preparation method thereof Download PDFInfo
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- CN108939949B CN108939949B CN201810780596.XA CN201810780596A CN108939949B CN 108939949 B CN108939949 B CN 108939949B CN 201810780596 A CN201810780596 A CN 201810780596A CN 108939949 B CN108939949 B CN 108939949B
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- polyimide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
Abstract
The invention belongs to the technical field of preparation of affinity membranes, and relates to a polyimide affinity membrane with high adsorption performance to bilirubin and a preparation method thereof. The invention adopts polyimide with a large amount of active carboxyl as a main membrane material, adopts a phase inversion method to prepare the polyimide membrane with a porous structure, and obtains the affinity membrane with a large amount of amino or hydroxyl through high-temperature crosslinking treatment. The invention is helpful to greatly simplify the preparation steps of the affinity membrane, simultaneously remarkably improve the density of active groups, keep higher permeation flux, and realize high-efficiency adsorption and separation of bilirubin, thereby realizing large-scale application. The method has simple process flow, and the prepared affinity membrane contains a large amount of amino or hydroxyl, so that the prepared polyimide affinity membrane has good bilirubin adsorption capacity, mechanical stability and chemical stability, and uniform membrane pore size, and the composite affinity membrane can be widely applied to the removal of bilirubin in blood.
Description
Technical Field
The invention belongs to the technical field of preparation of affinity membranes, and particularly relates to a preparation method of a high-flux porous affinity membrane with high adsorption performance on bilirubin.
Background
The separation process generally occupies 30-60% of the cost of biological separation, and biological macromolecules generally have biological activity, are sensitive to separation media, have poor thermal stability and low concentration and are difficult to purify. The affinity membrane technology is a novel separation technology combining membrane separation and affinity chromatography, feed liquid flows through membrane pores in a convection mode, and internal diffusion resistance is avoided, so that the operation speed can be improved to the maximum extent on the premise of not influencing adsorption binding action. Due to the outstanding advantages of affinity membrane separation technology, the application of the affinity membrane separation technology in the fields of biology, medicine, beverages and the like is deeply researched recently. Adsorption and flux of affinity membranes are key factors affecting membrane performance, and how to improve separation selectivity and permeation flux of the membranes becomes a hot point of research.
The processes of ultrafiltration, nanofiltration and reverse osmosis membrane preparation often use polyimide materials because of their high heat resistance, solvent resistance and chemical stability. Polyimide (P84) contains a large number of carboxyl groups in the molecule, has high reactivity, and can react with small molecules or single molecules containing amino or hydroxyl groups, so that high molecules with more affinity groups are obtained. At present, no affinity membrane for bilirubin separation is reported, which is prepared from a polyimide material and subjected to membrane modification by using a crosslinking agent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a polyimide affinity membrane which is easy to prepare. The invention adopts polyimide (P84) with a large amount of active carboxyl as a main membrane material, adopts a phase inversion method to prepare the polyimide membrane with a porous structure, and carries out high-temperature crosslinking treatment on commercial polyethylene glycol, polyethylene imine, 2, 4, 6-triaminopyrimidine, hexamethylenetetramine, Congo red and the like to obtain the affinity membrane with a large amount of amino or hydroxyl. The invention is helpful to greatly simplify the preparation steps of the affinity membrane, simultaneously remarkably improve the density of active groups, keep higher permeation flux, and realize high-efficiency adsorption and separation of bilirubin, thereby realizing large-scale application.
The technical scheme of the invention is as follows:
a polyimide affinity membrane with high adsorption performance to bilirubin has an asymmetric structure and comprises a separation and adsorption functional layer and a supporting layer, wherein the supporting layer is positioned below the separation and adsorption functional layer;
the separation and adsorption function layer is an ultrathin porous membrane formed by a phase inversion method, and the thickness of the separation and adsorption function layer is within 200 nm; the components of the ultrathin porous membrane comprise polyimide (p84), an additive, a cross-linking agent and a solvent;
the additive is one or more of nano silicon oxide, aluminum oxide, titanium oxide, ferroferric oxide, lanthanum strontium cobalt iron, a molecular sieve, graphene, polyethylene glycol, polyvinylpyrrolidone, graphene, inorganic salt such as lithium chloride, sodium chloride and sodium sulfate;
the cross-linking agent is one or a mixture of more than two of polyethylene glycol, polyethyleneimine, 2, 4, 6-triaminopyrimidine, hexamethylenetetramine and Congo red, and the mass percentage concentration of the cross-linking agent in the system is 0.2-5%;
the solvent is one or a mixture of more than two of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide;
the supporting layer is a polyester or polypropylene non-woven fabric, the thickness of the supporting layer is 50-500 mu m, and the pore diameter is 0.1-10 mu m.
A preparation method of a polyimide affinity membrane with high adsorption performance to bilirubin comprises the following steps:
(1) separation and adsorption functional layer for preparing porous affinity membrane
Adopting polyester or polypropylene non-woven fabric with nominal aperture of 0.1-10 microns as a base film; dissolving polyimide (p84) with the mass percent of 5-15% in a strong polar solvent to prepare a casting solution; then adding an additive with the total mass fraction of 0-8% to form a porous structure; stirring uniformly to obtain uniform polymer solution or dispersion, standing for defoaming, preparing a composite film on the non-woven fabric by adopting an immersion precipitation phase inversion method, and storing in deionized water;
(2) preparation of polyimide affinity membrane with adsorption and separation functions
Soaking the prepared composite membrane in 0.2-5% cross-linking agent water solution at 25-80 deg.C for 10-30 min to obtain polyimide affinity membrane with adsorption and separation functions, washing with deionized water, and storing.
The invention has the beneficial effects that: the method has simple process flow, and the prepared affinity membrane contains a large amount of amino or hydroxyl, so that the prepared polyimide affinity membrane has good bilirubin adsorption capacity, mechanical stability and chemical stability, the membrane aperture is uniform, and the composite affinity membrane can be widely applied to the removal of bilirubin in blood.
Detailed Description
The following further describes the specific embodiments of the present invention in combination with the technical solutions.
Example 1
5g of P84 is dissolved in 45g of N, N-dimethylformamide solution to prepare polyimide solution with the mass percent of 10%, membrane formation is carried out by adopting a phase inversion method, then deionized water is used for soaking, the polyimide solution is added into polyethylene glycol solution with the mass percent of 0.5% for crosslinking, and crosslinking is carried out for 30 minutes at the temperature of 50 ℃. The adsorption capacity of the prepared affinity membrane on 100mg/L bilirubin is 23mg/g, inFlux at 0.1MPa is 687L/m2h。
Example 2
6g P84 is dissolved in 49gN, N-dimethylformamide solution, 1g of lithium chloride is added to prepare polyimide solution with the mass percent of 12%, the polyimide solution is soaked in deionized water after film formation by a phase inversion method, the deionized water is added into 2, 4, 6-triaminopyrimidine solution with the mass percent of 0.5% to carry out crosslinking, and the crosslinking is carried out for 30 minutes at the temperature of 40 ℃. The prepared affinity membrane has an adsorption capacity of 42mg/g for 100mg/L bilirubin and a flux of 573L/m under 0.1MPa2h。
Example 3
6g P84 is dissolved in 49gN, N-dimethylformamide solution, and 1g of polyvinylpyrrolidone is added to prepare polyimide solution with the mass percent of 12%, the polyimide solution is soaked in deionized water after film formation by a phase inversion method, and then the polyimide solution is added into Congo red solution with the mass percent of 0.1% to be crosslinked, and the crosslinking is carried out for 30 minutes at the temperature of 50 ℃. The prepared affinity membrane has an adsorption capacity of 40mg/g for 50mL of 100mg/L bilirubin and a flux of 406L/m under 0.1MPa2h。
Claims (1)
1. A preparation method of a polyimide affinity membrane with high adsorption performance to bilirubin is characterized in that the polyimide affinity membrane with high adsorption performance to bilirubin has an asymmetric structure and comprises a separation and adsorption functional layer and a supporting layer, wherein the supporting layer is positioned below the separation and adsorption functional layer;
the separation and adsorption function layer is an ultrathin porous membrane formed by a phase inversion method, and the thickness of the separation and adsorption function layer is within 200 nm; the components of the ultrathin porous membrane comprise polyimide, an additive, a cross-linking agent and a solvent;
the polyimide is P84, and the molecule of the polyimide contains a large amount of reactive carboxyl groups;
the additive is one or more than two of nano silicon oxide, aluminum oxide, titanium oxide, ferroferric oxide, lanthanum strontium cobalt iron, a molecular sieve, graphene, polyethylene glycol, polyvinylpyrrolidone, lithium chloride, sodium chloride and sodium sulfate;
the cross-linking agent is one or a mixture of more than two of polyethylene glycol, polyethyleneimine, 2, 4, 6-triaminopyrimidine, hexamethylenetetramine and Congo red, and the mass percentage concentration of the cross-linking agent in the system is 0.2-5%;
the solvent is one or a mixture of more than two of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide;
the supporting layer is a polyester or polypropylene non-woven fabric, the thickness of the supporting layer is 50-500 mu m, and the pore diameter is 0.1-10 mu m;
the preparation method comprises the following steps:
(1) separation and adsorption functional layer for preparing porous affinity membrane
Adopting polyester or polypropylene non-woven fabric with nominal aperture of 0.1-10 microns as a base film; dissolving polyimide with the mass percent of 5-15% in a strong polar solvent to prepare a membrane casting solution; then adding an additive with the total mass fraction of 0-8% to form a porous structure; stirring uniformly to obtain a uniform polymer solution, standing for defoaming, preparing a composite membrane on the non-woven fabric by adopting an immersion precipitation phase inversion method, and storing in deionized water;
(2) preparation of polyimide affinity membrane with adsorption and separation functions
Soaking the prepared composite membrane in a cross-linking agent water solution for 10-30 minutes at an operation temperature of 25-80 ℃ to obtain the polyimide affinity membrane with the adsorption and separation functions, and finally washing the polyimide affinity membrane with deionized water for storage and use.
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| WO2014125298A1 (en) * | 2013-02-18 | 2014-08-21 | Fujifilm Manufacturing Europe Bv | Gas separation membranes |
| CN105709616A (en) * | 2016-03-09 | 2016-06-29 | 中国海洋大学 | Method for preparing organic-solvent-resistant ultrafiltration membrane, prepared ultrafiltration membrane and application of ultrafiltration membrane |
| CN106582318A (en) * | 2016-12-20 | 2017-04-26 | 南京工业大学 | Graphene oxide-modified organic solvent-resistant nanofiltration membrane, preparation method and application |
| CN107261869A (en) * | 2016-04-08 | 2017-10-20 | 财团法人纺织产业综合研究所 | Polyimide composition and method for producing separation membrane |
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| JPS57177303A (en) * | 1982-01-18 | 1982-11-01 | Nitto Electric Ind Co Ltd | Selective permeable film |
| US20030126990A1 (en) * | 2001-12-20 | 2003-07-10 | Koros William J. | Crosslinked and crosslinkable hollow fiber membrane and method of making same |
| CN100593520C (en) * | 2006-05-26 | 2010-03-10 | 中国科学院化学研究所 | Polyimide copolymer infiltration vaporization separation film for treating phenols-containing waste water and preparing method thereof |
| CN106890571A (en) * | 2017-03-06 | 2017-06-27 | 江苏凯米膜科技股份有限公司 | A kind of preparation method of organic tubular nanofiltration membrane |
| CN107469637A (en) * | 2017-07-14 | 2017-12-15 | 中国海洋大学 | A kind of preparation method of high flux solvent-resistant polyimide hybrid composite membrane |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014125298A1 (en) * | 2013-02-18 | 2014-08-21 | Fujifilm Manufacturing Europe Bv | Gas separation membranes |
| CN105709616A (en) * | 2016-03-09 | 2016-06-29 | 中国海洋大学 | Method for preparing organic-solvent-resistant ultrafiltration membrane, prepared ultrafiltration membrane and application of ultrafiltration membrane |
| CN107261869A (en) * | 2016-04-08 | 2017-10-20 | 财团法人纺织产业综合研究所 | Polyimide composition and method for producing separation membrane |
| CN106582318A (en) * | 2016-12-20 | 2017-04-26 | 南京工业大学 | Graphene oxide-modified organic solvent-resistant nanofiltration membrane, preparation method and application |
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