CN101804307A - Anti-coagulation composite ultrafiltration membrane and preparation method thereof - Google Patents
Anti-coagulation composite ultrafiltration membrane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an anti-coagulation composite ultrafiltration membrane, which comprises a supporting layer, a polysulfone-based membrane layer and a sulfonated chitosan membrane layer, wherein the thicknesses of the supporting layer, the polysulfone-based membrane layer and the sulfonated chitosan membrane layer range from 30 to 100 micrometers; the thickness of the sulfonated chitosan membrane layer is between 0.01 and 0.5 micrometer, and the viscosity-average molecular weight of the sulfonated chitosan membrane layer is 30,000 to 300,000. The anti-coagulation composite ultrafiltration membrane of the invention is improved in membrane surface performance, hydrophily, mechanical strength and anti-coagulation performance, has high bioactivity, blood compatibility and anti-coagulation performance and uses a greatly reduced amount of or no heparin in a blood purification process. The membrane preparation process is simple and can realize industrial production.
Description
Technical field
The present invention relates to a kind of anti-coagulation composite ultrafiltration membrane and preparation method thereof, belong to the polymeric membrane technical field.
Background technology
Polysulfones is the engineering material of artificial synthetic in recent years a kind of superior performance, its excellent biological compatibility, have excellent mechanical property, characteristics such as heat-resisting, alkaline-resisting, corrosion-resistant simultaneously, and low price, be one of at present the most frequently used membrane material, prepared film is widely used in blood purification and handles.Yet,, take to add polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene glycol hydrophilic materials such as (PEG) both at home and abroad usually in order to improve the hydrophilicity of PS membrane because polysulfones belongs to the strong-hydrophobicity material.Can increase film to complement activation in the blood and add polyvinylpyrrolidone hydrophilic materials such as (PVP), owing to the activation degree can increase along with the increase of polyvinylpyrrolidone hydrophilic material content such as (PVP), thereby influence the intrinsic biocompatibility of PS membrane material, yet in long blood purification process, the composite film material of use often causes blood coagulation easily.At present, the method for taking to add heparin clinically usually improves the anticoagulation function of composite membrane.
Heparin is typical anticoagulation medicine, the condensation process that can stop blood, can be used for the formation of anti-tampon, heparin also has the clarification blood plasma lipide, reduces effects such as blood cholesterol levels and enhancing cancer therapy drug simultaneously, clinically be widely used as control thrombosis and embolism before and after the various operations, preclude blood is solidified and as the anti-coagulants of preserving new blood during blood transfusion.And heparin mainly be from internal organ such as mammiferous liver, lung, the heart, spleen, extract, refining forming, not only cost an arm and a leg, complex process, raw material sources be limited, and the side effect of the hemorrhagic tendency of causing arranged in animal body.Pharmaceutically to improve bioaffinity, improve curative effect of medication and will seek the similar material of molecular structure.Sulfated chitosan or sulfated chitosan are the products that shitosan and derivative thereof and sulfonated reagent reaction obtain, and its structure and heparin are similar, and the while also has the good anticoagulant property and the activity of reducing blood lipid, and is cheap.With having the highly blood coagulation resistant activity, the composite membrane that the good biocompatibility and the bio-medical material of biodegradability and synthetic material are made, comprehensive its advantage separately, remedy the deficiency of homogenous material performance, and reduce on being expected in the clinical blood purification process or do not use heparin, thereby thoroughly solve the anticoagulation problem, important in theory and practical significance are arranged, this also is international in recent years bio-medical material and the active hot research problem of medical domain.
Summary of the invention
The object of the present invention is to provide a kind of anti-coagulation composite ultrafiltration membrane and preparation method thereof with good biologically active, blood compatibility and anticoagulant property.
The present invention is that the technical scheme that achieves the above object is: a kind of anti-coagulation composite ultrafiltration membrane, it is characterized in that: comprise supporting layer, polysulfones base membrane layer and sulfated chitosan rete, the polysulfones base membrane layer is attached on the supporting layer, sulfated chitosan rete cross-linked graft is on the polysulfones base membrane layer, the thickness of supporting layer, polysulfones base membrane layer and sulfated chitosan rete is at the 30-100 micron, and the thickness of sulfated chitosan rete is between the 0.01-0.5 micron, and the viscosity average molecular weigh of sulfated chitosan rete is at 30000-300000.
The preparation method of anti-coagulation composite ultrafiltration membrane of the present invention, it is characterized in that: by mass percentage, with the pore-foaming agent of the polysulfones of 12-20%, 3-10% for and the organic solvent of 70-80% make preparation liquid after fully mixing, vacuum defoamation, preparation liquid is heated to 40-50 ℃, and the speed of preparation liquid with 50-140cm/min is coated on the supporting layer by knifing machine, sky exposes to the sun behind the 5-15s, the supporting layer that is coated with preparation liquid is immersed 40-50 ℃ solidify form compound film sheet in the bath water, compound film sheet is soaked in deionized water dry after 3-5 days with polysulfones base membrane layer; The sulfated chitosan that makes is dissolved in the deionized water by mass ratio 1: 20-250, filter screen with 3-5 micron filter core aperture filters sulfated chitosan solution, make active casting solution, under 40-60 ℃ of temperature, active casting solution is coated on the polysulfones base membrane layer of compound film sheet, behind the insulation 1-2h, diaphragm is soaked in temperature at 50～70 ℃, concentration is to carry out heat cross-linking 1-2h in the glutaraldehyde water solution of 0.2～1wt%, with sulfated chitosan rete cross-linked graft on the polysulfones base membrane layer, carry out rinsing with deionized water at last, can make anti-coagulation composite ultrafiltration membrane;
Wherein, above-mentioned sulfated chitosan makes according to the following steps:
(1), degradation of chitosan: in mass ratio with the shitosan of 5-10g and distilled water with 1: the 10-20 ratio drops in the container disperses, and water-bath is heated to 60-90 ℃, and dripping 0.5-1ml concentration in the stirring in 0.5h is the 0.5-3%H of mass fraction
2O
2Stir 1-3h again and stop degradation reaction after the time, solution is carried out Separation of Solid and Liquid, the liquid phase substance that separation is obtained and concentration are that mass fraction 95% ethanol mixes and precipitates, and the mass ratio of liquid phase substance and ethanol is 1: 3-4, again through separate, washing and dehydration, 40-50 ℃ of vacuum drying, make the degrade chitosan thing, the deacetylation of degrade chitosan is at 75-100%, viscosity average molecular weigh 30000-300000;
(2), sulfated chitosan is synthetic: the degrade chitosan that makes is added in the reactor, the temperature of reaction is controlled at-5-2 ℃, by the 1g degrade chitosan: 8-12ml concentration is that the mass fraction 80-95% concentrated sulfuric acid adds in the reactor and stirs, under the heterogeneous reaction condition, reaction 2-4h obtains the milky thick liquid, is that 95% ethanol of mass fraction is purified with concentration again, through 40-50 ℃ of vacuum drying, make rough sulfated chitosan;
(3), the purifying of sulfated chitosan: the rough sulfated chitosan that will make is added to temperature by mass ratio 1: 5-7 to be mixed in-25--35 ℃ absolute ethyl alcohol, treat its complete post precipitation, with concentration is that the 90-95% ethanol of mass fraction washs, soaks into until its solution and be neutral, soaked into 5-10 hour with absolute ethyl alcohol again, after removing ethanol, with sediment vacuum drying under 40-50 ℃ of temperature, make the sulfated chitosan of viscosity average molecular weigh at 30000-300000.
The present invention has the following advantages after adopting technique scheme:
1, the present invention adopts polysulfones as the film base material material, keep advantages such as original polysulfones physical and chemical performance is stable, mechanical performance is good, acidproof, alkaline-resisting on the one hand, on the other hand since each construction unit of sulfated chitosan in all contain hydroxyl and amino, and have good hydrophilicity and under acid condition amino proton change into-NH
3 +And having the lotus electropositive, adsorbable bear electrochondria, and the particle of lotus positive electricity is had repulsive interaction makes hydrophilic film or has stronger anti-solute pollution capacity with the film of solute same sex electric charge.
2, the present invention adopts sulfated chitosan as one of membrane material, become the heparan structure to form brand-new being used for and the contacted bio-medical material of blood by chitosan material through chemical modification, direct and the contacted filtering layer of blood by the conduct of sulfated chitosan rete, because sulfated chitosan is the hydrophilic macromolecule natural macromolecular material, not only have excellent biological compatibility and anticoagulation function, and have degradable and an avirulence, to the harmless effect of human body cell, absorbed by cell degradation in vivo, and the anti-coagulation composite ultrafiltration membrane of its preparation not only physico-chemical property is stable, the mechanical strength height, have excellent clearance rate and anticoagulation function, and has good blood compatibility, less protein adsorption and minimum blood coagulation stimulate, to plurality of advantages such as complement activation is low, be that a kind of comparatively desirable cost is low, preparation equipment simply is used for the new material that blood purification is used.
3, the present invention adopts PS membrane as base membrane layer, again at its surface cross linking grafting sulfated chitosan rete, the bonding strength height between the rete not only, can be high temperature-resistant disinfected, number of chemical reagent or gamma-radiation sterilization, and blood compatibility is good, has reduced blood platelet and albuminous absorption, and the contamination resistance of composite membrane is greatly improved, significantly reduced heparin consumption in addition can inapplicable heparin, reduced the cost of blood purification.
4, preparation technology of the present invention is simple, the process serialization strong, good reproducibility, production cost are low, be easy to industrialized production.
Description of drawings
Below in conjunction with accompanying drawing embodiments of the invention are described in further detail.
Fig. 1 is a structural representation of the present invention.
Fig. 2 is anti-coagulation composite ultrafiltration membrane of the present invention and the PS membrane comparison diagram to medium and small molecule clearance rate.
Fig. 3 is a blood platelet dialysis front and back change curve behind the employing anti-coagulation composite ultrafiltration membrane of the present invention.
Wherein: 1-supporting layer, 2-polysulfones base membrane layer, 3-sulfated chitosan rete.
The specific embodiment
See shown in Figure 1, anti-coagulation composite ultrafiltration membrane of the present invention, comprise supporting layer, polysulfones base membrane layer and sulfated chitosan rete, the polysulfones base membrane layer is attached on the supporting layer, sulfated chitosan rete cross-linked graft is on the polysulfones base membrane layer, supporting layer, the thickness of polysulfones base membrane layer and sulfated chitosan rete is at the 30-100 micron, and the thickness of sulfated chitosan rete is between the 0.01-0.5 micron, the viscosity average molecular weigh of this sulfated chitosan rete is at 30000-300000, supporting layer of the present invention is a nonwoven, or adopting 200-300 purpose silk screen, this anti-coagulation composite ultrafiltration membrane has good biologically active, blood compatibility and anticoagulant property.
Sulfated chitosan of the present invention makes according to the following steps,
(1), degradation of chitosan: in mass ratio with the shitosan of 5-10g and distilled water with 1: the 10-20 ratio drops in the container disperses, and water-bath is heated to 60-90 ℃, and dripping 0.5-1ml concentration in the stirring in 0.5h is the 0.5-3%H of mass fraction
2O
2Stir 1-3h again and stop degradation reaction after the time, solution is carried out Separation of Solid and Liquid, the liquid phase substance that separation is obtained is after mass fraction 95% ethanol mixes with concentration and precipitates, and the mass ratio of liquid phase substance and ethanol is 1: 3-4, again through separating, wash and dehydration, can adopt absolute ethyl alcohol repeatedly to dewater, 40-50 ℃ of vacuum drying, vacuum can be controlled in-0.6-0.9bar, makes the degrade chitosan thing, and the deacetylation of degrade chitosan is at 75-100%, viscosity average molecular weigh 30000-300000, its yield is at 40-50%.Concrete parameter is shown in Table 1.
Table 1
(2), sulfated chitosan is synthetic: the degrade chitosan that makes is added in the reactor, the temperature of reaction is controlled at-5-2 ℃, by the 1g degrade chitosan: 8-12ml concentration is that the mass fraction 80-95% concentrated sulfuric acid adds in the reactor and stirs, under the heterogeneous reaction condition, reaction 2-4h, obtain the milky thick liquid, be that 95% ethanol of mass fraction is purified with concentration again, through 40-50 ℃ of vacuum drying to constant weight, vacuum can be controlled in-0.6-0.9bar, make rough sulfated chitosan, its conversion ratio is at 60-70%, and concrete parameter is shown in Table 2.
Table 2
(3), the purifying of sulfated chitosan: the rough sulfated chitosan that will make is added to temperature by mass ratio 1: 5-7 to be mixed in-25--35 ℃ absolute ethyl alcohol, treat its complete post precipitation, with concentration is that the 90-95% ethanol of mass fraction washs, infiltration is neutral until its solution, available ethanol cyclic washing and infiltration are neutral until its solution, soaked into 5-10 hour with absolute ethyl alcohol again, filter core aperture elimination ethanol with the 3-5 micron, after removing ethanol, with sediment vacuum drying under 40-50 ℃ of temperature, vacuum can be controlled in-0.6-0.9bar, make the sulfated chitosan of viscosity average molecular weigh at 30000-300000, its yield is at 80-95%, obtain required highly purified sulfated chitosan, concrete parameter is shown in Table 3, and it is standby that the sulfated chitosan that makes is put into drier.
Table 3
| Embodiment 1 | |
|
Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| The absolute ethyl alcohol temperature (℃) | ??-25 | ??-27 | ??-30 | ??-32 | ??-33 | ??-35 |
| Rough sulfated chitosan (g) | ??0.6 | ??0.62 | ??0.65 | ??0.67 | ??0.68 | ??0.7 |
| Absolute ethyl alcohol (g) | ??3 | ??3.2 | ??3.3 | ??3.5 | ??3.6 | ??4.9 |
| Infiltrating time (h) | ??5 | ??6 | ??7 | ??8 | ??9 | ??10 |
| The vacuum drying temperature (℃) | ??40 | ??42 | ??44 | ??46 | ??48 | ??50 |
| Vacuum (bar) | ??-0.6 | ??-0.7 | ??-0.8 | ??-0.8 | ??-0.8 | ??-0.9 |
The preparation method of anti-coagulation composite ultrafiltration membrane of the present invention, by mass percentage, polysulfones with 12-20%, the pore-foaming agent of 3-10% for and the organic solvent of 70-80% make preparation liquid after fully mixing, this organic solvent is the N-N-methyl-2-2-pyrrolidone N-, dimethyl formamide, dimethylacetylamide or methyl-sulfoxide one of them, after vacuum defoamation, preparation liquid is heated to 40-50 ℃, and the speed of preparation liquid with 50-140cm/min is coated on the supporting layer by knifing machine, this preparation liquid preferably is coated on the supporting layer with the speed of 60-120cm/min, sky exposes to the sun behind the 5-15s, the supporting layer that is coated with preparation liquid is immersed 40-50 ℃ solidify form compound film sheet in the bath water, compound film sheet is soaked in deionized water dry after 3-5 days with polysulfones base membrane layer; The sulfated chitosan that makes is dissolved in the deionized water by mass ratio 1: 20-250, filter screen with 3-5 micron filter core aperture filters sulfated chitosan solution, make active casting solution, under 40-60 ℃ of temperature, active casting solution is coated on the polysulfones base membrane layer of compound film sheet, behind the insulation 1-2h, the compound film sheet that will have active casting solution soaks in temperature at 50～70 ℃, concentration is to carry out heat cross-linking 1-2h in the glutaraldehyde water solution of 0.2～1wt%, with sulfated chitosan rete cross-linked graft on the polysulfones base membrane layer, carry out rinsing with deionized water at last, can make anti-coagulation composite ultrafiltration membrane of the present invention, preparation liquid and other parameter are shown in Table 4
Table 4
The thickness of anti-coagulation composite ultrafiltration membrane of the present invention is at the 30-100 micron, wherein the thickness of sulfated chitosan rete is between the 0.01-0.5 micron, anti-coagulation composite ultrafiltration membrane of the present invention is tested, see shown in Figure 2 with former polysulfones contrast, have the high performance clearance rate of medium and small molecule, see shown in Figure 3, no significant change before and after the blood platelet dialysis, and anticoagulation function with excellence.
Anti-coagulation composite ultrafiltration membrane of the present invention has improved the surface property of film, its hydrophilicity, mechanical strength and anticoagulation ability have been improved, be reduced in the use of heparin in the blood purification process greatly even can not use heparin, and filming technology is simple, can realize industrialized production.
Claims (5)
1. anti-coagulation composite ultrafiltration membrane, it is characterized in that: comprise supporting layer, polysulfones base membrane layer and sulfated chitosan rete, the polysulfones base membrane layer is attached on the supporting layer, sulfated chitosan rete cross-linked graft is on the polysulfones base membrane layer, the thickness of supporting layer, polysulfones base membrane layer and sulfated chitosan rete is at the 30-100 micron, and the thickness of sulfated chitosan rete is between the 0.01-0.5 micron, and the viscosity average molecular weigh of sulfated chitosan rete is at 30000-300000.
2. anti-coagulation composite ultrafiltration membrane according to claim 1 is characterized in that: described supporting layer is nonwoven or 200-300 purpose silk screen.
3. the preparation method of an anti-coagulation composite ultrafiltration membrane as claimed in claim 1, it is characterized in that: by mass percentage, polysulfones with 12-20%, the pore-foaming agent of 3-10% for and the organic solvent of 70-80% make preparation liquid after fully mixing, vacuum defoamation, preparation liquid is heated to 40-50 ℃, and the speed of preparation liquid with 50-140cm/min is coated on the supporting layer by knifing machine, sky exposes to the sun behind the 5-15s, the supporting layer that is coated with preparation liquid is immersed 40-50 ℃ solidify form compound film sheet in the bath water, compound film sheet is soaked in deionized water dry after 3-5 days with polysulfones base membrane layer; The sulfated chitosan that makes is dissolved in the deionized water by mass ratio 1: 20-250, filter screen with 3-5 micron filter core aperture filters sulfated chitosan solution, make active casting solution, under 40-60 ℃ of temperature, active casting solution is coated on the polysulfones base membrane layer of compound film sheet, behind the insulation 1-2h, diaphragm is soaked in temperature at 50～70 ℃, concentration is to carry out heat cross-linking 1-2h in the glutaraldehyde water solution of 0.2～1wt%, with sulfated chitosan rete cross-linked graft on the polysulfones base membrane layer, carry out rinsing with deionized water at last, can make anti-coagulation composite ultrafiltration membrane;
Wherein, above-mentioned sulfated chitosan makes according to the following steps:
(1), degradation of chitosan: in mass ratio with the shitosan of 5-10g and distilled water with 1: the 10-20 ratio drops in the container disperses, and water-bath is heated to 60-90 ℃, and dripping 0.5-1ml concentration in the stirring in 0.5h is the 0.5-3%H of mass fraction
2O
2Stir 1-3h again and stop degradation reaction after the time, solution is carried out Separation of Solid and Liquid, the liquid phase substance that separation is obtained and concentration are that mass fraction 95% ethanol mixes and precipitates, and the mass ratio of its liquid phase substance and ethanol is 1: 3-4, again through separate, washing and dehydration, 40-50 ℃ of vacuum drying, make the degrade chitosan thing, the deacetylation of degrade chitosan is at 75-100%, viscosity average molecular weigh 30000-300000;
(2), sulfated chitosan is synthetic: the degrade chitosan that makes is added in the reactor, the temperature of reaction is controlled at-5-2 ℃, by the 1g degrade chitosan: 8-12ml concentration is that the mass fraction 80-95% concentrated sulfuric acid adds in the reactor and stirs, under the heterogeneous reaction condition, reaction 2-4h obtains the milky thick liquid, is that 95% ethanol of mass fraction is purified with concentration again, through 40-50 ℃ of vacuum drying, make rough sulfated chitosan;
(3), the purifying of sulfated chitosan: the rough sulfated chitosan that will make is added to temperature by mass ratio 1: 5-7 to be mixed in-25--35 ℃ absolute ethyl alcohol, treat its complete post precipitation, with concentration is that the 90-95% ethanol of mass fraction washs, soaks into until its solution and be neutral, soaked into 5-10 hour with absolute ethyl alcohol again, after removing ethanol, with sediment vacuum drying under 40-50 ℃ of temperature, make the sulfated chitosan of viscosity average molecular weigh at 30000-300000.
4. the preparation method of anti-coagulation composite ultrafiltration membrane according to claim 2 is characterized in that, described organic solvent be N-N-methyl-2-2-pyrrolidone N-, dimethyl formamide, dimethylacetylamide or methyl-sulfoxide one of them.
5. the preparation method of anti-coagulation composite ultrafiltration membrane according to claim 2, it is characterized in that: described preparation liquid is coated on the supporting layer with the speed of 60-120cm/min.
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| CN103406033A (en) * | 2013-09-09 | 2013-11-27 | 南京大学 | Preparation method of chitosan-polysulfone hollow fiber membrane |
| CN105435660A (en) * | 2015-12-24 | 2016-03-30 | 中国科学院烟台海岸带研究所 | Anti-pollution composite multi-layer polymer separation membrane and preparation method thereof |
| CN106943901A (en) * | 2017-05-12 | 2017-07-14 | 中南大学 | Biocompatibility PS membrane that sulfonation hydroxypropyl chitosan is modified and preparation method thereof |
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| CN109316983A (en) * | 2018-11-07 | 2019-02-12 | 中南大学 | A kind of sulfonation dihydroxypropylchitosan modified polysulfone film and preparation method thereof |
| CN109603591A (en) * | 2019-01-18 | 2019-04-12 | 苏州君康医疗科技有限公司 | Anticoagulation composite hollow fiber membrane and preparation method |
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| CN110548426A (en) * | 2019-08-28 | 2019-12-10 | 陈泉学 | Coating process of ultrafiltration membrane |
| CN110756066A (en) * | 2019-11-25 | 2020-02-07 | 中南大学 | Sulfonated citric acid chitosan modified polysulfone hemodialysis membrane and preparation method thereof |
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| CN103406033A (en) * | 2013-09-09 | 2013-11-27 | 南京大学 | Preparation method of chitosan-polysulfone hollow fiber membrane |
| CN105435660A (en) * | 2015-12-24 | 2016-03-30 | 中国科学院烟台海岸带研究所 | Anti-pollution composite multi-layer polymer separation membrane and preparation method thereof |
| CN105435660B (en) * | 2015-12-24 | 2018-09-14 | 中国科学院烟台海岸带研究所 | A kind of antipollution composite multi-layer polymer separation film and preparation method thereof |
| CN106943901B (en) * | 2017-05-12 | 2019-05-21 | 中南大学 | The modified biocompatibility PS membrane and preparation method thereof of sulfonation hydroxypropyl chitosan |
| CN106943901A (en) * | 2017-05-12 | 2017-07-14 | 中南大学 | Biocompatibility PS membrane that sulfonation hydroxypropyl chitosan is modified and preparation method thereof |
| CN109316986B (en) * | 2018-11-07 | 2021-09-21 | 中南大学 | Acrylic acid and sulfonated dihydroxypropyl chitosan modified polysulfone membrane and preparation method thereof |
| CN109316983A (en) * | 2018-11-07 | 2019-02-12 | 中南大学 | A kind of sulfonation dihydroxypropylchitosan modified polysulfone film and preparation method thereof |
| CN109316983B (en) * | 2018-11-07 | 2021-01-15 | 中南大学 | Sulfonated dihydroxypropyl chitosan modified polysulfone membrane and preparation method thereof |
| CN109316986A (en) * | 2018-11-07 | 2019-02-12 | 中南大学 | A kind of acrylic acid and sulfonation dihydroxypropylchitosan modified polysulfone film and preparation method thereof |
| CN109603591A (en) * | 2019-01-18 | 2019-04-12 | 苏州君康医疗科技有限公司 | Anticoagulation composite hollow fiber membrane and preparation method |
| CN110280152A (en) * | 2019-06-25 | 2019-09-27 | 江苏立生血液净化科技有限公司 | Anticoagulation hemodialysis membrane and preparation method thereof |
| CN110548426A (en) * | 2019-08-28 | 2019-12-10 | 陈泉学 | Coating process of ultrafiltration membrane |
| CN110548426B (en) * | 2019-08-28 | 2022-04-01 | 陈泉学 | Coating process of ultrafiltration membrane |
| CN110756066A (en) * | 2019-11-25 | 2020-02-07 | 中南大学 | Sulfonated citric acid chitosan modified polysulfone hemodialysis membrane and preparation method thereof |
| CN110756066B (en) * | 2019-11-25 | 2021-09-21 | 中南大学 | Sulfonated citric acid chitosan modified polysulfone hemodialysis membrane and preparation method thereof |
| CN114561013A (en) * | 2022-04-28 | 2022-05-31 | 富海(东营)新材料科技有限公司 | Process for purifying polysulfone resin material by critical phase-change extraction method |
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