CN103055725B - Heparan polyurethane blended modified polyethersulfone hollow fiber membrane and preparation method and application thereof - Google Patents
Heparan polyurethane blended modified polyethersulfone hollow fiber membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a heparan polyurethane blended modified polyethersulfone hollow fiber membrane. The preparation method is characterized by comprising the following steps of: adding 10 to 25 weight parts of diphenylmethane diisocyanate, 5 to 13 weight parts of dimethylolpropionic acid and 62 to 85 weight parts of solvent into a dissolving kettle, performing reaction for 4 to 12 hours at a temperature of 70 to 90 DEG C, washing the product with methanol and distilled water and drying to obtain carboxyl-containing polyurethane; adding 10 weight parts of polyurethane into 100 weight parts of concentrated sulfuric acid to carry out sulfonation to obtain polyurethane containing carboxyl and a sulfonic acid group; adding 1 to 10 weight parts of heparan polyurethane, 10 to 25 weight parts of polyethersulfone and 70 to 89 weight parts of solvent into the dissolving kettle to dissolve for 2 to 24 hours at a temperature of 75 to 95 DEG C so as to obtain hollow fiber membrane spinning dope; and preparing the hollow fiber membrane with excellent blood compatibility, permanent hydrophilicity, capacity of resisting to protein pollution and an anticoagulation function by adopting a dry spraying and wet spinning technology.
Description
Technical field
The present invention relates to a kind of heparan polyurethane comixing modified poly (ether-sulfone) hollow-fibre membrane and its production and use, belong to functional high molecule material and preparation field thereof.
Background technology
Polyether sulfone (Polyethersulfone is called for short PES) material is first to succeed in developing and commercial a kind of special engineering plastics in 1972 Nian You Britain ICI companies, and its trade mark is " Victrex PES ".PES is because its vitrification point is high, and materialization good stability, is a kind of engineering speciality polymer material of excellent performance.Polyether sulfone is prepared into flat sheet membrane or hollow-fibre membrane, the existing a lot of reports in the fields such as blood purification and water treatment that are applied to, but utilize heparan polyurethane to carry out modification to poly (ether sulfone) film, improve the blood compatibility of membrane material, there is no so far research report and product both at home and abroad and come out.
Polyether sulfone or PS membrane are carried out to modification a lot of to improve film research report of biocompatibility in blood purification application, mainly comprise three major types method (Zhao CS et al., Progress in Materials Science, 2013,58:76 – 150): (1) body modification, polyether sulfone materials body is carried out to modification, afterwards film forming; (2) surface modification, by chemical method, photochemical method (as ultraviolet irradiation) or plasma technique at film surface grafting hydrophilic macromolecule or bioactive macromolecule, as PEG, PVP; Or by physical method face coat hydrophilic macromolecule.(3) blend method, as blended polyethylene pyrrolidones (PVP), polyethylene glycol (PEG), phospholipid polymer (MPC), polyethylene glycol oxide (PEO), or bioactive macromolecule DNA;
In to the modification of polyether sulfone or PS membrane, most grafting methods that adopt.Although grafting is very effective to improving biocompatibility, also impracticable for some method of modification of hollow-fibre membrane.Because the hollow-fibre membrane less to diameter (if haemodialysis is with being generally 0.2 millimeter, i.e. 200 μ m) be difficult to by as photochemical method at other molecule of film inwall grafting.And blend method not only can carry out modification to hollow-fibre membrane, and there is practical value.The people such as Zhu LP (ACTA Polymerica Sinica, 2008,4:309) just adopt the principle of MOLECULE DESIGN to synthesize serial amphipathy macromolecule in order to modified membrane, the hydrophily of modification caudacoria and contamination resistance are all improved.The people such as Rahimpour (Journal of Membrane Science, 2008,311 (1-2): 349) adopt the method for polycondensation to synthesize poly-(amino-acid imide) in order to blending and modifying PES membrane material, the water flux of modification caudacoria and anti-protein contamination ability are all improved.People (the Journal of Membrane Science such as the Wang YQ of University Of Tianjin, 2006,283 (1-2): 440) synthesized polypropylene glycol and oxirane addition polymers (polyethers) in order to modified PES film, made the hydrophily of modification caudacoria and anti-protein contamination ability all obtain raising.People (the Journalof Colloid and Interface Science such as Wang M and for example, 2006,300 (1): 286) synthesized poly-(acrylonitrile (AN)-(diacrylamine base)-dimethyl propylene alkyl sulfonic acid (AM PS) copolymer), then using it as additive blending and modifying phenolic polyether sulphone film, obtained charged membrane.The people such as Matsuura (Desalination, 2002,149:303; Journal of Environmental Engineering-ASCE, 2004,130 (12): 1450) synthesized a kind of large molecule (SMM) of surface modification in order to modified PES film, make film modification after contamination resistance significantly improve.More than report is mainly hydrophily and the anti-protein contamination ability for film, and anticoagulant functions when film is applied to blood purification does not significantly improve, or does not at least relate to the anticoagulation function of film.And synthetic need to improve for the polymer of Modified Membrane and the compatibility of PES.
Summary of the invention
Primary and foremost purpose of the present invention is to provide a kind of heparan polyurethane comixing modified poly (ether-sulfone) hollow-fibre membrane and its production and use for the deficiencies in the prior art.Be characterized in utilizing the anticoagulation function of heparin functional group, the polyurethane of synthetic a kind of heparan, adopt the polyurethane comixing modified poly (ether-sulfone) hollow-fibre membrane containing sulfonic acid group and carboxyl, the poly (ether sulfone) film material of this blending and modifying has permanent hydrophilic (pure water contact angle is at 50～65 °), anti-protein contamination ability and excellent blood compatibility.
Object of the present invention is realized by following technical measures, and wherein said raw material umber, except specified otherwise, is parts by weight.
The chemical reaction structural formula of heparan polyurethane comixing modified poly (ether-sulfone) hollow-fibre membrane is:
In formula, n is 5 ~ 200.
The initiation material of heparan polyurethane comixing modified poly (ether-sulfone) hollow-fibre membrane is composed of the following components:
1) initiation material of heparan polyurethane is
10～25 parts of methyl diphenylene diisocyanates
5～13 parts of dihydromethyl propionic acids
62～85 parts of solvents
2) raw material of hollow-fibre membrane stoste is
1～10 part of heparan polyurethane
10～25 parts of polyether sulfones
70～89 parts of solvents.
The preparation method of heparan polyurethane comixing modified poly (ether-sulfone) hollow-fibre membrane comprises the following steps:
1) preparation of heparan polyurethane
(1) by 10～25 parts of methyl diphenylene diisocyanates, preferably 15 ~ 20 parts, 5～13 parts of dihydromethyl propionic acids, preferably 8 ~ 11 parts, 62～85 parts of solvents, add with agitator, in the dissolution kettle of temperature and reflux condenser, under agitation in 70～90 ℃ of reaction 4～12h of temperature, methyl alcohol and distilled water washing for product, dry, obtain carboxylic polyurethane;
(2) by 10 parts of the carboxylic polyurethane of (1) step gained, add 100 parts of concentrated sulfuric acids, carry out sulfonation, obtain precipitating with distilled water containing the polyurethane reaction liquid of carboxyl and sulfonic acid group, then drying, obtain faint yellow opaque hard containing carboxyl and sulfonic heparan polyurethane;
2) preparation of hollow-fibre membrane stoste
By 1～10 part of above-mentioned heparan polyurethane, preferably 3 ~ 8 parts, 10～25 parts of polyether sulfones, preferably 15 ~ 20 parts, 70～89 parts of solvents, add in the dissolution kettle with agitator, thermometer and reflux condenser, under agitation in 75 ~ 95 ℃, dissolve 2-24h, make polyether sulfone solution, deaeration, placement " slaking " make hollow-fibre membrane spinning solution.
3) preparation of hollow-fibre membrane
By the press filtration of hollow-fibre membrane spinning solution, with measuring pump, through two concentrically ringed doughnut spinning heads, to extrude, spinning solution extruded velocity is 3～10ml/min; As-spun fibre in air after 8 ~ 40cm distance in 20 ~ 50 ℃ of water-baths of temperature coagulation forming; Through plasticizing-bath drawing-off, reel, speed is 8 ~ 50m/min again, obtains polyether sulphone hollow fibre film, and its internal diameter is 200～1000 μ m, and wall thickness is 50～500 μ m.Hollow-fibre membrane, at 50～60 ℃ of poach 8 ~ 72h of temperature, is removed residual solvent.
In described hollow-fibre membrane, the number-average molecular weight of polyether sulfone is 20000～60000.
Described solvent is 1-METHYLPYRROLIDONE, any in dimethyl formamide or dimethylacetylamide.
Described heparan polyurethane comixing modified poly (ether-sulfone) hollow-fibre membrane is made filter, for blood purification, comprises small throughput haemodialysis, high flux hemodialysis, blood filtration and plasma separation.
Performance test:
Modified poly (ether-sulfone) hollow-fibre membrane prepared by the present invention, the aperture of membranous wall is 0.005～0.4 μ m, pure water ultrafiltrate coefficient 20～3000ml/m
2.h.mmHg, pure water contact angle is at 50～65 °, and albumin rejection is 0～100%, maximum tolerable pressure 760mmHg.And the method for testing of these performance indications is referring to document: Zou W et.al., Journal of Membrane Science, 2010,358:76.
Tool of the present invention has the following advantages:
The materialization good stability of the modified poly (ether-sulfone) doughnut membrane material that 1, the present invention makes, acid-alkali-corrosive-resisting; Because water insoluble containing carboxyl and sulfonic polyurethane, after blend, in poly (ether sulfone) film, be also just difficult for separating out, there is permanent hydrophilic (pure water contact angle is at 50～65 °), anti-protein contamination ability and excellent blood compatibility,
2, blending modified polyether sulphone (PES) hollow-fibre membrane and the polyether sulphone hollow fibre film comparison that there is no modification, the polyether sulphone hollow fibre film protein solution flux response rate of modification rises to more than 90% from 50%; Albumin absorption is from 20 μ g/cm
2be reduced to 5 μ g/cm
2; More than activated partial prothrombin time is increased to 100s from 50s, thereby, can well be applied to blood purification field.
3, preparation method provided by the invention is simple, easy to operate, easily realizes industrialization.
The specific embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this present embodiment is only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
Embodiment 1.
By 10 parts of methyl diphenylene diisocyanates, 5 parts of dihydromethyl propionic acids, 85 parts of 1-METHYLPYRROLIDONEs, add with agitator, in the dissolution kettle of temperature and reflux condenser, under agitation in 85 ℃ of reaction 6h of temperature, methyl alcohol and distilled water washing for product, dry, obtain containing carboxyl polyurethane; To add 100 parts of concentrated sulfuric acids to carry out sulfonation containing 10 parts of carboxyl polyurethane, distilled water washing afterwards, dry, obtains containing carboxyl and sulfonic group polyurethane; Again will be containing 10 parts of carboxyl and sulfonic group polyurethane, 15 parts of polyether sulfones, 75 parts of 1-METHYLPYRROLIDONEs, put into dissolution kettle, under agitation in 85 ℃ of temperature, dissolve 24h, make polyether sulfone solution; After filtration, deaeration, placement " slaking ", make polyether sulfone spinning solution.
By the press filtration of polyether sulfone spinning solution, and extrude through two concentrically ringed doughnut spinning heads with measuring pump, spinning solution extruded velocity is 5ml/min; As-spun fibre in air after 20cm distance in 35 ℃ of water-baths of temperature coagulation forming; Through plasticizing-bath drawing-off, reel, speed is 10m/min again, obtains polyether sulphone hollow fibre film, and its internal diameter is 800 μ m, and wall thickness is 80 μ m.Hollow-fibre membrane is processed 10h in temperature 50 C water, removes residual solvent and initator.Cut off fiber is isometric, tie up bunchy, with casting glue embedding, dress up filter.Pure water ultrafiltrate coefficient 200ml/m
2.h.mmHg, filter after albumin solution, the response rate of pure water flux is 92%, and the part prothrombin activating time (APTT) increases by 125%.
Embodiment 2.
By 10 parts of methyl diphenylene diisocyanates, 5 parts of dihydromethyl propionic acids, 85 parts of 1-METHYLPYRROLIDONEs, add with agitator, in the dissolution kettle of temperature and reflux condenser, under agitation in 85 ℃ of reaction 6h of temperature, methyl alcohol and distilled water washing for product, dry, obtain containing carboxyl polyurethane; To add 100 parts of concentrated sulfuric acids to carry out sulfonation containing 10 parts of carboxyl polyurethane, distilled water washing afterwards, dry, obtain containing carboxyl and sulfonic group polyurethane; Obtain containing carboxyl and sulfonic group polyurethane; Again will be containing 5 parts of carboxyl and sulfonic group polyurethane, 85 parts of 10 parts of polyether sulfones and 1-METHYLPYRROLIDONEs are put into dissolution kettle, under agitation in 75 ℃ of temperature, dissolve 20h, make polyether sulfone solution; After filtration, deaeration, placement " slaking ", make polyether sulfone spinning solution.
By the press filtration of polyether sulfone spinning solution, and extrude through two concentrically ringed doughnut spinning heads with measuring pump, spinning solution extruded velocity is 6ml/min; As-spun fibre in air after 20cm distance in 35 ℃ of water-baths of temperature coagulation forming; Through plasticizing-bath drawing-off, reel, speed is 15m/min again, obtains polyether sulphone hollow fibre film, and its internal diameter is 800 μ m, and wall thickness is 60 μ m.Hollow-fibre membrane is processed 10h in temperature 50 C water, removes residual solvent and initator etc.Cut off fiber is isometric, tie up bunchy, with casting glue embedding, dress up filter.Pure water ultrafiltrate coefficient 150ml/m
2.h.mmHg, filter after albumin solution, the response rate of pure water flux is 98%, and the part prothrombin activating time (APTT) increases by 150%.
Embodiment 3.
By 15 parts of methyl diphenylene diisocyanates, 8 parts of dihydromethyl propionic acids, 77 parts of dimethylacetylamides, add with agitator, in the dissolution kettle of temperature and reflux condenser, under agitation in temperature 70 C reaction 12h, methyl alcohol and distilled water washing for product, dry, obtain containing carboxyl polyurethane; To add 100 parts of concentrated sulfuric acids to carry out sulfonation containing 10 parts of carboxyl polyurethane, distilled water washing afterwards, dry.Obtain containing carboxyl and sulfonic group polyurethane; Again will be containing 10 parts of carboxyl and sulfonic group polyurethane, 75 parts of 15 parts of polyether sulfones and dimethylacetylamides are put into dissolution kettle, under agitation in 90 ℃ of temperature, dissolve 8h, make polyether sulfone solution; After filtration, deaeration, placement " slaking ", make polyether sulfone spinning solution.
By the press filtration of polyether sulfone spinning solution, and with measuring pump, through two concentrically ringed doughnut spinning heads, extrude spinning solution extruded velocity 4ml/min; As-spun fibre in air after 20cm distance in 35 ℃ of water-baths of temperature coagulation forming; Through plasticizing-bath drawing-off, reel, speed is 20m/min again, obtains polyether sulphone hollow fibre film, and its internal diameter is 300 μ m, and wall thickness is 60 μ m.Hollow-fibre membrane is processed 10h in temperature 50 C water, removes residual solvent and initator etc.Cut off fiber is isometric, tie up bunchy, with casting glue embedding, dress up filter.Pure water ultrafiltrate coefficient 250ml/m
2.h.mmHg, filter after albumin solution, the response rate of pure water flux is 95%, and the part prothrombin activating time (APTT) increases by 150%.
Embodiment 4.
By 15 parts of methyl diphenylene diisocyanates, 8 parts of dihydromethyl propionic acids, 77 parts of dimethylacetylamides, add with agitator, in the dissolution kettle of temperature and reflux condenser, under agitation in 85 ℃ of reaction 4h of temperature, methyl alcohol and distilled water washing for product, dry, obtain containing carboxyl polyurethane; To add 100 parts of concentrated sulfuric acids to carry out sulfonation containing 10 parts of carboxyl polyurethane, distilled water washing afterwards, dry.Obtain containing carboxyl and sulfonic group polyurethane; Again will be containing 5 parts of carboxyl and sulfonic group polyurethane, 70 parts of 25 parts of polyether sulfones and 1-METHYLPYRROLIDONEs are put into dissolution kettle, under agitation in 95 ℃ of temperature, dissolve 20h, make polyether sulfone solution; After filtration, deaeration, placement " slaking ", make polyether sulfone spinning solution.
By the press filtration of polyether sulfone spinning solution, and extrude through two concentrically ringed doughnut spinning heads with measuring pump, spinning solution extruded velocity is 5ml/min; As-spun fibre in air after 20cm distance in 35 ℃ of water-baths of temperature coagulation forming; Through plasticizing-bath drawing-off, reel, speed 25m/min, obtains polyether sulphone hollow fibre film again, and its internal diameter is 250 μ m, and wall thickness is 40 μ m.Hollow-fibre membrane is processed 10 hours in temperature 50 C water, removes residual solvent and initator etc.Cut off fiber is isometric, tie up bunchy, with casting glue embedding, dress up filter.Pure water ultrafiltrate coefficient 100ml/m
2.h.mmHg, filter after albumin solution, the response rate of pure water flux is 95%, and the part prothrombin activating time (APTT) increases by 90%.
Embodiment 5.
By 20 parts of methyl diphenylene diisocyanates, 11 parts of dihydromethyl propionic acids, 69 parts of dimethyl formamides, add with agitator, in the dissolution kettle of temperature and reflux condenser, under agitation in 90 ℃ of reaction 4h of temperature, methyl alcohol and distilled water washing for product, dry, obtain containing carboxyl polyurethane; To add 100 parts of concentrated sulfuric acids to carry out sulfonation containing 10 parts of carboxyl polyurethane, distilled water washing afterwards, dry.Obtain containing carboxyl and sulfonic group polyurethane; Will be containing 1 part of carboxyl and sulfonic group polyurethane, 89 parts of 10 parts of polyether sulfones and 1-METHYLPYRROLIDONEs, put into dissolution kettle, under agitation in 95 ℃ of temperature, dissolves 2h, makes polyether sulfone solution; After filtration, deaeration, placement " slaking ", make polyether sulfone spinning solution.
By the press filtration of polyether sulfone spinning solution, and extrude through two concentrically ringed doughnut spinning heads with measuring pump, spinning solution extruded velocity is 5ml/min; As-spun fibre in air after 20cm distance in 35 ℃ of water-baths of temperature coagulation forming; Through plasticizing-bath drawing-off, reel, speed is 25m/min again, obtains polyether sulphone hollow fibre film, and its internal diameter is 280 μ m, and wall thickness is 50 μ m.Hollow-fibre membrane is processed 10 hours in temperature 50 C water, removes residual solvent and initator etc.Cut off fiber is isometric, tie up bunchy, with casting glue embedding, dress up filter.Pure water ultrafiltrate coefficient 80ml/m
2.h.mmHg, filter after albumin solution, the response rate of pure water flux is 92%, and the part prothrombin activating time (APTT) increases by 90%.
Embodiment 6.
By 25 parts of methyl diphenylene diisocyanates, 13 parts of dihydromethyl propionic acids, 62 parts of dimethyl formamides, add with agitator, in the dissolution kettle of temperature and reflux condenser, under agitation in 75 ℃ of reaction 10h of temperature, methyl alcohol and distilled water washing for product, dry, obtain containing carboxyl polyurethane; To add 100 parts of concentrated sulfuric acids to carry out sulfonation containing 10 parts of carboxyl polyurethane, distilled water washing afterwards, dry.Obtain containing carboxyl and sulfonic group polyurethane; Again will be containing 10 parts of carboxyl and sulfonic group polyurethane, 75 parts of 15 parts of polyether sulfones and dimethylacetylamides, put into dissolution kettle, under agitation in 80 ℃ of temperature, dissolves 10h, makes polyether sulfone solution; After filtration, deaeration, placement " slaking ", make polyether sulfone spinning solution.
By the press filtration of polyether sulfone spinning solution, and extrude through two concentrically ringed doughnut spinning heads with measuring pump, spinning solution extruded velocity is 5ml/min; As-spun fibre in air after 20cm distance in 35 ℃ of water-baths of temperature coagulation forming; Through plasticizing-bath drawing-off, reel, speed is 15m/min again, obtains polyether sulphone hollow fibre film, and its internal diameter is 450 μ m, and wall thickness is 60 μ m.Hollow-fibre membrane is processed 10h in temperature 50 C water, removes residual solvent and initator etc.Cut off fiber is isometric, tie up bunchy, with casting glue embedding, dress up filter.Pure water ultrafiltrate coefficient 300ml/m
2.h.mmHg, filter after albumin solution, the response rate of pure water flux is 95%, and the part prothrombin activating time (APTT) increases by 180%.
Claims (6)
1. a heparan polyurethane comixing modified poly (ether-sulfone) hollow-fibre membrane, is characterized in that the chemical reaction structural formula of this blending modified polyether sulphone (PES) is:
In formula, n is 5～200.
2. heparan polyurethane comixing modified poly (ether-sulfone) hollow-fibre membrane according to claim 1, is characterized in that the initiation material of this blending modified polyether sulphone (PES) hollow-fibre membrane is composed of the following components, is by weight:
1) initiation material of heparan polyurethane is
10～25 parts of methyl diphenylene diisocyanates
5～13 parts of dihydromethyl propionic acids
62～85 parts of solvents
2) raw material of hollow-fibre membrane stoste is
1～10 part of heparan polyurethane
10～25 parts of polyether sulfones
70～89 parts of solvents.
3. according to the preparation method of heparan polyurethane comixing modified poly (ether-sulfone) hollow-fibre membrane described in claim 1 or 2, it is characterized in that the method comprises the following steps:
1) preparation of heparan polyurethane
(1) count by weight, by 10～25 parts of methyl diphenylene diisocyanates, 5～13 parts of dihydromethyl propionic acids, 62～85 parts of solvents, add with agitator, in the dissolution kettle of thermometer and reflux condenser, under agitation in 70～90 ℃ of reaction 4～12h of temperature, methyl alcohol and distilled water washing for product, dry, obtain carboxylic polyurethane;
(2) by 10 parts of the polyurethane of (1) step gained, add 100 parts of concentrated sulfuric acids, carry out sulfonation, obtain precipitating with distilled water containing the polyurethane reaction liquid of carboxyl and sulfonic acid group, drying, obtains faint yellow opaque hard containing carboxyl and sulfonic heparan polyurethane;
3) preparation of hollow-fibre membrane spinning solution
By 1～10 part of above-mentioned heparan polyurethane, 10～25 parts of polyether sulfones, 70～89 parts of solvents, add in the dissolution kettle with agitator, thermometer and reflux condenser, under agitation in 75～95 ℃, dissolve 2～24h, make polyether sulfone solution, deaeration, placement " slaking ", make hollow-fibre membrane spinning solution;
4) spinning of hollow-fibre membrane
By the press filtration of polyether sulfone spinning solution, with measuring pump, through two concentrically ringed doughnut spinning heads, to extrude, spinning solution extruded velocity is 3～10ml/min; As-spun fibre in air after 8～40cm distance in 20～50 ℃ of water-baths of temperature coagulation forming; Through plasticizing-bath drawing-off, reel, speed is 8～50m/min again, obtains polyether sulphone hollow fibre film, and its internal diameter is 200～1000 μ m, and wall thickness is 50～500 μ m, and hollow-fibre membrane, at 50～60 ℃ of poach 8～72h of temperature, is removed residual solvent.
4. the preparation method of heparan polyurethane comixing modified poly (ether-sulfone) hollow-fibre membrane according to claim 3, the number-average molecular weight that it is characterized in that polyether sulfone in hollow-fibre membrane is 20000～60000.
5. the preparation method of heparan polyurethane comixing modified poly (ether-sulfone) hollow-fibre membrane according to claim 3, is characterized in that solvent is 1-METHYLPYRROLIDONE, any in dimethyl formamide or dimethylacetylamide.
6. the purposes of heparan polyurethane comixing modified poly (ether-sulfone) hollow-fibre membrane according to claim 1, it is characterized in that this heparin polyurethane comixing modified poly (ether-sulfone) hollow-fibre membrane makes filter, for blood purification, comprise small throughput haemodialysis, high flux hemodialysis, blood filtration and plasma separation.
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| CN103861484B (en) * | 2014-03-10 | 2016-03-02 | 石家庄达爱医疗器械科技有限公司 | Polyether sulphone hollow fibre film and preparation method thereof, haemodialyser |
| CN104984670A (en) * | 2015-06-24 | 2015-10-21 | 苏州乔纳森新材料科技有限公司 | Blood purification membrane and preparation method thereof |
| CN105013355B (en) * | 2015-06-30 | 2017-06-16 | 四川大学 | Heparan polyether sulphone hollow fibre film and preparation method thereof and purposes |
| CN108043251B (en) * | 2017-12-26 | 2020-12-18 | 中南大学湘雅医院 | Polysulfone or polyethersulfone dialysis membrane and preparation method thereof |
| CN108939957B (en) * | 2018-08-01 | 2020-11-27 | 中南大学湘雅医院 | Preparation method of Avacopan modified dialysis membrane |
| CN109316985B (en) * | 2018-11-07 | 2021-09-21 | 中南大学 | Sulfonated dihydroxypropyl chitosan modified polyurethane hemodialysis membrane and preparation method thereof |
| CN109316982B (en) * | 2018-11-07 | 2021-04-27 | 中南大学 | Heparinoid modified polyurethane/polyether sulfone blended hollow fiber membrane 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 |
| CN116284645B (en) * | 2021-12-20 | 2024-05-07 | 煤炭科学技术研究院有限公司 | Safe composite grouting reinforcement material with heat conduction function and preparation method |
| CN115120787B (en) * | 2022-06-30 | 2023-06-23 | 上海翊科聚合物科技有限公司 | Preparation method and application of hemodialysis composite membrane |
| CN116284671B (en) * | 2023-05-24 | 2023-08-08 | 苏州心锐医疗科技有限公司 | Heparin-like polyurethane with self-repairing performance and preparation method and application thereof |
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