CN108939940B - Modified PVDF flat separation membrane with anticoagulation performance - Google Patents
Modified PVDF flat separation membrane with anticoagulation performance Download PDFInfo
- Publication number
- CN108939940B CN108939940B CN201810877651.7A CN201810877651A CN108939940B CN 108939940 B CN108939940 B CN 108939940B CN 201810877651 A CN201810877651 A CN 201810877651A CN 108939940 B CN108939940 B CN 108939940B
- Authority
- CN
- China
- Prior art keywords
- pvdf
- separation membrane
- membrane
- paa
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a modified PVDF flat separation membrane with anticoagulation performance, belonging to the technical field of membranes. The preparation method of the PVDF flat separation membrane comprises the following steps: (1) preparing polyacrylic acid grafted polyvinylidene fluoride copolymer PVDF-g-PAA; (2) preparing a PVDF-g-PAA flat separation membrane; (3) argatroban (argatroban) graft-modified PVDF-ARG membranes were prepared. The invention uses acrylic acid as a medium to modify the PVDF membrane by micromolecular argatroban with high-efficiency anticoagulation effect, so as to obtain the PVDF separation membrane material with good anticoagulation effect. Can obviously prolong the calcium recovery time of the membrane, obviously reduce the adhesion of platelet red blood cells on the surface of the membrane, reduce the hemolysis rate, improve the anticoagulation performance and greatly improve the blood compatibility. Has the characteristics of simple process, easy industrial implementation and the like.
Description
The present application is a divisional application of the following applications: the application date is 7/8/2014, the application number is 201410325836.9, and the invention is named as an anticoagulation PVDF flat plate separation membrane and a preparation method thereof.
Technical Field
The invention belongs to the technical field of membranes, and particularly relates to a modified PVDF flat separation membrane with anticoagulation performance.
Background
Cardiovascular diseases are one of the common diseases which seriously threaten human life and health nowadays, blood purification is an important means for treating the diseases, and a blood purifier is a commonly used instrument. The hemodialysis membrane is a core component of a purification filter, and currently, common hemodialysis membranes comprise polyether sulfone, cellulose, polyacrylonitrile and the like. Polyvinylidene fluoride (PVDF) is a high polymer material with excellent performance, and the outstanding chemical stability, radiation resistance, pollution resistance and heat resistance of the PVDF enable the PVDF to be widely applied to the field of membrane separation and be expected to become a potential hemodialysis membrane material. But the PVDF has poor blood compatibility due to the performance of the PVDF, and is easy to cause thrombus when in contact with blood.
Improving the hemocompatibility of PVDF membranes is critical in determining whether they can be hemodialysis materials. The method for improving the blood compatibility of the PVDF membrane mainly comprises the step of introducing functional groups including hydrophilic substances (such as polyethylene glycol, zwitter ions and the like) and monomers with an anticoagulation effect (such as heparin and phosphorylcholine) on the surface of the PVDF membrane. The functional groups are introduced mainly by membrane surface grafting and membrane bulk grafting. In order to prevent the membrane pore structure on the membrane surface from being damaged, many researchers select a membrane bulk grafting method to modify the PVDF membrane, which mainly includes Atom Transfer Radical Polymerization (ATRP), click chemistry, ozone pretreatment, alkali treatment, and the like. The alkali treatment method is the most simple and feasible method and has low cost.
The novel synthesized small molecular thrombin inhibitor, argatroban, can be quickly, selectively and reversibly combined with thrombin in a free state in blood, continuously inactivates the thrombin, blocks the positive feedback of a coagulation waterfall, and indirectly inhibits the generation of the thrombin and the generation of fibrin; thrombin capable of binding fibrinogen forms a polymer, inhibiting the progression of thrombosis; can inhibit thrombin mediated platelet aggregation and thromboxane A2(TXA2) The release of (2) activates the natural anticoagulant Protein C (PC) to play a strong anticoagulation and anti-thrombus role. The argatroban micromolecules are covalently grafted to the PVDF membrane, and the modification effect can be maintained for a long time.
Disclosure of Invention
Aiming at the problem that the existing PVDF membrane is contacted with blood to generate coagulation, the technical problem to be solved by the invention is to provide a modified PVDF flat separation membrane with anticoagulation performance. The invention utilizes argatroban to carry out graft modification on PVDF, and the modification method is an alkali liquor pretreatment method.
The preparation method of the anticoagulation PVDF flat separation membrane comprises the following steps: (1) preparing PVDF-g-PAA copolymer; 2) preparing a PVDF-g-PAA flat separation membrane; (3) argatroban (argatroban) graft-modified PVDF-ARG membranes were prepared.
The method for preparing the PVDF-g-PAA copolymer is an alkali liquor pretreatment method and comprises the following steps: pretreating PVDF powder with an alkali solution; adding PVDF powder treated by the alkali solution into a three-neck flask, adding N, N-dimethylformamide DMF, stirring and dissolving in water bath at 60-80 ℃, and introducing nitrogen; adding acrylic acid AA and an initiator azobisisobutyronitrile AIBN into a three-neck flask under the condition of introducing nitrogen, and continuously introducing nitrogen after dissolving; stirring and reacting for 8-12 hours to obtain PVDF-g-PAA copolymer; precipitating the reacted solution in excessive methanol, filtering, washing with distilled water, filtering, and washing repeatedly for several times until impurities are removed; drying in 60 deg.C oven.
Further, the method for preparing the PVDF-g-PAA copolymer comprises the following steps:
(1) preparing a potassium hydroxide solution, placing the solution in a constant-temperature water bath at 60 ℃, adding PVDF powder into the potassium hydroxide solution after 10min, adding absolute ethyl alcohol into the solution, stirring to fully disperse the PVDF powder in the solution, stirring for reaction for 10-20min, performing suction filtration, and repeatedly washing with distilled water to remove potassium fluoride and alkali liquor in a product; (2) weighing PVDF powder treated by an alkali solution, adding into a three-neck flask, adding N, N-Dimethylformamide (DMF), stirring and dissolving in water bath at 60-80 ℃, and introducing nitrogen for 30 min; adding acrylic acid AA and 0.1g of initiator Azobisisobutyronitrile (AIBN) into a three-neck flask under the condition of introducing nitrogen, continuously introducing nitrogen for 20 minutes after dissolving, and stirring for reacting for 8-12 hours to obtain PVDF-g-PAA copolymer; precipitating the reacted solution in excessive methanol, filtering, washing with distilled water to remove unreacted monomer, initiator and homopolymer, and drying to obtain the copolymer product in 60 deg.c oven.
The concentration of the potassium hydroxide solution is 2.5mol/L
The content of the PVDF powder in the potassium hydroxide solution in the step (1) is 100-150g/L
The addition amount of the absolute ethyl alcohol in the step (1) is 20-30ml/L
The content of the PVDF powder subjected to alkali treatment in the step (2) in a reaction system is 50-100g/L
The addition amount of AA in the step (2) is 0.5-1.5 times of the mass of the PVDF powder treated by alkali
In the step (2), the addition amount of AIBN is 1-3% of the mass of the PVDF powder subjected to alkali treatment
The preparation method of the PVDF-g-PAA flat separation membrane comprises the following steps: weighing a certain amount of PVDF-g-PAA copolymer powder and a pore-forming agent polyethylene glycol (PEG), putting the PVDF-g-PAA copolymer powder and the pore-forming agent polyethylene glycol (PEG) into a flask containing a certain amount of DMF, stirring and dissolving under the water bath heating condition of 60 ℃ to obtain a casting solution, and standing and defoaming for 10-12 h; pouring a small amount of casting film liquid on a glass plate, scraping the casting film liquid into a film by using a film scraping rod, soaking the glass plate into a coagulating bath at 25 ℃ for curing to form a film, placing the glass plate into distilled water for 72 hours after the film is formed and peeled off from the glass plate, and changing the water 2-3 times every day; and washing the membrane with distilled water to obtain the PVDF-g-PAA flat separation membrane.
The content of the PVDF-g-PAA copolymer in the casting film liquid is 10-20% (wt%).
The molecular weight of the PEG is 10000, and the addition amount of the PEG is 30-60% of the mass of the copolymer.
The coagulating bath is pure water.
The preparation method of the PVDF-ARG membrane comprises the following steps: soaking the PVDF-g-PAA plate separation membrane in 20ml of ethanol, adding 4- (4, 6-dimethoxytriazine-2-yl) -4-methylmorpholine hydrochloride (DMTMM) into the ethanol to activate carboxyl on the surface of the membrane, adding argatroban powder after activating for half an hour, reacting for 24 hours at normal temperature, taking out the membrane, washing with distilled water for 3-5 times, and washing to obtain the PVDF-ARG plate separation membrane.
The area of the membrane is 3 multiplied by 3cm2。
The mass ratio of DMTMM to argatroban is 1: 0.8-1: 1.5.
The concentration of the argatroban in ethanol is 10 mg/ml-20 mg/ml.
Advantageous effects
The invention modifies the PVDF membrane by using acrylic acid as a medium to the micromolecule argatroban with high-efficiency anticoagulation effect for the first time, so as to obtain the PVDF separation membrane material with good anticoagulation effect. The invention has the characteristics of simple process, easy industrial implementation and the like. The PVDF-ARG membrane prepared by the invention has the advantages of obviously prolonged calcium-restoring time, obviously reduced adhesion of platelet red blood cells and the like on the surface of the membrane, reduced hemolysis rate, improved anticoagulation performance and greatly improved blood compatibility. The PVDF-ARG membrane prepared by the invention can be further developed and utilized as a hemodialysis separation membrane material.
Detailed Description
The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1:
(1) alkali treatment of PVDF powder: preparing 2.5mol/L potassium hydroxide solution, pouring 400ml of the prepared potassium hydroxide solution into a flask, placing the flask into a constant-temperature water bath at 60 ℃, adding 60g of PVDF powder into the flask after half an hour, adding 12ml of absolute ethyl alcohol into a reaction system to fully disperse the PVDF in the system, stirring and reacting for 15min, carrying out suction filtration on the obtained product, washing the product for multiple times by using distilled water, and finally placing the washed powdery solid product into a 60 ℃ drying oven for drying for later use.
(2) Preparation of PVDF-g-PAA copolymer: 10g of PVDF powder after alkali treatment was weighed and added to a 250ml three-necked flask, and then 120ml of DMF solvent was added thereto, and the mixture was heated and stirred in a constant temperature water bath at 65 ℃ to be dissolved completely. Introducing nitrogen, weighing 10gAA and 0.2g of initiator AIBN, adding into the reaction system, and stirring and reacting for 12h in a nitrogen environment to obtain the PVDF-g-PAA copolymer. After the reaction is finished, precipitating the reaction solution by using about 250ml of methanol, filtering, repeatedly washing by using distilled water to remove unreacted monomers, initiators and homopolymers, finally pumping to dry, and putting the copolymerization product into a 60 ℃ oven to dry.
(3) Preparing a PVDF-g-PAA flat membrane: 6g of PVDF-g-PAA copolymer powder and 3g of PEG serving as a pore-forming agent are added into a flask containing 28.5g of DMF, the mixture is heated and stirred under the condition of water bath at 60 ℃ until the mixture is completely dissolved to obtain a casting solution, and the casting solution is kept stand and defoamed for 10 hours. Selecting distilled water as a coagulating bath, placing the coagulating bath in a constant-temperature water tank at 25 ℃, pouring a small amount of casting solution on a smooth and dry glass plate, scraping the glass plate by using a film scraping rod to form a film, quickly immersing the glass plate into the coagulating bath to solidify the film into the film, placing the film in the distilled water for 24 hours after the film falls off from the glass plate to remove residual solvent and pore-forming agent on the film, and finally washing the film by using the distilled water to obtain the copolymer flat film.
(4) Preparation of PVDF-ARG film: cutting PVDF-g-PAA flat plate separation membrane into 3 x 3cm2Soaking the membrane in 10ml of ethanol, adding 150mg of DMTMM into the ethanol to activate carboxyl on the surface of the membrane, adding 150mg of argatroban powder after half an hour, reacting for 24 hours at normal temperature, taking out the membrane, and washing the membrane with a large amount of distilled water to obtain the PVDF-ARG flat separation membrane.
Compared with a pure PVDF membrane, the prepared PVDF-ARG flat membrane has the advantages that the calcium recovery time is obviously prolonged, the platelet adhesion on the surface of the membrane is obviously reduced, the Activated Partial Thromboplastin Time (APTT) is obviously prolonged, and the anticoagulation performance is improved.
Example 2:
(1) alkali treatment of PVDF powder: the same as in example 1.
(2) Preparation of PVDF-g-PAA copolymer: 10g of PVDF powder after alkali treatment was weighed and added to a three-necked flask, and 120ml of DMF solvent was added thereto, and the mixture was heated and stirred in a constant-temperature water bath at 70 ℃ to dissolve the PVDF powder. Introducing nitrogen, weighing 5gAA and 0.2g of initiator AIBN, adding into the reaction system, and stirring and reacting for 12h in a nitrogen environment to obtain the PVDF-g-PAA copolymer. After the reaction is finished, precipitating the reaction solution by using about 250ml of methanol, filtering, repeatedly washing by using distilled water to remove unreacted monomers, initiators and homopolymers, finally pumping to dry, and putting the copolymerization product into a 60 ℃ oven to dry.
(3) Preparing a PVDF-g-PAA flat membrane: the same as in example 1.
(4) Preparation of PVDF-ARG film: the same as in example 1.
Example 3:
(1) alkali treatment of PVDF powder: the same as in example 1.
(2) Preparation of PVDF-g-PAA copolymer: the same as in example 1.
(3) Preparing a PVDF-g-PAA flat membrane: the same as in example 1.
(4) Preparation of PVDF-ARG film: cutting the PVDF-g-PAA flat separation membrane into 3 x 3cm2 membranes, soaking the membranes in 10ml ethanol, adding 200mg DMTMM into the ethanol to activate carboxyl on the membrane surface, adding 200mg argatroban powder after half an hour, reacting for 24 hours at normal temperature, taking out the membranes, and then washing the membranes with a large amount of distilled water to obtain the PVDF-ARG flat separation membrane.
Claims (6)
1. A modified PVDF flat separation membrane with anticoagulation performance is characterized by being prepared by the following method:
(1) preparing polyacrylic acid grafted polyvinylidene fluoride copolymer PVDF-g-PAA;
(2) preparing a PVDF-g-PAA flat separation membrane;
(3) argatroban (argatroban) graft-modified PVDF-ARG membranes were prepared as follows:
soaking a PVDF-g-PAA plate separation membrane in 20ml of ethanol, adding 4- (4, 6-dimethoxytriazine-2-yl) -4-methylmorpholine hydrochloride DMTMM, activating for half an hour, adding argatroban powder, reacting for 24 hours at normal temperature, taking out the membrane, and repeatedly washing the membrane with distilled water to obtain the PVDF-ARG plate separation membrane; the mass ratio of DMTMM to argatroban is 1: 0.8-1.5; the concentration of the argatroban in ethanol is 20 mg/ml.
2. The modified PVDF flat separation membrane with anticoagulant property as claimed in claim 1, wherein the preparation method of the polyacrylic acid grafted polyvinylidene fluoride copolymer in step (1) is a potassium hydroxide lye pretreatment method, and the steps are as follows: pretreating PVDF powder by using a potassium hydroxide solution; adding PVDF powder treated by the alkali solution into a three-neck flask, adding N, N-Dimethylformamide (DMF), stirring and dissolving in water bath at 60-80 ℃, and introducing nitrogen; adding acrylic acid AA and an initiator azobisisobutyronitrile AIBN into a three-neck flask under the condition of introducing nitrogen, and continuously introducing nitrogen after dissolving; stirring and reacting for 8-12 hours to obtain PVDF-g-PAA copolymer; precipitating the reacted solution in excessive methanol, filtering, washing with distilled water, filtering, and washing repeatedly for several times until impurities are removed; drying in 60 deg.C oven.
3. The modified PVDF flat separation membrane with anticoagulation performance according to claim 2, wherein in the step (1), the preparation method of the polyacrylic acid grafted polyvinylidene fluoride copolymer is characterized in that the alkali solution is a potassium hydroxide solution, the concentration of the alkali solution is 2.5mol/L, the content of PVDF powder in the potassium hydroxide solution is 100-150g/L, and the alkali treatment time is 10-20 min; the mass ratio of the PVDF powder after the alkali treatment to the AA monomer is 1:0.5-1: 1.5.
4. The modified PVDF flat separation membrane with anticoagulation property according to claim 1, wherein the preparation method of polyacrylic acid grafted polyvinylidene fluoride copolymer in step (1) comprises the following steps:
(1) preparing a potassium hydroxide solution, placing the solution in a constant-temperature water bath at 60 ℃, adding PVDF powder into the potassium hydroxide solution after 10min, adding absolute ethyl alcohol into the solution, stirring to fully disperse the PVDF powder in the solution, stirring for reaction for 10-20min, performing suction filtration, and repeatedly washing with distilled water to remove potassium fluoride and alkali liquor in a product;
(2) weighing PVDF powder treated by an alkali solution, adding the PVDF powder into a three-neck flask, adding a certain amount of N, N-Dimethylformamide (DMF), stirring and dissolving in a water bath at 60-80 ℃, and introducing nitrogen for 30 min; adding Acrylic Acid (AA) and an initiator Azobisisobutyronitrile (AIBN) into a three-neck flask under the condition of introducing nitrogen, continuously introducing nitrogen for 20 minutes after dissolving, and stirring for reacting for 8-12 hours to obtain a PVDF-g-PAA copolymer; precipitating the reacted solution in excessive methanol, filtering, washing with distilled water to remove unreacted monomer, initiator and homopolymer, and drying to obtain the copolymer product in 60 deg.c oven.
5. The modified PVDF flat separation membrane with anticoagulant property as claimed in claim 1, wherein the PVDF-g-PAA flat separation membrane prepared in step (2) is prepared by the following steps:
placing PVDF-g-PAA copolymer and a pore-foaming agent polyethylene glycol (PEG) in DMF, stirring and dissolving under the water bath heating condition of 60 ℃ to obtain a membrane casting solution; the content of the PVDF-g-PAA copolymer in the casting solution is 10-20% (wt%); the addition amount of the PEG is 30-60% of the mass of the copolymer; standing and defoaming for 10-12 h; pouring a small amount of casting film liquid on a glass plate, scraping the casting film liquid into a film by using a film scraping rod, soaking the glass plate into a coagulating bath at 25 ℃ for curing to form a film, placing the glass plate into distilled water for 72 hours after the film is formed and peeled off from the glass plate, and changing the water 2-3 times every day; and washing the membrane with distilled water to obtain the PVDF-g-PAA flat separation membrane.
6. The modified PVDF flat separation membrane with anticoagulation property according to claim 5, wherein the content of PVDF-g-PAA copolymer in the membrane casting solution is 10-20%, the addition amount of polyethylene glycol (PEG) is 30-60% of the mass of the copolymer, and the PEG number average molecular weight is 10000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810877651.7A CN108939940B (en) | 2014-07-08 | 2014-07-08 | Modified PVDF flat separation membrane with anticoagulation performance |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410325836.9A CN105311970B (en) | 2014-07-08 | 2014-07-08 | A kind of anticoagulation PVDF flat-plate separation films and preparation method thereof |
| CN201810877651.7A CN108939940B (en) | 2014-07-08 | 2014-07-08 | Modified PVDF flat separation membrane with anticoagulation performance |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410325836.9A Division CN105311970B (en) | 2014-07-08 | 2014-07-08 | A kind of anticoagulation PVDF flat-plate separation films and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108939940A CN108939940A (en) | 2018-12-07 |
| CN108939940B true CN108939940B (en) | 2021-02-09 |
Family
ID=55240885
Family Applications (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810877695.XA Active CN108939941B (en) | 2014-07-08 | 2014-07-08 | A kind of PVDF flat-plate separation film with anticoagulant functions |
| CN201410325836.9A Expired - Fee Related CN105311970B (en) | 2014-07-08 | 2014-07-08 | A kind of anticoagulation PVDF flat-plate separation films and preparation method thereof |
| CN201810877615.0A Active CN108939939B (en) | 2014-07-08 | 2014-07-08 | Anticoagulation modified PVDF (polyvinylidene fluoride) flat separation membrane |
| CN201810877651.7A Active CN108939940B (en) | 2014-07-08 | 2014-07-08 | Modified PVDF flat separation membrane with anticoagulation performance |
Family Applications Before (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810877695.XA Active CN108939941B (en) | 2014-07-08 | 2014-07-08 | A kind of PVDF flat-plate separation film with anticoagulant functions |
| CN201410325836.9A Expired - Fee Related CN105311970B (en) | 2014-07-08 | 2014-07-08 | A kind of anticoagulation PVDF flat-plate separation films and preparation method thereof |
| CN201810877615.0A Active CN108939939B (en) | 2014-07-08 | 2014-07-08 | Anticoagulation modified PVDF (polyvinylidene fluoride) flat separation membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (4) | CN108939941B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108939941B (en) * | 2014-07-08 | 2019-10-15 | 天津工业大学 | A kind of PVDF flat-plate separation film with anticoagulant functions |
| CN106310970B (en) * | 2016-09-23 | 2019-03-05 | 天津工业大学 | A kind of modified polyvinilidene fluoride hollow-fibre membrane for haemodialysis |
| CN108686520A (en) * | 2018-06-12 | 2018-10-23 | 漳州龙文琪睿生物科技有限公司 | A kind of preparation method of hemodialysis membrane raw material |
| CN109224889B (en) * | 2018-08-29 | 2021-04-09 | 中南大学湘雅医院 | Blood purification membrane with anticoagulation performance and preparation method thereof |
| CN109174061A (en) * | 2018-09-30 | 2019-01-11 | 天津市金鳞水处理科技有限公司 | A kind of preparation method of the modified seperation film of heavy metal ion adsorbed type PVDF |
| CN109174062A (en) * | 2018-09-30 | 2019-01-11 | 天津市金鳞水处理科技有限公司 | A kind of modified seperation film of heavy metal ion adsorbed type PVDF |
| CN113952849A (en) * | 2021-10-13 | 2022-01-21 | 天津工业大学 | Membrane adsorbent for removing heavy metal ions in water and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679563A (en) * | 2007-04-24 | 2010-03-24 | 索维索莱克西斯公开有限公司 | vinylidene fluoride copolymers |
| US20100260828A1 (en) * | 2008-11-03 | 2010-10-14 | The Board Of Trustees Of The University Of Illinois | Modulation of Platelet Aggregation |
| CN102038955A (en) * | 2009-10-30 | 2011-05-04 | 中南大学湘雅医院 | Method for preparing anticoagulant polysulfones material by fourier reaction grafting |
| CN102603986A (en) * | 2012-02-24 | 2012-07-25 | 常州大学 | Surface solid phase graft modified PVDF (Polyvinylidene Fluoride) and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008093154A (en) * | 2006-10-11 | 2008-04-24 | Tokai Univ | Chemical substance sustainedly-releasing hollow fiber membrane |
| EP2655452B1 (en) * | 2010-12-22 | 2017-02-22 | Solvay Specialty Polymers Italy S.p.A. | Hydrophilic vinylidene fluoride polymers |
| CN108939941B (en) * | 2014-07-08 | 2019-10-15 | 天津工业大学 | A kind of PVDF flat-plate separation film with anticoagulant functions |
-
2014
- 2014-07-08 CN CN201810877695.XA patent/CN108939941B/en active Active
- 2014-07-08 CN CN201410325836.9A patent/CN105311970B/en not_active Expired - Fee Related
- 2014-07-08 CN CN201810877615.0A patent/CN108939939B/en active Active
- 2014-07-08 CN CN201810877651.7A patent/CN108939940B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679563A (en) * | 2007-04-24 | 2010-03-24 | 索维索莱克西斯公开有限公司 | vinylidene fluoride copolymers |
| US20100260828A1 (en) * | 2008-11-03 | 2010-10-14 | The Board Of Trustees Of The University Of Illinois | Modulation of Platelet Aggregation |
| CN102038955A (en) * | 2009-10-30 | 2011-05-04 | 中南大学湘雅医院 | Method for preparing anticoagulant polysulfones material by fourier reaction grafting |
| CN102603986A (en) * | 2012-02-24 | 2012-07-25 | 常州大学 | Surface solid phase graft modified PVDF (Polyvinylidene Fluoride) and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 抗凝改性血液净化滤器膜构建及性能研究;文锐;《中国博士学位论文全文数据库 医药卫生科技辑》;20110115;正文第5-7、23、36页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108939940A (en) | 2018-12-07 |
| CN105311970B (en) | 2018-09-21 |
| CN108939939B (en) | 2021-02-09 |
| CN108939939A (en) | 2018-12-07 |
| CN108939941A (en) | 2018-12-07 |
| CN105311970A (en) | 2016-02-10 |
| CN108939941B (en) | 2019-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108939940B (en) | Modified PVDF flat separation membrane with anticoagulation performance | |
| Xiang et al. | Ionic-strength-sensitive polyethersulfone membrane with improved anti-fouling property modified by zwitterionic polymer via in situ cross-linked polymerization | |
| Song et al. | Hemocompatibility and ultrafiltration performance of surface-functionalized polyethersulfone membrane by blending comb-like amphiphilic block copolymer | |
| Qin et al. | High efficient protocol for the modification of polyethersulfone membranes with anticoagulant and antifouling properties via in situ cross-linked copolymerization | |
| Li et al. | Modification of polyethersulfone hemodialysis membrane by blending citric acid grafted polyurethane and its anticoagulant activity | |
| Xiang et al. | Blood compatibility comparison for polysulfone membranes modified by grafting block and random zwitterionic copolymers via surface-initiated ATRP | |
| CN110652890B (en) | Surface hydrophilic modification method for polyacrylonitrile separation membrane | |
| CN102580574B (en) | Antipollution self-cleaning polyvinylidene fluoride membrane and method for producing same | |
| Xu et al. | Dual functionalized poly (vinylidene fluoride) membrane with acryloylmorpholine and argatroban to improve antifouling and hemocompatibility | |
| CN109675134A (en) | A kind of anticoagulant method of modifying of haemodialyser and its application | |
| CN106466562B (en) | The preparation method of anticoagulation hemodialysis membrane | |
| Xie et al. | A robust way to prepare blood-compatible and anti-fouling polyethersulfone membrane | |
| Ran et al. | A new approach for membrane modification based on electrochemically mediated living polymerization and self-assembly of N-tert-butyl amide-and β-cyclodextrin-involved macromolecules for blood purification | |
| CN105521715B (en) | A kind of blending polyvinylidene fluoride hollow fiber membrane and preparation method thereof | |
| CN107115796B (en) | Preparation method of hydrophilic polyacrylonitrile separation membrane | |
| CN110743392B (en) | PVDF hollow fiber membrane material with anticoagulation property for hemodialysis and preparation method thereof | |
| CN103464222B (en) | The preparation method of the special anion exchange resin of a kind of adsorbing liquaemin | |
| CN102977275A (en) | Use of phosphorylcholine groups for improving biocompatibility of adsorption resin | |
| CN104069743A (en) | Preparation method of polylactic acid hemodialysis membrane with zwitterionic surface | |
| JPH0751355A (en) | Medical synthetic high polymer and medical material | |
| Xiang et al. | Improved antifouling properties and blood compatibility of 3-methacryloxypropyl trimethoxysilane–based zwitterionic copolymer modified composite membranes via in situ post-crosslinking copolymerization | |
| CN105289546A (en) | Preparation method of adsorbent special for heparin sodium | |
| JPH07184990A (en) | High polymer material for medical treatment and medical treating material | |
| CN102344521A (en) | Polymethyl polyglycol methacrylate containing sorbitol ester mononitrate structure as well as preparation method and use method thereof | |
| Lin et al. | Preparation of modified polysulfone material decorated by sulfonated citric chitosan for haemodialysis and its haemocompatibility |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |