CN108939941A - A kind of PVDF flat-plate separation film with anticoagulant functions - Google Patents
A kind of PVDF flat-plate separation film with anticoagulant functions Download PDFInfo
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- CN108939941A CN108939941A CN201810877695.XA CN201810877695A CN108939941A CN 108939941 A CN108939941 A CN 108939941A CN 201810877695 A CN201810877695 A CN 201810877695A CN 108939941 A CN108939941 A CN 108939941A
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Abstract
The invention discloses a kind of PVDF flat-plate separation film with anticoagulant functions, belongs to technical field of membrane.The PVDF flat-plate separation film preparation method with anticoagulant functions is the following steps are included: (1) prepares polyacrylic acid grafted polyvinylidene fluoride copolymer PVDF-g-PAA；(2) PVDF-g-PAA flat-plate separation film is prepared；(3) the PVDF-ARG film of argatroban (argatroban) graft modification is prepared.Small molecule argatroban with efficient anticoagulation is modified pvdf membrane using acrylic acid for medium by the present invention, obtains the PVDF separation membrane material with good anticoagulation.It can be obviously prolonged the recalcification time of film, substantially reduce sticking for the blood platelet erythrocyte in film surface, reduce hemolysis rate, anticoagulation function is improved, be greatly improved blood compatibility.Have the characteristics that simple process, industrializing implementation are easy.
Description
The application is the divisional application of following application: the applying date is on July 8th, 2014, application No. is
201410325836.9 entitled a kind of anticoagulation PVDF flat-plate separation film and preparation method thereof.
Technical field
The invention belongs to technical field of membrane, in particular to a kind of PVDF flat-plate separation film with anticoagulant functions.
Background technique
Cardiovascular disease is to seriously threaten one of human life and the common disease of health now, and blood purification is to treat this
The important means of kind disease, common instrument are blood purification.Hemodialysis membrane is the core component for purifying filter, currently,
Common hemodialysis membrane has polyether sulfone, cellulose, polyacrylonitrile etc..Kynoar (PVDF) is a kind of height of function admirable
Molecular material, chemical stability, radiation hardness characteristic, resistance tocrocking and heat resistance outstanding make it be widely used in UF membrane neck
Domain, and be expected to become potential Hemodialysis Membrane Material.But the performance of PVDF itself determines that its blood compatibility is poor, with blood
Liquid easily causes thrombus when contacting.
The blood compatibility for improving pvdf membrane is the key that determine that can it become haemodialysis material.Improve pvdf membrane blood
The method of liquid phase capacitive mainly introduces functional groups, including hydroaropic substance (such as polyethylene glycol, two on pvdf membrane surface
Property ion etc.) and monomer (such as heparin, Phosphorylcholine) with anticoagulant effect.The mode for introducing functional groups mainly has film
Surface grafting and membrane body grafting.The membrane pore structure of film surface is destroyed in order to prevent, therefore Many researchers selection membrane body connects
The mode of branch is modified pvdf membrane, mainly locates in advance including Transfer Radical Polymerization (ATRP), click chemistry, ozone
Reason and alkali process etc..It is wherein especially the most simple and easy with alkali process method and low in cost.
Small molecule thrombin inhibitor --- the argatroban of novel synthesis, can quick, selective, reversible and blood
The fibrin ferment of middle free state combines, continual inactivation fibrin ferment, blocks the positive feedback of blood coagulation waterfall, inhibits blood coagulation indirectly
The generation of enzyme and fibrinous generation；Polymer can be formed with the fibrin ferment in conjunction with fibrinogen, inhibit the progress of thrombus；
It can inhibit the platelet aggregation and thromboxane A of thrombin-mediated simultaneously2(TXA2) release, activate natural anti-coagulants PROTEIN C
(PC), powerful anticoagulant, antithrombotic effect are played.By on argatroban small molecule covalence graft to pvdf membrane, modified effect more can
Permanent holding.
Summary of the invention
Aiming at the problem that blood coagulation occurs for existing pvdf membrane and contacting blood, the technical issues of present invention intends to solve, is to provide one
Kind has the PVDF flat-plate separation film of anticoagulant functions.The present invention carries out graft modification, modification side to PVDF using argatroban
Method is Alkaline pretreatment method.
The PVDF flat-plate separation film preparation method with anticoagulant functions includes the following steps: that (1) prepares PVDF-g-
PAA copolymer；2) PVDF-g-PAA flat-plate separation film is prepared；(3) argatroban (argatroban) graft modification is prepared
PVDF-ARG film.
The method for preparing PVDF-g-PAA copolymer is Alkaline pretreatment method, comprising the following steps: aqueous slkali is located in advance
Manage PVDF powder；PVDF powder after alkaline solution treatment is added in three-necked flask, and n,N-Dimethylformamide DMF is added, in
60-80 DEG C of stirring in water bath dissolution, leads to nitrogen；Acrylic acid AA is added into three-necked flask in the case where logical nitrogen, initiator is even
Nitrogen bis-isobutyronitrile AIBN continues logical nitrogen after dissolution；It is stirred to react 8-12 hours and obtains PVDF-g-PAA copolymer；After reaction
Solution precipitates in excessive methanol, filters, and with filtering after distilled water flushing, repeats to rinse for several times, until impurity eliminates；It is put into 60
DEG C oven drying.
Further, the method for preparing PVDF-g-PAA copolymer the following steps are included:
(1) potassium hydroxide solution is prepared, above-mentioned solution is placed in 60 DEG C of waters bath with thermostatic control, it is molten in potassium hydroxide after 10min
PVDF powder is added in liquid, then dehydrated alcohol is added into above-mentioned solution and stirs, keeps PVDF powder fully dispersed in the solution,
It is stirred to react 10-20min, is filtered, and washed repeatedly with distilled water to remove the potassium fluoride and lye in product；(2) weigh through
PVDF powder after alkaline solution treatment is added in three-necked flask, is added n,N-Dimethylformamide (DMF), and 60-80 DEG C of water-bath is stirred
Dissolution is mixed, 30min nitrogen is led to；Acrylic acid AA, 0.1g initiator azo two are added into three-necked flask in the case where logical nitrogen
Isobutyronitrile (AIBN) continues logical nitrogen 20 minutes after dissolution, is stirred to react 8-12 hours and obtains PVDF-g-PAA copolymer；Reaction
Solution afterwards precipitates in excessive methanol, filters, unreacted monomer, initiator, homopolymer are removed with distilled water flushing,
It finally drains and copolymerization product is put into 60 DEG C of oven dryings.
The concentration of the potassium hydroxide solution is 2.5mol/L
Content of the PVDF powder in potassium hydroxide solution is 100-150g/L in the step (1)
The additive amount of dehydrated alcohol is 20-30ml/L in the step (1)
The content of PVDF powder in the reaction system in the step (2) through alkali process is 50-100g/L
The additive amount of AA is 0.5-1.5 times of the PVDF powder quality through alkali process in the step (2)
The additive amount of AIBN is the 1%-3% of the PVDF powder quality through alkali process in the step (2)
The PVDF-g-PAA flat-plate separation film the preparation method is as follows: weighing a certain amount of PVDF-g-PAA copolymer powder
It is put into the flask for filling quantitative DMF with pore-foaming agent polyethylene glycol (PEG), stirring and dissolving obtains under 60 DEG C of condition of water bath heating
Casting solution, 10~12h of standing and defoaming；A small amount of casting solution is toppled on glass plate, is formed a film with knifing stick striking, and 25 DEG C of immersion is coagulated
Gu film-forming in bath, after film is shaped from glass plate and fallen off, then is placed in distilled water 72 hours, changes daily water 2~3 times；
PVDF-g-PAA flat-plate separation film can be obtained after distilled water flushing is clean.
The content of the casting solution liquid PVDF-g-PAA copolymer is 10-20% (wt%).
The PEG molecular weight is 10000, and additive amount is the 30-60% of copolymer quality.
The coagulating bath is pure water.
The PVDF-ARG film the preparation method is as follows: PVDF-g-PAA flat-plate separation film is immersed in 20ml ethyl alcohol,
It then will be in film surface to addition 4- (4,6- dimethoxy-triazine -2- base) -4- methyl morpholine hydrochloride (DMTMM) in ethyl alcohol
Argatroban powder is added after activating half an hour in activated carboxylic, after reacting for 24 hours under room temperature, takes out diaphragm and is then rushed with distilled water
It washes 3~5 times, PVDF-ARG flat-plate separation film can be obtained after rinsing well.
The area of the diaphragm is 3 × 3cm2。
The mass ratio of the DMTMM and argatroban are 1:0.8~1:1.5.
Concentration of the argatroban in ethyl alcohol is 10mg/ml~20mg/ml.
Beneficial effect
The present invention utilize for the first time acrylic acid be medium by the small molecule argatroban with efficient anticoagulation to pvdf membrane
It is modified, obtains the PVDF separation membrane material with good blood coagulation resisting function.The present invention has simple process, industrializing implementation
The features such as being easy.The recalcification time of PVDF-ARG film prepared by the present invention is obviously prolonged, the blood platelet erythrocyte in film surface
It is substantially reduced etc. sticking, hemolysis rate reduces, and anticoagulation function improves, and is greatly improved blood compatibility.Present invention preparation
PVDF-ARG film can be used as haemodialysis separation membrane material and further develop and use.
Specific embodiment
The following examples can make those skilled in the art that the present invention be appreciated more fully, but not limit in any way
The present invention.
Embodiment 1:
(1) alkali process of PVDF powder: preparing the potassium hydroxide solution of 2.5mol/L, by the prepared hydroxide of 400ml
Potassium solution pours into flask, by flask as in 60 DEG C of waters bath with thermostatic control, after half an hour, then 60gPVDF powder is added in flask,
12ml dehydrated alcohol is added into reaction system, keeps PVDF fully dispersed in system, is stirred to react 15min, by products therefrom
It filters, and is repeatedly washed with distilled water, the pulverulent solids product after washing is finally put into dried for standby in 60 DEG C of baking ovens.
(2) tri- mouthfuls of 250ml burnings of PVDF powder addition after 10g alkali process the preparation of PVDF-g-PAA copolymer: are weighed
In bottle, 120mlDMF solvent is added, heating stirring dissolves under 65 DEG C of waters bath with thermostatic control, is allowed to be completely dissolved.Logical nitrogen, weighs
10gAA, 0.2g initiator A IBN are added in reaction system, and 12h is stirred to react in nitrogen environment and obtains PVDF-g-PAA copolymerization
Object.After reaction, it with the methanol extraction reaction solution of about 250ml, filters, and uses distilled water repeated flushing, removing unreacted
Monomer, initiator, homopolymer, finally drain, copolymerization product be put into 60 DEG C of baking ovens dry.
(3) prepare PVDF-g-PAA plate membrane: by 6gPVDF-g-PAA copolymer powder, 3g pore-foaming agent PEG is added to Sheng
In the flask for having 28.5g DMF, heating stirring stands casting solution up to being completely dissolved to obtain casting solution under 60 DEG C of water bath conditions
Deaeration 10h.It selects distilled water as coagulating bath, is placed in 25 DEG C of thermostatic water bath, a small amount of casting solution is poured into smooth, dry
Glass plate on, with knifing stick striking form a film, glass plate is immersed rapidly to film-forming in coagulating bath, to film from glass plate take off
Fall behind, film is placed in distilled water for 24 hours finally to be cleaned and be total to distilled water except the residual solvent and pore-foaming agent on striping
Polymers plate membrane.
(4) PVDF-g-PAA flat-plate separation film the preparation of PVDF-ARG film: is cut into 3 × 3cm2Diaphragm, soaked
Then bubble the activated carboxylic in film surface is added after half an hour to addition 150mg DMTMM in ethyl alcohol in 10ml ethyl alcohol
150mg argatroban powder, after reacting for 24 hours under room temperature, take out diaphragm then with a large amount of distilled water flushings it is clean after can obtain
PVDF-ARG flat-plate separation film.
Compared to pure pvdf membrane, the recalcification time for the PVDF-ARG plate membrane being prepared is obviously prolonged, the blood of film surface
Platelet, which sticks, to be substantially reduced, and activated partial thromboplastin time (APTT) is obviously prolonged, and anticoagulation function improves.
Embodiment 2:
(1) alkali process of PVDF powder: with embodiment 1.
(2) preparation of PVDF-g-PAA copolymer: weighing the PVDF powder after 10g alkali process and be added in three-necked flask,
120mlDMF solvent is added, heating stirring dissolves under 70 DEG C of waters bath with thermostatic control.Logical nitrogen, weighs 5gAA, 0.2g initiator
AIBN is added in reaction system, and 12h is stirred to react in nitrogen environment and obtains PVDF-g-PAA copolymer.After reaction, it uses
The methanol extraction reaction solution of about 250ml filters, and uses distilled water repeated flushing, removes unreacted monomer, initiator, equal
Polymers is finally drained, and copolymerization product is put into 60 DEG C of baking ovens dry.
(3) PVDF-g-PAA plate membrane is prepared: with embodiment 1.
(4) preparation of PVDF-ARG film: with embodiment 1.
Embodiment 3:
(1) alkali process of PVDF powder: with embodiment 1.
(2) preparation of PVDF-g-PAA copolymer: with embodiment 1.
(3) PVDF-g-PAA plate membrane is prepared: with embodiment 1.
(4) preparation of PVDF-ARG film: PVDF-g-PAA flat-plate separation film is cut into the diaphragm of 3 × 3cm2, is soaked
Then bubble the activated carboxylic in film surface is added after half an hour to addition 200mg DMTMM in ethyl alcohol in 10ml ethyl alcohol
200mg argatroban powder, after reacting for 24 hours under room temperature, take out diaphragm then with a large amount of distilled water flushings it is clean after can obtain
PVDF-ARG flat-plate separation film.
Claims (1)
1. a kind of PVDF flat-plate separation film with anticoagulant functions, which is characterized in that prepared by following methods:
(1) polyacrylic acid grafted polyvinylidene fluoride copolymer PVDF-g-PAA is prepared；
(2) PVDF-g-PAA flat-plate separation film is prepared；
(3) the PVDF-ARG film of argatroban (argatroban) graft modification is prepared；
The preparation method of step (1) the polyacrylic acid grafted polyvinylidene fluoride copolymer the following steps are included:
(1) potassium hydroxide solution is prepared, above-mentioned solution is placed in 60 DEG C of waters bath with thermostatic control, after 10min in potassium hydroxide solution
PVDF powder is added, then dehydrated alcohol is added into above-mentioned solution and stirs, keeps PVDF powder fully dispersed in the solution, stirs
10-20min is reacted, is filtered, and washed repeatedly with distilled water to remove the potassium fluoride and lye in product；
(2) it weighs the PVDF powder after alkaline solution treatment to be added in three-necked flask, quantitative n,N-Dimethylformamide is added
(DMF), 60-80 DEG C of stirring in water bath dissolution, leads to 30min nitrogen；Acrylic acid is added into three-necked flask in the case where logical nitrogen
(AA), initiator azodiisobutyronitrile (AIBN) continues logical nitrogen 20 minutes after dissolution, is stirred to react 8-12 hours and obtains
PVDF-g-PAA copolymer；Solution after reaction precipitates in excessive methanol, filters, with distilled water flushing to remove unreacted
Monomer, initiator, homopolymer, finally drain and copolymerization product be put into 60 DEG C of oven dryings；
Step (2) the PVDF-g-PAA flat-plate separation film the preparation method is as follows:
PVDF-g-PAA copolymer and pore-foaming agent polyethylene glycol PEG are placed in DMF, stirring and dissolving under 60 DEG C of condition of water bath heating
Obtain casting solution；The content of PVDF-g-PAA copolymer is 10-20% (wt%) in the casting solution；The additive amount of the PEG
For the 30-60% of copolymer quality；10~12h of standing and defoaming；Topple over a small amount of casting solution on glass plate, with the striking of knifing stick at
Film immerses film-forming in 25 DEG C of coagulating bath, after film is shaped from glass plate and fallen off, then is placed in distilled water 72 hours,
It changes water 2~3 times daily；PVDF-g-PAA flat-plate separation film can be obtained after distilled water flushing is clean；
Step (3) the PVDF-ARG membrane preparation method for preparing argatroban (argatroban) graft modification is as follows:
PVDF-g-PAA flat-plate separation film is immersed in 20ml amount of alcohol, 4- (4,6- dimethoxy-triazine -2- are then added
Base) -4- methyl morpholine hydrochloride DMTMM, argatroban powder is added after activating half an hour, after reacting for 24 hours under room temperature, takes out film
Piece is clean with distilled water repeated flushing, can obtain PVDF-ARG flat-plate separation film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810877695.XA CN108939941B (en) | 2014-07-08 | 2014-07-08 | A kind of PVDF flat-plate separation film with anticoagulant functions |
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 |
| CN201810877695.XA CN108939941B (en) | 2014-07-08 | 2014-07-08 | A kind of PVDF flat-plate separation film with anticoagulant functions |
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| CN201410325836.9A Division CN105311970B (en) | 2014-07-08 | 2014-07-08 | A kind of anticoagulation PVDF flat-plate separation films and preparation method thereof |
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| CN108939941A true CN108939941A (en) | 2018-12-07 |
| CN108939941B CN108939941B (en) | 2019-10-15 |
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| CN201810877695.XA Active CN108939941B (en) | 2014-07-08 | 2014-07-08 | A kind of PVDF flat-plate separation film with anticoagulant functions |
| CN201810877651.7A Active CN108939940B (en) | 2014-07-08 | 2014-07-08 | Modified PVDF flat separation membrane with anticoagulation performance |
| 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 |
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| 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 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| JP2008093154A (en) * | 2006-10-11 | 2008-04-24 | Tokai Univ | Chemical substance sustainedly-releasing hollow fiber membrane |
| CN101679563A (en) * | 2007-04-24 | 2010-03-24 | 索维索莱克西斯公开有限公司 | vinylidene fluoride copolymers |
| 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 |
| CN103282393A (en) * | 2010-12-22 | 2013-09-04 | 索尔维特殊聚合物意大利有限公司 | Hydrophilic vinylidene fluoride polymers |
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| US8563690B2 (en) * | 2008-11-03 | 2013-10-22 | The Board Of Trustees Of The University Of Illinois | Modulation of platelet aggregation |
| 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 CN201810877651.7A patent/CN108939940B/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
Patent Citations (5)
| 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 |
| CN101679563A (en) * | 2007-04-24 | 2010-03-24 | 索维索莱克西斯公开有限公司 | vinylidene fluoride copolymers |
| 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 |
| CN103282393A (en) * | 2010-12-22 | 2013-09-04 | 索尔维特殊聚合物意大利有限公司 | Hydrophilic vinylidene fluoride polymers |
| CN102603986A (en) * | 2012-02-24 | 2012-07-25 | 常州大学 | Surface solid phase graft modified PVDF (Polyvinylidene Fluoride) and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105311970A (en) | 2016-02-10 |
| CN108939941B (en) | 2019-10-15 |
| CN108939940B (en) | 2021-02-09 |
| CN108939939A (en) | 2018-12-07 |
| CN108939940A (en) | 2018-12-07 |
| CN105311970B (en) | 2018-09-21 |
| CN108939939B (en) | 2021-02-09 |
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