CN103706266A - In-situ polymerization mico-crosslinking polyvinylpyrrolidone modified polyether sulfone hollow fiber membrane and preparation method and use thereof - Google Patents
In-situ polymerization mico-crosslinking polyvinylpyrrolidone modified polyether sulfone hollow fiber membrane and preparation method and use thereof Download PDFInfo
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Abstract
The invention discloses an in-situ polymerization mico-crosslinking polyvinylpyrrolidone modified polyether sulfone hollow fiber membrane and a preparation method and a use thereof. The preparation method is characterized by comprising the following steps: adding 10-25 parts of polyether sulfone and 90-75 parts of solvent into a reaction kettle, adding vinyl pyrrolidone accounting for 2-20% of mass of the polyether sulfone solution after the polyether sulfone is dissolved, carrying out a polymerization reaction for 2-24 hours at a temperature of 50-95 DEG C in the presence of a crosslinking agent and an initiator to obtain a polyvinylpyrrolidone modified polyether sulfone solution, stewing to cure the polyvinylpyrrolidone modified polyether sulfone solution to prepare modified polyether sulfone spinning dope, and directly mico-crosslinking polyvinylpyrrolidone between polyether sulfone lattice chains; and preparing a modified polyether sulfone hollow fiber membrane with hydrophilia, protein pollution resistance and anticoagulant function by utilizing a dry spraying-wet spinning method. The membrane is made into a filter and has excellent blood compatibility to be used for purifying blood, and the anti-protein pollution recovery rate is increased from 50% to 95%; the albumin adsorption is decreased from 20 micrograms/cm<2> to 5 micrograms/cm<2>; the activated partial thromboplastin time is increased from 50 seconds to 96 seconds.
Description
Technical field
The present invention relates to the micro-PVPP modified poly (ether-sulfone) of a kind of in-situ polymerization hollow-fibre membrane and its production and use, the preparation field of function of dominant macromolecular material.
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 special engineering plastics, because its vitrification point is high, 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 the micro-PVPP of in-situ polymerization 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.
Poly (ether sulfone) film is 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): (1) body modification (2) blend method; (3) surface modification.Body modification is directly on polyether sulfone chain, to pass through chemical method, thereby introduce functional group, it is carried out to chemical modification.Such as people (European Polymer Journal, 2005,41 (7): 1554) make solvent with the concentrated sulfuric acid, chlorosulfonic acid, as sulfonating agent, carries out sulfonation modifying to polyether sulfone and obtains sulfonated polyether sulfone such as Guan R.Body modification also can produce and allow the negative effects such as its chain rupture, hydraulic performance decline when polyether sulfone chain is carried out to chemical modification, thereby limits its application.Physical blending method is directly modifier to be blended in polyether sulfone solution, then prepares film forming.Method by physical modification poly (ether sulfone) film is comparatively convenient, but simple blend modifier when polyether sulfone film forming exists the comparatively serious problem that washes out, and the compatibility of modifier and polyether sulfone is also bad, and blending and modifying amount is limited.For the shortcoming of blending modification method, have to research and propose to adopt the method introducing functional group of chemical bonding to come modified poly (ether sulfone) film surface.But this kind of method chemical reaction flow process is longer, process is complicated, and productive rate is lower, and power consumption is polluted large.
Polyvinylpyrrolidone (PVP) is a kind of polyamide of water-soluble linear structure, there is stronger hydrophily, the extensive use in the preparation of hydrophily hyperfiltration/microfiltration film of Chang Zuowei additive or modifier (people such as Chen LP, Polymer, 2002,43:1429).In view of the good modification performance of PVP, it has been widely used in the middle of the modification of multiple film material.But because PVP is very easily water-soluble, this can slowly wash out film polyvinylpyrrolidone after modification, the hydrophilic less stable of film (people such as Wan LS, Journal of Polymer Science Part B:Polymer Physics, 2006,44 (10): 1490).
Summary of the invention
The object of the invention is the micro-PVPP modified poly (ether-sulfone) of a kind of in-situ polymerization hollow-fibre membrane of developing for the deficiencies in the prior art and its production and use, be characterized in that the micro-PVPP of in-situ polymerization can well be fixed between polyether sulfone lattice chain, blending modified polyether sulphone (PES) hollow-fibre membrane, this hollow-fibre membrane eluting rate is low, has advantages of that lasting, stable hydrophily, anti-protein contamination ability and blood compatibility are good.
Object of the present invention is realized by following technical measures: wherein said raw material umber, except specified otherwise, is parts by weight.
The micro-PVPP modified poly (ether-sulfone) of in-situ polymerization hollow-fibre membrane is made by following component:
1) polyether sulfone solution is made by following component
10～25 parts of polyether sulfones
90～75 parts of solvents
2) the micro-PVPP modified polyether of in-situ polymerization sulfolane solution is made by following component
2～20% of monomer vinyl pyrrolidones polyether sulfone solution quality
0.5～10% of crosslinking agent monomer molar mark
0.25～5% of initator monomer molar mark
Wherein, crosslinking agent is N, N'-methylene-bisacrylamide or GMA; Initator is dibenzoyl peroxide or azodiisobutyronitrile.
Described solvent is any in 1-METHYLPYRROLIDONE, DMF, DMA or dimethyl sulfoxide (DMSO).
The preparation method of the micro-PVPP modified poly (ether-sulfone) of in-situ polymerization hollow-fibre membrane comprises the following steps:
1) preparation of modified poly (ether-sulfone) spinning solution
By in 10～25 parts of polyether sulfones and 90～75 parts of reactors that add with agitator, thermometer and heater of solvent, stirring and dissolving add after completely monomer vinyl pyrrolidones be polyether sulfone solution quality 2～20%, crosslinking agent be reaction monomers molar fraction 0.5～10%, initator is 0.25～5% of reaction monomers molar fraction, under agitation, in 50～95 ℃ of polymerisation 2-24h of temperature, obtain polyvinyl pyrrolidone modified polyether sulfone solution, through placing " slaking ", make modified poly (ether-sulfone) spinning solution;
2) preparation of modified poly (ether-sulfone) hollow-fibre membrane
By the press filtration of modified poly (ether-sulfone) spinning solution, with measuring pump, through two concentrically ringed doughnut spinneret orifices, to extrude, spray silk diameter of bore is 200～1000um, and the outer bore dia of spray silk is 300～1500um, and 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 modified poly (ether-sulfone) hollow-fibre membrane, and its internal diameter is 200～1000 μ m, and wall thickness is 50～200 μ m;
3). the post processing of modified poly (ether-sulfone) hollow-fibre membrane
Modified poly (ether-sulfone) hollow-fibre membrane, at 50～60 ℃ of poach 8～72h of temperature, is removed residual solvent.
Polyether sulfone number-average molecular weight in described hollow-fibre membrane is 20000～60000.
The micro-PVPP modified poly (ether-sulfone) of described in-situ polymerization hollow-fibre membrane is made filter, is widely used in blood purification, comprises small throughput haemodialysis, high flux hemodialysis, blood filtration and plasma separation.
Performance test:
Prepared modified poly (ether-sulfone) hollow-fibre membrane above, the aperture of membranous wall is 0.005～0.4 μ m, pure water ultrafiltrate coefficient 90～1800ml/m
2.h.mmHg, pure water contact angle is at 30～70 °, 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.
Compared with prior art, tool has the following advantages in the present invention:
1, preparation method of the present invention is one-step method, and micro-cross-linking polyethylene pyrrolidone is that direct polymerization is between polyether sulfone solution lattice chain.Polyvinyl pyrrolidone modified polyether sulphone hollow fibre film eluting rate is low, makes it to have lasting, stable hydrophily, anti-protein contamination ability and excellent blood compatibility.
2, very homogeneous, good film-forming property of the polyether sulfone spinning solution of the micro-PVPP modification of in-situ polymerization of the present invention, makes prepared hollow-fibre membrane physics, chemical stability good, and acid and alkali-resistance is corrosion-resistant.
3, modified poly (ether-sulfone) hollow-fibre membrane of the present invention its flux response rate when anti-protein contamination test rises to 82%～95% from 50%; Albumin absorption is from 20 μ g/cm
2be reduced to 5 μ g/cm
2; Activated partial thromboplastin time is increased to 85s～96s from 50s.
4, preparation method of the present invention is simple, and efficient, easy to operate, cost is low, is conducive to suitability for industrialized production.
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 polyether sulfones, 90 parts of DMAs, put into the reactor with agitator, thermometer and heater, under agitation in 65 ℃ of temperature, dissolve completely.Add 10 parts of vinyl pyrrolidones, N, the addition of N'-methylene-bisacrylamide is 1% of reaction monomers molar fraction, the addition of azodiisobutyronitrile is 1% of reaction monomers molar fraction.After under agitation progressively adding, in 95 ℃ of reaction 4h of temperature, make polyvinyl pyrrolidone modified polyether sulfone solution.Deaeration after filtration, places " slaking " and makes 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 7ml/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 14m/min again, obtains polyether sulphone hollow fibre film, and its internal diameter is 1000 μ m, and wall thickness is 90 μ m.Hollow-fibre membrane is processed 48h 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 1200ml/m
2.h.mmHg, filter after albumin solution, the response rate of pure water flux is 82%, and the part prothrombin activating time (APTT) increases by 70%.
Embodiment 2.
By 25 parts of polyether sulfones, 75 parts of 1-METHYLPYRROLIDONEs, put into the reactor with agitator, thermometer and heater, under agitation in 65 ℃ of temperature, dissolve completely.Add 6 parts of vinyl pyrrolidones, N, the addition of N'-methylene-bisacrylamide is 0.5% of reaction monomers molar fraction, the addition of azodiisobutyronitrile is 0.25% of reaction monomers molar fraction.After under agitation progressively adding, in 65 ℃ of reaction 24h of temperature, make polyvinyl pyrrolidone modified polyether sulfone solution.Deaeration after filtration, places " slaking " and makes 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 3ml/min; As-spun fibre in air after 40cm distance in 35 ℃ of water-baths of temperature coagulation forming; Through plasticizing-bath drawing-off, reel, speed is 8m/min again, obtains polyether sulphone hollow fibre film, and its internal diameter is 700 μ m, and wall thickness is 200 μ m.Hollow-fibre membrane is processed 72h 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 90ml/m
2.h.mmHg, filter after albumin solution, the response rate of pure water flux is 86%, and the part prothrombin activating time (APTT) increases by 72%
Embodiment 3.
By 15 parts of polyether sulfones, 85 parts of DMAs, put into the reactor with agitator, thermometer and heater, under agitation in 65 ℃ of temperature, dissolve completely.Add 20 parts of vinyl pyrrolidones, N, the addition of N'-methylene-bisacrylamide is 10% of reaction monomers molar fraction, the addition of azodiisobutyronitrile is 5% of reaction monomers molar fraction.After under agitation progressively adding, in 95 ℃ of reaction 2h of temperature, make polyvinyl pyrrolidone modified polyether sulfone solution.Deaeration after filtration, places " slaking " and makes 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 temperature 50 C water-bath coagulation forming; Through plasticizing-bath drawing-off, reel, speed is 13m/min again, obtains polyether sulphone hollow fibre film, and its internal diameter is 650 μ m, and wall thickness is 80 μ m.Hollow-fibre membrane is processed 36 hours in 55 ℃ of water of temperature, 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 750ml/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 86%
Embodiment 4.
By 18 parts of polyether sulfones, 82 parts of DMFs, put into the reactor with agitator, thermometer and heater, under agitation in 65 ℃ of temperature, dissolve completely.Add 2 parts of vinyl pyrrolidones, the addition of GMA is 1% of reaction monomers molar fraction, and the addition of azodiisobutyronitrile is 1% of reaction monomers molar fraction.After under agitation progressively adding, in 80 ℃ of reaction 8h of temperature, make polyvinyl pyrrolidone modified polyether sulfone solution.Deaeration after filtration, places " slaking " and makes 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 17m/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 60 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 350ml/m
2.h.mmHg, filter after albumin solution, the response rate of pure water flux is 85%, and the part prothrombin activating time (APTT) increases by 70%.
Embodiment 5.
By 18 parts of polyether sulfones, 82 parts of DMAs, put into the reactor with agitator, thermometer and heater, under agitation in 65 ℃ of temperature, dissolve completely.Add 6 parts of vinyl pyrrolidones, N, the addition of N'-methylene-bisacrylamide is 5% of reaction monomers molar fraction, the addition of dibenzoyl peroxide is 1% of reaction monomers molar fraction.Under agitation, by reacting 12h in 65 ℃ of temperature after adding, make polyvinyl pyrrolidone modified polyether sulfone solution.Deaeration after filtration, places " slaking " and makes 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 10ml/min; As-spun fibre in air after 8cm distance in 20 ℃ of water-baths of temperature coagulation forming; Through plasticizing-bath drawing-off, reel, speed is 50m/min again, obtains polyether sulphone hollow fibre film, and its internal diameter is 250 μ m, and wall thickness is 55 μ m.Hollow-fibre membrane is processed 36h in 55 ℃ of water of temperature, 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 390ml/m
2.h.mmHg, filter after albumin solution, the response rate of pure water flux is 90%, and the part prothrombin activating time (APTT) increases by 88%.
Embodiment 6.
By 20 parts of polyether sulfones, 80 parts of dimethyl sulfoxide (DMSO)s, put into the reactor with agitator, thermometer and heater, under agitation in 65 ℃ of temperature, dissolve completely.Add 6 parts of vinyl pyrrolidones, N, the addition of N'-methylene-bisacrylamide is 5% of reaction monomers molar fraction, the addition of azodiisobutyronitrile is 3% of reaction monomers molar fraction.After under agitation progressively adding, in temperature 50 C reaction 24h, make polyvinyl pyrrolidone modified polyether sulfone solution.Deaeration after filtration, places " slaking " and makes 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 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 15m/min again, obtains polyether sulphone hollow fibre film, and its internal diameter is 200 μ m, and wall thickness is 50 μ m.Hollow-fibre membrane is processed 8h in temperature 60 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 92%.
Claims (5)
1. the micro-PVPP modified poly (ether-sulfone) of in-situ polymerization hollow-fibre membrane, is characterized in that:
1) polyether sulfone solution is made by following component, is by weight:
10～25 parts of polyether sulfones
90～75 parts of solvents
2) the micro-PVPP of in-situ polymerization is made by following component:
2～20% of monomer vinyl pyrrolidones polyether sulfone solution quality
0.5～10% of crosslinking agent monomer molar mark
0.25～5% of initator monomer molar mark
Wherein, crosslinking agent is N, N'-methylene-bisacrylamide or GMA; Initator is dibenzoyl peroxide or azodiisobutyronitrile.
2. the micro-PVPP modified poly (ether-sulfone) of in-situ polymerization hollow-fibre membrane according to claim 1, is characterized in that solvent is any in 1-METHYLPYRROLIDONE, DMF, DMA or dimethyl sulfoxide (DMSO).
3. according to the preparation method of the micro-PVPP modified poly (ether-sulfone) of in-situ polymerization described in claim 1 or 2 hollow-fibre membrane, it is characterized in that the method comprises the following steps:
1) preparation of modified poly (ether-sulfone) spinning solution
By in 10～25 parts of polyether sulfones and 90～75 parts of reactors that add with agitator, thermometer and heater of solvent, after stirring and dissolving is complete, add monomer vinyl pyrrolidones be polyether sulfone solution quality 2～20%, crosslinking agent be reaction monomers molar fraction 0.5～10%, initator is 0.25～5% of reaction monomers molar fraction, under agitation, in 50～95 ℃ of polymerisation 2-24h of temperature, obtain polyvinyl pyrrolidone modified polyether sulfone solution, through placing " slaking ", make modified poly (ether-sulfone) spinning solution;
2) preparation of modified poly (ether-sulfone) hollow-fibre membrane
By the press filtration of modified poly (ether-sulfone) spinning solution, with measuring pump, through two concentrically ringed doughnut spinneret orifices, to extrude, spray silk diameter of bore is 200～1000um, and the outer bore dia of spray silk is 300～1500um, and 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 modified poly (ether-sulfone) hollow-fibre membrane, and its internal diameter is 200～1000 μ m, and wall thickness is 50～200 μ m;
3). the post processing of modified poly (ether-sulfone) hollow-fibre membrane
Modified poly (ether-sulfone) hollow-fibre membrane, at 50～60 ℃ of poach 8～72h of temperature, is removed residual solvent.
4. the preparation method of the micro-PVPP modified poly (ether-sulfone) of in-situ polymerization hollow-fibre membrane according to claim 3, is characterized in that the polyether sulfone number-average molecular weight in hollow-fibre membrane is 20000～60000.
5. the purposes of the micro-PVPP modified poly (ether-sulfone) of in-situ polymerization hollow-fibre membrane according to claim 1, it is characterized in that this modified poly (ether-sulfone) hollow-fibre membrane makes filter, be widely used in blood purification, comprise small throughput haemodialysis, high flux hemodialysis, blood filtration and plasma separation.
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