CN103193941A - Polyether sulfone copolymer modified by sulphobetaine metacrylic acid ester as well as preparation method and application of polyether sulfone copolymer - Google Patents
Polyether sulfone copolymer modified by sulphobetaine metacrylic acid ester as well as preparation method and application of polyether sulfone copolymer Download PDFInfo
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- CN103193941A CN103193941A CN2013101165219A CN201310116521A CN103193941A CN 103193941 A CN103193941 A CN 103193941A CN 2013101165219 A CN2013101165219 A CN 2013101165219A CN 201310116521 A CN201310116521 A CN 201310116521A CN 103193941 A CN103193941 A CN 103193941A
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- methacrylic acid
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- polyether sulfone
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Abstract
The invention discloses a polyether sulfone copolymer modified by sulphobetaine metacrylic acid ester as well as a preparation method and an application of the polyether sulfone copolymer. The polyether sulfone copolymer disclosed by the invention is prepared by taking sulphobetaine metacrylic acid ester and polyether sulfone as raw materials, taking dimethylsulfoxide as a solvent and carrying out free radical polymerization under the action of a catalyst. The polyether sulfone copolymer disclosed by the invention is white solid at normal temperature, is soluble in dimethylsulfoxide and N-methylpyrrolidone and is insoluble in water, methyl alcohol and alcohol. Flat sheet membranes and hollow fiber membranes prepared by the polyether sulfone copolymer disclosed by the invention are excellent in capability of resisting pollutants such as protein and thrombocyte, so that the flat sheet membranes and the hollow fiber membranes can be used as materials directly contacted to the blood, cytoskeletons, separated organism fermentation liquid or water treatment materials.
Description
Technical field
The invention belongs to the preparing technical field of pollution-resistant membrane, relate in particular to polyethersulfone (PES) multipolymer and preparation method thereof and the purposes of a kind of sultaine methacrylic ester (SBMA) modification.
Background technology
Polyethersulfone all is widely used in industry and medicinal industry, but its characteristic of easily polluting has seriously limited their application.Because its pollution is to be caused by hydrophobicity, more existing reports carry out hydrophilic modifying to it, and have obtained certain antipollution effect.Existing hydrophilic modification method comprises: the self-assembly layer by layer of chemical graft or surface-coated hydrophilic molecules, hydrophilic molecules, plasma body or ultraviolet ray cause the hydrophilic molecules surface reaction, add (Zhao such as hydrophilic monomer copolymerization or the blend of adding hydrophilic high mol, CS, et al, Progress in Materials Science, 2008.291:4258-4291).Wherein, polyoxyethylene glycol (PEG) modification is the most frequently used pollution-resistant membrane modifying method, but because the easy oxidized degraded of PEG causes adorned material surface to lose antifouling property.
Sultaine methacrylic ester (SBMA) is a kind of amphipathic compound.This compound is by atom transition free radical polymerization reaction (ATRP), can some material surface form poly-SBMA side chain (Zhang, Z, et al, Biomaterials, 2013.58:76-150).Because the zwitterionic electrostatic interaction of SBMA makes material surface cover one deck in conjunction with water, thereby prevented that effectively the surface from by albumen, bacterium and biostrome pollution, therefore can prolong the work-ing life of material greatly.Compare with the PEG modification, the chemical property of SBMA is more stable, can be applicable to more field, such as and the blood material and the cytoskeleton that directly contact, or for separating of aspects such as fermented liquid and water treatments.
The report of at present existing SBMA modified polyvinilidene fluoride, polypropylene and regenerated cellulose mould material, but because the chemical structure of polyethersulfone is comparatively stable, be difficult to modified-reaction takes place, the report for preparing the SBMA modified poly (ether-sulfone) by chemical process is not also arranged now.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, ester modified polyethersulfone copolymer of a kind of sultaine methacrylic acid and preparation method thereof and purposes are provided.
Purpose among the present invention is achieved through the following technical solutions: the ester modified polyethersulfone copolymer of a kind of sultaine methacrylic acid, and its molecular structural formula is:
This multipolymer is white amorphous solid, and molecular weight is about 60000-140000, and the molecular weight polydispersity index is 1.5～3.0, dissolves in methyl-sulphoxide and N-Methyl pyrrolidone, is insoluble to the second alcohol and water.
The preparation method of the polyethersulfone copolymer that described sultaine methacrylic acid is ester modified may further comprise the steps:
(1) the employing relative molecular weight is that the polyethersulfone of 35000-55000 is raw material, is solvent with the chloroform, and trimethylchlorosilane and Paraformaldehyde 96 are reactant, SnCl
4Be catalyzer, react 48h down at 55 ℃, prepare the chloromethyl polyethersulfone; Wherein, PES, trimethylchlorosilane, Paraformaldehyde 96 and SnCl
4Mass ratio be 30:100:20:0.5;
(2) chloromethyl polyethersulfone and the sultaine methacrylic ester mass ratio with 1:2-10 is dissolved in the methyl-sulphoxide, stirs logical nitrogen 2-5 hour simultaneously to dissolving fully;
(3) add cuprous chloride and 2-2 dipyridyl, the mass ratio of sultaine methacrylic ester, cuprous chloride and dipyridyl is 100:1:2;
(4) reacted 2-10 hour down at 45-85 ℃; Stop logical nitrogen termination reaction, obtain containing the dimethyl sulfoxide solution of the ester modified polyethersulfone copolymer of sultaine methacrylic acid;
(5) add methanol extraction and go out the ester modified polyethersulfone copolymer of sultaine methacrylic acid, washing and vacuum-drying.
The ester modified polyethersulfone copolymer of described sultaine methacrylic acid can be used for preparing flat sheet membrane, and the preparation method comprises the steps:
(1) polyethersulfone and the ester modified polyethersulfone copolymer of sultaine methacrylic acid with 1.8～3.6g is dissolved in the 10 mL N ?methyl-2-pyrrolidones by mass ratio 1-10:1;
(2) stirring and dissolving 10-12 hour, remove bubble, the film-casting liquid that obtains clarifying;
(3) utilize scraper on sheet glass or adopt automatic knifing machine scrape thickness be 50 ?the film of 800 μ m, it is immersed in obtains flat sheet membrane in the pure water; The average membrane pore size of flat sheet membrane be about 0.01 ?0.5 μ m.
The ester modified polyethersulfone copolymer of described sultaine methacrylic acid can be used for preparing hollow-fibre membrane, and the preparation method comprises the steps:
(1) polyethersulfone and the ester modified polyethersulfone copolymer of sultaine methacrylic acid with 1.8～3.6 kg is dissolved in the 10 L N ?methyl-2-pyrrolidones (NMP) by mass ratio 1-10:1;
(2) stirring and dissolving 10-12 hour, through de-bubbled, make the film-casting liquid of clarification;
(3) adopt coaxial tubular fibre spinning nozzle, film-casting liquid is extruded through spinning nozzle, extruded velocity is 5-20ml/min, nascent fibre in air through 5-30 cm apart from after be coagulation forming in 20-70 ℃ the water-bath in temperature, winding speed is 5-40 m/min; Its cross section of the hollow-fibre membrane for preparing is for circular, and internal diameter is about 150-1500 μ m, and wall thickness is about 100-550 μ m, and average membrane pore size is about 0.001-0.8 μ m.
The invention has the beneficial effects as follows that the flat sheet membrane of the present invention's preparation and hollow-fibre membrane can be as the material that contacts with blood, cytoskeleton, separating bio fermented liquid material and material for water treatment owing to the ability of pollutents such as its excellent anti albumen and thrombocyte.
Description of drawings
Fig. 1 is the structure iron of the flat sheet membrane of embodiment 2 preparations.
Embodiment
The molecular structural formula of the polyethersulfone copolymer (SBMA-g-PES) that the sultaine methacrylic acid of the present invention's preparation is ester modified is:
This multipolymer (SBMA-g-PES) is white amorphous solid, and molecular weight is about 60000-140000, and the molecular weight polydispersity index is 1.5～3.0, dissolves in methyl-sulphoxide (DMSO) and N-Methyl pyrrolidone (NMP), is insoluble to the second alcohol and water.
The ester modified polyethersulfone copolymer of sultaine methacrylic acid of the present invention prepares by the following method:
1, the employing relative molecular weight is that the polyethersulfone of 35000-55000 is raw material, is solvent with the chloroform, and trimethylchlorosilane and Paraformaldehyde 96 are reactant, SnCl
4Be catalyzer, react 48h down at 55 ℃, prepare chloromethyl polyethersulfone (CMPES); Wherein, PES, trimethylchlorosilane, Paraformaldehyde 96 and SnCl
4Mass ratio be 30:100:20:0.5.
2, chloromethyl polyethersulfone and the sultaine methacrylic ester mass ratio with 1:2-10 is dissolved in the methyl-sulphoxide (DMSO), stirs logical nitrogen 2-5 hour simultaneously to dissolving fully;
3, add cuprous chloride and 2-2 dipyridyl (BPy), the mass ratio of sultaine methacrylic ester, cuprous chloride and dipyridyl is 100:1:2;
4, reacted 2-10 hour down at 45-85 ℃; Stop logical nitrogen termination reaction, obtain containing the dimethyl sulfoxide solution of the ester modified polyethersulfone copolymer of sultaine methacrylic acid;
5, add methanol extraction and go out the ester modified polyethersulfone copolymer of sultaine methacrylic acid, washing and vacuum-drying.
The ratio of this chemical reaction and condition are that the technician obtains by long-felt and experience accumulation, and those skilled in the art can not obtain its method of preparation from existing reaction technology.The report that up to the present, the SBMA modified PES is not also arranged.
The ester modified polyethersulfone copolymer of sultaine methacrylic acid of the present invention can be used for preparing flat sheet membrane, and the preparation method is as follows:
1, polyethersulfone and the ester modified polyethersulfone copolymer of sultaine methacrylic acid with 1.8～3.6g is dissolved in the 10mL N ?methyl-2-pyrrolidone (NMP) by mass ratio 1-10:1;
2, stirring and dissolving 10-12 hour, remove bubble, the film-casting liquid that obtains clarifying;
3, utilize scraper on sheet glass or adopt automatic knifing machine to scrape thickness and be the film of 50-800 μ m, it be immersed in obtain flat sheet membrane in the pure water.
The average membrane pore size of above-mentioned flat sheet membrane is 0.01-0.5 μ m, and the albumin rejection changes adjustable with ratio.
The ester modified polyethersulfone copolymer of sultaine methacrylic acid of the present invention can be used for preparing hollow-fibre membrane, and the preparation method is as follows:
1, polyethersulfone and the ester modified polyethersulfone copolymer of sultaine methacrylic acid with 1.8～3.6kg is dissolved in the 10L N ?methyl-2-pyrrolidone (NMP) by mass ratio 1-10:1;
2, stirring and dissolving 10-12 hour, through de-bubbled, make the film-casting liquid of clarification;
3, adopt coaxial tubular fibre spinning nozzle, film-casting liquid is extruded through spinning nozzle, extruded velocity is 5-20ml/min, nascent fibre in air through 5-30cm apart from after be coagulation forming in 20-70 ℃ the water-bath in temperature, winding speed is 5-40m/min.
Its cross section of above-mentioned hollow-fibre membrane is circular, and internal diameter is 150-1500 μ m, and wall thickness is 100-550 μ m, and average membrane pore size is 0.001-0.8 μ m, and the albumin rejection changes adjustable with ratio.
Describe the present invention below with reference to the accompanying drawings in detail, it is more obvious that purpose of the present invention and effect will become.
Embodiment 1
0.36g CMPES is added among the 10ml DMSO, stirring and dissolving 12 hours, added 1.8g SBMA stirring and dissolving 2 hours, logical nitrogen was removed oxygen in 5 hours, add 18mg CuCl and 72mg BPy, reacted 5 hours down at 70 ℃, stop logical nitrogen termination reaction, namely obtain to contain the DMSO solution of SBMA-g-PES product.SBMA-g-PES is carried out ultimate analysis detect, recording nitrogen element content is 3.26%, and the conversion percentage of grafting is 83%.
Embodiment 2
Being 83% with the SBMA-PSU(percentage of grafting) 3.6g and 3.6g PES be dissolved among the 40mL NMP, stirred 12 hours, and remove bubble.Utilize scraper to scrape membrane at sheet glass, it is immersed in NMP: in the precipitation bath of pure water=6:4, obtain the PES flat sheet membrane of SBMA modification.The flat sheet membrane thickness of gained is about 70 μ m, and average membrane pore size is 3.82 μ m, and the albumin rejection is 5%.Its structure as shown in Figure 1.
Embodiment 3
Being 158% with the SBMA-PSU(percentage of grafting) 0.36g and 3.6g PES be dissolved among the 20mL NMP, stirred 12 hours, and remove bubble.Utilize scraper to scrape membrane at sheet glass, it is immersed in the pure water precipitation bath, obtain the PES flat sheet membrane of SBMA modification.The flat sheet membrane thickness of gained is about 50 μ m, and average membrane pore size is 0.27 μ m, and the albumin rejection is 95%.
Embodiment 4
Being 83% with the SBMA-g-PES(percentage of grafting) 180g is dissolved among the 1L NMP, and mix with the 1L NMP that is dissolved with 180g PES, stirred 12 hours, and remove bubble.This spinning solution is extruded through coaxial tubular fibre spinning nozzle, and extruded velocity is 10ml/min, and behind the gap of 10cm, coagulation forming in 55 ℃ pure water, winding speed are 10.5m/min to nascent fibre in air.The hollow-fibre membrane of gained, its internal diameter are 800 μ m, wall thickness 150 μ m, and it is 54% that mercury injection apparatus detects porosity, and mean pore size is 0.25 μ m, and the albumin rejection is 61%.
Embodiment 5
Being 158% with the SBMA-g-PES(percentage of grafting) 18g is dissolved among the 100L NMP, and mix with the 1L NMP that is dissolved with 180g PES, stirred 12 hours, and remove bubble.This spinning solution is extruded through coaxial tubular fibre spinning nozzle, and extruded velocity is 10ml/min, and behind the gap of 10cm, coagulation forming in 55 ℃ pure water, winding speed are 10.5m/min to nascent fibre in air.The hollow-fibre membrane of gained, its internal diameter are 800 μ m, wall thickness 100 μ m, and it is 45% that mercury injection apparatus detects porosity, and mean pore size is 0.21 μ m, and the albumin rejection is 89%.
Embodiment 6
Carry out albumin and oxyphorase adsorption experiment with obtaining flat sheet membrane among the embodiment 2, it is respectively 1mg/cm to the adsorptive capacity of two kinds of albumen
2And 3mg/cm
2Under the same experiment condition, pure PES hollow-fibre membrane is respectively 30mg/cm to the adsorptive capacity of two kinds of albumen
2And 57mg/cm
2Be that the PES film that obtains among the embodiment 2 after the modification is original PES film 1/30 and 1/19 to the absorption of thrombocyte and oxyphorase.When illustrating that PES material after the modification is as the blood contact material, can be good at resisting protein adsorption.
Embodiment 7
The hollow-fibre membrane that obtains among the embodiment 4 is prepared into the kidney machine membrane module, and its adsorptive capacity to plasma proteins is 5% of common kidney machine, and the thrombocyte adsorption rate is 1% of common kidney machine.
Embodiment 8
The hollow-fibre membrane that obtains among the embodiment 4 is prepared into membrane module, for the treatment of sandlwood sugar ester fermented liquid, circulates after 24 hours, wash half an hour with clear water, its flux recovery rate is more than 95%.The flux recovery rate of corresponding PES film only is about 30%.
Above-described embodiment is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (4)
1. the polyethersulfone copolymer that the sultaine methacrylic acid is ester modified is characterized in that, its molecular structural formula is:
This multipolymer is white amorphous solid, and molecular weight is about 60000-140000, and the molecular weight polydispersity index is 1.5～3.0, dissolves in methyl-sulphoxide and N-Methyl pyrrolidone, is insoluble to the second alcohol and water.
2. the preparation method of the ester modified polyethersulfone copolymer of the described sultaine methacrylic acid of claim 1 is characterized in that, may further comprise the steps:
(1) the employing relative molecular weight is that the polyethersulfone of 35000-55000 is raw material, is solvent with the chloroform, and trimethylchlorosilane and Paraformaldehyde 96 are reactant, SnCl
4Be catalyzer, react 48h down at 55 ℃, prepare the chloromethyl polyethersulfone; Wherein, PES, trimethylchlorosilane, Paraformaldehyde 96 and SnCl
4Mass ratio be 30:100:20:0.5;
(2) chloromethyl polyethersulfone and the sultaine methacrylic ester mass ratio with 1:2-10 is dissolved in the methyl-sulphoxide, stirs logical nitrogen 2-5 hour simultaneously to dissolving fully;
(3) add cuprous chloride and 2-2 dipyridyl, the mass ratio of sultaine methacrylic ester, cuprous chloride and dipyridyl is 100:1:2;
(4) reacted 2-10 hour down at 45-85 ℃; Stop logical nitrogen termination reaction, obtain containing the dimethyl sulfoxide solution of the ester modified polyethersulfone copolymer of sultaine methacrylic acid;
(5) add methanol extraction and go out the ester modified polyethersulfone copolymer of sultaine methacrylic acid, washing and vacuum-drying.
3. the purposes of the ester modified polyethersulfone copolymer of a sultaine methacrylic acid is characterized in that the ester modified polyethersulfone copolymer of sultaine methacrylic acid can be used for preparing flat sheet membrane, and the preparation method comprises the steps:
(1) polyethersulfone and the ester modified polyethersulfone copolymer of sultaine methacrylic acid with 1.8～3.6g is dissolved in the 10mL N ?methyl-2-pyrrolidone by mass ratio 1-10:1;
(2) stirring and dissolving 10-12 hour, remove bubble, the film-casting liquid that obtains clarifying;
(3) utilize scraper on sheet glass or adopt automatic knifing machine scrape thickness be 50 ?the film of 800 μ m, it is immersed in obtains flat sheet membrane in the pure water; The average membrane pore size of flat sheet membrane be about 0.01 ?0.5 μ m.
4. the purposes of the ester modified polyethersulfone copolymer of a sultaine methacrylic acid is characterized in that the ester modified polyethersulfone copolymer of sultaine methacrylic acid can be used for preparing hollow-fibre membrane, and the preparation method comprises the steps:
(1) polyethersulfone and the ester modified polyethersulfone copolymer of sultaine methacrylic acid with 1.8～3.6kg is dissolved in the 10L N ?methyl-2-pyrrolidone (NMP) by mass ratio 1-10:1;
(2) stirring and dissolving 10-12 hour, through de-bubbled, make the film-casting liquid of clarification;
(3) adopt coaxial tubular fibre spinning nozzle, film-casting liquid extruded through spinning nozzle, extruded velocity be 5 ?20ml/min, nascent fibre in air through 5 ?30cm apart from after in temperature be 20 ?coagulation forming in 70 ℃ the water-bath, winding speed be 5 ?40m/min; Its cross section of the hollow-fibre membrane for preparing is for circular, internal diameter be about 150 ?1500 μ m, wall thickness be about 100 ?550 μ m, average membrane pore size be about 0.001 ?0.8 μ m.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015075178A1 (en) * | 2013-11-22 | 2015-05-28 | Basf Se | Polymeric antifouling additives for membranes |
| CN104984664A (en) * | 2015-06-20 | 2015-10-21 | 杭州汉膜新材料科技有限公司 | Method for preparing amino acid modified polyether sulfone hematodialysis membrane |
| CN109180939A (en) * | 2018-07-06 | 2019-01-11 | 杭州安诺过滤器材有限公司 | A kind of polyether sulfone and preparation method thereof of the side chain containing more Sulfonic acid structures |
| CN110193295A (en) * | 2019-06-19 | 2019-09-03 | 黑龙江大学 | A kind of preparation method of high no pollution flux PVDF tube-type micropore film |
| CN116589681A (en) * | 2023-07-17 | 2023-08-15 | 富海(东营)新材料科技有限公司 | Sulfonated polyether sulfone as well as preparation method and application thereof |
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| CN101530753A (en) * | 2009-03-30 | 2009-09-16 | 浙江大学 | PEG grafted polysulphone or polyether sulphone hollow fibrous membrane, preparation method and application thereof |
| CN102311526A (en) * | 2011-06-07 | 2012-01-11 | 天津大学 | Composite high-density long-tail-chain-containing bottle brush type polymer chain modified material and preparation method thereof |
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- 2013-04-03 CN CN201310116521.9A patent/CN103193941B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101530753A (en) * | 2009-03-30 | 2009-09-16 | 浙江大学 | PEG grafted polysulphone or polyether sulphone hollow fibrous membrane, preparation method and application thereof |
| CN102311526A (en) * | 2011-06-07 | 2012-01-11 | 天津大学 | Composite high-density long-tail-chain-containing bottle brush type polymer chain modified material and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015075178A1 (en) * | 2013-11-22 | 2015-05-28 | Basf Se | Polymeric antifouling additives for membranes |
| CN104984664A (en) * | 2015-06-20 | 2015-10-21 | 杭州汉膜新材料科技有限公司 | Method for preparing amino acid modified polyether sulfone hematodialysis membrane |
| CN109180939A (en) * | 2018-07-06 | 2019-01-11 | 杭州安诺过滤器材有限公司 | A kind of polyether sulfone and preparation method thereof of the side chain containing more Sulfonic acid structures |
| CN109180939B (en) * | 2018-07-06 | 2021-03-09 | 杭州安诺过滤器材有限公司 | Polyether sulfone with side chain containing polysulfonic acid structure and preparation method thereof |
| CN110193295A (en) * | 2019-06-19 | 2019-09-03 | 黑龙江大学 | A kind of preparation method of high no pollution flux PVDF tube-type micropore film |
| CN116589681A (en) * | 2023-07-17 | 2023-08-15 | 富海(东营)新材料科技有限公司 | Sulfonated polyether sulfone as well as preparation method and application thereof |
| CN116589681B (en) * | 2023-07-17 | 2023-09-12 | 富海(东营)新材料科技有限公司 | Sulfonated polyether sulfone as well as preparation method and application thereof |
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