CN103193941B - 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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- CN103193941B CN103193941B CN201310116521.9A CN201310116521A CN103193941B CN 103193941 B CN103193941 B CN 103193941B CN 201310116521 A CN201310116521 A CN 201310116521A CN 103193941 B CN103193941 B CN 103193941B
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- sultaine
- polyethersulfone
- 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, particularly relate to polyethersulfone (PES) multipolymer of a kind of sultaine methacrylic ester (SBMA) modification and preparation method thereof and purposes.
Background technology
Polyethersulfone is all widely used in industry and medicinal industry, but its characteristic easily polluted seriously limits their application.Because its pollution is caused by hydrophobicity, there are reports carries out hydrophilic modifying to it, and obtains certain antipollution effect.Existing hydrophilic modification method comprises: the LBL self-assembly of chemical graft or surface-coated hydrophilic molecules, hydrophilic molecules, plasma body or ultraviolet cause hydrophilic molecules surface reaction, add hydrophilic monomer copolymerization or add (the Zhao such as hydrophilic high mol is blended, CS, et al, Progress inMaterials Science, 2008.291:4258-4291).Wherein, polyoxyethylene glycol (PEG) modification is the most frequently used pollution-resistant membrane modifying method, but due to 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, by atom transition free radical polymerization reaction (ATRP), can form poly-SBMA side chain (Zhang, Z, et al, Biomaterials, 2013.58:76-150) at some material surface.Zwitterionic electrostatic interaction due to SBMA makes material surface cover one deck Bound moisture, thus effectively prevent surface polluted by albumen, bacterium and biostrome, therefore greatly can extend the work-ing life of material.Compared with PEG modification, the chemical property of SBMA is more stable, can be applicable to more field, such as the material directly contacted with blood and cytoskeleton, or for separating of the aspect such as fermented liquid and water treatment.
The at present report of existing SBMA modified polyvinilidene fluoride, polypropylene and regenerated cellulose mould material, but due to the chemical structure of polyethersulfone comparatively stable, be difficult to modified-reaction occurs, also do not have the report being prepared SBMA modified poly (ether-sulfone) by chemical process now.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, polyethersulfone copolymer providing a kind of sultaine methacrylate modified and preparation method thereof and purposes.
Object in the present invention is achieved through the following technical solutions: the polyethersulfone copolymer that a kind of sultaine is methacrylate modified, and its molecular structural formula is:
This multipolymer is white, amorphous solid, and molecular weight is about 60000-140000, and molecular weight polydispersity index is 1.5 ~ 3.0, dissolves in methyl-sulphoxide and N-Methyl pyrrolidone, is insoluble to second alcohol and water.
The preparation method of the polyethersulfone copolymer that described sultaine is methacrylate modified, comprises the following steps:
(1) employing relative molecular weight is the polyethersulfone of 35000-55000 is raw material, and take chloroform as solvent, trimethylchlorosilane and paraformaldehyde are reactant, SnCl
4for catalyzer, at 55 DEG C, react 48h, prepare chloromethyl polyethersulfone; Wherein, PES, trimethylchlorosilane, paraformaldehyde and SnCl
4mass ratio be 30:100:20:0.5;
(2) chloromethyl polyethersulfone and sultaine methacrylic ester being dissolved in methyl-sulphoxide with the mass ratio of 1:2-10, stirring logical nitrogen 2-5 simultaneously little of dissolving completely;
(3) add cuprous chloride and 2-2 dipyridyl, the mass ratio of sultaine methacrylic ester, cuprous chloride and dipyridyl is 100:1:2;
(4) at 45-85 DEG C, 2-10 hour is reacted; Stop logical nitrogen termination reaction, obtain the dimethyl sulfoxide solution containing the methacrylate modified polyethersulfone copolymer of sultaine;
(5) add methanol extraction and go out the methacrylate modified polyethersulfone copolymer of sultaine, washing also vacuum-drying.
The methacrylate modified polyethersulfone copolymer of described sultaine can be used for preparing flat sheet membrane, and preparation method comprises the steps:
(1) by the polyethersulfone of 1.8 ~ 3.6g and the methacrylate modified polyethersulfone copolymer of sultaine in mass ratio 1-10:1 be dissolved in 10 mL N ?in methyl-2-pyrrolidone;
(2) stirring and dissolving 10-12 hour, removes bubble, obtains the film-casting liquid clarified;
(3) utilize scraper on a glass or adopt automatic knifing machine to scrape film that thickness is 50 ?800 μm, be immersed in pure water and obtain flat sheet membrane; The average membrane pore size of flat sheet membrane be about 0.01 ?0.5 μm.
The methacrylate modified polyethersulfone copolymer of described sultaine can be used for preparing hollow-fibre membrane, and preparation method comprises the steps:
(1) by the polyethersulfone of 1.8 ~ 3.6 kg and the methacrylate modified polyethersulfone copolymer of sultaine in mass ratio 1-10:1 be dissolved in 10 L N ?in methyl-2-pyrrolidone (NMP);
(2) stirring and dissolving 10-12 hour, through de-bubbled, the film-casting liquid of obtained clarification;
(3) adopt coaxial hollow fiber spinneret, extruded by film-casting liquid through spinning nozzle, extruded velocity is 5-20ml/min, and nascent fibre is coagulation forming in the water-bath of 20-70 DEG C in temperature in atmosphere after 5-30 cm distance, and winding speed is 5-40 m/min; Its cross section of the hollow-fibre membrane prepared is for circular, and internal diameter is about 150-1500 μm, and wall thickness is about 100-550 μm, and average membrane pore size is about 0.001-0.8 μm.
The invention has the beneficial effects as follows, flat sheet membrane prepared by the present invention and hollow-fibre membrane due to the ability of its pollutent such as excellent anti-albumen and thrombocyte, can as with the material of contacting blood, cytoskeleton, separating bio fermented liquid material and material for water treatment.
Accompanying drawing explanation
Fig. 1 is the structure iron of flat sheet membrane prepared by embodiment 2.
Embodiment
The molecular structural formula of the polyethersulfone copolymer (SBMA-g-PES) that sultaine prepared by the present invention is methacrylate modified is:
This multipolymer (SBMA-g-PES) is white, amorphous solid, molecular weight is about 60000-140000, molecular weight polydispersity index is 1.5 ~ 3.0, dissolves in methyl-sulphoxide (DMSO) and N-Methyl pyrrolidone (NMP), is insoluble to second alcohol and water.
The polyethersulfone copolymer that sultaine of the present invention is methacrylate modified, prepares by the following method:
1, employing relative molecular weight is the polyethersulfone of 35000-55000 is raw material, and take chloroform as solvent, trimethylchlorosilane and paraformaldehyde are reactant, SnCl
4for catalyzer, at 55 DEG C, react 48h, prepare chloromethyl polyethersulfone (CMPES); Wherein, PES, trimethylchlorosilane, paraformaldehyde and SnCl
4mass ratio be 30:100:20:0.5.
2, chloromethyl polyethersulfone and sultaine methacrylic ester being dissolved in methyl-sulphoxide (DMSO) with the mass ratio of 1:2-10, stirring logical nitrogen 2-5 simultaneously little of dissolving completely;
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, at 45-85 DEG C, 2-10 hour is reacted; Stop logical nitrogen termination reaction, obtain the dimethyl sulfoxide solution containing the methacrylate modified polyethersulfone copolymer of sultaine;
5, add methanol extraction and go out the methacrylate modified polyethersulfone copolymer of sultaine, washing also vacuum-drying.
The ratio of this chemical reaction and condition are that technician is obtained by long-felt and experience accumulation, and those skilled in the art can not obtain its method of preparation from existing reaction technology.Up to the present, the report of SBMA modified PES is not also had.
The methacrylate modified polyethersulfone copolymer of sultaine of the present invention can be used for preparing flat sheet membrane, and preparation method is as follows:
1, by the polyethersulfone of 1.8 ~ 3.6g and the methacrylate modified polyethersulfone copolymer of sultaine in mass ratio 1-10:1 be dissolved in 10mL N ?in methyl-2-pyrrolidone (NMP);
2, stirring and dissolving 10-12 hour, removes bubble, obtains the film-casting liquid clarified;
3, utilize scraper on a glass or adopt automatic knifing machine to scrape thickness for the film of 50-800 μm, be immersed in pure water and obtain flat sheet membrane.
The average membrane pore size of above-mentioned flat sheet membrane is 0.01-0.5 μm, and albumin rejection is adjustable with ratio change.
The methacrylate modified polyethersulfone copolymer of sultaine of the present invention can be used for preparing hollow-fibre membrane, and preparation method is as follows:
1, by the polyethersulfone of 1.8 ~ 3.6kg and the methacrylate modified polyethersulfone copolymer of sultaine in mass ratio 1-10:1 be dissolved in 10L N ?in methyl-2-pyrrolidone (NMP);
2, stirring and dissolving 10-12 hour, through de-bubbled, the film-casting liquid of obtained clarification;
3, adopt coaxial hollow fiber spinneret, extruded by film-casting liquid through spinning nozzle, extruded velocity is 5-20ml/min, and nascent fibre is coagulation forming in the water-bath of 20-70 DEG C in temperature in atmosphere after 5-30cm distance, and winding speed is 5-40m/min.
Its cross section of above-mentioned hollow-fibre membrane is circular, and internal diameter is 150-1500 μm, and wall thickness is 100-550 μm, and average membrane pore size is 0.001-0.8 μm, and albumin rejection is adjustable with ratio change.
Describe the present invention in detail with reference to the accompanying drawings below, object of the present invention and effect will become more obvious.
Embodiment 1
0.36g CMPES is added in 10ml DMSO, stirring and dissolving 12 hours, add 1.8gSBMA stirring and dissolving 2 hours, logical nitrogen 5 hours removing oxygen, add 18mg CuCl and 72mg BPy, react 5 hours at 70 DEG C, stop logical nitrogen termination reaction, namely obtain the DMSO solution containing SBMA-g-PES product.Carry out ultimate analysis detection to SBMA-g-PES, recording nitrogen element content is 3.26%, and conversion percentage of grafting is 83%.
Embodiment 2
Being 83% by SBMA-PSU(percentage of grafting) 3.6g and 3.6g PES is dissolved in 40mL NMP, and stir 12 hours, and remove bubble.Utilize scraper to scrape membrane on a glass, be 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 μm, and average membrane pore size is 3.82 μm, and albumin rejection is 5%.Its structure as shown in Figure 1.
Embodiment 3
Being 158% by SBMA-PSU(percentage of grafting) 0.36g and 3.6g PES is dissolved in 20mL NMP, and stir 12 hours, and remove bubble.Utilize scraper to scrape membrane on a glass, be immersed in pure water precipitation bath, obtain the PES flat sheet membrane of SBMA modification.The flat sheet membrane thickness of gained is about 50 μm, and average membrane pore size is 0.27 μm, and albumin rejection is 95%.
Embodiment 4
Being 83% by SBMA-g-PES(percentage of grafting) 180g is dissolved in 1L NMP, and mixes with the 1L NMP being dissolved with 180g PES, stir 12 hours, and remove bubble.Extruded through coaxial hollow fiber spinneret by this spinning solution, extruded velocity is 10ml/min, and nascent fibre is in atmosphere behind the gap of 10cm, and coagulation forming in the pure water of 55 DEG C, winding speed is 10.5m/min.The hollow-fibre membrane of gained, its internal diameter is 800 μm, wall thickness 150 μm, and it is 54% that mercury injection apparatus detects porosity, and mean pore size is 0.25 μm, and albumin rejection is 61%.
Embodiment 5
Being 158% by SBMA-g-PES(percentage of grafting) 18g is dissolved in 100L NMP, and mixes with the 1L NMP being dissolved with 180g PES, stir 12 hours, and remove bubble.Extruded through coaxial hollow fiber spinneret by this spinning solution, extruded velocity is 10ml/min, and nascent fibre is in atmosphere behind the gap of 10cm, and coagulation forming in the pure water of 55 DEG C, winding speed is 10.5m/min.The hollow-fibre membrane of gained, its internal diameter is 800 μm, wall thickness 100 μm, and it is 45% that mercury injection apparatus detects porosity, and mean pore size is 0.21 μm, and albumin rejection is 89%.
Embodiment 6
Carry out albumin and oxyphorase adsorption experiment by obtaining flat sheet membrane in embodiment 2, it is respectively 1mg/cm to the adsorptive capacity of two kinds of albumen
2and 3mg/cm
2.Under same experiment condition, the pure adsorptive capacity of PES hollow-fibre membrane to two kinds of albumen is respectively 30mg/cm
2and 57mg/cm
2.Namely obtaining the absorption of modified PES film to thrombocyte and oxyphorase in embodiment 2 is original PES film 1/30 and 1/19.When modified PES material being described as contacting blood material, can be good at resisting protein adsorption.
Embodiment 7
The hollow-fibre membrane obtained in embodiment 4 is prepared into kidney machine membrane module, and it is 5% of common kidney machine to the adsorptive capacity of plasma proteins, and platelet adhesion rate is 1% of common kidney machine.
Embodiment 8
The hollow-fibre membrane obtained in embodiment 4 is prepared into membrane module, and for the treatment of rhamnolipid fermented liquid, circulate 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 is only about 30%.
Above-described embodiment is used for explaining and the present invention is described, instead of limits the invention, and in the protection domain of spirit of the present invention and claim, any amendment make the present invention and change, all fall into protection scope of the present invention.
Claims (4)
1. the polyethersulfone copolymer that sultaine is methacrylate modified, is characterized in that, its molecular structural formula is:
Wherein:
This multipolymer is white, amorphous solid, and molecular weight is 60000-140000, and molecular weight polydispersity index is 1.5 ~ 3.0, dissolves in methyl-sulphoxide and N-Methyl pyrrolidone, is insoluble to second alcohol and water.
2. a preparation method for the polyethersulfone copolymer that sultaine described in claim 1 is methacrylate modified, is characterized in that, comprises the following steps:
(1) employing relative molecular weight is the polyethersulfone of 35000-55000 is raw material, and take chloroform as solvent, trimethylchlorosilane and paraformaldehyde are reactant, SnCl
4for catalyzer, at 55 DEG C, react 48h, prepare chloromethyl polyethersulfone; Wherein, PES, trimethylchlorosilane, paraformaldehyde and SnCl
4mass ratio be 30:100:20:0.5;
(2) chloromethyl polyethersulfone and sultaine methacrylic ester being dissolved in methyl-sulphoxide with the mass ratio of 1:2-10, stirring logical nitrogen 2-5 simultaneously little of dissolving completely;
(3) add cuprous chloride and 2,2-dipyridyl, the mass ratio of sultaine methacrylic ester, cuprous chloride and dipyridyl is 100:1:2;
(4) at 45-85 DEG C, 2-10 hour is reacted; Stop logical nitrogen termination reaction, obtain the dimethyl sulfoxide solution containing the methacrylate modified polyethersulfone copolymer of sultaine;
(5) add methanol extraction and go out the methacrylate modified polyethersulfone copolymer of sultaine, washing also vacuum-drying.
3. a purposes for the polyethersulfone copolymer that sultaine is methacrylate modified, is characterized in that, the methacrylate modified polyethersulfone copolymer of sultaine can be used for preparing flat sheet membrane, and preparation method comprises the steps:
(1) by the polyethersulfone of 1.8 ~ 3.6g and the methacrylate modified polyethersulfone copolymer of sultaine in mass ratio 1-10:1 be dissolved in 10mLN ?in methyl-2-pyrrolidone;
(2) stirring and dissolving 10-12 hour, removes bubble, obtains the film-casting liquid clarified;
(3) utilize scraper on a glass or adopt automatic knifing machine to scrape film that thickness is 50 ?800 μm, be immersed in pure water and obtain flat sheet membrane; The average membrane pore size of flat sheet membrane be 0.01 ?0.5 μm.
4. a purposes for the polyethersulfone copolymer that sultaine is methacrylate modified, is characterized in that, the methacrylate modified polyethersulfone copolymer of sultaine can be used for preparing hollow-fibre membrane, and preparation method comprises the steps:
(1) by the polyethersulfone of 1.8 ~ 3.6kg and the methacrylate modified polyethersulfone copolymer of sultaine in mass ratio 1-10:1 be dissolved in 10LN ?in methyl-2-pyrrolidone (NMP);
(2) stirring and dissolving 10-12 hour, through de-bubbled, the film-casting liquid of obtained clarification;
(3) coaxial hollow fiber spinneret is adopted, film-casting liquid is extruded through spinning nozzle, extruded velocity be 5 ?20ml/min, nascent fibre in atmosphere through 5 ?after 30cm distance in temperature be 20 ?coagulation forming in the water-bath of 70 DEG C, winding speed be 5 ?40m/min; Its cross section of the hollow-fibre membrane prepared for circular, internal diameter be 150 ?1500 μm, wall thickness be 100 ?550 μm, average membrane pore size be 0.001 ?0.8 μm.
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| EP3071318A1 (en) * | 2013-11-22 | 2016-09-28 | 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 |
| 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 |
| 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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| 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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| 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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