CN103252177A - Glycosyl/sulfonated modified affiliative polymer hollow fiber separating membrane, and preparation method and use thereof - Google Patents
Glycosyl/sulfonated modified affiliative polymer hollow fiber separating membrane, and preparation method and use thereof Download PDFInfo
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Abstract
The invention discloses a glycosyl/sulfonated modified affiliative polymer hollow fiber separating membrane and a preparation method thereof. The membrane is composed of polymer resin, sulfonated polymer resin and saccharide polymer, has a good specificity adsorption effect on LDL (low-density lipoprotein) under optimized raw materials and proportion, is good in stability and biocompatibility, reusable and low in cost, and can be put into large-scale clinical application. The preparation method comprises the following processes of: dissolving the polymer resin, sulfonated polymer resin, saccharide polymer and a pore-foaming agent for the membrane in a dissolvent according to a certain proportion to prepare a uniform spinning membrane-preparing solution, filtering the spinning membrane-preparing solution, defoaming the filtered spinning membrane-preparing solution in vacuum, spinning through a immersion-precipitation phase transformation method to prepare the hollow fiber membrane, and then sufficiently rinsing the prepared hollow fiber membrane in deionized water and ultrapure water in order. The blending dissolving preparation method adopted by the invention has the advantages that the operation is simple and safe and the raw materials are cheap and easily available.
Description
Technical field
The invention belongs to bio-separation engineering field, be specifically related to the affine polymer hollow fiber separating film of a kind of glycosyl/sulfonation modifying, Preparation Method And The Use.
Background technology
Angiocardiopathy is the primary disease (" first killer ") that threatens human health, shows according to the World Health Organization's assessment report in 2008, and the number of dying from angiocardiopathy accounts for 29% of the total death toll in the whole world.Epidemiological study and clinical practice show, the LDL excessive concentration in angiocardiopathy and the blood and cause in the LDL intravasation wall thus and be oxidized to the low-density lipoprotein of oxidized form (ox～LDL) has substantial connection.
(low density lipoprotein LDL) is the principal mode that the synthetic endogenous cholesterol of liver and cholesteryl ester are transported to its hetero-organization to low-density lipoprotein.LDL is the spheric granules that diameter is about 20～30 nm, and its number-average molecular weight excursion is 2～35 * 10
6, lipid content accounts for 79% in the particle, and wherein CHF 8%, cholesteryl ester 38%, phosphatide is about 22%, triglycerides 10%, carrying an ester gp is 21%.The main apolipoprotein of LDL is ApoB(93%), surplus is ApoA, ApoC, ApoD, ApoE etc.
LDL excessive concentration in blood then can cause blood viscosity to rise, and in blood vessel breakage or stenosis, easy and other albumen formation patches of oxidized LDL cause atherosclerotic thereby continue accumulation.LDL content can obviously improve cardiovascular rheological characteristic in the reduction blood, therefore becomes the important measures that reduce the cardiovascular disease incidence rate.The blood purification therapy is a kind of method that can effectively reduce LDL concentration in the blood, and result for the treatment of is quick, remarkable, and effect and unconspicuous serious heredity hypercholesterolemiapatients patients are particularly suitable for controlling by fat-reducing medicament and meals.But it should be noted that (alleviating on the angiocardiopathy has very useful effect for high density lipoprotein, HDL) cholesterol level in keeping blood for other useful components, especially HDL in the blood.Therefore, when carrying out the LDL specific adsorption, should farthest reduce sorbing material to the non-specific adsorption of other useful components in the blood.
Aspect preparation LDL sorbing material, the researcher has done a large amount of work, and carrier and the part of prepared LDL sorbing material are varied.Carrier mainly comprises polysulfones, polyvinyl alcohol, glucan, shitosan etc.Part can be divided into immunity absorption and affine absorption two classes by the mechanism difference, mainly comprises heparin, polypeptide, chlorosulfonic acid etc.Processing method is then based on chemical synthesis.Chinese patent CN200610200095.7 has announced a kind of sorbing material with taurine and two kinds of adsorption function bases of heteroauxin, by the acting in conjunction of functional group, LDL is had higher adsorption capacity, and is less to the non-specific adsorption of HDL simultaneously.Canadian Patent CA2001358 has announced and a kind of LDL antibody has been coupled to the sorbing material surface, makes the method for its specific adsorption LDL, and adsorptive selectivity height, adsorption effect are obvious.German patent DE 3782657D has announced a kind of preparation method of porous cellulose, and it has the selective of height to the absorption of LDL, and adsorbance increases along with cellulosic increase, and adsorbance is big and blood compatibility is better.But the cost of material of above-mentioned sorbing material is higher, is difficult for obtaining, and the preparation technology of sorbing material is comparatively complicated, can't satisfy the needs of extensive clinical use.
Summary of the invention
Technical problem to be solved by this invention provides a kind ofly has the simple and sorbing material with low cost than high selectivity, biocompatibility, preparation technology to low-density lipoprotein (LDL).Sorbing material provided by the invention is the affine polymer hollow fiber separating film of a kind of glycosyl/sulfonation modifying, described polymer hollow fiber separating film is made up of fluoropolymer resin, sulfonated polymer resin and carbohydrate macromolecule, the mass fraction of fluoropolymer resin is 10%～70% in the described polymer hollow fiber separating film, the mass fraction of sulfonated polymer resin is 2%～30%, and the high molecular mass fraction of carbohydrate is 5%～90%; Sulfonic group and the high molecular hydroxyl of carbohydrate of possess hydrophilic property is rich on described polymer hollow fiber separating film surface, and described polymer hollow fiber separating film has selective identification absorption property to the low-density lipoprotein white matter; Described polymer hollow fiber separating film aperture is 0.01～0.5 μ m.
Glycosyl/sulfonation modifying of the present invention is affine, and the polymer hollow fiber separating film has the principle of specific adsorption to be to LDL: have the character of positive charge at LDL, the sulfonated polymer resin that has negative electrical charge in the polymer hollow fiber separating film produces suction-operated by charge interaction to LDL; The hydroxyl that carbohydrate macromolecule in the polymer hollow fiber separating film contains has poor phase isomery character, the recognition reaction site can be provided, produce the specificity combination with the protein structure among the LDL, and then absorption LDL, and, described carbohydrate molecule can not have positive charge, weakens the electric charge of LDL is adsorbing to prevent the sulfonated polymer resin.In order to reach above-mentioned effect, that the present invention selects is not positively charged, can produce the carbohydrate macromolecule of specificity combination with protein structure among the LDL.Therefore, glycosyl/sulfonation modifying of the present invention is affine polymer hollow fiber separating film is that the specificity of the electric charge suction-operated of the sulfonic acid group by the sulfonated polymer resin and carbohydrate high molecular weight hydroxy is in conjunction with synergistic result to the specific adsorption effect of LDL, in order to make these two kinds of effects reach synergy preferably, the mass fraction of fluoropolymer resin is 10%～70% in the described polymer hollow fiber separating film, the mass fraction of sulfonated polymer resin is 2%～50%, and the high molecular mass fraction of carbohydrate is 5%～90%; Preferably, the mass fraction of fluoropolymer resin is 15%～60% in the described polymer hollow fiber separating film, and the mass fraction of sulfonated polymer resin is 5%～35%, and the high molecular mass fraction of carbohydrate is 10%～75%.Fluoropolymer resin is as the matrix of polymer hollow fiber separating film, can be preferably fixedly sulfonated polymer resin and carbohydrate macromolecule, and excellent biological compatibility is arranged, be comparatively ideal backing material.Described polymer hollow fiber separating film is the doughnut structure, has selected suitable aperture (aperture is 0.01～0.5 μ m), is conducive to improve the adsorption effect of polymer hollow fiber separating film.
Further, described fluoropolymer resin is polysulfones or polyether sulfone; Wherein, the polysulfones number-average molecular weight is 40000～120000; The polyether sulfone number-average molecular weight is 40000～150000.Preferably, the polysulfones number-average molecular weight is 60000～90000; The polyether sulfone number-average molecular weight is 60000～110000.
Further, described sulfonated polymer resin is SPSF or sulfonated polyether sulfone; Wherein, the SPSF number-average molecular weight is 60000～120000, sulfonation degree is 5%～80%; The sulfonated polyether sulfone number-average molecular weight is 60000～150000, and sulfonation degree is 5%～80%.Preferably, described SPSF number-average molecular weight be 80000～95000, sulfonation degree 10%～30%; The sulfonated polyether sulfone number-average molecular weight is 85000～120000, and sulfonation degree is 10%～30%.
Further, described carbohydrate macromolecule be selected from glucan, peptide glycan, the marine alga polysaccharide any one or multiple arbitrarily, the high molecular molecular weight of described carbohydrate is 6～400,000; Preferably, the high molecular molecular weight of described carbohydrate is 10～300,000.
Further, described polymer hollow fiber separating film can be made up of polysulfones, SPSF and carbohydrate macromolecule, also can be formed by polyether sulfone, SPSF and carbohydrate macromolecule, also can be formed by polysulfones, sulfonated polyether sulfone and carbohydrate macromolecule, can also be formed by polyether sulfone, sulfonated polyether sulfone and carbohydrate macromolecule.
Glycosyl/sulfonation modifying provided by the invention is affine, and the polymer hollow fiber separating film has good selection adsorption effect to low-density lipoprotein, can be used as hemodialysis membrane or membrane for purifying blood, is used for haemodialysis or blood purification.Glycosyl/sulfonation modifying of the present invention is affine polymer hollow fiber separating film can reach 61.2～61.5%, 0.2～0.3% adsorption effect respectively to the adsorption rate of low-density lipoprotein (LDL) and HDL (HDL).
The present invention also provides the preparation method of the affine polymer hollow fiber separating film of a kind of glycosyl/sulfonation modifying, comprises the steps::
(1) preparation of preparation liquid: fluoropolymer resin, sulfonated polymer resin and organic solvent are mixed, under 10～90 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains polymer resin solution; The carbohydrate macromolecule is dissolved in dimethyl sulfoxide (DMSO), under 20～90 ℃, carries out stirring and dissolving, treat that solute dissolves fully after, filter cleaner makes concentration and is 10～30% carbohydrate Polymer Solution; The above-mentioned polymer resin solution that makes, carbohydrate Polymer Solution and pore-foaming agent are mixed, under 10～90 ℃, mix 6～48h, then with obtaining preparation liquid behind inert gas deaeration 6～48h;
(2) preparation liquid is extruded the immersion coagulant liquid from spinning head, formed as-spun fibre, fully after the rinsing, taking-up is dried, and namely makes the affine polymer hollow fiber separating film of glycosyl/sulfonation modifying.
Further, the proportioning that fluoropolymer resin described in the step (1), sulfonated polymer resin and organic solvent mix is: the mass fraction of fluoropolymer resin is 15～25%, the mass fraction of sulfonated polymer resin is 5～15%, and the mass fraction of organic solvent is 60～80%.
Further, the organic solvent described in the step (1) is selected from dimethyl formamide (DMF), N, N-dimethylacetylamide (DMAC) and N-methyl pyrrolidone (NMP).
Further, the proportioning that polymer resin solution described in the step (1), carbohydrate Polymer Solution and pore-foaming agent mix is: the mass fraction of polymer resin solution is 30～70%, the mass fraction of carbohydrate Polymer Solution is 20～60%, and the mass fraction of pore-foaming agent is 1～20%.
Further, the pore-foaming agent described in the step (1) be selected among PEG400, PEG600, PEG800, PEG1000, PEG2000, PVP-K17, PVP-K30, the PVP-K90 any one or multiple arbitrarily.
Further, described fluoropolymer resin is polysulfones or polyether sulfone; Wherein, the polysulfones number-average molecular weight is 40000～120000; The polyether sulfone number-average molecular weight is 40000～150000.Preferably, the polysulfones number-average molecular weight is 60000～90000; The polyether sulfone number-average molecular weight is 60000～110000;
Further, described sulfonated polymer resin is SPSF or sulfonated polyether sulfone; Wherein, the SPSF number-average molecular weight is 60000～120000, sulfonation degree is 5%～80%; The sulfonated polyether sulfone number-average molecular weight is 60000～150000, and sulfonation degree is 5%～80%.Preferably, described SPSF number-average molecular weight be 80000～95000, sulfonation degree 10%～30%; The sulfonated polyether sulfone number-average molecular weight is 85000～120000, and sulfonation degree is 10%～30%.
Further, described carbohydrate macromolecule be selected from glucan, peptide glycan, the marine alga polysaccharide any one or multiple arbitrarily, the high molecular molecular weight of described carbohydrate is 6～400,000; Preferably, the high molecular molecular weight of described carbohydrate is 10～300,000.
The present invention adopts blending method to prepare the affine polymer hollow fiber separating film of glycosyl/sulfonation modifying, utilize the sulfonated polymer elecrtonegativity to the electropositive selective and carbohydrate of LDL selective to protein arranged, with the two blend, and adding pore-foaming agent, utilize the spinning of immersion precipitation phase inversion, be prepared into hollow-fibre membrane.
Method preparation process of the present invention is simple and raw material are cheap and easy to get, properties of product are stable can repeatedly be used, and greatly reduces medical treatment cost, and good biocompatibility, little to the side effect of patient's generation, it is all higher that LDL is selectively reached adsorption rate, is expected to for clinical expansion.
The affine polymer hollow fiber separating film of glycosyl/sulfonation modifying of method preparation of the present invention has good selection adsorption effect to low-density lipoprotein, can be used as hemodialysis membrane or membrane for purifying blood, is used for haemodialysis or blood purification.According to the affine polymer hollow fiber separating film of glycosyl/sulfonation modifying of method of the present invention preparation, can reach 61.2～61.5%, 0.2～0.3% adsorption effect respectively to the adsorption rate of low-density lipoprotein (LDL) and HDL (HDL).
Beneficial effect of the present invention is:
Glycosyl/sulfonation modifying provided by the invention is affine, and the polymer hollow fiber separating film can be selected absorption to low-density lipoprotein, be had excellent biological compatibility and excellent stability.The present invention has determined carbohydrate hydroxyl and the synergistic optimal proportion scope of sulfonic acid group in preparation process, filtered out the selective height to LDL, the efficient height, the comparatively ideal tunica fibrosa of adsorption rate, selected polysulfones, SPSF and macromolecule sugar are biocompatibility material preferably, can play the selection absorption to low-density lipoprotein after its blend under the condition that keeps better biocompatibility preferably.Film can repeatedly use, and stability is good, good reproducibility, and side effect is little, and clinical expansion prospect is preferably arranged.
Method by physical blending prepares solution, and working condition gentleness, technology are simple, and spray silk jet stability is good in the spinning process, and the tunica fibrosa morphosis can be controlled by the condition of regulating spinning process at an easy rate, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is embodiments of the invention related data and test result figure.
The specific embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
To dry polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000 of handling in 25: 15: 60 ratios (mass ratio), sulfonation degree=50%), NMP slowly adds in the there-necked flask successively, carry out stirring and dissolving under 90 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; In 90: 10 ratios (mass ratio) dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=100000) are slowly added in the there-necked flask, under 90 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 10% sugar juice.Mixed solution, sugar juice and pore-foaming agent PEG400 with polysulfones and SPSF adds in the there-necked flask successively in 70: 20: 10 ratios (mass ratio), mixes 12h under 90 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 12h.Preparation liquid is extruded from spinning head under 2MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 24h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with the dilution of 0.5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 58.7～59.1%, 0.3～0.4%.
To dry polysulfones (number-average molecular weight=40000), SPSF (number-average molecular weight=60000 of handling in 25: 15: 60 ratios (mass ratio), sulfonation degree=5%), NMP slowly adds in the there-necked flask successively, carry out stirring and dissolving under 10 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; In 90: 10 ratios (mass ratio) dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=100000) are slowly added in the there-necked flask, under 80 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 10% sugar juice.Mixed solution, sugar juice and pore-foaming agent PEG400 with polysulfones and SPSF adds in the there-necked flask successively in 70: 20: 10 ratios (mass ratio), mixes 48h under 10 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 48h.Preparation liquid is extruded from spinning head under 2MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 24h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, with the dilution of 0.5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 58.1～58.4%, 0.3～0.5%.
To dry polysulfones (number-average molecular weight=120000), SPSF (number-average molecular weight=80000 of handling in 20: 10: 70 ratios (mass ratio), sulfonation degree=80%), NMP slowly adds in the there-necked flask successively, carry out stirring and dissolving under 50 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; Slowly add the mixture (number-average molecular weight=100000) of dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=100000) and glucan in the there-necked flask in 85: 15 ratios (mass ratio), under 50 ℃, carry out stirring and dissolving, after treating that solute dissolves fully, filter cleaner obtains concentration and is 15% sugar juice.Mixed solution, sugar juice and pore-foaming agent PEG600 with polysulfones and SPSF adds in the there-necked flask successively in 70: 20: 10 ratios (mass ratio), mixes 18h under 50 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 12h.Preparation liquid is extruded from spinning head under 500kPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 24h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 57.2～57.7%, 0.3～0.4%.
To dry polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=120000 of handling in 25: 15: 60 ratios (mass ratio), sulfonation degree=10%), NMP slowly adds in the there-necked flask successively, carry out stirring and dissolving under 80 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; In 75: 25 ratios (mass ratio) dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=60000) are slowly added in the there-necked flask, under 80 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 25% sugar juice.Mixed solution, sugar juice and pore-foaming agent PEG600 with polysulfones and SPSF adds in the there-necked flask successively in 30: 60: 10 ratios (mass ratio), mixes 12h under 80 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 12h.Preparation liquid is extruded from spinning head under 500kPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 24h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 53.1～53.4%, 0.3～0.4%.
To dry polysulfones (number-average molecular weight=80000), SPSF (number-average molecular weight=95000 of handling in 15: 15: 70 ratios (mass ratio), sulfonation degree=50%), NMP slowly adds in the there-necked flask successively, carry out stirring and dissolving under 50 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; In 90: 10 ratios (mass ratio) dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=60000) are slowly added in the there-necked flask, under 80 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 10% sugar juice.Mixed solution, sugar juice and pore-foaming agent PEG600 with polysulfones and SPSF adds in the there-necked flask successively in 30: 60: 10 ratios (mass ratio), mixes 24h under 50 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 24h.Preparation liquid is extruded from spinning head under 2MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 48h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 59.4～59.8%, 0.2～0.4%.
To dry polysulfones (number-average molecular weight=100000), SPSF (number-average molecular weight=95000 of handling in 15: 5: 80 ratios (mass ratio), sulfonation degree=30%), NMP slowly adds in the there-necked flask successively, carry out stirring and dissolving under 80 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; In 90: 10 ratios (mass ratio) dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=200000) are slowly added in the there-necked flask, under 60 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 10% sugar juice.In 40: 40: 20 ratios (mass ratio) above two kinds of solution and pore-foaming agent PVP-K30 are added in the there-necked flask successively, under 50 ℃, mix 24h, then with namely obtaining preparation liquid behind the nitrogen deaeration 12h.Preparation liquid is extruded from spinning head under 2MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 48h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 52.7～52.9%, 0.3～0.5%.
To dry polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000 of handling in 25: 5: 70 ratios (mass ratio), sulfonation degree=30%), NMP slowly adds in the there-necked flask successively, carry out stirring and dissolving under 80 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; In 88: 12 ratios (mass ratio) dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=400000) are slowly added in the there-necked flask, under 80 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 12% sugar juice.Mixed solution, sugar juice and pore-foaming agent PVP-K30 with polysulfones and SPSF adds in the there-necked flask successively in 30: 60: 10 ratios (mass ratio), mixes 24h under 80 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 24h.Preparation liquid is extruded from spinning head under 500kPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 48h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 51.4～52.0%, 0.2～0.4%.
To dry polyether sulfone (number-average molecular weight=40000), sulfonated polyether sulfone (number-average molecular weight=95000 of handling in 25: 15: 60 ratios (mass ratio), sulfonation degree=5%), NMP slowly adds in the there-necked flask successively, carry out stirring and dissolving under 60 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polyether sulfone and sulfonation ether polysulfones; In 90: 10 ratios (mass ratio) dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=100000) are slowly added in the there-necked flask, under 60 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 10% sugar juice.Mixed solution, sugar juice and pore-foaming agent PEG400 with polyether sulfone and sulfonation ether polysulfones adds in the there-necked flask successively in 60: 30: 10 ratios (mass ratio), mixes 20h under 60 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 20h.Preparation liquid is extruded from spinning head under 2MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 24h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 56.1～56.8%, 0.5～0.4%.
To dry polyether sulfone (number-average molecular weight=60000), sulfonated polyether sulfone (number-average molecular weight=85000 of handling in 25: 15: 60 ratios (mass ratio), sulfonation degree=30%), NMP slowly adds in the there-necked flask successively, carry out stirring and dissolving under 60 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polyether sulfone and sulfonated polyether sulfone; In 90: 10 ratios (mass ratio) dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=100000) are slowly added in the there-necked flask, under 30 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 10% sugar juice.Mixed solution, sugar juice and pore-foaming agent PVP-K90 with polyether sulfone and sulfonation ether polysulfones adds in the there-necked flask successively in 50: 45: 5 ratios (mass ratio), mixes 12h under 60 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 12h.Preparation liquid is extruded from spinning head under 2MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 48h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 55.6～55.9%, 0.3～0.4%.
To dry polyether sulfone (number-average molecular weight=150000), sulfonated polyether sulfone (number-average molecular weight=80000 of handling in 20: 5: 75 ratios (mass ratio), sulfonation degree=30%), DMF slowly adds in the there-necked flask successively, carry out stirring and dissolving under 80 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polyether sulfone and sulfonated polyether sulfone; In 70: 30 ratios (mass ratio) dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=60000) are slowly added in the there-necked flask, under 80 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 30% sugar juice.Mixed solution, sugar juice and pore-foaming agent PEG400 with polyether sulfone and sulfonation ether polysulfones adds in the there-necked flask successively in 60: 30: 10 ratios (mass ratio), mixes 15h under 80 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 24h.Preparation liquid is extruded from spinning head under 1MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 36h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 54.2～54.8%, 0.3～0.4%.
To dry polyether sulfone (number-average molecular weight=90000), SPSF (number-average molecular weight=60000 of handling in 25: 15: 60 ratios (mass ratio), sulfonation degree=80%), DMF slowly adds in the there-necked flask successively, carry out stirring and dissolving under 60 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; In 70: 30 ratios (mass ratio) dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=200000) are slowly added in the there-necked flask, under 60 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 30% sugar juice.Mixed solution, sugar juice and pore-foaming agent PVP-K17 with polysulfones and SPSF adds in the there-necked flask successively in 60: 30: 10 ratios (mass ratio), mixes 12h under 70 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 12h.Preparation liquid is extruded from spinning head under 2MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 36h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 57.9～58.2%, 0.3～0.5%.
To dry polysulfones (number-average molecular weight=90000), sulfonated polyether sulfone (number-average molecular weight=120000 of handling in 25: 15: 60 ratios (mass ratio), sulfonation degree=40%), DMAC slowly adds in the there-necked flask successively, carry out stirring and dissolving under 70 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; Slowly add the mixture (number-average molecular weight=400000) of dimethyl sulfoxide (DMSO), marine alga polysaccharide (number-average molecular weight=400000) and peptide glycan in the there-necked flask in 72: 28 ratios (mass ratio), under 70 ℃, carry out stirring and dissolving, after treating that solute dissolves fully, filter cleaner obtains concentration and is 28% sugar juice.Mixed solution, sugar juice and pore-foaming agent PVP-K17 with polysulfones and SPSF adds in the there-necked flask successively in 70: 20: 10 ratios (mass ratio), mixes 6h under 80 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 24h.Preparation liquid is extruded from spinning head under 2MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 48h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 58.4～59.1%, 0.3～0.4%.
To dry polysulfones (number-average molecular weight=90000), sulfonated polyether sulfone (number-average molecular weight=95000 of handling in 25: 15: 60 ratios (mass ratio), sulfonation degree=30%), DMAC slowly adds in the there-necked flask successively, carry out stirring and dissolving under 50 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; In 90: 10 ratios (mass ratio) dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=100000) are slowly added in the there-necked flask, under 50 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 10% sugar juice.Mixed solution, sugar juice and pore-foaming agent PEG400 with polysulfones and SPSF adds in the there-necked flask successively in 70: 20: 10 ratios (mass ratio), mixes 24h under 50 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 24h.Preparation liquid is extruded from spinning head under 500kPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 24h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 54.3～54.7%, 0.2～0.4%.
To dry polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000 of handling in 25: 15: 60 ratios (mass ratio), sulfonation degree=50%), DMF slowly adds in the there-necked flask successively, carry out stirring and dissolving under 80 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; In 80: 20 ratios (mass ratio) dimethyl sulfoxide (DMSO), marine alga polysaccharide (number-average molecular weight=100000) are slowly added in the there-necked flask, under 20 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 20% sugar juice.Mixed solution, sugar juice and pore-foaming agent PEG400 with polysulfones and SPSF adds in the there-necked flask successively in 60: 30: 10 ratios (mass ratio), mixes 6h under 80 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 6h.Preparation liquid is extruded from spinning head under 2MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 48h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 61.2～61.5%, 0.2～0.3%.
To dry polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000 of handling in 25: 15: 60 ratios (mass ratio), sulfonation degree=50%), DMF slowly adds in the there-necked flask successively, carry out stirring and dissolving under 60 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; In 80: 20 ratios (mass ratio) dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=100000) are slowly added in the there-necked flask, under 80 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 20% sugar juice.Mixed solution, sugar juice and pore-foaming agent PEG2000 with polysulfones and SPSF adds in the there-necked flask successively in 45: 40: 15 ratios (mass ratio), mixes 24h under 60 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 24h.Preparation liquid is extruded from spinning head under 500kPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 24h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 60.8～61.1%, 0.3～0.5%.
To dry polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000 of handling in 15: 5: 80 ratios (mass ratio), sulfonation degree=50%), DMF slowly adds in the there-necked flask successively, carry out stirring and dissolving under 80 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; In 83: 17 ratios (mass ratio) dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=80000) are slowly added in the there-necked flask, under 40 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 17% sugar juice.Mixed solution, sugar juice and pore-foaming agent PEG800 with polysulfones and SPSF adds in the there-necked flask successively in 70: 20: 10 ratios (mass ratio), mixes 18h under 70 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 24h.Preparation liquid is extruded from spinning head under 2MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 48h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 59.3～60.1%, 0.4～0.6%.
To dry polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000 of handling in 15: 5: 80 ratios (mass ratio), sulfonation degree=50%), DMF slowly adds in the there-necked flask successively, carry out stirring and dissolving under 80 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; In 70: 30 ratios (mass ratio) dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=250000) are slowly added in the there-necked flask, under 70 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 30% sugar juice.Mixed solution, sugar juice and pore-foaming agent PEG800 with polysulfones and SPSF adds in the there-necked flask successively in 45: 45: 10 ratios (mass ratio), mixes 30h under 40 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 12h.Preparation liquid is extruded from spinning head under 1MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 24h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 59.6～60.2%, 0.3～0.5%.
To dry polysulfones (number-average molecular weight=90000), sulfonated polyether sulfone (number-average molecular weight=150000 of handling in 15: 5: 80 ratios (mass ratio), sulfonation degree=50%), DMF slowly adds in the there-necked flask successively, carry out stirring and dissolving under 80 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and sulfonated polyether sulfone; In 70: 30 ratios (mass ratio) dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=100000) are slowly added in the there-necked flask, under 80 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 30% sugar juice.Mixed solution, sugar juice and pore-foaming agent PEG1000 with polysulfones and sulfonated polyether sulfone adds in the there-necked flask successively in 45: 45: 10 ratios (mass ratio), mixes 24h under 40 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 24h.Preparation liquid is extruded from spinning head under 2MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 48h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 54.1～54.8%, 0.3～0.5%.
To dry polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000 of handling in 15: 5: 80 ratios (mass ratio), sulfonation degree=30%), DMF slowly adds in the there-necked flask successively, carry out stirring and dissolving under 80 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; In 75: 25 ratios (mass ratio) dimethyl sulfoxide (DMSO), peptide glycan (number-average molecular weight=150000) are slowly added in the there-necked flask, under 50 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 25% sugar juice.Mixed solution, sugar juice and pore-foaming agent PEG1000 with polysulfones and SPSF adds in the there-necked flask successively in 50: 42: 8 ratios (mass ratio), mixes 6h under 90 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 10h.Preparation liquid is extruded from spinning head under 1MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 48h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 59.2～59.5%, 0.4～0.5%.
To dry polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000 of handling in 15: 5: 80 ratios (mass ratio), sulfonation degree=50%), DMAC slowly adds in the there-necked flask successively, carry out stirring and dissolving under 60 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; In 70: 30 ratios (mass ratio) dimethyl sulfoxide (DMSO), marine alga polysaccharide (number-average molecular weight=100000) are slowly added in the there-necked flask, under 65 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 30% sugar juice.Mixed solution, sugar juice and pore-foaming agent PVP-K90 with polysulfones and SPSF adds in the there-necked flask successively in 45: 45: 10 ratios (mass ratio), mixes 24h under 20 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 24h.Preparation liquid is extruded from spinning head under 2MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 48h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 58.3～58.7%, 0.3～0.4%.
To dry polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000 of handling in 15: 5: 80 ratios (mass ratio), sulfonation degree=30%), DMAC slowly adds in the there-necked flask successively, carry out stirring and dissolving under 80 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; In 70: 30 ratios (mass ratio) dimethyl sulfoxide (DMSO), marine alga polysaccharide (number-average molecular weight=150000) are slowly added in the there-necked flask, under 80 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 30% sugar juice.Mixed solution, sugar juice and pore-foaming agent PVP-K90 with polysulfones and SPSF adds in the there-necked flask successively in 39: 60: 1 ratios (mass ratio), mixes 20h under 50 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 20h.Preparation liquid is extruded from spinning head under 2MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 48h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 59.2～59.5%, 0.2～0.3%.
To dry polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000 of handling in 15: 15: 70 ratios (mass ratio), sulfonation degree=50%), DMAC slowly adds in the there-necked flask successively, carry out stirring and dissolving under 20 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; Slowly add the mixture of dimethyl sulfoxide (DMSO), marine alga polysaccharide (number-average molecular weight=100000) and glucan (number-average molecular weight=100000) in the there-necked flask in 70: 30 ratios (mass ratio), under 80 ℃, carry out stirring and dissolving, after treating that solute dissolves fully, filter cleaner obtains concentration and is 30% sugar juice.In mixed solution, sugar juice and pore-foaming agent PEG800: the PVP-K30=1 of 39: 60: 1 ratios (mass ratio) with polysulfones and SPSF: 1 adds in the there-necked flask successively, under 80 ℃, mix 24h, then with namely obtaining preparation liquid behind the nitrogen deaeration 24h.Preparation liquid is extruded from spinning head under 2MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 48h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 58.5～58.9%, 0.3～0.4%.
To dry polysulfones (number-average molecular weight=110000), SPSF (number-average molecular weight=95000 of handling in 15: 15: 70 ratios (mass ratio), sulfonation degree=50%), DMAC slowly adds in the there-necked flask successively, carry out stirring and dissolving under 30 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; In 70: 30 ratios (mass ratio) dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=100000) are slowly added in the there-necked flask, under 55 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 30% sugar juice.Mixed solution, sugar juice and pore-foaming agent PVP-K17 with polysulfones and SPSF adds in the there-necked flask successively in 50: 40: 10 ratios (mass ratio), mixes 24h under 50～80 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 24h.Preparation liquid is extruded from spinning head under 2MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 8h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 60.1～60.8%, 0.3～0.5%.
To dry polysulfones (number-average molecular weight=90000), SPSF (number-average molecular weight=95000 of handling in 15: 15: 70 ratios (mass ratio), sulfonation degree=60%), DMAC slowly adds in the there-necked flask successively, carry out stirring and dissolving under 45 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polysulfones and SPSF; In 70: 30 ratios (mass ratio) dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=100000) are slowly added in the there-necked flask, under 45 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 30% sugar juice.Mixed solution, sugar juice and pore-foaming agent PVP-K90 with polysulfones and SPSF adds in the there-necked flask successively in 60: 39: 10 ratios (mass ratio), mixes 24h under 40 ℃, then with namely obtaining preparation liquid behind the nitrogen deaeration 24h.Preparation liquid is extruded from spinning head under 2MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 48h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 60.4～61.1%, 0.3～0.4%.
To dry polyether sulfone (number-average molecular weight=110000), SPSF (number-average molecular weight=95000 of handling in 15: 15: 70 ratios (mass ratio), sulfonation degree=50%), DMAC slowly adds in the there-necked flask successively, carry out stirring and dissolving under 80 ℃, after treating that solute dissolves fully, filter cleaner obtains the mixed solution of polyether sulfone and SPSF; In 70: 30 ratios (mass ratio) dimethyl sulfoxide (DMSO), glucan (number-average molecular weight=400000) are slowly added in the there-necked flask, under 50 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains concentration and is 30% sugar juice.In mixed solution, sugar juice and pore-foaming agent PEG800: the PVP-K30=1 of 70: 25: 5 ratios (mass ratio) with polysulfones and SPSF: 1 adds in the there-necked flask successively, under 50 ℃, mix 24h, then with namely obtaining preparation liquid behind the nitrogen deaeration 12h.Preparation liquid is extruded from spinning head under 2MPa, immersed in the coagulant liquid, form as-spun fibre, immerse successively respectively in deionized water and the ultra-pure water behind the rinsing 48h, taking-up is dried, and namely makes the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying.Get the serum of 0.5ml hyperlipidemia patient, dilute with 0. 5ml physiological saline, wash away the affine polymer hollow-fibre membrane of glycosyl/sulfonation modifying with the speed of per minute 20ml, carry out three times, the adsorption rate of LDL and HDL is respectively 59.5～60.5%, 0.2～0.3%.
Above-described embodiment only is not used in for explanation the present invention and limits the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
1. affine polymer hollow fiber separating film of glycosyl/sulfonation modifying, it is characterized in that: described polymer hollow fiber separating film is made up of fluoropolymer resin, sulfonated polymer resin and carbohydrate macromolecule, the mass fraction of fluoropolymer resin is 10%～70% in the described polymer hollow fiber separating film, the mass fraction of sulfonated polymer resin is 2%～30%, and the high molecular mass fraction of carbohydrate is 5%～90%; Sulfonic group and the high molecular hydroxyl of carbohydrate of possess hydrophilic property is rich on described polymer hollow fiber separating film surface, and described polymer hollow fiber separating film has selective identification absorption property to the low-density lipoprotein white matter; Described polymer hollow fiber separating film aperture is 0.01～0.5 μ m.
2. the affine polymer hollow fiber separating film of a kind of glycosyl/sulfonation modifying as claimed in claim 1, it is characterized in that: described fluoropolymer resin is polysulfones or polyether sulfone; Wherein, the polysulfones number-average molecular weight is 40000～120000; The polyether sulfone number-average molecular weight is 40000～150000.
3. the affine polymer hollow fiber separating film of a kind of glycosyl/sulfonation modifying as claimed in claim 1, it is characterized in that: described sulfonated polymer resin is SPSF or sulfonated polyether sulfone; Wherein, the SPSF number-average molecular weight is 60000～120000, sulfonation degree is 5%～80%; The sulfonated polyether sulfone number-average molecular weight is 60000～150000, and sulfonation degree is 5%～80%.
4. the affine polymer hollow fiber separating film of a kind of glycosyl/sulfonation modifying as claimed in claim 1, it is characterized in that: described carbohydrate macromolecule be selected from glucan, peptide glycan, the marine alga polysaccharide any one or multiple arbitrarily, the high molecular molecular weight of described carbohydrate is 6～400,000.
5. the preparation method of the affine polymer hollow fiber separating film of the described glycosyl/sulfonation modifying of claim 1 comprises the steps::
(1) preparation of preparation liquid: fluoropolymer resin, sulfonated polymer resin and organic solvent are mixed, under 10～90 ℃, carry out stirring and dissolving, treat that solute dissolves fully after, filter cleaner obtains polymer resin solution; The carbohydrate macromolecule is dissolved in dimethyl sulfoxide (DMSO), under 20～90 ℃, carries out stirring and dissolving, treat that solute dissolves fully after, filter cleaner makes concentration and is 10～30% carbohydrate Polymer Solution; The above-mentioned polymer resin solution that makes, carbohydrate Polymer Solution and pore-foaming agent are mixed, under 10～90 ℃, mix 6～48h, then with obtaining preparation liquid behind inert gas deaeration 6～48h;
(2) preparation liquid is extruded the immersion coagulant liquid from spinning head, formed as-spun fibre, fully after the rinsing, taking-up is dried, and namely makes the affine polymer hollow fiber separating film of glycosyl/sulfonation modifying.
6. the preparation method who states as claim 5, it is characterized in that: the proportioning that the fluoropolymer resin described in the step (1), sulfonated polymer resin and organic solvent mix is: the mass fraction of fluoropolymer resin is 15～25%, the mass fraction of sulfonated polymer resin is 5～15%, and the mass fraction of organic solvent is 60～80%.
7. the preparation method who states as claim 5, it is characterized in that: the organic solvent described in the step (1) is selected from dimethyl formamide, N, N-dimethylacetylamide and N-methyl pyrrolidone.
8. the preparation method who states as claim 5, it is characterized in that: the proportioning that the polymer resin solution described in the step (1), carbohydrate Polymer Solution and pore-foaming agent mix is: the mass fraction of polymer resin solution is 30～70%, the mass fraction of carbohydrate Polymer Solution is 20～60%, and the mass fraction of pore-foaming agent is 1～20%.
9. the preparation method who states as claim 5 is characterized in that: the pore-foaming agent described in the step (1) be selected among PEG400, PEG600, PEG800, PEG1000, PEG2000, PVP-K17, PVP-K30, the PVP-K90 any one or multiple arbitrarily.
10. the purposes of the affine polymer hollow fiber separating film of each described glycosyl/sulfonation modifying of claim 1-4 in haemodialysis or blood purification.
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| CN201310180111.0A CN103252177B (en) | 2013-05-14 | 2013-05-14 | The affine polymeric hollow fibre diffusion barrier of a kind of glycosyl/sulfonation modifying, Preparation Method And The Use |
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| CN201310180111.0A CN103252177B (en) | 2013-05-14 | 2013-05-14 | The affine polymeric hollow fibre diffusion barrier of a kind of glycosyl/sulfonation modifying, Preparation Method And The Use |
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| CN103252177B CN103252177B (en) | 2015-10-21 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104437133A (en) * | 2014-11-10 | 2015-03-25 | 苏州蔻美新材料有限公司 | Alginate fiber hematodialysis membrane and preparation method thereof |
| CN105536566A (en) * | 2016-01-19 | 2016-05-04 | 长安大学 | Composite membrane with function of separating lithium ions and cobalt ions and preparation method thereof |
| CN109745877A (en) * | 2019-03-18 | 2019-05-14 | 山东星火科学技术研究院 | The preparation method of sulfonated polyether-ether-ketone and chitosan static spinning membrane |
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| CN102120148A (en) * | 2011-01-19 | 2011-07-13 | 天津大学 | Preparation method for composite film of chitosan/sulfonated polyethersulfone and polyethersulfone and application thereof |
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| CN102120148A (en) * | 2011-01-19 | 2011-07-13 | 天津大学 | Preparation method for composite film of chitosan/sulfonated polyethersulfone and polyethersulfone and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437133A (en) * | 2014-11-10 | 2015-03-25 | 苏州蔻美新材料有限公司 | Alginate fiber hematodialysis membrane and preparation method thereof |
| CN105536566A (en) * | 2016-01-19 | 2016-05-04 | 长安大学 | Composite membrane with function of separating lithium ions and cobalt ions and preparation method thereof |
| CN105536566B (en) * | 2016-01-19 | 2017-12-12 | 长安大学 | A kind of composite membrane for separating lithium ion and cobalt ions and preparation method thereof |
| CN109745877A (en) * | 2019-03-18 | 2019-05-14 | 山东星火科学技术研究院 | The preparation method of sulfonated polyether-ether-ketone and chitosan static spinning membrane |
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