CN103877634B - A blood dialysis apparatus and blood dialyzer - Google Patents

A blood dialysis apparatus and blood dialyzer Download PDF

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CN103877634B
CN103877634B CN 201410083974 CN201410083974A CN103877634B CN 103877634 B CN103877634 B CN 103877634B CN 201410083974 CN201410083974 CN 201410083974 CN 201410083974 A CN201410083974 A CN 201410083974A CN 103877634 B CN103877634 B CN 103877634B
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polyether sulfone
hollow fiber
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CN103877634A (en )
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韩全
张恒
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石家庄达爱医疗器械科技有限公司
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Abstract

一种血液透析器及血液透析装置,该血液透析器包括:外壳、由中空纤维丝管组成的纤维束、端盖、封装胶、环形导流分布环、透析液入口、透析液出口、血液入口及血液出口;环形导流分布环位于正对透析液入口和/或透析液出口的位置,环形导流分布环的一端与外壳的末端连接,环形导流分布环的另一端沿外壳纵向朝向与其正对的透析液入口或透析液出口方向倾斜;中空纤维丝管采用聚醚砜中空纤维膜制备,聚醚砜中空纤维膜的纺丝原液包含:250-650重量份改性聚醚砜共混物、20-400重量份亲水性分子化合物、1-90重量份纳米改性羟基二氧化钛混合物及20-120重量份醇类溶剂。 A blood dialysis apparatus and blood dialyzer, which hemodialyzer comprising: a housing, a hollow fiber bundle of fiber filaments tubes, end caps, plastic packaging, distribution ring annular deflector, the dialysate inlet dialysate outlet, the blood inlet and a blood outlet; annular flow distribution ring located at a position directly dialysate inlet and / or outlet of the dialysis liquid, the tip end of the housing an annular flow distribution ring, and the other end of the housing along the longitudinal direction of the annular guide ring toward its distribution dialysate inlet or outlet dialysate facing inclined direction; hollow tube filaments prepared using a polyether sulfone hollow fiber membrane, a polyether sulfone hollow fiber spinning dope film containing: 250-650 parts by weight of the modified polyether sulfone blend was 20-400 parts by weight of a hydrophilic polymer compound, 1-90 parts by weight of a mixture of nano-modified hydroxy titanium dioxide and 20 to 120 parts by weight of an alcohol solvent. 本发明的血液透析器提高了透析液与纤维丝管表面的接触面积及去除率,具有较高的去除率及超滤系数。 Hemodialyzer according to the present invention increases the contact area and the surface removal dialysate tube filaments, having high removal rate and ultrafiltration coefficient.

Description

一种血液透析器及血液透析装置 A blood dialysis apparatus and blood dialyzer

技术领域 FIELD

[0001] 本发明属于医疗器械技术领域,具体涉及一种血液透析器及血液透析装置。 [0001] The present invention belongs to the technical field of medical devices, particularly, to a hemodialysis and hemodialysis apparatus.

背景技术 Background technique

[0002] 血液透析器主要用于在肾脏疾病治疗时进行血液透析和血液过滤。 [0002] Hemodialysis is mainly used for hemodialysis and hemofiltration in the treatment of kidney disease. 现有的血液透析器的结构主要包括:外壳、由纤维丝管组成的纤维束、封装胶、端盖、透析液入口、透析液出口、血液入口、血液出口以及位于透析液入口和出口处的阻液板,其中纤维束装入外壳内,透析液入口与血液出口位于外壳的一端,而透析液出口和血液入口位于外壳的另一端, 纤维束两端用封装胶密封,阻液板分别位于外壳两端正对透析液入口及透析液出口处且与外壳平行,以防止透析液直接进入透析室时对纤维束造成损伤。 Structure of a conventional hemodialyzer mainly comprising: a housing, a tow of filaments tubes, plastic packaging, end caps, the inlet dialysate, the dialysate outlet, the blood inlet, a blood outlet and a dialysate inlet and outlet positioned at fluid blocking plate, wherein the fiber bundle into the housing, a blood outlet and dialysate inlet located at one end of the housing, and the dialysate inlet and a blood outlet at the other end of the housing, ends of the fiber bundle package sealant, liquid barrier plate is respectively two upright housing and the housing parallel to the dialysate inlet and a dialysate outlet, in order to prevent damage to the fiber bundle directly into the dialyzer dialysate compartment.

[0003] 使用上述血液透析器进行血液透析时,易出现浓差极化现象,透析液与纤维丝管表面的接触面积较小,去除率较低,且纤维丝管断丝率较高。 When [0003] using the hemodialyzer hemodialysis, prone to concentration polarization, small contact surface area dialysate tube filaments, the removal rate is low, and a high rate of breakage tube filaments.

[0004] 另外,透析膜是血液透析器最重要的部分,透析膜材料是影响血液透析治疗效果的关键因素。 [0004] Furthermore, dialysis membrane is the most important portion of hemodialysis, the dialysis membrane material is a critical factor affecting the therapeutic effect of hemodialysis. 目前,临床常用的透析膜可分为三类:1、未修饰的纤维素膜;2、改性或再生纤维素膜;3、合成膜。 At present, commonly used in clinical dialysis membrane can be divided into three categories: 1, unmodified cellulose membrane; 2, modified or regenerated cellulose membrane; 3, synthetic membranes. 这三类透析膜在生物相容性、水通透性、尿毒症毒素清除等方面均有较大的区别。 These three types of dialysis membrane have a larger difference in a biocompatible, water permeability, etc. remove uremic toxins. 清除溶质和超滤是透析器的两个主要功能,清除率和超滤系数是评价透析膜质量的关键指标。 Solute clearance and ultrafiltration are two main functions of the dialyzer, and ultrafiltration coefficient clearance is a key indicator of the quality evaluation of the dialysis membrane. 膜的传递特性决定了溶质的清除率和对液体的去除率。 It determines the transfer characteristics of the film solute clearance and removal of liquid. 常用小分子物质(如尿素、肌酐)及中分子物质(如维生素Β12、β2_微球蛋白)作为评价透析器清除率的指标。 Indicators used small molecules (such as urea, creatinine), and the molecular substances (such as vitamins Β12, β2_ microglobulin) as an evaluation of the clearance of the dialyzer.

[0005] 膜的表面性质决定了血液和膜之间相互作用的特性及程度,包括蛋白质的吸附、 血栓的形成、补体激活和免疫反应等。 [0005] surface properties of the film characteristics and determines the degree of interaction between the blood and the membrane, including protein adsorption, thrombus formation, activation of complement and immune reactions. 理想的生物相容性膜应与人体的血管内皮性能极为接近,无毒性,无抗原性,不激活补体、白细胞和单核细胞,无细胞因子的释放,具有优良的生物相容性,对凝血系统也没有影响。 The ideal membrane should be biocompatible with vascular endothelial performance very close to the human body, non-toxic, non-antigenic, does not activate complement, leukocytes and mononuclear cells, cytokine-release, it has excellent biocompatibility, coagulation The system also has no effect. 透析膜作为一种异体物质,始终不同于人体血管内皮细胞,与血液相接触,不可避免会引起机体的反应,高通量、高效、具有较优的生物相容性、 亲水性及去除率仍将是今后透析膜发展的主要方向。 As a variant dialysis membrane material, always different from human vascular endothelial cells in contact with blood, body inevitably cause a reaction, high-throughput, efficient, having superior biocompatibility, hydrophilicity and removal It will continue to be the main direction of the future development of the dialysis membrane.

[0006] 聚醚砜中空纤维膜由于其优异的性能(如对中分子溶质较高的清除率)而被用作血液透析器的透析膜,但目前生产的聚醚砜中空纤维膜的生物相容性和血液相容性、亲水性、光滑度及去除率相对较低。 [0006] Polyethersulfone hollow fiber membranes due to their excellent properties (such as higher in solute clearance) is used as the dialysis membrane of the hemodialyzer, but biological polyethersulfone hollow fiber membrane production phase current compatibility and blood compatibility, hydrophilicity, smoothness and removal is relatively low.

[0007] 因此,如何对血液透析器的结构及透析膜材料进行改进,以降低浓差极化现象,提高透析液与纤维丝管表面的接触面积及去除率,降低纤维丝管断丝率,同时使透析膜具有较好的生物相容性及血液相容性、亲水性及光滑度,并具有较高的去除率及超滤系数成为目前研究的重点。 [0007] Therefore, how to structure and material of a dialysis membrane of a hemodialyzer improved, to reduce the concentration polarization, to increase the contact area and the surface removal dialysate tube filaments to reduce filament breakage rate of the pipe, while the dialysis membrane having good blood compatibility and biocompatibility, hydrophilicity and smoothness, and has a high removal rate and ultrafiltration coefficient become the focus of current research.

发明内容 SUMMARY

[0008] 针对上述问题,本发明的一个目的在于提供一种血液透析器,该血液透析器在外壳的侧面透析液通路中设置具有一定倾斜角度的环形导流分布环,大幅度降低了浓差极化现象,有效地提高了透析液与纤维丝管表面的接触面积及去除率,并降低了纤维丝管断丝率,同时该血液透析器的中空纤维丝管采用改性的聚醚砜中空纤维膜制备,具有较好的生物相容性及血液相容性、亲水性及光滑度,并具有较高的去除率及超滤系数。 [0008] In view of the above problems, an object of the present invention to provide a blood dialyzer, the blood flow dialyzer disposed annular ring having a certain distribution in the side surface inclination angle of dialysate passage of the housing, a significant reduction in the concentration polarization, effectively improving the removal of the contact area and the dialysate tube surface filaments, the filaments and reducing the tube broken wires, while the hollow fiber hemodialyzer wire tube using modified polyether sulfone hollow preparation fiber membrane, having a good biocompatibility and blood compatibility, hydrophilicity and smoothness, and has a high removal rate and ultrafiltration coefficient.

[0009] 本发明的另一个目的在于提供一种血液透析装置。 [0009] Another object of the present invention is to provide a hemodialysis apparatus.

[0010] 为达到上述目的,本发明提供一种血液透析器,其包括:外壳、由中空纤维丝管组成的纤维束、端盖、封装胶、环形导流分布环、透析液入口、透析液出口、血液入口及血液出口;其中,所述环形导流分布环位于正对所述透析液入口和/或透析液出口的位置,所述环形导流分布环的一端与所述外壳的末端连接,所述环形导流分布环的另一端朝向与其正对的透析液入口或透析液出口方向倾斜; [0010] To achieve the above object, the present invention provides a blood dialyzer, comprising: a housing, a hollow fiber bundle of fiber filaments tubes, end caps, plastic packaging, distribution ring annular deflector, the dialysate inlet dialysate an outlet, the blood inlet and blood outlet; wherein the distribution ring annular deflector positioned positive and / or position of the dialysate inlet of the dialysate outlet, the annular end flow distribution ring connected to one end of the housing , the other end of the dialysate flow distribution of the annular ring facing towards its inlet or outlet dialysate tilted;

[0011] 其中,所述中空纤维丝管采用聚醚砜中空纤维膜制备,所述聚醚砜中空纤维膜的纺丝原液包含: [0011] wherein said hollow tube filaments prepared using a polyether sulfone hollow fiber membrane, a polyethersulfone hollow fiber membrane dope comprises:

[0012] 250-650重量份的改性聚醚砜共混物; [0012] 250-650 parts by weight of the modified polyether sulfone blend;

[0013] 20-400重量份的亲水性分子化合物; [0013] 20-400 parts by weight of a hydrophilic polymer compound;

[0014] 1 -90重量份的纳米改性羟基二氧化钛混合物;及 [0014] 1-90 parts by weight of a mixture of titanium dioxide nano-modified hydroxy; and

[0015] 20-120重量份的醇类溶剂, [0015] 20-120 parts by weight of an alcoholic solvent,

[0016]其中,所述改性聚醚砜共混物包含聚醚砜、聚乙烯吡咯烷酮、氢氧化钠及过硫酸钠,所述纳米改性羟基二氧化钛混合物包含纳米水溶性二氧化钛及醇。 [0016] wherein said modified polyether sulfone blend comprises polyether sulfone, polyvinyl pyrrolidone, sodium hydroxide, and sodium persulfate, the nano-hydroxy-modified nano-titania mixture comprising titanium dioxide and a water-soluble alcohol.

[0017] 优选地,所述环形导流分布环相对于所述外壳的纵向倾斜的角度为2-6°,优选4° ; [0017] Preferably, the annular flow distribution of the longitudinal oblique angle with respect to the housing ring is 2-6 °, preferably 4 °;

[0018] 优选地,所述环形导流分布环的直径为53-55mm,优选54mm; [0018] Preferably, the diameter of the annular flow distribution ring is 53-55mm, preferably 54mm;

[0019] 优选地,所述环形导流分布环的宽度小于与其正对的透析液入口或透析液出口沿外壳纵向的宽度; [0019] Preferably, the annular flow distribution ring width smaller than its positive dialysate to the dialysate inlet or outlet of the housing along a longitudinal width;

[0020] 优选地,所述环形导流分布环的宽度为7-9mm,优选8mm。 Width [0020] Preferably, the annular flow distribution ring is 7-9mm, preferably 8mm.

[0021] 优选地,所述聚醚砜中空纤维膜的纺丝原液包含: [0021] Preferably, the dope polyethersulfone hollow fiber membrane comprising:

[0022] 250-450重量份的改性聚醚砜共混物; [0022] 250-450 parts by weight of the modified polyether sulfone blend;

[0023] 50-150重量份的亲水性分子化合物; [0023] 50 to 150 parts by weight of a hydrophilic polymer compound;

[0024] 10-90重量份的纳米改性羟基二氧化钛混合物;及 [0024] 10 to 90 parts by weight of a mixture of titanium dioxide nano-modified hydroxy; and

[0025] 50-100重量份的醇类溶剂。 [0025] 50-100 parts by weight of an alcohol solvent.

[0026] 优选地,所述改性聚醚砜共混物中包含850-980重量份的聚醚砜、20-150重量份的聚乙烯吡咯烷酮、0.01-1重量份的氢氧化钠及0.1-1重量份的过硫酸钠; [0026] Preferably, the modified polyether sulfone blend comprises 850-980 parts by weight of polyether sulphone, 20-150 parts by weight of polyvinyl pyrrolidone, 0.01 parts by weight of sodium hydroxide and 0.1 1 part by weight of sodium persulfate;

[0027] 优选地,所述改性聚醚砜共混物中包含900-980重量份的聚醚砜、20-100重量份的聚乙烯吡咯烷酮、0.05-0.1重量份的氢氧化钠及0.5-1重量份的过硫酸钠; [0027] Preferably, the modified polyether sulfone blend comprises 900-980 parts by weight of polyether sulphone, 20-100 parts by weight of polyvinyl pyrrolidone, 0.05 to 0.1 parts by weight of sodium hydroxide and 0.5 1 part by weight of sodium persulfate;

[0028]所述改性聚醚砜共混物中的聚乙烯吡咯烷酮优选为聚乙烯吡咯烷酮kl5、聚乙烯吡咯烷酮k30或聚乙烯吡咯烷酮k90,所述聚醚砜优选为聚醚砜P-3500或聚醚砜E6020。 [0028] The polyvinylpyrrolidone-modified polyether sulfone blend preferably polyvinylpyrrolidone kl5, polyvinylpyrrolidone or polyvinyl pyrrolidone k30 k90, the polyethersulfone is preferably polyethersulfone or poly P-3500 ether sulfone E6020. [0029]优选地,所述纳米改性羟基二氧化钛混合物包含纳米水溶性二氧化钛与乙二醇; [0030]优选地,所述纳米改性羟基二氧化钛混合物中包含100-800重量份的水溶性二氧化钛及600-980重量份的乙二醇; [0029] Preferably, the nano-hydroxy-modified nano-titania mixture comprising a water-soluble glycol and titanium dioxide; [0030] Preferably, the nano-hydroxy-modified titanium dioxide mixture contains 100-800 parts by weight of titanium dioxide and a water-soluble 600-980 parts by weight of ethylene glycol;

[0031]优选地,所述纳米改性羟基二氧化钛混合物中包含200-400重量份的水溶性二氧化钛及600-900重量份的乙二醇; [0031] Preferably, the nano-hydroxy-modified titanium dioxide mixture comprising 200-400 parts by weight of a water-soluble titania and 600-900 parts by weight of ethylene glycol;

[0032]优选地,所述水溶性二氧化钛的粒径为I -I Onm; [0032] Preferably, the water-soluble titanium dioxide particle diameter I -I Onm;

[0033]优选地,所述亲水性分子化合物为聚乙烯吡咯烷酮或聚乙二醇;优选地,所述亲水性分子化合物为聚乙烯吡咯烷酮kl5、聚乙烯吡咯烷酮k30、聚乙烯吡咯烷酮k90或分子量为2000的聚乙二醇; [0033] Preferably, the hydrophilic polymer compound is polyvinylpyrrolidone or polyethylene glycol; Preferably, the hydrophilic polymer compound is polyvinylpyrrolidone kl5, polyvinylpyrrolidone K30, polyvinylpyrrolidone or molecular weight k90 polyethylene glycol 2000;

[0034] 优选地,所述醇类溶剂为聚乙二醇或丙三醇,优选分子量为2000的聚乙二醇。 [0034] Preferably, the alcoholic solvent is glycerol or polyethylene glycol, preferably polyethylene glycol having a molecular weight of 2000.

[0035]优选地,所述改性聚醚砜共混物的制备方法包括: [0035] Preferably, the method of preparing modified polyether sulfone blend comprising:

[0036]将聚醚砜、聚乙烯吡咯烷酮、氢氧化钠及过硫酸钠混合,并在95-120°C优选100-110°c氮气保护下混合一定时间,混合30-120分钟优选60-90分钟,发生交联反应,制备得到改性聚醚砜共混物。 [0036] A polyether sulfone, polyvinyl pyrrolidone, sodium hydroxide, and sodium persulfate mixed, and mixing a predetermined time at 95-120 ° C preferably 100-110 ° c protection of nitrogen, preferably 30-120 minutes mixing 60-90 minutes, crosslinking reaction, modified polyethersulfone blends prepared.

[0037]优选地,所述改性羟基二氧化钛混合物的制备方法包括: [0037] Preferably, the method of preparing the modified hydroxy titanium dioxide mixture comprising:

[0038]将纳米水溶性二氧化钛与醇混合,在20-60°C优选40-50°C氮气保护下搅拌,搅拌10-60分钟优选20-40分钟后得到改性羟基二氧化钛混合物。 [0038] The nano-titanium dioxide mixed with a water-soluble alcohol, stirred at 20-60 ° C preferably 40-50 ° C nitrogen atmosphere, stirred 10 to 60 minutes preferably 20-40 minutes to obtain a modified hydroxy titanium oxide mixture.

[0039 ]优选地,所述聚醚砜中空纤维膜的制备方法包括以下步骤: [0039] Preferably, the method of preparing a polyether sulfone hollow fiber membranes comprising the steps of:

[0040]在有机溶剂中加入改性聚醚砜共混物、亲水性分子化合物、纳米改性羟基二氧化钛混合物及醇类溶剂,采用干-湿法在氮气保护下搅拌制备得到纺丝液,将纺丝液进行熟化,并通过喷丝板挤出,通过空气段,然后通过纯水凝固浴制备得到聚醚砜中空纤维膜; [0040] added to the modified polyether sulfone blend in an organic solvent, a hydrophilic polymer compound, a mixture of nano-modified hydroxy titanium dioxide and an alcohol solvent, dry - wet under nitrogen with stirring to give a spinning solution was prepared, the spinning solution is aged, and extruded through a spinneret, through an air segment, the bath was then prepared polyethersulfone hollow fiber membrane obtained by coagulation of pure water;

[0041 ]优选地,所述聚醚砜中空纤维膜的制备方法包括以下步骤:在有机溶剂中加入改性聚醚砜共混物、亲水性分子化合物、纳米改性羟基二氧化钛混合物及醇类溶剂,采用干-湿法在55-100°C优选60-85°C氮气保护下搅拌4-24小时优选12-24小时得到纺丝液,将纺丝液熟化12-72小时,优选24-36小时,并通过喷丝板挤出,并通过l-800mm优选300-500mm的空气段,然后以6-15米/分钟优选6-9米/分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜。 [0041] Preferably, the method of preparing a polyether sulfone hollow fiber membranes comprising the steps of: addition of modified polyether sulfone blend in an organic solvent, a hydrophilic polymer compound, a mixture of nano-modified hydroxy titanium dioxide and alcohol the solvent dry - wet stirred at 55-100 ° C preferably 60-85 ° C nitrogen for 4-24 hours, preferably 12-24 hours to give a spinning solution, spinning was aged for 12-72 hours, preferably 24- 36 hours, and extruded through a spinneret, through an air segment and l-800mm preferably 300-500mm, and a speed of 6-15 m / min, preferably 6-9 m / min through a coagulation bath of pure water, and dried to give preparation polyether sulfone hollow fiber membrane.

[0042] 优选地,所述有机溶剂为二甲基乙酰胺、二甲基甲酰胺或二甲基亚砜。 [0042] Preferably, the organic solvent is dimethylacetamide, dimethylformamide or dimethyl sulfoxide.

[0043] 本发明进一步提供一种包含上述血液透析器的血液透析装置。 Hemodialysis apparatus [0043] The present invention further provides a composition comprising the above-described hemodialyzer.

[0044] 与现有技术相比,本发明具有以下优点: [0044] Compared with the prior art, the present invention has the following advantages:

[0045] -、与设置有阻液板(与外壳平行)的血液透析器相比,本发明通过在血液透析器的侧面透析液通路中设置具有一定倾斜角度的环形导流分布环,使得透析过程中透析液沿中空纤维丝管外表面的切线方向流动,大幅度降低了浓差极化现象,有效地提高了透析液与纤维丝管表面的接触面积,同时能够达到透析液紊流的效果,扩大弥散效果,提高去除率;另外本发明的血液透析器通过设置环形导流分布环更有利于防止透析液直接进入透析室时对纤维束造成损伤,降低纤维丝管断丝率; [0045] - compared with the blocking plate is provided with a liquid (the housing parallel to) a blood dialyzer, the present invention is provided by annular flow distribution ring having an angle of inclination of the side surface of the dialysate in the dialyzer the blood passage, such that the dialysis during dialysate flow in a tangential direction of the outer surface of the hollow tube filaments, a significant reduction in the concentration polarization, the contact area to effectively improve the dialysate tube surface filaments, while being able to achieve a dialysate turbulence expanding diffusion effects and improve removal; hemodialyzer further provided by the present invention an annular distribution ring flow guide is more conducive to prevent damage to the dialysate compartment of the dialyzer directly into the fiber bundle, reducing fiber breakage rate wire tube;

[0046] 二、本发明的血液透析器的中空纤维丝管采用改性的聚醚砜中空纤维膜制备,相对于未改性的聚醚砜中空纤维膜,本发明通过对聚醚砜及纳米二氧化钛进行改性制备的改性聚醚砜中空纤维膜具有出色的生物相容性和血液相容性,且无毒性,无抗原性,不激活补体、白细胞和单核细胞,无细胞因子的释放,对凝血系统也没有影响; [0046] Second, the hollow fiber hemodialyzer wire tube of the present invention is prepared using a polyether sulfone hollow fiber membranes modified with respect to the unmodified polyether sulfone hollow fiber membrane, through the present invention and polyethersulfone nano modified polyether sulfone hollow fiber membrane prepared modified titanium dioxide has excellent biocompatibility and blood compatibility and non-toxic, non-antigenic, does not activate complement, leukocytes and mononuclear cells, no cytokine release and it has no effect on the coagulation system;

[0047]三、相对于未改性的聚醚砜中空纤维膜,本发明的血液透析器中的改性聚醚砜中空纤维膜的表面粗糙度明显降低,大幅度降低了其对血液的影响,血液残留较少,有效地降低了补体激活及血液阻力,且具有较高的亲水性和较大的水通量; [0047] Third, the unmodified polyether sulfone hollow fiber membranes with respect to the surface roughness modified polyether sulfone hollow fiber membrane hemodialyzer according to the present invention is significantly reduced, greatly reducing its effect on the blood , less residual blood, effectively reduces the complement activation and blood resistance, and has high hydrophilicity and a large water flux;

[0048]四、相对于未改性的聚醚砜中空纤维膜,本发明的血液透析器中的改性聚醚砜中空纤维膜具有较高的去除率及超滤系数,在测试条件为QB=200ml/min,QD=500ml/min,TMP= 1000 mmHg条件下,对尿素、肌酐、磷酸盐及维生素B的去除率分别达到210ml/min、190ml/ min、170ml/min及180ml/min,超滤系数达到200ml/kpa.h;另外,采用本发明的改性聚醚砜中空纤维膜制备的血液透析器血液透析15分钟后血液中白细胞、血小板计数、及补体C3a、 C5a的水平等均优于相同条件下采用未改性的聚醚砜中空纤维膜制成的血液透析器透析后血液中各成分含量; [0048] Fourth, with respect to the polyethersulfone hollow fiber membrane unmodified, modified polyether sulfone hollow fiber membrane hemodialyzer according to the present invention has a high removal rate and ultrafiltration coefficient, the test condition is QB = 200ml / min, QD = 500ml / min, TMP = 1000 mmHg condition, for removal of urea, creatinine, phosphate, and vitamin B respectively 210ml / min, 190ml / min, 170ml / min and 180ml / min, ultra filter coefficient 200ml / kpa.h; Further, a hemodialyzer was prepared hemodialysis hollow fiber membranes modified polyether sulfone present invention 15 minutes after the white blood cells, platelet count, and complements C3a, C5a Priority level etc. using the components in the blood after the prepared unmodified polyether sulfone hollow fiber membrane hemodialyzer dialysis under the same conditions;

[0049] 五、本发明的血液透析器中的改性聚醚砜中空纤维膜具有较高的化学稳定性,可以用γ射线、环氧乙烷及蒸汽等消毒,材料玻璃化温度为200摄氏度。 [0049] V. modified polyether sulfone hollow fiber membrane hemodialyzer according to the present invention has a high chemical stability, can be used γ-rays, ethylene oxide and steam sterilization, the material glass transition temperature of 200 ° C .

附图说明 BRIEF DESCRIPTION

[0050] 以下,结合附图来详细说明本发明的实施方案,其中: [0050] Hereinafter, detailed description in conjunction with the accompanying drawings embodiments of the present invention, wherein:

[0051] 图1为本发明的血液透析器的部分外观及剖面图,其中示出了血液透析器在透析液入口侧的剖面图; Partial cross-sectional view and [0051] FIG 1 hemodialyzer of the present invention, which shows a cross-sectional view of the blood in the dialyzer inlet side of the dialysate;

[0052]图2为本发明的血液透析器的剖面图; [0052] The sectional view of FIG. 2 hemodialyzer of the present invention;

[0053] 图3为本发明的血液透析器在透析液入口侧的俯视图; [0053] FIG. 3 hemodialyzer of the present invention in a plan view of the inlet side of the dialysate;

[0054] 图4为本发明的血液透析器在透析液入口侧的放大剖面图; Hemodialyzer [0054] FIG. 4 of the present invention in a side sectional view showing enlarged the dialysate inlet;

[0055] 图5为本发明的血液透析器在透析液入口部分的透析液流向俯视图; Hemodialyzer [0055] FIG. 5 is a plan view of the present invention, the dialysate to the inlet portion of the dialysate;

[0056] 图6为本发明的血液透析器在透析液入口部分的透析液流向图; Hemodialyzer [0056] FIG. 6 of the present invention, the dialysate flows in the inlet portion of FIG dialysate;

[0057]图7示出了本发明的改性聚醚砜中空纤维膜的表面形态; [0057] FIG. 7 shows the surface morphology of the present invention modified polyether sulfone hollow fiber membranes;

[0058]图8示出了现有技术中未改性的聚醚砜中空纤维膜的表面形态; [0058] FIG. 8 shows the surface morphology of the prior art unmodified polyether sulfone hollow fiber membranes;

[0059] 图9示出了本发明的改性聚醚砜中空纤维膜的光滑度电镜图; [0059] FIG. 9 shows a SEM smoothness invention FIG modified polyether sulfone hollow fiber membranes;

[0060] 图10示出了现有技术中未改性的聚醚砜中空纤维膜的光滑度电镜图; [0060] FIG. 10 shows electron micrographs of the smoothness of the prior art unmodified polyether sulfone hollow fiber membranes;

[0061] 图11示出了本发明的改性聚醚砜中空纤维膜的结构电镜图; [0061] FIG. 11 shows an electron microscope picture of the structure of the present invention modified polyether sulfone hollow fiber membranes;

[0062] 图12示出了本发明的改性聚醚砜中空纤维膜与水接触的视图; [0062] FIG. 12 shows a view of the present invention modified polyether sulfone hollow fiber membrane in contact with water;

[0063] 图13示出了现有技术中未改性的聚醚砜中空纤维膜与水接触的视图。 [0063] FIG. 13 illustrates a view of a prior art non-modified polyether sulfone hollow fiber membrane in contact with water.

[0064] 附图标记说明 [0064] REFERENCE NUMERALS

[0065] 1 外壳 [0065] 1 housing

[0066] 2中空纤维丝管 [0066] The second hollow tube filaments

[0067] 3透析液出口 [0067] 3 dialysate outlet

[0068] 6 端盖 [0068] The cover 6

[0069] 7封装胶 [0069] The sealing adhesive 7

[0070] 8环形导流分布环 [0070] The distribution ring annular deflector 8

[0071] 9外壳的透析液流道 [0071] The housing 9 of the dialysate flow path

[0072] 10透析液入口 [0072] 10 dialysate inlet

[0073] 11血液出口 [0073] 11 blood outlet

[0074] 12血液入口 [0074] 12 blood inlet

具体实施方式 detailed description

[0075] 以下参照具体的实施例来说明本发明。 Example [0075] Here will be described specifically with reference to the present invention. 本领域技术人员能够理解,这些实施例仅用于说明本发明,其不以任何方式限制本发明的范围。 Those skilled in the art will appreciate that these embodiments are merely illustrative of the invention, which do not limit the scope of the present invention in any way.

[0076] 下述实施例中所用的试剂材料等,如无特殊说明,均为市售购买产品。 The reagent material used in Examples [0076] The following embodiments and the like, if no special instructions, are commercially available products purchased.

[0077] 参照图1至图4所示,本发明提供的血液透析器包括外壳I、由中空纤维丝管2组成的纤维束、端盖6、封装胶7、环形导流分布环8、透析液入口10、透析液出口3、血液入口12及血液出口11。 [0077] Referring to FIG. 1 to FIG. 4, the present invention provides a hemodialysis comprises a housing I, hollow fiber bundles composed of filaments tube 2, the end cap 6, 7 plastic packaging, distribution ring annular deflector 8, dialyzed fluid inlet 10, a dialysate outlet 3, the blood inlet 12 and blood outlet 11. 其中,纤维束填充于外壳1内,透析液入口10与血液出口11位于外壳1的一端, 而透析液出口3与血液入口12位于外壳1的另一端,纤维束两端通过封装胶7固定于端盖6的边缘处,端盖6位于外壳1的两端,使纤维束的中空纤维丝管2内部形成密封的血液通路,中空纤维丝管2外部与外壳1形成透析液通路。 Wherein the fiber bundle is filled in the housing 1, the dialysate inlet 10 and a blood outlet 11 located at one end of the housing 1, and the other end of the dialysate outlet 3 of the housing 1 and the blood inlet 12 located at both ends of the fiber bundle 7 is fixed by adhesive to the package the blood circuit at the edge of the end cap 6, the cap 6 of the housing 1 at both ends of the inside of the hollow fiber bundle 2 of filaments form a sealed tube, a hollow fiber tube 2 outside the housing 1 is formed wire dialysate passage.

[0078] 环形导流分布环8呈环状(如图3所示),在血液透析器的侧面透析液通路中,且位于正对透析液入口10和/或透析液出口3的位置,所述环形导流分布环8的一端与外壳1的末端连接,环形导流分布环8的另一端沿外壳1纵向朝向与其正对的透析液入口10或透析液出口3方向倾斜,即环形导流分布环8相对于外壳1倾斜一定角度α(如图6所示)。 [0078] The annular guide ring 8 annular distribution (FIG. 3), the side surface of the dialysate in the dialyzer blood passage, and a position located just the dialysate inlet 10 and / or the dialysate outlet 3, the said annular flow distribution ring 8 at one end of the housing 1 is connected to the end of the annular flow distribution toward the other end in the longitudinal direction of the housing 1 the ring 8 with its positive dialysate inlet 10 or the dialysate outlet 3 is inclined direction, i.e., annular deflector distribution ring 8 relative to the housing 1 is inclined at an angle [alpha] (Figure 6). 本发明的血液透析器设置环形导流分布环8后,透析液的流向如图5及图6所示,透析液进入透析液入口10 后,接触到环形导流分布环8,并将环形导流分布环8和透析液流道9之间的区域充满,然后透析液沿着环形导流分布环8的方向流向密封胶7的方向,从而使透析液以一定角度与中空纤维丝管2接触,并流向透析液出口3方向。 Hemodialysis present invention is provided an annular distribution ring flow guide 8, the dialysate flow in FIG. 5 and FIG. 6, the dialysate into the dialysate inlet 10, after contact with the annular flow distribution ring 8 and the annular full loop region between the flow distributor 98 and the dialysate flow path, the direction and the dialysate ring 8 distributed along the direction of flow of the annular flow of the sealant 7, whereby the dialysate tube at a second contact angle with the hollow filaments and the dialysate flow direction of the outlet 3. 如此设计,可在透析过程中引导透析液沿中空纤维丝管2外表面切线方向流动,从而大幅度降低了浓差极化现象,有效地提高了透析液与中空纤维丝管表面的接触面积,同时能够达到透析液紊流的效果,扩大弥散效果,提高去除率,并有利于防止透析液直接进入透析室时对纤维束造成损伤,降低纤维丝管断丝率。 Thus design, may be directed along the dialysate flow tangential direction of the outer surface 2 of the hollow tube filament during the dialysis process, thus greatly reducing concentration polarization, the contact area to effectively improve the dialysate tube surface of the hollow filaments, while being able to achieve a dialysate turbulence, dispersion expansion effects and improve the removal rate, and facilitate preventing damage dialysate into the dialysate chamber directly to the fiber bundle, reducing fiber breakage rate wire tube. [0079]本发明的血液透析器中,环形导流分布环8相对于外壳1倾斜的角度α为2-6°,优选4°。 [0079] hemodialyzer according to the present invention, the annular flow distribution ring 8 is inclined at an angle with respect to the housing 1 α is 2-6 °, preferably 4 °. 如果倾斜角过大则将导致透析液不能顺畅分布,增大透析液的阻力,导致透析液进口内局部水流紊乱;如果倾斜角过小则达不到大幅度降低浓差极化现象,提高透析液与纤维丝管表面的接触面积及去除率,并降低纤维丝管断丝率的效果。 If the inclination angle is too large will cause the dialysate can not be smoothly distributed, increasing the resistance of the dialysate, the dialysate inlet resulting in local flow disturbances; if the inclination angle is too small, not reach a significant reduction in concentration polarization, improving dialysis the contact area and the removal liquid and the surface of the tube filaments, wire tube and the effect of reducing the rate of fiber breakage.

[0080] 优选地,环形导流分布环8的直径为53_55mm,优选54mm;宽度为7_9mm,优选8mm; Diameter [0080] Preferably, the annular flow distribution ring 8 is 53_55mm, preferably 54mm; width 7_9mm, preferably 8mm;

[0081]优选地,所述环形导流分布环8的宽度小于与其正对的透析液入口10或透析液出口3沿外壳1纵向的宽度。 Width [0081] Preferably, the annular flow distribution ring 8 is smaller than its positive dialysate inlet of a dialysate outlet 10 or the width of the housing 3 along a longitudinal direction.

[0082] 本发明的血液透析器中,中空纤维丝管2的内径为150-400μπι,厚度为15-60μπι,中空纤维丝管2的内壁具有l-5nm的微孔。 [0082] hemodialyzer of the invention, the inner diameter of the hollow fiber wire tube 2 is 150-400μπι, thickness 15-60μπι, the inner wall of the hollow filaments having a 2 l-5nm of micropores. 外壳1内填充的纤维束约占血液透析器总体积的55%-85%,另外也可根据实际应用中外壳1的尺寸,选择纤维束的填充密度,优选纤维束的面积为0.8-3.0平方米,由中空纤维丝管2形成的血室容积为30-120ml,外壳1内填充的中空纤维丝管2的数量优选12000-35000根,中空纤维丝管2的长度优选300mm,纤维束中所有中空纤维丝管2的总表面积为0.6-4.0平方米。 About 55% -85% of the total blood volume of the dialyzer fiber bundle within the housing 1 is filled, the other may be based on the actual size of the housing 1 of the application, the fiber bundle is selected packing density, fiber bundle area is preferably 0.8 to 3.0 square m, the volume of the blood chamber 2 is formed as a hollow tube filaments 30-120ml, the number of filaments of hollow tube 1 within the housing 2 is preferably filled root 12000-35000, 300mm length of the hollow filament tube 2 is preferably, all the fiber bundle total surface area of ​​the hollow filament tube 2 is 0.6 to 4.0 square meters.

[0083] 封装胶7可为现有技术中常用的材料,包括但不限于聚氨酯或聚亚氨树脂,优选聚氨酯树脂,封装胶7的厚度为5-20_。 [0083] packaging adhesive 7 may be a material commonly used in the prior art, including but not limited to the thickness of the polyurethane or imino resin, preferably polyurethane resin, packaging adhesive 7 is 5-20_.

[0084] 外壳1的形状可为本领域常规的形状,本发明优选圆筒状,圆筒状外壳的内径优选30-48_。 Shape [0084] The housing 1 may present the shape of a conventional art, the present invention is preferably a cylindrical shape, the inner diameter of the cylindrical housing is preferably 30-48_. 另外,外壳的尺寸可根据实际情况确定。 Further, the size of the housing may be determined according to the actual situation.

[0085] 本发明的血液透析器中的中空纤维丝管2采用改性的聚醚砜中空纤维膜制备,以下为本发明的改性的聚醚砜中空纤维膜的制备实施例。 [0085] Preparation 2 using modified polyethersulfone hollow fiber membrane hemodialyzer according to the present invention, the hollow tube filaments, the present embodiment prepared modified polyether sulfone hollow fiber membrane of the invention.

[0086]实施例1聚醚砜中空纤维膜1的制备[0087] 1、各成分的制备: [0086] Example 1 Preparation of a polyether sulfone hollow fiber membrane of Embodiment 1 [0087] 1. Preparation of the ingredients:

[0088] 羟基二氧化钛混合物:将1-10纳米300g水溶性二氧化钛与700g乙二醇混合,在45 °〇氮气保护下搅拌30分钟后得到羟基二氧化钛混合物。 [0088] hydroxy-titania mixture of: to 10 nm 300g 700g of ethylene glycol and a water-soluble titanium dioxide were mixed and stirred at 45 ° square nitrogen for 30 minutes to give a mixture of hydroxy-titania.

[0089] 改性聚醚砜共混物:将900g聚醚砜P-3500、100g聚乙烯吡咯烷酮k90、0.05g氢氧化钠及〇.5g过硫酸钠混合,并在95°C氮气保护下混合35分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0089] Modified polyether sulfone blend of: 900g polyethersulfone P-3500,100g k90,0.05g polyvinylpyrrolidone and sodium persulfate 〇.5g combined and mixed at 95 ° C for nitrogen for 35 minutes to make the components cross-linking reaction, modified polyethersulfone blends prepared.

[0090] 2、聚醚砜中空纤维膜的制备: [0090] 2, polyethersulfone hollow fiber membrane prepared:

[0091] 在二甲基亚砜中加入300g改性聚醚砜共混物、90g聚乙烯吡咯烷酮k90、30g纳米改性羟基二氧化钛混合物以及70g聚乙二醇(2000),采用干-湿法在60°C氮气保护下搅拌24小时得到纺丝液,将纺丝液熟化12小时后,通过喷丝板挤出,并通过320mm的空气段后,以6米/ 分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜1。 [0091] Add 300g modified polyether sulfone blend dimethylsulfoxide, 90g polyvinylpyrrolidone k90,30g nano-modified hydroxy titanium dioxide mixture and 70g of polyethylene glycol (2000), by dry - wet method after stirring 60 ° C under nitrogen for 24 hours to obtain a spinning solution, the spinning solution was aged for 12 hours and extruded through a spinneret, and air through the section of 320mm at a speed of 6 m / min through a coagulation bath of pure water , and dried to give preparation 1 polyethersulfone hollow fiber membrane.

[0092]实施例2聚醚砜中空纤维膜2的制备[0093] 1、各成分的制备: [0092] Preparation Example 2 Polyethersulfone hollow fiber membrane of Example 2 [0093] 1. Preparation of the ingredients:

[0094] 羟基二氧化钛混合物:将1-10纳米255g水溶性二氧化钛与745g乙二醇混合,在45 °〇氮气保护下搅拌30分钟后得到羟基二氧化钛混合物。 [0094] hydroxy-titania mixture of: to 10 nm 255g 745g of ethylene glycol and a water-soluble titanium dioxide were mixed and stirred at 45 ° square nitrogen for 30 minutes to give a mixture of hydroxy-titania.

[0095] 改性聚醚砜共混物:将980g聚醚砜P-3500、20g聚乙烯吡咯烷酮k90、0.08g氢氧化钠及0. Sg过硫酸钠混合,并在100°C氮气保护下混合60分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0095] Modified polyether sulfone blend of: 980g polyethersulfone P-3500,20g k90,0.08g polyvinylpyrrolidone and sodium persulfate 0. Sg combined and mixed at 100 ° C for nitrogen for 60 minutes to make the components cross-linking reaction, modified polyethersulfone blends prepared.

[0096] 2、聚醚砜中空纤维膜的制备: [0096] 2, polyethersulfone hollow fiber membrane prepared:

[0097] 在二甲乙酰胺中加入280g改性聚醚砜共混物、70g聚乙烯吡咯烷酮k90、20g纳米改性羟基二氧化钛混合物以及90g聚乙二醇(1800),采用干-湿法在60°C氮气保护下搅拌24小时得到纺丝液,将纺丝液熟化12小时后,通过喷丝板挤出,并通过400mm的空气段后,以9米/ 分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜2。 [0097] Add 280g modified polyether sulfone blend of dimethylacetamide, 70g of polyvinylpyrrolidone k90,20g nano-modified hydroxy titanium dioxide mixtures and 90g of polyethylene glycol (1800), by dry - wet in 60 ° after stirring under nitrogen for 24 hours C to give a spinning solution, the spinning solution was aged for 12 hours and extruded through a spinneret, and air through the section of 400mm at a speed of 9 m / min through a coagulation bath of pure water, and dried prepared polyethersulfone hollow fiber membrane 2.

[0098]实施例3聚醚砜中空纤维膜3的制备[0099] 1、各成分的制备: [0098] Example 3 Preparation of a polyether sulfone hollow fiber membrane of Example 3 [0099] 1. Preparation of the ingredients:

[0100] 羟基二氧化钛混合物:将1-10纳米200g水溶性二氧化钛与800g乙二醇混合,在50 °〇氮气保护下搅拌30分钟后得到羟基二氧化钛混合物。 [0100] hydroxy-titania mixture of: to 10 nm 200g 800g of ethylene glycol and a water-soluble titanium dioxide were mixed and stirred at 50 ° square nitrogen for 30 minutes to give a mixture of hydroxy-titania.

[0101] 改性聚醚砜共混物:将950g聚醚砜P-3500、50g聚乙烯吡咯烷酮k90、0.05g氢氧化钠及0. Sg过硫酸钠混合,并在95°C氮气保护下混合30分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0101] Modified polyether sulfone blend of: 950g polyethersulfone P-3500,50g k90,0.05g polyvinylpyrrolidone and sodium persulfate 0. Sg combined and mixed at 95 ° C for nitrogen 30 minutes, the components cross-linking reaction, modified polyethersulfone blends prepared.

[0102] 2、聚醚砜中空纤维膜的制备: [0102] 2, polyethersulfone hollow fiber membrane prepared:

[0103] 在二甲基亚砜中加入320g改性聚醚砜共混物、120g聚乙烯吡咯烷酮k90、80g纳米改性羟基二氧化钛混合物以及50g聚乙二醇(2000),采用干-湿法在80°C氮气保护下搅拌8 小时得到纺丝液,将纺丝液熟化24小时后,通过喷丝板挤出,并通过500mm的空气段后,以6.5米/分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜3。 [0103] Add 320g modified polyether sulfone blend dimethyl sulfoxide, polyvinyl pyrrolidone 120g k90,80g nano-modified hydroxy titanium dioxide mixture and 50g of polyethylene glycol (2000), by dry - wet method after stirring 80 ° C for 8 hours to give a nitrogen atmosphere spinning solution, the spinning solution was aged for 24 hours, extruding through a spinneret, and air through the section of 500mm at a speed of 6.5 m / min through a coagulation bath of pure water , and dried to give preparation 3 polyethersulfone hollow fiber membrane.

[0104] 实施例4聚醚砜中空纤维膜4的制备 Polyethersulfone hollow fiber membrane prepared in Example 4 4 ​​[0104] Embodiment

[0105] 1、各成分的制备: [0105] 1. Preparation of the ingredients:

[0106] 羟基二氧化钛混合物:将1-10纳米250g水溶性二氧化钛与750g乙二醇混合,在40 °〇氮气保护下搅拌30分钟后得到羟基二氧化钛混合物。 [0106] hydroxy-titania mixture of: to 10 nm 250g 750g of ethylene glycol and a water-soluble titanium dioxide were mixed and stirred at 40 ° square nitrogen for 30 minutes to give a mixture of hydroxy-titania.

[0107] 改性聚醚砜共混物:将960g聚醚砜p-3500、40g聚乙烯吡咯烷酮k90、0.08g氢氧化钠及0. Sg过硫酸钠混合,并在95°C氮气保护下混合45分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0107] Modified polyether sulfone blend of: 960g polyethersulfone p-3500,40g k90,0.08g polyvinylpyrrolidone and sodium persulfate 0. Sg combined and mixed at 95 ° C for nitrogen for 45 minutes to make the components cross-linking reaction, modified polyethersulfone blends prepared.

[0108] 2、聚醚砜中空纤维膜的制备: [0108] 2, polyethersulfone hollow fiber membrane prepared:

[0109] 在二甲基亚砜中加入400g改性聚醚砜共混物、60g聚乙烯吡咯烷酮k90、90g纳米改性羟基二氧化钛混合物以及50g聚乙二醇(2000),采用干-湿法在80°C氮气保护下搅拌24小时得到纺丝液,将纺丝液熟化24小时后,通过喷丝板挤出,并通过450mm的空气段后,以8米/ 分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜4。 [0109] Add 400g modified polyether sulfone blend dimethylsulfoxide, 60g polyvinylpyrrolidone k90,90g nano-modified hydroxy titanium dioxide mixture and 50g of polyethylene glycol (2000), by dry - wet method after stirring 80 ° C for 24 hours to obtain a nitrogen atmosphere spinning solution, the spinning solution was aged for 24 hours, extruding through a spinneret, and air through the section of 450mm at a speed of 8 m / min through a coagulation bath of pure water , and dried to give preparation 4 polyethersulfone hollow fiber membrane.

[0110] 实施例5聚醚砜中空纤维膜5的制备 Preparation 5 Polyethersulfone hollow fiber membrane of Example 5 [0110] Embodiment

[0111] 1、各成分的制备: [0111] 1. Preparation of the ingredients:

[0112] 羟基二氧化钛混合物:将1-10纳米220g水溶性二氧化钛与780g乙二醇混合,在45 °〇氮气保护下搅拌30分钟后得到羟基二氧化钛混合物。 [0112] hydroxy-titania mixture of: to 10 nm 220g 780g of ethylene glycol and a water-soluble titanium dioxide were mixed and stirred at 45 ° square nitrogen for 30 minutes to give a mixture of hydroxy-titania.

[0113] 改性聚醚砜共混物:将910g聚醚砜P-3500、90g聚乙烯吡咯烷酮k90、0.09g氢氧化钠及0.6g过硫酸钠混合,并在110°C氮气保护下混合40分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0113] Modified polyether sulfone blend of: 910g polyethersulfone P-3500,90g k90,0.09g polyvinylpyrrolidone and sodium hydroxide 0.6g of sodium persulfate mixed, and mixed at 110 ° C for 40 nitrogen min, so that the components cross-linking reaction, modified polyethersulfone blends prepared.

[0114] 2、聚醚砜中空纤维膜的制备: [0114] 2, polyethersulfone hollow fiber membrane prepared:

[0115] 在二甲基亚砜中加入430g改性聚醚砜共混物、50g聚乙二醇(2000)、80g纳米改性羟基二氧化钛混合物以及50g聚乙二醇(2000),采用干-湿法在80°C氮气保护下搅拌24小时得到纺丝液,将纺丝液熟化24小时后,通过喷丝板挤出,并通过400mm的空气段后,以6.5米/ 分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜5。 [0115] Add 430g modified polyether sulfone blend dimethylsulfoxide, 50g of polyethylene glycol (2000), 80g of nano-modified hydroxy titanium dioxide mixtures and 50g of polyethylene glycol (2000), dry - wet stirred at 80 ° C for 24 hours to obtain a nitrogen atmosphere spinning solution, the spinning solution was aged 24 hours later, extruded through a spinneret, and air through the 400mm sections, at a speed of 6.5 m / min through pure coagulation bath water, and dried to give preparation 5 polyethersulfone hollow fiber membrane.

[0116] 实施例6聚醚砜中空纤维膜6的制备 Preparation 6 polyethersulfone hollow fiber membrane of Example 6 [0116] Embodiment

[0117] 1、各成分的制备: [0117] 1. Preparation of the ingredients:

[0118] 羟基二氧化钛混合物:将1-10纳米230g水溶性二氧化钛与770g乙二醇混合,在45 °〇氮气保护下搅拌35分钟后得到羟基二氧化钛混合物。 [0118] hydroxy-titania mixture of: to 10 nm 230g 770g of ethylene glycol and a water-soluble titanium dioxide were mixed and stirred at 45 ° square nitrogen for 35 minutes to give a mixture of hydroxy-titania.

[0119] 改性聚醚砜共混物:将920g聚醚砜P-3500、80g聚乙烯吡咯烷酮k30、0.08g氢氧化钠及0. Sg过硫酸钠混合,并在120°C氮气保护下混合50分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0119] Modified polyether sulfone blend of: 920g polyethersulfone P-3500,80g k30,0.08g polyvinylpyrrolidone and sodium persulfate 0. Sg combined and mixed at 120 ° C for nitrogen 50 minutes, so that the components cross-linking reaction, modified polyethersulfone blends prepared.

[0120] 2、聚醚砜中空纤维膜的制备: [0120] 2, polyethersulfone hollow fiber membrane prepared:

[0121] 在二甲基亚砜中加入310g改性聚醚砜共混物、80g聚乙烯吡咯烷酮k90、55g纳米改性羟基二氧化钛混合物以及80g聚乙二醇(2000),采用干-湿法在65°C氮气保护下搅拌24小时得到纺丝液,将纺丝液熟化24小时后,通过喷丝板挤出,并通过400mm的空气段后,以6.5 米/分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜6。 [0121] Add 310g modified polyether sulfone blend dimethylsulfoxide, 80g polyvinylpyrrolidone k90,55g nano-modified hydroxy titanium dioxide mixture and 80g of polyethylene glycol (2000), by dry - wet method after stirring at 65 ° C nitrogen for 24 hours to obtain a spinning solution, the spinning solution was aged for 24 hours, extruding through a spinneret, and air through the section of 400mm at a speed of 6.5 m / min through a coagulation bath of pure water , and dried to give preparation 6 polyethersulfone hollow fiber membrane.

[0122] 实施例7聚醚砜中空纤维膜7的制备 Example 7 Preparation of a polyether sulfone hollow fiber membrane 7 of the [0122] embodiment

[0123] 1、各成分的制备: [0123] 1. Preparation of the ingredients:

[0124] 羟基二氧化钛混合物:将1-10纳米240g水溶性二氧化钛与760g乙二醇混合,在45 °〇氮气保护下搅拌30分钟后得到羟基二氧化钛混合物。 [0124] hydroxy-titania mixture of: to 10 nm 240g 760g of ethylene glycol and a water-soluble titanium dioxide were mixed and stirred at 45 ° square nitrogen for 30 minutes to give a mixture of hydroxy-titania.

[0125] 改性聚醚砜共混物:将910g聚醚砜P-3500、90g聚乙烯吡咯烷酮kl5、0.05g氢氧化钠及0. Sg过硫酸钠混合,并在98°C氮气保护下混合60分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0125] Modified polyether sulfone blend of: 910g polyethersulfone P-3500,90g kl5,0.05g polyvinylpyrrolidone and sodium persulfate 0. Sg combined and mixed at 98 ° C in a nitrogen atmosphere for 60 minutes to make the components cross-linking reaction, modified polyethersulfone blends prepared.

[0126] 2、聚醚砜中空纤维膜的制备: [0126] 2, polyethersulfone hollow fiber membrane prepared:

[0127] 在二甲基亚砜中加入250g改性聚醚砜共混物、150g聚乙烯吡咯烷酮k90、70g纳米改性羟基二氧化钛混合物以及50g丙三醇,采用干-湿法在80°C氮气保护下搅拌18小时得到纺丝液,将纺丝液熟化36小时后,通过喷丝板挤出,并通过400mm的空气段后,以7米/分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜7。 [0127] Add 250g modified polyether sulfone blend dimethyl sulfoxide, polyvinyl pyrrolidone 150g k90,70g nano-modified hydroxy titanium dioxide and 50g glycerol mixture, dry - 80 ° C in a wet nitrogen after stirring for 18 hours to give protected spinning liquid, the spinning solution was aged 36 hours, extruding through a spinneret, and air through the section of 400mm at a speed of 7 m / min through a coagulation bath of pure water, and dried to give preparation polyether sulfone hollow fiber membrane 7.

[0128] 实施例8聚醚砜中空纤维膜8的制备 Example 8 Preparation of a polyether sulfone hollow fiber membrane 8 [0128] Embodiment

[0129] 1、各成分的制备: [0129] 1. Preparation of the ingredients:

[0130] 羟基二氧化钛混合物:将1-10纳米260g水溶性二氧化钛与740g乙二醇混合,在45 °〇氮气保护下搅拌30分钟后得到羟基二氧化钛混合物。 [0130] hydroxy-titania mixture of: to 10 nm 260g 740g of ethylene glycol and a water-soluble titanium dioxide were mixed and stirred at 45 ° square nitrogen for 30 minutes to give a mixture of hydroxy-titania.

[0131] 改性聚醚砜共混物:将940g聚醚砜P-3500、60g聚乙烯吡咯烷酮k30、0.05g氢氧化钠及0. Sg过硫酸钠混合,并在95°C氮气保护下混合90分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0131] Modified polyether sulfone blend of: 940g polyethersulfone P-3500,60g k30,0.05g polyvinylpyrrolidone and sodium persulfate 0. Sg combined and mixed at 95 ° C for nitrogen for 90 minutes to make the components cross-linking reaction, modified polyethersulfone blends prepared.

[0132] 2、聚醚砜中空纤维膜的制备: [0132] 2, polyethersulfone hollow fiber membrane prepared:

[0133] 在二甲基亚砜中加入320g改性聚醚砜共混物、70g聚乙二醇(2000)、50g纳米改性羟基二氧化钛混合物以及80g丙三醇,采用干-湿法在65°C氮气保护下搅拌18小时得到纺丝液,将纺丝液熟化36小时后,通过喷丝板挤出,并通过350mm的空气段后,以8米/分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜8。 [0133] Add 320g modified polyether sulfone blend dimethylsulfoxide, 70g of polyethylene glycol (2000), 50g of nano-modified hydroxy titanium dioxide and 80g glycerol mixture, dry - 65 in wet ° C with stirring under nitrogen for 18 hours to give a spinning solution, the spinning solution was aged 36 hours later, extruding through a spinneret, and air through the section of 350mm at a speed of 8 m / min through a coagulation bath of pure water, and dried to give preparation 8 polyethersulfone hollow fiber membrane.

[0134] 实施例9聚醚砜中空纤维膜9的制备 Preparation 9 Polyethersulfone hollow fiber membrane of Example 9 [0134] Embodiment

[0135] 1、各成分的制备: [0135] 1. Preparation of the ingredients:

[0136] 羟基二氧化钛混合物:将1-10纳米280g水溶性二氧化钛与720g乙二醇混合,在40 °〇氮气保护下搅拌30分钟后得到羟基二氧化钛混合物。 [0136] hydroxy-titania mixture of: to 10 nm 280g 720g of ethylene glycol and a water-soluble titanium dioxide were mixed and stirred at 40 ° square nitrogen for 30 minutes to give a mixture of hydroxy-titania.

[0137] 改性聚醚砜共混物:将930g聚醚砜P-3500、70g聚乙烯吡咯烷酮k30、0.08g氢氧化钠及0.5g过硫酸钠混合,并在95°C氮气保护下混合110分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0137] Modified polyether sulfone blend of: 930g polyethersulfone P-3500,70g k30,0.08g polyvinylpyrrolidone and sodium hydroxide 0.5g of sodium persulfate mixed, and mixed at 95 ° C for 110 nitrogen min, so that the components cross-linking reaction, modified polyethersulfone blends prepared.

[0138] 2、聚醚砜中空纤维膜的制备: [0138] 2, polyethersulfone hollow fiber membrane prepared:

[0139] 在二甲基亚砜中加入280g改性聚醚砜共混物、90g聚乙烯吡咯烷酮k30、60g纳米改性羟基二氧化钛混合物以及50g聚乙二醇(2000),采用干-湿法在60°C氮气保护下搅拌18小时得到纺丝液,将纺丝液熟化36小时后,通过喷丝板挤出,并通过350mm的空气段后,以6.5 米/分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜9。 [0139] Add 280g modified polyether sulfone blend dimethylsulfoxide, 90g polyvinylpyrrolidone k30,60g nano-modified hydroxy titanium dioxide mixture and 50g of polyethylene glycol (2000), by dry - wet method after stirring 60 ° C under nitrogen for 18 hours to give a spinning solution, the spinning solution was aged 36 hours, extruding through a spinneret, and air through the section of 350mm at a speed of 6.5 m / min through a coagulation bath of pure water , and dried to give preparation 9 polyethersulfone hollow fiber membrane.

[0140] 实施例10聚醚砜中空纤维膜10的制备 [0140] Example 10 Preparation of a polyether sulfone hollow fiber membranes 10

[0141] 1、各成分的制备: [0141] 1. Preparation of the ingredients:

[0142] 羟基二氧化钛混合物:将1-10纳米310g水溶性二氧化钛与690g乙二醇混合,在45 °〇氮气保护下搅拌30分钟后得到羟基二氧化钛混合物。 [0142] hydroxy-titania mixture of: a water-soluble titanium dioxide to 10 nm 310g was mixed with 690g of ethylene glycol was stirred at 45 ° square nitrogen for 30 minutes to give a mixture of hydroxy-titania.

[0143] 改性聚醚砜共混物:将980g聚醚砜P-3500、20g聚乙烯吡咯烷酮k30、0.05g氢氧化钠及0. Sg过硫酸钠混合,并在100°C氮气保护下混合40分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0143] Modified polyether sulfone blend of: 980g polyethersulfone P-3500,20g k30,0.05g polyvinylpyrrolidone and sodium persulfate 0. Sg combined and mixed at 100 ° C for nitrogen for 40 minutes to cross-linking reaction of the components, modified polyethersulfone blends prepared.

[0144] 2、聚醚砜中空纤维膜的制备: [0144] 2, polyethersulfone hollow fiber membrane prepared:

[0145] 在二甲基亚砜中加入450g改性聚醚砜共混物、60g聚乙二醇(2000)、30g纳米改性羟基二氧化钛混合物以及90g聚乙二醇(2000),采用干-湿法在65°C氮气保护下搅拌18小时得到纺丝液,将纺丝液熟化36小时后,通过喷丝板挤出,并通过350mm的空气段后,以6.5米/ 分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜10。 [0145] Add 450g modified polyether sulfone blend dimethylsulfoxide, 60g of polyethylene glycol (2000), 30g of nano-modified hydroxy titanium dioxide mixtures and 90g of polyethylene glycol (2000), dry - after the wet mixture was stirred at 65 ° C nitrogen for 18 hours to give a spinning solution, the spinning solution was aged 36 hours, extruding through a spinneret, and air through the section of 350mm at a speed of 6.5 m / min through pure water coagulation bath, a polyether sulfone hollow fiber membrane was prepared and dried to give 10.

[0146] 实施例11聚醚砜中空纤维膜11的制备 Example 11 Preparation of a polyether sulfone hollow fiber membrane 11 [0146] Embodiment

[0147] 1、各成分的制备: [0147] 1. Preparation of the ingredients:

[0148] 羟基二氧化钛混合物:将1-10纳米400g水溶性二氧化钛与600g乙二醇混合,在45 °〇氮气保护下搅拌30分钟后得到羟基二氧化钛混合物。 [0148] hydroxy-titania mixture of: a water-soluble 400g to 10 nm titanium dioxide mixed with 600g of ethylene glycol was stirred at 45 ° square nitrogen for 30 minutes to give a mixture of hydroxy-titania.

[0149] 改性聚醚砜共混物:将930g聚醚砜E6020、70g聚乙烯吡咯烷酮k30、0.05g氢氧化钠及0.Sg过硫酸钠混合,并在120°C氮气保护下混合60分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0149] Modified polyether sulfone blend of: 930g E6020,70g polyethersulfone and polyvinylpyrrolidone k30,0.05g 0.Sg sodium persulfate mixed, and mixed at 120 ° C for 60 minutes nitrogen the crosslinking reaction of the components, modified polyethersulfone blends prepared.

[0150] 2、聚醚砜中空纤维膜的制备: [0150] 2, polyethersulfone hollow fiber membrane prepared:

[0151] 在二甲基亚砜中加入340g改性聚醚砜共混物、90g聚乙烯吡咯烷酮k30、20g纳米改性羟基二氧化钛混合物以及100g聚乙二醇(2000),采用干-湿法在70°C氮气保护下搅拌24 小时得到纺丝液,将纺丝液熟化36小时后,通过喷丝板挤出,并通过400mm的空气段后,以7 米/分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜11。 [0151] Add 340g modified polyether sulfone blend dimethylsulfoxide, 90g polyvinylpyrrolidone k30,20g nano-modified hydroxy titanium dioxide mixture and 100g of polyethylene glycol (2000), by dry - wet method after stirring 70 ° C for 24 hours to obtain a nitrogen atmosphere spinning solution, the spinning solution was aged 36 hours, extruding through a spinneret, and air through the section of 400mm at a speed of 7 m / min through a coagulation bath of pure water , and dried to give preparation 11 polyethersulfone hollow fiber membranes.

[0152] 实施例12聚醚砜中空纤维膜12的制备 Preparation 12 Polyethersulfone hollow fiber membrane of Example 12 [0152] Embodiment

[0153] 1、各成分的制备: [0153] 1. Preparation of the ingredients:

[0154] 羟基二氧化钛混合物:将1-10纳米380g水溶性二氧化钛与620g乙二醇混合,在45 °〇氮气保护下搅拌30分钟后得到羟基二氧化钛混合物。 [0154] hydroxy-titania mixture of: a water-soluble 380g to 10 nm titanium dioxide mixed with 620g of ethylene glycol was stirred at 45 ° square nitrogen for 30 minutes to give a mixture of hydroxy-titania.

[0155] 改性聚醚砜共混物:将920g聚醚砜E6020、80g聚乙烯吡咯烷酮k30、0.08g氢氧化钠及〇.9g过硫酸钠混合,并在120°C氮气保护下混合90分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0155] Modified polyether sulfone blend of: 920g E6020,80g polyethersulfone and polyvinylpyrrolidone k30,0.08g 〇.9g sodium persulfate mixed, and mixed at 120 ° C for 90 minutes nitrogen the crosslinking reaction of the components, modified polyethersulfone blends prepared.

[0156] 2、聚醚砜中空纤维膜的制备: [0156] 2, polyethersulfone hollow fiber membrane prepared:

[0157] 在二甲基亚砜中加入370g改性聚醚砜共混物、50g聚乙烯吡咯烷酮k30、40g纳米改性羟基二氧化钛混合物以及80g聚乙二醇(2000),采用干-湿法在70°C氮气保护下搅拌18小时得到纺丝液,将纺丝液熟化24小时后,通过喷丝板挤出,并通过400mm的空气段后,以6.5 米/分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜12。 [0157] Add 370g modified polyether sulfone blend dimethylsulfoxide, 50g polyvinylpyrrolidone k30,40g nano-modified hydroxy titanium dioxide mixture and 80g of polyethylene glycol (2000), by dry - wet method after stirring 70 ° C for 18 hours to give a nitrogen atmosphere spinning solution, the spinning solution was aged for 24 hours, extruding through a spinneret, and air through the section of 400mm at a speed of 6.5 m / min through a coagulation bath of pure water , and dried to give preparation 12 polyethersulfone hollow fiber membrane.

[0158] 实施例13聚醚砜中空纤维膜13的制备 Preparation 13 Polyethersulfone hollow fiber membrane of Example 13 [0158] Embodiment

[0159] 1、各成分的制备: [0159] 1. Preparation of the ingredients:

[0160] 羟基二氧化钛混合物:将1-10纳米350g水溶性二氧化钛与650g乙二醇混合,在50 °〇氮气保护下搅拌30分钟后得到羟基二氧化钛混合物。 [0160] hydroxy-titania mixture of: a water-soluble 350g to 10 nm titanium dioxide mixed with 650g of ethylene glycol was stirred at 50 ° square nitrogen for 30 minutes to give a mixture of hydroxy-titania.

[0161] 改性聚醚砜共混物:将920g聚醚砜E6020、80g聚乙烯吡咯烷酮kl5、0.05g氢氧化钠及0. Sg过硫酸钠混合,并在110°C氮气保护下混合45分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0161] Modified polyether sulfone blend of: 920g E6020,80g polyethersulfone and polyvinylpyrrolidone kl5,0.05g sodium persulfate 0. Sg combined and mixed at 110 ° C for 45 minutes nitrogen the crosslinking reaction of the components, modified polyethersulfone blends prepared.

[0162] 2、聚醚砜中空纤维膜的制备: [0162] 2, polyethersulfone hollow fiber membrane prepared:

[0163] 在二甲基亚砜中加入280g改性聚醚砜共混物、80g聚乙烯吡咯烷酮kl 5、20g纳米改性羟基二氧化钛混合物以及100g聚乙二醇(2000),采用干-湿法在70°C氮气保护下搅拌18 小时得到纺丝液,将纺丝液熟化24小时后,通过喷丝板挤出,并通过400mm的空气段后,以8 米/分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜13。 [0163] Add 280g modified polyether sulfone blend dimethylsulfoxide, 80g polyvinylpyrrolidone kl 5,20g nano-modified hydroxy titanium dioxide mixtures and 100g of polyethylene glycol (2000), dry - wet after stirring at 70 ° C for 18 hours to give a nitrogen atmosphere spinning solution, the spinning solution was aged for 24 hours, extruding through a spinneret, and air through the section of 400mm at a speed of 8 m / min through a water coagulation bath was prepared and dried to obtain a polyether sulfone hollow fiber membrane 13.

[0164] 实施例14聚醚砜中空纤维膜14的制备 Preparation of polyether sulfone hollow fiber membrane 14 Example 14 [0164] Embodiment

[0165] 1、各成分的制备: [0165] 1. Preparation of the ingredients:

[0166] 羟基二氧化钛混合物:将1-10纳米330g水溶性二氧化钛与670g乙二醇混合,在45 °〇氮气保护下搅拌30分钟后得到羟基二氧化钛混合物。 [0166] hydroxy-titania mixture of: a water-soluble 330g to 10 nm titanium dioxide mixed with 670g of ethylene glycol was stirred at 45 ° square nitrogen for 30 minutes to give a mixture of hydroxy-titania.

[0167] 改性聚醚砜共混物:将930g聚醚砜E6020、70g聚乙烯吡咯烷酮kl5、0.08g氢氧化钠及0. Sg过硫酸钠混合,并在100°C氮气保护下混合90分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0167] Modified polyether sulfone blend of: 930g E6020,70g polyethersulfone and polyvinylpyrrolidone kl5,0.08g sodium persulfate 0. Sg combined and mixed at 100 ° C for 90 minutes nitrogen the crosslinking reaction of the components, modified polyethersulfone blends prepared.

[0168] 2、聚醚砜中空纤维膜的制备: [0168] 2, polyethersulfone hollow fiber membrane prepared:

[0169] 在二甲基亚砜中加入300g改性聚醚砜共混物、70g聚乙烯吡咯烷酮kl 5、50g纳米改性羟基二氧化钛混合物以及70g聚乙二醇(2000),采用干-湿法在70°C氮气保护下搅拌18小时得到纺丝液,将纺丝液熟化24小时后,通过喷丝板挤出,并通过400mm的空气段后,以6.5 米/分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜14。 [0169] Add 300g modified polyether sulfone blend dimethylsulfoxide, 70g polyvinylpyrrolidone kl 5,50g nano-modified hydroxy titanium dioxide mixtures and 70g of polyethylene glycol (2000), dry - wet after stirring at 70 ° C for 18 hours to give a nitrogen atmosphere spinning solution, the spinning solution was aged for 24 hours, extruding through a spinneret, and air through the section of 400mm at a speed of 6.5 m / min by water coagulation bath was prepared and dried to obtain a polyether sulfone hollow fiber membrane 14.

[0170] 实施例15聚醚砜中空纤维膜15的制备 Example 15 Preparation of a polyether sulfone hollow fiber membrane 15. [0170] Embodiment

[0171] 1、各成分的制备: [0171] 1. Preparation of the ingredients:

[0172] 羟基二氧化钛混合物:将1-10纳米355g水溶性二氧化钛与645g乙二醇混合,在45 °〇氮气保护下搅拌30分钟后得到羟基二氧化钛混合物。 [0172] hydroxy-titania mixture of: a water-soluble titanium dioxide to 10 nm 355g was mixed with 645g of ethylene glycol was stirred at 45 ° square nitrogen for 30 minutes to give a mixture of hydroxy-titania.

[0173] 改性聚醚砜共混物:将980g聚醚砜E6020、20g聚乙烯吡咯烷酮k90、0.05g氢氧化钠及〇.9g过硫酸钠混合,并在95°C氮气保护下混合120分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0173] Modified polyether sulfone blend of: 980g E6020,20g polyethersulfone and polyvinylpyrrolidone k90,0.05g 〇.9g sodium persulfate mixed, and mixed at 95 ° C for 120 minutes nitrogen the crosslinking reaction of the components, modified polyethersulfone blends prepared.

[0174] 2、聚醚砜中空纤维膜的制备: [0174] 2, polyethersulfone hollow fiber membrane prepared:

[0175] 在二甲基亚砜中加入280g改性聚醚砜共混物、150g聚乙烯吡咯烷酮k90、30g纳米改性羟基二氧化钛混合物以及80g聚乙二醇(2000),采用干-湿法在70°C氮气保护下搅拌18 小时得到纺丝液,将纺丝液熟化24小时后,通过喷丝板挤出,并通过400mm的空气段后,以7 米/分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜15。 [0175] Add 280g modified polyether sulfone blend dimethyl sulfoxide, polyvinyl pyrrolidone 150g k90,30g nano-modified hydroxy titanium dioxide mixture and 80g of polyethylene glycol (2000), by dry - wet method after stirring 70 ° C for 18 hours to give a nitrogen atmosphere spinning solution, the spinning solution was aged for 24 hours, extruding through a spinneret, and air through the section of 400mm at a speed of 7 m / min through a coagulation bath of pure water , and dried to give preparation 15 polyethersulfone hollow fiber membrane.

[0176] 实施例16聚醚砜中空纤维膜16的制备 Preparation 16 Polyethersulfone hollow fiber membrane of Example 16 [0176] Embodiment

[0177] 1、各成分的制备: [0177] 1. Preparation of the ingredients:

[0178] 羟基二氧化钛混合物:将1-10纳米390g水溶性二氧化钛与610g乙二醇混合,在45 °〇氮气保护下搅拌30分钟后得到羟基二氧化钛混合物。 [0178] hydroxy-titania mixture of: a water-soluble 390g to 10 nm titanium dioxide mixed with 610g of ethylene glycol was stirred at 45 ° square nitrogen for 30 minutes to give a mixture of hydroxy-titania.

[0179] 改性聚醚砜共混物:将950g聚醚砜E6020、50g聚乙烯吡咯烷酮k90、0.08g氢氧化钠及0.4g过硫酸钠混合,并在95°C氮气保护下混合30分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0179] Modified polyether sulfone blend of: 950g E6020,50g polyethersulfone and polyvinylpyrrolidone k90,0.08g sodium persulfate 0.4g were mixed and mixed in nitrogen atmosphere 95 ° C for 30 minutes. each component cross-linking reaction, modified polyethersulfone blends prepared.

[0180] 2、聚醚砜中空纤维膜的制备: [0180] 2, polyethersulfone hollow fiber membrane prepared:

[0181] 在二甲基亚砜中加入250g改性聚醚砜共混物、150g聚乙烯吡咯烷酮k90、40g纳米改性羟基二氧化钛混合物以及60g聚乙二醇(2000),采用干-湿法在70°C氮气保护下搅拌18 小时得到纺丝液,将纺丝液熟化36小时后,通过喷丝板挤出,并通过400mm的空气段后,以6.5米/分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜16。 [0181] Add 250g modified polyether sulfone blend dimethyl sulfoxide, polyvinyl pyrrolidone 150g k90,40g nano-modified hydroxy titanium dioxide mixture and 60g of polyethylene glycol (2000), by dry - wet method after stirring 70 ° C for 18 hours to give a nitrogen atmosphere spinning solution, the spinning solution was aged 36 hours, extruding through a spinneret, and air through the section of 400mm at a speed of 6.5 m / min through a coagulation bath of pure water , and dried to give preparation 16 polyethersulfone hollow fiber membrane.

[0182] 实施例17聚醚砜中空纤维膜17的制备 Example 17 Preparation of a polyether sulfone hollow fiber membrane 17 Embodiment [0182]

[0183] 1、各成分的制备: [0183] 1. Preparation of the ingredients:

[0184] 羟基二氧化钛混合物:将1-10纳米225g水溶性二氧化钛与775g乙二醇混合,在45 °〇氮气保护下搅拌30分钟后得到羟基二氧化钛混合物。 [0184] hydroxy-titania mixture of: to 10 nm 225g 775g of ethylene glycol and a water-soluble titanium dioxide were mixed and stirred at 45 ° square nitrogen for 30 minutes to give a mixture of hydroxy-titania.

[0185] 改性聚醚砜共混物:将970g聚醚砜E6020、30g聚乙烯吡咯烷酮k90、0.05g氢氧化钠及0. Sg过硫酸钠混合,并在95°C氮气保护下混合45分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0185] Modified polyether sulfone blend of: 970g E6020,30g polyethersulfone and polyvinylpyrrolidone k90,0.05g sodium persulfate 0. Sg combined and mixed at 95 ° C for 45 minutes nitrogen the crosslinking reaction of the components, modified polyethersulfone blends prepared.

[0186] 2、聚醚砜中空纤维膜的制备: [0186] 2, polyethersulfone hollow fiber membrane prepared:

[0187] 在二甲基亚砜中加入280g改性聚醚砜共混物、120g聚乙烯吡咯烷酮k90、60g纳米改性羟基二氧化钛混合物以及70g聚乙二醇(2000),采用干-湿法在65°C氮气保护下搅拌18 小时得到纺丝液,将纺丝液熟化36小时后,通过喷丝板挤出,并通过400mm的空气段后,以6.5米/分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜17。 [0187] Add 280g modified polyether sulfone blend dimethyl sulfoxide, polyvinyl pyrrolidone 120g k90,60g nano-modified hydroxy titanium dioxide mixture and 70g of polyethylene glycol (2000), by dry - wet method after stirring at 65 ° C nitrogen for 18 hours to give a spinning solution, the spinning solution was aged 36 hours, extruding through a spinneret, and air through the section of 400mm at a speed of 6.5 m / min through a coagulation bath of pure water , and dried to give preparation 17 polyethersulfone hollow fiber membrane.

[0188] 实施例18聚醚砜中空纤维膜18的制备 Preparation 18 Polyethersulfone hollow fiber membrane of Example 18 [0188] Embodiment

[0189] 1、各成分的制备: [0189] 1. Preparation of the ingredients:

[0190] 羟基二氧化钛混合物:将1-10纳米245g水溶性二氧化钛与755g乙二醇混合,在45 °〇氮气保护下搅拌20分钟后得到羟基二氧化钛混合物。 [0190] hydroxy-titania mixture of: to 10 nm 245g 755g of ethylene glycol and a water-soluble titanium dioxide were mixed and stirred at 45 ° under a nitrogen atmosphere for 20 minutes square to give a mixture of hydroxy-titania.

[0191] 改性聚醚砜共混物:将940g聚醚砜E6020、60g聚乙烯吡咯烷酮k90、0.08g氢氧化钠及0. Sg过硫酸钠混合,并在95°C氮气保护下混合90分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0191] Modified polyether sulfone blend of: 940g E6020,60g polyethersulfone and polyvinylpyrrolidone k90,0.08g sodium persulfate 0. Sg combined and mixed at 95 ° C for 90 minutes nitrogen the crosslinking reaction of the components, modified polyethersulfone blends prepared.

[0192] 2、聚醚砜中空纤维膜的制备: [0192] 2, polyethersulfone hollow fiber membrane prepared:

[0193] 在二甲基亚砜中加入380g改性聚醚砜共混物、50g聚乙烯吡咯烷酮k90、90g纳米改性羟基二氧化钛混合物以及50g聚乙二醇(2000),采用干-湿法在65°C氮气保护下搅拌18小时得到纺丝液,将纺丝液熟化36小时后,通过喷丝板挤出,并通过400mm的空气段后,以6.5 米/分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜18。 [0193] Add 380g modified polyether sulfone blend dimethylsulfoxide, 50g polyvinylpyrrolidone k90,90g nano-modified hydroxy titanium dioxide mixture and 50g of polyethylene glycol (2000), by dry - wet method after stirring at 65 ° C nitrogen for 18 hours to give a spinning solution, the spinning solution was aged 36 hours, extruding through a spinneret, and air through the section of 400mm at a speed of 6.5 m / min through a coagulation bath of pure water , and dried to give preparation 18 polyethersulfone hollow fiber membrane.

[0194] 实施例19聚醚砜中空纤维膜19的制备 Example 19 Preparation of a polyether sulfone hollow fiber membrane 19 [0194] Embodiment

[0195] 1、各成分的制备: [0195] 1. Preparation of the ingredients:

[0196] 羟基二氧化钛混合物:将1-10纳米100g水溶性二氧化钛与900g乙二醇混合,在20 °〇氮气保护下搅拌60分钟后得到羟基二氧化钛混合物。 [0196] hydroxy-titania mixture: 100g After the water-soluble titanium dioxide to 10 nm, was stirred at 20 ° square with nitrogen 900g of ethylene glycol and mixed for 60 minutes to obtain a mixture of hydroxy-titania.

[0197] 改性聚醚砜共混物:将910g聚醚砜E6020、150g聚乙烯吡咯烷酮k90、0.01g氢氧化钠及0.1 g过硫酸钠混合,并在95°C氮气保护下混合30分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0197] Modified polyether sulfone blend of: 910g polyethersulfone E6020,150g k90,0.01g polyvinylpyrrolidone and 0.1 g sodium persulfate are mixed and mixed in nitrogen atmosphere 95 ° C for 30 minutes. each component cross-linking reaction, modified polyethersulfone blends prepared.

[0198] 2、聚醚砜中空纤维膜的制备: [0198] 2, polyethersulfone hollow fiber membrane prepared:

[0199] 在二甲基亚砜中加入370g改性聚醚砜共混物、400g聚乙烯吡咯烷酮k90、60g纳米改性羟基二氧化钛混合物以及20g聚乙二醇(2000),采用干-湿法在55°C氮气保护下搅拌12 小时得到纺丝液,将纺丝液熟化36小时后,通过喷丝板挤出,并通过300mm的空气段后,以6.5米/分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜19。 [0199] Add 370g modified polyether sulfone blend dimethyl sulfoxide, 400 g of polyvinylpyrrolidone k90,60g nano-modified hydroxy titanium dioxide mixture and 20g of polyethylene glycol (2000), by dry - wet method after stirring 55 ° C for 12 hours to give a nitrogen atmosphere spinning solution, the spinning solution was aged 36 hours, extruding through a spinneret, and air through the section of 300mm at a speed of 6.5 m / min through a coagulation bath of pure water , and dried to give preparation 19 polyethersulfone hollow fiber membrane.

[0200] 实施例20聚醚砜中空纤维膜20的制备 Example 20 Preparation of a polyether sulfone hollow fiber membrane 20. [0200] Embodiment

[0201] 1、各成分的制备: [0201] 1. Preparation of the ingredients:

[0202] 羟基二氧化钛混合物:将1-10纳米800g水溶性二氧化钛与670g乙二醇混合,在40 °〇氮气保护下搅拌10分钟后得到羟基二氧化钛混合物。 [0202] hydroxy-titania mixture: 800g to 10 nm after the water-soluble titanium dioxide mixed with 670g of ethylene glycol was stirred at 40 ° under a nitrogen atmosphere for 10 minutes to square-hydroxy-titania mixture.

[0203] 改性聚醚砜共混物:将850g聚醚砜E6020、60g聚乙烯吡咯烷酮k90、lg氢氧化钠及0.5g过硫酸钠混合,并在100°C氮气保护下混合45分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0203] Modified polyether sulfone blend of: 850g polyethersulfone E6020,60g polyvinylpyrrolidone k90, lg of sodium hydroxide and 0.5g of sodium persulfate mixed and mixed in a nitrogen atmosphere 100 ° C for 45 minutes, so that crosslinking reaction of the components, modified polyethersulfone blends prepared.

[0204] 2、聚醚砜中空纤维膜的制备: [0204] 2, polyethersulfone hollow fiber membrane prepared:

[0205] 在二甲基亚砜中加入650g改性聚醚砜共混物、150g聚乙烯吡咯烷酮k90、10g纳米改性羟基二氧化钛混合物以及80g聚乙二醇(2000),采用干-湿法在85°C氮气保护下搅拌4 小时得到纺丝液,将纺丝液熟化72小时后,通过喷丝板挤出,并通过Imm的空气段后,以6.5 米/分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜20。 [0205] Add 650g modified polyether sulfone blend dimethyl sulfoxide, polyvinyl pyrrolidone 150g k90,10g nano-modified hydroxy titanium dioxide mixture and 80g of polyethylene glycol (2000), by dry - wet method after stirring 85 ° C under nitrogen for 4 hours to give a spinning solution, the spinning solution was aged 72 hours and extruded through a spinneret, and air through the rear section Imm at a speed of 6.5 m / min through a coagulation bath of pure water , and dried to give preparation 20 polyethersulfone hollow fiber membrane.

[0206]实施例21聚醚砜中空纤维膜21的制备[0207] 1、各成分的制备: [0206] Example 21 Preparation of a polyether sulfone hollow fiber membrane 21 Embodiment [0207] 1. Preparation of the ingredients:

[0208] 羟基二氧化钛混合物:将1-10纳米390g水溶性二氧化钛与980g乙二醇混合,在60 °〇氮气保护下搅拌40分钟后得到羟基二氧化钛混合物。 [0208] hydroxy-titania mixture of: to 10 nm 390g 980g of ethylene glycol and a water-soluble titanium dioxide were mixed and stirred at 60 ° for 40 minutes square nitrogen dioxide to give a mixture of dihydroxydiphenylsulfone.

[0209] 改性聚醚砜共混物:将950g聚醚砜E6020、80g聚乙烯吡咯烷酮k90、0.1g氢氧化钠及Ig过硫酸钠混合,并在95°C氮气保护下混合90分钟,使各组分发生交联反应,制备得到改性聚醚砜共混物。 [0209] Modified polyether sulfone blend of: 950g E6020,80g polyethersulfone and polyvinylpyrrolidone k90,0.1g Ig sodium persulfate mixed, and mixed at 95 ° C for 90 minutes a nitrogen atmosphere, so that crosslinking reaction of the components, modified polyethersulfone blends prepared.

[0210] 2、聚醚砜中空纤维膜的制备: [0210] 2, polyethersulfone hollow fiber membrane prepared:

[0211] 在二甲基亚砜中加入430g改性聚醚砜共混物、20g聚乙烯吡咯烷酮k90、Ig纳米改性羟基二氧化钛混合物以及120g聚乙二醇(2000),采用干-湿法在100°C氮气保护下搅拌18 小时得到纺丝液,将纺丝液熟化30小时后,通过喷丝板挤出,并通过800mm的空气段后,以15 米/分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜21。 [0211] Add 430g modified polyether sulfone blend dimethylsulfoxide, 20g polyvinyl pyrrolidone k90, Ig-hydroxy-modified nano-titania and the mixture was 120g polyethylene glycol (2000), by dry - wet method after stirring a nitrogen atmosphere 100 ° C for 18 hours to give a spinning solution, the spinning solution was aged for 30 hours extruded through a spinneret, and air through the section of 800mm at a speed of 15 m / min through a coagulation bath of pure water , and dried to give preparation 21 polyethersulfone hollow fiber membrane.

[0212] 比较例未改性的聚醚砜中空纤维膜的制备 Preparation of [0212] Comparative Example unmodified polyether sulfone hollow fiber membranes

[0213] 在二甲基甲酰胺中加入220g聚醚砜及120g聚乙二醇(400),采用干-湿法在72°C氮气保护下搅拌8小时得到纺丝液,将纺丝液熟化24小时后,通过喷丝板挤出,并通过400mm的空气段后,以12米/分钟的速度通过纯水凝固浴、干燥制备得到未改性的聚醚砜中空纤维膜。 [0213] Add 220g 120g polyether sulfone and polyethylene glycol (400) in dimethyl formamide, dry - wet stirred at 72 ° C under nitrogen for 8 hours to give a spinning solution, the spinning solution was aged after 24 hours, extruding through a spinneret, and air passing through the rear section of 400mm at a speed of 12 m / min through a coagulation bath of pure water, polyether sulfone hollow fiber membrane was prepared and dried to give unmodified.

[0214] 测试例1膜表面粗糙度及光滑度测试 [0214] Test Example 1 film surface roughness and smoothness testing

[0215] 测试一:采用3D表面显微镜(东芝三维图像计测台视显微镜,TM3000),分别对本发明实施例1制备的改性聚醚砜中空纤维膜及比较例中制备的未改性的聚醚砜中空纤维膜进行表面形态测试,测试得到的表面形态图如图7及图8所示,测试得到的参数如表1所示。 [0215] Test 1: The surface of a microscope 3D (three-dimensional image measuring table Toshiba stereomicroscope, TM3000), modified polyether sulfone hollow fiber membrane prepared in Example 1 unmodified Comparative Example were prepared in the embodiment of the present invention is poly ether sulfone hollow fiber membrane morphology test, the test to obtain the surface morphology as shown in FIGS. 7 and 8, the test result parameters as shown in table 1. [0216] 测试二:分别米用扫描电镜(日本JEOL的JSM-6510扫描电子显微镜)对本发明实施例1制备的改性聚醚砜中空纤维膜及比较例中制备的未改性的聚醚砜中空纤维膜进行光滑度测试,扫描得到的图片如图9及图10所示。 [0216] Test II: each m by scanning electron microscope (JSM-6510 of Japan JEOL scanning electron microscope) Unmodified Modified Comparative Example prepared polyether sulfone hollow fiber membrane prepared in Example 1 of the embodiment of the present invention polyethersulfones hollow fiber membrane smoothness test, the scanned image 10 shown in FIG. 9 and FIG.

[0217]表1本发明的改性聚醚砜中空纤维膜与未改性聚醚砜中空纤维膜的粗糙度比较 [0217] Roughness Comparison modified polyether sulfone hollow fiber membrane of the present invention in Table 1 and the unmodified polyether sulfone hollow fiber membranes

Figure CN103877634BD00161

[0219]从表1看出,在表面积相同或相似的情况下,本发明的改性聚醚砜中空纤维膜的粗糙度Ra、Rq及Rmax均小于未改性的聚醚砜中空纤维膜的相应数值。 [0219] As seen from Table 1, in the same or a similar surface area, the roughness Ra of the modified polyether sulfone hollow fiber membrane of the present invention, Rq of less than Rmax, and a polyether sulfone hollow fiber membranes of unmodified the corresponding value. 这也可从图7及图8看出, 相对于未改性的聚醚砜中空纤维膜,本发明制备的改性聚醚砜中空纤维膜的表面粗糙度明显降低,从而大幅度降低了其对血液的影响,有效地降低了补体激活及血液阻力。 This can also be seen from Figure 7 and 8, unmodified polyether sulfone hollow fiber membranes with respect to the surface roughness modified polyether sulfone hollow fiber membrane prepared in the present invention significantly reduced, thereby drastically reducing their Effects of blood, effectively reduces the complement activation and blood resistance.

[0220]图9及图10分别为本发明的改性聚醚砜中空纤维膜与比较例中未改性的聚醚砜中空纤维膜的光滑度电镜图,从图9及图10也可看出本发明的改性聚醚砜中空纤维膜的表面光滑度明显高于未改性的聚醚砜中空纤维膜的表面光滑度。 [0220] FIGS. 9 and 10 modified with a polyether sulfone hollow fiber membrane smoothness electron micrograph of Comparative Example unmodified polyether sulfone hollow fiber membrane of the present invention, respectively, in FIG. 9 and FIG. 10 can also see the surface smoothness of the modified polyether sulfone hollow fiber membrane of the present invention is significantly higher than the surface smoothness of the unmodified polyether sulfone hollow fiber membranes.

[0221 ]测试例2血液透析后各成分比较 [0221] Comparative Test Example 2 The ingredients after hemodialysis

[0222] 分别采用本发明实施例1制备的改性聚醚砜中空纤维膜及比较例中制备的未改性的聚醚砜中空纤维膜在相同条件下制备血液透析器(膜面积为1.4m 2,膜内径为220μπι),然后分别采用两种血液透析器对血液进行透析,透析15分钟后,根据国标YY0053-2008、GB/ T16886.1和GB/T16886.4中规定的检测方法,测试血液中各成分含量,测试结果如表2所示。 [0222] The present invention were used (membrane area unmodified modified polyether sulfone hollow fiber membrane prepared in Comparative Example 1 prepared in Example polyethersulfone hollow fiber membrane hemodialyzer was prepared under the same conditions as the embodiment 1.4m 2, the inner diameter of the membrane 220μπι), respectively, and then using two hemodialyzer blood dialysis, dialysis after 15 minutes, according to the method for detecting a predetermined GB YY0053-2008, GB / T16886.1 and GB / T16886.4, the test content of each component in blood, the test results shown in table 2.

[0223] 表2采用本发明的改性纤维膜制备的血液透析器与采用比较例中未改性纤维膜制备的血液透析器透析15分钟后血液中各成分含量比较 [0223] Table 2 hemodialyzer made with the present invention using a modified fiber membrane after the content of each component hemodialyzer prepared in Comparative Example unmodified fiber membrane dialyzer blood 15 minutes in Comparative

Figure CN103877634BD00171

[0225] 从表2看出,采用本发明的改性聚醚砜中空纤维膜制备的血液透析器血液透析15 分钟后血液中白细胞、血小板计数、补体C3a、C5a的水平均低于采用未改性的聚醚砜中空纤维膜制成的血液透析器透析后血液中相应成分的含量。 [0225] As seen from Table 2, using a hemodialyzer blood preparation according to the invention modified polyether sulfone hollow fiber membrane dialyzer after 15 minutes white blood cells, platelet count, complement C3a, C5a was lower than using the unmodified the content of the respective component blood made of polyethersulfone hollow fiber membrane hemodialyzer dialysis.

[0226] 测试例3膜结构电镜图 [0226] Test Example 3 electron micrograph of the film structure

[0227] 采用扫描电镜(日本JEOL的JSM-6 510扫描电子显微镜)对本发明实施例1制备的改性聚醚砜中空纤维膜进行结构扫描(测试条件:HFW90.13μπι,WDlO. 9mm,HV20 . Okv,高真空, 放大1500倍),扫描得到的图片如图11所示。 [0227] The scanning electron microscope (Japan JEOL JSM-6 510 is a scanning electron microscope) modified polyether sulfone hollow fiber membrane prepared in Example 1 of the present invention for structural scans (test conditions:. HFW90.13μπι, WDlO 9mm, HV20. OKV, high vacuum, enlarged 1500 times), the scanned image as shown in FIG.

[0228] 图11示出了本发明的改性聚醚砜中空纤维膜的结构图,如图11所示,本发明的改性聚醚砜中空纤维膜表面光滑,结构均匀,具有l_5nm的微孔。 [0228] FIG. 11 shows a structural view modified polyether sulfone hollow fiber membrane of the present invention, shown in Figure 11, modified polyether sulfone hollow fiber membrane of the present invention, the surface of a smooth, uniform structure, with micro l_5nm hole.

[0229] 测试例4去除率测试 [0229] Test Example 4 Test removal

[0230] 分别采用本发明实施例1制备的改性聚醚砜中空纤维膜及比较例中制备的未改性的聚醚砜中空纤维膜在相同条件下制备血液透析器(膜面积为1.4m 2,膜内径为220μπι),然后根据国标¥¥〇〇53-2008、68/1'16886.1和68/116886.4中规定的检测方法,分别对两种血液透析器的去除率进行测试(测试条件:QB=200ml/min,QD=500ml/min,TMP=1000 mmHg),测试结果如表3所示。 [0230] The present invention were used (membrane area unmodified modified polyether sulfone hollow fiber membrane prepared in Comparative Example 1 prepared in Example polyethersulfone hollow fiber membrane hemodialyzer was prepared under the same conditions as the embodiment 1.4m 2, the inner diameter of the membrane 220μπι), then a predetermined detection method in accordance with GB ¥¥ 〇〇53-2008,68 / 1'16886.1 and 68 / 116886.4, respectively, for both hemodialysis removal test (test conditions: QB = 200ml / min, QD = 500ml / min, TMP = 1000 mmHg), the test results shown in table 3.

[0231] 表3本发明的改性聚醚砜中空纤维膜与未改性的聚醚砜中空纤维膜的去除率比较 [0231] Table removal modified polyether sulfone hollow fiber membranes with unmodified polyether sulfone hollow fiber membrane of the invention comparison 3

[0232] [0232]

Figure CN103877634BD00181

[0233] 从表3看出,采用本发明的改性聚醚砜中空纤维膜制备的血液透析器在QB=200ml/ min,QD=500ml/min,TMP=1000 mmHg条件下,对尿素、肌酐、磷酸盐及维生素B的去除率分别达至丨J210ml/min、190ml/min、170ml/min 及180ml/min,超滤系数达到200ml/kpa.h,均高于米用未改性的聚醚砜中空纤维膜制备的血液透析器的相应数值,表明采用本发明的改性聚醚砜中空纤维膜制备的血液透析器具有较优的去除率及超滤系数。 [0233] As seen from Table 3, the present invention is a modified polyethersulfone hemodialyzer hollow fiber membrane prepared in QB = 200ml / min, QD = 500ml / min, TMP = 1000 mmHg under conditions, urea, creatinine , phosphates and removal, respectively, of vitamin B to Shu J210ml / min, 190ml / min, 170ml / min and 180ml / min, the ultrafiltration coefficient of 200ml / kpa.h, rice were higher than with non-modified polyether the corresponding value hemodialyzer prepared sulfone hollow fiber membrane according to the present invention show a modified polyethersulfone hemodialyzer having a hollow fiber membrane prepared superior removal and ultrafiltration coefficient.

[0234] 测试例5亲水性测试 [0234] Test Example 5 Hydrophilic test

[0235] 采用光学接触角仪(瑞典Attension theta Iite),分别对本发明实施例1制备的改性聚醚砜中空纤维膜及比较例中制备的未改性的聚醚砜中空纤维膜进行亲水性测试。 Modified polyether sulfone hollow fiber membrane [0235] The optical contact angle meter (Sweden Attension theta Iite), respectively, prepared in Example 1 of the present invention unmodified prepared in Comparative Example polyethersulfone hollow fiber membrane hydrophilic test.

[0236] 图12和图13分别示出了本发明的改性聚醚砜中空纤维膜与未改性的聚醚砜中空纤维膜与水接触的视图。 [0236] Figures 12 and 13 show a view of a modified polyether sulfone hollow fiber membrane of the present invention and the unmodified polyether sulfone hollow fiber membrane in contact with water. 如图12和图13所示,本发明的改性聚醚砜中空纤维膜与水接触后的左、右接触角分别为53.1°、52.6°,采用未改性的聚醚砜中空纤维膜与水接触后的左、右接触角分别为67.0°、65.9°。 12 and 13, the modified left polyethersulfone hollow fiber membrane of the present invention in contact with water, the right contact angles of 53.1 °, 52.6 °, using a polyether sulfone hollow fiber membrane and unmodified left after the water contact, the right contact angles of 67.0 °, 65.9 °. 由此说明,相对于未改性的聚醚砜中空纤维膜,本发明的改性聚醚砜中空纤维膜具有较好的亲水性。 Thus described, with respect to the polyethersulfone hollow fiber membrane unmodified, modified polyether sulfone hollow fiber membrane of the present invention has good hydrophilicity.

[0237] 以上对本发明具体实施方式的描述并不限制本发明,本领域技术人员可以根据本发明做出各种改变或变形,只要不脱离本发明的精神,均应属于本发明所附权利要求的范围。 [0237] The foregoing description of specific embodiments of the present invention is not limited to the present invention, those skilled in the art may make various changes or modification in accordance with the present invention, without departing from the spirit of the invention, the appended claims should belong to the present invention range.

Claims (23)

  1. 1. 一种血液透析器,其包括:外壳、由中空纤维丝管组成的纤维束、端盖、封装胶、环形导流分布环、透析液入口、透析液出口、血液入口及血液出口;其中,所述环形导流分布环位于正对所述透析液入口和/或透析液出口的位置,所述环形导流分布环的一端与所述外壳的末端连接,所述环形导流分布环的另一端朝向与其正对的透析液入口或透析液出口方向倾斜; 其中,所述中空纤维丝管采用聚醚砜中空纤维膜制备,所述聚醚砜中空纤维膜的纺丝原液包含: 250-650重量份的改性聚醚砜共混物; 20-400重量份的亲水性分子化合物; 1-90重量份的纳米改性羟基二氧化钛混合物;及20-120重量份的醇类溶剂, 其中,所述改性聚醚砜共混物包含聚醚砜、聚乙烯吡咯烷酮、氢氧化钠及过硫酸钠,所述纳米改性羟基二氧化钛混合物包含纳米水溶性二氧化钛及醇。 A hemodialyzer comprising: a housing, a hollow fiber bundle of fiber filaments tubes, end caps, plastic packaging, distribution ring annular deflector, the dialysate inlet dialysate outlet, the blood inlet and blood outlet; wherein the annular flow distribution ring is located directly on the dialysis fluid inlet and / or outlet of the dialysate position, one end of the annular flow distribution ring connected to the end of the housing, the annular flow distribution ring the other end toward its positive dialysate inlet or outlet dialysate inclined direction; wherein said hollow tube filaments prepared using a polyether sulfone hollow fiber membrane, a polyethersulfone hollow fiber membrane dope comprises: 250 650 parts by weight of the modified polyether sulfone blend; 20-400 parts by weight of a hydrophilic polymer compound; 1-90 parts by weight of a mixture of titanium dioxide nano-modified hydroxy; and 20-120 parts by weight of an alcohol solvent, wherein the modified polyether sulfone blend comprising a polyether sulfone, polyvinyl pyrrolidone, sodium hydroxide, and sodium persulfate, the nano-hydroxy-modified nano-titania mixture comprising titanium dioxide and a water-soluble alcohol.
  2. 2. 根据权利要求1所述的血液透析器,其特征在于,所述环形导流分布环相对于所述外壳的纵向倾斜的角度为2-6° ; 所述环形导流分布环的直径为5 3-5 5mm; 所述环形导流分布环的宽度小于与其正对的透析液入口或透析液出口沿外壳纵向的宽度; 所述环形导流分布环的宽度为7-9_。 The hemodialysis device according to claim 1, wherein the distribution ring annular deflector oblique angle relative to the longitudinal housing of the 2-6 °; said annular guide ring diameter distribution 5 3-5 5mm; the width of the annular guide ring is smaller than the distribution of its positive or dialysate inlet of the dialysate outlet of the width of the longitudinal direction of the housing; the width of the annular guide ring is 7-9_ distribution.
  3. 3. 根据权利要求1或2所述的血液透析器,其特征在于,所述环形导流分布环相对于所述外壳的纵向倾斜的角度为4° ; 所述环形导流分布环的直径为54mm; 所述环形导流分布环的宽度为8_。 The hemodialysis device of claim 1 or claim 2, wherein the distribution ring annular deflector oblique angle relative to the longitudinal of the housing 4 °; said annular guide ring diameter distribution 54mm; width of the annular flow distribution ring is 8_.
  4. 4. 根据权利要求1或2所述的血液透析器,其特征在于,所述聚醚砜中空纤维膜的纺丝原液包含: 250-450重量份的改性聚醚砜共混物; 50-150重量份的亲水性分子化合物; 10-90重量份的纳米改性羟基二氧化钛混合物;及50-100重量份的醇类溶剂。 The hemodialysis device of claim 1 or claim 2, wherein the polyether sulfone hollow fiber membrane dope comprises: 250-450 parts by weight of the modified polyether sulfone blend; 50 150 parts by weight of a hydrophilic polymer compound; 10-90 parts by weight of a mixture of titanium dioxide nano-modified hydroxy; and 50-100 parts by weight of an alcohol solvent.
  5. 5. 根据权利要求1或2所述的血液透析器,其特征在于,所述改性聚醚砜共混物中包含850-980重量份的聚醚砜、20-150重量份的聚乙烯吡咯烷酮、0.01-1重量份的氢氧化钠及0.1-1重量份的过硫酸钠; 所述改性聚醚砜共混物中的聚乙烯吡咯烷酮为聚乙烯吡咯烷酮kl5、聚乙烯吡咯烷酮k30或聚乙烯吡咯烷酮k90,所述聚醚砜为聚醚砜P-3500或聚醚砜E6020。 Hemodialyzer according to claim 1 or claim 2, wherein the modified polyether sulfone blend comprises 850-980 parts by weight of polyether sulphone, 20-150 parts by weight of polyvinyl pyrrolidone , 0.01 parts by weight of sodium hydroxide and 0.1 parts by weight of sodium persulfate; polyvinylpyrrolidone said modified polyethersulfone blend of polyvinylpyrrolidone kl5, polyvinylpyrrolidone or polyvinyl pyrrolidone k30 k90, the polyethersulfone is a polyether sulfone or polyether sulfone P-3500 E6020.
  6. 6. 根据权利要求5所述的血液透析器,其特征在于,所述改性聚醚砜共混物中包含900-980重量份的聚醚砜、20-100重量份的聚乙烯吡咯烷酮、0.05-0.1重量份的氢氧化钠及0.5-1重量份的过硫酸钠。 The hemodialyzer according to claim 5, wherein the modified polyether sulfone blend comprises 900-980 parts by weight of polyether sulphone, 20-100 parts by weight of polyvinyl pyrrolidone, 0.05 -0.1 parts by weight of sodium hydroxide and 0.5 parts by weight of sodium persulfate.
  7. 7. 根据权利要求1或2所述的血液透析器,其特征在于,所述纳米改性羟基二氧化钛混合物包含纳米水溶性二氧化钛与乙二醇。 The hemodialysis device of claim 1 or claim 2, wherein the nano-hydroxy-modified nano-titania mixture comprising titanium dioxide and a water-soluble glycol.
  8. 8. 根据权利要求7所述的血液透析器,其特征在于,所述纳米改性羟基二氧化钛混合物中包含100-800重量份的水溶性二氧化钛及600-980重量份的乙二醇。 Hemodialysis according to claim 7 claim, wherein the nano-glycol modified hydroxy titanium dioxide mixture contains 100-800 parts by weight of a water-soluble titania and 600-980 parts by weight.
  9. 9. 根据权利要求7所述的血液透析器,其特征在于,所述纳米改性羟基二氧化钛混合物中包含200-400重量份的水溶性二氧化钛及600-900重量份的乙二醇。 Hemodialysis according to claim 7 claim, wherein the nano-glycol modified hydroxy titanium dioxide mixture contains 200-400 parts by weight of a water-soluble titania and 600-900 parts by weight.
  10. 10. 根据权利要求7所述的血液透析器,其特征在于,所述水溶性二氧化钛的粒径为1-10nm〇 10. A particle according to claim hemodialysis claim 7, wherein said water-soluble titanium dioxide is 1-10nm〇
  11. 11. 根据权利要求1或2所述的血液透析器,其特征在于,所述亲水性分子化合物为聚乙烯吡咯烷酮或聚乙二醇。 Hemodialyzer according to claim 1 or claim 2, wherein the hydrophilic polymer compound is polyvinylpyrrolidone or polyethylene glycol.
  12. 12. 根据权利要求1或2所述的血液透析器,其特征在于,所述亲水性分子化合物为聚乙烯吡咯烷酮kl5、聚乙烯吡咯烷酮k30、聚乙烯吡咯烷酮k90或分子量为2000的聚乙二醇。 Hemodialyzer according to claim 1 or claim 2, wherein the hydrophilic polymer compound is polyvinylpyrrolidone kl5, polyvinylpyrrolidone K30, or polyvinylpyrrolidone k90 polyethylene glycol having a molecular weight of 2000 .
  13. 13. 根据权利要求1或2所述的血液透析器,其特征在于,所述醇类溶剂为聚乙二醇或丙二醇。 Hemodialyzer according to claim 1 or claim 2, wherein the alcohol solvent is a polyethylene glycol or propylene glycol.
  14. 14. 根据权利要求13所述的血液透析器,其特征在于,所述醇类溶剂为分子量为2000的聚乙二醇。 14. The hemodialysis device according to claim 13, wherein the alcohol solvent is a polyethylene glycol having a molecular weight of 2000.
  15. 15. 根据权利要求1或2所述的血液透析器,其特征在于,所述改性聚醚砜共混物的制备方法包括: 将聚醚砜、聚乙烯吡咯烷酮、氢氧化钠及过硫酸钠混合,并在95-120°C氮气保护下混合30-120分钟,发生交联反应,制备得到改性聚醚砜共混物。 15. The hemodialyzer claim 1 or claim 2, wherein the method of preparing a modified polyethersulfone blends include: polyether sulfone, polyvinyl pyrrolidone, sodium hydroxide and sodium persulfate mixing, and mixed at 95-120 ° C for 30-120 minutes nitrogen, crosslinking reaction, modified polyethersulfone blends prepared.
  16. 16. 根据权利要求15所述的血液透析器,其特征在于,所述改性聚醚砜共混物的制备方法包括: 将聚醚砜、聚乙烯吡咯烷酮、氢氧化钠及过硫酸钠混合,并在100-110°c氮气保护下混合60-90分钟,发生交联反应,制备得到改性聚醚砜共混物。 16. A hemodialyzer according to claim 15, wherein the method of preparing a modified polyethersulfone blends include: polyether sulfone, polyvinyl pyrrolidone, sodium hydroxide, and sodium persulfate mixed, and mixed at 100-110 ° c for 60-90 min nitrogen, crosslinking reaction, modified polyethersulfone blends prepared.
  17. 17. 根据权利要求1或2所述的血液透析器,其特征在于,所述改性羟基二氧化钛混合物的制备方法包括: 将纳米水溶性二氧化钛与醇混合,在20-60°C氮气保护下搅拌10-60分钟后得到改性羟基^氧化钦混合物。 17. The hemodialyzer claim 1 or claim 2, wherein the preparation of the mixture of titanium dioxide modified hydroxyl comprises: a nano-titanium dioxide mixed with a water-soluble alcohol, stirred at 20-60 ° C under a nitrogen blanket after 10 to 60 minutes to obtain a modified hydroxy ^ Chin oxide mixture.
  18. 18. 根据权利要求17所述的血液透析器,其特征在于,所述改性羟基二氧化钛混合物的制备方法包括: 将纳米水溶性二氧化钛与醇混合,在40-50°C氮气保护下搅拌20-40分钟后得到改性羟基^氧化钦混合物。 18. A hemodialyzer according to claim 17, characterized in that the preparation of the mixture of titanium dioxide modified hydroxyl comprises: a nano-titanium dioxide mixed with a water-soluble alcohol, stirred at 40-50 ° C under nitrogen for 20 after 40 minutes to obtain a modified hydroxy ^ Chin oxide mixture.
  19. 19. 根据权利要求1所述的血液透析器,其特征在于,所述聚醚砜中空纤维膜的制备方法包括以下步骤: 在有机溶剂中加入改性聚醚砜共混物、亲水性分子化合物、纳米改性羟基二氧化钛混合物及醇类溶剂,采用干-湿法在氮气保护下搅拌制备得到纺丝液,将纺丝液进行熟化,并通过喷丝板挤出,通过空气段,然后通过纯水凝固浴制备得到聚醚砜中空纤维膜。 19. The hemodialyzer according to claim 1, wherein the method of preparing a polyether sulfone hollow fiber membranes comprising the steps of: adding a blend of polyethersulfone modified, hydrophilic molecules in an organic solvent compound, a mixture of nano-modified hydroxy titanium dioxide and an alcohol solvent, dry - wet under nitrogen with stirring to give a spinning solution was prepared, the spinning solution is aged, and extruded through a spinneret, through an air segment, then preparing a coagulation bath of pure water to obtain a polyether sulfone hollow fiber membrane.
  20. 20. 根据权利要求19所述的血液透析器,其特征在于,所述聚醚砜中空纤维膜的制备方法包括以下步骤: 在有机溶剂中加入改性聚醚砜共混物、亲水性分子化合物、纳米改性羟基二氧化钛混合物及醇类溶剂,采用干-湿法在55-100°C氮气保护下搅拌4-24小时得到纺丝液,将纺丝液熟化12-72小时,并通过喷丝板挤出,并通过l-800mm的空气段,然后以6-15米/分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜。 20. The hemodialysis device according to claim 19, wherein the method of preparing a polyether sulfone hollow fiber membranes comprising the steps of: adding a blend of polyethersulfone modified, hydrophilic molecules in an organic solvent compound, a mixture of nano-modified hydroxy titanium dioxide and an alcohol solvent, dry - wet stirred at 55-100 ° C under nitrogen for 4-24 hours to obtain a spinning solution, spinning was aged for 12-72 hours, and by spraying extruded wire board, and l-800mm section through the air, and then the coagulation bath at a speed of 6-15 m / min with pure water, dried polyethersulfone hollow fiber membrane prepared.
  21. 21. 根据权利要求20所述的血液透析器,其特征在于,所述聚醚砜中空纤维膜的制备方法包括以下步骤: 在有机溶剂中加入改性聚醚砜共混物、亲水性分子化合物、纳米改性羟基二氧化钛混合物及醇类溶剂,采用干-湿法在60_85°C氮气保护下搅拌12-24小时得到纺丝液,将纺丝液熟化24-36小时,并通过喷丝板挤出,并通过300-500mm的空气段,然后以6-9米/分钟的速度通过纯水凝固浴、干燥制备得到聚醚砜中空纤维膜。 Claim 21. The hemodialysis claim 20, characterized in that the method of preparing a polyether sulfone hollow fiber membranes comprising the steps of: adding a blend of polyethersulfone modified, hydrophilic molecules in an organic solvent compound, a mixture of nano-modified hydroxy titanium dioxide and an alcohol solvent, dry - wet stirred at 60_85 ° C nitrogen for 12-24 hours to give a spinning solution, spinning was aged for 24-36 hours, and through a spinneret extruded, and air passing through the section of 300-500mm, and the coagulation bath at a speed of 6-9 m / min with pure water, dried polyethersulfone hollow fiber membrane prepared.
  22. 22. 根据权利要求19-21中任一项所述的血液透析器,其特征在于,所述有机溶剂为二甲基乙酰胺、二甲基甲酰胺或二甲基亚砜。 19-21 22. The hemodialyzer according to any one of claims, wherein the organic solvent is dimethylacetamide, dimethylformamide or dimethyl sulfoxide.
  23. 23. -种血液透析装置,其包含根据权利要求1-22中任一项所述的血液透析器。 23. - Species hemodialysis apparatus, according to claims 1-22 comprising a hemodialyzer according to any one.
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