KR20010002988A - A polysulfone based hollow fiber membrane for hemodialysis, and a process for preparing the same - Google Patents
A polysulfone based hollow fiber membrane for hemodialysis, and a process for preparing the same Download PDFInfo
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- KR20010002988A KR20010002988A KR1019990023088A KR19990023088A KR20010002988A KR 20010002988 A KR20010002988 A KR 20010002988A KR 1019990023088 A KR1019990023088 A KR 1019990023088A KR 19990023088 A KR19990023088 A KR 19990023088A KR 20010002988 A KR20010002988 A KR 20010002988A
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- hollow fiber
- fiber membrane
- polysulfone
- polymer
- hemodialysis
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- 239000012528 membrane Substances 0.000 title claims abstract description 72
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 61
- 229920002492 poly(sulfone) Polymers 0.000 title claims abstract description 53
- 238000001631 haemodialysis Methods 0.000 title claims abstract description 20
- 230000000322 hemodialysis Effects 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 55
- 230000035699 permeability Effects 0.000 claims abstract description 27
- 238000009987 spinning Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- -1 glycols compounds Chemical class 0.000 claims abstract description 15
- 229920000151 polyglycol Polymers 0.000 claims abstract description 11
- 239000010695 polyglycol Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 14
- 230000001112 coagulating effect Effects 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 238000005345 coagulation Methods 0.000 claims description 10
- 230000015271 coagulation Effects 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000007711 solidification Methods 0.000 abstract description 5
- 230000008023 solidification Effects 0.000 abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 abstract description 2
- 230000009977 dual effect Effects 0.000 abstract 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 238000000926 separation method Methods 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 229920003169 water-soluble polymer Polymers 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000000701 coagulant Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 229920001477 hydrophilic polymer Polymers 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000008280 blood Substances 0.000 description 3
- 210000004369 blood Anatomy 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000007717 exclusion Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 102000036675 Myoglobin Human genes 0.000 description 2
- 108010062374 Myoglobin Proteins 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- FDJOLVPMNUYSCM-UVKKECPRSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2,7, Chemical compound [Co+3].N#[C-].C1([C@H](CC(N)=O)[C@@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)[N-]\C2=C(C)/C([C@H](C\2(C)C)CCC(N)=O)=N/C/2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O FDJOLVPMNUYSCM-UVKKECPRSA-L 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- MZNSQRLUUXWLSB-UHFFFAOYSA-N 2-ethenyl-1h-pyrrole Chemical compound C=CC1=CC=CN1 MZNSQRLUUXWLSB-UHFFFAOYSA-N 0.000 description 1
- 229920001007 Nylon 4 Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 229920003174 cellulose-based polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
- A61M1/14—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis
- A61M1/16—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis with membranes
- A61M1/1621—Constructional aspects thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
- B01D69/087—Details relating to the spinning process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/218—Additive materials
- B01D2323/2182—Organic additives
- B01D2323/21839—Polymeric additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/218—Additive materials
- B01D2323/2182—Organic additives
- B01D2323/21839—Polymeric additives
- B01D2323/2187—Polyvinylpyrolidone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Heart & Thoracic Surgery (AREA)
- Urology & Nephrology (AREA)
- Engineering & Computer Science (AREA)
- Anesthesiology (AREA)
- Emergency Medicine (AREA)
- Dispersion Chemistry (AREA)
- Vascular Medicine (AREA)
- Manufacturing & Machinery (AREA)
- Biomedical Technology (AREA)
- Hematology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
본 발명은 혈액투석용 폴리설폰계 중공사 막 및 그의 제조방법에 관한 것이다. 선택투과성을 갖는 분리막 재질에 관해서는 많은 연구가 이루어져, 셀룰로스계 폴리머, 폴리아미드계 폴리머, 폴리아크릴계 폴리머, 폴리비닐계 폴리머 등이 개발되어 사용되고 있다. 그러나 이러한 재질들은 내생물분해성, 내화학성, 내열성 등에 결점이 있다. 이러한 단점들을 보완하기 위해 폴리설폰계 폴리머가 분리막의 재질로 사용되고 있다.The present invention relates to a polysulfone hollow fiber membrane for hemodialysis and a method of manufacturing the same. Much research has been made on separator materials having selective permeability, and cellulose-based polymers, polyamide-based polymers, polyacrylic-based polymers, and polyvinyl-based polymers have been developed and used. However, these materials have drawbacks in biodegradability, chemical resistance and heat resistance. To overcome these shortcomings, polysulfone polymer is used as a material of the separator.
폴리설폰계 폴리머는 내생물분해성, 내화학성, 내열성, 난연성 및 기계적 성질 등이 우수하여 혈액투석용, 정밀여과용, 한외여과용, 역삼투용 및 기체분리용 복합막의 지지체로서 사용되고 있다.Polysulfone polymers have excellent biodegradability, chemical resistance, heat resistance, flame retardancy, and mechanical properties, and are used as a support for hemodialysis, microfiltration, ultrafiltration, reverse osmosis, and gas separation composite membranes.
일반적으로 폴리설폰계 중공사 막은 폴리설폰계 폴리머, 유기용매 및 첨가제로 구성된 방사 도프(dope)와 내부응고액을 2중 관형노즐로 공기중으로 방사한 후 외부응고액으로 고화시켜 제조한다.Generally, polysulfone hollow fiber membranes are prepared by spinning a spinning dope and an internal coagulating solution composed of a polysulfone polymer, an organic solvent and an additive into the air with a double tubular nozzle and then solidifying the external coagulating solution.
방사 도프 제조시 용매로는 m-크레졸, 클로로벤젠, N-메틸-2-피롤리돈, 디메틸설폭사이드, 디메틸아세트아마이드, 디메틸포름아마이드 및/또는 이들의 혼합물 등이 사용되며, 첨가제로는 폴리에틸렌글리콜, 폴리비닐알콜, 폴리비닐피롤리돈 및/또는 이들의 혼합물 등의 수용성 고분자가 많이 사용되고 있다. 상기 첨가제들은 방사 도프의 점도 상승과 막의 투수성 증가를 위해 사용된다.In the preparation of the spinning dope, m-cresol, chlorobenzene, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylacetamide, dimethylformamide and / or mixtures thereof are used. Water-soluble polymers such as glycol, polyvinyl alcohol, polyvinylpyrrolidone and / or mixtures thereof are frequently used. The additives are used to increase the viscosity of the spinning dope and to increase the permeability of the membrane.
내부 및 외부응고액으로는 주로 물이 많이 사용되고 있으나 상기 첨가제들이 함유되어 있는 수용액을 사용하기도 한다.As the internal and external coagulating solution, water is mainly used, but an aqueous solution containing the additives may be used.
일반적으로 분리막(membrane)에 있어서 가장 중요한 2가지 성능은 분리능 및 투과능이나 이 두가지 성능은 서로 양립할 수 없어서 분리능이 커지면 투과능은 상대적으로 작아질 수 밖에 없고 투과능을 키우려면 분리능이 낮아질 수 밖에 없다. 따라서 분리막 개발의 주요 과제는 일정한 분리능을 가지면서 더 높은 투과능을 갖는 분리막을 제조하는 것이다.In general, the two most important performances of the membrane are separation and permeability, but the two performances are not compatible with each other. As the resolution increases, the permeability is inevitably smaller and the resolution can be lowered to increase permeability. There is nothing else. Therefore, the main task of the membrane development is to prepare a membrane having a higher permeability while having a constant resolution.
특히 혈액투석용 분리막인 경우에는 인간의 건강 등을 고려할 때 다양한 물질로 구성되어 있는 혈액중에서 분리하고자 하는 특정 분리물질만을 선택적으로 제거할 수 있는 분리능과 투석시간 단축을 위한 투과능이 동시에 요구되고 있다.In particular, in the case of a hemodialysis membrane, in consideration of human health, a separation ability capable of selectively removing only a specific separation substance to be separated from blood composed of various substances and a permeability for shortening the dialysis time are simultaneously required.
그러나 폴리설폰계 폴리머는 소수성(hydrophobic) 이기 때문에 이들 폴리머로 제조한 분리막은 친수성 폴리머로 제조한 분리막에 비해 투과능이 낮은 문제가 있다.However, since polysulfone polymers are hydrophobic, membranes made of these polymers have a problem of lower permeability than membranes made of hydrophilic polymers.
이와 같은 문제를 해결하기 위한 종래기술로 일본공고특허 90-18,695호, 일본공개특허 소 61-93801호, 동 61-402호 및 동 62-38,205호 등에서는 방사 도프 제조시 수용성 폴리머인 비닐피롤리돈계 폴리머를 첨가하는 방법을 제안하고 있다.In order to solve such a problem, Japanese Patent Publications No. 90-18,695, Japanese Patent Laid-Open Nos. 61-93801, 61-402, and 62-38,205 disclose vinylpyrrole, which is a water-soluble polymer in the production of spinning dope. A method of adding a pig type polymer is proposed.
그러나 방사 도프에 첨가된 수용성 폴리머는 강한 친수성으로 제막시 수세공정에서 대부분 중공사 막 밖으로 빠져나가게 되고 일부만이 중공사 막 내에 잔존하게 된다. 그 결과 중공사 막의 투과능(수투과도)이 근본적으로 개선되지 않는 문제가 있다.However, the water-soluble polymer added to the spinning dope has a strong hydrophilicity, and most of the water soluble polymer is released out of the hollow fiber membrane during the washing process and only a part thereof remains in the hollow fiber membrane. As a result, there exists a problem that the permeability (water transmittance) of a hollow fiber membrane does not fundamentally improve.
또 다른 종래기술로는 일본공개특허 소 58-104940호 에서는 가교제를 사용하여 친수성 고분자를 폴리설폰 중공사 막 표면에 고정하는 방법을 제시하고 있지만, 공정 및 조작이 복잡하다.As another conventional technique, Japanese Laid-Open Patent Publication No. 58-104940 discloses a method of fixing a hydrophilic polymer to a polysulfone hollow fiber membrane using a crosslinking agent, but the process and operation are complicated.
일본공개특허 소 63-97205호 및 동 63-97634호에서는 열처리나 방사선처리에의해 친수성 고분자를 폴리설폰 중공사 막 표면에 고정하는 방법을 제시하고 있지만, 공정이 복잡하고 고가의 설비가 필요한 문제가 있다.Japanese Patent Laid-Open Nos. 63-97205 and 63-97634 disclose a method of fixing a hydrophilic polymer to the surface of a polysulfone hollow fiber membrane by heat treatment or radiation treatment, but the process is complicated and requires expensive equipment. have.
미국특허 5,340,480호 에서는 폴리설폰 수지, 폴리글리콜, 폴리비닐피롤리돈 및 유기용매로 구성된 방사 도프와 폴리비닐피롤리돈이 0.1~4% 첨가된 수용액인 내부응고제를 사용하여 내표면 및 외표면에 스킨층을 갖는 중공사 막을 제조하는 방법을 제시하고 있지만, 혈액투석용 분리막에서 요구하는 충분한 투과능을 얻을 수 없다.U.S. Patent No. 5,340,480 discloses internal and external surfaces using a spinning dope composed of polysulfone resin, polyglycol, polyvinylpyrrolidone and an organic solvent and an internal coagulant which is an aqueous solution containing 0.1 to 4% of polyvinylpyrrolidone. Although a method for producing a hollow fiber membrane having a skin layer has been proposed, sufficient permeability required by a hemodialysis membrane cannot be obtained.
본 발명은 중공사 막 내에 잔존하는 수용성 폴리머의 함량을 용이하게 조절하므로서 폭넓은 수투과도를 갖는 혈액투석용 폴리설폰계 중공사 막 및 그의 제조방법을 제공하고자 한다.The present invention is to provide a polysulfone-based hollow fiber membrane for hemodialysis having a wide water permeability and easily to adjust the content of the water-soluble polymer remaining in the hollow fiber membrane and a method for producing the same.
본 발명은 폭넓은 수투과도를 갖는 혈액투석용 폴리설폰계 중공사 막 및 그의 제조방법에 관한 것이다.The present invention relates to a polysulfone hollow fiber membrane for hemodialysis having a wide water permeability, and a method for producing the same.
더욱 구체적으로 본 발명은 폴리설폰계 폴리머, 유기용매, 비닐피롤리돈계 폴리머 및 폴리글리콜로 구성된 방사 도프(dope)와 내부응고액을 2중 관형노즐로 공기중으로 방사한 후 외부응고액으로 고화시켜 폴리설폰 중공사 막을 제조함에 있어서, 내부응고액으로 글리콜류 화합물 또는 글리콜류 화합물을 함유하는 용액을 사용하는 것을 특징으로 하는 혈액투석용 폴리설폰계 중공사 막의 제조방법에 관한 것이다.More specifically, the present invention is to spin the internal dope and the spinning dope consisting of a polysulfone polymer, an organic solvent, a vinylpyrrolidone polymer and polyglycol in a double tube nozzle to solidify the external coagulation In preparing a polysulfone hollow fiber membrane, the present invention relates to a method for producing a polysulfone-based hollow fiber membrane for hemodialysis, characterized in that a solution containing a glycol compound or a glycol compound is used as an internal coagulation solution.
또한 본 발명은 내표면과 외표면으로 구성된 비대칭 단일막 구조이고, 주성분인 폴리설폰계 폴리머 내에 비닐피롤리돈계 폴리머 1~10중량%와 폴리글리콜 1중량% 이하가 함유되어 있음을 특징으로 하는 혈액투석용 폴리설폰계 중공사 막에 관한 것이다.In another aspect, the present invention is an asymmetric single-membrane structure consisting of the inner surface and the outer surface, the blood is characterized in that the polysulfone-based polymer as the main component contains 1 to 10% by weight of vinylpyrrolidone-based polymer and less than 1% by weight of polyglycol The present invention relates to a polysulfone hollow fiber membrane for dialysis.
본 발명은 중공사 막 내에 수용성 폴리머인 비닐피롤리돈계 폴리머의 잔존량을 임의로 조절하므로서 폭넓은 수투과도로 중공사 막을 제조하는 것을 특징으로 한다.The present invention is characterized in that the hollow fiber membranes are manufactured with a wide range of water permeability by arbitrarily adjusting the residual amount of the vinylpyrrolidone polymer which is a water-soluble polymer in the hollow fiber membranes.
이하, 본 발명을 상세하게 설명하기로 한다.Hereinafter, the present invention will be described in detail.
먼저, 폴리설폰계 폴리머를 유기용매에 용해시킨 다음 여기에 수용성 폴리머인 비닐피롤리돈계 폴리머와 폴리글리콜을 첨가하여 방사 도프를 제조한다.First, a polysulfone polymer is dissolved in an organic solvent, and then a spinning dope is prepared by adding a vinylpyrrolidone polymer and a polyglycol, which are water-soluble polymers.
비닐피롤리돈계 폴리머와 폴리글리콜은 분리막내에 공경(pore)을 형성하는 역할을 하며 친수성이 강하여 방사 후 응고 및 수세과정에서 중공사 막 밖으로 빠져나가려는 경향이 크다.Vinylpyrrolidone-based polymers and polyglycols play a role of forming pores in the separator and have a high hydrophilicity, so they tend to escape out of the hollow fiber membrane during solidification and washing after spinning.
비닐피롤리돈계 폴리머는 중공사 막 내에 많이 잔존할 수 있도록 분자량이 10,000 이상인 것을 사용하는 것이 바람직 하다. 폴리글리콜로는 폴리에틸렌글리콜 또는 폴리비닐알콜 등을 사용하고, 비닐피롤리돈계 폴리머로는 폴리비닐피롤리돈 등을 사용하는 것이 바람직 하다. 유기용매로는 m-크레졸, 클로로벤젠, N-메틸-2-피롤리돈, 디메틸설폭사이드, 디메틸아세트아마이드, 디메틸포름아마이드 및/또는 이들의 혼합물 등을 사용한다.It is preferable to use a vinyl pyrrolidone-based polymer having a molecular weight of 10,000 or more so that it can remain in the hollow fiber membrane. It is preferable to use polyethylene glycol, polyvinyl alcohol, etc. as polyglycol, and polyvinylpyrrolidone etc. as vinylpyrrolidone type polymer. As the organic solvent, m-cresol, chlorobenzene, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylacetamide, dimethylformamide and / or mixtures thereof are used.
방사 도프를 구성하는 폴리설폰계 폴리머의 함량은 10~25중량%, 비닐피롤리돈계 폴리머와 폴리글리콜의 전체함량은 10~25중량%가 되도록 한다.The content of the polysulfone polymer constituting the spinning dope is 10 to 25% by weight, and the total content of the vinylpyrrolidone polymer and the polyglycol is 10 to 25% by weight.
방사 도프가 상기 조건들을 벗어나게 조성되는 경우에는 중공사 막 제조공정성이 나빠지며 본 발명에서 희망하는 막의 구조를 얻을 수 없게 되어 중공사 막의 수투과도 범위가 좁아진다If the spinning dope is formed out of the above conditions, the hollow fiber membrane manufacturing processability is deteriorated, and the structure of the membrane desired in the present invention cannot be obtained, so that the water permeability range of the hollow fiber membrane is narrowed.
다음으로는 통상의 2중 관형노즐을 사용하여 상기 방사 도프와 내부응고액을 공기중으로 방사하고, 외부응고액에서 응고, 수세 및 권취하여 폴리설폰계 중공사를 제조한다. 이때 2중 관형노즐로는 외경 0.3~0.5mm, 내경 0.2~0.25mm, 내부노즐 지름이 0.1~0.15mm 수준의 환상 슬릿 구금 등을 사용할 수 있다 방사시 2.5g/분 수준으로 폴리머를 토출하고, 에어 갭(air gap)은 약10cm 정도가 되도록 한다.Next, the spinning dope and the internal coagulating solution are spun into the air using a conventional double tubular nozzle, and the polysulfone hollow fiber is manufactured by coagulation, washing and winding in the external coagulating solution. At this time, as a double tubular nozzle, an annular slit mold having an outer diameter of 0.3 to 0.5 mm, an inner diameter of 0.2 to 0.25 mm, and an inner nozzle diameter of 0.1 to 0.15 mm can be used. The air gap is about 10 cm.
상기 내부응고액으로는 글리콜류 화합물 또는 글리콜류 화합물이 함유된 용액을 사용한다. 내부응고액 조성시 사용하는 글리콜류 화합물로는 디에틸렌글리콜을 사용하는 것이 바람직하다. 이들은 중공사 막 내에 존재하는 비닐피롤리돈계 폴리머와 복합체(complex)를 구성하여 보다 많은 비닐피롤리돈계 폴리머가 중공사 막 내에 잔존하도록 하는 역할을 한다.As the internal coagulating solution, a solution containing a glycol compound or a glycol compound is used. It is preferable to use diethylene glycol as a glycol compound used at the time of internal coagulating liquid composition. They form a complex with the vinylpyrrolidone-based polymers present in the hollow fiber membranes so that more vinylpyrrolidone-based polymers remain in the hollow fiber membranes.
외부응고액으로는 물을 주로 사용하나 필요에 따라서 알칼리토금속 및 글리콜류 화합물을 첨가할 수도 있다.Water is mainly used as the external coagulant, but alkaline earth metals and glycol compounds may be added as necessary.
본 발명은 방사도프에 친수성 폴리머인 비닐피롤리돈계 폴리머를 첨가함과 동시에 내부응고액 중으로 글리콜류 화합물 또는 그의 용액을 사용하여 중공사 막 내부에 많은 양의 비닐피롤리돈계 폴리머를 잔존시킴과 동시에 방사 도프와 내부응고액의 함량을 조절하여 중공사 막 내에 잔존하는 비닐필롤리돈계 폴리머의 잔존량을 용이하게 조절하여 폭넓은 수투과도를 갖는 중공사 막을 제조함을 특징으로 한다.The present invention adds a hydrophilic polymer vinylpyrrolidone-based polymer to the spinning dope and at the same time a large amount of vinylpyrrolidone-based polymer remains inside the hollow fiber membrane using a glycol compound or a solution thereof in the internal coagulation solution. By controlling the content of the spinning dope and the internal coagulating solution is easy to control the remaining amount of the vinylpyrrolidone-based polymer remaining in the hollow fiber membrane to produce a hollow fiber membrane having a wide water permeability.
내부응고액 중에 글리콜류 화합물이 첨가되지 않는 경우, 비닐피롤리돈계 폴리머는 친수성이 강하여 방사 후 응고 및 수세과정에서 대부분 물에 씻겨 폴리설폰계 중공사 막 밖으로 빠져나가게 된다. 즉, 방사 및 응고과정에서 폴리설폰 폴리머가 급속하게 고화될 때 상기 폴리머 메트릭스 안에 갖혀서 미처 빠져나오지 못한 일부의 비닐피롤리돈계 폴리머 만이 폴리설폰계 중공사 막 내에 잔존하게 된다.When the glycol compound is not added to the internal coagulating solution, the vinylpyrrolidone-based polymer is hydrophilic, and is mostly washed in water during the coagulation and washing process after spinning, so that the polysulfone-based hollow fiber membrane is taken out. That is, when the polysulfone polymer rapidly solidifies during spinning and solidification, only some of the vinylpyrrolidone-based polymers contained in the polymer matrix remain in the polysulfone-based hollow fiber membrane.
특히 상기 막 표면은 외부응고액과 직접 접촉하여 급속하게 고화되므로 막의 내부보다는 표면에 상대적으로 많은 비닐피롤리돈계 폴리머가 잔존하게 된다.In particular, since the surface of the membrane solidifies rapidly by being in direct contact with the external coagulant solution, more vinylpyrrolidone-based polymer remains on the surface than the inside of the membrane.
본 발명의 경우에는 내부응고액 내에 함유되어 있는 글리콜류 화합물이 비닐피롤리돈계 폴리머의 응고액 및 물에 대한 용해도를 저하시키고 폴리설폰계 수지와의 친화력을 향상시켜서, 최종 폴리설폰계 중공사 막 내에 비닐피롤리돈계 폴리머의 잔존량을 많게할 수 있다.In the case of the present invention, the glycol compound contained in the internal coagulation solution lowers the solubility of the vinylpyrrolidone polymer in the coagulation solution and water and improves the affinity with the polysulfone resin, thereby improving the final polysulfone hollow fiber membrane. The residual amount of the vinylpyrrolidone polymer in the polymer can be increased.
상기와 같이 비닐피롤리돈계 폴리머의 물에 대한 용해도가 저하되는 이유는 비닐피롤리돈계 폴리머의 친수성기인 피롤리돈기와 글리콜류 화합물의-OH기가 수소결합하여 복합체(complex)를 구성하기 때문으로 판단된다.As described above, the solubility of the vinylpyrrolidone polymer in water is lowered because the pyrrolidone, which is a hydrophilic group of the vinylpyrrolidone polymer, and the -OH group of the glycol compound are hydrogen-bonded to form a complex. do.
이와 같이 비닐피롤리돈계 폴리머와 글리콜류 화합물의 복합체가 형성되면 비닐피롤리돈계 폴리머의 물 및 응고액에 대한 용해도가 떨어져 폴리설폰계 중공사 막 내에 많은 양의 비닐피롤리돈계 폴리머가 잔존하게 된다. 또한 상기 복합체는 막 내에 잔존하는 비닐피롤리돈계 폴리머를 균일하게 분산시키는 역할도 한다.As such, when the composite of the vinylpyrrolidone-based polymer and the glycol compound is formed, the solubility of the vinylpyrrolidone-based polymer in water and the coagulant is reduced, and a large amount of the vinylpyrrolidone-based polymer remains in the polysulfone hollow fiber membrane. . The complex also serves to uniformly disperse the vinylpyrrolidone-based polymer remaining in the film.
상기 복합체가 형성되지 않는 경우에는 폴리설폰계 수지 자체의 소수성에 의해 메트릭스내에 잔존하는 비닐피롤리돈계 폴리머 친수성 부분은 안쪽으로 집합(aggregation)되고 소수성 부분은 바깥쪽으로 집합하게 된다. 그 결과 실제 분리물질과 접촉하게 되는 중공사 막의 부분이 소수성일 가능성이 높아져 분리공정이 어렵게 된다.When the composite is not formed, the hydrophilicity of the polysulfone resin itself causes the vinyl pyrrolidone-based polymer hydrophilic portion remaining in the matrix to be aggregated inward and the hydrophobic portion aggregated outward. As a result, the portion of the hollow fiber membrane which comes into contact with the actual separation material is more likely to be hydrophobic, making the separation process difficult.
그러나 본 발명의 경우에는 비닐피롤리돈계 폴리머와 글리콜류 화합물의 복합체가 형성되기 때문에 상기와 같은 문제를 해결 할 수 있다.However, in the case of the present invention, since the complex of the vinylpyrrolidone-based polymer and the glycol compound is formed, the above problems can be solved.
본 발명의 혈액투석용 폴리설폰계 중공사 막은 내표면과 외표면으로 구성된 비대칭 단일막 구조이고, 주성분인 폴리설폰계 폴리머 내에 비닐피롤리돈계 폴리머 1~10중량%와 폴리글리콜 1중량% 이하가 함유되어 있다.Polysulfone hollow fiber membrane for hemodialysis of the present invention is an asymmetric single membrane structure composed of the inner surface and the outer surface, 1-10% by weight of vinylpyrrolidone-based polymer and 1% by weight or less of polypyrrolidone polymer It is contained.
또한 중공사막의 외표면 내 비닐피롤리돈계 폴리머 함량이 10~40중량%이고, 수투과도가 4~300㎖/mmHg㎡hr 이다.In addition, the vinylpyrrolidone-based polymer content in the outer surface of the hollow fiber membrane is 10 to 40% by weight, and the water permeability is 4 to 300 ml / mmHg m 2 hr.
본 발명의 방법으로 제조한 혈액투석용 폴리설폰 중공사 막은 친수성이 개선되고 사이즈가 크고 균일한 공경이 많이 형성되어 있어서 비슷한 제거능을 가진(비슷한 공경 사이즈를 가진) 다른 분리막에 비해 상대적으로 높은 투과능을 갖는다. 즉, 분리능의 저하없이 투과능이 향상되어 분리공정의 효율성이 좋아진다.Polysulfone hollow fiber membranes for hemodialysis prepared by the method of the present invention have a relatively high permeability compared to other membranes having similar removal ability (similar pore size) due to improved hydrophilicity and large size and uniform pore size. Has In other words, the permeability is improved without degrading the resolution and the efficiency of the separation process is improved.
본 발명에 있어서 수투과도 및 분리물질 제거율은 아래와 같은 방법으로 측정한다.In the present invention, the water permeability and separation material removal rate are measured by the following method.
·수투과도 평가Water permeability evaluation
유효길이가 15~25cm인 중공사막으로 묘듈(Module)을 제조한다. 25℃에서 내압방식(Inside pressurizing type)으로 압력이 0.5kg/㎠인 물을 상기 모듈내로 일정시간동안 흘려보낸 다음, 중공사막을 투과한 물의 양을 측정한다.A module is manufactured from a hollow fiber membrane having an effective length of 15 to 25 cm. Water having a pressure of 0.5 kg / cm 2 was flowed into the module for a predetermined time at 25 ° C. using an inside pressurizing type, and then the amount of water that passed through the hollow fiber membrane was measured.
·분리물질 제거율 평가Evaluation of removal rate of separated substance
ATI-6000 스펙트로포토메터를 이용하여 비탁시간분석법으로 폴리설폰 중공사 막 투과 전후의 혈액내 사이터크롬-씨(Cytochrome-C), 비타민 B12또는 마이오그로빈(Myoglobin)의 농도를 측정한 다음 이들을 아래 식에 대입하여 산출한다.Using a ATI-6000 spectrophotometer, the concentration of cytochrome-C, vitamin B 12 or myoglobin in the blood before and after permeation of polysulfone hollow fiber membranes was measured by non-tax time analysis. Substitute these in the following formula to calculate.
분리물질 제거율(%)=× 100Separation material removal rate (%) = × 100
식에서, A는 폴리설폰 중공사 막 투과전 용액내 분리물질의 농도이고 B는 투과후 용액내 분리물질의 농도이다.Where A is the concentration of the separation material in the solution before polysulfone hollow fiber membrane permeation and B is the concentration of the separation material in the solution after permeation.
이하 실시예를 통하여 본 발명을 더욱 구체적으로 살펴본다. 그러나 본 발명이 아래 실시예에만 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited only to the following examples.
실시예 1Example 1
폴리설폰 수지(P-3500 : 아코모 회사제품) 14중량%, 폴리비닐피롤리돈 10중량% 및 폴리에틸렌글리콜 6중량%를 N-메틸피롤리돈 70중량%에 투입한 후 교반, 용해시켜 투명한 방사 도프를 제조한다.14% by weight of polysulfone resin (P-3500: manufactured by Akomo Co., Ltd.), 10% by weight of polyvinylpyrrolidone and 6% by weight of polyethylene glycol were added to 70% by weight of N-methylpyrrolidone, followed by stirring and dissolving. Prepare spinning dope.
한편 물 25중량%에 디메틸렌글리콜 75중량%를 첨가, 용해하여 내부응고액을 제조한다. 상기 방사 도프와 내부응고액을 통상의 2중 관형노즐로 방사하여 외경이 280㎛이고 내경이 200㎛인 중공사를 제조한다. 제조한 중공사를 10cm의 에어 갭으로 유도하여 통과시킨 후 물(외부응고액) 속에서 응고/수세하고 50m/분의 권취 속도로 권취하여 폴리설폰 중공사를 제조한다.Meanwhile, 75% by weight of dimethylene glycol is added and dissolved in 25% by weight of water to prepare an internal coagulation solution. The spinning dope and the internal coagulating solution were spun with a conventional double tubular nozzle to produce a hollow fiber having an outer diameter of 280 mu m and an inner diameter of 200 mu m. After the prepared hollow fiber is led through the air gap of 10cm, it is solidified / washed in water (external coagulating liquid) and wound at a winding speed of 50m / min to produce polysulfone hollow fiber.
상기 폴리설폰 중공사를 모듈내에 설치하여 폴리설폰 중공사 막을 제조한다.The polysulfone hollow fiber is installed in a module to produce a polysulfone hollow fiber membrane.
제조한 폴리설폰 중공사 막의 수투과도 및 분리능을 측정한 결과는 표 2와 같다.The results of measuring the water permeability and resolution of the prepared polysulfone hollow fiber membrane are shown in Table 2.
실시예 2 및 비교실시예 1Example 2 and Comparative Example 1
방사 도프 및 내부응고액 조성을 표 1과 같이 변경한 것을 제외하고는 실시예 1과 동일한 공정 및 조건으로 폴리설폰 중공사 막을 제조한다. 제조한 폴리설폰 중공사 막의 수투과도 및 투과능을 측정한 결과는 표 2와 같다.A polysulfone hollow fiber membrane was prepared in the same process and conditions as in Example 1 except that the spinning dope and the internal coagulating solution were changed as shown in Table 1. The results of measuring the water permeability and permeability of the prepared polysulfone hollow fiber membrane are shown in Table 2.
<표 1> 제조 조건TABLE 1 Manufacturing Conditions
<표 2> 물성 평가 결과<Table 2> Property Evaluation Results
본 발명의 혈액투석용 중공사 막은 친수성이 우수하여 폭넓은 수투과도를 갖는다. 아울러 본 발명은 간단하고 효율적인 방법으로 혈액투석용 중공사 막에 친수성을 부여하고, 사이즈가 크고 균일한 공경을 많이 형성할 수 있다.The hollow fiber membrane for hemodialysis of the present invention is excellent in hydrophilicity and has a wide water permeability. In addition, the present invention can impart hydrophilicity to the hollow fiber membrane for hemodialysis in a simple and efficient manner, and can form many large and uniform pore sizes.
Claims (6)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019990023088A KR20010002988A (en) | 1999-06-19 | 1999-06-19 | A polysulfone based hollow fiber membrane for hemodialysis, and a process for preparing the same |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1019990023088A KR20010002988A (en) | 1999-06-19 | 1999-06-19 | A polysulfone based hollow fiber membrane for hemodialysis, and a process for preparing the same |
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| KR20010002988A true KR20010002988A (en) | 2001-01-15 |
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| Country | Link |
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| KR (1) | KR20010002988A (en) |
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1999
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