EP0751818A1 - Membrane pour dialyse a flux eleve en polyacrylonitrile - Google Patents

Membrane pour dialyse a flux eleve en polyacrylonitrile

Info

Publication number
EP0751818A1
EP0751818A1 EP95913112A EP95913112A EP0751818A1 EP 0751818 A1 EP0751818 A1 EP 0751818A1 EP 95913112 A EP95913112 A EP 95913112A EP 95913112 A EP95913112 A EP 95913112A EP 0751818 A1 EP0751818 A1 EP 0751818A1
Authority
EP
European Patent Office
Prior art keywords
weight
membrane
membrane according
copolymer
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP95913112A
Other languages
German (de)
English (en)
Inventor
Karl Henke
Walter Löffelmann
Harald Schmitt
Michael Schmitt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Akzo Nobel NV
Original Assignee
Akzo Nobel NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Akzo Nobel NV filed Critical Akzo Nobel NV
Publication of EP0751818A1 publication Critical patent/EP0751818A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B01D67/0011—Casting solutions therefor
    • 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
    • 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
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • 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
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • B01D71/421—Polyacrylonitrile
    • 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
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
    • 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
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
    • B01D71/441—Polyvinylpyrrolidone
    • 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
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • 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
    • 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
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/48—Polyesters

Definitions

  • the invention relates to an asymmetric semipermeable hollow fiber membrane for dialysis and / or ultrafiltration, in particular hemodialysis from a copolymer of acrylonitrile and acrylic ester and an ionic or or ionizable monomer and process for their production.
  • a process for the production of hollow fibers from acrylonitrile polymers is known from US Pat. No. 4,181,694, an acrylonitrile polymer which consists of at least 60% by weight of acrylonitrile units in an aqueous 65 to 95% by weight nitric acid (at 0 to 5 ° C) is dissolved in order to obtain a spinning solution. This solution is then extruded through spinnerets and at the same time an internal coagulation liquid is introduced. According to this process, hollow fibers are obtained which consist of an outer layer with a porous one Structure, a middle layer with so-called caverns, and an inner layer with a porous structure. These are double asymmetrical membranes with skin on both sides. Caverns here mean "relatively large" holes in the membrane wall.
  • DE-PS 27 40 252 claims dried porous membranes with acrylonitrile polymer units, which consist of a carrier layer and a surface layer on both sides. A method for producing these membranes, which have a skin on both outer surfaces, is also claimed.
  • U.S. Patent 4,545,910 claims membranes that have the performance data of a conventional ultrafiltration membrane.
  • the material for the membrane can be selected from a variety of materials, including also made of polyacrylonitrile compounds.
  • US Pat. No. 5,039,420 claims a membrane which consists of a copolymer of acrylonitrile and a C2 ⁇ C4-hydroxyalkyl ester of methacrylic acid as comonomers.
  • the membranes produced by the abovementioned processes have only unsatisfactory values for the biocompatibility, for example in the release of histamine or in the generation of bradykinin.
  • European application 0 547 471 describes membranes and processes for their production which are distinguished by very good values for bicompatibility, for example in the release of histamine or in the generation of bradykinin.
  • a wet spinning process is used to produce these membranes, the starting polymer being a copolymer composed of 90.50 to 95.00% by weight of acrylonitrile, 4.99 to 8.60% by weight of acrylic ester and 0.01 to 0.90% by weight of the ionic or ionizable monomers is used, characterized in that the
  • the object of the invention is to provide a membrane which can be used for dialysis and / or ultrafiltration and which does not adsorb any .beta.2-microglobulin during its use as a hemodialysis membrane and does not show any significant change in the sieving characteristics with respect to .beta.2-microglobulin even with prolonged use. showing no back filtration during use, and the ultrafiltration rate w äßrige albumin Citrochromaims on "has a favorable ratio of the ultrafiltration rate wetter.
  • the object of the invention is furthermore to a to provide a corresponding method for producing such membranes.
  • an asymmetrical semipermeable membrane for dialysis and / or ultrafiltration made from a copolymer of acrylonitrile and acrylate and an ionic or ionizable monomer in the form of a hollow thread with a separating layer inside the hollow thread, the copolymer being composed is composed of 90.50-95.00% by weight of acrylonitrile, 4.99 to 8.60% by weight of acrylic ester and 0.01 to 0.90% by weight of the ionic or ionizable monomer, characterized in that the membrane is up to 5% based contains on copolymer on polyvinyl pyrrolidone in finely divided form.
  • the membrane preferably contains at most 1.0% by weight of polyvinylpyrrolidone.
  • the membrane is further characterized by a sieving coefficient for ⁇ 2-microglobulin of at least 0.3, in particular at least 0.5, preferably at least 0.7.
  • UFR water UFR aqueous solution albumin / citrochromium ⁇ ' : 1 from. This ratio is preferably 2: 1 to 7: 1, in particular 3: 1 to 5: 1.
  • a wet spinning process is used to produce this membrane, a copolymer composed of 90.50 to 95.00% by weight of acrylonitrile, 4.99 to 8.60% by weight of acrylic ester and 0.01 to 0.90% by weight of the ionic or ionizable monomers - is used, characterized in that the
  • a membrane produced in this way not only has excellent biocompatibility, that is to say no bradykinin generation or histamine release takes place, but also a high sieving coefficient for ⁇ 2-microglobulin, which does not change, or at most insignificantly, even with prolonged use. It was also particularly surprising that membranes are accessible by means of the invention which have a favorable, ie a low ratio of ultrafiltration rate with water to the ultrafiltration rate aqueous solution albumin / cytrochrome C.
  • the measurement of the ultrafiltration rate is a method familiar to the person skilled in the art to characterize hollow fiber membranes. It has the dimension ml / (m hmmHg).
  • aqueous phosphate-buffered saline solution containing 50 g of albumin, 0.1 g of cytrochrome C and 0.03 g of sodium dithionite per liter of solution is used to determine the ultrafiltration rate of aqueous albumin / cytrochrome solution.
  • Bovine serum albumin (BSA) was used as the albumin.
  • the membrane does not build up, i.e. that there are no harmful substances inside the hollow thread, i.e. deposit on the skin, which acts as a separating layer and is located in the interior of the hollow thread, the lumen of the hollow thread is not narrowed, so that the flow through the lumen of the entire hollow thread is practically constant during operation, i.e. remains very even.
  • Polyvinyl pyrrolidone is a known polymer that is commercially available. More details about this polymer include the ISP PVP Polyvinylyrrolidone Polymers from ISP International Specialty Products 1361 Alps Road, Wayne, NJ 07470 USA.
  • the determination of the sieving coefficient is in itself a method familiar to the person skilled in the art and can be carried out in various ways. In the context of the invention, the sieving coefficient was carried out on the membranes by the following method.
  • a human plasma with about 40 mg / 1 ß-microglobulin content was used as the test solution. Modules with an area between 250 and 400 cm were used. The blood side flow was adjusted to 5 ml / min, the filtrate flow to 0.25 ml / min. The temperature was 37 ° C. Work was carried out with recirculation and return of the filtrate to the pool. The measurement took place after 60 minutes. The evaluation was carried out according to the following formula:
  • the spinning bath is generally circulated during spinning. It goes without saying that the concentration ratios of the precipitation bath are kept constant by metering in or partially removing the individual components such as solvent, water and glycerol, that is to say that the selected concentration ratios of the precipitation bath remain largely unchanged during spinning. Since polyvinylpyrrolidone also gets into the coagulation bath during spinning, care must be taken to ensure that the coagulation bath does not become too strong Enriched polyvinyl pyrrolidone. This can be done, for example, by removing the circulation stream polyvinylpyrrolidone.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Artificial Filaments (AREA)

Abstract

L'invention concerne une membrane semi-perméable asymétrique utilisée pour la dialyse et/ou l'ultrafiltration, réalisée à partir d'un copolymère d'acrylonitrile et d'ester acrylique et d'un monomère ionique ou ionisable, se présentant sous forme de filament creux. Le copolymère comprend entre 90,50 et 95,00 % en poids d'acrylonitrile, entre 4,99 et 8,60 % en poids d'ester acrylique et entre 0,01 et 0,90 % en poids du monomère ionique ou ionisable. Par rapport au copolymère, la membrane contient jusqu'à 5 % de polyvinylpyrrolidone finement divisée. La membrane comporte une couche de séparation à l'intérieur du filament creux et peut être utilisée longtemps sans rétrofiltration ni formation de dépôt.
EP95913112A 1994-03-22 1995-03-14 Membrane pour dialyse a flux eleve en polyacrylonitrile Withdrawn EP0751818A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4409890 1994-03-22
DE4409890 1994-03-22
PCT/EP1995/000949 WO1995025582A1 (fr) 1994-03-22 1995-03-14 Membrane pour dialyse a flux eleve en polyacrylonitrile

Publications (1)

Publication Number Publication Date
EP0751818A1 true EP0751818A1 (fr) 1997-01-08

Family

ID=6513528

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95913112A Withdrawn EP0751818A1 (fr) 1994-03-22 1995-03-14 Membrane pour dialyse a flux eleve en polyacrylonitrile

Country Status (4)

Country Link
EP (1) EP0751818A1 (fr)
JP (1) JPH09510379A (fr)
CN (1) CN1145593A (fr)
WO (1) WO1995025582A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100804330B1 (ko) * 1998-11-09 2008-02-15 아사히 카세이 쿠라레 메디칼 가부시키가이샤 혈액 정화기
DE10030307A1 (de) * 2000-06-27 2002-01-17 Geesthacht Gkss Forschung Mit Blut und Gewebe verträgliche Membranen aus P(AN/NVP)-Mischpolymeren und deren Anwendung im medizinischen Bereich
CN100446843C (zh) * 2007-02-01 2008-12-31 江南大学 一种具有抗凝血性能的丙烯酸酯类共聚物膜的制备方法
CN104888625A (zh) * 2015-05-20 2015-09-09 苏州市贝克生物科技有限公司 一种聚丙烯腈血液透析膜及其制备方法
CN109647225B (zh) * 2019-01-22 2021-07-20 东华大学 一种含有定向毒素去除通道的纳米纤维复合血液透析膜及其制备

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS533353B2 (fr) * 1971-12-27 1978-02-06
JPS5892410A (ja) * 1981-11-30 1983-06-01 Asahi Medical Kk 高透過性半透膜
SE460521B (sv) * 1987-08-31 1989-10-23 Gambro Dialysatoren Permselektiv asymmetriskt membran samt foerfarande foer dess framstaellning
EP0547471B1 (fr) * 1991-12-14 1997-03-12 Akzo Nobel N.V. Membrane de polyacrylonitrile
US5340480A (en) * 1992-04-29 1994-08-23 Kuraray Co., Ltd. Polysulfone-based hollow fiber membrane and process for manufacturing the same
EP0636404B1 (fr) * 1993-07-30 1998-01-14 Bayer Ag Membranes en copolymères d'acrylonitrile, procédé de leur préparation et leur utilisation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9525582A1 *

Also Published As

Publication number Publication date
CN1145593A (zh) 1997-03-19
WO1995025582A1 (fr) 1995-09-28
JPH09510379A (ja) 1997-10-21

Similar Documents

Publication Publication Date Title
EP0168783B1 (fr) Fibre creuse microporeuse asymétrique en particulier pour l'hémodialyse et procédé pour sa préparation
DE60034416T2 (de) Dialysatoren zur Blutbehandlung sowie ihr Herstellungsverfahren
EP0172437B1 (fr) Membrane pour dialyse en cellulose modifiée ayant une biocompatibilité
AT12003U1 (de) Permselektive asymmetrische hohlfasermembran für die abtrennung toxischer mediatoren aus blut
DE69919831T2 (de) Leukozytenfilter und Verfahren zu seiner Herstellung
DE3342823C2 (fr)
DE2328853B2 (de) Hohlfasern aus regenerierter kupfer- ammoniak-cellulose und verfahren zu ihrer herstellung
DE69827229T2 (de) Verwendung eines neutralen oder kationischen Polymers, das zur Verhinderung der Aktivierung der Blut-oder Plasmakontaktphase in Berührung mit einer teildurchlässigen Membran
DE2642245C3 (de) Polyvinylalkohol-Hohlfaser und ihre Verwendung
DE2823985A1 (de) Dialysemembran
DE4308807A1 (de) Verfahren zur Herstellung hydrophiler Membranen
DE2812174A1 (de) Die blutgerinnung nicht foerdernde, biologisch vertraegliche gegenstaende
DE2705735C3 (de) Dialysemembran für die Hämodialyse
EP0547471B1 (fr) Membrane de polyacrylonitrile
DE69623196T3 (de) Permselektive Membranen und Verfahren zu ihrer Herstellung
DE3044435C2 (fr)
CH629515A5 (en) Polycarbonate membrane for use in haemodialysis
DE3042110C2 (fr)
EP0751818A1 (fr) Membrane pour dialyse a flux eleve en polyacrylonitrile
DE3524596A1 (de) Dialysemembran aus modifizierter cellulose mit verbesserter biokompatibilitaet
DE102017204524A1 (de) Hohlfasermembran mit verbesserten Diffusionseigenschaften
DE3006880C2 (de) Plasmaphoresemembran
DE3629925C2 (de) Celluloseester-Hohlfaser-Membran zur Plasma-Abtrennung
DE60131170T2 (de) Künstliche Lunge des Membrantyps
DE3043073A1 (de) Filtrationsmembran und verfahren zur hydrophilierung

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19960912

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE ES FR GB IE IT SE

17Q First examination report despatched

Effective date: 19981211

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19990422