CA1226069A - Safe data processing device - Google Patents
Safe data processing deviceInfo
- Publication number
- CA1226069A CA1226069A CA000478040A CA478040A CA1226069A CA 1226069 A CA1226069 A CA 1226069A CA 000478040 A CA000478040 A CA 000478040A CA 478040 A CA478040 A CA 478040A CA 1226069 A CA1226069 A CA 1226069A
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- CA
- Canada
- Prior art keywords
- hollow fibers
- fiber
- fibers
- group
- aqueous
- 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.)
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Classifications
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F11/00—Error detection; Error correction; Monitoring
- G06F11/07—Responding to the occurrence of a fault, e.g. fault tolerance
- G06F11/16—Error detection or correction of the data by redundancy in hardware
- G06F11/1629—Error detection by comparing the output of redundant processing systems
- G06F11/1641—Error detection by comparing the output of redundant processing systems where the comparison is not performed by the redundant processing components
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F11/00—Error detection; Error correction; Monitoring
- G06F11/07—Responding to the occurrence of a fault, e.g. fault tolerance
- G06F11/0796—Safety measures, i.e. ensuring safe condition in the event of error, e.g. for controlling element
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F11/00—Error detection; Error correction; Monitoring
- G06F11/07—Responding to the occurrence of a fault, e.g. fault tolerance
- G06F11/16—Error detection or correction of the data by redundancy in hardware
- G06F11/1629—Error detection by comparing the output of redundant processing systems
- G06F11/1633—Error detection by comparing the output of redundant processing systems using mutual exchange of the output between the redundant processing components
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F11/00—Error detection; Error correction; Monitoring
- G06F11/07—Responding to the occurrence of a fault, e.g. fault tolerance
- G06F11/16—Error detection or correction of the data by redundancy in hardware
- G06F11/1629—Error detection by comparing the output of redundant processing systems
- G06F11/165—Error detection by comparing the output of redundant processing systems with continued operation after detection of the error
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F11/00—Error detection; Error correction; Monitoring
- G06F11/07—Responding to the occurrence of a fault, e.g. fault tolerance
- G06F11/16—Error detection or correction of the data by redundancy in hardware
- G06F11/1675—Temporal synchronisation or re-synchronisation of redundant processing components
- G06F11/1683—Temporal synchronisation or re-synchronisation of redundant processing components at instruction level
Abstract
Description
La presente invention concerxie de nouvelies fibres creuses h proprietes ult.r. afilt.rantes.
Par fibres creuses, dans le present expose, on designe des i':Lbres posse'dant un canal continup dispose l,ongitudi.nal.ement & l' intera.eur de J,a fibre o Les fibres creuses ont doraie lieu, dans un passe recent, h des etudes nombreuses et a un grand ncmbre de publications les plus diverses. Une ret.rospective sur le suj.et figure par exemple dans Lhoyclopedia of Polymer Science and Technology, 15, a0 258 - 272 (1971).
Les fibres creuses en esters cellulosiques tels que llacetate'de cellulose ont sp6cialement ete developpees : elles pr6sentent toutefois des inconvenients inherents h la nature du polym6re qui les constitue; parmi ces inconveni.ents, on peut citer les risques de-modifications des proprietes des fibres suite une hydrol.yse lente et/ou partielle des fonctions esters, cette hydrolyse ayant lieu soit simplement au cours du tempse soit par exemple9 sous l'action d'agents do nettoyage. C9est pourquoi on a cherche a realiser des fibres creuses a base dtautres materiaux:
20 eomme mat6riaux ut3l.is'ables, les polym6res de l'acrylonitrile se sont reve'les particul:i6rement :int6ressants.
Pa.ral.l6lement a cette evolution concernant la nature chimique des fibres creuses' des etudes ont porte sur 14adaptation de la structure des fibres. En particulier, on a recherche des fibres creuses ayant une permeabilite amelioree vis \ vis des fluides les traversant.
C est ainsi que dans le brevet amerieain no 3,423,491, on a propos6 de filer a l'etat fondu un melange d.e polymb.re thermo-plastique et d'un plastifiant, puis d'eliminer le plas-tifiant 30 par lix:i,viation. .Le polym6re thermoplast:i.que peut dtre du poly-acrylonitrile'avec dEs comonomeres non ioniques tels que l'acetate de vinyle. La teneur en plastifiant du melange po:Lym6r. e thermo-- ~ -plastique/plastifiant est bien entendujlamitee par le Lait que ce mel.arge doit pouvoir 6tre file en fondu. De fait9 ce proc~de et les fibres creuses ainsi prepax ees sont efficaces principalement en osmose inverse en raison de leur taux de rejet de sel qui n'est pas nu1, et qui est m8me pratiquement superieur ~Z75~.
Pour certaines applications telles que l'ultrafiltration et la dialyse (notamment l' hemodialyse ), des fibres creuses ayant un tel taux de rejet de sel ne sont pas souhaitables et peuvent m8me Otre h proserire.
On a alors propos- 4 de realiser des fibres creuses ~
peau en po].ymbres d'acrylonitrile' la paroi de ces fibres etant constituees essentiellement d'une peau et d'un susbtrat poreux.
Ces fibres sont decrites dans le brevet americain 3.674.628.
Elles ont aussi ete deerites dans le rapport de recherches et developpement du Gouvernoment des Etats-Unis no PB.'19208¾60 Leur proced4 de prepa.r,ation consiste a) b, injecter une solution de polymbre dans une filibre orifice en couronney b) .6, figer une 'zone periphEra.que du filament sortant de la fa.libre y puis samultanement ou subsequemment 9 c) h coaguler la zone p-eripherique interne et/ou xterne de la fibre. Pratiquement, le figeage est effectue par passage dans l'air de la fibre en voie de formation a la sortie de. la i'i.1.i6re qui est une fs.libre dite :Cmergeante; la coagulation est effectu6e par action d'un agent coa;ulant, c'est A dire non solvant du polymbre constituant la fibre.
Un procede semblable a egalement et6 propose pour les fibres cellulosiques (Encyclo Polym. Sc. Tech., 159 263 (1971)) mais il conduit h des fibres d t osmose inverse ayant deq taux de rejet de sels 6leves. On sait en effet, cozn.me le conf'irme le breve't americain 3 423 491, que le procede de preparati.on The present invention relates to new fibers hollow with ult.r. properties afilt.rantes.
By hollow fibers, in the present description, we mean i ': Lbres with a continup channel has l, ongitudi.nal.ement & inside J, a fiber o Hollow fibers have occurred in a recent past, h numerous studies and a large number of publications the most diverse. A retrospective on the subject and appears by example in Lhoyclopedia of Polymer Science and Technology, 15, a0 258 - 272 (1971).
Hollow fibers in cellulose esters such as The cellulose acetate has been specially developed: they have drawbacks inherent in the nature of the polymer which constitutes them; among these disadvantages, we can cite the risks of modification of the properties of fibers following a slow and / or partial hydrolysis of the ester functions, this hydrolysis taking place either simply during tempse or by example9 under the action of cleaning agents. That's why we has sought to make hollow fibers based on other materials:
As useful materials, acrylonitrile polymers are are revealed particularly: interesting.
Pa.ral.l6lement to this evolution concerning nature Hollow fiber chemical 'studies have focused on adaptation fiber structure. In particular, we looked for hollow fibers with improved permeability to fluids passing through them.
This is how, in American patent no. 3,423,491, it has been proposed to spin a mixture of thermopolymer in the molten state plastic and plasticizer and then remove the plasticizer 30 by lix: i, viation. .Thermoplast polymer: i.e. may be poly-acrylonitrile with non-ionic comonomers such as acetate vinyl. The plasticizer content of the mixture po: Lym6r. e thermo-- ~ -plastic / plasticizer is of course claimed by Milk that this mel.arge must be able to be fade out. In fact9 this process and the hollow fibers thus prepaxed are effective mainly in reverse osmosis due to their rejection rate of salt which is not bare, and which is even practically higher ~ Z75 ~.
For certain applications such as ultrafiltration and dialysis (especially hemodialysis), hollow fibers having such a salt rejection rate is not desirable and can Even Being Prosecuted.
We then proposed- 4 to make hollow fibers ~
skin in.]. acrylonitrile symbols, the wall of these fibers being essentially consisting of a skin and a porous substrate.
These fibers are described in American patent 3,674,628.
They were also found in the research report and development of the United States Governorate no PB.'19208¾60 Their prepa.r process4 consists of a) b, inject a polymber solution into a fiber orifice in Couronney b) .6, fix a 'periphEra.que zone of the outgoing filament in the free way then samultaneously or subsequently 9 c) coagulate the internal peripheral area and / or fiber external. In practice, the freezing is carried out by passage in the air of the fiber being formed at the exit of. the i'i.1.i6re which is a free said: Cmergeante; coagulation is carried out by the action of a costly agent, that is to say, no solvent for the fiber constituent.
A similar process has also been proposed for cellulosic fibers (Encyclo Polym. Sc. Tech., 159 263 (1971)) but it leads to reverse osmosis fibers having rates of rejection of elevated salts. We know indeed, cozn.me confirms it american patent 3,423,491, that the preparati.on process
2 des fibres influe generalement beaucoup sur les propra.e-ttes et/ou performances des fibres.
Bien que les fibres d peau constituent un progrbs important, elles presentent da.ns certains cas des inconvenientso C'est ainsi que lorsqufon veut ameliorer la turbulence des fluides traversant les appareils h fibres creuses en mettant ces fibres sous des confa.gu_r.ations particulieres telles qulondulations, friw sage' tressage et autres, la peau de ces fibres constituent ua:i point de fraga.lite susceptible de donner naissance & des cir=cula-tions parasites do fluides. La fragilite de ces fibres se manifestent encore a diverses occasions : lorsqu;on veut les manipuler dans des appareils automatiques oa elles circulent h grarides vitesse et avec de fortes aecelerations ou decelerata.ons y lorsqutelles son't utilisees avec une pression differentielle de part et d9autre des parois de ces fibres; dans ce dernier eas, qui est celui de l9ultrafi].tration, on constate que les fibres creuses sont dtautexa,t plus fragiles que la teneur en comonomere ionique do laacrylonitri.le est plus elevee9 par exemple sup~:rieure ~ 5 I
en nombre.
Un but de ltinvention est done de fournir des fibres creuses en polymbre dfacrylonitrile nlayant pas 1es inconvenients de 14 art anterieur et notarnment des fibres sans peau ~ pe.rmeabili-t6 6levee.
11 a maintenant ete trouvey et cfest ce qui fait ltobjet de.la presente a.nvention9 des fibres creuses caracterisees en ce qu :
1) Elles sont constituees dtun copolym6re dvacr.ylonitrile et dtun monom6re ole:finiquement insature porteur de groupements sulfon7.ques eventuellement salifies (ce monomere etant, dans ce qua.
suity d6signe en abreÃ;e par 1'expression comonom6.re sulfonique)o 2) Eiles sont microporeuses et possedent dGS micx=onorEs de diarnbtre moyen i nferieur h 100 A
_ 3 1.0 69 2 of fibers generally has a great influence on the properties and / or fiber performance.
Although skin fibers are a progr important, they present in some cases inconvenientso This is how when we want to improve the turbulence of fluids passing through hollow fiber devices by putting these fibers under special confa.gu_r.ations such as rondulations, friw sage 'braiding and others, the skin of these fibers constitute ua: i point of fraga.lite likely to give birth & cir = cula-parasitic fluids. The fragility of these fibers still manifest on various occasions: when we want them handle in automatic devices where they circulate h grarides speed and with strong aecelerations or decelerata.ons y when used with a differential pressure of on both sides of the walls of these fibers; in this last eas, which is that of l9ultrafi] .tration, we see that the hollow fibers are dtautexa, t more fragile than the ionic comonomer content do laacrylonitri.le is higher for example sup ~: rieure ~ 5 I
in number.
An object of the invention is therefore to provide fibers hollow in acrylonitrile polymbre does not play the disadvantages of 14 prior art and in particular fibers without skin ~ pe.rmeabili-t6 high.
11 has now been found and this is the subject de.la presents a.nvention9 hollow fibers characterized in qu:
1) They consist of a nylonitrile copolymer and an ole monomer: finely unsaturated carrying groups sulfon7.ques possibly salified (this monomer being, in this qua.
suity means abbreviated by the expression comonom6.re sulfonique) o 2) They are microporous and have dGS micx = onorEs average diameter below 100 A
_ 3 1.0 69
3) Leurs psrois ont un -caux do vide compris entre 40 % et 80 ~.
Par -taux de vide de 1a pa.roi d'une fibre creuse v mioroporeuses on designe le nombre 100 ( 1 - 2) Vi V1 etant le volume occupe par la paroi d'un echanta.llon E1 de fibre creuse microporeuse de poids p V2 eta.n.t le volume occu.pe par la pa-roi d'un echantillon E2 de fibre creuse a structure compacte ayan.t un poids p et constztue du m8me ma=teriau polymerique que la fibre ereuse microporeuseo Par fibre creuse a, structtire compacte on designe une fibre creuse etanohe N l'eau sous une pression relative interieure de 3 baxs o Dans la pratique les volumes V1 et V2 so calculent 6 parta.r des mesures de la longueur et des diambtres internes et externes des echantillons E1 et E2, ces mesures etant elles mÃmes ef:Ceotuees par simples observations optiques, tel au microscope pour les di,ambtreso En ou=tre, lf echanta.l.lon E2 de figure creuse structure compacte de volume V2 est obtenu par seohage & 60 C
et sous une pression absolue de 10 mm de mercure de 1Rechantillon E1 de fibre creuse microporeuse de :vo7.ume V1; bien que les dimen-sions de ltechantil7.on de fibre creuse varient au cours du sechage ( 3.1l, y a certain retrait), le poids p de matibre sbche est cependant conserve et le volume V2 de ltechan.tillon E2 est le mÃme (precisement en raison de sa structure compacte) quo le volume diun, eohantillon Fictif E3 ayan.t m@rne longueur et mgme dia.sn6tre int'exne que E1 et ne se distinguent de E1 que par son diambtre extcrne. Il s A ensui-t que le -taux de vide 100 ('! - V2 ) co=F:spo:ad ^ V1 au retraa,t volumique dti au passage de la s-tructure microporeuse a la structLre compacte.
Comme comononibre su? fonique de 1 ' ac:ryl.ona.tr:iJ.e y on 3) Their psrois have an empty -cale between 40% and 80 ~.
Vacuum rates of 1a pa.roi of a hollow fiber v mioroporous we designate the number 100 (1 - 2) Vi V1 being the volume occupied by the wall of an echanta.llon E1 of microporous hollow fiber of weight p V2 was the volume used by the king of a sample E2 of hollow fiber with compact structure ayan.t a weight p and is the same ma = polymeric material as erous fiber microporous By hollow fiber a, compact structure we mean a etanohe hollow fiber N water under internal pressure of 3 baxes o In practice the volumes V1 and V2 so calculate 6 parta.r measures of length and internal diameters and external of samples E1 and E2, these measurements being themselves ef: Ceotuees by simple optical observations, such under the microscope for di, ambtreso In ou = tre, lf echanta.l.lon E2 of hollow figure compact structure of volume V2 is obtained by seohage & 60 C
and under an absolute pressure of 10 mm of mercury from 1Sample E1 of microporous hollow fiber of: vo7.ume V1; although the dimen-ltechantil7.on sions of hollow fiber vary over the drying (3.1l, there is some shrinkage), the weight p of sbche material is however kept and the volume V2 of ltechan.tillon E2 is the even (precisely because of its compact structure) that the volume diun, fictitious sample E3 ayan.tm@rne length and mgme dia.sn6tre int'exne que E1 and are distinguished from E1 only by its diameter external. It follows that the vacuum rate 100 ('! - V2) co = F: spo: ad ^ V1 at the retreat, t volume by the passage of the microporous structure has a compact structure.
Like comononibre su? fonique de 1 'ac: ryl.ona.tr: iJ.ey on
4 u-tilise gexa,eralerncnt des produi-ts de formule CHR1 r CR3 - A (7:) :
dan.s laquelle Y represente un groupe - S03k1 ou -S03M, M etant un atome meta7..;Lique, do prefErence un m6tal a3.ca.l.in, R1 et R3 representent l'atome dihydrogene ...ou un groupe methyle' A presente un lien valexa.ciel.' un groupe A' ou un groupe - 0 - A' --, oA A' represente un groupement divalent hydroca.rbone aliphatique satuxe ou non sature droit ou ramifie, un noyau aromatique non substitue, ou une chatne monoaromatique-monoa7.iphatique dans laquelle l'une des valences libres est portee par un atome de carbone aliphatique, et l'autre par un atome de carbone du noyau aromatique.
Comme comonom6re sulfonique de l'acryloni-trile, on peu-t citer plus specifiquement les acides va.nylsulfoni.qiae, allyl-suli'oniqu.e., methallylsulfonique, styrenesu.lfonique, vinyloxy-benz6nesulfonique, allyloxy- et met.halyloxybenzbnesulfonzque, allyloxy- et methallyloxyethylsul.:fonique, ainsi que les sels de ces ;aivers acides, de p.reference leuxs sels alcalinso La proportion de comonomAre sulfonique da.ns le copoly-mbre d'acr.ylonitrile est genera,l.ement comprise entre I et 50 % en nombre de motifs monomeres sulfoniques9 de pre.ference entre 5 e-t 15 Les copol,ym6res d' acrylor.Li.trile ont une viscosite specifique, mesuree & 25 Cen solution a. 2 g/l dans le dimethylformamide, compra.-~
se habitueliernent entre 0,1 et 3, de preference entre 0,5 et 1,50 Le diametre des micropores des fibres selon l'inventi.on est determine au mrLeroseope electroa,.ique par observation des sufaces et/ou des coupes des fibres; 1'observata.on est faite,de preference au grossassement 20o0000 .
Le diambtre exterieur des fibres creuses de l'invention est ha:bituellement compris entre 50 et 1000,w, de pre:cerence entre 100 e-t 600,a/ 1.'epaisseur de leur paroi est general.ement comprise entre 5 et 40 %, de'preference entre 10 et 25 % du diambtre 4 use gexa, eralerncnt products of formula CHR1 r CR3 - A (7 :):
in which Y represents a group - S03k1 or -S03M, Being a meta7 atom; Lique, preferably a metal a3.ca.l.in, R1 and R3 represent the dihydrogen atom ... or a methyl group ' Has a valexa.ciel link. ' a group A 'or a group - 0 - A' -, oA A 'represents a divalent aliphatic hydroca.rbone group satuxe or not saturates straight or branched, an aromatic nucleus not substitutes, or a monoaromatic-monoa7.iphatic catne in which one of the free valences is carried by an atom of aliphatic carbon, and the other by a carbon atom of the nucleus aromatic.
As a sulfonic comonomer of acrylonitrile, we can more specifically, the acids va.nylsulfoni.qiae, allyl-suli'oniqu.e., methallylsulfonique, styrenesu.lfonique, vinyloxy-benz6nesulfonique, allyloxy- et met.halyloxybenzbnesulfonzque, allyloxy- and methallyloxyethylsul.:fonique, as well as the salts of these; acidic universes, of reference to two alkaline salts The proportion of sulfonic comonomAre in copoly-acrylonylon nitrile is generally between I and 50% by number of sulfonic monomeric units 9 preferably between 5 and 15 Copol, ym6res of acrylor.Li.trile have a specific viscosity, measure & 25 Cen solution a. 2 g / l in dimethylformamide, compra.-~
get used between 0.1 and 3, preferably between 0.5 and 1.50 The diameter of the micropores of the fibers according to the invention is determined at mrLeroseope electroa, .ique by observation of sufaces and / or fiber sections; The observation is made, of preference to swelling 20,000,000 .
The outer hollow fiber diameter of the invention is ha: usually between 50 and 1000, w, pre: cerence between 100 and 600, a / 1.the thickness of their wall is generally included.
between 5 and 40%, preferably between 10 and 25% of the diameter
5 . '~
exterieur. Les fibres creuses selon l inven-tion sont general.ement exemptes de vacuoles, i.e,, espaces vides, inclus dans :J.es parois des fibres, et dont la plus grande dimension es-t superieure a 5..w environ, et ne comportent pas de peau ou couche dense en surface, Leur taux de rejet vis A vis des sels est nul (mesure sous une pression de 2 bars pour une solution aqueuse de NaCI a 90 g/l).
Ltinvention concern.e egalement un procede de preparation .10 de fibres creuses et notamment de fibres creuses telles que definies ci-avante Ce procede' est caracterise en ce que loon injecte dans tane filibre & orifice annulaire un collodion forme d'une solu-tion de copolym6re d4acrylonitrile et c3e comonombre sul.fonique dans un solvant, ou melasage de solvants, organique polaire et que, immediatement h la sortie de la fil3.6re, on coagule ltinterieur et 1 t ext.e7rieiar de la fibre creuse naissante h l9 aide d 1un fluide coagu:l.ant choisi dans le groupe constitue pa.r s a) les solutions aqueuses de sels mineraux ayant des 20 concentrations a.nferieures la saturation, habituellement compri-ses entre 1 et 35 % en poids do preference compr:i.ses entre 5 et 20 %9 b) un solvant organique po7aire ou melange de sol vaxa,ts organiques polaires, ce solvant ou melange de solvants eta.n.t non solvant va.s & vis du copolymbre dlacrylonitrile et miscible au solvant du collodion.
Par bcollodion" on designe une solution de eopolymbre d1aarylonitrile et de cona.onom6re sulfonique dest:inee & 6tre filee.
Comme solvant organique polaire susceptible de former 30 le collodion, on utilise dtune mani6re generale les solvants connus v3,s h vis des copoZym6res acryl.onitrile/monombre sulfonique; plus speca.fiquement on peut citer le dim.ethylsulfoxyde, le d:iraÃthyl-5 . '~
-10,069 outside. The hollow fibers according to the invention are generally.
free of vacuoles, ie, empty spaces, included in: J.es walls fibers, and the largest dimension of which is greater than 5..w approximately, and do not have a dense skin or layer in surface, Their rejection rate with respect to salts is zero (measurement under a pressure of 2 bars for an aqueous NaCl solution a 90 g / l).
The invention also relates to a preparation process.
.10 hollow fibers and in particular hollow fibers such as defined above This process is characterized in that loon injects into tane fiber & annular orifice a collodion forms a solu-acrylonitrile copolymer and this sulphonic comonomer in a solvent, or mixture of solvents, polar organic and that, immediately at the exit of the wire 3.6, we coagulate the interior and 1 t ext.e7rieiar of the incipient hollow fiber using a fluid coagu: the chosen one in the group constitutes pa.rs a) aqueous solutions of mineral salts having 20 concentrations below saturation, usually including its between 1 and 35% by weight preferably includes: i.se between 5 and 20% 9 b) a common organic solvent or soil mixture vaxa, polar organic ts, this solvent or mixture of solvents eta.nt non-solvent va.s & screw of the acrylonitrile copolymbre and miscible with collodion solvent.
By bcollodion "we designate a solution of eopolymbre of arylonitrile and of sulfonic conaonomer intended to be spun.
As a polar organic solvent capable of forming In collodion, known solvents are generally used v3, sh vis of the acryl.onitrile / sulfonic monomer co-polymers; more specically, mention may be made of dimethylsulfoxide, d: iraethyl
6 ~~26069 acetam.ide, 1.ehexamethylphosphotriamide t surtout le dimethyl-formamide (D147F) o Au lieu d'un solvant unique le collodion peut 8tre obtenu & partir d'un melange de solvants; & ce solvant ou mels.nge de sol.vants on peut egalement adjoindre une fraction mineure de non so:tvant de pol.yinere p dans le mesuse otL Io ensomble reste solvant du polym6re de :L,oacrylonitrile.
La concentration du collodion en copolym6re de l acrylo-na.tra.le est genera:l.ement superieure h 5% en poids et inferieure ,10 la saturati n; elle est de preference superieure & 20 / en poids.
Le eollodion est ensuite coagule par simple mise en contact du collodion avec le fluide coagulant, imm,eda.a-tement 'a la sortie de la filicrea Une telle coagulation immediate-ment a la sortie d -une filibre immergee a bien aussi ete prevue dans le brevet des EõTT.A, 3.674.628, mais da.ns ce dernier procede la da,fference de temperature entre le collodion et le fluide coa-gulant etant suffisamment grande pour.. effectuer un figeage imme-d:iat. Dans le procede de lla.nventions II 'nty a pas cette etape 20 de figeage et la difference de temperature entre le collodion et le bain coagulant est pratiquement infer.ieure & 30 C.
Za coagulation externe de la fibre creuse naissante . est 'effectuee pratiquement en faisant circuler la dite fibre en voie de formation dans un bain de fluide coagulant (en abrege "bain coagulant").
La coagulation interne de la fibre creuse naissante est effectuee pratiquement par injection de fluide coagulant dans l'Arae clest b. dire dans 11a.ntera.eur de la fibre en vo ie de formation.
30 La tera.perature des fluides coagulants et du collodion peuvent vara,er dans de larges la.mi-tes; elles sont generalement comprises entre -10 et +40 C9 de preference comp.rises entre 0 et .~ 7 e_ 30 C. De basses temperatures favor:i.sen-t en gEZa.cral 19absence de vacuolesa Zes tanperatures du co].lodion, du fluide coagulant interne et de la fili6re sont riabi-tuellement 6gales pour des raisons d' ordre technol.og.. que; par contre la t emp6rature du bain coagulant peut ~tre da.fi'erente des trois temperatu-res pr6citees Lorsque le fluide coagulant est une solution aqueuse de sel mineral., on utili.se avan'tageusement, comme sel mi.nera.:t, un sel soluble (dans 1'eau) de metal alcalin ou aJ.cal.ino-terreux9 on pr 6fbre generalement utiliser le chlorure de sodium. On peut toutefois 6galement utiliser l.es chlorures, sulfates, nitrates et perchlorates de lithium, sodium, potassium, magnesa.um, calcium, dans la limite de leur solubilit6.
le pouvoir non solvant de ces solutions aqueuses peut btre modifie' par adjonction de solvants organiques polaires misci-bles, par exempl.e de dimethylformamide, en proportion de preference infera.eure & 40 Lorsque le fluide coagulant est un solvant ou mela;cnge de solvants organiques polaires, on utili.se avantageusement comme non solvant du copolymLre de 1'acrylons.trile des alcools tels que le methanol, I'ethanol., les propanol.sy 1.es butanol.s, les diols a.liphatiques, notamment 1' e-thylbne glycol, ou encore des c6tones aliphatiques, telles que l'ac6tone et la methyl6thylcetone; le pouvoir non solvant de ce solvant ou melange de solvants peut Otre modifi6, par adjonction de quanti.tes rnineures (general.ement mcaa.ns de 25 %) de sol.vants du copolym6re de l4acryloni'trile tels que ceux cites pr6cedemment (dime-thylformamide, dimethylsulfo-xyde,'dim6thylace'tamide, hexam6thylphosphot.ra.amide).
Au cours de la coagulation une partie du solvant du collodion migre dans le fluide coagulant ce qui, par vo:i,e de cons6quence e peut en modifier quel.que peu la composition.
Dans le but d9assurer uno :Corme regulibre et symetrique aux fibres creuses, on pref6re positionner la fiii6re selon un ~ 8 -x.~~~~69 axe vertical avec ecouLement du coLloda.on de haut en bas; les fi.l:i.eres sont pratiquem.ent des :ilieres :iunwmergees o La ma.se en contact do la fibre naissante avec les fluides coagulants est p:oux---,uivie au Dzoins jusqu'h ce que la fibre soit su.ffisamrnent durcie pour 8tre manipulable et pour ne plus fluer dans les conditions operatoireso La coagu.l ation tell.e que decrite ci--avant peut 0-tre suivie d'un lavage h l' eau pure poux eliminer l' essentiel des eonstituants non polymeriques de la fibre (solva.nts et/ou sels 7p notamment).
yQs fibres telles que preparees par le procede de coagulation decrit ei-avant peuvent Otre ameliorees par un traite-anent thermique aqueux dans le but d'ameliorer lev-rs performances e-t notamment leiz.x permeabilite Les fibres creitses soumises 'a ce traiteinent peuve-at avoir subi un lavage partiel d 1' eau pure ou h l' aide d'un melange eau/solvant organique ma:is, quoi quli1 en soa.t, au moment du trai-tement thermique aqueux9 les fibres contiennent ava.ntageu sement encore un peu du ou des solvan-ts constituan.t initialement 20 le collodion; plus precisementy la teneur des fibres creuses en solvarzt residue;ire lors du trai-tement thermique aqueux est gene6-ralem.emt comprise entre 5 et 20 %, de preference entre 10 et 17 Ce traitement thermique aqueux consiste a irnmerger les fibres creuses dans de l'eau ou uxt melange aqueux non solvant ~
une temperature comprise entre 60 et 250 C, de preference entre 80 et 990 C, L'eau ou lee melanges aqueux utilises peuvent Otre en phase vapeur; il est toutefois p-r. eferable de les uta.:Liser en phase liquideo Bien entendu le traitement selon 1'invention au 30 dessus de 100 C peut necessiter d'operer sous pression lorsqu'on veut utiliser de 1'eau liquide pour effectuer le -traitoment ther-mique aqueux, ~, .~ 9 La toneur en eau des melanges aqueux utila.sables dan.s le traitement selon 11invention est habituellement superieure h 50 % en poids, de preference superieure a. 90 %a LPeau peut Ã'tre melangee & des solvants organiques ou h des elec-trolytes znineraux ou organiques ma.a,s on prefbre alors utiliser des m.elanges neutres chimiquement et notamnment non basiques, dans le but de ne pas provoquer dga-ttaque cha.mique du copolym6xe dlacryloni-trile. Un pH
de 6 8 conv3.ent generalementm Selon un mode operato:i.re avantageux, le traitement .10' thermique aqueux selon ltinvention est effectue en continu en faisant circuler en continu la fibre dans le bain de traitement, qui est un bain dteau chaude, la pression etant alors la pression atmospherique et la temperatvxe 6tant au plus egale & 100 C. I,a duree de traitement est habituellement de 5 secondes & 5 min.utes mais a.l nly a pas de la.myte superieure critique pour la duree du traitemento Le traitement thermique aqueux decrit ci-avant est en outre et do preference accompagne dtun etirage longitudinal des fibres; cot eti.rage est habituellement de 50 & 500 %, de preference 20 de 100 A 250 %o On peut enfin conferer une meilleure stabi:Lite dimension-nelle aux fibres etirees en effectuant une relaxation par se j ourne-rnent ulterieur de ces fibres sans contrainte dtallongement dans un bain aqueux A temperature de preference inferieure & celle du trai-tement thermiquea T,es fibres selon l1invention peuvent 8tre conservees h l$ etat humide en particulier glycerine (imaners:ion des fibres dans un melange eau/glycerine ~ au moins 40 % en poids de glycerine)4 30 I,es fibres selon ltinvention possedent une exceliente permeabili,te 4 19 eau qui 1,es rend specialernen-t avantageuse en ultra filtration ainsi qup en dialyse, no-taulment en her,aod:ia.lyse, Elles ont une faible tendance au colmatage aimi qu4une bonne aptitude a, la separa'tion des solutes macromoleculaires : elles peuvent ainsi Ãtre uti:Lisees dans les tr6s noztibreuses applica-tions connues do :Llultrafi].tration. Elles ont encore une bonne resistance h la pressiond Parmi 1.es applications des fibres creuses selon l4 inven--tion, il faut encore citer la rea7.:l.sation des. reacteurs enzymati-ques; u.n, tel reacteur muni des installations annexes a ete repre--, sente & la figure 1 ci-jo3,nte.
Le reacteur 1 comprend une plurala,te de fibres creuses 2 et un systLme de compart3.ments qui permet de real.iser deux circulations de liquides l9une A llinterieur des fibres creuses, 1, t autre a 1 P exterieurQ Le 1.iqu:ide circu].ant h l p exterieur des fibres creuses parcourt successivement le compartiment 3, la canalisation 4, le vase dQ expansion 5, la canalisation 6 et la pompe 7; l.e liquide oircu7,ant & llinterieur des fibres creuses parcourt successivement le compa.rtisaent 8, la canalisation 9, le vase d lexpansion 10 y la canalisation 11, la pompe 12, le coanparti--ment 13, :1es fibres 2.
Dans un tel reacteur s on fait ci rculer 1, o enzyme en solution ou suspension d'un c8te des parois des fibres creuses et un substratum, en solution ou suspension, de ltautre c8te de ces mOmes paroisa Pour la clarte de lPexpose ou choisira arbitrairement, dan.s c e qui suit, de faire circuler 1 f enzyrne des fibres cr euses et le substratum A l4interieur, etant entendu que lfinverse est parfaitEment realisable.
Ainsi donc' dans l' appareil. de la figure 1, l 9 enzyme parcourt le circuit 3, 4, 5, 6 g 79 et le substratum parcourt le circuit 8, 99 10, 11, 12, 13 et le canal interieczr des fibres.
Les =couples enzymes/substratum suscept:i.bles dp Otre m:I.s en action dsxzs les reacteurs enzyi:natiques sont tels que l.es fibres - 11 -~
10;~6060 creuses soient pratiquement :imperrri4ables vis ~ vis de l t exa.zyme et permeables vis At vis du substratum et de produits de re ction enzymatique; de cette ma.na,.bre la sepaxation de l' enzyme d' avec son milieu reactionnel (substratum ~ produits de reacta.on) est aisee et les pertes en enzymes sont minimes.
Les fibres creuses selon l'invention permettent en partieulier de traiter leuree par l'ure'ase d'ot~, leur utilisation dans les reins artificiels.
Les exemp:l.es suivants donnes h titre non limitatif illus-trent :L'i.nvention en montrant comment elle peut 8tre mise en pratique. Toutes les fibres.creuses de ces exemp3.es ont un taux de rejet de sel nu1..
Exemple 1 On prepare un "collodion" par dissolution dans 76,5 g de dimethylformam:ide (DMF) do 23'5 g d'un copolym6re acrylonitrile - methallylsulfonate de sodium (9 % en poids de m6thallylsul-f onate' soit 3,2 % en nombre de motifs monombres sulfoniques;
vi,scosite sp6ci:fique mesuree a 25 C en solution h 2 g/l dans le DMF :`0990).
Ce oollodion est in;jecte' N raison de ¾,5 em3/rnn. dans l'orifice annulaire en forme de couronne d'une f:ili6re, ayant un da.ambtre axa.terieur : 0 m 6 mm et un diambtre exterieur : 0,8 mm, La fil.i6re est dispos6e selon un axe vertical et soxi extr6mite a.nferieure (orifice) plonge dans un.e solutiozi aqueuse a 200 g/l de chiorure de sodium AL 2 C4 Au centre de 1'orifa.ce annulaire de la fi.li6re' il y a un devxibme orifice de 0,3 mm de diam6tre et par lequel estinjectee dans 1'9im.e de la fibre creuse naissante une solution aqueuse ~ 200 g/1 de chlorure. de sodium et 23 C raison de 1,7 cm3/mxa La fibre cr use.naissan.te parcourt verticalement le bain coagulant sur une _longueur de 1 an A une vitesse de 9:m/mn; a la sortie de ce bain coagulant, la fibre creuse parcourt horizon--r 12 taleraent ur.t ba:i.n d p eau bouillante de 30: cm de longueur ~a 1 entrEe et, hL la sortie de ce bain, elle est gui-dee par des galets, la vitesse dtentree de la fibre dans ce bain 6tant de 9 m/inn et la vitesse de sortie de 27 m/mn; h, la sor-L-ie, on enroule la fibre sur u.n rouleau, on termine le traitement do la fibre par un lavage h leeau pure par arrosage pendant,l mn sur des spires en.roulees sur le rouleau le taux ds6tixage des fibres a ainsa, ke de 3p.
La fibre ainsi obtenue h un di.oxa6tre in-terieur de 350,a;6 un diarn6tre exterieur de 520 ;t4 un taux de vide de 61 %; l9 obser-I0 vation au micr.oscope electron.:i.que (grossissement : 20.000) de coupes de cette fibre' niontre qut il nQy a pas de pore de diambtre super;Leur ou egal 6. 100 A.
A partir de la fibre ainsi pr6paree, on realise un appaxeil ( ou rnodule ) d'ultrafiltration possedant 180 fibres de 80 cm de long et de 64 cm chacune de longueur utile9 di.sposees paral.lA7.ement, 64 em representant la longueur disponible pour 1 f ultrafiltration ; 1 t appreil. a donc une surface moyen_ne d 96change de 0~13 m2q On fait circuler A llextera.eur de ces fibres et sous 20 une pression relative do 2 bars une solution aqueuse ~ 1 g/l dtalbumine bovine de poids moleculaire 70.0000 On obtient un ultrafiltrat avec un debit de 121 1/jem2 et un taux de rejet de 100 %, le taux de rejet 6tan.t dei'ini par 1 o expr essxon s 100 x(1 -concen-tration en sol.ute de 1 sul-trafil-brat concentration en solute du liquide h LL1.tra fil-trer D9autres performances do ces fibres sont relatees dans le tableau I, en meme temps que les performances des fibres des exempl,es 2 & 7.
30 EX~mple 2 On reproduit 1'exemple 1 en changeant :Le taux daetirage dans 1 s eau bouillante s la fibre est etir::e ~L 1,5 fois sa lo.,agueur initiale, La fibre creuse obtenue a un di.am6tre inter.ieur de 370 -0J9 et exte'rieur de 660 -W, Le taLnc de vide est de 54 /. Il n'y a pas de pores de diam6tre superieur ou egal A 100 A.
Exem :L 3 On reproduit I.* exemple 1 en changeant le taux d' eta.rage da.ns l4eau bouillante : la fibre est etiree h 5 fois sa longueur ]117. t7.,a1 e o La fibre creuse obtenue a un diambtre a.nterieur de 255.jX) et exterieur de 385.tt~ Le taux de vide est de 56 %. T1 nay a pas de pores de diametre superieur ou egal ~'a 100 A.
Exemple 4 On reproduit ltexempl.e 1 en supprimant le traitement h i'eau boua.llanteo Exemple 5 On reproduit 1'exemple 1 avec 1es modifications suavan-tes - Le fluide coagulant ~ 1':i.nterieur de la fibre creuse naissante est une solution aqueuse h 50 g/1 de NaCl (23 C).
- Le bain coagulant externe est un m6lange eau/dimei;hyli'oxmamide . en proportions volumiques 3/1 con.tenant 50. g/], de NaC1 (2500).
Les fibres creuses obtenues ont un taux de vide de 68 un diambtre exte'rieur de 415 -u et a,nterieur de 261 /1Ja. Il n'y a pas de pores de diam6tre superieur ou egal & 100 A.
Ex..., eRRIe 6 On reproduit leexemple 5 en utilisant uri bain coagulant externe h 0 C. Les fibres ont un taux de vide de 57 %q un diam6-tre exte'rieur de 450 /-4Jet interieur de 280.u% 11 n'y a pas de pores de diaa1ubtre sup6r:i.eur ou 6gal A 100 A.
Exemule 7 On reproduit ltexemple 6 en remplagant 1'eau du bain coagulant externe par du methanot et en supprimant le sel (NaCI).
Les fibres ont un taux de vide de 69 ~ fl un di:unbtre exte'rieur de w 14 435 a)et iz2terieux= de 275.,40o 11 n y a' pas de pores de diam6tre super. i.eur ou ega7, a. 100 A.
Dans le tableau I on a'indi.que, pour les divers exemplesy quelques caracteris-tiques des P9.bres pr6parees dans les exemples pr6cedents.
~- 15 _ _..._.___.__.-------_.__ - -~ ----_._ I
_..------- -----O o 0 o= ~ 0 c- a, LrN
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ectS E i fA
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ca aP oo Ua -N ~ S=1 cN. r ~ ~ 0 N
'C~ R3 f~ ~ N N N ~:.-f ~ F-1 A 4-!
ot d - -0 P4 0 '~"
w H 0 o 0 0 o o o o 110 10 ~ (1) O r-I o o 0 o o o o o o a o~ m~ i o;o o O o 0 0 o 0 m = s = o = o o o Pl tA 02 0 0 tf\ 0 0 u1 O O U1 O~~ N d' s ' ~ d- d- d-i E-H vo i4 W
n _ ---~ -~ --- -~- -- ---a CH a) oN c~o ~ ! m -P *CS3 Id 0 (a O .' =
(1) f-I (1) 0 r-I =r N'CS O p7 f p) I ay O =~ dS N
~ t~ ~ Q) =ri ! ~ ~ =~ ~ ~ ~ i ~ ~
43y~ rd _P
-- r-1 c~ ~r.{ QS ~ r I N N (t3 rC1 td 'd O rCS O
~.-. .._ _-. ---~ . - -- - -- ~
N cp N OI,frl-t cnv .cd !
or~n.'~ =ri U3 ~
4~ ~ =ca 0 !
p Rw Uo r--! r~i O~.~ N M N N ~ 1 li ttl ! N f !
.~w+, f.~~N~ ~~~a . , , r_.
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pi [Yl ifl L[1 \.o [ -.~ 16 ~
ioz6069 Exem pl e Un collodion prepar e comme h 1'exempJ.e 1 est injecte b raison de 9'4 cm3/mn dans l' orifice ar~nu~.aire d'u.ne fili6re semblable t, celle de 1'exemple 1 La fili6re est dispos6e selon un axe ver:tical et son extr6mite inferieure (orifice) plonge dans une solution aqueuse A 200 g/l de NaCl & 8 C.
Au centre de l'orifice annulaire de la fila,bre, i1 y a un deuxiZme orifice de 0 p 3 mm de diam.btre et par lequel est :injectee dans 1QAme de la fibre creuse naissante une soluta.on aqueuse h 200 g/l de NaCl et ~t 23 C h raison de 1'16 cm3/mn.
La fibre creuse naissan'te parcourt-le.bain coagulant sur une longu.eur de 1 mh une vitesse de 12 m/mn.
A la sortie de ce bain coagul.ant, la fibre ereuse parcourt un bain d'eau boua.llante de 30 cm de longueurp la vitesse d entree de la fibre dans ce bain etant d e 12 m/mn et la vitesse de sortie do 30 m/xnr~; on termine le traitement de la fibre par un lavage & lteau pure par arrosa;ge pendant 'I mn sur des spires enroulees sur un rouleau, La fibre aa.nsi obtenue a un diam6tre de ` 350.,w9 un diam6-tre ex'te'r.ieur de 500.JA)o Le taux de vide est de 60 ~. 11 nly a pas de pores de diara6tre superieur ou egal h 100 A.
A partir de la fibre ainsi preparee' on realise un reacteur enzymatique possedant 300 fibres de 72 cm chacune, di.s-pos6es parall6lemente 72 cm representant la longueur dispon:i.ble powr l tult.rafiltration.
Cet appareil est ut3.la.s6 dans un.e installation telle que'decrite h la figure 1.
A l'int6rxeur des fibres, on fait circuler 1 litre de solution aqueuse d1ur6e h 45 g/l avec un debit de 10,5 1/h.
A l'exterieur des fibres on fait circuler. 0,5 1 dE solu-tion aqueus e d'urease h 10 g/1 avec un d6bit de '"1 t5 1/h.
La temperattz.~re do 1' enremble est de 30 C.
Pou-r determiner la va,tesse dE transformation de 1'ureey on dose pera.oda.quement l.e carbonate d' ammonium forme dans la solution d1ur6e h ltaide dlune solution HC1 N/10 et de ltorar.ge de methyle comme inda.cateur A partir du resui=tat de ce dosage, on calcule la quantite corresp.ondante d'uree qui a6te transfor-m6e' sans faire intervenir dans ce calcul le carbonate d'ammonauwm present dans le circuit de 1.'vsease0 Au bout de 15 mn, 1'uree est transformee ~ raison de 0,8 g/1 Au bout de 45 mn, l'ux Ee est tran:sform6e & raison do 1985 g/1.', h. titre comparatif, si on avait*op6r e par simple melan--ge, 1.gur4e aurait ete transFormee respectivement & raison de 1,5 et3,5g/la Par ailleurs' on n'observe pas d'urease dans le circuit passant par :Ls interieur des fa.bres ~- 18 --6 ~~ 26069 acetam.ide, 1.ehexamethylphosphotriamide t especially dimethyl-formamide (D147F) o Instead of a single solvent, the collodion can be obtained from a mixture of solvents; & this solvent or mels.nge of soil. before we can also add a minor fraction of no n / a: removing pol.yinere p in the mesuse otL Io asleep remains solvent of the polymer of: L, oacrylonitrile.
The concentration of collodion in copolymer of acrylo-na.tra.le is genera: slightly higher than 5% by weight and lower , 10 saturation; it is preferably superior & 20 / in weight.
The eollodion is then coagulated by simple placing in contact with the collodion with the coagulating fluid, imm, eda.a-at the exit of the filicrea Such immediate coagulation-ment at the outlet of a submerged fiber has also been planned in the patent of EõTT.A, 3,674,628, but in the latter process the da, temperature reference between the collodion and the coa-gulant being large enough to .. perform a frozen freeze d: iat. In the process of ln.nventions II 'nty does not have this step 20 of freezing and the temperature difference between the collodion and the coagulating bath is practically lower & 30 C.
Za external coagulation of the nascent hollow fiber . is practically done by circulating said fiber in the process of formation in a bath of coagulating fluid (abbreviated "coagulating bath").
The internal coagulation of the nascent hollow fiber is practically by injection of coagulating fluid into the Arae clest b. say in 11a.ntera.eur of the fiber in way of training.
30 The tera.perature of coagulating fluids and collodion can vary in wide la.mi-tes; they are generally between -10 and +40 C9 preferably comp.rises between 0 and . ~ 7 th_ 30 C. Low temperatures favor: i.sen-t en gEZa.cral 19absence vacuolesa Zan tanperatures of co] .lodion, coagulating fluid internal and industry are substantially equal for technol.og .. reasons; on the other hand the temperature of the bath coagulant can be da.fi'erente of the three aforementioned temperatu-res When the coagulating fluid is an aqueous solution of mineral salt., it is advantageously used, as mi.nera.:t salt, a soluble (in water) salt of alkali or aJ.cal.ino-earthy metal 9 on generally prefers to use sodium chloride. We can however also use chlorides, sulfates, nitrates and lithium perchlorates, sodium, potassium, magnesa.um, calcium, within the limit of their solubility.
the non-solvent power of these aqueous solutions can be modified by adding miscible polar organic solvents wheat, for example dimethylformamide, in proportion preferably infera.eure & 40 When the coagulating fluid is a solvent or mela; cnge polar organic solvents, it is advantageously used as non-solvent for the copolymer of acrylates. Trile of alcohols such as methanol, ethanol., propanol.sy 1.es butanol.s, diols a.liphatiques, in particular e-ethylene glycol, or ketones aliphatics, such as acetone and methyl ethyl ketone; the non-solvent power of this solvent or mixture of solvents can Be modified by adding minor amounts (generally mcaa.ns of 25%) of sol. before the acrylonitrile copolymer such than those cited above (dime-thylformamide, dimethylsulfo-xyde, 'dim6thylace'tamide, hexam6thylphosphot.ra.amide).
During the coagulation part of the solvent of the collodion migrates in the coagulating fluid which, by vo: i, e of Consequently, it can modify its composition somewhat.
In order to ensure uno: Regular and symmetrical corme with hollow fibers, we prefer to position the fiier according to a ~ 8 -x. ~~~~ 69 vertical axis with flow of coLloda.on from top to bottom; the fi.l: i.eres are practically: ilieres: iunwmergees o The contact with the nascent fiber with the coagulating fluids is p: oux ---, followed at Dzoins until the fiber is sufficiently hardened to be easy to handle and not to no longer flow under operating conditions The coagu.l ation tell.e described above can be 0 followed by washing with pure lice water remove most of the non-polymeric fiber constituents (solva.nts and / or salts 7p in particular).
yQs fibers as prepared by the process of coagulation described above can be improved by a treatment aqueous thermal anent in order to improve lev-rs performances and in particular leiz.x permeability The fibers critsées subjected to this process can have undergone a partial washing of pure water or using a mixture of water / organic solvent ma: is, whatever qua1 in soa.t, at the time aqueous heat treatment9 the fibers contain ava.ntageu still a little bit of the constituent solvan-t (s) initially 20 the collodion; more precisely the content of hollow fibers in solvarzt residue; ire during aqueous heat treatment is annoyed ralem.emt between 5 and 20%, preferably between 10 and 17 This aqueous heat treatment consists in immersing the hollow fibers in water or uxt non-solvent aqueous mixture ~
a temperature between 60 and 250 C, preferably between 80 and 990 C, The water or aqueous mixtures used can be vapor phase; however, it is pr. eferable de les uta.:Read in liquid phase Of course the treatment according to the invention in 30 above 100 C may require operating under pressure when wants to use liquid water to perform the -treatment ther-watery mique, ~, . ~ 9 The water content of aqueous mixtures usable in dan.s treatment according to the invention is usually greater than 50% by weight, preferably greater than. 90% of the water can be mixed with organic solvents or zninal electrolytes or organic ma.a, if we prefer to use neutral mixtures chemically and in particular non-basic, in order not to cause chagaic dga-ttaque of the acrylonitrile copolymer. PH
of 6 8 conv3.ent generallym According to an operato mode: i.e advantageous, the treatment .10 'aqueous thermal according to ltinvention is carried out continuously in continuously circulating the fiber in the treatment bath, which is a hot water bath, the pressure then being the pressure atmospheric and the temperature being at most equal to 100 C. I, a treatment time is usually 5 seconds & 5 minutes.
but al nly there is no critical upper.myte for the duration of the treatment The aqueous heat treatment described above is in addition and do preferably accompanied by a longitudinal stretching of fibers; cot eti.rage is usually 50 & 500%, preferably 20 from 100 to 250% o We can finally confer a better stabi: Lite dimension-with stretched fibers by performing relaxation by joining subsequent to these fibers without stretching constraint in a aqueous bath At temperature preferably lower than that of heat treatment Your fibers according to the invention can be stored hl $ wet state in particular glycerine (imaners: ion of fibers in a water / glycerine mixture ~ at least 40% by weight of glycerin) 4 30 I, the fibers according to the invention have an excelient permeabili, te 4 19 eau which 1, es makes it particularly advantageous in ultra filtration as well as in dialysis, no-taulment in her, aod: ia.lyse, They have a low tendency to clogging and a good aptitude for the separation of macromolecular solutes: they can thus be used: Read in very noztibrous applications known do: Llultrafi] .tration. They still have good pressure resistance Among 1.es applications of hollow fibers according to l4 inven--tion, we must also cite the rea7.:l.sation des. enzymatic reactors ques; one such reactor with associated facilities has been identified--, feel & Figure 1 below jo3, nte.
Reactor 1 includes a plurality of hollow fibers 2 and a system of compartments which allows two circulation of liquids inside the hollow fibers, 1, t other a 1 P exterieurQ Le 1.iqu: ide circu] .ant hlp exterieur des hollow fibers successively traverses compartment 3, the line 4, the expansion vessel 5, line 6 and the pump 7; the liquid oircu7, anterior to the hollow fibers successively traverses the compa.rtisaent 8, the pipeline 9, the expansion tank 10 and pipeline 11, pump 12, co-parti-ment 13,: 1es fibers 2.
In such a reactor, the following is performed: 1, o enzyme in solution or suspension of one side of the walls of the hollow fibers and a substratum, in solution or suspension, on the other side of these same walls For the clarity of the exhibit or will choose arbitrarily, dan.sce below, to circulate 1 f enzyrne of hollow fibers and the substratum Inside, it being understood that the opposite is perfectly achievable.
So therefore 'in the device. of figure 1, l 9 enzyme travels the circuit 3, 4, 5, 6 g 79 and the substratum travels the circuit 8, 99 10, 11, 12, 13 and the interieczr fiber channel.
= Enzymes / substratum couples susceptible: i.bles dp Otre m: Is in action dsxzs the native enzyi: reactors are such as the fibers - 11 - ~
10; ~ 6060 hollow are practically: imperrri4able vis ~ vis lt exa.zyme and permeable vis At vis the substratum and re ction products enzymatic; of this ma.na, .bre the separation of the enzyme with its reaction medium (substratum ~ reacta.on products) is easy and the loss of enzymes is minimal.
The hollow fibers according to the invention allow in partieulier to treat decoy by the urease ot ~, their use in artificial kidneys.
The following examples are given without limitation.
trent: The i.nvention showing how it can be implemented convenient. All the hollow fibers of these examples have a rate nu1 salt rejection ..
Example 1 We prepare a "collodion" by dissolving in 76.5 g of dimethylformam: ide (DMF) do 23'5 g of an acrylonitrile copolymer - sodium methallylsulfonate (9% by weight of methallylsul-fate 'or 3.2% by number of sulfonic monomer units;
vi, specific scosite: measured at 25 C in solution h 2 g / l in the DMF: `0990).
This oollodion is injected; N due to ¾, 5 em3 / rnn. in the annular orifice in the shape of a crown of an ilium, having a da.amba axa.terieur: 0 m 6 mm and an outer diameter: 0.8 mm, The thread is arranged along a vertical and soxi axis lower end (orifice) immersed in an aqueous solutio 200 g / l of sodium chloride AL 2 C4 In the center of the orifice annular of the fi.li6re 'there is a devxibme orifice of 0.3 mm diameter and through which is injected into the 9th dimension of the hollow fiber incipient aqueous solution ~ 200 g / 1 of chloride. sodium and 23 C at 1.7 cm3 / mxa The fiber cr use.naissan.te runs vertically through the bath coagulating over a length of 1 year At a speed of 9: m / min; at the exit of this coagulating bath, the hollow fiber travels horizon--r 12 taleraent ur.t ba: in dp boiling water 30: cm long ~ at 1 entry and, hL out of this bath, it is guided by pebbles, the speed of entry of the fiber into this bath being 9 m / inn and the exit speed of 27 m / min; h, sor-L-ie, we wind the fiber on a roller, we finish the treatment of the fiber by washing in pure water by watering for 1 minute on coiled turns.
on the roller, the separation rate of the fibers thus 3, ke.
The fiber thus obtained has a di.oxa6tre interior of 350, a; 6 an outside diameter of 520; at a vacuum rate of 61%; l9 obser-I0 vation with electron microscope: i.que (magnification: 20,000) of cuts of this fiber 'niontre qut there is no pore diambtre super; Them or equal 6. 100 A.
From the fiber thus prepared, a ultrafiltration unit (or module) with 180 fibers of 80 cm long and 64 cm each useful length 9 di.sposées paral.lA7.ement, 64 em representing the length available for 1 ultrafiltration; 1 t device. therefore has an average exchange area from 0 ~ 13 m2q One circulates A llextera.eur of these fibers and under 20 a relative pressure of 2 bars an aqueous solution ~ 1 g / l bovine albumin of molecular weight 70.0000 We obtain an ultrafiltrate with a flow rate of 121 1 / jem2 and a rejection rate of 100%, the rejection rate 6tan.t dei'ini by 1 o expr essxon s 100 x (1 -concen-tration in sol.ute of 1 sul-trafil-brat liquid solute concentration h LL1.tra fil-trer Other performances of these fibers are reported in Table I, together with the performance of the fibers of the exempl, es 2 & 7.
30 EX ~ mple 2 Example 1 is reproduced by changing: The draw rate in 1 s boiling water s the fiber is stretched: e ~ L 1.5 times its lo.
initial, The hollow fiber obtained has an inside diameter of 370 -0J9 and outside 660 -W, The vacuum range is 54 /. he there are no pores with a diameter greater than or equal to 100 A.
Example: L 3 We reproduce I. * example 1 by changing the rate of shelving in boiling water: the fiber is stretched at 5 times its length ] 117. t7., a1 eo The hollow fiber obtained has a diameter inside of 255.jX) and outside 385.tt ~ The vacuum rate is 56%. T1 nay with no pore diameter greater than or equal to 100 A.
Example 4 We reproduce the example 1 by removing the processing h water boua.llanteo Example 5 Example 1 is reproduced with the following modifications.
your - The coagulating fluid ~ 1 ': i.nterieur of the emerging hollow fiber is an aqueous solution at 50 g / l of NaCl (23 C).
- The external coagulating bath is a water / dimei; hyli'oxmamide mixture . in volume proportions 3/1 containing 50. g /], of NaC1 (2500).
The hollow fibers obtained have a void rate of 68 outside diameter from 415 -u and a, from 261 / 1Ja. There is no pore diameter greater than or equal to 100 A.
Ex ..., eRRIe 6 Example 5 is reproduced using a coagulating bath external h 0 C. The fibers have a void rate of 57% q a diam6-be outside 450 / -4 Inside jet 280.u% 11 there is no larger diameter pores: i.or or equal to 100 A.
Example 7 Example 6 is reproduced by replacing the bath water external coagulant with methanot and removing the salt (NaCI).
The fibers have a void rate of 69 ~ fl a di: an outside exterior of w 14 435 a) and iz2terieux = from 275., 40o 11 there are no pores in diameter Great. i.or or ega7, a. 100 A.
In Table I it is indicated that, for the various examples are some of the features of the Prepared Papers in the previous examples.
~ - 15 _ _..._.___.__. ------- _.__ - - ~ ----_._ I
_..------- -----O o 0 o = ~ 0 c- a, LrN
-P oo, 0 ~ o -4- o uti na, N 'I' co O
ectS E i fA
U1 N - .. -. - - _ - i-- - ---N cd ~
ca aP oo Ua -N ~ S = 1 cN. r ~ ~ 0 N
'C ~ R3 f ~ ~ NNN ~: .-f ~ F-1 A 4-!
ot d - -0 P4 0 '~ "
w H 0 o 0 0 oooo 110 10 ~ (1) O rI oo 0 oooooo ao ~ m ~ io; oo O o 0 0 o 0 m = s = o = ooo Pl tA 02 0 0 tf \ 0 0 u1 OO U1 O ~~ N d 's' d- d- d-i EH vo i4 W
n _ --- ~ -~ --- - ~ - - --a CH a) oN c ~ o ~! m -P * CS3 Id 0 (a O. '=
(1) fI (1) 0 rI = r N'CS O p7 fp) I ay O = ~ dS N
~ t ~ ~ Q) = laugh! ~ ~ = ~ ~ ~ ~ i ~ ~
43y ~ rd _P
- r-1 c ~ ~ r. {QS ~ r INN (t3 rC1 td 'd O rCS O
~ .-. .._ _-. --- ~. - - - -- ~
N cp N OI, frl-t cnv .cd!
or ~ n. '~ = ri U3 ~
4 ~ ~ = ca 0 !
p Rw Uo r--! r ~ i O ~. ~ NMNN ~ 1 li ttl! N f!
. ~ w +, f. ~~ N ~ ~~~ a . ,, r_.
---- l ------a ~.,.
pi [Yl ifl L [1 \ .o [-. ~ 16 ~
ioz6069 EXAMPLE A collodion prepared as in example 1 is injected b at a rate of 9'4 cm3 / min in the ar ~ orifice. area of a die similar t, that of example 1 The sector is arranged along a vertical axis and its lower end (orifice) immersed in an aqueous solution At 200 g / l NaCl & 8 C.
In the center of the annular orifice of the fila, bre, there is a second orifice of 0 p 3 mm in diameter and through which : injected into 1QAme of emerging hollow fiber a soluta.on aqueous at 200 g / l NaCl and ~ t 23 C h at the rate of 1'16 cm3 / min.
The emerging hollow fiber runs through it.
over a length of 1 mh a speed of 12 m / min.
At the end of this coagulating bath, the erous fiber travels a 30 cm long moving water bath at speed of fiber entry into this bath being 12 m / min and the speed outlet do 30 m / xnr ~; we end the fiber treatment by washing with pure water by watering for 1 minute on coils wound on a roll, The fiber aa.nsi obtained has a diameter of `350., w9 a diameter-be outside 500.JA) o The vacuum rate is 60 ~. 11 nly a no pore diameter greater than or equal to 100 A.
From the fiber thus prepared, a enzymatic reactor with 300 fibers of 72 cm each, di.s-laid parallel 72 cm representing the available length: i.ble powr l tult.rafiltration.
This device is ut3.la.s6 in an installation such as described in Figure 1.
Inside the fibers, circulate 1 liter of aqueous solution of 45 h / l with a flow rate of 10.5 l / h.
Outside the fibers we circulate. 0.5 1 of solu-aqueous urease at 10 g / l with a flow rate of "1 t5 1 / h.
The temperature of the package is 30 C.
To determine the va, transformation ture of uréey the ammonium carbonate formed in the urea solution using HC1 N / 10 solution and ltorar.ge methyl as an indicator From the result of this assay, the corresponding quantity of urea which has been transformed is calculated.
even without using ammonium carbonate in this calculation present in the circuit of 1.'vsease0 After 15 min, the urea is transformed ~ due to 0.8 g / 1 After 45 min, the flow is clear: shaped & reason 1985 g / 1. ', H. comparative title, if we had * operated by simple melan--age, 1.gur4e would have been transformed respectively & at the rate of 1.5 and3.5g / la Furthermore, we do not observe any urease in the circuit passing by: The interior of the fa.bres ~ - 18 -
Claims (39)
sont définies comme il suit : The embodiments of the invention about which an exclusive right of property or privilege is claimed are defined as follows:
d'un solvant organique polaire miscible, b) un solvant organique polaire, ce solvant étant non solvant vis à vis du copolymère d'acrylonitrile et miscible au solvant du collodion. 1. Process for the preparation of hollow fibers, characteristic in that one injects into a die with an annular orifice a collodion formed from a solution of acrylonitrile copolymer and of olefinically unsaturated comonomer carrying groups sulfonic acids optionally salified in an organic solvent polar and that, immediately at the exit of the die, we coagulate inside and outside of the emerging hollow fiber using of a coagulating fluid chosen from the group consisting of a) aqueous solutions of mineral salts having concentrations below saturation and between 1 and 35% by weight, these solutions optionally including up to 40%
a miscible polar organic solvent, b) a polar organic solvent, this solvent being non solvent with respect to the acrylonitrile copolymer and miscible with collodion solvent.
dans laquelle Y représente un groupe -SO3H ou -SO3M, M étant un atome métallique, R1 et R3 représentent un atome d'hydrogène ou un groupe méthyle, et A représente un lien valenciel, un groupe A' ou un groupe - 0 - A' - , où A' représente un groupement divalent hydrocarboné aliphatique, un noyau aromatique non substitué, ou une chaîne monoaromatique-monoaliphatique dans la-quelle l'une des valences libres est portée par un atome de car-bone aliphatique et l'autre par un atome de carbone aromatique. 5. Method according to claim 1, characterized in what the sulfonic comonomer used has the formula CHR1 = CR3 - A - Y
in which Y represents a group -SO3H or -SO3M, M being a metal atom, R1 and R3 represent a hydrogen atom or a methyl group, and A represents a valence bond, a group A 'or a group - 0 - A' -, where A 'represents a group divalent aliphatic hydrocarbon, a non-aromatic nucleus substituted, or a monoaromatic-monoaliphatic chain in the-which one of the free valences is carried by an atom of car-aliphatic bone and the other by an aromatic carbon atom.
est choisi dans le groupe que constituent les chlorures, sulfates, nitrates et perchlorates de lithium, sodium, potassium, magnesium, calcium, dans la limite de leur solubilité. 11. Method according to claim 10, characterized in what said alkali or alkaline earth metal salt used is chosen from the group consisting of chlorides, sulfates, nitrates and perchlorates of lithium, sodium, potassium, magnesium, calcium, within the limit of their solubility.
dudit fluide coagulant. 14. Method according to claim 13, characterized in what the sector is immersed in a coagulating bath constituted of said coagulating fluid.
longitudinalement à l'intérieur de la fibre, exempt de matériau macromoléculaire, caractérisées en ce que:
1) elles sont constituées d'un copolymère d'acrylonitrile et d'un comonomère oléfiniquement insaturé porteur de groupements sulfoniques éventuellement salifiés, 2) elles possèdent des micropores de diamètre moyen inférieur à 100 .ANG., 3) leurs parois ont un taux de vide compris entre 40 %
et 80 %. 30. Hollow fibers having a continuous channel, arranged longitudinally inside the fiber, free of material macromolecular, characterized in that:
1) they consist of an acrylonitrile copolymer and an olefinically unsaturated comonomer carrying groups possibly salified sulphonics, 2) they have medium diameter micropores less than 100 .ANG., 3) their walls have a vacuum rate of between 40%
and 80%.
CHR1 = CR3 - A - Y (I) dans laquelle Y représente un groupe -SO3H ou -SO3M, M étant un atome métallique, R1 et R3 représentent l'atome d'hydrogène ou un groupe méthyle; A représente un lien valenciel, un groupe A' ou un groupe - O- A' -, où A' représente un groupement divalent hydrocarboné aliphatique, un noyau aromatique non substitué, ou une chaîne monoacromatique-monoaliphatique dans laquelle l'une des valences libres est portée par un atome de carbone aliphatique et l'autre par un atome de carbone aromatique. 32. Hollow fibers according to claim 30, character-laughs in that the sulfonic comonomer has the formula:
CHR1 = CR3 - A - Y (I) in which Y represents a group -SO3H or -SO3M, M being a metal atom, R1 and R3 represent the hydrogen atom or a methyl group; A represents a valence link, a group A 'or a group - O- A' -, where A 'represents a divalent group aliphatic hydrocarbon, an unsubstituted aromatic ring, or a monoacromatic-monoaliphatic chain in which one free valences is carried by an aliphatic carbon atom and the other by an aromatic carbon atom.
spécifique comprise entre 0,1 et 3, cette viscosité étant mesurée a 25° C en solution a 2 g/l dans le diméthylformamide. 36. Hollow fibers according to claim 30, character-that the acrylonitrile copolymer has a viscosity specific between 0.1 and 3, this viscosity being measured at 25 ° C in solution at 2 g / l in dimethylformamide.
spécifique comprise entre 0,5 et 1,5, cette viscosité étant mesurée à 25°C en solution a 2 g/l dans le diméthylformamide. 37. Hollow fibers according to claim 36, character-that the acrylonitrile copolymer has a viscosity specific between 0.5 and 1.5, this viscosity being measured at 25 ° C in solution at 2 g / l in dimethylformamide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3412049.1 | 1984-03-30 | ||
| DE19843412049 DE3412049A1 (en) | 1984-03-30 | 1984-03-30 | SIGNAL-SAFE DATA PROCESSING DEVICE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1226069A true CA1226069A (en) | 1987-08-25 |
Family
ID=6232226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000478040A Expired CA1226069A (en) | 1984-03-30 | 1985-04-01 | Safe data processing device |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0156388A3 (en) |
| JP (1) | JPS60214048A (en) |
| AU (1) | AU572975B2 (en) |
| CA (1) | CA1226069A (en) |
| DD (1) | DD231869A5 (en) |
| DE (1) | DE3412049A1 (en) |
| DK (1) | DK128085A (en) |
| ES (1) | ES8607583A1 (en) |
| FI (1) | FI850869L (en) |
| HU (1) | HU193090B (en) |
| YU (1) | YU22685A (en) |
| ZA (1) | ZA852137B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4959836A (en) * | 1987-12-09 | 1990-09-25 | Siemens Transmission Systems, Inc. | Register robustness improvement circuit and method |
| DE4107639A1 (en) * | 1991-03-09 | 1992-09-10 | Standard Elektrik Lorenz Ag | DEVICE FOR SIGNAL-SAFE REMOTE CONTROL OF A SUBSTATION IN A RAILWAY SYSTEM |
| JP3216996B2 (en) * | 1996-07-19 | 2001-10-09 | 三菱電機株式会社 | Dual electronic interlocking device |
| GB0602641D0 (en) | 2006-02-09 | 2006-03-22 | Eads Defence And Security Syst | High speed data processing system |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2182259A5 (en) * | 1972-04-24 | 1973-12-07 | Cii | |
| DE2939935A1 (en) * | 1979-09-28 | 1981-04-09 | Licentia Patent-Verwaltungs-Gmbh, 6000 Frankfurt | SECURE DATA PROCESSING DEVICE |
| DE3003291C2 (en) * | 1980-01-30 | 1983-02-24 | Siemens AG, 1000 Berlin und 8000 München | Two-channel data processing arrangement for railway safety purposes |
| JPS57164636A (en) * | 1981-04-03 | 1982-10-09 | Hitachi Ltd | Control method for transmission system |
| DE3211265C2 (en) * | 1982-03-26 | 1984-06-20 | Siemens AG, 1000 Berlin und 8000 München | Two-channel fail-safe microcomputer switchgear, especially for railway safety systems |
| DE3279929D1 (en) * | 1982-06-16 | 1989-10-12 | Boeing Co | Autopilot flight director system |
| EP0164414A4 (en) * | 1983-12-12 | 1986-06-05 | Parallel Computers Inc | Computer processor controller. |
-
1984
- 1984-03-30 DE DE19843412049 patent/DE3412049A1/en not_active Ceased
-
1985
- 1985-02-15 YU YU00226/85A patent/YU22685A/en unknown
- 1985-03-04 FI FI850869A patent/FI850869L/en not_active Application Discontinuation
- 1985-03-14 ES ES541268A patent/ES8607583A1/en not_active Expired
- 1985-03-18 AU AU40066/85A patent/AU572975B2/en not_active Expired - Fee Related
- 1985-03-20 JP JP60054741A patent/JPS60214048A/en active Pending
- 1985-03-21 DK DK128085A patent/DK128085A/en not_active Application Discontinuation
- 1985-03-21 ZA ZA852137A patent/ZA852137B/en unknown
- 1985-03-28 DD DD85274552A patent/DD231869A5/en unknown
- 1985-03-28 EP EP85103743A patent/EP0156388A3/en not_active Withdrawn
- 1985-03-29 HU HU851218A patent/HU193090B/en unknown
- 1985-04-01 CA CA000478040A patent/CA1226069A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FI850869L (en) | 1985-10-01 |
| EP0156388A3 (en) | 1988-07-27 |
| DK128085D0 (en) | 1985-03-21 |
| YU22685A (en) | 1987-10-31 |
| ZA852137B (en) | 1985-11-27 |
| ES541268A0 (en) | 1986-06-01 |
| FI850869A0 (en) | 1985-03-04 |
| DE3412049A1 (en) | 1985-10-17 |
| HU193090B (en) | 1987-08-28 |
| AU4006685A (en) | 1985-10-03 |
| JPS60214048A (en) | 1985-10-26 |
| AU572975B2 (en) | 1988-05-19 |
| DD231869A5 (en) | 1986-01-08 |
| ES8607583A1 (en) | 1986-06-01 |
| HUT37517A (en) | 1985-12-28 |
| EP0156388A2 (en) | 1985-10-02 |
| DK128085A (en) | 1985-10-01 |
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