SE432113B - PROCEDURE FOR MANUFACTURING FIBERS WITH POROS STRUCTURE - Google Patents
PROCEDURE FOR MANUFACTURING FIBERS WITH POROS STRUCTUREInfo
- Publication number
- SE432113B SE432113B SE7714702A SE7714702A SE432113B SE 432113 B SE432113 B SE 432113B SE 7714702 A SE7714702 A SE 7714702A SE 7714702 A SE7714702 A SE 7714702A SE 432113 B SE432113 B SE 432113B
- Authority
- SE
- Sweden
- Prior art keywords
- fiber
- fibers
- glycerol
- water
- porous
- Prior art date
Links
- 239000000835 fiber Substances 0.000 title claims description 85
- 238000000034 method Methods 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 13
- 229920002284 Cellulose triacetate Polymers 0.000 claims description 10
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 10
- 238000009987 spinning Methods 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 108090000790 Enzymes Proteins 0.000 description 14
- 102000004190 Enzymes Human genes 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000008363 phosphate buffer Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- YQDHCCVUYCIGSW-LBPRGKRZSA-N ethyl (2s)-2-benzamido-5-(diaminomethylideneamino)pentanoate Chemical group NC(=N)NCCC[C@@H](C(=O)OCC)NC(=O)C1=CC=CC=C1 YQDHCCVUYCIGSW-LBPRGKRZSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000010828 elution Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 4
- 102000004142 Trypsin Human genes 0.000 description 4
- 108090000631 Trypsin Proteins 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000012588 trypsin Substances 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- 238000009739 binding Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000002255 enzymatic effect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 229920002307 Dextran Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 108010073038 Penicillin Amidase Proteins 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000002523 gelfiltration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229940056360 penicillin g Drugs 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- NGHVIOIJCVXTGV-ALEPSDHESA-N 6-aminopenicillanic acid Chemical compound [O-]C(=O)[C@H]1C(C)(C)S[C@@H]2[C@H]([NH3+])C(=O)N21 NGHVIOIJCVXTGV-ALEPSDHESA-N 0.000 description 1
- NGHVIOIJCVXTGV-UHFFFAOYSA-N 6beta-amino-penicillanic acid Natural products OC(=O)C1C(C)(C)SC2C(N)C(=O)N21 NGHVIOIJCVXTGV-UHFFFAOYSA-N 0.000 description 1
- 102000014914 Carrier Proteins Human genes 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- RSYYQCDERUOEFI-JTQLQIEISA-N N-benzoyl-L-arginine Chemical compound NC(=N)NCCC[C@@H](C(O)=O)NC(=O)C1=CC=CC=C1 RSYYQCDERUOEFI-JTQLQIEISA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 108091008324 binding proteins Proteins 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229930195712 glutamate Natural products 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
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- 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
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28023—Fibres or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
- B01J47/127—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes in the form of filaments or fibres
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Zoology (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Genetics & Genomics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Biotechnology (AREA)
- Biomedical Technology (AREA)
- Biochemistry (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Preliminary Treatment Of Fibers (AREA)
- Reinforced Plastic Materials (AREA)
- Peptides Or Proteins (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Description
77174702-3 De pa detta sätt framställda porösa fibrerna har en effektiv ytarea, som är mycket större än för tidigare kända fibrer. Fibrerna kan innehålla funktionella grupper av vilket som helst kemiskt slag, varvid detta är beroende av den polymer som används för tillverkning av fibrerna. De funktionella grupper som finnes kan redan vara anpassade till den avsedda användningen för fibrerna eller ocksa kan de funktionella grupperna modi- fieras genom efterföljande kemiska reaktioner, sa att önskade reaktiva grupper erhålles. The porous fibers produced in this way have an effective surface area which is much larger than for previously known fibers. The fibers may contain functional groups of any chemical type, depending on the polymer used to make the fibers. The functional groups that exist can already be adapted to the intended use of the fibers or the functional groups can also be modified by subsequent chemical reactions, so that the desired reactive groups are obtained.
De mekaniska egenskaperna hos de enligt uppfinningen framställ- da fibrerna är beroende av den använda polymeren och förhållandena vid spinningen. Dessa egenskaper kan varieras inom vissa gränser. För ett givet polymermaterial kan ocksa de förhållanden, under vilka de porösa fibrerna framställes, varieras inom vida gränser. För varje uppsättning av sadana betingelser erhålles en viss effektiv ytarea och en viss uppsättning mekaniska egenskaper hos de framställda fibrerna. Fibrerna kan således lätt anpassas till den avsedda användningen. Naturligtvis är de mekaniska egenskaperna hos porösa fibrer, framställda enligt föreliggandeuuppfinning, ej jämförbara med de mekaniska egenskaper som erfordras hos fibrer för textil användning.The mechanical properties of the fibers produced according to the invention depend on the polymer used and the conditions in the spinning. These properties can be varied within certain limits. For a given polymeric material, the conditions under which the porous fibers are produced can also be varied within wide limits. For each set of such conditions, a certain effective surface area and a certain set of mechanical properties of the fibers produced are obtained. The fibers can thus be easily adapted to the intended use. Of course, the mechanical properties of porous fibers, made according to the present invention, are not comparable to the mechanical properties required of fibers for textile use.
Fibrer framställda enligt uppfinningen kan användas för ett flertal olika ändamål. Da de exempelvis användes som bärande struktur för kemiska reagens, för jonbytargrupper och för kelateringsgrupper, erbjuder de ett större antal funktionella grupper än konventionella reaktiva fibrer. Fibrerna enligt uppfinningen kan användas för framställning av material, som kan extrahera individuella ämnen fràn blandningar, som innehåller manga olika komponenter. i Fibrer framställda enligt uppfinningen kan ocksa användas som bärande struktur för bindning av lösliga katalysatorer, i synnerhet om dessa är ensymer. I det senare fallet erhålles "bundna" katalysatorer, som uppvisar en mycket koncentrerad aktivitet och en hög katalytisk verkningsgrad, även pa substrat med en hög molekylvikt.Fibers made according to the invention can be used for a number of different purposes. For example, since they are used as a support structure for chemical reagents, for ion exchange groups and for chelating groups, they offer a greater number of functional groups than conventional reactive fibers. The fibers of the invention can be used to make materials which can extract individual substances from mixtures containing many different components. Fibers prepared according to the invention can also be used as a support structure for the binding of soluble catalysts, especially if these are enzymes. In the latter case, "bound" catalysts are obtained, which show a very concentrated activity and a high catalytic efficiency, even on substrates with a high molecular weight.
Vidare kan fibrer framställda enligt uppfinningen användas som molekylsilar.Furthermore, fibers prepared according to the invention can be used as molecular sieves.
I det följande skall uppfinningen ytterligare illustreras medelst nagra utföringsexempel pa framställning och användning av porösa fibrer enligt uppfinningen. 10 15 20 25 30 35 40 7714702-3 Exempel l Framställning av porösa fibrer baserade på cellulosatriacetat I en tvâhalsad flaska med en volym av l l och försedd med me- kanisk omrörare löstes 50 g cellulosatriacetat (en kommersiell pro- dukt från firman Montefibre, Pallanza, Italien) i 664 g metylen- klorid. Till denna lösning sattes långsamt 200 g glycerol och hela massan omrördes under 15 minuter vid 800 r/min. Den så erhållna homo- geniserade blandningen kyldes till OOC och hälldes i en behållare försedd med ett spinnmunstycke med 500 hål med en diameter av 125 um.In the following, the invention will be further illustrated by means of some embodiments of the production and use of porous fibers according to the invention. Example 15 Preparation of porous fibers based on cellulose triacetate In a two-necked bottle with a volume of 11 and equipped with a mechanical stirrer, 50 g of cellulose triacetate (a commercial product from the company Montefibre, Pallanza) were dissolved. , Italy) in 664 g of methylene chloride. To this solution was slowly added 200 g of glycerol and the whole mass was stirred for 15 minutes at 800 rpm. The homogenized mixture thus obtained was cooled to 0 ° C and poured into a container provided with a 500-hole spinneret with a diameter of 125 μm.
Massan spanns, genom att den utsattes för ett kvävgastryck av 1 atm, och fibrerna uppsamlades på en rulle efter koagulering i ett toluen- bad vid 20°C. Koaguleringsbadet hade en längd av ca 80 cm. De så er- hållna fibrerna torkades i en torr luftström vid rumstemperatur under 2 timmar och lagrades därefter i en sluten behållare.The pulp was tensioned by subjecting it to a nitrogen pressure of 1 atm, and the fibers were collected on a roll after coagulation in a toluene bath at 20 ° C. The coagulation bath had a length of about 80 cm. The fibers thus obtained were dried in a dry stream of air at room temperature for 2 hours and then stored in a closed container.
Fibrerna hade följande sammansättning,;i vilkt räknat: cellulosatriacetat 18 %, glycerol 70 %, återstoden dvs. 12 % spinn- lösningsmedel. Förhållandet mellan glycerolšoch polymer var 70:18 = 3,86, medan detta förhållande var 4,00 i den för spinning färdiga blandningen. Tillnärmelsevis all den glycerol som fanns i spinnlös- ningen från början, inneslöts således i den¿koagulerade polymer- matrisen, varigenom fiberstrukturen blev porös., De framställda fibrerna kunde befrias från glycerol helt enkelt genom tvättning i vatten. Sedan fibrerna helt befriats från glycerol och spinnlösningsmedlen, hade fibrerna en skenbar specifik vikt av 0,253 + 0,005 g per lineär meter, såsom mätt på det i Exempel 8 beskrivna sättet.The fibers had the following composition, in which: cellulose triacetate 18%, glycerol 70%, the residue i.e. 12% spinning solvent. The ratio of glycerol to polymer was 70:18 = 3.86, while this ratio was 4.00 in the ready-to-spin mixture. Virtually all of the glycerol present in the spin solution from the beginning was thus entrapped in the coagulated polymer matrix, whereby the fiber structure became porous. The fibers produced could be freed from glycerol simply by washing in water. After the fibers were completely freed of the glycerol and the spin solvents, the fibers had an apparent specific gravity of 0.253 + 0.005 g per linear meter, as measured in the manner described in Example 8.
Exempel 2 Framställning av porösa fibrer baserade på poly-L-gamma-metylglutamat I en tvåhalsad flaska med volymen l l och försedd med mekanisk omrörare hälldes 290 g av PLG-30 (tillverkat av Kyowa-Hakko Kogyo Co Ltd..Tokyo, Japan), som är en lösning med en vikt/volymkoncentration av poly-L-gamma-metylglutamat med en molekylvikt av 100000-300000 i 1,2-dikloretan (symmetrisk). Under långsam omrörning tillsattes först 145 g 1,2-dikloretan (symmetrisk) och därefter 50 g av en 50 vikt- pflxæntiglösning av glycerol i vatten. Den slutliga lösningen innehöll sålunda: 23 g poly-L-gamma-metylglutamat 412 g symmetrisk 1,2-dikloretan 28 g vatten I I 28 g glycerol l0 15 20 25 30 35 77142702-3 Blandningen kyldes till 0°C och emulgerades genom omrörning under 30 minuter med 800 r/min, varefter blandningen hälldes i en behållare, som dessförinnan kylts till -6°C och som var försedd med ett spinnmunstycke med 48 hål med en diameter av 80 um. Blandningen spanns, genom att den utsattes för ett kvävgastryck av 0,8 atm.Example 2 Preparation of porous fibers based on poly-L-gamma-methyl glutamate In a two-necked bottle with a volume of 11 and equipped with a mechanical stirrer, 290 g of PLG-30 (manufactured by Kyowa-Hakko Kogyo Co Ltd..Tokyo, Japan) were poured. which is a solution with a weight / volume concentration of poly-L-gamma-methyl glutamate with a molecular weight of 100,000-300000 in 1,2-dichloroethane (symmetrical). With slow stirring, first 145 g of 1,2-dichloroethane (symmetrical) and then 50 g of a 50% by weight solution of glycerol in water were added. The final solution thus contained: 23 g of poly-L-gamma-methylglutamate 412 g of symmetrical 1,2-dichloroethane 28 g of water II 28 g of glycerol 10 77 7722142702-3 The mixture was cooled to 0 ° C and emulsified by stirring under 30 minutes at 800 rpm, after which the mixture was poured into a container, which had previously been cooled to -6 ° C and which was provided with a 48-hole spinneret with a diameter of 80 μm. The mixture was tensioned by exposing it to a nitrogen gas pressure of 0.8 atm.
Fibrerna uppsamlades på en rulle efter koagulering i ett bad av petroleumeter som hölls vid 40-70°C. De koagulerade fibrerna kyldes slutligen till -3°C. De erhållna fibrerna torkades i en luftström vid rumstemperatur under en timme och lagrades därefter i en sluten behållare. Fibrerna hade följande sammansättning, i vikt räknat: 25,5 % poly-L-gamma-metylglutamat, 26,0 % H20; 26,0 % glycerol; 22,5 % spinnlösningsmedel. Förhållandet mellan den dispersa fasen (vatten och glycerol) och polymer i fibrerna var sålunda (26 + 26): 25,5 = 2,04, medan samma förhållande i den för spinning klara bland- ningen var 56:23 = 2,43. -z r i ». 1 Exemgel 3 Framställning av porösa fibrer baserade på polyvinylklorid I en tvåhalsad flaska med volymen 1 l och försedd med mekanisk: omrörare hälldes 47,5 g_av Solvik-523 K (tillverkat av Solvik, Via Filippo Turati 8, Milano, Italien), somíär en sampolymer av vinyl klorid_och vinylacetat innehållande 12 viktprocent vinylacetat, tillsammans med 452,5 g metylenklorid. Denna blandning omrördes, tills sampolymeren var helt löst, varefter 95 g glyceroI'tillsattes långsamt under omrörning. Blandningen kyldes till lO°C och emulgera- des genom omrörning under 15 minuter vid 800 r/min. Den så erhållna massan hälldes i en behållare, som hölls vid l0°C och som var för- sedd med ett spinnmunstycke med l00 hål med en diameter av 80 um.The fibers were collected on a roll after coagulation in a bath of petroleum ether maintained at 40-70 ° C. The coagulated fibers were finally cooled to -3 ° C. The resulting fibers were dried in a stream of air at room temperature for one hour and then stored in a closed container. The fibers had the following composition, by weight: 25.5% poly-L-gamma-methyl glutamate, 26.0% H 2 O; 26.0% glycerol; 22.5% spin solvent. The ratio between the dispersed phase (water and glycerol) and polymer in the fibers was thus (26 + 26): 25.5 = 2.04, while the same ratio in the spinning-ready mixture was 56:23 = 2.43. -z r i ». 1 Example gel 3 Preparation of porous fibers based on polyvinyl chloride In a two-necked bottle with a volume of 1 l and equipped with a mechanical: stirrer was poured 47.5 g_of Solvik-523 K (manufactured by Solvik, Via Filippo Turati 8, Milan, Italy), which is a copolymer of vinyl chloride and vinyl acetate containing 12% by weight of vinyl acetate, together with 452.5 g of methylene chloride. This mixture was stirred until the copolymer was completely dissolved, after which 95 g of glycerol was slowly added with stirring. The mixture was cooled to 10 ° C and emulsified by stirring for 15 minutes at 800 rpm. The mass thus obtained was poured into a container maintained at 10 DEG C. and provided with a spinning nozzle having 100 holes with a diameter of 80 .mu.m.
Spinningen genomfördes med användning av ett tryck av 0,6 atm och fibrerna uppsamlades på en rulle efter koagulering i ett bad av n-hexan, som hölls vid 20°C. De så erhållna fibrerna torkades i en torr luftström under två timmar och lagrades i en sluten behållare.The spinning was performed using a pressure of 0.6 atm and the fibers were collected on a roll after coagulation in a bath of n-hexane, which was kept at 20 ° C. The fibers thus obtained were dried in a dry stream of air for two hours and stored in a closed container.
Fibrerna hade följande sammansättning, i vikt räknat: 29,5 % sam- polymer Solvik-523 K; 57,9 % glycerol; 12,6 % spinnlösningsmedel. Även i detta fall hade varje gram av koagulerad polymermatris hållit kvar l,96 g glycerol, som var finfördelat i polymermatrisen, så att denna var porös. 10 15 20 25 30 35 40 7714702-3 Exempel 4 Användning av porösa fibrer av cellulosatriacetat som ett substrat för kemisk immobilisering av proteiner Följande tre typer av fibrer undersöktes: A) En porös fiber som erhölls genom att man på det i Exempel 1 beskrivna sättet spann 50 g cellulosatriacetat löst i 664 g metylen- klorid och 200 g glycerol som den dispersa fasen till 500 enfiber~ trådar, vardera med 3,7 denier.The fibers had the following composition, by weight: 29.5% copolymer Solvik-523 K; 57.9% glycerol; 12.6% spin solvent. Also in this case, each gram of coagulated polymer matrix had retained 1.96 g of glycerol, which was finely divided in the polymer matrix so that it was porous. Example 15 Use of porous fibers of cellulose triacetate as a substrate for chemical immobilization of proteins The following three types of fibers were examined: A) A porous fiber obtained by using the method described in Example 1 Spread 50 g of cellulose triacetate dissolved in 664 g of methylene chloride and 200 g of glycerol as the dispersed phase into 500 monofilament yarns, each with 3.7 denier.
B) En porös fiber framställd på samma sätt som fibern enligt A) men med användning av 100 g glycerol som den dispersa fasen. Även i detta fall framställdes 500 enfibertrådar vardera med 3,7 denier.B) A porous fiber prepared in the same way as the fiber according to A) but using 100 g of glycerol as the dispersed phase. Also in this case, 500 monofilaments were each made with 3.7 denier.
C) En icke porös fiber framställd på samma sätt som fibern enligt A) och B) men utan användning av någon dispers fas. Även i detta fall framställdes 500 enfibertrâdar vardera med 3,9 denier.C) A non-porous fiber prepared in the same way as the fiber according to A) and B) but without the use of any dispersed phase. Also in this case, 500 monofilament yarns each of 3.9 denier were produced.
De ovan angivna denier-värdena är medelvärden erhållna från 10 avläsningar utförda på följande sätt: Ett prov om 500 enfiber- trådar med en längd av 100 cm utsattes för Sítvättningar i destille- rat vatten, varvid man för varje tvättning använde 50 ml vatten och en kontakttid av 10 min. Tvättningen genomfördes under omrörning vid rumstemperatur. Efter tvättningen torkades provet i en ugn vid 70°C och ett tryck av 0,1 mm Hg under 8 timmar, varefter provet vägdes.The above denier values are averages obtained from 10 readings made as follows: A sample of 500 monofilaments with a length of 100 cm was subjected to Sitt washing in distilled water, using for each wash 50 ml of water and a contact time of 10 min. The washing was carried out with stirring at room temperature. After washing, the sample was dried in an oven at 70 ° C and a pressure of 0.1 mm Hg for 8 hours, after which the sample was weighed.
Från den så erhållna torrvikten för hela provet bestämdes denier- värdet för varje individuell enfibertråd, genom att den“erhållna torrvikten i gram multiplicerades med 9000:500.From the dry weight thus obtained for the whole sample, the denier value of each individual monofilament was determined by multiplying the “obtained dry weight in grams by 9000: 500.
Från varje fiber togs ett prov på sådant sätt att det innehöll lika stor mängd, dvs. 1,78 g, cellulosatriacetat, och sålunda togs exakt 9,89 g av fibern A), 5.78 g av fibern B) och 1,85 g av fibern C). Varje prov infördes i en Erlenmeyer-flaska med volymen 300 ml och tvättades fem gånger med destillerat vatten, varje gång med 200 ml vatten, och behandlades därefter under fyra timmar under långsam omrörning och vid rumstemperatur med 200 ml av en 0,5 M vattenlösning av natriumhydroxid. Denna behandling omvandlar den ursprungliga polymeren till cellulosa och är sådan, att den åtmin- stone delvis bibehåller fíberns ursprungliga struktur, såsom framgår av de i det fölfande beskrivna resultaten. Efter hydrolyseringen tvättades varje prov med vatten, tills det blev neutralt, och be- handlades vid rumstemperatur under långsam omrörning och under 20 timmar med 165 ml av en vattenlösning av 0,05 M fosfatbuffert, pH = 8,0, innehållande 0,285 g bensokinon (denna behandling aktiverar fibern och gör den ägnad att kemiskt binda protein enligt den metod lO 15 20 25 30 35 77í41u2-s 6 som finnes beskriven i den svenska patentansökningen 7604136-7).From each fiber a sample was taken in such a way that it contained an equal amount, ie. 1.78 g, cellulose triacetate, and thus exactly 9.89 g of fiber A), 5.78 g of fiber B) and 1.85 g of fiber C) were taken. Each sample was placed in a 300 ml Erlenmeyer flask and washed five times with distilled water, each time with 200 ml of water, and then treated for four hours with slow stirring and at room temperature with 200 ml of a 0.5 M aqueous solution of sodium hydroxide. This treatment converts the original polymer to cellulose and is such that it at least partially retains the original structure of the fiber, as can be seen from the results described below. After the hydrolysis, each sample was washed with water until neutral, and treated at room temperature with slow stirring and for 20 hours with 165 ml of an aqueous solution of 0.05 M phosphate buffer, pH = 8.0, containing 0.285 g of benzoquinone ( this treatment activates the fiber and makes it suitable for chemically binding protein according to the method 10 15 20 25 30 35 77í41u2-s 6 described in the Swedish patent application 7604136-7).
Efter denna behandling tvättades varje fiberprov växelvis med vatten och med en 0,05 M fosfatbuffert med pH = 8,0, tills tvätt- vatten ej längre innehöll något ämne med absorptionsförmåga vid 250 nm. Därefter underkastades fiberproven ett prov med avseende på bindning av tripsin. Varje fiberprov bringades i kontakt med 47 ml av en 0,05 M fosfatbuffert, pH = 8,0, som var nedkyld till 2°C och som innehöll 47 mg tripsin med en specifik aktivitet av 30 BAEE-enheter per mg (en enzymisk BAEE-enhet är den mängd enzym som hydrolyserar en pmol per minut av N-alfa-benzoy1-L-argininmetylester vid ett pH av 8,0 och vid en temperatur av 25°C). Reaktionen genomfördes under 24 timmar under långsam omrörning och vid 2°C. Efter fullbordad reaktion tvättades de tre fiberproven växelvis med vatten och med en 0,05 M fosfatbuffert, pH = 8,0, tills ingen enzymaktivitet kunde i tvät ttnet - Q upptäckäâ. Efter fullbordad proteinbindingsreaktion mattes den reste- rande enzymaktiviteten hos reaktionslösningen. Den var: 7§9 BAEE-enheter/ml Lösning i kontakt med fiberprøv 13): 13,1 - " .- 25,2 - " - Vid mätning av den vid fiberproven bundna enzymaktiviteten Lösning i kontakt med fiberprov A): Lösning i kontakt med fiberprov C): erhölls följande värden: Fiber A) 650 BAEE-enheter per gram torr produkt Fiber B) 450 - " - ^ _h 'Fiber C) 80 - " - Exempel 5 -~¿ Användning av porösa fibrer baserade på cellulosatriacetat som ett substrat för kemisk immobilisering av proteiner 494 g av fibern A) enligt Exempel 4 tvättades med vatten, hydrolyserades därefter med 100 ml av 0,5 M NaOH och underkastades -därefter en aktiveringsreaktion med 83 ml av 0,05 M fosfatbuffert, pH = 8,0, innehållande 0,142 g bensokinon. Därefter tvättades fibern.After this treatment, each fiber sample was washed alternately with water and with a 0.05 M phosphate buffer at pH = 8.0, until wash water no longer contained any substance with an absorbance at 250 nm. Thereafter, the fiber samples were subjected to a trypsin binding test. Each fiber sample was contacted with 47 ml of a 0.05 M phosphate buffer, pH = 8.0, which was cooled to 2 ° C and contained 47 mg of trypsin with a specific activity of 30 BAEE units per mg (an enzymatic BAEE unit is the amount of enzyme which hydrolyses one pmol per minute of N-alpha-benzoyl-L-arginine methyl ester at a pH of 8.0 and at a temperature of 25 ° C). The reaction was carried out for 24 hours with slow stirring and at 2 ° C. After completion of the reaction, the three fiber samples were washed alternately with water and with a 0.05 M phosphate buffer, pH = 8.0, until no enzyme activity could be detected in the wash. After completion of the protein binding reaction, the remaining enzyme activity of the reaction solution was matted. It was: 7§9 BAEE units / ml Solution in contact with fiber samples 13): 13,1 - ".- 25,2 -" - When measuring the enzyme activity bound to the fiber samples Solution in contact with fiber samples A): Solution in contact with fiber sample C): the following values were obtained: Fiber A) 650 BAEE units per gram of dry product Fiber B) 450 - "- ^ _h 'Fiber C) 80 -" - Example 5 - ~ ¿Use of porous fibers based on cellulose triacetate as a substrate for chemical immobilization of proteins 494 g of the fiber A) according to Example 4 were washed with water, then hydrolyzed with 100 ml of 0.5 M NaOH and then subjected to an activation reaction with 83 ml of 0.05 M phosphate buffer, pH = 8.0, containing 0.142 g of benzoquinone. Then the fiber was washed.
Denna procedur är identisk med den som användes i Exempel 4. Det så erhållna fiberprovet reagerades med enzymet penicillinacylas under följande betingelser. Provet kontakterades under långsam om- rörning under 24 timmar vid rumstemperatur med 25 ml av en 0,04 M fosfatbuffert, pH = 7,6, som innehöll 38 enheter/ml av penicillin- acylas från Escherichia Coli (ATCC-9637) med en specifik aktivitet _ _ __ _ lar l nmol/min av 5 enheter per .ng protein. (En enzymisk enhet ar den mängd enzym scm cmvand 10 15 20 25 30 35 7714702-3 ...n- 7 av penicillin G till 6-aminopenicillansyra och fenylättiksyra under följande betingelser: temperatur 37°C, pH = 8,0, fosfatbuffert 0,01! och penicillin G = 2 % vikt volym, total volym 200 ml och totalt 15-30 enzymiska enheter närvarande. Under dessa betingelser överens- stämmer måttet på den enzymiska reaktionens begynnelsehastighet, såsom uttryckt i umol per minut, med de enzymiska enheterna själva.) Sedan provet tvättats för avlägsnande av oreagerat enzym på det i Exempel 4 beskrivna sättet, bestämdes den enzymiska aktivitet som fanns kvar bunden vid fiberprovet. Denna aktivitet var 444 umol per minut och per gram av torr produkt.This procedure is identical to that used in Example 4. The fiber sample thus obtained was reacted with the enzyme penicillin acylase under the following conditions. The sample was contacted with slow stirring for 24 hours at room temperature with 25 ml of a 0.04 M phosphate buffer, pH = 7.6, containing 38 units / ml of penicillin acylase from Escherichia Coli (ATCC-9637) with a specific activity _ _ __ _ allows l nmol / min of 5 units per .ng protein. An enzymatic unit is the amount of enzyme converted to penicillin G to 6-aminopenicillanic acid and phenylacetic acid under the following conditions: temperature 37 ° C, pH = 8.0, phosphate buffer 0.01! And penicillin G = 2% by weight, total volume 200 ml and a total of 15-30 enzyme units present, under these conditions the measure of the initial rate of the enzymatic reaction, as expressed in μmol per minute, corresponds to the enzyme units After the sample was washed to remove unreacted enzyme in the manner described in Example 4, the enzymatic activity remaining bound to the fiber sample was determined. This activity was 444 μmol per minute and per gram of dry product.
Exempel 6 Användning av porösa fibrer av poly-L-gammaetylglutamat som ett substrat för kemisk immobilisering av proteiner 3,92 g av den enligt Exempel 2 framställda fibern av poly-L- gammametylglutamat tvättades med 50 ml destillerat vatten 4 gånger för avlägsnande av glycerol och därefter 5 gånger med absolut metanol 50 ml varje gång, för avlägsnande av vatten,foch uppslammades slut- ligen i 50 ml absolut metanol innehållande 2,0 mmol hydrazinhydrat.Example 6 Use of porous fibers of poly-L-gammaethyl glutamate as a substrate for chemical immobilization of proteins 3.92 g of the fiber of poly-L-gamma methyl glutamate prepared according to Example 2 were washed with 50 ml of distilled water 4 times to remove glycerol and then 5 times with absolute methanol 50 ml each time, to remove water, and finally slurried in 50 ml of absolute methanol containing 2.0 mmol of hydrazine hydrate.
Blandningen hölls under långsam omrörning vid rumstemperatur. Reak- tionen övervakades genom titrering av förlusten av hydrazin från reaktionslösningen. Sedan 0,98 mmol hydrazin försvunnit från lös- ningen, avbröts reaktionen, genom att fibersubstratet filtrerades bort från metanollösningen och tvättades 3 gånger med 50~ml metanol.The mixture was kept under slow stirring at room temperature. The reaction was monitored by titrating the loss of hydrazine from the reaction solution. After 0.98 mmol of hydrazine had disappeared from the solution, the reaction was stopped by filtering off the fibrous substrate from the methanol solution and washing 3 times with 50 ml of methanol.
Fibersubstratet tvättades därefter med kallt vatten(l-2°C) och ned- sänktes därefter i l00 ml av 0,5 M vattenlösning av HGl, som hölls på ett isbad. Till denna blandning, som hölls under omrörning, till- sattes i små steg under 15 minuter 1 g natriumnitrit. Efter denna tillsättning hölls massan under omrörning i kallt tillstånd under en timme, varefter fibersubstratet tvättades med en kall 0,01 M vattenlösning av HCl. Till sist indränktes fibern i 100 ml av 0,1 M fosfatbuffert, pH = 8,5, innehållande 100 mg tripsin med en specifik aktivitet av 30 BAEE-enheter/mg. Massan rördes om under natten vid OOC. Fibersubstratet tvättades med vatten, tills ingen enzymaktivi- tet längre kunde upptäckas i vattnet, varefter den vid fibern bundna enzymaktiviteten uppmättes. Den uppgick till 350 BAEE-enheter per gram torr produkt. 10 l5 20 25 30 35 40 7714702-3 å Exempel 7 Användning av porösa fibrer av polyvinylklorid som ett substrat för kemisk immobilisering av proteiner 3,39 g av den i enlighet med Exempel 3 framställda fibern tvättades 4 gånger med vatten, varje gång 50 ml vatten, och därefter 5 gånger med absolut metanol, 50 ml metanol varje gång, och ned- sänktes slutligen i 100 ml absolut metanol innehållande l ml kon- centrerad svavelsyra under 6 timmar. Fibern uppsamlades därefter på ett filter och tvättades med 50 ml toluen. Den så behandlade fibern nedsänktes i en lösning 2 gånger med 50 ml metanol och 4 gånger av 5 g fosgen i 100 ml toluen vid rumstemperatur och hölls under omrörning över natten. Därefter avlägsnades överskottet av fosgen genom tvättning med toluen (5 gånger med 50 ml), varefter fibern torkades i rumstemperatur i en torr kvävgasström. Fibern nedsänktes därefter i 100 ml av en 0,1 M fosfatbuffert,:pH = 7,5, kyld till OOC och innehållande 100 mg tripsin med en specifik aktivitet av 30 BAEE- enheter/mg. Massan hölls under omrörning i kållt tillstånd under 20 timmar. Till sist avlägsnades oreagerat enzym genom tvättning av vatten, tills ingen enzymaktivitet kunde upptäckas i tvättvattnet.The fibrous substrate was then washed with cold water (1-2 ° C) and then immersed in 100 ml of 0.5 M aqueous solution of HG1, which was kept on an ice bath. To this mixture, which was kept under stirring, was added in small steps over 15 minutes 1 g of sodium nitrite. After this addition, the mass was kept under stirring in the cold state for one hour, after which the fibrous substrate was washed with a cold 0.01 M aqueous solution of HCl. Finally, the fiber was soaked in 100 ml of 0.1 M phosphate buffer, pH = 8.5, containing 100 mg of trypsin with a specific activity of 30 BAEE units / mg. The mass was stirred overnight at 0 ° C. The fibrous substrate was washed with water until no more enzyme activity could be detected in the water, after which the enzyme activity bound to the fiber was measured. It amounted to 350 BAEE units per gram of dry product. Example 7 Use of porous fibers of polyvinyl chloride as a substrate for chemical immobilization of proteins 3.39 g of the fiber prepared according to Example 3 were washed 4 times with water, each time 50 ml water, and then 5 times with absolute methanol, 50 ml of methanol each time, and finally immersed in 100 ml of absolute methanol containing 1 ml of concentrated sulfuric acid for 6 hours. The fiber was then collected on a filter and washed with 50 ml of toluene. The fiber thus treated was immersed in a solution twice with 50 ml of methanol and 4 times of 5 g of phosgene in 100 ml of toluene at room temperature and kept under stirring overnight. Thereafter, the excess phosgene was removed by washing with toluene (5 times with 50 ml), after which the fiber was dried at room temperature in a dry stream of nitrogen. The fiber was then immersed in 100 ml of a 0.1 M phosphate buffer, pH = 7.5, cooled to 0 ° C and containing 100 mg of trypsin with a specific activity of 30 BAEE units / mg. The mass was kept under stirring in a cold state for 20 hours. Finally, unreacted enzyme was removed by washing water until no enzyme activity could be detected in the wash water.
Det så erhållna fibermaterialet uppvisade en enzymaktivitet av 250 BAEE-enheter per gram torr produkt. a Exempel 8 Användning_avpporösa fibrer av cellulosatriacetat som molekylsil 137 g av cellulosatriacetatfiber framställd på det i Exempel l beskrivna sättet och innehållande 24,6 g polymer klipptes upp i stapelfibrer med en längd av 0,3-0,6 cm och packades i en kolonn med en diameter av 2,5 cm upp till en nivå av 34,7 cm, så att fibern upptog en total volym av l70 ml i bädden. Den så packade fibern befriades från luftbubblor och tvättades samtidigt genom eluering av densamma med ca 5 l vatten, som dessförinnan avgasats under vakuum. Den så erhållna kolonnen visade sig ha egenskaperna av en molekylsil. Då den utsattes för gelfiltreringsmätningar med använd- ning av en vattenlösning av KCl (l3,3 g/1) som eluant, erhöll man för Blue Dextran 2000 (en produkt från Pharmacia-Fine Chemicals AB, Uppsala, Sverige) med en molekylvikt av 2 000 000 en elueringsvolym av 73 ml. Detta värde var konstant inom ett flödesintervall från 5 ml/h till 50 ml/h. Elueringsvolymen för kaliumbikromat med en molekylvikt av 294 varierade däremot mellan 128 ml vid 7,5 ml/h och ll8 ml vid 45 ml/h. Dessa data visar, att fibern fungerar som en molekylsil. Samtidigt erhålles en metod för bestämning av fiberns 10 15 7714702-5 9 skenbara densitet: 170 ml (total bäddvolym) - 73 ml (tom volym i kolonnen) = 97 ml. Sålunda upptog 24,6 g polymer en volym av 97 ml, varför 24,6:97 = 0,253 g/ml.The fibrous material thus obtained showed an enzyme activity of 250 BAEE units per gram of dry product. Example 8 Use of porous cellulose triacetate fibers as molecular sieve 137 g of cellulose triacetate fiber prepared in the manner described in Example 1 and containing 24.6 g of polymer were cut into staple fibers 0.3-0.6 cm in length and packed in a column with a diameter of 2.5 cm up to a level of 34.7 cm, so that the fiber took up a total volume of l70 ml in the bed. The fiber so packed was freed from air bubbles and washed simultaneously by eluting it with about 5 liters of water, which had previously been degassed under vacuum. The column thus obtained was found to have the properties of a molecular sieve. When subjected to gel filtration measurements using an aqueous solution of KCl (13.3 g / l) as eluent, Blue Dextran 2000 (a product of Pharmacia-Fine Chemicals AB, Uppsala, Sweden) having a molecular weight of 2 was obtained. 000,000 an elution volume of 73 ml. This value was constant in a flow range from 5 ml / h to 50 ml / h. In contrast, the elution volume of potassium bichromate having a molecular weight of 294 varied between 128 ml at 7.5 ml / h and 18 ml at 45 ml / h. These data show that the fiber acts as a molecular sieve. At the same time a method is obtained for determining the apparent density of the fiber: 170 ml (total bed volume) - 73 ml (empty volume in the column) = 97 ml. Thus, 24.6 g of polymer occupied a volume of 97 ml, so that 24.6: 97 = 0.253 g / ml.
All fiber i kolonnen omvandlades därefter till cellulosa genom behandling med en 0,5 M vattenlösning av natriumhydroxid vid rums- temperatur under 8 timmar, varefter fibern packades i samma kolonn som tidigare och underkastades samma gelfiltreringsmätningar. Resul- taten blev: Total bäddvolynl = 100 ml Elueringsvolym för Blue-Dextran 2000 = 38 ml Elueringsvolym för kaliumbikromat = 92 ml I detta fall var elueringsvolymén för kaliumbikromat åter kon- stant inom samma flödesintervall.All fiber in the column was then converted to cellulose by treatment with a 0.5 M aqueous solution of sodium hydroxide at room temperature for 8 hours, after which the fiber was packed in the same column as before and subjected to the same gel filtration measurements. The results were: Total bed volume = 100 ml Elution volume for Blue-Dextran 2000 = 38 ml Elution volume for potassium bichromate = 92 ml In this case, the elution volume for potassium bichromate was again constant within the same flow range.
Slutligen bestämdes fiberns torrvikt genom torkning av fibern vid 80°C under vakuum. Torrvikten var 14,1 gi Den skenbara densiteten hos den erhållna cellulosafibern var sålundašl4,l : (100-38) = 0,227 g/ml. IFinally, the dry weight of the fiber was determined by drying the fiber at 80 ° C under vacuum. The dry weight was 14.1 g. The apparent density of the resulting cellulosic fiber was thus 4.11: (100-38) = 0.227 g / ml. IN
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IT30799/76A IT1065294B (en) | 1976-12-23 | 1976-12-23 | PROCEDURE FOR THE PREPARATION OF POROUS STRUCTURED FIBERS, POROUS FIBERS OBTAINED AND USES OF THE SAME |
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SE7714702L SE7714702L (en) | 1978-06-24 |
SE432113B true SE432113B (en) | 1984-03-19 |
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SE7714702A SE432113B (en) | 1976-12-23 | 1977-12-22 | PROCEDURE FOR MANUFACTURING FIBERS WITH POROS STRUCTURE |
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JP (1) | JPS5381718A (en) |
AU (1) | AU509081B2 (en) |
BE (1) | BE862287A (en) |
CH (1) | CH636381A5 (en) |
CS (1) | CS208154B2 (en) |
DD (2) | DD142897A5 (en) |
DE (1) | DE2757787B2 (en) |
DK (1) | DK575677A (en) |
FR (1) | FR2375280A1 (en) |
GB (1) | GB1572196A (en) |
HU (1) | HU177739B (en) |
IT (1) | IT1065294B (en) |
LU (1) | LU78740A1 (en) |
NL (1) | NL7714212A (en) |
NO (1) | NO774403L (en) |
SE (1) | SE432113B (en) |
YU (1) | YU299777A (en) |
ZA (1) | ZA776996B (en) |
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DE2755341C2 (en) | 1977-12-12 | 1983-09-08 | Akzo Gmbh, 5600 Wuppertal | Hydrophilic polyester fibers |
DE2906056A1 (en) * | 1979-02-16 | 1980-08-28 | Linde Ag | METHOD FOR RECOVERY OF THE SALTS OF ANTHRACHINON DISULPHONIC ACIDS FROM A WASHING LIQUID FLOW |
JPS56140113A (en) * | 1980-03-28 | 1981-11-02 | Kuraray Co Ltd | Synthetic polyvinyl alcohol fiber having improved adhesive property to cement and its preparation |
FR2565841B1 (en) * | 1984-06-14 | 1989-08-18 | Inst Nat Rech Chimique | MATERIAL WITH A LARGE SPECIFIC SURFACE AND ITS APPLICATIONS FOR PROMOTING CONTACT BETWEEN MEDIA OR REAGENTS INVOLVING PHYSICAL AND / OR CHEMICAL, AND / OR BIOLOGICAL PHENOMENES |
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BE336521A (en) * | 1925-09-17 | |||
GB802689A (en) * | 1955-08-06 | 1958-10-08 | British Nylon Spinners Ltd | Improvements in or relating to yarn comprising crimped filaments and its manufacture |
IL32406A (en) * | 1968-06-26 | 1973-01-30 | Snam Progetti | Enzyme preparations comprising a solution or dispersion of enzyme occluded in filaments of cellulose esters or synthetic polymers |
IT941398B (en) * | 1971-04-28 | 1973-03-01 | Snam Progetti | DEVICE TO CARRY OUT ANALS IN THE FIELD OF ORGANIC CHEMISTRY |
IT1012509B (en) * | 1971-05-26 | 1977-03-10 | Snam Progetti | PROCEDURE FOR THE PREPARATION OF ORGANIC COMPOUNDS CONTAINING MARKED ATOMS |
DE2158124C3 (en) * | 1971-11-24 | 1975-03-13 | Boehringer Mannheim Gmbh, 6800 Mannheim | Use of polyamide fleece or felt as an absorbent carrier for diagnostic agents |
JPS4911793A (en) * | 1972-05-10 | 1974-02-01 | ||
JPS554842B2 (en) * | 1972-06-30 | 1980-02-01 | ||
CH586726A5 (en) * | 1972-08-02 | 1977-04-15 | Basf Ag | |
IT1017564B (en) * | 1974-04-30 | 1977-08-10 | Snam Progetti | PROCESS FOR THE PREPARATION OF FUNCTIONALIZED ADENINE DERIVATIVES AND PRODUCTS THUS OBTAINED |
IT1046849B (en) * | 1974-06-12 | 1980-07-31 | Snam Progetti | PROCESS FOR THE PREPARATION OF RENATED MACROMOLECULAR ADENINE DERIVATIVES AND PRODUCTS SO OBTAINED |
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1976
- 1976-12-23 IT IT30799/76A patent/IT1065294B/en active
-
1977
- 1977-11-24 ZA ZA00776996A patent/ZA776996B/en unknown
- 1977-11-28 AU AU30993/77A patent/AU509081B2/en not_active Expired
- 1977-12-06 GB GB50824/77A patent/GB1572196A/en not_active Expired
- 1977-12-14 CH CH1538477A patent/CH636381A5/en not_active IP Right Cessation
- 1977-12-16 YU YU02997/77A patent/YU299777A/en unknown
- 1977-12-20 CS CS778594A patent/CS208154B2/en unknown
- 1977-12-21 DD DD77212117A patent/DD142897A5/en unknown
- 1977-12-21 LU LU78740A patent/LU78740A1/xx unknown
- 1977-12-21 NO NO774403A patent/NO774403L/en unknown
- 1977-12-21 DD DD77202853A patent/DD136856A5/en unknown
- 1977-12-21 NL NL7714212A patent/NL7714212A/en not_active Application Discontinuation
- 1977-12-22 HU HU77SA3083A patent/HU177739B/en unknown
- 1977-12-22 DK DK575677A patent/DK575677A/en not_active Application Discontinuation
- 1977-12-22 SE SE7714702A patent/SE432113B/en unknown
- 1977-12-22 FR FR7738885A patent/FR2375280A1/en active Granted
- 1977-12-23 DE DE2757787A patent/DE2757787B2/en not_active Ceased
- 1977-12-23 BE BE183815A patent/BE862287A/en not_active IP Right Cessation
- 1977-12-23 JP JP15460777A patent/JPS5381718A/en active Pending
Also Published As
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DD136856A5 (en) | 1979-08-01 |
YU299777A (en) | 1982-08-31 |
DK575677A (en) | 1978-06-24 |
LU78740A1 (en) | 1978-04-17 |
FR2375280A1 (en) | 1978-07-21 |
AU509081B2 (en) | 1980-04-17 |
BE862287A (en) | 1978-06-23 |
HU177739B (en) | 1981-12-28 |
DE2757787A1 (en) | 1978-06-29 |
FR2375280B1 (en) | 1981-06-19 |
NO774403L (en) | 1978-06-26 |
CH636381A5 (en) | 1983-05-31 |
JPS5381718A (en) | 1978-07-19 |
DE2757787B2 (en) | 1979-08-16 |
IT1065294B (en) | 1985-02-25 |
DD142897A5 (en) | 1980-07-16 |
ZA776996B (en) | 1978-09-27 |
SE7714702L (en) | 1978-06-24 |
GB1572196A (en) | 1980-07-23 |
CS208154B2 (en) | 1981-08-31 |
AU3099377A (en) | 1979-06-28 |
NL7714212A (en) | 1978-06-27 |
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