DD142897A5 - USING FIBERS WITH POROESER STRUCTURE - Google Patents

Description

21211

Using Fas von_ ren with porous he St stru ctu re Field of the Invention

The invention relates to the use of fibers or _c threads or yarns having a porous structure,

These fibers with a porous structure have a very effective surface, a good dimensional stability, good mechanical properties, a good resistance to deformation and / or life and are very versatile in their application.

They can be used, for example, as a substrate of chemical reagents, as a substrate for chelating agents, for producing ion exchange materials as substrates for insolubilizing soluble catalysts, as substrates for insolubilization of proteins and. Enzymes, as substrates for the insolubilization of selective enzyme inhibitors, for the preparation of materials suitable for the removal of individual substances from mixtures consisting of several components, and as materials which behave like molecular sieves.

Characteristic of the known technical solutions

There is no information as to whether or not there are already porous structure fibers that are so versatile

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are applicable »gives. There is also no information available on how to prepare such porous structure porous fibers.

The aim of the invention is the use of porous structure fibers which can be advantageously and very versatile in chemical reactions.

Porous structure fibers are made by:

a) a polymer dissolves or melts,

b) homogeneously dispersed in the polymer composition a non-miscible liquid or an insoluble pesticide in a finely divided state,

c) the resulting mixture is spun and ά) the disperse phase is removed.

The polymer of a) is selected from cellulose, cellulose esters, cellulose ethers, cellulose nitrate. Polyamides, polyesters, polyesteramides, polyimides, polypeptides, polymers and copolymers of acrylonitrile, methacrylonitrile, acrylic acid and methacrylic acid esters, vinyl esters and ethers, polymers of vinyl chloride, vinylidene chloride, vinyl butyral and styrene,

The spinning according to c) takes place by hate spinning, drying «

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spin oaer melt spinning,

The porous fibers thus produced have a useful surface area larger than the fibers known hitherto; they may contain functional groups of any nature; this represents a puncture of the polymer chosen for their preparation, the only limitation being the ability of the respective polymer to form fibers. The functional groups which are present may already be adapted to the intended use for the fibers or may be added by such groups chemical reactions to form the corresponding reactive groups are modified «

The mechanical properties of these porous fibers are a function of the polymer and the spinning conditions. These properties can be varied within a wide range because the number of polymer materials useful in the invention is very large Polymer material also varies the conditions under which the porous fibers can be obtained within a wider range. Thus, each particular condition corresponds to a suitable useful surface and a particular number of mechanical properties. "The fibers can thus be chosen according to the particular application for which they are intended. Of course, the mechanical properties are not comparable with those required for textile purposes

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The porous fibers may be very suitable for many practical applications. When used as support members for chemical reagents, for ion exchange groups, for chelating groups, they have a number of suitable functional groups which are larger than those in customary reactive polyesters. The new porous fibers can be used to make materials suitable for removing individual substances from mixtures containing many individual components.

Such fibers may be used as support members for the insolubilization of soluble catalysts, especially if enzymes are involved. In the latter case, insolubilized catalysts are obtained which have a highly concentrated activity and a high catalytic activity even on substrates with a high molecular weight.

Finally, the new porous fibers have the properties of molecular sieves,

Ausführunssbeistdel

ii iMiiHr ι> r-nirrni ^J ^ * Vf.-Jitr * ^ ~ '^> ^ ^ iirir

To further illustrate the invention, the preparation and use of porous structure fibers is described in the following examples, but this is not intended to be limiting.

of cellulose triacetate.

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Into a 1 l two-necked flask equipped with a mechanical stirrer, 50 g of cellulose triacetate (commercial product of Montefibre, Pallanza (Efovara, Italy) dissolved in 664 g of methylene chloride were slowly added to 200 g of glycerol and all the h2o was stirred for 15 minutes at 800 rpm. the homogenized mixture thus obtained was cooled to 0 ⁰ G and poured into a vessel having a spinning nozzle having 500 holes of the respective diameter of 125 microns. the composition was then processed using spun a nitrogen pressure of 1 atm "and the filaments were collected on a orphan after coagulation in a toluene bath of 20 ⁰ C, the bath tank had a length of about 80 cm * bo parsers are obtained were in a dry air stream at room temperature for two Dried hours and then stored in a closed container «

The fibers had the following composition by weight: cellulose triacetate 18 % _t glycerol 70 %, balance, d. h # 12 / o Spinning solution. The ratio of glycerine to polymers was 70:18 = 3.86, when it was 4.00 in the solution ready for spinning. "Past all of the glycerol that was present at the beginning was practically included in the coagulated polymer matrix which made their structure porous "

The paser can be freed of glycerine by mere washing in water, after complete stripping of the spinning solutions by means of medium and of the glycerine the paser has an apparent specific gravity of 0.253 + 0.005 g per linear meter, measured according to the procedure described in Example 8 *

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porous structure on the base

Poly-L-gamma-never tyl glut ama t

Into a 1-liter two-necked flask equipped with a mechanical stirrer were poured 290 g of PLG 30 (commercial product of Kyowa-Hakko Kogyo Co., Ltd., Tokyo, Japan), which was a solution by weight / volume Concentration of polygamma-methylglutamate having a molecular weight of 100,000 to 300,000 in 1,2-dichloroethane (symmetric). Slow stirring was followed by the first 145 g of 1j2-dichloroethane (symmetrical) and then 50 g of a 50% by weight solution of glycerol in water. »In summary, the final mixture contained:

23 g poly-L-gamma-methylgrutamate 412 g symm. 1,2-dichloroethane 28 g water 28 g glycerol «,

The mixture was cooled to 0 ⁰ C and emulsified by stirring for 30 minutes at 800 rpm, after which it was poured into a previously cooled to -6 ⁰ C container with a spinneret with 48 holes of diameter of 80 microns oeiFe "The mixture was then carried wherein the filaments were collected on a roll after coagulation in a Petrolätherbad, which was maintained at 40-70 ⁰ G, application of a nitrogen pressure of 0.8 atm, spun, the coagulated filaments were finally en cooled to -3 ⁰ G »The filaments thus obtained were, after drying in an air stream at room temperature for one hour

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stored in a closed container. The filament had the following composition, by weight _s : Poly-L-ganma-methylglutamate: 25.5 #, H ₂ ⁰ ϊ 26.0 % _s Glycerin: 26.0 %, Spinning solvent: 22.5 % * The ratio of disperse phase (water and glycerine) sum polymers in the filaments was (26 + 26): 25.5 = 2.04, whereas in the solution prepared for spinning it was 56:23 = 2.43 »

chloride

Into a 1-liter 2-necked flask with mechanical stirrer were added 47.5 g of Solvik 523K (commercial product of Solvik, Via Filippo Turati 8, Milan, Italy), which is a copolymer of vinyl chloride and vinyl acetate, and containing 12 wt. -> · contains % vinyl acetate, together with 452.5 g of methyl cast «lenchlor.id». This mixture was stirred until complete dissolution of the polymer, after which 95 g of glycerol were slowly added with stirring. The mixture was cooled to 10 ⁰ C and emulsified by stirring for 15 minutes at 800 rpm. The mass thus obtained was poured into a container which was maintained at 10 ^° C. by a thermostat and equipped with a spinneret with 100 holes of the respective diameter of 80 microns. Then, by applying a pressure of 0.6 atm, the filaments were collected on a roller after coagulation in a bath of n- »hexane maintained at 20 ^° C. The filaments thus obtained, after drying in a dry air stream, were stored for two hours in a closed container.

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the following composition by weight; Solvik 523K ~ Copolymer: 295 ₅ %, Glycerol: 57.9 % _t Spinning solvent: 12.6%. Also in this palle, each gram of the coagulated polymer matrix had retained 1.96 grams of glycerine scattered in vacuoles giving the porous structure.

Example 4

proteins ^

Bs were examined the following three types of pasers:

A. A porous structure paser obtained by spinning according to the procedure described in Example 1 of 50 g of cellulose triacetate dissolved in 664 g of methylene chloride and 200 g of glycerol in the dispersed phase to give 500 monofilaments each having 3 to 7 denier.

B * A porous structure paser obtained under the same conditions as described under A * but with 100 g of glycerin as the dispersed phase and 500 monofilaments of 3 _S 7 den. per monofilament.

Cc A pore with a non-porous structure, obtained according to similar conditions of Ao and Bo, but without the disperse phase; 500 monofilaments of 3.9 denier each.

The specified * value represents the average

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Count obtained from 10 readings performed as follows: a sample of 500 monofilaments 100 cm in length was subjected to five consecutive washes of distilled water, with 50 ml of water and a contact time of 10 for each wash Minutes with stirring at room temperature. After washing, the sample was dried in an oven at 70 ^° C. and 0.1 mmHg for 8 hours and finally weighed. From the dry weight thus obtained, the value for each monofilament was calculated by using the following formula: dry weight in grams χ 900: 500. For each fiber, a sample was taken such that it contained the same amount, i. h * 1.78 g cellulose triacetate and exactly 9 _S 89 g of fiber Α •, 5.78 g of fiber B and 1.85 g of fiber C ₀ . Each sample was placed in a 300 ml Erlenmeyer flask and washed five times each with 200 ml of distilled water and then with gentle stirring at room temperature for four hours with 200 ml of a 0.5M aqueous solution of sodium hydroxide, This treatment converts the original polymer into cellulose so as to at least partially maintain the original structure of the fiber, as can be seen from the following results. Subsequently, after hydrolysis ia.it sodium carbonate, each sample was washed with water until neutral and at room temperature with gentle stirring for 20 hours with 165 ml of an aqueous solution of 0.5 M phosphate buffer, pH = 8.0, of 0.285 g of benzoquinone This treatment activates the fiber and makes it chemically bond the protein according to the method described in GDR Patent 123,608 of April 3 , 1976 to the same Applicant

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suitable),

After this treatment, each sample was washed alternately with water and 0.05 M phosphate buffer of pH 8.0 until the washings contained no substance with an absorbance at 250 mm, after which the sample was subjected to the trypsin insolubility test. each sample was mixed with 47 ml of 0.05 m phosphate buffer of pH ₅ 8jO cooled to 2 ⁰ C, is brought into contact, which contained 47 mg of trypsin having a specific activity of 30 BAEE units per mg (an enzymatically ^ BAEE- Unit is the amount of enzyme that hydrolyzes 1 micromole of N-> benzoyl-L-arginine methyl ester per minute at pH 8.0 and 25 ⁰ G). The reaction was carried out under mild stirring conditions at 2 for 24 hours ⁰ C performed. After completion of the reaction, the three samples were washed alternately with water and with O ₅ 05 m phosphate buffer of pH 8.0 until no enzyme activity was detectable. At the completion of the protein insolubilization reaction, the residual enzyme activity of the reaction solution was measured. It was 7 _{? In} the sample A contacting solution _. 9 BAEE unit / ml

in the sample B _c contacting solution 13? 1 BASE-Einh * / ml """" C, "" 25.2 BAEE-Einb, / ml

The measurement of the enzyme activity bound to the fibers gave the following results; Paser A ₆ 650 BAEE units / g of dry product

B 450 τ? jt H H U U I! Q 80 It η It t! It

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Example 5

Use of porous structure fibers on Basiajvon

tion of Prote ine n ".

4.94 g of Paser A. of the preceding example were washed with water and then hydrolyzed with 100 ml of 0.5 ml of LFE.0H and finally the activation reaction with benzoquinone with 83 ml of 0.05 M ~ Ph subjected to the pH 8.0, containing 0.142 g Benzochonon and ge ~ ₀ wash was carried out in the same manner as in the previous example, "the obtained product was reacted with the penicillin acylase enzyme under the following conditions: the sample was with gentle stirring for 24 hours at room temperature with 25 ml 0.04 m ~ pH 7.6 phosphate buffer containing 38 units of Escherichia coli penicillin acylase (ATCO 9637) with a specific activity of 5 units per mg protein per ml contained.

(1 "liazymeinheit is the amount of enzyme which converts 1 ilikromol penicillin G per minute in 6-aminopenicillanic acid and phenylacetic acid under the following conditions; temperature: 37 ⁰ C. pH = 8.0 phosphate buffer: 0.01 molar and penicillin G = 2% Weight / volume, total volume; 200 ml at 15-30 total enzyme units:

Under these conditions, the original rate of enzyme reaction, expressed in Hikromol per Hout, coincides with the enzyme units themselves). Finally, the sample which had been washed to remove the unreacted enzyme was measured according to the procedure of the preceding example of the determination of the enzyme activity.

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remaining bound to the paser remained γ / ar. The activity was 444 micromoles per well and per g of dry product.

6

2 ^

3 g of 92 g of poly-L-gamma-methyl glutaiate paser, the preparation of which was described in Example 2, were washed with 50 ml of distilled water four times to remove glycerol and then five times with 50 ml of absolute methanol to remove water and finally slurried in 50 ml of absolute methanol containing 2cO mmol hydrazine hydrate. The mixture was stirred slowly at room temperature. The reaction was monitored by titrating the removal of hydrazine from the reaction solution. After the removal of O ₅ 98 ml of hydrazine from the solution, the reaction was stopped by filtering the solution in methanol, and the fibrous substrate was washed three times with 50 ml of methanol. It was then washed with cold water (1-2 ⁰ C) and immersed in 100 ml of O ₅ 5 m «ivrige HCl on an ice bath. To this stirred mixture was then added in small portions, for about 15 minutes, 1 g of sodium nitrite. After the addition, the mass was stirred in the cold for an additional hour after which the fibrous substrate was washed with cold 0.01mv / aqueous HCl. Finally, the paser was dissolved in 100 ml of O ₅ 1 M phosphate buffer of pH Y'ert S ₅ 5? the 100 mg i'ryTjsin with a specific activity of 30

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BAE3 units / mg contained _s soaked. The Hasse was stirred at ⁰ ° C. overnight. The fibrous substrate was washed with water until no enzymatic activity was found in the decolorizing solutions and was subjected to an examination of the enzymatic activity remaining on the fibers 350 BABE units per g of dry product yielded »

Use of fibers with a porous structure to polyvinyl chloride as a substrate for the chemical immobilization of

3 * 39 g of fibers, prepared as described in Example 3, were washed four times with 50 ml of water and then five times with 50 ml of absolute methanol and finally immersed in 100 ml of absolute methanol containing 1 ml of concentrated, sulfuric acid, and 6 Heated under reflux for hours. They were then collected on a filter and washed swept with 50 ml of methanol and four times with 50 ml of toluene. The paser thus treated was then immersed in a solution of 5 g of phosgene in 100 ml of toluene at room temperature and stirred overnight, followed by excess phosgene freed by washing with (5 x 50 ml) toluene and finally dried at room temperature in a stream of dry nitrogen. The fiber was then cooled to _{5 s} 5 0 ⁰ C, immersed in 100 ml O ₅ 1-m phosphate buffer, pH Y containing 100 mg trypsin having a specific activity of 30 BAEE units / mg. The masoe was stirred in the cold for 20 hours. Finally, unreacted Eniayra was

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removed by washing with water until no enzyme activity was detectable in the washings. The paserra material thus obtained showed an enzyme activity of 250 BAES ~ units / g dry product.

Structure made of cellulose

137 g of cellulose triacetate fiber prepared as described in Example 1 containing 24 _S 6 g of polymers were cut into stacks of 0.3 to 0.6 cm in length and placed in a 2.5 cm diameter column of 34 s 7 cm so that a total bed volume of 170 ml was taken. The thus-packed fibers were released from air bubbles and washed at the same time by eluting with about 5 liters of water which had been degassed under vacuum. The column thus obtained showed the properties of a molecular sieve. In gel filtration using an aqueous solution of KCl (13.3 g per liter) as the eluant, Blue Dextran 2000 (commercial product of Pharmacia-Pine Chemicals AB-Uppsala) was obtained. Sweden) with a molecular weight of 2000000 an elution volume of 73 ml. "This value remained constant in the flow interval from 5 ml hourly to 50 ml hourly. The elution volume of potassium bichromate having a molecular weight of 294 was zY / een 128 ml per hour at 7 _S 5 ml and 118 ml at 45 ml per hour variable. These data show that the paser has the properties of molecular sieves and at the same time provide a method of measuring their apparent density; 170 ml (total bed volume) -> 73 DiI (volume of

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Vacancies in the column) = 97 ml. Thus, 24 »6 g of polymer took up 97 ml of volume, which corresponds to 24.6 × 97 = 0.253 g per ml. The entire fiber of the column was then treated by treatment with 0.5 μl At room temperature, aqueous sodium hydroxide was converted into cellulose at room temperature for 8 hours, which was filled in the same column as before and re-subjected to the same gel filtration measurement. The following results were obtained:

Total bed volume 100 ml

Elution volume of Blue-Dextra 2000 = 38 ml elution volume of potassium bichromate = 92 ml.

In this case, the elution volume of potassium bichromate t was again constant in the same flow interval.

Finally, the dry weight of the Paser was determined by drying at 80 ⁰ C in vacuo; it was 14 »1 g. Thus, the apparent density of the cellulose fiber thus obtained was 14.1: (100-38) = 0.227 g / ml.

Claims (1)

invention claim -Ι "1IMiIIgHmHTTIm m ι nf Γι in μ ι ιι in u- 11 I ι N-Ii mn ιπ 1, use of fibers with porous structure through. a) Dissolve or melt a polymer such as cellulose, cellulose esters, cellulose ethers, cellulose nitrates, polyamides, polyesters, polyesteramides, polyimides, polypeptides, polymers and copolymers of acrylonitrile, methacrylonitrile, acrylic acid and methacrylic esters, vinyl esters and ethers, polymers of vinyl chloride, vinylidene chloride, vinyl butyral and styrene; b) homogeneously dispersing a immiscible liquid or an insoluble solid in a finely divided state; c) spinning the resulting mixture by hate, dry or melt spinning; d) removing the disperse phase were obtained characterized in that they have been used as a substrate of chemical reagents. 2 ". Use of fibers with a porous structure according to item 1, characterized by? that they are used as a substrate for chelating agents, 3c Use of porous structure fibers according to item 1, characterized in that they are used for the production of ion exchange materials. 1 2 1 1 7 * " ¹⁷ ~ 26. 3" 1979 55 201 11; 4, use of porous structure fibers according to item 1, characterized in that they are used as substrates for solubilization of soluble catalysts * 5, use of porous structure fibers according to item 1, characterized in that they have been used as substrates for the dissolution of proteins and enzymes, 6 _e Use of porous structure fibers according to item 1 * characterized in that they are used as substrates for the dissolution of selective enzyme inhibitors * 7c Use of porous structure passers according to item 1, characterized in that they are used for the production of materials "for the purpose of removing individual substances from mixtures consisting of several components". 8, use of porous structure porous fibers characterized in that they are used as materials that behave like molecular sieves.