CS208154B2 - Method of preparation of the fibrous material with porous structure - Google Patents

Abstract

To prepare porous fibres, a soluble or meltable polymer is used as the starting material, the polymer is dissolved or melted, an immiscible liquid or a finely divided solid is uniformly dispersed in the dissolved or melted mass, and the mixture thus obtained is then spun. When the dispersed phase, whether liquid or solid, is removed, empty spaces remain in the body of the fibre.

Description

The invention relates to a process for the preparation of a fibrous material having a porous structure, in which the starting solution of the fibrous material, which may be a variety of polymer, is treated with an immiscible liquid.

To date, no method is known in which a fibrous material with a porous structure is formed from a fiber forming polymer pitch and in which a immiscible liquid is dispersed as in the method of the invention.

The process of preparing a fibrous material having a porous structure according to the invention consists in preparing, in a first stage, a solution of a fiber forming polymer, such as cellulose acetate, cellulose triacetate and poly-L-gaimimaaneaethylglutamate. a concentration of from 0.1 to 15% (based on the volume of the solution), preferably using methylenechiloiride cellulose di- and triacetate and symmetrical 1,2-dichloroethane for poly-L-gamma-methylglutamate, glycerine is dispersed homogeneously in the polymer blend in an amount of 0.01 to 1% by weight based on the weight of the polymer flow, and this blend is spun at -15 to 40 ° C and then removed. dispersed phase.

In a preferred embodiment of the process according to the invention, said spinning is carried out by the wet spinning process.

The fibrous material obtained by the process of the invention has a porous structure. and large effective surface, good dimensional stability, good mechanical properties, considerable storage life and great versatility.

As already mentioned, in the first phase of the process according to the invention a solution of the fiber-forming material, i.e. a solution of the polymer in the solvent, is formed.

To the homogeneous mass thus obtained is added immiscible. liquid. This mixture is then homogenized in a conventional manner and then wound up as described above.

The fibrous material thus obtained, which is in the form of textile fibers, differs from this. The material differs in that it contains liquid or solid. a dispersed phase which makes this structure porous. Next, the dispersion phase is removed by washing with suitable solvents.

The porous fibrous material thus obtained has a surface area greater than that of fibrous. the material obtained by the procedures currently used. The material according to the invention may contain functional groups of different chemical nature, depending on the polymer used to prepare this. the only material is the ability of the polymeric material to form fibers. These functional groups contained in the fibrous material can serve a variety of uses of these ylanics, and these groups can be modified in various ways by subsequent chemical treatment to obtain suitable reactive groups.

The mechanical properties of the fibrous material obtained by the process of the invention depend to some extent on the polymer used and the spinning conditions. These properties can vary widely, since the number of polymeric substances that can be used for the purposes of the present invention is considerable. In addition, it should be noted that the polymeric material sold may also vary within a wide range of conditions under which a porous fibrous material is obtained. It follows that certain surface conditions and certain mechanical properties correspond to the individual conditions laid down. It follows from the above that according to the invention, a given porous fibrous material can be prepared according to the specific application for which the material is intended. It goes without saying that mechanical properties will not be comparable to those of materials for textile use.

The fibrous material of the invention has considerable utility in numerous practical applications. The fibrous material according to the invention, when used, for example as a carrier material for chemical agents, ion exchange groups or chelating groups, provides a number of functional groups that are larger than the reactive fibrous materials used to date. The fibrous material of the invention can be used to prepare materials that are capable of binding individual substances from mixtures containing many components.

The fibrous material of the present invention can be used to insolubilize soluble catalysts, especially when they are enzymes. In this case, insoluble catalysts are obtained which exhibit highly concentrated activity and high catalytic activity, especially in the case of high molecular weight substances.

Finally, it should be emphasized that the fibrous material of the present invention has molecular sieve properties. In order to better explain the nature of the invention, the following are exemplary embodiments characterizing the use of the material obtained according to the invention.

In summary, the fibrous material having a porous structure obtained by the process of the invention can be used as a substrate for chemical agents, as a substrate for chelating agents, as a substrate for insolubilizing soluble catalysts, as a substrate for insolubilizing proteins and enzymes, such as a substrate for the insolubilization of selective enzyme inhibitors, such a fibrous material having a porous structure can also be used to prepare ion-exchange materials, to prepare materials that are capable of removing individual substances from mixtures containing multiple components, and as a molecular sieve.

In order that the invention may be more fully understood, the following are exemplary embodiments in which the preparation and use of a fibrous material having a porous structure according to the invention is described, without limiting the scope of the invention.

Example 1

Preparation of fibrous material with a porous structure based on cellulose triacetate

According to this embodiment, 50 g of cellulose triacetate is dissolved in 664 g of methylene chloride in a 1 liter two-necked flask equipped with a mechanical stirrer. 200 g of glycerin are added slowly to this solution and the mixture is stirred for 15 minutes at 800 rpm. The homogenized mixture thus obtained is then cooled to 0 ^DEG C. and further poured into a 500-ml spinneret, each having a diameter of 125 μιη. The above mass was then rolled using a nitrogen pressure of 0.1 MPa, and fibers are collected on a winding roll for simultaneous coagulation in the toluene bath at 20 ^DEG C. The flask bath has a length of about 80 cm. The fibrous mass thus obtained is then dried in a stream of dry air at ambient temperature for two hours and then stored in a closed container.

The fiber composition thus obtained has the following composition (all percentages by weight):

cellulose triacitate: 18% glycerin: 70% spinning solvents: 12 o / o (up to 100%)

The ratio between glycerine and polymer was 70: 18 = 3.86, the ratio in the original coiling composition being 4.00. Almost all of the glycerin present at the outset was rapidly expelled from the coagulated polymer, thereby obtaining a porous structure.

The fibrous mass can also be freed of glycerin by simply washing with water. After the fibrous material was completely free of spinning solvents and glycerin, the fibers had a specific gravity of 0.2: 53 + 0.005 g per 1 m length, as measured by the procedure of Example 8.

Example 2

Preparation of fibrous material with porous structure based on poly-L-gamma-methylglutarate

According to this embodiment, 290 g of a poly-L-gamma-imeth-l-l-a-m-a-m-a-m-a-100-m-3 solution in symmetrical 1,2-dichloromethane are poured into a 1 liter two-necked flask equipped with stirrer. . With slow stirring, 145 g of symmetrical 1,2-dichloroethane are then added to the mixture, followed by 50 g of a 50 why solution of glycerine in water. ¹ weight:

The resulting mixture contains:

2: 3 grams of poly-L-gamma-methylglutamate 412 grams of 1,2-diohtorethane (sym.)

2® grams of water grams of glycerin.

The mixture is then cooled. to a temperature of 0 ° C and emulsified by stirring at 800 ct / min for 30 minutes, then the mixture is poured into a container that has been pre-cooled to -6 ° C and the spinneret is also placed in the container 48 holes, each hole having a diameter of 80 microns. The above mixture is then wound using a nitrogen pressure of 0.08 MPa and the fibers are collected on a take-up roller while coagulating in a petroleum ether bath, maintaining the bath at a temperature ranging from 40 to 70 ° C, and coagulated the fibers are then finally cooled to -3 ° C. The fibers thus obtained, after being dried in a stream of dry air at room temperature for one hour, are stored in a closed vessel. · Fibers have the following composition (all percentages are Wm-rotating):

half-L-game methyl methyl glutamate: 25.5% water: 26.0% glycerin: 26.0% spinning solvents: 22.5%.

The ratio between the disperse phase (which is water and glycerin) and the polymer in the obtained fibers:

(25 · · | · 26): 25.5 - 2.04, with in the ready-to-wind mixture it is:

: 23 = 2.43.

Example 3

Preparation of a fibrous material with a porous structure based on polyvinyl chloride

According to. In this embodiment, 47.5 g of vinyl chloride-vinyl acetate copolymer containing 12% by weight of vinyl acetate together with 452.5 g of methylene chloride are poured into a 1 liter, two-necked, equipped with mechanical stirrer. This mixture was. then · stir until. all of the polymer does not dissolve, and then 95 g of glycerin is added slowly while stirring. The mixture is cooled to 19 ° C and then granulated by stirring at 800 rpm for 15 minutes. Thus-. the prepared mass is then poured into a thermostatically controlled vessel at 10 ° C equipped with a 100-hole spinneret, each hole having a diameter of 80 µm. Winding is carried out using a pressure of 0.06 MPa-strand shromažňují on the winding roller with simultaneous coagulation of normal hexane .lázni · · maintained at 20 ^DEG C. The thus obtained fibers · after drying in a stream of dry air · · Store in a closed container for two hours. These fibers have the following composition (in weight%):

copolymer of vinyl chloride with vinyl acetate: 29.5% glycerine: 57.9% spinning solvents: 12.6%.

Also in this case, each graim of the coagulated polymer contained 1.96 g of glycerin, which is dispersed in vacuoles and which makes the structure porous.

Example 1 a d 4

Use of fibrous material with cellulose triacetate porous structure as substrate for chemical immobilization of proteins

According to this embodiment, the following three types of fibers were tested:

A. Fiber1 having a porous structure, obtained as described in Example 1, wherein 50 g of cellulose triacetate is dissolved in 664 g of methylene chloride, 200 g of glycerin is added as a dispersion phase and the simes are wound as 500 mOnofibrile fibers of 3.33 fineness dtex for each thread.

B. A fibrous material with a porous structure, obtained by the same procedure and under the same conditions as in Example A, but using 100 g of glycerin as the dispersion phase, yielding 500 monotibrillation fibers of 3,3 3.33 dtex per fiber.

C. A fibrous material having a porous structure, obtained by the same procedure and under the same conditions as in Procedure A, but without the dispersed phase, whereby 500 mono-fibrous fibers of 3.5 dtex are obtained for each fiber.

The dtex value is the average value obtained from 10 data, and this note is determined as follows: A sample consisting of 500 monofilamentary fibers of 100 cm length is subjected to five successive p-washes with distilled water. each wash uses 50 ml of water and the contact time is 10 minutes, with stirring and at ambient temperature. The samples were dried after being washed in an oven heated to 70 [deg.] C. and at a pressure of 0.1 [mu] m Hg for 8 hours and finally weighed. From the dry sample mass determined above, the above value is determined for each individual monofibril fiber using the following formula:

dry weight (in grams) x 9000: 500.

For each fiber, a sample was then taken to contain an equal amount of 1.78 g of cellulose triacetate, which is 9.89 g of fiber A, 5.78 g of fiber В and 1.85 g of fiber C. Each sample is then placed in a 300 ml Erlenmeyer and then washed 5 times, 200 ml each, with distilled water, and then treated for 4 hours with gentle stirring at ambient temperature of 200 ml 0, 5 molar aqueous sodium hydroxide solution. By this treatment, the original polymer is converted to cellulose while at the same time in such a state that it retains at least partially the original fiber structure, as will be seen from the results that will be discussed below. After hydrolysis with sodium carbonate, each sample is then washed with water until neutral and then treated at ambient temperature with slow stirring over a period of 20 hours with 165 ml of an aqueous solution of 0.05 molar phosphate buffer at pH 8.0. it contains 0.285 g of benzoquinoin (this processing activates the fibers and causes these fibers to then be able to chemically bind proteins according to the procedure disclosed in Czechoslovak patent 194 238 from the same applicant).

After this treatment, each sample is washed in alternating order with water and a 0.05 molar phosphate buffer at pH 8.0, and washing is performed until the washing water does not contain a substance having an absorbency at 250 mm. , and then the sample is subjected to a tripsin insolubilization test. Each sample is contacted with 47 ml of a 0.05 molar phosphate buffer at pH 8.0, which is cooled to 2 ° C, containing 47 mg of trypsin with a specific activity of 30 BAEE units per milligram (the enzymatic BAEE unit is amount of enzyme which hydrolyzes one mikroimol alfabenzoyl-N-L-argininmethylového ester per minute at pH 8.0 and at a temperature of 25 ³ C). The reaction is carried out for 24 hours with slow stirring at 2 ° C. After completion of the reaction, the three samples were washed in alternating order with water and a 0.05 molar phosphate buffer solution having a pH of 8.0 until no enzymatic activity was noted. After completion of this protein insolubilization reaction, the residual enzymatic activity of the reaction solution is determined. The results are shown in the following table:

• solution contacting sample A:

7.9 BAEE units / ml solution contacting sample B:

13.1. BAEE units / ml solution contacting sample C:

25.2 BAEE units / ml

The following results were found when determining the enzymatic activity of the fibers themselves:

fiber A: 650 BAEE units per gram dry product fiber B: 450 BAEE units per gram dry product fiber C: 80 BAEE units per gram dry product

Example 1 a d 5

Use of a fibrous material with a porous structure based on cellulose triacetate as a substrate for chemical protein mobilization

In this embodiment, 4.94 g of the fibrous material A from the previous example is washed with water, then hydrolyzed with 100 ml of 0.5 molar sodium hydroxide solution and then subjected to a reaction in which it is activated with benzoquinone with 83 ml of 0. A molar phosphate buffer at pH 8.0 having a benzoquinoin content of 0.142 g is then washed. The procedure of this example is identical to the procedure of the previous example. The product thus obtained is then reacted with the enzyme penicillin acylase under the following conditions:

the sample is contacted with slow stirring for 24 hours at ambient temperature with 25 ml of a 0.04 molar phosphate buffer at pH 7.6 containing 38 units per ml of penicillin acylase obtained from Escherichia Coli (ATCC-9637 ], with a specific activity of 5 units per milligram of protein. (One enzymatic unit is the amount of enzyme that converts 1 milkromol pen cillin G to 6-am; non-penicillanic acid and phenylacetic acid per minute, under the following conditions:

temperature: 37 ° C, pH: 8.0, phosphate buffer: 0.01 M, peinilcilin G: 2% by weight, total volume: 20-0 ml, 15 to 30 enzyme units in total.

Under these conditions, the value of the initial rate of enzymatic reaction agrees, expressed in micromoles per minute, with the enzymatic units per se]. Finally, a sample that has been washed to remove unreacted enzyme by the same procedure as in the previous example is subjected to the enzymatic activity exhibited by filamentous mama. The activity is 444 micricimoles per minute per gram of dry product.

Example 6

Use of fibrous material with a porous structure based on pod-L-gamma-methylglutamate as a substrate for chemical immobilization of proteins.

According to this embodiment, 3.92 g of a poly-L-gamamethylglutamate-based fibrous material, prepared in the same manner as the product of Example 2, was washed with 50 ml of distilled water for a total of four times to remove glycerin, then five times, each time. 50 ml of absolute methanol to remove water and finally diluted with 50 ml of absolute methanol containing 2.0 millimoles of hydrazine hydrate. The mixture was then stirred slowly at room temperature. The reaction is monitored by titrating the released hydrazine from the reaction solution. After 0.98 millimoles of hydrazine are removed from the solution, the reaction is stopped, the solution is filtered and washed three times with 50 ml of methanol each time, washing with the fibrous material. The fluffy material is then washed with cold water (at a temperature ranging from 1 to 2 ° C) and then immersed in 100 ml of a 0.5 molar aqueous hydrochloric acid solution on a water bath containing ice. 1 g of sodium nitrite is added in small portions over a period of about 15 minutes, after the addition is complete, the mass obtained is stirred and kept cool for one hour, and then the obtained fibrous material is washed with cold Finally, the fibers are immersed in 100 ml of a 0.1 molar phosphate buffer, pH 8.5, containing 100 mg of trypsin The specific activity of this tryptine is 30 BAEE · units The mass thus prepared is then stirred overnight at 0 DEG C. The fibrous material thus obtained is then washed and washed. As long as no enzymatic activity is recorded in the wash water, the composition is further tested for enzymatic activity of the fibrous material, the enzymatic affinity being 350 BAEE units per gram of dry product.

Example 7

Use of fibrous material with porous structure - based on polyvinyl chloride as a substrate for chemical immobilization of proteins

According to this embodiment, 3.39 g of fibrous material prepared in the same manner as in Example 3 is washed four times with water, each time with 50 ml, and then five times with absolute methanol, each time with 50 ml, and finally Immerse the material in 100 ml of absolute methanol containing 1 ml of concentrated sulfuric acid, and then heat the mixture at reflux for 6 hours. The solid was collected on a filter and washed twice with 50 ml methanol and 4 times 50 ml toluene. The treated fiber mass is then immersed in a solution of 5 g of phosgene in 100 ml of toluene at ambient temperature and then stirred overnight. The excess phosgene is then evacuated by washing with toluene (5 times, 50 ml each) and finally the product is dried at ambient temperature in a stream of dry nitrogen. Thereafter, the fibrous material is immersed in 100 ml of 0.1 M phosphate buffer at pH 7.5, then cooled to 0 cc, said solution containing 100 mg of trypsin having a specific activity of 33 BAEE units per milligram. The mass thus prepared is then kept under stirring in the cold state for 20 hours. Finally, the unreacted enzyme is removed from the material obtained by washing with water, and washing is continued until no enzymatic activity is detected in the washing liquid. The fiber material thus prepared has an enzymatic activity of 250 BAEE units per gram of dry product.

Example 8

Use of a fibrous material with a porous structure based on cellulose triacetate as a molecular sieve

According to this embodiment, 137 g of thieryl cellulose fibrous material prepared as described in Example 1 and containing 24.6 g of polymer is cut into samples ranging in length from 0.3 to 0.6 cm, and these columns are then packed with a column having a diameter of 2.5 .mu.m to a height of 34.7 cm, the material taking up a volume of 170 ml. The material is then freed of air bubbles and at the same time washed with about 5 liters of water which has been degassed in vacuo. The packing of the column was then tested as a molecular sieve. When the material was subjected to a gel filtration method using an aqueous potassium chloride solution as eluent (13.3 g per liter), this column had a Blue Dextran 2000 (Pharmacia-Fine Chemicals AB Up »p ') sale, Sweden), which has a molecular limit of 2,000,000 and an elution volume of 73 ml, which is constant over a flow interval ranging from 5 to 50 ml per hour. ranged from 128 milliliters at 7.5 ml per hour to 118 ml at 45 ml per hour, and these values show that the fibrous material exhibits a molecular sieve of molecular sieve ¹ and can also measure bulk density:

170 ml (total bed volume) - 73 ml (empty column volume) - 97 ml

Since 24.6 g of polymer takes up a volume of 97 milliliters, then 24.6: 97 is 0.253 g per milliliter. All the fibrous material contained in the column is then converted to cellulose treated.

Claims (2)

SUBJECT A process for the preparation of a fibrous material having a porous structure, characterized in that, in a first stage, a solution of a fiber forming polymer, such as cellulose diacetate, cellulose triacetate and poly-L-gamma-methylglutamate, is present in a concentration of 0.1-15% by volume. solution, preferably used as solvents for cellulose di- and triacetate methylene chloride and for poly-L-gamma-imeithylglutamate symmetrical 1,2-dichloroate with 0.5 molar aqueous sodium hydroxide solution at room temperature for 8 hours, The same knees are then filled with mateialial and the gel filtration procedure is carried out again. The results obtained are as follows: total bed volume: 100 ml elution volume of Blue-Dextran 2000: 38 ml elution volume of potassium dichromate: 92 ml. In this case, the elution volume of potassium dichromate is again constant over the same flow interval. Finally, the dry weight of the fibrous material is determined by drying at 80 ° C under vacuum. This weight is 14.1 g. Thus, the bulk density of the cellulosic fibrous material is: 14.1: (100-38) = 0.227 grams per milliliter. In this case, glycerine is dispersed homogeneously in the polymer mixture in a quantity of 0.01 to 1% by weight, based on the weight of the polymer flow, and the mixture thus obtained is spun at a temperature of -15 to 40 ° C and then the dispersed phase is removed. 2. The process of claim 1 wherein said spinning is carried out by a wet spinning process.