FI70587B - POROEST FYLLMEDELINNEHAOLLANDE REAKTIVT MATERIAL MED OEPPNA CELER - Google Patents

Description

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(51) Kv.ik /.- int.ci. * C 08 J 9/00, 5/20 // C 08 L 29/14, 75/04 gUQ | y || __p || ^ | ^^ | ^ Q (21) Patent application Patentansökning 801 746 (22) Application date Ansökningsdag 29.05 80 (Fl) '' (23) Start date — Giltighetsdag 29.05.80 (41) Published public - Biivit offcntllg)) gj

National Board of Patents and Registration Pending, | a kuui.juikaisur pvm. -

Patent and registration authorities ^ Ansökan utiagd och uti.skriften publicerad 06.06.86 (86) Kv. application - Int. ansökan (32) (33) (31) Requested priority - Begärd priority (71) Leningradsky Institut Textilnoi i Legkoi Promysh1ennosti Imeni S.M.

Kirova, ulitsa Gertsena 18, Leningrad, USSR (SU) (72) Sasho Pet rov Alexandrov, Leningrad,

Gadylsha Mubarakshinovich Mubarakshin, Leningrad,

Leonard Abramovich Volf, Leningrad,

This invention relates to a porous, open-celled, reactive material containing a filler-reactive material. The present invention relates to a porous, open-celled, filler-containing reactive material. with ion exchange properties.

This material is useful in water treatment processes, wastewater treatment, sorption of various products from liquid and gaseous media, as well as seective recovery of metals;

Hundreds of grades of synthetic resins are now known in the art for general or special applications and are available under various trade names and trademarks. Insoluble synthetic ion exchange resins (ionites) having a three-dimensional structure formed by macromolecules are classified into cationites, anionites, and amphoteric ionites, depending on the sign of charge of the exchanged ions. The group of ionites usually covers complexing sorbents which absorb substances from solutions by chemosorption, not by ion exchange. The ion exchange process in which the ionites participate can be considered as a heterogeneous chemical reaction in which the mobile ions participate, while the stationary macromolecule of the opposite sign forms a polymer matrix (substrate).

Ionites are produced mainly as spherical or irregularly shaped particles. The most suitable is the spherical shape of the particles, as it results in the lowest liquid flow resistance in the columns. In terms of structural features, ionites can be classified into two types: gel-like, which have no transition pores at all, and macroporous ionites, which have pores piercing the solid phase with a diameter of several hundred Angstroms. Examples of gel-like ion exchange resins are usually regular or standard ion exchange resins which are macrogrid-like and uniformly porous. Regular solid ion exchange resins in the form of grains or granules having a gel-type structure obtained by polymerization or polycondensation have an expansion capacity determined by the density and stiffness of the intramolecular crosslinks. In the dry and slightly swollen state, these ionites have no detectable porosity, which limits their use to anhydrous solutions as well as to the sorption of high-beam ions such as large organic ions.

The permeability of the polymer matrix of an ionite is one of its most important properties that determines its useful use, which is why, in recent times, much attention has recently been paid to the production of porous ionites. Due to their well-developed surface, they are highly active in the reaction of polymer-analog transformations and sorption processes; however, due to their high divinylbenzene content (up to 50%), they have a lower exchange capacity than gel ionites and do not swell substantially in water.

The rate of the exchange process is essentially determined by the diffusion rate of the counterions into the ion exchange grains. With a relatively large grain size and a relatively small surface area, the ion exchange resins swell only slightly due to crosslinking, resulting in a slow diffusion process of 3,70587 and a consequent decrease in ion exchange rate.

Another disadvantage of the numerous synthetic ionites usually lies in their low chemical and thermal stability as well as low mechanical strength. The losses of ionites due to the fracture of the grains along the cracks formed during the crushing of the resin, its shrinkage during the heat treatment or the wetting of the ionite with water are in certain cases as high as 10-15%.

A structure of ionites or wood is required to prevent the rupture of the particles. In this context, ion exchange fibers are becoming increasingly important.

The substantially more developed surface area of the fibers, the surface layer of which is enriched with maximally active functional groups, the high wettability and capillarity of the fibrous materials guarantee a higher process speed than those of the granulated materials. In addition, the effective grain size of the granulated ionites is between 0.43 and 0.63 mm, while the transverse dimension of most reactive fibrous materials is 20-30 times smaller and ranges from 0.02 to 0.03 mm. As a result, the ion diffusion pathway in fibrous materials is also 20-30 times shorter. This phenomenon is the main reason for the higher kinetics of reactive fibers compared to granulated materials. It is also important that most of the modified fibers with reactive groups have a high porosity, often up to 2,100-200 m / g. The conversion rate of the functional groups of such fibers is the highest.

However, reactive fibers, such as the nonwoven materials based thereon, when packed in a column, clog quite rapidly, thus substantially increasing the hydrodynamic resistance of the filtration layer.

To overcome this disadvantage, it is necessary for the filtration layer to have the flexibility of elastic foams.

A process for preparing foamed polyurethane molds containing ionic groups is known in the art (U.S. Patent 3,988,268). Amphoteric foams are prepared from reagents that contain both cationic and anionic groups. Thus, a process for preparing 4,70587 foamed polyurethane resins by reacting isocyanates such as 1-methyl-2,4-diisocyanate with organic compounds such as castor polyglycol ester is known in the art. The mixture is heated to 170 ° C, held for three hours and then cooled to room temperature. Examples of the disadvantages of these materials are the low content of ionic groups, which makes them unsuitable for use in chemisorption processes.

They are mainly intended as a soil matrix for crop production.

Also known are foamed ion exchange materials (cf. U.S. Patent No. 3,867,319, U.S. Patent No. 3,947,387) prepared by a non-foamed polymer obtained in the presence of a volatile polar compound that forms a plasticizer for ionic groups. The polymer contains 0.4-10 mol% of oxalic acid groups, mainly sulfone groups, and consists of sulfonated polystyrene. The material obtained by this process has a low exchange capacity (the number of ionic groups, especially sulfone groups is 0.2-20 mol%) and low mechanical strength. In addition, these materials are characterized by stiffness and brittleness.

U.S. Patent 3,094,494 discloses ionic cellular materials consisting of a foamed polyurethane acting as a polymer matrix and a filler - a synthetic ion exchange resin - in an amount of 0.5 to 160 parts by weight per 100 parts by weight of the polymer matrix. To prepare these materials, 100 parts of a polypropylene glycol oligomer (prepared by heating 2 parts of a mixture of 100 g of polypropylene glycol with a molecular weight of 2000 and 35 parts by weight of toluene nisisocyanate (isomer mixture 80/20) are added to 67 parts by weight of finely divided ion exchange (sulfonated styrene and divinylbenzene in their sodium form), and mixed to a uniform mixture, after which a mixture of 2.4 parts of water, 1 part of methylmorpholine, 1 part of triethylamine, 0.6 parts of dimethylpolysiloxane is added to the mixture and stirred until foamed. it is allowed to remain in it until it is completely foamed.The materials produced by this method are flexible, pliable, gas permeable and liquid permeable.The ion exchange resin is easily accessible to liquids, however, under the influence of working solutions, the fine ion exchange resin is leached out of the material by poor thus guaranteeing exchange capacity during exploitation and shortening the service life of these materials. In addition, these materials are characterized by relatively low kinetic properties.

Because of these disadvantages, it is impractical to use ion exchange cell materials and resin-filled cell foams for applications such as environmental pollution control. Due to the low values of the exchange capacity, the hydrophobicity and the low speed of the exchange processes, the use of such materials cannot guarantee the treatment of wastewater from harmful products to the desired permissible concentration values. In addition, the possibility of varying the properties of the material to expand their field of application is either prevented or completely eliminated.

This invention relates to a porous, open-celled, filler-containing reactive material having an excellent rate of osmotic stability, mechanical strength and elastic properties.

The material according to the invention is characterized in that the polymatrix consists of foamed polyvinylformal or foamed polyurethane and the reactive filler consists of hay-split ion exchange fibers and / or complexing fibers in an amount of 10-80% by weight of the final material.

It is preferred that the content of reactive fibers be between 50 and 70% by weight of the final material. This gives the material maximum exchange capacity and mechanical strength, while keeping its elastic properties unchanged.

Reactive ion exchange fibers utilize strongly acidic and weakly acidic, strongly basic and weakly basic ionites and polyamolytes based on polyvinyl alcohol fibers. Fibers made of polyvinyl alcohol 6 70587 are characterized by a special combination of properties that are most important in the production and use of reactive fibers · It is possible to incorporate a sulphon group into polyvinyl alcohol fibers, perform esterification of the fibers with bifunctional silicon carboxylic acids and grafting of exchange groups via carboxy and hydroperoxy groups. In this way, it is possible to produce reactive fibers with an exchange capacity of up to 6 mg / equiv / g.

It is also possible to use strongly acidic and weakly acidic, strongly basic and weakly basic ionites and polyamolytes based on structured polyacrylic fibers as reactive ion exchange fibers. The presence of reactive nitrile and carboxy groups in these fibers makes it possible to roll ionites characterized by a wide range of properties and exchange capacity values. Polyamolytes with a capacity of up to 8-9 mg-eq / g are obtained by initial depletion of nitrile groups. Polyacrylic ion exchange fibers are characterized by high chemical stability and their use makes it possible to carry out sorption-desorption processes over a wide range of oB at elevated temperatures.

Reactive ion exchange fibers utilize strongly acidic and weakly acidic, strongly basic and weakly basic ionites and polyampholytes based on cellulose-separated fibers. These ionites are characterized by a high hydrophilic nature, which guarantees a high rate of diffusion processes. Sci.Lioose regenerated ion exchange fibers have a sufficiently high mechanical strength, especially in neutral solutions, which has. great importance for the use of these materials in the food industry, for example. The low cost of cellulose-regenerated reactive fibers makes it possible to use them for disposable i or. 1 for the production of a special material for the sorption of particularly valuable metals.

In accordance with the present invention, ion exchange fibers based on phenolic aldehyde fibers having a three-dimensional structure and improved chemical stability are also utilized.

Utilizing polyolefin and polyvinyl halide ion 7 70587 exchange fibers, which are characterized by high mechanical strength and chemical stability.

As the complexing reactive fibers, complexing polyacrylic fibers having phosphate and thiol groups are utilized.

As complexing reactive fibers, polyvinyl alcohol fibers containing functional groups that can form donor-acceptor (coordination) bonds with ions, atoms, and molecules in them are utilized. Polyvinyl alcohol fibers containing phosphate, nitrogen and oxygen are also utilized.

In addition, cellulose-reacted fibers having phosphate groups and nitrogen-containing cellulose-regenerated fibers and sulfur-containing cellulose-regenerated fibers having thiol and thione groups are utilized as complexing reactive fibers.

The porous, open-cell filled reactive material has numerous valuable properties, characterized by combinations of high kinetic properties, osmotic stability and mechanical strength of reactive fibers, and elastic properties of foams. An important advantage of porous, open-cell reactive materials over granulated materials lies in their substantially higher sorption and desorption rates. This is because the apparent size of the ion exchange granules is 20-30 times larger than the diameter of the reactive fibers on the surface of which the active groups have developed. The diffusion pathway of sorbed ions towards the active groups of the ion exchange fiber is substantially lower and the rate of sorption-desorption processes with porous, filled reactive materials is 20-30 times higher than with granulated materials.

Porous, filled, reactive materials do not substantially deteriorate when subjected to significant mechanical loads and sharp variations in the ionic strengths of solutions.

The porous, open-celled, filled, reactive materials of this invention are flexible and elastic and have high impact and compression resistance. The materials are hydrophilic and have a well-developed network of interconnected capillaries and pores. In the dry state, the thin-porous condensation structure of the material disappears while it becomes a crypto condensation structure. Only the porosity obtained by foaming and pasting into the structure. Only the porosity obtained by flotation and by attaching a fibrous filler to the material is retained. In the dry state, the material is rigid, can be easily machined (sawing, cutting, planing) to give it the desired shapes and dimensions. The presence of a system of relatively coarse open pores and interconnected capillaries substantially facilitates impregnation of the material with working solutions. The thin walls of the pores wet rapidly and swell so that the cryptocondensation structure expands again and absorbs the volume it had before drying when wet. In the expanded state, the material has a very high elasticity and is capable of very pronounced reversible deformations. Due to the fact that water is a foamed polyvinyl formal and the plasticizer of the fibers, even prolonged use of the porous reactive material according to the present invention does not lead to its deteriorated elasticity.

In porous, filled, reactive materials, the cell size is substantially less than the length of the fiber while the fibers are firmly bonded to the polymer matrix. In use, such porous, filled, reactive materials, due to their high osmotic stability and mechanical strength, also have high mass stability.

The porous, open-celled, filled, reactive; the materials can be made using standard equipment used in the manufacture of foamed polyvinyl formal and foam polyurethane.

The sorption process of these materials can be carried out by known methods in columns, filter presses without any substantial structural changes in the process equipment and technology.

To prepare an open-celled, porous, filled reactive material based on the foamed polyvinyl formal according to the invention, an aqueous solution of polyvinyl alcohol (utilizing polyvinyl alcohol having a molecular weight of 30,000 to 150,000) in foam 70587 9 is applied in the presence of a surfactant with a mechanical sieve. Formaldehyde in the form of a 37% aqueous solution and aqueous sodium chloride solution are added during the flotation process. Flotation should preferably be performed at a flotation rate of 3-10; in doing so, it is possible to make use of vane mixers (agitators) operating in the speed range of 500-10,000 rpm. As the blowing agent, it is possible to use ionic and nonionic surfactants, such as alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, amines having various degrees of substitution, polyhydroxyethylene esters of alkyl phenols, polyhydroxyethyl esters of fatty acids and the like.

Mineral acids such as hydrochloric, nitric, sulfuric acid, etc. are used as the catalysts for the condensation structure formation of the foamed polyvinyl formal. The catalyst should preferably be added one or more minutes before the end of the flotation process.

After the desired degree of flotation is reached, the fibrous filler is added to the reaction mass in a screw mixer or in the same vessel in which the flotation is carried out at low agitator speed (100-300 rpm). The length of the fiber may be from 1-2 mm to 50-600 mm and preferably 3-8 mm.

Any type of reactive fiber is used - both ion exchange and complexing fibers - either individually or in various possible combinations to provide similar ratios to the desired materials.

The structuring (acetalization) of polyvinyl alcohol is carried out at a temperature between 20 and 100 ° C; depending on the temperature used, the setting time varies from 1 to 50 hours. The viscosity of the systems gradually increases, which further improves the stability of the foam. The fine particles of the new phase are obtained from the solution during acetalization, whereby a condensation structure is formed and the resulting foam is simultaneously vulcanized. During the condensation structure formation, the particles of the new phase (polyvinyl formal) adhere to the surface of the fibers and join together to form a network structure that also contains the fibers. Because the fiber length is substantially (1-2 hundred times) greater than the pore size, they are contained in several cells 10,70587 simultaneously, pass through cell walls, or also join cell walls. In this way, a certain reinforcement of the system takes place, whereby the mechanical strength of the porous material increases considerably. When this occurs, there is no noticeable deterioration in the elasticity and flexibility of the polymer matrix, as the fibers as such have a high elasticity.

The resulting materials are washed thoroughly with softened water to remove excess acid, salt and formalin, followed by drying at 70-90 ° C.

During the preparation of the porous reactive material, the degree of acetalization of the polyvinyl alcohol is brought to a value which ensures the formation of a condensation structure on the walls of the foam cell. Upon drying, this thin-pore condensation structure disappears while becoming a cryptocondensation structure. Only the coarser porosity obtained in the flotation and as a result of the addition of the fibrous filler is retained. In the dry state, the material is rigid, it can be subjected to any kind of machining to give the desired shape and dimensions to the part. The presence of an advanced sys-treur in the material of the pores and capillaries substantially facilitates the impregnation of the material with aqueous solutions. Their walls moisten and swell rapidly, the cryptocondensation structure expands again and assumes the volume it occupied in the wet state before drying. In this expanded state, where the foamed polyvinyl fox soil contains a complex fiber-pore system consisting of the finest components, the material has a very high elasticity and is able to withstand very large reversible deformations under stress. Since water is the plasticizer of the required pc lyvinyl formal, even long-term use of the porous, reactive material does not lead to loss of elasticity.

The method of making a porous reactive material based on foamed polyurethane comprises the steps of mixing diisocyanate with polyester in a high speed mixer, mixing in the decomposed reactive fibers, catalyst and a small amount of water, pouring the reaction mixture into molds for foaming and vulcanizing the material.

To obtain a porous, open-celled, filled reactive material based on an elastic, foamed polyurethane of the present invention, all starting components are mixed in a blender (one-step process) or the polyester isocyanate is obtained from the polyester and the excess diisocyanate is then mixed with other diisocyanates. In the one-step process, the reaction takes place at a high rate, in the two-step method much more slowly. In the latter case, it is possible to adjust the density of the material.

Utilization is used of polyesters (condensation products of polyfunctional acids and polyfunctional alcohols), polyethers (condensation products of alkene oxides and bifunctional alcohols) and nitrogen-containing polyfunctional alcohols of polyfunctional alcohols or polyesters (of ethylene oxides and polyfunctional amines).

Phenolates, methyl and ethyl morpholines, pyridine and dimethylaniline are used as catalysts for the reaction in which the diisocyanate and the hydroxy groups of the polyesters or polyhydric alcohols interact, which control the reaction rate and the duration of the process.

Sodium salts of sulfonic acids and other surfactants are used as emulsifiers. Dibutyl phthalate, tricresyl phosphate and the like are used as plasticizers.

The density of the foamed mixture and the number of crosslinks are adjusted by varying the amount of water and diisocyanate added to the polyester. The higher and the amount of water and diisocyanate, the lower the apparent density of the material and the greater the number of crosslinking bridges between the chains; the latter improve the stiffness of the material.

The vulcanization of the porous reactive material takes place within a few hours.

The reactivity of the final materials is tested under laboratory conditions as follows:

To determine the static exchange capacity, a weighed portion of porous material (0.5-0.6 g) is immersed in a 0.1 N solution of base, acid or sodium chloride and stirred for 30 minutes. The number of ions exchanged in the middle i2 705 8 7 is determined from the difference between the final concentrations of the solution outputs.

To determine the total exchange capacity, the material is in contact with the solution for 48 hours. The ion group utilization factor, which describes the exchange rate, consists of the static exchange capacity with a contact time of 2 minutes between the material and the solution and the ratio between the total exchange capacity.

To determine the percentage decrease in material capacity, the materials are subjected to repeated periods of use.

The obtained filled reactive materials are substantially (20-25 times) better than the corresponding granulated materials in their kinetic properties, osmotic stability and mechanical strength.

The materials have elastic properties and are able to withstand considerable reversible stresses.

Unlike prior art ionites, porous fiber-sampled reactive materials are not substantially degraded by significant mechanical loads and sharp variations in the ionic strength of solutions.

Any type of reactive fiber with ion exchange and complexing properties, both individually and in various combinations, can be utilized in the manufacture of porous, filled reactive materials. The materials are characterized by a completely range of valuable properties, a wide range of applications and are suitable for use in liquid and gaseous media with a low concentration of recoverable material.

In use, porous, reactive materials, due to their high osmotic stability and mechanical strength, are characterized by high mass stability.

With respect to the use of materials, sorption and ion exchange processes can be performed by conventional methods in columns, presses and other equipment without significant structural changes in the process equipment.

For a better understanding of this invention, some typical examples are provided below for illustrative purposes.

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Example 1

A porous reactive material containing 20% foamed polyvinyl formal and 80% sulfonated polyvinyl alcohol fibers.

100 ml of a 1% solution of polyvinyl alcohol are foamed in an open vessel in the presence of an emulsifier by means of a mechanical stirrer under normal pressure for 10-15 minutes, after which 10 ml of a 37% solution of formaldehyde and 10 ml of a 24% aqueous solution of sodium chloride are added to the foam. 1-2 minutes before the end of the flotation, 10 ml of catalyst are added for the condensation formation reaction - concentrated hydrochloric acid. An amount of 40 g (80% by weight of the final material) of ion exchange fiber prepared by sulfonation of polyvinyl alcohol fibers is added to the uniform foam with constant stirring. The fiber is cut to a length of 5-8 mm. The resulting mass is poured into a mold and kept in a thermostated vessel at 70 ° C for 60 minutes for vulcanization, followed by a further 24 hours at room temperature to improve the degree of completeness of the process. After separation of the liquid phase, the resulting material is washed to remove unreacted components and dried.

The material thus prepared is a strongly acidic cationite. The static exchange capacity with respect to 0.1 N calcium chloride solution is 4.4-4.6 mg -equiv./g. The utilization factor of the ion groups (static exchange capacity to total exchange capacity) in 2 minutes is 88%.

After ten ion exchange cycles, the static exchange capacity has decreased by 2.3% compared to the initial value. The apparent density of the material, which is 15 to 160 kg / m 2, remains unchanged during the use of the material.

Example 2

A porous reactive material containing 20% foamed polyvinyl formal and 80% strongly acidic ion exchange fiber based on polyacrylonitrile.

The procedure is similar to that described in Example 1 above, except that instead of polyvinyl alcohol fibers, 40 g (80% by weight) of a strongly acidic ion exchange fiber based on po 1 y ak r yy 1 i n i t r 1 i.

i4 70587

The material obtained is strongly oxygen cationite. The static exchange capacity with respect to Q, 1-N sodium chloride solution is 3.6-3.8 mg -equiv./g; the utilization factor of ionic groups is 86%.

After ten ion exchange cycles, the static exchange capacity has decreased by 2.1% compared to the initial value.

The apparent density of the material, which is 140-150 kg / m \, remains unchanged during the operation or use of the material.

Example 3

Porous, reactive material containing 30% foamed polyvinyl formal and 70% sulfonated phenolic aldehyde fiber.

The procedure is similar to that described in Example 1 above except that 23.3 g (70% by weight) of sulfonated phenolic aldehyde fiber are utilized instead of polyvinyl alcohol fibers.

The resulting material is a strongly acidic cationite. The static exchange capacity with respect to 0.1 N calcium chloride solution is 2.9-3.0 mg -equiv./g. The utilization factor of the ion groups in two minutes is 85%.

3

The apparent density of the material, which is 130-150 kg / m, remains unchanged during the use of the material.

Example 4

Porous reactive material containing 30% foamed polyvinyl formal and 70% weakly acidic polyacrylonitrile fiber.

The material preparation procedure is similar to that described in Example 1 except that 23.3 g (70% by weight) of a weakly acidic polyacrylonitrile fiber prepared by alkaline saponification of the freshly prepared polyacrylonitrile fiber is utilized instead of polyvinyl alcohol fibers.

The material obtained is a weakly acidic cationite with a static exchange capacity with respect to a 0.1 N alkali solution of 6.5-8.0 mg -equiv./g. The utilization factor of the ion groups in two minutes is 89%.

After ten ion exchange cycles, the static exchange capacity has decreased by 2.8% compared to the initial value.

3 during use of the material.

The apparent density of 110-15Q kg / m 2 remains unchanged

Example 5

A porous, reactive material containing 30% foamed polyvinyl formal and 70% weakly acidic ion exchange resin based on polyvinyl alcohol fiber.

The procedure is similar to that used in Example 1 except that 23.3 g (70% by weight) of a weakly acidic polyvinyl alcohol fiber is utilized.

The resulting material is a weakly acidic cationite. The static exchange capacity with respect to the 0.1 N alkali solution is 3.5-4.5 mg equivalents, / g. The utilization factor of the ion groups in two minutes is 87%.

After ten ion exchange cycles, the static exchange capacity has decreased by 2.4% compared to the initial value.

3

The apparent density of the material, which is 110-150 kg / m, remains unchanged during the use of the material.

Example 6

A porous, reactive material containing 30% foamed polyvinyl formal and 70% weakly acidic ion exchange fiber based on cellulose regenerated fiber.

The production procedure is similar to that shown in Example 1 except that 23.3 g (70% by weight) of a weakly acidic cellulose-regenerated fiber containing graft polyacrylic acid or polymethacrylic acid is utilized instead of polyvinyl alcohol fiber.

The resulting material is a weakly acidic cationite. The static exchange capacity with respect to the 0.1 N alkali solution is 4.5-5.2 mg-equiv, / g. The utilization factor of the ion groups in two minutes is 92%.

After ten ion exchange cycles, the static exchange capacity has decreased by 3.5% compared to the initial value.

3

The apparent density of the material, which is 120-140 kg / m, remains unchanged during use.

Example 7

A porous reactive material containing 40% foamed polyvinyl formal and 60% weakly basic ion exchange fiber based on polyacrylonitrile fiber.

The production procedure is similar to that described in Example 1 above, except that 15 g (60% by weight) of hydrazidated polyacrylonitrile fiber is used instead of polyvinyl alcohol fibers.

The resulting material consists of a weakly basic anionite; the static exchange capacity with respect to the 0.1 N hydrochloric acid solution is 2.5-2.7 mg -equiv./g. The utilization factor of the ion groups in two minutes is 89%.

After ten ion exchange cycles, the static exchange capacity has decreased by 1.9% compared to the initial value.

The apparent density of the material, which is 10Q-110 kg / m 2, remains unchanged during use.

Example 8

Porous reactive material containing 60% foamed polyvinyl formal and 40% weakly basic polyvinyl alcohol fiber.

The preparation procedure is similar to that described in Example 1 except that 8 g (40% by weight) of polyvinyl alcohol fiber containing graft poly-2-methyl-5-vinylpyridine is added.

The material obtained is a weakly basic anionite; the static exchange capacity with respect to the 0.1 N hydrochloric acid solution is 1.1-1.3 mg -equiv./g. The utilization factor of the ion groups in 2 minutes is 86%.

After ten cycles of ion exchange, the static exchange capacity has decreased by 2.4% compared to the initial value.

3

The apparent density of the material, which is 170-180 kg / m, remains unchanged during use.

Example 9

A porous, reactive material containing 70% foamed polyvinyl formal and 30% weakly basic cellulose regenerated fiber.

The preparation procedure is similar to that described in Example 1 except that 4.4 g (3% by weight) of cellulose-regenerated fiber containing graft poly-2-methyl-5-vinylpyridine is utilized instead of polyvinyl alcohol fibers.

The material obtained is a weakly basic anionite, the static exchange capacity with respect to a 0.1 N hydrochloric acid solution is 0.8-0.9 mg -equiv./g. The utilization rate of the ion groups in 2 minutes is 86%.

After ten ion exchange cycles, the static exchange capacity has decreased by 2.1% compared to the initial value.

3

The apparent density of the material, which is 110-120 kg / m, remains unchanged during use.

Example 10

Porous reactive material containing 40% foamed polyvinyl formal and 60% strongly basic polyvinyl alcohol fiber.

The preparation procedure is similar to Example 1 except that 15 g (60% by weight) of polyvinyl alcohol fiber containing a grafted polymethylvinylpyridine quaternary salt is added.

The resulting material is a strongly basic anionite; the static exchange capacity with respect to 0.1 N sodium chloride solution is 1.1-1.3 mg -equiv./g. The utilization factor of the ion groups in 2 minutes is 91%.

After ten ion exchange cycles, the static exchange capacity has decreased by 1.8% compared to the initial value.

3

The apparent density of the material, which is 200-210 kg / m, remains unchanged during use.

Example 11

Porous reactive material containing 40% foamed polyvinyl formal and 60% strongly basic ion exchange fiber based on polyacrylonitrile.

The production procedure is similar to that shown in Example 1 except that 15 g (60% by weight) of polyacrylonitrile fiber with a grafted quaternary salt of polymethylvinylpyridine is utilized instead of polyvinyl alcohol fibers.

The resulting material is a strongly basic anionite; the static exchange capacity with respect to 0.1 N sodium chloride solution is 2.1-2.0 mg -equiv./g. The utilization factor of the ion groups in two minutes is 86%.

After ten ion exchange cycles, the static exchange capacity has decreased by 2.1% compared to the initial value.

3

The apparent density of the material, which is 180-190 kg / m, remains unchanged during use.

____ - ΤΓ ..- 18 70587

Example 12

Porous reactive material containing 50% foamed polyurethane and 50% strongly basic ion exchange fiber based on polyvinyl chloride.

The foaming mixture contains (by weight): polyesters (such as polyethylene adipate or polypropylene oxide or a copolymer of tetrahydrofuran and propylene oxide dispersed in cation exchange fibers based on sulphurized polyvinyl chloride) - 6.84 g (34.2% by weight) isocyanate (in the form of mixtures of two isomers, 2,4 and 2,6 in a ratio of 65/35 or 80/20) to 2.67 g (13.4% by weight) of an activating mixture with a surfactant (0 , 32 g to 1.6% by weight), dimethylaniline catalyst (0.1 g to 0.5% by weight) water (0.07 g to 0.3% by weight) and paraffin oil (0.01 g to 0.05% by weight).

The polyester is thoroughly mixed for 1-2 minutes in a high speed mixer (65-100 rps) with a short cut cation exchange fiber based on polyvinyl chloride containing sulpho groups in an amount of 10 g (50% by weight). The other components of the mixture are then added and the whole mixture is mixed for 2-3 minutes and poured into a mold where foaming takes place and where the material is then vulcanized.

The resulting material is a strongly acidic cationite; the static exchange capacity with respect to the 0.1 N calcium chloride solution is 2.1-2.2 mg -equiv./g. The utilization factor of the ion groups in two minutes is 65%.

After ten ion exchange cycles, the static exchange capacity has decreased by 2.5% compared to the initial value.

3

The apparent density of the material, which is 200-220 kg / m, remains unchanged during use.

Example 13

Porous reactive material containing 50% foamed polyurethane and 50% cation exchange polyolefin fibers.

The preparation procedure is similar to that described in Example 12 above, except that 10 g (50% by weight) of polypropylene fiber with graft polymethacrylic acid is used instead of polyvinyl chloride fiber.

i9 7 0 5 8 7

The static exchange capacity of the obtained material with respect to the Q, 1-N alkali solution is 3.2-3.3 mg -equiv./g.

3

The apparent density of the material, which is 180-200 kg / m, remains unchanged during use.

Example 14

A porous reactive material containing 60% foamed polyurethane and 40% weakly acidic ion exchange fiber based on phenol tormaldehyde fiber.

The preparation procedure is similar to that described in Example 12 above, except that 6.7 g (40% by weight) of phenolic formaldehyde fiber containing carboxyl groups are utilized instead of polyvinyl chloride fiber.

The resulting material is a weakly acidic cationite; the static exchange capacity with respect to the 0.1 N alkali solution is 1.2 to 1.3 mg equivalents. -c The utilization factor of the ion groups in two minutes is 54%.

3

The apparent density of the material, which is 300-320 kg / m, remains unchanged during use.

Example 15

Porous, reactive material containing 60% foamed polyurethane and 40% weakly basic ion exchange fiber. based on polyvinylidene chloride.

The preparation procedure is similar to that shown in Example 12 except that instead of 10 g, 6.7 g (40% by weight) of ion exchange fiber made from mixtures of halogen-containing polymers and a polymer of the pyridine series are added to polyvinyl chloride-based ion exchange fiber.

The material obtained is a weakly basic anionite; its static exchange capacity of a 0.1 N hydrochloric acid solution is disproportionate 3.2-4.1 mg -equiv./g. The utilization factor of the ion groups is 83%.

After ten ion exchange cycles, the static exchange capacity has decreased by 3.1% compared to the initial value.

3

The apparent density of the material, which is 250-280 kg / m, remains unchanged during use.

Example 16

Porous reactive material containing 60% foamed polyurethane and 40% strongly basic ion exchange fiber based on poly / inyl halides.

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The preparation procedure is similar to that shown in the previous Examples 12 and 15 except that a strongly basic polyvinyl chloride fiber made from blends of halide-containing polymers and pyridine series polymers is added.

The material obtained is a strongly basic anionite. The static exchange capacity with respect to 0.1 N sodium chloride solution is 1.5-1.6 mg -equiv./g. The utilization factor of the ion groups is 86%.

Example 17

Porous reactive material containing 60% foamed polyurethane and 40% weakly acidic ion exchange fiber based on polyvinyl chloride.

The preparation process is similar to Example 12 except that instead of 10 g of a strongly acidic cation exchange fiber based on polyvinyl chloride, 6.7 g (40% by weight) of polyvinyl chloride fiber containing graft carboxyl groups are utilized.

The material is a weakly acidic cationite. The static exchange capacity with respect to a 0.1 N alkali solution is 3.1-3.4 mg -equiv./g. The utilization factor of the ion groups is 87%.

After ten ion exchange cycles, the static exchange capacity has decreased by 2.4% compared to the initial value.

The apparent density of the material, which is 220-240 kg / m 2, remains unchanged during use.

Example 18

Porous reactive material containing 70% foamed polyurethane and 30% strongly basic ion exchange fiber based on phenol aldehyde fiber.

The preparation process is similar to that described in Example 12 above except that 4.4 g (30% by weight) of aminated (with ethylenediethylamine chlorohydrate) phenol-formaldehyde fiber is added instead of 10 g of polyvinyl chloride fiber.

The material obtained is a strongly basic anionite. The static exchange capacity with respect to 0.1 N sodium chloride solution is 0.2, 2 mg -equiv./g.

After ten ion exchange cycles, the static exchange capacity has decreased by 1.4% compared to the initial value. The apparent density of the material is 280-300 kg / m 2; it remains unchanged during use.

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Example 19

A porous, reactive material containing 8% foamed polyurethane and 20% strongly basic ion exchange fiber based on cellulose regenerated fiber.

The preparation procedure is similar to that shown in Example 12 except that instead of 10 g of polyvinyl chloride-based ion exchange fibers, 2.5 g (20% by weight) of cellulose-regenerated fiber with grafted 2-methyl-5-vinylpyridine are added.

The resulting material consists of a strongly basic anionite. The static exchange capacity with respect to 0.1 N sodium chloride solution is 0.4-0.6 mg -equiv./g, the utilization factor of the ion groups is 88%.

After ten ion exchange cycles, the exchange capacity 3 has decreased by 1.1%. The apparent density of the material, which is 220-240 kg / m, remains unchanged during use.

Example 20

A porous reactive material containing 30% foamed polyvinyl formal and 70% amphoteric ion exchange fiber based on polyvinyl alcohol.

The preparation procedure is similar to that described in Example 1 except that instead of 40 g of sulfonated polyvinyl alcohol fiber, 23.3 g (70% by weight) of amphoteric ion exchange fiber prepared by amination of polyvinyl alcohol fiber with ethyleneimine vapors and grafting of polyacrylic acid is added.

The material obtained is amphoteric ionite. The static exchange capacity for 0.1 N hydrochloric acid is 1.5-1.6 mg-equiv / g and for 0.1-N alkali solution 5.6 mg-equiv / g. The utilization factor of the ion groups is 88%. The apparent density of the material, which is 100-3,110 kg / m, remains unchanged during use.

Example 21

Porous reactive material containing 30% foamed polyvinyl iformal and 70% amphoteric ion exchange fiber based on polyacrylonitrile.

The preparation procedure is similar to that described in Example 1 except that instead of 40 g of polyvinyl alcohol fiber, 23.3 g (70% by weight) of "Fly" polyacrylonitrile fibers containing amino and carboxy groups are added.

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The material obtained is amphoteric ionite. The static exchange capacity for the Q, 1-N hydrochloric acid solution is 2.9-3.1 mg-equiv / g and for the Q, 1-N alkaline solution 6.1-6.3 mg-equiv / g. The utilization factor of the ion groups is 88%.

3

The apparent density of the material, which is 120-300 kg / m, remains unchanged during use.

Example 22

Porous reactive material containing 30% foamed polyvinyl formal and 70% amphoteric ion exchange fiber based on cellulose regenerated fiber.

The preparation procedure is similar to Example 1 except that 23.3 g (70% by weight) of amphoteric cellulose-regenerated fiber prepared by treating with a mixture of triethanolamine and epichlorohydrin and then oxidizing is added instead of 40 g of polyvinyl alcohol fiber.

The material obtained is amphoteric ionite. The static exchange capacity with respect to the 0.1 N calcium chloride solution is 1.2-1.3 mg-equiv./g; 1.8-2.0 mg -equiv./g for a 0.1 N hydrochloric acid solution.

3

The apparent density of the material, which is 150-190 kg / m, remains unchanged during use.

Example 23

Porous reactive material containing 50% foamed polyurethane and 50% amphoteric ion exchange fibers based on polyolefin fibers.

The preparation procedure is similar to Example 12 except that instead of 10 g of polyvinyl chloride fiber, 10 g (50% by weight) of amphoteric polypropylene fiber containing amino and carboxy groups are added.

The material obtained is amphoteric ionite. The static capacity for a 0.1 N hydrochloric acid solution is 0.9-1.0 mg-equiv / g and for a 0.1 N alkaline solution 1.3-1.5 mg-equiv / g.

Example 24

Porous reactive material containing 30% foamed polyvinyl formal and 70% complexing fibers based on polyacrylonitrile fibers.

The manufacturing procedure is similar to Example 1 except that

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7 0 5 8 7 23 that instead of 40 g of ion exchange fiber, 23.3 g (70% by weight) of phosphorus-containing polyacrylonitrile fibers are added.

The resulting material has complexing properties with respect to certain elements (copper, cobalt, tin, nickel).

Example 25

A porous active material containing 30% foamed polyvinyl iformal and 70% complexing fibers based on cellulose regenerated fibers.

The preparation process is similar to Example 1 except that 23.3 g (70% by weight) of a cellulose graft copolymer containing thioamide moieties is added.

The resulting materials have complexing properties with respect to precious metals and mercury ions in acidic solutions.

Example 26

Porous reactive material containing 40% foamed polyurethane and 60% complexing fibers based on polyvinyl alcohol fibers.

The preparation procedure is similar to that described in Example 12 except that instead of 10 g of ion exchange fiber, 15 g (60% by weight) of polyvinyl alcohol crosslinked with maleic anhydride and aminoethylated with ethyleneimine are added.

The resulting materials have complexing properties with respect to cations of metals of varying valence.

Example 27

Porous reactive material containing 90% foamed polyurethane and 10% complexing fibers based on cellulose regenerated fibers.

The manufacturing process is similar to that described in Example 12 except that 1.1 g (10% by weight) of cellulose-regenerated phosphorylated fibers are added instead of 10 g of ion exchange fibers.

The obtained materials have complexing properties with respect to arsenic, molybdenum, tungsten, germanium, etc. ions.

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Example 28

Porous reactive material containing 40% carboxyl group ion exchange fibers and 20% complexing phosphorylated fibers based on cellulose-regenerated fibers and 40% foamed polyurethane.

The preparation procedure is similar to that shown in Example 12 except that instead of 10 g of ion exchange fiber, 6.6 g (40% by weight) of ion exchange fiber and 2.5 g (20% by weight) of complexing fiber based on cellulose-regenerated fibers are added.

The exchange capacity of the obtained material with respect to 0.1 N calcium chloride solution is 4.1 mg-equiv./g. The apparent density of the material, 3 which is 190 kg / m, remains unchanged during use.

Example 29

A porous reactive material containing 40% foamed polyvinyl formal, 30% ion exchange fiber and 30% complexing fiber based on polyacrylonitrile fibers.

The production procedure is similar to that described in Example 1 except that instead of 80% ion exchange fibers, 30% ion exchange polyacrylonitrile fiber and 30% complexing fiber based on phosphorus-containing polyacrylonitrile fibers are added.

The exchange capacity of the obtained material is 6.4 mg-equiv./g with respect to 0.1 N calcium chloride solution. The apparent density of the material, 3 which is 185 kg / m, remains unchanged during use.

Claims (4)

25 70587 A porous, open-celled, filler-containing reactive material consisting of a polymer matrix and a reactive filler, characterized in that the polymer matrix consists of foamed polyvinyl formal or foamed polyurethane and the reactive filler consists of 80% finely divided ion exchange fibers and / or complex fibers the weight of the final material. Material according to Claim 1, characterized in that the amount of reactive fibers is 50 to 70% by weight of the final material. Material according to Claims 1 and 2, characterized in that strongly or weakly acidic, strongly or weakly basic ionites or polyamolytes based on polyvinyl alcohol fibers, polyacrylic fibers, polyacrylic fibers, cellulose-regenerated fibers, phenolic alcohols are used as reactive ion exchange fibers. Material according to Claims 1 and 2, characterized in that fibers based on polyacrylic fibers, polyvinyl alcohol fibers or cellulose-regenerated fibers are used as complexing fibers.