HU196080B - Process for producing pearl polymers of uniform grain size - Google Patents

Abstract

The present invention relates to a method for producing graft polymers by suspending pollutants of mono- or polyvinyl compounds in aqueous solutions. A typical feature of the present invention is that the polymerization mixture is conducted in DC at a temperature of 5 to 70 ° C in the aqueous solution used as the continuous phase when the Y] <Qnst: ^ mouo ~ a * 10 '^ means the volume of the continuous phase and Vmono jc'etn. the volume of the monomer or the polymerization mixture is between 0.1 and 60, b) the uniform size polymerization mixture in the aqueous solution obtained by spraying the polymerization mixture into the aqueous solution droplets to the monomer droplets and the aqueous solution. the difference between the density of the reaction vessel from the spray area of the reaction vessel to the encapsulation area and continuously encapsulated therein by coacervation known from the field of microconsulation, by complex coacervation or by phase boundary reaction, and c) droplets of the encapsulated polymerization mixture are heated in an aqueous suspension by heating at 40-95 ° C. merizálják. (11) 196080 B International class logo: (51) NSZO * C 08 F 2/18 B 01 J 13/02 -1-

Description

There is a growing need for modern ion-exchange technologies to address the specificities of certain types of ion-exchangers. With increasing demands on capacity, kinetics and stability to mechanical and osmotic loads, more and more uniformity of particle size is increasingly required. Particularly high demands are placed on the uniformity of fineness when the hydrodynamics is a decisive parameter in the applied process.

Thus, for example, high performance, high throughput ion exchange filters require the most uniform, coarse particle size, since the fine particle is located in the space between the large grain particles, thus increasing the filter resistance. Due to the increased resistance, higher pressures are required to achieve the required high permeability, which in turn can easily cause the pearls to be exchanged to break.

Equally important is the high uniformity of pitch for replacers placed in mixed bed filters. If the particle size is significantly different, this results in the fine portions of the specifically heavier ion exchanger being mixed with the coarse grains of the specific lighter ion exchanger. Even in the case of the insulating layer process, there is always a requirement for the mixed bed filters to have a uniform mesh size of the four components, i.e. the ion exchanger, the insulating material and the cation exchanger. The use of a uniform particle size resin is also advantageous for the smooth operation of the countercurrent process detailed in U.S. Patent No. 1,442,689.

Various attempts have already been made to produce ion exchangers and the underlying matrices having the most uniform particle size, either by known processes for the preparation of ion exchangers or the underlying matrices, either from pearl polymers or from pellet condensates. , or by slurry condensation from the starting compounds or by mass-milling of the resulting crosslinked polymers or polycondensates. In both processes, the particle size distribution will be often represented by a Gaussian curve. Physical separation processes such as sieving or fractional flotation are required to achieve the desired uniformity of particle size. These types of separation processes are both expensive and have the serious disadvantage that the larger and smaller diameter particles that are forced during the process are either not sold at all or difficult to sell. The amount of unwanted larger or smaller particle size increases with increasing demands for particle size uniformity.

In the case of pearl polyethers, the average particle size can be influenced to some extent, but the width of the particle size spectrum can only be influenced by very limited polymerization conditions. Thus, for example, U.S. Patent No. 4,129,707 describes suspension polymerizations that achieve narrower limits of particle size distribution, but only reduce the amount of unwanted larger and smaller diameter particles, and thus do not produce uniformly sized particles. .

According to the process disclosed in U.S. Patent No. 3,784,491, which is intended to produce polymer particles of uniform size, beads of uniform size are not available. According to this process, the liquid droplets formed from the mixture to be polymerized are coated with soluble gelatin-containing complex coacervates to prevent agglomeration. However, since the liquid droplets are subjected to shear forces prior to coating, which cause the droplets to merge and disperse, the process also involves coating at a variety of particle sizes. The coating therefore does not lead to the desired polymer particles of uniform serum size. In addition, soluble gelatin-containing complex coacervates recommended for coating liquid droplets are liquid and, consequently, the droplets are not leached from the shear-induced distribution after coating. In addition, under the alkaline polymerization conditions employed, the liquid coatings dissolve.

A more advantageous process for preparing uniform particle size bead polymers is described in U.S. Patent No. 3,922,255. According to this process, the equal size monomer droplets produced by the jets are transferred to a rain reactor, in which time the polymerization proceeds as far as it will go. can be removed from the column without damage. In this, the residence time is adjusted by the flow of a continuous phase directed against the fold drop force of the droplets. Apart from the high / low technical demand, this is it. The major disadvantage of the process is that the residence time fluid flow must have a high linear velocity, which results in a velocity software in the cross-section of the column which results in a different ion exchange quality from the polymerizates due to the different residence time of each monomer droplet in the polymerization column. The difference in quality caused by the extreme hydrodynamic conditions of the polymerization column between the polymer-derived beads severely limits the applicability of the process.

Methods for encapsulating liquids (e.g., U.S. Patent Nos. 3,429,827 and 3,577,515) could not provide an incentive to solve the above-mentioned technical problem, i.e. the production of beads of uniform particle size and quality, since they are not uniform in particle size. no capsules with uniform physical properties could be prepared.

Thus, for example, the process of encapsulating liquids in U.S. Patent No. 3,429,827 does not provide an equal size capsule because, due to the encapsulation conditions used, the formation of evenly round droplets is not completely prevented by the formation of the capsule wall too early. at least severely obstructs (see, for example, U.S. Patent 3,577,515, column 2, line 65 to column 3, line 5).

The modifications made in U.S. Patent No. 3,577,515 to avoid the disadvantages of U.S. Patent No. 3,429,827 do not lead to uniform size capsules, since drops, before they can form a stable capsule wall, are subject to fusion and shear force. they divide into a wide variety of sizes and are consequently converted into capsules of various sizes.

It has been found that pearl polymers of uniform particle size and uniform quality are obtained by concentrating the monomer or polymerization mixture to be polymerized into a liquid (substantially continuous fluid) which is substantially immiscible with the monomer and / or polymerization mixture. particle size inonomer droplets or polymerization mixture droplets are prepared, these uniform size droplets are encapsulated under stable polymerization conditions in accordance with known microencapsulation methods, followed by the step of polymerizing and encapsulating the The terms and conditions set out in this section are maintained.

The invention thus relates to the production of bead polymers by slurry polymerization of mono or poly (vinyl) compounds in aqueous solutions.

a) directing the polymerization mixture at a temperature of 5 to 70 ° C directly into an aqueous solution containing 0.01 to 10 7% of the stabilizer used as the continuous phase when W - where V _{kQ (} , _f is the continuous phase and V _no is the monomer and the volume ratio of the polymerization mixture is between 0.1 and 60,

b) the droplets of the uniform size polymerization mixture in the aqueous solution obtained by spraying the polymerization mixture into an aqueous solution are transferred hydrodynamically from the spraying area of the reaction vessel to the encapsulation area by hydrodynamic release; continuously encapsulated by known coacervation, complex coacervation, or phase interface reaction, and

c) polymerizing the encapsulated polymerization droplets in an aqueous suspension by heating at 40 to 95 ° C.

Encapsulation with a stable casing under polymerization conditions is then carried out in two sub-steps where the casing formed around the droplets is known to be stable under shear forces but is no longer stable under polymerization conditions in accordance with known microencapsulation techniques.

In this case, the coatings in a second process step, which may be carried out continuously or discontinuously, must be cured to coatings which are stable under the conditions of polymerization. The curing step may be carried out in a separate process in a separate reaction vessel, but preferably in the same reaction vessel.

However, if the coating around the droplets is stable under the polymerization conditions after the microencapsulation process, then the curing step is omitted and the polymerization conditions are encapsulated with the stable coating in a single step.

In the process of the invention, the sheath is said to be stable against shear when it is capable of resisting, without damage, a stirring motion of the strength used under standard suspension polymerization conditions to produce droplets of equal size.

By combining, in accordance with the present invention, the formation of uniform size monomer or polymerization mixture droplets, the stabilization of these droplets by encapsulation, and the polymerization of droplets coated with a stable coating under polymerization conditions, all of which are carried out under defined conditions. , which have pearls having approximately the same particle size and physical properties such as grain stability, fracture toughness, etc.

The process of the invention is suitable for the preparation of beads of uniform particle size from a variety of monomers. The applicability of the process is only conditional on the polymerization mixture being liquid under the spray conditions. For the purposes of the present invention, a polymerization mixture is a monomer or a mixture of minomeric monomers to be polymerized with conventional pilimerization additives.

Examples of common polymerization additives include, in particular, polymerization initiators (radicals such as azo-isobutylnitrile and dibenzoyl peroxide), polymerization inhibitors, and inert liquids which polymerize, e.g. .

The polymerization mixtures may further comprise dyes and, if the sizing agent is to be polymerized for the liquid-liquid extraction, also include the liquid-liquid extraction agent.

The polymerization mixtures may also contain compounds which react with other compounds to form the wall of the capsule.

The process of the invention is suitable for the preparation of both gel-form and macroporous bead polymers.

Examples of monomers useful in the process of the present invention include simple unsaturated compounds such as mono-vinyl compounds such as silyl, vinyl vapor, ethyl styrene, α-methylstyrene, and their halogenated derivatives, such as chlorostyrene, and vinyl benzal chloride, acrylic acid, its salts and esters, in particular its methyl and ethyl esters, methacrylic acid, its salts and esters, in particular its methyl ester, and nitriles and amides of acrylic acid and methacrylic acid.

Examples of polyunsaturated compounds are in particular: polyvinyl compounds such as cinylbenzene, divinyltoluene, trivinylbenzene, divinylnaphthalene, trivinylnaphthalene, diethylene glycol divinyl ether, trivinylcyclohexane, 1,7-octadiene, 1,6-heptadiene, 1,5-hexadiene, methacrylic acid esters of polyhydric alcohols, such as ethylene glycol dimethacrylate and methylene-Ν, Ν-bis-acrylonide.

Particularly suitable monomers in the process of the invention are the following; amongst the monovinyl compounds, styrene, α-methylstyrene, ethylstiol, chlorostyrene, esters and / or amides of acrylic acid and methacrylic acid, acrylonitrile, among the irvinyl compounds are divinylbenzene, divinyltoluene, tri vinylbenzene, diethylene glycol divinyl ether, trivinyl cyclohexane, 1,7-octadiene, 1,6-heptadiene, 1,5 hexadiene and / or methacrylic acid esters of polyhydric alcohols.

The formation of uniformly sized particles by spraying is known. See, e.g., Naefe et al., Chem. Ing. Techn., 50, 321 (1978), and U.S. Patent No. 3,922,255. Naefe et al. (see above quotation) can calculate the outflow velocities needed to produce particles of equal size.

The spraying of monomers or the polymerization mixture into a continuously immiscible liquid (continuous phase) which is substantially immiscible with the monomer or polymerization mixture is carried out in the simplest case by means of a capillary, through which the the mixture is priced into the continuous phase. As the current of the monomer exits into the continuous phase, the monomeric liquid stream is divided into equally large steps. In technical devices, capillary holes or similar devices may be used instead of individual capillaries. The particle size is determined by the internal diameter of the capillary or capillary-sized holes.

The sputtering area in the process of the invention is the area of the reaction vessel where the liquid jet of the monomer enters the continuous phase and when the ray is disintegrated, the monomer droplets formed in the continuous phase take on a final curve shape.

To this area is added the encapsulation area, i.e. the area of the reaction vessel where the formed monomer droplets are provided with a coating that is stable under polymerization conditions and against shear forces.

It is an essential element of the invention that the sputtering area and the encapsulation area are two different areas, that is, successively introduced by the monomer droplets, and that the sputtering and encapsulation do not occur in the same portion of the reaction vessels as in the known processes, e.g. 827. The separation of the sputtering and encapsulation areas according to the invention prevents the monomeric liquid jet particles from encapsulating before they completely disintegrate into eseppes, thereby encapsulating particles of different shapes and sizes and subsequently polymerizing. The sputtering and encapsulation areas can be separated by mechanical means such as narrowing the reaction tube, incorporating funnel molds into the reaction vessel which do not impede the free movement of the monomer droplets in the continuous flow phase. However, these areas can also directly overlap.

It is also an essential aspect of the invention that from the formation of the monomer droplets to the time they are encapsulated, the eseppe is not subjected to forces that cause the integrity of each drop to be altered. According to the invention, the forces to be avoided are, in particular, the shear forces which affect the monomer droplets when the system consisting of a monomer droplet in a continuous phase is agitated.

The effect of shear forces on uniformly sized monomer droplets formed during liquid jet disintegration is avoided in accordance with the present invention by removing these droplets hydrodynamically from the spray area and subsequently passing it through the encapsulation area.

In accordance with the present invention, they utilize the motion due to the difference in density between the monomer droplets and the continuous phase, i.e., the buoyancy force on the eseppe and the droplet drop in the continuous phase, and further utilize the flow motion of the continuous phase to transport the droplets through the reaction vessel. removal from the area of entry and passage through the area of encapsulation. These effects are exploited because the droplets and the continuous phase are passed in the same direction through the reaction vessel.

For continuous fluid, substantially immiscible with monomeric or polymerization mixture, continuously supplied to lipophilic monomers such as styrene, acrylic acid esters, methacrylic acid esters, acrylonitrile, methacrylonitrile, divinylbenzene, It does. proved to be dilute aqueous solutions of water or substances needed for encapsulation, such as dilute bases. An example of such a base is soda. Aqueous solutions of suitable suspension stabilizers, such as gelatins, may also be used. For folic, water-soluble monomers such as acrylic acid, methacrylic acid or water-soluble polar polymerization mixtures, hydrophobic media such as aliphatic or aromatic hydrocarbons and halogenated hydrocarbons as well as silicone oils have proved to be a suitable continuous phase.

^{V kon;} rnono ^{space V} f 8 ° can NENT ^ati ratio value below 0.1. (Μ ^ _θη , denotes the volume of the continuous phase, V denotes the volume of the monomer or polymerization mixture). The volume ratio is from 0.1 to 60 according to the encapsulation procedure used. Preferably, when encapsulated by the coacervation process, it is from 3 to 60, and when encapsulated by the complex-coacase skeletal and phase boundary reaction method, it is preferably from about 1 to 20.

The upper bound of the volume ratios is determined by the economics of the process, since the increase in this ratio reduces the space-time yield of the encapsulated monomer droplets. Because encapsulation of monomer droplets of the same size is not different in itself. from known continuous and discontinuous encapsulation, basically the volumetric ratios and concentrations of the various components described and quoted for known encapsulation methods can be used in the following summary works: Kondo: Surf. Colloid Sci, 10, l / 1978, Kirk-Othmer, Encyclopedia of Chemival Technology, 2nd Edition, Volume 13, 436-456. p.

The spraying of the monomer and / or polymerization mixture is generally carried out at a temperature of 0 to 95 ° C, preferably 5 to 70 ° C.

When the monomers or the polymerization mixture are sprayed into the continuous phase, the continuous phase is flowing in a direction parallel to the radius of the polymerization mixture. The use of concentric dual nozzles for spraying has proven to be extremely advantageous. In these nozzles, the polymerization mixture flows through the inner nozzle and the continuous phase flows from the two concentrically arranged nozzles to the outer nozzle.

In order to exclude interfering conditions affecting the uniformity of droplet size during atomization of the liquid jet, it may be advantageous to place the incoming polymerization mixture under the influence of longitudinal vibrations of appropriate frequency. This can occur, for example, due to periodic pressure fluctuations, such as sound waves or periodic movement of the nozzle.

Preferably, the continuous phase comprises solutes (drop stabilizer) which prevent the droplets of the polymerization mixture from melting before the encapsulation step. Suitable stabilizers are, for example, suspending excipients known in the art of bead polymerization, such as polyvinyl alcohol or carboxymethyl cellulose. Particularly advantageous has been the use of drop stabilizers which can simultaneously serve to build up the capsule wall. Examples of such stabilizers are gelatins and agar.

The concentration of stabilizers in the continuous phase is generally 0.01 to 10% by weight, based on the weight of the continuous phase.

Encapsulation is used to create uniform sized droplets of the polymerization mixture. For encapsulation, the droplets are moved from the area where they are formed (spray area) to the adjacent encapsulation area. The temperature of the encapsulation area can be set independently from the temperature of the spray area. In addition, the encapsulation area is provided with equipment that allows the addition of further liquid components.

The encapsulation of stabilized uniform particle size polymerization blend droplets is carried out continuously according to microencapsulation methods known per se. Examples of such known methods include:

a) Coacervation

During coacervation, a colloid-rich phase is formed which is located around the droplets of the polymerization mixture. Hydrophilic colloids such as gelatin or agar are suitable for encapsulation by coacervation. For example, an aqueous saline solution is introduced into the encapsulation area to induce coacervation. As the salt, when gelatin is used as the hydrophilic colloid, alkali sulfates, especially sodium sulfate, have proven to be suitable. Coacervation can be accomplished particularly easily by employing an aqueous solution of a hydrophilic colloid, such as gelatin or agar, as the continuous phase in which the liquid jet of the polymerization mixture decomposes. The liquid jet distribution is performed at temperatures above the colloidal gel temperature.

The formation of the coacervate shell is accompanied by its consolidation by cooling to below the gelation temperature. The coacervate casing thus produced, although resistant to shear, is often not stable under the conditions of polymerization. In order to obtain a stable coating under polymerization conditions, the encapsulated particles are subjected to chemical starch (hardening). Methods are known for obtaining a chemical starch, such as gelatin starch with aldehydes such as formaldehyde (e.g., U.S. Patent No. 2,800,458). The chemical starch (hardening) of the particles may be continuous or non-continuous in the same or another. reaction vessel.

b) Complex coacervation

During complex coacervation, a colloid-rich phase is formed from two different electrically charged colloids (polyelectrolytes), which are located around the monomer droplets. For example, systems consisting of gelatin and gum arabic or gelatin and special mixtures of copolymerates are suitable for encapsulation after complex coacervation. Such a special blend of copolymerizates is, for example, one in which the acrylamide and maleic or maleic anhydride groups are in a statistical distribution, or, for example, a copolymer in which the acrylic amide, acrylic and maleic acid groups are in statistical distribution. Such blends of copolymerizates are described in U.S. Patent 4,181,639 as coinplex coacervation components. For example, to induce complex coacervation, the pH of the encapsulation area is adjusted by the addition of acids, for example, in the case of the selenium / gum arabic system, so that only one of the originally charged polyelectrolyte trolley changes its charge pattern. Once the complex coacervate casing is formed around the droplets of the polymerization mixture, the drop moves towards an area of the encapsulation area which is set at a temperature below the gelation temperature. The resulting complex-coacervate envelope, although resistant to shear, is often not stable to polymerization conditions. In order to obtain a stable coating under polymerization conditions, the encapsulated particles are subjected to further chemical starch. Such methods of chemical starching, for example starch of capsule walls containing celatin with aldehydes such as formaldehyde, are known, for example, from U.S. Patent No. 2,800,457.

c) The phase boundary surface reaction during encapsulation with the phase boundary surface reaction encapsulates the capsule wall enclosing the droplets of the polymerization mixture by adding droplets to the continuous phase with the component added to the continuous phase in the polymerization mixture and reacting the film. In practice, encapsulation by the phase boundary surface reaction is accomplished by adding component 1 to the polymerization mixture, which is miscible with the polymerization mixture but is not substantially miscible with the continuous phase. After the polymerization mixture is divided into droplets of azqnos size, during which the droplets may be stabilized with any suspending excipients, the droplets move towards the encapsulation area. Here we add the 2 components. These 2 components are soluble in the continuous phase. There are a large number of K _t / K ₂ component pairs which react on a phase fish surface during film formation. By way of example, halides of polybasic acids, such as sebacic acid chloride, diverted phthalic acid chloride, phospho-gene, multivalent isocyanates, such as tolirol-2,4-di-isocyanate, lexamylcyl diisocyanate, polybasic succinic acid, , 3-benzenesulfonic acid chloride, polyhydric amines such as hexamethylenediamine, polyhydric hydroxyl compounds such as pyrogallol or bisphenol, which are polymeric carboxylic acid amides and carboxylic acid esters, and polyureas and polyureas; reacting with polymeric sulfonamides and sulfonic acid esters (see, for example, PG Morgan, Lutherfacial Polycolidensation, Versatile Method or Polymer Preparation, Soc. Journal of Plastics Engineers 15,485). The different reactivity of the different pairs of KJK.2 components is taken into account by adjusting the residence time and the set temperatures in the encapsulation area. In some cases, it has been found advantageous to use reaction-accelerating agents, such as bases, for polycondensation reactions that produce acids. These excipients are preferably added to the continuous phase of the encapsulation area.

Preferably, complex coacervation is used.

The process steps that make up the essential elements of the invention - the creation of equal size polymerization mixture droplets by spraying the polymerization mixture directly with the continuous feed phase and encapsulation of equal size droplets - can be carried out in a particularly simple manner in a reaction column. The apparatus outlined in Figure 1 is preferably used when the density of the polymerization mixture to be encapsulated is less than or equal to that of the continuous phase. In Figure 1, section 6 indicates the spray zone of reaction column I, i.e., the area where the jet of the polymerization mixture sprayed on the nozzle 2 disintegrates and the droplets formed during the jet decomposition assume their final spherical shape. Solution 3 (continuous phase) flows from the inlet pipe 3 to stabilize the droplets of equal size. In the lower part of section 7, the component which induces encapsulation is continuously added at the inlet 4. Through the inlet 5, reinforcing parts can be introduced. In 8 stages, starch can occur. The temperatures in each of the stages 6, 7 and 8 of the reaction column 1 can be set independently and provided with control devices such as thermometers and pH measuring devices. It can be seen from Figure 1 that the encapsulated droplets of the polymerization mixture are formed independently of the shear forces. Overflow 9 of the reaction column 1 encapsulates droplets whose integrity is no longer compromised by subsequent mechanical forces such as mixing in the polymerization vessel 10.

For encapsulation of polymerization mixtures having a density greater than the continuous phase, a substantially identical reaction column 1 as shown in Figure 1 is suitable, but in this case the introduction of the polymerization mixtures 6 and 2 and the introduction of the continuous phase 3 into the tube it is located at the top and the outlet 8 and outlet 9 are at the bottom end of the reaction column.

Polymerization of the encapsulated polymerization mixture

The droplets of the polymerization mixture after encapsulation are in a state which permits their handling, such as stirring during heating, without compromising the integrity of the encapsulated droplets. In this respect, there is a significant difference to conventional suspension polymerizations, whereby droplets are not constant as single individuals as a result of disintegration and fusion until a certain degree of polymerization is reached. In contrast, the encapsulated monomer droplets retain their integrity and thus their uniform size.

The polymerizer of the polymerization mixture in the encapsulated droplets is shaken by heating the optionally hardened capsules in an aqueous suspension for several hours at 40-95 ° C. The polymerization of the droplets of the encapsulated polymerization mixture can be carried out in the same vessels as the conventional slurry polymerization.

Removing the capsule wall

After the polymerization process, the bead polymer appears in a solid, shape-retaining form. The capsule wall can be removed from this bead polymer in a separate process step. However, the capsule wall can also be removed by converting the bead polymerized motifs into ion exchangers during the introduction of functional groups.

a) Removal of the capsule wall in a separate process step To remove the capsule wall, the encapsulated bead polymer is subjected to a chemical treatment which breaks down the capsule wall. The nature of the sulfur treatment is determined by the chemical structure of the capsule wall. For example, casing walls consisting of gelatin and hardened gelatin may be removed by heating the encapsulated bead polymers with dilute aqueous acids such as dilute sulfuric acid or aqueous bases such as dilute sodium hydroxide for several hours. Similarly or similarly, the capsule wall consisting of polyamides, such as hexamethylenediamine and adipic acid, or polyesters such as terephthalic acid chloride and bisphenol A, or polycarbamers, such as is formed from isocyanate and hexamethylene diamine.

b) Removal of the capsule wall during introduction of functional groups In most cases, the introduction of functional groups into polymers occurs under drastic conditions. For example, to introduce sulfonic acid groups into cross-linked polystyrene, the bead polymer is treated with hot concentrated sulfuric acid. In the alkaline saponification of crosslinked polyacrylic acid esters, the bead polymers are heated for several hours with 40% sodium hydroxide. Under these circumstances, the capsule wall is simultaneously degraded and the capsule wall is removed simultaneously with the introduction of the functional group, and the removal of the capsule wall with the introduction of the functional group can be carried out in a single step. The introduction of functional groups is not influenced by the capsule.

Introduction of functional groups

The introduction of functional groups into uniform particle size bead polymers of the present invention is accomplished by known methods. An overview of these procedures can be found, for example, in Ullmanns Enzyklopaedie dér Technischen Chemie, 4 Editions, Volume 13, pp. 300-303.

Single particle size bead polymers produced by the process of the present invention can be used as such, for example, as so-called adsorbent resins or as inert insulating layers in mixed bed filters. They can also be used as stickers for the preparation of ion exchangers, as noted above.

The process of the invention is illustrated in the following examples. In these examples, parts are by weight unless otherwise indicated.

Example 1

In the apparatus described in Figure 1, a solution of 86 parts of styrene, 8 parts of divinylbenzene, 5 parts of ethylstyrene and 1 part of dibenzoyl peroxide was heated to 45 ° C through a capillary 2 (0.35 mm inside diameter, capillary material of stainless steel). Spray at 2.7 ml / min. The continuous phase used is a 10% aqueous gelatin solution (from porcine gelatin) which is heated to 55 ° C. This continuous phase has a pH of 7.8 and is introduced at a flow rate of 12 ml / min. The 6 spraying areas were maintained at 50 ° C. A 20% aqueous solution of sodium sultate was administered via line 4 at a rate of 4.7 mL / min.

In the encapsulating area 7, the temperature of the continuous phase is controlled to decrease from 50 ° C at the lower end to 15 ° C at the upper end. A 5% aqueous solution of sodium sulfate at 15 ° C at 100 ml / min was introduced through inlet 5.

The overflow spill capsule suspension 9 is passed into a stirred tank 10, stirred for 2 hours and then washed with water at 15 ° C. The suspension is then treated with 10 ml of 36% formalin and 10 g of disodium hydrogen phosphate dodecahydrate per liter of aqueous phase with stirring. The suspension is then kept for 2 hours at 25 ° C and the capsules are freed of excess formalin by washing with water. The polymerization mixture in the capsules is polymerized by suspending the hardened capsules in water. It is heated for 10 hours at 70 ° C. The thus encapsulated bead polymer, which is composed of gelatinous polyvinyl crosslinked with divinylbenzene, is separated after washing, washing and drying, without prior removal of the capsule wall, by sulfonation in a known manner (see Ullmann, loc. old) is converted to a strongly acidic cation exchanger.

The resulting highly acidic cation exchanger (Na form) has a particle size in the range of 0.8 to 1.2 mm, with 80% of the beads in the range of 0.9 to 1.1 mm.

If the same polymerization mixture is bead polymerized in the usual manner with 0.2% aqueous solution of carboxymethylcellulose sodium, and then only 53% of the beads in the heart are in the size range of 0.8-1.2 mm, and only 29% of the beads have a

In the size range 0.9-1.1 mm.

Example 2

In the apparatus described in Figure 1, 91 parts of styrene, 5 parts of divinylbenzene, 3 parts of ethylstyrene, 1 part of azo-isobutyronitrile and 60 parts of idododecane were heated to 40 ° C through capillary 2 (inner diameter 0.4 mm, material of stainless steel). solution is sprayed at a rate of 4.8 ml / min. The continuous phase is an aqueous solution heated to 45 ° C containing 1% by weight of porcine gelatin and 1% by weight of gum arabic. The pH of the continuous phase is 5.7 and this phase is introduced through the inlet pipe 3 at a rate of 15.3 ml / min. The spray area was maintained at 6 ° C to 45 ° C. 0.1 N hydrochloric acid is passed through line 4 at the rate required to lower the pH of the continuous phase to 4.0 (± 0.1).

In the encapsulation area (7), the temperature of the continuous phase is controlled to decrease from 45 ° C at the lower end to 15 ° C at the upper end. Ice water was introduced at inlet 5 at a rate of 20 ml / min.

The overflow outlet capsule / slurry 9 is passed into a container with mixer 10 where it is stirred for 3 hours at 0 ° C. The suspension is then treated with 30 ml of 36% formalin per liter of aqueous phase, 5% sodium hydroxide to maintain the alkaline reaction, and 20 g of disodium hydrogen phosphate dodecahydrate per liter of aqueous phase, followed by the capsule suspension was stirred for 4 hours at 25 ° C.

The hardened capsules are then washed with water and stirred for 10 hours at 70 ° C for polymerization in water. After separation of the aqueous phase, the encapsulated bead polymer is washed and dried.

The resulting encapsulated bead polymer, which is a nacroporous, divinylbenzene-crosslinked polystyrene, is subsequently removed without acetic acid phthalamide methyl ester according to the procedure described in U.S. Patent 3,989,650 without prior removal of the capsule wall. methylation, alkaline hydrolysis and quaternization with methyl chloride to form a strongly basic anion exchange.

The resulting highly basic anion exchanger (CL form) has a particle size in the range 0.8-1.3 mm and 91% of the beads have a particle size in the range 0.9-1.2 mm.

Polymerization of the same polymerization mixture in the customary 0.2% aqueous carboxymethylcellulose sodium bath followed by aminomethylation and quaternization results in an anion exchanger having a bead size of 54%. in the size range of 0.8-1 β mm, and only 31% of the beads fall within the range of 0.1-1.2 mm.

Example 3

In the apparatus described in Figure 1, through the capillary 2 (0.35 mm internal diameter, stainless steel capillary material), 1 part azo-isobutyronitrile, 1.5 parts sebacic acid chloride, 86 parts styrene, 8 parts divinylbenzene and A freshly prepared mixture of 5 parts ethyl styrene calcium chloride, anhydrous, cooled to 5 ° C was sprayed at a rate of 2.4 ml / min. The continuous phase used is a 0.5% aqueous solution of polyvinyl alcohol cooled to 5 ° C and introduced into the inlet tube 3 at a rate of 7.4 ml / min. The spraying area 6 is maintained at 5 ° C. An aqueous solution containing 12% by weight of soda and 8% by weight of hexamethyldiamine was added via line 4 to the column at a rate of 2.2 ml / min. During this process, the encapsulation area 7 is maintained at 25 ° C.

The overflow capsule suspension 9 is discharged into a container with a stirrer and washed therein with water at room temperature.

The bead polymerization mixture in the capsules is then polymerized by stirring the aqueous suspension of the capsules for 10 hours at 70 ° C.

The resulting encapsulated bead polymer, consisting of a gel-shaped polystyrene crosslinked with dibenzobenzene, was treated with 50% sulfuric acid at 120 ° C to remove the capsule wall. After separation of the aqueous phase, the bead polymer was washed and dried.

The resulting gel-shaped polystyrene bead polymer has a particle size in the range of 0.5-0.9 mm and 82% of the bead has a particle size in the range 0.63-0.8 mm.

If the same polymerization mixture is subjected to conventional bead polymerization in a 0.2% aqueous carboxymethylcellulose sodium bath, a bead polymer is obtained in which 74% of the beads have a particle size of 0.5-0.9 mm, and Only 27% of the ⁸ beads are in the 0.63-9.8mm size range.

Example 4

In the apparatus described in Figure 1, 86 parts of styrene, 8 parts of diphthylbenzene, 5 parts of ethyl styrene are sprayed through capillary 2 (internal diameter 0.35 mm, capillary material stainless steel) at room temperature at 2.3 ml / min. solution of azo-isobutyronitrile and 3 parts of hexamethylene diisocyanate. The continuous phase consisted of a 0.5% aqueous solution of polyvinyl alcohol at 22 ° C. This continuous phase was introduced at 8.6 mL / min through 3 inlet tubes. An aqueous solution containing 12% by weight of soda and 8% by weight of hexamethyldiamine is introduced at line 4 at a rate of 2.2 ml / min. Both the spraying area 6 and the encapsulation area 7 are maintained at room temperature. The overflow exit capsule dispersion 9 is transferred to the mixer container 10, where it is washed with water at room temperature, and then the aqueous suspension is heated at 70 ° C for 10 hours to polymerize the polymerization mixture in the capsule while stirring.

The encapsulated gel-like bead polymer obtained in this manner, consisting of polystyrene crosslinked with divtail benzene, is subsequently converted to a highly acidic ketone exchanger by known sulfurization without prior removal of the capsule wall.

The resulting acidic cation exchanger (Na form) has a particle size in the range of 0.8-1.2 mm and 81% of the beads have a particle size in the range 0.8-1.1.

If the same polymerization mixture is subjected to the usual bead polymerization in a 0.2% aqueous Cl-Box-methylcellulose bath and subsequently sulfonated, a highly acidic cation exchanger is obtained in which only 53% of the beads exhibit 0 , 1-1.2 mm bead etching, and only 29% of the beads have a grain size in the 0.1-1.1 mm size range.

Example 5

In the apparatus illustrated in Figure 1, 86 parts of styrene, 8 parts of divinylbenzene, 5 parts of ethylstyrene and 1 part of dibenzoyl peroxide are passed through capillary 2 (0.35 mm internal diameter, capillary material) at 40 ° C. solution was sprayed at a rate of 2.4 ml / min. The continuous phase used is an aqueous solution of 1% by weight of pigskin gelatin, 1% by weight of acrylamide maleic anhydride copolymer of Example 4 of U.S. Pat. No. 4,181,639 and its hydrolysis product, and 0.05% by weight of carboxylate. -methylcellulose sodium (Brooksfield viscosity 0.65Ό, 85 Pa in 2% solution at 20 ° C at 20 rpm).

The temperature of this continuous phase is 45 ° C, pH 5.3 and 5.1 ml / min through the inlet pipe 3. The spraying area 6 is maintained at 45 ° C. 0.1 N hydrochloric acid was introduced through line 4 at a rate necessary to lower the pH of the continuous phase to 3.0 (± 0.1).

In the encapsulation area 7, the temperature of the continuous phase is controlled to decrease from 45 'C at the upper end to 15 C at the lower end. The area of the reaction column 8 is cooled with ice water to transfer the overflow xapsule slurry 9 to the mixing vessel 10 at a temperature of 5 ° C. In addition, 12% formalin solution at a rate of 7.5 ml per 1 liter of capsule suspension overflow was continuously introduced into the reaction column via line 5 and 15% sodium hydroxide was added to maintain a pH of 8. reaction column area should be 11.5.

When the agitator container 10 becomes full, the inlet is discontinued and the spill capsule suspension is discharged into another agitator container.

The aqueous phase is drained and replaced with a solution of 10 g of disodium hydrogen phosphate dodecahydrate per liter in a full 10 stirred vessel.

The polymerization mixture in the capsules is then polymerized by stirring the capsules in aqueous suspension at 70 ° C for 10 hours. .

The encapsulated gel-like bead polymer obtained in this manner, consisting of polystyrene crosslinked with diva-benzene, is subsequently separated from the aqueous phase, washed, dried and then, without prior removal of the capsule wall, subjected to sulfurization in a highly acidic form by known means.

The resulting cation exchanger (Na form) has a particle size in the range of 0.1-1.2 mm and a particle size of 72% of the beads has a particle size of 0.91.1 mm.

When the same polymerization mixture is subjected to conventional bead polymerization in a 0.2% aqueous carboxymethylcellulose sodium bath and subsequent sulfonation, a cation exchanger is obtained in which only 50% of the beads exhibit 0.8 l. , 2mm particle size, and n beads particle8 '

Only 28% of the 196,080 are in the 9.1-1.1mm range.

Example 6

In the apparatus shown in Figure 1, 95 parts of methacrylic acid methyl ester, 5 parts divinyl toluene, 2 parts hexadiene were sprayed through capillary 2 (internal diameter 0.21 mm, capillary material, stainless steel) at 2.3 ml / min. 1.5 and 1 part of a solution of azo-butyric acid nitrile at 40 ° C. The continuous phase is an aqueous 8% gelatin solution (porcine gelatin) at 55 ° C. The pH of the continuous phase is 7.8 and the phase is passed through the inlet pipe 3 at a rate of 12 ml / min. The spraying area 6 is maintained at 50 ° C. A 20% aqueous sodium sulfate solution was added via line 4 at a rate of 5.0 mL / min.

Encapsulation and polymerization were carried out as described in Example 1.

90% of the beads have a particle size of 0.45-0.6 mm.

The pearl polymer can be converted to a weak acidic ion exchanger of uniform particle size by alkaline hydrolysis.

Example 7

The apparatus shown in Figure 1 is used with the exception that a nozzle with 4 holes (0.21 mm diameter) is used instead of capillary 2. A solution of 90 parts of acrylic acid methyl ester, 8 parts of technical divinylbenzene, 2 parts of octadiene-1.5 and 0.8 g of dibenzene peroxide is sprayed through this nozzle at a rate of 1.15 L / h at 40 ° C. The aqueous continuous phase was prepared as in Example 5 and added via the inlet pipe 3 at a rate of 1.5 liters / hour.

Encapsulation and polymerization were carried out as described in Example 5.

This gives a bead polymer in which 89% of the beads have a particle size of 0.4-0.5 mm.

The resulting pearl polymer obtained by acid hydrolysis yields a weakly acid cation exchanger having 83% of the beads having a particle size of 0.4-0.5 mm.

Example 8

In the apparatus shown in Fig. 1, according to Example 7, 92 parts of acrylonitrile, 6 parts of diethylene glycol dimethyl acrylate, 2 parts of diethylene glycol divinyl ether, 2 parts of toluene-2,4- diisocyanate and 25 parts of a 15 ° C solution of isooctane and 1 part of azole-butyric acid nitrile. The continuous phase used is an aqueous solution containing 03% hydroxyethylcellulose and 101% common salt and a temperature of 15 ° C. The continuous phase was passed at 1.8 liters / hour through the inlet pipe 3. An aqueous solution of 12% by weight of soda and 8% by weight of hexamethylenediamine is passed through line 4 at a rate of 420 ml / h. Encapsulation and polymerization were carried out as described in Example 4.

This gives a pearl polymer in which 87% of the beads have a particle size of 0.4 to 5 mm.

The resulting bead polymer, after removal of the isooctane, is used as the absorbent resin.

Example 9

In the apparatus of Example 1, 60 parts of technical divinylbenzene (62% DVB content), 40 parts of a-methylethanol, 150 parts of toluene were sprayed through 2 capillaries (0.24 mm diameter) at a rate of 2.8 ml / min. and 0.6 parts of a solution of azo-isobutyric acid nitrile at 42 ° C.

The aqueous continuous phase was prepared as in Example 5 and added through the inlet tube 3 at a rate of 3.1 ml / min.

Encapsulation and polymerization were carried out as described in Example 5.

The resulting pearl polymer was obtained with acetone, methanol. - and water, so we get rid of toluene.

Thus, a bead polymer having a particle size of 94% by weight of the beads is 0.45 °, 56 mm is obtained.

The resulting bead polymer can be used to adsorb chlorinated hydrocarbons from aqueous solutions.

Example 10

In the apparatus shown in Fig. 1, 45 parts of methacrylic acid ethyl ester, 4 parts of methacrylamide, 45 parts of chlorostyrene, 4 parts of technical divinylbenzene are sprayed through a capillary 2 (0.3 mm diameter) at a rate of 3.9 ml / min. 2 parts of a solution of tri-vinylcyclohexane and 0.6 [mu] g of azoisoisobutyronitrile at 40 ° C. The continuous phase (6% porcine gelatin solution, 50 ° C, pl = 7.7) was passed through the inlet tube 3 at a rate of 7.8 ml / min. The temperature of the spray area is maintained at 45 ° C. A 20% sodium sulfate solution was added via line 4 at a rate of 7.9 mL / min.

Encapsulation and polymerization were carried out as described in Example 1.

This gives a bead polymer in which 94% of the beads have a particle size of 0.5-0.7 mm. The resulting pearl polymer can be used as a separating resin ^{w for} mixed bed filters.

Claims (5)

Claims A process for preparing bead polymers by slurry polymerization of mono or polyvinyl compounds in aqueous solutions, characterized in that: a) the polymerization mixture was fed cocurrently at 5-70 ° C in an aqueous solution used containing 0.01-10% stabilizer-continuity when the contact V: V - ^ KOC where _lt represents the volume V and _n0 is the continuous phase, monomer and / or polymerization mixture in a volume ratio of from 0.1 to 60 b) the droplets of uniform size polymerization mixture obtained by spraying the polymerization mixture into the aqueous solution are transferred hydrodynamically from the spraying area of the reaction vessel to the encapsulation areas by hydrodynamically differing in density continuously encapsulated by known coacervation, complex coacervation, or phase interface reaction, and c) polymerizing the encapsulated droplets of the encapsulated polymerization mixture by heating the aqueous suspension at 40-95 ° C. 2. The process of claim 1, wherein the continuous phase is encapsulated by gelatin solution as a continuous phase by coacervation or complex coacervation. 196 080 3. A process according to claim 1, wherein the complex coacervation component is a copolymerization mixture comprising gelatin or gelatin and acrylamide and maleic anhydride groups in a statistical distribution and a copolymer having acrylamide and maleic acid groups in the statistical distribution. 4. Process according to any one of claims 1 to 3, characterized in that it is a monomer 5 styrene,? -Methyl-styrene, ethyl-styrene, chlorine filters, methacrylic acid ester or amide, acrylonitrile, divinylbenzene, di-vinyl toluene, diethylene glycol divinyl ether, trivinylcyclohexane, heptadiene-1. , 5, actadiene-1.7.