Method of producing polymer beads of uniform size

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing beads having a uniform particle size distribution. Described is a method of producing monodisperse cross-linked polymer beads, comprising the following steps: (a) introducing droplets having a harmonic mean size from 50 to 1500 mcm and comprising at least one monomer, at least one cross-linking agent and a free-radical polymerisation initiator into an aqueous medium through openings in a moulding column to produce an aqueous suspension of droplets having a volume fraction of droplets from 35 to 64%; wherein the droplets are not encapsulated; wherein the monomers are selected from a group comprising monoethylene unsaturated compounds and polyethylene unsaturated compounds, monoethylene unsaturated monomers are selected from a group comprising (meth)acrylic acids and esters thereof, methyl-substituted styrenes, vinyl pyridines and vinyl esters, ethers and ketones; (b) forcing the aqueous suspension of droplets to move down a pipe such that: (I) the ratio of droplet harmonic mean size to inside pipe diameter is from 0.001 to 0.035; (II) mean linear flow velocity in the pipe is from 0.5 to 2.5 ft/s (0.15 to 0.75 m/s); and (III) temperature in the pipe is maintained at least 20°C below the temperature at which the polymerisation initiator has a half-life of 1 hour; wherein the droplets are forced up the moulding column, and the redirected down into the pipe, with subsequent redirection up into a reactor; and (c) polymerising the droplets in the reactor.

EFFECT: obtaining polymer beads of a uniform size by forcing a jet down into a reactor and without partial polymerisation or encapsulation.

10 cl, 3 ex

The present invention relates to a method of fabrication of polymeric beads having essentially uniform particle size. Such beads can be used to obtain ion-exchange resins.

Polymer beads, characterized by an essentially uniform particle size, can be made "discharge a jet of liquid organic monomer mixtures through the holes in the aqueous phase. Then the suspended monomer droplets are transported to the reactor in which the polymerization proceeds. The problem of coalescence of the droplets, which leads to less uniform distributions in size, mainly downdraft, still allow a variety of ways, including injection jet directly into the reactor and partly by polymerization or by encapsulating droplets to slow coalescence. For example, in US No. 3922255 we are talking about partial polymerization of the droplets before nicholaisen flow in the reactor.

The problem that caused the creation of the present invention is the development of an improved method of making polymer beads according to the method of discharge of the jet downdraft in the reactor and without partial polymerization or encapsulate.

SUMMARY of the INVENTION

The object of the present invention is a method of manufacturing the mould is increasing monodisperse crosslinked polymer beads, includes the following stages:

(a) introducing droplets with harmonic average size of from 50 to 1500 μm and comprising at least one monomer, at least one crosslinking agent and initiator of free radical polymerization, in an aqueous environment through the holes with obtaining aqueous suspension of droplets with volume fraction of droplets from 35 to 64%, where these droplets are not encapsulated;

(b) forcing a water suspension of droplets move down the pipe in such a way that: (I) the value of the ratio of the harmonic mean size of droplets to the inner diameter of the tube is from 0.001 to 0,035; (II) the average linear flow velocity is from 0.5 to 2.5 ft/s (0.15 to 0.75 m/s) and (III) the temperature of the support at the level of at least 20°C below the temperature at which the polymerization initiator shows the half-life of 1 h; and

(C) polymerization of the droplets in the reactor.

DETAILED description of the INVENTION

In all cases, unless otherwise indicated, percentages are by mass percent. Used in the present description the term "(meth)acrylic" refers to acrylic or methacrylic. The monomers that can be used when performing the present invention include monoethanolamine connection and polyethylenepolyamine monomers, i.e. cross-linking agents, including, for example, butadiene is a romantic connection, trivinylcyclohexane, di - and tri(meth)acrylate compound and simple diphenylamine connection. One preferred cross-linking agent is divinecaroline a crosslinking agent such as divinylbenzene. Monomethylethanolamine monomers include, for example, (meth)acrylic acids and their esters, styrene, chloro - and/or methylamine sterols, vinylpyridine and vinyl esters, ethers, and ketones. Preferred monomers are not soluble in the aqueous phase, although more water-soluble monomers can also be used by adding to the aqueous phase of salts like NaCl or Na₂SO₄to reduce the solubility of the monomer phase in the aqueous phase. The term "styrene polymer" refers to a copolymer obtained by polymerization of monomers comprising styrene monomer (substituted or unsubstituted styrene, for example styrene, α-methylsterols, atistical) and/or at least one crosslinking agent, where the combined weight of styrene and a cross-linking agent is at least 50 wt.% all monomer weight. In some embodiments, the styrene polymer is prepared from a mixture of monomers, which represents at least 75% styrene and cross-linking agents, more preferably at least 90% styrene and diphenylamines cross-linking agents, and most prefer is Ino from a mixture of monomers, which consists essentially of styrene and at least one diphenylamine a crosslinking agent. In other embodiments, the styrene polymer obtained from a monomer mixture comprising essentially at least one diphenylamine a crosslinking agent. The term "acrylic polymer" used in respect of a copolymer formed from a mixture of vinyl monomers containing at least one (meth)acrylic acid or ester or (meth)Acrylonitrile, together with at least one cross-linking agent, where the combined weight of (meth)acrylic acid (acid), or a complex ester (esters), or (meth)Acrylonitrile and a cross-linking agent (agent) is at least 50 wt.% all monomer weight, preferably at least 75%, more preferably at least 90%and most preferably from a mixture of monomers, which consists essentially of at least one (meth)acrylic acid or ester and at least one crosslinking agent. In some embodiments, the ester of (meth)acrylic acid represents a C₁-C₄alkilany ester.

The term "gel" resin applied to the resin, which is synthesized from a copolymer of very low porosity (from 0 to 0.1 cm³/g), with pores small medium size (from 0 to 17 Å) and low specific surface area according to BET (from 0 to 10 m²/g). is he notion "macrostate" (or MS) resin applied to the resin, which are synthesized from wysokometanowego copolymer with a higher specific surface area than that of gel resins. The total porosity MS resin is in the range from 0.1 to 0.7 cm³/g, the average pore size is in the range from 17 to 500 Å, and the specific surface area according to BET is in the range from 10 to 200 m²/year / MS resin is usually obtained by introducing a monomer mixture of an organic solvent (porogen"). The term "adsorbent resin applied to the resin, which may or may not be functionalized and which has a very large specific surface area and porosity. These adsorbents have a specific surface area ranging from 200 to 1300 m²/g, an average pore size ranging from 17 to 1000 Å and a total porosity in the range from 0.7 to 200 cm³/year

Acceptable initiators of polymerization in the monomer phase include, for example, benzoyl peroxide, tert-butyl hydroperoxide, cumene peroxide, peroxide of tetralin, acetyl peroxide, peroxide of caproyl, perbenzoic tert-butyl, diphthalate tert-butyl and methyl ethyl ketone peroxide. As catalysts may also be used azoinitiator. Suitable azoinitiator include, for example, 2,2'-azobisisobutyronitrile and 2,2'-azobis-(2,4-dimethylpentanenitrile), which is technically available under the trade designation VAZO 52 in firm DuPot, Wilmington, stdelivery. Typical effective amounts of an organic initiator relatively dry monomer is, it has been found that from about 0.5 to about 2 wt.%, preferably from about 0.8 to about 1.5 wt.%.

Organic droplets comprising at least one monomer, forming through holes in the generator drops by well-known methods, including vibrating discharge jet and natural forcing of the jet. The flow rate of the monomers can be varied from 5 to 1000 ml/h/hole, and typically from 50 to 250 ml/h/hole. The frequency of the vibration generator of droplets can be from 10 to 20000 Hz if you use technically accessible pathogens vibration, and to reach 500000 Hz if you use a piezoelectric vibration exciters. Typical vibration frequency range from 400 to 2500 Hz. Typical hole diameters range from 20 to 1000 μm, alternatively from 30 to 600 μm. Droplets pump in water composition in forming the tube is then transported through nishogakusha conveying line or pipe in the reactor. In some versions of the invention, droplets pump up in forming the column, then redirect, for example by means of a U-shaped pipe or elbow, nicholasi flow with subsequent other parentral the tion, this time the upward flow in the reactor. In some versions of the invention the flow of the forming column does rotate in a substantially horizontal line, then another turn in Nicholaus transport line. Typically downward transport line is not more than 20 degrees relative to the vertical, alternatively no more than 10 degrees. In a preferred embodiment, the volume fraction of droplets emerging from the forming of the column is at least 38%, alternatively at least 40%, alternatively at least 42%, the preferred volume ratio is not more than 63%, alternatively no more than 60%, alternatively no more than 58%, alternatively no more than 55%, alternatively no more than 50%, alternatively no more than 47%. Dense placement of uniform spherical droplets corresponds to 65%volume concentration, which usually causes coalescence and poor quality product.

It was found that essentially unpolymerized monomer droplets can be transported using some conditions downstream, without causing coalescence or destruction of drops and without the use of expensive and more complex processing in encapsulation columns or pillars partial polymerisocyanate flow provides more flexibility in the placement process equipment, than wrapping up Monomeric droplets from forming columns in the reactor. The method allows to place the reactor at a lower level (either in parallel or diagonally, or below a pressure jet installation). This design greatly reduces the capital cost of installation of equipment and the process and simplifies the injection jet in multiple reactors. Thus, in particular, has the advantage in upgrading existing installations suspension polymerization for installations discharge of the jet, since the downward flow does not require moving existing reactors that would require the use of a rising supply. The encapsulation is the manufacture of shells, which protect droplets as described for example in US no 4427794. Coacervation is a process of encapsulation, which form the shell, and then utverjdayut cooling drops below the gelatinization temperature of the shell. In some cases shell utverjdayut chemically, as well as, in particular, formaldehyde (see, for example, US No. 2800458). Complex coacervation is a process of encapsulation by using differently charged colloids (polyelectrolytes) to obtain the shell.

The value of the ratio of the mean diameter of the droplets to the inner diameter of the pipe downstream is 0,do 0,035. So, for example, with an average diameter of 200 μm droplets in the pipe internal diameter of 1 inch (25.4 mm) ratio is 200(10^-6)m/25.4mm(10^-3)m=0,00787. In some versions of the invention the value of this ratio is at least 0,002 alternatively at least 0,003 alternatively at least 0,004 alternatively at least 0,005. In some versions of the invention the value of this ratio is not more than 0,032 alternatively no more than 0,03 alternatively no more 0,028 alternatively no more than 0,025 alternatively no more 0,023 alternatively not more than 0,02.

The average linear velocity of flow of the aqueous suspension of droplets in the pipe downstream ranging from 0.5 to 2.5 ft/s (0.15 to 0.75 m/s). The average linear flow velocity is the average velocity of aqueous and organic phases. In some versions of the invention, the average linear flow velocity is at least 0.6 m/s (0.18 m/s), alternatively at least 0.7 ft (0.21 m/s). In some versions of the invention, the average linear flow velocity is not more than 2.2 m/s (0.66 m/s), alternatively no more than 2 ft/s (0.6 m/s), alternatively no more than 1.9 ft/s (0,57 m/s), alternatively no more than 1.8 ft/s (0.54 m/s), what about the other variation is not more than 1.7 m/s (0.51 m/s). In some versions of the invention, the pipe downstream has a diameter of 0.75 in (1.9 cm) to 6 inch (15.2 cm), alternatively from 0.75 in (1.9 cm) to 4 inches (10.2 cm), alternatively from 0.75 in (1.9 cm) to 3 inches (7.62 cm), alternatively from 1 (2.54 cm) to 3 inches (7.62 cm). Speed to a pressure jet installation (forming column), which typically has a larger diameter than the downward transport pipe, characterized by the apparently lower values, but are non-critical.

The temperature in the pipe downstream support at least 20°C below the temperature at which the polymerization initiator shows the half-life of 1 h This ensures that due to the significant limitations of the concentration of free radicals generated by the initiator in the organic droplets polymerization of the monomers proceeds weak or absent. In some versions of the invention the temperature of the support at least 25°C below the temperature at which the polymerization initiator shows the half-life of 1 hour, alternatively at least 30°C lower. In some versions of the invention the temperature is lower by at least 5°C., alternatively at least 10°C., alternatively at least 15°C.

The aqueous phase AC is the rule contains colloidal stabilizer and viscosity modifier. Examples of colloidal stabilizers known to specialists in this field of technology are proteins such as gelatin, soy protein, hydrolyzed soy protein, wheat protein, spirulina and rice protein; polysaccharides such as hydroxyethyl cellulose, methylhydroxyethylcellulose, hypromellose, carboxymethylcellulose, pectin, xanthan gum, Gellan gum, sodium lignosulphonate, agar, carrageenan, sodium alginate, starch, Arabic gum and tragacanth gum. Examples of the viscosity modifier are polyvinyl alcohol, polyvinylpyrrolidone, polyvinylcaprolactam, polyacrylic acid, polydimethyldiallylammonium, hydrolyzed styrene/maleic anhydride and hydrolyzed copolymer metilfenidato ether/maleic anhydride. Can also be entered other additives, such as surfactants, buffers, and water inhibitors. In a preferred embodiment, the colloidal stabilizer in the aqueous phase is a naturally occurring or synthetic water-soluble polymer around the droplets of the monomer forms a thin layer with an interfacial tension of at least 3 Dina/cm, alternatively at least 8 Dyne/cm, without phase change or formation of covalent bonds. In against prognosti this process of encapsulation include phase changes, such as gelatinization caused by lowering the temperature or by adding multivalent ions or electrolytes; or the formation of covalent bonds, for example, by reaction with formaldehyde. Encapsulated drops usually are stable for long periods of time, while the drop in the implementation of the present invention can be unstable. Especially preferred colloidal stabilizers include, for example, polyacrylic acid with gelatinous type a, polydimethyldiallylammonium with gelatinous type a, carboxymethylcellulose, carboxymethylcellulose with hydroxycolecalciferol and phosphate ester, polyether, hypromellose, hypromellose with hydroxycolecalciferol and phosphate ester, polyether, methylhydroxyethylcellulose. In a preferred embodiment, the total number of colloidal stabilizers in the aqueous phase ranges from 0.05 to 1%, alternatively from 0.05 to 0.5%.

In one embodiment, the aqueous compositions are tested for acceptability using "testing shaking"during which Vasiliy (225 ml) vessel load of approximately 28 ml of Monomeric composition and approximately 115 ml aqueous composition, it is fixed to the lever shaft of the motor and rotate with a speed of 1 rpm for 15 sec. Then the contents of the vessel are poured into a graduated cylinder. The composition of the aqueous phase is acceptable, if after 3 min separated not more than 2 ml Monomeric composition.

The aqueous phase in the reactor is generally characterized by a higher concentration of stabilizer suspension than the aqueous phase in forming the casing and the pipe. This is done by the introduction of concentrated aqueous material ("sludge") directly into the reactor. In a preferred embodiment, the aqueous phase in the reactor contains colloidal stabilizer in a total amount of from 0.5 to 8%, alternatively from 2 to 4%.

An alternative method of achieving a higher concentration of stabilizer suspension in the reactor is in the flow of concentrated water flow either directly into the upper part of the reactor, or into the conveying line. Concentrated aqueous stream is directed with such speed, whereby the concentration of colloidal stabilizers remains constant throughout the filling in the total number of from 0.25 to 8%, alternatively from 0.5 to 2%.

Harmonic average size of the droplets ranges from 50 to 1500 μm. In some versions of the invention, the harmonic average size is at least 100 microns, alternatively at least 150 μm. In some versions of the invention g is armanichesky the average size is not more than 1000 μm, another variation is not more than 900 microns, alternatively not more than 800 μm.

In some versions of the invention, the harmonic average size of the droplets ranges from 100 to 200 microns. In these embodiments, for gel copolymer the ratio of the average diameter of the droplets to the inner diameter of the pipe downstream is from 0.002 up to 0.016, alternatively from 0,005 to 0,0012, and the average linear flow velocity is from 0.71 to 1.70 ft/s (from 0.22 to 0.52 m/s), alternatively from 0.95 to 1.45 ft/s (from 0.29 to 0.44 m/s).

In some versions of the invention, the harmonic average size of the droplets to gel copolymer is from 200 to 400 μm. In these embodiments, for gel copolymer the ratio of the average diameter of the droplets to the inner diameter of the pipe downstream is from 0.004 to 0.026, alternatively from 0.01 to 0,021, and the average linear flow velocity is from 0.72 to 2.05 ft/s (from 0.22 to 0.63 m/s), alternatively from 1.05 to 1.90 ft/s (from 0.34 to 0.58 m/s).

In some versions of the invention, the harmonic average size of the droplets to gel copolymer is from 400 to 600 μm. In these embodiments, for gel copolymer the ratio of the average diameter of the droplets to the inner diameter of the pipe downstream is from 0.008 to 0,031 alternatively from between 0.014 to 0.026, and the average linear velocity flux is and is from 0.77 to to 2.29 ft/s (from 0.23 to 0.70 m/s), another option from 1.14 to 1.90 ft/s (from 0.34 to 0.58 m/s).

In some versions of the invention, the harmonic average size of the droplets to gel copolymer is from 600 to 800 microns. In these embodiments, for gel copolymer the ratio of the average diameter of the droplets to the inner diameter of the pipe downstream is from 0,012 to 0,031 alternatively from 0.017 to 0,027, and the average linear flow velocity is from 0.86 to 2.36 ft/s (from 0.26 to 0.72 m/s), alternatively from 1.23 to 1.98 ft/s (from 0.37 to 0.60 m/s).

In some versions of the invention, the harmonic average size of the droplets for the MS copolymer is from 100 to 200 μm. In these embodiments, for gel copolymer the ratio of the average diameter of the droplets to the inner diameter of the pipe downstream is from 0.002 up to 0.016, alternatively from 0,012 0,005 to, and the average linear flow velocity is from 0.84 to 1.91 ft/s (from 0.26 to 0.58 m/s), alternatively from 1.11 to 1.64 ft/s (from 0.34 to 0.50 m/s).

In some versions of the invention, the harmonic average size of the droplets for the MS copolymer ranges from 200 to 400 μm. In these embodiments, for gel copolymer the ratio of the average diameter of the droplets to the inner diameter of the pipe downstream is from 0.004 to 0.026, alternatively from 0.01 to 0,021, and the average linear flow velocity with the hat from 0.86 to 2.28 ft/s (from 0.26 to 0.70 m/s), another option from 1.21 to 1.92 ft/s (from 0.37 to 0.58 m/s).

In some versions of the invention, the harmonic average size of the droplets for the MS copolymer ranges from 400 to 600 μm. In these embodiments, for gel copolymer the ratio of the average diameter of the droplets to the inner diameter of the pipe downstream is from 0.008 to 0,028 alternatively from 0.013 to 0,023, and the average linear flow velocity is from 0.94 to 2.33 ft/s (from 0.29 up to 0.71 m/s), alternatively from 1,28 to 1.98 ft/s (from 0.39 to 0.60 m/s).

In some versions of the invention, the harmonic average size of the droplets for the MS copolymer ranges from 600 to 800 microns. In these embodiments, for gel copolymer the ratio of the average diameter of the droplets to the inner diameter of the pipe downstream is from 0,012 to 0,028 alternatively from 0,023 0,015 to, and the average linear flow velocity is from 1.08 to 2.45 ft/s (from 0.33 to 0.74 m/s), alternatively from 1,43 to 2.14 ft/s (from 0.43 to 0.65 m/s).

One measure of the uniformity of particle size is the coefficient of uniformity (KO), which is calculated as follows:

TO=d₆₀/d₁₀

where d₆₀denotes the particle diameter at which 60% of the particle volume has a smaller diameter, and d₁₀denotes the particle diameter at which 10% of the particle volume has a smaller diameter. In predpochtitelno option is TO not more than 1.3, another variation is not more than 1.25 or, alternatively not more than 1.2, alternatively not more than 1,15, alternatively no more than 1,10.

Uniform droplets typically generate introducing a stream of monomer periodic perturbations. This can be done by vibration of the jet monomer (see, for example, US No. 4444961) or vibration of the aqueous phase near monomer, or vibration of the holes (see, for example, US No. 4623706). More large-scale vibration generators drops include many holes, and in this case, it may vibrate a big camera (see, for example, US No. 4666673) or may vibrate the plate with holes, containing many holes. Vibration can be done in any direction, but usually she axial or perpendicular to the axis.

Used reactor system mixing specialists in the field of technology suspension polymerization are known. This system requires sufficient flow for suspension of droplets in order to ensure good heat transfer and to avoid coalescence and the formation of clots while preventing destruction of the drops. Up to the present time apply such agitators as the underwater wings, Kaplan turbines with variable pitch turbines with flat blades, agitator with a reverse curve and pulse the mixer. Preferred more Maalox large values of the ratio of the diameter of the stirrer to the diameter of the tank. These agitators maximize the flow in the reactor to avoid swimming droplets in stagnant layer and at the same time they also prevent the scattering of high energy, which leads to the destruction of drops. Balanced multiple mixers avoids local scattering of high energy, which leads, apparently, to local destruction of the drops. In these processes the suspension polymerization has already been successfully applied fully equipped with baffles (i.e., supply optimal power) and partly equipped with baffles reactors. Among other conventional designs chisels types of boots include a flat plate, oval plate, pipe, plate type "beaver tail". The appropriate choice of the bump and the design helps to optimize the flow and at the same time to avoid the local scattering of high energy, which leads, apparently, to local destruction of the drops. This process has already successfully demonstrated the values of the ratio between the liquid column and the diameter of the tank at the end of filling both more and less than 1. The ratio between the liquid column and the diameter of the tank is greater than 1 at the end of filling is preferred for heat transfer, and effects of flow several mixers and power.

In some versions of the invention, Polimeri is consistent droplets functionalist as ion-exchange resin by known methods. So, for example, styrene beads can be sulfonated with getting sulfosalicylate resins or chlorotoluron obtaining chloromethylene functional groups, which can then be introduced into the reaction with amines, aminoalcohols, aminjikarai acids, etc. with getting amine, a Quaternary salt and other functional groups; acrylic beads can be functionalized by reaction with (meth)acrylic acid with alcohols or amines.

EXAMPLES

Example # 1 - gel-cation

The gel copolymer beads of uniform particle size were prepared by loading into the reactor an aqueous slurry containing 2.7 wt.% polydiallyldimethyl (in quantitative analysis 15%), to 0.016 wt.% NaNO₂and 0.23 wt.% gelatin in boric acid and caustic buffer. A second injection of an aqueous phase, comprising 0.1 wt.% gelatin 250 BLOOM type a, 0.007 wt.% NaNO₂boric acid and caustic buffer is used to fill the forming columns and transfer lines. Monomer phase, which included 80,4 wt.% styrene, 19 wt.% divinylbenzene (in quantitative analysis 55%), 0.32 wt.% di(4-tert-butylcyclohexyl)PEROXYDICARBONATE, 0.3 wt.% of benzoyl peroxide was applied to the generator monomer droplets with a speed of Monomeric flow of 160 ml/h/hole. The generator of droplets containing several thousand 150-micrometer hole is Tille, excited to vibrations 986 Hz. In this case, the generator of droplets consisted of a spherical part which, with the use of sealing rings hermetically secured a movable plate with holes. A spherical part and a plate with holes is entirely placed inside the forming column. A spherical part and a plate with holes was attached to the pusher, which came out from the base forming the column through a seal, sealed with o-rings. This plunger was attached to the modal exciter. Modal exciter provided a vibration in General pusher, the spherical part and the plate with the holes in the axial direction with the desired amplitude and frequency. The overall speed of the monomer flow was $ 770 lb/h (350 kg/h). Water, the source material was applied to form the column at a flow rate of 1.6 gallons/min (0.36 m /h). During commissioning of the conveyor line is filled and purged of any gas through the valve. All volatile material was dumped through the valve. When he reached the stable state, the valve was closed, and the dispersion of droplets directed into the reactor with stirring, sufficient for suspension of droplets without changing the size of the droplets. To compensate for siphonaria downstream filling was carried out under a gauge is a t in the reactor 3.5 psi (125,1 kPa absolute). The reactor was filed downward flow through 1-inch (0,025-meter) shipping line within 5,9 h to achieve 40% vol. the drops. Such flow downstream through the conveying line was carried out at a temperature of 30°C below the temperature of the polymerization reaction. This corresponds to the ratio of the diameter of the drops/pipe diameter of 0.017 and the average linear velocity of 1.39 ft/s (from 0.42 m/s). In order to maintain the concentration suspendida agents in the aqueous phase at a constant level of 2.7 wt.% polydiallyldimethyl and 0.23 wt.% gelatin while filling in the upper part of the reactor is sent with a flow rate of 4.4 lb/min (2.0 kg/min) auxiliary flow 11 wt.% polydiallyldimethyl, of 0.04 wt.% NaNO₂and 0.64 wt.% gelatin in boric acid and caustic buffer. Then the reactor was heated to the reaction temperature and held the polymerization until the conversion of monomer into polymer >95%. Mixing was performed using Kaplan turbines with variable pitch. After separation from the aqueous phase copolymer beads and washing of the beads was achieved following properties: HMS 0,428 mm and coefficient of uniformity was 1.04. The copolymer was sulfurously with obtaining a strongly acidic cation-exchange resin with the following properties: perfect beads >99%, the ability to retain moisture: 46,8%, the mass is technology: 5,15 mEq./g, volumetric capacity: 2.04 mEq./ml, HMS: 0,580 mm and uniformity coefficient of 1.10.

Example No. 2 - gel-anion

The gel copolymer beads of uniform particle size was obtained by loading the reactor water slurry containing 2.7 wt.% polydiallyldimethyl (in quantitative analysis 15%), to 0.016 wt.% NaNO₂and 0.23 wt.% gelatin in boric acid and caustic buffer. A second injection of an aqueous phase, comprising 0.1 wt.% gelatin 250 BLOOM type a, 0.007 wt.% NaNO₂boric acid and caustic buffer is used to fill the forming columns and transfer lines. Monomeric phase, consisting of 92.7 wt.% styrene, 6.9 wt.% divinylbenzene (in quantitative analysis 63%) and 0.3 wt.% of benzoyl peroxide was applied to the generator monomer droplets with a speed of monomer stream 140 ml/h/hole. The generator of droplets containing several thousand 220-micrometer holes, excited to vibration with a frequency of 952 Hz. The overall speed of the monomer flow was $ 770 lb/h (350 kg/h). Water, the source material was applied to form the column at a flow rate of 1.6 gallons/min (0.36 m /h). During commissioning of the conveyor line is filled and purged of any gas through the valve. All volatile material was dumped through the valve. When he reached the stable state, the valve was closed, and the variance of the voltage drops is alali into the reactor with stirring, sufficient for suspension of droplets without changing the size of the droplets. To compensate for ciphervalue downstream filling was carried out under a gauge pressure in the reactor 3.5 psi (of 124.1 kPa absolute). The reactor was filed downward flow through a 1.0 inch (0,025-meter) shipping line for 6.5 h to achieve 40% vol. the drops. Such flow downstream through the conveying line was carried out at a temperature of 30°C below the temperature of the polymerization reaction. This corresponds to the ratio of the diameter of the drops/pipe diameter 0,016 and the average linear velocity of 1.3 ft/s (0,39 m/s). In order to maintain the concentration suspendida agents in the aqueous phase at a constant level of 2.7 wt.% polydiallyldimethyl and 0.23 wt.% gelatin in the upper part of the reactor during the filling was sent with a flow rate of 3.8 lb/min (1.7 kg/min) auxiliary flow 11 wt.% polydiallyldimethyl, of 0.04 wt.% NaNO₂and 0.64 wt.% gelatin in boric acid and caustic buffer. Then the reactor was heated to the reaction temperature and held the polymerization until the conversion of monomer into polymer >95%. After separation from the aqueous phase copolymer beads and washing of the beads was achieved following properties: HMS 0,444 mm and coefficient of uniformity of 1.05. The copolymer chlormethiazole and and minirovali with obtaining a strongly basic anion-exchange resin with the following properties: perfect bead 97%, the ability to retain moisture: 52.3%and mass capacity: 4.00 mEq./g, volumetric capacity of 1.34 mEq./ml, HMS: 0,673 mm and uniformity coefficient of 1.09.

Example No. 3 - MS anion

The gel copolymer beads of uniform particle size was obtained by loading the reactor water slurry containing 2.7 wt.% polydiallyldimethyl (in quantitative analysis 15%), to 0.016 wt.% NaNO₂and 0.23 wt.% gelatin in boric acid and caustic buffer. A second injection of an aqueous phase, comprising 0.1 wt.% gelatin 250 BLOOM type a, 0.007 wt.% NaNO₂boric acid and caustic buffer is used to fill the forming columns and transfer lines. Monomer phase, which included 55,1 wt.% styrene, 2,95 wt.% divinylbenzene (in quantitative analysis 63%), 41,2 wt.% 4-methyl-2-pentanol and from 0.76 wt.% peroxide benzoyl (in quantitative analysis 75%) was applied to the generator monomer droplets with a speed of Monomeric flow 300 ml/h/hole. The generator of droplets containing several thousand 300-micrometer holes, excited to vibration with a frequency of 400 Hz. The overall rate of organic flux was 2027 lb/h (922 kg/h). Water, the source material was applied to form the column at a flow rate of 3.3 gallons per minute (0.76 m /h). During the commissioning of 1.5 inch shipping line was filled and purged of any gas through the clap is N. All volatile material was dumped through the valve. When he reached the stable state, the valve was closed, and the dispersion of droplets directed into the reactor with stirring, sufficient for suspension of droplets without changing the size of the droplets. To compensate for siphonaria downstream filling was carried out under a gauge pressure in the reactor 3.5 psi (125,1 kPa absolute). The reactor was filed downward flow through the conveying line during 4,4 h to achieve 52% vol. the drops. Such flow downstream through the conveying line was carried out at a temperature of 30°C below the temperature of the polymerization reaction. In order to maintain the concentration suspendida agents in the aqueous phase at a constant level of 2.7 wt.% polydiallyldimethyl and 0.23 wt.% gelatin in the transfer line reactor during the filling was sent with a flow rate of 1.04 lb/min (0.24 m /h) extra stream 11 wt.% polydiallyldimethyl, of 0.04 wt.% NaNO₂and 0.64 wt.% gelatin in boric acid and caustic buffer. This corresponds to the ratio of the diameter of the drops/pipe diameter 0,019 and the average linear velocity of 1.63 ft/s (from 0.49 m/s). Then the reactor was heated to the reaction temperature and held the polymerization until the conversion of monomer into polymer >95%. Next, the reactor is revali to 100°C for removal by distillation of 4-methyl-2-pentanol. After separation from the aqueous phase copolymer beads, washing the beads and drying of the beads was achieved following properties: HMS 0,614 mm and coefficient of uniformity of 1.14. The copolymer has chlormethiazole and minirovali dimethylethanolamine with obtaining a strongly basic anion-exchange resin with the following properties: perfect bead 97%, the ability to retain moisture: 55,9%, mass capacity: 3,84 mEq./g, volumetric capacity: 1.15 mEq./ml, HMS: 0,978 mm and uniformity coefficient of 1.12.

Example 4: preparation and testing of the aqueous phase

Preparing an aqueous phase containing:

The first five components were combined with stirring at room temperature. Part of water was heated to 45+/-5°C and dissolving slowly with stirring was added gelatin type A. Further, this gelatinous mixture was added to the other components and p the system brought up to 10-11.

Preparing Monomeric phase, including:

1 ounce (28.4 g) monomer phase was mixed with 4 ounces (to 113.4 g) is heated (63°C) aqueous phase in a heated (63°C) flat-bottomed laboratory vessel for stirring and was stirred for 15 s at 60 rpm After transfer in polymer graduated cylinder after 3 min was less than 1 ml colestyramine monomer.

Then these phases were used as the final reactor of the composition in example 1. The final copolymer before screening possessed the following properties:

1. A method of manufacturing monodisperse crosslinked polymer beads, comprising the following stages:
(a) introducing droplets with harmonic average size of from 50 to 1500 μm and Lucaya at least one monomer, at least one crosslinking agent and initiator of free radical polymerization, in an aqueous environment to form the string through holes with obtaining aqueous suspension of droplets with volume fraction of droplets from 35 to 64%, where these droplets are not encapsulated;
in which monomers selected from the group including
monomethylethanolamine connection and polyethylenepolyamine connection monomethylethanolamine monomers chosen from the group comprising (meth)acrylic acids and their esters, methylsiloxane sterols, vinylpyridine and vinyl esters, ethers, and ketones;
(b) forcing a water suspension of droplets move down the pipe downstream in such a way that: (I) the value of the ratio of the harmonic mean size of droplets to the inner diameter of the pipe downstream is from 0.001 to 0,035; (II) the average linear velocity of the downward flow in the pipe downstream ranging from 0.5 to 2.5 ft/s (0.15 to 0.75 m/s) and (III) the temperature in the pipe downstream support level is at least 20°C below the temperature at which the polymerization initiator shows the half-life of 1 h;
in which droplets pump up in forming the column, then redirect to the downward flow in the pipe downstream, then forwards, sunrise is the overall flow in the reactor; and
(C) polymerization of the droplets in the reactor.

2. The method according to claim 1, further comprising a functionalization polymerized droplets as ion exchange resins.

3. The method according to claim 1, in which the volume fraction of droplets in the pipe downstream ranges from 35 to 60%.

4. The method according to claim 1, in which the harmonic average size of the droplets in the pipe downstream is from 150 to 1000 microns.

5. The method according to claim 4, in which the harmonic average size of the droplets in the pipe downstream is from 150 to 500 μm, the ratio of the harmonic mean size of droplets to the pipe diameter downstream is from 0.002 up to 0.022, and the average linear velocity of the downward flow is from 0.5 to 1.8 ft/s (0.15 to 0.54 m/s).

6. The method according to claim 5, in which the volume fraction of droplets in the pipe downstream ranges from 35 to 60%.

7. The method according to claim 4, in which the harmonic average size of the droplets in the pipe downstream ranges from 450 to 900 μm, the ratio of the harmonic mean size of droplets to the pipe diameter downstream is from 0.008 to to 0.032, and the average linear velocity of the downward flow in the pipe downstream is from 0.9 to 2.5 ft/s (from 0.27 to 0.75 m/s).

8. The method according to claim 7, in which the volume fraction of droplets in the pipe downstream ranging from 35% to 60%.

9. The method according to claim 1, in which the harmonic average is th size of the droplets in the pipe downstream is from 150 to 900 μm, the value of the ratio of the harmonic mean size of droplets to the pipe diameter downstream is from 0.002 up to 0.032, the average linear velocity of the downward flow in the pipe downstream is equal to from 0.5 to 1.9 ft/s (0.15 to 0.57 m/s)volume fraction of droplets in the pipe downstream is from 35 to 55% and droplets will polimerizuet obtaining styrene polymer.

10. The method according to claim 9, further comprising the functionalization of polymerized droplets as ion exchange resins.