DE2606715A1 - CONTINUOUS PROCESS FOR AGGLOMERATING AQUATIC LATICES AND APPROPRIATE DEVICE - Google Patents

Description

DR. BERG DIPL.-ING. STAFF DIPL.-ING. SCHWABE DR. DR. SANDMAIR

PATENT LAWYERS

8 MÜNCHEN 86, POSTFACH 860245 2606715

Attorney's file 26 85 ¹ J February 19, 1976

Monsanto Ocxnpany
St. Louis, Missouri, USA

Continuous process for agglomerating aqueous latices and suitable ones for them contraption

The invention relates to a continuous process for agglomerating polymer latices with the formation of large ones Particles and a device suitable for carrying out the method.

Latices of various polymers are suitable for a wide variety of uses. More recently are Large scale rubber latices used in the manufacture of rubber reinforced plastics such as impact resistant polystyrene and ABS materials (acrylonitrile butadiene styrene copolymers) ver-08-12-0295A GW

* (089) 988272 8 Some OU9830föoOj6 mken: Bayerische Vetemsbanlc Munich 453100

98 70 43 Telegrams: BERGSTAPFPATENT Munich Hypo-Bank Munich 389 2623

983310 TELEX: 0S24S60 BERG d Postscheck Munich 65343-808

has been applied. Although the rubbers can be mixed mechanically with such polymers, greatly improved results are achieved Results when you create a chemical bond between the Rubber phase and the matrix achieved by applying at least part of the matrix polymer to the rubber particles grafted on. It has also been shown that the impact resistance or impact strength of the rubber-modified compositions in certain cases and within certain limits depends on the size of the rubber particles dispersed in the masses, so there is a need to keep the particle size of those obtained by conventional latex polymerization processes Enlarge rubber particles.

In U.S. Patent 3,558,541 there is an improved batch run Process for agglomerating latices is described based on the application of acid anhydrides and latices containing salts containing organic acids as emulsifying agents. The acid anhydride destroys the emulsifying agent because of its higher ionization constants, so that it is not stabilized Latex makes it possible for the particles to meet and agglomerate to form larger particles, which are then stabilized will.

This process has been found to be extremely effective in producing latexes having particle sizes that are different from the polymer depend and extend up to about 1 μια. It exists however, for certain latices there is still a need for it

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to achieve even larger particles with certain latices and the amount of the relatively expensive acid anhydride and the for obtaining particles of a given size To reduce time expenditure.

In U.S. Patent 3,551,370 there is an improved batch run Process for agglomerating aqueous latices of a suitable polymer described, according to which an inorganic Electrolyte is added to the latex before it is mixed with a water-soluble acid anhydride. In such In batch operations, mixing is necessary for handling large volumes of the latex and anhydride solution in a large stirring tank, which creates considerable difficulties in getting the materials in time and mix evenly before the pH drops too far in local areas, with the mixing resulting in one considerable coagulation and uneven deposits as well as loss of the precipitated latex.

The object of the invention is now to overcome these disadvantages of the conventional batch-wise process and to provide a method and apparatus with which the polymerizate particles are rapidly, uniformly and with achievement reproducible results can be agglomerated to a desired particle size.

This object is achieved by the continuous 08-12-0295A GW according to the invention

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Process for agglomerating polymer particles dissolved in an aqueous latex, which is characterized in that man

A) an aqueous solution of a water-soluble, organic acid anhydride and an aqueous latex of a polymer formed from at least one ethylenically unsaturated monomer with low heat resistance is introduced continuously and simultaneously into a mixing zone, the polymer particles are small and stick to each other when they meet and the latex is a salt as an emulsifier an organic acid having an ionization constant lower than that of the acid of the anhydride;

B) the solution of the water-soluble, organic acid anhydride with the latex is continuously formed in the mixing zone mixed in a mixture;

C) the mixture continuously through a perforated device, which forms a wall section of the mixing zone, leads from the mixing zone into a conduit connected thereto;

D) the mixture continuous with laminar flow caused by the perforated device and one Residence time through the line leads to the hydrolysis of the acid anhydride, the agglomeration of the polymer particles to a predetermined size and sufficient to form an agglomerated mixture;

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E) the agglomerated mixture continuously out of line through a low shear zone (i.e., a Zone in which a low shear effect is exerted), which is connected to the line via an end region and has a removal opening at the other end area;

F) the agglomerated agglomerated moving through the low shear zone Mixing by adding an emulsifying material, which from the acid-stable emulsifying compounds, basic Compounds and combinations thereof comprising group is selected, continuously stabilized, the stabilization occurs before subjecting the agglomerated mixture to substantial shear which causes coagulation would cause the agglomerated mixture; and

G) the stabilized, agglomerated mixture with the aid of a removal device that mixes the agglomerated Mixing while flowing causes continuous from the opposite end of the low shear zone withdraws.

The invention is also a device for continuous Agglomeration of particles in an aqueous latex, which is characterized by

A) a mixing zone (stirred tank) with a first feed opening for a stream of an agglomerating solution, a second feed opening for a latex stream, one in

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mixing means located in the zone for mixing the feed streams to form a mixture and a perforated means forming at least part of a wall portion of the mixing zone and a passage opening represents for the mixture which forms a laminar flow in the mixture;

B) an annular line for forwarding the laminar flowing mixture with a first opening which is connected to the perforated device matches and is connected to it, and a second opening at the opposite end the management;

C) one over one end to the second opening of the conduit connected zone with low shear action (or flow-through chamber) for conveying an agglomerated mixture with a first inlet port at one end of the low-shear zone, that with the second port of the conduit is connected, at least one further arranged at the opposite end of the zone with low gravity Inlet opening for feeding an emulsifying material to stabilize the agglomerated mixture and a Outlet opening at the opposite end; and

D) one with the outlet port of the low shear zone connected removal device for removing the stabilized, agglomerated mixture.

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Further embodiments, objects and advantages of the invention result from the further description, the examples and the drawings.

In the drawings show:

Fig. 1 is a schematic side view of an apparatus suitable for carrying out the invention, in which the Conduit is oriented in the preferred generally vertical configuration;

Fig. 2 is a schematic side view of the low shear zone and the removal device and the additional ones Inlet openings for feeding the emulsifying materials;

Fig. 3 is a schematic front view of the low shear zone and the extraction device with the inlet or loading openings are indicated;

4 is a schematic view of a mixing zone comprising a cylindrical stirring tank with a multi-blade stirrer and guide plates arranged between the agitator surfaces and a perforated device as with a conduit having connected upper wall section,

Figure 5 is a schematic view of a mixing zone containing a zy-08-12-0295A GW. 60 9 838/0862

Lindrischen stirred tank includes, the a ship propeller-like Comprises a stirrer located generally in the center of the tank;

Fig. 6 is a schematic view of an apparatus which is arranged such that the mixture when performing the Process generally flows down the conduit and essentially all of the elements of the apparatus clarifies which are necessary to carry out the procedure;

Fig. 7 is a schematic view of an apparatus which is arranged such that the mixture during operation in flows generally horizontally through the conduit, showing substantially all of the elements of the apparatus, which are necessary for the implementation of the procedure;

Fig. 8 is a schematic view of a device arrangement (not to scale) showing essentially all of the devices Figure 8 shows the apparatus necessary to carry out the process including a latex delivery system and a mix-delivery system for the anhydride solution.

As can be seen without further ado, various factors influence it the optimal implementation of the procedure, so that different Variables must be taken into account when the procedural

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conditions are determined which are necessary for a given latex and / or a given increase in particle size. The effects of these variables also affect the combination of elements to be used in the device and are used in the further explained in more detail.

The aqueous latices to be treated in the present invention are those of polymers with low heat resistance properties, the particles of which have surfaces that are in the during the To carry out the process, the conditions applied are sufficiently soft or sticky so that the particles after the protection is eliminated or impaired by the emulsifier, adhere to one another when they meet. Such Polymers can be inherently soft and / or sticky, like rubbers, or they can be converted into this state, by causing them to swell with a solvent before carrying out the process according to the invention.

Thus, the polymers with low heat resistance are which are used in the process according to the invention in order to produce rubber-like polymers, such as diene rubbers, Polyisoprene rubbers, acrylate rubbers, ethylene-propylene rubbers and mixtures thereof.

The preferred latices are those made from diene rubbers or mixtures of diene rubbers, ie latexes of any rubber-like polymers (ie polymers with a transition temperature 08-2-0295AGw 60983S / 0862 determined in accordance with ASTM specification D-746-52T

second order of not more than 0 ⁰ C, preferably not more than -20 ⁰ C) from one or more conjugated 1,3-dienes, ie butadiene, isoprene, piperylene, chloroprene etc. These rubbers include homopolymers of conjugated 1,3- Serve and copolymers or block copolymers with up to an equal amount by weight of one or more copolymerizable, monoethylenically unsaturated monomers, such as monovinylidene aromatic hydrocarbons (e.g. styrene; ar-alkylstyrenes, such as o-, m- and p-methylstyrene, 2,4-dimethylstyrene, ar-ethylstyrene, p-tert-butylstyrene etc .; X -alkylstyrenes, such as ^ C-methyl styrene, # -ethyl styrene, £ \ -methyl-p -methyl styrene etc.} vinyl naphthalene etc. ); ar-h'alogenmonovinylidene aromatic hydrocarbons (e.g. o-, m- and p-chlorostyrene, 2,4-dibromostyrene, 2-methyl-4-chlorostyrene, etc.); Acrylonitrile; Methacrylonitrile; Alkyl acrylates (e.g. methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.) and the corresponding alkyl methacrylates; Acrylamides (e.g. acrylamide, methacrylamide, N-butyl acrylamide, etc.); unsaturated ketones, e.g. B. vinyl methyl ketone, methyl isopropyl ketone etc); <X -olefins (e.g. ethylene, propylene, etc.); Pyridines; Vinyl esters (e.g. vinyl acetate, vinyl stearate, etc.); Vinyl and vinylidene halides (e.g. vinyl and vinylidene chloride and vinylidene chlorides and bromides, etc.); and the like

A preferred group of rubbers includes those essentially 75.0 to 100.0% by weight of butadiene and / or isoprene and up to 25.0% by weight of a monomer which is derived from the monovinylidene aromatic Hydrocarbons (e.g. styrene) and un-

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saturated nitriles (ζ. Β. acrylonitrile) or mixtures thereof
comprehensive group is selected. Particularly advantageous substrates are butadiene homopolymers or interpolymers which contain 90.0 to 95.0% by weight of butadiene and 5.0 to 10.0% by weight of acrylonitrile or styrene.

When the level of a non-rubbery monomer in a rubber interpolymer reaches 50% by weight of the interpolymer, there is a tendency to coagulate so that the preferred rubbery interpolymers normally contain less than about 35.0% of a non-rubbery monomer, especially if they are with these monomers by one
polar monomer.

Although the rubber polymer contains small amounts, generally less than about 2.0% by weight, of a crosslinking agent, an excessively strong crosslinking polymer should be avoided since this makes the surface relatively hard and
Particles no longer adhere to one another when they meet. After agglomerating according to the invention, the particles
if desired, with possible advantages for the stability of the agglomerated particles, to a high degree, although this high degree of crosslinking is undesirable for certain processes to which the rubber is subsequently fed and in which
dissolution or optimal dispersion of the rubber is sought.

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The polymer solids content of the latices can vary from only about 5.0 wt% to about 60.0 wt% extend with the preferred latices having a solids content of about 20.0 to 40.0%. The more dilute latices cannot reach an optimal one so well within a reasonable period of time Particle size can be brought, while the more concentrated latices in certain cases a more difficult process control cause. In general, however, the particle size of the agglomerates increases as the solids content of the latex increases.

The latex must contain an emulsifier which is the salt of an organic acid with an ionization constant which is lower than that of the anhydride to be used in the process. For example, the latex contains the commonly used fatty acid soaps, such as sodium oleate, sodium stearate, sodium palmitate, the corresponding potassium salts, as well as mixtures thereof, such as. B. rubber soaps. In general, such fatty acid soaps are the alkali metal salts of aliphatic carboxylic acids with 12 to 22 carbon atoms, although, for certain applications, the ammonium salts are also used can use. In addition, the latex can also contain other emulsifying agents, such as anionic or nonionic materials, provided that these other emulsifying agents are not contained in such a concentration that the latex becomes stable to the acid anhydride. It can be seen that the amount of emulsifier normally increases with concentration of the latex and the particular polymer varies. Preferential

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wise no latices are used which contain a substantial excess of the emulsifier over the amount is necessary for stability.

Various types of organic anhydrides can be used according to the invention can be used provided that they are sufficiently soluble in water and that their acid content is relatively high Has ionization constant. An effective acid anhydride must be so soluble in water that it hydrolyzes and Provides acid groups that react with a sufficient amount of the emulsifier, thereby increasing the stability of the latex is reduced, with the result that the particles are subject to agglomeration when they meet. The ionization constant depends on the particular acidity of the emulsifier from, the water-soluble acid anhydrides generally having significantly higher ionization constants than those usually used alkali metal soaps.

Examples of such acid anhydrides are acetic anhydride, maleic anhydride and propionic anhydride. It seems without Meaning whether the acid is a saturated or a dicarboxylic acid. So before a noticeable If rapid and homogeneous mixing with the latex is achieved by hydrolysis, it may be desirable to use the anhydride initially to be mixed with a suitable solvent that is easily miscible with water. For example, you can use methanol, ethanol and acetone with advantage for dissolving maleic anhydride

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and propionic anhydride and the more soluble acetic anhydride use, a ratio of 1 to 3 parts of solvent per part of anhydride being found to be satisfactory has proven. The organic solution obtained can then be mixed with a small volume of water, after which the The mixture obtained is added to the latex. Alternatively, the more soluble anhydrides are preferably dissolved in a small volume Water which is then added to and mixed with the latex so that a homogeneous mixture is quickly achieved. One can also facilitate the dissolution of the anhydride in a carrier for addition to the latex through the application of heat, but with one too early hydrolysis of the anhydride should be avoided.

The amount of anhydride required will vary depending on the emulsifying agent present in the latex with which the Reaction is to be brought about, and with the desired particle size of the agglomerated particles. It has furthermore showed that the acid anhydride in latexes of rubber interpolymers, containing polar monomers is more effective because the increase in the amount of the polar monomer leads to a decrease the amount of anhydride which is required for an equivalent increase in particle size.

Although in most cases an amount of the anhydride that is one tenth of the stoichiometrically equivalent amount of the emulsifier corresponds to (which corresponds to a molar ratio of 1 to 20 since there are two acid groups),. to a certain

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Leads to agglomeration, the anhydride is preferably used in an amount of at least a quarter of the stoichiometrically equivalent amount. For the purpose of optimal management the acid anhydride is added in excess over the stoichiometrically equivalent amount of the emulsifying agent, often one being applying multiple excess. Amounts that are more than five times the stoichiometric amount lead to the reaction rate does not result in any additional advantages, but rather the stability of the agglomerated latex or the Adversely affect properties of the polymer by introducing excessive acidity or a corrosive effect.

As already mentioned, the acid anhydride must be used to achieve suitable Results are distributed homogeneously in the latex. However, the mixing of the anhydride with the latex must take place before any appreciable effect Hydrolysis of the anhydride or take place under minimal agitation conditions. When the anhydride is hydrolyzed and the latex-anhydride mixture is then subjected to a noticeable stirring action, the polymer particles tend to coagulate instead of Agglomerate under controllable conditions, noting that the coagulated material cannot be used.

Accordingly, the anhydride or any carrier solution thereof should be rapidly dispersed throughout the latex prior to any noticeable dissociation of the anhydride takes place. As a result, solutions of the anhydride in water should not be used for long periods of time leave them standing, or they should be kept under certain conditions

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which inhibit hydrolysis of the anhydride, for example by storing them under refrigeration. In certain cases it may be desirable to mix the anhydride and latex for minimal hydrolysis while refrigerated, although the relatively slow rate of hydrolysis of the anhydrides generally allows mixing using standard stirring techniques enables.

It has been found that the temperature at which the agglomeration reaction is carried out has no appreciable effect on the particle size of the agglomerated particles, although it does have an effect on the time required for the reaction to proceed and for the desired particle size to form . Since the rate of hydrolysis of the anhydride is slowed down by lowering the temperature and the Brownian motion of the particles is thereby also reduced, the time required to achieve equivalent results is lengthened by lowering the temperature, the reaction being carried out at any temperature above the freezing point of the latex in a satisfactory manner provided that the anhydride is sufficiently soluble at that temperature. The agglomeration reaction carried out in the line is suitably effected at room temperature or above, preferably at a temperature in the range from 30 to 50 ^° C. using flow-through times or residence times of 0.5 to 60 minutes, preferably 0.5 to 10 minutes. One can take longer periods of time, but without noticeable advantages

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and apply higher temperatures.

The particle size of the agglomerate can be determined by selecting the conditions the agglomeration reaction, such as the time, the temperature, the anhydride and the ratio of anhydride to emulsifier, being controlled. In addition, the particle size increases as the latex content increases. It is according to the invention possible to easily achieve an increase in the diameter of the latex particles which is originally a particle diameter have in the range from 0.01 to 0.2 μm (weight average), while the agglomerated latex particles have a particle diameter of 0.1 to 0.8 μm. With certain latices could depending on the emulsifying system they contain Particles with a size of up to 0.8 to 1.0 μm and can be achieved even greater. The weight average particle diameter can be determined according to the published method by M. J. Graves et al. "Size Analysis of Subsieve Powders Using a Centrifugal Photosedimentometer", British Chemical Engineering, 9 (1964) 742-744. According to the invention, a particle size analyzer (model 3000) from Martin Sweets was used Company, 3131 West Market Street, Louisville, Kentucky, USA used.

After the agglomeration reaction has proceeded to the desired extent, the agglomerated latex must protect against the formation of a coagulum can be stabilized before subjecting it to a greater extent of a stirring action. This can be

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can be achieved by adding an additional, acid-stable emulsifier or a basic alkali metal compound adds, which reacts with the acid of the originally present emulsifier and in this way the alkali metal soap in regenerated in an amount sufficient to achieve stability. In all cases the agitation used to disperse the added material into the latex should be at a minimum be held, wherein the emulsifier or the alkali metal compound is preferably added in an aqueous solution, to facilitate dispersion and to stir as little as possible. After reaching the dispersion of the stabilizer, the latex can be stirred to the extent necessary for subsequent processing and other reactions such as grafting and the like., is required.

The amount of stabilizing emulsifier can vary from just about 0.03 to 15.0 parts per 100 parts of polymer and up to even larger amounts as there is no tendency for there is a redispersion of the agglomerated particles. In general, amounts of from about 0.07 to 3.00 parts are used, preferably from 0.1 to 1.0 parts per 100 parts of the polymer.

Anionic emulsifiers, like the alkali metal salts of long chain sulfonic acids and sodium dodecyldiphenylbisulfonate as well as nonionic emulsifiers such as ethoxylated octyphenol. Normally it is necessary to add the nonionic agents in larger amounts than the anionic agents.

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If the emulsifier is to be regenerated, use suitably an alkali metal hydroxide or other basic compound such as a carbonate. The amount added corresponds to preferably at least the stoichiometric amount required for the reaction with the added anhydride is, although you can use slightly smaller amounts, although this results in a lower stability of the latex. Amounts that are more than twice the stoichiometrically equivalent amount are detrimental to certain latices Effect from, so that the preferred amounts 0.9 to 1.5 times the anhydride stoichiometrically equivalent amount (which is equivalent to 1.8 to 3.0 times the molar amount of the anhydride).

Various water-soluble, use monovalent and polyvalent metal salts and ammonium salts, including halides, sulfates, nitrates and phosphates, which depends on the latex and the presence of groups which could be adversely affected thereby. Examples for preferred materials to be used are magnesium sulfate, aluminum sulfate, sodium chloride, potassium chloride, sodium sulfate, Ammonium chloride, ammonium sulfate and like phosphate salts, etc. From the standpoint of minimal contamination the preferred electrolytes are the salts of the alkali metals and the ammonium salts. The alkali metal and ammonium halides and sulfates have proven themselves from the standpoint of process control, cost, minimal latex degradation, and optimal

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paint reaction with the acid anhydride proved to be extremely beneficial.

The amount of the inorganic electrolyte varies with the particular one Latex, the special acid anhydride and its amount as well as the desired particle size. In general, cheap ones are obtained Results with as little as 0.05 part of the electrolyte per 100 parts of the polymer of the latex, although the amount of the electrolyte is preferably at least 0.2 parts per 100 parts of the latex polymer is. The maximum amount of electrolyte depends on the particular acid anhydride and the one selected Electrolytes. When using sodium chloride and in the presence of a part of acetic anhydride in a polybutadiene latex with a solids content of 38% the maximum amount of the electrolyte to be added without causing coagulation is about 3.0 parts per 100 parts of the latex polymer. Magnesium sulphate and aluminum sulphate can, however, be used in larger quantities for the purposes of knowledge without any Causing coagulation or precipitation of the latex.

Before the polymerization, the inorganic electrolyte can be used to form the latex polymer to form the emulsion of the monomers can be added or it can be added to the polymerized latex admit. In the latter case, care should be taken to ensure that the electrolyte is sufficiently slow or diluted in a dilute manner Solution is added to cause excessive concentration at any point within the latex and cause coagulation

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to prevent. The attempts to use the electrolyte along with the Adding acid anhydride has been found to be unreliable because coagulation occurs relatively frequently.

In practice it has been shown that the continuous agglomeration process is easier to control than the traditional batch process and is also a smoother one Particle size leads, and without the usual quality fluctuations intermittent procedures or severe coagulation occur.

According to preferred procedures, the claimed method carried out as follows:

The step (A) is carried out in such a way that an aqueous solution of an organic anhydride and an aqueous latex one Adds polymer with low heat resistance simultaneously and continuously. The feeding takes place in such a way that the already described stoichiometric amounts of the solution and the latex are introduced under pressure into the mixing zone, with a supply pressure is maintained in the mixing zone which is sufficient to reduce the pressure gradient of that flowing in the line To overcome the mixture and the pressure drop of the mixture flowing through the perforated device, so that a The flow rate and the residence time of the mixture in the line are sufficient to remove the polymer particles agglomerate into particles of a predetermined size.

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It will be apparent to those skilled in the art that the feed pressure is predominant depends on the pressure gradient or the hydraulic pressure in the pipe during which it passes through the perforated Device resulting pressure drop is relatively small.

The conduit is generally upwardly directed and preferably arranged essentially vertically. With this arrangement, the pressure gradient is greater, so that the feed pressures accordingly increase. The charges can be brought to the required pressure in any suitable manner, for example with the help of pumps, by incline or by using gas pressure. The feed streams are in In the form of separate streams introduced under pressure into the mixing zone, preferably via openings on opposite sides Portions of the mixing zone to ensure that the feed streams mix quickly, and a mixing interface is brought about which ensures even mixing before excessive hydrolysis and Agglomeration can occur.

The anhydride is a liquid and is soluble in water, but does not readily dissolve, so that it must be rapidly agitated with high shear forces in order for it to dissolve quickly. The anhydride dissolves readily at a temperature in the range of about 5 to 50 ⁰ C, preferably 20 to 40 ⁰ C. It can dissolution times of less than 10 seconds, preferably less than 5 seconds are employed. The through

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high shear mixing means colloid mixers or mixers for continuously dispersing and dissolving the anhydride are preferred. It have Electronic or hydrodynamic ultrasonic mixing devices have proven to be practical, for example those under the designation "Sonifier-Disruptor" from Heat Systems-Ultrasonic, Inc., Plainview, L.I., New York, USA or under the name "Sonalator" from Sonic Engineering Corporation, Connecticut Avenue, Norwalk, Connecticut, USA.

The anhydride is mixed with the latex as quickly as possible in step (B) so that a uniform mixture is achieved before the additional hydrolysis of the anhydride takes place during the mixing. When mixing at temperatures of 30 ⁰ C times are preferably less than about 30 seconds while applying at 40 ⁰ C, mixing times of less than 20 seconds, and at 5O ⁰ C, mixing times of less than about 10 seconds. In operation, the time to dissolve the anhydride to form the solution and the time to mix to form the mixture are performed using a time-temperature schedule which ensures that the total time used is less than the time required is to hydrolyze the amount of anhydride corresponding to about 30% of the equivalent molar amount of the emulsifier contained in the latex before the material in the conduit is subjected to the agglomeration step. Preferably the degree of hydrolysis is less than about 30% of the equivalent molar amount

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of the emulsifier and ranges from about 10 to 20%, more preferably from about 5 to 10%.

If the latex contains a buffer, the time to hydrolyze the anhydride should be less than the time required to hydrolyze the amount of anhydride equal to 30% of the equivalent of the emulsifier contained in the latex plus the buffer. The mean residence time of the mixture in the mixing zone is critical for the implementation of the process. The pH value of an average rubber latex to be agglomerated is usually in a range from 9 to 10. As soon as the anhydride solution mixes with the latex, the pH value decreases rapidly if you use a residence time of seconds at temperatures of 30 to 50 ⁰ C, which are preferred for an effective procedure. The latex becomes sensitive to the action of shear forces when the pH value falls below the pK value of the emulsifier, which is around pH 7 for a rubber reserve soap. Thus, before the pH value drops below the pK value of this emulsifying agent, the mixture is passed from the mixing zone into the line with laminar flow, in which the agglomeration takes place without stirring and without coagulation. If the pH of the mixture in the mixing zone falls below the pK value of the emulsifying agent, the latex becomes too unstable for thorough mixing under high flow or shear, so that strong coagulation can occur. The pH is then best controlled using the time-temperature cycles already described for dissolving and mixing the anhydride.

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The step (B) is carried out in such a way that the solution and the latex continuously in the mixing zone to form a mixture under the action of a high flow mixing action mixed. The flow rate of the mixture should be so high that it moves as quickly without the latex precipitating out mixed as possible. In general, the agitation is carried out by the use of high-flow stirrers, the effect the circulation of the mixture, such as propellers, flat-blade turbines or multiple-blade stirrers, in which between the wings guide plates are arranged. The mixing stage is carried out using a minimum average residence time the mixing is carried out in the mixing zone, in which uniform mixing can be achieved.

Stirring with the use of strong currents Mixing devices take place in the mixing zone, which is designed so that the circulation value of the mixture in the mixing zone during the residence time of the mixture before it exits the zone is in a range of about 3 to 10. The mixing performance in this mixing zone can be calculated using the following equation for a continuously operated stirred tank with turbine (CST):

Qp = 0.5 ND ³

T =
NV

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D = the diameter of the stirrer (cm)

Q = volumetric pumping speed of the stirrer (l / min) P

t = residence time in the stirred tank (minutes) V = volume of the stirred tank (1)

T = average number of revolutions in the agitation tank per average residence time.

The concepts of this construction are readily apparent to those skilled in the art and can be found in the article by J. B. Gray et al V. W. UhI, Mixing Theory and Practice, Vol. 1 (1966) 205.

The mixing zone is preferably a cylindrical one Tank with a stirrer located generally in the center of the container. The tank generally has a length / Diameter ratio of about 0.3 to 2, preferably from 0.5 to 1. The tank has an integrated perforated wall section Means approximately the same diameter as the tank and preferably also the same diameter as the conduit.

The preferred design enables uniform mixing in the tank and an even flow of the mixture through the perforated disc, which causes a laminar flow in the pipe, so that a highly turbulent flow suitable for mixing in the tank and essentially only one in the line laminar flow exist when the mixture is passed through the mixing tank under pressure.

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The stirrers used in the mixing tank can be any conventional stirrer that creates a strong flow, such as turbine stirrers or propeller or blade stirrers, of which the turbine stirrers are preferred. The speed of rotation the impeller blade can vary with the size of the mixing zone, which determines the diameter of the blades. As a measure of the degree of stirring in a liquid mixing system, the speed is usually the stirrer tip is used. The tip speed (TS) of a stirrer in m / min is given by the following Formula:

TS = } p D _a χ speed,

in the D for the diameter of the stirrer blades in meters and a

the speed stands for the speed of rotation of the stirrer in revolutions per minute. Mixing is achieved with high flow at top speeds in the range from 9 to 457 m / min, preferably from 12 to 31 m / min.

The agitator may be provided with a scraper attached to the shaft of the agitator and in relation to the turbine blades is vertically attached to the stirrer and which serves to remove any coagulated material from the perforated device wipe free that may form and tend to cluster around the perforation and seal it. The scraper can be inclined against the surface of the perforated device and so an effect with low tensile forces and result in minimal mixing shear. Alternatively

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the scraper can be used with a distance of less than 1.27 cm, preferably less than 0.6 cm from the perforated device, whereby the perforated device through the Seer flow of the mixture flowing past is cleaned.

The method according to the invention and the device used for it have the advantage that large volumes of latex can be agglomerated with the latex and anhydride continuous and be mixed quickly without coagulation in a relatively small mixing zone while maintaining a minimum residence time.

Step (C) is carried out in such a way that a flow is achieved through the mixing zone by the application of pressure, by passing the vigorously agitated mixture continuously through a perforated device which is an integral wall section of the Represents mixing zone, transferred into a line connected to it. The perforated device preferably consists of a perforated one cylindrical plate, which gives the mixture flowing through it a laminar flow, so that the turbulence is kept to a minimum and no coagulation occurs when the mixture agglomerates in the laminar flow conduit. The perforated device then serves as a breaker plate, which the highly turbulent flow in the mixing zone of the laminar flow in the conduit separates so that the laminar flow is essentially free of any turbulence and the shear rate in the laminar flow conduit is less than about 1 second.

⁰⁸ - ¹² - ^{0295A GM} 60983B / 0862

260-715

The perforated device has a multiplicity of perforations and serves as a breaker plate during the implementation of the method, which exerts a back pressure on the mixing zone side of the device that is sufficient to overcome the pressure difference, caused by the agitation in the mixing zone, thereby reducing the pressure differential through the perforated device is balanced in the mixing zone and a laminar flow is ensured through the perforated device in the line and caused. The perforated device also provides a pressure drop on the line side of the device during operation, which corresponds to no less than the highest pressure gradient in the mixing zone, creating a laminar flow through it the perforated device is ensured. The perforations preferably have a length / diameter ratio of about 0.1 to 4, while the total free area of the perforations is about 1 to 10% of the total area of the perforated device. The perforated devices have a diameter that is about the same as the diameter of the mixing zone and the diameter of the pipe. In practice it depends on the size of the device on the size of the pipe, which is necessary to ensure a residence time for the mixture during the the particles at a flow rate which gives a shear rate of less than 1 second "to a predetermined one Agglomerate particle size. The lines can have a diameter of 10 to 61 cm or more and have a length which is designed in such a way that a volume throughput consistent with the residence time and a shear rate of less than 1 second result, d. H. a length of 12 to 152 cm

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ORIGINAL INSPECTED

or more. With the diameter of the perforations described, the perforated plate can have a thickness of 0.16 to 1.27 cm exhibit. The device is suitably made of stainless steel, preferably glass-lined steel or glass.

The step (D) is carried out in such a way that the mixture runs continuously through the line with laminar flow, the residence time being sufficient to hydrolyze the anhydride sufficiently, so that the particles form an agglomerated mixture into a predetermined '. Agglomerate particle size. The particles of the latex usually have a diameter of about 0.01 to 0.2 μm and are agglomerated into particles, which have an average diameter of about 0.1 to 1.0 μm, preferably of about 0.3 to 0.8 μm. The educated Particles are monodisperse and have a narrow particle size distribution with a particle size range of 1.1 to 1.4 (weight average / number average particle diameter). The method for determining the weight average particle size diameter has already been described. The number average particle size diameter determined by taking a photomicrograph of a dispersion of the particles and measuring the particles, the mean diameter being determined as the number mean diameter.

The anhydride hydrolyzes during the residence time in the line, the pH being from about 7 to any desired value decreases in the range between 3 and 7, the particle size depending on the pH value ultimately reached and the particles so

609836/0862

08-12-0295A GW

are larger, the lower the pH value. The pH can be adjusted by stoichiometric control of the addition of the anhydride in the molar amounts that are required to achieve a predetermined pH, can be controlled if the stoichiometric Knows equivalents introduced by the emulsifier contained in the latex. Passing through the Mixing during the residence time through the line allows the agglomeration reaction to proceed, with the residence time is controlled in such a way that there is a residence time which is sufficient to achieve a given particle size. These Residence time ranges from about 0.5 to 60 minutes, preferably from about 1 to 10 minutes. Within this range for the residence time can be produced particles whose diameter is from about 0.2 to 1.0 μm, preferably from about 0.3 to 0.8 μΐη (weight average) varies.

The line is adjusted accordingly so that a predetermined dwell time is achieved. In general, a length / Diameter ratio of about 10 to 36, preferably 15 to 25, is used, the volume being measured to be at the given flow rate through the conduit gives a predetermined residence time.

The diameter of the line is designed so that the shear effect on the wall of the pipe in the case of latices, the pH of which has been lowered to less than 7 and which have therefore become unstable are less than about 1 second. The shear rate

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on the wall can be estimated by the following equation:

Schergeschwxndxgkext on the wall
the line

where Q is the total volumetric flow rate (1 / sec) and
r means the radius of the pipe (cm).

It can be seen that the shear rate depends on the radius (diameter) of the conduit. Thus, one will have a shear rate less than about 1 second disconcerted minimum diameter preferred. There have been lines with one Diameters of 5 to 61 cm have proven practical, with a 30.5 cm diameter conduit having a throughput of about 2650 liters of latex with a solids content of about 30 to 40 % By weight per hour at a shear rate of less than about 1 second. It is readily apparent to the person skilled in the art that higher shear rates depending on the stability of the latex can be used without coagulation occurs.

The maximum diameter of the conduit depends on the diameter of the mixing zone and the perforated device. According to a Embodiment, the line can be substantially upward, preferably aligned in a substantially vertical arrangement 08-12-0295A GW

6G983S / Q862

ORIGINAL INSPECTED

2605715

so that the mixture flows upward through the conduit.

The method according to the invention can be carried out with the defined device also be carried out in such a way that the conduit is directed generally downwards so that the mixture of a Mixing zone flows down through a perforated device through the conduit. The low shear zone includes in this case the extension of the conduit and has at least one inlet through which the agglomerated mixture stabilizing emulsifying material is added. The extraction device is directly connected to the low-shear zone connected and has a control device for the liquid level of the mixture, for example a manometer-like A tube assembly comprising a generally vertically disposed tube arm extending to a height which is sufficient to control the flow while the method is being carried out.

The device for the claimed method can also be horizontal Arrangement are operated in which the line is oriented generally horizontally. The mixing zone is therefore connected horizontally to the axis of the substantially horizontally disposed conduit, the perforated means generally is arranged vertically in the downstream wall of the mixing zone and the mixing zone with the horizontally arranged Line connects. The low shear zone, which is generally operated in a horizontal orientation, represents

08-Ϊ2-0295Α GW S ₀₉₈₃₆ , 08S2

represents an extension of the line and has an outlet opening connected to a removal device in its lower section and a mixture level control device with which the flow is controlled while the method is being carried out.

The temperature of the line can be adjusted with the help of a temperature control device, for example a heat exchanger jacket, can be controlled so that the temperature gradient between the line and the laminar flowing mixture is kept to a minimum and the laminar flow is maintained without shear or agitation which keeps coagulation to a minimum during the agglomeration reaction.

The step (E) is carried out in such a way that the agglomerated Mixture continuously transferred from the conduit through a low-shear zone that is terminated at one end with the Line is connected and has an outlet opening at its opposite end. In the low shear zone exerted a shear rate of less than 1 second. According to a preferred embodiment, the zone is lower Shear action generally designed horizontally as a flow chamber, the lower wall portion of which with a line connected first inlet port and the outlet port is integrated. The chamber has upwardly extending side wall portions so that the depth of the chamber is at least twice as great as the diameter of the pipe. The dimensions are like that designed that the agglomerated mixture with preferably one

08-12-0295A GW 609836/0862

exposed upper surface flows through the device, so that the shear action is reduced and it becomes possible for any remove upstream precipitated material floating on the surface of the material.

According to a preferred embodiment of the invention flows the laminar flowing mixture of step (D) generally up through the conduit so that any coagulated material low density that forms during agglomeration is fed into the low shear zone and floats there so that it can be removed in that zone, leaving the conduit essentially free of coagulated material remains, which ensures a laminar flow.

Step (F) is carried out by agglomerating those moving through the low shear zone Mixture continuously stabilized with an emulsifying material, which is fed in such a way that either one acid-stable emulsifying compound is added or the salt is regenerated by adding a basic compound, or a combination these measures apply, this stabilization being done before the agglomerated mixture of a substantial Exposed to shear that would lead to coagulation of the agglomerated mixture. The stabilization of the agglomerated mixture has already been described. According to the invention, the emulsifying material is in step (F) via openings in the agglomerated mixture introduced into the side walls of the

08-12-0295A cw 609836/0862

Low shear zone are arranged. According to a preferred Embodiment can be at least one opening in located near an outlet opening of the low-shear zone in the side wall sections, so that the emulsifying Material can be added before a flow mixing takes place in the extraction device, so that the mixture can be stabilized against coagulation of the latex during mixing under the action of flow. The emulsifying one Material is dispensed under pressure in a stoichiometric amount ranging from about 0.03 to 15 parts per 100 parts of the The latex peeled off was added to the outlet port. The emulsifying material can according to a preferred embodiment with the aid of arranged in the extraction device additional openings are supplied, whereby an additional stabilization of the agglomerated mixture is achieved. These openings can be connected to a pressure nozzle or nozzle device, the the distribution of the emulsifying material in the extraction device supports the mixing of the flowing material caused. Further devices for distributing the emulsifying materials in the agglomerated mixture can be feed devices, such as a porous sintered ring or a fiber wick applied around the outlet opening of the zone with lower Shear action are arranged, and from which the material is fed into the flowing mixture. The zone with low According to one embodiment, preferably has a shear effect a liquid level control, which is connected to the extraction device, and which serves to monitor the liquid level in the Control low shear zone.

$ 09838/0862

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Step (G) is carried out in such a way that the stabilized, agglomerated mixture with the aid of a removal device, which ensures thorough mixing by the action of flow in the stabilized agglomerated mixture is continuously withdrawn from the low shear zone. The mixing under the action of flow in the removal stage (G) takes place with the help of the pressure drop in the stabilized, agglomerated mixture, when this flows through the extraction device. According to a preferred embodiment, the removal device be an annular tube which is connected to the outlet opening and has at least one reduction in diameter, the causes an increase in the flow rate and a mixing effect. It can also be the ones commonly used in industry used, in-line flow mixers can be used.

A level control device can preferably also be used to control the liquid level in the zone with low shear action be connected to the extraction device.

According to one embodiment of the invention, the method can under Use of the device can be used to effect two agglomerating processes in parallel, so that one agglomerated Mixtures with particles of two different diameters are obtained, d. H. a method for making particles is carried out with a particle diameter of 0.3 μm and a method for production of particles with a particle diameter of 0.6 µm through and unites the two streams to form a

08-12-0295A cw 609836/0862 _ftpirfM41

ORfGiNAL INSPECTED

schickungsStroms, the particle size distribution having two maxima which is then subjected to a grafting reaction as a rubber phase to form highly impact-resistant polymers can be. The particle size can be from 0.1 to 1.0 μm Extend (weight average), the small particles preferably having a diameter of about 0.1 to 0.4 μm and the large ones Particles preferably have a diameter of about 0.5 to 1.0 μm.

In Fig. 1, a mixing zone 9 is shown, which has a cylindrical Agitation tank 10, a first feed opening 11, a second feed opening 12, a mixing device with a Turbine stirrer 13 and a perforated device, the one has perforated cylindrical plate 14 with perforations 15, includes. The material is introduced from the stirring tank through the plate into an annular conduit 16 which has a first opening 17, a second opening 18 and a temperature control device with a heat exchange jacket 19. The line is with one Low Shear Zone 20 (i.e., a zone where there is little shear applied to the material flowing therethrough is exercised) connected to a first inlet port 21, at least one further inlet port 22 and an outlet port

23 is equipped. The outlet opening is with a removal device connected comprising an annular tube 24 having at least one reduction in diameter, the tube

24 is provided with at least one inlet opening 25. The extraction device is connected to a manometer-like level control device 26. Which has a first pipe 27 and a second

08-12-0295A cw € 0 98 36/0862

Has tube 28. With the first loading opening 11 is a first feed device connected to a pump 29, while the. second feed opening 12 is connected to a second feed device with a pump 29 '.

In Fig. 2 is a schematic view of the zone 30 with less Shear action shown, with additional inlet openings 31, an annular bottom wall portion 32, extending upwards extending side wall portions 33, an outlet opening and a removal device 35 is provided, the inlet openings 36 and diameter reductions 37.

3 is a front partial sectional view of the low shear zone 30 and the extraction device 35 along the line 3-3 of FIG. The low shear zone includes an inlet port 31 and one Outlet opening 34. The extraction device is provided with an inlet opening 36 and diameter reductions 37.

4 shows a mixing zone 50 which has a multi-blade stirrer 51 arranged between the blades Wall guide plates 52 having a stirring tank 53, a first loading opening 54 and a second loading opening 55 includes. A perforated device with perforations 57 is also shown. The stirrer 51 is equipped with scrapers 58 which are in contact with the perforated device 56.

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In Fig. 5, a mixing zone 60 is shown as a mixing device has a screw propeller-like stirrer 61.

In Fig. 6 a device arrangement is shown in which the process can be carried out in such a way that the mixture generally flows downwards during agglomeration the annular conduit flows. This device arrangement includes a mixing zone 70, a conduit 72, a perforated device 71, a low shear zone 73 with a Inlet port 74 and a removal device 75 with an inlet port 76 and a liquid level control device 77. The line has a first opening 78 and a second opening 79, while the low shear zone has an inlet port 80 and an inlet port 81 and the extraction zone a Have inlet port 82 and an outlet port 83. The mixing zone is provided with a stirrer 84.

In Fig. 7 a device arrangement is shown in which the Process can be carried out such that the mixture generally horizontally through the annular during agglomeration Line flows. This device arrangement comprises a mixing zone 90, a perforated device 91, an annular conduit 92 with a first opening 93 and a second opening 94, a zone 95 with low shear action with a first inlet opening 96, an outlet opening 97 and additional supply openings 98, an extraction device 99 with an inlet opening 100, an outlet port 101 and a liquid level control device 102, the mixing zone being equipped with a stirrer 103

€ 09836/0862

08-12-0295A GW. ORIGINAL INSPECTE »

260-715

is prepared.

A schematic flow diagram is shown in FIG. 8, the (not to scale) the continuously carried out method using the method according to the invention Device reproduces. This device comprises a storage tank 110 equipped with a stirrer for the latex, which consists of a not shown, continuously operated reactor is supplied, and equipped with a jacket for temperature control is. It also includes a pump 111, with the latex under pressure in a mixing zone 112, which is a stirrer 113 and a perforated device 114, inserted and inserted into an annular Line 115 is transferred with a first opening 116 equipped with a flange and a second opening 117 with a flange is. From this line 115 the material flows into a Low gravity zone 118, which has a first inlet port 119, an outlet opening 120, an additional inlet opening 121 and a removal device 122 is provided. The removal device 122 has an inlet opening 123, a Outlet port 124 and a liquid level control device 125, the apparatus further comprises a mixer 126 with high shear and a pump 127,

The following examples serve to further illustrate the invention .

08-12-0295A GW

ORIGINAL INSPECTED

example 1

Latex A

A latex of a rubber-like polymer from 97 parts of butadiene is prepared by polymerizing butadiene and acrylonitrile and 3 parts of acrylonitrile. The latex contains 40.0% solids and 1.2 parts sodium oleate per 100 parts of the latex as Emulsifier and, during the polymerization, 0.24 parts sodium sulfate per 100 parts of the latex. The particle size of the polymer results with 0.08 μΐη (weight average).

Latex B

The steps in Part A are repeated with a latex containing 0.25 parts of sodium sulfate per 100 during the polymerization Contains parts of the latex. After the end of the polymerization, 0.2 part of additional sodium sulfate is added as an agglomerating additive per 100 parts of the latex in the form of a 10% solution. The particle size of the polymer is found to be about 0.08 μm (Weight average).

Examples 2 to 6

The device shown in FIG. 8 is used, which has a mixing zone of the type shown in FIG. 4 with a diameter 5.1 cm and a length of 4.4 cm.

One prepares solutions of acetic anhydride by continuous Mix 15 parts of water per 100 parts of the latex

08-12-029 * 1 «609836/0862

with 0.2 to 0.8 parts of acetic anhydride per 100 parts of the Latex using an ultrasonic mixer (Ultrasonic Sonifier Model W-185) with a mean residence time of less than 10 seconds. The perforated device of the mixing zone consists of a glass plate with a diameter of 5.1 cm and a thickness of 0.3 cm, the 13 in evenly arranged Has perforations with a diameter of 0.3 cm, which corresponds to a perforation area of 5% of the total area of the plate. The line consists of a glass tube with a diameter of 5.1 cm and a length of 114 cm. The zone with low Shear has 12.7 cm side walls and a length of 25 cm. This zone is operated with a filling level of 75%, so that the mixture has a free surface. The zone with low shear has four inlet openings for feeding an emulsifying material (a 10% solution of dodecyldiphenyl ether disulfonate), which is added in an amount of 8 parts per 100 parts of the latex to form the agglomerated mixture to stabilize. The extraction device consists of a tube with a reduction in diameter from 2 to 1, whereby a Mixing of the stabilized, agglomerated mixture takes place under the action of the flow. The latex comes with a temperature of 42 ° C in an amount of 0.34 kg / hour simultaneously with a flow of the anhydride solution at a temperature of about 25 ° C introduced into the mixing zone, in which the mixing under high shear at the speed of the stirrer tips of 13.7 m / min. The mixture is then passed through the perforated device, which creates a laminar flow in

08-12-0295A GW

609836 / 0SS2 originally inspected

260Ö715

caused in the line. The mixture then flows with a calculated shear rate of 0.51 seconds and a residence time of 8.9 minutes through the line, during which the polymer particles agglomerate. Then the agglomerated Mixture stabilized and removed via the extraction device, mixing taking place through the action of the flow movement. In the following Table I are the ones carried out put together experimental investigations in which anhydride solutions were supplied in quantities that anhydride feeds from 0.2 to 0.8 parts of anhydride per 100 parts of the latex.

latex Table I. anhydride Particle size of the agglome example (Parts per 100 parts rated particles le of latex) (μπι) * A. 0.8 0.48 2 A. 0.4 0.36 3 a ' 0.2 0.12 4th B. 0.6 0.74 5 B. 0.4 0 _r 29 6th

* Weight average

Example 7
Latex C

One prepares one by polymerizing butadiene and acrylonitrile

08-12-0295A GW

- 45 - 260.715

Latex, which is a rubber polymer made from 95 parts of butadiene and Contains 5 parts of acrylonitrile. The latex contains 40% solids and 1.2 parts sodium oleate as an emulsifier. The polymerization will carried out with a redox system consisting of iron and sodium formaldehyde sulfoxylate. The emulsion is additionally coated with an acid-stable emulsifying agent Compound, namely 0.02 parts of sodium dodecyldiphenyl ether disulfonate per 100 parts of the latex stabilized. The watched Particle size of the polymer is about 0.10 μm (weight average) .

Examples 8 and 9

The procedures of Example 2 are repeated using latex C from Example 7. In the following Table II, the conducted experiments.

Table II

Example latex anhydride particle size of the agglomerate

(Parts per 100 parts of the rated particle (pm) latex)

8 C 0.7 0.69

9 C 0.4 0.30

ORIGINAL INSPHGTt = D 08-12-0295AGW 609836/0862

Claims (15)

-46- 260S715 claims 1. Continuous process for agglomerating polymer particles in an aqueous latex, characterized in that one A) an aqueous solution of a water-soluble, organic acid anhydride and an aqueous latex of a polymer formed from at least one ethylenically unsaturated monomer with low heat resistance is introduced continuously and simultaneously into a mixing zone, the polymer particles are small and stick to each other when they meet and the latex is a salt as an emulsifier an organic acid with an ionization constant lower than that of the acid of the anhydride? B) the solution of the water-soluble, organic acid anhydride with the latex is continuously formed in the mixing zone mixed in a mixture; C) the mixture continuously through a perforated device, which forms a wall section of the mixing zone, leads from the mixing zone into a conduit connected thereto; D) the mixture continuously with through the perforated device caused laminar flow and a residence time through the line, which is necessary for the hydrolysis of the acid anhydride, agglomerating the polymer particles to a predetermined size and forming an agglomerated one Mixture is sufficient; E) the agglomerated mixture continuously from the line 08-12-0295A cw SQ383S / Ö882 passes through a low shear zone connected to the conduit at one end and at the other The end region has a removal opening; F) the agglomerated agglomerated moving through the low shear zone Mixing by adding an emulsifying material, which consists of the acid-stable emulsifying compounds, basic compounds and combinations thereof comprising group is selected, continuously stabilized, wherein stabilization occurs before the agglomerated mixture is subjected to substantial shear, which would cause the agglomerated mixture to coagulate; and G) the stabilized, agglomerated mixture with the aid of a removal device that mixes the agglomerated Mixing while flowing causes continuous from the opposite end of the low shear zone withdraws. 2. The method according to claim 1, characterized in that that a diene rubber polymer is used as the polymer. 3. The method according to claim 1, characterized in that that acetic anhydride, maleic anhydride or a mixture thereof is used as the organic acid anhydride . 08-12-0295A GW 609836/0882 4. The method according to claim 1, characterized in that that a fatty acid soap is used as an emulsifier. 5. The method according to claim 1, characterized in that that the emulsifying compound is nonionic organic compounds, anionic organic compounds or mixtures thereof are used. 6. The method according to claim 1, characterized in that that the acid anhydride is first dissolved in a volume of water which is less than that of the latex, and introduces the solution together with the latex in stage A. 7. The method according to claim 1, characterized in that that one feeds the acid anhydride solution in stage &.) in a molar amount which is at least equal to that half the molar amount of the emulsifying agent contained in the latex. 8. The method according to claim 5, characterized in that that a latex is used which contains about 0.01 to 1.0 parts of sodium dodecyldiphenyl ether disulfonate per 100 parts of the latex polymer as an emulsifying compound. 9. The method according to claim 1, characterized in that to stabilize the agglomerated mixture 08-12-0295A GW 609838/0882 QHlQlUhL i '^ iiC ^ w? -49- 26O ', 715 in step (F) the acid stable emulsifying compound in an amount of about 0.03 to 15 parts per 100 parts of the Adding latex polymer. 10. The method according to claim 1, characterized in that that before carrying out step (A), about 0.05 to 3.0 parts per 100 parts of the latex polymer are added to the aqueous latex adding a water-soluble inorganic electrolyte, which is a salt with an alkali metal cation, an alkaline earth metal cation which is ammonium cation or mixtures of these cations. 11. The method according to claim 1, characterized in that that the introduction of the material in step (A) is carried out in such a way that the solution and the latex in the correct proportion into the mixing zone using a feed pressure sufficient to the pressure drop of the mixture flowing in the conduit and the pressure drop of the mixture through the perforated device to overcome and apply a flow rate and a residence time of the mixture in the line, which is sufficient to agglomerating the polymer particles into particles of a predetermined size. 12. The method according to claim 1, characterized in that that one carries out the mixing of stage (B) in such a way that a mean circulation value results, which per 08-12-0295A GW 809 3 38/0882 original average residence time of the mixture, ranging from 10 to 30 seconds, ranging from about 3 to lies.. 13. Continuous process for agglomerating polymer particles in aqueous latices with the formation of agglomerated polymer particles which have a particle size distribution have two maxima, using the method according to claim 1, characterized in that a first stabilized, agglomerated mixture in stage (G) subtracts, which has agglomerated polymer particles with a particle size of about 0.1 to 0.4 μπι and at the same time a second stabilized, agglomerated mixture withdraws in step (G), the agglomerated polymer particles with a Particle size of about 0.5 to 1.0 μια, the first and mixing the second mixture and preparing a third stabilized, agglomerated mixture having a particle size distribution with two maxima. 14. Apparatus for the continuous agglomeration of particles in an aqueous latex, characterized by A) a mixing zone (9) with a first feed opening (11) for a stream of an agglomerating solution, a second feed opening (12) for a latex stream, a mixing device (13) arranged in the zone for mixing of the feed streams forming a mixture and a perforated means (14, 15) the at least 08-12-0295A cw .609838 / 0882 260G715 forms part of a wall section of the mixing zone and represents a passage opening for the mixture, which in the mixture forms a laminar flow; B) an annular conduit (16) for forwarding the laminar flowing mixture with a first opening (17), which with coincides with and is connected to the perforated means, and a second opening (18) on the opposite one End of line; C) a low shear zone (20) for conveying an agglomerated mixture with an inlet opening (21) at one end of the low-shear zone connected to the second opening of the conduit, at least a further inlet port (22) at the opposite end of the low-shear zone for supply an emulsifying material for stabilizing the agglomerated mixture and an outlet opening (23) on the opposite end; and D) one with the outlet port of the low shear zone connected removal device (24) for removing the stabilized agglomerated mixture (Fig. 1). 15. The device according to claim 14, characterized in that " that the first and second feed openings (11, 12) on opposite wall sections of the mixing zone (9) 08-12-0295A GW 609838/0862 onmiNAL are arranged and the mixing device (13) in general comprises arranged in the middle of the mixing zone stirrer with high flow effect (Fig. 1). 609838/0882