DE2008572A1 - Emulsion polymerization process for the production of aqueous dispersions of organic polymer particles - Google Patents

Description

Scli / Gl · t3 ^ 744-3 ?.

THE DOl / GIIEMICAl COMPANI, Midland, Michigan /

EinuJ-sionpolymerisationsverfahreni for the production of aqueous dispersions organic polymer particles

The present invention relates to a method of manufacture v / aqueous dispersions of normally solid organic polymer particles by dispersing an oil phase of at least one emulsion-polymerizable monomer in an aqueous phase containing a stabilizing emulsifier, and treating the dispersion-under Emulsion polymerization conditions. This method is characterized in that 0.2-2 ■ weight- $, based on the obtained organic polymer, a polymer from a sulfoester of an α, ß-ethylenically unsaturated. Carboxylic acid can be added to the aqueous phase. In pre-

009839/2254

BAD OBSGlNAL

0.5-4.0 weight- ^, based on the organic polymers obtained, the stabilizing emulsifier is used. For the production of microspheres with liquid centers and seamless rigid walls made of a normally solid organic polymer will be at least a non-polymerizable, water-insoluble liquid mixed with the monomer. Polymer particles of this aqueous Have dispersions, whether they are in solid form or in the form of microspheres, generally diameter of 0.5 - 20 u, with some rope

Chen diameter up to 45 u.

The essence of the invention lies in the use of a polymer made from a sulfoester of an α, β-ethylenically unsaturated one Carboxylic acid as leveling aid or coalescing aid in carrying out an emulsion polymerization process.

The aqueous dispersions are themselves suitable as coating preparations, for example as paints, in which case they can be used in particular for the production of foam rubber are. Furthermore, these aqueous dispersions can be concentrated to form dispersions with higher solids contents. In addition, epidemics can be filtered off from the dispersions and used as fillers.

The microspheres can be used as exj) edible spheres Production of porous foams are used. Thermoplastic microspheres that encapsulate liquids are suitable for the production of, for example, insecticides, pharmaceuticals, Inks and fire retardants. It is also possible to remove the liquid by evaporation or the like to remove so that hollow microspheres are obtained,

009839/2254

which. Excellent as light fillers suitable for paints or paper coatings. Microspheres with polymeric liquid centers are suitable for manufacture of multipurpose plastic materials.

Monomers which are suitable for the production of organic polymeric particles by the process according to the invention polymerize under emulsion polymerization conditions with formation of water-insoluble polymers «Representative examples for such monomers are ethylenically unsaturated monomers, such as the monovinylidene aromatic compounds, the acyclic conjugated dienes, the esters of α, ß-ethylenically unsaturated carboxylic acids and others Ethylenically unsaturated monomers.

Of the monovinylidene aromatic compounds include, for example, styrene, substituted styrenes _s such as cc-methylstyrene, ar-methyl styrene!, Ar-ethylstyrene, a, ar-dimethylstyrene, ar, ar-Dimethy! Styrene, ar-tert-butylstyrene, methoxystyrene, ar, ar-diethylstyrene, acetylstyrene, monochlorostyrene, dichlorostyrene, other halostyrenes and vinylnaphthalene are mentioned. ,

Under the term "monovinylidene aromatic monomer or monovinylidene aromatic compound "should according to the invention it is understood that having an aromatic ring in each molecule of the monomer or compound is a radical of the formula

GH ₂ = G -

is linked, wherein R is hydrogen or a lower one Alkyl radical, such as alkyl with 1-4 carbon atoms, ' for example methyl, ethyl, n ~ propyl, η-butyl or isobutyl.

009839/2254

The acyclic conjugated dienes which are suitable for carrying out the invention are, for example, butadiene and substituted idols Butadiene compounds, as well as other acyclic compounds, the at least two places of ethylenic unsaturation have, the unsaturation being separated from one another by a simple carbon-carbon bond. Specific examples are 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, Piperylene, 2-neopentyl-1,3-butadiene and other hydrocarbon homologues of 1,3-butadiene. Further come the substituted dienes, such as, for example, 2-chloro-1,3-butadiene, 2-cyano-1,3-butadiene, the substituted straight-chain conjugated pentadienes and the straight-chain and branched ones Hexadienes in question.

Suitable esters of α, β-ethylenically unsaturated carboxylic acids are the alkyl acrylates in which the alkyl component is 1-12 Has carbon atoms, as well as the esters α, β-ethylenic unsaturated dicarboxylic acids, for example methyl maleate, Ethyl fumarate, propyl citraconate. and butyl itaconate.

Other suitable ethylenically unsaturated monomers are, for example chlorine-substituted aliphatic monoethylenically unsaturated monomers, for example vinyl chloride and vinylidene chloride, the acrylonitriles, such as acrylonitrile and methacrylonitrile, ethylenically unsaturated esters saturated carboxylic acids, such as vinyl acetate and vinyl propionate and the ethylenically unsaturated ketones, such as methyl isopropenyl ketone.

Small amounts, i.e. up to about 10% by weight, based on on the polymer of other ethylenically unsaturated monomers, can with the monomers described above in the Implementation of the process according to the invention copolymerized

009839/2254

ORIGINAL INSPECTED

will. typical such other monomers are α, β-ethylenic unsaturated carboxylic acids, such as acrylic acid, methacrylic acid and fumaric acid, crosslinking monomers, such as divinylbenzene, as well as other compounds, such as, for example, 2-hydroxyethyl acrylate and 2-sulfoethyl methacrylate. ■ -,

Of the suitable monomers, styrene is particularly suitable and methyl methacrylate. Of those used in small quantities It has been found that the use of divinylbenzene as a crosslinking agent in the monomeric mixture significantly reduces monomers Percentage of liquid that will be encapsulated increases can. However, the use of divinylbenzene is limited to concentrations up to about 3.0% by weight based on the weight of the monomer. limited in order to avoid the formation of large amounts of coagulum during the polymerization. .. ■■■■

Liquids that are "encapsulated by the process according to the invention are essentially inert, i.e. they do not react with the monomer or with the polymer formed. Liquids "suitable for this purpose" are non-polymerizable and do not inhibit emulsion polymerization of the monomeric components, such liquids' are generally soluble in the monomeric phase and in the · obtained polymers insoluble.

Even if there are special liquids that are suitable, depending on the monomer phase used and the monomer obtained depend, the liquids given below are nonetheless generally useful in the systems of the invention.

Examples of such suitable liquids are the inert ones

009839/2254

SAD

Hydrocarbons and halogenated hydrocarbons, the aroma ti- '. see hydrocarbons and halogen-substituted aromatic carbons, the chlorofluorocarbons and the tetraalkylsilanes. Liquid polymers with the properties mentioned above are also suitable, for example low molecular weight polymers of α-olefins, conjugated diolefins, monovinyiidenaromatic compounds and other ethylenically unsaturated monomers such as vinyl chloride, acrylonitrile and acrylamide. According to the invention, oil solutions of various solids, such as, for example, the normally solid organic polymers, can also be encapsulated. Of the more volatile liquids, neohexane and neopentane are preferred. A preferred liquid polymer is a low molecular weight polybutadiene.

The coalescing auxiliaries that are used to carry out the inventive Process are used are polymers of sulfoesters α, ß-ethylenically unsaturated carboxylic acids. Polymers draw from the sulfoesters used according to the invention make them hydrophobic and hydrophilic Have groups in the polymer molecules. Suitable coalescing aids are the H> "! F! cpolymers and copolymers from one or more of the Suli'oestex * and copolymers of the sulfoesters and one or more ethylenically unsaturated monomers.

Coalescing aids, d :: ..; particularly suitable for carrying out the invention -. 'iäEse "Yfci-i'nlircns β in rl, siuä copolymers of a sulfocter and one or more ethylenically unsaturated mono ::; -.;: cen, el ... · ■■■ with it Preferred copolyno.rö, which "It particularly effective coalescing auxiliaries wiriroiii w: iner; i ^^ entraTioifei) to yulfoestermonomeren of wenigstu: κ-: Vo uev / i.-iiub- ^, invoked aiii "cira; copolymers a.α 'Other Oopo i.ypiOr- ;, ^which:;.' Lü värla- une Κ - '^ λλλ ; .-: ^ lorhilfs]: ilLtel die-

0GS839 / 2254

nen, included-usually. Sulfoester monomers in concentrations of 15% by weight or above.

Representative examples of suIfoesters which polymerize with the formation of suitable coalescing aids are the suIfoesters from. a-methylene carboxylic acids, the mono- .and Disulfoester of ethylenically unsaturated vicinal dicarboxylic acids and the sulfonate salts of the above-mentioned sulfo * Of the SuIfοestern preferred are those of methylene carboxylic acids, especially 2-Sulfoäthylmethacrylat.

* Ethylenically unsaturated monomers with the SuIfDesters Can be copolymerized are, for example, the monovinyliaenaromatic compounds, the ethylenically unsaturated carboxylic acids and derivatives thereof, unsaturated AlKoho! Esters, unsaturated ketones, unsaturated ethers as well other compounds containing one or more ethylenic linkages which are capable of doing so; one To enter into addition polymerization. The monomers which are characterized in that homopolymers thereof in water are insoluble are preferred, the alkyl acrylates are particularly preferred. 3? For those who enjoy invention Purposes, the term "Hkylaicirylat" includes the alkyl! Esters', \ of acrylic acid, methacrylic acid and other α-substituted: acrylic acids. Such alkyl acrylates are also characterized characterized in that they have alkyl moieties of 1 - 12 carbon atoms own.

Preferred coalescing aids are the copolymers of preferred ethylenically unsaturated monomers and the suIfoester of α-methylenoarboxylic acids, for example copolymers from n-butyl aylate and 2-sulfoethyl methacrylate,]

BATH ORIGINAL

iUUOü / L

Copolymers of styrene and 2-sulfoethyl methacrylate and copolymers made of acrylonitrile and 2-sulfoethyl methacrylate. Particularly "preferred coalescing aids are the copolymers from the alkyl acrylates with alkyl proportions of 1-12 carbon atoms and the suIfoes of cc-methylenecarboxylic acids and in particular a copolymer of 70% by weight n-butyl acrylate and 30% by weight 5 & 2 sulfoethyl methacrylate. Stabilizing Emulsifiers which can be used for the purposes according to the invention are the water-soluble anionic and nonionic surfactants, being anionic surfactants Agents or mixtures of anionic and nonionic surfactants are preferred. The selection "of the emulsifying agents depends on the emulsion system, the desired particle size and the like. In systems, where a particle size between about 4 and 5 microns is sought, sodium dodecylbenzenesulfonate is preferred .

In some cases it is convenient to use a small amount, i. less than about 1.0% by weight on polymer solids, of an electrolyte to the polymerization mixture in order to minimize the formation of a coagulum and to increase the degree of positive encapsulation. However, the use of an electrolyte is not a criterion of the present. Invention. Examples of electrolytes, which can be used are the alkali and ammonium salts, for example sodium sulfate, potassium bisulfate, sodium nitrate and ammonium sulfate.

The concentration of the emulsifier is important when performing of the inventive method is critical in that when ! In the absence of an emulsifying agent, the polymer completely coagulates, whereby in the presence of an excess of an Eraul-

009839/2254

COPV

the desired partial coalescence does not occur is influenced by the copolymer from the sulfoester. According to a preferred embodiment, the con fluctuates; concentration of the emulsifier from about T to about 3% by weight, based on the organic polymer.

The concentration of the polymer from the sulfoester is similarly critical since no encapsulation is observed in its absence, and very little encapsulation and a significant amount of coagulum are observed if used in excess. . Different concentrations of the polymer of the SuIfo ester within a working range of 0.2-2.0 weight / weight, based on the organic polymer, influence the size of the microspheres obtained. Big amount of,. . For example, about 2% by weight of the polymer of the sulfoester generally have the effect of decreasing the size of the microspheres, and usually to an average diameter of 0.5-3 Preferred concentrations of the polymer from the sulfoester are between 0.25 weight / weight and T weight, in particular for the production of microspheres with an average diameter of 1-5%. . " _:

• If the inventive method in the presence of an electrolyte is additionally based on an emulsifying agent and a.; Copolymers au "performed a sulfo, it is zwecknäßsig ,, don electrolyte in Koniientrationen of 0.20 to 0.50 .Gewichte- ^ Gev / ichts- ^ _f based on .the resulting organic polymers einsuaetzen".

For piercing microspheres with liquid centers using the method according to the invention, it is.

009839/2254

IAD ORIGINAL

required to use such concentrations of the liquid to be encapsulated, which are below 50 volume- ^, "based on the oil phase of liquid and monomers !, lie, wobe.i the best results at concentrations of 15-20 volume- ^ be achieved.

Furthermore, the ratio of the volume of the oil phase to the volume of the aqueous phase has a decisive effect on the amount of liquid that is encapsulated in the microspheres. For example, at 27 volumes of neopentane, based on the oil phase, the greatest degree of encapsulation is observed in a system which has a total oil concentration of 44 volumes, based on the entire aqueous and the entire oil phase. In this system, an increase in the total oil phase to a value of more than 44 volume? » reduced encapsulation and increased coagulum formation. In another example, the highest degree of encapsulation in a system is observed at 27-40 volume - / ^ ileohexane, which has an overall oil phase of 55 volume- ^, based on the entire aqueous and the entire oil phase. The operating limits of the entire oil phase vary slightly with the encapsulated liquid and probably ten with the respective verwende- \ monomers. As a general rule, however, one can state that G total oil phase concentrations of 35 volume to 55 volume T, based on the total oil phase and the total aqueous phase, permit a process to be carried out, with concentrations of 44-55 volume being preferred v / earth.

The inventive method is carried out in such a way that zuerst- an oil phase is dispersed, the infrequent, least contains a fmulsionspolymerisierbares Monoineres in a wäss- · membered phase, a stabilizing emulsifier and a suitable auxiliary coalescing enthält..Die dispersion is usually in the way create that the two phases

0D3339 / 22SA

ÖAD ORIGINAL

20Q8572 - Π -

subjected to severe shear mixing conditions, for example in a homogenization facility. In the preparation of microspheres will not encapsulate the liquid unless dispersion of the phases is achieved.

The dispersion obtained from. The oil phase and the aqueous phase are fed to a suitable reaction vessel and subjected to emulsion polymerisation conditions, ie initiation by a catalyst which provides free radicals, such as, for example, potassium persulphate, at a temperature of 60-10O ⁰ C, the dispersion being stirred during the polymerisation period Emulsion polymerization is usually carried out in the presence of from 0.01 to 3% by weight, based on the weight of the monomer, of the free radical generating catalyst. 2'-azobisisobutyronitrile.

The following examples illustrate the invention. Unless otherwise stated, all parts and percentages relate. on weight.

Example 1 . ■ "

A 1.25 g portion of 2-hydroxyethyl acrylate and 98.75 g of methyl methacrylate are mixed in 25 g of hexane. The ^r se oil blend • is mit''einer aqueous solution of 125 g of deionized | Viassers mixed, 0.5 g of sodium sulfate, 0.5 g of potassium persulfate, 1.0 g Natfiumdodecylbenzolsulfonat and 1.0 g of a copolymer of "50 £ 2-Sulföäthylmethacrylat and 70 i" butyl acrylate.

• The mixture is sent through a hand-held homogenizer. An intimate view of the oil phase is achieved aqueous medium achieved. The intimate mixture is in a Bottle poured and by turning the bottle (end-over-end)

0093 39/2254

SAD ORIQlNAL ^C0PY

Rait about 4.5 U pm during a period of 16 hours in a water bath "moves at a temperature of 70 ⁰ C. After completion of the 16 hours. period of the lot are 94 ° i obtained in addition to a small Henge a coagulum. Under An optical microscope shows that the reaction product consists of microspheres which have a uniform size of approximately 1μ, with only a few particles having a size of up to 5μ , poured on a flat surface and at room temperature overnight to dry composure By heating of this film in a:. Yakuunofen at 150 ⁰ C and Ilesaung of weight loss it is found that the dry film contains 12 ^ neohexane the Plüssigkeitseinschluss in the microspheres.. is further confirmed by observing Brown's motion of a bubble on the surface of the encapsulated liquid igt.

Examples 2-12

Following the procedure described in Example 1, examples are carried out in order to determine the effect of the concentration varying amounts of sodium sulfate, sodium dodecylbenaene sulfate and the copolymer of 2-sulfoethyl methacrylate and Determine butyl acrylate. The results obtained when performing of these examples are in addition to the results of Example 1 (for comparative purposes) in FIG summarized in the following table I:

009839/2254

Table I.

At- sodium dodecyl ^ sodium 30/70 ft coaguluin microsphere- ft solids encapsulation game benzene sulphonate, sulphate, SSM / BA, (2) small size. (air-dry efficiency, Kr. 'g- ■ g. - ■ * (A) ■■■ M (3) net) ( 4) ft (5)

1, 1.0, 0.50, 0.5, 2 1-5. 49.6 ^! 89.0

2 -1.0 '- 0.5 75 ■ x 1-6; 35.1, .26.5 ... 3, 1.0, 0.25 0.5 2 1-3 _. 49.1 '. , 79.5

4, 2.0, 0.25,. 0.5 1 1-4, 50.2 84.5 ''

ο 5 "3.0 - - 0.5, 50, '1-3.. 44.6 '38, 5

S ^β "'3.0 0.25 x 0.5 20 1-4. 46.8 49.5,

S 7 1.0 ■ 0.25 1.0 1 1-3 48.3: 73.0 _>

^ S "... '. ■ 2.0 0.25 1.0 1 1-4 48.6". 71.0 "^

9 '3 _? 0 0.25 1.0 2 1-5 '47.3 5Ο, .5

10 1.0 0.25 1.5 .. 1 '. 1-3 49.1, 76.5

^ 11 2.0 0.25 1.5 '1 1-3 47.8 58.0

12, '3.0 0.25 1.5 1.> -3 ■ 47.2' 48.5

(1) Copolymer of 30 ? Ο 2-sulfoethyl methacrylate and 70 ft n-butyl acrylate.

(Z) G weight - based on the monomer of a fully coagulated polymer.

■ (3) Average diameter of the microspheres, determined by means of a

optical microscope, '' ■ '.'<: Ni

_m (4.) G-ev / ichts- ^ polymer solids. - CD

D (5) Weight ^ encapsulated neohexane based on the amount of heohexane in the C3O

O polymerization batch. cn

-O

Examples 13-17

There are different polymerization mixtures prepared and polymerized according to the procedure described in Example 1, except that various emulsifier used instead of ITatriumdodecylbenzolsulfonat v / ground, wherein the polymerization at 9O ^Ü O is carried out for a period of 4 hours. The results of these examples are summarized in Table II.

009839/2254

Example emulsifier;
Mr. (1) Sodium dodecylbenzene
sulfonate % Eoagulum
(2) Tabel II Encapsulation
efficiency, i <>
(5) 13th ü Sodium dodecyldiphenyl
oxide disulfonate 1 Milaroküg
grpsse X oak- $ solids
3) (air-dried
net) (4) 84.5 14th Dihexy! Ester of sodium
sulf obernstein acid 7th 1-3 49.7 91.0 15th Dioethyl ester of urodium
sulfosuccinic acid 20th 2-3 48.1 "49.5 ο
O 16 Alkylbenzenesodium
sulfonate ■ 20th 1-2 42.4 25.5 CD
CO
CO 17th 8th 1-2 43.2 91.0 \
I. 9/22 (1) Emulsifier at a concentration of 1-3 49.5 obtained polymers. <n
* - 1 certainly oh. ts- ^, based on that

(2) to (5) see table

CD CD CX3 CJl

Examples 18-26

An oil phase composed of 50 parts of styrene, 1.0 part of 2-hydroxyethyl acrylate and 50 parts of a low molecular weight liquid polybutadiene and an aqueous phase composed of 0.5 part of potassium persulfate, 0.5 part of sodium sulfate, 1.0 part of a copolymer !! from 30 io 2-sulfoethyl methacrylate and 70 # butyl acrylate and 100 parts of deionized water are intimately mixed using a hand homogenizer. The intimate mixture is poured into a bottle and then agitated by turning the bottle (end-over-end) at about 4 rpm for a period of 16 hours in a water bath at 70 ° C. The particles formed occupy two separate phases. A microscopic examination shows that a shell made of polystyrene surrounds the low molecular weight polybutadiene. Similar batches are made, with the exception that they contain various coalescing aids, and are polymerized according to the method outlined above. The results of these examples are summarized in Table III.

008 * 38/2254

example 18th Coalescing No. 19th tools 20th 30/70 SEM / BA * 21st 50/50 SEM / BA * 22nd 20/80 SEM / BA * 23 70/30 SEM / BA * 24 50/50 SEM / STY * to 25th 70/30 SEM / STY * 26th 70/30 SEM / VCN * a » 50/50 SEM / FROM * >> 100 SEM *

Tabel 96.5 III Maximum size of the $> Extraction io sales 94.7 Microspheres (3) (2) 97.1 20th 97.9 58.8 30th 97.6 62.4 35 98.1 39.9 20th 29.9 36.4 5 42.0 43.2 3 29.4 41.7 4th 17.1 ■■. '.'; ' ■ 4; ', ■ 2.4 ·. ■ '8': 27.4

OT

* Is the numerical ratio the ratio of the sulfoester to the ethylenically unsaturated Monomers, then SEM is 2-sulfoethyl methacrylate, STY 'styrene, VON acrylonitrile and BA Butyl acrylate.

(1) Weight - »^ of the polymer microspheres," based on the oil phase.

(2) Weight of the polymer formed, based on the monomer weight *:

(3) 3> diameter of the largest particles in jx _t determined by means of an optical microscope.

- 13 -

As can be seen from the table above, copolymers' " the most effective coalescing aids from sulfoester and butyl acrylate, especially the coalescing aids used to carry out Examples 13-20.

Examples 27-54

An oil phase made up of 20 parts of a low molecular weight liquid Polybutadiene, 80 parts of styrene and 1.00 part of 2-hydroxyethyl acrylate ' and an aqueous phase according to Example 18 become intimate using a Hajid homogenizer mixed. The intimate mixture is poured into a bottle and polymerized according to the procedure described in Example 18 ·. The results are summarized in Table IV. For comparison purposes, some polymerization approaches, which have the same amount of different coalescing aids which are used according to Examples 19-26, polymerized in a similar way »The results, these examples are summarized in Table IV.

009333/2214

Coalescing . # Extraction 97.6 Tabel F / at tools (D 98.0 $ Sales Maximum size of the game
Mr. 30/70 SEM / BA * 98.6 (2) Microspheres (3) 27 50/50 SEM / BA * 92.0 100.0 25 · 28 20/80 SEM / BA * 96.9 96.1 25th 29 7O / 3Q SEM / BA * '87, 2 97.6 20th O 30 50/50 SEM / STY * • 93.0 94.0 20th 231 70/30 SEM / STT * 90.5 84.5 12th »32 70/30 SEM / FROM * 84.1 10 «33 100 SEM * 84.7 8th * »34 91.6 8th

* See table III. . ,,

(1) to (3) compare Table III.

OO QO cn

Also the copolymers made from the sulfoester and from n ~ butyl acrylate are the best Iioalescence tools.

Example 35

An oil phase containing 10 parts of acrylonitrile, 45 parts of styrene and 45 parts of a liquid polybutadiene, and the aqueous phase of Example 18, are mixed and polymerized according to the procedure described in Example 18. A yield of 97 % and a conversion of 96 # are obtained. The size of the microspheres varies from less than 1 to 2Q u.

Example 36 - "

The ingredients listed below are put into a 340 g bottle given:

Concentration (g )

Styrene 50.0

Deionized water. 150.0

Sodium sulfate "0.5

Potassium persulfate 0.5

Sodium dodecylbenzenesulfonate 3.0

Oopolymeres of 30% 2-Sulfoäthylmethacrylat and 70 fo n-butyl acrylate "0.5

The hash and its contents are cooled in ice, whereupon 50 g of a liquid butadiene are sugesetst. The Hasche is closed and scliüxtelt ge in a maintained at a temperature of 7O ⁰ C VJasserbad over a period of 4 hours, ~ ,. woravs.f opened the bottle and the contents filtered vrir-rcL, the contents consist of 20 g of a coagulum and 235 g

00882 S / 2254

COPY BAD ORIQÜMAL

an aqueous "dispersion having a polymer solids content of .3S -, - 7 ^. The particles of the dispersion are examined under an optical microscope. Most! particles are about 6Ms in diameter approximately 18µ, with" - some particles having 2 u .. The aqueous' ■ dispersion can be gehalt'konzentrieren in a simple manner by evaporation .on a high Peststoff - a diameter of only 1:. '""" .. · ■''- ■ - -

0 0 9 8 3 3/2254

Claims (9)

1. Method of making an aqueous dispersion normally solid organic polymer particles by dispersing an oil phase of at least one emulsion polymer sizable monomers in an aqueous phase, which have a stabilizing effect Contains emulsifier, whereupon the dispersion emulsion polymerization is subjected, characterized in that 0.2-2% by weight, based on the obtained organic polymers, a polymer from a sulfoester of an α, β-ethylenically unsaturated carboxylic acid of the aqueous Phase can be added. 2. The method according to claim 1, characterized in that 0.5-4 weight yes, based on the organic polymer obtained, of the stabilizing. Emulsifiers are used. 3. The method according to claim 1, characterized in that the SuliCoesterpolymer used a copolymer of at least 20% by weight of the sulfate and one ethylenically unsaturated Monomer which is capable of becoming an essentially water-insoluble homopolymer to be polymerized. 4. The method according to claim 3, characterized in that the ethylenically unsaturated monomer used is an alkyl acrylate with an alkyl portion of 1-12 carbon atoms is. ' 5. The method according to claim 4> characterized in that 'the copolymer used is an Oopolymer of 2-Snlfoäthylmethacrylat and is butyl acrylate. - 003833/2254 6. The method according to any one of claims 1, - 5, characterized in that the emulsifier used from Dodecy.lbenzolnatriumsulfonat "consists. 7. The method according to any one of claims 1-6, characterized in that the emulsionspolymerisier'bare monomers used; made of methyl methacrylate, styrene or a mixture of. Is made up of styrene and butadiene. 8. The method according to any one of claims 1 · - 7, "characterized in that the -used aqueous medium 0.25 - TVO weight ^, "based on the polymer,;" "an inorganic electrolyte contains; "/ \ ~ ·. ·. ' 9. The method according to any one of claims 1 - 8, characterized in that that microspheres with liquid centers and seamless stiff Λ '/ walls made of a normally solid organic Polymers are produced in such a way: 'that a Liquid insoluble in water and non-polymerizable. which is soluble in the monoiling and is insoluble in the organic polymer, with the emulsion polymerizable / mono-. meren mixed -is. : 10 "'Procedure according to. Claim 9, characterized in that the .ss the non-polymerizable liquid used is a low-boiling one aliphat'is rather hydrocarbon to ff is t, 11 »Method according to" claim "-9; characterized in that the used / ended non-polymerizable liquid - a low molecular weight Polybutadiene is * QO983972 254 ΟΟΡΎ