DE2038738A1 - Process for the production of rubber-reinforced synthetic resins - Google Patents

Description

Dlpl.-Ing. EIDENEIER Dipl.-Chem. Dr. RUFF Dipl.-Ing. J. BEIER

7 STUTTGART 1 Neckarstrasse 50 Telephone 22 70 51

August 4, 1970 B / Eb

Applicant Inj Cities Service Company. 60 Wall Street, New York «H.Y, / USA

A 12 912

Method of manufacture

of kautachukvarst & rkte synthetic resins

The invention relates to the polymerization of a Made from vinyl aromatic and vinyl cyanide monomers in the presence of a butadiene polymer latex to produce a resinous product in which some of the monomers The invention relates in particular to a method of manufacture

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a synthetic one. Resin with. low gloss and high Impact resistance by polymerizing a mixture of Styrene and acrylonitrile monomers in the presence of a latex made of butadiene-styvol-oopolymer with low gel content under Use of an inorganic peroxide initiator and a mercaptan polymerization regulator.

The polymerization of a vinyl aromatic monomer such as styrene, and mixtures of such Hat "nit rials a vinyl cyanide monomer such as acrylonitrile _t inwensenheit in an aqueous Kauieion from an ethylenically unsaturated rubber, sb.B. a butadiene polymer latex «is generally known

Such polymerization reactions are often carried out by a free Radically set in motion and where sufficient water and surfactant now emulsify the Monomers used lead, at least in part, to grafting of the monomers onto the rubber to produce synthetic resins with better physical properties and chemical properties. A large selection of such synthetic harshes and suitable synthesis processes, Lautschuk-Ieticee, monomer mixtures and mixing ratios of co-actants of a conventional type are described, for example, in IIS patents 2,994,963; 3,010,936; 3 073 798 | 3 0? 4 906 | 3 130 177 $ 3 13 * 746f 3 233 275 and 3,336,417. Typical for these conventional, rubber-reinforced resins is that they have impact resistance and surface properties have "somewhere between the high impact resistance and the low surface gloss of the rubber component and the low impact resistance and high surface gloss of a vinyl aromatic -

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Vinyl cyanide copolymers lie · The physical properties of the resins produced by these known processes depend mainly on the proportions of rubber and monomers that are used in the polymerization · Kit Successfully used these known processes ζ · Β · for the production of resins with a medium gloss and an Izod «impact strength (ASÜM test D 256-470?) of 0.325 to 0 * 4-58 mkg / cm notch (6 to 9 foot pounds per inch of notch) or more, in which rubber contents of approx. 30 to 50 weight percent was used. While the reduction in the rubber content leads to an improvement in the surface gloss (generally associated with a significant decrease in the impact resistance), further increases in the rubber content rarely have more than a minor effect on the reduction in gloss and can significantly reduce the hardness and rigidity of the hardened product Reduce. In order to obtain a high impact strength product having a rough treatment resistant, matte surface which is desirable for heavy use such as baggage wrapping, it has heretofore been necessary to either mechanically matte the surface of an extruded resin sheet or to pre-fabricate the resin the extrusion with a leveling agent, such as diatomaceous earth,

to mix. Because the introduction of a leveling agent tends to reduce the impact resistance of the resin, this technique requires the use of materials with extremely high rubber content, which are often relatively soft and have an undesirably high degree of flexibility.

The object of the invention is to provide a method for production of rubber-reinforced synthetic resins with high impact resistance and low surface gloss, which are also resistant to solvents. A special feature of the invention is to provide a method for catalytic

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Polymerization of a mixture of styrene and acrylonitrile in the presence of an ethylenically unsaturated butadiene polymer rubber latex to create medium particle size for the production of a resinous product «from plates or foils with an unusually high impact resistance and resistance to rough handling "Produce a durable matt surface through extrusion permit. Further objects, advantages and features of the invention » result from the following description «

It has now been found that the tasks set by because the procedure according to the invention can be solved. Generally the invention lies in the application of a fortunate combination of. Materials and conditions the polymerization of a mixture of vinyl aromatic and vinyl cyanide monomers which are about 18 to 57 moles Percent vinyl cyanide "contains monomers" in a reaction zone from an aqueous emulsion of about 0.1 to 1.25 parts by weight of an ethylenically unsaturated rubber per part of monomer mixture »a free radical forming initiator "and a mercaptan polymerization ·· Regulator · 'The method according to the invention is thereby marked that nan

a) all initiator which forms free radicals uses an inorganic peroxide,

b) alfi rubber is a butadiene polymer that contains up to approx. 50 percent by weight of styrene combined with it and an average particle size between

approx _t 0.2 and 0.6 micron, a gel content of less than approx. 85 % and a swelling index in benzene of more than approx. 15 is used,

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- * - 203S73S

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c) uses the mercaptan polymerization regulator in an amount of less than approx. 0 _# 050 equivalent Herkaptan per kg of rubber and monomers «

d) an initial amount of approx. 20 to 80 % of the monomers at a polymerization temperature between approx. # 5 and 60 ° C in the presence of an initial amount of the regulator of at least approx then introducing a supplementary amount of bogus la tor into the raaktioiissone which is sufficient to increase the total amount of the regulator introduced into the reaction zone by at least 25 % and to maintain a polymerization temperature between approx. 45 and 60 ° C at least about 90 % of the monomers have reacted.

The resin "" produced by the goal of the invention have an unexpectedly high impact resistance and are suitable for the extrusion to films or plates that have a counter rough treatment have resistant surface * ^ ·

Bae improved procedures according to the invention UBi "et'Ii öi <ι carry out by, dac Zautectak-Let" «* the 'In'. ή τ the inorganic P «roxi4 * -Katalyautor and tiiieii ¹ J, ι '» j ι Mercaptan-Poljmerieatione-legulatora misriit nnä "! risk held · SeaktioMmieolmnt; on co, ^ i ^Γ ·» Ι ί · warmed by a Ufflittraog the Mojiouwiro., J Inosfii '.fi dta ca · 20 % bie 80 % dar HönomejPd uO | $ ^ A "Ki ΐ« eiii'lj', BaaJctiosealachung zueätslichar He rc apt on «ßtigulatov - ^{1 r} \\ ι \ τ

10 5S0Ö / 2109 _0RIQINAL

A 12 91g

and maintain the polymerization temperature until at least Approx. 90 percent by weight of the total monomers have been converted. In a preferred AiMfÜlmmgaform of the invention Procedure carried out ff by adding the rubber latex for approx.

"-Mischt 20% to 80% and preferably about 40% to 60% of the monomers to the inorganic Ptroadd-Hatalyeator and part of the MercaptanwPolymerleation.e-Hegiilatore and the reaction mixture kept in motion in the manner just mentioned temperature heated to a reaction _f The initially added monomers su cause a period of about 10 to 110 minutes and preferably about 60 minutes during which at least about d ⁽ iCall'te -Wr start released monomers uagesetsst Hz ^ ₁ « tr · ¹ -η aar H? üktionBffliächUBg sueätz-Ii die a Mercaptan iisnl Ii .3?. 'af; lldie! ^M momero> .uge _t ititen and the PolyiBiirlaattotiet t «v _r * * nt» t * ιβι' οΐιήΐΐβίΐί olu wa igatens ca « ^ Q G ^ Wichtffpi'iu u ('*' π ι« \: v ^r -} . *

der («saunten ftoii 11 'i""i ^r 1 a * n > ■ J ιϊί«

Gege1 ^h win ¹¹ OnJJC ι *. "' ^J μ

with «Inii« 'LI'"I fii ti ca- ί '2 L t ι ,,'.!

1 ill * 1 1 * I IK

! ' I ilFi / ill I h '"

.. ^{Hs; i; e} ': ψ ^ -% rl: ί ■ *;..

cb ti ¹ J ₁ (To ζ ent KlI " 1 ^ h to- i »? Üch t «from ι about t lie '. ■>!.! ■:,:, ::: IjIi ₁ "'' ,, I || H ¹¹ Jl ¹ I. t; ΙΙίίΙ 5 _h ; «,,. ,
. ■ <: '''i Li ■:.; »:: i: ■ '.; ■ ·.: ·,.,;:; icj C];:,;!: Jt; .;

,, JIIl- ;,. "" I - '■:. ■

A 12 912

can then be done in a conventional manner, e.g. by the reaction mixture is poured into an aqueous electrolyte solution, to coagulate the resin product «the mixture is heated to agglomerate the coagulate su, the solid resin by nitration wins, and then heats it to dryness *

The butadiene polymer rubber useful in practicing the invention is a butadiene homopolymer or a butadiene-styrene copolymer having less than 50 percent by weight bonded styrene, preferably less than 33 percent by weight bonded styrene, and ideally about 23 to 30 percent by weight bonded styrene · The butadiene polymer should have a gel content of less than about 85 % and preferably less than about 0 % and a swelling index in benzene of more than about 15 and preferably more than about 40. · A butadiene polymer with a gel content of more than about 85 weight results in a resin with high gloss and low Izod impact strength

It is important to the invention that a latex of such a rubber is used in which the size distribution of the emulsified particles is in a narrow range, as is generally found in latices which agglomerated at low temperature by known methods to an average particle size from about 0.2 to 0.6 microns. The preferred ZJatex particle size range is between about 0.24 and 0.56 microns.

The latices of such rubbers are preferably used in an amount comprised between about 0.1 and 1.25 and preferably between about 0.25 and. 0.36 parts by weight Rubber makes up per part of mixed vinyl aromatic and vinyl cyanide monomers

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The mixture of vinyl aromatic monomers, e.g. styrene halogenated styrene or ^ -Methylstyrene, and the vinyl cyanide monomer, e.g. acrylonitrile or methacrylonitrile »may contain vinyl cyanide components, which lies between a fetch percentage as low as 18 and as high as 57. However, it is generally preferred to adjust the vinyl cyanide content in size to keep from about 40 to 46 percent of the monomer mixture.

The use of an inorganic peroxide initiator is essential for satisfactory performance of the method according to the invention, and excellent results are obtained through the use of the alkali metal «- or Ammonitimparflulfate obtained. In general is necessary above! the »® preferred initiators in one Use quantity © that is at least approx * 0.004 and preferably at least approx. 0.007 peroxide equivalents per kg Rubber 'unil. Mixed monomer © corresponds to Ea there no ». sharp critical® upper limit * Bs, however, is rare Advantageous to exceed 0.075 equivalents of peroxide per kg of rubber and mixed monomers »and superior Results are generally achieved when using in the range between about 0.020 and 0.059 equivalents of peroxide per kg of rubber and mixed monomers works.

Although any mercaptan can be used as a length regulator in the method according to the invention, the use of an ilkylmeroaptana and in particular a higher tertiary llkjimercaptana is strongly preferred. These preferred materials include the tertiary Q ^ ¹ "* ^S 14 ** ^{m <s>} ^ g

■ Elevations from it · The contraction of such mercaptans 'in the Heaktlonsndech ^ u is an essential feature of the

_0RieiNÄL

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Invention · It is essential that the reaction mixture in the aggregate always contains less than approx. 0.030 equivalents of mercaptan per kg of rubber, monomers and resin, since it has been found that the impact strength of the product decreases significantly if this proportion is exceeded. It is possible to work with a meroaptan content as low as 0.002 equivalents per kg of rubber, monomers and resin, but the resin obtained can be uncomfortably stiff. 0.009 to about 0.019 equivalents per kg of rubber, monomers and resin are used. The concentration of the mercaptan in the reaction mixture during the initial polymerization of the monomers is from about 0.0035 to about 0.028, and preferably from about 0.009 to about 0.026 equivalents per kg of rubber, monomers and resin. When the first approx. 20 to 80 % of the monomers have reacted, the amount of mercaptan in the reaction mixture is increased by at least approx. 25 and preferably approx. 65 to 150 % ; but it 1st important that the mercaptan Konzentratlon Indians Beaktionsmischung less than about x 0.030, preferably about 0.004 to about 0.027 Iquivalente per kg rubber, monomer and ^s is arz · Sort where only bargain added one of the monomers of Beaktionsmischung at the beginning the additional mercaptan can be added to the reaction mixture separately from the remaining monomers, but it is convenient to add them together

The level of the water content of the reaction mixture according to the invention is of no importance, and satisfactory results are achieved in systems which contain only about 50% by weight of water, up to those which contain 90% and more water. In general, however, a system is preferably used which contains between approx. 60 and weight percent water,

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In order to obtain resin products with the proper physical properties described above, it is essential that the reaction temperature is kept in the range between approx. 45 and 60 ° C up to at least approx. 90 weight ep ro tent and preferably at least approx. 9? Percentage by weight of the monomer mixture have been converted · Maintaining a reaction temperature between approx. 52 and 58 ° C until the monomer conversion is essentially complete _f represents a particularly preferred embodiment of the invention · It is extremely desirable to keep the reaction temperature as nearly constant as possible, with Excellent results can be obtained when the fenpera door fluctuation is limited to a range of approx. 2 ° C.

The polymerization process according to the invention is, like the conventional processes, preferably in the presence of a surfactant performed »While getting any cationic or non-ionic surfactant Can use smock, it is generally preferred to use readily available anionic surfactants To use smocks, for example the alkali metal salts higher alkylbenzenesulfonic acids or resin soaps or Higher Fatty Acids · These preferred surfactants include, for example, ordinary ones Materials like sodium stearate "potassium oleate and dl" mixed soap that can be made by saponifying tall oil with Caustic soda or Itzkali is given. It is generally advantageous to use between about 0.3 and 3% by weight, based on the total rubber and the monomer, but you can use more or less "for" it is preferable to use between approx. 1.3 and 2.5 percent by weight »based on the camouflaged rubber and the monomer.

Λ ö ΟΛΟ t * · ') f. Β κ-' if β UO / A 'U9

A 12 912

Kan can often use larger amounts up to 5 percent by weight or use more · Me · is However is general is not desirable because such high levels of surfactant often plasticize the resin product.

Further features of the invention and the numerous advantages associated with the goal of the invention, can be seen from the following examples

example 1

A styrene-butadiene-rubber emulsion containing 26 rubber solids was placed in a reactor. The composition of the emulsified copolymer was 50 percent by weight styrene and 70 percent by weight butadiene. The mean particle size was 0.25 microns. Sas copolymer had a swelling index of 132 and contained 2 % gel. The mercaptan polymerization begulator used was a mixed tertiary mercaptan (MTM) of 60 % C <| 2 ~ t 20 % C ^ ₄ and 20 % C ^ tertiary mercaptans “A solution of 55t5 parts of styrene, 10.5 parts of acrylonitrile and 0.3 part of the mixed tertiary mercaptan (MTM) _9, that is 0.0137 equivalents of mercaptan per kg of rubber and monomers, was prepared. Half of this solution and O ₉ 3 parts of potassium persulfate was added to the emulsion "The reactor was sealed and stirred for one hour at 55 ° 0th Stirring was then continued at 55 ° C while the remainder of the solution of styrene, acrylonitrile and MTM was added at a constant addition rate over a period of 2 hours. After all monomers were added

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the beating continued at 55 ° O for a further 2 hours, after which the honey conversion "was about 95%." An antioxidant was then added to the reaction mixture and the emulsion was coagulated by adding buckets of calcium chloride solution. The product was dried and molded by injection molding · The

Oardner-Glai χ jbu 50 and the Issöd impact strength of 0.815

nkg / ca notch (15 »0 ft» 2bß -. / in · notch) determined · These results show. _Sl that through Irbeiteii under the conditions

according to the invention a ΐΒδ- * Κβ: «ΐ with very high slip resistance and geirf ngeo Oberfläoli «n.glaniJ can be produced *

A sä 'Cf ,,; ,, ■ "■: · ■; ■■. * B \ ι tadi « η «0οj * o i-yaer ^ attit _} umt 3 0% g e'oundenea

Styrene is free; _t an ai11; 1 ere f e ilchengiroBii of O ¹ ₁ 25 microns

and a Qjiiel'ü! ttiigeiiidex ν on i? 4 and contained? 0 % gel,

WiJ ": ■!, § by adding water to a content of 65 parts

Μββκ, Γ tuad 7 parts of copolymer discontinued «The Miachung was in a. «! Autoclave given a stainless steel, »Bern Latex

m O ₁ C were Eaiiumpersulfat parts * · 0.5 Telj β S ¹ ₁ 3.5 CyToI

Parts Acxylx; ;: ■ ·: il and 0.09 feile gs & ißchtee tertiary M »r-

captaiit dae en ^^ a concentration of 0 _f 0196 equivalents of mercaptan, per kg of hoo eggs and rubber »is'U given.

The stirred Ηβΐ ..itior.affiiachux'ig was heated to 55 ° C and

during 5 ~ atü'adigen F,? action on this Teisperatur held Hach IBIA f ¹ U of the first hour, over a period of 2 Stunder at kcnetanter Sugabegeechwindigkeit another 10.5 feile .btyrol, 3 $ 5 parts of acrylonitrile and 0.09 Parts of MM added * " ^! 3ie SodkonEewtration at WfM in the

A 12 912

Reaction amisclumg after this subsequent addition of additional conomers and kercaptan was 0.0235 equivalents of kercaptan per kg of monomer, rubber and resin · After completion of the addition, stirring was continued at 55 ° 0 for a further 2 hours · 1.2 ropes of phenolic antioxidant were then added « and the latex was coagulated by adding a calcium chloride solution. The coagulated polymer was separated from the aqueous phase and dried. The dried ABS resin contained 20 percent by weight rubber. Bs was introduced into a screw injection molding machine under the following conditions and molded into a flat surface using a chrome plated mold!

frommel-iPemperaturei 227 ° 0 (440 ° I) yona-temperaturet 32 ° G (90 ° *)

Injection pressure! 120 x 123.5 kg / cm ²

(1,700 - 1,750. P »e.i.)

UpK the snail! 104 cycle lasts 30 seconds

The molded article had a Gardner Glans of 32 and an Izod Impact Strength of O _t 73 nkg / ea notch (13.4 ft.lbe./in· notch). This example shows how an ABS resin with high Impact resistance and matt surface can be produced by working under the conditions according to the invention.

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example

Example 2 is repeated at 50 ° C. using a 7 hour reaction time, ie 2 hours for the polymerization of the initially specified monomers _9, 2 hours for the addition of the remainder of the solution of bonomers and mercaptan and 5 hours for the rest Polymerization bia to • ABS resin produced in 95% usage conversion «Bae had a Qardner gloss of 15 and an Izod impact strength of 0.8 akg / em Serb (14.8 ft * lbs * / in · notch) · This in turn shows "how an ABS-larss with a high degree of SciIeςί m ^{+: i} " ^x it and low surface gloss is produced by the procedure according to the invention * "rdon liuan.

Venn Bei ». "> 11 Her * iniiirtn Ib. To j ι 01 τΑ ι * E <Igt ¹¹ Ih W ι hch Ii ^ cIiI ι ^ψ ,

ti ι I * i hifiji Lnit ΐΐαο received

j- niV (.fi) «Oiet. ^ i example

oi JiBS resin with ρ I I Jim Λ. Lk #

^ 1

Vi (!, B ) i ipit ί

ABS -Βίά ^{::; ϊ} ίί ν »Ι, ::. ■ '■';:,

GH ίΐϊΈ

(50

4a, is generated

.ce-1CIi; ♦, Dittoes

.!, 1. '. ,, Iort üiii der, · ¹ ::;:; ·; *!:,?:!:>. door ir. * a

912

Example 6

Example 2 is repeated, except that all of the styrene, Acrylonitrile and MH are added to the latex at the start of the reaction · The ABS resin produced has the following properties ι

Izod impact strength 0.158 mkg / cm height

(2.9 ft.lbs./in. Notch) m

Gardner-Glen «» 21

This example shows that the impact resistance of the obtained ABS resin is markedly deteriorated, if everything Mercaptan the styrene-butadiene-letex at the beginning of the Reaction is added.

Example 7

Example 2 was repeated, except that the styrene-butadiene copolymer rubber latex had a particle size of 0.2 microns, a swelling index of 5, a gel content of 99% and contained divinylbenzene »The manufactured ABS resin had the following properties;

Izod impact strength is 0.076 mkg / cm & srbe

(ΛΛ ft.lbs./inc. Notch)

Gardner-ulanz: 67

The above results show how the impact resistance is significant reduced and the gloss is increased if the properties and characteristics of the styrene-butadiene-CopolyDer-Kaut "

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schuklatex are outside the limits of the invention. In In this case the swelling index was below approx. 15 and the gel content above the upper limit of approx. 85%.

Example 8

Example 2 was repeated except that the styrene-butadiene copolymer rubber latex had a particle size of 0.06 microns and contained 0% gel. The ABS resin produced had the following properties:

Izod »Scuff resistance in 0.38 mkg / cm notch

(7.0 f.lbs./in «notch)

Gardner-Shines $ 0

Beast seigt example, as a Stjpjol-Batadien copolymer rubber latex having smaller particle size than the acceptable * as the minimum size of about 0.2 microns results in a greatly reduced impact strength.

Example 9

Example 2 was repeated, except that the styrene-bufcadiene copolymer chewing compound of 25 percent by weight styrene and V5 percent by weight acrylonitrile was suspended, had a particle size of 0.5 microns, a gel content of 30 % and a swelling index of 43. ABS resin made from Baa had a Gardner gloss, τοη 28 and an Izod impact strength of 0.75 mkg / cm Kerb® (13 * 8 ft.lbe »/ in. Notch). This example shows how durc! "Proceeding according to the invention ABS" Earze with high impact resistance and low gloss can be obtained.

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Claims (1)

A 12 912 Claims Process for the production of rubber-coated synthetic table resins by polymerizing a mixture of vinyl aromatic and vinyl cyanide monomers with about 18 to Mol per ε ent vinyl cyanide monomer in a reaction zone, which is an aqueous emulsion of about 0.1 to about 1 * 25 weight share of an ethylenically unsaturated rubber per rope Monomer mixture, an initiator which forms free bath scale or · Catalyst and a mercaptan Polymerisationsregu-Iator contains "characterized" that one a) an inorganic peroxide is used as all initiator which forms free radicals; b) as rubber, a butadiene polymer with up to approx. 50 ß weight percent bonded styrene and with an average article size between approx 0.2 and approx O ₉ 6 microns *, a gel content of less than approx 85 % and a swelling index In Benzene used by more than approx * 15 % t c) the Mercaptan- ^ Polymerlsatlons ragulator in one Amount of less than approx. 0.030 Kercaptan Iqui « valents per kg of rubber and monomers used d) "ine initial amount of about 20 to 80% monomers at a polymerization temperature between about 45 and 60 ° C in the presence of a regulator of at least about Anfangamenge O per kg Sautachujc and monomers uttsttst ₉ 0035 equivalents of mercaptan in the Beaktionssone and then an amount of error A 12 912 Regulator · introduces "sufficient" to increase the total amount of the regulator introduced in the reaction zone by at least 25 % "and maintains a polymerisation temperature between approx. 4-5 and approx. 60 ° C" to at least approx. 90 % the Monomer® are implemented 2. Process according to Claim 1, characterized in that the inorganic peroxide is an alkali metal persulfate or aaonium w-persulphate is used. 3 "Method according to claim 1 or 2, characterized thereby" that as a vinyl aromatic monomer styrene »halogen! he tea Styrene or dC-methylstyrene and as vinyl cyanide « Monomer acrylonitrile or methacrylonitrile can be used 4. Process according to claim 2 or 3 »characterized» that the ferrous sulfate is used in an amount between approx. »0« 004 and approx. 0.075 equivalents per kg of rubber and monomers * 5 · Method according to one of the preceding claims "da" by knowing that it is a tertiary regulator Alkyl mercaptan bewealtt wi 6 · Process according to a d-aie the preceding claims "characterized by""&& a Hieelurag aue vlmylaro" matlsohen and vinyl cyanide monomers, which contain between approx. 40 and approx. 4 € WoI Pros®at Tiayicjenid anomer, * '■ * f * ή Λ e / ^<! '1 Λ A ν ■ ί if W! ■ / t I 0 8 A 12 912 . . in the presence of an aqueous emulsion of about 0.23 about 0.37 parts by weight of an ethylenically unsaturated rubber per part of the monomer mixture is polymerized. 7. The method according to any one of the preceding claims », characterized» that the rubber is a butadiene polymer with up to about 33 percent by weight of bonded styrene with a mean particle size of about 0.24 to about 0.56 microns, a gel content of less than 70 % and a swelling index in benzene of more than approx. 40. 8 · Method according to one of the preceding claims » characterized in that the Hercaptan poly * merization Rtgulatoa? in an amount between approx. 0.009 and approx. 0.019 equivalents of mercaptan per kg of rubber and monomers are used. 9. The method according to any one of the preceding claims, characterized in that the polymerization is initiated at a polymerization temperature of about 52 ° 0 to about 58 ° C by adding the catalyst in a reaction zone, dl8 the rubber, between about 40 and about 60 % of the regulator and between about 40 and about 60% of the monomers, at least about half of the monomers in the reaction zone are converted before the rest of about 60 to about 40 % of the regulator is reacted the remaining approx. 60 to approx. 40 % of the monomers are in the reaction zone, and the reaction time is kept within a temperature range between approx. 52 and 58 ° 0 until at least approx. 95 % of the monomers have reacted. 109808/210 0 A 12 912 10 · Method according to one of the preceding claims, characterized marked »that ale Hercaptan Polymerization Regulator a mixture of tertiary alkyl mercaptans with 12 bie 16 carbon atoms is used 11. Process according to one of Claims 2 to 10, characterized in that the persulfate salt is used in an amount between approx. O ₁ 020 and approx. 0.059 equivalents per kg of rubber and monomers. 12. The method according to any one of claims 9 to 11, characterized in that the monomer quantity of about 60 to about 40% and the regulator quantity of about 60% to about 40 % are added partially to the reaction zone. 13. Process according to one of claims 9 to 11, characterized in that the monomer quantity of approx. 60 to approx. 40 % and the regulator quantity of approx. 60 to approx. 40 # of the reaction zone continuously at constant speed be admitted. 14. The method according to any one of the preceding claims _5, characterized in that the reaction zone is kept within a temperature range of about 2 ° O between about 52 ° O and about 58 ° C. 109800/2109