DE19715821A1 - Thermoplastic molding compound - Google Patents

Abstract

The invention relates to a molding material comprising 45 to 95 wt. % styrene and 1.1-diphenylethylene copolymer(S/DPE copolymer) with 37 to 85 wt. % polymerized styrene units and 15 to 63 wt. % polymerized 1.1-diphenylethylene units or a styrene-S/DPE double block copolymer whose S/DPE block has the above-mentioned composition. The inventive molding material also contains 5 to 55 wt. % of a rubber-elastic microsuspension graft polymer consisting of particles with a diameter d50 of 30 mu m or less with a rubber-elastic graft core consisting of units of one or several C2-36-alkyl-acrylic esters with a glass transmission temperature Tg lower than -10 DEG C and a graft shell made of at least 50 wt. % polymerized styrene units.

Description

Copolymers of styrene and 1,1-diphenylethylene (DPE) and its technical equivalents ("S / DPE copolymers"; "poly (S / DPE)") are characterized by a higher compared to polystyrene Heat resistance and a higher rigidity (DE-A-44 36 499). The disadvantage is the low toughness of these copolymers.

The prior art is also on DE-A-44 07 022 and German patent application 190 05 828.0, not previously published point out.

It is also known from DE-A-44 43 886, particles with a To produce diameters from 1 to 100 μm by a process, which is called microsuspension (MS) method. This Particles have also been incorporated into other thermoplastics, to improve their mechanical properties. In doing so however, S / DPE copolymers are not mentioned, although this one represent the brittle material.

It is an object of the invention to provide impact-resistant molding compositions To provide the basis of S / DPE copolymers that the Disadvantages of the pure copolymers do not have. A task The invention is in particular based on molding compositions of S / DPE copolymers to provide the one have toughness. Another object of the invention is it to specify a process that allows impact-resistant shape masses with different surface structures from glossy to matt and with different opacity (from translucent to opaque) depending on the process conditions.

It has now been found that S / DPE copolymers obtain advantageous properties in the above sense if they are mixed with particulate butadiene-styrene graft rubbers with an average particle diameter d ₅₀ of 30 μm or less, as can be produced by microsuspension polymerization ( hereinafter also referred to as "MS particles"). In the following, a suspension is to be understood as a disperse phase of solid particles in a continuum, in contrast to a dispersion as a disperse phase of liquid particles or droplets.

Immediate subject matter of the invention is a molding composition which contains 10 to 99% by weight of a copolymer of styrene and 1,1-diphenylethylene (S / DPE copolymer) with a proportion by weight of 37 to 85% by weight of units of styrene polymerized in and 15 to 63% by weight .-% polymerized units of 1,1-diphenylethylene or a styrene-S / DPE two-block copolymer, (wherein the S / DPE block has the above composition), and 1 to 90 wt .-% of a particulate, a particle diameter d ₅₀ rubber-elastic graft polymers having a graft core made of a rubber-elastic polymer of one or more C _2-36 alkyl acrylic esters with a glass transition temperature T _g of below -10 ° C. and a graft shell of at least 50% by weight polymerized units of styrene.

For example, particles with an average diameter d ₅₀ of 0.03 to 30 μm are suitable; a particle diameter of 0.5 to 20 μm is preferred, particularly preferably 0.8 to 10 μm. In any case, these particles are significantly larger and have different properties than conventional particulate graft rubbers, such as are found in conventional impact-modified polymers (e.g. HIPS). The specified mean values can easily be determined in the usual way by measuring light microscopic images.

It is understood that the average particle diameter of the Graft core must be slightly smaller than the intended particles size of the finished MS polymers.

Particularly favorable results are achieved if instead of or in addition to the pure S / DPE copolymers Structure [S] - [S / DPE] can be used (where [S] is a block of a styrene homopolymer, [S / DPE] a block of an S / DPE Copolymers with statistically distributed monomer units meaning tet). Such [S] - [S / DPE] block copolymers can be sequenced by tial anionic polymerization can be obtained. The block copolymers are more complex to produce, but they lead to ge compared to the use of S / DPE copolymers to even better me mechanical properties, for example even higher toughness and elongation at break; it is believed that the use of block copolymers have a better bond between the MS particles and the polymer matrix.  

A molding composition according to the invention preferably contains 45 to 90 and in particular 50 to 85% by weight of the S / DPE copolymer or S-S / DPE Diblock copolymers and 10 to 55 or 15 to 50% by weight of the particulate microsuspension graft polymer.

For various reasons, e.g. B. to improve the mechanical Properties of the molding compounds is a mixture of at least each an S / DPE copolymer and S-S / DPE two-block copolymers worth it. If the molding compound ent an S-S / DPE two-block copolymer holds, this advantageously has a DPE content in the S / DPE block in the range from 25 to about 63% by weight.

The microsuspension graft polymers according to the invention contain, for. B. a core of at least 70 (particularly favorably at least 80) wt .-% units of the C _2-36 alkyl acrylic ester.

As an acrylic ester for producing a graft according to the invention The core is preferably butyl acrylate or ethylhexyl acrylate or their mixture used.

The microsuspension graft polymer generally has an envelope at least 50% by weight styrene; as further monomers z. B. Methyl methacrylate, α-methylstyrene, acrylonitrile and methacrylic nitrile can be used.

The SS / DPE two-block copolymers used, if used, generally have a weight-average molecular weight M _w of 10,000 to 2,000,000, determined by means of GPC after calibration against a polystyrene standard. A weight-average molecular weight M _w of 20,000 to 1,000,000 and in particular 50,000 to 500,000 g / mol is preferred.

When using S-S / DPE two-block copolymers, the polysty rol block z. B. a weight fraction of 5 to 75 wt .-% or S / DPE block content makes up 25 to 75% by weight.

The weight ratio of shell and core in the microsuspension spo Lymerisat the molding composition according to the invention is generally at 5: 95 to 80:20; a weight ratio of shell and core is preferred from 10: 90 to 70: 30 and in particular 15: 80 to 60: 40.

An S / DPE copolymer or block copolymer is advantageously used Copolymer uses an S / DPE block with statistical ver division of the styrene and diphenylethylene units.  

A molding composition according to the invention is obtained in particular when one or more C _2-36 alkyl acrylic esters in the presence of at least 1 g / l of a protective colloid selected from carboxy methyl cellulose, hydroxymethyl cellulose, poly-N-vinyl pyrrolidone, polyvinyl alcohol, polyalkylene oxides, polyacrylic acid and Dispersed poly-N-vinylimidazole in an aqueous environment by vigorous stirring in such a way that a droplet size of less than 30 μm is obtained, the dispersion in the usual way radicals to give a polyacrylic ester suspension and after addition of styrene and, if appropriate, other monomers to form a relatively coarse particle Polymerized graft rubber (ie a microsuspension) and mixes the graft rubber in a manner known per se with the S / DPE copolymer or styrene-S / DPE two-block copolymers.

In any case, the MS particles according to the invention are thereby receive that the liquid monomer or monomers that are used for grafting core (s) should be polymerized before the polymerization with Water and a protective colloid by intensive stirring to a Medium droplet suspension of monomer droplets of less than 30 µm and then polymerized / who the, the required stirring speed and / or duration is determined by depending on the particle size of stirring speed and duration in a preliminary test by Aus measure and count determined by light microscopy.

Molding compositions are obtained which are characterized by high toughness, Characterized rigidity, elongation at break and heat resistance.

The copolymerization of 1,1-diphenylethylene with styrene is known and described in DE-A-44 36 499 and the citation there literature.

The S / DPE copolymers have a molar ratio of DPE-Ein units to styrene units in the range from 1: 1 to 1:25, preferably example from 1: 1.05 to 1:15 and particularly preferably in the range of 1: 1.1 to 1:10. Because diphenylethene usually by itself not polymerized are products with molar ratios of more than 1: 1 not easily accessible.

According to the method specified in DE-A-44 36 499 Diphe submitted nylethen and styrene during the reaction after a Gradient methods metered in such a way that with increasing reac duration the amount of diphenylethene added per unit of time essentially according to the amount of styrene still present is reduced. Through this type of implementation, the monomer ratio almost constant throughout the polymerization held. To control the inflow gradient can be more advantageous  change the refractive index, which is a function of the Monomer ratio is to be exploited.

The anionic polymerization is carried out in the usual way organometallic compounds triggered, especially the Alkali metal compounds, in particular of lithium, which in the Usually as a solution in a chemically indifferent (inert) Koh hydrogen are used. Examples of such initiators are methyl lithium, ethyl lithium, propyllithium, n-butyllithium, sec. Butyllithium and tert. Butyllithium. The crowd judges in a known manner according to the desired molecular weight of the Po lymeren, but is usually in the range of 0.002 to 5 Mol% when referring to the monomers.

To achieve higher polymerization rates, ge small amounts of polar, aprotic solvents are added.

For example, diethyl ether, diisopropyl ether, Diethylene glycol dimethyl ether, diethylene glycol dibutyl ether or especially tetrahydrofuran (THF). The polar cosolvent will non-polar solvent in this process variant in the Re gel added in a small amount of about 0.5 to 5 vol .-%. THF is particularly preferred in an amount of 0.1 to 0.3 Vol .-%. In pure THF, the reaction parameters are unfavorable influences, so that the polymer high residual fractions of DPE monomers contains.

The polymerization temperature can be between 0 ° and 130 ° C. Temperatures of 50 ° to 90 ° C. are preferred. Generally speaking under isothermal conditions, d. H. keeping the buttocks constant Polymerization temperature polymerized. You can check the temperature but also in the range from 0 ° to 130 ° C, preferably from 30 ° let rise up to 120 ° C. It is particularly useful initially polymerize isothermally and towards the end of the reaction, d. H. at low monomer concentrations adiabatically increase the temperature let rise to keep the polymerization times short.

The response times are usually in the range of 0.1 to 24, preferably from 0.5 to 12 and particularly preferably from 1 to 10 h.

The production of two-block copolymers from a polystyrene block and an S / DPE block by sequential anionic Polymerization of the blocks is u. a. also in DE-A-44 36 499 described in detail. For the purposes of the invention, the DPE content in the S / DPE block in the range from 15 to 63% by weight (preferably 25 to 63% by weight).  

The block transitions can be both sharply separated and ver be lubricated.

A smeared transition means part of the chain molecule in which the monomer composition differs from that of the Block A gradually and not suddenly change to that of Block B. different. The monomers of block A are in the region of the transition and that of block B more or less statistically distributed. The Target molecular weight of the blocks is based on the ratio adjusted from initiator to monomer.

Of course, as stated above, mixtures of S / DPE Copolymers and S-S / DPE two-block copolymers are used.

The graft rubber to be used according to the invention (the Mikrosus pension polymer) consists of a polymer core composed of monomers which are referred to below as M _K and a graft shell (shell) made of monomers M _S. The particle core generally has a glass transition temperature T _g of below 0 ° C., preferably below -10 ° C.

Monomers M _K forming rubber-elastic polymers are preferably n-butyl acrylate and / or 2-ethylhexyl acrylate, which make up 50 to 100% by weight of the core material. The core preferably consists of more than 70, particularly preferably more than 80% by weight of acrylate.

In addition to these so-called "soft" monomers leading to elastomeric poly mers, so-called hard monomers such as methyl methacrylate, styrene and α-methylstyrene and acrylonitrile are also suitable in proportions of up to 50% by weight. In principle, however, all monomers polymerizable with free radicals are suitable as comonomers, the glass transition temperature T _{g being} decisive for their selection and amount.

Often also - usually in a minor amount, e.g. B. up to 5, preferably up to 2.5%, based on the other monomers, at least one crosslinker used. Are suitable as crosslinkers bifunctional or polyfunctional comonomers, e.g. B. butadiene, Isoprene, divinyl esters of dicarboxylic acids such as succinic acid and adipic acid, diallyl and divinyl ether bifunctional Alko Get like ethylene glycol and butane-1,4-diol, diesters of acrylic acid and methacrylic acid with the bifunctional alcohols mentioned, 1,4-divinylbenzene and triallyl cyanurate. Is particularly preferred the use of the (meth) acrylic acid ester of tricyclodecenyl alcohol (dihydrodicyclopentadienyl acrylate) and the allyl ester of acrylic acid or methacrylic acid.  

The shell is intended to convey the compatibility of the microsuspension rubber with the matrix polymers of the mixture according to the invention and therefore generally consists of 100 to 50, preferably 100 to 80, particularly preferably 90 to 97% by weight of styrene (M _S ). Suitable comonomers (M _S ) are all monomers polymerizable with free radicals, preferably acrylonitrile and esters of (meth) acrylic acid, particularly preferably acrylonitrile.

The particulate graft polymers according to the invention which form a microsus pension are obtained above all by the process described in DE-A-44 43 886: The liquid monomer (s) M _K which is to be polymerized into the core are mixed with water and a the appropriate amount of protection applied colloid by intensive stirring - e.g. B. with an intensive mixer of any design - processed at high speed to a dispersion of the smallest possible monomer droplets. The polymerisation initiator is added either before or only after the monomer has been dispersed, possibly also only after the dispersion has been heated. It can also be metered in during the polymerization. The desired particle size is expediently determined in a prior experiment by taking light microscope photographs of a suspension produced with a certain amount of protective colloid and counting the number of particles which have a certain diameter, and possibly varying the amount of protective colloid.

The M _K monomer (s) is generally dispersed at a temperature of 0 to 100 ° C., preferably at room temperature, and 0.25 to 10 kg of water are generally used per kilogram of monomers.

The protection suitable for stabilizing the dispersion Colloids are water-soluble polymers, which are the monomers droplets and envelop the polymer particles formed therefrom and protect against coagulation in this way.

As protective colloids z. B. cellulose derivatives such as carboxymethyl cellulose and hydroxymethyl cellulose, poly-N-vinyl pyrrolidone, polyvinyl alcohol and polyethylene oxide, anionic polymers such as polyacrylic acid and cationic such as poly-N-vinylimi dazol. The amount of these protective colloids is preferably 0.1 to 5% by weight, based on the total mass of the monomers M _K.

Free radical formers are suitable as polymerization initiators especially those which are noticeably soluble in the monomers and which preferably has a half-life of 10 between 25 and 150 ° C  Have hours. For example, peroxides such as Lauroyl peroxide, peroxysulfates, t-butyl perpivalate and azo compounds such as azodiisobutyronitrile. For the production of the The graft core and the graft shells are different possible initiators. The amount of initiators is generally 0.1 to 2.5 wt .-%, based on the amount of monomers ren.

Furthermore, the dispersion can contain buffer substances such as Na ₂ HPO ₄ / NaH ₂ PO ₄ or Na citrate / citric acid in order to set an essentially constant pH. In the polymerization, in particular the shell-building monomers M _S , a molecular weight regulator from the family of the thio alcohols, such as ethylhexylthioglycolate or t-dodecyl mercaptan, is also generally added. Suitable polymers are obtained if necessary with up to 10% by weight molecular weight regulator.

The polymerization is started by heating the dispersion where with only moderate stirring, so that the droplets no longer know be divided. This continues until the Sales based on the amount of monomer, over 50%, preferably over 85% lies.

When the polymerization of the graft core has ended, the reaction with the monomers M _S from which the shell is to be formed is continued in the usual way. However, the grafting can also begin when the polymerization conversion of the monomer M _{K is} still below 50% or below 85%. In this case, the shell and core form a more fluid transition compared to the sharper demarcation of core and shell polymer in the case of the complete conversion of the core monomers.

In some cases, especially if the graft cores are relatively small and if you want to incorporate a larger amount of the core polymer into the particles, multi-layer graft polymers are recommended, e.g. B. the structure P _K -P _a -P _K -P _a , where P _{a means} a shell different from P _K (also from other monomers), thereby modifying and possibly improving the properties of the graft polymers.

The polymerization temperature is usually 25 to 150 ° C, preferably 40 to 120 ° C and can for the core and the shell (Shell) can be selected differently. The lower limits these areas correspond to the decay temperatures of each  used polymerization initiators.

In the graft polymers according to the invention, the mass ratio of the sum of all shells to the core is about 5: 95 to 80:20, preferably 10: 90 to 70: 30, particularly preferably 15:80 to 60:40. The average diameter of the graft polymer particles is 30 μm or less, preferably 0.5 to 20 µm, particularly preferably 0.8 to 10 µm. The mean diameter corresponds to the d ₅₀ value, according to which 50% by weight of all particles have a smaller diameter and 50% by weight a larger diameter than the diameter which corresponds to the d ₅₀ value. The average particle diameter can be determined in the usual way by measuring light microscopic images. The measurement results provide a number average that can be converted into other average values (e.g. weight average) using the usual computational methods.

The rubber-elastic particles are incorporated into the S / DPE copolymer Melt incorporated so that the resulting molding compound a thermoplastic matrix and graft po dispersed therein lymerisat particles is built up.

Preparation of the mixtures

The thermoplastic molding compositions according to the invention can by Mixing the individual components in conventional mixing devices such as Kneaders, Banbury mixers and single screw extruders, preferably however, can be obtained with a twin screw extruder. To one To obtain the most homogeneous molding compound possible is an intensive one Mixing necessary. The order of adding the components can be varied. The processing temperature range should be between 200 and 300 ° C (preferably 220 to 280 ° C).

The inventive impact modifiers are used Graft polymers generally in amounts of 1 to 90, preferably as 2 to 60 wt .-%, based on the amount of their mixture with the base polymer. Shaped bodies of such mixtures are highly light-scattering and therefore generally opaque to opaque.

If a matting effect with high transparency is desired, concentrations of 2 to 20% by weight of graft are recommended polymer. Since at these low concentrations only one right a relatively small increase in impact strength in this case, conventional, finely divided rubber elastic modifiers of the usual kind (e.g. with a Particle diameter of less than 1 µm - e.g. B. from 50 to 500 nm) in the usual amounts, minus the amount of as  Matting agents used MS graft polymers according to the invention share risk.

The particles according to the invention achieve a matting effect, without noticeably affecting the mechanical properties, like this with conventional matting agents like chalk or Silica gel can be observed.

The in the preparation of the MS polymers according to the invention Protective colloids used can remain in the molding compound. They have because of their higher molecular mass and larger space fulfillment of the molecules far less than that in the manufacture conventional impact modifiers usual (low molecular) emulsifiers seeking to surface the Hiking plastic. High molecular protective colloids tend to do so far less for sweating out of a molded part than emulga goals.

In addition, those with the particles according to the invention modified molding compounds and the molded parts made from them better printable than molding compounds that have no or other particles contain and have so-called anti-blocking properties, d. H. the achieved matt ("roughened") surfaces of the moldings adhere not to each other. Particles according to the invention, to a Stacking foils stacked on top of each other can be done easily separate from each other, unlike foils that contain such particles not included.

The molding compositions can also contain additives of all kinds. May be mentioned for. B. lubricants and mold release agents, pigments, flame preservatives, dyes, stabilizers, fiber and powder shaped fillers and reinforcing agents and antistatic agents, each be added in the usual amounts.

Moldings can be made from the molding compositions according to the invention reduced surface gloss (mattness) and high toughness produce. The polymer does not separate in the molded body components.  

Examples A) Preparation of an (S) - (S / DPE) block copolymer (A1 - cf. Tab.)

It is cleaned for the purposes of anionic polymerization 1,1-diphenylethylene and styrene and over anhydrous Alumina dried solvent used.

Solutions with living anions were basically pure nitrogen handled. Percentages refer to the Ge unless otherwise stated.

A 10 liter metal boiler with a double jacket for cooling and heating and stirrer was stirred for several hours with a solution of Boiled butyllithium in cyclohexane under reflux, the solution left, 5290 ml cyclohexane, 1303 ml (1182 g; 11.35 mol) styrene and 60.1 ml of a 0.281 m sec-butyllithium solution in cyclohexane submitted at 23 ° C, brought to 50 ° C over the heating jacket and 2 Hours stirred. The mixture was then warmed to 70 ° C., 1132 ml (1158 g; 6.43 mol) of titrated 1,1-diphenylethylene added and in 200 ml steps every 10 min a total of 2030 ml (1842 g; 18 mol) Styrene added. After a further 3 hours, was with ethanol Titrated to colorlessness by pouring in a thin stream more ethanol precipitated, filtered off, several times with ethanol washed and dried for 2 hours at 200 ° C. at 1 mbar.

Yield: 4128 g (98.7%); Styrene content (FTIR): 72.4% (72.3% theor.); DPE content (FTIR): 27.6% (27.7% calc.); Glass temperatures T _g (DSC): 109 ° C (width of the glass step: 9 ° C) and 150 ° C (width of the glass step: 15 ° C); Molar mass [g / mol] (GPC, polystyrene calibration): M _N = 147,000, M _w = 202,000.

Microsuspensions
Polyvinyl alcohol (Mowiol® 8-88 from Hoechst AG) was used as the protective colloid. According to the manufacturer, the first number after the brand name indicates the viscosity of a 4% by weight solution of polyvinyl alcohol (PVA) in water at 20 ° C [mPa / s], measured according to DIN 53 015, the second number the degree of saponification in mol%.

Micro suspension M1:
Particulate graft polymer made from n-butyl acrylate (core) and styrene / acrylonitrile (shell); according to the invention.

784 g n-butyl acrylate, 16 g dihydrodicyclopentadienyl acrylate, 1500 g deionized water, 16 g polyvinyl alcohol (10% in Water) and 4 g of dilauroyl peroxide were in the specified Rei  Ordered together under nitrogen and with a trade usual homogenizer (Dispermat CV; manufacturer VMA-Gelzmann) at a speed of 7000 rpm at 23 ° C for 20 minutes a dispersion with a droplet diameter of less than 2.5 µm processed. 10% of the dispersion was mixed with nitrogen submitted flushed reactor, brought to 75 ° C and with a Blade stirrer stirred (300 rpm). The rest of the dispersion was added within three hours and another hour stirred.

To produce the graft shell, the suspension obtained was a mixture of 192.0 g of water, 15.36 g of polyvinyl alcohol as a 10% solution in water and a mixture of 364.8 g of styrene and 19.2 g of acrylonitrile within 80 minutes at 75 ° C and 300 U / min added and post-polymerized for three hours. The average particle size d ₅₀ , determined by light microscopy by measuring and counting the particles, was 2.5 μm. The suspension was used as it was to prepare the mixture of the invention.

Micro suspension M2:
Example 1 was repeated with the preparation of the graft core described there and the following amounts for the graft shell: template 626.0 g of water, 26.42 g of PVA as a 10% strength solution in water. Feed 627.5 g styrene, 33.0 g acrylonitrile.

Production of a molding compound according to the invention

The S-S / DPE copolymer was in an extruder (ZSK 30 from. Werner and Pfleiderer) melted at 250 ° C. M1 and M2 were continuously entered, the water content of the dispersions in Extruder removed, extruded and granulated. It was checked on Standard test specimens according to DIN regulations.

Modulus of elasticity: DIN 53 455
Impact strength according to Charpy (a _n ): DIN 53 453
Notched impact strength according to Charpy (a _k ): DIN 53 453

table

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Claims (23)

1. Molding composition containing 10 to 99 wt .-% of a copolymer of styrene and 1,1-diphenylethylene (S / DPE copolymer) with a weight fraction of 37 to 85 wt .-% copolymerized units of styrene and 15 to 63 wt % polymerized units of 1,1-diphenylethylene or a styrene-S / DPE two-block copolymer, the S / DPE block having the above composition and 1 to 90% by weight of a particulate, a particle diameter d ₅₀ of 30 µm or less, rubber-elastic graft polymer with a rubber-elastic polymer of one or more C _2-36 alkyl acrylic ester with a glass transition temperature T _g of below -10 ° C as a graft core and a graft shell from at least 50 wt .-% polymerized units of styrene and optionally further monomers. 2. Molding composition according to claim 1, as is obtained when one or more C _2-36 alkyl acrylic esters in the presence of at least 1 g / l of a protective colloid selected from carboxymethyl cellulose, hydroxymethyl cellulose, poly-N-vinyl pyrrolidone, polyvinyl alcohol , Polyalkylene oxides, polyacrylic acid and poly-N-vinylimidazole dispersed by vigorous stirring in an aqueous environment so that a particle size of less than 30 microns is obtained, the dispersion radical in the usual manner to a suspension of a graft core polymer and after the addition of styrene and optionally further monomers are polymerized to a suspension of a graft rubber and the graft rubber is mixed in a manner known per se with the S / DPE copolymer or styrene-S / DPE two-block copolymers. 3. Molding composition according to claim 1 or 2, containing a graft rubber with an average diameter d ₅₀ of 0.03 to 30 microns. 4. Molding composition according to claim 3, containing a graft rubber with an average diameter d ₅₀ of 0.5 to 20 microns. 5. Molding composition according to claim 3, containing a graft rubber with an average diameter d ₅₀ of 0.8 to 10 microns. 6. Molding composition according to claim 1 or 2, containing a graft rubber obtained in the absence of emulsifiers is. 7. Molding composition according to claim 1 or 2, containing 45 to 90 wt .-% of the S / DPE copolymer or S-S / DPE two-block copolymer and 10 to 55% by weight of the particulate microsuspension graft polymer. 8. Molding composition according to claim 1 or 2, containing 50 to 85 wt .-% of the S / DPE copolymer or S-S / DPE two-block copolymer and 15 to 50% by weight of the particulate microsuspension graft polymer. 9. Molding composition according to claim 1 or 2, containing an S-S / DPE Diblock copolymer containing DPE in the S / DPE block in the Range from 25 to 63% by weight. 10. Molding composition according to claim 1 or 2, containing an S-S / DPE Two-block copolymer with a weight proportion of the polystyrene Blocks from 5 to 75 and an S / DPE block portion from 25 to 75 % By weight. 11. Molding composition according to claim 1 or 2, containing a mixture from at least one S / DPE copolymer and S-S / DPE-two block copolymers. 12. Molding composition according to claim 1 or 2, containing a microsuspen graft polymer with a core of more than 70 wt .-% units of the C _2-36 alkyl-acrylic ester. 13. Molding composition according to claim 1 or 2, containing a microsuspion graft polymer with a core of more than 80 wt .-% units of the C _2-36 alkyl-acrylic ester. 14. Molding composition according to claim 1 or 2, containing a microsuspen sion graft polymer based on butyl acrylate or ethylhexyl acrylate. 15. Molding composition according to claim 1 or 2, containing a microsuspen sion graft polymer with a shell of at least 50 % By weight of styrene and at least one further monomer selected from methyl methacrylate, α-methylstyrene, acrylonitrile and methacrylonitrile.   16. Molding composition according to claim 1 or 2, containing an SS / DPE two-block copolymer with a weight-average molecular weight M _w of 10,000 to 2,000,000, determined by means of gel permeation chromatography after calibration against a polystyrene standard. 17. Molding composition according to claim 12, comprising an SS / DPE two-block copolymer with a weight-average molecular weight M _w of 20,000 to 1,000,000 g / mol. 18. Molding composition according to claim 12, comprising an SS / DPE two-block copolymer with a weight-average molecular weight M _w of 50,000 to 500,000 g / mol. 19. Molding composition according to claim 1 or 2, containing a microsuspen sion polymer with a weight ratio of shell and Kern from 5: 95 to 80: 20. 20. Molding composition according to claim 19, containing a microsuspension polymer with a weight ratio of shell and core from 10: 90 to 70: 30. 21. Molding composition according to claim 19, containing a microsuspension polymer with a weight ratio of shell and core from 15: 80 to 60: 40. 22. A method for producing molding compositions according to claim 1, because characterized in that as S / DPE copolymer or - Block copolymer uses a copolymer that contains an S / DPE block with statistical distribution of styrene and diphenylethylene Units. 23. A method for producing molding compositions according to claim 1, there characterized in that the liquid monomer or monomers, which are polymerized to the core of the graft copolymer should (s), before polymerization with water and protection colloid essentially in the absence of emulsifiers Stir to a suspension of monomer droplets with a And then divided into diameters of less than 30 µm is / are polymerized, with the required stirring speed and / or duration is determined in that the particle size depending on the stirring speed and duration in a preliminary test by measuring and counting determined by light microscopy.