CZ200010A3 - Thermoplastic sand mixture with little coloring, process of its preparation and its use - Google Patents

Abstract

Thermoplastic molding composition comprising as components A) to F), A) 5 to 80 wt. % graft polymer A) s biomodal particle size distribution, z, based on A), al) 40 to 90 wt. % rubber elastic particulate graft base a1), obtained by polymerization, based on al), a11) 70 to 100 wt. % of at least one conjugate % diene, a12) 0 to 30 wt. % of at least one other monoethylenic unsaturated monomer; and al 3) 0-10 wt. %, preferably 0.01 to 5 wt. % and especially preferably 0.02 to 2 wt. % of at least one % polyfunctional, cross-linked monomer, α) 10 to 60 wt. % of graft substrate a2) z, based on a2), a21) 65 to 95 wt. % of at least vinylaromatic monomer, a22) 5 to 35 wt. % of acrylonitrile, a23) 0 to 30 wt. % at least one additional monoethylenic unsaturated monomer and a24) 0 to 10 wt. % of at least one multifunctional, % of crosslinked monomer, B) 20 to 95 wt. % % of a thermoplastic polymer B) having a viscosity number of VZ 50 to 120) ml / g of, based on B), b1) 69 to 81 wt. % at least one vinylaromatic monomer, b2) 19 to 31 wt. % of acrylonitrile, b3) 0 to 30 wt. % of at least one other monoethylenically unsaturated monomer, and optionally others thermoplastic polymers C), D) and / or E) consisting of at least one vinylaromatic monomer and optionally additives F) obtained by 1) the production of graft polymers by emulsion polymerization, 2) mixing the graft polymer A) with polymer B) and, if present, s other components C), D), E) and / or F), in the mixing the apparatus, wherein a substantially molten liquid is formed polymer mixture, 3) substantially molten by rapid cooling liquid polymer blends.

Description

Low-color thermoplastic molding composition, process for its manufacture and use

Technical field

The present invention relates to a thermoplastic molding composition. In addition, the invention relates to a method for producing a thermoplastic molding composition and to the use of a thermoplastic molding composition.

BACKGROUND OF THE INVENTION

ABS moldings (polybutadiene rubber particles grafted with polystyrene acrylonitrile, in a polystyrene acrylonitrile matrix) are characterized by good mechanical properties, for example high strength and toughness, particularly good impact toughness at low temperatures, due to the low glass transition temperature Tg.

However, ABS polymers often have a coloration, such as yellowish to brownish, especially those made by emulsion polymerization. This coloring can be expressed, for example, by the yellowness index YI, which for such ABS polymers with a clear coloration of more than 30 to over 50. The yellow color index YI depends on several factors, inter alia, the rubber content in the ABS . Furthermore, for example, a yellowish-brown coloration can often occur during the production of molding compositions, their further processing into moldings and the use of moldings. The yellowish or brownish coloration promotes high temperatures, such as occur in injection molding or blending with extruder ingredients, and the more pronounced the inherent color of the untreated ABS granulate prior to injection molding or extrusion is more pronounced. In particular, the yellow color of the polymers is problematic because the yellow color deteriorates the desired color shade or requires the use of larger amounts of expensive dyes (higher color costs). Further, a shallow depth of color induced by high is often observed in the dyed ABS molding compositions

Since the initial color level and the color depth of the colored molding are responsible for the color impression of the molding, the utility value of the molding composition is reduced many times by its own color and by yellowing.

EP-A 6341 discloses the treatment of acrylonitrile rubber in an extruder flushed with inert gases such as N2 or CO2, thereby minimizing the yellow color of the polymer. Operation of the extruder under inert conditions is disadvantageous since this process is expensive and costly.

DE-AS 2503966 discloses an ABS molding composition whose color stability is improved by the use of C1-C6-alcohol during emulsion polymerization of butadiene. However, the extent of yellowish reduction is still not satisfactory. Furthermore, the alcohol may adversely affect the determined properties of the molding compositions.

DE-AS 2427960 discloses ABS molding compositions whose rubber particles have been agglomerated by the addition of agglomeration dispersions and thus have a broad or bimodal particle size distribution.

DE-OS 3505749 discloses the precipitation of styrene-grafted polybutadiene rubber and acrylonitrile from its latex by means of a polybutadiene-containing sulfur grafting additive, thereby improving the thermostability of the precipitated and processed polybutadiene rubber molding composition. High levels of sulfur compounds often lead to the unpleasant odor of the molding composition.

EP-A 678531 discloses ABS molding compositions with polybutadiene graft rubber having a bimodal particle size distribution, wherein the styrene and acrylonitrile monomers grafted onto the polybutadiene particles are mainly added during the first half of the monomer addition time. Although such ABS blends have high toughness and good processability, they exhibit a distinct yellow coloration.

WO 95/22570 discloses a process for producing an ABS polymer in which a rubber latex produced in a small particle emulsion is partially agglomerated and the bimodal latex in the emulsion is grafted with a SAN. Then, the graft polymer is separated from the aqueous phase and its melt is mixed with the SAN polymer melt, wherein the SAN grafting envelopes and SAN matrices do not differ in AN content by more than 6 wt. When dewatering or mixing the graft polymer melt and the SAN matrix, further partial agglomeration of the grafted particles occurs. Also such molding compositions exhibit a disadvantageous yellow coloration.

SUMMARY OF THE INVENTION

The object of the invention is to eliminate the existing disadvantages. In particular, molding compositions must be provided which have a low coloration, i.e., a low starting level of yellow coloration and, in addition, have a low tendency to yellow coloration. In particular, they have essentially no yellow color even after prolonged heat accumulation or hot working (for example in injection molding when mixed on an extruder).

In addition, it is an object to provide molding compositions with good dyeability which, after coloring, have the smallest deviations of the existing color tone from the desired color tone and are sufficient to color them with small amounts of dyes. The dyed molding compositions must have a high color depth, so that the unstained molding compositions must have as low a light scattering as possible.

In the present invention, the desired low coloration can be characterized by a yellowness index YI <25 or an absorption value <0.1%. In the present invention, the desired high color depth, i.e. low light scattering, can be characterized by a scattering value of <4.9 . The numerical values given refer to the dyed molding composition and are determined as described in the examples.

It is further an object to provide molding compositions whose low coloration is not at the expense of their other advantageous properties, for example mechanical properties such as toughness and strength, and the degree of surface gloss. In particular, it is an object to provide molding compositions whose mechanical properties such as toughness and cold toughness and strength are even improved with respect to the prior art.

Therefore, thermoplastic molding compositions have been found containing as components A) to F) based on the total weight of the molding composition,

A) 5 to 80 wt. % of graft polymer A) with a bimodal particle size distribution, z, based on A), a1) of 40 to 90 wt. % of the rubber-elastic particulate graft base a1) obtained by polymerization based on a1), all) 70 to 100 wt. X1 of at least one conjugated diene, a12) 0 to 30 wt. % of at least one other monoethylenically unsaturated monomer and a13) 0 to 10 wt. X, preferably 0.01 to 5 and particularly preferably 0.02 to 2 wt. % of at least one polyfunctional, crosslinked monomer, a2) 10 to 60 wt. X of the graft substrate a2) z, based on a2), a21) 65 to 95 wt. % Of at least vinylaromatic monomer, a22) 5 to 35 wt. X of acrylonitrile, • β

and 23) Ο to 30 wt. % of at least one additional monoethylenic unsaturated monomer and a24) 0 to 10 wt. %, Preferably 0.01 to 5 and particularly preferably 0.02 to 2 wt. % of at least one polyfunctional, crosslinked monomer,

B) 20 to 95 wt. % of thermoplastic polymer B) with a viscosity number VZ (determined according to DIN 53726 at 25 ° C, 0.5 wt.% dimethylformamide) 50 to 120 ml / g z, based on B), b1) 69 to 81 wt. % of at least one vinylaromatic monomer, b2) 19 to 31 wt. b3) 0 to 30 wt. % of at least one other monoethylenically unsaturated monomer,

C) 0 to 50 wt. % of thermoplastic polymer C) with a viscosity number VZ of 50 to 120 ml / g z, based on C), cl) 69 to 81 wt. Of at least one vinylaromatic monomer, c2) 19 to 31 wt. From acrylonitrile, c3) 0 to 30 wt. From at least one other monoethylenically unsaturated monomer, wherein components B) and C) differ in their VZ viscosity number by at least 5 units (ml / g), or differ in their acrylonitrile content by at least 5 units (wt Z), or differ in both characters, viscosity number VZ and alkylnitrile content by at least 5 units,

D) 0 to 95 wt. From thermoplastic polymer D) z, based on D), d1) 63 to below 69 wt. % of at least one vinylaromatic monomer, d2) over 31 to 37 wt. % of acrylonitrile, d3) 0 to 40 wt. From at least one other monoethylenically unsaturated monomer,

E) 0 to 50 wt. From thermoplastic polymer E) z, based on E 1, e1) 4 to 96 wt. % Of at least one vinylaromatic monomer; Of at least one monomer selected from the group of methyl methacrylate, maleic anhydride and maleimide, and (3) 0 to 50 wt. From acrylonitrile, where polymer E) is different from polymers B) and, if present, C) and D),

F) 0 to 50 wt. From additives F) obtained

1) production of graft polymers by emulsion polymerization process,

2) mixing the graft polymer A) with polymer B) and, if present, with other components C), D), E) and / or

F), in a mixing device, whereby a substantially molten liquid polymer mixture is formed,

3) rapidly cooling the substantially molten liquid polymer. 9 • 9

- 7 mixtures.

In addition, a method for producing thermoplastic molding compositions, using thermoplastic molding compositions to produce moldings, and moldings made from thermoplastic molding compositions have been found.

It is understood that the sum of components A) to F), optionally the sum of monomers all) to a1), optionally the sum of monomers a21) to a24), or the sum of monomers b1) to b3), or the sum of monomers c1) to c3), or the sum % of monomers d1) to d3), or the sum of monomers e1) to e3) is 100 wt. 2.

Component A) is a graft copolymer with a bimodal particle size distribution and is included in the molding composition according to the invention with a proportion of 5 to 80, preferably 10 to 70 and particularly preferably 15 to 60 wt. 2, based on the sum of components A) and

B) and also, if any, C), D), E) and F). The graft polymer A) is formed from a soft rubber-elastic, particulate graft base a1) and a hard graft substrate a2).

The graft base a1) is contained with a proportion of 40 to 90 wt. 2, preferably 45 to 85 wt. 2 and particularly preferably 50 to 80 wt. 2, based on component A).

The graft base a1) is obtained by polymerizing from 70 to 100 wt. 2, preferably 75 to 100 wt. 2 and particularly preferably 80 to 100 wt. 2) of at least one conjugated diene; 2, preferably 0 to 25 wt. 2 and particularly preferably 0 to 20 wt. % Of at least one additional monoethylenic unsaturated monomer; %, preferably 0.01 to 5, and particularly preferably 0.02 to 2 wt. % of at least one polyfunctional, crosslinked monomer.

Possible conjugated dienes (a) are butadiene, isoprene, chloroprene or mixtures thereof. In particular, butadiene or isoprene or mixtures, in particular butadiene, are used.

In addition, the component a1) of the molding composition may contain, instead of the monomers a1), other monomers a1) which, to a certain extent, alter the mechanical and thermal properties of the core. An example for such monoethylenically unsaturated comonomers is:

R ²

C-CH3;

or C 1 -C 6 -alkyl and n is 0, methacrylic acid, further vinyl aromatic monomers such as styrene and styrene derivatives of the general formula (I) in which R ¹ and R ² denote hydrogen 1, 2 or 3, methacrylonitrile 1, acrylonitryl, acrylic acid, dicarboxylic acid such as maleic acid and fumaric acid as well as their anhydrides such as maleic anhydride, nitrogen functional monomers such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, vinylimidazole, vinylpyrrolidone, vinylcaprolactam, vinylcarbazole, vinylaniline, acrylamide,

C 1 -C 6 -alkyl acrylate such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert. butylacrylan, ethylahexylacrylan and the corresponding C 1 -C 6 -alkyl esters of acrylic acid and phenylmethacrylanic acid, methacrylic acid, as well as hydroxyethyl acrylate, aromatic and araliphatic esters of methacrylic acid such as phenylacrylan, benzylacrylan, benzylmethacrylan, 2-phenylethylacrylethyl, 2-phenylethylacrylethyl,

N-substituted maleimides such as methyl-methyl-, N-phenyl- and N-cyclohexylmaleimide, unsaturated ethers such as vinyl methyl ether, as well as mixtures of these monomers.

Preference is given to using as monomers a2) styrene, α-methylstyrene, n-butyl acrylate or mixtures thereof, particularly preferably styrene and n-butyl acrylate or mixtures thereof, and in particular styrene. Styrene or n-butyl acrylate or mixtures thereof are used in particular in an aggregate amount of up to 20 wt. % based on a1).

The graft base a1) may comprise crosslinked monomers a1). Suitable polyfunctional, crosslinked monomers [alpha] 3) are those with at least two ethylenically unsaturated, 1,3-unconjugated double bonds. Examples which may be mentioned are trialyl cyanurate, divinylbenzene, divinyl dicarboxylic acid esters such as dialyl maleate, dialyl fumarate, dialyl phthalate, as well as allyl acrylate and allyl methacrylate, dihydrodicyclopentadiene acrylate, dialyl ethers and divinyl ethers of bifunctional alcohols and alcohols such as ethylene esters ethyleneglycol diacrylan, hexadioldimethacrylan.

In a particular embodiment, a graft base z, based on a1), is used,

all) 70 to 99.9 wt. %, preferably 90 to 99 wt. and (2) 0.1 to 30 wt. %, Preferably 1 to 10 wt. % styrene.

The grafted substrate a2) is present in a proportion of 10 to 60 wt. %, Preferably 15 to 55 wt. %, Particularly preferably 20 to 50 wt. Z, relative to component A).

The grafted substrate a2) is obtained by polymerizing from 65 to 95 wt. %, Preferably 70 to 90 wt. % Z, and particularly preferably 75 to 85 wt. Of at least vinylaromatic monomer, a22) 5 to 35 wt.%, Preferably 10 to 30 wt. %, And particularly preferably 15 to 25 wt. % Of acrylonitrile, a23) 0 to 30 wt. % Z, preferably 0 to 20 wt. % Z and particularly preferably 0 to 15 wt. Of at least one other monoethylenic unsaturated monomer and a24) 0 to 10 wt. %, Preferably 0.01 to 5 and particularly preferably 0.02 to 2 wt. From at least one polyfunctional, crosslinked monomer.

Possible vinylaromatic monomers a21) are styrene and styrene derivatives of the general formula (I).

R2

wherein R ¹ and R ^{2 are} hydrogen or C 1 -C 6 -alkyl and ⁿ is 0, 1, 2 or 3. Preferably, styrene is used.

Other monomers a23) are suitable

11 the monomers mentioned above for component a12). Particularly suitable are methyl methacrylan and acrylans such as n-butyl acrylate. Particularly suitable as monomer a23) is methyl methacrylate MMA, an amount of up to 20 wt. % MMA based on a2).

The grafted substrate a2) may comprise crosslinked monomers a24). Other polyfunctional, crosslinked monomers a24) may be considered for the other a3) monomers mentioned above.

Graft polymers are made by emulsion polymerization. Generally, it is polymerized at a temperature of 20 to 100 ° C, preferably 30 to 80 ° C. Typically, conventional emulsifiers are used, for example, alkali metal salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, higher C30-C30 fatty acids, sulfosuccinates, ether sulfonates or resin soaps. Preference is given to using alkali metal salts, in particular sodium and potassium salts, alkylsulfonates or fatty acids of 10 to 18 carbon atoms.

As a rule, emulsifiers are used in amounts of 0.5 to 5 wt. %, In particular 0.5 to 3 wt. Z, based on the monomers used in the production of the graft base a1).

Preferably a water dispersion is used for the production, the finished dispersion having a solids content of 20 to 50 wt. Z. Usually the water / monomers ratio is 2: 1 to 0.7: 1.

All the free-radical binders which disintegrate at the selected reaction temperature, i.e., those which themselves thermally disintegrate, as well as those which disintegrate in the presence of a redox system, are suitable for starting the polymer and for the start of the reaction. Suitable polymer initiators are preferably free radical binders, for example peroxides such as persulfates (sodium or potassium persulfate) and azo compounds such as azodiisobutyronitrile. However, redox systems may also be used, particularly those based on hydroperoxides such as cumene hydroperoxide.

Generally, the polymerization initiators are used in an amount of 0.1 to 1 wt. Z, based on monomers a1) and a1).

Radical binders as well as emulsifiers and optionally molecular weight regulators (see the following paragraph) are added to the reaction batch, for example, discontinuously as a total amount at the start of the reaction, or separately in multiple batches at the start and at one or more moments or continuously over a predetermined time interval. . Continuous addition may also occur along a gradient, which may be ascending or descending, linearing or exponential, or also stepped (stepped function).

Also preferred are molecular weight regulators such as ethylhexylthioglycolate, n- or dodecylmercaptan or other mercaptans, terpineol and dimeric α-methylstyrene or others to regulate the molecular weight of a suitable compound. The molecular weight regulators are added to the reaction batch discontinuously or continuously, as already described for free radical binders or emulsifiers.

If molecular weight regulators are used in the polymerization, they can be added in the manner described above in the production of the graft base a1) or in the production of the graft substrate a2) or in the production of a1) and a2). In relation to the grafted substrate, the details below are given.

Buffer substances such as Na 2 HPO 4 / NaH 2 PO 4, sodium bicarbonate or citric acid / citrate buffer can be used to obtain a constant pH, preferably 6-9. The regulator and buffer substances are used in conventional amounts, so no details are given.

In a particularly preferred embodiment, a reducing agent is added during grafting of the graft base a1) to monomers a21) to a23).

«· • ·

The graft base can, in a particular embodiment, also be produced by polymerizing monomers a1) in the presence of fine particle latex (so-called Saatlatex-Fahrweise polymerization). This latex is available and may consist of monomers constituting rubber-elastic polymers, or other monomers as already mentioned. Suitable latexes consist, for example, of polybutadiene or polystyrene. Polystyrene latex is particularly preferred.

is available by polymerization, part) as gradient, conditions

In another preferred embodiment, the graft base a1) can be produced by a so-called fed-batch process. In this process, the proportion of monomers (a1) is determined and started, whereupon the remainder of monomers (a1) (feed rate during polymerization) is added (flow rate (shape, time, etc.) depends on further polymerization). Preferably, in the feed process, the proportion of monomers a1) available is 5 to 50 wt. X, particularly preferably 8 to 40 wt. X, based on a1). Preferably, the feed portion a1) can flow within 1 to 18 hours, especially within 2 to 16 hours, particularly preferably within 4 to 12 hours.

Furthermore, soft and a1-a2) -a1-a2) particles.

grafted polymers with hard envelopes, for example with or a2) -al-a2), are also suitable, especially in the case of larger construction

The same polymerization conditions, in particular the type, amount and dosage of emulsifier and other polymerization auxiliaries, are chosen such that the obtained latex of graft polymer A has a mean particle size defined by a particle size d50 of 80 to 800, preferably 80 to 600 and particularly preferably 85 to 400.

The reaction conditions are coordinated with one another such that the polymer particles have a bimodal particle size distribution, that is

- 14 size distributions with two more or less significant maxima. The first maximum is clearly more pronounced (relatively narrow peak) than the second maximum and is generally 25 to 200 nm, preferably 60 to 170 nm, particularly preferably 70 to below 150 nm. The second maximum is relatively wider and is generally 150 to 800 nm, preferably 180 to 700 nm, particularly preferably 200 to 600 nm. The second maximum (150 to 800 nm) lies at larger particle sizes than the first maximum (25 to 200 nm).

Preferably, the bimodal particle size distribution is achieved by (partial) agglomeration of the polymer particles. For example, this can be carried out as follows: The monomers a1) which form the core are polymerized up to a turnover of at least 90%, preferably more than 95%, based on the monomers used. This turnover is generally achieved after 4 to 20 hours. The rubber latex obtained has a mean particle size d 50 of at most 200 nm, preferably below 150 nm, and a narrow particle size distribution (almost monodisperse system).

In the second step, the rubber latex is agglomerated. This is usually done by adding an acrylic ester polymer dispersion. Preferably, dispersions of copolymers of (C1-C4-alkyl) esters of acrylic acid, preferably ethyl acrylate, with 0.1 to 10 wt. X monomers forming polar polymers such as acrylic acid, methacrylic acid, acrylamide or methacrylamide, N-methylolmethacrylamide or N-vinylpyrrolidone. Especially preferred is a copolymer of 90 to 96 wt. % Of ethyl acrylate and 4 to 10 wt. X methacrylamide. The agglomeration dispersions may optionally also contain more of said acrylic ester polymers.

The concentration of acrylic ester polymers in the dispersion used for agglomeration must generally be between 3 and 40 wt. X. 0.2 to 20 wt. % by weight, preferably 1 to 5 wt. parts of the agglomeration dispersion per 100 parts of rubber latex, calculated on solids. The agglomeration is carried out by adding the agglomeration dispersion to the rubber. Rate of addition (<· · · · · ♦ <<<<<<<<<přídav přídav přídav přídav přídav přídav přídav přídav přídav přídav <přídav) ··

15 is not normally critical, generally lasting 1 to 60 minutes at a temperature between 20 and 90 ° C, preferably between 30 and 75 ° C.

In addition to the acrylic ester polymer dispersion, the rubber latex can also be agglomerated by other agglomerating agents, for example acetic anhydride. Agglomeration by pressure and glazing is also possible. These procedures are known to those skilled in the art.

Under these conditions, only a portion of the rubber particles agglomerate, resulting in a bimodal distribution. As a rule, more than 40%, preferably between 45 and 95% of the particles are present in the non-agglomerated state. The partially agglomerated rubber latex obtained is relatively stable so that it can be stored and transported without further coagulation.

To achieve a bimodal particle size distribution of the graft polymer A), it is also possible to separately produce two different graft polymers A ') and A' ') which differ in their mean particle size and to mix the graft polymers A') and A ') in the desired ratio.

Typically, the polymerization of the graft base a1) is carried out by selecting the reaction conditions so as to produce a graft base with a determined crosslinked state. Thus, for example, reaction temperature, reaction time, monomer ratio, regulator, free-radical starter and, for example, in the feed method, the feed rate and the amount and time of addition of the regulator and initiator are mentioned as essential parameters.

A method for characterizing the crosslinking state of the crosslinked polymer particles is by measuring the swelling index QI, which is a measure for swelling of a more or less crosslinked polymer by a solvent. Typical swelling agents are, for example, methyl ethyl ketone or toluene. Usually, the QI of the molding compositions according to the invention lie in the range of QI = 10 to 60, preferably 15 to 55 and particularly preferably 20 to 50.

• · • ·

Another way to characterize the amplification state is by measuring the NMR relaxation times of moving protons, the so-called T2 times. The more strongly the determined lattice is amplified, the lower its times T2. Typical T2 times for the graft base a1) of the invention are in the range of 2.0 to 5.0 ms, preferably 2.5 to 4.5 ms, and particularly preferably 2.5 to 4.0 ms, measured in the film test at 80 ° C.

Another measure for characterizing the graft base and its cross-linking state is the gel content, i.e. the proportion of the product that is cross-linked and thus is not soluble in the determined solvent. It is expedient to determine the gel content in the same solvent as the swelling index. The usual gel contents of the graft base a1) according to the invention are in the range of 50 to 90%, preferably 55 to 90% and particularly preferably 60 to 85%.

Determination of the swelling index of the following procedure: graft base, in a corresponding amount of solid water, for example according to the substance of the dispersion swells After 24 hours, about 0.2 g of steamed (for example 50 g) toluene is aspirated with toluene and weighed. After drying under vacuum, reweigh. The swelling index is the ratio of the weight after swelling to the dry weight after re-drying. On this basis, the gel fraction is calculated from the ratio of the dry weight after swelling to the pre-swelling weight (x 100%).

Determination of T2 time is accomplished by NMR relaxation measurement of the dewatered and film-spread graft base dispersion test. Thus, for example, the overnight test at, for example, 60 ° C for 3 hours is dried under vacuum and then measured at 80 ° C with a suitable measuring device, for example from Brucker. Only tests that were measured according to the same procedure are comparable, as relaxation is clearly temperature dependent.

The production of the grafted substrate a2) can occur under the same conditions as the production of the grafted base a1), wherein the base a2) can be produced in one or more process steps.

• • • •

For example, in a two-step grafting process, styrene alone or α-methylsryren can be produced first, and then styrene and acrylonitrile can be polymerized in two successive steps. This two-step grafting (first styrene, then styrene / acrylonitrile 1) is the preferred embodiment. Further details for the production of graft polymers A) are described in DE-OS 12 60 135 and DE-OS 31 49 358.

It is advantageous to carry out the graft polymerization on the graft base a1) again in aqueous emulsion. It can be carried out in the same system as the graft base polymerization, with the addition of an emulsifier and an initiator. These need not be identical to the emulsifiers or initiators used to produce the graft base a1). For example, it may be expedient to use as the initiator for the production of the graft base a1) persulfate and to polymerize the graft substrate a2) a redox initiation system. Usually, what has been said in the production of the graft base a1) is applicable to the choice of emulsifiers, initiators and auxiliary polymers and starting materials. The graft monomer mixture can be added to the reaction mixture once, in multiple stages or preferably continuously during the polymerization.

It may be advantageous to add crosslinked monomers a24) and molecular weight regulators as described in the polymerization of the graft substrate a2) to adjust the desired properties.

When molecular weight regulators are used for the grafted substrate a2), the amount is 0.001 to 5 wt. 2, preferably 0.005 to 2 wt. 2a particularly preferably 0.01 to 2 wt. 2, based on monomers a21) to a24). The regulators are added either at the beginning of the grafting reaction or later at once, or in several stages in the same or different parts uniformly throughout the feed time or together with the grafted polymers a21) to 24) throughout the feed time or over a specified feed time period. Closer to the addition has already been said in al).

• · »

In the above-described embodiment of the production of the graft substrate a2) in two stages, for example, a regulator may be added in the first stage and a crosslinker a24) in the second stage or vice versa. It is also possible to use both regulator and crosslinker in both steps, whereby the ratio of regulator / crosslinker a24) can be the same or different in the steps.

Further, the above-mentioned applies to the dosing of the regulator and the enhancer in the production of the graft base a1) and the graft substrate a2), both of which can be dosed in the same or different manner.

If, when grafting the graft base a1), non-graft polymers are formed from monomers a2), the amount of component A), which is generally below 20% by weight, is added. Z, preferably below 15 wt. OF.

Component B) is a thermoplastic polymer and is included in the molding composition of the invention with a proportion of 20 to 95 wt. %, Preferably 30 to 90 wt. % Z and particularly preferably 40 to 85 wt. Z, based on the sum of components A) and B) and, if present, C), D), E) and F).

Component B) is obtained by polymerizing from 69 to 81 wt. Z, preferably 70 to 78 wt.%, Preferably 70 to 77 wt. B) of 19 to 31 wt. Z, preferably 22 to 30 wt.%, Preferably 23 to 30 wt. From acrylonitrile,

And in particular b3) from 0 to 30 wt. %, Preferably 0 to 28 wt. From at least one other monoethylenically unsaturated monomer.

Vinylaromatic monomers are styrene

And styrene derivatives of general formula (I) as described for components a21). Styrene and / or amethystyrene is preferably used.

In a preferred embodiment, the grafted substrate a2) of the grafted polymer A) consists essentially of, based on a2), a21) 75 to 85 wt. % of styrene and / or α-methylstyrene, a22) 15 to 25 wt. % of acrylonitrile and thermoplastic polymer B) consisting essentially of, based on B) b1), 71 to 78 wt. b2) 22 to 29 wt. % acrylonitrile.

In a particular embodiment, component B) consists of two polymers B ') and B''). In this case, polymer B ') corresponds to the polymer B) described above, with only those formulas (I) being used as the vinylaromatic monomers b1') in which R @ ¹ and R @ ² denote hydrogen, i.e. unalkylated vinylaromates. ') uses styrene.

Polymer B '') corresponds to the polymer B) described above, wherein only those formulas (I) with R ¹ and R ² denoting a C ¹ -C 6 -alkyl radical, i.e. alkylated vinylaromates, are used as vinylaromatic polymers b 1 '). Preferably, α-methylstyrene is used as the monomer b1 ') in B'').

The polymers B '') are preferably copolymers of α-methylstyrene and acrylonitrile. Particularly preferably, component B), when it comprises two components B ') and B' '), consists of a copolymer of B') styrene and acrylonitrile and a copolymer of B '') α-methylstyrene and acrylonitrile.

If B) consists of B ') and B' '), the ratio B') / B '') is between 99: 1 and 1:99, preferably between 95: 5 and 5:95.

Further monomers b3) may furthermore be those mentioned for component a1). • •

20 methyl methacrylan and Ν-alkyl- and N-arylmalein imides, such as N-phenylmalein imide.

Polymers B), which are generally also referred to as SAN polymers because of their main styrene and acrylonitrile components, are known and in part also commercially customary.

Component B) has a viscosity number VZ (determined according to DIN 53 726 at 25 ° C, at a 0.5 wt.% Solution of component B) in dimethylformamide) of 50 to 120 ml / g, preferably 52 to 110 ml / g and particularly preferably 55 to 105 ml / g. It is obtained in a known manner by mass, solution, suspension, precipitation or emulsion polymerization, with mass and solution polymerization being preferred. Details of these methods are described, for example, in the Kunststoffhandbuch, Hrg. R. Vieweg and G. Daumiller, Volume V Polystyrol, Car 1-Hanser-Verlag Munich 1969, page 118 et seq.

Component C) is also a thermoplastic polymer and is present in the molding composition according to the invention with a proportion of 0 to 50 wt. %, Preferably 0 to 48 wt. % Z and particularly preferably 0 to 45 wt. Z, based on the sum of components A) and B) and, if present, C), D), E) and F).

Component C) is obtained by polymerizing from 69 to 81 wt. Z, preferably 71 to 78 wt.%, Preferably 72 to 77 wt.%, Of at least one tonic monomer,

Z, and in particular inylaromation 2) to 31 wt. %, Preferably 23 to 28, preferably 22 to 29 wt. Of acrylonitrile and

% Z and in particular up to 40 wt. one another,

%, Preferably 0 to 30 wt. From at least a monoethylenically unsaturated monomer.

Suitable vinylaromatic monomers (c1) are:

Styrene and styrene derivatives of general formula (I) as described for component a21). Styrene is preferably used. Other monomers c3) may be the monomers listed for component a1). Particularly suitable are methyl methacrylate, maleic anhydride and N-phenylmalein imide.

Component C) has a viscosity number VZ of 50 to 120 ml / g, preferably 52 to 110 ml / g, and particularly preferably 55 to 105 ml / g. It is obtained in a known manner by mass, solution, suspension, precipitation or emulsion polymerization, with mass and solution polymerization being preferred. Details of these methods are described, for example, in the Kunststoffhandbuch, Hrg. R. Vieweg and G. Daumiller, Volume V Polystyrol, Car1-Hanser-Verlag Munich 1969, page 118 et seq.

Components B) and C) are SAN-type polymers. which polymerized contain relatively little acrylonitrile (maximum 31 wt.%). The components differ according to the invention

B) and C)

- either in that the viscosity differs by at least 5 units of mean molar mass M different), the VZ numbers of components B) and C) (ml / g) (in this case, components B) and C) are relative to each other

- or in that the acrylonitrile content of B) and C) and c2), respectively, differs by at least 5 units (monomers b2), (weight Z),

or the two characteristics, the viscosity number VZ and the acrylonitrile content differ by at least 5 units.

Component D) is also a thermoplastic polymer and contains from 0 to 95 wt. % Z, preferably 0 to 80 wt. % Z and in particular 0 to 70 wt. Z, based on the sum of components A) and B] and, if any,

C), D), E) and F). Component D) is obtained by polymerization, based on D),? Β β β?. «R β β« β β r r r r · r r · r · · r · · r r

- 22 dl) 63 to below 69 wt. % X, preferably 64 to 68 wt. % Of at least one vinylaromatic monomer, d2) 31 to 37 wt. X, preferably from 32 to 36 wt. % Of acrylonitrile, d3) 0 to 40 wt. X, preferably 0 to 30 wt. X of at least one other monoethylenically unsaturated monomer.

Suitable vinylaromatic monomers d1) are styrene and styrene derivatives of the general formula (I) as described for component a21). Styrene and / or α-methylstyrene, in particular styrene, is preferably used. Other monomers d3) may be those mentioned for component a21). Particularly suitable are methyl methacrylan, maleic anhydride, N-phenylmalein imide and other N substituted maleic imides.

Component D) is also a polymer like components B) and C) but differs from B) and C) by a low content of vinylaromatic monomers d1) or a higher content of acrylonitrile d2) (over 31% by weight X).

Component D) generally has a viscosity number VZ of 55 to 110 ml / g, preferably 56 to 105 ml / g, and particularly preferably 58 to 103 ml / g. Component D) is obtained in a known manner by mass, solution, suspension, precipitation or emulsion polymerization. Details of these methods are described, for example, in the Kunststoffhandbuch, Hrg. R. Vieweg and G. Daumiller, Volume V Polystyrol, Car1-Hanser-Verlag Munich 1969, page 118 et seq.

Component E) is also a thermoplastic polymer and contains 0 to 50 wt. X, preferably. 0 to 40 wt. X, and particularly preferably 0 to 30 wt.%, X based on the sum of components A) and B) and, if present, C), D), E) and F). Component E) is obtained by polymerization, based on E), β *. * • *. · »· V & a>

··· · ··· · · ·

- 23 el) 4 to 96 wt. X, preferably 8 to 92 wt. % X and particularly preferably 10 to 90 wt. X2 of at least one vinylaromatic monomer, e2) 4 to 96 wt. X, preferably 8 to 92 wt. % X and particularly preferably 10 to 90 wt. X of at least one monomer selected from the group of maleic anhydride, maleimide, (C1-C20 alkyl) acrylans and (C1-C20-alkyl) methacrylanes and e3) 0 to 50 wt. X, preferably 0 to 40, and particularly preferably 0 to 30 wt. X acrylonitrile.

Suitable vinylaromatic monomers a1) are styrene and styrene derivatives of the general formula (I) described for a21). Styrene and / or α-methylstyrene are preferably used. In the case of (C 1 -C 20 -alkyl) methacrylanes (one of the monomers e2), MMA is preferred. Particularly preferably, component E) is a copolymer of styrene and maleic anhydride, or of styrene and maleimide, or of styrene, maleimide and MMA, or of styrene, maleimide, MMA and acrylonitrile.

According to the invention, the monomers e1) to e3) are selected such that the polymer E) differs from the polymers B) and, if they are also present in the molding composition, C) and D). Polymers E) can serve to increase the heat resistance of the thermoplastic molding composition.

Component E) generally has a viscosity number VZ of 50 to 120 ml / g, preferably 55 to 110 ml / g. Component E) is obtained in a known manner by mass, solution, suspension, precipitation or emulsion polymerization. Details of these methods are described, for example, in the Kunststoffhandbuch, Hrg. R. Vieweg and G. Daumiller, Volume V Polystyrol, Carl-Hanser-Verlag Munich 1969, page 118 et seq.

Components F) are ingredients that are contained in the &quot;

• · ·

Λ * * * t,

24 thermoplastic molding compositions according to the invention with a proportion of 0 to 50 wt. %, Preferably 0.1 to 45 wt. % Z and particularly preferably 0.2 to 30 wt. Z, based on the sum of components A) and B) and, if present, C), D), E) and F).

Component F) includes lubricants or mold release agents, waxes, pigments, dyes, flame retardants, antioxidants, light and heat stabilizers, matte finishes, antitrophic agents, fibrous and powdered fillers or reinforcing agents or antistatic agents and additives , which are described, for example, by Gachter and Miiller, and the fourth also commonly used in Plastics Additives edition, Hanser Publ.,

Handbook, Ed. Munich, 1996, some examples or mixtures thereof. The following are listed

Suitable lubricants and demoulding agents are, for example, stearic acids, stearyl alcohol, stearic acid esters or amides, silicone oils, montan waxes and based on polyethylene and polypropylene.

Pigments are, for example, titanium dioxide, phthalocyanine, ultramarine blue, iron oxides or carbon black, as well as whole classes of organic pigments.

By coloring is meant any coloring agent which can be used for transparent, semi-transparent or non-transparent coloring of polymers, in particular those suitable for coloring styrenic polymers. Such dyes are known to those skilled in the art.

As flame retardants, for example, halogen- or phosphorus-binding compounds, magnesium hydroxide, as well as other compounds or mixtures thereof used, can be used. Red phosphorus is also suitable.

Suitable antioxidants are, in particular, sterically hindering single-chain or multi-chain phenolic antioxidants which may be substituted in various ways and may also be bridged by substituents. . These include, in addition to the monomeric ones, also oligomeric compounds which can be formed from a plurality of phenolic base bodies. Hydroquinones and hydroquinone analogs and substituted compounds as well as antioxidants based on tocopherolene and derivatives thereof are also contemplated. Mixtures of various antioxidants may also be used. In principle, all commercially available or suitable styrene copolymers such as Topanol &quot; or Irganox &quot; may be used.

So-called co-stabilizers, in particular phosphorous or sulfur-binding co-stabilizers, may be used together with the phenolic antioxidants mentioned above. Such phosphorus- or sulfur-binding stabilizers are known and commercially known to those skilled in the art.

Suitable stabilizers against, for example, various substituted benzotriazoles, benzophenones and HALS stabilizers) such as are commercially available from Tinuvin®.

Resorcine action, (hindered lights are salicylates, amine light receive for example as

Inorganic substances such as talc, glass beads or metal carbonates (such as MgCO3, CaCO3), as well as polymer particles, in particular spherical particles having diameters d50 over 1 [mu] m, based on methyl methacrylate, styrene compounds, acrylonitrile, are suitable as matt appearance agents. or mixtures thereof. It is also possible to use polymers which are polymerized containing acidic and / or basic monomers.

Suitable antitrophic agents are, for example, polytetrafluoroethylene polymers (Teflon ^fi ) and ultra-high molecular weight polystyrene (Mw molecular weight over 2,000,000).

As examples for fibrous or pulverized • · • ·

26 fillers mention carbon or glass fibers in the form of glass fabric, glass mat, glass strands, glass shavings, glass beads and wollastonite, particularly preferably glass fibers. When using fiberglass, adhesive means may be provided for better compatibility with other components. The incorporation of glass fibers can occur both in the form of short fibers and in the form of rovings.

amorphous powdered calcium

Suitable fillers are silicic acid, quartz carbonate, mica, bentonites, talc, silicates such as wollastonite and kaolin, carbon black, magnesium (chalk), feldspar or, in particular,

Suitable anti-statics are, for example, amine derivatives such as N, N-bis (hydroxyalkyl) alkylamines or alkylene amines, polyethylene glycol ester, copolymers of ethylene oxide and propylene oxide (especially diblock and triblock copolymers of ethylene oxide and propylene oxide blocks).

The individual additives are used in customary amounts, so there is no need to provide details.

For the manufacture of thermoplastic compositions, the following is indicated in detail.

Graft polymers with a bimodal particle size distribution are produced by the emulsion polymerization process as described for component A). The bimodal particle size distribution is adjusted as previously described by appropriate measures. The (partial) agglomeration of the polymer particles by the addition of an agglomerating acrylic polymer dispersion is preferred. Instead, or in combination with (sub) agglomeration, other conventional measures for the skilled person to adjust the bimodal particle size distribution may be taken.

The graft polymer dispersion A) obtained can either be directly mixed with components B) to F) or can be processed before. The second procedure is preferred.

The processing of the graft polymer dispersion A) takes place in a known manner. As usual, the grafted polymer A) is first precipitated from the dispersion, for example by the addition of a precipitating salt solution (e.g. calcium chloride, magnesium sulfate, alum) or acids (such as acetic acid, hydrochloric acid or sulfuric acid) or vitrification. It is also possible to precipitate with a high shear force, whereby a high shear force is produced, for example, by means of a rotor / stator system or by pressing the dispersion through a narrow slot. The aqueous phases may be separated in a conventional manner by sieving. by filtration, decantation or centrifugation. Said dispersion water separation results in a graft polymer A) having a residual water content of up to 60 wt. 2, based on A), whereby residual water, for example, can both be trapped on the graft polymer on the surface and also be enclosed therein.

The graft polymer can then be dried in a manner known per se, for example by warm air or by means of a jet dryer. It is also possible to process the dispersion in a spray drier.

According to the invention, the graft polymer A) is mixed in a blender with polymer B) and, if present, with other components C), D), E) and / or F) to form a polymer mixture in the form of a substantially liquid melt.

Substantially liquid melt means that the polymer blend may contain, in addition to the bulk of the liquid melt, a certain proportion of solid components, for example, non-molten filler or reinforcing agent, such as glass fibers, metal flakes or also non-molten pigments, dyes and the like. Liquid melt means that the polymer blend is at least viscous, thus soft at least to the extent that it has plastic properties.

Mixing devices are those known to those skilled in the art. For example, components A) and B) and, if present, C), D), E) and F) can be mixed by coextrusion, kneading or rolling, whereby components A) to F) have previously been isolated from solution if necessary. obtained by polymerization or from an aqueous dispersion.

If one or more components are mixed in the form of an aqueous dispersion or an aqueous or non-aqueous solution, the water or solvent is separated from the mixing device, preferably the extruder, by means of a degassing unit.

Mixing devices for carrying out the process according to the invention are, for example, discontinuously operating, heated internal mixers with or without punches, continuously operating mixers such as continuous internal mixers, axial oscillating screw augers, Banbury mixers, extruders and also rolling mills, mixing double rolls with heated rollers and calenders.

Preferably, an extruder is used as the mixing device. For example, single-shaft or double-shaft extruders are particularly suitable for melt extrusion. A twin-shaft extruder is preferred.

In many cases, the melting of the mixture is already caused by the mechanical energy introduced by the mixing device, so that the mixing device does not need to be heated. Otherwise, the mixing device is generally heated. The temperature is selected according to the chemical and physical properties of components A) and B) and, if present, C), D), E) and F), and is selected to form a polymer blend substantially in the form of a liquid melt. Otherwise, the temperature should not be unnecessarily high to prevent thermal damage to the polymer blend. However, the mechanical energy introduced can also be so high that the mixer must even be cooled. Usually the agitator is operated at a temperature of 150 to 300 ° C, preferably 180 to 300 ° C.

Preferably, the graft polymer A) is mixed with polymer B) and, if present, with components C), D), E) and / or F) in the extruder, wherein the graft polymer A) dispersion is metered without prior separation of dispersion water. directly into the extruder. Water is usually removed along the extruder by suitable degassing devices. As degassing devices, for example, degassing apertures may be used which are provided with auxiliary screws (which prevent the polymer mixture from escaping).

In a further, also preferred embodiment, the graft polymer A) is mixed with the polymer B) and, if present, the other components C), D), E) and / or F) in the extruder, wherein the graft polymer A) is first screened , filtering, decanting or centrifuging to separate the dispersed water. By separating the dispersion water, graft polymers A) with a residual water content of up to 60 wt.

relative to A), the residual water being trapped both on the surface of the grafted polymer and also enclosed therein. The residual water obtained can then be removed as described by means of steam extruder degassing devices.

In a particularly preferred embodiment, however, the residual water in the extruder is not only removed as steam, but a portion of the residual water is removed mechanically in the extruder and leaves the extruder in the liquid phase. Polymer B) and, if present, components C), D), E) and / or F) are fed into the same extruder so that the finished molding mixture is extruded as the product of the process. This method (squeezing method) is described in more detail below.

The dispersion water is first removed from the graft polymer, for example by sieving, pressing, filtering, decanting, sedimenting, centrifuging, or partially thermal drying. A partially dewatered graft polymer containing up to 60 wt. % residual water is fed to the extruder.

· • * * «» »»

The dosed material is conveyed by a screw against the barrier acting as a barrier, which is generally located at the end of the squeezing section. With this barrier, pressure is increased and water is pressed from the grafted polymer. The pressure can be increased according to theological ratios of rubber by varying the location of the screw elements, kneaders or other barrier elements. In principle, all commercially available pressure boosting elements are suitable.

Examples of possible barrier elements are:

- conveying screw transport elements,

- auger elements with an incline relative to the conveyor, including augers with large pitch conveyor threads relative to the conveyor,

- kneading blocks with kneading discs of different widths not intended for transport,

- kneading blocks with incline for return transport,

- kneading blocks with conveyor climb,

- cylindrical discs, cam discs and blocks formed therefrom,

- neutral brake discs (throttle plate),

- mechanically adjustable throttles (sliding sheath, radial throttle, central throttle).

Two or more barrier elements can also be combined with each other. Also, the barrier effect of the barrier zone can be adapted to the length and intensity of the action of the individual barrier elements to the grafted rubber.

In the described squeezing section, the worm elements which are located upstream of the barrier zone (upstream of the first barrier element) are generally formed as conventional conveying screws. In a preferred embodiment, conveyor worms are used, the pitch of which increases in the direction of the barrier zone, i.e. is steep. This embodiment causes a relatively slow pressure build-up, referred to as a compression zone which may be advantageous for the dewatering of rubber.

In a further preferred embodiment, the pressure build-up occurs without the preceding compression zone (i.e. the conveying screw in the squeezing zone has a constant pitch), thus immediately before or in the barrier zone, respectively.

In the squeezing section, preferably all design features and all operating parameters of the extruder are aligned such that, at the selected screw speed, the elastomeric material is transported and compressed, but does not plasticize or melt, or only to a small extent.

Preferably, the squeezing section of the extruder consists of screw elements with an incline with respect to the direction of transport and / or kneading blocks for the pressure build-up.

The water pressed from the grafted section leaves the extruder in the liquid phase and, less preferred, exits up to it as steam in this section.

polymer in the squeezer not as steam. V to 20 wt. % water

The squeezing section is provided with one or more drainage holes, generally at normal pressure. The term normal pressure means that the water exits from the drain hole at atmospheric pressure. The drain holes are preferably located on the top side of the extruder, but lateral or downward placement is also possible. Furthermore, the drainage holes are preferably provided with a device which prevents the conveyed graft polymer A) from emerging. Auxiliary screws are particularly preferred for this purpose.

The drain holes are formed in a known manner. Preferably, drainage apertures are used which are sized such that the apertures cannot be entrained by the contents of the extruder. Particularly preferably recesses or bores in the extruder barrel are used as drain holes.

In a particularly preferred embodiment, no colander jackets or similar, rapidly clogged components such as screens are used as drain holes. Colanders are, as already described, susceptible to clogging.

The drainage aperture belonging to the barrier elements is usually spaced at least one screw diameter, preferably in the range of 1 to 4 screw diameters and particularly preferably 1 to 2 screw diameters, upstream of the barrier element, or in the case of multiple barrier elements upstream of the first barrier element ). By spacing is meant the distance between the center of the drainage opening and the edge of the first drainage element.

The temperature of the exiting water is generally 20 to 95 ° C, preferably 25 to 70 ° C, measured at the outlet. In the first squeezing section, depending on the elastomer component and the initially existing residual water content, 10 to 90 wt. %, preferably 20 to 80 wt. % at the beginning of the residual water contained.

In a preferred embodiment, the extruder is not heated in the dosing sections and in the squeezing sections. In one embodiment, the extruder is cooled in these sections.

The partially dewatered graft polymer A) is conveyed through the barrier zone and proceeds to the next section of the extruder.

In a preferred embodiment for the production of many impact-resistant thermoplastics, the second squeezing section described above is followed by a second squeezing section, which again consists of a conveying section and a barrier zone acting as a barrier. This section is designed essentially in the same way as the first squeezing section, in particular also with respect to the distance of the drainage opening from the following barrier zone.

The compressed water usually leaves the extruder through all the drainage holes. Depending on the properties of the elastomer components and the residual water content, it is also possible for the water to be squeezed out

• · ·

33 extends from only one or some of the usable drainage openings and the other drainage openings are dry, thus draining no or almost no water. This does not appear to be disadvantageous.

A portion of the residual water which is not separated by mechanical pressing can be discharged in the usual manner through the extruder degassing device as steam.

Preferably, at least 30 wt. X extrudes residual water (which, for example, can be surface-retained on the graft polymer A) and / or encloses it in the extruder as liquid water. Typically, 30 to 90 wt. X removes residual water in liquid form by squeezing and 10 to 70 wt. The X is removed by means of degassing devices as steam.

In the process described, polymer B) and, if present, polymers C), D) and / or E) are fed in the form of a polymer melt. The polymer melt can be supplied by means of an extruder or technically simpler devices such as melt pumps or metering screws.

The polymer melt B) is fed to the extruder over the spinning sections. The mixture of the extruded but not yet melted graft polymer A) and the polymer melt is melted and homogenized in the following sections, which comprise mixing, kneading and / or other jacketing elements.

For more details on this process, see, for example, WO-A

98/13412.

If the extruder is used as a mixing device for components A) and B) and, if present, C), D), E) and F), then, as is generally known, different zones of the extruder can be individually heated or cooled to adjust optimum temperature profile along the worm shaft. Furthermore, it is common for the skilled person that normally the individual sections of the extruder may be different in different ways.

- 34 long.

Depending on the chemical and physical properties of components A) and B) and, if present, C), D), E) and F), and the ratio of the amounts thereof, the temperatures and lengths of the sections selected may vary. The same applies to the screw speed, which can vary within a wide range. For example, a screw speed of the extruder are given in the range of 100 to 350 min ^-1.

According to the invention, the polymer mixture produced essentially in the form of a liquid melt in the mixing device of components A) and B) and, if present, C), D), E) and F) is subjected to rapid cooling according to the invention.

Rapid cooling usually occurs by bringing the polymer mixture substantially in the form of a liquid melt (hereinafter abbreviated to as a polymer melt) in contact with a cold medium or a cold surface.

Here, cold means a temperature which is below the temperature of the polymer melt, so that the polymer melt is cooled rapidly upon contact. Therefore, in any case, cold does not mean cooled. For example, a 200 ° C hot polymer melt can be subjected to rapid cooling with water that has previously been heated to, for example, 30 to 90 ° C. Crucially, the difference between the temperature of the polymer melt and the temperature of the cold medium or the cold surface is sufficient to rapidly cool the melt.

It quickly means that the polymer melt is transferred from the liquid melt state to a solid state in the interval of 0 to 10 s, preferably 0 to 5 s, and particularly preferably 0 to 3 s, and cooled.

Preferably, the polymer melt is rapidly cooled with a cold medium. Such a medium may be gases or liquids.

• ·

Cold gas (hereinafter referred to as cooling gas) refers to cooled or non-cooled air or, in particular to oxidatively sensitive polymer melts, gases such as carbon dioxide, nitrogen or noble gases. Preferably, air or nitrogen is used as the cooling gas. Typically, the cooling gas is blown through the polymer melt emerging from the mixing beam

Organic and inorganic cooling fluids may be used as cold liquid media (hereinafter referred to as cooling fluid). Suitable organic fluids are, for example, oils and other high-boiling organic fluids which do not enter into chemical or physical interactions with the cooling polymer melt (swelling, dissolution and the like), i.e. are chemically and physically inert to the polymer melt.

Preference is given to using inorganic cooling fluids, in particular aqueous solutions and water. Particularly preferred is water which can be used chilled (freezing point to room temperature), non-cooled or tempered (room temperature to boiling point).

Typically, the coolant is injected onto the exiting polymer melt, or the polymer melt exits the mixer directly into the coolant bath. The cooling fluid can also be applied to the protruding polymer melt as a wide fluid jet.

Spraying the polymer melt with a cooling fluid is particularly advantageous when using film mixing devices (rolling mills, twin rollers and calenders). The polymer melt emerging as a film is solidified into the film by spraying with cooling fluid.

It is particularly preferred that the polymer melt emerges directly from the mixing device into the cooling fluid bath, in particular.

36 preferably into a bath of water.

It is also possible by polymerization to be tempered and, in many cases, the preferred melt exiting the mixing device first to contact the cooling gas, for example by blowing it with air or a shielding gas such as nitrogen, is to cool slightly. This only strengthens the outer surface of the melt, while the interior of the polymer remains liquid. The rapid cooling itself then occurs by contacting the melt previously solidified on the surface with a cooling fluid, for example water, whereby the interior of the melt also cures.

For example, the polymer melt strands exiting the die head of the extruder may first be surface-solidified by air-blowing, and the strands are then transferred to a water bath where self-cooling occurs.

The quench-cured polymer melt can be further processed by a person skilled in the art. As a rule, the solid polymer is ground by grinding, cutting, granulating or other processes.

In a particularly preferred embodiment, rapid cooling and grinding is performed according to the underwater granulation method. In underwater granulation, the polymer melt emerges from the mixing device through injection plates, the bores of which are preferably oval and which are preferably circular. The injection plates are placed under water (or other coolant) or the injection plates are sprayed with water (or other coolant), which can happen under shielding gas. Immediately downstream of the injection plates, a cutting device, preferably rotating blades, separating the exiting polymer is located on the outside thereof. The polymer is then rapidly separated from the rotating blade and cooled rapidly in water (or other cooling medium), whereby more or less oval, pearly grains are generally cured.

• ·

However, other than circular bore arrangements and non-circular bore forms may also be used in injection molds.

In another embodiment, the so-called underwater cord granulation is used. In this case, the melt emerges from the injection plate as a strand, and immediately a stream of water or coolant is used and thereby cooled rapidly, then the strand is guided by an inclined plane into a water bath or coolant bath and granulated after cooling.

In a particularly preferred embodiment, the extruder is used as a mixing device for components A) and B) and, if present, C), D), E) and F) with also the underwater granulation prescribed. version sprayed with knives.

After the extruder outlet orifice (water-injected) with cutting devices, is followed in this underwater (or especially rotating

Preference is given to thermoplastic molding compositions comprising the components A) and B) described above and, if present, C), D), E) and F) with butadiene as conjugated diene all) obtained

1) production of graft polymer A) by emulsion polymerization process, obtaining polymer A) with water moisture containing up to 60 wt. 2, referred to A), residual water,

2) the water-containing graft polymer A) is mixed with the other components B) to F) in an extruder to form a substantially melt of the polymer blend and wherein at least 30% by weight of the polymer mixture is formed; the residual water of the graft polymer A) is compressed by increasing the pressure in the extruder as liquid water,

3) rapidly cooling the substantially melt of the polymer blend by an underwater granulation process.

• · • ·

The thermoplastic molding compositions can be processed according to known methods of thermoplastic processing, e.g. by extrusion, injection molding, calendering, blow molding, compression molding or sintering.

The molding compositions according to the invention have good mechanical properties, in particular good toughness, also good cold toughness and an excellent toughness to strength ratio. It shows an improved transition to a brittle fracture. The molding compositions have a slight coloration (yellow color index YI <25), as well as a slight tendency to yellow and also yellow only slightly after prolonged storage in the heat or heat treatment. The molding compositions are further characterized by a high color depth during dyeing (low light scattering with a scattering value < 4.9).

DETAILED DESCRIPTION OF THE INVENTION

1. Production of graft polymer A)

1.1 Production of graft base al)

43120 g of the monomer mixture listed in Table 1 is polymerized in the presence of tert. dodecyl mercaptan (TDM), 311 g of potassium salt of C12-C20 fatty acids, 82 g of potassium persulfate, 147 g of sodium bicarbonate and 58400 g of water at 65 ° C for polybutadienelate. The amount of TDM is given in wt. %, based on the monomer mixture, as well as the order of addition of monomers and TDM are shown in Table 1 and the following procedure, respectively. Otherwise, the procedure was as described in EP-A 62901, Example 1, column 9, line 20 to column 10, line 6. The turnover was 95% or more. The mean particle size d 50 of the latex was 80 to 120 nm, the swelling index was more than 18. The NMR time T2 was 2.5 to 3.8 ms. The solids content was 41 wt. %.

Method:

• · • ·

Varinata 0: The batch contains 1 wt. % TDM, the total amount of styrene and n-butyl acrylate (if these comonomers were used) as well as butadiene, so that the charge was 16.6 wt. of the total amount of monomers. 1 hour after the start of polymerization, the remaining butadiene was dosed over 5 hours. TDM dosing was performed at the start of polymerization.

Option 1: A total amount of styrene and 20 wt.% Butadiene and 20 wt. X TDM. The remaining 80 wt. X of butadiene was dosed over 5 hours, with 20 wt. X of the remaining TDM.

Option 2: As variant 0, the TDM was dosed in three equal-sized doses at the beginning, middle and end of the remaining butadiene addition phase.

Option 3

As variant 0, but with 1.2 wt. X TDM.

Option 4: As variant 0, 0.5 wt. X TDM 10 min after the start of the addition of the remaining butadiene.

Option 5: Like variant 4, but the batch contains only so much butadiene that the batch is 12.5 wt. X the total amount of monomer.

Option 6: As for Option 3, but containing only so much butadiene that the charge was 12.5 wt. X the total amount of monomer.

Option 7: As variant 3, wherein the batch additionally contains 0.2 wt. X butadiene diacrylate.

Option 8: Saatlatex containing polystyrene particles with a particle size d 50 of 29 nm, water, buffer salt and persulfate

40 sodium (solids content 33%) was used in an amount such that the polystyrene content was 1.9 wt. % based on the graft base monomers a1). A monomer mixture containing 0.33 wt. % TDM and the total amount of monomer styrene and so much butadiene that the mixture was 16.6 wt. % of the total amount of monomer. The remaining butadiene was then dosed over 6.5 hours, after which 0.33 wt. % TDM.

To the agglomeration of the latex, 35000 g of the obtained latex was agglomerated at 65 ° C by adding 2870 g of a dispersion (10 wt.% Solids content) of 96 wt. % ethyl acrylate and 4 wt. % of methacrylic acid amide (partial agglomeration).

• ·

Table 1: Grafted foundation

monomers / wt. % / _. _ " WHAT - · O r — 4 O Properties L0 ÍN 73 •E r * 93 Γ-Μ » O "-and O 21 78 LO WHAT LO fy · uo what LO O »—T O 18 WHAT 88 ÍC ΙΓ x in σ \ uo O r — l 1-d ⁴³ 62 78 97 what O i — í O 12 CM what 78 K3 in O UO i — l O 23 76 78 CN Γ- σ * O what i — i O 14 06 / 82 K1 001 O O O 32 70 82 example butadiene styrene F G Π5 i — i λ: <3 i-i> -U 2 JQ 1 G regulator TDM ' wt. % / variant no. swelling index gel content /% / light scattering

• »

- 42 Table 1 - continued:

rC 100 ALIGN! O O - ÍN ΡΌ AND 1 K14 100 ALIGN! O O i — H r — i 29 72 77 K13 93.1 LO σ O r-4 WHAT WHAT ΓΟ t 1 K12 93 O- O 1.2 32 «3, Γ 87 Kil 93 r- O 1.2 41 99 98 K10 σι r * O 1 + 0.5 lo <0 ΓΜ * 3 * Γ 98 σ 93 r * O 1 + 0.5 31 66 85 ΚΘ 93 r * O 1.2 fO (N CM 79 S8 example oP G + J 0 ε λ G 0) ε 0 G 0 ε butadiene styrene j n-butyl acrylate ε and \ G cx G o \ o 0 4-> KO G -1 b G 0 tn ε 0) 45 G variant no. Properties 1 swelling index content of gel /% / light scattering

> 1

G

O ε

o c

o ε

o jx ιΰ

-ο oV

G +>

O ε

λ

LO

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• · ·

- 43 9300 S conduct

1.2 Production of the washer a2)

To the agglomerated latex was added

130 g of potassium salt of C12-C20 fatty acids and 17 g of potassium persulphate. Subsequently, one of the following variants is followed:

Grafting Variation 1: 8970 g of the graft monomer mixture listed in Table 2 was added at 75 ^° C over 4 hours with stirring.

Grafting Option 2: The total amount of graft monomer mixture listed in Table 2 was 8970 g. % of the total amount of graft monomers. After a 30 minute residence time, a monomer mixture of the remaining styrene and total acrylonitrile and methyl methacrylane, respectively, was added over 2 hours.

Grafting variant 3: As grafting varinata 1, 0.5 wt. % TDM.

The turnover, based on the grafting monomers, was almost quantitative after a further 2 hours.

The resulting graft polymer dispersion having a bimodal particle size distribution has a mean particle size d 50 of 150 to 350 nm and a d 90 of 400 to 600 nm. The first maximum particle size distribution lies in the range 50 to below 150 nm, the second maximum in the range 200 to 600 nm. The density of the smaller graft polymer particles (first maximum 50 to below 150 nm) was 0.90 to 0.93 g / cm ³ , the density of large particles (second maximum 200 to 600 nm) was 0.96 to 0.98 g / cm ³ .

The obtained dispersion was added to the aqueous antioxidant dispersion and then coagulated by the addition of magnesium sulfate solution. The coagulated rubber was centrifuged from dispersion water and washed with water. Rubber with about 30 wt. % on the surface or inside the trapped residual water.

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46 2. Production of Polymers B), C), D) and E) to E) were produced as described in G. Daumiller, Vol. V 1969, pp. 122-124.

Thermoplastic polymers B) by continuous solution polymerization, Kunststoff-Handbuch, Hrg. R. Vieweg and Polystyrol, Carl-Hanser-Verlag Miinchen Table 3 summarizes the composition and properties.

Table 3: Components B) to D)

component BI B2 B3 Cl C2 Dl monomers (wt. X) styrene 75 75 0 75 75 67 α-methylstyrene 0 0 70 0 0 0 acrylonitrile 25 25 30 25 25 33 viscosity number VZ (ml / g) 67 80 80 80 100 ALIGN! 60

The E1 component consists of a copolymer of 63 wt. % styrene, 13 wt. % acrylonitrile and 25 wt. % Of N-phenylmaleinimide with a thermal shape stability of Vicat B of 144 ° C.

Component E2 consists of a copolymer of 59 wt. % styrene and 41 wt. % N-phenyl malimide.

3. Production of component F

Component F1 wt. % Of the titanium dioxide pigment and 40 wt. X component B2 was mixed on a kneader, plotted and granulated after cooling.

4. Manufacturing and blending • fc * v ·······

4.1. Mixing After Pre-drying the Graft Rubber A), Examples 1 and 2

Pfleiderer, power 10 kg / h.

ZSK 30, the residual water was components b) to the company Werner und a speed of 250 min ^-1 and was extruded at a melt

The graft rubber A) containing the vacuum-dried hot air and the other F) mixed in an extruder, type at 250 ° C The polymer blend molding mixture was subjected to rapid cooling, in which it was introduced into a water bath of 30 ° C. The cured molding mixture was granulated.

4.2.

Mixing without prior drying Examples 3 to 35V graft rubber A),

The graft rubber A) containing the residual water was fed into a ZSK extruder of the Werner und Pfleiderer type, whose two screw conveyors were fitted with barriers to increase the pressure at the front. Much of the residual water was mechanically pressed in this way and left the extruder in liquid form through the drainage holes. The other components B) to F) were introduced into the extruder as a melt downstream of the barrier zone and mixed with the dewatered component A). The remaining residual water was discharged through steam outlets at the rear of the extruder as steam. The extruder was run at a speed of 250 min ^-1 and the output of 80 kg / hour, or 250 kg / h, and was accordingly selected radius of the extruder screw.

The molding mixture was extruded and the melt of the polymer mixture was subjected to rapid cooling. Rapid cooling was carried out in Examples 7 to 28 by underwater granulation with a GALA underwater granulator: the extruder injection plate was placed under water at a water temperature of 60 ° C. The polymer emerging as the melt strand into the water bath was separated by rotating blades which were placed immediately on the outside of the injection plate. Pearled polymer grains were obtained.

«4

In Examples 3 to 6 and 29 to 35V, rapid cooling occurred as follows: the extruder injection plate was placed in the immediate vicinity of a 30 ° C water bath. The melt strand emerging from the injection plate was briefly guided through the air and then introduced directly into the water bath to cool rapidly. The cooled strands were granulated on a conventional granulator.

The components used and their amounts are listed in Tables 4 to 7.

5. Measurements made

Swelling index of the grafting base: a film was formed from the aqueous dispersion of the grafting base by evaporating water. To 0.2 g of this film was added 50 g of toluene. After 24 hours, toluene was aspirated from the swollen assay and the assay was weighed. After drying the test under vacuum at 110 ° C for 16 hours, the test was reweighed. Calculation was performed:

swollen weight, aspirated test swelling index QI = ---------------------------------- vacuum dried test weight test weight vacuum dried gel content = -------------------------------- 100% weight test before swelling

Rubber latex particle sizes:

The mean particle size d is the weight average particle size as determined by an analytical ultra centrifuge by W. Scholtan and H. Lange, Kolloid-Z. und Z.-Polymere 250 (1972) pages 782-796. The centrifuge measurement provides an integral weight distribution of the particle diameter of the assay. From this it is possible to determine how much weight

percent of the particles have a diameter equal to or less than a specified size.

The d 10 value indicates the diameter of the particles for which 10 wt .-%, all particles have a smaller diameter and 90 wt .-%. for the dao value, 90 wt. 2 10 wt. 2 larger diameter than Mass median larger diameter. Conversely, all particles have a smaller diameter that corresponds to the particle d 50, or the diameter and d 90 the volume mean diameter D 50 of the particles indicates the particle diameter at which it has 50 wt. 2 and 50 vol. 2 of all particles of larger diameter and 50 wt. 2 and 50 vol. The d 10, d 50 and d 90 values characterize the width Q of the particle distribution, with Q = (d 90 -d 10) / d 50. The smaller the Q, the narrower the distribution.

Cas T2: T2 time was measured by NMR relaxation of a dewatered and film-generated assay. Therefore, after venting overnight, the test was dried at 60 ° C for 3 hours under vacuum and measured with a Brucker apparatus at 80 ° C.

Yellow YI Index: The yellow YI index was determined by determining the color coordinates X, Y, Z according to DIN 5033 under standard light D 65 and 10 ° by a common observer according to the following equation:

YI = (131.48 X 116 116.46 Z) / Y

Viscosity number VZ: It was determined according to DIN 53726 to 0.5 wt. 2 of a solution of the polymer in dimethylformamide.

MVR Melting Index: Determined according to DIN 53735/30 at a melt temperature of 220 ° C and a load of 10 kg or 21.6 kg.

For the determination of the following mechanical and gloss values, test specimens of standard small bars (see DIN 53453), stepped bars, round disks with a diameter of 60 mm and a thickness of 2 mm were manufactured from the granulate by injection molding.

- 50 and rectangular blades, respectively, 2 mm thick. The melt temperature was 250 ° C and the molding temperature 60 ° C unless otherwise stated.

Gloss: Determined according to ISO 2813 on 40 x 60 mm rectangular disks at a 45 ° irradiation angle with a Byk measuring device.

ak: Charpy notch toughness ax was determined on standard small bars by bending impact test according to ISO 179-2 / leA (S) at 23 ° C, 10 ° C and -30 ° C.

an: Charpy impact resistance an was determined on standardized small bars according to ISO 179-2 / 1fU at -30 ° C.

Vicat: Vicat thermal shape stability was determined according to ISO 306 / B by a load of 50 N and a heating of 50 K / h.

aD: extrusion work ap was determined according to ISO 6603-2 on oval wheels or rectangular wheels 40 x 40 mm by plastic-test at -30 ° C and 23 ° C, the test specimens being produced at a melt temperature of 220, 250 and 280 ° C .

The tensile strength, ductility, and modulus of elasticity E were determined according to ISO 527 on bars fitted at 23 ° C.

Light scattering and absorption: granules were made by injection molding at a melt temperature of 240 ° C and a molding temperature of 80 ° C of the step plate, with a thinner step being 1 mm thick and a thicker step being 2 mm thick. Step plates were measured over both white and black background by spectral photometer VIS (Ultrascan from Hunter) to determine scattering and absorption. Specific absorption and scattering at 400 to 700 nm wavelengths were calculated using the BCS color measurement system.

6. Measurement results «· * ·» ·· »·» · # «

- 51 - 9 · c * · «« · Fc e · · · · The results of the measurements are summarized in the tables 4 to 7. Tables 4 and 6 contain mixtures of different component A and different B. Table 5 contains mixtures components A8 p different

B. components

Table 7 shows the composition of the invention and, for comparison, a molding composition not according to the invention with the same rubber content.

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- 55 Table 4 - continued:

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Table 5: Mixtures and measurement results. The indicated amounts of components are in wt. parts

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Table 6 - continued:

33 O 04 / < m OJ 57.5 B1 19.0 1— ( 1 1 59 25 1 1 32 45.4 Λ19 54.6 B1 23.2 30 1 1 1 O* OJ 28 AND 31 44.0 A18 56.0 B1 24.6 37 1 1 1 30 29 1 1 30 27.6 A17 72.4 B1 22.0 22nd what 96 12 1 1 22nd 3.35 0.039 29 29.5 A16 70.5 B1 22.1 22nd 1 100 ALIGN! 12 AND 43 3.15 0.049 28 27.0 A15 73.0 B2 22.8 23 1 100 ALIGN! O- 1 38 2.83 0.044 example component A component B YI yellow index CM 2 \ * at 0 m 04 / \ AT 0 O in 04 / (0 CM Ξ ►o O 0 O m 1 O O O 04 / Hi fC υ C -AT ti 0 • H > C Ή = O rS \ ε CM O \ O 04 / Oi W > 2 C -H ε O t-H \ £ CM O cH 04 / \ O 04 / 04 / H > 2 sT with • H O C m 04 / \ O 0 C in 04 / □ <0 light scattering absorption, /% / _

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Table 7: Mixtures and measurement results are in wt. parts

Component quantity data

example 34 35V (comparison) component A 29,9 A8 30,1 A5 component B 70,1 Bl 0 component D 0 69,9 Dl index YI 18.1 38.4 au (250 ° C / 23 ° C) ¹ > (kJ / m ² ) 21 17 ax (250 ° C / 100 ° C) ¹ > (kJ / m ² ) 19 Dec 12 ax (250 ° C / -30 ^° C) ¹ ) (kJ / m ² ) 8 6 Vicat (° C) 97 99 MVR 220/10 ² ) (ml / 10 min) 18 16 o (250 ° C / 23 ° C) ¹ ) (N / m) 31 25 light scattering 3.6 - absorption (%) 0,036 0,080

¹ > melt temperature / test temperature ² > melt temperature ( ⁰ C) / load (kg) not determined

The tables show that the molding compositions according to the invention have a slight coloration (a small yellow cattle YI index below 25 and an absorption below 0.1%) and are well colorable (light scattering below 4.9). At the same time, the molding compositions according to the invention are tough, also when cold (high values of an, ak and ao) and can be varied within a wide range in terms of flowability (MVR value).

Table 7 provides a direct comparison of two molding compositions having an identical rubber content of 30 + 0.1 wt. %. The molding composition according to the invention of Example 34 contains as polymer SAN a polymer B1 with a low acrylonitrile content of 25 wt. %. A molding composition which is not according to the invention.

60 of the invention according to Example 35V, comprises acrylic nitrile rich polymer D1 with 33 wt. % acrylonitrile.

The molding composition according to the invention according to Example 34 has a considerably lower yellowness index value (18.1 instead of 38.4) and at the same time has a significantly better notched toughness (as of 21/19/8 kJ / m ² instead of 17/12/6 kJ) m ² , aD 31 instead of 25 N / m at 23 ° C).

Compared to the prior art molding compositions, the notch toughness of the molding compositions of the invention is not only comparable, but clearly better. The achieved minimization of coloration thus does not lead to a deterioration of the mechanical properties, but rather to an improvement thereof.

Claims (3)

PATENT CLAIMS A thermoplastic molding composition comprising as components A) to F), A) 5 to 80 wt. % of graft polymer A) with a bimodal particle size distribution, z, based on A), a1) of 40 to 90 wt. % of the rubber-elastic particulate graft base a1) obtained by polymerization based on a1), all) 70 to 100 wt. % of at least one conjugated diene, a12) 0 to 30 wt. % of at least one additional monoethylenic unsaturated monomer and a13) 0 to 10 wt. X, preferably 0.01 to 5 wt. % and particularly preferably 0.02 to 2 wt. % of at least one polyfunctional, crosslinked monomer, a2) 10 to 60 wt. X of graft substrate a2) z, based on a2), a21) 65 to 95 wt. % of at least vinylaromatic monomer, a22) 5 to 35 wt. % of acrylonitrile, a23) 0 to 30 wt. % of at least one additional monoethylenic unsaturated monomer and a24) 0 to 10 wt. X, preferably 0.01 to 5 wt. % and particularly preferably 0.02 to 2 wt. X of at least one polyfunctional, crosslinked monomer, B) 20 to 95 wt. % of thermoplastic polymer B) with a viscosity number VZ (determined according to DIN 53726 at 25 ° C, 0.5 wt.% of dimethylformamide) 50 to 120 ml / g z, based on B), b1) 69 to 81 wt. X2 of at least one vinylaromatic monomer, b2) 19 to 31 wt. B3) 0 to 30 wt. X of at least one other monoethylenically unsaturated monomer, C) 0 to 50 wt. X of a thermoplastic polymer C) having a viscosity number VZ of 50 to 120 ml / g z, based on C), · · · · · · ······· 62 (cl) 69 to 81 wt. % of at least one vinylaromatic monomer, c2) 19 to 31 wt. c3) 0 to 30 wt. % of at least one other monoethylenically unsaturated monomer, wherein components B) and C) differ in their VZ viscosity number by at least 5 units (ml / g), or differ in their acrylonitrile content by at least 5 units (wt%), or differ in both characters, the viscosity number VZ and the alkylnitrile content by at least 5 units, D) 0 to 95 wt. % of thermoplastic polymer D) z, based on D), d1) 63 to below 69 wt. % of at least one vinylaromatic monomer, d2) over 31 to 37 wt. % of acrylonitrile, d3) 0 to 40 wt. % of at least one other monoethylenically unsaturated monomer, E) 0 to 50 wt. % thermoplastic polymer E) z, based on E), e1) 4 to 96 wt. % of at least one vinylaromatic monomer, e2) 4 to 96 wt. % of at least one monomer selected from the group of methyl methacrylate, maleic anhydride and maleimide; and (e) 0 to 50 wt. % of acrylonitrile, wherein polymer E) is different from polymers B) and, if present, C) and D), F) 0 to 50 wt. % of the additives F) obtained 1) production of graft polymers A) by emulsion polymerization process, 2) mixing the graft polymer A) with polymer B) and, if present, with other components C), D), E) and / or F), in a mixing device to form a substantially molten liquid polymer mixture, 3) rapidly cooling the substantially molten liquid polymer; - 63 mixture. The thermoplastic molding composition of claim 1, wherein the conjugated diene (a) is butadiene. Thermoplastic molding composition according to claim 1 or 2, wherein the inylaromatic monomer a21) and b1) and also if components C), D) and / or E), c1), d1) and e1) are comprised of styrene. or α-methylstyrene or a mixture of styrene and d-methylstyrene. Thermoplastic molding composition according to claims 1 to 3, wherein the graft substrate a2), based on a2), consists of a21) 75 to 85 wt. % of styrene and / or d-methylstyrene, and 22) 15 to 25 wt. The acrylonitrile and thermoplastic polymer B), based on B), consist of b1) from 71 to 78 wt. From styrene, b2) 22 to 29 wt. From acrylonitrile. Thermoplastic molding composition according to claims 1 to 4, wherein the monoethylenic unsaturated monomer a1) is composed of styrene or n-butyl acrylate or a mixture thereof. The thermoplastic molding composition of claim 5, wherein a portion of the styrene in the polymerized form is polymerized as polystyrene grafted latex and the other portion of the styrene is polymerized as monomer styrene. The thermoplastic molding composition according to claims 1 to 6, wherein the bimodal particle size distribution of the grafted polymer A) has two maxima which lie both for a particle size of 25 to 200 nm and for a particle size of 150 to 800 nm. Thermoplastic molding composition according to claims 1 to 7, wherein the bimodal particle size distribution of the grafted polymer A) is formed by agglomeration of the polymer particles. The thermoplastic molding composition according to claims 1 to 8, wherein in the first process step 1} a graft base a1) is produced in an emulsion using at least one molecular weight regulator. The thermoplastic molding composition according to claims 1 to 9, wherein in the first process step 1) the grafted substrate a2) is produced in emulsion using at least one molecular weight regulator. Thermoplastic molding composition according to claims 1 to 10, wherein the grafted substrate a2) comprises polyfunctional crosslinked monomers a24) and is produced in an emulsion using at least one molecular weight regulator. Thermoplastic molding composition according to claims 1 to 11, wherein the grafted substrate is formed from two stages of different monomer compositions. 13. Thermoplastic molding in step 1) a mixture according to claims 1 to 11 receives the graft polymer X residual water, referred to 12, wherein A), on who A). contains up to 60 wt. 14. Thermoplastic molding a mixture according to claims 1 to 11 13, where In the second process step 2), an extruder is used as the mixing device, wherein at least 30 wt. The residual water of graft polymer A) is extruded in the extruder as liquid water. The thermoplastic molding composition according to claims 1 to 3 is used in the third process step 3) for cooling underwater granulation using another cooling fluid. 14, where rapid water or The thermoplastic molding composition according to claims 1 to 14, wherein in the third process step 3), the melt of the polymer composition exits under air or a shielding gas and then rapidly sweeps. 9 9 9 9 - 65 is cooled by contact with water or other coolant. A method for producing a thermoplastic molding composition according to claims 1 to 16, characterized in that it is performed under the process conditions of claim 1. Use of the thermoplastic composition according to claims 1 to 16 for the production of moldings. Molding made from a thermoplastic molding composition according to claims 1 to 11.