EP2084231A1 - Molding materials comprising highly crosslinked organic nanoparticles - Google Patents

Abstract

Thermoplastic molding materials comprising A) from 10 to 99.9% by weight of a thermoplastic polymer, B) from 0.01 to 10% by weight of a copolymer obtainable by free-radically initiated aqueous emulsion polymerization of ethylenically unsaturated monomers in the presence of at least one dispersant and of at least one free-radical initiator by the feed process, wherein, for the emulsion polymerization, from 70 to 99.5% by weight of a,b-monoethylenically unsaturated compounds [monomers A], and from 0.5 to 30% by weight of compounds with at least two free-radically copolymerizable ethylenically unsaturated groups [monomers B], and optionally up to 5% by weight of a,b-monoethylenically unsaturated mono- or dicarboxylic acids having from 3 to 6 carbon atoms and/or amides thereof [monomers C] are used, where the monomers A to C add up to 100% by weight (total amount of monomers) and the monomer feeds are effected such that ≥ 60% by weight of the total amount of monomers B is added to the polymerization mixture under polymerization conditions at a time after which ≥ 60% by weight of the total amount of monomers has been metered into the polymerization mixture under polymerization conditions, C) from 0 to 70% by weight of further additives, where the sum of the percentages by weight of components A) to C) adds up to 100%.

Description

 Molding compounds with highly crosslinked organic nanoparticles

description

The invention relates to thermoplastic molding compositions comprising

A) 10 to 99.9% by weight of a thermoplastic polymer,

B) 0.01 to 10 wt .-% of a copolymer obtainable by free-radically initiated aqueous emulsion polymerization of ethylenically unsaturated monomers in

Presence of at least one dispersant and at least one free radical initiator according to the feed process, wherein for the emulsion polymerization

From 70 to 99.5% by weight of α, β-monoethylenically unsaturated compounds [monomers A], and

0.5 to 30% by weight of compounds having at least two free-radically copolymerizable ethylenically unsaturated groups [monomers B], and optionally up to 5% by weight of α, β-monoethylenically unsaturated monosubstituted 3 to 6 C atoms. or dicarboxylic acids and / or their amides [monomers C],

can be used, wherein the monomers A to C add to 100 wt .-% (total monomer) and the monomer feeds are such that> _ added 60 wt .-% of the total amount of monomers B to the polymerization under polymerization conditions at a time are added after the polymerization mixture> 60 wt .-% of the total amount of monomers under polymerization conditions,

C) 0 to 70% by weight of further additives,

wherein the sum of the weight percentages of components A) to C) is 100%.

Furthermore, the invention relates to the use of the molding compositions for the production of moldings of any kind and the moldings obtainable in this case.

Examples of inorganic nanoparticles in thermoplastics (PBT) include i.a. Layered silicates (JP-A 03/62856) with a high aspect ratio.

Spherical particles are known for example from WO 2001/72881, organically modified particles of this form are known from WO 2005/82994. The addition of the nanoparticles should in particular improve the mechanical properties of thermoplastics.

The recent patent application DE-A 10 2006 020275.9 proposes new processes for the preparation of aqueous copolymer dispersions which have a lower coagulum content.

Uses include the production of adhesives, sealants, plastic plasters, paper coating slips, nonwoven fabrics, paints, and as coating agents.

It is an object of the present invention to provide thermoplastic molding compositions (in particular polyesters and polyamides) which have improved mechanical properties.

Accordingly, the molding compositions defined above were found.

Preferred embodiments are given in the dependent claims.

Basically, the beneficial effect of plastics of any kind. An enumeration of suitable thermoplastics A) can be found for example in the plastic paperback (Hrsg. Saechtling), edition 1989, where sources are also called. Processes for the production of such thermoplastics are known per se to the person skilled in the art. Some preferred types of plastic will be explained in more detail below, with polyamides and polyesters being preferred.

1. Polyoxymethylene homopolymers or copolymers

Such polymers are known per se to the person skilled in the art and are described in the literature.

Generally, these polymers have at least 50 mole percent of repeating units -CH 2 O- in the polymer backbone.

The homopolymers are generally prepared by polymerization of formaldehyde or trioxane, preferably in the presence of suitable catalysts.

In the context of the invention, preference is given to polyoxymethylene copolymers as component A, in particular those which, in addition to the repeating units -CH 2 O-, also contain up to 50, preferably 0.1 to 20, in particular 0.3 to 10, mol% and very particularly preferably 2 to 6 mol% of recurring units -O-CC- (R ⁵ ) - R ¹ R ⁴

where R ¹ to R ⁴ independently of one another are a hydrogen atom, a C 1 - to C ₄ -alkyl group or a halogen-substituted alkyl group having 1 to 4 C atoms and R ^{5 is} a -CH 2 -, -CH 2 O-, a C 1 - to C ₄ -function Alkyl or Ci to C4-haloalkyl substituted methylene group or a corresponding oxymethylene group and n has a value in the range of 0 to 3. Advantageously, these groups can be introduced into the copolymers by ring opening of cyclic ethers. Preferred cyclic ethers are those of the formula

wherein R ¹ to R ⁵ and n have the abovementioned meaning. Only examples are ethylene oxide, 1, 2-propylene oxide, 1, 2-butylene oxide, 1, 3-butylene oxide, 1, 3-dioxane, 1, 3-dioxolane and 1, 3-dioxepane called cyclic ethers and linear oligo- or polyformals such as polydioxolane or polydioxepan called comonomers.

Also suitable as component A) are oxymethylene terpolymers which are, for example, by reaction of trioxane, one of the cyclic ethers described above, with a third monomer, preferably bifunctional compounds of the formula

CH ₂ -CH-CH ₂ -Z-CH ₂ -CH-CH ₂

O O

and or

wherein Z is a chemical bond, -O-, -ORO- (R = Ci to Cs-alkylene or C3 to Cs-cycloalkylene) are prepared.

Preferred monomers of this type are ethylene diglycide, diglycidyl ether and diether from glycidylene and formaldehyde, dioxane or trioxane in a molar ratio of 2: 1 and diether from 2 mol glycidyl compound and 1 mol of an aliphatic diol having 2 to 8 carbon atoms such as the diglycidyl ethers of ethylene glycol, 1, 4-butanediol, 1, 3-butanediol, cyclobutane-1, 3-diol, 1, 2-propanediol and cyclohexane-1, 4-diol, to name just a few examples.

Processes for the preparation of the homopolymers and copolymers described above are known to the person skilled in the art and described in the literature, so that further details are unnecessary here.

The preferred polyoxymethylene copolymers have melting points of at least 150 ^° C. and weight average molecular weights M _w in the range of 5,000 to 200,000, preferably 7,000 to 150,000.

End-group stabilized polyoxymethylene polymers having C-C bonds at the chain ends are particularly preferred.

2. polycarbonates and polyesters

Suitable polycarbonates are known per se. They are e.g. in accordance with the processes of DE-B-1 300 266 by interfacial polycondensation or according to the process of DE-A-14 95 730 by reacting biphenyl carbonate with bisphenols. Preferred bisphenol is 2,2-di (4-hydroxyphenyl) propane, generally - as hereinafter referred to as bisphenol A.

Instead of bisphenol A, it is also possible to use other aromatic dihydroxy compounds, in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxy-naphthalene, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenyl ether, 4,4 'Dihydroxydiphenylsulfit, 4,4'-dihydroxydiphenylmethane, 1, 1-di- (4-hydroxyphenyl) ethane or 4,4-dihydroxydiphenyl and mixtures of the aforementioned dihydroxy compounds.

Particularly preferred polycarbonates are those based on bisphenol A or bisphenol A together with up to 30 mol% of the abovementioned aromatic dihydroxy compounds.

The relative viscosity of these polycarbonates is generally in the range of 1, 1 to 1, 5, in particular 1, 28 to 1, 4 (measured at 23 ° C in a 0.5 wt .-% solution in dichloromethane).

Suitable polyesters are also known per se and described in the literature. They contain an aromatic ring in the main chain derived from an aromatic dicarboxylic acid. The aromatic ring may also be substituted, for example by halogen, such as chlorine and bromine, or by C 1 -C 4 -alkyl groups, such as methyl, ethyl, i- or n-propyl and n, i and tert-butyl groups. The polyesters can be prepared by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives thereof with aliphatic dihydroxy compounds in a manner known per se.

Such polyalkylene terephthalates are known per se and described in the literature. They contain an aromatic ring in the main chain derived from the aromatic dicarboxylic acid. The aromatic ring may also be substituted, e.g. by halogen, such as chlorine and bromine, or by C 1 -C 4 -alkyl groups, such as methyl, ethyl, isopropyl or n-propyl and n, i and t-butyl groups.

These polyalkylene terephthalates can be prepared by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxy compounds in a manner known per se.

Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof. Up to 30 mol%, preferably not more than 10 mol% of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids.

Of the aliphatic dihydroxy compounds are diols having 2 to 6 carbon atoms, in particular 1, 2-ethanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-hexanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol and neopentyl glycol or their mixtures preferred.

Particularly preferred polyesters (A) are polyalkylene terephthalates which are derived from alkanediols having 2 to 6 C atoms. Of these, preference is given in particular to polyethylene terephthalate and polybutylene terephthalate or mixtures thereof, it also being possible to use polyethylene terephthalate as a recyclate of up to 50% by weight, based on A).

The viscosity number of the polyesters (A) is generally in the range from 60 to 220, preferably from 100 to 150 ml / g (measured in a 0.5% strength by weight solution in a phenol / o-dichlorobenzene mixture (wt. Ver. 1: 1 at 25 ° C).

Particular preference is given to polyesters whose carboxyl end group content is up to 100 meq / kg, preferably up to 50 meq / kg and in particular up to 40 meq / kg of polyester. Such polyesters can be prepared, for example, by the process of DE-A 44 01 055. The carboxyl end group content is usually determined by titration methods (eg potentiometry). Another group to be mentioned are fully aromatic polyesters derived from aromatic dicarboxylic acids and aromatic dihydroxy compounds.

Suitable aromatic dicarboxylic acids are the compounds already described for the polyalkylene terephthalates. Preference is given to mixtures of 5 to

100 mol% isophthalic acid and 0 to 95 mol% terephthalic acid, in particular mixtures of about 80% terephthalic acid with 20% isophthalic acid to about equivalent mixtures of these two acids used.

The aromatic dihydroxy compounds preferably have the general formula

in which Z represents an alkylene or cycloalkylene group having up to 8 C atoms, an arylene group having up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in the m the value 0 to 2 has. The compounds may also carry C 1 -C 6 -alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents on the phenylene groups.

As a parent of these compounds his example

dihydroxydiphenyl,

Di (hydroxyphenyl) alkane,

Di (hydroxyphenyl) cycloalkane, di (hydroxyphenyl) sulfide,

Di (hydroxyphenyl) ether,

ketone di- (hydroxyphenyl),

Di (hydroxyphenyl) sulfoxide, α, α'-di (hydroxyphenyl) dialkylbenzene, di (hydroxyphenyl) sulfone, di (hydroxybenzoyl) benzene

Resorcinol and

Hydroquinone and their nuclear alkylated or ring-halogenated derivatives called.

Of these will be

4,4'-dihydroxydiphenyl,

2,4-di- (4'-hydroxyphenyl) -2-methylbutane α, α'-di- (4-hydroxyphenyl) -p-diisopropylbenzene,

2,2-di (3'-methyl-hydroxyphenyl) propane and 2,2-di (3'-chloro-4'-hydroxyphenyl) propane, and in particular

2,2-di (4'-hydroxyphenyl) propane 2,2-di (3 ', 5'-dichlorodihydroxyphenyl) propane, 1,1-di- (4'-hydroxyphenyl) cyclohexane, 3,4'-dihydroxybenzophenone , 4,4'-dihydroxydiphenylsulfone and 2,2-di- (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane or mixtures thereof.

Of course, it is also possible to use mixtures of polyalkylene terephthalates and wholly aromatic polyesters. These generally contain 20 to

98 wt .-% of the polyalkylene terephthalate and 2 to 80 wt .-% of wholly aromatic

Polyester.

Of course, polyester block copolymers such as copolyetheresters may also be used. Such products are known per se and are known in the literature, e.g. in US Pat. No. 3,651,014. Also in the trade, corresponding products are available, e.g. Hytrel® (DuPont).

Preferred dicarboxylic acids are naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof. Up to 10 mol% of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids.

Of the aliphatic dihydroxy compounds, diols having 2 to 6 carbon atoms, in particular 1, 2-ethanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-hexanediol, 1, 4-cyclohexanediol and neopentyl glycol or mixtures thereof are preferred.

Particularly preferred polyesters include polyalkylene terephthalates derived from alkanediols having 2 to 6 C atoms. Of these, particularly preferred are polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate.

The viscosity number of the polyesters is generally in the range from 60 to 200 ml / g (measured in a 0.5% strength by weight solution in a phenol / o-dichlorobenzene mixture (weight ratio 1: 1) at 23 ° C. ).

3. polyolefins

Polyethylene and polypropylene as well as copolymers based on ethylene or propylene, if appropriate also with higher α-olefins, may be mentioned here in general. decision Speaking products are available under the trade names Lupolen® or Hosta- Ien® / Moplen® from BASELL.

4. polymethacrylates

These include, in particular, polymethyl methacrylate (PMMA) and copolymers based on methyl methacrylate with up to 40% by weight of further copolymerizable monomers, such as those obtainable, for example, under the name Plexiglas®.

5. Polyamides

The polyamides of the molding compositions according to the invention generally have a viscosity number of 90 to 350, preferably 1 10 to 240 ml / g, determined in a 0.5 wt .-% solution in 96 wt .-% sulfuric acid at 25 ° C according to ISO 307.

Semicrystalline or amorphous resins having a weight average molecular weight of at least 5,000, e.g. U.S. Patents 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,312,966, 2,512,606 and 3,393,210 are preferred.

Examples include polyamides derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam and polyamides obtained by reacting dicarboxylic acids with diamines.

As dicarboxylic acids alkanedicarboxylic acids having 6 to 12, in particular 6 to 10 carbon atoms and aromatic dicarboxylic acids can be used. Here only adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acid are mentioned as acids.

Suitable diamines are, in particular, alkanediamines having 6 to 12, in particular 6 to 8, carbon atoms and also m-xylylenediamine, di (4-aminophenyl) methane, di (4-aminocyclohexyl) methane, 2,2-di (4- aminophenyl) propane or 2,2-di (4-aminocyclohexyl) propane.

Preferred polyamides are polyhexamethylene adipamide, polyhexamethylene sebacamide and polycaprolactam and copolyamides 6/66, in particular with a content of 5 to 95 wt .-% of caprolactam units.

In addition, polyamides may also be mentioned which are obtainable, for example, by condensation of 1,4-diaminobutane with adipic acid at elevated temperature (polyamide). 4.6). Production processes for polyamides of this structure are described, for example, in EP-A 38 094, EP-A 38 582 and EP-A 39 524.

Furthermore, polyamides which are obtainable by copolymerization of two or more of the abovementioned monomers or mixtures of a plurality of polyamides are suitable, the mixing ratio being arbitrary.

Furthermore, such partially aromatic copolyamides as PA 6 / 6T and PA 66 / 6T have proven to be particularly advantageous, the triamine content is less than 0.5, preferably less than 0.3 wt .-% (see EP-A 299 444).

The production of the preferred partly aromatic copolyamides with a low triamine content can be carried out by the processes described in EP-A 129 195 and 129 196.

Of course, mixtures (blends) of such polymers can be used.

6. Vinyl aromatic polymers

The molecular weight of these known and commercially available polymers is generally in the range of 1,500 to 2,000,000, preferably in the range of 70,000 to 1,000,000.

Representative here are vinyl aromatic polymers of styrene, chlorostyrene, α-methylstyrene and p-methylstyrene called; in minor proportions (preferably not more than 20, in particular not more than 8% by weight), comonomers such as (meth) acrylonitrile or (meth) acrylic acid esters may also be involved in the synthesis. Particularly preferred vinyl aromatic polymers are polystyrene and impact modified polystyrene. It is understood that mixtures of these polymers can be used. The preparation is preferably carried out according to the method described in EP-A-302 485.

Preferred ASA polymers are composed of a soft or rubber phase of a graft polymer of:

Ai 50 to 90 wt .-% of a graft base based on

At 95 to 99.9 wt .-% of a C2-Cio-alkyl acrylate and

A12 0.1 to 5 wt .-% of a difunctional monomer having two olefinic, non-conjugated double bonds, and A2 10 to 50 wt .-% of a graft

A21 20 to 50% by weight of styrene or substituted styrenes of the general formula I or mixtures thereof, and

A22 10 to 80% by weight of acrylonitrile, methacrylonitrile, acrylic acid esters or methacrylic acid esters or mixtures thereof,

in mixture with a hard matrix based on a SAN copolymer A3) from:

A31 50 to 90, preferably 55 to 90 and in particular 65 to 85 wt .-% styrene and / or substituted styrenes of the general formula I and

A32 10 to 50, preferably 10 to 45 and in particular 15 to 35 wt .-% acrylonitrile and / or methacrylonitrile.

The component Ai) is an elastomer, which has a glass transition temperature of less than -20, in particular less than -30 ⁰ C.

For the preparation of the elastomer, the main monomers used are an) esters of acrylic acid having 2 to 10 C atoms, in particular 4 to 8 C atoms. Particularly preferred monomers which may be mentioned here are tert-butyl, isobutyl and n-butyl acrylate and also 2-ethylhexyl acrylate, of which the latter two are particularly preferred.

In addition to these esters of acrylic acid, 0.1 to 5, in particular 1 to 4 wt .-%, based on the total weight An + A12 of a polyfunctional monomer having at least two olefinic, non-conjugated double bonds used. Of these, difunctional compounds, i. preferably used with two non-conjugated double bonds. Examples include divinylbenzene, diallyl fumarate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, tricyclodecenyl acrylate and dihydrodicyclopentadienyl acrylate, of which the last two are particularly preferred.

Processes for the preparation of the graft base Ai are known per se and e.g. described in DE-B 1 260 135. Corresponding products are also commercially available.

In some cases, production by emulsion polymerization has proved to be particularly advantageous. The exact polymerization conditions, in particular the type, dosage and amount of the emulsifier are preferably selected so that the latex of the acrylic acid ester which is at least partially crosslinked has an average particle size (weight average dδo) in the range from about 200 to 700, in particular from 250 to 600 nm. Preferably, the latex has a narrow particle size distribution, ie the quotient

d9o ^d io

Q =

^J 50

is preferably less than 0.5, in particular less than 0.35.

The proportion of the graft base Ai on the graft polymer A1 + A2 is 50 to 90, preferably 55 to 85 and in particular 60 to 80 wt .-%, based on the total weight of A1 + A2.

A grafted shell A2 grafted onto the grafting base Ai is prepared by copolymerizing

A21 20 to 90, preferably 30 to 90 and in particular 30 to 80 wt .-% of styrene or substituted styrenes of the general formula

wherein R represents alkyl radicals having 1 to 8 C atoms, hydrogen atoms or halogen atoms and R ^{1 represents} alkyl radicals having 1 to 8 C atoms or halogen atoms and n is 0, 1, 2 or 3, and

A22 10 to 80, preferably 10 to 70 and in particular 20 to 70 wt .-% acrylonitrile, methacrylonitrile, acrylic acid esters or methacrylic acid esters or mixtures thereof is available.

Examples of substituted styrenes are α-methylstyrene, p-methylstyrene, p-chlorostyrene and p-chloro-α-methylstyrene, of which styrene and α-methylstyrene are preferred.

Preferred acrylic or methacrylic acid esters are those whose homopolymers or copolymers with the other monomers of component A22) have glass transition temperatures of more than 2O ⁰ C; In principle, however, other acrylic acid esters may also be used, preferably in such amounts that gives a total of the glass transition temperature T ₉ above 20 ⁰ C for the component A2.

Particular preference is given to esters of acrylic or methacrylic acid with C 1 -C 8 alcohols and esters containing epoxy groups, such as glycidyl acrylate or glycidyl methacrylate. As very particularly preferred examples are methyl methacrylate, t-butyl methacrylate, glycidyl methacrylate and n-butyl acrylate called, the latter due to its property to form polymers with very low T ₉ , is preferably used in not too high a proportion.

The graft shell A2) may be in one or more, e.g. two or three process steps are made, the gross composition remains unaffected.

Preferably, the graft shell is made in emulsion as described e.g. in DE-PS 12 60 135, DE-OS 32 27 555, DE-OS 31 49 357 and DE-OS 34 14 118 is described.

Depending on the conditions selected, a certain proportion of free copolymers of styrene or substituted styrene derivatives and (meth) acrylonitrile or (meth) acrylic esters is formed in the graft copolymerization.

The graft copolymer Ai + A2 generally has an average particle size of 100 to 1,000 nm, especially 200 to 700 nm, (dso-weight average). The conditions in the preparation of the elastomer Ai) and in the grafting are therefore preferably chosen so that particle sizes result in this range. Measures for this are known and e.g. in DE-PS 1 260 135 and DE-OS 28 26 925 and in Journal of Applied Polymer Science, Vol. 9 (1965), pp 2929 to 2938 described. The particle size of the latex of the elastomer can be e.g. be accomplished by agglomeration.

For the purposes of this invention, the graft polymer (A1 + A2) also includes the free, non-grafted homopolymers and copolymers formed in the graft copolymerization to prepare component A2).

The following are some preferred graft polymers:

1: 60 wt .-% graft Ai from An 98 wt .-% n-butyl acrylate and

A12 2 wt .-% Dihydrodicyclopentadienylacrylat and 40 wt .-% graft A2 from

A21 75% by weight of styrene and A22 25% by weight of acrylonitrile 2: Grafting base as in 1 with 5 wt .-% of a first graft shell of styrene and

35 wt .-% of a second graft of A21 75 wt .-% of styrene and

A ₂₂ 25 wt .-% acrylonitrile

3: Pfropfgrundlage as in 1 with 13 wt .-% of a first graft of styrene and

27% by weight of a second grafting step of styrene and acrylonitrile in a weight ratio of 3: 1

The products contained as component A3) may e.g. are prepared according to the method described in DE-AS 10 01 001 and DE-AS 10 03 436. Also commercially available such copolymers are available. Preferably, the weight average molecular weight determined by light scattering is in the range of 50,000 to 500,000, more preferably 100,000 to 250,000.

The weight ratio of (Ai + A2): A3 is in the range of 1: 2.5 to 2.5: 1, preferably 1: 2 to 2: 1, and more preferably 1: 1.5 to 1.5: 1.

Suitable SAN polymers as component A) are described above (see A31 and A32).

The viscosity number of the SAN polymers, measured according to DIN 53 727 as 0.5 wt .-% solution in dimethylformamide at 23 ⁰ C is generally in the range of 40 to 100, preferably 50 to 80 ml / g.

ABS polymers as polymer (A) in the multiphase polymer mixtures according to the invention have the same structure as described above for ASA polymers. Instead of the acrylate rubber Ai) of the graft base in the ASA polymer, conjugated dienes are usually used, so that the following composition is preferably obtained for the graft base A ₄ :

A41 70 to 100 wt .-% of a conjugated diene and A42 0 to 30 wt .-% of a difunctional monomer having two olefinic non-conjugated double bonds

Graft A2 and the hard matrix of SAN copolymer A3) remain unchanged in composition. Such products are commercially available. The production methods are known to the person skilled in the art, so that further details are unnecessary. The weight ratio of (A ₄ + A2): A3 is in the range of 3: 1 to 1: 3, preferably 2: 1 to 1: 2.

Particularly preferred compositions of the thermoplastic molding compositions comprise, as component A), a mixture of:

Ai) 10 to 90 wt .-% of a polybutylene terephthalate

A2) 0 to 40 wt .-% of a polyethylene terephthalate

A3) 1 to 40 wt .-% of an ASA or ABS polymers or mixtures thereof

Such products are available under the trademark Ultradur® S (formerly Ultrablend® S) from BASF Aktiengesellschaft.

Further preferred compositions of component A)

Ai) 10 to 90 wt .-% of a polycarbonate

A2) 0 to 40 wt .-% of a polyester, preferably

Polybutylene terephthalate, A ₃ ) 1 to 40 wt .-% of an ASA or ABS polymers or their

Mixtures.

Such products are available under the trademark Terblend® from BASF AG.

7. Polyarylene ether

Polyarylene ethers A) are preferably to be understood as meaning both polyarylene ethers per se, polyarylene ether sulfides, polyarylene ether sulfones or polyarylene ether ketones. Their arylene groups may be identical or different and independently of one another denote an aromatic radical having 6 to 18 C atoms. Examples of suitable arylene radicals are phenylene, bisphenylene, terphenylene, 1, 5-naphthylene, 1, 6-naphthylene, 1, 5-anthrylene, 9,10-anthrylene or 2,6-anthrylene. Of these, 1, 4-phenylene and 4,4'-biphenylene are preferred. Preferably, these aromatic radicals are not substituted. However, they can carry one or more substituents. Suitable substituents are, for example, alkyl, arylalkyl, aryl, nitro, cyano or alkoxy groups and also heteroaromatics such as pyridine and halogen atoms. The preferred substituents include alkyl radicals having up to 10 carbon atoms such as methyl, ethyl, i-propyl, n-hexyl, i-hexyl, Ci- to Cio-alkoxy such as methoxy, ethoxy, n-propoxy, n-butoxy, aryl radicals with bis to 20 carbon atoms, such as phenyl or naphthyl, and fluorine and chlorine. These may be linked together in addition to -O-, for example via -S-, -SO-, -SO ₂ -, -CO-, -N = N-, -COO-, an alkylene radical or a chemical bond. In The polyarylene ethers (B), the arylene groups may also be linked together via different groups.

The preferred polyarylene ethers include those having repeating units of the general formula I.

Likewise, their nuclear-substituted derivatives can be used. Suitable substituents are preferably C 1 -C 6 -alkyl, such as methyl, ethyl or t-butyl, C 1 -C 6 -alkoxy, such as methoxy or ethoxy, aryl, in particular phenyl, chlorine or fluorine. The variable X may be -SO ₂ -, -SO-, -S-, -O-, CO, -N = N-, -RC = CR ³ -, -CR ^b R ^c - or a chemical bond. The variable Z may be -SO 2 -, -SO-, -CO-, -O-, -N = N- or -RC = CR ³ . Here, R and R ^{3 are} each hydrogen, C 1 -C 6 -alkyl, for example methyl, n-propyl or n-hexyl, C 1 -C 6 -alkoxy, including methoxy, ethoxy or butoxy or aryl, in particular phenyl. The radicals R ^b and R ^c may each be hydrogen or a C 1 to ^C 6 alkyl group, in particular methyl. However, they can also be linked to a C ₄ -C 10 -cycloalkyl ring, preferably cyclopentyl or cyclohexyl ring, which in turn may be substituted by one or more alkyl groups, preferably methyl. In addition, R ^b and R ^{c may} also be a C 1 to ^C 6 alkoxy group, for example methoxy or ethoxy, or an aryl group, especially phenyl. The abovementioned groups may each themselves be substituted by chlorine or fluorine.

Listed below are some of the preferred repeating units I:

)

Especially preferred are polyarylene ethers containing as repeating units (h), (b), (124) or (I25). These include, for example, polyarylene ether sulfones having 0 to 100 mol%, preferably 5 to 95 mol% of structural units (h) and 0 to 100 mol%, preferably 5 to 95 mol% of structural units (I2).

The polyarylene ethers may also be copolymers or block copolymers in which polyarylene ether segments and segments of other thermoplastic polymers such as polyamides, polyesters, aromatic polycarbonates, polyestercarbonates, polysiloxanes, polyimides or polyetherimides are present. The molecular weights of the blocks or the graft arms in the copolymers are generally in the range from 1 000 to 30 000 g / mol. The blocks of different structure may be arranged alternately or statistically. The proportion by weight of the polyarylene ether segments in the co- or block copolymers is generally at least 3, preferably at least 10 wt .-%. The proportion by weight of the polyarylene ether sulfones or ketones can be up to 97% by weight. Preference is given to copolymers or block copolymers having a weight fraction of polyarylene ether segments of up to 90% by weight. Particular preference is given to copolymers or block copolymers having from 20 to 80% by weight of polyarylene ether segments.

In general, the polyarylene ethers have average molecular weights M _n (number average) in the range from 10,000 to 60,000 g / mol and viscosity numbers of 30 to 150 ml / g on. Depending on the solubility of the polyarylene ethers (A) or (B), the viscosity numbers are either in 1% strength by weight N-methylpyrrolidone solution, in mixtures of phenol and o-dichlorobenzene or in 96% sulfuric acid at 2O ⁰ C or 25 ° C.

The polyarylene ethers are known per se or can be prepared by methods known per se.

For example, polyphenylene ethers can be prepared by oxidative coupling of phenols. Polyarylene ether sulfones or ketones are produced, e.g. by condensation of aromatic bishalogen compounds and the alkali double salts of aromatic bisphenols. They can also be prepared, for example, by self-condensation of alkali metal salts of aromatic halophenols in the presence of a catalyst.

The monomers are preferably polymerized in the melt or in an inert, high-boiling solvent. These include chlorobenzene, dichlorobenzene, xylene and trichlorobenzene. In addition, sulfones or sulfoxides, including especially dimethylsulfone, diethylsulfone, 1, 1-dioxotetrahydrothiophene (sulfolane) or diphenylsulfone, dimethyl sulfoxide or diethyl sulfoxide, preferably dimethyl sulfoxide into consideration. The preferred solvents also include N-alkylpyrrolidones, in particular N-methylpyrrolidone. Furthermore, N-substituted acid amides, for example N, N-dimethylformamide or N, N-dimethylacetamide can be used. It is also possible to use mixtures of different solvents.

Preferred process conditions for the synthesis of polyarylene ether sulfones or ketones are described for example in EP-A-113 112 and 135 130.

The preferred polyarylene ether generally have a melting point of at least 320 ⁰ C (polyarylene ether sulfones) or of at least 370 ⁰ C (Poly-arylenether- ketone) on.

According to the invention, the molding compositions may contain polyarylene ether sulfones or ketones obtainable by reacting a polyarylene ether sulfone or ketone with a reactive compound. The reactive compounds contain, in addition to a C, C double or triple bond, one or more carbonyl, carboxylic acid, carboxylate, acid anhydride, acid imide, carboxylic acid ester, amino, hydroxyl, epoxy, oxazoline , Urethane, urea, lactam or halobenzyl group.

Examples of suitable compounds are maleic acid, methylmaleic acid, itaconic acid, tetrahydrophthalic acid, their anhydrides and imides, fumaric acid, the mono- and diesters of these acids, for example of C 1 -C 6 -alkanols, the mono- or diamides of these acids, such as N-phenylmaleimide, maleic hydrazide. Preference is given to using α, β-unsaturated dicarboxylic acids or their anhydrides, diesters and monoesters of the general structure IV and V below.

in which

R ¹ , R ² , R ³ and R ⁴ independently of one another can be hydrogen and C ¹ -C ⁶ -alkyl groups.

Particularly suitable compounds are maleic anhydride, fumaric acid and itaconic acid.

The polymers and the reactive compound can be reacted with each other, for example, in an aromatic solvent. Particularly suitable solvents have proven to be chlorobenzene, o-dichlorobenzene and N-methylpyrrolidone. In general, a conventional radical initiator is used. The reaction is generally carried out at 75 to 150 ⁰ C. The reaction product is obtained by precipitation with a customary precipitant, such as low molecular weight alcohol and ketone, or by removal of the solvent (for example in the vented extruder, thin-film evaporator).

However, the reactants can also, for example, at a temperature of 270 - 35O ⁰ C in the melt in a continuously or batchwise working mixing unit (eg single- or twin-screw extruder, kneader) are implemented.

The reactive compound is preferably added in liquid form, in particular within the kneading zone of a mixing unit, to the melt of the polymer.

Preference is given to using modified polyarylene ether sulfones or ketones which are obtained by reacting from 80 to 99.9% by weight, in particular from 90 to 99% by weight, of the unmodified polyarylene ether sulfones or ketones, with from 0.1 to 20% by weight. , In particular 1 to 10 wt .-% of the reactive compound have been obtained. Particularly preferred as component with 0.1 to 1, 5 wt .-% maleic anhydride grafted polyarylene ether. In this case, polyarylene ether sulfones containing 5 to 95 mol% of units U and 5 to 95 mol% of units b are preferred.

Polyarylene ether sulfones having 80 to 95, preferably 85 to 95 mol% of units of the formula 12 and 11 and correspondingly 5 to 20, preferably 5 to 15 mol% of the units of the formula 11 or 12 are mentioned in particular here.

As free radical initiators, the compounds described in the literature (e.g., J.K. Kochi, "Free Radicals", J. Wiley, New York, 1973) can generally be used.

Usually, the radical initiators are used in amounts of about 0.01 to about 1 wt .-%, based on the polyarylene ether sulfones or ketones used. Of course, mixtures of different radical initiators can be used.

Correspondingly modified polyphenylene ethers are i.a. from WO 87/00540, which can be used in particular in mixtures with polyamide.

The proportion by weight of thermoplastics is generally in the range of 10 to 99.9, preferably 20 to 99.9 and in particular from 50 to 98 wt .-%.

As component B), the molding compositions according to the invention comprise a copolymer B) as defined above in amounts of from 0.01 to 10, preferably from 0.03 to 8, in particular from 0.1 to 5 wt .-%.

The process for the preparation of the copolymer B) is carried out semicontinuously in a polymerization vessel, wherein the polymerization vessel is to be understood as meaning all vessels in which an aqueous emulsion polymerization can be carried out. Polymerization vessels include, for example, in particular glass reactors, enamelled steel reactors or stainless steel reactors whose size can be from 0.5 l to 100 m ³ .

Suitable monomers A include, in particular, simple free-radically polymerizable ethylenically unsaturated monomers, such as, for example, ethylene, vinylaromatic monomers, such as styrene, .alpha.-methylstyrene, o-chlorostyrene or vinyltoluenes, esters of vinyl alcohol and 1 to 18 C atoms Monocarboxylic acids, such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, esters of α, β-monoethylenically unsaturated mono- and dicarboxylic acids preferably having 3 to 6 carbon atoms, in particular acrylic acid, methacrylic acid, maleic acid, marsäure and Itaconsäure, with in general 1 to 12, preferably 1 to 8 and in particular 1 to 4 C-containing alkanols, such as especially acrylic and Methacrylsäuremethyl-, -ethyl, -n-butyl, -iso-butyl and - 2-ethylhexyl ester, maleic acid dimethyl ester or di-n-butyl maleate, nitriles of α, β-monoethylenically unsaturated carboxylic acids, such as acrylonitrile, and also C4-8-conjugated dienes, such as 1,3-butadiene and isoprene. The monomers mentioned usually form the main monomers which, based on the total amount of monomers A to be polymerized by the process according to the invention, normally contain> 50% by weight,> 80% by weight or> 90% by weight. % on itself. In general, these monomers [1 20 ⁰ C, atm = 1, 013 bar (absolute)] exhibit in water ser under normal conditions only a moderate to low solubility.

Other monomers A, which usually increase the internal strength of the films of the polymer matrix, normally have at least one hydroxyl, N-methylol or carbonyl group. Of particular importance in this context are the methacrylic acid and acrylic acid C 1 -C 8 -hydroxyalkyl esters, such as n-hydroxyethyl, n-hydroxypropyl or n-hydroxybutyl acrylate and methacrylate, and also compounds such as diacetoneacrylamide and acetylacetoxyethyl acrylate or methacrylate. According to the invention, the abovementioned monomers, based on the total amount of monomers A to be polymerized, are available in amounts of <5% by weight, often> 0.1 and <3% by weight and frequently> 0.2 and <2% by weight .-% used for the polymerization.

Also suitable as monomers A are siloxane-containing ethylenically unsaturated monomers, such as the vinyltrialkoxysilanes, for example vinyltrimethoxysilane, alkylvinyldialkoxysilanes, acryloyloxyalkyltrialkoxysilanes, or methacryloxyalkyltrialkoxysilanes, for example acryloxyethyltrimethoxysilane, methacryloxyethyltrimethoxysilane, acryloxypropyltrimethoxysilane or methacryloxypropyltrimethoxysilane. These monomers are in total amounts of <5 wt .-%, often of> _ 0.01 and <_ 3 wt .-% and often of> _ 0.05 and <_ 1 wt .-%, each based on the total amount the monomers A, used.

In addition, as monomers A additionally such ethylenically unsaturated monomers AS, which contain either at least one acid group and / or their corresponding anion or such ethylenically unsaturated monomers AK, the at least one amino, amido, ureido or N-heterocyclic group and / or their nitrogen-protonated or alkylated ammonium derivatives are used. Based on the total amount of the monomers A to be polymerized, the amount of monomers AS or monomers AK is <10% by weight, often> 0.1 and <7% by weight and frequently> 0.2 and <5% by weight. -%.

As monomers AS, ethylenically unsaturated monomers having at least one acid group are used. The acid group may be, for example, a sulfonic acid. be re-, sulfuric acid, phosphoric acid and / or phosphonic acid group. Examples of such monomers AS are 4-styrenesulfonic acid, 2-methacryloxyethylsulfonic acid, vinylsulfonic acid and vinylphosphonic acid and phosphoric acid monoesters of n-hydroxyalkyl acrylates and n-hydroxyalkyl methacrylates, such as, for example, phosphoric acid monoesters of hydroxyethyl acrylate, n-hydroxypropyl acrylate, n-hydroxybutyl acrylate and hydroxyethyl methacrylate, n-hydroxyalkyl methacrylate. Hydroxypropyl methacrylate or n-hydroxybutyl methacrylate. However, the ammonium and alkali metal salts of the aforementioned at least one acid group-containing ethylenically unsaturated monomers can also be used according to the invention. Particularly preferred alkali metal is sodium and potassium. Examples of these are the ammonium, sodium and potassium salts of 4-styrenesulfonic acid, 2-methacryloxyethylsulfonic acid, vinylsulfonic acid and vinylphosphonic acid, and the mono- and di-ammonium, sodium and potassium salts of the phosphoric acid monoesters of hydroxyethyl acrylate, n-hydroxypropyl acrylate, n- Hydroxybutyl acrylate and hydroxyethyl methacrylate, n-hydroxypropyl methacrylate or n-hydroxybutyl methacrylate.

Preference is given to using 4-styrenesulfonic acid, 2-methacryloxyethylsulfonic acid, vinylsulfonic acid and vinylphosphonic acid as monomers AS.

The monomers AK used are ethylenically unsaturated monomers which contain at least one amino, amido, ureido or N-heterocyclic group and / or their nitrogen-protonated or alkylated ammonium derivatives.

Examples of monomers AK which contain at least one amino group are 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 4-amino-n-butyl acrylate, 4-amino-n-butyl methacrylate, 2- (N- Methyl amino) ethyl acrylate, 2- (N-methylamino) ethyl methacrylate, 2- (N-ethylamino) ethyl acrylate, 2- (N-ethylamino) ethyl methacrylate, 2- (Nn-propylamino) ethyl acrylate, 2- (Nn-propylamino ) ethyl methacrylate, 2- (N-iso-propylamino) ethyl acrylate, 2- (N-iso-propylamino) ethyl methacrylate, 2- (N-tert-butylamino) ethyl acrylate, 2- (N-tert-butyl)

Butylamino) ethyl methacrylate (for example commercially available as NORSOCRYL ^® TBAEMA Fa. Elf Atochem), 2- (N, N-dimethylamino) ethyl acrylate (for example commercially available as NORSOCRYL ^® ADAME Fa. Elf Atochem), 2- (N N- ₁ dimethylamino) ethyl methacrylate (for example commercially available as NORSOCRYL ^® MADAME Fa. Elf Atochem), 2- (N, N-diethylamino) ethyl acrylate, 2- (N N- ₁

Diethylamino) ethyl methacrylate, 2- (N, N-di-n-propylamino) ethyl acrylate, 2- (N, N-di-n-propylamino) ethyl methacrylate, 2- (N, N-di-iso-propylamino) ethyl acrylate, 2 (N, N-diisopropylamino) ethyl methacrylate, 3- (N-methylamino) propyl acrylate, 3- (N-methylamino) propyl methacrylate, 3- (N-ethylamino) propyl acrylate, 3- (N-ethylamino) propyl methacrylate, 3- (Nn-propylamino) propyl acrylate, 3- (N-

Propylamino) propyl methacrylate, 3- (N-iso-propylamino) propyl acrylate, 3- (N-iso-propylamino) propyl methacrylate, 3- (N-tert-butylamino) propyl acrylate, 3- (N-tert. Butylamino) propyl, 3- (N, N-dimethylamino) propyl acrylate, 3- (N ₁ N-dimethylamino) propyl, 3- (N, N-diethylamino) propyl, 3- (N ₁ N-diethylamino) propyl, 3- (N, N-di-n-propylamino) propyl acrylate, 3- (N, N-di-n-propylamino) propyl methacrylate, 3- (N, N-di-iso-propylamino) propyl acrylate and 3- (N ₁ N- Diisopropylamino) propyl methacrylate.

Examples of monomers AK containing at least one amido group are N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-n-propylacrylamide, Nn-propylmethacrylamide, N-iso-propylacrylamide, N-iso-propylmethacrylamide, N tert-butylacrylamide, N-tert-butylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide, N, N-di-n-propylacrylamide, N, N -Di-n-propylmethacrylamide, N, N-di-iso -propylacrylamide, N, N-diisopropylmethacrylamide, N, N-di-n-butylacrylamide, N, N-di-n-butylmethacrylamide, N- ( 3-N ^', N-dimethylaminopropyl) methacrylamide, rylamid Diacetonac-, N, ^N' methylenebisacrylamide, N- (diphenylmethyl) acrylamide, N-

Cyclohexylacrylamide, but also N-vinylpyrrolidone and N-vinylcaprolactam.

Examples of monomers AK, a ureido group containing at least ₁ N N ^'- divinylethyleneurea and 2- (1-imidazolin-2-onyl) ethyl methacrylate (for example commercially available as Norsocryl® 100 from Elf Atochem.).

Examples of monomers AK containing at least one N-heterocyclic group are 2-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, 2-vinylimidazole and N-vinylcarbazole.

4-vinylpyridine, 2-vinylimidazole, 2- (N, N-dimethylamino) ethyl acrylate, 2- (N ₁ N-dimethylamino) ethyl methacrylate, 2- (N, N- 2-vinylpyridine,: The following compounds are preferably used as monomers AK diethylamino) ethyl acrylate, 2- (N ₁ N-diethylamino) ethyl methacrylate, and 2- (1-imidazolin-2-onyl) ethyl methacrylate.

Depending on the pH of the aqueous reaction medium, a part or the total amount of the abovementioned nitrogen-containing monomers AK can be present in the nitrogen-protonated quaternary ammonium form.

AK as monomers having a quaternary Alkylammoniumstruktur on the nitrogen, may be mentioned by way of example 2- (N, N ₁ NT rimethylammonium) ethylacrylatchlorid (commercially available for example as Norsocryl® ADAMQUAT MC 80 from. Elf Atochem), 2- (N, N, N-trimethylammonium) ethylmethacrylate chloride (for example, commercially available as Norsocryl® MADQUAT MC 75 from Elf Atochem), 2- (N-methyl-N, N-diethylammonium) ethylacrylate chloride, 2- (N-methyl-N, N-diethylammonium) ethyl methacrylate chloride, 2- (N-methyl-N, N-dipropylammonium) ethyl acrylate chloride, 2- (N-methyl-N, N-dipropylammonium) ethyl methacrylate, 2- (N-benzyl-N, N-dimethylamino) monium) ethyl acrylate chloride (for example commercially available as Norsocryl® A-DAMQUAT BZ 80 from Elf Atochem), 2- (N-benzyl-N, N-dimethylammonium) ethyl methacrylate chloride (for example commercially available as Norsocryl® MADQUAT BZ 75 from Fa Elf Atochem), 2- (N-benzyl-N, N-diethylammonium) ethyl acrylate chloride, 2- (N-benzyl-N, N-diethylammonium) ethyl methacrylate chloride, 2- (N-benzyl-N, N-dipropylam-monium). ethyl acrylate chloride, 2- (N-benzyl-N, N-dipropylammonium) ethyl methacrylate chloride, 3- (N, N, N-trimethylammonium) propyl acrylate chloride, 3- (N, N, N-trimethylammonium) propyl methacrylate chloride, 3- (N-Methyl-N, N-diethyl-ammonium) -propyl-acrylate chloride, 3- (N-methyl-N, N-diethyl-ammonium) -propylmethacrylate chloride, 3- (N-methyl-N, N-dipropylammonium) -propyl-acrylate chloride, 3- (N Methyl N, N-dipropyl ammonium) propyl methacrylate chloride, 3- (N-benzyl-N, N-dimethyl ammonium) propyl acrylate chloride, 3- (N-benzyl-N, N-dimethyl ammonium) propyl methacrylate chloride, 3- (N- benzyl-N, N-diethylammonium) propylacryla chloride, 3- (N-benzyl-N, N-diethylammonium) propyl methacrylate chloride, 3- (N-benzyl-N, N-dipropylammonium) propyl acrylate chloride, and 3- (N-benzyl-N, N-dipropylammonium) propyl methacrylate chloride , Of course, in place of the chlorides mentioned, the corresponding bromides and sulfates can be used.

Preference is given to 2- (N, N, N-trimethylammonium) ethyl acrylate chloride, 2- (N, N, N-trimethylammonium) ethyl methacrylate chloride, ₁ 2- (N-benzyl-N, N-dimethylammonium) ethyl acrylate chloride and 2- (N- Benzyl-N, N-dimethylammonium) ethyl methacrylate chloride.

Of course, mixtures of the aforementioned ethylenically unsaturated monomers A can be used.

The total amount of the monomers A is 70 to 99.5 wt .-%, advantageously 80 to 99 wt .-% and particularly advantageously 90 to 98 wt .-%, each based on the total amount of monomers.

According to the invention, it is possible that optionally a partial amount of the monomers A are initially charged in the polymerization vessel and the total amount or residual amount of monomers A remaining are added to the polymerization vessel batchwise under polymerization conditions in several portions or continuously with constant or changing flow rates. Advantageously, <30% by weight and in particular advantageously <10% by weight of the monomers A are introduced into the polymerization vessel and the total amount or the remaining amount of monomers A is metered into the polymerization vessel continuously with constant or varying flow rates.

As monomers B, compounds having at least two free-radically copolymerizable ethylenically unsaturated groups are used. Examples of this are at least two vinyl radicals containing monomers, at least two vinylidene radicals having monomers and at least two alkenyl radicals having monomers. Particularly advantageous are the diesters of dihydric alcohols with .alpha.,. Beta.-monoethylenically unsaturated monocarboxylic acids, of which the acrylic and methacrylic acids are preferred. Examples of such monomers having two non-conjugated ethylenically unsaturated double bonds are alkylene glycol diacrylates and dimethacrylates, such as ethylene glycol diacrylate, 1,2-propylene glycol diacrylate, 1,3-propylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate and ethylene glycol dimethacrylate, 1, 2-propylene glycol dimethacrylate, 1, 3-propylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate, 1, 4-butylene glycol dimethacrylate and o-, m- and / or p-divinylbenzene, vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate, Diallyl phthalate, methylenebisacrylamide, cyclopentadienyl acrylate, triallyl cyanurate or triallyl isocyanurate.

Of course, mixtures of the aforementioned monomers B can be used.

Advantageously, o- / m- / p-divinylbenzene, 1,4-butylene glycol diacrylate, vinyl acrylate, vinyl methacrylate, allyl acrylate and / or allyl methacrylate are used as monomers B.

The total amount of the monomers B is 0.5 to 30 wt .-%, preferably 1 to

20 wt .-% and particularly advantageously 2 to 10 wt .-%, each based on the total monomer.

According to the invention, it is possible that optionally a partial amount of the monomers B are initially charged in the polymerization vessel and the total amount or residual amount of monomers B remaining are added to the polymerization vessel batchwise under polymerization conditions in several portions or continuously with constant or varying flow rates. Advantageously, <_ 10% by weight and in particular advantageously <5% by weight of the monomers B are introduced into the polymerization vessel and the total amount or the residual amount of monomers B added is metered into the polymerization vessel.

As monomers C 3 to 6 C-atoms having α, ß-monoethylenically unsaturated mono- or dicarboxylic acids and / or their amides are used. Examples of these are acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid and their corresponding amides. However, the ammonium and alkali metal salts of the abovementioned ethylenically unsaturated mono- or dicarboxylic acids can also be used according to the invention. Particularly preferred alkali metal is sodium and potassium. Examples of these are the ammonium, sodium and potassium salts of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and crotonic acid. Of course, mixtures of the aforementioned monomers C can be used.

Acrylic acid, methacrylic acid, itaconic acid, acrylamide and / or methacrylamide are advantageously used as monomers C.

The total amount of monomers C is generally <5% by weight, often> 0.1 and <3% by weight and frequently> 0.2 and <2% by weight, in each case based on the total monomer amount.

According to the invention, it is possible that optionally a partial amount of the monomers C are initially charged in the polymerization vessel and the total amount or remaining amount of monomers C are added to the polymerization under polymerization conditions discontinuously in several portions or continuously borrowed with constant or changing flow rates. Advantageously, <_ 30 wt .-% and particularly advantageously <10 wt .-% of the monomers C are introduced into the polymerization vessel and the total amount or the remaining amount of monomers C added to the polymerization continuously with constant or changing flow rates.

With particular advantage, the monomers A to C are chosen so that> 95 wt .-% and particularly advantageously> 97 wt .-% of all monomers at 20 ⁰ C and 1 atm (absolute) a solubility in deionized water of <10 wt. -% and in particular <5 wt .-% have.

Advantageously, the monomers A and the monomers C in nature and amount are chosen so that a copolymer composed solely of these monomers would have a glass transition temperature ^ 40 ⁰ C, preferably> 70 ⁰ C and particularly advantageously> _ 90 ⁰ C.

Usually, the determination of the glass transition temperature according to DIN 53 765 (differential scanning calorimetry, 20 K / min, midpoint measurement).

Fox (TG Fox, Bull. Am. Phys. Soc. 1956 [Ser. II] 1, page 123 and according to LJII-Mann ^'s Encyclopedia of Industrial Chemistry, Vol. 19, page 18, 4th edition, Verlag Chemie, Weinheim, 1980) applies to the glass transition temperature T ₉ of at most weakly crosslinked copolymers in a good approximation:

1 / Tg = XVTg ¹ + X ² / T _g 2 + .... X ⁿ / T _g ",

where x ¹ , x ² , .... x ⁿ the mass fractions of the monomers 1, 2, .... n and T ₉ ¹ , T ₉ ² , .... T ₉ "the glass transition temperatures of each of only one of Monomers 1, 2, .... n mean polymers prepared in degrees Kelvin. The T _g values for the homopolymers of most of the monomers are known and are listed, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., Vol. A21, page 169, Verlag Chemie, Weinheim, 1992; Other sources of glass transition temperatures of homopolymers include, for example, J. Brandrup, EH Immergut, Polymer Handbook, 1 ^st Ed., J. Wiley, New York, 1966; 2 ^nd ed. J. Wiley, New York, 1975 and 3 ^rd Ed. J. Wiley, New York, 1989.

In the present inventive method, water, preferably drinking water and particularly preferably deionized water is used, the total amount of which is such that it is 30 to 90 wt .-% and advantageously 50 to 80 wt .-%, each based on the accessible by the inventive method aqueous copolymer dispersion.

According to the invention, it is possible to optionally introduce a partial or total amount of water in the polymerization vessel. However, it is also possible to meter in the total amount or any remaining amount of water together with the monomers A, B and / or C, in particular in the form of an aqueous monomer emulsion. Advantageously, a small subset of water is introduced into the polymerization vessel and a larger subset of water in the form of an aqueous monomer emulsion is added under polymerization conditions.

In the context of the process according to the invention, dispersants are used which keep dispersed both the monomer droplets and the copolymerizate particles formed in the aqueous phase and thus ensure the stability of the aqueous copolymer dispersion produced. Suitable as such are both the protective colloids commonly used to carry out free-radical aqueous emulsion polymerizations and emulsifiers.

Suitable protective colloids are, for example, polyvinyl alcohols, cellulose derivatives or vinylpyrrolidone-containing copolymers. A detailed description of other suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular substances, pages 41 1 to 420, Georg Thieme Verlag, Stuttgart, 1961.

Of course, mixtures of emulsifiers and / or protective colloids can be used. Frequently, dispersants used are exclusively emulsifiers whose relative molecular weights, in contrast to the protective colloids, are usually below 1000 g / mol. They may be anionic, cationic or nonionic in nature. Of course, in the case of the use of mixtures of surfactants, the individual components must be compatible with each other, which can be checked in case of doubt by hand on fewer preliminary tests. In general, anionic emulsifiers are mixed with one another and with nonionic emulsifiers. see emulsifiers compatible. The same applies to cationic emulsifiers, while anionic and cationic emulsifiers are usually incompatible with each other.

Common emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C ₄ to C 12), ethoxylated fatty alcohols (EO degree: 3 to 50, alkyl radical: Cs to C 36) and alkali metal and ammonium salts of alkyl sulfates (alkyl radical: Cs to C12), of sulfuric monoesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C12 to Cis) and ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical: C ₄ to C12), of alkylsulfonic acids (alkyl radical: C12 to Cis) and of alkylarylsulfonic acids (alkyl radical: Cg to Cis). Further suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular substances, pages 192 to 208, Georg-Thieme-Verlag, Stuttgart, 1961.

As surface-active substances are also compounds of general formula I

wherein R ¹ and R ² is C ₄ - to C2 to ₄ alkyl and one of R ¹ or R ² can also be hydrogen, and A and B alkali metal ions and / or ammonium ions to be proven. In the general formula I, R ¹ and R ^{2 are} preferably linear or branched alkyl radicals having 6 to 18 C atoms, in particular having 6, 12 and 16 C atoms or H atoms, where R ¹ and R ^{2 are} not both simultaneously H and Atoms are. A and B are preferably sodium, potassium or ammonium ions, with sodium ions being particularly preferred. Particularly advantageous are compounds I in which A and B are sodium ions, R ^{1 is} a branched alkyl radical having 12 C atoms and R ^{2 is} an H atom or R ¹ . Frequently, technical mixtures are used which have a proportion of 50 to 90% by weight of the monoalkylated product, for example Dowfax® 2A1 (trademark of the Dow Chemical Company). The compounds I are well known, for. Example, from US-A 4,269,749, and commercially available.

Nonionic and / or anionic emulsifiers are preferably used for the process according to the invention. However, it is also possible to use cationic emulsifiers. Particular preference is given to using anionic emulsifiers, such as alkylarylsulfonic acids, alkyl sulfates, sulfuric acid semi-esters of ethoxylated alkanols and / or their corresponding alkali metal salts. As a rule, the amount of dispersant used is> 0.1 and <15% by weight and preferably> 0.5 to <5% by weight, in each case based on the total monomer amount.

According to the invention, it is possible to optionally introduce a partial or total amount of dispersant in the polymerization vessel. However, it is also possible to meter in the total amount or any residual amount of dispersant together with the monomer A, B and / or C, in particular in the form of an aqueous monomer emulsion under polymerization conditions.

The release of the free-radically initiated aqueous emulsion polymerization takes place by means of a free-radical polymerization initiator (free-radical initiator). In principle, these can be both peroxides and azo compounds. Of course, redox initiator systems are also suitable. As peroxides may in principle inorganic peroxides, such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of peroxodisulfuric, such as their mono- and di-sodium, potassium or ammonium salts or organic peroxides, such as alkyl hydroperoxides, for example tert-butyl, p-menthyl or cumyl hydroperoxide, as well as dialkyl or diarylperoxides, such as di-tert-butyl or di-cumyl peroxide are used. As an azo compound substantially 2,2 - azobis (isobutyronitrile), ^2,2'-azobis (2,4-dimethylvaleronitrile), and ^2,2'-azobis (amidino propyl) dihydrochloride (AIBA, corresponding to V-50 from Wako Chemicals ) Use. Suitable oxidizing agents for redox initiator systems are essentially the abovementioned peroxides. Suitable reducing agents may be sulfur compounds having a low oxidation state, such as alkali metal sulfites, for example potassium and / or sodium sulfite, alkali hydrogen sulfites, for example potassium and / or sodium hydrogen sulfite, alkali metal metabisulfites, for example potassium and / or sodium metabisulfite, formaldehydesulfoxylates, for example potassium and / or Sodium formaldehyde sulfoxylate, alkali metal salts, especially potassium and / or sodium salts, aliphatic sulfinic acids and alkali metal hydrogen sulfides, such as, for example, potassium and / or sodium hydrosulfide, salts of polyvalent metals, such as iron (II) sulfate, iron (II) ammonium sulfate, Iron (II) phosphate, endiols such as dihydroxymaleic acid, benzoin and / or ascorbic acid and reducing saccharides such as sorbose, glucose, fructose and / or dihydroxyacetone are used. In general, the amount of the radical initiator used, based on the total amount of monomers, 0.01 to 5 wt .-%, preferably 0.1 to 3 wt .-% and particularly preferably 0.2 to 1, 5 wt .-%.

According to the invention, it is possible to optionally introduce a partial or the total amount of radical initiator in the polymerization vessel. However, it is also possible to meter in the total amount or any remaining amount of radical initiator to the polymerization vessel under polymerization conditions. It is also possible to use according to the invention other optional auxiliaries known to the person skilled in the art, for example so-called thickeners, defoamers, neutralizing agents, preservatives, radical chain-transferring compounds and / or complexing agents.

In order to optimally adjust the rheology of the aqueous copolymer dispersions obtainable according to the invention during production, handling, storage and application, so-called thickeners or rheology additives are frequently used as the formulation constituent. The skilled worker is aware of a large number of different thickeners, for example organic thickeners, such as xanthan thickeners, guar thickeners (polysaccharides), carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose (cellulose derivatives), alkali-swellable dispersions (acrylate thickeners) or hydrophobically modified polyether-based polyurethanes (US Pat. Polyurethane thickener) or inorganic thickeners, such as bentonite, hectorite, smectite, attapulgite (Bentone) and titanates or zirconates (metal organyls).

In order to avoid foaming in the preparation, handling, storage and application of the aqueous copolymer dispersions obtainable according to the invention, so-called defoamers are used. The defoamers are familiar to the person skilled in the art. These are essentially mineral oil and the silicone oil defoamers. Defoamers, especially the highly active silicone-containing, are generally very carefully selected and dosed, as they can lead to surface defects (craters, dents, etc.) of the coating. It is essential that the addition of finely divided, hydrophobic particles, for example hydrophobic silica or wax particles, in the defoamer liquid, the defoaming effect can be increased.

If necessary, acids or bases known to those skilled in the art as neutralizing agents can be used to adjust the pH of the aqueous polymer dispersions obtainable in accordance with the invention.

In order to prevent the infestation of the aqueous copolymer dispersions obtainable according to the invention during preparation, handling, storage and application by microorganisms, such as, for example, bacteria, (fungi) fungi or yeasts, preservatives or biocides familiar to the person skilled in the art are frequently used. In particular, combinations of active compounds of methyl and chloroisothiazolinones, benzisothiazolinones, formaldehyde or formaldehyde-releasing agents are used.

In addition to the abovementioned components, in the process according to the invention for the preparation of the aqueous copolymer dispersions it is optionally also possible to use free-radical chain transfer compounds in order to reduce the molecular weight of the .alpha To reduce or control polymerization accessible copolymers. These are essentially aliphatic and / or araliphatic halogen compounds, such as n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylene dichloride, chloroform, bromoform, bromotrichloromethane, Dibromdichlormethan, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide, organic thio compounds such as primary , secondary or tertiary aliphatic thiols such as ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-butanethiol, 2-methyl-2-propanethiol, n-pentanethiol, 2-pentanethiol, 3-pentanethiol, 2-methyl 2-butanethiol, 3-methyl-2-butanethiol, n-hexanethiol, 2-hexanethiol, 3-hexanethiol, 2-methyl-2-pentanethiol, 3-methyl-2-pentanethiol, 4-methyl-2-pentanethiol , 2-methyl-3-pentanethiol,

3-methyl-3-pentanethiol, 2-ethylbutanethiol, 2-ethyl-2-butanethiol, n-heptanethiol and its isomeric compounds, n-octanethiol and its isomeric compounds, n-nonanethiol and its isomeric compounds, n-decanethiol and its isomers Compounds, n-undecanethiol and its isomeric compounds, n-dodecanethiol and its isomeric compounds, n-tridecanethiol and its isomeric compounds, substituted thiols, such as, for example, 2-hydroxyethanethiol, aromatic thiols, such as benzenethiol, ortho, meta, or para methylbenzenethiol, and all other in polymer Handbook 3 ^rd edition, 1989, J. Brandrup and EH Immergut, John Wiley & Sons, section II, pages 133 to 141, sulfur compounds described, as well as aliphatic and / or aromatic aldehydes such as acetaldehyde, propionaldehyde and / or benzaldehyde, unsaturated fatty acids, such as oleic acid, dienes with non-conjugated double bonds, such as divinylmethane or vinylcyclohexane or hydrocarbons with easily abstractable en hydrogen atoms, such as toluene, are used. It is advantageous to use tert-dodecylmercaptan, 2,4-diphenyl-4-methyl-1-pentene and terpinolene (see, for example, DE-A 10046930 or DE-A 10148511).

The total amount of the further optional auxiliaries, based on the total monomer amount, is generally <10% by weight, <5% by weight, often <3% by weight and frequently <2% by weight.

According to the invention, it is possible to optionally introduce partial or total amounts of further optional auxiliaries in the polymerization vessel. However, it is also possible to meter in total amounts or any residual amounts of further optional auxiliaries under polymerization conditions, optionally as a constituent of the monomer mixture or of the aqueous monomer emulsion containing same.

Optionally, the free-radically initiated aqueous emulsion polymerization according to the invention may also be carried out in the presence of a polymer seed, for example in the presence of from 0.01 to 10% by weight, often from 0.01 to 5% by weight and often from 0.04 to 3.5% by weight .-% of a polymer seed, in each case based on the total amount of monomers, take place. A polymer seed is used in particular when the particle size of the polymer particles to be prepared by free-radical aqueous emulsion polymerization is to be specifically adjusted (see, for example, US Pat. No. 2,520,959 and US Pat. No. 3,397,165).

In particular, polymer seed particles are used whose particle size distribution is narrow and whose weight-average diameter D _w <100 nm, frequently> 5 nm to <50 nm and often> 15 nm to <35 nm. The determination of the weight-average particle diameter is known to the person skilled in the art and is carried out, for example, by the method of the analytical ultracentrifuge. Weight-average particle diameter in this document is understood to mean the weight-average Dw5o value determined by the method of the analytical ultracentrifuge (cf., for this purpose, SE Harding et al., Analytical Ultra-centrifugation in Biochemistry and Polymer Science, Royal Society of Chemistry, Cambridge, Great Britain 1992 , Chapter 10, Analysis of Polymer Dispersions with an Eight Cell AUC Multiplexer: High Resolution Particle Size Distribution and Density Gradient Techniques, W. Mächtle, pages 147 to 175).

Within the scope of this document, narrow particle size distribution is to be understood as meaning the ratio of the weight-average particle diameter D _{w determined} by the method of the analytical ultracentrifuge and the number-average particle diameter DN 50 [D _W 5O / DN 50] <2.0, preferably <1.5 and particularly preferably <1, 2 or <1, 1.

Usually, the polymer seed is used in the form of an aqueous polymer dispersion. The aforementioned amounts are based on the polymer solids content of the aqueous Polymersaatdispersion; they are therefore given as parts by weight of polymer seed solids, based on the total amount of monomers.

If a polymer seed is used, advantageously a foreign polymer seed is used. In contrast to a so-called in situ polymer seed, which is prepared before the actual emulsion polymerization in the reaction vessel and which has the same monomeric composition as the polymer prepared by the subsequent free-radically initiated aqueous emulsion polymerization, a foreign polymer seed is understood to mean a polymer seed which is in a Separate reaction step was prepared and their monomeric composition of the polymer prepared by the free-radically initiated aqueous emulsion polymerization is different, but this means nothing else than that used to prepare the Fremdpolymersaat and for the preparation of the aqueous polymer dispersion different monomers or monomer mixtures with different composition become. The preparation of a foreign polymer seed is familiar to the person skilled in the art and is usually carried out in such a way that a relatively small amount of monomers and a relatively large amount of emulsifiers in a reaction vessel initially charged and at the reaction temperature, a sufficient amount of polymerization initiator is added.

A polymer seed having a glass transition temperature> 50 ⁰ C, often> 60 ⁰ C or> 70 ° C and often> 80 ⁰ C or> 90 ° C is preferably used according to the invention. Particular preference is given to a polystyrene or a polymethyl methacrylate polymer seed.

According to the invention, it is possible to optionally introduce a partial or the total amount of foreign polymer seed as a further optional adjuvant in the polymerization vessel. However, it is also possible to meter in the total amount or any residual amounts of foreign polymer seed under polymerization conditions.

By polymerization conditions are meant those temperatures and pressures below which the free-radically initiated aqueous emulsion polymerization proceeds with sufficient polymerization rate. However, this is particularly dependent on the radical initiator used. Advantageously, the nature and amount of the radical initiator, polymerization temperature and polymerization pressure are selected such that the free-radical initiator has a half-life of <3 hours, particularly advantageously <1 hour and most preferably <30 minutes.

Depending on the radical initiator chosen, the reaction temperature for the free-radical aqueous emulsion polymerization according to the invention is the entire range from 0 to 170 ^° C. In this case, temperatures of 50 to 150 ° C, in particular 60 to 130 ° C and advantageously 70 to 120 ° C are applied in the rule. The free-radical aqueous emulsion polymerization according to the invention can be carried out at a pressure of less than or equal to 1 atm, so that the polymerization temperature can exceed 100 ^° C. and can be up to 170 ^° C. Preferably, in the presence of volatile monomers, such as ethylene, butadiene or vinyl chloride is polymerized under elevated pressure. The pressure may be 1, 2, 1, 5, 2, 5, 10, 15 bar (absolute) or even higher values. If emulsion polymerizations are carried out under reduced pressure, pressures of 950 mbar, often 900 mbar and often 850 mbar (absolute) are set. The free-radical aqueous emulsion polymerization according to the invention is advantageously carried out at elevated pressure under an inert gas atmosphere, for example under nitrogen or argon.

In general, the process according to the invention is carried out such that a partial amount of the deionized water, of the dispersant and optionally a partial amount of the monomers A, B and / or C and of the free-radical initiator are initially introduced in the polymerization vessel at 20 to 25 ° C. (room temperature) under an inert gas atmosphere Then, the template mixture is heated with stirring to the appropriate polymerization temperature and then the residual amounts of deionized water and Dispersing aids and the total amounts or any remaining amounts of monomers A, B and / or C and radical initiator are metered. In this case, the metering of the monomers A, B and / or C, of the free-radical initiator and of the other components can be carried out batchwise in several sub-quantities as well as continuously with consistent or varying flow rates.

In a further preferred embodiment, the metering of the monomers A to C takes place in the form of two monomer emulsions, the first monomer emulsion (monomer emulsion 1) containing 60% by weight of the total monomer amount but <40% by weight of the total amount of the monomers B contains, while the second monomer emulsion (monomer emulsion 2) contains <_ 40 wt .-% of the total amount of monomers, but ^ 60 wt .-% of the total amount of monomers B. In this case, the process according to the invention takes place such that first monomer emulsion 1 and then monomer emulsion 2 is fed to the polymerization vessel under polymerization conditions. According to the invention, it is possible for a subset of the monomer emulsion 1 to be initially charged in the polymerization vessel and for the total amount or remaining amount of the monomer emulsion 1 to be added to the polymerization vessel batchwise under polymerization conditions in several portions or continuously with constant or varying flow rates. Following this, the monomer emulsion 2 is added to the polymerization vessel batchwise under polymerization conditions in several portions or continuously with constant or changing flow rates. Preferably, the dosage of the monomer emulsions 1 and 2 is carried out continuously with constant flow rates.

Advantageously, the choice of reaction conditions and the reaction procedure is such that after initiation of the radical polymerization reaction, the monomers A to C and the radical initiator are fed to the polymerization in the polymerization so that the monomer conversion at any time> _ 80 wt .-%, advantageously> _ 90% by weight, and particularly advantageously> 95% by weight, based on the total amount of monomers fed to the polymerization mixture at this time, which can be easily verified by reaction calorimetric measurements familiar to the person skilled in the art.

In principle, small quantities can also be used in the process according to the invention

(<10 wt .-% based on the total amount of water) of water-soluble organic solvents, such as methanol, ethanol, isopropanol, butanols, pentanols, but also acetone, etc. are used. However, the process according to the invention is preferably carried out in the absence of such solvents.

The reaction of the process according to the invention is advantageously carried out such that the polymerization mixture under polymerization> 60 wt .-% and <95 wt .-%, preferably> 60 wt .-% and <90 wt .-% and particularly preferably> 70 wt .-% and <90 wt .-% of the total amount of monomers B are added, after the polymerization were added under polymerization conditions> 70 wt .-%, preferably> 75 wt .-% and particularly preferably> 80 wt .-% of the total amount of monomer.

The aqueous copolymer dispersions obtained by the process according to the invention usually have a copolymer solids content of> 10 and <70% by weight, frequently> 20 and <65% by weight and often> 40 and <60% by weight, based in each case on the aqueous copolymer dispersion, on. The number-average particle diameter (cumulant z-average) determined by quasi-elastic light scattering (ISO standard 13,321) is generally between 10 and 2,000 nm, frequently between 20 and 300 nm and often between 30 and 200 nm.

Of course, the residual amounts of unreacted monomers A to C and other low-boiling compounds in the aqueous copolymers dispersions obtained according to the invention can be determined by chemical and / or physical methods familiar to the person skilled in the art [see, for example, EP-A 771328, DE-A 19624299, DE-A 19621027, DE-A 19741 184, DE-A 19741 187, DE-A 19805122, DE-A 19828183, DE-A 19839199, DE-A 19840586 and 198471 15].

Furthermore, from the aqueous copolymer dispersions according to the invention in a simple manner (for example freeze or spray drying), the corresponding copolymer powders are available. In this case, the aqueous polymer dispersions according to the invention are suitable in particular for spray-drying and in this case also have high powder yields and, at the same time, low caking tendency even without further spray aids.

As a further constituent, the molding compositions of the invention may contain from 0 to 70, preferably up to 50, in particular up to 40 wt .-% of further additives C).

Preferred fibrous reinforcing materials in amounts of up to 35% by weight, preferably 15 to 35% by weight, are carbon fibers, potassium titanate whiskers, aramid fibers and most preferably glass fibers. When using glass fibers, these can be used for better compatibility, e.g. be equipped with the thermoplastic polyamide (A) with a size and a coupling agent. In general, the glass fibers used have a diameter in the range of 6 to 20 microns.

The incorporation of these glass fibers can take place both in the form of short glass fibers and in the form of endless strands (rovings). In the finished injection molded part, the average length of the glass fibers is preferably in the range of 0.08 to 0.5 mm. As particulate fillers are amorphous silica, magnesium carbonate (chalk), kaolin (especially calcined kaolin), powdered quartz, mica, talc, feldspar and in particular calcium silicates such as wollastonite.

Preferred combinations of fillers are e.g. 20 wt .-% glass fibers with 10 to 15 wt .-% wollastonite and 15 wt .-% glass fibers with 15 wt .-% wollastonite.

Other additives C) are, for example, in amounts of up to 30, preferably 1 to 40 wt .-%, in particular 10 to 15 wt .-% of elastomeric polymers (often referred to as impact modifiers, elastomers or rubbers).

In general, these are copolymers which are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or methacrylic acid esters having 1 to 18 C atoms in the alcohol component.

Such polymers are e.g. in Houben-Weyl, Methods of Organic Chemistry, Vol. 14/1 (Georg Thieme Verlag, Stuttgart, 1961). Pages 392 to 406 and in the monograph of CB. Bucknall, "Toughened Plastics" (Applied Science Publishers, London, 1977).

In the following some preferred types of such elastomers are presented.

Preferred types of such elastomers are the so-called ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) rubbers.

EPM rubbers generally have virtually no double bonds, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.

As diene monomers for EPDM rubbers, for example, conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-1, 4-diene, hexa-1, 4-diene, hexa-1, 5 -diene, 2,5-dimethylhexa-1,5-diene and octa-1,4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadienes and also alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5- Butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyltricyclo (5.2.1.0 ² ' ^6. ) - 3,8-decadiene or mixtures thereof. Preference is given to hexa-1, 5-diene, 5-ethylidenenorbornene and dicyclopentadiene. The diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8 wt .-%, based on the total weight of the rubber. EPM or EPDM rubbers may preferably also be grafted with reactive carboxylic acids or their derivatives. Here, for example, acrylic acid, methacrylic acid and derivatives thereof, for example glycidyl (meth) acrylate, and maleic anhydride may be mentioned.

Another group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or the esters of these acids. In addition, the rubbers may still contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, e.g. Esters and anhydrides, and / or monomers containing epoxy groups. These dicarboxylic acid derivatives or monomers containing epoxy groups are preferably incorporated into the rubber by addition of monomers containing dicarboxylic acid or epoxy groups of the general formulas I or II or III or IV to the monomer mixture

R ¹ C (COOR ² ) = C (COOR ³ ) R ⁴ (I)

(Ii)

CHR ⁷ = CH (CH ₂ ) _m O (CHR ⁶ ) _α CH CHR ⁵ (IM)

CH = CR ⁹ COO (CH ₂ ) _p CH-CHR ⁸ (IV)

\ /

O wherein R ¹ to R ^{9 are} hydrogen or alkyl groups having 1 to 6 carbon atoms and m is an integer from 0 to 20, g is an integer from 0 to 10 and p is an integer from 0 to 5

The radicals R ¹ to R ⁹ preferably denote hydrogen, where m is O or 1 and g is 1. The corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.

Preferred compounds of the formulas I, II and IV are maleic acid, maleic anhydride and epoxy group-containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate, glycidyl methacrylate and the esters with tertiary alcohols, such as t-butyl acrylate. Although the latter have no free carboxyl groups, their behavior is close to the free acids and are therefore termed monomers with latent carboxyl groups. Advantageously, the copolymers consist of 50 to 98 wt .-% of ethylene, 0.1 to 20 wt .-% of monomers containing epoxy groups and / or methacrylic acid and / or acid-anhydride-containing monomers and the remaining amount of (meth) acrylic acid esters.

Particularly preferred are copolymers of

50 to 98.9, in particular 55 to 95% by weight of ethylene,

0.1 to 40, in particular 0.3 to 20 wt .-% glycidyl acrylate and / or glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydride, and

1 to 45, in particular 5 to 40 wt .-% n-butyl acrylate and / or 2-ethylhexyl acrylate.

Further preferred esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters.

In addition, vinyl esters and vinyl ethers can also be used as comonomers.

The ethylene copolymers described above can be prepared by methods known per se, preferably by random copolymerization under high pressure and elevated temperature. Corresponding methods are generally known.

Preferred elastomers are also emulsion polymers, their preparation e.g. at Blackley in the monograph "Emulsion Polymerization". The emulsifiers and catalysts which can be used are known per se.

Basically, homogeneously constructed elastomers or those with a shell structure can be used. The shell-like structure is determined by the order of addition of the individual monomers; the morphology of the polymers is also influenced by this order of addition.

Representatives which may be mentioned here as monomers for the preparation of the rubber part of the elastomers are acrylates such as, for example, n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene, and mixtures thereof. These monomers can be copolymerized with other monomers such as styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate. The soft or rubber phase (with a glass transition temperature below 0 ^° C.) of the elastomers can be the core, the outer shell or a middle shell (in the case of elastomers with more than two-shelled construction); in the case of multi-shell elastomers, it is also possible for a plurality of shells to consist of a rubber phase.

In addition to the rubber phase, one or more hard components (with glass transition temperatures of more than 2O ⁰ C) on the structure of the elastomer, so these are generally prepared by polymerization of styrene, acrylonitrile, methacrylonitrile, α-methylstyrene, p-methylstyrene, Acrylsäureestern and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as the main monomers. In addition, smaller proportions of other comonomers can also be used here.

In some cases it has proven to be advantageous to use emulsion polymers which have reactive groups on the surface. Such groups are e.g. Epoxy, carboxyl, latent carboxyl, amino or amide groups, and functional groups obtained by concomitant use of monomers of the general formula

R ¹⁰ R ¹¹

CH ₂ = CXNCR ¹²

O can be introduced

where the substituents may have the following meanings:

R ^{10 is} hydrogen or a C 1 to C 4 alkyl group,

R ^{11 is} hydrogen, a C 1 - to C 5 -alkyl group or an aryl group, in particular phenyl,

R ^{12 is} hydrogen, a C 1 to C 10 alkyl, a C 6 to C 12 aryl group or -OR ¹³

R ^{13 is} a C 1 - to C 5 -alkyl or C 6 - to C 12 -aryl group which may optionally be substituted by O- or N-containing groups,

X is a chemical bond, a C 1 -C 10 -alkylene or C 6 -C 12 -arylene group

O

- C - YY OZ or NH-Z and Z is a C 1 -C 10 -alkylene or C 6 -C 12 -arylene group.

The graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups on the surface.

Further examples which may be mentioned are acrylamide, methacrylamide and substituted esters of acrylic acid or methacrylic acid, such as (Nt-butylamino) -ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) -methyl acrylate and (N, N-) Diethylamino) ethyl acrylate.

Furthermore, the particles of the rubber phase can also be crosslinked. Examples of monomers acting as crosslinkers are buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and also the compounds described in EP-A 50 265.

Furthermore, so-called graft-linking monomers can also be used, i. Monomers having two or more polymerizable double bonds, which react at different rates in the polymerization. Preferably, those compounds are used in which at least one reactive group polymerizes at about the same rate as the other monomers, while the other reactive group (or reactive groups) e.g. polymerized much slower (polymerize). The different polymerization rates bring a certain proportion of unsaturated double bonds in the rubber with it. If a further phase is subsequently grafted onto such a rubber, the double bonds present in the rubber react at least partially with the grafting monomers to form chemical bonds, ie. the grafted phase is at least partially linked via chemical bonds to the graft base.

Examples of such graft-crosslinking monomers are allyl-containing monomers, in particular allyl esters of ethylenically unsaturated carboxylic acids, such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids. In addition, there are a variety of other suitable graft-linking monomers; for further details, reference is made here, for example, to US Pat. No. 4,148,846.

In general, the proportion of these crosslinking monomers in the impact-modifying polymer is up to 5% by weight, preferably not more than 3% by weight, based on the impact-modifying polymer. In the following, some preferred emulsion polymers are listed. First, graft polymers having a core and at least one outer shell, which have the following structure:

Instead of graft polymers having a multi-shell structure, homogeneous, i. single-shell elastomers of buta-1, 3-diene, isoprene and n-butyl acrylate or copolymers thereof are used. These products can also be prepared by concomitant use of crosslinking monomers or monomers having reactive groups.

Examples of preferred emulsion polymers are n-butyl acrylate / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers, graft polymers having an inner core of n-butyl acrylate or butadiene-based and an outer shell of the above copolymers and copolymers of ethylene with comonomers which provide reactive groups.

The described elastomers may also be prepared by other conventional methods, e.g. by suspension polymerization.

Silicone rubbers, as described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290, are likewise preferred.

Of course, it is also possible to use mixtures of the abovementioned rubber types. Further customary additives C) are, for example, stabilizers and oxidation inhibitors, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, dyes and pigments and plasticizers.

Pigments and dyes are generally included in amounts of up to 4, preferably 0.5 to 3.5 and especially 0.5 to 3 wt .-%.

The pigments for coloring thermoplastics are well known, see e.g. R. Gächter and H. Müller, Taschenbuch der Kunststoffadditive, Carl Hanser Verlag, 1983, pp. 494 to 510. The first preferred group of pigments are white pigments such as zinc oxide, zinc sulfide, lead white (2 PbCO3.Pb (OH) 2 ), Lithopone, antimony white and titanium dioxide. Of the two most common crystal modifications (rutile and anatase-type) of titanium dioxide, in particular the rutile form is used for the whitening of the molding compositions according to the invention.

Black color pigments which can be used according to the invention are iron oxide black (Fe.sub.3O.sub.4), spinel black (Cu (Cr, Fe) .sub.2O4), manganese black (mixture of manganese dioxide, silicon dioxide and iron oxide), cobalt black and antimony black, and particularly preferably carbon black, which is usually in the form of Furnace or gas black is used (see G. Benzing, pigments for paints, Expert Verlag (1988), p 78ff).

Of course, inorganic color pigments such as chromium oxide green or organic colored pigments such as azo pigments and phthalocyanines can be used according to the invention to adjust certain hues. Such pigments are generally commercially available.

Furthermore, it may be advantageous to mix said pigments or dyes, e.g. Carbon black with copper phthalocyanines, since in general the color dispersion in the thermoplastic is facilitated.

Oxidation retardants and heat stabilizers which can be added to the thermoplastic compositions according to the invention are, for example, halides of metals of group I of the Periodic Table, for example sodium, potassium, lithium halides, optionally in combination with copper (I) halides, For example, chlorides, bromides or iodides. The halides, especially of copper, may also contain electron-rich p-ligands. As an example of such copper complexes may be mentioned Cu-halide complexes with eg triphenylphosphine. Furthermore, zinc fluoride and zinc chloride can be used. Further, sterically hindered phenols, hydroquinones, substituted members of this group, secondary aromatic amines, optionally in combination with phosphorus-containing acids or their salts, and mixtures thereof Compounds, preferably in concentrations up to 1 wt .-%, based on the weight of the mixture, can be used.

Examples of UV stabilizers are various substituted resorcinols, salicylates, benzotriazoles and benzophenones, which are generally used in amounts of up to 2 wt .-%.

Lubricants and mold release agents, which are generally added in amounts of up to 1% by weight of the thermoplastic composition, are stearic acid, stearyl alcohol, stearic acid alkyl esters and amides and esters of pentaerythritol with long-chain fatty acids. Also salts of calcium, zinc or aluminum of stearic acid as well as dialkyl ketones, e.g. Distearyl ketone, are used.

Among the additives are also stabilizers which prevent the decomposition of the red phosphorus in the presence of moisture and atmospheric oxygen. Examples include compounds of cadmium, zinc, aluminum, tin, magnesium, manganese and titanium. Particularly suitable compounds are e.g. Oxides of said metals, furthermore carbonates or oxicarbonates, hydroxides and salts of organic or inorganic acids such as acetates or phosphates or hydrogen phosphates.

As flame retardants here only red phosphorus and the other known per se for polymers flame retardants are mentioned.

The thermoplastic molding compositions according to the invention in the presence of the components B) - D) can be prepared by processes known per se, by mixing the starting components in conventional mixing devices such as screw extruders, Brabender mills or Banbury mills and then extruded. In this case, component B) can be metered or premixed as an aqueous emulsion dispersion or as a copolymeric powder. After extrusion, the extrudate is cooled and comminuted.

The molding compositions of the invention are characterized by better mechanical properties, such as good impact strength and high elongation at break. In particular, they can be easily processed thermoplastically and are therefore suitable for the production of fibers, films and moldings. Fiber-reinforced molded bodies have a very good surface, so that they are particularly suitable for applications in vehicle construction and for E / E applications.

Further preferred applications are crash-relevant applications (automotive sector), as a higher energy consumption is possible. Examples

The following components were used:

Component A / 1:

Polybutylene terephthalate (PBT) with a viscosity number VZ of 130 ml / g, measured according to DIN 53728 or ISO 1628 on a 0.5 wt .-% solution in a 1: 1 mixture of phenol and o-dichlorobenzene at 25 ° C. , and a carboxyl end group content of 34 meq / kg. The commercial product Ultradur® B 4520 from BASF was used. The PBT contained as

Component C1:

Pentaerythritol tetrastearate in an amount of 0.65 wt .-%, based on 100 wt .-% of component A.

Component A / 2:

Polyamide 6,6, e.g. Ultramid® A3, characterized by a viscosity number of 150 ml / g (measured in 0.5% strength by weight sulfuric acid at 25 ° C. according to ISO 307), containing

Component C / 2:

0.2% by weight of Irganox® 1098 antioxidant from Ciba, based on A),

Component A / 3:

Polyamide 6, e.g. Ultramid® B3, characterized by a viscosity number of 150 ml / g, containing 0.2% by weight of component C / 2.

Component A / 4:

Polyamide 6, eg Ultramid® B3, characterized by a viscosity number of 150 ml / g. Component C / 3:

Glass fibers with a mean diameter of 10 microns.

Component C / 4:

Ca montanate.

Preparation of the aqueous copolymer dispersions

1) for PBT compounds

Copolymer dispersion B1 ("TCON 134")

In a 5 L pressure reactor, equipped with a MIG stirrer and 4 metering devices 1297 g of deionized water and 50 g of a 20 wt .-% aqueous alkylaryl sulfonate solution (Disponil LDBS 20 from Cognis) were submitted at room temperature and under a nitrogen atmosphere. Subsequently, the reactor contents were heated with stirring to 80 ⁰ C, and when reaching 80 ⁰ C 101 g of a 7 wt .-% aqueous sodium persulfate solution were added. Thereafter, the total amount of feed 1A was added within 80 minutes and time-delayed starting after 30 minutes, the feed 2 within 65 minutes each continuously with constant flow rates. Immediately after the end of feed 1 A, feed 1 B was started and metered in continuously within 15 minutes with constant flow rates. Subsequently allowed to the reactor contents for 5 hours at 80 ⁰ C to react further. Thereafter, the reactor contents were cooled to room temperature and the pressure vessel was relieved to atmospheric pressure. Coarse fractions were separated from the dispersion by filtration through a sieve (mesh size 100 microns).

Feed 1A homogeneous emulsion

300 gped water 135 g 20 wt. % aqueous alkylarylsulfonate solution (Disponil LDBS 20 from Cognis)

45 g of acrylonitrile

817.5 g of styrene

37.5 g of divinylbenzene (from Merck, 65% active substance) Feed 1 B homogeneous emulsion from 65 g of deionized water

15 g of 20% strength by weight aqueous alkylaryl sulphonate solution (Disponil LDBS 20 from Cognis)

20 g of acrylonitrile 60 g of styrene 20 g of divinylbenzene (from Aldrich, 65% active substance)

Inlet 2

57 g of a 7 wt .-% aqueous sodium persulfate solution

The aqueous copolymer dispersion B1 obtained had a solids content of 34.5% by weight, based on the total weight of the aqueous dispersion. The glass transition temperature was determined to be 1 14 ° C and the particle size to 57 nm.

Copolymer dispersion B2 ("TCON 147")

In a 5 l pressure reactor equipped with a MIG stirrer and 4 metering devices, 1297 g of deionized water and 50 g of a 20% by weight aqueous alkylarylsulfonate solution (Disponil LDBS 20 from Cognis) were added at room temperature and under a nitrogen atmosphere. submitted. Subsequently, the reactor contents were heated with stirring to 80 ⁰ C, and when reaching 80 ⁰ C, 95 g of a 0.75 wt .-% aqueous sodium persulfate solution was added. Thereafter, the total amount of feed 1A was added within 80 minutes and time-delayed starting after 30 minutes, the feed 2 within 65 minutes each continuously with constant flow rates. Immediately after the end of feed 1 A, feed 1 B was started and metered in continuously within 15 minutes with constant flow rates. Subsequently allowed to the reactor contents for 5 hours at 80 ⁰ C to react further. Thereafter, the reactor contents were cooled to room temperature and the pressure vessel was relieved to atmospheric pressure. Coarse fractions were separated from the dispersion by filtration through a sieve (mesh size 100 microns).

Feed 1A homogeneous emulsion

300 gped water

135 g of 20% strength by weight aqueous alkylarylsulfonate solution

(Disponil LDBS 20 from Cognis) 862.5 g of styrene

37.5 g of divinylbenzene (from Merck, 65% active substance) Feed 1 B homogeneous emulsion from 65 g of deionized water

15 g of 20% strength by weight aqueous alkylaryl sulphonate solution (Disponil LDBS 20 from Cognis)

20 g of methyl methacrylate 60 g of styrene 20 g of divinylbenzene (from Aldrich, 65% active substance)

Inlet 2

53 g of a 0.95 wt .-% aqueous sodium persulfate solution

The aqueous copolymer dispersion B2 obtained had a solids content of 34.2% by weight, based on the total weight of the aqueous dispersion. The glass transition temperature was determined to 120 ⁰ C and the particle size to 77 nm.

Copolymer dispersion B3 ("TCON 150")

In a 5 l pressure reactor equipped with a MIG stirrer and 4 metering devices, 1297 g of deionized water and 50 g of a 20% by weight aqueous alkylarylsulfonate solution (Disponil LDBS 20 from Cognis) were added at room temperature and under a nitrogen atmosphere. submitted. Subsequently, the reactor contents were heated with stirring to 80 ⁰ C, and when reaching 80 ° C, 101 g of a 7 wt .-% aqueous sodium persulfate solution was added. Thereafter, the total amount of feed 1A was added within 70 minutes and time-delayed starting after 30 minutes, the feed 2 within 70 minutes each continuously with constant flow rates. Immediately after the end of feed 1 A, the feed 1 B was started and metered in continuously within 30 minutes with constant flow rates. Subsequently, the reactor contents were allowed to react for a further 5 hours at 80 ^° C. Thereafter, the reactor contents were cooled to room temperature and the pressure vessel was relieved to atmospheric pressure. Coarse fractions were separated from the dispersion by filtration through a sieve (mesh size 100 microns).

Feed 1A homogeneous emulsion

235 g of water

120 g of 20% strength by weight aqueous alkylarylsulfonate solution (Disponil LDBS 20 from Cognis)

760 g of styrene 40 g of divinylbenzene (from Merck, 65% active substance) Feed 1 B homogeneous emulsion from 130 g of deionized water

30 g of 20% strength by weight aqueous alkylarylsulfonate solution (Disponil LDBS 20 from Cognis)

40 g of methyl methacrylate 120 g of styrene 40 g of divinylbenzene (from Aldrich, 65% active substance)

Inlet 2

57 g of a 7 wt .-% aqueous sodium persulfate solution

The aqueous copolymer dispersion B3 obtained had a solids content of 34.6% by weight, based on the total weight of the aqueous dispersion. The glass transition temperature was determined to 122 ° C and the particle size to 85 nm.

2) for PA compounds

Copolymer dispersion B4 ("TCON 102")

In a 5 L pressure reactor, equipped with a MIG stirrer and 4 metering devices 1297 g of deionized water and 50 g of a 20 wt .-% aqueous alkylaryl sulfonate solution (Disponil LDBS 20 from Cognis) were submitted at room temperature and under a nitrogen atmosphere. Thereafter, the reactor contents under Rüh- was ren at 80 ⁰ C is heated, and upon reaching 80 ⁰ C 101 g of a 7 wt .-% aqueous solution of sodium persulfate were added. Thereafter, the total amount of feed 1 was added within 90 minutes and time-delayed starting after 30 minutes, the feed 2 within 60 minutes each continuously with constant flow rates. Subsequently allowed to the reactor contents for 5 hours at 80 ⁰ C to react further. Thereafter, the reactor contents were cooled to room temperature and the pressure vessel was relieved to atmospheric pressure. Coarse fractions were separated from the dispersion by filtration through a sieve (mesh size 100 microns).

Feed 1 homogeneous emulsion

350 gped water

150 g of 20% strength by weight aqueous alkylarylsulfonate solution

(Disponil LDBS 20 from Cognis) 950 g of styrene

50 g of divinylbenzene (from Merck, 65% active substance) Inlet 2

57 g of a 7 wt .-% aqueous sodium persulfate solution

The aqueous copolymer dispersion B4 obtained had a solids content of 33.3% by weight, based on the total weight of the aqueous dispersion. The glass transition temperature was determined to be 1 19 ° C and the particle size to 52 nm.

Copolymer dispersion B5 ("TCON 177 + 178")

The copolymer dispersion Dxy was prepared analogously to the preparation of the copolymer dispersion Daa with the difference that the following composition of the feeds 1 A, 1 B and 2 was selected:

Feed 1A homogeneous emulsion

300 gped water

135 g of 20% strength by weight aqueous alkylarylsulfonate solution (Disponil LDBS 20 from Cognis)

862.5 g of styrene 37.5 g of divinylbenzene (from Merck, 65% active substance)

Feed 1 B homogeneous emulsion

65 g deionized water 15 g 20 wt. % aqueous alkylarylsulfonate solution (Disponil LDBS 20 from Cognis)

20 g of glycidyl methacrylate

60 g of styrene

20 g of divinylbenzene (from Aldrich, 65% active substance)

Inlet 2

57 g of a 7 wt .-% aqueous sodium persulfate solution

The aqueous copolymer dispersion B5 obtained had a solids content of 35.1% by weight, based on the total weight of the aqueous dispersion. The

Glass transition temperature was determined to be 1 19 ° C and the particle size to 80 nm.

The solids contents were generally determined by drying a defined amount of the particular aqueous copolymer dispersion (about 5 g) at 140 ^° C. in a drying oven until the weight remained constant. Two separate measurements were carried out in each case. The values given in the examples represent the mean of these two results. The determination of the glass transition temperature was carried out according to DIN 53765 by means of a DSC820 instrument, TA8000 series from Mettler-Toledo Int. Inc ..

The average particle diameter of the polymer particles was determined by dynamic light scattering on a 0.005 to 0.01% strength by weight aqueous polymer dispersion at 23 ° C. by means of an Autosizer NC from Malvern Instruments, England. The mean diameter of the cumulant evaluation (cumulant z-average) of the measured autocorrelation function (ISO standard 13321) is given.

Preparation of the spray-dried polymer powder

The spray drying was carried out in a Minor laboratory dryer of Ga. GEA Wiegand GmbH (business unit stainless steel) with two-fluid nozzle atomization and powder separation in a fabric filter. The tower inlet temperature of the nitrogen was 130 ⁰ C, the starting temperature 60 ⁰ C. per hour 2 kg of a spray feed were metered.

As spraying the dispersions B1, B2, B3, B4 and B5 were used, which were previously adjusted with deionized water to a solids content of 25 wt .-%.

At the same time as the spray feed, 0.4% by weight of the hydrophobic antiblocking agent Sipernat® D 17, based on the solids content of the spray feed, was continuously metered into the head of the spray tower via a weight-controlled twin screw.

The hydrophobic antiblocking agent Sipernat® D 17 from Degussa is a precipitated silica having a specific surface area (based on ISO 5794-1, Annex D) of 100 m 2 / g, an average particle size (based on ASTM C 690 -1992) of 7 microns and a tamped density (based on ISO 787-11) of 150 g / L, the surface of which was rendered hydrophobic by treatment with special chlorosilanes.

After spray-drying, the corresponding dispersion powders were obtained in the following yields B1: 91%, B2: 92%, B3: 92%, B4: 79% and B5: 92%.

Production of molding compounds

The components B) were on a twin-screw extruder (ZSK 30) at a temperature of

a) 260 ⁰ C for PBT and PA 6 b) 280 ⁰ C for polyamide 66 compounded.

The following mechanical measurements were made:

Tensile test ISO 527-2

Impact bending test ISO 179-2 / 1 at 23 ° C, 50% rel. Humidity,

Impact test ISO 179-2 at -30 ⁰ C,

Impact bending test ISO 179-2 / 1 eA (S) at 23 ° C, 50% rel. humidity

The compositions of the molding compositions and the results of the measurements are shown in the tables.

Table 1: Polyester molding compounds

Table 2: Polyamides

Claims

claims

1. Thermoplastic molding compositions containing

A) 10 to 99.9% by weight of a thermoplastic polymer,

B) 0.01 to 10 wt .-% of a copolymer obtainable by free-radically initiated aqueous emulsion polymerization of ethylenically unsaturated monomers in the presence of at least one dispersant and at least one free radical initiator according to the feed process, wherein the

emulsion

70 to 99.5% by weight of α, β-monoethylenically unsaturated compounds

[Monomers A], and 0.5 to 30% by weight of compounds having at least two free-radically copolymerizable ethylenically unsaturated groups [monomers B], and optionally up to 5% by weight of .alpha., .Beta. monoethylenically unsaturated mono- or dicarboxylic acids and / or their amides [monomers C],

be used, wherein the monomers A to C add to 100 wt .-% (total monomer) and the monomer feeds are such that> _ 60 wt .-% of the total amount of monomers B the polymerization under polymerization to a

Are metered in after the polymerization mixture> _ 60 wt .-% of the total amount of monomers were added under polymerization conditions,

C) 0 to 70% by weight of further additives,

wherein the sum of the weight percentages of components A) to C) is 100%.

2. Molding compositions according to claim 1, wherein 1 to 20 wt .-% of monomers B are used for the preparation of component B).

3. Molding compositions according to claim 1 or 2, wherein 2 to 10 wt .-% of monomers B are used for the preparation of component B).

4. Molding compositions according to one of claims 1 to 3, wherein> 60 wt .-% and

<95 wt .-% of the total amount of monomers B are metered for the preparation of component B).

5. Molding compositions according to any one of claims 1 to 4, wherein in the preparation of B) the monomers B are added at a time after the polymerization mixture> 70 wt .-% of the total amount of monomers were added under polymerization.

6. Molding compositions according to one of claims 1 to 5, wherein the monomers A and the monomers C are selected in type and amount so that a copolymer composed solely of these monomers B) would have a glass transition temperature> _ 40 ⁰ C.

7. Molding compositions according to one of claims 1 to 6, in which component B) is added as an aqueous dispersion or as a powder in the compounding of components A) to C).

8. Use of the molding compositions according to claims 1 to 7 for the production of moldings of any kind, fibers and films.

9. moldings obtainable from the thermoplastic molding compositions according to claims 1 to. 7th