WO2010028975A2 - Thermally conductive polyamide having increased flow capability - Google Patents

Abstract

The invention relates to thermoplastic moulding masses containing: A) 10 to 99 percent by weight of at least one thermoplastic polyamide; B) 0.01 to 30 percent by weight of at least one highly branched or hyper-branched polyether amine; C) 0.5 to 80 percent by weight of a thermally conductive filler; D) 0 to 70 percent by weight of further adjuncts, wherein the sum of the weight percentages of components A) to D) is 100 %.

Description

 Thermally conductive polyamide with increased flowability

description

The invention relates to thermoplastic molding compositions comprising

A) 10 to 99% by weight of at least one thermoplastic polyamide,

B) 0.01 to 30% by weight of at least one highly branched or hyperbranched polyetheramine,

C) 0.5 to 80% by weight of a thermally conductive filler,

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

where the sum of the weight percent of components A) to D) is 100%.

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

Polyetheramine (polyols) are usually prepared from trialkanolamines, e.g. Triethanol- amine, tripropanolamine, triisopropanolamine, optionally in admixture with mono- or dialkanolamines obtained by catalysis of these monomers, e.g. acidic or basic catalysis, etherified with elimination of water. The preparation of these polymers is e.g. in US Pat. No. 2,178,173, US Pat. No. 2,290,415, US Pat. No. 2,407,895 and DE 40 03 243. The polymerization can be carried out either statistically or block structures can be prepared from individual alkanolamines which are linked together in a further reaction (see also US Pat. No. 4,404,362).

The in the o.g. Literature described polyetheramine (polyols) are in free or quaternized form, e.g. used as emulsifiers for oil / water mixtures, as aftertreatment agent for dyed leather (DE 41 04 834) or as a lubricant for metal processing (CS 265 929).

In the recent EP application (EP 07123450.4) they are proposed as flow improvers for polyamides.

Lubricants are generally added for the flow improvement of thermoplastic polyesters and polycarbonates (see Gächter, Müller: Kunststoffadditive, 3rd ed. P. 479, 486-488, Carl Hanser Verlag 1989). Disadvantages here are in particular the blooming of the additives during processing. WO 97/45474 and EP-A 14 24 360 and WO 2006/42705 disclose dendritic polymers and dendrimers as additives for improving the flowability of thermoplastics. The disadvantage here is a very reduced effectiveness, as a function of the matrix polymer and / or in the case of high molecular weight thermoplastics.

The object of the present invention was therefore to increase the flowability and / or heat aging of polyamide molding compositions, wherein the decrease in molecular weight should be as low as possible. Furthermore, the additive should be present in as small amounts as possible in the matrix. The mechanics of the molding compounds should be preserved as much as possible and the additive should not bloom during processing.

Accordingly, the thermoplastic molding compounds mentioned at the beginning, their use, and the moldings, films and fibers obtainable from them have been found. Preferred embodiments of the invention can be found in the subclaims.

Note on the amounts given below: in the case of the thermoplastic molding composition, the amounts of components A) to D) within the ranges mentioned are selected such that the sum of components A) to C) and optionally D) is 100% by weight. % added; Component D) is optional.

As component A), the molding compositions according to the invention contain 10 to 99, preferably 20 to 79.95 and in particular 20 to 49.95% by weight of at least one thermoplastic polyamide A).

The polyamides of the molding compositions according to the invention generally have a viscosity number of 70 to 350, preferably 70 to 200 ml / g, determined in a 0.5 wt .-% solution in 96 wt .-% sulfuric acid at 25 ° C according to ISO 307th

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 m-xylylenediamine, di (4-aminophenyl) methane, di (4-amino-cyclohexyl) methane, 2,2-di (4 -aminophenyl) -propane, 2,2-di (4-aminocyclohexyl) propane or 1, 5-diamino-2-methyl-pentane.

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

Further suitable polyamides are obtainable from ω-aminoalkyl nitriles such as, for example, aminocapronitrile (PA 6) and adiponitrile with hexamethylenediamine (PA 66) by so-called direct polymerization in the presence of water, as for example in DE-A 10313681, EP-A 1 198491 and EP 922065 described.

In addition, mention should also be made of polyamides which are e.g. are obtainable by condensation of 1, 4-diaminobutane with adipic acid at elevated temperature (polyamide 4.6). Manufacturing processes for polyamides of this structure are known e.g. in EP-A 38 094, EP-A 38 582 and EP-A 39 524 described.

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, in particular those whose triamine content is less than 0.5, preferably less than 0.3 wt .-% (see EP-A 299 444 ).

The preparation of the preferred partially aromatic copolyamides having a low triamine content can be carried out by the processes described in EP-A 129,195 and 129,196.

The preferred partially aromatic copolyamides A) contain, as component a-i), 40 to 90% by weight of units derived from terephthalic acid and hexamethylenediamine. A small proportion of the terephthalic acid, preferably not more than 10% by weight of the total aromatic dicarboxylic acids used, can be replaced by isophthalic acid or other aromatic dicarboxylic acids, preferably those in which the carboxyl groups are in the para position.

In addition to the units derived from terephthalic acid and hexamethylenediamine, the partly aromatic copolyamides contain units derived from ε-caprolactam (a2) and / or units derived from adipic acid and hexamethylenediamine (a3). The proportion of units derived from ε-caprolactam is at most 50% by weight, preferably 20 to 50% by weight, in particular 25 to 40% by weight, while the proportion of units derived from adipic acid and Hexamethylenediamine, up to 60 wt .-%, preferably 30 to 60 wt .-% and in particular 35 to 55 wt .-% is.

The copolyamides may also contain both units of ε-caprolactam and units of adipic acid and hexamethylenediamine; In this case it is to be ensured that the proportion of units which are free of aromatic groups is at least 10% by weight, preferably at least 20% by weight. The ratio of the units derived from ε-caprolactam and from adipic acid and hexamethylenediamine is subject to no particular restriction.

Polyamides having from 50 to 80, in particular from 60 to 75,% by weight of units derived from terephthalic acid and hexamethylenediamine (units a ₁ )) and from 20 to 50, preferably from 25 to 40,% by weight have proven particularly advantageous for many applications. Units derived from ε-caprolactam (units a2)), proved.

In addition to the above-described units ai) to a3), the partly aromatic copolyamides according to the invention may also contain minor amounts, preferably not more than 15% by weight, in particular not more than 10% by weight, of further polyamide units (a ₄ ), as described in US Pat other polyamides are known. These building blocks can be derived from dicarboxylic acids having 4 to 16 carbon atoms and aliphatic or cycloaliphatic diamines having 4 to 16 carbon atoms and from aminocarboxylic acids or corresponding lactams having 7 to 12 carbon atoms. Suitable monomers of these types are only suberic acid, azelaic acid, sebacic acid or isophthalic acid as representatives of the dicarboxylic acids, 1,4-butanediamine, 1,5-pentanediamine, piperazine, 4,4'-diaminodicyclohexylmethane, 2,2- (4,4 ') - Diaminodicyclohexyl) propane or 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane as representatives of the diamines and capryllactam, enantiolactam, omega-aminoundecanoic acid and laurolactam as representatives of lactams or aminocarboxylic called.

The melting points of the partially aromatic copolyamides A) are in the range from 260 to more than 300 ° C., this high melting point also being associated with a high glass transition temperature of generally more than 75, in particular more than 85 ° C.

Binary copolyamides based on terephthalic acid, hexamethylenediamine and ε-caprolactam have, at levels of about 70% by weight of units derived from terephthalic acid and hexamethylenediamine, melting points in the region of 300 ° C. and a glass transition temperature of more than 1 10 ° C on. Binary copolyamides based on terephthalic acid, adipic acid and hexamethylenediamine (HMD) reach melting points of 300 ° C. or more even at lower contents of about 55% by weight of units of terephthalic acid and hexamethylenediamine, the glass transition temperature being not as high as in the case of binary copolyamides which contain ε-caprolactam instead of adipic acid or adipic acid / HMD.

The following non-exhaustive list contains the mentioned, as well as other polyamides A) in the context of the invention and the monomers contained.

AB-polymers:

PA 4 pyrrolidone

PA 6 ε-caprolactam

PA 7 ethanolactam

PA 8 capryllactam

PA 9 9-aminopelargonic acid

PA 1 1 1 1-aminoundecanoic acid

PA 12 laurolactam

AA / BB-polymers

PA 46 tetramethylenediamine, adipic acid

PA 66 hexamethylenediamine, adipic acid

PA 69 hexamethylenediamine, azelaic acid

PA 610 hexamethylenediamine, sebacic acid

PA 612 hexamethylenediamine, decanedicarboxylic acid

PA 613 hexamethylenediamine, undecanedicarboxylic acid

PA 1212 1, 12-dodecanediamine, decanedicarboxylic acid

PA 1313 1, 13-diaminotridecane, undecanedicarboxylic acid

PA 6T hexamethylenediamine, terephthalic acid

PA 9T nonyldiamine / terephthalic acid

PA MXD6 m-xylylenediamine, adipic acid

PA 6I hexamethylenediamine, isophthalic acid

PA 6-3-T trimethylhexamethylenediamine, terephthalic acid

PA 6 / 6T (see PA 6 and PA 6T)

PA 6/66 (see PA 6 and PA 66)

PA 6/12 (see PA 6 and PA 12)

PA 66/6/610 (see PA 66, PA 6 and PA 610)

PA 6I / 6T (see PA 6I and PA 6T)

PA PACM 12 diaminodicyclohexylmethane, laurolactam

PA 6I / 6T / PACM such as PA 6I / 6T + diaminodicyclohexylmethane PA 12 / MACMI laurolactam, dimethyldiaminodicyclohexylmethane,

Isophthalic acid PA 12 / MACMT laurinlactam, dimethyldiaminodicyclohexylmethane,

Terephthalic acid PA PDA-T Phenylenediamine, terephthalic acid

However, it is also possible to use mixtures of the above polyamides.

As component B), the molding compositions according to the invention contain from 0.01 to 30, preferably from 0.05 to 10, and in particular from 0.05 to 5,% by weight of at least one hyperbranched polyetheramine.

Component B) is obtainable by reacting at least one tertiary amine with hydroxy functional groups, preferably at least one di-, tri- or tetraalkanolamine with optionally secondary amines which carry hydroxyl groups as a substituent, in particular dialkanolamines or optionally with di- or higher-functional polyether polyols, preferably in Presence of a transetherification and etherification catalyst.

Preferred tertiary dialkanolamines having hydroxy functional groups are

Diethanolalkylamines having C1 to C30, in particular C1 to C18-alkyl radicals,

diethanolamine,

Dipropanolamine diisopropanolamine,

dibutanolamine,

Dipentanolamin,

dihexanolamine,

N-methyl-diethanolamine, N-methyl-dipropanolamine,

N-methyl-diisopropanolamine,

N-methyl dibutanolamine,

N-methyl-Dipentanolamin,

N-methyl-dihexanolamine, N-ethyl-diethanolamine,

N-ethyl-dipropanolamine,

N-ethyl diisopropanolamine,

N-ethyl-dibutanolamine,

N-ethyl-dipentanolamine, N-ethyl-dihexanolamine,

N-propyl diethanolamine,

N-propyl-dipropanolamine,

N-propyl-diisopropanolamine, N-propyl-dibutanolamine, N-propyl-dipentanolamine, N-propyl-dihexanolamine,

Diethanolethylamin,

Diethanolpropylamin,

diethanol,

Dipropanolmethylamin,

Cyclohexanol diethanolamine, dicyclohexanolethanolamine,

dibutyldithiocarbamate,

Dicyclohexyldiethanolamin,

Dicyclohexanolethylamin,

Benzyldiethanolamine, dibenzylethanolamine,

Benzyldipropanolamin,

Tripentanolamin,

Trihexanolamin,

Ethylhexylethanolamine, octadecyldiethanolamine,

Polyethanolamine,

Preferred trialkanolamines are

trimethanolamine

triethanolamine,

tripropanolamine,

triisopropanolamine,

Tributanolamine, tripentanolamine,

or derivatives derived therefrom.

/

Preferably R ¹ = CH ₂ -CH ₂ to (CH ₂ Je, preferably (CH ₂ ) ₂ - (CH ₂ ) ₄ R ² -R 5 = C ₂ to C ₆ , preferably C ₂ and C ₃ , for example N, N, N ', N'-tetrahydroxyethylethylenediamine, N, N, N', N'-tetrahydroxyethylbutylenediamine, N, N, N ', N'-tetrahydroxypropylethylenediamine, N, N, N', N'-tetrahydroxyisopropylethylenediamine, N, N, N ' , N'-Tetrahydroxypropylbutylenediamine, N, N, N ', N'-tetrahydroxyisopropylbutylenediamine. Particularly preferred component B) is obtainable by intermolecular polycondensation of at least one trialkanolamine of the general formula

in which the radicals R ¹ to R ³ independently of one another are identical or different, preferably alkylene, groups having 2 to 10 C atoms, preferably 2 to 6 C atoms.

The starting material used is preferably triethanolamine, tripropanolamine, triisopropanolamine or tributanolamine or mixtures thereof; optionally in combination with dialkanolamines, such as diethanolamine, dipropanolamine, diisopropanolamine, dibutanolamine, N, N'-dihydroxyalkyl-piperidine (alkyl = C1-C8), dicyclohexanolamine, dipentanolamine, dihexanolamine, with dialkanolamines being preferred.

Furthermore, the o.g. Trialkanolamine optionally be used in combination with di- or higher functional polyetherols, in particular based on ethylene oxide and / or propylene oxide.

However, very particular preference is given to using triethanolamine and triisopropanolamine or mixtures thereof as starting material.

The highly functional highly branched or hyperbranched polyetheramines formed by the process according to the invention are terminated with hydroxyl groups after the reaction, ie without further modification. They dissolve well in various solvents.

Examples of such solvents are aromatic and / or (cyclo) aliphatic hydrocarbons and mixtures thereof, halogenated hydrocarbons, ketones, esters and ethers.

Preference is given to aromatic hydrocarbons, (cyclo) aliphatic hydrocarbons, alkanoic acid alkyl esters, ketones, alkoxylated alkanoic acid alkyl esters and mixtures thereof.

Particularly preferred are mono- or polyalkylated benzenes and naphthalenes, ketones, Alkansäurealkylester and alkoxylated Alkansäurealkylester and mixtures thereof. Preferred aromatic hydrocarbon mixtures are those which comprise predominantly aromatic C 7 - to C 14 -hydrocarbons and may have a boiling range of from 10 to 300 ° C., particular preference is given to toluene, o-, m- or p-xylene, trimethylbenzene isomers, tetramethylbenzene isomers, ethylbenzene , Cumene, tetrahydronaphthalene and mixtures containing such.

Examples include the Solvesso® brands of ExxonMobil Chemical, especially Solvesso® 100 (CAS No. 64742-95-6, predominantly Cg and Cio aromatics, boiling range about 154-178 ° C), 150 (boiling range about 182 -207 ° C) and 200 (CAS No. 64742-94-5), and Shell's Shellsol® grades. Hydrocarbon mixtures on paraffins, cycloparaffins and aromatics are also known under the designations crystal oil (for example crystal oil 30, boiling range about 158-198 ° C. or crystal oil 60: CAS No. 64742-82-1), white spirit (for example likewise CAS No. 64747). 82-1) or solvent naphtha (light: boiling range about 155-180 ° C, heavy: boiling range about 225-300 °), commercially available. The aromatic content of such hydrocarbon mixtures is generally more than 90% by weight, preferably more than 95, more preferably more than 98, and very preferably more than 99% by weight. It may be useful to use hydrocarbon mixtures with a particularly reduced content of naphthalene.

The content of aliphatic hydrocarbons is generally less than 5, preferably less than 2.5 and more preferably less than 1 wt .-%.

Halogenated hydrocarbons are, for example, chlorobenzene and dichlorobenzene or isomeric mixtures thereof.

Esters include, for example, n-butyl acetate, ethyl acetate, 1-methoxypropyl acetate-2 and 2-methoxyethyl acetate.

Ethers are, for example, THF, dioxane and the dimethyl, ethyl or n-butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol.

Examples of ketones are acetone, 2-butanone, 2-pentanone, 3-pentanone, hexanone, isobutyl methyl ketone, heptanone, cyclopentanone, cyclohexanone or cycloheptanone.

Examples of (cyclo) aliphatic hydrocarbons are decalin, alkylated decalin and isomer mixtures of straight-chain or branched alkanes and / or cycloalkyls.

Preference is furthermore given to n-butyl acetate, ethyl acetate, 1-methoxypropyl acetate-2,3-methoxyethyl acetate, 2-butanone, isobutyl methyl ketone and mixtures thereof, in particular with the abovementioned aromatic hydrocarbon mixtures. Such mixtures can be prepared in a volume ratio of 5: 1 to 1: 5, preferably in a volume ratio of 4: 1 to 1: 4, more preferably in a volume ratio of 3: 1 to 1: 3 and most preferably in a volume ratio of 2: 1 to 1: 2 ,

Preferred solvents are butyl acetate, methoxypropyl acetate, isobutyl methyl ketone, 2-butanone, Solvesso® brands and xylene.

Other suitable solvents for the polyetheramines are, for example, water, alcohols, such as methanol, ethanol, butanol, alcohol / water mixtures, acetone, 2-butanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, ethylene carbonate or propylene carbonate.

In the context of this invention, a highly functional hyperbranched or hyperbranched polyetheramine is to be understood as meaning a product which, in addition to the ether groups and the amino groups which form the polymer backbone, also has an average of at least three, preferably at least six, more preferably at least has ten functional groups. The functional groups are OH groups. In principle, the number of terminal or pendant functional groups is not limited to the top, but products having a very large number of functional groups may have undesirable properties such as high viscosity or poor solubility. The high-functionality polyetheramine polyols of the present invention generally have not more than 500 terminal or pendant functional groups, preferably not more than 100 terminal or pendant groups.

In the context of this invention, hyperbranched polyetheramines are understood as meaning undyed macromolecules having hydroxyl, ether and amine groups which are structurally as well as molecularly nonuniform. They can be constructed on the one hand, starting from a central molecule analogous to dendrimers, but with uneven chain length of the branches. On the other hand, they can also be constructed linearly with functional side groups or, as a combination of the two extremes, they can have linear and branched molecular parts. For the definition of dendrimeric and hyperbranched polymers see also PJ. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, no. 14, 2499.

The polyetheramines are prepared either in bulk or in solution. Suitable solvents are the solvents already mentioned above. It is a preferred embodiment to carry out the reaction without solvent.

The temperature during production should be sufficient for the reaction of the amino alcohol. As a rule, a temperature of 100 ° C is required for the reaction 350 ° C, preferably 150 to 300, more preferably 180 to 280 ° C and especially 200 to 250 ° C required.

In a preferred embodiment, the condensation reaction is carried out in bulk. The water or low molecular weight reaction products liberated in the reaction may be removed from the reaction equilibrium to accelerate the reaction, e.g. by distillation, if appropriate under reduced pressure.

Separation of the water or low molecular weight reaction products can also be accomplished by passing a stream of gas substantially inert under the reaction conditions (stripping), e.g. Nitrogen or noble gas, for example helium, neon or argon, be supported.

To accelerate the reaction, it is also possible to add catalysts or catalyst mixtures. Suitable catalysts are compounds which catalyze etherification or transetherification reactions, e.g. Alkali metal hydroxides, alkali metal carbonates, alkali hydrogen carbonates, preferably of sodium, potassium or cesium, acidic compounds such as iron chloride or zinc chloride, formic acid, oxalic acid or phosphorus-containing acidic compounds such as phosphoric acid, polyphosphoric acid, phosphorous acid or hypophosphorous acid.

Preference is given to using phosphoric acid, phosphorous acid or hypophosphorous acid, if appropriate in a form diluted with water.

The addition of the catalyst is generally carried out in an amount of 0.001 to 10, preferably from 0.005 to 7, particularly preferably 0.01 to 5 mol%, based on the amount of alkanolamine or alkanolamine used.

Furthermore, it is also possible to control the intermolecular polycondensation reaction both by adding the appropriate catalyst and by selecting a suitable temperature. Furthermore, the average molecular weight of the polymer can be adjusted via the composition of the starting components and over the residence time.

The polymers prepared at elevated temperature are usually stable at room temperature for a longer period of time, for example for at least 6 weeks, without turbidity, precipitation and / or viscosity increase.

There are various possibilities for stopping the intermolecular polycondensation reaction. For example, the temperature can be lowered to a range in which the reaction comes to a standstill and the polycondensation product is storage-stable. This is usually below 60 ° C, preferably below 50 ° C, especially It prefers below 40 ° C and most preferably at room temperature the case.

Furthermore, one can deactivate the catalyst, for basic catalysts e.g. by adding an acidic component, e.g. a Lewis acid or an organic or inorganic protic acid, in the case of acidic catalysts by addition of a basic component, e.g. a Lewis base or an organic or inorganic base.

Further, it is possible to stop the reaction by dilution with a pre-cooled solvent. This is particularly preferred if it is necessary to adjust the viscosity of the reaction mixture by adding solvent.

The high-functionality highly branched or hyperbranched polyetheramines according to the invention generally have a glass transition temperature of less than 50 ° C., preferably less than 30 and particularly preferably less than 10 ° C.

The OH number is usually 50 to 1000 mg KOH / g, preferably 100 to 900 mg KOH / g and most preferably 150 to 800 mg KOH / g.

The weight-average molecular weight M _w is usually between 1,000 and 500,000, preferably from 2,000 to 300,000 g / mol, the number average molecular weight M _n between 500 and 50,000, preferably between 1,000 and 40,000 g / mol, measured by gel permeation chromatography with hexafluoroisopropanol as the mobile phase and polymethylmethacrylate (PMMA) as standard.

The preparation of the highly functional polyetheramines according to the invention is usually carried out in a pressure range from 0.1 mbar to 20 bar, preferably at 1 mbar to 5 bar, in reactors or reactor cascades which are operated batchwise, semicontinuously or continuously.

By the aforementioned adjustment of the reaction conditions and optionally by the choice of the suitable solvent, the products according to the invention can be further processed after preparation without further purification.

If necessary, the reaction mixture may be discolored, for example, by treatment with activated carbon or metal oxides such as alumina, silica, magnesia, zirconia, boria or mixtures thereof, in amounts of, for example, 0.1 to 50% by weight, preferably 0.5 to 25 wt .-%, particularly preferably 1 to 10 wt .-% at temperatures of for example 10 to 100 ° C, preferably 20 to 80 ° C and particularly preferably 30 to 60 ° C are subjected. Optionally, the reaction mixture may also be filtered to remove any precipitates that may be present.

In a further preferred embodiment, the product is stripped, that is freed from low molecular weight, volatile compounds. For this purpose, after reaching the desired degree of conversion, the catalyst can optionally be deactivated and the low molecular weight volatiles, e.g. Water, the amino alcohols used as starting material or volatile oligomeric or cyclic compounds by distillation, optionally with the introduction of a gas, preferably nitrogen, or noble gases, optionally at reduced pressure, are removed.

The highly functional highly branched polyetheramines formed by the process according to the invention are terminated with hydroxyl groups after the reaction, ie without further modification. They dissolve well in various solvents, e.g. in water, alcohols, such as methanol, ethanol, butanol, alcohol / water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxyethyl acetate, terahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate or propylene carbonate.

As component C), the molding compositions according to the invention contain 0.5 to 80, preferably 20 to 70 and in particular 50 to 60 wt .-% of a thermally conductive filler.

Preferred fillers are Al oxides, MgO, ZnO, ZrO, boron nitrides, graphite or carbon fibers or mixtures thereof.

Suitable Al oxides preferably have an aspect ratio of less than 10, preferably less than 7.5 and in particular less than 5.

The preferred average particle diameter (dso) is from 0.2 to 20, preferably from 0.3 to 15 and in particular from 0.35 to 10 microns according to laser granulometry according to ISO 13320-1.

Such products are commercially available, for example, from Almatis.

As a rule, a dso value is understood to mean the particle size value (particle diameter) at which 50% of the particles have a smaller particle size and 50% have a larger particle size.

The dio value is preferably less than 10 μm, in particular less than 5 μm and very particularly preferably less than 2.2 μm. Preferred d ₉₀ values are less than 50 μm and in particular less than 30 μm and very particularly preferably less than 30 μm.

Aluminas, alumina, AI2O3, MG. 101, 96. The oxides occur in various modifications, of which the hexagonal α-oxide is the only thermodynamically stable modification. Well characterized is still the face-centered cubic Y-Al2O3. It is formed from the aluminum hydroxides by heating to 400-800 ° C and, like the other modifications, can be converted by annealing to more than 1 100 ° into the 0AI2O3. By β-Al ₂ O ₃ is meant a group of oxides containing small amounts of foreign ions in the crystal lattice. Other modifications, as well as the numerous transitional forms between the aluminum hydroxides and the two, are less significant. Preference is given to α-Al ₂ O ₃ , density 3.98, hardness 9, mp 2053 ° C, which is insoluble in water, acids u. Bases is. Technically, the α-Al ₂ O _{3 is obtained} from bauxite according to the Bayer process. The main quantity serves for the electrolytic production of aluminum. The oxides are as a thin protective layer on aluminum; By chemical or anodic oxidation, this oxide layer can be strengthened.

In nature, 0Al2O3 occurs as corundum, mp 2050 ° C. Corundum is usually clouded by impurities and often colored. Today corundum is technically obtained as electrocorundum; This melts from Bauxid won AI2O3. in an electric arc furnace above 2000 ° C. This gives a very hard product with about 99% α-Al ₂ O ₃ .

The so-called active oxides are prepared by precipitation methods from aluminum salt solution - e.g. via thermally treated aluminum hydroxide gels - or by calcination from α-aluminum hydroxide at low temperatures or by impact heating.

Component B) preferably has a BET specific surface area (according to ISO 9277) of <12, preferably at least 0.1, preferably at least 0.3 m ² / g.

The preferred density is 2.5 to 4.5, especially 3.9 to 4.0 g / cm ³ .

The sodium oxide content is preferably less than 0.4, in particular from 0.01 to 0.35 wt .-%, based on 100 wt .-% B).

The thermal conductivity in accordance with DIN 52612 is preferably at least 20 W / mK and in particular at least 25 W / mK.

Suitable Mg oxides preferably have an aspect ratio of less than 10, preferably less than 7.5 and in particular less than 5. Preferred oxides have a BET surface area according to DIN 66131 of less than or equal to 14 m ² / g, preferably less than or equal to 10 m ² / g.

The preferred average particle diameter (d ₅₀ ) is from 0.2 to 20, preferably from 0.3 to 15 and in particular from 0.35 to 10 microns according to laser granulometry according to ISO 13320 EN.

Such products are commercially available, for example, from Almatis.

Suitable boron nitrides have in particular a hexagonal modification. The particle sizes d ₅₀ are generally 1 to 50 .mu.m, preferably 2 to 20 .mu.m, the thermal conductivity is> 100 W / m K, preferably> 150 W / m K.

As component D), the molding compositions according to the invention may contain from 0 to 70, in particular up to 30% by weight of further additives and processing aids which are different from C) / B) and / or A).

According to the invention, the thermoplastic molding compositions may contain, as component D1), from 0.01 to 30% by weight of at least one polyethyleneimine homopolymer or copolymer. The proportion of D1) is preferably from 0.3 to 4% by weight and in particular from 0.3 to 3% by weight, based on A) to D).

The preferred ratio of B to D1) is 10: 1 to 1:10, especially 2: 1 to 1: 2.

For the purposes of the present invention, polyethyleneimines are to be understood as meaning both homopolymers and copolymers which are obtainable, for example, by the processes in Ullmann Electronic Release under the heading "aziridines" or according to WO-A 94/12560.

The homopolymers are generally obtainable by polymerization of ethyleneimine (aziridine) in aqueous or organic solution in the presence of acid-releasing compounds, acids or Lewis acids. Such homopolymers are branched polymers, which usually contain primary, secondary and tertiary amino groups in the ratio of about 30% to 40% to 30%. The distribution of the amino groups can be determined in general by means of ¹³ C-NMR spectroscopy.

Comonomers used are preferably compounds which have at least two amino functions. Examples of suitable comonomers are alkylenediamines having 2 to 10 C atoms in the alkylene radical, with ethylenediamine and propylenediamine being preferred. Further suitable comonomers are diethylene triamine, triethylene tetramine, tetraethylene pentamine, dipropylene triamine, tripropylene tetramine, dihexamethylenetriamine, aminopropylethylenediamine and Bisaminopropylethy- lendiamin.

Polyethyleneimines typically have a weight average molecular weight of from 100 to 3,000,000, preferably from 800 to 2,000,000 (as determined by light scattering).

In addition, crosslinked polyethyleneimines which are obtainable by reaction of polyethyleneimines with bifunctional or polyfunctional crosslinkers which have as a functional group at least one halohydrin, glycidyl, aziridine, isocyanate unit or a halogen atom are suitable. Examples include its epichlorohydrin or bischlorohydrin ether of polyalkylene glycols having 2 to 100 ethylene oxide and / or propylene oxide units and the compounds listed in DE-A 19 93 17 20 and US 4,144,123. Methods of making crosslinked polyethyleneimines include, but are not limited to, from the o.g. Fonts and EP-A 895 521 and EP-A 25 515 known.

Furthermore, grafted polyethyleneimines are suitable, it being possible for all compounds which can react with the amino or imino groups of the polyethyleneimines to be used as the grafting agent. Suitable grafting agents and processes for the preparation of grafted polyethyleneimines can be found, for example, in EP-A 675 914.

Likewise suitable polyethyleneimines in the context of the invention are amidated polymers which are usually obtainable by reacting polyethyleneimines with carboxylic acids, their esters or anhydrides, carboxamides or carboxylic acid halides. Depending on the proportion of amidated nitrogen atoms in the Polyethyleniminkette the amidated polymers can be subsequently crosslinked with said crosslinkers. Preferably, up to 30% of the amino functions are amidated, so that sufficient primary and / or secondary nitrogen atoms are available for a subsequent crosslinking reaction.

Also suitable are alkoxylated polyethyleneimines, which are obtainable, for example, by reacting polyethyleneimine with ethylene oxide and / or propylene oxide. Such alkoxylated polymers are also crosslinkable.

Further suitable polyethyleneimines according to the invention are hydroxyl-containing polyethyleneimines and amphoteric polyethyleneimines (incorporation of anionic groups) and lipophilic polyethyleneimines which are generally obtained by incorporation of long-chain hydrocarbon radicals into the polymer chain. Processes for the preparation of such polyethyleneimines are known to the person skilled in the art, so that further details are unnecessary. As component D), the molding compositions according to the invention may contain 0 to 3, preferably 0.05 to 3, preferably 0.1 to 1, 5 and in particular 0.1 to 1 wt .-% of a lubricant.

Preference is given to Al, alkali metal, alkaline earth metal salts or ester or amides of fatty acids having 10 to 44 carbon atoms, preferably having 14 to 44 carbon atoms.

The metal ions are preferably alkaline earth and Al, with Ca or Mg being particularly preferred.

Preferred metal salts are Ca-stearate and Ca-montanate as well as Al-stearate.

It is also possible to use mixtures of different salts, the mixing ratio being arbitrary.

The carboxylic acids can be 1- or 2-valent. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and particularly preferably stearic acid, capric acid and montanic acid (mixture of fatty acids having 30 to 40 carbon atoms).

The aliphatic alcohols can be 1 - to 4-valent. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, with glycerol and pentaerythritol being preferred.

The aliphatic amines can be monohydric to trihydric. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, with ethylenediamine and hexamethylenediamine being particularly preferred. Correspondingly, preferred esters or amides are glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate.

It is also possible to use mixtures of different esters or amides or esters with amides in combination, the mixing ratio being arbitrary.

As further components D), the molding compositions according to the invention may contain heat stabilizers or antioxidants or mixtures thereof selected from the group of copper compounds, sterically hindered phenols, sterically hindered aliphatic amines and / or aromatic amines.

Copper compounds are in the novel PA molding compositions to 0.05 to 3, preferably 0.1 to 1, 5 and in particular 0.1 to 1 wt .-%, preferably as Cu (l) halide, in particular in a mixture with an alkali halide, preferential example KJ, in particular in the ratio 1: 4, or a sterically hindered phenol or an amine stabilizer or mixtures thereof.

Suitable salts of monovalent copper are preferably copper (I) acetate, copper (I) chloride, bromide and iodide. They are contained in amounts of 5 to 500 ppm copper, preferably 10 to 250 ppm, based on polyamide.

The advantageous properties are obtained in particular when the copper is present in molecular distribution in the polyamide. This is achieved by adding to the molding compound a concentrate containing polyamide, a salt of monovalent copper and an alkali halide in the form of a solid, homogeneous solution. A typical concentrate is e.g. from 79 to 95 wt .-% polyamide and 21 to 5 wt .-% of a mixture of copper iodide or bromide and potassium iodide. The concentration of the solid homogeneous solution of copper is preferably between 0.3 and 3, in particular between 0.5 and 2 wt .-%, based on the total weight of the solution and the molar ratio of copper (I) iodide to potassium iodide is between 1 and 11, 5, preferably between 1 and 5.

Suitable polyamides for the concentrate are homopolyamides and copolyamides, in particular polyamide 6 and polyamide 6.6.

Suitable hindered phenols are in principle all compounds having a phenolic structure which have at least one sterically demanding group on the phenolic ring.

Preferably, e.g. Compounds of the formula

in Betracht, in der bedeuten:

into consideration, in which mean:

R ¹ and R ^{2 are} an alkyl group, a substituted alkyl group or a substituted triazole group, wherein the radicals R ¹ and R ^{2 may be the} same or different and R ^{3 is} an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group.

Antioxidants of the type mentioned are described, for example, in DE-A 27 02 661 (US Pat. No. 4,360,617).

Another group of preferred sterically hindered phenols are derived from substituted benzenecarboxylic acids, especially substituted benzenepropionic acids. Particularly preferred compounds of this class are compounds of the formula

ihrerseits substituiert sein können (mindestens eine davon ist eine sterisch anspruchsvolle Gruppe) und R⁶ einen zweiwertigen aliphatischen Rest mit 1 bis 10 C-Atomen bedeutet, der in der Hauptkette auch C-O-Bindungen aufweisen kann.wherein R ⁴ , R ⁵ , R ⁷ and R ^{8 are} independently alkyl groups

may in turn be substituted (at least one of which is a sterically demanding group) and R ^{6 is} a divalent aliphatic radical having 1 to 10 carbon atoms, which may also have CO bonds in the main chain.

Preferred compounds corresponding to this formula are

(Irganox® 245 from Ciba-Geigy

(Irganox® 259 from Ciba-Geigy)

By way of example, the following may be mentioned by way of example as sterically hindered phenols:

2,2'-methylenebis (4-methyl-6-tert-butylphenol), 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate ], Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], distearyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,6, 7-Trioxa-1-phosphabicyclo [2.2.2] oct-4-ylmethyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 3,5-di-tert-butyl-4-hydroxyphenyl 3,5-distearylthiotriazylamine, 2- (2'-hydroxy-3'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2,6-di-tert-butyl 4-hydroxymethylphenol, 1, 3,5-trimethyl-2,4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -benzene, 4,4'-methylene-bis ( 2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxybenzyl-dimethylamine. Have been found to be particularly effective and therefore preferably used are 2,2'-methylenebis (4-methyl-6-tert-butylphenyl), 1, 6-hexanediol bis (3,5-di-tert-butyl) butyl-4-hydroxyphenyl] -propionate (Irganox® 259), pentaerythrityl-tetrakis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate] and N, N'-hexamethylene-bis- 3,5-di-tert-butyl-4-hydroxyhydrocinnamide (Irganox® 1098) and the above-described Irganox® 245 from Ciba Geigy, which is particularly well suited.

The phenolic antioxidants which may be used singly or as mixtures are in an amount of 0.05 to 3% by weight, preferably 0.1 to 1.5% by weight, more preferably 0.1 to 1% by weight .-%, based on the total weight of the molding compositions A) to D) included.

In some cases, sterically hindered phenols having no more than one sterically hindered group ortho to the phenolic hydroxy group have been found to be particularly advantageous; especially when assessing color stability when stored in diffused light for extended periods of time.

Fibrous or particulate fillers D) which may be mentioned are carbon fibers, glass fibers, glass beads, amorphous silicic acid, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar, which are present in amounts of up to 40% by weight. , In particular 1 to 15 wt .-% are used.

Preferred fibrous fillers are carbon fibers, aramid fibers and potassium titanate fibers, glass fibers being particularly preferred as E glass. These can be used as rovings or cut glass in the commercial forms.

For better compatibility with the thermoplastic, the fibrous fillers can be surface-pretreated with a silane compound.

Suitable silane compounds are those of the general formula

(X- (CH ₂ ) n) k -Si (OC _m H ₂ m ₊ i) 4-k

in which the substituents have the following meanings:

X NH-, CH ₂ -CH-, HO-,

\ /

O n is an integer from 2 to 10, preferably 3 to 4 m, an integer from 1 to 5, preferably 1 to 2 k, an integer from 1 to 3, preferably 1 Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.

The silane compounds are generally used in amounts of 0.01 to 2, preferably 0.025 to 1, 0 and in particular 0.05 to 0.5 wt .-% (based on the fibrous fillers fillers) for surface coating.

Also suitable are acicular mineral fillers.

In the context of the invention, the term "needle-shaped mineral fillers" is understood to mean a mineral filler with a pronounced, needle-like character. An example is acicular wollastonite. Preferably, the mineral has a UD (length diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 11: 1. The mineral filler may optionally be pretreated with the silane compounds mentioned above; however, pretreatment is not essential.

As further fillers kaolin, calcined kaolin, wollastonite, talc and chalk are mentioned, as well as platelet- or needle-shaped nanofillers preferably in

Amounts between 0.1 and 10%. Boehmite, bentonite, montmorillonite, vermicullite, hectorite and laponite are preferably used for this purpose. In order to obtain a good compatibility of the platelet-shaped nanofillers with the organic binder, the platelet-shaped nanofillers according to the prior art are organically modified. The addition of the platelet- or needle-shaped nanofillers to the nanocomposites according to the invention leads to a further increase in the mechanical strength.

In particular, talc is used which is a hydrated magnesium silicate of the composition Mg3 [(OH) 2 / Si4θio] or 3MgO4SiO2 H2O. These so-called three-layer phyllosilicates have a triclinic, monoclinic or rhombic crystal structure with a bubble-like appearance. On further trace elements Mn, Ti, Cr, Ni, Na and K may be present, wherein the OH group may be partially replaced by fluoride.

Particular preference is given to using talc, the particle size of which is 99.5% <20 μm. The particle size distribution is usually determined by sedimentation analysis and is preferably:

<20 μm 99.5% by weight

<10 μm 99% by weight

<5 μm 85% by weight

<3 μm 60% by weight <2 microns 43 wt .-%.

Such products are commercially available as Micro-Tale I.T. extra (Omya) available.

Examples of impact modifiers as component D) are rubbers which may have functional groups. It is also possible to use mixtures of two or more different impact-modifying rubbers.

Rubbers which increase the toughness of the molding compositions generally contain an elastomeric fraction which has a glass transition temperature of less than -10 ° C, preferably less than -30 ° C, and contain at least one functional group associated with the polyamide can react. Suitable functional groups are, for example, carboxylic acid, carboxylic acid anhydride, carboxylic ester, carboxamide, carboxylic imide, amino, hydroxyl, epoxide, urethane or oxazoline groups, preferably carboxylic anhydride groups.

Preferred functionalized rubbers include functionalized polyolefin rubbers which are composed of the following components:

1. 40 to 99 wt .-% of at least one alpha-olefin having 2 to 8 carbon atoms,

2. 0 to 50% by weight of a diene,

3. 0 to 45 wt .-% of a C ₁ -C ₁₂ alkyl ester of acrylic acid or methacrylic acid or mixtures of such esters,

4. 0 to 40% by weight of an ethylenically unsaturated C 2 -C 20 -mono- or dicarboxylic acid or a functional derivative of such an acid,

5. 0 to 40 wt .-% of a monomer containing epoxy groups, and

6. 0 to 5 wt .-% of other radically polymerizable monomers,

wherein the sum of the components 3) to 5) is at least 1 to 45 wt .-%, based on the components 1) to 6).

As examples of suitable α-olefins, there may be mentioned ethylene, propylene, 1-butylene, 1-pentylene, 1-hexylene, 1-heptylene, 1-octylene, 2-methylpropylene, 3-methyl-1-butylene and 3-ethyl-1. butylene, with ethylene and propylene being preferred.

Examples of suitable diene monomers are conjugated dienes having 4 to 8 C atoms, such as isoprene and butadiene, non-conjugated dienes having 5 to 25 C 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 dicyclopentadiene, as well as alkenylnorbornene 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 their Called mixtures. Preference is given to hexa-1, 5-diene, 5-ethylidene-norbornene and dicyclopentadiene. The diene content is preferably 0.5 to 50, in particular 2 to 20 and particularly preferably 3 to 15 wt .-%, based on the total weight of the olefin polymer. Examples of suitable esters are methyl, ethyl, propyl, n-butyl, i-butyl and 2-ethylhexyl, octyl and decyl acrylates or the corresponding esters of methacrylic acid. Of these, methyl, ethyl, propyl, n-butyl and 2-ethylhexyl acrylate or methacrylate are particularly preferred.

Instead of or in addition to the esters, acid-functional and / or latent acid-functional monomers of ethylenically unsaturated mono- or dicarboxylic acids may also be present in the olefin polymers.

Examples of ethylenically unsaturated mono- or dicarboxylic acids are acrylic acid, methacrylic acid, tertiary alkyl esters of these acids, in particular tert-butyl acrylate and dicarboxylic acids, such as maleic acid and fumaric acid, or derivatives of these acids and their monoesters.

Latent acid-functional monomers are understood as meaning those compounds which form free acid groups under the polymerization conditions or during the incorporation of the olefin polymers into the molding compositions. Examples of these are anhydrides of dicarboxylic acids having 2 to 20 carbon atoms, in particular maleic anhydride and tertiary C ₁ -C ₁₂ alkyl esters of the abovementioned acids, in particular tert-butyl acrylate and tert-butyl methacrylate.

As other monomers come z. As vinyl esters and vinyl ethers into consideration.

Particularly preferred are olefin polymers from 50 to 98.9, in particular 60 to 94.85 wt .-% of ethylene, and 1 to 50, in particular 5 to 40 wt .-% of an ester of acrylic or methacrylic acid 0.1 to 20.0 , in particular 0.15 to 15 wt .-% glycidyl acrylate and / or glycidyl methacrylate, acrylic acid and / or maleic anhydride.

Particularly suitable functionalized rubbers are ethylene-methyl methacrylate-glycidyl methacrylate, ethylene-methyl acrylate-glycidyl methacrylate, ethylene-methyl acrylate-glycidyl acrylate and ethylene-methyl methacrylate-glycidyl acrylate polymers.

The preparation of the polymers described above can be carried out by processes known per se, preferably by random copolymerization under high pressure and elevated temperature.

The melt index of these copolymers is generally in the range of 1 to 80 g / 10 min (measured at 190 ° C and 2.16 kg load). Other suitable rubbers are commercial ethylene-α-olefin copolymers which contain polyamide-reactive groups. The preparation of the underlying ethylene-α-olefin copolymers is carried out by transition metal catalysis in the gas phase or in solution. Suitable comonomers are the following α-olefins: propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1 Undecene, 1-dodecene, styrene and substituted styrenes, vinyl esters, vinyl acetates, acrylic esters, methacrylic esters, glycidyl acrylates and methacrylates, hydroxyethyl acrylates, acrylamides, acrylonitrile, allylamine; Serve, such as butadiene isoprene.

Particularly preferred are ethylene / 1-octene copolymers, ethylene / 1-butene copolymers, ethylene-propylene copolymers, wherein compositions of

25 to 85 wt .-%, preferably 35 to 80 wt .-% of ethylene, 14.9 to 72 wt .-%, preferably 19.8 to 63 wt .-% of 1-octene or 1-butene or propylene or mixtures thereof

0.1 to 3 wt .-%, preferably 0.2 to 2 wt .-% of an ethylenically unsaturated mono- or dicarboxylic acid or a functional derivative of such an acid.

are particularly preferred.

The molecular weight of these ethylene-α-olefin copolymers is between 10,000 and 500,000 g / mol, preferably between 15,000 and 400,000 g / mol (Mn as determined by GPC in 1, 2,4-trichlorobenzene with PS calibration).

The proportion of ethylene in the ethylene-α-olefin copolymers is between 5 and 97, preferably between 10 and 95, in particular between 15 and 93 wt .-%.

In a particular embodiment, ethylene-α-olefin copolymers prepared by means of so-called "single site catalysts" are used Further details can be found in US 5,272,236 In this case, the ethylene-α-olefin copolymers have a molecular weight distribution which is narrow for polyolefins 4, preferably less than 3.5.

Another group of suitable rubbers are core-shell graft rubbers. These are graft rubbers made in emulsion, which consist of at least one hard and one soft component. A hard component is usually understood to mean a polymer having a glass transition temperature of at least 25 ° C., and a polymer having a glass transition temperature of at most 0 ° C. under a soft component. These products have a structure of a core and at least one shell, the structure resulting from the order of monomer addition. The soft components are generally derived from butadiene, isoprene, alkyl acrylates, alkyl methacrylates or siloxanes and optionally further comonomers. Suitable siloxane cores can be prepared, for example, starting from cyclic oligomeric octamethyltetrasiloxane or tetravinyltetramethyltetrasiloxane. These can be reacted, for example, with γ-mercaptopropylmethyldimethoxysilane in a ring-opening cationic polymerization, preferably in the presence of sulfonic acids, to the soft siloxane cores. The siloxanes can also be crosslinked by, for example, carrying out the polymerization reaction in the presence of silanes having hydrolyzable groups such as halogen or alkoxy groups such as tetraethoxysilane, methyltrimethoxysilane or phenyltrimethoxysilane. Suitable comonomers here are, for example, styrene, acrylonitrile and crosslinking or graft-active monomers having more than one polymerizable double bond, such as diallyl phthalate, divinylbenzene, butanediol diacrylate or trialyl (iso) cyanurate. The hard constituents are generally derived from styrene, alpha-methylstyrene and their copolymers, in which case comonomers are preferably acrylonitrile, methacrylonitrile and methyl methacrylate.

Preferred core-shell graft rubbers include a soft core and a hard shell or hard core, a first soft shell and at least one other hard shell. The incorporation of functional groups such as carbonyl, carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic acid ester, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl groups, he - follows preferably by the addition of suitably functionalized monomers in the polymerization of the last shell. Examples of suitable functionalized monomers are maleic acid, maleic anhydride, mono- or diesters or maleic acid, tert-butyl (meth) acrylate, acrylic acid, glycidyl (meth) acrylate and vinyloxazoline. The proportion of monomers having functional groups is generally from 0.1 to 25 wt .-%, preferably 0.25 to 15 wt .-%, based on the total weight of the core-shell graft rubber. The weight ratio of soft to hard components is generally 1: 9 to 9: 1, preferably 3: 7 to 8: 2.

Such rubbers are known per se and described for example in EP-A-0 208 187. The incorporation of oxazine groups for functionalization may be e.g. according to EP-A-0 791 606.

Another group of suitable impact modifiers are thermoplastic polyester elastomers. Polyester elastomers are understood as meaning segmented copolyester esters which contain long-chain segments which are generally derived from poly (alkylene) ether glycols and short-chain segments which are derived from low molecular weight diols and dicarboxylic acids. Such products are known per se and are known in the literature, e.g. in US 3,651,014. Also commercially available are corresponding products under the names Hytrel ™ (Du Pont), Arnitel ™ (Akzo) and Pelprene ™ (Toyobo Co. Ltd.).

Of course, mixtures of different rubbers can be used. As a further component D) thermoplastic molding compositions according to the invention can contain conventional processing aids such as stabilizers, oxidation retardants, other agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, flame retardants, etc.

Examples of antioxidants and heat stabilizers include phosphites and further amines (eg TAD), hydroquinones, various substituted representatives of these groups and mixtures thereof in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions.

UV stabilizers which are generally used in amounts of up to 2% by weight, based on the molding composition, of various substituted resorcinols, salicylates, benzotriazoles and benzophenones may be mentioned.

It is possible to add inorganic pigments, such as titanium dioxide, ultramarine blue, iron oxide and carbon black and / or graphite, furthermore organic pigments, such as phthalocyanines, quinacridones, perylenes and also dyes, such as nigrosine and anthraquinones, as colorants.

As nucleating agents, sodium phenylphosphinate, alumina, silica and preferably talc may be used.

As flame retardants red phosphorus, P- and N-containing flame retardants and halogenated FS-agent systems and their synergists may be mentioned.

Preferred stabilizers are aromatic secondary amines in amounts of up to 2, preferably 0.5 to 1, 5 and in particular 0.7 to 1 wt .-%, according to the general formula I:

in which

m, n = 0 or 1,

A and B = tertiary C-atom substituted by C ₁ -C ₄ -alkyl or phenyl, R ¹ , R ² = hydrogen or a C ₁ -C ₆ -alkyl group in the ortho or para position, which may optionally be substituted by 1 to 3 Phenyl radicals, halogens, carboxyl group or a transition metal salt of this carboxyl group, and R ³ , R ⁴ = hydrogen or a methyl radical in the ortho or para position when m plus n is 1 or a tertiary C ₃ -C ₉ alkyl group in the ortho or para position, which is optionally substituted by 1 to 3 phenyl radicals may be substituted when m plus n is 0 or 1, mean.

Preferred radicals A or B are symmetrically substituted tertiary carbon atoms, with dimethyl-substituted tertiary carbon being particularly preferred. Also preferred are tertiary carbons which have 1 to 3 phenyl groups as substituents.

Preferred radicals R ¹ or R ² are para-t-butyl or tetramethylsubstituiert.es n-butyl, wherein the methyl groups may preferably be replaced by 1 to 3 phenyl groups. Preferred halogens are chlorine and bromine. Transition metals are, for example, which can form transition metal salts with R ¹ or R ² = carboxyl.

Preferred radicals R ³ or R ⁴ are for m plus n = 2 hydrogen, as well as for m plus n = 0 or 1, a t-butyl radical in the ortho or para position, which may be substituted in particular by 1 to 3 phenyl radicals.

Examples of secondary aromatic amines D) are

4,4'-bis (α, α'-tertiaryoctyl) diphenylamine

4,4'bis (α, α-dimethylbenzyl) diphenylamine 4,4'-bis (α-methylbenzhydryl) diphenylamine

4- (1,1,3,3-tetramethylbutyl) -4'-triphenylmethyldiphenylamine

4,4'-bis (α, α-p-trimethylbenzyl) diphenylamine

2,4,4'-tris (α, α-dimethylbenzyl) diphenylamine

2,2'-dibromo, 4,4'-bis (α, α-dimethylbenzyl) diphenylamine 4,4'-bis (α, α-dimethylbenzyl) -2-carboxydiphenylamini-nickel-4,4'-bis (α , α-dimethylbenzyl) diphenylamine

2-sec-butyl-4,4'-bis (α, α-dimethylbenzyl) diphenylamine

4,4'-bis (α, α-dimethylbenzyl) -2- (α-methlheptyl) diphenylamine

2- (α-methylpentyl) -4,4'-ditrityldiphenylamine 4-α, α-dimethylbenzyl-4'-isopropoxydiphenylamine

2- (α-methylheptyl) -4 '- (α, α-dimethylbenzyl) diphenylamine

2- (α-methylpentyl) -4'-trityldiphenylamine

4,4'-bis (tertiary-butyl) diphenylamine and:

10

10

15

The preparation is carried out according to the methods described in BE-A 67/05 00 120 and CA-A 9 63 594. Preferred secondary aromatic amines are diphenylamine and its derivatives, which are commercially available as Naugard® (Chemtura). These are preferred in combination with up to 2000, preferably 100 to 2000, preferably 200 to 500 and in particular 200 to 400 ppm of at least one phosphorus-containing inorganic acid or derivatives thereof.

Preferred acids are hypophosphorous acid, phosphorous acid or phosphoric acid and their salts with alkali metals, with sodium and potassium being particularly preferred. Preferred mixtures are in particular hypophosphorous and phosphorous acid or their alkali metal salts in a ratio of 3: 1 to 1: 3. Organic derivatives of these acids are preferably understood to mean ester derivatives of the abovementioned acids.

The thermoplastic molding compositions according to the invention can be prepared by processes known per se, in which mixing the starting components in conventional mixing devices such as screw extruders, Brabender mills or Banbury mills and then extruded. After extrusion, the extrudate can be cooled and comminuted. It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise mixed. The mixing temperatures are usually 230 to 320 ° C.

According to a further preferred procedure, the components B) and C) and optionally D) can be mixed with a prepolymer, formulated and granulated. The resulting granules are then condensed in solid phase under inert gas continuously or discontinuously at a temperature below the melting point of component A) to the desired viscosity.

The thermoplastic molding compositions of the invention are characterized by good mechanics and heat aging and good processability / flowability and thermal stability and weld line strength (vibration welding).

These are suitable for the production of fibers, films and moldings of any kind. Here are some preferred examples:

Household articles, electronic components, medical devices, motor vehicle components, housings of electrical appliances, housings of electronic components in motor vehicles, fenders, door covers, tailgates, spoilers, intake pipes, water tanks, housings of electric Tools, housings of electronic components (gen.), Over-sharpening of electronic components (eg coils).

Examples 1V to 4

The following components were used:

Component A / 1:

Polyamide 66 with a viscosity number VZ of 180 ml / g, measured as 0.5 wt .-% solution in 96 wt .-% sulfuric acid at 25 ° C according to ISO 307. (Ultramid® A24 E BASF SE was used ).

The preparation of components B / 1 to B / 4 was carried out according to the examples of EP 07123450.4.

Analysis of the products according to the invention:

The polyetheramine polyols were analyzed by gel permeation chromatography with a refractometer as detector. Hexafluoroisopropanol (HFIP) was used as the mobile phase, and polymethyl methacrylate (PMMA) was used as the standard for determining the molecular weight.

The OH number was determined in accordance with DIN 53240, Part 2.

Table 1: Starting materials and end products

TIPA = triisopropanolamine TEA = triethanolamine

Component C):

Finely ground alumina (CL4400 FG from Alcoa Inc.) with an average particle size d50 of 7 μm (measured by laser diffraction according to ISO 13320-1), a specific see BET surface area of 0.6 m ² / g (determined according to ISO 9277) and an Al 2 O 3 content of> 99.8%.

Component D1):

Polyethyleneimine (PEI) with a Mw of 1300 g / mol (GPC), Lupasol® G 20 from BASF SE was used.

Component D2):

Glass fibers with an average thickness of 10 μm (aminosilane size).

Component D3):

Fusabond® N NM493D from DuPont, ethylene-octene copolymer functionalized with maleic anhydride, MFR 1, 5 g / 10 '(D1238, 190 ° C / 2.16 kg).

Production of molding compounds

The components A) to D) were on a twin-screw extruder at 280 to

Blended 290 ° C and extruded in a water bath. After granulation and drying, specimens were sprayed and tested on an injection molding machine.

The thermal conductivity was determined on 2 mm thick round plates by means of Netzsch (NETZSCH-LFA 447 Nano Flash (R)) laser flash apparatus according to ASTM E1461;

Impact strength according to ISO 179/1 immediately at 23 ° C and 50% rel. Humidity;

Tensile properties according to ISO 527-2.

The MVR was measured on the granules according to ISO 1133, at 270 ° C melt temperature, 5 kg load and 4 min dwell time.

The determination of the VZ of the products was carried out according to ISO 307 on 0.5% [m / v] solution in 96% [mm] H ₂ SO ₄ at 25 ° C.

The results of the tests and compositions of the molding compositions are shown in Table 2. Table 2:

Table 3: Heat aging

Legend: o average + improved

++ greatly improved

Claims

claims 1. Thermoplastic molding compositions containing A) 10 to 99% by weight of at least one thermoplastic polyamide, B) 0.01 to 30% by weight of at least one highly branched or hyperbranched polyetheramine, C) 0.5 to 80% by weight of a thermally conductive filler, D) 0 to 70% by weight of further additives, wherein the sum of the weight percent of components A) to D) is 100%. 2. Thermoplastic molding compositions according to claim 1, wherein the component B) has a glass transition temperature of less than 50 ° C. 3. Thermoplastic molding compositions according to claims 1 or 2, wherein component B) has an OH number of 100 to 900 mg KOH / g. 4. Thermoplastic molding compositions according to claims 1 to 3, comprising as component D1) 0.01 to 30 wt .-% of a polyethyleneimine homopolymer or copolymer. 5. Thermoplastic molding compositions according to claims 1 to 4, wherein component B) has on average at least 3 further functional OH groups, in addition to the ether and the amino groups which form the polymer backbone. 6. Thermoplastic molding compositions according to claims 1 to 5, wherein component B) is obtainable by reacting at least one trialkanolamine with optionally dialkanolamines or optionally with di- or higher functional polyetherols. 7. Thermoplastic molding compositions according to claims 1 to 6, in which component B) is obtainable by intermolecular polycondensation of at least one trialkanolamine of the general formula

in which the radicals R ¹ to R ³ independently of one another are identical or different alkylene groups having 2 to 10 C atoms. 8. Thermoplastic molding compositions according to claims 1 to 7, in which the Component C) is composed of Al oxides, MgO, ZnO, boron nitride, ZrO, graphite, carbon fibers or mixtures thereof. 9. Use of the thermoplastic molding compositions according to claims 1 to 7 for the production of fibers, films and moldings of any kind. 10. fibers, films and moldings, obtainable from the thermoplastic moldings according to claims 1 to 7.