WO2005082994A1

WO2005082994A1 - Composites consisting of thermoplastic materials wherein fillers are distributed in a monodispersed manner

Info

Publication number: WO2005082994A1
Application number: PCT/EP2005/001545
Authority: WO
Inventors: Hans-Helmut Görtz; Andreas Eipper; Thomas Breiner; Andreas Hartwig; Monika Sebald
Original assignee: Basf Aktiengesellschaft; Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
Priority date: 2004-02-18
Filing date: 2005-02-16
Publication date: 2005-09-09
Also published as: DE102004008202A1

Abstract

The invention relates to thermoplastic moulded masses containing, as essential constituents: A) between 1 and 99.9 wt. % of a thermoplastic polymer, B) between 0.01 to 50 wt. % of a spherical, organically modified nanofiller, and C) between 0 and 70 wt. % of other additives, the weight per cent of the constituents A) to C) always amounting to 100 %.

Description

Composites made of thermoplastics with monodispersed fillers

description

The invention relates to thermoplastic molding compositions containing as essential components

A) 1 to 99.9% by weight of a thermoplastic polymer B) 0.01 to 50% by weight of a spherical, organically modified nano-filler and in addition C) 0 to 70% by weight of other additives, the Weight percentages of components A) to C) always give 100%.

The invention further relates to processes for the production and the use of the molding compositions according to the invention for the production of moldings of any type and the moldings obtainable here.

Fillers such as glass fibers, minerals or glass balls are often used to improve the properties of polymers. With all these fillers, the dimensions are in

Glass fibers are used, for example, to increase the stiffness of the polymers. On the other hand, these types of fillers usually lead to a significant deterioration in other mechanical properties of the polymers, such as elongation at break.

A new class of composites are materials that consist of polymers and nanoparticles. While there are numerous examples in the literature of such composites consisting of polyester and high aspect ratio particles, e.g. Layered silicates (JP-A 03/62856), is little known about nanocomposites with spherical particles.

WO 01/72881 discloses polycondensation in the presence of finely divided mineral particles with a size of less than 200 nm.

The composites produced in this way have improved thermal-mechanical properties. However, a disadvantage of these compositions is the complex preparation by addition during the polymerization. In the previous application DE-A 10241510.2, processes for the production of spherical, organically modified nanoparticles are proposed, as well as their incorporation into organic binding materials.

The object of the present invention was therefore to provide thermoplastic molding compositions which have a significant improvement in the dispersion of nanofillers in the thermoplastic matrix, mechanical properties such as elongation at break and modulus of elasticity being greatly improved.

Accordingly, the molding compositions defined above and processes for their production were found. Preferred embodiments can be found in the subclaims.

As component A), the molding compositions according to the invention contain 1 to 99.9, preferably 20 to 99 and in particular 30 to 80% by weight of a thermoplastic polymer.

Basically, the advantageous effect of the molding compositions according to the invention can be seen in thermoplastics of all kinds. A list of suitable thermoplastics can be found, for example, in the plastic paperback (ed. Saechtling), edition 1989, where sources of supply are also mentioned. Methods for producing such thermoplastic materials are known per se to the person skilled in the art. Some preferred types of plastic are explained in more detail below.

1. Polycarbonate and polyester

Polyesters A) based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound are generally used.

A first group of preferred polyesters are polyalkylene terephthalates, which in particular have 2 to 10 carbon atoms in the alcohol part.

Such polyalkylene terephthalates are known per se and are described in the literature. They contain an aromatic ring in the main chain, which comes from the aromatic dicarboxylic acid. The aromatic ring can also be substituted, e.g. by halogen such as chlorine and bromine or by CrC-palkyl groups such as methyl, ethyl, i- or n-propyl and n-, i- or t-butyl groups.

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

The aliphatic dihydroxy compounds are diols with 2 to 8 carbon atoms, in particular 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclohexanediol, 1 , 4-Cyclohexanedimethanol and neopentyl glycol or mixtures thereof are preferred.

Particularly preferred polyesters (A) are polyalkylene terephthalates which are derived from alkanediols having 2 to 6 carbon atoms. Of these, particularly preferred are polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof. PET and / or PBT which contain up to 1% by weight, preferably up to 0.75% by weight 1,6-hexanediol and / or 2-methyl-1,5-pentanediol as further monomer units are further preferred.

The viscosity number of the polyesters (A) is generally in the range from 50 to 220, preferably from 80 to 160 (measured in a 0.5% strength by weight solution in a phenol / o-dichlorobenzene mixture (weight ratio 1: 1 at 25 ° C) according to ISO 1628.

Particularly preferred are 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 polyester. Such polyesters can for example by the method of

DE-A 44 01 055 can be produced. The carboxyl end group content is usually determined by titration methods (e.g. potentiometry).

Particularly preferred molding compositions contain, as component A), a mixture of polyesters other than PBT, such as, for example, polyethylene terephthalate (PET) and / or polycarbonate. The proportion e.g. The polyethylene terephthalate and / or the polycarbonate in the mixture is preferably up to 50, in particular 10 to 30,% by weight, based on 100% by weight of A).

Furthermore, it is advantageous to use PET recyclates (also called scrap PET), optionally in a mixture with polyalkylene terephthalates such as PBT.

Recyclates are generally understood to mean:

1) So-called post industrial recyclate: this is production waste in the case of polycondensation or in processing, e.g. sprues in injection molding processing, commodity goods in injection molding processing or extrusion or the edge portions of extruded sheets or foils.

2) Post consumer recyclate: these are plastic items that are collected and processed by the end consumer after use. The most dominant item in terms of quantity are blow-molded PET bottles for mineral water, soft drinks and juices.

Both types of recyclate can either be in the form of regrind or in the form of granules. In the latter case, the pipe cyclates are melted and granulated in an extruder after separation and cleaning. This usually facilitates handling, flowability and meterability for further processing steps.

Recyclates, both granulated and in the form of regrind, can be used, the maximum edge length being 6 mm, preferably less than 5 mm.

Due to the hydrolytic cleavage of polyesters during processing (due to traces of moisture), it is advisable to pre-dry the recyclate. The residual moisture content after drying is preferably 0.01 to 0.7, in particular 0.2 to 0.6%.

Another group to be mentioned are fully aromatic polyesters which are derived from aromatic dicarboxylic acids and aromatic dihydroxy compounds.

Aromatic dicarboxylic acids which are suitable are the compounds already described for the polyalkylene terephthalates. Mixtures of 5 to 100 mol% isophthalic acid and 0 to 95 mol% terephthalic acid, in particular mixtures of approximately 80% terephthalic acid with 20% isophthalic acid to approximately equivalent mixtures of these two acids, are used.

The aromatic dihydroxy compounds preferably have the general formula

in which Z represents an alkylene or cycloalkylene group with up to 8 C atoms, an arylene group with up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in which m is the value Has 0 to 2. The compounds on the phenylene groups can also be C _r C ₆ alkyl or Ö

Alkoxy groups and fluorine, chlorine or bromine as substituents.

Examples of these are the parent bodies of these compounds

dihydroxydiphenyl,

Di (hydroxyphenyl) alkane,

Di (hydroxyphenyl) cycloalkane,

Di (hydroxyphenyl) sulfide,

Di (hydroxyphenyl) ether, di (hydroxyphenyl) ketone,

Di- (hydroxyphenyl) sulfoxide,, α'-di- (hydroxyphenyl) dialkylbenzene,

Di (hydroxyphenyl) sulfone, di (hydroxybenzoyl) benzene

Resorcinol and hydroquinone and their kemalkylated or kemhalogenated derivatives are mentioned.

Of these will be

4,4'-Dihydroxydiphenyl, 2,4-di- (4'-hydroxyphenyl) -2-methyl! Butane α, α'-di- (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-di- (3rd '-methyl-4'-hydroxyphenyl) propane and 2,2-di- (3'-chloro-4'-hydroxyphenyl) propane,

as well as 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'-dihydroxydiphenyl sulfone and 2,2-di (3 ' _I 5'-dimethyl-4'-hydroxyphenyl) propane

or mixtures thereof are preferred.

Of course, mixtures of polyalkylene terephthalates and fully aromatic polyesters and / or polycarbonates can also be used. These generally contain 20 to 98% by weight, preferably 50 to 96% by weight of the polyalkylene terephthalate and 2 to 80% by weight, preferably 4 to 50% by weight of the fully aromatic polyester and / or Polycarbonates. Of course, polyester block copolymers such as copolyether esters can also be used. Products of this type are known per se and are described in the literature, for example in US Pat. No. 3,651,014. Corresponding products are also commercially available, for example Hytrel ^® (DuPont).

Halogen-free polycarbonates are also preferably used as component A). Suitable halogen-free polycarbonates are, for example, those based on diphenols of the general formula

wherein Q is a single bond, a C to C ₈ alkylene, a C ₂ - to C ₃ alkylidene, a C ₃ - to Cβ-cycloalkylidene group, a C ₆ - to C ₂ -arylene group and -O-, -S - or - SO - and m is an integer from 0 to 2.

The diphenols can also have substituents on the phenylene radicals, such as C to C ₆ alkyl or C _r to C ₆ alkoxy.

Preferred diphenols of the formula are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1 bis (4-hydroxyphenyl) -cyclohexane. 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) -3,3,5- are particularly preferred. trimethylcyclohexane.

Both homopolycarbonates and copolycarbonates are suitable as component A; in addition to the bisphenol A homopolymer, the copolycarbonates of bisphenol A are preferred.

The suitable polycarbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of at least trifunctional compounds, for example those having three or more than three phenolic compounds OH groups.

Polycarbonates which have relative viscosities η- _e i of 1.10 to 1.50, in particular of 1.25 to 1.40, have proven particularly suitable. This corresponds to average molecular weights M _w (weight average) of 10,000 to 200,000, preferably 20,000 to 80,000. The diphenols of the general formula are known per se or can be prepared by known processes.

The polycarbonates can be produced, for example, by reacting the diphenols with phosgene using the phase boundary process or with phosgene using the homogeneous phase process (the so-called pyridine process), the molecular weight to be adjusted in each case being achieved in a known manner by a corresponding amount of known chain terminators , (Regarding polydiorganosiloxane-containing polycarbonates, see for example DE-OS 33 34782).

Suitable chain terminators are, for example, phenol, pt-butylphenol but also long-chain alkylphenols such as 4- (1,3-tetramethylbutyl) phenol, according to DE-OS 2842 005 or monoalkylphenols or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents according to DE-A 35 06472, such as p-nonylphenyl, 3,5-di-t-butylphenol, pt-octylphenol, p-dodecylphenol, 2- (3,5-dimethyl-heptyl) -phenol and 4- (3,5- dimethylheptyl) phenol.

Halogen-free polycarbonates in the sense of the present invention means that the polycarbonates are composed of halogen-free diphenols, halogen-free chain terminators and optionally halogen-free branching agents, the content of minor ppm amounts of saponifiable chlorine resulting, for example, from the production of the polycarbonates with phosgene by the phase boundary process, is not to be regarded as containing halogen in the sense of the invention. Such polycarbonates with ppm contents of saponifiable chlorine are halogen-free polycarbonates in the sense of the present invention.

Amorphous polyester carbonates may be mentioned as further suitable components A), phosgene being replaced by aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units during the preparation. For further details, reference is made to EP-A 711 810.

Further suitable copolycarbonates with cycloalkyl radicals as monomer units are described in EP-A 365 916.

Bisphenol A can also be replaced by Bisphenol TMC. Such polycarbonates are available under the trademark APEC HT ^® from Bayer.

2. Vinyl aromatic polymers

The molecular weight of these known and commercially available polymers is generally in the range from 1,500 to 2,000,000, preferably in the range from 70,000 to 1,000,000. Vinyl aromatic polymers made from styrene, chlorostyrene, a-methylstyrene and p-methylstyrene are only representative here; 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 can also be involved in the structure. Particularly preferred vinyl aromatic polymers are polystyrene and impact modified polystyrene. It goes without saying that mixtures of these polymers can also be used. The production is preferably carried out according to the method described in EP-A-302485.

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

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

An 95 to 99.9 wt .-% of a C ₂ -C ₁₀ alkyl acrylate and

A ₁₂ 0.1 to 5 wt .-% of a difunctional monomer with two olefinic, non-conjugated double bonds, and

A ₂ 10 to 50 wt .-% of a graft

A ₂ 20 to 50 wt .-% 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 a mixture with a hard matrix based on a SAN copolymer A ₃ ) made of:

A ₃₁ 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% by weight of acrylonitrile and / or methacrylonitrile.

Component A ₁ ) is an elastomer which has a glass transition temperature of below -20, in particular below -30 ° C.

The main monomers used for the production of the elastomer are an) esters of acrylic acid with 2 to 10 C atoms, in particular 4 to 8 C atoms. Particularly preferred monomers here are tert-, iso- and n-butyl acrylate and 2-ethylhexyl called 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,% by weight, based on the total weight of An + A _{12, of} a polyfunctional monomer with at least two olefinic, non-conjugated double bonds are used. Of these, difunctional compounds, ie with two non-conjugated double bonds, are preferably used. Examples include divinylbenzene, diallyl fumarate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, tricyclodecenyl acrylate and dihydrodicyclopentadienyl acrylate, the latter two being particularly preferred.

Methods for producing the graft base A ^ 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 proven 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 d ₅₀ ) in the range from about 200 to 700, in particular from 250 up to 600 nm. The latex preferably has a narrow particle size distribution, ie the quotient

"90 ^" "10 - * 50 is preferably less than 0.5, in particular less than 0.35.

The proportion of the graft base Ai in the graft polymer Aι + A ₂ is 50 to 90, preferably 55 to 85 and in particular 60 to 80% by weight, based on the total weight of Aι + A ₂ .

A graft cover A _{2 is} grafted onto the graft base Ai, which is obtained by copolymerization of

A ₂ ι 20 to 90, preferably 30 to 90 and in particular 30 to 80 wt .-% styrene or substituted styrenes of the general formula

wherein R alkyl radicals with 1 to 8 carbon atoms, hydrogen atoms or halogen atoms and

R ^{1 represents} alkyl radicals with 1 to 8 carbon atoms or halogen atoms and n has the value 0.1,

Has 2 or 3, and

A ₂₂ 10 to 80, preferably 10 to 70 and in particular 20 to 70% by weight of acrylonitrile, methacrylonitrile, acrylic acid esters or methacrylic acid esters or mixtures thereof can be obtained.

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

Preferred acrylic or methacrylic acid esters are those whose homopolymers or copolymers with the other monomers of component A ₂ ) have glass transition temperatures of more than 20 ° C .; in principle, however, other acrylic acid esters can also be used, preferably in amounts such that overall a glass transition temperature T _{g of} above 20 ° C. results for component A ₂ .

Esters of acrylic or methacrylic acid with C _r C ₈ alcohols and esters containing epoxy groups, such as glycidyl acrylate or glycidyl methacrylate, are particularly preferred. Methyl methacrylate, t-butyl methacrylate, glycidyl methacrylate and n-butyl acrylate may be mentioned as very particularly preferred examples, the latter being preferably used in a not too high proportion owing to its property of forming polymers with a very low T _g .

The graft shell A ₂ ) can be produced in one or more, for example two or three, process steps, the gross composition remains unaffected.

Preferably the graft shell is made in emulsion as e.g. is described in DE-PS 1260 135, DE-OS 3227555, DE-OS 31 49 357 and DE-OS 34 14 118.

Depending on the conditions selected, a certain proportion of free copolymers of styrene or substituted styrene derivatives and (meth) acrylonitrile or (meth) acrylic acid esters are formed in the graft copolymerization. The graft copolymer Ai + A ₂ generally has an average particle size of 100 to 1,000 nm, in particular from 200 to 700 nm, (d ₅₀ weight average). The conditions in the production of the elastomer Di) and in the grafting are therefore preferably chosen such that particle sizes result in this range. Measures for this are known and are described, for example, in DE-PS 1 260 135 and DE-OS 2826 925 and in Journal of Applied Polymer Science, Vol. 9 (1965), pp. 2929 to 2938. The particle enlargement of the latex of the elastomer can be accomplished, for example, by means of agglomeration.

In the context of this invention, the graft polymer (A-ι + A ₂ ) also includes the free, non-grafted homopolymers and copolymers formed in the graft copolymerization for the preparation of component A ₂ ).

Some preferred graft polymers are listed below:

1: 60% by weight of graft base A made of An 98% by weight n-butyl acrylate and A ₁₂ 2% by weight dihydrodicyclopentadienyl acrylate and 40% by weight graft cover A ₂ made of A ₂ ι 75% by weight styrene and A ₂ 25% by weight acrylonitrile

2: Graft base as in 1 with 5% by weight of a first graft shell made of styrene and 35% by weight of a second grafting stage made of A ₂₁ 75% by weight styrene and A ₂ 25% by weight acrylonitrile

3: Graft base as in 1 with 13% by weight of a first grafting stage made of styrene and 27% by weight of a second grafting stage made of styrene and acrylonitrile in a weight ratio of 3: 1

The products contained as component A ₃ ) can be produced, for example, by the process described in DE-AS 10 01 001 and DE-AS 1003436. Such copolymers are also commercially available. The weight average molecular weight determined by light scattering is preferably in the range from 50,000 to 500,000, in particular from 100,000 to 250,000.

The weight ratio of i + A ₂ ): A3 is in the range from 1: 2.5 to 2.5: 1, preferably from 1: 2 to 2: 1 and in particular from 1: 1.5 to 1.5: 1. Suitable SAN polymers as component A) are described above (see A ₃₁ and A ₃₂ ).

The viscosity number of the SAN polymers, measured in accordance with DIN 53 727 as a 0.5% by weight solution in dimethylformamide at 23 ° C., is generally in the range from 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 A of the graft base in the ASA polymer, conjugated dienes are usually used, so that the following composition preferably results for the graft base A ₄ :

On 70 to 100 wt .-% of a conjugated diene and A ₄₂ 0 to 30 wt .-% of a difunctional monomer with two olefinic non-conjugated double bonds

The composition of graft A and the hard matrix of SAN copolymer A3) remain unchanged. Such products are commercially available. The manufacturing processes are known to the person skilled in the art, so that further information on this is unnecessary.

The weight ratio of (A ₄ + A ₂ ): A ₃ is in the range from 3: 1 to 1: 3, preferably from 2: 1 to 1: 2.

Particularly preferred compositions of the molding compositions according to the invention contain as component A) a mixture of:

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

A ₂ ) 0 to 40% by weight of a polyethylene terephthalate AA ₃ 3)) 11 to 4400 GWeeww ..-- %% of an ASA or ABS polymer or mixtures thereof

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

Contain further preferred compositions of component A)

A 10 to 90 wt .-% of a polycarbonate

A ₂ ) 0 to 40% by weight of a polyester, preferably polybutylene terephthalate,

A ₃ ) 1 to 40 wt .-% of an ASA or ABS polymer or mixtures thereof.

Such products are available under the trademark Terblend ^® from BASF AG. 3. Polyamides

The polyamides of the molding compositions according to the invention generally have a viscosity number of 90 to 350, preferably 110 to 240 ml / g, determined in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25.degree ISO 307.

Semi-crystalline or amorphous resins with a molecular weight (weight average) 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 with 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurinlactam, and polyamides obtained by reacting dicarboxylic acids with diamines.

Alkanedicarboxylic acids having 6 to 12, in particular 6 to 10, carbon atoms and aromatic dicarboxylic acids can be used as dicarboxylic acids. Only adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acid may be mentioned here as acids.

Particularly suitable diamines are alkane diamines with 6 to 12, in particular 6 to 8, carbon atoms and 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 adipic acid amide, polyhexamethylene sebacic acid amide and polycaprolactam and copolyamides 6/66, in particular with a proportion of 5 to 95% by weight of caprolactam units.

Polyamides may also be mentioned, e.g. can be obtained by condensation of 1,4-diaminobutane with adipic acid at elevated temperature (polyamide-4,6). Manufacturing processes for polyamides of this structure are e.g. in EP-A 38 094, EP-A 38582 and EP-A 39 524.

Polyamides obtainable by copolymerizing two or more of the aforementioned monomers or mixtures of two or more polyamides are also suitable, the mixing ratio being arbitrary.

Furthermore, those partially aromatic copolyamides such as PA 6 / 6T and PA 66 / 6T have proven to be particularly advantageous whose triamine content is less than 0.5, preferably is less than 0.3% by weight (see EP-A 299444).

The preferred partially aromatic copolyamides with a low triamine content can be prepared by the processes described in EP-A 129 195 and 129 196.

4. Thermoplastic polyurethanes

Other suitable thermoplastics are thermoplastic polyurethanes (TPU), as are described, for example, in EP-A 115 846 and EP-A 115 847 and EP-A 117664.

5. Other thermoplastics

Other suitable polymers include polyphenyl ethers, polyolefins such as polyethylene and / or polypropylene homo- or copolymers, and also polyketones, polyylene ethers (so-called HT thermoplastics), in particular polyether sulfones, polyvinyl chlorides, poly (meth) acrylates and mixtures (blends) all thermoplastics listed above.

As component B), the molding compositions according to the invention contain 0.01 to 50, preferably 0.05 to 20 and in particular 1 to 10% by weight of a spherical, organically modified nanofiller.

A "spherical" filler means (a difference to the layered silicates) fillers with a hollow volume, which is at best in the form of an ideal sphere (i.e. particles with a three-dimensional structure).

Aspect ratios (L / D, i.e. length to diameter) of 15: 1, preferably 10: 1 and in particular 2: 1 are correspondingly preferred.

The average particle size (d ₅₀ value) is advantageously from 2 to 250, in particular from 10 to 200 nm and very particularly preferably from 15 to 170 nm.

The particle size determination and distribution is usually carried out by dynamic light scattering, ultracentrifuge or field flow fractionation, and the aspect ratio by combining the above methods with transmission or scanning electron microscopy.

The agglomerated nanopowders to be used as the starting material are, in particular, oxidic or nitridic compounds which have been produced by flame pyrolytic means or by precipitation. But also agglomerated nanofillers other bases, such as barium sulfate or barium titanate, are suitable. Oxides are preferably used, and particularly preferably flame-pyrolytically produced silicon dioxide.

The organic modification of the surface is preferably carried out in a solvent by treatment with a siloxane, chlorosilane, silazane, titanate or zirconate or mixtures thereof. These preferably have the general formulas Si (OR ') _n R ₄ - _n , SiClnRn-4, (R _m R " _m -3Si) ₂ NH, T OR'JnR-n, and Zr (OR ^, )" R ₄ - n,

in which

R'.R "identical or different hydrocarbon radicals with 1 to 8, preferably 1 to 4, carbon atoms, R is an unsaturated or saturated hydrocarbon radical with 1 to 150, preferably 1 to 50, carbon atoms which contains at least one epoxy, hydroxyl , Amino, carboxyl, (meth) acrylate, isocyanate, thiol, glycidyl or aromatic group with 5 to 20 C atoms, preferably 6 to 10 C atoms, m 1, 2 or 3 and n 1, 2 or 3

mean.

The group R 'bonded via the oxygen, like R ", is any organic group, preferably an alkyl group and particularly preferably methyl, ethyl or isopropyl. These groups are split off in the form of the alcohol during the organic modification. In the case After the modification with the silazane, ammonia is split off and, in the case of chlororsiole, hydrochloric acid. The alcohol, hydrochloric acid or ammonia formed is no longer contained in the nanocomposite produced in the subsequent steps.

The functional group R is preferably any organic group and is bonded directly to the silicon, titanium or zirconium via a hydrocarbon atom. When n or m is 1 or 2, the groups R may be the same or different. R is selected so that the group can react chemically with the monomers or polymers used to produce the nanocomposite or has a high affinity for this.

Suitable silane compounds, in particular for polyamides, polyesters and polycarbonates, are those of the general formula

(X- (CH ₂ ) _n ) _k -Si- (OC _m H _{2m + 1} ) ₄ . _k in which the substituents have the following meaning: X NH ₂ -, CH ₂ -CH-, HO-, benzyl, vinyl, phenyl O n is an integer from 0 to 10, preferably 0 to 4 m is an integer from 1 to 5, preferably 1 to 2 k integer from 1 to 3, preferably 1

Particularly preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes, which contain a glycidyl group as substituent X, and also phenyltriethoxysilane and phenyltrimethoxysalanized polymers, as well as, for example, silystyrene-PMMA, as well as (e.g., silane-functionalized PMMA) as well as polystyrene-functionalized silane (as well as polystyrene-silane) as well as (e.g., silane-PMMA) and also (e.g.

For the production of nanocomposites based on acrylates or methacrylates, R preferably contains an acrylate or methacrylate group and is particularly preferred - (CH ₂ ) ₃ -S- (CH ₂ ) 2-C (= O) O- (CH ₂ ) n-OC (= O) -CH = CH2 with n = 1 to 12 and - (CH ₂ ) ₃ -OC (= O) -C (CH3) = CH ₂ .

For the production of nanocomposites based on epoxides, R preferably contains an epoxy group or an amino, carboxylic acid, thiol or alcohol group which can react with an epoxy group. R is particularly preferably 2- (3,4-epoxycyclohexyl) ethyl, 3-glycidoxypropyl, 3-aminopropyl and 3-mercaptopropyl.

In the production of nanocomposites based on unsaturated polyesters or styrene-containing resins, R preferably contains a reactive double bond. In this application, R is particularly preferably vinyl or styryl or contains a vinyl or styryl group.

For the production of nanocomposites based on urethanes, polyureas or other isocyanate-based polymer systems, R preferably contains an isocyanate, amino, alcohol, thiol or carboxylic acid group. In this case, R is particularly preferably 3-isocyanatopropyl, 3-aminopropyl and 3-mercaptopropyl.

The organically modified nanofillers according to the invention can be used in the manufacture of the nanocomposites on their own or as a combination of different nanofillers or different particle size distributions. In order to be able to achieve particularly high filling levels, it is advisable to combine nanofillers with different particle size distributions and, if necessary, even to add micro-fillers. The solvent in which the modification of the nanofillers is preferably carried out is preferably a polar aprotic solvent and particularly preferably acetone, butanone, ethyl acetate, methyl isobutyl ketone, tetrahydrofuran and diisopropyl ether.

To accelerate the organic modification of the nanofillers in the organic solvent, an acid, e.g. Hydrochloric acid, can be added as a catalyst. In any case, catalytic amounts of water, preferably between 0.1% and 5%, must be present in order to carry out the modification. This water is often already present as an adsorbate on the surfaces of the agglomerated nanofillers used as the starting material. Additional water, e.g. can also be added in the form of a dilute acid.

An advantageous development of the invention is the modification of the surface of the nanofillers with dyes. In this case, the group R of the siloxane, titanate or zirconate used for the modification is a dye or can react with a dye. The dye can be bound to the surface of the nanofiller via a covalent bond or via an ionic bond. Surprisingly, it has been shown that the plastic components which contain the nanofillers modified with dyes have a better bleaching resistance than the plastic components which contain the same dyes without being bound to the nanofillers. In this way it is possible to provide transparent polymeric materials that are resistant to bleaching.

In order to accelerate the disintegration of the agglomerates during the organic modification in the organic solvent, an additional mechanical energy input can take place using the usual methods before or during the modification. This can e.g. by ultrasound, a high-speed stirrer, a dissolver, a bead mill or a rotor-stator mixer.

The organically modified nanofiller is preferably freed from the solvent and further processed as a dry powder.

According to the invention, polymer dispersions modified with nanofillers can be produced. This is done by incorporating the surface-modified nanofillers according to the invention into the monomer on which the polymer dispersions are based, then dispersing this monomer / nanofiller mixture in water with the addition of a surfactant and, if appropriate, subsequent dispersion or emulsion polymerization. As component C), the molding compositions according to the invention can contain 0 to 60, in particular up to 50% by weight of further additives and processing aids which are different from B).

As component C), the molding compositions according to the invention can contain 0 to 5, preferably 0.05 to 3 and in particular 0.1 to 2% by weight of at least one ester or amide of saturated or unsaturated aliphatic carboxylic acids with 10 to 40, preferably 16 to 22, C. Contain atoms with aliphatic saturated alcohols or amines with 2 to 40, preferably 2 to 6 carbon atoms.

The carboxylic acids can be 1- or 2-valent. Examples include 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 with 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 1- to 3-valent. Examples include stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, ethylenediamine and hexamethylenediamine being particularly preferred. Preferred esters or amides are correspondingly glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate.

Mixtures of different esters or amides or esters with amides can also be used in combination, the mixing ratio being arbitrary.

Other common additives C) are, for example, in amounts up to 40, preferably up to 30% by weight of rubber-elastic polymers (often also 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 with 1 to 18 C atoms in the alcohol component.

Such polymers are described, for example, in Houben-Weyl, Methods of Organic Chemistry, Vol. 14/1 (Georg-Thieme-Verlag, Stuttgart, 1961). Pages 392 to 406 and in the monograph by OB. Bucknall, "Toughened Plastics" (Applied Science Publishers, London, 1977). Some preferred types of such elastomers are presented below.

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

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

Examples of diene monomers for EPDM rubbers are 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 dicyclopentadiene and alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5-butylidene- 2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyl-tricyclo (5.2.1.0.2.6) -3,8-decadiene or mixtures thereof. Hexa-1,5-diene, 5-ethylidene norbornene and dicyclopentadiene are preferred. The diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8% by weight, based on the total weight of the rubber.

EPM or EPDM rubbers can preferably also be grafted with reactive carboxylic acids or their derivatives. Here are e.g. Acrylic acid, methacrylic acid and their derivatives, e.g. Glycidyl (meth) acrylate, as well as maleic anhydride.

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 can also contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, e.g. Contain 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 adding monomers of general formulas I or II or III or IV containing dicarboxylic acid or epoxy groups to the monomer mixture

R ¹ C (COOR ² ) = C (COOR ³ ) R ⁴ (I)

CHR ⁷ = CH (CH ₂ ) _m O - (CHR. ⁶ ) _Q CH CHR ^S (Hl)

CH ² = CR ⁹ COO (CH CH— CHR ^Ö ₍ | _V )

where R ¹ to R ^{9 represent} 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 are} preferably hydrogen, where m is 0 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 comes close to that of the free acids and is therefore referred to as monomers with latent carboxyl groups.

The copolymers advantageously consist of 50 to 98% by weight of ethylene, 0.1 to 20% by weight of monomers containing epoxy groups and / or monomers containing methacrylic acid and / or monomers containing acid anhydride groups and the remaining amount of (meth) acrylic acid esters.

Copolymers of are particularly preferred

50 to 98, in particular 55 to 95% by weight of ethylene,

0.1 to 40, in particular 0.3 to 20% by weight of glycidyl acrylate and / or glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydride, and

1 to 45, in particular 10 to 40% by weight of 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 processes known per se, preferably by random copolymerization under high pressure and elevated temperature. Appropriate methods are generally known.

Preferred elastomers are also emulsion polymers, the production of which e.g. is described in Blackley in the monograph "Emulsion Polymerization". The emulsifiers and catalysts that can be used are known per se.

In principle, homogeneous 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.

Only representative here are monomers for the production of the rubber part of the elastomers, such as acrylates. n-Butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof. These monomers can be combined with other monomers such as e.g. Styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate can be copolymerized.

The soft or rubber phase (with a glass transition temperature of below 0 ° C) of the elastomers can represent the core, the outer shell or a middle shell (in the case of elastomers with more than two-shell structure); in the case of multi-layer elastomers, several shells can also consist of a rubber phase.

If, in addition to the rubber phase, one or more hard components (with glass transition temperatures of more than 20 ° C) are involved in the construction of the elastomer, they are generally polymerized by styrene, acrylonitrile, methacrylonitrile, α-methylstyrene, p-methylstyrene, acrylic acid esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as main monomers. In addition, smaller proportions of further comonomers can also be used here.

In some cases it has proven advantageous to use emulsion polymers which have reactive groups on the surface. Such groups are, for example, epoxy, carboxyl, latent carboxyl, amino or amide groups as well as functional groups which are obtained by using monomers of the general formula R ¹⁰ R ¹¹

CH ₂ = CXNCR ¹²

O can be introduced

where the substituents can have the following meanings:

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

R ^{11 is} hydrogen, a C to C ₈ alkyl group or an aryl group, in particular phenyl,

R ^{12 is} hydrogen, a C to C ₀ alkyl, a C ₆ to C ₂ aryl group or -OR ¹³

R ^{13 is} a C to C ₈ alkyl or C ₆ to C ₁₂ aryl group which can optionally be substituted by O- or N-containing groups,

X is a chemical bond, a C to ₀ Cι alkylene or C ₆ -C ₁₂ arylene group or O

- C - Y Y O-Z or NH-Z and

Z is a C to C ₁₀ alkylene or C ₆ to 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 include 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) called ethyl acrylate.

The particles of the rubber phase can also be crosslinked. Monomers acting as crosslinking agents are, for example, buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and the compounds described in EP-A 50 265. So-called graft-linking monomers can also be used, ie monomers with two or more polymerizable double bonds which react at different rates during the polymerization. Compounds are preferably used in which at least one reactive group polymerizes at approximately the same rate as the other monomers, while the other reactive group (or reactive groups) polymerizes (polymerizes), for example, significantly more slowly. The different polymerization rates result in a certain proportion of unsaturated double bonds in the rubber. If a further phase is subsequently grafted onto such a rubber, the double bonds present in the rubber react at least partially with the graft monomers to form chemical bonds, ie the grafted phase is at least partially linked to the graft base via chemical bonds.

Examples of such graft-crosslinking monomers are monomers containing allyl groups, 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. There are also a large number of other suitable graft-crosslinking 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.

Some preferred emulsion polymers are listed below. First of all, there are graft polymers with a core and at least one outer shell that have the following structure:

These graft polymers, in particular ABS and / or ASA polymers in amounts of up to 40% by weight, are preferably used for impact modification of PBT, optionally in a mixture with up to 40% by weight of polyethylene terephthalate. Corresponding blend products are available under the trademark UltradurΘS (formerly UltrablendOS from BASF AG).

Instead of graft polymers with a multi-layer structure, homogeneous, i.e. single-shell elastomers of buta-1, 3-diene, isoprene and n-butyl acrylate or their copolymers are used. These products can also be produced by using crosslinking monomers or monomers with 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 with an inner core of n-butyl acrylate or based on a butadiene and an outer shell from the above mentioned copolymers and copolymers of ethylene with comonomers which provide reactive groups.

The elastomers described can also be made by other conventional methods, e.g. by suspension polymerization.

Silicone rubbers as described in DE-A 3725 576, EP-A 235690, DE-A 38 00 603 and EP-A 319290 are also preferred.

Mixtures of the rubber types listed above can of course also be used.

Fibers or particulate fillers C) include carbon fibers, glass fibers, glass spheres, amorphous silica, asbestos, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar, in quantities of up to 50 % By weight, in particular up to 40%.

Carbon fibers, aramid fibers and potassium titanate fibers are mentioned as preferred fibrous fillers, with glass fibers being particularly preferred as E-glass. These can be used as rovings or cut glass in the commercially available forms.

The fibrous fillers can be pretreated on the surface with a silane compound for better compatibility with the thermoplastic. Suitable silane compounds are those of the general formula

(X— (CH ₂ ) _n ) _k -Si- (OC _m H2m + l) 2-

in which the substituents have the following meaning:

X NH ₂ -, CH ₂ -CH-, HO-, \ / O n is an integer from 2 to 10, preferably 3 to 4 m is an integer from 1 to 5, preferably 1 to 2 k is an integer from 1 to 3, preferably 1

Preferred silane compounds are aminopropylthmethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.

The silane compounds are generally used in amounts of 0.05 to 5, preferably 0.5 to 1.5 and in particular 0.8 to 1% by weight (based on C) for surface coating.

Acicular mineral fillers are also suitable.

For the purposes of the invention, acicular mineral fillers are understood to be mineral fillers with a pronounced acicular character. An example is needle-shaped wollastonite. The mineral preferably has an L / D (length diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 11: 1. The mineral filler may optionally have been pretreated with the abovementioned silane compounds; however, pretreatment is not essential.

Other fillers that may be mentioned are kaolin, calcined kaolin, wollastonite, talc and chalk, and additionally platelet-shaped or needle-shaped nanofillers, preferably in amounts between 0.1 and 10%. Boehmite, bentonite, montmorillonite, vermicullite, hectorite and laponite are preferably used for this. In order to maintain good compatibility of the platelet-shaped nanofillers with the organic binder, the platelet-shaped nanofillers are organically modified according to the prior art. The addition of the platelet-shaped or needle-shaped nanofillers to the nanocomposites according to the invention leads to a further increase in the mechanical strength. As component C), the thermoplastic molding compositions according to the invention can contain customary processing aids such as stabilizers, oxidation retardants, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.

Examples of oxidation retarders and heat stabilizers are sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and their mixtures in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions called.

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

Inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, furthermore organic pigments such as phthalocyanines, quinacridones, perylenes and dyes such as nigrosine and anthraquinones can be added as colorants.

Sodium phenylphosphinate, aluminum oxide, silicon dioxide and preferably talc are used as nucleating agents.

Additional lubricants and mold release agents are usually used in amounts of up to 1% by weight. Long-chain fatty acids (eg stearic acid or behenic acid), their salts (eg Ca or Zn stearate) or montan waxes (mixtures of straight-chain, saturated carboxylic acids with chain lengths of 28 to 32 C atoms) and Ca or Na are preferred. Montanat and low molecular weight polyethylene or polypropylene waxes.

Examples of plasticizers are phthalic acid dioctyl ester, phthalic acid dibenzyl ester, phthalic acid butyl benzyl ester, hydrocarbon oils and N- (n-butyl) benzenesulfonamide.

The molding compositions according to the invention can also contain 0 to 2% by weight of fluorine-containing ethylene polymers. These are polymers of ethylene with a fluorine content of 55 to 76% by weight, preferably 70 to 76% by weight.

Examples of these are polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymers or tetrafluoroethylene copolymers with smaller proportions (generally up to 50% by weight) of copolymerizable ethylenically unsaturated monomers. These are described, for example, by Schildknecht in "Vinyl and Related Polymers", Wiley-Verlag, 1952, pages 484 to 494 and by Wall in "Fluoropolymers" (Wiley Science, 1972).

These fluorine-containing ethylene polymers are homogeneously distributed in the molding compositions and preferably have a particle size d ₅ o (number average) in the range of .0,05 to 10 .mu.m, in particular from 0.1 to 5 microns on. These small particle sizes can be achieved particularly preferably by using aqueous dispersions of fluorine-containing ethylene polymers and incorporating them into a polyester melt.

The molding compositions according to the invention are preferably obtained by organically modifying agglomerated nanofillers in an organic solvent on the surface with a siloxane, chlorosilane, silazane, titanate or zirconate and then mixing them with a polymer A).

Component B) can advantageously be added to the thermoplastic A) in the form of a dispersion with the organic solvent or by removing the solvent as a powder.

Furthermore, it has proven to be advantageous to add powder or dispersion to the monomers forming thermoplastic A) and then to carry out the polymerization in the presence of B), and to carry out the surface modification of B) in thermoplastic melt A) under shear stress.

The thermoplastic molding compositions according to the invention can be produced by processes known per se, in which the starting components are mixed in conventional mixing devices such as screw extruders, Brabender mills or Banbury mills and then extruded. After the extrusion, the extrudate can be cooled and crushed. Individual components can also be premixed and then the remaining starting materials can be added individually and / or also mixed. The mixing temperatures are usually 230 to 290 ° C.

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

The thermoplastic molding compositions according to the invention are notable for very good mechanics, in particular elongation at break and modulus of elasticity. Therefore, they are suitable for the production of fibers, foils and moldings of all kinds, in particular for applications in injection molding for components such as electrical applications such as cable trees, cable harness elements, hinges, plugs, plug parts, plug connectors, circuit carriers, electrical connecting elements, mechatronic components, optoelectronic components, especially for young people in the automotive sector and under the hood.

Examples

The following components were used

Component A / 1:

Polybutylene terephthalate with a viscosity number VZ of 130 ml / g and a carboxyl end group content of 34 meq / kg (Ultradur ^® B 4520 from BASF AG) (VZ measured in 0.5% by weight solution of phenol / o-dichlorobenzene, 1: 1 Mixture at 25 ° C), containing 0.65 wt .-% pentaerythritol tetrastearate (component C / 1 based on 100 wt .-% A).

Component A / 2:

Polyamide 6 (polycaprolactam) having a viscosity number VN of 150 ml / g, measured as 0.5 wt .-% solution in 96 wt .-% sulfuric acid at 25 ° C according to ISO 307 (B 3 was Umtramid ^® from BASF used).

Component B / 1: surface modification of fumed silica with 3-aminopropyltrimethoxysilane

100 g of pyrogenic silica with a specific surface area of 200 m ² / g (Aerosil 200) were weighed into a 2 l two-necked round bottom flask. 1000 g of 2-butanone (MEK) were added to the pyrogenic silica and the mixture was stirred with a KPG stirrer until a homogeneous suspension was formed (about 15-30 minutes). Then 56.66 g of 3-aminopropyltrimethoxysilane were added dropwise using a dropping funnel. The now thin suspension was stirred for a total of 48 hours. The 2-butanone was removed on a rotary evaporator at a bath temperature of 35 ° C. within 8 hours. After removing the solvent, a loose, coarse, porous powder remained.

The chemical connection of the silane to the surface of the pyrogenic silica was demonstrated by means of photoacoustic IR spectroscopy. In comparison to the spectrum of the unmodified silica, the sharp band of the free silane groups at 3750 cm ^"1 had disappeared and the intensity of the water band at 3700 to

3250 cm ^"1 lower. In addition, the spectra after the silanization showed bands of the CH ₂ groups of the alkoxysilane at 2900 cm ^{" 1} and 2800 cm ^"1 . Component B / 2:

Surface modification of pyrogenic silica with phenyltriethoxysilane

100 g of pyrogenic silica with a specific surface area of 200 m ² / g (Aerosil 200) were weighed into a 2 1 two-necked round bottom flask. 1000 g of 2-butanone (MEK) were added to the pyrogenic silica and the mixture was stirred for 30 minutes using a KPG stirrer, a homogeneous suspension being formed. 54 g of phenyltriethoxysilane were then added dropwise using a dropping funnel. The thin suspension was stirred for a total of 48 hours. The 2-butanone was removed on a rotary evaporator at a bath temperature of 35 ° C. within 8 hours. After removing the solvent, a loose, coarse, porous powder remained.

The chemical connection of the silane to the surface of the pyrogenic silica was demonstrated by means of photoacoustic IR spectroscopy. In comparison to the spectrum of the unmodified silica, the sharp band of the free silanol groups at 3750 cm ^"1 disappeared and the intensity of the H ₂ O band at 3700 to 3250 cm ^{" 1 was} lower.

Production of molding compounds

The molding compositions were produced on a Haake kneader by adding the powdered functionalized nanoparticles B) to the polymer melt A). The incorporation period was 10 minutes, regardless of the polymer matrix and the functionalized nanoparticles, and the processing temperature was 240 ° C. The inorganic content in the composites was 1.5-4.5% by weight. The morphology of selected composites of the polyester was examined by transmission electron microscopy.

B / 2 showed very good dispersion, the agglomerate size being between 20 and 200 nm. The aminopropyl-functionalized Aerosil B / 1 also showed better dispersion compared to the non-functionalized commercial Aerosil 200. Agglomerate sizes from 20 to 500 nm were observed.

Manufacture of miniature test specimens and property testing

The granulate was processed into test specimens on a Battenfeld miniature injection molding machine, the mechanical properties of which were determined in a tensile test (1/8 tensile rod analogous to ISO 527-2). The crystallization behavior was examined on selected test specimens.

The residue on ignition was determined by ashing 2 g of granules. The compositions of the molding compositions and the results of the measurements can be found in the tables.

Table 2:

Claims

claims

1. Thermoplastic molding compositions containing as essential components A) 1 to 99.9% by weight of a thermoplastic polymer

B) 0.01 to 50 wt .-% of a spherical, organically modified nano-filler and beyond

C) 0 to 70% by weight of further additives, the weight percentages of components A) to C) always giving 100%.

2. Thermoplastic molding compositions according to claim 1, in which component A) is composed of polyester or polyamides or polycarbonates or mixtures thereof.

3. Thermoplastic molding compositions according to claims 1 or 2, in which component B) has a (d ₅₀ ) value (average particle size) of 2 to 250 nm.

4. Thermoplastic molding compositions according to claims 1 or 3, in which component B) on the surface by treatment with a siloxane, chlorosilane. Silazan, titanate or zirconate is modified.

5. Thermoplastic molding compositions according to claims 1 to 4, in which the surface modifier of component B) from compounds of the general formulas Si (OR ') _n R n, SiCl _n R ₄ . _n , (R _m R ⁿ m-3 Si) ₂ NH, Ti (OR ') _n R ₄ . _n or Zr (OR ') _n j- _n or mixtures thereof, where

R'.R "same or different hydrocarbon radicals with 1 to 8 carbon atoms, R saturated or unsaturated hydrocarbon radical with 1 to 150 carbon atoms, which has at least one epoxy, OH, amino, carboxyl, (meth) acrylate, isocyanate -, Thiol, glycidyl or aromatic group, m = 1, 2 or 3 and n = 1, 2 or 3 mean.

6. Thermoplastic molding compositions according to claims 1 to 5, in which component B) has an aspect ratio (IJD) of 15 to 1.

7. Thermoplastic molding compositions according to claims 1 to 6, containing nitrides or oxides or their compounds as component B).

8. A method for producing the thermoplastic molding compositions according to claims 1 to 7, characterized in that agglomerated nanofillers in an organic solvent on the surface by treatment with a siloxane, chlorosilane, silazane, titanate or zirconate and then organically modified with a thermoplastic polymer A) mixes.

9. A method for producing the thermoplastic molding compositions according to claim 8, d. g. that one adds the organically modified component B) in the form of a dispersion with the organic solvent to the thermoplastic A).

10. The method according to claim 8, characterized in that the solvent is removed and the modified component B) is added as a powder to the thermoplastic A).

11. Use of the thermoplastic molding compositions according to claims 1 to 7 for the production of fibers, films and moldings.

12. Shaped bodies of any kind, obtainable from the thermoplastic molding compositions according to claims 1 to 7.