WO2011009798A1

WO2011009798A1 - Nanocomposite blend based on polyamides and polyarylene ether sulfones

Info

Publication number: WO2011009798A1
Application number: PCT/EP2010/060229
Authority: WO
Inventors: Christian Schmidt; Sachin Jain; Matthias Müller; Piyada Charoensirisomboon; Martin Weber
Original assignee: Basf Se
Priority date: 2009-07-21
Filing date: 2010-07-15
Publication date: 2011-01-27
Also published as: EP2456816A1

Abstract

The invention relates to thermoplastic molding compounds comprising: A) at least one thermoplastic polyamide, B) at least one polyarylene ether sulfone, and C) at least one oxide and/or oxide hydrate of at least one metal or semimetal having a weighted average diameter of the primary particles of 0.5 to 50 nm. The invention further relates to the use of the thermoplastic molding compounds for producing fibers, films, and molded parts, and to fibers, films, and molded parts obtainable from the thermoplastic molding compound according to the invention.

Description

Nanocomposite blends based on polyamides and polyarylene ether sulfones Description The invention relates to thermoplastic molding compositions comprising:

A) at least one thermoplastic polyamide,

B) at least one polyarylene ether sulfone and

C) at least one oxide and / or hydrated oxide of at least one metal or semi-metal having a number-average mean diameter of the primary particles of 0.5 to 50 nm.

Furthermore, the invention relates to the use of the thermoplastic molding compositions for the production of fibers, films and moldings as well as fibers, films and moldings, which are obtainable from the thermoplastic molding compositions according to the invention.

Blends of polyamides on the one hand and polyarylene ether sulfones as high glass transition temperature amorphous polymers on the other hand are known from the prior art. The incorporation of amorphous high-temperature polymers in polyamides aims at improving certain properties of polyamides, in particular the heat resistance and the dimensional stability as a result of reduced water absorption of the polyamide. Of central importance is the non-miscibility of the named components. Various methods have been proposed for obtaining a suitable morphology of the blends.

P. Charaoensirisomboon et al. discloses in Polymer 41 (2000), 5977-5984 blends of predominantly polysulfone (PSU) and polyamide, which are prepared by so-called reactive mixing. By using functionalized PSU, improved morphology is achieved.

DE 36 17 501 A1 discloses thermoplastic molding compositions comprising a polyamide and a polyarylene ether sulfone and a hydroxy-functionalized polymeric component. DE 2122735 discloses a thermoplastic polymer mixture containing an aromatic polysulfone and a polyamide. DE 101 49 870 discloses blends comprising a polyarylene ether sulfone, a thermoplastic polyamide and a functionalized polyarylene ether sulfone.

DE 196 45 131 A1 discloses a process for the preparation of blends of a thermoplastic polymer which may be, for example, a polyarylene ether, and Polyamide by dissolving the thermoplastic polymer in a lactam as a precursor of the polyamide.

EP 0 477 757 A2 discloses blends of polyamide with at least 50% by weight of hexamethylene terephthalate units and polyarylene ether sulfone, which have improved mechanical properties.

However, none of the above documents discloses the use of oxides and / or oxide hydrates having a number average diameter of the primary particles of 0.5 to 50 nm for controlling the morphology.

The average domain size of the phase formed by the polyarylene ether sulfone is in the prior art either always more than 2 micrometers or is based on the addition of specially modified reactive components as compatibilizers such as e.g. functionalized block copolymers.

However, such compatibilizers are expensive to produce and correspondingly expensive, so that a simpler and less expensive solution is desirable.

The thermoplastic molding compositions known from the prior art thus either have comparatively large domains of polyarylene ether sulfone or contain complex compatibilizers to be prepared. By large domains, the impact strength to be achieved is undesirably limited.

The addition of inorganic nanoparticles is often avoided in order not to adversely affect the mechanical properties, in particular the impact strength.

A better distribution of the disperse phase, ie a smaller domain size with the same total proportion, causes a greater effective surface area between the two phases and thus generally a better connection of the distributed phase, which in turn has a favorable effect on the mechanical properties. The best possible distribution of the blend component in the matrix is thus desirable. As a quantitative measure of such a distribution, a comparison of the domain sizes of the disperse phase with the same total proportion can be used.

In the case of the molding compositions known from the prior art, which are based on polyamide as the matrix phase and polyarylene ether sulfones as the disperse phase, the compatibility between the two phases is generally poor on account of the low affinity of the two phases. The resulting properties such as heat resistance, dimensional stability, flowability in the melt or even Notched impact strength is limited and not sufficient for all applications.

It was the object of the present invention to avoid the mentioned disadvantages of the prior art. It should be made available molding compositions which have a comparable distribution of polyamide and polyarylene ether an improved distribution of the disperse phase in the matrix and thus also an improved notched impact strength, conventional conventional costly compatibilizer preferably not or should be used in the smallest possible amount ,

The stated objects are achieved by the thermoplastic molding compositions according to the invention. Preferred embodiments of the invention are described in the description and the dependent claims. Combinations of preferred embodiments do not depart from the scope of the present invention.

composition

According to the invention, the thermoplastic molding compositions contain the following components:

A) at least one thermoplastic polyamide,

B) at least one polyarylene ether sulfone and

C) at least one oxide and / or oxide hydrate of at least one metal or semimetal having a number-weighted mean diameter of the primary particles of 0.5 to 50 nm.

In this case, component B) forms a first phase and component A) forms a separate second phase. The separate second phase is continuous, whereas the first phase formed by component B) is discontinuous and consists of spherical or spheroidal domains.

The composition of the thermoplastic molding compositions can vary over a wide range, provided that it is ensured that component A), i. the above separate second phase is continuous. It is known to the person skilled in the art that mixtures of polyamides and polyarylene ether sulfones are immiscible and that the polyamides form a continuous phase, provided that the polyamide is present in a sufficient amount or is processed in a suitable manner.

The novel thermoplastic molding compositions preferably comprise from 50 to 99.9% by weight of component A), from 0.05 to 40% by weight of component B) and from 0.05 to 10% by weight of component C). where the sum of the weight percentages components of components A) to C) based on the sum of the wt .-% of components A), B) and C) 100 wt .-% results.

The thermoplastic molding compositions preferably contain components B) and C) in a weight ratio B to C of 40: 1 to 2: 1, preferably 15: 1

1 to 3 to 1, in particular from 10 to 1 to 4 to 1.

The novel thermoplastic molding compositions preferably comprise from 60 to 98.9% by weight of component A), from 1 to 36% by weight of component B) and from 0.1 to 4% by weight of component C), where the sum of the percentages by weight of components A) to C) based on the sum of the wt .-% of components A), B) and C) 100 wt .-% results.

Component A

According to the invention, the thermoplastic molding compositions comprise as component A) at least one thermoplastic polyamide, preferably from 50 to 99.9% by weight, in particular from 60 to 98.9% by weight, based on the total weight of components A), B) and C. ).

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 at a concentration of 0.5 wt .-% in 96 wt .-% - sulfuric acid at 25 ° C according to ISO 307. Semicrystalline or amorphous polyamides having a weight average molecular weight of at least 5,000 g / mol, such as in US Pat. Nos. 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. Preference is given to using polyamides which are derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam, and also polyamides which are obtained by reacting dicarboxylic acids with diamines.

Suitable dicarboxylic acids are alkanedicarboxylic acids having 6 to 12, in particular 6 to 10, carbon atoms and aromatic dicarboxylic acids, in particular adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acid.

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 in particular 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, partially aromatic copolyamides such 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 .-% based on the total weight of the polyamide (see EP-A 299 444). The production of the preferred partly aromatic copolyamides with a low triamine content can be carried out by the processes described in EP-A 129 195 and 129 196.

The preferred partly aromatic copolyamides A) contain as component a-i) from 40 to 90% by weight of units derived from terephthalic acid and hexamethylenediamine, based on component A). 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 maximum 50 wt .-%, preferably from 20 to 50 wt .-%, in particular from 25 to 40 wt .-%, while the proportion of units derived from adipic acid and hexamethylenediamine, up to 60 wt .-%, preferably from 30 to 60 wt .-% and in particular from 35 to 55 wt .-%, in each case based on component A).

The copolyamides may also contain both units of ε-caprolactam and units of adipic acid and hexamethylenediamine; In this case, care must be taken that the proportion of units which are free of aromatic groups is at least 10% by weight, preferably at least 20% by weight, based on component A). 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 ai) and from 20 to 50, preferably from 25 to 40, have proven to be particularly advantageous for many applications. -% units derived from ε-caprolactam (units a2), proven, each based on the total weight of component A).

In addition to the above-described units ai) to a3), the preferred partially aromatic copolyamides A) 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 ), such as they are known from other polyamides. 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'-diamodicyclohexyl) propane or 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane as the representative of diamines and capryllactam, enanthlactam, omega-aminoundecanoic acid and laurolactam as representatives of lactams or aminocarboxylic acids.

The melting points of the preferred partly aromatic copolyamides A) are in the range of 260 to 300 ⁰ C, this high melting point greater than 75, especially more than 85 ° C is also associated with a high glass transition temperature of usually.

Binary copolyamides based on terephthalic acid, hexamethylenediamine and ε-caprolactam have, at levels of about 70 wt .-% of units derived from terephthalic acid and hexamethylenediamine, melting points in the range of 300 ⁰ C and a glass transition temperature of more than 110 ⁰ C. on. Binary copolyamides based on terephthalic acid, adipic acid and hexamethylenediamine (HMD) reach melting points of 300 ^° C. and 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 further preferred polyamides A) according to 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

PA 12 / MACMT laurolactam, dimethyldiaminodicyclohexylmethane,

terephthalic acid

PA PDA-T phenylenediamine, terephthalic acid

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

Polyamide-6, polyamide-6,6 or mixtures of the two abovementioned polyamides are particularly preferred as component A).

Component B

According to the invention, the thermoplastic molding compositions comprise at least one polyarylene ether sulfone, preferably from 0.05 to 40% by weight, in particular from 1 to 36% by weight, based on the total weight of components A), B) and C). Polyarylene ether sulfones and their preparation are well known to the person skilled in the art. Polyarylene ether sulfones are polymers which contain arylene units which are linked via oxygen atoms and moreover contain -SO ₂ - linkages.

Preferred polyarylene ether sulfones of component B) are composed of building blocks of the general formula I:

with the following meanings t, q: independently of one another 0, 1, 2 or 3,

Q, T, Y: independently of one another each a chemical bond or group selected from -O-, -S-, -SO ₂ -, S = O, C = O, -N = N-, -CR ^a R ^b - where R ^a and R ^b are each independently a hydrogen atom or a C 1 -C 12 -alkyl, C 1 -C 4 -alkoxy or C 3 -C 6 -aryl group, at least one of Q, T and Y being other than -O- , and at least one of Q, T and Y is -SO ₂ - and

Ar, Ar ¹ : independently of one another an arylene group having from 6 to 18 carbon atoms. If Q, T or Y is a chemical bond under the above conditions, then it is to be understood that the left neighboring and the right neighboring group are directly linked to each other via a chemical bond.

Preferably, however, Q, T and Y in formula (I) are independently selected from -O- and -SO 2 -, with the proviso that at least one of the group consisting of Q, T and Y is -SO 2 -. If Q, T or Y -CR ^a R ^b -, R ^a and R ^b are each independently a hydrogen atom or a Ci-Ci2-alkyl, Ci-Ci2-alkoxy or Cβ-Cis-aryl group.

Preferred C 1 -C 12 -alkyl groups include linear and branched, saturated alkyl groups having from 1 to 12 carbon atoms. In particular, the following radicals may be mentioned: C 1 -C 6 -alkyl radical, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, 2- or 3-methylpentyl and longer-chain radicals, such as unbranched heptyl, Octyl, nonyl, decyl, undecyl, lauryl and the mono- or polysubstituted analogs thereof.

Suitable alkyl radicals in the abovementioned usable C 1 -C 12 -alkoxy groups are the alkyl groups having from 1 to 12 carbon atoms defined above. Preferred cycloalkyl radicals include in particular C 3 -C 12 -CCCl 10 -alkyl radicals, such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl, cyclpentylethyl, -propyl, -butyl, -pentyl, -hexyl, cyclohexylmethyl, -dimethyl, -trimethyl.

Ar and Ar ¹ independently represent a Cβ-cis-arylene group. Starting from the starting materials described below Ar is preferably derived from an electron-rich, easily electrophilically attackable aromatic substance, preferably from the group consisting of hydroquinone, resorcinol, dihydroxynaphthalene, in particular 2,7-dihydroxynaphthalene, and 4,4'-bisphenol is selected. Preferably, Ar ^{1 is} an unsubstituted Cβ or C 12 arylene group.

Phenylene groups such as 1, 2, 1, 3 and 1, 4-phenylene, naphthylene groups, such as, for example, 1, 6, 1, 7, 2, 6 and 4, are used as Cβ-cis-arylene groups Ar and Ar ¹ 2,7-naphthylene, as well as derived from anthracene, phenanthrene and naphthacene arylene groups into consideration.

Ar and Ar ¹ in the preferred embodiment according to formula (I) are preferably selected independently from the group consisting of 1, 4-phenylene, 1, 3-phenylene, naphthylene, in particular 2, 7-dihydroxynaphthalene, and 4,4'- biphenylene. In the context of component B) preferably present building blocks are those which contain at least one of the following recurring structural units Ia to Io:

In addition to the preferably present blocks Ia to Io, those building blocks are also preferred in which one or more 1,4-dihydroxyphenyl units are replaced by resorcinol or dihydroxynaphthalene units.

Particularly preferred building blocks of the general formula I are the building blocks Ia, Ig and Ik. It is furthermore particularly preferred if the polyarylene ether sulfones of component B) are composed essentially of one kind of building blocks of general formula I, in particular of one building block selected from Ia, Ig and Ik.

In a particularly preferred embodiment, Ar = 1, 4-phenylene, t = 1, q = 0, T is a chemical bond and Y = SO 2. Particularly preferred polyarylene ether sulfones synthesized from the abovementioned repeat unit are termed polyphenylene sulfone (PPSU).

In another particularly preferred embodiment, Ar = 1, 4-phenylene, t = 1, q = 0, T = C (CH 3) 2 and Y = SO 2. Particularly preferred polyarylene ether sulfones built up from the abovementioned repeat unit are referred to as polysulfone (PSU).

In another particularly preferred embodiment, Ar = 1, 4-phenylene, t = 1, q = 0, T = Y = SO 2. Particularly preferred polyarylene ether sulfones synthesized from the abovementioned repeat unit are referred to as polyethersulfone (PESU). Abbreviations such as PPSU, PESU and PSU refer in the context of the present invention to DIN EN ISO 1043-1: 2001. In general, the preferred polyarylene ether sulfones B) have average molecular weights M _n (number average) in the range from 5000 to 60000 g / mol and relative viscosities from 0.20 to 0.95 dl / g. The relative viscosities depending on the solubility of the polyarylene ether sulfones either in 1 wt .-% sodium N-methylpyrrolidone solution, in mixtures of phenol and dichlorobenzene or in 96% sulfuric acid measured at each of 20 ⁰ C and 25 ⁰ C.

The polyarylene ether sulfones B) of the present invention preferably have weight average molecular weights M _{w of} from 10,000 to 150,000 g / mol, more preferably from 15,000 to 120,000 g / mol, more preferably from 18,000 to 100,000 g / mol as determined by gel permeation chromatography in the dimethylacetamide solvent against narrow polymethyl methacrylate as standard.

Production processes which lead to the abovementioned polyarylene ether sulfones are known to the person skilled in the art.

The polyarylene ether sulfones of component B) are preferably prepared by reacting at least one aromatic compound (r1) having two halogen substituents and at least one aromatic compound (r2) having two functional groups which are reactive with the abovementioned halogen substituents.

Aromatic compounds (r1) and (r2) as monomers suitable for the preparation of polyarylene ether sulfones are known to the person skilled in the art and are not subject to any fundamental restriction, provided that said substituents are sufficiently reactive in the context of a nucleophilic aromatic substitution. Another requirement is sufficient solubility in the solvent.

Suitable compounds (r1) are, in particular, dihalodiphenylsulfones, such as 4,4'-dichlorodiphenylsulfone, 4,4'-difluorodiphenylsulfone, 4,4'-dibromodiphenylsulfone, bis (2-chlorophenyl) sulfones, 2,2'-dichlorodiphenylsulfone and 2,2'-dichloromethane. difluorodiphenylsulphone.

Preferably, the aromatic compounds having two halogen substituents (r1) are selected from 4,4'-dihalodiphenylsulfones, in particular 4,4'-dichlorodiphenylsulfone or 4,4'-difluorodiphenylsulfone. Opposite to the above-mentioned halogen-reactive groups are, in particular phenolic OH and O ^"groups, the latter functional group is derived from the dihydroxy compounds in a known manner from such manufactured can be placed or intermediately arises. Accordingly, preferred compounds (r2) are those having two phenolic hydroxyl groups.

Preferred compounds (r2) having two phenolic hydroxyl groups are selected from the following compounds:

Dihydroxybenzenes, especially hydroquinone and resorcinol;

Dihydroxynaphthalenes, in particular 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene;

- Dihydroxybiphenyls, in particular 4,4'-biphenol and 2,2'-biphenol;

Bisphenyl ethers, especially bis (4-hydroxyphenyl) ether and bis (2-hydroxyphenyl) ether;

Bis-phenylpropanes, especially 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane;

Bisphenylmethanes, especially bis (4-hydroxyphenyl) methane;

Bisphenylsulfones, especially bis (4-hydroxyphenyl) sulfone;

Bisphenyl sulfides, especially bis (4-hydroxyphenyl) sulfide;

Bisphenyl ketones, especially bis (4-hydroxyphenyl) ketone;

- Bisphenylhexafluoropropane, in particular 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) hexafluoropropane; and

Bisphenylfluorenes, especially 9,9-bis (4-hydroxyphenyl) fluorene.

It is preferable, starting from the abovementioned aromatic dihydroxy compounds (r2), to prepare their dipotassium or disodium salts and to react with the compound (r1). The aforementioned compounds may be used singly or as a combination of two or more of the aforementioned compounds.

Hydroquinone, resorcinol, dihydroxynaphthalene, especially 2,7-dihydroxynaphthalene, and 4,4'-bisphenol are particularly preferred as the aromatic compound (r2) having two functional groups reactive with the halogeno substituents of the aromatic compound (r1).

The proportions to be used result from the stoichiometry of the elimination polycondensation reaction with arithmetic elimination of hydrogen chloride and are set by the expert in a known manner. In order to control the molecular weight and / or the end groups, it is possible to use one of the abovementioned components (r1) or (r2) in a molar excess over the respective other component, the excess component preferably being from 1.05 to 1 mol to 1, 1 to 1 mol is used. In the thermoplastic molding compositions according to the invention, component B) forms a separate phase with a number-average domain size which, according to transmission or scanning electron microscopy, is preferably less than 1100 nm, in particular from 100 to 1000 nm.

Component C

According to the invention, component C) is at least one oxide and / or hydrated oxide of at least one metal or semimetal having a number-weighted mean diameter of the primary particles of 0.5 to 50 nm.

The novel thermoplastic molding compositions preferably comprise from 0.05 to 10% by weight of component C), based on the total amount of components A), B) and C). The novel thermoplastic molding compositions particularly preferably contain from 0.1 to 4% by weight of component C), in particular from 0.1 to 3% by weight, very particularly preferably from 0.3 to 2% by weight, in each case based on the total amount of components A), B) and C).

Corresponding oxides and / or hydrated oxides are known per se to the person skilled in the art. The function of said oxides and / or oxide hydrates is to control the domain size and morphology of the thermoplastic molding compositions.

Component C) preferably has a higher affinity for component B) than for component A). This ensures that in the course of the production of the inventive thermoplastic molding compositions component C) predominantly at the interface of component A) and component B) or moves there, which has a favorable effect on the morphology and the properties to be achieved. To assist in adjusting the preferred location at the interface, component C) is preferably previously mixed with component A), which is then subsequently mixed with component B) and optionally with further A). In the course of mixing, component C) migrates to said interface. As a result, a small domain size of component B) is achieved in the thermoplastic molding composition according to the invention.

The aforementioned selective affinity can be preferably achieved by using an oxide and / or hydrated oxide of at least one metal or metalloid having a number average particle diameter of the primary particles of 0.5 to 50 nm having a hydrophobic surface. In the case of a hydrophobic surface, component C) can be characterized in this case preferably by at least one of the following features a) and / or b): a) Component C) is at least one oxide and / or hydrated oxide of at least one metal or semimetal with a number-average particle diameter of the primary particles of 0.5 to 50 nm, wherein according to transmission electron microscopy, the oxide and / or oxide hydrate is present at least 90% in the component B or at the interface of A) and B).

Methods for the determination of phases in polymer blends and the determination of nanoparticulate constituents in polymer blends are known to the person skilled in the art. In the context of the present invention, the phases and their constituents are determined by means of transmission electron microscopy. b) Component C) has a methanol wettability of at least 50%.

The methanol wettability is a measure of how hydrophobic an oxide and / or hydrated oxide of at least one metal or semi-metal is. In the process, oxides and / or hydrated oxides are wetted using a methanol / water mixture. The proportion of methanol in the mixture, expressed as weight percent, is a measure of the water repellency of the metal oxide. The higher the proportion of methanol, the more hydrophobic the substance is. The degree of hydrophobicity is determined by titration. For this purpose, 0.2 g of the sample are weighed in a 250 ml separating funnel and 50 ml ultrapure water added. The oxide or hydrated oxide with hydrophobic surface remains on the surface of the water. It is now added ml-wise methanol from a burette. In doing so, the separating funnel is shaken with a circular hand movement so that no swirls are created in the liquid. In this way, methanol is added until the powder is wetted. This can be seen from the decrease in the total powder from the water surface. The consumption of methanol is converted into wt .-% methanol and indicated as a value for the methanol wettability. The number-weighted average diameter of the primary particles in the thermoplastic molding composition is determined by transmission or scanning electron microscopy and subsequent image analysis by means of a statistically significant number of samples. Corresponding methods are known to the person skilled in the art. The diameter of the primary particles in the context of the present invention is the largest diameter through the geometric center of the particle. Oxides with a hydrophobic particle surface generally have a BET surface area according to DIN 66131 of at most 300 m ² / g. Component C) preferably has a BET specific surface area to DIN 66131 of 50 to 300 m ² / g, in particular from 100 to 200 m ² / g.

The novel thermoplastic molding compositions preferably contain, as component C), an amorphous oxide and / or hydrated oxide of silicon having a number-average particle diameter of the primary particles of 0.5 to 50 nm, in particular 1 to 20 nm.

Component C) is particularly preferably flame-pyrolytically produced silicon dioxide, the surface of which is hydrophobically modified.

Component C) particularly preferably has a number-weighted mean diameter of the primary particles of from 1 to 20 nm, preferably from 1 to 15 nm.

In a preferred embodiment, component C) is hydrophobically modified by a surface modifier, preferably an organosilane. Preferably, the metal and / or semimetal according to component C) is silicon.

The surface modification can be carried out by spraying the nanoparticles optionally with water and then with the surface modifier. The spraying can also be done in reverse order. The water used can be acidified with an acid, for example hydrochloric acid, to a pH of 7 to 1. If more surface modifiers are used, they may be applied as a mixture or separately, simultaneously or sequentially. The surface modifier (s) may be dissolved in suitable solvents. After the spraying is finished, mixing can be continued for 5 to 30 minutes. Preferably, the mixture is then thermally treated at a temperature of 20 to 400 ⁰ C over a period of 0.1 to 6 h. The thermal treatment can be carried out under protective gas, such as nitrogen.

An alternative method of surface modification of the nanoparticles can be carried out by treating the nanoparticles with the surface modifier in vapor form and then thermally treating the mixture at a temperature of 50 to 800 ⁰ C over a period of 0.1 to 6 h. The thermal treatment can be carried out under protective gas, such as nitrogen. The temperature treatment can also be carried out in several stages at different temperatures. The Application of the surface modifier (s) can be done with single, dual or ultrasonic nozzles.

The surface modification can be carried out continuously or batchwise in heatable mixers and dryers with sprayers. Suitable devices may be, for example: plowshare mixers, plate, fluidized bed or fluid bed dryers.

Surface modifiers which can be used advantageously in the context of the present invention are described in DE 10 2007 035 951 A1 in paragraph [0015], the contents of which are hereby fully incorporated by reference.

Organosilanes are preferred as surface modifiers. In particular, the following organosilanes can be used as surface-modifying agent: octyltrimethoxysilane, octyltriethoxysilane, hexamethyldisilazane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, hexadecyltrimethoxysilane, decyltriethoxysilane hexa-, dimethylpolysiloxane, glycidyloxypropyltrimethoxysilane, Glycidylo- xypropyltriethoxysilan, Nonafluorohexyltrimethoxysilan, Tridecaflou-rooctyltrimethoxy- silane, Tridecaflourooctyltriethoxysilan, aminopropyl triethoxysilane, hexamethyldisilazane.

Hexamethyldisilazane, hexadecyltrimethoxysilane, dimethylpolysiloxane, octyltrimethoxysilane and octyltriethoxysilane are particularly preferably used.

In particular, hexamethyldisilazane, octyltrimethoxysilane and hexadecyltrimethoxysilane are used, most preferably hexamethyldisilazane.

Component D

In the context of the present invention, the thermoplastic molding compositions may contain particulate or fibrous fillers, in particular glass fibers. Component D) is preferably from 0 to 60 wt .-% based on the total amount by weight of components A), B), C) and D).

The novel thermoplastic molding compositions may contain glass fibers as component D).

If the thermoplastic molding compositions of the invention contain any glass fibers, they preferably contain from 1 to 50 parts by weight of component D), based on 100 parts by weight of the thermoplastic molding composition.

In the thermoplastic molding compositions according to the invention, it is possible in particular for all those known to the person skilled in the art and suitable for use in thermoplastic molding compositions. suitable glass fibers are present. These glass fibers can be prepared by methods known to the person skilled in the art and, if appropriate, surface-treated. The glass fibers can be equipped with a size for better compatibility with the matrix material, as described, for example, in DE 101 17715.

In a preferred embodiment, glass fibers having a diameter of 5 to 15 .mu.m, preferably 7 to 13 .mu.m, more preferably 9 to 1 1 microns are used.

The incorporation of the glass fibers can take place both in the form of chopped glass fibers and in the form of endless strands (rovings). The length of the usable glass fibers is usually before incorporation as chopped glass fibers into the thermoplastic molding compositions 4 to 5 mm. After the processing of the glass fibers, for example by coextrusion, with the other components, the glass fibers are usually present in an average length of 100 to 400 .mu.m, preferably 200 to 350 .mu.m.

Component E

In addition, the thermoplastic molding compositions according to the invention may contain, as component E), further additives which are different from A) to D).

The molding compositions according to the invention may contain as component E) in particular additives such as processing aids, pigments, stabilizers, flame retardants or mixtures of different additives. Usual additives

For example, oxidation inhibitors, anti-heat decomposition and ultraviolet light decomposition agents, lubricants and mold release agents, dyes, plasticizers, or impact modifiers are also exemplified.

The molding compositions of the invention may contain a total of 0 to 70, in particular up to 50 wt .-% of component E) based on the sum of the wt .-% of components A) to E).

The thermoplastic molding compositions advantageously contain a lubricant. In the context of component E), the molding compositions of the invention may be from 0 to 3, preferably from 0.05 to 3, preferably from 0.1 to 1, 5 and in particular from 0.1 to 1 wt .-% of a lubricant based on the total amount of components A) to E).

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 mixtures of different salts are used, wherein the mixing ratio is 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.

The thermoplastic molding compositions according to the invention may also contain an impact modifier in the context of component E). In principle, the impact modifier known to those skilled in the art for polyamides can be used as an impact modifier.

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

Rubbers which enhance the toughness of the molding compositions, generally contain an elastomeric portion which has a glass transition temperature of less than -10 ⁰ C, preferably less than -30 ⁰ C., and they contain at least one functional elle group 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 Ci-Ci2-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 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 from 0.5 to 50, in particular from 2 to 20 and particularly preferably from 3 to 15 wt .-%, based on the total weight of the olefin finpolymerisats. 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 can 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 which may be mentioned are anhydrides of dicarboxylic acids having 2 to 20 C 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. Particular preference is given to olefin polymers comprising from 50 to 98.9, in particular from 60 to 94.85,% by weight of ethylene, and from 1 to 50, in particular from 5 to 40,% by weight of an ester of acrylic or methacrylic acid, of 0, 1 to 20.0, in particular from 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 ⁰ 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 as e.g. Butadiene and / or isoprene.

Particularly preferred are ethylene / 1-octene copolymers, ethylene / 1-butene copolymers, ethylene-propylene copolymers, wherein compositions from - From 25 to 85 wt .-%, preferably from 35 to 80 wt .-% of ethylene,

From 14.9 to 72 wt .-%, preferably from 19.8 to 63 wt .-% 1-octene or 1-butene or propylene or mixtures thereof From 0.1 to 3 wt .-%, preferably from 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 in the range of 10,000 to 500,000 g / mol, preferably 15,000 to 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 in the range of 5 to 97, preferably 10 to 95, especially 15 to 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 Pat. No. 5,272,236 In this case, the ethylene-α-olefin copolymers have a narrow one for polyolefins A molecular weight distribution of less than 4, preferably less than 3.5, as a further group of suitable rubbers are core-shell graft rubbers Such core-shell graft rubbers are known as rubbers in polyamides Preferred core-shell rubbers are those which in of the

WO2008 / 022910 on page 15, line 1 to line 42 will be described. 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 described in the literature, e.g. in US 3,651,014. Also commercially available are corresponding products under the names Hytrel ™ (DuPont), Arnitel ™ (Akzo) and Pelprene ™ (Toyobo Co. Ltd.).

Of course, mixtures of different rubbers can be used.

In the context of component E), the thermoplastic molding compositions according to the invention moreover conventional processing aids such as stabilizers, oxidation retardants, other means against thermal decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, flame retardants etc. included. 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.

As UV stabilizers, which are generally used in amounts of up to 2 wt .-%, based on the molding composition, 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.

In the context of component E), the novel thermoplastic molding compositions may contain from 0.01 to 2% by weight, preferably from 0.05 to 1.5% by weight, more preferably from 0.1 to 1.5% by weight. at least one heat stabilizer, each based on the total weight of components A) to E).

In a preferred embodiment, the heat stabilizers are selected from the group consisting of

(a) Compounds of monovalent or divalent copper, e.g. Salts of mono- or divalent copper with inorganic or organic acids or mono- or dihydric phenols, the oxides of mono- or divalent copper, or the complex compounds of copper salts with ammonia, amines, amides, lactams, cyanides or phosphines, preferably Cu (I) - or Cu (II) salts of the hydrohalic acids, the hydrocyanic acids or the copper salts of the aliphatic carboxylic acids. Particularly preferred are the monovalent

Copper compounds CuCI, CuBr, CuI, CuCN and CU2O, as well as the divalent copper compounds CuCb, CuSO ₄ , CuO, copper (II) acetate or copper (II) stea- rat. If a copper compound is used, the amount of copper is preferably 0.005 to 0.5, in particular 0.005 to 0.3 and particularly preferably 0.01 to 0.2 wt .-%, based on the sum of components A) to

E). The copper compounds are commercially available or their preparation is known in the art. The copper compound can be used as such or in the form of concentrates. Concentrate here is to be understood as meaning a polymer, preferably of the same chemical nature as component (A), which contains the copper salt in high concentration. The use of concentrates is a common method and is particularly often used when very small amounts of a feedstock are to be dosed. Advantageously, the copper compounds in combination with other metal halides, in particular alkali halides such as NaI, Kl, NaBr, KBr used, wherein the molar ratio of metal halide to copper 0.5 to 20, preferably 1 to 10 and particularly preferably 2 to 5.

(b) stabilizers based on secondary aromatic amines, these stabilizers preferably being present in an amount of 0.2 to 2, preferably 0.5 to 1.5,% by weight, based in each case on the total weight of the thermoplastic molding composition;

(c) stabilizers based on hindered phenols, these stabilizers preferably being present in an amount of from 0.05 to 1.5, preferably 0.1 to 1,% by weight, based in each case on the total weight of the thermoplastic molding composition; and

(d) mixtures of the abovementioned stabilizers.

Stabilizers based on secondary aromatic amines are known per se to a person skilled in the art and can be used advantageously in the context of the present invention. Stabilizers based on secondary aromatic amines are preferably present in an amount of from 0.2 to 2% by weight, in particular from 0.5 to 1.5% by weight, based on the total weight of the thermoplastic molding composition. Particularly preferred stabilizers based on secondary aromatic amines are described in US Pat

WO2008 / 022910 on page 9, line 36 to page 10, described before line 3.

Stabilizers based on sterically hindered phenols are also known to the person skilled in the art. Stabilizers based on sterically hindered phenols are preferably present in an amount of 0.05 to 1, 5 wt .-%, in particular 0.1 to 1 wt .-% based on the total weight of the thermoplastic molding composition. Particularly preferred stabilizers based on sterically hindered phenols are described in WO2008 / 022910 on page 10, line 3 to page 11, before line 10.

Production of molding compounds

The thermoplastic molding compositions according to the invention can be prepared by processes known per se, in which the starting components in customary Mixing devices such as screw extruders, in particular twin-screw extruders, Brabender mills or Banbury mills mixed and then optionally re-extruded. Another subject of the invention is accordingly a process for the preparation of the thermoplastic molding compositions according to the invention comprising the mixing of the components A), B) and C) and optionally D) and E). The mixing is preferably carried out in an extruder. The resulting extrudate can then be cooled and comminuted. Preferably, individual components are preferably premixed in the aforementioned mixing plants and then added the remaining starting materials individually and / or also premixed. The mixing temperatures are usually 230 to 320 ⁰ C and depend on the flow temperatures of the polymers used. Preferred embodiments relating to the sequence of the mixing steps will be described below.

In a first embodiment s1 component C) and parts of the component

A) premixed, whereby a so-called masterbatch (mb-AC) is formed. It is alternatively possible to premix the total amounts of A) and C) to be used. The latter embodiment is referred to as s2. Accordingly, the premix of A) and C) is generally referred to as variant s.

According to a second embodiment t1 component C) and parts of the component B) are premixed, whereby a so-called masterbatch (mb-BC) is formed. It is alternatively possible to premix the total amounts of B) and C) to be used. The latter embodiment is referred to as t2. The premix of

B) and C) is accordingly generally referred to as variant t. According to a third embodiment, the components A), B) and C) are mixed together without premixing. The order can vary. According to embodiment u1, first component A) is fed to the mixing plant, preferably to the extruder, and then components B) and C) are fed simultaneously or successively. According to embodiment u2, first component B) is fed to the mixing plant, preferably to the extruder, and then components A) and C) are fed simultaneously or in succession.

Variant s leads to thermoplastic molding compositions in which component C) is preferably in the region of the interface between components A) and B). The variants t and u lead to thermoplastic molding compositions in which component C) is preferably in component B). Of the abovementioned embodiments of the mixture of components A) to C), variant s is preferred. By premixing components A) and C), a particularly small number-average domain size of component B) is achieved. Variant s1 is particularly preferred.

A preferred method comprises the following steps:

(a) premixing the total amount of component C) and a partial amount or the total amount of component A) and then

(b) mixing the mixture obtained from (a) with the total amount of component B) and optionally the remaining portion of component A).

The thermoplastic molding compositions according to the invention are distinguished by good mechanical properties, in particular a good notched impact strength, at the same time good processability / flowability.

The thermoplastic molding compositions according to the invention themselves are suitable for the production of fibers, films and moldings of any kind. Examples of this are household articles, electronic components, medical devices, automotive 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.

Another subject of the invention are the said fibers, films or moldings, which are obtainable from the thermoplastic molding compositions according to the invention. In other words, a further subject of the invention is directed to fibers, films or moldings which contain the compositions defined within the scope of the thermoplastic molding compositions according to the invention.

Examples

The following components were used:

Component A-1: Polyamide 6 having a viscosity number VN according to ISO 307 at a concentration of 0.5% by weight in 96% strength by weight sulfuric acid (before extrusion) in the range from 146 to 151 ml / g.

Component B-1: Ultrason® S 2010, a polysulfone (PSU) having an ISO 307 viscosity of 63 ml / g. Component B-2: Ultrason P 1010, a polyphenylene sulfone (PPSU) having a reduced viscosity at a concentration of 1, 00 g / ml in N-methyl pyrrolidone at 25.0 ⁰ C from 53-56 ml / g. Component C-1: Aerosil® R8200, a hydrophobically modified flame-polyethylenically produced SiO 2 of the number-average particle size of about 14 nm with hexamethyldisilazane of hydrophobized particle surface, a BET specific surface area of about 160 m ² / g and a pH of 4% -iger dispersion of at least 5.

To determine the properties of tensile bars were prepared by extrusion and subsequent injection molding at 280 ⁰ C melt temperature and 80 ⁰ C mold temperature.

The Charpy notched impact strength was notched at 23 ° C according to ISO 179-2 / I eA (S) determined.

The viscosity number of the polyamides was measured according to ISO 307 on 0.5% strength by weight solutions in 96% by weight sulfuric acid.

The modulus of elasticity was determined on shoulder bars according to ISO 527-2: 1993 at 5 mm / min on dry samples at 23 ⁰ C. The flowability was determined using the spiral test (280 0C melt 80 ⁰ C mold temperature, 2 mm thickness). The determination of the number-weighted average domain size (ie diameter) and the number-weighted average particle diameter was carried out by means of scanning electron microscopy and subsequent image-analytical evaluation.

The properties of various comparative experiments and examples according to the invention and the corresponding compositions of the molding compositions are shown in Tables 1 to 4.

Series 1: Blends of polyamide-6 and polysulfone (PSU) Preparation of masterbatches mb-AC-1 from components A-1 and C-1 and mb-BC-1 from B-1 and C-1: The abovementioned masterbatches with a Composition according to Table 1 were obtained by mixing in a twin-screw extruder (ZSK 25) at 260 ⁰ C in the case of mb-AC-1 and 340 ⁰ C in the case of mb-BC-1. Table 1: Composition of the masterbatches mb-AC and mb-BC (data in g)

Production of blends Blends of components A-1 / B-1 / C-1 according to the compositions (parts by weight) 94/5/1, 89/10/1 and 78/20/2 were prepared as follows: u) mixing the above components in the extruder

s1) mixing mb-AC-1 with components A-1 and B-1 in the extruder

t1) mixing mb-BC-1 with components A-1 and B-1 in the extruder

Comparative Experiments: Mixtures of A-1 and B-1 (without C-1) according to the compositions (parts by weight) 95/5, 90/10 and 80/20 under the conditions mentioned.

All mixtures additionally contained 0.2 part by weight of calcium stearate based on 100 parts by weight of the thermoplastic molding composition.

The compositions of the individual molding compositions are summarized in Table 2.

Table 2: Compositions of the molding compositions

The properties of the resulting thermoplastic molding compositions are summarized in Table 3. Table 3: Properties of the resulting thermoplastic molding compositions

1 shows the distribution of component C-1 (dark spots) in component B-1 (medium gray, spherical domains) or at the interface between component A-1 (light gray) and component B-1 according to example 9.

Run 2: Blends of Polyamide-6 and Polyphenylene Sulfone (PPSU) A blend of polyamide-6 (component A-1), PPSU (component B-2), and component C-1 was prepared by mixing the foregoing ingredients in a "DSM Micro 15cc Twin Screw Compounder "system obtained at 290 ⁰ C, 80 rpm after 5 minutes of extrusion. The compositions and the mean domain size of component B-2 of Example 13 and a comparative example V12 are shown in Table 4.

Table 4: Composition of the molding compositions (% by weight) and number-average domain size of component B-2

Fig. 2 shows the influence of the component C-1 on the domain size distribution in blends of polyamide-6, PPSU and C-1. Example V12 (filled circles) shows, compared to the inventive example 13 (open circles), a distribution of number-weighted average domain sizes, which is shifted to significantly higher values.

Claims

claims

1. Thermoplastic molding compositions comprising the following components: A) at least one thermoplastic polyamide,

B) at least one polyarylene ether sulfone and

2. Thermoplastic molding compositions according to claim 1, comprising from 50 to 99.9 wt .-% of component A), from 0.05 to 40 wt .-% of component B) and from 0.05 to 10 wt .-% of Component C), wherein the sum of the weight percent of components A) to C) based on the total weight of components A), B) and C) 100 wt .-% results.

3. Thermoplastic molding compositions according to claims 1 or 2, containing from 60 to 98.9 wt .-% of component A), from 1 to 36 wt .-% of the component

B) and from 0.1 to 4 wt .-% of component C), wherein the sum of the weight percent of components A) to C) based on the total weight of components A), B) and C) 100 wt .-% results ,

4. Thermoplastic molding compositions according to one or more of claims 1 to 3, wherein component A) forms a first phase and component B) forms a separate second phase.

5. Thermoplastic molding compositions according to one or more of claims 1 to 4, wherein the number-average domain size of the phase which is formed by component B) according to transmission electron microscopy is less than 1 100 nm, in particular from 100 to 1000 nm.

6. Thermoplastic molding compositions according to one or more of claims 1 to 5, wherein component B) polyphenylene sulfone (PPSU), polyethersulfone (PESU) or polysulfone (PSU) is.

7. Thermoplastic molding compositions according to one or more of claims 1 to 6, wherein component C) has a number-weighted mean diameter of the primary particles of 1 to 20 nm.

8. Thermoplastic molding compositions according to one or more of claims 1 to

7, containing as component C) an amorphous oxide and / or hydrated oxide of silicon with a number-weighted average diameter of the primary particles of 1 to 20 nm.

9. Thermoplastic molding compositions according to one or more of claims 1 to

8, wherein component C) has a BET specific surface area to DIN 66131 of 50 to 300 m ² / g, preferably from 100 to 200 m ² / g.

10. Thermoplastic molding compositions according to one or more of claims 1 to

9, wherein component C) is hydrophobically modified by an organosilane, preferably hexamethyldisilazane.

1 1. Thermoplastic molding compositions according to one or more of claims 1 to 10, wherein component C) is produced by flame-pyrolytic silica, the surface of which is hydrophobically modified.

12. A process for the preparation of the thermoplastic molding compositions according to one or more of claims 1 to 1 1 comprising the mixing of the components A), B) and C).

13. The method of claim 12, comprising:

(b) mixing the mixture obtained from (a) with the total amount of

Component B) and optionally the remaining portion of component A).

14. Use of thermoplastic molding compositions according to one or more of claims 1 to 11 for the production of fibers, films and moldings.

15. Fibers, films and moldings, obtainable from the thermoplastic molding compositions according to one or more of claims 1 to 11.