DE102008008098A1 - Polyamide-elastomer-mixture, useful to produce molded parts used in automotive field, comprises a partly crystalline polyamide with specific solution viscosity, elastomer, and polyamide with less solution viscosity than specific viscosity - Google Patents

Abstract

Polyamide-elastomer-mixture comprises: (a) 30-95 wt.% of at least a partly crystalline polyamide with a solution viscosity of >= 1.75 (measured in m-cresol-solution, 0.5 wt.%, 20[deg] C); (b) 5-50 wt.% of at least an elastomer, which is produced by emulsion polymerization and subsequent spray drying of the latex produced by the emulsion polymerization; (c) optionally 0-20 wt.% of one or more polyamides with a solution viscosity of less than 1.75 (measured in m-cresol-solution, 0.5 wt.%, 20[deg] C), as well as 0-100 parts by weight of one or more additives. Independent claims are included for: (1) *a molded part obtained from the polyamide-elastomer-mixture; and (2) use of acrylonitrile-containing elastomers, which are produced by emulsion polymerization and subsequent drying of the latex obtained in the emulsion polymerization, for the production of polyamide-containing compositions.

Description

The The invention relates to polyamide-elastomer blends having improved Hydrolysis resistance. Here, the elastomer lies in Shape of a microparticle. The invention Polyamide-elastomer blends can be processed into molded parts, in the automotive sector, especially as media-carrying lines, Find use.

For the production of media-carrying lines in the automotive sector Materials with medium to high flexibility are required. Flexible polyamides that contain no plasticizers can basically be made in different ways.

One first method is based on a polymerization for the preparation of polyamide elastomers, wherein the flexibilization by the incorporation of polyether or polyester segments is effected.

A the second variant is based on a compounding process in which polyamides by adding ethylene / propylene or ethylene / butylene copolymers be adjusted flexibly.

Both Variants, d. H. the polymerization process as well as the compounding process but have the disadvantage that the products have a reduced chemical resistance and increased swelling in fuels and oils demonstrate. Furthermore, these products have the disadvantage of a bad one Hydrolysis resistance at elevated temperatures.

Another method uses the flexibilizing effect of crosslinked elastomer phases. That's how it describes DE 103 45 043 A1 Thermoplastics compositions and non-energetic radiation crosslinked microparticles having low oil swell. The microparticles used here are produced separately before mixing with the thermoplastics, ie also crosslinked. The crosslinking takes place either directly during the polymerization by selecting suitable monomers or after the polymerization with the aid of peroxides.

outgoing It was the object of the present invention to use polyamide provide based materials that have good flexibility and at the same time good properties regarding the Hydrolysis resistance and oil swelling have.

These Task is by the polyamide elastomer blend with the features of claim 1 and the moldings produced therefrom with the features of claim 23 solved. The other dependent Claims show advantageous developments. In the Claims 31 and 32 are inventive Called uses.

• a) 30 bis 95 Gew.-% mindestens eines teilkristallinen Polyamids mit einer Lösungsviskosität größer oder gleich 1,75 (gemessen in m-Kresol-Lösung, 0,5 Gew.-%, 20°C),
• b) 5 bis 50 Gew.-% eines vernetzten oder teilvernetzten und sprühgetrockneten Elastomers
• c) 0 bis 20 Gew.-% mindestens eines Polyamids mit einer Lösungsviskosität kleiner 1,75 (gemessen in m-Kresol-Lösung, 0,5 Gew.-%, 20°C),
• d) 0 bis 5 Gew.-% mindestens eines Additivs.

According to the invention, a polyamide-elastomer mixture is provided which consists of the following components:

• a) from 30 to 95% by weight of at least one semicrystalline polyamide having a solution viscosity of greater than or equal to 1.75 (measured in m-cresol solution, 0.5% by weight, 20 ° C.),
• b) 5 to 50 wt .-% of a crosslinked or partially crosslinked and spray-dried elastomer
• c) 0 to 20 wt .-% of at least one polyamide having a solution viscosity of less than 1.75 (measured in m-cresol solution, 0.5 wt .-%, 20 ° C),
• d) 0 to 5 wt .-% of at least one additive.

• b1) ≥ 55 Gew.-% mindestens eines radikalisch polymerisierbaren Monomers,
• b2) 5 bis 45 Gew.-% Acrylnitril,
• b3) 0 bis 5 Gew.-% eines Vernetzungsmittels,
• b4) 0 bis 10 Gew.-%, bezogen auf die Summe aus b1) bis b3), mindestens eines Trennmittels,

und hat nach Sprühtrocknung bevorzugt einen mittleren Partikeldurchmesser im Bereich von 2 μm bis 200 μm, insbesondere im Bereich von 5 bis 150 μm.The elastomer b) is preferably prepared from

• b1) ≥55% by weight of at least one free-radically polymerizable monomer,
• b2) 5 to 45% by weight of acrylonitrile,
• b3) 0 to 5% by weight of a crosslinking agent,
• b4) 0 to 10% by weight, based on the sum of b1) to b3), of at least one release agent,

and, after spray-drying, preferably has an average particle diameter in the range from 2 μm to 200 μm, in particular in the range from 5 to 150 μm.

Surprisingly, it was possible to show that the polyamide-elastomer mixtures according to the invention have a high resistance to hydrolysis. This could be evidenced by the fact that tensile bars made of the polyamide-elastomer mixture in a water / glycol (60:40) mixture at 135 ° C. and a storage time of 500 hours have a residual elongation at break of at least 20% (relative to the starting point) worth).

Preferably is the partially crystalline polyamide (a) selected from the Group consisting of the polyamides PA46, PA6, PA66, PA69, PA610, PA612, PA614, PA616, PA618, PA11, PA12, PA1010, PA1012, PA1212, PA MXD6, PA MXD6 / MXDI, PA9T, PA10T, PA12T, PA 6T / 6I, PA 6T / 66, PA 6T / 10T, their copolyamides and polyamide block copolymers with soft segments based on polyesters, polyethers, polysiloxanes or polyolefins, wherein the polyamide content of the polyamide block copolymers at least 40 wt .-% is, as well as their misery.

Especially is the partially crystalline polyamide (a) selected from the Group of the lactam-containing homopolyamides PA6 and PA12 and the copolyamides PA6 / 12, PAX / 66, PAX / 69, PAX / 610, PAX / 612, PAX / 614, PAX / 618, PA6T / X, PA6T / 6I / X, PA6T / 66 / X, wherein the lactam content of the copolyamides at least 20 wt% and X = 6 or 12, and polyamide block copolymers with soft segments based on polyesters, polyethers, polysiloxanes or polyolefins, wherein the lactam content of the polyamide block copolymers at least 40% by weight, and their misery.

According to the invention are preferably 40 to 85 wt .-%, particularly preferably 50 to 78 wt .-% component (a) in the polyamide-elastomer blend.

The At least one polyamide (a) preferably has an amino end group concentration in the range of 20 to 120 μeq / g, preferably from 30 to 100 μeq / g. The carboxy end group concentration of the polyamide (a) is preferably not more than 30 μeq / g, more preferably maximum 20 μeq / g.

The According to the invention containing polyamide (a) has preferably a solution viscosity (measured in m-cresol solution, 0.5% by weight 20 ° C) in the range from 1.75 to 2.4, especially from 1.8 to 2.3.

Preferably For example, the crosslinked or partially crosslinked elastomer is prepared by emulsion polymerization. As radically polymerizable monomers (b1) are preferred here Monomers used from the group consisting of butadiene, styrene, Isoprene, esters of acrylic and methacrylic acid, tetrafluoroethylene, Vinylidene fluoride, hexafluoropropene, 2-chlorobutadiene, 2,3-dichlorobutadiene and double bond-containing carboxylic acids, in particular Acrylic acid, methacrylic acid, maleic acid, Itaconic acid, double bond-containing hydroxy compounds, especially hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxybutyl methacrylate, aminotunctionalized (meth) acrylates, acrolein, N-vinyl-2-pyrollidone, N-allyl urea and N-allyl thiourea, secondary Amino (meth) acrylic acid esters, in particular 2-tert-butylaminoethyl methacrylate and 2-tert-butylaminoethylmethacrylamide and mixtures thereof.

In a first variant, the at least one crosslinking agent (b3) is a mono- or polyunsaturated, free-radically polymerizable monomer, in particular selected from the group consisting of compounds having preferably 2 to 4 copolymerizable C =C double bonds, in particular diisopropenylbenzene, divinylbenzene, divinyl ether, Divinyl sulfone, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, 1,2-polybutadiene, N, N'-m-phenylene maleimide, 2,4-toluylene bis (maleimide), triallyl trimellitate and acrylates and methacrylates of polyhydric C ₂ - to C ₁₀ -alcohols, in particular Ethylene glycol, 1,2-propanediol, butanediol, hexanediol, polyethylene glycol having 2 to 20, in particular 2 to 8, oxyethylene units, neopentyl glycol, bisphenol A, glycerol, trimethylolpropane, pentaerythritol, sorbitol with unsaturated polyesters of aliphatic diols and polyols, and maleic acid, Fumaric acid, itaconic acid and mixtures thereof.

A another variant of the invention provides that the at least one crosslinking agent (b3) is selected from the group consisting of divinylbenzene, trimethylolpropane trimethacrylate, Trimethylolpropane triacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate and mixtures thereof.

To a third variant of the invention is the at least one crosslinking agent (b3) selected from the Group consisting of organic peroxides, in particular dicumyl peroxide, t-butyl cumyl peroxide, bis (t-butylperoxy-isopropyl) benzene, di-t-butyl peroxide, 2,5-ditmethylhexane-2,5-dihydroperoxide, 2,5-dimethylhexine-3,2,5-dihydroperoxide, Dibenzoyl peroxide, bis (2,4-dichlorobenzoyl) peroxide, t-butyl perbenzoate and organic azo compounds, especially azo-bis-isobutyronitrile and azo-bis-cyclohexanenitrile and di- and polymercapto compounds, especially dimercaptoethane, 1,6-dimercaptohexane, 1,3,5-trimercaptotriazine and mercapto-terminated polysulfide rubbers, especially mercapto-terminated ones Reaction products of bis-chloroethylformal with sodium polysulfide.

The crosslinking to rubber microparticles during the polymerization can also without addition egg nes separate crosslinking agent by continuing the polymerization to high conversions, in particular of conversions ≥ 80%, based on the total amount of the monomer mixture used, or carried out in the monomer feed by polymerization with high internal conversions. Another possibility is to carry out the polymerization in the absence of regulators and / or at elevated temperature, in particular at temperatures ≥ 20 ° C. Under these conditions, the double bonds remaining with the concomitant use of dienes as a monomer in the polymer (b) are also accessible to crosslinking reactions.

It Alternatively, a radiation-induced crosslinking of the rubber polymer particles may also be used be performed.

In order for the polyamide-elastomer mixtures to have the properties according to the invention, the work-up of the microparticles must take place by spray-drying from the latex. As a result, spherical or nearly spherical microparticles are obtained whose mean diameter does not exceed 200 μm, preferably 100 μm ( 1 ). The elastomer of the invention, which is mixed in this form with the polyamide (a) and optionally additionally with the polyamide (c) and additives, thus consists of almost spherical particles having a diameter in the range of 2 to 200 .mu.m, preferably in the range of 5 to 150 microns and in particular in the range of 5 to 100 microns have. Other methods of processing the microparticles, in particular by evaporation, coagulation, co-coagulation with another latex polymer and by freeze coagulation result in irregularly shaped microparticles having a much larger average diameter ( 2 and 3 ).

at the workup by spray drying can additionally also commercially available flow aids or release agents be added.

Preferably, the release agent has neither a pronounced acidic or basic character. Separating agents which are either weak to very slightly acidic or which are weak to very weakly basic, ie which have a pk _s value> 4 or a pk _b value> 4, are therefore particularly preferred. In this case, the at least one release agent (b4) is preferably selected from the group consisting of silicas, in particular having a specific surface area of more than 5 m ² / g, calcium carbonate, magnesium carbonate, silicates, fatty acid salts, in particular alkali and alkaline earth metal salts, such as salts of Fatty acids having more than 10 carbon atoms, in particular calcium and magnesium salts of such fatty acids, such as calcium stearate, magnesium stearate, aluminum zinc stearate, tallow, mica, cellulose derivatives, starch, polyalkylene oxides, in particular polyethylene oxides, polyethylene glycols or polyethylene glycol ethers, polyvinylpyrrolidone, microparticles with high glass transition temperature with, for example, more as 80 ° C, calcium phosphate, alumina, barium sulfate, polymers such as polyvinyl alcohol, polyesters and polyolefins, fluorohydrocarbons. However, the elastomer (b) can also be converted without the addition of a separate release agent into the desired advantageous use form (spray-dried microparticle) and thus incorporated into the polyamide matrix.

In In a preferred embodiment, the concentration is of acrylonitrile (b2) in the crosslinked or partially crosslinked elastomer in the range of 10 to 40 wt .-%, particularly preferably in the range from 28 to 35% by weight.

According to the invention preferably 5 to 40 wt .-%, particularly preferably 10 to 30 wt .-% of the crosslinked or partially crosslinked elastomer (b) in the polyamide-elastomer blend contain.

When Polyamide (c) may be both partially crystalline polyamides as also contain amorphous or microcrystalline polyamides.

In a preferred embodiment contains the Polyamide molding compound in addition to the component (a) also up to 20 wt .-%, in particular up to 15% by weight, of at least one amorphous or microcrystalline polyamide (Component c) based on aliphatic, cycloaliphatic or aromatic diamines, dicarboxylic acids and / or aminocarboxylic acids, preferably having 6 to 36 carbon atoms, and mixtures of such Homopolyamides and / or copolyamides. In this embodiment the molding compositions contain preferably 2 to 20 wt .-%, in particular From 3 to 15% by weight of component (c).

The following systems are preferred for the amorphous or microcrystalline polyamides (component c) and / or copolyamides used according to the invention:
Polyamide based on aliphatic, cycloaliphatic or aromatic diamines, dicarboxylic acids, lactams and / or aminocarboxylic acids, preferably having 6 to 36 carbon atoms, or a mixture thereof Homopolyamides and / or copolyamides. The cycloaliphatic diamines are preferably MACM, IPD and / or PACM, with or without additional substituents. The aliphatic dicarboxylic acid is preferably an aliphatic dicarboxylic acid having 2 to 36, preferably 8 to 20, linear or branched carbon atoms, more preferably 10, 12, 13, 14, 16 or 18 carbon atoms.

there MACM stands for the ISO designation bis- (4-amino-3-methyl-cyclohexyl) -methane, which is under the trade name 3,3'-dimethyl-4-4'-diaminodicyclohexylmethane as Laromin C260 type (CAS No. 6864-37-5), preferably with melting point between -10 ° C and 0 ° C, commercially available is. A number, such as. B. in MACM12 stands for a aliphatic linear C12 dicarboxylic acid (DDS, dodecanedioic acid), with which the diamine MACM is polycondensed.

TPS stands for isophthalic acid and PACM stands for the ISO designation Bis- (4-amino-cyclohexyl) -methane, which under the trade name 4,4'-diaminodicyclohexylmethane as dicyanone type (CAS No. 1761-71-3), preferably with melting point between 30 ° C. and 45 ° C, is commercially available.

One Homopolyamide selected from the group MACM12, MACM13, MACM14, MACM16, MACM18, PACM12, PACM13, PACM14, PACM16, PACM18 and / or a copolyamide selected from the group MACM12 / PACM12, MACM13 / PACM13, MACM14 / PACM14, MACM16 / PACM16, MACM18 / PACM18. Also possible are mixtures of such polyamides.

polyamides based on aromatic dicarboxylic acids with 8 to 18, preferably 8 to 14 carbon atoms or a mixture of such Homopolyamides and / or copolyamides, preferably based on PXDA and / or MXDA, particularly preferably based on lactams and / or aminocarboxylic acids, being preferred among the aromatic dicarboxylic acids TPS, naphthalenedicarboxylic acid and / or IPS.

polyamides selected from the group: MACM9-18, PACM9-18, MACMI / 12, MACMI / MACMT, MACMI / MACMT / 12, 6I6T / MACMI / MACMT / 12, 3-6T, 6I6T, TMDT, 6I / MACMI / MACMT, 6I / PACMI / PACMT, 6I / 6T / MACMI, MACMI / MACM36, 6I, 12 / PACMI or 12 / MACMT, 6 / PACMT, 6 / 6I, 6 / IPDT or mixtures thereof, wherein 50 mol% of the IPS may be replaced by TPS.

The amorphous or microcrystalline polyamides (component C) have a glass transition temperature of greater 110 ° C, preferably greater than 130 ° C. and in particular greater than 150 ° C. The Relative solution viscosity is in the range of From 1.3 to less than 1.75 (measured in m-cresol, 0.5% by weight) is preferred in the range between 1.4 and 1.70 and especially in the range between 1.5 and 1.70.

The microcrystalline polyamides have a heat of fusion in the range of 4 to 40 J / g, especially in the range of 4 to 25 Y / g (determined by DSC), the amorphous polyamides have less heat of fusion as 4 y / g. Preference is given to microcrystalline polyamides based diamines MACM and PACM. Examples of such Polyamides are the systems PA MACM9-18 / PACM9-18, in particular PA MACM12 / PACM12 with a higher PACM content 55 mol% (based on the total amount of diamine) used according to the invention becomes.

According to the invention also provided a molding made of a polyamide elastomer blend, as previously described.

such Moldings preferably have an elongation at break of at least 20%, in particular of at least 30%, relative to the initial value and measured on tensile bars in a water / glycol (60:40) mixture at 135 ° C with a storage time of 500 h.

in the dry state, the moldings preferably have an elongation at break of at least 150%.

As well show the moldings high flexibility, resulting in a preferred tensile modulus of elasticity on ISO test bars in the dry state in the range of 300 to 1500 MPa shows.

Preferably, the molded article has a notched impact strength of -30 ° C, measured on ISO test bars, of at least 10 kJ / m ² .

The Molding preferably has an oil swell in IRM 903 after 4d at a temperature of 125 ° C of a maximum of 3%.

MVR (melt volume rate) at 275 ° C and a load of 21.6 kg is in the range of 50 to 200 cm ^3/10 min.

use finds the polyamide-elastomer mixture according to the invention in particular for the production of molded parts or smooth, corrugated or partially corrugated mono- or multi-layer pipes that are filled with water, oil, glycol, methanol, ethanol or fuel-containing liquid Media in contact. These include in particular vents for crankshaft housings, mono- and multilayer cables in the under- and overpressure area as well as with water and / or Glycol in contact with coolant lines or oil-bearing or in contact with oil standing lines in the automotive sector.

Based the following examples and figures, the inventive Subject to be explained in more detail, without this restrict to the specific embodiments shown here to want.

example 1

Table 1 below shows the compositions of a mixture according to the invention versus two mixtures known from the prior art (referred to as Comparative Examples 1 and 2). Table 1 Comparative Example 1 Comparative Example 2 example 1 Polyamide type A 70.8 70.8 70.8 Polyamide type B 8th 8th 8th Microparticles Type A (not inventive) 20 Microparticles Type B (not inventive) 20 Microparticles Type C (inventive) 20 Black MB based on PA12 1.2 1.2 1.2

• Polyamid Typ A: Polyamid 12 mit η_rel = 2,11, NH2: 52 μeq/g, COOH: 15 μeq/g
• Polyamid Typ B: Polyamid 12 mit η_rel = 1,65, NH2: 105 μeq/g, COOH: 10 μeq/g
• Mikropartikel Typ A (nicht erfinderisch): Copolymer aus Butadien: 68,8%, Acrylnitril: 26,7%, HEMA: 1,5% TMPTMA: 3,0%, aufgearbeitet durch Koagulation, Trocknen und anschließendem Vermahlen (1)
• Mikropartikel Typ B (nicht erfinderisch): Copolymer aus Butadien: 65,5%, Acrylnitril: 34,5%, HEMA: 0%, TMPTMA: 0%, aufgearbeitet durch Koagulation, Trocknen und anschließendem Vermahlen (2)
• Mikropartikel Typ C (erfinderisch): Copolymer aus Butadien: 65,5%, Acrylnitril: 34,5%, HEMA: 0%, TMPTMA: 0%, aufgearbeitet durch Sprühtrocknen (3)

The following starting materials were used for the preparation of the mixtures:

• Polyamide type A: polyamide 12 with η _rel = 2.11, NH2: 52 μeq / g, COOH: 15 μeq / g
• Polyamide type B: polyamide 12 with η _rel = 1.65, NH 2: 105 μeq / g, COOH: 10 μeq / g
• Microparticles Type A (non-inventive): copolymer of butadiene: 68.8%, acrylonitrile: 26.7%, HEMA: 1.5% TMPTMA: 3.0%, worked up by coagulation, drying and subsequent milling ( 1 )
• Microparticles Type B (non-inventive): copolymer of butadiene: 65.5%, acrylonitrile: 34.5%, HEMA: 0%, TMPTMA: 0%, worked up by coagulation, drying and subsequent milling ( 2 )
• Microparticles Type C (inventive): copolymer of butadiene: 65.5%, acrylonitrile: 34.5%, HEMA: 0%, TMPTMA: 0%, worked up by spray-drying ( 3 )

polyamide (a) and (c) as well as microparticles (b) were put together in the collection a twin-screw extruder (ZSK 30, Coperion) and metered at Cylinder temperatures from 200 to 280 ° C, one screw speed of 180 rpm and a throughput of 12 kg / h compounded. The Strands emerging at the nozzle were placed in a water bath cooled and subsequently granulated. After drying at 80 ° C, the molding compositions were molded parts and specimens sprayed.

• MVR: (Melt volume rate) bei 275°C nach ISO 1133
• SZ: Schlagzähigkeit und Kerbschlagzähigkeit nach ISO 179/1 eU (Charpy)

The molding compositions were tested as follows:

• MVR: (Melt volume rate) at 275 ° C ISO 1133
• SZ: impact resistance and notched impact strength after ISO 179/1 eU (Charpy)

Tensile modulus, tensile strength and elongation at break were reduced ISO 527 to ISO tension rods, standard ISO / CD 3167, type A1 , 170 × 20/10 × 4 mm at a temperature of 23 ° C determined. The mechanical values were determined in the dry state.

• n. b.: nicht bestimmt
• n. m.: nicht messbar
• o. B.: ohne Bruch

The relative viscosity (η _rel ) was measured at 20 ° C on a 0.5% m-cresol solution after DIN EN ISO standard 307 certainly. See example 1 See example 2 P 12 (Type A) Example 1 MVR (275 ° C / 5 kg) cm ^3/10 min 20 nm 27 nm MVR (275 ° C / 21.6 kg) cm ^3/10 min 205 135 ? 165 Modulus MPa 1110 1130 1600 1150 tensile strenght MPa 39 41 45 45 elongation at break % 210 240 230 250 Impact strength Charpy new, 23 ° C kJ / m ² if. if. if. if. Impact strength Carpy new, -30 ° C kJ / m ² if. if. if. if. Notched impact strength Charpy new, 23 ° C kJ / m ² 90 80 8th 100 Notched impact strength Charpy new, -30 ° C kJ / m ² 12 11 6 15 oil swell Wt .-% 3.6 2.1 1.1 1.8 Half-life hydrolysis test) H 115 210 nb 350

• nb: not determined
• nm: not measurable
• o. B .: without breakage

In addition, the hydrolysis resistance was determined in comparison to the mixtures of the comparative examples. For this purpose, it was stored in a water-glycol mixture with a mixing ratio of 60 to 40 at 135 ° C and a defined storage period. As Gykol the commercially available coolant additive Havoline XLC was used. For storage, tension bars with a thickness of 4 mm were used. In 4 It can be seen that the mixture according to the invention has a significantly higher residual elongation at break (relative to the starting value) than the mixtures known from the prior art. By using the spray-dried microparticle according to the invention, the half-life in the hydrolysis test could be doubled on average.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - DE 10345043 A1 [0006]

Cited non-patent literature

• - ISO 1133 [0050]
• - ISO 179/1 eU [0050]
• - ISO 527 [0051]
• - ISO / CD 3167, Type A1 [0051]
• - DIN EN ISO standard 307 [0052]

Claims (32)

Containing polyamide elastomer blend a) 30 to 95 wt .-% of at least one partially crystalline polyamide with a solution viscosity greater or equal to 1.75 (measured in m-cresol solution, 0.5% by weight, 20 ° C), b) 5 to 50 wt .-% of a crosslinked or partially crosslinked Elastomers produced by spray-drying, in the form of Microparticles, with an average diameter of 2 to 200 μm, c) 0 to 20 wt .-% of at least one polyamide having a solution viscosity less than 1.75 (measured in m-cresol solution, 0.5% by weight, 20 ° C), d) 0 to 5% by weight of at least one additive, in which the percentages by weight of components (a) to (d) on the total amount refer to the polyamide elastomer blend. Polyamide-elastomer mixture according to claim 1, thereby characterized in that the elastomer b) is made of b1)) ≥ 55 Wt .-% of at least one radically polymerizable monomer, b2) From 5 to 45% by weight of acrylonitrile, b3) 0 to 5% by weight of a crosslinking agent, b4) 0 to 10 wt .-% based on the sum of b1) to b3), at least a release agent, where the wt .-% - information of the components (b1) to (b4) refer to the total amount of component (b). A polyamide-elastomer blend according to claim 1 or 2, characterized in that the at least one semi-crystalline Polyamide (a) is selected from the group consisting of the polyamides PA46, PA6, PA66, PA69, PA610, PA612, PA614, PA616, PA618, PA11, PA12, PA1010, PA1012, PA1212, PA MXD6, PA MXD6 / MXDI, PA9T, PA10T, PA12T, PA 6T / 6I, PA 6T / 66, PA 6T / 10T, their copolyamides and their blends and polyamide block copolymers with soft segments based on polyesters, polyesters, polysiloxanes or polyolefins, wherein the polyamide content of the polyamide block copolymers at least 40 wt .-% is, and their misery. Polyamide-elastomer mixture according to one of the preceding Claims, characterized in that the at least a polyamide (a) has an amino end group concentration in the range of 20 to 120 μeq / g, especially from 30 to 100 μeq / g having. Polyamide-elastomer mixture according to one of the preceding Claims, characterized in that the at least a polyamide (a) a Carboxylendgruppenkon concentration of maximum 30 μeq / g, in particular of not more than 20 μeq / g. Polyamide-elastomer mixture according to one of the preceding Claims, characterized in that the at least a partially crystalline polyamide (a) a solution viscosity (measured in m-cresol solution, 0.5 wt .-% 20 ° C) in the range of 1.75 to 2.4, in particular from 1.8 to 2.3. A polyamide-elastomer blend according to any one of claims 2 to 6, characterized in that the at least one free radical polymerizable monomer (b1) is selected from the group consisting of butadiene, styrene, isoprene, esters of acrylic and methacrylic acid, Tetrafluoroethylene, vinylidene fluoride, hexafluoropropene, 2-chlorobutadiene, 2,3-dichlorobutadiene and double bond-containing carboxylic acids, especially acrylic acid, methacrylic acid, maleic acid, Itaconic acid, double bond-containing hydroxy compounds, especially hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxybutyl methacrylate, amine-functionalized (meth) acrylates, acrolein, N-vinyl-2-pyrrolidone, N-allyl urea and N-allyl thiourea, secondary Amino (meth) acrylic esters, in particular 2-tert-butylaminoethyl methacrylate and 2-tert-butylaminoethylmethacrylamide and mixtures thereof. Polyamide-elastomer mixture according to one of claims 2 to 7, characterized in that the at least one crosslinking agent (b3) is a di- or polyunsaturated, radically polymerizable monomer, in particular selected from the group consisting of compounds having preferably 2 to 4 copolymerisable C = C double bonds, in particular diisopropenylbenzene, divinylbenzene, divinyl ether, divinylsulfone, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, 1,2-polybutadiene, N, N'-m-phenylene maleimide, 2,4-toluylene bis (maleimide), triallyl trimellitate and also acrylates and methacrylates of polyvalent C ₂ - to C ₁₀ -alcohols, in particular ethylene glycol, 1,2-propanediol, butanediol, hexanediol, polyethylene glycol having 2 to 20, in particular 2 to 8, oxyethylene units, neopentyl glycol, bisphenol A, glycerol, trimethylolpropane, Pentaerythritol, sorbitol with unsaturated polyesters of aliphatic di- and polyols, and maleic acid, fumaric acid, itaconic acid and mixtures thereof. Polyamide elastomer mixture after the preceding Claim, characterized in that the at least one crosslinking agent (b3) is selected from the group consisting of divinylbenzene, Trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, Ethylene glycol diacrylate and mixtures thereof. A polyamide-elastomer blend according to any one of claims 2 to 9, characterized in that the at least one crosslinking agent (b3) is selected from the group consisting of organic Peroxides, in particular dicumyl peroxide, t-butylcumyl peroxide, bis (t-butylperoxy-isopropyl) benzene, Di-t-butyl peroxide, 2,5-ditmethylhexane-2,5-dihydro peroxide, 2,5-dimethylhexine-3,2,5-dihydroperoxide, Dibenzoyl peroxide, bis (2,4-dichlorobenzoyl) peroxide, t-butyl perbenzoate and organic azo compounds, especially azo-bis-isobutyronitrile and azo-bis-cyclohexanenitrile and di- and polymercapto compounds, especially dimercaptoethane, 1,6-dimercaptohexane, 1,3,5-trimercaptotriazine and mercapto-terminated polysulfide rubbers, especially mercapto-terminated ones Reaction products of bis-chloroethylformal with sodium polysulfide. Polyamide-elastomer mixture according to one of the preceding Claims 2 to 7, characterized in that the crosslinked or partially crosslinked elastomer b) without the addition of a separate crosslinking agent Polymerization at temperatures ≥ 20 ° C and / or Polymerization at conversions ≥ 80%, based on the Total amount of the monomer mixture used, is obtained. Polyamide-elastomer mixture according to one of claims 2 to 11, characterized in that the at least one release agent (b4) has a pk _s value ≥ 4 or a pk _b value ≥ 4. Polyamide-elastomer mixture according to one of claims 2 to 12, characterized in that the at least one release agent (b4) is selected from the group consisting of silicic acids, in particular having a specific surface area of more than 5 m ² / g, calcium carbonate, magnesium carbonate , Silicates, fatty acid salts, in particular alkali and alkaline earth metal salts, such as salts of fatty acids having more than 10 carbon atoms, in particular calcium and magnesium salts of such fatty acids, such as calcium stearate, magnesium stearate, aluminum zinc stearate, tallow, mica, cellulose derivatives, starch, polyalkylene oxides, especially polyethylene oxides , Polyethylene glycols or polyethylene glycol ethers, polyvinylpyrrolidone, high glass transition temperature microparticles having, for example, greater than 80 ° C, calcium phosphate, aluminum oxide, barium sulfate, polymers such as polyvinyl alcohol, polyesters and polyolefins, fluorohydrocarbons. Polyamide elastomer mixture after the preceding Claim, characterized in that the concentration of acrylonitrile in the crosslinked or partially crosslinked elastomer in the range of 10 to 40 wt .-%, in particular in the range of 28 to 35 wt .-% is. Polyamide-elastomer mixture according to one of the preceding Claims, characterized in that 5 to 40 wt .-%, in particular 10 to 30 wt .-% of the crosslinked or partially crosslinked Elastomers (b) are included. Polyamide-elastomer mixture according to one of the preceding Claims, characterized in that the at least a polyamide (c) a solution viscosity (measured in m-cresol solution, 0.5% by weight, 20 ° C) in the range from 1.4 to less than 1.75, in particular from 1.5 to 1.7. Polyamide-elastomer mixture according to one of the preceding Claims, characterized in that the at least a polyamide (c) is a lactam-free polyamide. Polyamide-elastomer mixture according to one of the preceding Claims, characterized in that the at least a polyamide (c) is an amorphous or microcrystalline polyamide. Polyamide-elastomer mixture according to one of the preceding Claims, characterized in that the at least a polyamide (c) is selected from the group of polyamides containing aliphatic, cycloaliphatic or aromatic diamines, Dicarboxylic acids and / or aminocarboxylic acids, in particular with 6 to 36 carbon atoms and mixtures of such homopolyamides and / or copolyamides. Polyamide-elastomer mixture according to one of the preceding claims, characterized the at least one polyamide (c) is selected from the group consisting of MACM12, MACM13, MACM14, MACM16, MACM18, PACM12, PACM13, PACM14, PACM16, PACM18 of the copolyamides MACM12 / PACM12, MACM13 / PACM13, MACM14 / PACM14, MACM16 / PACM16, MACM18 / PACM18 and mixtures of such polyamides. Polyamide-elastomer mixture according to one of the preceding Claims, characterized in that the at least a polyamide (c) has a glass transition temperature of greater or equal to 110 C, preferably greater than or equal to 130 ° C, and more preferably greater or equal to 150 C has. Polyamide-elastomer mixture according to any one of the preceding claims, characterized in that the polyamide elastomer blend has a MVR (melt volume rate) at 275 ° C and a load of 21.6 kg in the range of 50 to 200 cm ^3/10 min comprising , Polyamide-elastomer mixture according to one of the preceding Claims, characterized in that one of the polyamide-elastomer mixture available molding a residual elongation at break of at least 20% of the initial value after storage of tension rods in a water / glycol (60:40) mixture at 135 ° C and a Storage period of 500 h has. Molding available from a polyamide elastomer blend according to one of the preceding claims. Molding according to claim 23, characterized that the molded part has a residual elongation at break of at least 20% of the initial value after storage on battens in a Water / glycol (60:40) mixture at 135 ° C and storage time of 500 h. Molded part according to one of claims 23 or 24, characterized in that the molded part has an elongation at break in the dry state of at least 150%. Molded part according to one of claims 23 to 25, characterized in that the molded part to a train-E module ISO test bars in the dry state in the area from 300 to 1500 MPa. Molding according to one of claims 23 to 26, characterized in that the molded part has a notched impact strength at -30 ° C, measured on ISO test bars, of at least 10 kJ / m ² . Molded part according to one of claims 23 to 27, characterized in that the molded part an oil swell in IRM 903 after 4d at a temperature of 125 ° C of maximum 3 has. Molded part according to one of claims 23 to 29 in the form of a crankcase or in the form of smooth, corrugated or partially corrugated mono or multilayer cables, z. B. coolant lines. Use of the polyamide elastomer mixture according to one of claims 1 to 22 for the manufacture of water, oil, glycol, methanol, ethanol or fuel-containing liquid Media in contact molding in the automotive sector. Use according to the preceding claim, for Production of vents for crankcase, Mono- and multilayer lines in the under- and overpressure area, Coolant lines and oil-carrying or lines in contact with oil.