EP3652253A1

EP3652253A1 - Thermally stabilized compositions

Info

Publication number: EP3652253A1
Application number: EP18736957.4A
Authority: EP
Inventors: Detlev Joachimi; Thomas Linder
Original assignee: Lanxess Deutschland GmbH
Current assignee: Lanxess Deutschland GmbH
Priority date: 2017-07-13
Filing date: 2018-07-12
Publication date: 2020-05-20
Also published as: US20210079218A1; KR20200030529A; DE202018006238U1; WO2019012061A1; JP2020526648A; CN110832030A

Abstract

The invention relates to thermally stabilized polyamide 66 based compositions which contain reinforcing materials and which are based on at least one partially aromatic polyamide, at least one copper halide and at least one polyhydric alcohol, thus produced moulding compounds and also thus produced injection moulded, blow moulded or extruded products.

Description

Thermostabilized compositions

The present invention relates to reinforcing materials containing thermally stabilized polyamide 66 based compositions additionally comprising at least a partially aromatic polyamide, at least one copper halide and at least one polyhydric alcohol, molding compositions to be prepared therefrom, and injection molded, blown or extruded products to be produced therefrom.

Polyamides, in particular partially crystalline polyamides, are frequently used as materials for moldings which are exposed during their service life to elevated temperatures over an extended period of time. For a variety of applications, it is necessary that the materials are sufficiently stable against the resulting thermal oxidative damage, especially for applications in the engine compartment of motor vehicles. For "thermo-oxidative damage" see: P. Gijsman, e-Polymers, 2008, no. 065.

In particular, glass fiber reinforced polyamide 66 compounds have been established in the automotive industry for the production of high thermal stress products, where "high temperature" means temperatures in the range of 180 ° C to 240 ° C, temperatures that may occur in the engine compartment of motor vehicles with internal combustion engines today, In particular, when the products are turbocharged air ducts, intake pipes, valve covers, intercoolers or engine covers, because of the increase in the performance of automotive engines in recent years, there are ever-higher demands on the manufacturer for the materials to be used for the production of these products.

Polyamides generally show a deterioration in their mechanical properties when exposed to elevated temperatures for extended periods of time. This effect is based primarily on the oxidative damage of the polyamide at elevated temperatures (thermo-oxidative damage). A longer period in the sense of the present invention means longer than 100 hours, elevated temperatures in the sense of the present invention means higher than 80 ° C.

The stability of thermoplastic molding compositions or products made therefrom against thermo-oxidative damage is usually by comparing mechanical Properties, in particular the impact strength according to ISO180, the tensile stress and elongation at break measured in the tensile test according to ISO 527, and the modulus of elasticity at a defined temperature over a defined period of time. The thermo-oxidative degradation of polyamide-based molding compounds or products at elevated temperatures over a longer period can generally not be prevented with stabilizer systems, but only delayed. The requirements of polyamide-based molding compositions or of products to be produced therefrom in high-temperature applications are not sufficiently satisfied with the thermostabilizing systems known from the prior art. In particular, components of polyamide-based molding compositions, which also have at least one weld by vibration, Heizelement-, infrared, hot gas, ultrasonic, rotary or laser welding process, show reduced stability, especially in the weld after aging at temperatures in the above mentioned area.

State of the art

The thermal stabilization of poly (/ V, / V-hexamethylene adipamide) or poly (hexamethylene adipamide), also referred to below as polyamide 66 or PA 66 (CAS No. 32131-17-2), with the aid of a polyhydric alcohol and with a copper compound is known, for example, from WO 2010/014801 A1. WO 2010/014791 A1 in turn describes the thermal stabilization of PA66 with ethylene vinyl alcohol copolymer and copper iodide / potassium iodide.

Starting from the prior art, the object of the present invention was to improve the stabilization of reinforcing materials and copper salt-containing polyamide 66 based compositions and products to be produced from thermooxidative damage after 3000 hours hot air aging at temperatures of 220 ° C so that the impact strength on the non-notched test specimen does not fall to a value below 50% of the value of an injection-fresh test specimen.

invention

The solution to the problem and subject matter of the present invention are compositions containing

A) Polyamide 66

B) at least one partially aromatic polyamide,

C) at least one copper halide, D) at least one polyhydric alcohol, and

E) at least one reinforcing material,

with the proviso that A) and B) do not form a copolymer. For clarification, it should be noted that the scope of the invention encompasses all the general and preferred definitions and parameters listed below in any combination. Cited standards apply in the version valid at the filing date of the present application. definitions

The terms "over," "at," or "about," as used in the present specification, are intended to mean that the amount or value thereafter may be the concrete value or an approximately equal value The phrase is intended to convey that similar values are equivalent to those of the present invention Results or effects and are included in the invention.

The used in the present application marking the polyamides corresponds to international standard, wherein the first digit (s) indicate the C atomic number of Ausgangsdiamins and the last digit (s) the C atomic number of the dicarboxylic acid. If only one number is given, as in the case of PA 6, this means that an α, ω-aminocarboxylic acid or the lactam derived therefrom, in the case of PA 6, ie ε-caprolactam, has been used as starting material; Incidentally, reference is made to DIN EN ISO 1874-1: 201 1 -03. Impact resistance describes the ability of a material to absorb impact energy and impact energy. The impact strength is calculated as the ratio of impact energy and specimen cross section (unit of measurement kJ / m ² ). Through various types of (notched) impact test (Charpy, Izod) the impact strength can be determined. In contrast to the notched impact strength of the impact strength of the specimens is not notched. In the context of the present invention, tests were carried out with the test specimen standing upright, the pendulum striking the free end of the test specimen and determining the impact resistance on the non-notched or unnotched specimen according to IZOD according to ISO 180 1 U. Compositions according to the invention, which are collectively referred to as molding compounds in plastics technology, are preferably obtained as granules, in strand form or as powder in the processing of the components A) to E) to be used according to the invention. The preparation of compositions according to the invention takes place by mixing the components to be used according to the invention in at least one mixing unit, preferably in a compounder, more preferably a co-rotating twin-screw extruder, wherein compositions, also referred to as preparations, within the meaning of the invention, purely physical mixtures that arise during mixing of the components concerned include , The mixing process of components A) to E), and optionally other components for the preparation of compositions according to the invention in the form of powders, granules or in strand form, is often referred to in plastics technology as compounding. As a result, molding compositions are obtained as intermediates, based on the compositions of the invention. These molding compositions - also referred to as thermoplastic molding compositions - can either consist exclusively of the components A), B), C), D) and E), or in addition to the components A), B), C), D) and E ) contain at least one further component.

With regard to the d10, d50 and d90 values in this application, their determination and their meaning, reference is made to Chemie Ingenieur Technik (72) pp. 273-276, 3/2000, Wiley-VCH Verlags GmbH, Weinheim, 2000, according to which the d10 Value is the particle size below which 10% of the particle quantity lies, the d50 value is the particle size below which 50% of the particle quantity lies (median value) and the d90 value is that particle size below which 90% of the particle quantity lies.

Preferred embodiments of the invention

However, the preferred subject of the present invention are also combustion engine components, in particular motor vehicle combustion engine components based on compositions containing

A) Polyamide 66

B) at least one partially aromatic polyamide,

C) at least one copper halide,

D) at least one polyhydric alcohol, and

E) at least one reinforcing material,

with the proviso that A) and B) do not form a copolymer.

The present invention preferably relates to compositions and molding compositions and products based on these compositions, preferably engine components, in particular motor vehicle engine components, wherein for 100 parts by mass of component A) from 6.0 to 50.0 parts by mass of component B), 0.01 to 0.30 Mass fractions of component C), 1 to 5 parts by mass of component D) and 17.5 to 185 parts by mass of component E) are used.

Particular preference is given to using 100 parts by mass of component A) 20 to 25 parts by mass of component B), 0.01 to 0.1 parts by mass of component C), 4 to 5 parts by mass of component D) and 70 to 80 parts by mass of component E) ,

In a preferred embodiment, the compositions, as well as the molding compositions and products to be prepared therefrom, preferably combustion engine components, in particular motor vehicle engine components, in addition to the components A) to E) F) at least one alkali metal halide, preferably in amounts ranging from 0.05 to 0, 60 parts by mass per 100 parts by mass of component A). In a preferred embodiment, component C) and F) are always used together.

In a preferred embodiment, the compositions, as well as the molding compositions and products to be produced therefrom, preferably internal combustion engine components, in particular automotive combustion engine components, in addition to the components A) to F), or G) at least one mold release agent, preferably in Amounts in the range of 0.05 to 0.50 parts by mass per 100 parts by mass of component A).

In a preferred embodiment, the compositions, as well as the molding compositions and products to be produced therefrom, preferably combustion engine components, in particular motor vehicle engine components, in addition to the components A) to G) or in place of the components F) and / or G) H) at least one of the components B) to G) various other additive, preferably in amounts ranging from 0.05 to 3.00 parts by mass per 100 parts by mass of component A).

Component A)

Polyamide 66 having a relative solution viscosity in m-cresol in the range from 2.0 to 4.0 is preferably used as component A). Polyamide 66 with a relative solution viscosity in m-cresol in the range from 2.6 to 3.2 is particularly preferably used. In methods for determining the relative solution viscosity, the transit times of a dissolved polymer are measured by an Ubbelohde viscometer in order subsequently to determine the viscosity difference between the polymer solution and its solvent, here Cresol (1% solution) to determine. Applicable standards are DIN 51562; DIN ISO 1628 or equivalent standards. The viscosity measurement in the context of the present invention is carried out in sulfuric acid using an Ubbelohde viscometer according to DIN 51562 part 1, with the capillary II at 25 ° C. (± 0.02 ° C.).

The polyamide 66 to be used according to the invention as component A) preferably has 20 to 80 milliequivalent of amino end groups / 1 kg PA and 20 to 80 milliequivalent acid end groups / 1 kg PA, more preferably 35 to 60 milliequivalent amino end groups / 1 kg PA and 40 to 75 milliequivalent acid end groups / 1 kg PA, where PA stands for polyamide. The determination of the amino end groups was carried out in the context of the present invention according to the method: G.B. Taylor, J. Am. Chem. Soc. 69, 635, 1947. Polyamide 66 [CAS No. 32131 -17-2] to be used according to the invention as component A) is obtainable, for example, from Ascend Performance Materials LLC under the brand name Vydyne®.

Component B)

As component B) at least a partially aromatic polyamide is used. Partaromatic polyamides are polyamides whose monomers are derived in part from aromatic bases.

The partially aromatic polyamides to be used as component B) can be prepared by various processes and synthesized from different building blocks. For the preparation of partially aromatic polyamides a variety of procedures are known, depending on the desired end product different monomer units, various chain regulators for setting a desired molecular weight or monomers can be used with reactive groups for later intended aftertreatments.

The technically relevant processes for the preparation of the polyamides to be used as component B) usually proceed via the polycondensation in the melt. In the context of the present invention, the hydrolytic polymerization of lactams is understood as polycondensation.

Partially aromatic polyamides to be used according to the invention as component B) are based on α, ω-diamines and at least one benzenedicarboxylic acid.

Preferred benzenedicarboxylic acids are isophthalic acid or terephthalic acid, preferably isophthalic acid. Preferred optional additional aromatic units are selected from phenylenediamine or xylylenediamine. preferred α, ω-diamines are 1,4-diaminobutane (hexabutylenediamine) or 1,6-diaminobutane (hexamethylenediamine), in particular hexamethylenediamine.

Partially aromatic polyamides to be used particularly preferably as component B) are based on isophthalic acid (PA6I) [CAS No. 25668-34-2] or terephthalic acid (PA6T) [CAS No. 24938-70-3]. and hexamethylenediamine [CAS No. 124-09-4]. Very particular preference is PA6I, which is available inter alia as Durethan® T40 at LANXESS Deutschland GmbH, Cologne. Component C)

As component C) at least one copper halide, preferably at least one copper (L) halide is used. Particular preference is given to using at least copper (I) iodide [CAS No. 7681 -65-4]. Component D)

As component D) at least one polyhydric alcohol is used. Preferably, a polyhydric alcohol having more than two hydroxyl groups is used. Very particular preference is given to using at least one polyhydric alcohol from the group of dipentaerythritol, tripentaerythritol, pentaerythritol or mixtures thereof. Particularly preferred according to the invention is dipentaerythritol [CAS No. 126-58-9], which can be obtained, for example, from Sigma-Aldrich.

Component E)

As component E) preferably fibrous, needle-shaped or particulate fillers and reinforcing agents are used. At least one filler and reinforcing material from the group of carbon fibers [CAS No. 7440-44-0], glass beads, solid or hollow glass beads, in particular [CAS No. 65997-17-3], ground glass, amorphous silica [CAS no No. 7631-86-9], calcium silicate [CAS No. 1344-95-2], calcium metasilicate [CAS No. 10101 -39-0], magnesium carbonate [CAS No. 546-93-0], kaolin [CAS No. 1332 -58-7], calcined kaolin [CAS No. 92704-41-1], chalk [CAS No. 1317-65-3], kyanite [CAS No. 1302-76-7], powdered or ground quartz [CAS No 14808-60-7], mica [CAS No. 1318-94-1], phlogopite [CAS No. 12251 -00-2], barium sulfate [CAS No. 7727-43-7], feldspar [CAS No. 68476 -25-5], wollastonite [CAS No. 13983-17-0], montmorillonite [CAS No. 67479-91 -8] and glass fibers [CAS No. 65997-17-3].

A "fiber" in the sense of the present invention is a macroscopically homogeneous body with a high ratio of length to its cross-sectional area The fiber cross-section may be of any shape but is generally round or oval. According to "http://de.wikipedia.org/wiki/Faser-Kunststoff-Verbund" one differentiates

chopped fibers, also referred to as short fibers, with an average length in the range of 0.1 to 5 mm, preferably in the range of 3 to 4.5 mm,

Long fibers with a mean length in the range of 5 to 50 mm and

Endless fibers with a mean length L> 50 mm.

Fiber lengths can be determined, for example, by microfocus X-ray computed tomography (μ-CT); J. Kastner et. al., Quantitative measurement of fiber lengths and distribution in fiber-reinforced plastic parts by μ-ray computed tomography, DGZfP Annual Meeting 2007 - Lecture 47, pages 1-8.

Particular preference is given to using glass fibers, very particular preference being given to glass fibers made of E glass. The glass fibers are particularly preferably used as short glass fibers for molding compositions which are used in injection molding. In the case of the use of the compositions according to the invention as a matrix polymer for composites, the glass fibers are preferably used as continuous fibers and / or long fibers.

The fibrous or particulate fillers and reinforcing agents are provided in a preferred embodiment for better compatibility with the component A) with suitable surface modifications, preferably with surface modifications containing silane compounds. Particularly preferred as component E) glass fibers having a circular cross-sectional area and a filament diameter in the range of 6 to 14 μηι or glass fibers with flat shape and non-circular cross-sectional area used whose main cross-sectional axis has a width in the range of 6 to 40 μηι and the secondary cross-sectional axis Width in the range of 3 to 20 μηι, wherein for the assessment of the affiliation of a glass fiber product to this dimensional range, the information given in the technical data sheets of the glass fiber manufacturers are used. By way of example and with particular preference the glass fiber CS7928 from Lanxess Deutschland GmbH (circular cross section, 1 μm average diameter) can be used. Cross-sectional area or filament diameter are determined in the context of the present invention by means of at least one optical method according to DIN 65571. Optical methods are a) light microscope and micrometer eyepiece (distance measurement cylinder diameter), b) light microscope and digital camera with subsequent planimetry (cross-sectional measurement), c) laser interferometry and d) projection. All length, width or diameter data for the fillers and reinforcing materials listed here are averaged data (d ₅ o value) and refer to the state before compounding. With regard to the d ₅₀ values in this application, their determination and their significance, reference is made to Chemie Ingenieur Technik 72, 273-276, 3/2000, Wiley-VCH Verlags GmbH, Weinheim, 2000, according to which the d ₅₀ value is that particle size , below which 50% of the particle quantity lie (median value).

Component F)

As component F) at least one alkali metal halide is used. Preferred alkali metal halides are alkali metal chlorides, alkali metal bromides or alkali metal iodides, more preferably alkali metal halides of the metals sodium or potassium, most preferably potassium bromide or potassium iodide.

Preferably, at least one member of component C) is used together with at least one member of component F). According to the invention, preference is given to using copper (I) iodide with potassium bromide. In an alternative embodiment, preference is given to using copper (I) iodide with potassium iodide.

Component G)

The mold release agents to be used according to the invention as component G) are preferably ester derivatives or amide derivatives of long-chain fatty acids, in particular ethylene-bis-stearylamide, glycerol tristearate, stearyl stearate, montan ester waxes, in particular esters of montan acids with ethylene glycol and low molecular weight polyethylene or polypropylene waxes in oxidized and non-oxidized form. Particularly preferred release agents according to the invention are contained in the group of esters or amides of saturated or unsaturated aliphatic carboxylic acids having 8 to 40 carbon atoms with saturated aliphatic alcohols or amines having 2 to 40 carbon atoms. In a further preferred embodiment, the compositions or molding compositions according to the invention comprise mixtures of said mold release agents. Montan ester waxes preferably used as mold release agents, also referred to as montan waxes for short [CAS No. 8002-53-7], are esters of mixtures of straight-chain, saturated carboxylic acids with chain lengths in the range from 28 to 32 carbon atoms. Corresponding montan ester waxes are obtained, for example, from Clariant International Ltd. offered as Licowax®. Particularly preferred according to the invention is Licowax® E, or a mixture of waxes, preferably mixtures of ester waxes and amide waxes, as described in EP2607419 A1. Component H)

As additive H) to be used additive is preferably at least one substance from the group of thermostabilizers different from components C) and D), UV stabilizers, gamma ray stabilizers, hydrolysis, antistatic agents, nucleating agents, plasticizers, processing aids, impact modifiers, dyes, pigments and flame retardants used. The above and other suitable additives are state of the art and can be found by the person skilled in the art, for example, in the Plastics Additives Handbook, 5th Edition, Hanser Verlag, Munich, 2001, pages 80-84, 546-547, 688, 872-874, 938, 966 become. The additives to be used as component H) can be used alone or in mixture or in the form of masterbatches.

According to the invention to be used as additives additional heat stabilizers, which are different from the components C) and D) are preferably different from component F) metal halides or alkaline earth metal halides, preferably calcium chloride or manganese chloride, hindered phenols and / or phosphites, phosphates, preferably disodium dihydrogen diphosphate, hydroquinones, substituted resorcinols, salicylates, benzotriazoles or benzophenones, as well as various substituted representatives of these groups and / or mixtures thereof. Explicitly excluded are aromatic secondary amines and hindered aromatic amines (HALS).

According to the invention to be used as an additive UV stabilizers are preferably substituted resorcinols, salicylates, benzotriazoles or benzophenones. In the case of to be used as an additive impact modifiers or elastomer modifiers are preferably copolymers, which are preferably composed of at least two monomers of the following series: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic acid esters or methacrylic acid esters with 1 to 18 carbon atoms in the alcohol component. The copolymers may contain compatibilizing groups, preferably maleic anhydride or epoxide.

Dyes or pigments to be used as an additive according to the invention are preferably inorganic pigments, more preferably titanium dioxide, ultramarine blue, iron oxide, zinc sulfide or carbon black, and also organic pigments, more preferably phthalocyanines, quinacridones, perylenes and dyes, more preferably nigrosine or anthraquinones, and other colorants. Nucleating agents to be used as an additive according to the invention are preferably sodium or calcium phenylphosphinate, aluminum oxide, silicon dioxide or talc. It is particularly preferred to use talc [CAS No. 14807-96-6] as the nucleating agent, in particular microcrystalline talc, with microcrystalline talc having an average particle size d ₅₀ , measured according to Sedigraph, in the range from 0.5 to 10 μm. See: Micromeritics Instrument Corp, The Science and Technology of Small Particles, Norcross, USA, Part # 512/42901/00.

Flame retardants to be used according to the invention as an additive are preferably mineral flame retardants, nitrogen-containing flame retardants or phosphorus-containing flame retardants.

Among the mineral flame retardants magnesium hydroxide is particularly preferred. Magnesium hydroxide [CAS No. 1309-42-8] may be contaminated due to its origin and method of production. Typical impurities are z. As silicon, iron, calcium and / or aluminum-containing species that may be incorporated, for example in the form of oxides in the magnesium hydroxide crystals. The surface of the magnesium hydroxide to be used according to the invention may be uncoated or else provided with a size, a size being understood to mean an impregnating liquid in order to give the surface of a substance specific properties. Preferably, the magnesium hydroxide to be used according to the invention is provided with sizes based on stearates or aminosiloxanes, particularly preferably with aminosiloxanes. Preferably used magnesium hydroxide has an average particle size d ₅₀ in the range of 0.5 μηι to 6 μηι, with a d ₅₀ in the range of 0.7 μηι to 3.8 μηι preferably and d ₅₀ in the range of 1, 0 μηι to 2 , 6 μηι is particularly preferred and the average particle size is determined according to ISO 13320 by laser diffractometry.

Suitable magnesium hydroxide types according to the invention are, for example, Magnifin® H5IV from Martinswerk GmbH, Bergheim, Germany or Hidromag® Q2015 TC from Penoles, Mexico City, Mexico.

Preferred nitrogen-containing flame retardants are the reaction products of trichlorotriazine, piperazine and morpholine according to CAS No. 1078142-02-5, in particular MCA PPM triazine HF from the company MCA Technologies GmbH, Biel-Benken, Switzerland, furthermore melamine cyanurate and condensation products of melamine such as Meiern, Melam, melon or higher condensed compounds of this type. Preferred inorganic nitrogen-containing compounds are ammonium salts. It is also possible to use salts of aliphatic and aromatic sulfonic acids and mineral flame retardant additives such as aluminum hydroxide, Ca-Mg carbonate hydrates (eg DE-A 4 236 122). Also suitable are flame retardant synergists from the group of oxygen-nitrogen or sulfur-containing metal compounds, with zinc-free compounds, in particular molybdenum oxide, magnesium oxide, magnesium carbonate, calcium carbonate, calcium oxide, titanium nitride, magnesium nitrite, calcium phosphate, calcium borate, magnesium borate or mixtures thereof being particularly preferred.

In an alternative embodiment, it is also possible to use zinc-containing compounds as component H), if required. These preferably include zinc oxide, zinc borate, zinc stannate, zinc hydroxystannate, zinc sulfide and zinc nitride, or mixtures thereof.

Preferred phosphorus-containing flame retardants are organic metal phosphinates, in particular aluminum tris (diethylphosphinate), aluminum salts of phosphonic acid, red phosphorus, inorganic metal hypophosphites, in particular aluminum hypophosphite, other metal phosphonates, in particular calcium phosphonate, derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthren-10 oxides (DOPO derivatives), resorcinol bis (diphenyl phosphate) (RDP), including oligomers and bisphenol A bis diphenyl phosphate (BDP) including oligomers, furthermore melamine pyrophosphate and melamine polyphosphate, furthermore melamine poly (aluminum phosphate), melamine poly (zinc phosphate) or phenoxyphosphazene oligomers and mixtures thereof.

Further flame retardants to be used as component H) are carbon formers, particularly preferably phenol-formaldehyde resins, polycarbonates, polyimides, polysulfones, polyethersulfones or polyether ketones, and also anti-dripping agents, in particular tetrafluoroethylene polymers.

The flame retardants to be used as component H) can be added in pure form, as well as via masterbatches or compactates.

In an alternative embodiment, however, flame retardants may also be used - if necessary, taking into account the disadvantages of the loss of halogen freedom of the flame retardants - halogen-containing flame retardants. Preferred halogen-containing flame retardants are commercially available organic halogen compounds, particularly preferably ethylene-1,2-bistetrabromophthalimide, Decabromodiphenylethane, tetrabromobisphenol A epoxyoligomer, tetrabromobisphenol A oligocarbonate, tetrachlorobisphenol A oligocarbonate, polypentabromobenzyl acrylate, brominated polystyrene or brominated polyphenylene ethers, which can be used alone or in combination with synergists, especially antimony trioxide or antimony pentoxide, wherein among the halogen-containing flame retardants brominated polystyrene is particularly preferred. Brominated polystyrene is commercially available in various product grades. Examples include FireMaster ^® PBS64 the Fa.. Lanxess, Cologne, Germany and Saytex ^® HP-3010 from the company Albemarle, Baton Rouge, United States.

Among the flame retardants to be used as component H) are aluminum tris (diethylphosphinate)] [CAS no. No. 225789-38-8] and the combination of aluminum tris (diethylphosphinate) and melamine polyphosphate or the combination of aluminum tris (diethylphosphinate) and at least one aluminum salt of phosphonic acid are very particularly preferred, with the latter combination being particularly preferred. As a suitable aluminum tris (diethylphosphinate) comes z. As the Exolit ^® OP1230 or OP1240 Exolit ^® Fa. Clariant International Ltd. Muttenz, Switzerland in question. Melamine polyphosphate is commercially available in various product qualities. Examples of these are, for example, Melapur® 200/70 from BASF, Ludwigshafen, Germany and Budit® 3141 from Budenheim, Budenheim, Germany. Preferred aluminum salts of phosphonic acid are selected from the group of primary aluminum phosphonate [Al (H ₂ P0 ₃ ) ₃ ],

basic aluminum phosphonate [ΑΙ (ΟΗ) Η ₂ Ρ0 ₃ ) ₂ · 2Η ₂ 0],

AI ₂ (HP0 ₃₎ ₃ Al ₂ 0 ₃ x n H ₂ 0 with x in the range 2.27 to 1 and n ranges from 0 to 4,

Al ₂ (HPO ₃ ) ₃ · (H ₂ O) _q (Z ₁ )

with q in the range from 0 to 4, in particular aluminum phosphonate tetrahydrate [ΑΙ ₂ (ΗΡ0 ₃ ) ₃ .4Η ₂ 0] or secondary aluminum phosphonate [Al ₂ (HPO ₃ ) ₃ ],

Al ₂ M _z (HPO ₃ ) _y (OH) _v · (H ₂ O) _w (Z ₂ )

wherein M is at least one alkali metal ion and z ranges from 0.01 to 1.5, y is from 2.63 to 3.5, v is from 0 to 2 and w is from 0 to 4, and

Al ₂ (HPO ₃ ) _u (H ₂ PO ₃ ) _t * (H ₂ O) _s (Z ₃ )

wherein u is in the range of 2 to 2.99, t is in the range of 2 to 0.01, and s is in the range of 0 to 4, where in formula (Z2) z, y and v and in formula (Z3) u and t can only assume numbers such that the corresponding aluminum salt of the phosphonic acid as a whole is uncharged. Preferred alkali metals in formula (Z2) are sodium and potassium.

The aluminum salts of phosphonic acid described can be used individually or in a mixture. Particularly preferred aluminum salts of phosphonic acid are selected from the group

primary aluminum phosphonate [Al (H ₂ P0 ₃ ) ₃ ],

secondary aluminum phosphonate [Al ₂ (HPO ₃ ) 3],

basic aluminum phosphonate [Al (OH) H ₂ P0 ₃ ) ₂ -2H ₂ 0],

Aluminum phosphonate tetrahydrate [Al ₂ (HPO ₃ ) ₃ -4H ₂ O] and

ΑΙ ₂ (ΗΡ0 ₃ ) ₃ · χ Al ₂ 0 ₃ n H ₂ 0 with x in the range of 2.27 to 1 and n in the range of 0 to 4.

Very particular preference is given to secondary aluminum phosphonate [Al ₂ (HPO ₃ ) ₃ , CAS no. 71449-76-8] and secondary aluminum phosphonate tetrahydrate [Al ₂ (HPO ₃ ) ₃ -4H ₂ O, CAS No. 156024-71 -4], especially preferred is secondary aluminum phosphonate [Al ₂ (HPO ₃ ) ₃ ].

The preparation of the aluminum salts of phosphonic acid to be used according to the invention as component H) is described, for example, in WO 2013/083247 A1.

In one embodiment of the present invention, it is possible to use polyamide 6 (PA 6) as component H, with the proviso that the PA 6 does not form a copolymer with either component A) or component B). PA 6 [CAS No. 25038-54-4] is a partially crystalline thermoplastic, available for example from Lanxess Deutschland GmbH, Cologne, under the name Durethan®. According to DE 10 2011 084 519 A1, partially crystalline polyamides have a melting enthalpy in the range from 4 to 25 J / g, measured by the DSC method according to ISO 1 1357 during the second heating and integration of the melt peak. In contrast, amorphous polyamides have a melting enthalpy of less than 4 J / g, measured by the DSC method according to ISO 1 1357 at the 2nd heating and integration of the melting peak. The present invention preferably relates to compositions comprising A) PA 66, B) PA6I, C) copper (I) iodide, D) dipentaerythritol, E) glass fibers, as well as molding compositions and products to be produced therefrom. The present invention preferably relates to compositions comprising A) PA 66, B) PA6T, C) copper (I) iodide, D) dipentaerythritol, E) glass fibers, as well as molding compositions and products to be produced therefrom.

The present invention preferably relates to compositions comprising A) PA 66, B) PA6I, C) copper (I) iodide, D) dipentaerythritol, E) glass fibers, F) potassium bromide, as well as molding compositions and products to be produced therefrom.

The present invention preferably relates to compositions comprising A) PA 66, B) PA6T, C) copper (I) iodide, D) dipentaerythritol, E) glass fibers, F) potassium bromide, as well as molding compositions and products to be produced therefrom.

The present invention preferably relates to compositions comprising A) PA 66, B) partially aromatic PA, C) copper (I) iodide, D) dipentaerythritol, E) glass fibers, F) potassium bromide, H) PA 6, as well as molding compositions and products to be produced therefrom.

The present invention preferably relates to compositions comprising A) PA 66, B) PA6I, C) copper (I) iodide, D) dipentaerythritol, E) glass fibers, F) potassium bromide, H) PA 6, as well as molding compositions and products to be produced therefrom. The present invention preferably relates to compositions comprising A) PA 66, B) PA6T, C) copper (I) iodide, D) dipentaerythritol, E) glass fibers, F) potassium bromide, H) PA 6, as well as molding compositions and products to be produced therefrom.

method

The present invention also relates to a process for the preparation of products by mixing the components of the compositions according to the invention, to form a molding compound in the form of a strand, cooled to Granulierfähigkeit and granulated and as a matrix material of injection molding, blow molding or extrusion processing, preferred subjected to injection molding. Products according to the invention may also be composites based on continuous fibers or long fibers, preferably glass-based continuous fibers or glass-based long fibers, as known to the person skilled in the art, for example from DE 10 2006 013 684 A1 or DE 10 2004 060 009 A1. These are preferably components A) to E) and, if appropriate, at least one further component of components F), G) and H). Preferably, the mixing in the above-mentioned in at least one mixing unit. The mixing of the components preferably takes place at temperatures in the range from 220 to 400 ° C., particularly preferably in the range from 260 to 330 ° C., by mixing together, mixing, kneading, extruding or rolling. Preferred mixing units are to be selected from compounder, co-rotating twin-screw extruder or Buss kneader. It may be advantageous to premix individual components. Compounds are mixtures of raw materials to which fillers, reinforcing agents or other additives have additionally been added. By compounding thus at least two substances are connected together to form a homogeneous mixture. The process of making a compound is called compounding. Preferably, in a first step, at least one of components B), C), D) or E) is mixed with component A) or with PA6 as component H) to form a premix. It is also possible to mix at least one other component in this first step with component A) or with H) PA 6, preferably at least one of components F) or G). Preferably, this first step is carried out at temperatures <50 ° C in a mixing unit, preferably in a helical mixer, double cone mixer, Lödige mixer. Alternatively, premixing on a co-rotating twin-screw extruder, Buss kneader or planetary roller extruder at a temperature above the melting point of component A) PA66 or H) PA6 may be advantageous. Preferably, the mixing units are equipped with a degassing function.

After mixing, the resulting molding compositions are preferably discharged as a strand, cooled to Granulierfähigkeit and granulated. In one embodiment, the resulting granules are dried, preferably at temperatures in the range of 70 to 130 ° C, preferably in a vacuum oven or in a dry air dryer. For further processing in injection molding, the residual moisture should be set to a value preferably less than 0.12%. For extrusion processing, especially in the blow molding process, a residual moisture content of a maximum of 0.06% should be maintained. It may be advantageous to produce so-called semi-finished products from a physical mixture prepared at room temperature, preferably at a temperature in the range from 10 to 40 ° C., a so-called dry blend, premixed components and / or individual components. Semi-finished products in the sense of present invention are prefabricated items and arise in a first step in the manufacturing process of a product. For the purposes of the present invention, semi-finished products are not bulk materials, granules or powders because, unlike semifinished products, they are not geometrically determined, solid bodies and thus no "half-completion" of a final product has yet occurred. According to the invention, the term product therefore also includes semi-finished products.

The methods of injection molding, blow molding and extrusion of thermoplastic molding materials are known to the person skilled in the art.

Processes according to the invention for the production of polyamide-based products by extrusion or injection molding are at melt temperatures in the range from 250 to 310 ° C., more preferably in the range from 270 to 300 ° C., and in the case of injection molding at fill pressures of at most 2500 bar, preferably at fill pressures of a maximum of 2000 bar, particularly preferably carried out at filling pressures of a maximum of 1500 bar and very particularly preferably at filling pressures of a maximum of 750 bar.

The products to be produced from the molding compositions according to the invention can preferably be used for applications which require a high stability against heat aging, preferably in the automotive, electrical, electronic, telecommunications, solar, information technology, computer industries Household, in sports, medicine or the entertainment industry. Preferred for such applications is the use for products in vehicles, particularly preferably in motor vehicles (motor vehicles) with an internal combustion engine, in particular in the motor vehicle engine compartment. The compositions according to the invention are particularly preferably suitable for producing welded components which have at least one weld seam by means of vibration, heating element, infrared, hot gas, ultrasound, rotational or laser welding methods.

The present invention therefore also relates to the use of thermoplastic molding compositions containing the above-mentioned components in the form of compositions for producing products with increased stability against thermo-oxidative damage, preferably of motor vehicle products, more preferably of motor vehicle compartment products, in particular preferably of products having at least one weld, in particular a weld by vibration, heating element, infrared, hot gas, ultrasonic, rotary or laser welding. The molding compositions according to the invention are also suitable for applications or moldings or articles where, in addition to the thermo-oxidative stability, a stability to photo-oxidative damage is required, preferably solar systems. In a preferred embodiment, the products to be produced according to the invention are semi-finished products in the form of thermostabilized composites based on continuous fibers, also referred to as organic sheets, but also over-molded or over-molded composite structures. The compositions according to the invention or the heat stabilizer system according to the invention can be used either in the thermoplastic matrix of the composite structure or in the molding compound to be sprayed or in both components or contained therein. Thermostabilized composites are known, for example, from WO 2011/014754 A1, oversprayed composite structures are described, for example, in WO 2011/014751 A1. However, the present invention also relates to a process for thermostabilizing polyamide 66 and in particular the welds of polyamide 66-based components by using a partially aromatic polyamide, dipentaerythritol, and copper (I) iodide stabilizer system, preferably a stabilizer system of PA6I, dipentaerythritol, copper ( l) iodide, and potassium bromide, wherein the polyamide 66 is not present as a copolymer with the partially aromatic polyamide.

However, the present application also relates to a method for reducing photooxidative damage and / or thermo-oxidative damage of offset with at least one reinforcing polyamide 66 or products to be produced therefrom in the form of films, fibers or moldings, by a stabilizer system based on a partially aromatic polyamide, at least a polyhydric alcohol and at least one copper halide, and the polyamide 66 is not present as a copolymer with the partially aromatic polyamide. The products are preferably composite structures based on polyamide 66 and overmoulded composite structures, but also polyamide 66 based components provided with weld seams.

It is preferable to use partially aromatic polyamide, dipentaerythritol and copper (I) iodide as the stabilizer system, more preferably a stabilizer system of PA6I, dipentaerythritol, copper (I) iodide and potassium bromide or potassium iodide. In a further particularly preferred variant, the stabilizer system used is partially aromatic polyamide, dipentaerythritol, copper (I) iodide, potassium iodide and sodium hypophosphite. Finally, the invention relates to the use of a stabilizer system based on a partly aromatic polyamide, at least one polyhydric alcohol and at least one copper halide to reduce photooxidative damage and / or thermo-oxidative damage to polyamide 66 mixed with at least one reinforcing agent or products to be produced therefrom in the form of films, fibers or moldings, wherein the polyamide 66 is not present as a copolymer with the partially aromatic polyamide.

However, the preferred subject matter of the present invention is also combustion engine components, in particular motor vehicle internal combustion engine components, based on compositions comprising A) polyamide 66

B) at least one partially aromatic polyamide,

C) at least one copper halide,

D) at least one polyhydric alcohol, and

E) at least one reinforcing material,

with the proviso that A) and B) do not form a copolymer, which are turbocharged air ducts, intake pipes, valve covers, intercoolers or engine covers.

Examples

In order to demonstrate the advantages of compositions according to the invention and of products to be produced therefrom, molding compositions were first prepared in the extruder. Products obtained by injection molding from the molding compositions in the form of flat bars were then tested as unnotched test specimens, in a fresh state and after prior aging, in the impact test according to DIN EN ISO 180 1 -U.

Production of the polyamide molding compositions

The individual components listed in Table 1 were mixed in a twin-screw extruder of the type ZSK 26 Compounder Coperion Werner & Pfleiderer (Stuttgart, Germany) at a temperature of about 290 ° C, discharged as a strand in a water bath, cooled to Granulierfähigkeit and granulated. The granules were dried for about two days at 70 ° C in a vacuum oven to a residual moisture content of less than 0.12%.

Materials used in the context of the present invention:

Component A): Polyamide 66, Vydyne® 50 BWFS from Ascend Performance Materials

LLC

Component B): partly aromatic polyamide PA6I, Durethan® T40 from Lanxess

Germany GmbH

Component C): copper (I) iodide, d ₉₉ <70 μηι

Component D): dipentaerythritol [CAS No. 126-58-9]

Component E): Glass fibers, Chopped Strands CS7928 from Lanxess Deutschland GmbH

Other components used:

Polyamide 6, Durethan® B29 from Lanxess Deutschland GmbH

Potassium bromide, d ₉₉ <70 μηι

Montanesterwachs Licowax® E of Clariant GmbH

Soot masterbatch: 50% in polyethylene

Masterbatch Nigrosin Base NB (Solvent Black 7) 40% in PA6 Table 1: Compositions of the molding compositions (mass fractions based on 100 parts by mass of PA 66)

Ingredient Vgl.1 Ex. 1 Ex. 2

PA66 100.00 100.00 100.00

PA6I 0.00 20.12 20.26

Copper (I) iodide 0.06 0.07 0.07

Dipentaerythritol 3.39 4.42 4.45

Fiberglass 59.39 77.38 77.93

The glass fiber content was in all molding compounds 35% of the total weight. Since the compositions are based on 100 parts by mass of PA 66 and this proportion changes due to the different amounts of admixtures, the different numerical values for the mass fractions of glass fibers are obtained.

injection:

The injection molding of the resulting molding compositions was carried out on an injection molding machine type SG370-173732 Fa. Arburg. The melt temperature was 290 ° C and the mold temperature 80 ° C. Flat bars were sprayed as test specimens according to DIN EN ISO 180 1 -U of the nominal size 80 mm x 10 mm x 4 mm.

Aging and testing:

To test the aging behavior, the specimens were stored at 220 ° C in a convection oven for 1, 000 h, 2,000 h and 3,000 h and then tested under the conditions of ISO 180 1-U on a Zwick impact tester. The results obtained from the measurements were compared to the initial value and from this the determination of the impact resistance after hot air aging was determined. Table 2: Results of hot air aging at 220 ° C

(Impact tests were carried out at room temperature (23 +/- 2 ° C)

Recipe Cgl.1 Ex. 1 Ex. 2

Aging Durability Impact (unnotched) IZOD

at 220 ° C (kJ / m ² )

0 h 64 59 50

1000 h 30 53 46

rel. Received 47% 90% 92%

2000 h 5 47 43

rel. Received 8% 80% 86%

3000 h 1 53 47

rel. Received 2% 90% 94%

Surprisingly, the impact resistance is maintained by the use of partially aromatic polyamides in PA 66 compounds after hot air aging at 220 ° C even after 3000h significantly above a value (relative receipt) of 50%, a proof of the significantly improved thermal aging resistance of inventive compositions or products thereof ,

Claims

claims

1 . Containing compositions

A) Polyamide 66

B) at least one partially aromatic polyamide,

C) at least one copper halide,

D) at least one polyhydric alcohol, and

E) at least one reinforcing material,

with the proviso that A) and B) do not form a copolymer.

2. Compositions according to claim 1, characterized in that for 100 parts by mass of component A) 6.0 to 50.0 parts by mass of component B), 0.01 to 0.30 parts by mass of component C), 1 to 5 parts by mass of the component D) and 17.5 to 185 parts by mass of component E) are used.

3. Compositions according to claim 1 or 2, characterized in that in addition to the components A) to E) nor F) at least one alkali metal halide, preferably in amounts ranging from 0.05 to 0.60 parts by mass per 100 parts by weight of component A) , is used.

4. Compositions according to claim 3, characterized in that component C) and F) are always used together.

5. Compositions according to one of claims 1 to 4, characterized in that in addition to the components A) to F), or instead of the component F), G) at least one mold release agent, preferably in amounts ranging from 0.05 to 0 , 50 parts by mass per 100 parts by mass of component A) is used.

6. Compositions according to one of claims 1 to 5, characterized in addition to the components A) to G) or in place of the components F) and / or G) nor H) at least one of the components B) to G) different further additive , preferably in amounts ranging from 0.05 to 3.00 parts by mass per 100 parts by mass of component A) is used.

7. Compositions according to one of claims 1 to 6, characterized in that are used as partially aromatic polyamides based on isophthalic acid or terephthalic acid and hexamethylenediamine, preferably based on isophthalic acid and hexamethylenediamine.

8. A composition according to any one of claims 1 to 7, characterized in that as component C) at least one copper (L) halide is used, preferably copper (I) iodide.

9. Compositions according to one of claims 1 to 8, characterized in that as component D) a polyhydric alcohol having more than two hydroxyl groups is used.

10. A composition according to claim 9, characterized in that a polyhydric alcohol from the group dipentaerythritol, tripentaerythritol, pentaerythritol and mixtures thereof is used, preferably dipentaerythritol.

1 1. Compositions according to one of claims 1 to 10, characterized in that as component E) at least one filler and reinforcing material from the group carbon fibers, glass beads, solid or hollow glass beads, ground glass, amorphous silica, kyanite, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin , calcined kaolin, chalk, powdered or ground quartz, mica, phlogopite, barium sulfate, feldspar, wollastonite, montmorillonite and glass fibers, preferably glass fibers.

12. Molding compounds and products to be produced therefrom containing a composition according to one of claims 1 to 11.

13. Combustion engine components, in particular motor vehicle engine components based on compositions according to one of claims 1 to 10.

14. A process for the production of products, characterized in that one mixes the components of the compositions according to one of claims 1 to 1 1, discharges to a molding compound in the form of a strand, cooled to Granulierfähigkeit and granulated and injection molding as a matrix material, a blow molding process or an extrusion, preferably subjected to injection molding.

15. Use of a stabilizer system based on a partly aromatic polyamide, at least one polyhydric alcohol and at least one copper halide for reducing photooxidative damage and / or thermo-oxidative damage to polyamide 66 mixed with at least one reinforcing substance or products to be produced therefrom in the form of films, fibers or molded parts, wherein the polyamide 66 is not present as a copolymer with the partially aromatic polyamide.