Compositions containing polyarylene (ether) sulfones

Abstract

The present invention relates to compositions comprising polyarylene(ether)sulfones and polyamides, their uses, and fibers, films and molded articles made from the compositions of the invention.

Description

[Technical field]

[0001] The present invention relates to compositions comprising polyarylene (ether) sulfones and polyamides.

[0002] Polyarylene(ether)sulfones belong to a group of high-temperature resistant polymers that exhibit high heat resistance, excellent mechanical performance and inherent flame retardancy (EM Koch, H.-M. Walter, Kunststoffe 80 (1990) 1146; E. Doering, Kunststoffe 80, (1990) 1149, N. Inchaurondo-Nehm, Kunststoffe 2008 190). Polyarylene(ether)sulfones are amorphous polymers and are sensitive to organic solvents. Furthermore, due to the high content of aromatic units, their thermal insulation properties, such as the comparative tracking index (CTI), are low compared to other thermoplastic materials.

[0003] To overcome the aforementioned shortcomings of polyarylene (ether) sulfones, compositions based on polyarylene (ether) sulfones and polyamides may be interesting, since polyamides show good resistance to many solvents and also high CTI values. Polyarylene (ether) sulfones and polyamides are immiscible, so binary blends have poor mechanical properties (M. Weber in “Polymer Blends and Alloys” G. Shonaike, GP Simon (Eds.), Marcel Dekker Inc. 1999, p. 275).

[0004] Several approaches are known for compatibilizing polyarylene (ether) sulfones with polyamides. Polyhydroxyethers are known to improve the compatibility of polyarylene (ether) sulfone / polyamide blends (DE-A-3617501). Furthermore, reactive blends of anhydride-functionalized polyarylene (ether) sulfones with polyamides have been described in several patents and papers (C.-L- Myers, ANTEC 1, 1420 (1992); EP 613916, WO 97 / 04018; W. Kaufhold, H. Schnablegger, RT Kumpf, H. Pielarzik, RE Cohen, Acta Polym. 46, 307 (1995)). None of the described approaches fully meets the desired requirements, so there is a continuous need for new compounds with improved performance.

[0005] In EP 0 477 757, polymer blends based on polyarylene (ether) sulfones and aliphatic aromatic polyamides are described. From EP 2 594 610, laminates based on various polyarylene (ether) sulfones and polyamides are known, which show improved CTI values. Flame retardant tests on the laminates show good flame retardant behavior.

[0006] The problem underlying the present invention was to address the deficiencies of known polyarylene(ether)sulfone / polyamide blends and provide a material or composition that is suitable for injection molding and exhibits improved CTI values ​​and good flame retardancy.

[0007] This problem has been solved by the composition of the present invention. In particular, the present invention provides: A) 20-80% by weight of at least one polyarylene(ether)sulfone having up to 0.05% by weight of phenolic end groups; B) 10-50% by weight of at least one semi-aromatic polyamide; C) 4-15% by weight of at least one aluminum phosphinate; D) 0.01 to 2% by weight of at least one acid scavenger; E) 0-10% by weight of at least one compatibilizer; F) 0-60% by weight of at least one fibrous or particulate filler; G) 0 to 30% by weight of at least one impact modifier; and H) 0-40% by weight of at least one auxiliary; The present invention provides a composition comprising: wherein the sum of the weight percent of the components of the composition is 100 weight percent. As used herein, "at least one" generally means one or more than one, e.g., three or four or five or more, and may mean more than one or not counted. For example, it may mean one or a mixture of two or more. When used in reference to a compound, "at least one" is meant to describe one or more compounds that differ in chemical structure, i.e., chemical properties.

[0008] Furthermore, in this specification, "polymer" may mean a homopolymer or a copolymer or a mixture thereof. Those skilled in the art understand that any polymer, whether homopolymer or copolymer, is by its nature typically a mixture of polymeric individuals that differ in structure, such as chain length, degree of branching, or nature of the end groups. Thus, in the following, "at least one" as a prefix to a polymer means that it may include different types of polymers, whereby each type may have the structure differences mentioned above.

[0009] The composition of the present invention comprises 20-80% by weight of at least one polyarylene(ether)sulfone having up to 0.05% by weight of phenolic end groups.

[0010] Polyarylene (ether) sulfone is a kind of polymer known to those skilled in the art. In principle, any structure of polyarylene (ether) sulfone is included in the present invention, provided that, for component A), the polyarylene (ether) sulfone contains a maximum of 0.05% by weight of phenolic end groups. In the following more detailed description, it is always a prerequisite that the polyarylene (ether) sulfone contains a maximum of 0.05% by weight of phenolic end groups when used as component A).

[0011] The polyarylene(ether)sulfone is represented by the general formula II [ka] [Wherein, the symbols t, q, Q, T, Y, Ar and Ar 1 is defined as follows: t, q are each independently 0, 1, 2 or 3; Q, T, and Y each independently represent a chemical bond or -O-, -S-, -SO2-, S=O, C=O, -N=N-, or CR a R b -, and R a and R b are each independently a hydrogen atom, (C1-C 12 ) Alkyl, (C1-C 12 )Alkoxy, (C3-C 12 ) cycloalkyl or (C6-C 18 ) an aryl group, and at least one of Q, T and Y is -SO2-; and Ar and Ar 1 are independent of each other (C6~C 18 ) arylene] It may be preferable that the unit is composed of the following units:

[0012] Within the above preconditions, when Q, T or Y is a chemical bond, this means that the adjacent group on the left side and the adjacent group on the right side are directly connected by a chemical bond.

[0013] According to one preferred embodiment, t and q are independently 0 or 1.

[0014] According to a preferred embodiment, Q, T, and Y in formula II are independently a chemical bond, -O-, -SO2-, and CR a R b -, with the proviso that at least one of Q, T, and Y is present and is -SO2-. a and R b are preferably each independently hydrogen or (C1-C4) alkyl.

[0015] -CR a R b - In R a and R b are preferably independently hydrogen, (C 12 ) Alkyl, (C1-C 12 )Alkoxy and (C6-C 18 ) aryl.

[0016] (C1~C 12 )Alkyl refers to a straight or branched chain saturated hydrocarbon group having 1 to 12 carbon atoms. The following moieties are specifically included: (C1-C6)alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, 2 or 3 methylpentyl, and (C7-C 12 ) Alkyl, for example, unbranched heptyl, octyl, nonyl, decyl, undecyl, lauryl, and their mono- or polybranched analogs.

[0017] "C1~C 12 The term "-alkoxy" refers to a straight or branched alkyl group having 1 to 12 carbon atoms attached via an oxygen at any position in the alkyl group, such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy.

[0018] (C3~C 12)Cycloalkyl refers to a monocyclic saturated hydrocarbon group having 3 to 12 carbon ring members, and in particular includes (C3-C8)cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylethyl, -propyl, -butyl, -pentyl, -hexyl, -cyclohexylmethyl, -dimethyl, and trimethyl.

[0019] Ar and Ar 1 are independent of each other (C6~C 18 ) an arylene group. According to a particular embodiment, Ar 1 is unsubstituted (C6-C 12 ) an arylene group.

[0020] Ar and Ar 1 are preferably independently selected from phenylene, bisphenylene and naphthylene groups, and from arylene groups derived from anthracene, phenanthrene or naphthacene. For example, Ar and Ar 1 is independently selected from 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,6-naphthylene, 1,7-naphthylene, 2,6-naphthylene, and 2,7-naphthylene, 2,7-dihydroxynaphthylene, and 4,4'-bisphenylene.

[0021] In particular, Ar and Ar 1 is independently selected from phenylene and naphthylene groups, for example, independently selected from 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,6-naphthylene, 1,7-naphthylene, 2,6-naphthylene and 2,7-naphthylene, more particularly, independently selected from 1,4-phenylene, 1,3-phenylene and naphthylene. Furthermore, in accordance with another embodiment of the present invention, Ar and Ar 1 are independently selected from arylene groups derived from anthracene, phenanthrene, or naphthacene. According to yet a further embodiment, Ar and Ar1 is independently selected from 2,7-dihydroxynaphthylene and 4,4'-bisphenylene.

[0022] It may be preferred if the polyarylene(ether)sulfone according to component A) comprises at least one of the following repeat units IIa to IIo: [ka] [ka]

[0023] In addition to the units IIa-IIo which may preferably be present, other repeat units are those in which one or more 1,4-phenylene units derived from hydroquinone are replaced by 1,3-phenylene units derived from resorcinol or naphthylene units derived from dihydroxynaphthalene.

[0024] Particularly preferred units of general formula II are units IIa, IIg and / or IIk. According to a particular embodiment, it is particularly preferred that the polyarylene(ether)sulfone of component A) is essentially composed of one type of unit of one class of general formula II, said one type may in particular be selected from IIa, IIg and IIk.

[0025] According to a preferred embodiment, the polyarylene(ether)sulfone of component A) is composed of repeating units where Ar is 1,4-phenylene, t is 1, q is 0, T is a chemical bond and Y is SO2. This polyarylene(ether)sulfone is also referred to as polyphenylenesulfone (PPSU) (formula IIg).

[0026] According to a further preferred embodiment, the polyarylene(ether)sulfone of component A) is composed of repeat units where Ar is 1,4-phenylene, t is 1, q is 0, T is C(CH3)2 and Y is SO2. This polyarylene(ether)sulfone is also referred to as polysulfone (PSU) (formula IIa).

[0027] According to yet another preferred embodiment, the polyarylene (ether) sulfone of component A) is composed of repeat units in which Ar is 1,4-phenylene, t is 1, q is 0, and T and Y are SO2. This polyarylene (ether) sulfone is also referred to as polyether sulfone (PESU) (formula IIk).

[0028] For the purposes of this disclosure, the abbreviations PPSU, PESU and PSU are in accordance with DIN EN ISO 1043-1:2001.

[0029] The amount of component A) present in the composition of the invention is 20-80% by weight. According to a preferred embodiment, the amount of component A) is 20-75% by weight, in particular 20-70% by weight, more particularly 20-65% by weight, even more particularly 20-60% by weight of the composition. More particularly, this embodiment uses 20-55% by weight, more particularly 20-50% by weight, even more particularly 20-45% by weight of component A). In a further preferred embodiment, the amount of component A) is 25-75% by weight, in particular 25-70% by weight, more particularly 25-65% by weight, even more particularly 25-60% by weight of the composition. A more particular embodiment of the invention uses 25-55% by weight, more particularly 25-50% by weight, even more particularly 25-45% by weight of component A). According to another preferred embodiment, the amount of component A) is 30-75%, in particular 30-70%, more particularly 30-65%, even more particularly 30-60% by weight of the composition. More particular embodiments of the invention use 30-55%, more particularly 30-50%, even more particularly 30-45% by weight of component A). In some cases an amount of 30-40%, more particularly 30-35% by weight of component A) may be preferred.

[0030] The polyarylene(ether)sulfones of component A) have Cl- or OCH3- end groups and a content of OH or phenolate end groups of up to 0.05% by weight. The amount of phenolic end groups is determined by potentiometric titration.

[0031] According to a preferred embodiment, the polyarylene (ether) sulfone of component A) has a maximum of 0.04% by weight, more particularly a maximum of 0.03% by weight of phenolic end groups. According to a further preferred embodiment, the polyarylene (ether) sulfone of component A) has a maximum of 0.02% by weight, more particularly a maximum of 0.01% by weight, even more particularly a maximum of 0.005% by weight of phenolic end groups. It may be preferred if the polyarylene (ether) sulfone of component A) is substantially free of phenolic end groups.

[0032] For the purposes of the present invention, the expression "phenolic end group" refers to a hydroxy group attached to an aromatic ring, optionally also present in deprotonated form. Those skilled in the art know that the phenolic end group can also take the form known as a phenolate end group, by cleavage of the proton as a result of exposure to a base. The expression "phenolic end group" therefore explicitly includes not only aromatic OH groups, but also phenolate groups.

[0033] The proportion of phenolic end groups is preferably determined by potentiometric titration. For this, the polymer is dissolved in dimethylformamide and titrated with a toluene / methanol solution of tetrabutylammonium hydroxide. The end point is recorded potentiometrically. The proportion of halogen end groups is preferably determined by elemental analysis.

[0034] The weight-average molar mass M of the polyarylene(ether)sulfones A) of the present invention w is preferably 10 000 to 150 000 g / mol, in particular 15 000 to 120 000 g / mol, particularly preferably 18 000 to 100 000 g / mol, determined by gel permeation chromatography in dimethylacetamide as solvent against narrowly distributed polymethyl methacrylate as standard.

[0035] The preparation processes leading to the above-mentioned polyarylene(ether)sulfones are known per se to the person skilled in the art and are described, for example, in Herman F. Mark, "Encyclopedia of Polymer Science and Technology", 3rd Edition, Vol. 4, 2003, chapter "Polysulfones", pages 2-8, and Hans R. Krickheldorf, "Aromatic Polyethers", Handbook of Polymer Synthesis, 2nd Edition, 2005, pages 427-443.

[0036] The synthesis of polyarylene (ether) sulfones can generally be carried out by polycondensation of appropriate monomers in dipolar aprotic solvents at elevated temperatures (RN Johnson et al., J.Polym. Sci. A-1 5 (1967) 2375; JE McGrath et al., Polymer 25 (1984) 1827).

[0037] The preparation of polyarylene (ether) sulfones with simultaneously controlled end groups is generally known to those skilled in the art and is known in the literature (eg, McGrath et al., Polym. Eng. Sci. 17, 647 (1977)).

[0038] The known polyarylene(ether)sulfones usually have halogen end groups, in particular -F or -Cl, or phenolic OH or phenolate end groups, where the latter can be present as such or in reacted form, in particular in the form of -OCH3 end groups.

[0039] Particularly preferred is the reaction of at least one aromatic compound having two halogen substituents with at least one aromatic compound having two functional groups reactive towards said halogen substituents in an aprotic polar solvent and in the presence of anhydrous alkali metal carbonate, in particular sodium carbonate, potassium carbonate, calcium carbonate or mixtures thereof, very particularly preferably potassium carbonate.One particularly suitable combination is N-methylpyrrolidone as solvent and potassium carbonate as base.

[0040] The polyarylene (ether) sulfones as component A) preferably have either halogen end groups, in particular chlorine end groups, or etherified end groups, in particular alkyl ether end groups, which are obtained by reaction of OH end groups or, respectively, phenolate end groups with a suitable etherifying agent.

[0041] Examples of suitable etherifying agents are monofunctional alkyl or aryl halides, such as C1-C6-alkyl chlorides, C1-C6-alkyl bromides or C1-C6-alkyl iodides, preferably methyl chloride or benzyl chloride, bromide or iodide or mixtures thereof. For the purposes of the polyarylene (ether) sulfones of component A), preferred end groups are halogen, especially chlorine, alkoxy, especially methoxy, aryloxy, especially phenoxy, or benzyloxy.

[0042] As component B), the composition according to the invention comprises 10 to 50% by weight of at least one semi-aromatic polyamide.

[0043] "Semi-aromatic polyamide" in this context means that the polyamide used as component B) is built up from aliphatic and aromatic monomers, the polymer comprising aliphatic and aromatic units.

[0044] Examples of polyamides suitable as component B) according to the invention include polyamides obtainable by reaction of at least one dicarboxylic acid with at least one diamine, in which some of the monomers contain aromatic units, so that the resulting polyamide is partially aromatic.

[0045] The at least one dicarboxylic acid that may be preferably used is selected from alkanedicarboxylic acids having 4 to 12 carbon atoms, more particularly 6 to 12, in particular 6 to 10, and aromatic dicarboxylic acids. Examples of suitable dicarboxylic acid chains are adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid and isophthalic acid.

[0046] The at least one diamine includes alkane diamines having 6 to 12 carbon atoms, in particular 6 to 10 carbon atoms, and aromatic diamines. Examples of suitable diamines are m-xylylenediamine (MXDA), di-(4-aminophenyl)methane, di-(4-aminocyclohexyl)methane, 2,2-di-(4-aminophenyl)propane, 2,2-di-(4-aminocyclohexyl)propane, 1,5-diamino-2-methylpentane, hexamethylenediamine, 1,9-nonanediamine, trimethylhexamethylenediamine, dimethyldiaminodicyclohexylmethane, and phenylenediamine.

[0047] According to a further embodiment, the at least one polyamide as component B) may be obtained by copolymerization of two or more monomers, such as the monomers mentioned above. Mixtures of several polyamides in any desired mixing ratio may also be suitable.

[0048] Further suitable components B) include polyamides, some of which are derived from cyclic amides, in particular lactams having a ring number of 7 to 13. Examples of such lactams are ε-caprolactam, ω-caprylolactam, ω-laurolactam.

[0049] According to a particular embodiment, the polyamide B) may be obtained by using a molar ratio of MXDA and adipic acid of 1:1.

[0050] Furthermore, semi-aromatic copolyamides have often proven to be particularly suitable as component B), such as PA 6 / 6T and PA 66 / 6T, which generally have a triamine content of less than 0.5% by weight, typically less than 0.3% by weight (see EP-A-299444).The at least one semi-aromatic polyamide as component B) may also be at least one high-temperature resistant polyamide (PA 6T / 6I / MXD6), as disclosed in EP-A-1994075.

[0051] It may also be preferable to use as component B) at least one semi-aromatic copolyamide having a low triamine content, as described, for example, in EP-A-129195 and EP-A-129196.

[0052] The at least one polyamide that may be used as component B) of the composition of the present invention may be specifically selected from the following non-exhaustive list: [Table 1]

[0053] Preferably, the at least one semi-aromatic polyamide as component B) is selected from PA 9T, PA 4T, PA 6I / 6T and PA 6T66.

[0054] According to a particular embodiment, component B) is PA 9T. In a further embodiment, component B) is PA 4T. Yet another embodiment of the present invention uses PA6T6I as at least one semi-aromatic polyamide as component B). According to yet another embodiment, at least one polyamide B) is PA 6T66.

[0055] It may be preferred that the composition of the invention comprises component B) in an amount of 10-45%, more particularly 10-40%, by weight of the composition. Furthermore, it may be preferred that the polyamide component B) is present in an amount of 10-35%, more particularly 10-30%, by weight. It may be even more suitable to use component B) in an amount of 12-45%, more particularly 12-40%, in particular 12.5-40%, by weight. In a very specific embodiment of the invention, the composition comprises 12.5-35%, more particularly 15-35%, more particularly 15-30%, by weight of component B).

[0056] The composition of the present invention contains 4 to 15% by weight of aluminum phosphinate as component C). The aluminum phosphinate must have high thermal stability and relatively low volatility. For example, aluminum diethylphosphinate is particularly suitable as component C). Aluminum diethylphosphinate is commercially available, for example Exolith OP1230 (Clariant).

[0057] According to a particular embodiment, component C) is used in an amount of 4-14% by weight, more particularly 4-13% by weight of the composition. A more particular embodiment of the invention uses 4-12.5% ​​by weight, more particularly 7-12.5% ​​by weight of component C). According to a further embodiment, the amount of component C) is suitably 4-10% by weight.

[0058] The acid scavengers (component D)) of the compositions of the invention are present in an amount of 0.01 to 2% by weight. Suitable acid scavengers that can be used as component D) in the compositions of the invention are selected, for example, from metal salts of phosphonic acids, half-ester metal salts of phosphonic acids and stannates, and any mixtures of these acid scavengers. According to one embodiment, acid scavengers based on metal mono- or di-salts of phosphonic acids or mixtures of phosphonic acids, or half-ester salts of these metals, as described in EP 2100916 A1, are used. The metals are typically selected from metals of groups 1, 2 and 3 of the periodic table, or selected from Ti, Zn and Al. According to a further embodiment, acid scavengers based on stannates, such as, for example, commercially available zinc stannate (ZnSnO3) (for example from Flamtard S), are used. Component D) is preferably used in an amount of 0.01 to 1.8% by weight, more particularly 0.05 to 1.5% by weight, of the composition.

[0059] According to a further aspect of the invention, the composition of the invention further comprises at least one compatibilizer as component E). According to the invention, the optional component E) is used in an amount of 0-10% by weight, preferably 0-8% by weight, more particularly 0-5% by weight, even more particularly 0-4% by weight of the composition. By "compatibilizer" is understood a compound which enhances the compatibility between the components of the polymer blend. That is to say, according to this aspect of the invention, component E) compatibilizes in particular the polyarylene(ether)sulfone A) and polyamide B) components of the composition of the invention.

[0060] When present (amount >0% by weight), component E) is preferably used in an amount of 0.5 to 10% by weight of the composition. It may be preferred that 1 to 9% by weight, in particular 1.5 to 8% by weight, more particularly 2 to 8% by weight of component E) is present in the composition of the invention. According to a still further embodiment, component E) is present in an amount of 0.5 to 7.5% by weight, more particularly 0.5 to 5% by weight.

[0061] Suitable compatibilizers E) are selected from polyarylene(ether)sulfones having at least 0.2% by weight, preferably at least 0.25% by weight, of phenolic end groups, for example as determined by potentiometric titration. According to a further embodiment, the polyarylene(ether)sulfones useful as component E) have at least 0.3% by weight, more particularly at least 0.35% by weight, of phenolic end groups.

[0062] According to a further embodiment of the present invention, the polyarylene(ether)sulfones that can be used as component E) in the compositions of the present invention comprise at least one polyarylene(ether)sulfone having an average of at least 1.5 phenolic end groups per polymer chain. The term "on average" herein means a numerical average.

[0063] Polyarylene (ether) sulfones are a type of polymer known to those skilled in the art. Their formation and simultaneous control of end groups are also generally known to those skilled in the art and have been described above in connection with component A). In particular, the synthesis of such polyarylene (ether) sulfones may generally be carried out by polycondensation of suitable monomers in dipolar aprotic solvents at elevated temperatures (RN Johnson et al., J.Polym. Sci. A-1 5 (1967) 2375; JE McGrath et al., Polymer 25 (1984) 1827). To be suitable as component E) in the composition of the present invention, the polyarylene (ether) sulfone contains at least 0.2% by weight (or any of the limits defined herein) of phenolic end groups.

[0064] The polyarylene(ether)sulfone may preferably be composed of units of general formula II as defined above, preferably as defined above for component A). Particularly preferred polyarylene(ether)sulfone refers to polyethersulfone (PESU). This embodiment is very particularly preferred.

[0065] The preferred polyarylene(ether)sulfones used as optional component E) generally have an average molar mass M in the range from 5000 to 60000 g / mol. n (number average), and a relative viscosity of 0.20 to 0.95 dl / g. The relative viscosity of the polyarylene (ether) sulfones is measured in accordance with DIN EN ISO 1628 1 in a 1% by weight solution in N-methylpyrrolidone at 25° C.

[0066] The polyarylene(ether)sulfones A) used as optional component E) preferably have a weight-average molar mass M of 10 000 to 150 000 g / mol, in particular 15 000 to 120 000 g / mol, particularly preferably 18 000 to 100 000 g / mol. w and was measured by gel permeation chromatography in dimethylacetamide as solvent against narrowly distributed polymethyl methacrylate as standard.

[0067] A preferred method for preparing polyarylene(ether)sulfones suitable as component E) is described below and comprises the following steps in the order abc: (a) providing at least one polyarylene(ether)sulfone E*) in the presence of a solvent (S), in which the content of phenolic end groups in the polyarylene(ether)sulfone is appropriate for the desired component E), the phenolic end groups being present in the form of phenolate end groups, the polyarylene(ether)sulfone preferably being composed of units of general formula II as defined above, (b) adding at least one acid, preferably at least one polybasic carboxylic acid; and (c) obtaining a polyarylene(ether)sulfone suitable as component E) in solid form.

[0068] The polyarylene(ether)sulfone E*) here is preferably provided in the form of a solution in the solvent (S).

[0069] In principle, there are various ways to provide polyarylene (ether) sulfones suitable as component E). As an example, suitable polyarylene (ether) sulfones E*) can be directly contacted with a suitable solvent and used in the process of the invention directly, i.e. without further reaction. Alternatively, prepolymers of polyarylene (ether) sulfones can be used and reacted in the presence of a solvent, so that the described polyarylene (ether) sulfones E*) are produced in the presence of a solvent.

[0070] However, the polyarylene(ether)sulfone (E*) is preferably prepared by the reaction of at least one starting compound of structure X-Ar-Y (s1) with at least one starting compound of structure HO-Ar in the presence of a solvent (S) and a base (B). 1 -OH(s2) with at least one starting compound provided in step (a), Y is a halogen atom; - X is selected from halogen atoms and OH, - Ar and Ar 1 are each independently an arylene group having 6 to 18 carbon atoms.

[0071] The ratio of (s1) to (s2) here is selected to give the desired content of phenolic end groups. Suitable starting compounds are known to those skilled in the art or can be prepared by known methods.

[0072] Hydroquinone, resorcinol, dihydroxynaphthalenes, in particular 2,7-dihydroxynaphthalene, 4,4'-dihydroxydiphenylsulfone, bisphenol A, and 4,4'-dihydroxybiphenyl are particularly preferred as starting compounds (s2).

[0073] However, trifunctional compounds can also be used, in which case branched structures result. When a trifunctional starting compound (s2) is used, 1,1,1-tris(4-hydroxyphenyl)ethane is preferred.

[0074] The quantitative proportions used are in principle a function of the stoichiometry of the polycondensation reaction, which proceeds with the cleavage of a theoretical amount of hydrogen chloride, and are adjusted by the skilled person in the art in a known manner. However, in order to increase the number of phenolic OH end groups, an excess of (s2) is preferred.

[0075] In this embodiment, the molar (s2) / (s1) ratio is particularly preferably between 1.005 and 1.2, in particular between 1.01 and 1.15, very particularly preferably between 1.02 and 1.1.

[0076] Alternatively, starting compounds (s1) with X=halogen and Y=OH can also be used. In this case, excess hydroxyl groups are obtained by adding starting compounds (s2). In this case, the ratio of phenolic end groups used to halogen is preferably 1.01 to 1.2, in particular 1.03 to 1.15, very particularly preferably 1.05 to 1.1.

[0077] In order to provide a sufficiently high molecular weight, it is preferred that the conversion in the polycondensation reaction is at least 0.9. When a prepolymer is used as a precursor for the polyarylene(ether)sulfone, the degree of polymerization is based on the number of actual monomers.

[0078] The preferred solvent (S) is an aprotic polar solvent. Furthermore, the boiling point of the suitable solvent is in the range of 80 to 320° C., particularly 100 to 280° C., preferably 150 to 250° C. Examples of suitable aprotic polar solvents are high-boiling ethers, esters, ketones, asymmetric halogenated hydrocarbons, anisole, dimethylformamide, dimethylsulfoxide, sulfolane, N-ethyl-2-pyrrolidone, and N-methyl-2-pyrrolidone.

[0079] The reaction of starting compounds (s1) with (s2) is preferably carried out in an aprotic polar solvent (S) as described above, in particular N-methyl-2-pyrrolidone.

[0080] A person skilled in the art knows per se that the reaction of the phenolic OH group is preferably carried out in the presence of a base (Ba) in order to increase the reactivity of the starting compound (s1) towards halogen substituents.

[0081] The base (Ba) is preferably anhydrous. Particularly suitable bases are anhydrous alkali metal carbonates, preferably sodium carbonate, potassium carbonate, calcium carbonate or mixtures thereof, with potassium carbonate being particularly preferred.

[0082] A particularly preferred combination is N-methyl-2-pyrrolidone as the solvent (S) and potassium carbonate as the base (Ba).

[0083] The reaction of suitable starting compounds (s1) and (s2) is carried out at a temperature of 80 to 250° C., preferably 100 to 220° C., the upper temperature limit being provided by the boiling point of the solvent. The reaction preferably takes place within 2 to 12 hours, in particular 3 to 8 hours.

[0084] It has proven advantageous to filter the polymer solution after step (a) and before carrying out step (b), in order to remove salts formed during the polycondensation reaction and any gels that may form.

[0085] It has also proven advantageous for the purposes of step (a) to adjust the amount of polyarylene(ether)sulfone E*) to between 10 and 70% by weight, preferably between 15 and 50% by weight, relative to the total weight of the mixture of polyarylene(ether)sulfone E*) and solvent S).

[0086] For the purposes of step (b), at least one acid, preferably at least one polybasic carboxylic acid, is added to the polyarylene(ether)sulfone E*) from step (a), preferably to a solution of the polyarylene(ether)sulfone E*) in the solvent (S).

[0087] It is also possible to add at least one polybasic carboxylic acid to the precipitating agent.

[0088] "Polybasic" means a basicity of at least 2. The basicity is the number (average, where appropriate) of COOH groups per molecule. Polybasic means a basicity of 2 or more. For the purposes of the present invention, preferred carboxylic acids are dibasic and tribasic carboxylic acids.

[0089] The polybasic carboxylic acids can be added in various ways, in particular in solid or liquid form or in the form of a solution, preferably in a solvent that is miscible with the solvent (S).

[0090] The number average molar mass of the polybasic carboxylic acid is preferably at most 1500 g / mol, in particular at most 1200 g / mol. At the same time, the number average molar mass of the polybasic carboxylic acid is preferably at least 90 g / mol.

[0091] Particularly suitable polybasic carboxylic acids have the general structure (IX): HOOC-R-COOH formula (IX) in which R represents a hydrocarbon moiety having from 2 to 20 carbon atoms and optionally further functional groups, preferably selected from OH and COOH. This is due to.

[0092] Preferred polybasic carboxylic acids are C4-C 10 Dicarboxylic acids, especially succinic acid, glutaric acid, adipic acid, and tricarboxylic acids, especially citric acid. Particularly preferred polybasic carboxylic acids are succinic acid and citric acid.

[0093] To obtain a proper conversion of the phenolate end groups to phenolic end groups, it has proven advantageous to adjust the amount of polybasic carboxylic acid used in relation to the amount of phenolate end groups.

[0094] For the purposes of step (b), it is preferred to add polybasic carboxylic acids such that the amount of carboxy groups is 25-200 mol %, preferably 50-150 mol %, particularly preferably 75-125 mol %, relative to the molar amount of phenol end groups.

[0095] If too little acid is added, the precipitation properties of the polymer solution will be insufficient, whereas a significant excess addition may cause discoloration of the product during further processing.

[0096] For the purposes of step (c), the polyarylene(ether)sulfone E) is obtained in solid form. In principle, various processes can be used to obtain the material in solid form. However, it is preferred to obtain the polymer composition by precipitation.

[0097] A preferred precipitation process can in particular be carried out via mixing of the solvent (S) with an anti-solvent (S'). The anti-solvent is a solvent in which the polymer composition is not soluble. This anti-solvent is preferably a mixture of a non-solvent and a solvent. A preferred non-solvent is water. A preferred mixture of a solvent and a non-solvent (S') is preferably a mixture of a solvent (S), in particular N-methyl-4-pyrrolidone, and water. It is preferred to add the polymer solution from step (b) to the anti-solvent (S'), which results in precipitation of the polymer composition. In this case, it is preferred to use an excess of the anti-solvent. It is particularly preferred that the polymer solution from step (a) is added in finely dispersed form, in particular in the form of droplets.

[0098] When the poor solvent (S') used comprises a mixture of a solvent (S), particularly N-methyl-2-pyrrolidone, and a non-solvent, particularly water, the preferred solvent:non-solvent mixing ratio is 1:2 to 1:100, particularly 1:3 to 1:50.

[0099] A mixture of water and N-methyl-2-pyrrolidone (NMP) in combination with N-methyl-2-pyrrolidone as solvent (S) is preferred as anti-solvent (S'). An NMP / water mixture in a ratio of 1:3 to 1:50, in particular 1:30, is particularly preferred as anti-solvent (S').

[0100] Precipitation is particularly efficient when the content of the polymer composition in the solvent (S) is between 10 and 50% by weight, preferably between 15 and 35% by weight, relative to the total weight of the mixture consisting of the polymer composition and the solvent (S).

[0101] The potassium content of component C) is preferably at most 600 ppm. The potassium content is determined by atomic spectroscopy.

[0102] Also suitable as component E) are certain functionalized polyarylene(ether)sulfones, for example those containing naphthalic anhydride end groups as described in WO 2018 / 141552, the content of phenolic end groups being as defined above. The polyarylene(ether)sulfones described in WO 2018 / 141552 suitable as compatibilizer component E) according to the invention are preferably composed of units of the general formula II as defined for the polyarylene(ether)sulfones of component A), preferably as defined above, and of the formula (I): [ka] naphthalic anhydride end groups, the content of phenolic end groups being as defined above for component E).

[0103] The naphthalic anhydride end group containing polyarylene (ether) sulfone according to WO 2018 / 141552 is also referred to below as "PNA". PNA may be branched and capable of having more than two end groups per individual polymer chain. Typically, PNA is linear and has two end groups per individual polymer chain.

[0104] The amount of end groups of formula (I) may be small or very small, i.e. only a few end groups are end groups of formula (I). It may be preferred that the polyarylethersulfone contains up to 10% end groups of formula (I), in other words up to 10 out of 100 end groups are end groups of formula (I). If the PNA is mathematically linear, up to every 5 individual polymer chains have one end group of formula (I), or up to every 10 individual polymer chains have two end groups of formula (I). Those skilled in the art will understand that in practice other distributions will fulfil the requirements. It may be preferred that up to 25%, i.e. up to 25 out of 100 end groups are end groups of formula (I). Any percentage of end groups between 10% and 80% may be end groups of formula (I), for example 20%, 30%, 40%, 50%, 60% or 70%, or any unequal percentage between 10% and 80%. It may be preferable that 10% to 80% of the terminal groups are the terminal groups of formula (I), and it may be more preferable that 15% to 70%, for example 25% to 60%, for example 30% to 50% of the terminal groups are the terminal groups of formula (I).

[0105] The nature of the non-terminal end group of formula (I) is not particularly limited, with the prerequisite that the PNA is suitable as component E) (compatibilizer) if it contains at least 0.2% by weight of phenolic end groups as defined, preferably as defined above. Possible non-terminal end groups of formula (I) are phenolic OH or phenolate end groups, phenolic alkoxy end groups (among which OCH3 end groups may be preferred), amino end groups (among which -NH2 may be preferred), halogen end groups (may be F or Cl). Of the halogen end groups, Cl is most preferred. It is also possible for the non-terminal end group of formula (I) to be an anhydrous phenol end group. In general, the non-terminal end groups of formula (I) are Cl. - , O.H. - and OCH3.

[0106] For example, any of the PNA types PNA-1 through PNA-10 listed in Table A may be used as component E), preferably provided that each PNA has at least 0.2 wt. % phenolic end groups as defined, preferably as defined above: [Table 2]

[0107] For the purposes of this disclosure, the abbreviations PPSU, PESU and PSU are in accordance with DIN EN ISO 1043-1: 2001. According to one particular embodiment, component E) is selected from PNAs based on PPSU, in particular any of the PPSUs mentioned individually above.

[0108] The synthesis of PNAs is described in WO 2018 / 141552.

[0109] A particular embodiment of the present invention relates to compositions which do not comprise component E), in which the amount of E) as defined herein is 0% by weight.

[0110] According to a further aspect of the invention, the composition of the invention further comprises at least one fibrous or particulate filler (optional component F)). According to the invention, component F) is used in an amount of 0 to 60% by weight, in particular 0 to 50% by weight, more particularly 0 to 40% by weight, even more particularly 0 to 30% by weight of the composition.

[0111] When present, component F) is preferably used in an amount of 5-60% by weight of the composition. According to this aspect of the invention, it may be preferred if 5-50% or 10-50% by weight, in particular 15-40% by weight, more particularly 20-30% by weight of component F) is present in the composition of the invention. According to a still further embodiment, an amount of 25-30% by weight of component F) is used.

[0112] According to one embodiment, component F) is preferably at least one fibrous filler. The at least one fibrous filler is preferably selected from carbon fibers, potassium titanate whiskers, aramid fibers and glass fibers, more particularly from carbon fibers and glass fibers. According to one preferred embodiment, component F) is glass fiber. When using at least one glass fiber, it can be provided with a sizing, preferably a polyurethane sizing, and / or a coupling agent, to improve compatibility with the matrix material. The diameter of the at least one carbon fiber and / or glass fiber used is generally in the range of 5 to 20 μm, more particularly from 5 to 18 μm.

[0113] The at least one glass fiber may be a short glass fiber or have the form of a continuous filament fiber (roving). The average length of the at least one glass fiber in the finished injection molded article is preferably in the range of 0.08 to 2 mm.

[0114] At least one carbon fiber and / or glass fiber may also be used in the form of a woven fabric, a mat, or a glass silk roving.

[0115] According to a further embodiment, component F) is at least one particulate filler.Suitable particulate fillers may be selected from amorphous silica, carbonates such as magnesium carbonate and chalk, powdered quartz, mica, various silicates such as clay, muscovite, biotite, suzoite, tinmaretite, talc, chlorite, phlogopite, feldspar, calcium silicates such as wollastonite, and aluminum silicates such as kaolin, in particular calcined kaolin.

[0116] It may be preferable if at least 95% by weight, preferably at least 98% by weight, of the particles of the particulate filler have a diameter (maximum diameter passing through the geometric centre), measured on the final product, of less than 45 μm, preferably less than 40 μm, in which case the value known as the aspect ratio of the particles, measured on the final product, is in the range from 1 to 25, preferably in the range from 2 to 20. The aspect ratio is the ratio of the diameter to the thickness of the particle (in each case the maximum and minimum dimensions passing through the geometric centre).

[0117] The particle diameter here can be measured, by way of example, by recording an electron micrograph of a thin layer of the polymer mixture and evaluating at least 25, preferably at least 50, filler particles. The particle diameter can also be measured by sedimentation analysis, as described in Transactions of ASAE, p. 491 (1983). Sieve analysis can also be used to measure the mass fraction of fillers with a diameter of less than 40 μm.

[0118] The at least one particulate filler is particularly preferably selected from talc, kaolin, such as calcined kaolin, and wollastonite. The particulate filler used according to the invention may be a mixture of two or all of said fillers. Among these, talc is particularly preferred, in which at least 95% by weight of the particles have a diameter of less than 40 μm and an aspect ratio of 1.5 to 25, in each case measured on the final product. Preferably, kaolin may have at least 95% by weight of particles with a diameter of less than 20 μm and preferably an aspect ratio of 1.2 to 20, in each case measured on the final product.

[0119] According to one particular embodiment, the composition of the invention is free of component F) (0% by weight).

[0120] Yet another aspect of the present invention relates to compositions further comprising at least one impact modifier (optional component G). The impact modifier component G) may be at least one impact-modifying rubber. Also, a mixture of two or more different impact-modifying rubbers may be used.

[0121] According to the invention, component G) is used in an amount of 0-30%, more particularly 0-20%, even more particularly 0-10% by weight of the composition. If present, component G) is preferably used in an amount of 5-30% by weight of the composition. According to this aspect of the invention, it may be preferred that 5-25%, in particular 5-20%, more particularly 10-20% by weight of component G)% is present in the composition of the invention. According to a still further embodiment, component G) is present in an amount of 25-30% by weight.

[0122] For purposes of this invention, rubbers are generally crosslinkable polymers that have elastomeric properties at room temperature.

[0123] Preferred rubbers, which increase the toughness of the composition, usually have two important features: they contain an elastomeric portion with a glass transition temperature below -10°C, preferably below -30°C, and they contain at least one functional group capable of interacting with the polyamide B) or the polyarylene(ether)sulfone A) or both. Examples of suitable functional groups are carboxylic acid groups, carboxylic anhydride groups, carboxylic ester groups, carboxamide groups, carboximide groups, amino groups, hydroxyl groups, epoxy groups, urethane groups and oxazoline groups.

[0124] At least one functionalized rubber currently preferred as component G) comprises a functionalized polyolefin rubber composed of the following components: d1) 40-99% by weight of at least one α-olefin having 2-8 carbon atoms; d2) 0 to 50% by mass of diene; d3) At least one C1-C of acrylic acid or methacrylic acid 12 - 0-45% by weight of alkyl esters or mixtures of esters of this type; d4) at least one ethylenically unsaturated C2-C 20 0-40% by weight of mono- or dicarboxylic acids or functional derivatives of these acids; d5) 1 to 40 mass% of at least one monomer containing an epoxy group; and d6) At least one monomer capable of free radical polymerization.

[0125] Examples of suitable at least one α-olefin (d1) are ethylene, propylene, 1-butylene, 1-pentylene, 1-hexylene, 1-heptylene, 1-octylene, 2-methylpropylene, 3-methyl-1-butylene and 3-ethyl-1-butylene. Ethylene and propylene may be preferred.

[0126] Examples of suitable at least one diene monomer (d2) are conjugated dienes having 4 to 8 carbon atoms, such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms, such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene and 1,4-octadiene, cyclic dienes, such as cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene, and alkenylnorbornenes, such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene and 2-isopropenyl-5-norbornene, and tricyclodienes, such as 3-methyltricyclo[5.2.1.02·6]-3,8-decadiene, or mixtures thereof. 1,5-hexadiene, 5-ethylidenenorbornene and dicyclopentadiene are preferred. The diene content is generally 0 to 50 mass%, preferably 0.5 to 50 mass%, particularly preferably 2 to 20 mass%, and more particularly preferably 3 to 15 mass%, based on the total mass of the olefin polymer.

[0127] Examples of suitable at least one ester (d3) are methyl, ethyl, propyl, n-butyl, isobutyl, 2-ethylhexyl, octyl and decyl acrylates and the corresponding methacrylates. Among these, methyl, ethyl, propyl, n-butyl and 2-ethylhexyl acrylates and methacrylates are particularly preferred.

[0128] Instead of or in addition to the at least one ester (d3), the olefin polymer may comprise an acid-functional and / or latent acid-functional monomer in the form of at least one ethylenically unsaturated mono- or dicarboxylic acid (d4).

[0129] Examples of the at least one monomer (d4) are acrylic acid, methacrylic acid, the tertiary alkyl esters of these acids, in particular tert-butyl acrylate, and dicarboxylic acids, such as maleic acid and fumaric acid, as well as derivatives of these acids and their half esters.

[0130] For the purposes of the present invention, latent acid functional monomers are compounds which form free acid groups under the polymerization conditions or during the incorporation of the olefin polymer into the composition. Examples of these are the anhydrides of dicarboxylic acids having 2 to 20 carbon atoms, in particular maleic anhydride, and the tertiary C1-C anhydrides of said acids. 12 -alkyl esters, in particular tert-butyl acrylate and methacrylate. The ethylenically unsaturated dicarboxylic acids and anhydrides (d4) have the following formulae III and IV: [ka] [In the formula, R 5 , R 6 , R 7 and R 8 are each independently H or C1-C6-alkyl.

[0131] The epoxy group-containing monomer d5 has the following formulae V and VI: [ka] [In the formula, R 9 , R 10 , R 11 and R 12 are each independently H or C1-C6-alkyl, m is an integer from 0 to 20, and p is an integer from 0 to 10.

[0132] R 5 ~R12 is preferably hydrogen, m is preferably 0 or 1, and p is preferably 1.

[0133] Preferred compounds (d4) and (d5) may be selected from maleic acid, fumaric acid and maleic anhydride, respectively, and alkenyl glycidyl ethers and vinyl glycidyl ethers, respectively.

[0134] Particularly preferred compounds of formulae III and IV, and V and VI respectively, may be maleic acid and maleic anhydride, and acrylates and / or methacrylates, respectively, both containing epoxy groups, especially glycidyl acrylate and glycidyl methacrylate.

[0135] Particularly preferred at least one olefin polymer may be one made from 49.9 to 98.9% by weight, in particular 59.85 to 94.85% by weight of ethylene and 1 to 50% by weight, in particular 5 to 40% by weight of an ester of acrylic acid or methacrylic acid, and 0.1 to 20.0% by weight, in particular 0.15 to 15% by weight of glycidyl acrylate and / or glycidyl methacrylate, acrylic acid and / or maleic anhydride.

[0136] Particularly suitable functionalized rubbers G) may be selected from ethylene-methyl methacrylate-glycidyl methacrylate polymers, ethylene-methyl acrylate-glycidyl methacrylate polymers, ethylene-methyl acrylate-glycidyl acrylate polymers and ethylene-methyl methacrylate-glycidyl acrylate polymers, and any mixtures thereof.

[0137] Examples of other monomers (d6) are, for example, vinyl esters and vinyl ethers, and mixtures thereof.

[0138] Said polymers may be prepared by methods known per se or available to a person skilled in the art by application of general knowledge, for example by random copolymerization, preferably at high pressure and temperature.

[0139] The melt index of the copolymers may generally be from 1 to 80 g / min 10 min (measured at 190° C. and 2.16 kg load).

[0140] Additionally, functionalized ethylene-α-olefin copolymers such as ethylene-propylene grafted maleic anhydride or ethylene-1-butene grafted maleic anhydride may also be used as impact modifiers in the compositions of the present invention.

[0141] Core-shell graft rubbers are another group of suitable impact modifiers G) that may be used according to the invention. These are graft rubbers that can be prepared in emulsion and are composed of at least one hard component and one soft component. The hard component is usually at least one polymer with a glass transition temperature of at least 25°C, and the soft component is usually at least one polymer with a glass transition temperature below 0°C. These products generally have a structure made up of a core (graft base) and at least one shell (graft), which structure is typically the result of the sequence of monomer addition. The soft component generally originates from butadiene, isoprene, at least one alkyl acrylate, at least one alkyl methacrylate or at least one siloxane, and optionally at least one other comonomer. Suitable siloxane cores may be prepared, for example, starting from cyclic oligomeric octamethyltetrasiloxane or tetravinyltetramethyltetrasiloxane. These may be reacted, for example, with γ-mercaptopropylmethyldimethoxysilane in a ring-opening cationic polymerization, preferably in the presence of sulfonic acid, to obtain a soft siloxane core. At least one siloxane may be crosslinked, for example, by carrying out the polymerization in the presence of at least one silane having at least one hydrolyzable group, such as halo or alkoxy, such as tetraethoxysilane, methyltrimethoxysilane or phenyltrimethoxysilane. Examples of at least one comonomer suitable for this are styrene, acrylonitrile, and crosslinking or grafting monomers having two or more polymerizable double bonds, such as diallyl phthalate, divinylbenzene, butanediol diacrylate or triallyl (iso)cyanurate. The hard component generally derives from styrene, α-methylstyrene, or copolymers thereof, where the at least one comonomer may preferably be acrylonitrile, methacrylonitrile or methyl methacrylate.

[0142] At least one core-shell graft rubber may preferably comprise a soft core and a hard shell, or a hard core, a first soft shell and at least one further soft shell, where the incorporation of at least one functional group, such as carbonyl, carboxylic acid, anhydride, amide, imide, carboxylic ester, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl, may preferably occur by adding at least one suitable functionalized monomer during the polymerization of the final shell.

[0143] Examples of suitable functionalized monomers are maleic acid, maleic anhydride, half-esters or diesters, or maleic acid, tert-butyl (meth)acrylate, acrylic acid, glycidyl (meth)acrylate and vinyloxazoline. The proportion of monomers having functional groups may generally be 0.1-25% by weight, preferably 0.25-15% by weight, based on the total weight of the core-shell graft rubber. The weight ratio of the soft component to the hard component may generally be 1:9-9:1, preferably 3:7-8:2.

[0144] Rubbers of this type are known per se or are available to the person skilled in the art by using general knowledge and are described, for example, in EP-A-208187.

[0145] Thermoplastic polyester elastomers are another group of suitable impact modifiers that can be used as component G). For the purposes of the present invention, polyester elastomers are generally segmented copolyetheresters that may comprise long-chain segments derived from poly(alkylene) ether glycols and short-chain segments derived from low molecular weight diols and dicarboxylic acids. Products of this type are known per se or available to the skilled artisan and are described, for example, in U.S. Pat. No. 3,651,014. Corresponding products are also commercially available as Hytrel® (Du Pont), Arnitel® (Akzo) and Pelprene® (Toyobo Co. Ltd.).

[0146] According to one particular embodiment, the composition of the invention is free of component G) (0% by weight).

[0147] The composition of the invention may optionally further comprise one or more auxiliaries H). According to the invention, component H) is used in an amount of 0-40% by weight, in particular 0-30% by weight, more particularly 0-20% by weight, even more particularly 0-10% by weight, for example 0-5% by weight. When present, the composition may preferably comprise 0.01-20% by weight, more particularly 1-20% by weight, of auxiliaries H). More preferably, H) may be used in an amount of 0.01-15% by weight, for example 0.5-10% by weight. It may be even more preferred that the composition of the invention comprises 0.5-8% by weight of H).

[0148] The at least one auxiliary may be selected from, for example, processing aids, pigments, stabilizers, or may be a mixture of various additives. Other examples of conventional additives are oxidation retardants, agents that inhibit degradation caused by heat or ultraviolet light, lubricants and mold release agents, dyes, and plasticizers, which may be used alone or in combination with other auxiliary agents.

[0149] The amount of pigments and dyes may generally be 0 to 6% by mass, preferably 0.05 to 5% by mass, and particularly 0.1 to 3% by mass.

[0150] Pigments for coloring thermoplastics are well known, see for example R. Gaechter and H. Mueller, Taschenbuch der Kunststoffadditive [Handbook of Plastic Additives], Carl Hanser Verlag, 1983, pp. 494-510. A first preferred group of pigments that may be mentioned are white pigments, such as zinc oxide, zinc sulfide, lead white [2PbCO3·Pb(OH)2], lithopone, antimony white, and titanium dioxide. Of the two best known crystalline forms of titanium dioxide (rutile and anatase), it is typically the rutile form that is used for the white coloring of the disclosed compositions. Black pigments which can be used according to the invention are iron oxide black (Fe3O4), spinel black [Cu(Cr,Fe)2O4], manganese black (a mixture composed of manganese dioxide, silicon dioxide and iron oxide), cobalt black and antimony black, but also carbon black, which is mainly used in the form of furnace black or gas black, particularly preferably. In this connection, see G. Benzing, Pigmente fuer Anstrichmittel [Pigments for paints], Expert-Verlag (1988), p. 78 ff.

[0151] A particular shade can be achieved, for example, by using inorganic chromatic pigments, such as chromium oxide green, or organic chromatic pigments, such as azo pigments or phthalocyanines. Pigments of this type are known to those skilled in the art.

[0152] Examples of oxidation inhibitors and heat stabilizers that can be added to the compositions of the present invention are halides of metals of group I of the periodic table of the elements, for example chlorides, bromides or iodides, such as sodium halides, potassium halides or lithium halides.Zinc fluoride and zinc chloride can also be used.It is also possible to use sterically hindered phenols, hydroquinones, substituted representatives of said groups, secondary aromatic amines, optionally in combination with phosphorus-containing acids, or their salts, or mixtures of said compounds, preferably in concentrations up to 1% by weight.

[0153] Examples of UV stabilizers are various substituted resorcinols, salicylates, benzotriazoles, and benzophenones, commonly used in amounts up to 2% by weight.

[0154] Examples of lubricants, release agents, the amount of which is generally up to 2% by weight, preferably up to 1% by weight, are stearyl alcohol, alkyl stearates, stearamides, and esters of pentaerythritol and long-chain fatty acids. It is also possible to use dialkyl ketones, for example distearyl ketone. The compositions according to the invention contain 0.1 to 2% by weight, more preferably 0.1 to 1.75% by weight, particularly preferably 0.1 to 1.5% by weight, in particular 0.1 to 0.9% by weight of stearic acid and / or stearates. In principle, it is also possible to use other stearic acid derivatives, for example esters of stearic acid.

[0155] Stearic acid is preferably produced by hydrolysis of fats. The products thus obtained are usually mixtures composed of stearic acid and palmitic acid. These products therefore have a wide softening range, for example 50-70°C, depending on the product composition. It may be preferable to use products with a stearic acid content of more than 20% by weight, particularly preferably more than 25% by weight. It is also possible to use pure stearic acid (more than 98% by weight).

[0156] Component H) can also contain stearates. Stearates can be produced by reaction of the corresponding sodium salts with metal salt solutions (e.g. CaCl2, MgCl2, aluminum salts) or by direct reaction of fatty acids with metal hydroxides (see, for example, Baerlocher Additives, 2005). Typically, it is preferred to use aluminum tristearate.

[0157] Another possible additive is a nucleating agent, for example talc powder.

[0158] The preparation of the composition may be carried out by processes known in the art, such as extrusion. For example, the components are fed into a melt mixing device such as an extruder (single or twin screw), a Brabender mixer or a Banbury mixer or a kneader, mixed and extruded. The extrudate is typically cooled and ground. Typically, after extrusion, the strands are cooled and pelletized to obtain pellets or granules.

[0159] A particular embodiment of the present invention is as follows: A) 20-75% by weight of at least one polyarylene(ether)sulfone having up to 0.05% by weight of phenolic end groups; B) 12.5-40% by weight of at least one semi-aromatic polyamide; C) 4-12.5% ​​by weight of aluminum phosphinate; D) 0.05 to 1.5 wt. % of at least one acid scavenger; E) 0-10% by weight of at least one compatibilizer; F) 5-50% by weight of at least one fibrous or particulate filler; G) 0 to 30% by weight of at least one impact modifier; and H) 0-40% by weight of at least one auxiliary; wherein the sum of the weight percent of the components of said composition is 100 weight percent.

[0160] Further preferred embodiments are as follows: A) 20-60% by weight of at least one polyarylene(ether)sulfone having up to 0.05% by weight of phenolic end groups; B) 12.5-40% by weight of at least one semi-aromatic polyamide; C) 4-12.5% ​​by weight of aluminum phosphinate; D) 0.05 to 1.5 wt. % of at least one acid scavenger; E) 0-10% by weight of at least one compatibilizer; F) 10-50% by weight of at least one fibrous or particulate filler; G) 0 to 30% by weight of at least one impact modifier; and H) 0-40% by weight of at least one auxiliary; wherein the sum of the weight percent of the components of said composition is 100 weight percent.

[0161] More specific embodiments are as follows: A) 20-80% by weight of at least one polyarylene(ether)sulfone having up to 0.05% by weight of phenolic end groups; B) 10-50% by weight of at least one semi-aromatic polyamide; C) 4-15% by weight of at least one aluminum phosphinate; D) 0.01 to 2% by weight of at least one acid scavenger; E) 0-10% by weight of at least one compatibilizer; F) 0-60% by weight of at least one fibrous or particulate filler; G) 0 to 30% by weight of at least one impact modifier; and H) 0-40% by weight of at least one auxiliary; wherein the sum of the mass % of the components of said composition is 100 mass %.

[0162] A more specific embodiment of the present invention is as follows: A) 20-75% by weight of at least one polyarylene(ether)sulfone having up to 0.05% by weight of phenolic end groups; B) 12.5-40% by weight of at least one semi-aromatic polyamide; C) 4-12.5% ​​by weight of aluminum phosphinate; D) 0.05 to 1.5% by weight, more particularly 0.05 to 0.5% by weight, of at least one acid scavenger; E) 0-10% by weight of at least one compatibilizer; F) 5-50% by weight of at least one fibrous or particulate filler; G) 0 to 30% by weight of at least one impact modifier; and H) 0-40% by weight of at least one auxiliary; wherein the sum of the mass % of the components of said composition is 100 mass %.

[0163] A more specific embodiment of the present invention is as follows: A) 20-60% by weight of at least one polyarylene(ether)sulfone having up to 0.05% by weight of phenolic end groups; B) 12.5-40% by weight of at least one semi-aromatic polyamide; C) 4-12.5% ​​by weight of aluminum phosphinate; D) 0.05 to 1.5% by weight, more particularly 0.05 to 0.5% by weight, of at least one acid scavenger; E) 0-10% by weight of at least one compatibilizer; F) 10-50% by weight of at least one fibrous or particulate filler; G) 0 to 30% by weight of at least one impact modifier; and H) 0-40% by weight of at least one auxiliary; wherein the sum of the mass % of the components of said composition is 100 mass %.

[0164] The components of the composition of the present invention can be mixed in any desired order, and the order in which the individual components are administered into the mixing device can vary, for example, two or optionally three components can be premixed or all components can be mixed together.

[0165] For product performance, homogeneous mixing is important. To achieve this, a mixing time of 0.1 to 30 minutes is generally applied at a temperature of 280 to 390°C, preferably 290 to 380°C. The strands obtained after compounding are cooled and pelletized.

[0166] The compositions according to the invention exhibit a unique combination of good mechanical performance as well as CTI values ​​(Comparative Tracking Index) and fire behavior.

[0167] The compositions of the present invention can be advantageously used for the manufacture of fibers, films, foams or molded articles. According to a further aspect, the present invention relates to fibers, films or molded articles comprising the compositions described herein. Due to the good comparative tracking index, the compositions of the present invention are particularly suitable for the manufacture of electrical or electronic components in general. The compositions of the present invention have high temperature resistance and good chemical resistance, so they are particularly suitable for the manufacture of electrical or electronic components exposed to high temperatures and / or chemicals. In general, the products that may be obtained from the compositions of the present invention may be industrial items in the vehicle field, such as automobiles or airplanes. Similarly, they may be household items, such as electrical appliances or food contact items. Furthermore, battery housings, piping parts, energy absorbing foams may also be manufactured using the compositions of the present invention.

[0168] EXAMPLES: The following examples further illustrate the present invention but are not intended to limit it.

[0169] Component A: As component A, a polyethersulfone having a viscosity number of 49.0 ml / g was used. The product used had 0.19% by weight of Cl end groups (elemental analysis) and 0.23% by weight of OCH3 end groups ( 1 H-NMR). The amount of OH end groups was below the detection limit (<0.02% by mass). This component A is referred to as "component A1" in the examples.

[0170] Component B: Component B1: Polyamide 9T having a viscosity number of 120 ml / g (measured in concentrated H2SO4 at 25° C.).

[0171] Component B1: Polyamide 6T6I having a viscosity number of 120 ml / g (measured in concentrated H2SO4 at 25° C.).

[0172] Component C: Component C1: Flame retardant Exolith OP1230.

[0173] Ingredient CV: Daihachi Chemicals flame retardant CR-733S (organophosphate).

[0174] Component D: Component D1: Acid scavenger Flamtard S.

[0175] Component DV: Aluminum hydroxide, supplied by Alteo as a dry powder.

[0176] Component E: OH-terminated PESU (PESU-OH) was prepared according to the following procedure: In a 4 liter HWS vessel equipped with stirrer, Dean-Stark trap, nitrogen inlet and temperature control, 278.27 g (0.969 mol) of 4,4'-dichlorodiphenylsulfone (DCDPS), 250.17 g (1.00 mol) of 4,4'-dihydroxydiphenylsulfone (DHDPS) and 152.03 g (1.10 mol) of potassium carbonate (particle size 39.3 μm) are suspended in 1000 ml of NMP under nitrogen atmosphere. The mixture is heated to 190°C under stirring. 30 l / h of nitrogen is purged through the mixture and the mixture is maintained at 190°C for 6 hours. After this, 500 ml of NMP is added to cool the mixture. The mixture is allowed to cool to below 60°C under nitrogen. After filtration, 11 g of succinic acid is added to the solution, the solution is stirred for 30 minutes and the polymer solution is precipitated in water. The precipitated product is extracted with hot water (20 hours at 85°C) and dried under reduced pressure at 120°C for 24 hours. The VN of the product is 48.3 ml / g, and the amount of OH end groups is 0.22% by weight (measured by potentiometric titration). This component E is referred to as "component E1" in the examples.

[0177] Component F: Glass fiber, chopped strands with a diameter of 10 μm (length 4.5 mm), and a PU-based sizing. This component F is referred to as "component F1" in the examples.

[0178] Component H: Component H1: Naugard 445.

[0179] Ingredient H2: Sodium hypophosphite.

[0180] Compound Preparation and Testing Compounding was carried out using a twin screw extruder (ZSK30) with barrel temperatures set to maintain a melt temperature below 380°C. Molding of test samples was carried out at a melt temperature of 340°C and a mold temperature of 120°C. Tensile tests were carried out according to ISO 527 (E-modulus, strength, tensile elongation). For some samples, tensile tests were also carried out at 150°C. Impact strength was tested according to ISO 179 1eU and notched impact was tested according to ISO 179 1eA. CTI was measured according to IEC 60112 on samples with a thickness of 4 mm. FR performance was tested according to UL-94 on samples with a thickness of 0.8 mm. Solution viscosity of polyarylene (ether) sulfone was measured using a 0.01 g / ml solution in N-methylpyrrolidone at 25°C.

[0181] [Table 3]

[0182] [Table 4]

[0183] As can be seen from the examples, the compositions according to the invention show a unique combination of good mechanical performance and CTI values ​​and FR behaviour (UL-94). The reference tests show poor FR performance.

Claims

1. below, A) 20 to 80% by weight of at least one polyarylene(ether) sulfone having a maximum of 0.05% by weight of phenolic end groups; B) 10 to 50% by weight of at least one semi-aromatic polyamide; C) 4 to 15% by weight of at least one aluminum phosphinate; D) 0.01 to 2% by weight of at least one acid scavenger; E) 0-10% by weight of at least one compatibilizer; F) 0 to 60% by weight of at least one fibrous or particulate filler; G) 0 to 30% by weight of at least one impact modifier; and H) 0 to 40% by weight of at least one auxiliary; wherein the sum of the weight percent of the components of said composition is 100 weight percent.

2. 2. The composition of claim 1, wherein the at least one polyamide of component B) is selected from the group consisting of PA 9T, PA 4T, PA 6T6I and PA 6T66.

3. 2. The composition of claim 1, wherein the aluminum phosphinate is aluminum diethylphosphinate.

4. 10. The composition of claim 1, wherein the at least one acid scavenger D) is selected from metal salts of phosphonic acids, metal salts of half esters of phosphonic acids, and stannates.

5. 10. The composition of claim 1, wherein the acid scavenger D) is zinc stannate.

6. The composition of claim 1 comprising 20 to 75% by weight of component A).

7. The composition of claim 1 comprising 12.5 to 40% by weight of component B).

8. The composition of claim 1 comprising 4 to 12.5 wt. % of component C).

9. The composition of claim 1 comprising 0.05 to 1.5% by weight of component D).

10. The composition of claim 1 comprising 5 to 50% by weight of component F).

11. 11. Use of a composition according to any one of claims 1 to 10 for the production of fibres, films, foams or moulded articles.

12. 12. The use according to claim 11, wherein the fiber, film, foam or molded article is an electrical or electronic component.

13. A fiber, film or molded article comprising the composition of any one of claims 1 to 10.

14. 14. The fiber, film, foam or molded article of claim 13 which is an electrical or electronic component.