High temperature resistant thermoplastic molding composition containing a thermotropic polymer - Patents.com

Abstract

The present invention relates to a thermoplastic molding composition comprising as components at least one non-sulfonated polyarylene ether sulfone polymer (P), at least one sulfonated polyarylene ether sulfone polymer (sP), at least one fibrous and / or particulate filler and at least one thermotropic polymer. The present invention further relates to a method for producing moldings using said thermoplastic molding composition and to the moldings obtainable by this method.

Description

[Technical field]

[0001] The present invention relates to a thermoplastic molding composition comprising as components at least one non-sulfonated polyarylene ether sulfone polymer (P), at least one sulfonated polyarylene ether sulfone polymer (sP), at least one fibrous and / or particulate filler and at least one thermotropic polymer. The present invention further relates to a method for producing moldings using said thermoplastic molding composition and to the moldings obtainable by this method.

[0002] Polyarylene ether sulfone polymers are high-performance thermoplastics characterized by high heat resistance, good mechanical properties and inherent flame retardancy (EM Koch, H.-M. Walter, Kunststoffe 80 (1990) 1146; E. Doering, Kunststoffe 80, (1990) 1149, N. Inchaurondo-Nehm, Kunststoffe 98, (2008) 190).

[0003] The polyarylene ether sulfone polymers can be formed, inter alia, either by the hydroxide method, in which a salt is first formed from the dihydroxy moiety and a hydroxide, or by the carbonate method.

[0004] General information regarding the formation of polyarylene ether sulfone polymers by the hydroxide method is found, inter alia, in RN Johnson et. al., J. Polym. Sci. A-1 5 (1967) 2375, while the carbonate method is described in JE McGrath et. al., Polymer 25 (1984) 1827.

[0005] Methods for forming polyarylene ether sulfone polymers from aromatic bishalogen compounds and aromatic bisphenols or their salts in aprotic solvents in the presence of one or more alkali metal or ammonium carbonates or bicarbonates are known to those skilled in the art and are described, for example, in EP-A 297 363 and EP-A 135 130.

[0006] High performance thermoplastics, such as polyarylene ether sulfone polymers, are formed by polycondensation reactions that are typically carried out in polar aprotic solvents such as DMF (dimethylformamide), DMAc (dimethylacetamide), sulfolane, DMSO (dimethylsulfoxide) and NMP (N-methylpyrrolidone) at high reaction temperatures.

[0007] For challenging applications, polyarylene ether sulfone polymers are reinforced with fibrous or particulate fillers, especially glass fibers.This usually results in a significant increase in stiffness and strength, but the toughness of such thermoplastic compounds is significantly limited due to the weak interaction of the fibrous or particulate fillers with their polymer matrix.Several approaches are known in the art to functionalize polyarylene ether sulfone polymers for better adhesion to fibrous or particulate fillers.

[0008] EP 855 430 A1 describes the use of polyarylene ether sulfone polymers having carboxylic acid groups as compatibilizers between polyarylene ether sulfone polymers and fibrous or particulate fillers, while EP 2576676 A1 teaches the use of polyarylene ether sulfone polymers having hydroxyl end groups as additives to improve the performance of fiber or filler reinforced polyarylene ether sulfone polymer compounds.

[0009] Due to the high glass transition temperature of the polyarylene ether sulfone polymer, the temperature requirements during processing of such thermoplastic compounds are quite demanding.But also during their use, these articles need to have good thermal stability.There is still a demand for thermoplastic molding compositions with improved mechanical properties and good processing stability, and for moldings made from these thermoplastic molding compositions.

[0010] The object of the present invention is therefore to provide a thermoplastic molding composition which does not retain or only retains the disadvantages of the prior art in a reduced form.The thermoplastic molding composition should be easy to manufacture.Furthermore, the thermoplastic molding composition should be suitable for producing moldings.

[0011] The object of the present invention is to provide a thermoplastic molding composition comprising as components: (I) 25 to 94% by weight of at least one non-sulfonated polyarylene ether sulfone polymer (P); (II) from 1 to 10% by weight of at least one sulfonated polyarylene ether sulfone polymer (sP) having from 1 to 7.5 mol% of sulfonated repeat units containing at least one -SO3Y group, where Y is hydrogen or a cationic equivalent, based on the total amount of said at least one sulfonated polyarylene ether sulfone polymer (sP) contained in the thermoplastic molding composition, (III) 4 to 70% by weight of at least one fibrous and / or particulate filler; (IV) 1 to 10% by weight of at least one thermotropic polymer where each weight percentage is based on the total weight of the thermoplastic molding composition.

[0012] It has been surprisingly found that the thermoplastic molding compositions according to the invention exhibit high temperature resistance and good processability.Moreover, the molded articles produced from these thermoplastic molding compositions exhibit excellent thermal stability, good mechanical properties, good melt stability, and improved appearance after heat aging.Moreover, the molded articles produced from these thermoplastic molding compositions exhibit good tensile properties after annealing and after storage in ATF.

[0013] The invention is described in more detail below.

[0014] Component (I) The thermoplastic molding composition comprises as component (I) at least one non-sulfonated polyarylene ether sulfone polymer (P), where the terms "at least one non-sulfonated aromatic dihalogen sulfone polymer (P)" and "component (I)" are used synonymously and therefore have the same meaning.

[0015] The thermoplastic molding composition comprises 25 to 94% by weight of component (I), based on the total weight of the thermoplastic molding composition.

[0016] The term "at least one non-sulfonated polyarylene ether sulfone polymer (P)" is understood in this case to mean exactly one non-sulfonated polyarylene ether sulfone polymer (P) as well as mixtures of two or more non-sulfonated polyarylene ether sulfone polymers (P).

[0017] In the context of the present invention, "non-sulfonated" means that the non-sulfonated polyarylene ether sulfone polymer (P) does not contain groups resulting from sulfonation of the aromatic dihalogen sulfone contained in the non-sulfonated polyarylene ether sulfone polymer (P). The sulfonation method is known to those skilled in the art. In particular, in the context of the present invention, "non-sulfonated" means that the non-sulfonated polyarylene ether sulfone polymer (P) does not contain any -SO2X group [wherein X is O in combination with OH and one cation equivalent]. -It means that the composition does not contain any of the following:

[0018] In the context of the present invention, "one cation equivalent" refers to one cation with one positive charge or one charge equivalent of a cation with two or more positive charges, e.g. Li + , Na + , K + , Mg 2+ , Ca 2+ or NH4 + means...

[0019] In a preferred embodiment, the thermoplastic molding composition comprises 30 to 88.5% by weight, more preferably 35 to 83.5% by weight and most preferably 40 to 80% by weight of component (I), each based on the total weight of the thermoplastic molding composition.

[0020] The method for producing component (I) is known to those skilled in the art. In a preferred embodiment, component (I) is prepared by reacting a reaction mixture (R 1 ) containing as components (IA1) at least one non-sulfonated aromatic dihalogen sulfone, (IB1) at least one aromatic dihydroxy compound, (IC) at least one carbonate compound, and (ID) at least one aprotic polar solvent. GI ) is converted to

[0021] Another subject of the invention is therefore a thermoplastic molding composition, the component (I) comprising as components: (IA1) at least one non-sulfonated aromatic dihalogen sulfone (IB1) at least one aromatic dihydroxy compound, (IC) at least one carbonate compound; (ID) at least one aprotic polar solvent A reaction mixture (R GI ) is converted to

[0022] The reaction mixture (R GI ) Preferably, the preparation of the non-sulfonated polyarylene ether sulfone polymer (P) comprises, as step I), a reaction mixture (R 1 ) containing the above-mentioned components (IA1), (IB1), (IC) and (ID). GI )

[0023] The components (IA1) and (IB1) participate in a polycondensation reaction.

[0024] Component (ID) acts as a solvent and component (IC) acts as a base to deprotonate component (IB1) during the condensation reaction.

[0025] The reaction mixture (R GI ) is understood to mean the mixture used in the process for producing the non-sulfonated polyarylene ether sulfone polymer (P). GI All details given for the reaction mixture (R GI ) is carried out during the process in which components (IA1) and (IB1) react by polycondensation to obtain the non-sulfonated polyarylene ether sulfone polymer (P), which is the end product. The mixture obtained after the polycondensation, which contains the non-sulfonated polyarylene ether sulfone polymer (P), is called the product mixture (P GI The product mixture (P GI ) usually further comprises at least one aprotic polar solvent (component (ID)) and a halide compound. The halide compound is contained in the reaction mixture (R GI During the conversion, component (IC) first reacts with component (IB1) to deprotonate component (IB1). The deprotonated component (IB1) then reacts with component (IA1), where the halide compound is formed. This method is known to those skilled in the art.

[0026] The reaction mixture (R GIThe components of are preferably reacted simultaneously. The individual components may be mixed in an upstream process and reacted subsequently. It is also possible to feed the individual components into a reactor in which they are mixed and then reacted.

[0027] In the process according to the invention, the reaction mixture (R GI The individual components of (IB1) are preferably reacted simultaneously in step I). The reaction is preferably carried out in one step. This means that the deprotonation of component (IB1) as well as the condensation reaction between components (IA1) and (IB1) are carried out in a single reaction step without isolating intermediate products, such as the deprotonated species of component (IB1).

[0028] The process according to step I) is preferably carried out according to the so-called "carbonate process". The process is preferably not carried out according to the so-called "hydroxide process". This means that the process according to the invention is not carried out in two stages with isolation of the phenolate anion. Therefore, in a preferred embodiment, the reaction mixture (R GI ) is essentially free of sodium hydroxide and potassium hydroxide. More preferably, the reaction mixture (R GI ) is essentially free of alkali metal hydroxides and alkaline earth metal hydroxides.

[0029] The term "essentially free of..." in this case refers to the reaction mixture (R GI ) is added to the reaction mixture (R GI ), less than 100 ppm, preferably less than 50 ppm, of sodium hydroxide and potassium hydroxide, preferably alkali metal hydroxides and alkaline earth metal hydroxides.

[0030] The reaction mixture (R GI It is even more preferred that the reaction mixture (R) does not contain toluene or monochlorobenzene. GI ) is particularly preferably free of any substances which form azeotropes with water.

[0031] The ratio of components (IA1) and (IB1) results in principle from the stoichiometry of the polycondensation reaction, which proceeds with the theoretical elimination of hydrogen chloride, and is established in a manner known to those skilled in the art.

[0032] Preferably, the ratio of halogen end groups originating from component (IA1) to phenolic end groups originating from component (IB1) is adjusted by establishing a controlled excess of component (IB1) relative to component (IA1) as starting compound.

[0033] More preferably, the molar ratio of component (IB1) to component (IA1) is from 0.96 to 1.08, particularly from 0.98 to 1.06, and most preferably from 0.985 to 1.05.

[0034] Preferably, the conversion in the polycondensation reaction is at least 0.9.

[0035] The process step I) for the preparation of the non-sulfonated polyarylene ether sulfone polymer (P) is typically carried out under the conditions of the so-called "carbonate process". GI ) are reacted under the conditions of the so-called "carbonate process". The polycondensation reaction is generally carried out at a temperature in the range of 80 to 250°C, preferably in the range of 100 to 220°C. The upper limit of the temperature is determined by the boiling point of the at least one aprotic polar solvent (component (ID)) at standard pressure (1013.25 mbar). The reaction is generally carried out at standard pressure. The reaction is preferably carried out over a time interval of 0.5 to 12 h, in particular in the range of 1 to 10 h.

[0036] The product mixture (P GI The isolation of the non-sulfonated polyarylene ether sulfone polymer (P) obtained in the process can be carried out, for example, by separating the product mixture (P) in water or a mixture of water and another solvent. GIThe precipitated non-sulfonated polyarylene ether sulfone polymer (P) can then be extracted with water and then dried. In one embodiment of the present invention, the precipitate can also be absorbed in an acidic medium. Suitable acids are, for example, organic or inorganic acids, such as carboxylic acids, for example acetic acid, propionic acid, succinic acid or citric acid, and mineral acids, for example hydrochloric acid, sulfuric acid or phosphoric acid.

[0037] The halide compound is reacted with the product mixture (P GI The halide compounds can be removed by methods commonly known in the art, such as filtration, centrifugation, decantation, and the like.

[0038] Therefore, the present invention relates to a method comprising the steps of: II) The product mixture (P) obtained in step I) GI ) is filtered, centrifuged or decanted. Also provided is a method further comprising the steps of:

[0039] After the polycondensation, in a preferred embodiment, conversion with an aliphatic organohalogen compound is carried out, whereby the reactive hydroxyl groups are end-capped and the polymer is further stabilized.Conversion with an aliphatic organohalogen compound can be carried out before or after the filtration.

[0040] Preferred aliphatic organohalogen compounds are alkyl halides, especially alkyl chlorides, especially primary alkyl chlorides, having a linear or branched alkyl group having 1 to 10 carbon atoms, particularly preferably methyl halides, especially methyl chloride.

[0041] The reaction with the aliphatic organohalogen compound is preferably carried out at a temperature of 90° C. to 160° C., in particular 100° C. to 150° C. The reaction time may vary widely and is usually at least 5 minutes, in particular at least 15 minutes. The reaction time is preferably 15 minutes to 8 hours, in particular 30 minutes to 4 hours.

[0042] Various methods can be used for adding said aliphatic organohalogen compound.The amount of said aliphatic organohalogen compound added can be stoichiometric or excess, and said excess can be, for example, up to 5 times excess.In a preferred embodiment, said aliphatic organohalogen compound is added continuously, particularly by continuously introducing in the form of gas stream.

[0043] Ingredient (IA1) The reaction mixture (R GI ) comprises at least one non-sulfonated aromatic dihalogen sulfone as component (IA1).

[0044] The term "at least one non-sulfonated aromatic dihalogen sulfone" is understood in this case to mean exactly one non-sulfonated aromatic dihalogen sulfone as well as mixtures of two or more non-sulfonated aromatic dihalogen sulfones. In this case, the terms "at least one non-sulfonated aromatic dihalogen sulfone" and "component (IA1)" are used synonymously and therefore have the same meaning.

[0045] Said at least one non-sulfonated aromatic dihalogen sulfone (component (IA1)) is preferably at least one non-sulfonated aromatic dihalogen diphenyl sulfone.

[0046] In the context of the present invention, "non-sulfonated" means that the aromatic dihalogen sulfone does not contain groups resulting from sulfonation of the aromatic dihalogen sulfone. The sulfonation methods are known to those skilled in the art. In particular, in the context of the present invention, "non-sulfonated" means that the aromatic dihalogen sulfone does not contain any -SO2X group, where X is O in combination with OH and one cation equivalent. - It means that the composition does not contain any of the following:

[0047] "One cation equivalent" in the context of the present invention refers to one cation with one positive charge or one charge equivalent of a cation with two or more positive charges, e.g. Li + , Na + , K + , Mg 2+ , Ca 2+ or NH4 + means...

[0048] Component (IA1) is preferably used as a monomer. This is because the reaction mixture (R GI ) means that component (IA1) is preferably contained as a monomer and not as a prepolymer.

[0049] The preferred non-sulfonated aromatic dihalogen sulfone is non-sulfonated 4,4'-dihalogen diphenyl sulfone. Particularly preferred are 4,4'-dichlorodiphenyl sulfone, 4,4'-difluorodiphenyl sulfone and / or 4,4'-dibromodiphenyl sulfone. Particularly preferred are 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone, and most preferred is 4,4'-dichlorodiphenyl sulfone.

[0050] Therefore, another subject of the present invention is also a process, in which component (IA1) is selected from the group consisting of 4,4'-dichlorodiphenylsulfone and 4,4'-difluorodiphenylsulfone.

[0051] Preferably, component (IA1) is present in the reaction mixture (R GI At least 50% by weight, based on the total weight of component (IA1) in the composition (IA1), of at least one non-sulfonated aromatic dihalogen sulfone selected from the group consisting of 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone.

[0052] In a particularly preferred embodiment, component (IA1) is GIBased on the total weight of component (IA1) in the composition (IA1), the composition (IA1) comprises at least 80% by weight, preferably at least 90% by weight, more preferably at least 98% by weight of at least one non-sulfonated aromatic dihalogen sulfone selected from the group consisting of 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone.

[0053] In a further particularly preferred embodiment, component (IA1) consists essentially of at least one non-sulfonated aromatic dihalogen sulfone selected from the group consisting of 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone.

[0054] In a further preferred embodiment, component (IA1) consists of 4,4'-dichlorodiphenylsulfone.

[0055] Ingredients (IB1) The reaction mixture (R GI ) preferably comprises at least one aromatic dihydroxy compound as component (IB1). The term "at least one aromatic dihydroxy compound" is understood in this case to mean exactly one aromatic dihydroxy compound as well as mixtures of two or more aromatic dihydroxy compounds. Preferably, component (IB1) is exactly one aromatic dihydroxy compound or a mixture of exactly two dihydroxy compounds. Most preferably, component (IB1) is exactly one aromatic dihydroxy compound.

[0056] In this case the terms "at least one aromatic dihydroxy compound" and "component (IB1)" are used synonymously and therefore have the same meaning.

[0057] The aromatic dihydroxy compound used is typically a compound having two phenolic hydroxyl groups. GI ) contains at least one carbonate compound, so that the reaction mixture (R GI The hydroxyl groups of component (IB1) in (IB1) may be present in partially deprotonated form.

[0058] Component (IB1) is preferably used as a monomer. This is because the reaction mixture (R GI ) means that component (IB1) is preferably contained as a monomer and not as a prepolymer.

[0059] Suitable aromatic dihydroxyl compounds are, for example, selected from the group consisting of 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl sulfone and bisphenol A (IUPAC name: 4,4'-(propane-2,2-diyl)diphenol).

[0060] In one embodiment of the present invention, the reaction mixture (R GI In another embodiment, the reaction mixture (R GI ) does not contain any hydroquinone.

[0061] Component (IB1) is preferably present in the reaction mixture (R GI Based on the total weight of component (IB1) in (IB1), it comprises at least 50% by weight, more preferably at least 80% by weight, particularly preferably at least 90% by weight and in particular at least 98% by weight of an aromatic dihydroxyl compound selected from the group consisting of 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl sulfone and bisphenol A. 4,4'-dihydroxybiphenyl and 4,4'-dihydroxydiphenyl sulfone are preferred as aromatic dihydroxyl components, with 4,4'-dihydroxybiphenyl being particularly preferred as aromatic dihydroxyl component.

[0062] In a particularly preferred embodiment, component (IB1) consists of 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfone or a mixture of these compounds.

[0063] Ingredients (IC) The reaction mixture (R GI) comprises at least one carbonate compound as component (IC). The term "at least one carbonate compound" is understood in this case to mean exactly one carbonate compound as well as mixtures of two or more carbonate compounds. Said at least one carbonate compound is preferably at least one metal carbonate. The metal carbonate is preferably anhydrous. The terms "at least one carbonate compound" and "component (IC)" are used in this case synonymously and therefore have the same meaning.

[0064] The metal carbonate is preferably an alkali metal carbonate and / or an alkaline earth metal carbonate. At least one metal carbonate selected from the group consisting of sodium carbonate, potassium carbonate and calcium carbonate is particularly preferred as the metal carbonate. Potassium carbonate is most preferred.

[0065] For example, component (IC) may be present in the reaction mixture (R GI %, more preferably at least 70% and most preferably at least 90% by weight of potassium carbonate, based on the total weight of the at least one carbonate component in the composition.

[0066] In a preferred embodiment, component (IC) consists of potassium carbonate. Potassium carbonate having a volume-weighted mean particle size of less than 200 μm is particularly preferred as potassium carbonate. The volume-weighted mean particle size of said potassium carbonate is determined using a particle sizer in a suspension of potassium carbonate in N-methylpyrrolidone. The amount of metal carbonate used, expressed as alkali metal (M) per equivalent hydroxyl group (OH), is preferably in the range of 1.00 to 2.00.

[0067] Ingredient(ID) The reaction mixture (R GI) preferably comprises at least one aprotic polar solvent as component (ID). "At least one aprotic polar solvent" is understood according to the invention to mean exactly one aprotic polar solvent as well as mixtures of two or more aprotic polar solvents. In this case the terms "at least one aprotic polar solvent" and "component (ID)" are used synonymously and therefore have the same meaning.

[0068] Suitable aprotic polar solvents are, for example, selected from the group consisting of anisole, dimethylformamide, dimethylsulfoxide, sulfolane, N-methylpyrrolidone, N-ethylpyrrolidone and N-dimethylacetamide.

[0069] Preferably, component (ID) is selected from the group consisting of N-methylpyrrolidone, N-dimethylacetamide, dimethylsulfoxide and dimethylformamide. N-methylpyrrolidone is particularly preferred as component (ID).

[0070] The component (ID) is added to the reaction mixture (R GI It is preferred that the composition contains at least one solvent selected from the group consisting of N-methylpyrrolidone, N-dimethylacetamide, dimethylsulfoxide and dimethylformamide in an amount of at least 50% by weight, based on the total weight of component (ID) in the composition. N-methylpyrrolidone is particularly preferred as component (ID).

[0071] In a further preferred embodiment, component (ID) consists of N-methylpyrrolidone.

[0072] In a preferred embodiment, component (ID) consists of N-methylpyrrolidone, also called NMP or N-methyl-2-pyrrolidone.

[0073] The non-sulfonated polyarylene ether sulfone polymer (P) used as component (I) preferably has a low polydispersity (Q) and a high glass transition temperature (T gThe non-sulfonated polyarylene ether sulfone polymer (P) further comprises very small amounts of impurities, such as azeotroping agents, such as toluene or chlorobenzene.

[0074] The non-sulfonated polyarylene ether sulfone polymer (P) generally has a polydispersity (Q) of ≦4.5, preferably ≦4.0.

[0075] The polydispersity (Q) is determined by the weight average molecular weight (M W ) and number average molecular weight (M n In a preferred embodiment, the polydispersity (Q) of the non-sulfonated polyarylene ether sulfone polymer (P) is in the range of 2.0 to ≦4.5, preferably in the range of 2.0 to ≦4.0.

[0076] The weight average molecular weight (M W ) and the number average molecular weight (M n ) is measured using gel permeation chromatography.

[0077] The polydispersity (Q) and the average molecular weight of the non-sulfonated polyarylene ether sulfone polymer (P) were measured by gel permeation chromatography (GPC) in dimethylacetamide (DMAc). The mobile phase (eluent) used was DMAc containing 0.5 wt% lithium bromide. The concentration of the polyarylether polymer (P) (P solution) was 4 mg per milliliter of solution. After filtration (pore size 0.2 μm), 100 μl of this solution was injected into the GPC system. Four different columns (heated to 80° C.) were used for the separation (GRAM precolumn, GRAM 30A, GRAM 1000A, GRAM 1000A; separation material: polyester copolymer of PSS). The GPC system was operated at a flow rate of 1 ml per minute. A DRI-Agilent 1100 was used as the detection system. Molecular weight M in the range of 800 to 1,820,000 g / mol n A PMMA standard of PSS with 100% purity was used for its calibration.

[0078] Suitable non-sulfonated polyarylene ether sulfone polymers (P) generally have a weight average molecular weight (M) in the range of 10,000 to 150,000 g / mol, preferably in the range of 15,000 to 120,000 g / mol, particularly preferably in the range of 20,000 to 90,000 g / mol. W The weight average molecular weight (M W ) is measured by gel permeation chromatography (GPC), which is carried out as described above.

[0079] Suitable non-sulfonated polyarylene ether sulfone polymers (P) generally have a glass transition temperature in the range of 185-250°C, preferably in the range of 185-245°C, particularly preferably in the range of 185-240°C.

[0080] Suitable non-sulfonated polyarylene ether sulfone polymers (P) generally have a high glass transition temperature (T g The glass transition temperature (T g The measurements of T were carried out on a DSC 2000 (TA Instruments) at a heating rate of 20 K / min. For the measurements, about 5 mg of the material was sealed in an aluminum crucible. In a first heating pass, the sample was heated to 280° C., then rapidly cooled to −100° C., and then in a second heating pass, heated to 280° C. at 20 K / min. g The value is determined from the second heating run described above.

[0081] In a further preferred embodiment, the thermoplastic molding composition contains at least one non-sulfonated polyarylethersulfone polymer (P) having less than 0.05% by weight of OH end groups, based on the number-average molecular weight (Mn) of the non-sulfonated polyarylethersulfone polymer (P). The amount of OH end groups is determined by potentiometric titration using DMF as solvent.

[0082] Particularly preferred as component (I) are non-sulfonated polyarylene ether polymers (P) selected from the group consisting of polyethersulfone (PESU), polyphenylenesulfone (PPSU) and polysulfone (PSU), with polyethersulfone (PESU) and polyphenylenesulfone (PPSU) being particularly preferred.

[0083] In one embodiment, the thermoplastic molding composition does not include polysulfone (PSU).

[0084] The abbreviations PPSU, PESU and PSU in this case comply with DIN EN ISO 1043-1:2001.

[0085] Component (II) The thermoplastic molding composition comprises as component (II) at least one sulfonated polyarylene ether sulfone polymer (sP), where the terms "at least one sulfonated aromatic dihalogen sulfone polymer (sP)" and "component (II)" are used synonymously and therefore have the same meaning.

[0086] The thermoplastic molding composition comprises 1 to 10% by weight of component (II), based on the total weight of the thermoplastic molding composition.

[0087] The term "at least one sulfonated polyarylene ether sulfone polymer (sP)" is understood in this case to mean exactly one sulfonated polyarylene ether sulfone polymer (sP) as well as mixtures of two or more sulfonated polyarylene ether sulfone polymers (sP).

[0088] The at least one sulfonated polyarylene ether sulfone polymer (sP) comprises 1 to 7.5 mol % of sulfonated repeat units containing at least one -SOY group, where Y is hydrogen or a cation equivalent, based on the total amount of the at least one sulfonated polyarylene ether sulfone polymer (sP) contained in the thermoplastic molding composition.

[0089] The total amount of said at least one sulfonated polyarylene ether sulfone polymer (sP) in the context of the present invention preferably means the total amount of repeat units and end groups contained in said at least one sulfonated polyarylene ether sulfone polymer (sP).

[0090] In the context of the present invention, "sulfonated" means that the sulfonated polyarylene ether sulfone polymer (sP) contains groups resulting from the sulfonation of aromatic dihalogen sulfone. The sulfonation of aromatic dihalogen sulfone is known to those skilled in the art. In particular, "sulfonated" means that the sulfonated polyarylene ether sulfone polymer (sP) contains sulfonated repeating units, hereinafter also referred to as sulfonated repeating units, that contain at least one -SO3Y group, where Y is hydrogen or a cation equivalent.

[0091] In the context of the present invention, a "cation equivalent" refers to a cation with one positive charge or one charge equivalent of a cation with two or more positive charges, e.g. Li + , Na + , K + , Mg 2+ , Ca 2+ , NH4 + , preferably Na + , K + means...

[0092] In the context of the present invention, "at least one -SO3Y group" means exactly one -SO3Y group as well as two or more -SO3Y groups. Preference is given to exactly two -SO3Y groups. This means that the sulfonated repeat unit contained in the at least one sulfonated polyarylene ether sulfone polymer (sP) preferably contains two -SO3Y groups.

[0093] In a preferred embodiment, the thermoplastic molding composition comprises from 1.5 to 9% by weight, more preferably from 2 to 8.5% by weight and most preferably from 2.5 to 8% by weight of component (II), each based on the total weight of the thermoplastic molding composition.

[0094] Methods for the preparation of component (II) are known to those skilled in the art. In a preferred embodiment, component (II) is prepared by reacting a reaction mixture (R 1 ) containing as components (IIA1) at least one non-sulfonated aromatic dihalogen sulfone, (IIA2) at least one sulfonated aromatic dihalogen sulfone, (IIB1) at least one aromatic dihydroxy compound, (IIC) at least one carbonate compound, and (IID) at least one aprotic polar solvent. GII ) is converted to

[0095] Another subject of the invention is therefore a thermoplastic molding composition, the component (II) being (IIA1) The reaction mixture (R GII 90 to 99 mol % of at least one non-sulfonated aromatic dihalogen sulfone, based on the sum of the mol % of components (IIA1) and (IIA2) contained in (IIA2) The reaction mixture (R GII 1 to 10 mol %, based on the sum of the mol % of components (IIA1) and (IIA2) contained in the above, of at least one sulfonated aromatic dihalogen sulfone containing at least one -SOY group, where Y is hydrogen or a cation equivalent, (IIB1) at least one aromatic dihydroxy compound, (IIC) at least one carbonate compound; (IID) at least one aprotic polar solvent A reaction mixture (R GII ) is converted to

[0096] The reaction mixture (R GII ) Preferably, the sulfonated polyarylene ether sulfone polymer (sP) is prepared by reacting, as step I), a reaction mixture (R 1 ) containing the above-mentioned components (IIA1), (IIA2), (IIB1), (IIC) and (IID). GII )

[0097] The components (IIA1), (IIA2) and (IIB1) participate in a polycondensation reaction.

[0098] Component (IID) acts as a solvent and component (IIC) acts as a base to deprotonate component (IIB1) during the condensation reaction.

[0099] The reaction mixture (R GII ) is understood to mean the mixture used in the process for producing the sulfonated polyarylene ether sulfone polymer (sP). GII All details given for the reaction mixture (R GII ) is carried out during the process of reacting components (IIA1), (IIA2) and (IIB1) by polycondensation to obtain the sulfonated polyarylene ether sulfone polymer (sP) as the end product. The mixture obtained after the polycondensation containing the sulfonated polyarylene ether sulfone polymer (sP) end product is called product mixture (P GII The product mixture (P GII The reaction mixture (R ) usually further comprises at least one aprotic polar solvent (component (IID)) and a halide compound. The halide compound is GII During the conversion, component (IIC) first reacts with component (IIB1) to deprotonate component (IIB1). The deprotonated component (IIB1) then reacts with components (IIA1) and (IIA2), where the halide compound is formed. This method is known to those skilled in the art.

[0100] The reaction mixture (R GIIThe components of are preferably reacted simultaneously. The individual components may be mixed in an upstream process and reacted subsequently. It is also possible to feed the individual components into a reactor in which they are mixed and then reacted.

[0101] In the process according to the invention, the reaction mixture (R GII Said individual components of (IIB1) are preferably reacted simultaneously in step I). This reaction is preferably carried out in one step. This means that the deprotonation of component (IIB1) and the condensation reaction between components (IIA1), (IIA2) and (IIB1) are carried out in a single reaction step without isolating the intermediate products thereof, e.g. the deprotonated species of component (IIB1).

[0102] The process according to step I) is preferably carried out according to the so-called "carbonate process". The process is preferably not carried out according to the so-called "hydroxide process". This means that the process according to the invention is not carried out in two stages with isolation of the phenolate anion. Therefore, in a preferred embodiment, the reaction mixture (R GII ) is essentially free of sodium hydroxide and potassium hydroxide. More preferably, the reaction mixture (R GII ) is essentially free of alkali metal hydroxides and alkaline earth metal hydroxides.

[0103] The term "essentially free of..." in this case refers to the reaction mixture (R GI ) is added to the reaction mixture (R GII ), less than 100 ppm, preferably less than 50 ppm, of sodium hydroxide and potassium hydroxide, preferably alkali metal hydroxides and alkaline earth metal hydroxides.

[0104] The reaction mixture (R GII It is further preferred that the reaction mixture (R) does not contain toluene or monochlorobenzene. GII ) is particularly preferably free of any substances which form azeotropes with water.

[0105] The ratio of components (IIA1), (IIA2) and (IIB1) essentially follows from the stoichiometry of the polycondensation reaction, which proceeds with the theoretical elimination of hydrogen chloride, and is established in a manner known to those skilled in the art.

[0106] Preferably, the ratio of halogen end groups originating from components (IIA1) and (IIA2) to phenolic end groups originating from component (IIB1) is adjusted by establishing a controlled excess of component (IIB1) relative to components (IIA1) and (IIA2) as starting compounds.

[0107] More preferably, the molar ratio of component (IIB1) to components (IIA1) and (IIA2) is from 0.96 to 1.08, particularly from 0.98 to 1.06, and most preferably from 0.985 to 1.05.

[0108] For example, the reaction mixture (RGII) contains 0.9 to 0.99 mol of component (IIA1) and 0.01 to 0.1 mol of component (IIA2) per 1 mol of component (IIB1).

[0109] Preferably, the conversion in the polycondensation reaction is at least 0.9.

[0110] The process step I) for the preparation of the non-sulfonated polyarylene ether sulfone polymer (P) is typically carried out under the conditions of the so-called "carbonate process". GII ) are reacted under the conditions of the so-called "carbonate process". The polycondensation reaction is generally carried out at a temperature in the range of 80 to 250°C, preferably in the range of 100 to 220°C. The upper limit of the temperature is determined by the boiling point of the at least one aprotic polar solvent (component (IID)) at standard pressure (1013.25 mbar). The reaction is generally carried out at standard pressure. The reaction is preferably carried out over a time interval of 0.5 to 12 h, in particular in the range of 1 to 10 h.

[0111] The product mixture (P GII The isolation of the sulfonated polyarylene ether sulfone polymer (sP) obtained in the process can be carried out, for example, by separating the product mixture (P) in water or a mixture of water with another solvent. GII The sulfonated polyarylene ether sulfone polymer (sP) precipitated can be subsequently extracted with water and then dried. In one embodiment of the present invention, the precipitate can also be absorbed in an acidic medium. Suitable acids are, for example, organic or inorganic acids, such as carboxylic acids, for example acetic acid, propionic acid, succinic acid or citric acid, and mineral acids, for example hydrochloric acid, sulfuric acid or phosphoric acid.

[0112] The halide compound is reacted with the product mixture (P GII The halide compounds can be removed by methods commonly known in the art, such as filtration, centrifugation, decantation, and the like.

[0113] Therefore, the present invention relates to a method further comprising: II) The product mixture (P) obtained in step I) GII Filtration, centrifugation or decantation of A method is also provided, including:

[0114] Component (IIA1) The reaction mixture (R GII ) comprises at least one non-sulfonated aromatic dihalogen sulfone as component (IIA1).

[0115] The term "at least one non-sulfonated aromatic dihalogen sulfone" is understood in this case to mean exactly one non-sulfonated aromatic dihalogen sulfone as well as mixtures of two or more non-sulfonated aromatic dihalogen sulfones. In this case, the terms "at least one non-sulfonated aromatic dihalogen sulfone" and "component (IIA1)" are used synonymously and therefore have the same meaning.

[0116] The reaction mixture (RGII ) is the reaction mixture (RG II Preferably, the reaction mixture (R) contains 90 to 99 mol % of at least one non-sulfonated aromatic dihalogen sulfone as component (IIA1), based on the total mol % of components (IIA1) and (IIA2) contained in the reaction mixture (R). GII ) is reacted with the reaction mixture (R GII Based on the total mol % of components (IIA1) and (IIA2) contained in the copolymer (IIA1), the copolymer contains 93 to 98.5 mol % and most preferably 93.5 to 98 mol % of at least one non-sulfonated aromatic dihalogen sulfone as component (IIA1).

[0117] The above statements and preferences regarding component (IIA1) apply accordingly regarding component (IA1). Components (IIA1) and (IA1) may be the same or different. In one embodiment, component (IIA1) is the same as (IA1). In another embodiment, component (IIA1) is different from (IA1).

[0118] Ingredients (IIA2) In this case, the terms "at least one non-sulfonated aromatic dihalogen sulfone" and "component (IIA1)" are used synonymously and therefore have the same meaning.

[0119] The reaction mixture (R GII ) is preferably added to said reaction mixture (RG II Preferably, the reaction mixture (R) contains 1 to 10 mol % of component (IIA2) of at least one sulfonated aromatic dihalogen sulfone, based on the sum of the mol % of components (IIA1) and (IIA2) contained in the reaction mixture (R). GII ) is reacted with the reaction mixture (R GII Based on the total mol % of components (IIA1) and (IIA2) contained in the copolymer (IIA1), the copolymer contains 1.5 to 7 mol % and most preferably 2 to 6.5 mol % of at least one sulfonated aromatic dihalogen sulfone as component (IIA2).

[0120] The term "at least one sulfonated aromatic dihalogen sulfone" is in this case understood to mean exactly one sulfonated aromatic dihalogen sulfone as well as mixtures of two or more sulfonated aromatic dihalogen sulfones.

[0121] In the context of the present invention, "sulfonated" means that the sulfonated aromatic dihalogen sulfone contains at least one group resulting from the sulfonation of the aromatic dihalogen sulfone. The sulfonation of aromatic dihalogen sulfone is known to those skilled in the art. In particular, "sulfonated" means that the aromatic dihalogen sulfone contains at least one -SOY group, where Y is hydrogen or a cation equivalent.

[0122] In the context of the present invention, a "cation equivalent" refers to a cation with one positive charge or one charge equivalent of a cation with two or more positive charges, e.g. Li + , Na + , K + , Mg 2+ , Ca 2+ , NH4 + , preferably Na + , K + means...

[0123] "At least one -SO3Y group" in the context of the present invention means exactly one -SO3Y group as well as two or more -SO3Y groups. Preference is given to exactly two -SO3Y groups. This means that said at least one sulfonated aromatic dihalogen sulfone is preferably at least one disulfonated aromatic halogen sulfone.

[0124] The reaction mixture (R GII The sum of the mol% of components (IIA1) and (IIA2) contained in (IIA1) is usually 100 mol%.

[0125] Component (IIA2) is, based on the total weight of component (IIA2), 4,4′-dichlorodiphenylsulfone-3,3′-disulfonic acid, 4,4′-difluorodiphenylsulfone-3,3′-disulfonic acid, 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid disodium salt, 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt, 4,4'-Difluorodiphenylsulfone-3,3'-disulfonic acid disodium salt, and 4,4'-Difluorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt It is preferred that the composition contains at least 50% by weight of at least one sulfonated aromatic dihalogen sulfone selected from the group consisting of:

[0126] In a particularly preferred embodiment, component (IIA2) is GII %, preferably at least 90% by weight, more preferably at least 98% by weight, of at least one sulfonated aromatic dihalogen sulfone selected from the group consisting of 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid, 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid, 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid disodium salt, 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt, 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid disodium salt, and 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt, respectively, based on the total weight of component (IIA2) in (IIA3).

[0127] Component (IIA2) is, based on the total weight of component (IIA2), 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid disodium salt, 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt, 4,4'-Difluorodiphenylsulfone-3,3'-disulfonic acid disodium salt, and 4,4'-Difluorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt Even more preferably, the composition comprises at least 50% by weight of at least one sulfonated aromatic dihalogen sulfone selected from the group consisting of:

[0128] In an even more particularly preferred embodiment, component (IIA2) is GII %, preferably at least 90% by weight, more preferably at least 98% by weight, based on the total weight of component (IIA2) in the composition (IIA3), of at least one sulfonated aromatic dihalogen sulfone selected from the group consisting of 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid disodium salt, 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt, 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid disodium salt, and 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid dipotassium salt.

[0129] The terms "sulfonic acid" and "-SO3Y group" in relation to component (IIA2) are used synonymously and have the same meaning. Thus, the term "sulfonic acid" in 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid and 4,4'-difluorodiphenylsulfone-3,3'-disulfonic acid means "-SO3Y group" where Y is hydrogen or a cation equivalent.

[0130] 4,4'-Dichlorodiphenylsulfone-3,3'-disulfonic acid and 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid disodium salt are particularly preferred as component (IIA2), with 4,4'-dichlorodiphenylsulfone-3,3'-disulfonic acid disodium salt being more preferred.

[0131] Ingredients (IIC) The reaction mixture (R GII) comprises at least one carbonate compound as component (IIC). The term "at least one carbonate compound" is understood in this case to mean exactly one carbonate compound as well as mixtures of two or more carbonate compounds. Said at least one carbonate compound is preferably at least one metal carbonate. The metal carbonate is preferably anhydrous. The terms "at least one carbonate compound" and "component (IIC)" are used in this case synonymously and therefore have the same meaning.

[0132] The statements and preferences made above in view of component (IIC) apply accordingly in view of component (IC). Components (IIC) and (IC) may be the same or different. In one embodiment, component (IIC) is the same as (IC). In another embodiment, component (IIC) is different from (IC). It is preferred that the amount of metal carbonate used, expressed as alkali metal (M) per equivalent hydroxyl group (OH), is preferably in the range of 1.00 to 2.00.

[0133] Ingredient(IID) The reaction mixture (R GII ) preferably comprises at least one aprotic polar solvent as component (IID). "At least one aprotic polar solvent" is understood according to the invention to mean exactly one aprotic polar solvent as well as mixtures of two or more aprotic polar solvents. In this case the terms "at least one aprotic polar solvent" and "component (IID)" are used synonymously and therefore have the same meaning.

[0134] The statements and preferences made above in view of component (IID) apply accordingly in view of component (ID). Components (IID) and (ID) may be the same or different. In one embodiment, component (IID) is the same as (ID). In another embodiment, component (IID) is different from (ID).

[0135] The sulfonated polyarylene ether sulfone polymer (sP) used as component (II) preferably has a low polydispersity (Q) and a high glass transition temperature (T g The sulfonated polyarylene ether sulfone polymer (sP) further comprises very small amounts of impurities, such as azeotroping agents, such as toluene or chlorobenzene.

[0136] The sulfonated polyarylene ether sulfone polymer (sP) generally has a polydispersity (Q) of ≦4.5, preferably ≦4.0.

[0137] The polydispersity (Q) is determined by the weight average molecular weight (M W ) and number average molecular weight (M n In a preferred embodiment, the polydispersity (Q) of the sulfonated polyarylene ether sulfone polymer (sP) is in the range of 2.0 to ≦4.5, preferably in the range of 2.0 to ≦4.0.

[0138] The weight average molecular weight (M W ) and the number average molecular weight (M n ) is measured by gel permeation chromatography as described above for component (I).

[0139] Suitable sulfonated polyarylene ether sulfone polymers (sP) generally have a weight average molecular weight (M) in the range of 10,000 to 150,000 g / mol, preferably in the range of 15,000 to 120,000 g / mol, particularly preferably in the range of 20,000 to 90,000 g / mol. W The weight average molecular weight (M W ) is measured by gel permeation chromatography (GPC), which is carried out as described above.

[0140] Suitable sulfonated polyarylene ether sulfone polymers (sP) generally have a glass transition temperature in the range of 185 to 255°C, preferably in the range of 185 to 250°C, particularly preferably in the range of 185 to 245°C.

[0141] Particularly preferred as component (I) are sulfonated polyarylene ether polymers (P) selected from the group consisting of sulfonated polyethersulfone (sPESU), sulfonated polyphenylenesulfone (sPPSU) and sulfonated polysulfone (sPSU), with sulfonated polyethersulfone (sPESU) and sulfonated polyphenylenesulfone (sPPSU) being particularly preferred.

[0142] In one embodiment, the thermoplastic molding composition does not include sulfonated polysulfone (sPSU).

[0143] The abbreviations PPSU, PESU and PSU in this case comply with DIN EN ISO 1043-1:2001.

[0144] Ingredient (III) The thermoplastic molding composition comprises at least one fibrous and / or particulate filler as component (III), where the terms "at least one fibrous and / or particulate filler" and "component (III)" are used synonymously and therefore have the same meaning.

[0145] The thermoplastic molding composition contains 4 to 70% by weight of component (III), based on the total weight of the thermoplastic molding composition.

[0146] The term "at least one fibrous and / or particulate filler" is understood in this case to mean precisely one type of at least one fibrous and / or particulate filler as well as mixtures of two or more types of at least one fibrous and / or particulate filler.

[0147] In a preferred embodiment, the thermoplastic molding composition comprises 8.5 to 60% by weight, more preferably 12.5 to 50% by weight and most preferably 15 to 45% by weight of component (III), each based on the total weight of the thermoplastic molding composition.

[0148] In a preferred embodiment, the thermoplastic molding composition comprises as component (III) at least one fibrous filler selected from the group consisting of carbon fibers, potassium titanate whiskers, aramid fibers and glass fibers and / or at least one particulate filler selected from the group consisting of amorphous silica, magnesium carbonate, chalk, powdered quartz, mica, clay, muscovite, biotite, szolite, tinmaretite, talc, chlorite, phlogopite, feldspar, wollastonite and kaolin.

[0149] Component (IV) The thermoplastic molding composition comprises, as component (IV), at least one thermotropic polymer. In this case, the terms "at least one thermotropic polymer" and "component (IV)" are used synonymously and therefore have the same meaning.

[0150] The thermoplastic molding composition contains 1 to 10% by weight of component (IV), based on the total weight of the thermoplastic molding composition.

[0151] The term "at least one thermotropic polymer" is understood in this case to mean exactly one thermotropic polymer as well as mixtures of two or more thermotropic polymers.

[0152] According to the invention, the thermoplastic molding composition comprises as component (IV) at least one, but preferably one, thermotropic polymer.

[0153] In a preferred embodiment, the thermoplastic molding composition comprises from 1.5 to 9% by weight, more preferably from 2 to 8% by weight and most preferably from 2.5 to 7.5% by weight of component (IV), each based on the total weight of the thermoplastic molding composition.

[0154] The expression "thermotropic polymer" in this case means a polymer that has liquid crystal properties within a defined temperature range. Particularly suitable thermotropic polymers are those that are liquid crystal in the temperature range in which the thermoplastic molding composition of the invention is processed.

[0155] The transition temperature T of the liquid crystal phase in the melt of a thermotropic polymer suitable as component (IV) k The transition temperature T of the preferred liquid crystal polymer (thermotropic polymer) that can be used as component (IV) is generally 350° C. or less. k The transition temperature T is preferably 340° C. or less. The preferred thermotropic polymers have a transition temperature T k It has the following characteristics.

[0156] The transition temperature T k can be determined by differential scanning calorimetry (DSC) measurements using a heating rate of 20 K / min, where the T k The value is determined in a second heating procedure.

[0157] The thermotropic polymer that can be used as component (IV) is preferably at least one selected from the group consisting of thermotropic polyesters, thermotropic polyesteramides, thermotropic polyamides and thermotropic polyesterimides.

[0158] The term "thermotropic polyester" in this case means thermotropic polyesters as well as thermotropic copolyesters. Thermotropic polyesters and / or thermotropic copolyesters are particularly preferred as component (IV), with wholly aromatic thermotropic polyesters and / or wholly aromatic thermotropic copolyesters being particularly preferred as component (IV).

[0159] Suitable thermotropic polyesters are, for example, derived from one or more of the following monomer units: p-hydroxybenzoic acid, m-hydroxybenzoic acid, terephthalic acid, isophthalic acid, hydroxyquinone, phenylhydroquinone, alkyl-substituted hydroquinones, in particular 2-methylhydroquinone, 2-ethylhydroquinone, 2-n-propylhydroquinone, 2-isopropylhydroquinone, 2-tert-butylhydroquinone, halogen-substituted 2-n-hydroquinones, in particular 2-chlorohydroquinone.

[0160] Other examples of monomers suitable for the preparation of the thermotropic polyesters are 4,4'-dihydroxydiphenyl ether, 1,3-dihydroxybenzene, 4,4'-biphenol, 2,6,2',6'-tetramethylbiphenol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,6-naphthalenedicarboxylic acid, 6-hydroxy-2-naphthalenecarboxylic acid, 4,4'-bis(p-hydroxyphenoxy)diphenylsulfone, 2,6-dihydroxyanthraquinone, 4,4'-diphenyletherdicarboxylic acid, and 4,4'-dihydroxybenzophenone. Particularly suitable compounds are p-acetoxybenzoic acid and 2,6-acetoxynaphthalenecarboxylic acid, as well as hydroxy compounds activated by esterification.

[0161] Equally suitable are thermotropic polyesters derived from the abovementioned dicarboxylic acids and aliphatic or cycloaliphatic polyols, preferably diols. Diols which can be used are compounds of formula (ii): H.O.R. 8 -OH formula (ii).

[0162] R 8 Here, C2-C in substituted or unsubstituted form. 18 -Alkylene units, preferably C2-C 10 R represents an alkylene unit. Examples of suitable units are ethylene, propylene, butylene, pentylene, and hexylene. It is particularly preferred that each of the two hydroxy groups is bonded to the first or last carbon atom.8 may further be an unsubstituted or substituted alicyclic moiety having 3 to 13 carbon atoms, preferably 5 to 8 carbon atoms, such as cyclopropylene, cyclopentylene, or cyclohexylene. Preferred diols are ethylene glycol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanedimethanol.

[0163] As component (IV), thermotropic polyesters are particularly preferably derived from 4-hydroxybenzoic acid and / or 6-hydroxy-2-naphthoic acid and optionally further monomers.

[0164] Particularly preferred thermoplastic molding compositions comprise, as component (IV), the structures (ia) and / or (ib) [ka] wherein thermotropic polyesters having repeat units of structures (ia) and (ib) are especially preferred.

[0165] Preferably, said at least one thermotropic polyester is composed of at least 50 mol %, more preferably at least 75 mol %, even more preferably at least 85 mol %, and most preferably at least 95 mol %, of repeat units of structures (ia) and (ib), based on the total amount of said at least one thermotropic polyester.

[0166] The thermotropic polyester generally contains 10 to 90 mol % of the unit (ia) and 10 to 90 mol % of the unit (ib) and optionally 0 to 30 mol % of one or more further repeating units.

[0167] The thermoplastic molding composition in particular comprises, as component (IV), at least one thermotropic polymer composed of 10 to 90 mol % of units (ia) and 10 to 90 mol % of units (ib), the sum of the molar proportions being 100 mol %, based on the thermotropic polymer.

[0168] Thermotropic polyesteramides may also be used as component (IV), where these comprise repeat units of structure (iii) alone and / or in combination with repeat units of formulae (ia) and / or (ib). [ka]

[0169] The part L is hydrogen, C1-C 10 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, or n-butyl, preferably methyl, C1-C 10 -alkoxy, for example methoxy, ethoxy, n-propoxy, isopropoxy or n-butoxy, preferably methoxy, or halogen, preferably chlorine.

[0170] The molar mass Mw (weight average) of the at least one thermotropic polymer used in the present invention as component (IV) is generally between 1500 and 150000 g / mol, preferably between 2500 and 50000 g / mol. Mw can be determined by light scattering at 25° C. in a solution of phenol and ortho-dichlorobenzene in a 1:1 ratio. The HDT A heat distortion temperature of the above thermotropic polymers measured according to DIN ISO 75-1 (method A, outer fiber stress σ f 1.80N / mm 2 The temperature rise rate (constant temperature rise rate: 120 K / h) may be 140 to 220°C.

[0171] This type of liquid crystal polymer is known per se or can be produced by known methods.Suitable production methods are described, for example, in US-A-4 161 470.Other production methods can be found, for example, in EP-A-139 303, EP-A-226 839, EP-A-226 978, EP-A-225 539, EP-A-226 847 and EP-A-257 558.

[0172] Component (V) In one embodiment, the thermoplastic molding composition can comprise at least one additive as component (V), which further component (V) is typically present in the range of 0 to 40% by weight, preferably in the range of 0 to 30% by weight and particularly preferably in the range of 0 to 20% by weight, each based on the total weight of the thermoplastic molding composition.

[0173] Component (V) is preferably at least one additive selected from the group consisting of processing aids, pigments, stabilizers, flame retardants, impact modifiers or mixtures thereof. Common materials that can be utilized are, for example, heat stabilizers, UV stabilizers, lubricants, pigments and dyes. Component (V) can be present in an amount of 0 to 40% by weight, preferably 0 to 25% by weight, each based on the total weight of the thermoplastic molding composition.

[0174] The pigments are usually used in an amount of 0-6% by weight, preferably 0-5% by weight. Pigments for coloring thermoplastic materials are generally known and can be found in R. Gaechter and H. Mueller, Taschenbuch der Kunststoffadditive, Carl Hanser Verlag. As preferred pigments, zinc oxide or titanium oxide can be used. Furthermore, carbon black can be applied as a pigment (see G. Benzing, "Pigmente fuer Anstrichmittel", Expert Verlag (1988) p.78). To produce other colors, chromium-based or organic pigments can be utilized.

[0175] As heat stabilizers well known additives such as sterically hindered phenols or secondary amines can be utilized. For UV protection benzotriazoles, benzophenones or other known UV stabilizers can be applied.

[0176] As lubricants or release agents, stearyl alcohol, stearic acid, stearic acid esters or amides or esters of pentaerythritol can be used. Preferably, stearic acid can be used.

[0177] The skilled artisan knows the methods for the preparation of said thermoplastic molding compositions, which are generally prepared by mixing the components (I), (II) and (III), (IV) and optionally (V).

[0178] For the preparation of the thermoplastic molding composition, the components can be, for example, dry blended or compounded in the molten state in a compounding unit. Preferably, the components for the preparation of the thermoplastic molding composition are compounded in an extruder, preferably a twin-screw extruder. The temperature of the molten resin in the barrel is preferably kept below 400°C, more preferably below 380°C.

[0179] The present invention is further illustrated by the following examples, which should not be construed as limiting the invention. EXAMPLES

[0180] Ingredients Used Component I Ingredient I1 As component I1, a polyethersulfone (PESU) was used having a viscosity number of 49.0 ml / g. The product used contained 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 wt%).

[0181] Component I2 Polyphenylene sulfone (PPSU) having a viscosity number of 59.0 ml / g was used as component I2. The amount of OH end groups was below the detection limit (<0.02 wt%).

[0182] Component II Ingredient II1 The preparation of sulfonated PESU (sPESU) was carried out according to the following procedure: In a 4 l HWS vessel equipped with stirrer, Dean-Stark trap, nitrogen inlet and temperature control, 562.83 g (1.960 mol) of 4,4'-dichlorodiphenylsulfone (DCDPS), 24.56 g (0.05 mol) of disodium 3,3'-disulfonate-4,4'-dichlorodiphenylsulfone (sDCDPS), 500.34 g (2.00 mol) of 4,4'-dihydroxydiphenylsulfone (DHDPS) and 304.062 g (2.20 mol) of potassium carbonate (particle size 39.3 μm) are suspended in 1050 ml of NMP under nitrogen atmosphere. The mixture is heated to 190° C. with stirring. The mixture is purged with 30 l / h of nitrogen and the mixture is held at 190° C. for 9 h. After this time, 1950 ml of NMP is added and the mixture is cooled. The mixture is cooled under nitrogen to below 60° C. After filtration, the polymer solution is precipitated in water. The precipitated product is extracted with hot water (85° C. for 20 h) and dried under reduced pressure at 120° C. for 24 h.

[0183] The viscosity number (VN) of the product was 62.0 ml / g, and the amount of incorporated sDCDPS units was 2 mol% ( 1 H-NMR).

[0184] Ingredient II2 In a 4 l HWS vessel equipped with stirrer, Dean-Stark trap, nitrogen inlet and temperature control, 545.60 g (1.90 mol) of 4,4'-dichlorodiphenylsulfone (DCDPS), 49.12 g (0.10 mol) of disodium 3,3'-disulfonate-4,4'-dichlorodiphenylsulfone (sDCDPS), 500.34 g (2.00 mol) of 4,4'-dihydroxydiphenylsulfone (DHDPS) and 304.062 g (2.20 mol) of potassium carbonate (particle size 39.3 μm) are suspended in 1050 ml of NMP under nitrogen atmosphere. The mixture is heated to 190° C. with stirring. The mixture is purged with 30 l / h of nitrogen and the mixture is held at 190° C. for 9.5 h. After this time, 1950 ml of NMP is added and the mixture is cooled. The mixture is cooled under nitrogen to below 60° C. After filtration, the polymer solution is precipitated in water. The precipitated product is extracted with hot water (85° C. for 20 h) and dried under reduced pressure at 120° C. for 24 h.

[0185] The VN of the product was 64.1 ml / g, and the amount of incorporated sDCDPS units was 3.9 mol% ( 1 H-NMR).

[0186] Component II3 The preparation of sulfonated PPSU (sPPSU) was carried out according to the following procedure: In a 4 liter HWS vessel equipped with stirrer, Dean-Stark trap, nitrogen inlet and temperature control, 516.88 g (1.80 mol) of 4,4'-dichlorodiphenylsulfone (DCDPS), 98.25 g (0.20 mol) of disodium 3,3'-disulfonate-4,4'-dichlorodiphenylsulfone (sDCDPS), 372.42 g (2.00 mol) of 4,4'-dihydroxybiphenyl (DHBP) and 304.06 g (2.20 mol) of potassium carbonate (particle size 37.5 μm) are suspended in 1250 ml of NMP under nitrogen atmosphere. The mixture is heated to 190° C. with stirring. The mixture is purged with 30 l / h of nitrogen and the mixture is held at 190° C. for 6 h. After this time, 1750 ml of NMP is added to cool the mixture. The mixture is cooled to below 60° C. under nitrogen 6. After filtration, the polymer solution is precipitated in water, the precipitated product is extracted with hot water (85° C. for 20 h) and dried under reduced pressure at 120° C. for 24 h.

[0187] The VN of the product was 63.4 ml / g, and the amount of sDCDPS-based units was 6.5 mol% ( 1 (Determined by H-NMR).

[0188] Ingredient II4 The preparation of sulfonated PPSU (sPPSU) was carried out according to the following procedure: In a 4 l HWS vessel equipped with stirrer, Dean-Stark trap, nitrogen inlet and temperature control, 574.34 g (2.00 mol) of 4,4'-dichlorodiphenylsulfone (DCDPS), 24.56 g (0.05 mol) of disodium 3,3'-disulfonate-4,4'-dichlorodiphenylsulfone (sDCDPS), 372.42 g (2.00 mol) of 4,4'-dihydroxybiphenyl (DHBP) and 293.0 g (2.12 mol) of potassium carbonate (particle size 37.5 μm) are suspended in 1250 ml of NMP under nitrogen atmosphere. The mixture is heated to 190° C. with stirring. The mixture is purged with 30 l / h of nitrogen and the mixture is held at 190° C. for 6 h. After this time, 1750 ml of NMP is added to cool the mixture. The mixture is cooled to below 60° C. under nitrogen. After filtration, the polymer solution is precipitated in water, the precipitated product is extracted with hot water (85° C. for 20 h) and dried under reduced pressure at 120° C. for 24 h.

[0189] The VN of the product was 75.4 ml / g, and the amount of sDCDPS-based units was 1.9 mol% ( 1 (Determined by H-NMR).

[0190] Ingredient IIV1 The preparation of sulfonated PPSU (sPPSU) was carried out according to the following procedure: In a 4 liter HWS vessel equipped with stirrer, Dean-Stark trap, nitrogen inlet and temperature control, 488.19 g (1.70 mol) of 4,4'-dichlorodiphenylsulfone (DCDPS), 148.56 g (0.30 mol) of disodium 3,3'-disulfonate-4,4'-dichlorodiphenylsulfone (sDCDPS), 372.42 g (2.00 mol) of 4,4'-dihydroxybiphenyl (DHBP) and 317.88 g (2.30 mol) of potassium carbonate (particle size 37.5 μm) are suspended in 1250 ml of NMP under nitrogen atmosphere. The mixture is heated to 190° C. with stirring. The mixture is purged with 30 l / h of nitrogen and the mixture is held at 190° C. for 7.5 h. After this time, 1750 ml of NMP is added and the mixture is cooled. The mixture is cooled under nitrogen to below 60° C. After filtration, the polymer solution 7 is precipitated in water. The precipitated product is extracted with hot water (85° C. for 20 h) and dried under reduced pressure at 120° C. for 24 h.

[0191] The VN of the product was 61.1 ml / g, and the amount of sDCDPS-based units was 11.2 mol% ( 1 (Determined by H-NMR).

[0192] Ingredient IIV2 The preparation of OH-terminated PESU (PESU-OH) was carried out according to the following procedure: In a 4 l 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. with stirring. The mixture is purged with 30 l / h of nitrogen and the mixture is held at 190° C. for 6 h. After this time, 500 ml of NMP is added to cool the mixture. The mixture is cooled to below 60° C. under nitrogen. After filtration, the polymer solution is precipitated in water. The precipitated product is extracted with hot water (85° C. for 20 h) and dried under reduced pressure at 120° C. for 24 h.

[0193] The VN of the product was 48.3 ml / g and the amount of OH end groups was 0.22 wt. % (determined by potentiometric titration).

[0194] Ingredient IIV3 The preparation of carboxyl-functionalized PPSU (PPSU-co DPA) according to EP 855430 was carried out according to the following procedure: In a 4 l HWS vessel equipped with stirrer, Dean-Stark trap, nitrogen inlet and temperature control, 585.81 g (2.04 mol) of 4,4'-dichlorodiphenylsulfone (DCDPS), 42.95 g (0.15 mol) of diphenoxyvaleric acid (DPA), 344.49 g (1.70 mol) of 4,4'-dihydroxybiphenyl (DHDP) and 310.97 g (2.25 mol) of potassium carbonate (particle size 39.3 μm) are suspended in 1538 ml of NMP under nitrogen atmosphere. The mixture is heated to 190° C. with stirring. The mixture is purged with 30 l / h of nitrogen and the mixture is held at 190° C. for 6 h. After this time, 1462 ml of NMP are added to cool the mixture. The mixture is cooled to below 60° C. under nitrogen. After filtration, the polymer solution is precipitated in water. The precipitated product is extracted with hot water (85° C. for 20 h) and dried under reduced pressure at 120° C. for 24 h.

[0195] The VN of the product was 48.3 ml / g, and the amount of DPA-based units was 6.2 mol% ( 1 (Determined by H-NMR).

[0196] Component III Glass fibre, chopped strands (length 4.5 mm) with a diameter of 10 μm and a PU based sizing.

[0197] Component IV As component (IV) a thermotropic polyester is used having repeat units of the formulae ia and ib (defined above) and characterized by a modulus of elasticity of 7.8 GPa and a HDT A heat distortion temperature of 187° C., measured according to DIN ISO 75-1.

[0198] The viscosity number (VN) is preferably determined using an Ubbelohde viscometer at a concentration of 1 g polymer in 100 ml NMP at 25°C.

[0199] The amount of OH end groups is determined by potentiometric titration using DMF as the solvent.

[0200] Preparation / Testing of the Thermoplastic Molding Composition Compounding was carried out using a twin-screw extruder (ZSK 18) and the barrel temperatures were set to keep the melt temperature below 400° C. The molding of the test samples was carried out at a melt temperature of 350° C. and a mold temperature of 140° C. Tensile tests were carried out according to ISO 527 (modulus, strength, tensile elongation).

[0201] The impact strength was tested according to ISO 179 1eU. The melt flow of the products was tested according to ISO 1133 at a melt temperature of 360° C. and a load of 10 kg.

[0202] The tensile test pieces were stored at 200°C for 500h and then subjected to tensile tests.

[0203] Tensile test specimens were stored in ATF (Shell Donax, pour point -48°C) at 150°C for 500h, and then tensile tests were performed.

[0204] The content of units derived from the sulfonated monomer (sDCDPS) and DPA is 1 Determined by H-NMR.

[0205] Table 1: [Table 1]

[0206] Table 2: [Table 2]

[0207] The thermoplastic molding compositions according to the invention exhibit excellent mechanical performance and surprisingly the best retention of tensile properties after storage in ATF and after long annealing.

Claims

1. A thermoplastic molding composition comprising, as components, (I) 25 to 94% by weight of at least one non-sulfonated polyarylene ether sulfone polymer (P), (II) 1 to 10% by weight of at least one sulfonated polyarylene ether sulfone polymer (sP), having at least one -SO ３ Y group [where Y is hydrogen or a cation equivalent] in the at least one sulfonated polyarylene ether sulfone polymer (sP) contained in the thermoplastic molding composition, based on the total amount of the at least one sulfonated polyarylene ether sulfone polymer (sP), having 1 to 7.5 mol%, at least one sulfonated polyarylene ether sulfone polymer (sP), (III) 4 to 70% by weight of at least one fibrous and / or particulate filler, (IV) 1 to 10% by weight of at least one thermotropic polymer wherein the % by weight values are each based on the total weight of the thermoplastic molding composition, the HDTA heat distortion temperature of component (IV) according to DIN ISO 75-1 is 140 to 220 °C, component (IV) is at least one thermotropic polymer selected from the group consisting of thermotropic polyesters, thermotropic polyester amides, thermotropic polyamides and thermotropic polyester imides, and component (IV) is at least one thermotropic polymer comprising at least 50 mol% of repeating units of structure (ia) and / or (ib) 【Chemical 1】 based on the total amount of the at least one thermotropic polymer described above. The thermoplastic molding composition as described above.

2. The thermoplastic molding composition according to claim 1, wherein component (IV) is at least one thermotropic polymer composed of 10 to 90 mol% of the unit (ia) and 10 to 90 mol% of the unit (ib), where the sum of the molar ratios is 100 mol% based on the thermotropic polymer described above.

3. Component (I) comprises, as components, (IA1) at least one non-sulfonated aromatic dihalogen sulfone (IB1) at least one aromatic dihydroxy compound, (IC) at least one carbonate compound, (ID) at least one aprotic polar solvent A reaction mixture (R ＧＩ ) is converted by a method comprising the step of producing the thermoplastic molding composition according to claim 1.

4. Component (II) is the reaction mixture (R ＧＩＩ ), which, as components, (IIA1) Based on the total mol% of components (IIA1) and (IIA2) contained in the reaction mixture (R ＧＩＩ ), 90 to 99 mol% of at least one non-sulfonated aromatic dihalogen sulfone, (IIA2) Based on the total mol% of components (IIA1) and (IIA2) contained in the reaction mixture (R ＧＩＩ ), 1 to 10 mol% of at least one -SO ３ Y group [where Y is hydrogen or a cation equivalent] of at least one sulfonated aromatic dihalogen sulfone, (IIB1) at least one aromatic dihydroxy compound, (IIC) at least one carbonate compound, (IID) at least one aprotic polar solvent The thermoplastic molding composition according to claim 1, produced by a method comprising a step of converting a reaction mixture (R ＧＩＩ ).

5. Component (IA1) is at least 50% by weight, based on the total weight of the component (IA1) contained in the reaction mixture (R ＧＩ ), of one or more non-sulfonated aromatic dihalogen sulfones selected from the group consisting of 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone. The thermoplastic molding composition according to claim 3.

6. The component (IIA1) is at least 50% by weight, based on the total weight of the component (IIA1) contained in the reaction mixture (R ＧＩＩ ), of one or more non-sulfonated aromatic dihalogen sulfones selected from the group consisting of 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone, the thermoplastic molding composition according to claim 4.

7. Component (IIA2) is at least 50% by weight, based on the total weight of the component (IIA2) contained in the reaction mixture (R ＧＩＩ ), of one or more sulfonated aromatic dihalogen sulfones selected from the group consisting of disulfonated 4,4'-dichlorodiphenyl sulfone and disulfonated 4,4'-difluorodiphenyl sulfone. The thermoplastic molding composition according to claim 4.

8. Component (IB1) is at least 50% by weight, based on the total weight of component (IB1) contained in the reaction mixture (R ＧＩ ), of one or more aromatic dihydroxy compounds selected from the group consisting of 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl and bisphenol A. The thermoplastic molding composition according to claim 3.

9. Component (IIB1) is at least 50% by weight, based on the total weight of the component (IIB1) contained in the reaction mixture (R ＧＩＩ ), of one or more aromatic dihydroxy compounds selected from the group consisting of 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl and bisphenol A. The thermoplastic molding composition according to claim 4.

10. The thermoplastic molding composition according to claim 1, wherein component (III) is at least one fibrous filler selected from the group consisting of carbon fiber, potassium titanate whisker, aramid fiber, and glass fiber and / or at least one particulate filler selected from the group consisting of amorphous silica, magnesium carbonate, chalk, powdered quartz, mica, clay, muscovite, biotite, szolayite, susmaretite, talc, chlorite, phlogopite, feldspar, wollastonite, and kaolin.

11. The thermoplastic molding composition according to claim 1, wherein in component (II), Y is a cation equivalent.

12. A method for producing a molded article, using the thermoplastic molding composition according to any one of claims 1 to 11.

13. A molded article obtained by the method according to claim 12.

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