DE10149870A1 - Molding composition based on polyarylene ether sulfone and thermoplastic polyamide, used for making film, fiber or molding, e.g. for vehicle component, contains polyarylene ether sulfone modified with trifunctional compound and anhydride - Google Patents

Abstract

Molding composition contains: (A) polyarylene ether sulfone; (B) thermoplastic polyamide; (C) polyarylene ether sulfone with 0.01-10 wt.% units derived from compound with \- 3 hydroxyl or halogen substituents linked directly to aromatic ring and substitutable under polyarylene ether sulfone synthesis conditions and also anhydride groups; (D) filler; (E) impact-modifying rubber; and (F) additives. Molding composition contains: (A) 1-98.5 wt.% polyarylene ether sulfone; (B) 1-98.5 wt.% thermoplastic polyamide; (C) 0.5-30 wt.% polyarylene ether sulfone with 0.01-10 wt.% units derived from compound with \- 3 hydroxyl or halogen substituents linked directly to aromatic ring and substitutable under polyarylene ether sulfone synthesis conditions and also anhydride groups; (D) 0-60 wt.% filler; (E) 0-40 wt.% impact-modifying rubber; and (F) 0-40 wt.% additives. Independent claims are also included for the following: (1) Production of the molding compositions by mixing components A to F; (2) Moldings, films or fibers made from the molding compositions.

Description

• A) 1 bis 98.5 Gew.-% mindestens eines Polyarylenethersulfons,
• B) 1 bis 98,5 Gew.-% mindestens eines thermoplastischen Polyamids,
• C) 0,5 bis 30 Gew.-% mindestens eines Polyarylenethersulfons,
  enthaltend 0.01 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Komponente C, sich von einer Verbindung X ableitende Einheiten, wobei Verbindung X drei oder mehr als drei Hydroxy- oder Halogensubstituenten enthält, welche unabhängig voneinander direkt an einen aromatischen Ring gebunden und unter den Bedingungen der Polyarylenethersulfonsynthese substituierbar sind,
  und weiterhin enthaltend Anhydridendgruppen,
• D) 0 bis 60 Gew.-% mindestens eines Füllstoffs,
• E) 0 bis 40 Gew.-% mindestens eines schlagzähmodifizierenden Kautschuks und
• F) 0 bis 40 Gew.-% eines oder mehrerer unterschiedlicher Zusatzstoffe,

enthalten, wobei die Gewichtsprozente der Komponenten A bis F zusammen 100% ergeben. The present invention relates to molding compositions which

• A) 1 to 98.5% by weight of at least one polyarylene ether sulfone,
• B) 1 to 98.5% by weight of at least one thermoplastic polyamide,
• C) 0.5 to 30% by weight of at least one polyarylene ether sulfone,
  containing 0.01 to 10% by weight, based on the total weight of component C, of units derived from a compound X, compound X containing three or more than three hydroxyl or halogen substituents which are independently bonded directly to an aromatic ring and under the conditions of polyarylene ether sulfone synthesis are substitutable,
  and further containing anhydride end groups,
• D) 0 to 60% by weight of at least one filler,
• E) 0 to 40% by weight of at least one impact-modifying rubber and
• F) 0 to 40% by weight of one or more different additives,

included, the weight percentages of components A to F together making 100%.

In addition, the present invention relates to methods for Production of these molding compounds, the use of these molding compounds for the production of molded parts, foils or fibers as well Moldings, films and fibers from the molding compositions according to the invention.

Molding compounds based on polyarylene ether sulfones and Polyamides are well known (for example from DE-A 21 22 735, DE-A1 41 21 705, EP-A 477 757). Such molding compounds have usually improved over pure polyarylene ether sulfones Flow properties due to the intolerance of The toughness of these is polyarylene ether sulfones and polyamides However, molding compositions are unsatisfactory.

Molding compounds with improved compatibility of Polyarylene ether sulfones and polyamides and a higher resulting Toughness has also been described. These molding compounds contain polyarylene ether sulfones with anhydride end groups as Compatibility mediators, for example via ester groups (see EP-A1 613 916) or via oxygen atoms (see WO 97/04018) the polyarylene ether sulfone chain are linked.

A disadvantage of these molding compositions is that they are relatively large Amount of anhydride-terminated polyarylene ether sulfones as Tolerance mediators must be used, which on the one hand leads to higher costs and on the other hand to corrosion problems on the Shaping tools for the processing of these Molding compounds can lead to high temperatures.

The present invention was based on the object thermoplastic molding compositions based on polyarylene ether sulfones and To provide polyamides that are known to the Molding compounds with significantly reduced proportions of Anhydride end groups as a compatibilizer a comparably good one Compatibility of polyarylene ether sulfone and polyamide and thus have a comparably good toughness, or at comparable high proportions of anhydride end groups Compatibility promoters compared to the known molding compounds improved compatibility of polyarylene ether sulfone and Polyamide and thus have improved toughness.

This task is performed by the molding compounds defined at the outset are described in more detail below.

Component A

The molding compositions according to the invention contain component A in Amounts from 1 to 98.5, in particular from 5 to 94% by weight, and particularly preferably from 10 to 88% by weight, based on the Total weight from A to F.

According to the invention, component A is a polyarylene ether sulfone used. Mixtures of two or more can also be used different polyarylene ether sulfones as component A be used.

The arylene groups of the polyarylene ether sulfones A can be the same or different and independently of one another represent an aromatic radical having 6 to 18 carbon atoms. Examples of suitable arylene radicals are phenylene, bisphenylene, terphenylene, 1,5-naphthylene, 1,6-naphthylene, 1,5-anthrylene, 9,10-anthrylene or 2,6-anthrylene. Among them, 1,4-phenylene and 4,4'-biphenylene are preferred. These aromatic radicals are preferably not substituted. However, you can carry one or more substituents. Suitable substituents are, for example, alkyl, arylalkyl, aryl, nitro, cyano or alkoxy groups and heteroaromatics such as pyridine and halogen atoms. The preferred substituents include alkyl radicals with up to 10 carbon atoms such as methyl, ethyl, i-propyl, n-hexyl, i-hexyl, C ₁ - to C ₁₀ -alkoxy radicals such as methoxy, ethoxy, n-propoxy, n-butoxy, aryl radicals with up to 20 carbon atoms such as phenyl or naphthyl as well as fluorine and chlorine.

Furthermore, substituents are preferred which are obtained by reacting the polyarylene ether sulfones with a reactive compound which, in addition to a CC double or triple bond, contains one or more carbonyl, carboxylic acid, carboxylate, acid anhydride, acid amide, acid imide, carboxylic acid ester, Contains amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl groups. The arylene groups of the polyarylene ether sulfones can in addition to -SO ₂ -, for. B. via -O-, -S-, -SO-, -CO-, -N = N-, -COO-, an alkylene radical, which can be substituted if desired, or a chemical bond can be linked.

Preferred polyarylene ether sulfones (component A) which can be used according to the invention are composed of recurring units of the formula I.


wherein
t and q independently of one another represent 0, 1, 2 or 3,
Q, T, and Z each independently represent a chemical bond or a group selected from -O-, -S-, -SO ₂ -, S = O, C = O, -N = N-, -R ^a C = CR ^b - and -CR ^c R ^d -, mean, where
R ^a and R ^b each independently represent a hydrogen atom or a C ₁ -C ₁₂ alkyl group and
R ^c and R ^d each independently represent a hydrogen atom or a C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy or C ₆ -C ₁₈ aryl group, where R ^c and R ^d if they are are an alkyl, alkoxy or aryl group, can be substituted independently of one another by fluorine and / or chlorine atoms or where R ^c and R ^d together with the carbon atom to which they are attached form a C ₃ -C ₁₂ -cycloalkyl group which can be substituted by one or more C ₁ -C ₆ alkyl groups,
with the proviso that at least one of the groups T, Q and Z stands for -SO ₂ - and, if t and q stand for 0, Z stands for -SO ₂ -,
Ar and Ar ¹ each independently represent a C ₆ -C ₁₈ arylene group, these being substituted by C ₁ -C ₁₂ alkyl, C ₆ -C ₁₈ aryl, C ₁ -C ₁₂ alkoxy groups or halogen atoms can.

Different units of the formula I can also be used statistically or distributed in blocks in the polyarylene ether sulfone.

The polyarylene ether sulfones A are preferably linear. The Polyarylene ether sulfones A can also chain-branching units included by installing connections with three or more than three functional groups under the conditions of polyarylene ether sulfone synthesis are formed (for a more detailed description of the branching units and the production of branched polyarylene ether sulfones hereby to the following description of components C, C 'and Connection X referenced).

The preparation of polyarylene ether sulfones A which can be used according to the invention, for example by condensation of aromatic bishalogen compounds and the alkali double salts of aromatic bisphenols, can be carried out, for example, in accordance with GB 1 152 035 and US 4,870,153, to which reference is expressly made here. Suitable process conditions for the synthesis of polyarylene ether sulfones are described, for example, in EP-A-0 113 112 and EP-A-0 135 130. The reaction of the monomers in aprotic polar solvents in the presence of anhydrous alkali carbonate is particularly suitable. A particularly preferred combination is N-methylpyrrolidone as a solvent and potassium carbonate as a catalyst. The reaction in the melt is also preferred. Examples of suitable polyarylene ether sulfones A are those having at least one of the following recurring structural units I ₁ to I ₁₅ :

Particularly preferred units of the formula I are units of the formulas I ₁ and I ₂ which can be present individually or in a mixture.

Depending on the synthesis conditions, the polyarylene ether sulfones have different functional groups. These functional Groups can be bound to atoms of the polymer chain or as End groups of the polymer chain are present.

These functional groups include halogen, in particular Chlorine, alkoxy, especially methoxy or ethoxy, aryloxy, preferably phenoxy or benzyloxy groups. As further examples of such functional groups are hydroxyl, amino, epoxy or To name carboxyl groups. These include polyarylene ether sulfones with amino or epoxy end groups or mixtures thereof prefers.

The preparation of polyarylene ether sulfones A containing Functional groups are in DE-A1 199 61 040 and those mentioned therein Literature described.

The polyarylene ether sulfones A can also be copolymers or block copolymers in which polyarylene ether sulfone segments and segments of other thermoplastic polymers, such as polyesters, aromatic Polycarbonates, polyester carbonates, polysiloxanes, polyimides or polyetherimides are present. The molecular weights (Number average) of the block or graft arms in the copolymers are in usually in the range of 1000 to 30 000 g / mol. The blocks different structure can alternate or statistically be arranged. The weight fraction of the polyarylene ether sulfones in the copolymers or block copolymers is generally at least 10% by weight. The weight fraction of the polyarylene ether sulfones can be up to to be 97% by weight. Copolymers or block copolymers are preferred with a weight fraction of polyarylene ether sulfones with up to 90% by weight. Copolymers or block copolymers are particularly preferred with 20 to 80 wt .-% polyarylene ether sulfones.

In general, the polyarylene ether sulfones A have average molecular weights M _n (number average) in the range from 5000 to 60,000 g / mol and relative viscosities from 0.20 to 0.95 dl / g. Depending on the solubility of the polyarylene ether sulfones, the relative viscosities are measured either in 1% strength by weight N-methylpyrrolidone solution, in mixtures of phenol and dichlorobenzene or in 96% strength sulfuric acid at 20 ° C. or 25 ° C. in each case.

Component B

The molding compositions according to the invention contain component B in Quantities from 1 to 98.5, in particular from 5 to 94% by weight, particularly preferably from 10 to 88% by weight, based on the Total weight from A to F.

According to the invention, component B is one or more thermoplastic polyamides used that have a viscosity number of 80 to 350, particularly preferably 120 to 350, in particular 150 to 240 ml / g (measured in 0.5% by weight solution in 96% by weight Have sulfuric acid according to DIN 53 727).

Suitable polyamides can be used as semicrystalline or amorphous resins with a molecular weight M _w (weight average) of at least 5,000, as z. For example, U.S. Patents 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,312,966, 2,512,606, and 3,393,210 are available.

Examples of this are polyamides, which differ from lactams with 7 to Derive 13 ring members, such as polycaprolactam, polycapryllactam and polylaurin lactam and polyamides, which are produced by the reaction of Dicarboxylic acids can be obtained with diamines.

Polyamides B can e.g. B. by condensation of equimolar amounts a saturated or an aromatic dicarboxylic acid with 4 to 16 carbon atoms with a saturated or aromatic Diamine, which has up to 16 carbon atoms, or by Condensation of ω-aminocarboxylic acids or polyaddition of corresponding lactams are produced.

Polyamides suitable according to the invention are also aliphatic (Co) polyamides.

As dicarboxylic acids of aliphatic polyamides are in particular Alkanedicarboxylic acids with 6 to 12, in particular 6 to 10 Suitable for carbon atoms. Here are only adipic acid, suberic acid, Azelaic acid, sebacic acid and dodecanedioic acid than in question coming acids called.

Suitable diamines of aliphatic polyamides are preferred Alkanediamines with 4 to 12, in particular 4 to 8 Carbon atoms, e.g. B. 1,4-butanediamine, 1,5-pentanediamine or piperazine, and as cyclic diamines, for example Di- (4-aminocyclohexyl) methane or 2,2-di- (4-aminocyclohexyl) propane.

Coming as polyamide-forming monomers for aliphatic polyamides of course also aminocarboxylic acids or the corresponding Lactams with e.g. B. 6 to 13 carbon atoms. Suitable monomers of this type are, for example, caprolactam, Capryllactam, enanthlactam, ω-aminoundecanoic acid or Laurolactam.

Examples of preferred aliphatic polyamides are Polyhexamethylene adipamide (nylon 66), Polyhexamethylene azelaic acid amide (nylon 69), polyhexamethylene sebacic acid amide (nylon 610), Polyhexamethylene dodecanedioic acid amide (Nylon 612), which by Ring opening of lactam obtained polyamides such as Polycaprolactam, polylauric acid lactam, also poly-11-aminoundecanoic acid and a polyamide made from di (p-aminocyclohexyl) methane and dodecanedioic acid and copolyamides 6/66, in particular with a proportion of 5 to 95% by weight of caprolactam units.

In addition, polyamides should also be mentioned, which, for. B. by Condensation of 1,4-diaminobutane with adipic acid with increased Temperature are available (polyamide 4.6). production method for polyamides of this structure, e.g. B. in EP-A 38 094, EP-A 38 582 and EP-A 39 524.

Furthermore, polyamides which are obtained by copolymerization of two or several of the aforementioned monomers are available, or Mixtures of several polyamides are suitable, the Mixing ratio is arbitrary.

In a preferred embodiment of the invention, partially aromatic polyamides are used. These can by copolycondensation of z. B. adipic acid, isophthalic acid and / or terephthalic acid with hexamethylenediamine or of caprolactam, terephthalic acid with hexamethylenediamine. Such partially aromatic copolyamides preferably contain, as component b _1, 20 to 90% by weight of units which are derived from terephthalic acid and hexamethylenediamine. A small proportion of the terephthalic acid, preferably not more than 10% by weight of the total aromatic dicarboxylic acids used, can be replaced by isophthalic acid or other aromatic dicarboxylic acids, preferably those in which the carboxyl groups are in the para position.

In addition to the units derived from terephthalic acid and hexamethylene diamine, the partially aromatic copolyamides may contain units derived from s-caprolactam (b ₂ ) and / or units derived from adipic acid and hexamethylene diamine (b ₃ ).

The proportion of units b ₂ derived from ε-caprolactam is usually 10 to 80% by weight, preferably 20 to 50% by weight, in particular 25 to 40% by weight, while the proportion of units which differ Derive adipic acid and hexamethylenediamine b ₃ , up to 70 wt .-%, preferably 30 to 60 wt .-% and in particular 35 to 55 wt .-%. The sum of the percentages by weight of components b ₁ to b ₃ always amounts to 100.

In the case of copolyamides, both units of ε-caprolactam and Contain units of adipic acid and hexamethylenediamine ensure that the proportion of units that are free of aromatic groups, is at least 10% by weight, preferably at least 20% by weight. The ratio of units that from ε-caprolactam and from adipic acid and hexamethylenediamine derive is not subject to any particular restriction.

• 1. b'₁) 30 bis 44, vorzugsweise 32 bis 40 und insbesondere 32 bis 38 mol-% Einheiten, welche sich von Terephthalsäure ableiten,
• 2. b'₂) 6 bis 20, vorzugsweise 10 bis 18 und insbesondere 12 bis 18 mol-% Einheiten, welche sich von Isophthalsäure ableiten,
• 3. b'₃) 43 bis 49,5, vorzugsweise 46 bis 48,5 und insbesondere 46,3 bis 48,2 mol-% Einheiten, welche sich von Hexamethylendiamin ableiten,
• 4. b'₄) 0,5 bis 7, vorzugsweise 1,5 bis 4 und insbesondere 1,8 bis 3,7 mol-% Einheiten, welche sich von aliphatischen cyclischen Diaminen mit 6 bis 30, vorzugsweise 13 bis 29 und insbesondere 13 bis 17 C-Atomen ableiten,

wobei die Molprozente der Komponenten b'₁ bis b'₄ zusammen 100% ergeben. In a further embodiment, component B is composed of 40 to 100, preferably 50 to 100 and in particular 70 to 100% by weight, based on the total weight of component B, of a partially aromatic partially crystalline thermoplastic polyamide which is composed of

• 1. b ' ₁ ) 30 to 44, preferably 32 to 40 and in particular 32 to 38 mol% of units which are derived from terephthalic acid,
• 2. b ' ₂ ) 6 to 20, preferably 10 to 18 and in particular 12 to 18 mol% of units which are derived from isophthalic acid,
• 3. b ' ₃ ) 43 to 49.5, preferably 46 to 48.5 and in particular 46.3 to 48.2 mol% of units which are derived from hexamethylenediamine,
• 4. b ' ₄ ) 0.5 to 7, preferably 1.5 to 4 and in particular 1.8 to 3.7 mol% of units which differ from aliphatic cyclic diamines with 6 to 30, preferably 13 to 29 and in particular 13 derive up to 17 carbon atoms,

wherein the molar percentages of components b ' ₁ to b' ₄ together give 100%.

The diamine units b ' ₃ and b' ₄ are preferably reacted equimolar with the dicarboxylic acid units b ' ₁ and b' ₂ .

Suitable monomers b ' ₄ are preferably cyclic diamines of the formula (II)


in the
R ^{1 is} hydrogen or a C ₁ -C ₄ alkyl group,
R ^{2 is} a C ₁ -C ₄ alkyl group or hydrogen and
R ^{3 represents} a C ₁ -C ₄ alkyl group or hydrogen.

Preferred diamines b ' ₄ are bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) 2,2'-propane and bis (4-amino-3-methylcyclohexyl ) -2,2-propane.

1,3- and 1,4-Cyclohexanediamine and isophoronediamine may be mentioned as further monomers b ' ₄ .

In addition to the units b ' ₁ to b' ₄ described above, the partially aromatic copolyamides B can contain up to 4, preferably up to 3.5% by weight, based on B, of further polyamide-forming monomers b ' ₅ , such as those of other polyamides are known.

Aromatic dicarboxylic acids which have 8 to 16 carbon atoms are suitable as further polyamide-forming monomers b ' ₅ . Suitable aromatic dicarboxylic acids are, for example, substituted terephthalic and isophthalic acids such as 3-t-butylisophthalic acid, polynuclear dicarboxylic acids, e.g. B. 4,4'- and 3,3'-diphenyldicarboxylic acid, 4,4'- and 3,3'-diphenylmethane dicarboxylic acid, 4,4'- and 3,3'-diphenylsulfone dicarboxylic acid, 1,4- or 2,6- Naphthalenedicarboxylic acid and phenoxy terephthalic acid.

Further polyamide-forming monomers b ' ₅ can be derived from dicarboxylic acids with 4 to 16 carbon atoms and aliphatic diamines with 4 to 16 carbon atoms and from aminocarboxylic acids or corresponding lactams with 7 to 12 carbon atoms. Suitable monomers of these types here are only suberic acid, azelaic acid or sebacic acid as representatives of the aliphatic dicarboxylic acids, 1,4-butanediamine, 1,5-pentanediamine or piperazine, as representatives of the diamines and caprolactam, capryllactam, enanthlactam, ω-aminoundecanoic acid and laurolactam Representatives of lactams or aminocarboxylic acids called.

Semi-aromatic copolyamides B with triamine contents less than 0.5, preferably less than 0.3 wt .-% are preferred.

Copolyamides with a low triamine content show the same Solution viscosity lower melt viscosities in comparison to products of the same composition that have a higher Have triamine content. This improves both Processability as well as the product properties considerably.

The melting points of the partially aromatic copolyamides are usually in the range from 200 ° C to 340 ° C, preferably from 250 to 330 ° C, this melting point with a high Glass transition temperature of usually 100 ° C or more, especially more than 130 ° C (when dry) is connected.

Semi-aromatic copolyamides B are generally notable for Degrees of crystallinity> 30%, preferably> 35%, and in particular > 40% off.

The degree of crystallinity is a measure of the proportion of crystalline fragments in the copolyamide and is crystallized by X-ray diffraction or indirectly by measuring ΔH _. certainly.

Of course, mixtures of different can partly aromatic copolyamides and mixtures of aliphatic and partially aromatic (co) polyamides are used, the Mixing ratio is arbitrary.

Suitable processes for the preparation of the polyamides B are Known specialist.

The batch process is the preferred method of production (discontinuous production method) called. The watery Monomer solution in 0.5 to 3 h in an autoclave Temperatures of 280-340 ° C heated, a pressure of 10-50, in particular 15-40 bar is achieved by relaxing excess water vapor kept as constant as possible for up to 2 h becomes. Then you relax the autoclave at constant Temperature within a period of 0.5-2 h until one has reached a final pressure of 1 to 5 bar. Then the Polymer melt discharged, cooled and granulated.

Another method is based on the methods described in EP-A 129 195 and 129 196. Then z. B. for the production of partially aromatic copolyamides an aqueous solution of the monomers b ' ₁ ) to b' ₄ ) and optionally b ' ₅ ) with a monomer content of 30 to 70, preferably 40 to 65 wt .-% under increased pressure (1 to 10 bar) and with simultaneous evaporation of water and formation of a prepolymer heated to a temperature of 280 to 330 ° C within less than 60 s, then prepolymers and steam are continuously separated, the steam rectified and the entrained diamines returned. Finally, the prepolymer is passed into a polycondensation zone and under an excess pressure of 1 to 10 bar and a temperature of 280 to 330 ° C. with a residence time of 5-30 min. polycondensed. It goes without saying that the temperature in the reactor is above the melting point of the prepolymer formed at the respective water vapor pressure.

Due to these short dwell times, the formation of triamines largely prevented.

The polyamide prepolymer obtained in the manner mentioned, which in usually a viscosity number of 40 to 70 ml / g, preferably of 40 to 60 ml / g, measured on a 0.5 wt .-% solution in 96% sulfuric acid at 25 ° C, is continuously out taken from the condensation zone.

It is advantageous to melt through the polyamide prepolymer a discharge zone with simultaneous removal of the in the Discharge melt contained residual water. suitable Discharge zones are, for example, degassing extruders. The one from the water freed melt can then be poured into strands and granulated become.

This granulate is in the solid phase under inert gas continuously or discontinuously at a temperature below the Melting point, e.g. B. from 170 to 240 ° C, to the desired Viscosity condenses. For the discontinuous Solid phase condensation can e.g. B. tumble dryer, for continuous Solid-phase condensation with hot inert gas through tempered tubes be used. Continuous is preferred Solid phase condensation, with nitrogen or in particular as the inert gas superheated steam, advantageously that at the top of the column resulting water vapor is used.

In a further embodiment, it is also possible Components A, C, D, E and / or F already in the degassing extruder for To give prepolymers of component B, in which case the Degassing extruder usually with suitable mixing elements, like kneading blocks. Then you can also extruded, chilled and granulated as a strand.

Component C

The molding compositions according to the invention contain component C in Quantities from 0.5 to 30, in particular from 1 to 25% by weight, particularly preferably from 2 to 20% by weight, based on the total weight from A to F.

As component C of the molding compositions according to the invention branched polyarylene ether sulfones containing anhydride end groups used. Polyarylene ether sulfones C are from the already at Component A described structural units, where Component C, however, 0.01 to 10 wt .-%, preferably 0.05 to 7.5% by weight, particularly preferably 0.1 to 6.0% by weight, very particularly preferably 0.2 to 2.5% by weight, based in each case on the Total weight of component C, derived from a compound X. Contains units, wherein compound X three or more than three Contains hydroxy or halogen substituents, which are independent directly bound to one another by an aromatic ring and among the Conditions of polyarylene ether sulfone synthesis substitutable are, and wherein component C further anhydride end groups contains.

Examples of compounds X of the type of the aromatic compound containing three or more than three hydroxyl groups for the preparation of the polyarylene ether sulfones are:
Phloroglucin (= 1,3,5-trihydroxybenzene), 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2 (= trimeric isopropenylphenol), 4,6-dimethyl-2,4 , 6-tri- (4-hydroxyphenyl) -heptane (= hydrogenated trimeric isopropenylphenol), 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tris (4-hydroxyphenyl) -ethane and propane, tetra- (4-hydroxyphenyl) methane, 1,4-bis - [(4 ', 4 "-dihydroxytriphenyl) methyl] -benzene and 2,2-bis- [4,4'-bis- ( 4-hydroxyphenyl) cyclohexyl] propane are particularly suitable tri- or more than trihydric phenols which can be prepared by reacting p-alkyl-substituted monophenols with unsubstituted o-positions with compounds providing formaldehyde or formaldehyde, such as, for example, the trisphenol from p -Cresol and formaldehyde, the 2,6-bis- (2'-hydroxy-5'-methyl-benzyl) -4-methylphenol, and the following may also be mentioned: 2,6-bis- (2'-hydroxy-5 ' -isopropyl-benzyl) -4-isopropenylphenol and bis- [2-hydroxy-3- (2'-hydroxy-5'-methylbenzyl-5-methylphenyl] methane.

Component C preferably contains 1,1,1-tris (4-hydroxyphenyl) ethane as compound X-deriving units.

As a further trihydric or more than trihydric phenols, those are suitable which have halogen atoms in addition to the phenolic hydroxyl groups, e.g. B. the halogen-containing trihydroxyaryl ethers of the formula III


wherein Ar ^{2 is} a mono- or polynuclear, divalent aromatic radical and Hal is chlorine or bromine. Examples of such connections are:
1,3,5-tris (4-hydroxyphenoxy) -2,4,6-trichlorobenzene, 1,3,5-tris [4- (4-hydroxyphenylisopropyl) phenoxy] -2, 4,6-trichlorobenzene, 1,3,5-tris- [4- (4-hydroxy) biphenoxy] -2,4,6-trichlorobenzene, 1,3,5-tris- [4- (4-hydroxy- phenylsulfonyl) phenoxy] -2,4,6-trichlorobenzene and
1,3,5-tris [4- (4-hydroxy-phenyl-isopropyl) -phenoxy] -2,4,6-tribromobenzene,
the manufacture of which is described in German Offenlegungsschrift 17 68 620. There is also an exact explanation for the symbol Ar ² (page 3 of DOS 17 68 620).

Suitable as compound X for the polyarylene ether sulfones Halogenaryl compounds with three or more than three among the Reaction conditions of polyarylene ether sulfone production substitutable aryl-bonded halogen substituents are those their halogen substituents by electron-withdrawing groups are activated; be mentioned for example 1,3,5-tri- (4-chlorophenylsulfonyl) benzene, 2,4,4'-trichlorodiphenylsulfone, 1-chloro 2,6-bis (4-chlorophenyl sulfonyl) benzene. The activation of the Halogen substituents can pass through not only through the sulfonyl group other electron-withdrawing groups take place, i.e. those with a positive sigma value. (See Chem. Rev. 49 (1951) page 273 ff. and quart. Rev. 12 (1958) 1 ff.); are preferred Substituents whose sigma values are greater than +1.

In addition to the sulfone group are, for example, the carbonyl or the Nitro group or the cyan group as an electron attractive group for the activation of the halogen atoms in the branching of the aromatic polyarylene ether sulfones suitable three or more than three haloaryl compounds bearing halogen substituents suitable.

According to the invention, the branched polyarylene ether sulfones C contain anhydride end groups. The polyarylene ether sulfones C preferably contain anhydride end groups of the structure according to formula IV.

The polyarylene ether sulfones C particularly preferably contain anhydride end groups of the structure shown in formula V.

Preferred polyarylene ether sulfones C contain
0 to 100 mol% of repeating units of the formula I1,
0 to 100 mol% of repeating units of the formula I2,
where the molar percentages of recurring units of the formulas I1 and I2 together make up 100 mol%, and
0.01 to 10% by weight, preferably 0.05 to 7.5% by weight, particularly preferably 0.1 to 6% by weight, very particularly preferably 0.2 to 2.5% by weight, in each case based on the total weight of the polyarylene ether sulfones C, units derived from compound X, in particular 1,1,1-tris (4-hydroxyphenyl) ethane, and ester-bonded anhydride end groups of the formula IV or, particularly preferably, oxygen-bonded anhydride end groups of the formula V.

Polyarylene ether sulfones C are in a first step after the already described in the manufacture of component A. Methods produced, but a corresponding part of the difunctional monomer components, for example the aromatic Bishalogen compounds and / or the alkali double salts aromatic bisphenols, preferably aromatic bisphenols or their double salts, by the desired amount of compound X is replaced (the reaction product of this first Production step is hereinafter referred to as polyarylene ether sulfone C ' designated). Synthesis methods for these polyarylene ether sulfone C 'are also described in US 3,960,815.

In a second step, the conversion from C 'to branched anhydride end-modified polyarylene ether sulfones C.

The connection of anhydride end groups to polyarylene ether sulfones is known. The connection can, for example, as described by C.L. Myers, ANTEC '92, 1992, 1, 1420, by implementation amino terminated polyarylene ether sulfones with an excess Amount of dianhydride take place.

Polyarylene ether sulfones C 'with hydroxy end groups are preferred for the synthesis of the anhydride end groups Polyarylene ether sulfones C used. Polyarylene ether sulfones C 'with repeating units I and hydroxy end groups can for example by appropriate choice of the molar ratio between Dihydroxy and dichloromonomers can be prepared (see e.g. J.E. McGrath et al. Polym. Closely. Sci. 17, 647 (1977); H.-G. Elias "Macromolecules" 4th ed., Pp. 490-493, (1981), Hüthig & Wepf-Verlag, Basel or EP-A1 613 916).

Polyarylene ether sulfones C 'are preferably used which are 0.02 have up to 2% by weight of hydroxyl end groups. Be very special preferred those that have 0.1 to 1.5 wt .-% hydroxy end groups.

To produce the preferred polyarylene ether sulfones C which contain anhydride end groups of the formula IV bonded via ester groups, polyarylene ether sulfones C 'are used with anhydrides of the general formula IVa


implemented. Here R ⁴ can be chlorine or bromine, preferably chlorine. However, R ⁴ can also represent a C ₁ to C ₁₀ alkoxy group, preferably an nC ₁ to C ₁₀ alkoxy group. Examples include methoxy, ethoxy, n-butoxy, i-butoxy and n-pentoxy, among which the n-butoxy group is preferred. In addition, R ^{4 can} also be a C ₆ to C ₁₀ aryloxy group, preferably phenoxy. The alkoxy or aryloxy groups can either be unsubstituted or have substituents. Suitable substituents are, for example, halogen atoms such as chlorine, bromine or in particular fluorine.

Trimellitic anhydride chloride (IVa ₁ ) and trimellitic anhydride butyl ester (IVa ₂ )


are particularly preferred as the anhydride component.

These methods of making the preferred Polyarylene ether sulfones C, the anhydride end groups bonded via ester groups Formula IV included are detailed in EP-A1 613 916 described.

To produce the particularly preferred polyarylene ether sulfones C which contain anhydride end groups of the formula V which are bonded via oxygen atoms, polyarylene ether sulfones C 'with phthalic anhydrides of the general formula Va


wherein X 'is fluorine, chlorine, bromine or iodine, reacted in a solvent in the presence of potassium fluoride. These processes are described in detail in WO 97/04018.

Chlorophthalic anhydrides are compounds of the formula Va and the fluorophthalic anhydrides are preferred. Particularly preferred become 3-fluorophthalic anhydride or 3-chlorophthalic anhydride used. But it can also be beneficial to have a mix of different phthalic anhydrides Va, for example one Mixture of 3-fluorophthalic anhydride and Use 3-chlorophthalic anhydride. It is possible that different phthalic anhydrides Va simultaneously with the Implement polyarylene ether sulfones C '. But it is also possible to do this successively, for example, first 3-fluorophthalic anhydride and then implement 3-chlorophthalic anhydride.

The proportion of anhydride end groups in the polyarylene ether sulfone C can through the well-known methods of general organic analysis how titration, IR, UV and NMR spectroscopy can be determined.

The polyarylene ether sulfones C generally have the same molecular weights as that underlying polyarylene ether sulfones C ', d. H. on Molecular weight reduction takes place in the course of the implementation of C ' the anhydrides not or only to a minor extent.

Component D

The molding compositions according to the invention can optionally 0 to 60 wt .-% Contain reinforcing agents or fillers. Preferably 0 to 50, in particular 0 to 40 wt .-% fibrous or particulate Fillers or reinforcing materials or their mixtures in the contain molding compositions according to the invention. The quantities each refer to the total mass of components A to F.

Preferred fibrous fillers or reinforcing materials are Carbon fibers, potassium titanate whiskers, aramid fibers and especially preferably glass fibers. When using glass fibers you can these for better compatibility with the matrix material a size, preferably a polyurethane size and one Adhesion promoter must be equipped. In general they have used carbon and glass fibers a diameter in the range from 6 to 20 µm.

The incorporation of the glass fibers can take the form of Short glass fibers as well as in the form of endless strands (rovings). in the finished injection molded part is the average length of the glass fibers preferably in the range of 0.08 to 0.5 mm.

Carbon or glass fibers can also be in the form of fabrics, Mats or glass silk rovings can be used.

Suitable particulate fillers are amorphous silica, Carbonates such as magnesium carbonate (chalk), powdered quartz, Mica, various silicates such as clays, muscovite, biotite, Suzoite, tin maletite, talc, chlorite, phlogophite, feldspar, Calcium silicates such as wollastonite or aluminum silicates such as kaolin, especially calcined kaolin.

According to a particularly preferred embodiment particulate fillers are used, of which at least 95% by weight, preferably at least 98% by weight of the particles have a diameter (largest extension), determined on the finished product, less have than 45 microns, preferably less than 40 microns and their so-called aspect ratio in the range of 1 to 25, preferably in Range from 2 to 20, determined on the finished product.

The particle diameter can be z. B. determined thereby be that electron micrographs of thin sections of the Polymer mixture added and at least 25, preferred at least 50 filler particles used for the evaluation become. Likewise, the determination of the particle diameter can be over Sedimentation analysis carried out, according to Transactions of ASAE, Page 491 (1983). The weight percentage of fillers, the less than 40 µm can also be measured using sieve analysis. The aspect ratio is the ratio of particle diameter too thick (greatest extent to smallest extent).

Particularly preferred as particulate fillers are talc, Kaolin, such as calcined kaolin or wollastonite or mixtures from two or all of these fillers. Below that is talc a proportion of at least 95% by weight of particles with a Diameter less than 40 µm and an aspect ratio of 1.5 to 25, each determined on the finished product, especially prefers. Kaolin preferably has a content of at least 95 wt .-% of particles with a diameter of less than 20 microns and an aspect ratio of 1.2 to 20, each determined on finished product.

Component E

The molding compositions according to the invention can optionally be used impact modifying rubbers E included. Their share is from 0 to 40, in particular from 0 to 25% by weight, particularly preferably from 0 to 20% by weight, based on the total weight from A to F.

Mixtures of two or more can also be used as component E. different impact-modifying rubbers used become.

Rubbers generally include polymers at room temperature understand rubber-elastic properties.

Preferred rubbers which increase the toughness of the molding compositions, usually have two main characteristics: they contain an elastomeric portion that has a glass transition temperature of less than -10 ° C, preferably less than -30 ° C, and they contain at least one functional group associated with the polyarylene ether sulfones A or C or the polyamides B can interact. Suitable functional groups are for example carboxylic acid, carboxylic anhydride, carboxylic acid ester, Carboxamide, carboximide, amino, hydroxyl, epoxy, Urethane or oxazoline groups.

• 1. e₁) 40 bis 99 Gew.-% mindestens eines α-Olefins mit 2 bis 8 C-Atomen;
• 2. e₂) 0 bis 50 Gew.-% eines Diens;
• 3. e₃) 0 bis 45 Gew.-% eines C₁-C₁₂-Alkylesters der Acrylsäure oder Methacrylsäure oder Mischungen derartiger Ester;
• 4. e₄) 0 bis 40 Gew.-% einer ethylenisch ungesättigten C₂-C₂₀-Mono- oder Dicarbonsäure oder einem funktionellen Derivat einer solchen Säure;
• 5. e₅) 1 bis 40 Gew.-% eines Epoxygruppen enthaltenden Monomeren; und
• 6. e₆) 0 bis 5 Gew.-% sonstiger radikalisch polymerisierbarer Monomerer.

The preferred functionalized rubbers E include functionalized polyolefin rubbers which are composed of the following components:

• 1. e ₁ ) 40 to 99% by weight of at least one α-olefin having 2 to 8 C atoms;
• 2. e ₂ ) 0 to 50% by weight of a diene;
• 3. e ₃ ) 0 to 45% by weight of a C ₁ -C ₁₂ alkyl ester of acrylic acid or methacrylic acid or mixtures of such esters;
• 4. e ₄ ) 0 to 40% by weight of an ethylenically unsaturated C ₂ -C ₂₀ mono- or dicarboxylic acid or a functional derivative of such an acid;
• 5. e ₅ ) 1 to 40% by weight of a monomer containing epoxy groups; and
• 6. e ₆ ) 0 to 5% by weight of other radically polymerizable monomers.

Examples of suitable α-olefins d ₁ include ethylene, propylene, 1-butylene, 1-pentylene, 1-hexylene, 1-heptylene, 1-octylene, 2-methylpropylene, 3-methyl-1-butylene and 3-ethyl- 1-butylene can be mentioned, with ethylene and propylene being preferred.

Suitable diene monomers e ₂ are, for example, conjugated dienes having 4 to 8 C atoms, such as isoprene and butadiene, and non-conjugated dienes having 5 to 25 C atoms, such as penta-1,4-diene, hexa-1,4-diene , Hexa-1,5-diene, 2,5-dimethylhexa-1,5-diene and octa-1,4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene, and alkenylnorbornenes such as 5-ethylidene-2 -norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes, such as 3-methyltricyclo- (5.2.1.0.2.6) -3,8-decadiene, or their Called mixtures. Hexa-1,5-diene, 5-ethylidene-norbornene and dicyclopentadiene are preferred. The diene content is generally 0 to 50, preferably 0.5 to 50, in particular 2 to 20 and particularly preferably 3 to 15% by weight, based on the total weight of the olefin polymer.

Examples of suitable esters e ₃ are methyl, ethyl, propyl, n-butyl, i-butyl and 2-ethylhexyl, octyl and decyl acrylates or the corresponding esters of methacrylic acid. Of these, methyl, ethyl, propyl, n-butyl and 2-ethylhexyl acrylate or methacrylate are particularly preferred.

Instead of the esters e ₃ or in addition to these, the olefin polymers may also contain acid-functional and / or latent acid-functional monomers of ethylenically unsaturated mono- or dicarboxylic acids e ₄ .

Examples of monomers e ₄ are acrylic acid, methacrylic acid, tertiary alkyl esters of these acids, in particular t-butyl acrylate and dicarboxylic acids, such as maleic acid and fumaric acid, or derivatives of these acids and their monoesters.

Latent acid-functional monomers are to be understood as those compounds which form free acid groups under the polymerization conditions or when the olefin polymers are incorporated into the molding compositions. Examples of these are anhydrides of dicarboxylic acids having 2 to 20 carbon atoms, in particular maleic anhydride and tertiary C ₁ -C ₁₂ -alkyl esters of the abovementioned acids, in particular t-butyl acrylate and t-butyl methacrylate.

Ethylenically unsaturated dicarboxylic acids and anhydrides e ₄ can be represented by the following general formulas VI and VII:


wherein R ⁵ , R ⁶ , R ⁷ and R ^{8 are} independently H or C ₁ -C ₆ alkyl.

Monomers e ₅ bearing epoxy groups can be represented by the following general formulas VIII and IX


wherein R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 are} independently H or C ₁ -C ₆ alkyl, m is an integer from 0 to 20 and p is an integer from 0 to 10.

R ⁵ to R ¹² are preferably hydrogen, m for the value 0 or 1 and p for the value 1.

Preferred compounds e ₄ and e ₅ are maleic acid, fumaric acid and maleic anhydride or alkenyl glycidyl ether and vinyl glycidyl ether.

Particularly preferred compounds of the formulas VI and VII or VIII and IX are maleic acid and maleic anhydride and Epoxy group-containing esters of acrylic acid and / or methacrylic acid, especially glycidyl acrylate and glycidyl methacrylate.

Olefin polymers of are particularly preferred
49.9 to 98.9, in particular 59.85 to 94.85% by weight of ethylene, and
1 to 50 in particular 5 to 40% by weight of an ester of acrylic or methacrylic acid
0.1 to 20.0, in particular 0.15 to 15% by weight of glycidyl acrylate and / or glycidyl methacrylate, acrylic acid and / or maleic anhydride.

Particularly suitable functionalized rubbers E are ethylene Methyl methacrylate glycidyl methacrylate, ethylene methyl acrylate Glycidyl methacrylate, ethylene methyl acrylate glycidyl acrylate and Ethylene-methyl methacrylate-glycidyl acrylate polymers.

As other monomers e ₆ come z. B. vinyl esters or vinyl ethers or mixtures thereof.

The preparation of the polymers described above can be carried out according to known methods are carried out, preferably by statistical copolymerization under high pressure and elevated Temperature.

The melt index of the copolymers is generally in the range from 1 to 80 g / 10 min (measured at 190 ° C and 2.16 kg load).

So-called as a further group of suitable rubbers Core-shell graft rubbers to name. This is it to graft rubbers produced in emulsion, which consist of at least consist of a hard and a soft component. Under a hard component is usually understood to mean a polymer a glass transition temperature of at least 25 ° C, below one soft component a polymer with a Glass transition temperature of at most 0 ° C. These products have a structure a core (graft base) and at least one shell (Grafting pad), the structure being determined by the order of the Addition of monomers results. The soft components are derived i. a. of butadiene, isoprene, alkyl acrylates, alkyl methacrylates or Siloxanes and optionally other comonomers. suitable Siloxane cores can, for example, start from cyclic oligomeric octamethyltetrasiloxane or Tetravinyltetramethyltetrasiloxane be prepared. You can use, for example γ-mercaptopropylmethyldimethoxysilane in a ring-opening cationic polymerization, preferably in the presence of sulfonic acids, to the soft siloxane cores. The siloxanes can also be networked by e.g. B. the Polymerization reaction in the presence of silanes with hydrolyzable groups such as Halogen or alkoxy groups such as tetraethoxysilane, Methyltrimethoxysilane or phenyltrimethoxysilane is performed. As suitable comonomers are z. B. styrene, acrylonitrile and cross-linking or graft-active monomers with more than one polymerizable double bond such as diallyl phthalate, divinylbenzene, To name butanediol diacrylate or triallyl (iso) cyanurate. The hard ones Components derive i. a. of styrene, α-methylstyrene and their copolymers, preferably as comonomers List acrylonitrile, methacrylonitrile and methyl methacrylate are.

Preferred core-shell graft rubbers contain a soft one Core and a hard shell or hard core, a first soft shell and at least one other hard shell. The Incorporation of functional groups such as carbonyl, carboxylic acid, Acid anhydride, acid amide, acid imide, carboxylic acid ester, amino, Hydroxyl, epoxy, oxazoline, urethane, urea, lactam or Halogenbenzylgruppen, is preferably carried out by the Addition of suitably functionalized monomers to the Polymerization of the last shell. Suitable functionalized monomers are, for example, maleic acid, maleic anhydride, mono- or Diesters or maleic acid, tertiary butyl (meth) acrylate, Acrylic acid, glycidyl (meth) acrylate and vinyl oxazoline. The share of Monomers with functional groups is i. a. 0.1 to 25 wt .-%, preferably 0.25 to 15 wt .-%, based on the Total weight of the core-shell graft rubber. The Weight ratio of soft to hard components is i. a. 1: 9 to 9: 1, preferably 3: 7 to 8: 2.

Such rubbers are known per se and, for example, in EP-A 208 187.

Another group of suitable impact modifiers are thermoplastic polyester elastomers. Among polyester elastomers are understood to mean segmented copolyether esters which long chain segments, which are usually of Poly (alkylene) ether glycols and short chain segments that differ from low molecular weight Derive diols and dicarboxylic acids. Such products are known per se and in the literature, e.g. B. in the US-A 3 651 014. Corresponding are also in the trade Products under the names Hytrel® (Du Pont), Arnitel® (Akzo) and Pelprene® (Toyobo Co. Ltd.).

Of course, mixtures of different can Rubbers are used.

Component F

The molding compositions according to the invention can be used as component F Additives such as processing aids, pigments, stabilizers, Flame retardants or mixtures of different additives contain. Common additives are, for example Oxidation retarders, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, dyes and Plasticizers.

According to the invention, their proportion is from 0 to 40, preferably from 0 to 20% by weight, in particular 0 to 15% by weight, based on the total weight of components A to F. In the event that component F is a stabilizer the proportion of these stabilizers usually up to 2% by weight, preferably up to 1% by weight, in particular up to 0.5% by weight, based on the total weight from A to F.

Pigments and dyes are generally available in quantities of up to 6, preferably up to 5 and in particular up to 3% by weight, based on the Sum from A to F included.

The pigments for coloring thermoplastics are generally known, see e.g. BR Gächter and H. Müller, Taschenbuch der Kunststoffadditive, Carl Hanser Verlag, 1983, pp. 494 to 510. The first preferred group of pigments are white pigments such as zinc oxide, zinc sulfide, lead white (2 PbCO3.Pb (OH) ₂ ), Lithopone, antimony white and titanium dioxide. Of the two most common crystal modifications (rutile and anatase type) of titanium dioxide, the rutile form is used in particular for the white coloring of the molding compositions according to the invention.

Black color pigments which can be used according to the invention are iron oxide black (Fe ₃ O ₄ ), spinel black (Cu (Cr, Fe) ₂ O ₄ ), manganese black (mixture of manganese dioxide, silicon dioxide and iron oxide), cobalt black and antimony black and particularly preferably carbon black, which is mostly used in the form of furnace or gas black (see G. Benzing, Pigments for Paints, Expert Verlag (1988), p. 78ff).

Of course, you can adjust certain shades inorganic colored pigments such as chrome oxide green or organic Colored pigments such as azo pigments or phthalocyanines according to the invention be used. Pigments of this type are generally commercially available common.

Oxidation retarders and heat stabilizers that the thermoplastic compositions can be added according to the invention z. B. halides of metals of group I of the periodic table, z. B. sodium, potassium, lithium halides, for example Chlorides, bromides or iodides. Furthermore, zinc fluoride and Zinc chloride can be used. They are also sterically hindered Phenols, hydroquinones, substituted representatives of this group, secondary aromatic amines, optionally in combination with phosphoric acids or their salts, and mixtures of these Compounds, preferably in concentrations up to 1% by weight, based on the weight of the mixture A to F, can be used.

As a particularly preferred component F is the Molding compositions according to the invention copper (I) chloride, copper (I) bromide or Copper (I) iodide or mixtures thereof added. Is preferred Copper (I) iodide used. The amount used is generally up to 1.0, preferably up to 0.5 wt .-% based on the total weight from A to F.

Examples of UV stabilizers are various substituted ones Resorcins, salicylates, benzotriazoles and benzophenones, which in the generally used in amounts up to 2 wt .-%.

Lubricants and mold release agents, which are usually in quantities up to 1% by weight of the thermoplastic composition are added Stearic acid, stearyl alcohol, stearic acid alkyl esters and amides as well as esters of pentaerythritol with long-chain fatty acids. It can also salts of calcium, zinc or aluminum Stearic acid and dialkyl ketones, e.g. B. distearyl ketone used become.

Nucleating agents such as for example talc.

The molding compositions according to the invention can be prepared in a manner known per se Processes, for example by means of extrusion.

The molding compositions can, for. B. can be made by the Starting components in conventional mixing devices such as Screw extruders, preferably twin-screw extruders, Brabender mills or Banbury mills and kneaders and then mixes extruded. Usually the extrudate is made after extrusion cooled and crushed.

The order of mixing the components can vary two or possibly three components can be premixed all components can be mixed together become.

In order to obtain the most homogeneous molding compound possible intensive mixing advantageous. These are generally medium Mixing times from 0.2 to 30 minutes at temperatures from 280 to 370 ° C, preferably 290 to 360 ° C, required.

The molding compositions according to the invention are characterized in that they even with comparatively small proportions of Anhydride end groups as compatibilizers have good tolerability of polyarylene ether sulfone and polyamide and thus a good one Have toughness, or that they are known Molding compositions with comparable high proportions of anhydride end groups Compatibilizers an improved tolerability of Polyarylene ether sulfone and polyamide and thus an improved Have toughness.

The molding compositions according to the invention are suitable for the production of Moldings, foils or fibers, for example, as Household items, electrical or electronic components or medical-technical devices are used. They are suitable especially for the production of molded parts in the vehicle sector, especially in the automotive sector. Examples are suction pipes, Water boxes, housings, ventilation pipes, fasteners, To name cuffs or fan wheels.

Examples research methods

The viscosity number (VZ [ml / g]) of the polyarylene ether sulfones was determined in 1 wt .-% solution of N-methylpyrrolidone at 25 ° C.

The viscosity number (VZ [ml / g]) of the polyamides was in accordance with DIN 53 727 on 0.5% by weight solution in 96% by weight sulfuric acid 25 ° C determined.

The heat resistance of the samples was determined using the Vicat softening temperature (Vicat B [° C]) determined. This was according to DIN 53 460 with a force of 49.05 N and a temperature increase of 50 K / h on standard small bars.

The impact strength (a _n [kJ / m ² ]) was determined on ISO rods according to ISO 179 1 eU.

The notched impact strength (a _k [kJ / m ² ]) was determined on ISO bars according to ISO 179 1 eA.

The flowability (MVI [ml / 10 ']) was determined according to DIN 53 735 at 260 ° C and a load of 5 kg.

The content of anhydride end groups of the polyarylene ether sulfones [% by weight based on the weight of component C] was determined by means of quantitative IR absorption spectroscopy. A calibration curve was used, which was determined on mixtures of phthalic anhydride and component A with a defined composition. The peak height of the absorption at 1770 cm ^{-1 was} used in each case. In each case, 10% by weight solutions of the samples to be examined in dimethylformamide were used in measuring cuvettes with a layer thickness of 76 μm using calcium fluoride windows.

Production of molding compounds Component A

The polyarylene ether sulfone A1 used was one with recurring units of the formula I ₂ , Ultrason® S 2010, a commercial product of BASF Aktiengesellschaft. This product is characterized by a viscosity number of 56 ml / g, measured in 1% NMP solution at 25 ° C.

Component B

A polyamide 6, obtained from ε-caprolactam, was used as polyamide B1 used with a viscosity number of 150 ml / g.

Component C

Component C1 (for comparison) was prepared by nucleophilic aromatic polycondensation as follows:
143.54 g of dichlorodiphenyl sulfone and 114.14 g of bisphenol A were dissolved in 500 ml of N-methylpyrrolidone under a nitrogen atmosphere, and 71.87 g of anhydrous potassium carbonate were added. This mixture was first heated to 180.degree. C. for 1 h at atmospheric pressure while constantly distilling off the water of reaction and N-methylpyrrolidone and then reacted further at 190.degree. C. for 4.5 h. 4.32 g of 4-fluorophthalic anhydride and 1.51 g of potassium fluoride were then added to the mixture and the reaction was continued at 190 ° C. for 0.5 h. After cooling to 130 ° C., the mixture was diluted by adding 500 ml of N-methylpyrrolidone, the solid constituents were separated off by filtration and the polyarylene ether sulfone was isolated by precipitation in water. After extraction three times with water, the polymer was dried in vacuo at 160 ° C. The viscosity number V2 of the product C1 was 54.4 ml / g, the content of phthalic anhydride end groups was 1.01% by weight.

Component C2 (for comparison) was replaced by nucleophilic aromatic Polycondensation prepared as follows:

143.54 g of dichlorodiphenyl sulfone were added under a nitrogen atmosphere and 114.14 g bisphenol A dissolved in 500 ml N-methylpyrrolidone and mixed with 71.87 g of anhydrous potassium carbonate. This mix was at atmospheric pressure with constant distillation of the Water of reaction and N-methylpyrrolidone first at 180 ° C for 1 h heated and then reacted further at 190 ° C for 3 h. The mixture was then mixed with 8.64 g of 4-fluorophthalic anhydride and 3 g of potassium fluoride were added and the reaction at 190 ° C. for 0.5 h continued. After cooling to 130 ° C, the batch was through Add 500 ml of N-methylpyrrolidone diluted to the solid Components separated by filtration and the polyarylene ether sulfone isolated by precipitation in water. After three extraction with Water, the polymer was dried in vacuo at 160 ° C. The Viscosity number V2 of product C2 was 39.2 ml / g, the content of Phthalic anhydride end groups were 1.35% by weight.

Component C3 (for comparison) was replaced by nucleophilic aromatic Polycondensation prepared as follows:

284.55 g of dichlorodiphenyl sulfone were added under a nitrogen atmosphere and 228.28 g bisphenol A dissolved in 1000 ml N-methylpyrrolidone and treated with 143.74 g of anhydrous potassium carbonate. This mix was at atmospheric pressure with constant distillation of the Water of reaction and N-methylpyrrolidone first at 180 ° C for 1 h heated and then reacted further at 190 ° C for 6 h. The mixture was then 18.62 g of 4-fluorophthalic anhydride and 6.51 g of potassium fluoride were added and the reaction at 0.5 h 190 ° C continued. After cooling to 130 ° C, the batch diluted by adding 1000 ml of N-methylpyrrolidone, the solid Components separated by filtration and that Polyarylene ether sulfone isolated by precipitation in water. After three times Extraction with water, the polymer was dried in vacuo at 160 ° C. The viscosity number V2 of the product C3 was 64.6 ml / g, the The content of phthalic anhydride end groups was 1.14% by weight.

Component C4 was identified by nucleophilic aromatic Polycondensation prepared as follows:

Under a nitrogen atmosphere, 274.65 g of dichlorodiphenyl sulfone, 221.43 g bisphenol A and 6.12 g 1,1,1-tris (4-hydroxyphenyl) ethane dissolved in 1000 ml of N-methylpyrrolidone and with 143.74 g anhydrous potassium carbonate added. This mix was made at Atmospheric pressure with constant distillation of the water of reaction and N-methylpyrrolidone first heated to 180 ° C. for 1 h and then reacted further at 190 ° C. for 5 h. Then the Mix 56.52 g of 4-fluorophthalic anhydride and the Reaction continued at 190 ° C for 0.5 h. After cooling to 130 ° C was the approach by adding 1000 ml of N-methylpyrrolidone diluted, the solid components separated by filtration and the polyarylene ether sulfone is isolated by precipitation in water. To The polymer was extracted three times with water in vacuo Dried 160 ° C. The viscosity number V2 of the product C4 was 35.1 ml / g, the content of phthalic anhydride end groups was 3.6% by weight.

The components were in a twin-screw extruder at a Melt temperature of 270 to 300 ° C mixed. The melt was through passed a water bath and granulated.

The molding compounds were processed at 270 ° C. The mold temperature was 80 ° C in each case.

The composition of the molding compositions and the results of the tests are listed in Table 1. Table 1

The molding compounds named with the preceding V became the Cited comparison.

The molding compositions V2 to 5 each contained the same Weight fraction of component C. The molding compositions V6 to 8 contained each the same proportion by weight of anhydride end groups.

The tests prove that the molding compositions according to the invention compared to the known molding compounds at significantly reduced Proportions of anhydride end groups as compatibilizers a comparably good tolerance of polyarylene ether sulfone and polyamide and therefore a comparably good toughness have, or that the molding compositions according to the invention comparable high proportions of anhydride end groups as Compatibility promoters compared to the known molding compounds improved compatibility of polyarylene ether sulfone and polyamide and thus have improved toughness.

Claims (11)

1. Molding compositions containing A) 1 to 98.5% by weight of at least one polyarylene ether sulfone, B) 1 to 98.5% by weight of at least one thermoplastic polyamide, C) 0.5 to 30% by weight of at least one polyarylene ether sulfone,
containing 0.01 to 10 wt .-%, based on the total weight of component C, units derived from a compound X, compound X containing three or more than three hydroxyl or halogen substituents which are independently bonded directly to an aromatic ring and can be substituted under the conditions of polyarylene ether sulfone synthesis,
and further containing anhydride end groups, D) 0 to 60% by weight of at least one filler, E) 0 to 40% by weight of at least one impact-modifying rubber and F) 0 to 40% by weight of one or more different additives, where the weight percentages of components A to F together add up to 100%. 2. Molding compositions according to claim 1, wherein the polyarylene ether sulfones A
0 to 100 mol% repeating units


and
0 to 100 mol% repeating units


contain. 3. Molding compositions according to claims 1 to 2, wherein component B is a partially aromatic polyamide. 4. Molding compositions according to claims 1 to 2, wherein component B is an aliphatic polyamide. 5. Molding compositions according to claims 1 to 4, wherein the polyarylene ether sulfones C
0 to 100 mol% of repeating units of the formula I1,
0 to 100 mol% of repeating units of the formula I2,
where the molar percentages of recurring units of the formulas I1 and I2 together make up 100 mol%, and
0.01 to 10% by weight, based on the total weight of component C, of units derived from a compound X, compound X containing three or more than three hydroxyl or halogen substituents which are independently bonded directly to an aromatic ring and are substitutable under the conditions of polyarylene ether sulfone synthesis,
and also anhydride end groups of the formula V


contain. 6. Molding compositions according to claims 1 to 5, wherein the Polyarylene ether sulfones C 0.05 to 7.5 wt .-%, based on the Total weight of component C, from a compound X contains dissipative units. 7. Molding compositions according to claims 1 to 6, wherein the Polyarylene ether sulfones C differ from 1,1,1-tris (4-hydroxyphenyl) ethane as Compound X containing dissipative units. 8. A method for producing molding compositions according to the claims 1 to 7, characterized in that components A to F be mixed. 9. Use of the molding compositions according to claims 1 to 7 for Manufacture of molded parts, foils or fibers. 10. Moldings, foils or fibers, available from the molding compounds according to claims 1 to 7. 11. moldings, films or fibers according to claim 10, the Components of household items, electronic components, medical-technical devices or motor vehicle components.