WO2003033594A1

WO2003033594A1 - Thermoplastic moulding materials based on polyarylene ether sulfones and polyamides

Info

Publication number: WO2003033594A1
Application number: PCT/EP2002/010959
Authority: WO
Inventors: Martin Weber; Piyada Charoensirisomboon
Original assignee: Basf Aktiengesellschaft
Priority date: 2001-10-10
Filing date: 2002-09-30
Publication date: 2003-04-24
Also published as: DE10149870A1

Abstract

The invention relates to moulding materials containing A) between 1 and 98.5 wt. % of at least one polyarylene ether sulfone, B) between 1 and 98.5 wt. % of at least one thermoplastic polyamide, C) between 0.5 and 30 wt. % of at least one polyarylene ether sulfone containing between 0.01 and 10 wt. % - in relation to the total weight of constituent C - of units which are derived from a compound X comprising at least three hydroxy or halogen substituents which are independently directly linked to an aromatic ring and can be substituted under the conditions of a polyarylene ether sulfone synthesis, in addition to anhydride groups, D) between 0 and 60 wt. % of at least one filler, E) between 0 and 40 wt. % of at least one impact-resistant modified rubber, and F) between 0 and 40 wt. % of at least one different additional additive, the weight per cent of constituents A to F amounting to 100 %. The invention also relates to methods for producing said moulding materials, to the uses of the same, and to moulded parts, films or fibres which can be obtained from said moulding materials.

Description

Thermoplastic molding compounds based on polyarylene ether sulfones and polyamides

description

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 independent of one another directly are bound to an aromatic ring and can be substituted under the conditions of polyarylene ether sulfone synthesis,

and also 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, with the weight percentages of components A to F totaling 100%.

In addition, the present invention relates to processes for the production of these molding compositions, the use of these molding compositions for the production of moldings, films or fibers and also moldings, films and fibers from the molding compositions according to the invention.

Molding compositions based on polyarylene ether sulfones and polyamides are well known (for example from DE-A 21 22 735, DE-Al 41 21 705, EP-A 477 757). Such molding compositions usually have improved flow properties compared to pure polyarylene ether sulfones, owing to the incompatibility of poly However, the toughness of these molding compositions is unsatisfactory for arylene ether sulfones and polyamides.

Molding compositions with improved compatibility of polyarylene ether sulfones and polyamides and, as a result, a higher level

Toughness has also been described. These molding compositions contain polyarylene ether sulfones with anhydride end groups as compatibilizers, which are linked to the polyarylene ether sulfone chain, for example, via ester groups (see EP-AI 613 916) or via oxygen atoms (see WO 97/04018).

A disadvantage of these molding compositions is that a relatively large amount of anhydride-terminated polyarylene ether sulfones has to be used as a compatibilizer, which on the one hand leads to higher costs and on the other hand can lead to corrosion problems on the molding tools at the high temperatures required for processing these molding compositions.

The object of the present invention was to develop thermoplastic molding compositions based on polyarylene ether sulfones and

To provide polyamides which, compared to the known molding compositions, have a comparatively good compatibility of polyarylene ether sulfone and polyamide and thus a comparably good toughness, even with significantly reduced proportions of anhydride end groups, or which have a comparably good toughness with comparably high proportions of anhydride end groups the known molding compositions have improved compatibility of polyarylene ether sulfone and polyamide and thus have improved toughness.

This task is fulfilled by the molding compositions defined in the introduction, which are described in more detail below.

Component A

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

According to the invention, a polyarylene ether sulfone is used as component A. Mixtures of two or more different polyarylene ether sulfones can also be used as component A. The arylene groups of the polyarylene ether sulfones A can be the same or different and, independently of one another, can mean 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 ~ ~ to Cio-alkoxy radicals such as methoxy, ethoxy, n-propoxy, n-butoxy, aryl radicals with bis 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, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl groups are available. The arylene groups of the polyarylene ether sulfones can, in addition to -S0 ₂ -, for example via -0-, -S-, -SO-, -C0-, -N = N-, -C00-, 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 independently of one another are each a chemical bond or a group selected from -0-, -S-, -S0 ₂ -, S = 0, C = 0, -N = N-, -R ^a C = CR ^b - and -CRR ^d -, mean, where R ^a and R each independently represent a hydrogen atom or a Cχ-Cι ₂ alkyl group and

R ^c and R ^d are each independently of one another for a hydrogen atom or a C 1 -C ₂ alkyl, C 1 -C ₂ alkoxy or

C _ß- Cis-aryl group, where R ^c and R ^d , if they represent 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, one

Can form C ₃ -C ₂ cycloalkyl group which can be substituted with one or more C ₆ -C ₆ alkyl groups,

with the proviso that at least one of the groups T, Q and Z stands for -S0- and, if t and q stand for 0, Z stands for -S0-,

Ar and Ar ¹ each independently represents a C _ö -cis-arylene group, said C ₁ -C ₁₂ alkyl,

C _δ -Ciβ-aryl, -C-Cι ₂ alkoxy groups or halogen atoms can be substituted.

Various units of the formula I can also be present randomly or in blocks in the polyarylene ether sulfone.

The polyarylene ether sulfones A are preferably linear. However, the polyarylene ether sulfones A can also contain chain-branching units which are formed by the incorporation of compounds having three or more than three functional groups which can be substituted under the conditions of polyarylene ether sulfone synthesis. (for a more detailed description of the branching units and the production of branched polyarylene ether sulfones, reference is hereby made to the following description of components C, C 'and compound X).

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 Pat. No. 4,870,153, to which reference is hereby expressly made. 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 solvent and potassium carbo- nat 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 Ii to I15:

(HO)

(HD

(112)

(113)

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

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

These functional groups include halogen, especially chlorine, alkoxy, especially methoxy or ethoxy, aryloxy, preferably phenoxy or benzyloxy groups. Hydroxy, amino, epoxy or carboxyl groups may be mentioned as further examples of such functional groups. Among them, polyarylene ether sulfones with amino or epoxy end groups or mixtures thereof are particularly preferred.

The preparation of polyarylene ether sulfones A containing functional groups is described in DE-Al 199 61 040 and the literature cited therein.

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 generally in the range from 1,000 to 30,000 g / mol. The blocks different structures can be arranged alternately or statistically. The proportion by weight of the polyarylene ether sulfones in the copolymers or block copolymers is generally at least 10% by weight. The proportion by weight of the polyarylene ether sulfones can be up to 5 to 97% by weight. Co or block copolymers with a weight fraction of polyarylene ether sulfones of up to 90% by weight are preferred. Co or block copolymers with 20 to 80% by weight of polyarylene ether sulfones are particularly preferred.

10 In general, the polyarylene ether sulfones A have average molecular weights M _n (number average) in the range from 5,000 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 either in 1% by weight N-methylpyrrolidone solution,

15 measured in mixtures of phenol and dichlorobenzene or in 96% sulfuric acid at 20 ° C and 25 ° C, respectively.

Component B

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

25 As component B, one or more thermoplastic polyamides are used according to the invention which 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. -% sulfuric acid according to DIN 53 727).

30

Suitable polyamides can be used as semicrystalline or amorphous resins with a molecular weight M _w (weight average) of at least 5,000, as described, for example, in US Pat. Nos. 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,312,966 .

35 2 512 606 and 3 393 210 are described.

Examples include polyamides derived from lactams with 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurinlactam, and polyamides obtained by reacting 40 dicarboxylic acids with diamines.

Polyamides B can, for example, by condensation of equimolar amounts of a saturated or an aromatic dicarboxylic acid having 4 to 16 carbon atoms with a saturated or aromatic 45 diamine which has up to 16 carbon atoms, or by contacting densification of ω-aminocarboxylic acids or polyaddition of corresponding lactams.

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

Particularly suitable dicarboxylic acids of aliphatic polyamides are alkanedicarboxylic acids having 6 to 12, in particular 6 to 10, carbon atoms. Only adipic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid may be mentioned here as possible acids.

Suitable diamines of aliphatic polyamides are preferably alkanediamines having 4 to 12, in particular 4 to 8, carbon atoms, e.g. 1, 4-butanediamine, 1, 5-pentanediamine or piperazine, and also as cyclic diamines, for example di- (4-aminocyclohexyl) -methane or 2,2-di- (4-aminocyclohexyl) propane.

Of course, aminocarboxylic acids or the corresponding lactams with e.g. 6 to 13 carbon atoms. Suitable monomers of this type are, for example, caprolactam, capryllactam, oenanthlactam, co-aminoundecanoic acid or lauryl lactam.

Examples of preferred aliphatic polyamides are polyhexamethylene adipic acid amide (nylon 66), polyhexamethylene azelaic acid amide (nylon 69), polyhexamethylene sebacic acid amide (nylon 610), polyhexamethylene dodecanedioic acid amide (nylon 612), the polyamides obtained by ring opening of lactams, such as polycaprolactamamam, polylaurolactamamam, aminoundecanoic acid and a polyamide 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.

Polyamides may also be mentioned, e.g. can be obtained by condensing 1,4-diaminobutane with adipic acid at elevated temperature (polyamide-4, 6). Manufacturing processes for polyamides of this structure are e.g. in EP-A 38 094, EP-A 38 582 and EP-A 39 524.

Polyamides obtainable by copolymerizing two or more of the aforementioned monomers or mixtures of two or more polyamides are also suitable, the mixing ratio being arbitrary. In a preferred embodiment of the invention, partially aromatic polyamides are used. These can be prepared by copolycondensation of, for example, adipic acid, isophthalic acid and / or terephthalic acid with hexamethylene diamine or of caprolactam, terephthalic acid with hexamethylene diamine. Such partially aromatic copolyamides preferably contain, as a component, from 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 ε-caprolactam (b) and / or units derived from adipic acid and hexamethylene diamine (b).

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 , is up to 70 wt .-%, preferably 30 to 60 wt .-% and in particular 35 to 55 wt .-%. The sum of the weight percentages of the components bi to b ₃ always amounts to 100.

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

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

b'i) 30 to 44, preferably 32 to 40 and in particular 32 to 38 mol% of units which are derived from terephthalic acid, b ' ₂ ) 6 to 20, preferably 10 to 18 and in particular 12 to

18 mol% units derived from isophthalic acid

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,

b ' ₄ ) 0.5 to 7, preferably 1.5 to 4 and in particular 1.8 to

3.7 mol% of units which are derived from aliphatic cyclic diamines having 6 to 30, preferably 13 to 29 and in particular 13 to 17 C atoms,

where the molar percentages of components b'i to b ' ₄ together give 100%.

The diamine units b ' ₃ and b' ₄ are preferably implemented in equimolar amounts with the dicarboxylic acid units b'i and b '.

Suitable monomers b '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 is} 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'i 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 can be considered 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, eg. B. 4,4'- and 3,3'-diphenyldicarboxylic acid, 4,4'- and 3,3'-diphenylmethanedicarboxylic acid, 4,4'- and 3, 3'-diphenylsulfone dicarboxylic acid, 1,4- or 2, 6-naphthalene dicarboxylic 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, enanthanthactam, ω- Aminoundecanoic acid and laurolactam as representatives of lactams or aminocarboxylic acids.

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

Copolyamides with a low triamine content, with the same solution viscosity, have lower melt viscosities compared to products of the same composition, which have a higher triamine content. This significantly improves both the processability and the product properties.

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 having a high glass transition temperature of generally 100 ° C. or more, in particular more than 130 ° C (in the dry state).

Semi-aromatic copolyamides B are generally distinguished by degrees of crystallinity> 30%, preferably> 35%, and in particular> 40%.

The degree of crystallinity is a measure of the proportion of crystalline fragments in the copolyamide and is determined by X-ray diffraction or indirectly by measuring ΔH _{kr st-} . Mixtures of different partially aromatic copolyamides and mixtures of aliphatic and partially aromatic (co) polyamides can of course also be used, the mixing ratio being arbitrary. 5

Suitable processes for the preparation of the polyamides B are known to the person skilled in the art.

The batch process (discontinuous production method) may be mentioned as the preferred method of production. The aqueous monomer solution is heated in an autoclave to temperatures of 280-340 ° C. within 0.5 to 3 hours, a pressure of 10-50, in particular 15-40 bar being reached, which is achieved by releasing excess water vapor if possible 15 is kept constant up to 2 h. The autoclave is then depressurized at a constant temperature within a period of 0.5-2 hours until a final pressure of 1 to 5 bar has been reached. The polymer melt is then discharged, cooled and granulated.

20 Another procedure is based on that in the

Methods described in EP-A 129195 and 129 196. Thereafter, for example for the production of partially aromatic copolyamides, an aqueous solution of the monomers b'i) to b ' ₄ ) and optionally b' ₅ ) with a monomer content of 30 to 70, preferably 40 to

25 65% by weight under increased pressure (1 to 10 bar) and with simultaneous evaporation of water and formation of a prepolymer within less than 60 s to a temperature of 280 to 330 ° C., then prepolymers and steam are continuously separated, the steam rectified and the carried

30 diamines returned. Finally, the prepolymer is passed into a polycondensation zone and under an overpressure of 1 to 10 bar and a temperature of 280 to 330 ° C. with a residence time of 5 to 30 minutes. polycondensed. It goes without saying that the temperature in the reactor is higher than that of the respective

35 water vapor pressure required melting point of the resulting prepolymer.

These short dwell times largely prevent the formation of triamines. 0

The polyamide prepolymer obtained in the manner mentioned, which generally has a viscosity number of 40 to 70 ml / g, preferably 40 to 60 ml / g, measured on a 0.5% by weight solution in 96% sulfuric acid at 25 ° C, is continuously taken from 5 of the condensation zone. It is advantageous to discharge the polyamide prepolymer in a molten state through a discharge zone with simultaneous removal of the residual water contained in the melt. Suitable discharge zones are, for example, degassing extruders. The melt freed from the water can then be poured into strands and granulated.

These granules are solid or under inert gas continuously or discontinuously at a temperature below the melting point, e.g. from 170 to 240 ° C, condensed to the desired viscosity. For discontinuous solid phase condensation e.g. Tumble dryer, for the continuous solid phase condensation with hot inert gas tempered tubes are used. Continuous solid-phase condensation is preferred, nitrogen or in particular superheated water vapor, advantageously the water vapor obtained at the top of the column, being used as the inert gas.

In a further embodiment, it is also possible to add components A, C, D, E and / or F already in the degassing extruder to prepolymer component B, in which case the degassing extruder is usually used with suitable mixing elements, such as kneading blocks, Is provided. Then it can also be extruded, cooled and granulated as a strand.

Component C

The molding compositions according to the invention contain component C in amounts of 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 of A to F.

Branched polyarylene ether sulfones containing anhydride end groups are used as component C of the molding compositions according to the invention. Polyarylene ether sulfones C are composed of the structural units already described for component A, component C being, however, 0.01 to 10% by weight, 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 wt .-%, based in each case on the total weight of component C, of units derived from a compound X, compound X having three or more than three hydroxyl or Contains halogen substituents which are independently bonded directly to an aromatic ring and can be substituted under the conditions of polyarylene ether sulfone synthesis, and component C furthermore contains anhydride end groups. 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. Particularly suitable are those tri- or more than trivalent phenols which are obtained by reacting p-alkyl-substituted monophenols with unsubstituted o-positions with formaldehyde. hyd or formaldehyde-producing compounds can be prepared, such as, for example, the trisphenol from p-cresol and formaldehyde, the 2,6-bis- (2'-hydroxy-5'-methylbenzyl) -4-methylphenol. 2,6-bis- (2'-hydroxy-5'-isopropyl-benzyl) -4-isopropenylphenol and bis- [2-hydroxy-3- (2 '-hydroxy-5' -met hylbenzy1-5-ethy1-pheny1] methane.

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

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

O

wherein Ar ^{2 is} a mono- or polynuclear, divalent aromatic radical and Hai 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-hydroxyphenylisopropyl) phenoxy] -2, 4,6-tri-bromobenzene,

the manufacture of which is described in German Offenlegungsschrift 1,768,620. There is also an exact explanation for the symbol Ar ² (page 3 of DOS 1 768 620).

Halogen aryl compounds which are suitable as compound X for the polyarylene ether sulfones and have three or more than three aryl-bonded halogen substituents which can be substituted under the reaction conditions of polyarylene ether sulfone are those whose halogen substituents are activated by electron-withdrawing groups; Examples include 1, 3, 5-tri- (4-chlorophenylsulfonyl) benzene, 2,4, 'trichlorodiphenylsulfone, 1-chloro-2, 6-bis (4-chlorophenylsulfonyl) benzene. In addition to the sulfonyl group, the halogen substituents can also be activated by other electron-withdrawing groups, that is to say those with a positive sigma value. (See Chem. Rev. 49 (1951) page 273 ff. And Quart. Rev. 12 (1958) 1 ff.); preferred are substituents whose sigma values are greater than +1.

In addition to the sulfone group, the carbonyl or nitro group or the cyan group, for example, are suitable as electron-accepting groups for the activation of the halogen atoms in the halogenoaryl compounds bearing three or more halogen substituents suitable for branching the aromatic polyarylene ether sulfones.

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 II, 0 to 100 mol% of repeating units of the formula 12, the molar percentages of repeating units of the formulas II and 12 totaling 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, derived from compound X, in particular from 1, 1, 1-tris (4-hydroxyphenyl) ethane, derivative units 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 prepared in a first step according to the methods already described for the production of component A, but a corresponding part of the functional monomer components, for example the aromatic bis-halogen compounds and / or the alkali double salts of aromatic bisphenols, preferably the aromatic bisphenols or whose double salts are replaced by the desired amount of compound X (the reaction product of this first preparation step is referred to below as polyarylene ether sulfone C). Synthetic methods for this polyarylene ether sulfone C are also described in US 3,960,815.

In a second step, C is converted to the branched polyarylene ether sulfones C modified with anhydride end groups.

The attachment 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 reaction of an inoterminated polyarylene ether sulfone with an excess amount of dianhydride.

Polyarylene ether sulfones C having hydroxy end groups are preferably used for the synthesis of the polyarylene ether sulfones C modified with anhydride end groups. Polyarylene ether sulfones C with recurring Ending units I and hydroxy end groups can be prepared, for example, by a suitable choice of the molar ratio between dihydroxy and dichloromonomers (see, for example, JE McGrath et al: Polym. Eng. Sci. 17, 647 (1977); H.-G. Elias " Macromolecules "4th ed., Pp. 490-493, (1981), Hüthig & Wepf-Verlag, Basel or EP-AI 613 916).

Polyarylene ether sulfones C which have 0.02 to 2% by weight of hydroxyl end groups are preferably used. Those which have 0.1 to 1.5% by weight of hydroxyl end groups are particularly preferred.

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 with anhydrides of the general formula IVa are used

implemented. Here R ⁴ can be chlorine or bromine, preferably chlorine. However, R ⁴ can also represent a C 1 -C 1 -alkoxy group, preferably an n-C 1 -C 1 -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 - to Cio-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 (IVai) and trimellitic anhydride n-butyl ester (IVa ₂ )

are particularly preferred as the anhydride component. These processes for the preparation of the preferred polyarylene ether sulfones C which contain anhydride end groups of the formula IV bonded via ester groups are described in detail in EP-AI 613 916. i To prepare 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 are

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.

The chlorophthalic anhydrides and the fluorophthalic anhydrides are preferred as compounds of the formula Va. 3-Fluorophthalic anhydride or 3-chlorophthalic anhydride are particularly preferably used. However, it can also be advantageous to use a mixture of different phthalic anhydrides Va, for example a mixture of 3-fluorophthalic anhydride and 3-chlorophthalic anhydride. It is possible to react the different phthalic anhydrides Va simultaneously with the polyarylene ether sulfones C. However, it is also possible to implement these in succession, for example firstly 3-fluorophthalic anhydride and then 3-chlorophthalic anhydride.

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

The polyarylene ether sulfones C produced by these processes generally have the same molecular weights as the polyarylene ether sulfones C on which they are based, i.e. a molecular weight reduction does not take place in the course of the reaction of C with the anhydrides or only to a minor extent.

Component D

The molding compositions according to the invention can optionally contain 0 to 60% by weight of reinforcing agents or fillers. Preferably 0 to 50, especially 0 to 40 wt .-% are fibrous or particulate Contain fillers or reinforcing materials or mixtures thereof in the molding compositions according to the invention. The quantities given relate to the total mass of components A to F.

Preferred fibrous fillers or reinforcing materials are carbon fibers, potassium titanate whiskers, aramid fibers and particularly preferably glass fibers. If glass fibers are used, they can be equipped with a size, preferably a polyurethane size and a high-level agent, for better compatibility with the matrix material. In general, the carbon and glass fibers used have a diameter in the range from 6 to 20 μm.

Glass fibers can be incorporated both in the form of short glass fibers and in the form of endless strands (rovings). In the finished injection molded part, the average length of the glass fibers is preferably in the range from 0.08 to 0.5 mm.

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

Suitable particulate fillers are amorphous silica, carbonates such as magnesium carbonate (chalk), powdered quartz, mica, a wide variety of 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 (greatest dimension), determined on the finished product, of less than 45 μm, preferably less have than 40 μm and their so-called aspect ratio is in the range from 1 to 25, preferably in the range from 2 to 20, determined on the finished product.

The particle diameters can be determined, for example, by taking electron micrographs of thin sections of the polymer mixture and using at least 25, preferably at least 50 filler particles for the evaluation. The particle diameters can also be determined via sedimentation analysis, according to Transactions of ASAE, page 491 (1983). The proportion by weight of the fillers, which is less than 40 μ, can also be measured by sieve analysis. The aspect ratio is the ratio of particle diameter to thickness (largest dimension to smallest dimension). Particularly preferred particulate fillers are talc, kaolin, such as calcined kaolin or wollastonite, or mixtures of two or all of these fillers. Among them, talc with a proportion of at least 95% by weight of particles with a diameter of less than 40 μm and an aspect ratio of 1.5 to 25, each determined on the finished product, is particularly preferred. Kaolin preferably has a proportion of at least 95% by weight of particles with a diameter of less than 20 μm and an aspect ratio of 1.2 to 20, each determined on the finished product.

Component E

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

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

Rubbers are generally understood to mean polymers with rubber-elastic properties at room temperature.

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

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

ei) 40 to 99% by weight of at least one α-olefin having 2 to 8 C atoms;

e ₂ ) 0 to 50% by weight of a diene; e ₃ ) 0 to 45% by weight of a C 1 -C ₂ alkyl ester of acrylic acid or methacrylic acid or mixtures of such esters;

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;

es) 1 to 40% by weight of a monomer containing epoxy groups; and

e ₆ ) 0 to 5% by weight of other free-radically polymerizable monomers.

As examples of suitable o-olefins di, 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, ethylene and propylene being preferred.

Suitable diene monomers e are, for example, conjugated dienes with 4 to 8 C atoms, such as isoprene and butadiene, non-conjugated dienes with 5 to 25 C atoms, such as penta-1, 4-diene, hexa-1, 4-diene, hexa-1, 5-diene, 2, 5-dimethylhexa-l, 5-diene and octa-1, 4-diene, cyclic dienes such as cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene, and alkenylnorbornene 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 hybrids. 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 or in addition to the esters e ₃ , 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 ₂ -alkyl esters of the abovementioned acids, in particular t-butyl acrylate and t-butyl methacrylate.

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

R ^b (C00R ⁶ ) C = _C (COOR ⁷ ) R ⁸ (VI)

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

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

CHR ⁹ = CH - (CH ₂ ) - 0 - (CHR ¹⁰ ) - CH - CHR ¹⁰

\ / (VIII)

0

CH = CR ¹¹ - COO - (CH) CH .CHR ¹² (IX)

2 2 p ^ where R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 are} independently H or Ci-C _δ- 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 is 0 or 1 and p is 1. Preferred compounds e or 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 or epoxy group-containing esters of acrylic acid and / or methacrylic acid, in particular 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.

Other monomers e _{6 that} can be used are, for example, vinyl esters or vinyl ethers or mixtures thereof.

The polymers described above can be prepared by processes known per se, preferably by random 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. These are graft rubbers produced in emulsion, which consist of at least one hard and one soft component. A hard component is usually understood to mean a polymer with a glass transition temperature of at least 25 ° C., and a soft component is a polymer with a glass transition temperature of at most 0 ° C. These products have a structure consisting of a core (graft base) and at least one shell (graft pads), the structure being determined by the order in which the monomers are added. The soft components are generally derived from butadiene, isoprene, alkyl acrylates, alkyl methacrylates or Siloxanes and optionally other comonomers. Suitable siloxane cores can be prepared, for example, from cyclic oligomeric octamethyltetrasiloxane or tetravinyltetramethyltetrasiloxane. These can be reacted, for example, with γ-mercapropropyl methyldimethoxysilane in a ring-opening cationic polymerization, preferably in the presence of sulfonic acids, to give the soft siloxane cores. The siloxanes can also be crosslinked, for example by carrying out the polymerization reaction in the presence of silanes with hydrolyzable groups such as halogen or alkoxy groups such as tetraethoxysilane, methyltrimethoxysilane or phenyltrimethoxysilane. Examples of suitable comonomers here are styrene, acrylonitrile and crosslinking or graft-active monomers with more than one polymerizable double bond, such as diallyl phthalate, divinylbenzene, butanediol diacrylate or triallyl (iso) cyanurate. The hard constituents are generally derived from styrene, α-methylstyrene and their copolymers, the preferred comonomers here being acrylonitrile, methacrylonitrile and methyl methacrylate.

Preferred core-shell graft rubbers contain a soft core and a hard shell or a hard core, a first soft shell and at least one further hard shell. Functional groups such as carbonyl, carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic ester, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl groups are incorporated here preferably by adding suitably functionalized monomers in the polymerization of the last shell. Suitable functionalized monomers are, for example, maleic acid, maleic anhydride, mono- or diester or maleic acid, tertiary-butyl (meth) acrylate, acrylic acid, glycidyl (meth) acrylate and vinyloxazoline. The proportion of monomers with functional groups is generally 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 generally 1: 9 to 9: 1, preferably 3: 7 to 8: 2.

Rubbers of this type are known per se and are described, for example, in EP-A 208 187.

Another group of suitable impact modifiers are thermoplastic polyester elastomers. Polyester elastomers are understood to mean segmented copolyether esters which contain long-chain segments which are generally derived from poly (alkylene) ether glycols and short-chain segments which are derived from low molecular weight diols and dicarboxylic acids. Such products are known per se and are described in the literature, for example in US Pat. No. 3,651,014. Corresponding products are also commercially available under the names Hytrel ^® (Du Pont), Arnitel ^® (Akzo) and Pelprene ^® (Toyobo Co. Ltd.).

Mixtures of different rubbers can of course also be used.

Component F

The molding compositions according to the invention can contain, as component F, additives such as processing aids, pigments, stabilizers, flame retardants or mixtures of different additives. Typical additives are, for example, oxidation retardants, 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% by weight, 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 the Component F is stabilizers, the proportion of these stabilizers is 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 present in amounts of up to 6, preferably up to 5 and in particular up to 3% by weight, based on the sum of A to F.

The pigments for coloring thermoplastics are generally known, see, for example, R. 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 and zinc sulfide , Lead white (2 PbC0 ₃ -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 0 ₄ ), spinel black (Cu (Cr, Fe) θ ₄ >, manganese black (mixture of manganese dioxide, silicon dioxide and iron oxide), cobalt black and antimony black and particularly preferably carbon black , which is usually in the form of furnace or gas soot is used (see G. Benzing, Pigments for paints, Expert Verlag (1988), p. 78ff).

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

Oxidation retarders and heat stabilizers which can be added to the thermoplastic compositions according to the invention are e.g. Group I metals of the Periodic Table, e.g. Sodium, potassium, lithium halides, for example chlorides, bromides or iodides. Zinc fluoride and zinc chloride can also be used. Sterically hindered phenols, hydroquinones, substituted representatives of this group, secondary aromatic amines, optionally in combination with phosphorus-containing acids or their salts, and mixtures of these compounds, preferably in concentrations of up to 1% by weight, based on the weight of mixture A to F, can be used.

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

Examples of UV stabilizers are various substituted resorcinols, salicylates, benzotriazoles and benzophenones, which are generally used in amounts of up to 2% by weight.

Lubricants and mold release agents, which are generally added in amounts of up to 1% by weight of the thermoplastic composition, are stearic acid, stearyl alcohol, alkyl stearates and amides, and also esters of pentaerythritol with long-chain fatty acids. Salts of calcium, zinc or aluminum of stearic acid and dialkyl ketones, e.g. Distearyl ketone can be used.

Nucleating agents such as talcum are also suitable as additional additives.

The molding compositions according to the invention can be produced by processes known per se, for example by means of extrusion. The molding compositions can be produced, for example, by mixing the starting components in conventional mixing devices such as screw extruders, preferably twin-screw extruders, Brabender mills or Banbury mills and kneaders, and then extruding them. The extrudate is usually cooled and comminuted after the extrusion.

The order of mixing the components can be varied, so two or possibly three components can be premixed, but all components can also be mixed together.

In order to obtain a molding material that is as homogeneous as possible, intensive mixing is advantageous. This generally requires average mixing times of 0.2 to 30 minutes at temperatures of 280 to 370 ° C, preferably 290 to 360 ° C.

The molding compositions according to the invention are notable for the fact that even with comparatively small proportions of anhydride groups as compatibilizers, they have good compatibility of polyarylene ether sulfone and polyamide and thus good toughness, or that they have a compatibility with known molding compositions with comparatively high proportions of anhydride end groups improved compatibility of polyarylene ether sulfone and polyamide and thus have improved toughness.

The molding compositions according to the invention are suitable for the production of moldings, films or fibers which are used, for example, as household articles, electrical or electronic components or medical-technical devices. They are particularly suitable for the production of molded parts in the vehicle sector, in particular in the automotive sector. Examples include suction pipes, water boxes, housings, ventilation pipes, fastening parts, sleeves or fan wheels.

Examples

Test Methods

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

The viscosity number (VZ [ml / g]) of the polyamides was determined in accordance with DIN 53 727 on a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25 ° C. The heat resistance of the samples was determined using the Vicat softening temperature (Vicat B [° C]). This was determined 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 leU.

The notched impact strength (ajς [kJ / m ² ]) was determined on ISO bars according to ISO 179 leA.

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 cirr ^{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 AI used was one with recurring units of the formula I, Ultrason® S 2010, a commercial product from 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, with a viscosity number of 150 ml / g was used as the polyamide BI.

Component C

Component Cl (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 ° C. for 1 h at atmospheric pressure while constantly distilling off the reaction water and N-methylpyrrolidone and then reacted further at 190 ° C. for 4.5 h. Then 4.32 g of 4-fluorophthalic anhydride and 1.51 g of potassium fluoride were 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 VZ of the product Cl was 54.4 ml / g, the content of phthalic anhydride end groups was 1.01% by weight.

Component C2 (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 3 h. Then 8.64 g of 4-fluorophthalic anhydride and 3 g of potassium fluoride were 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 VZ of the product C2 was 39.2 ml / g, the content of phthalic anhydride end groups was 1.35% by weight.

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

284.55 g of dichlorodiphenyl sulfone and 228.28 g of bisphenol A were dissolved in 1000 ml of N-methylpyrrolidone under a nitrogen atmosphere, and 143.74 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 6 h. Then 18.62 g of 4-fluorophthalic anhydride and 6.51 g of potassium fluoride were added to the mixture and the reaction was continued at 190 ° C. for 0.5 h. After cooling to 130 ° C, the batch diluted by adding 1000 ml of N-methylpyrrolidone, the solid constituents separated by filtration and the polyarylene ether sulfone isolated by precipitation in water. After extraction three times with water, the polymer was dried in vacuo at 160 ° C. The viscosity number VZ of the product C3 was 64.6 ml / g, the content of phthalic anhydride end groups was 1.14% by weight.

Component C4 was prepared by nucleophilic aromatic polycondensation as follows:

Under a nitrogen atmosphere, 274.65 g of dichlorodiphenyl sulfone, 221.43 g of bisphenol A and 6.12 g of 1, 1, 1-tris (4-hydroxyphenyl) ethane were dissolved in 1000 ml of N-methylpyrrolidone, and 143.74 g of anhydrous potassium carbonate were added. This mixture was first heated to 180 ° C. for 1 h at atmospheric pressure while constantly distilling off the water of reaction and N-methylpyrrolidone and then reacted further at 190 ° C. for 5 h. Then 56.52 g of 4-fluorophthalic anhydride were added to the mixture and the reaction was continued at 190 ° C. for 0.5 h. After cooling to 130 ° C., the batch was diluted by adding 1000 ml of N-methylpyrrolidone, the solid constituents were separated off by filtration and the polyarylene ether sulfone was isolated by precipitation in water. After extracting it three times with water, it became. Polymer dried in a vacuum at 160 ° C. The viscosity number VZ of the product C4 was 35.1 ml / g, the content of phthalic anhydride end groups was 3.6% by weight.

The components were mixed in a twin-screw extruder at a melt temperature of 270 to 300 ° C. The melt was passed through 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 :

20

The molding compounds named with the preceding V were given for comparison.

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

The tests prove that the molding compositions according to the invention already reduced significantly compared to the known molding compositions

^3υ proportions of anhydride end groups as compatibilizers have a comparably good compatibility of polyarylene ether sulfone and polyamide and thus have a comparably good toughness, or that the molding compositions according to the invention have a comparatively high proportion of anhydride end groups

³⁵ plasticizers have an improved compatibility of polyarylene ether sulfone and polyamide and thus an improved toughness compared to the known molding compositions.

40

5

Claims

claims

1. Molding compositions containing

A) 1 to 98.5% by weight of at least one polyarylene ether sulfone,

B) from 1 to 98.5 wt .-% of at least one thermoplastic polyamide ^0,

C) 0.5 to 30% by weight of at least one polyarylene ether sulfone,

⁵ containing 0.01 to 10 wt .-%, 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 independently of one another directly on an aromatic ring ^are bound and can be substituted under the conditions of polyarylene ether sulfone synthesis,

and also containing anhydride end groups, 5

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 0

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 5 100%.

2. Molding compositions according to claim 1, wherein the polyarylene ether sulfones A

0 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.

Molding compositions according to claims 1 to 4, wherein the polyarylene ether sulfones C

0 to 100 mol% of repeating units of the formula II, 0 to 100 mol% of repeating units of the formula 12,

where the molar percentages of recurring units of the formulas II and 12 together make up 100 mol%, and

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 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, contains units derived from a compound X.

5

7. Molding compositions according to claims 1 to 6, wherein the polyarylene ether sulfones C contain 1, 1, 1-tris (4-hydroxyphenyl) ethane as compound X-deriving units.

10. 8. A process for the preparation of molding compositions according to claims 1 to 7, characterized in that components A to F are mixed.

9. Use of the molding compositions according to claims 1 to 7 for the production of moldings, films or fibers.

10. molded parts, films or fibers, obtainable from the molding compositions according to claims 1 to 7.

11. Molded parts, films or fibers according to claim 10, which are components of household items, electronic components, medical-technical devices or motor vehicle components.

25

30

5

0

5