Moulding compositions with improved notched impact-strength comprising poly(arylene ether) and poly(arylene sulfide)

0001The invention relates to thermoplastic molding compositions containing polyarylene ethers and polyarylene sulfides with improved notched impact strength.

0002Poylarylene ethers are high-temperature resistant materials that are particularly characterized by good thermal resistance, good mechanical properties and good dimensional stability. However, the processing properties for polyarylene ethers, in particular the flowability, are not sufficient for many applications. Furthermore, the area of ​​application of the polyarylene ethers is also limited by the low chemical resistance and notch sensitivity.

0003Attempts have been made to limit these disadvantages by producing polymer blends containing polyarylene ether.

0004No. 4,021,596 describes thermoplastic polymer blends which contain polyphenylene sulfide and polysulfone. The blends are said to have improved physical properties compared to polyarylene sulfide.

0005Blends made of polysulfone and polyphenylene sulfide are, however, incompatible and show phase separation. For this reason, the use of compatibility agents has been proposed.

0006A block copolymer is proposed in US Pat. No. 4,678,831 which has a polyphenylene sulfide component and a polysulfone component. It is used in blends of polyphenylene sulfide and polysulfone. However, the synthesis of the block polymers is very complex and costly. In addition, the polymer blends show reduced fluidity.

0007JP-A-1299872 (1989) describes a blend of polyphenylene sulfide and polysulfone, the aromatic polysulfone having terminal hydroxyl groups or alkali metal phenolate groups. The blend is said to have improved mechanical properties.

0008DE-A-44 20 643 describes polymer blends made from polyarylene ethers with hydroxy end groups, polyarylene ethers with end groups that are not hydroxy groups, polyarylene sulfides and fibrous or particulate fillers. They can also have impact-modifying rubbers. The molding compositions are said to have improved mechanical properties, improved chemical resistance and improved thermoplastic processing behavior.

0009The known polymer blends do not have a sufficiently high impact strength with good flowability and processing stability in all applications. In addition, the tracking resistance is sometimes insufficient.

0010The object of the present invention is to provide thermoplastic molding compositions which contain polyarylene ethers and polyarylene sulfides and avoid the disadvantages of the known molding compositions.

0011The object is achieved according to the invention by providing a thermoplastic molding composition containing, based on the total weight of components A to D and optionally E, which gives a total of 100% by weight,<ul id="ul0001" list-style="none" compact="compact"><li>a: 5 to 94% by weight of at least one polyarylene ether as component A,</li><li>b: 4 to 93% by weight of at least one polyarylene sulfide as component B,</li><li>c: 1 to 20% by weight of at least one polyarylene ether containing carboxyl groups as component C,</li><li>d: 1 to 20% by weight of at least one impact-modifying rubber which has functional groups which are reactive towards carboxyl groups, as component D,</li><li>e: 0 to 50% by weight of further additives as component E.</li></ul>

0012It has been found that the addition of reactive rubbers to mixtures of polyarylene ethers, polyarylene sulfides and polyarylene ethers containing carboxyl groups can improve the notched impact strength of the molding compositions and molded articles therefrom without impairing the flowability and the processing stability of the molding compositions. The tracking resistance is also improved.

0013The molding compositions thus obtained can be used for the production of fibers, films or moldings. The production can take place, for example, by extrusion, extrusion blow molding or injection molding. Examples of suitable moldings are household articles, parts of electronic components and components of medical-technical devices.

0014The components of the molding compositions according to the invention are first described below.

Component A

0015The molding compositions according to the invention contain 5 to 94, preferably 7 to 87% by weight of polyarylene ether as component A. In particular, the polyarylene ethers A are present in the molding compositions according to the invention in amounts of 50 to 85% by weight.

0016As component A, polyarylene ethers with repeating units of the general formula (I)<chemistry id="chem0001" num="0001"><img file="EP0903376A2_D0001.tif" /></chemistry> used. Their core-substituted derivatives can also be used. The preferred substituents are C._1-6Alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl, C_1-6Alkoxy such as methoxy or ethoxy, aryl, especially phenyl, chlorine or fluorine. The variable X can be -SO₂-, -SO-, -O-, -CO-, -N = N-, RC = CR^a-, -CR^bR^c- or a chemical bond. The variable Z can be used for -SO₂-, -SO-, - N = N- or -RC = CR^a-, stand. Here R and R represent^a each hydrogen, C_1-6-Alkyl, for example methyl, ethyl, n-propyl i-propyl or n-hexyl, C_1-6Alkoxy, including methoxy, ethoxy, n-propoxy, i-propoxy, or n-butoxy, or aryl, in particular phenyl. The radicals R^b and R^c can each be hydrogen or a C._1-6-Alkylgruppe, especially methyl, represent. You can also go to a C_4-10-Cycloalkyl ring such as cyclopentyl or cyclohexyl, which in turn can be substituted with one or more alkyl groups, preferably methyl. In addition, R^b and R^c also a C_1-6Alkoxy group, for example methoxy or ethoxy or an aryl group, in particular phenyl. The groups mentioned above can each be substituted with chlorine or fluorine. The polyarylene ethers can be composed entirely of the repeating units of the general formula (I).

0017The molecular weights (number average M_n) Suitable polyarylene ethers A are generally in the range from 1500 to 60,000 g / mol.

0018Suitable polyarylene ethers A also include copolymers composed of polyarylene ether segments and structural units selected from the group of polyesters, aromatic polycarbonates, polyester carbonates, polysiloxanes, polyimides, polyamideimides and polyetherimides. The molecular weights M_w the polyaryl ether blocks or the polyaryl ether graft arms in such copolymers are generally in the range from 1000-30,000 g / mol. The blocks of different structures can be arranged alternately or randomly in the copolymers. The proportion by weight of the polyarylene ethers in the copolymers is generally 3 to 97, preferably 10 to 90 and in particular 20 to 80% by weight.

0019Mixtures of different polyarylene ethers A can also be used.

0020Some suitable repeating units are listed below in addition to the preferred structures of formulas (II) and (III) given below:<chemistry id="chem0002" num="0002"><img file="EP0903376A2_D0002.tif" /></chemistry><chemistry id="chem0003" num="0003"><img file="EP0903376A2_D0003.tif" /></chemistry><chemistry id="chem0004" num="0004"><img file="EP0903376A2_D0004.tif" /></chemistry>

0021The particularly preferred polyarylene ethers A include those with<ul id="ul0002" list-style="none" compact="compact"><li>a1) 0 to 100 mol% of repeating units of the formula (II):<chemistry id="chem0005" num="0005"><img file="EP0903376A2_D0005.tif" /></chemistry> and</li><li>a2) 0 to 100 mol% of repeating units of the formula (III),<chemistry id="chem0006" num="0006"><img file="EP0903376A2_D0006.tif" /></chemistry></li></ul> where the mole percentage is based on the content of SO₂-Groups relates. The polyarylene ethers A with 3 to 97 mol% of repeating units of the formula (II) and 3 to 97 mol% of repeating units of the formula (III) are particularly preferred.

0022The production of polyarylene ethers is generally known (see, for example, GB-A-1 152 035; US 4,870,153; WO 84/03891), as is the production of polyarylene ethers with a block structure (DE-A-37 42 264). Methods for the synthesis of copolymers are described, for example, in A. Noshay et al., Block Copolymers, Academic Press, New York 1977.

0023The reaction of monomeric dihydroxy compounds with dihalogen compounds 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 carbonate as base or the reaction in the melt. In addition, the reaction of acid chlorides with aromatic compounds with abstractable hydrogen atoms in the presence of Lewis acids such as aluminum trichloride is suitable.

0024Polyarylene ethers A without hydroxy end groups can be prepared, for example, by a suitable choice of the molar ratio between dihydroxy and dichloromonomers (see, for example, McGrath et al, Polym. Eng. Sci. 17, 647 (1977); Elias "Makromoleküle", 4th edition (1981 ), Pages 490 to 493, Hütig &amp; Wepf.-Verlag, Basel).

0025Polyarylene ethers A are preferably used in which less than 0.03, preferably 0.025% by weight, based on the molecular weight M_n (Number average) of the polyarylene ethers, hydroxyl groups.

0026The polyarylene ethers A can contain, for example, halogen, methoxy, phenoxy, benzyloxy or amino end groups as end groups.

Component B

0027Polyarylene sulfides are component B of the molding compositions according to the invention. Their amount is 4 to 93% by weight. The molding compositions according to the invention preferably contain 10 to 85, in particular 10 to 25,% by weight of polyarylene sulfides.

0028In principle, all polyarylene sulfides can be used as component C. Polyarylene sulfides containing more than 30 mol%, in particular more than 70 mol%, of repeating units are preferred<chemistry id="chem0007" num="0007"><img file="EP0903376A2_D0007.tif" /></chemistry> contain. Examples of other recurring units are<chemistry id="chem0008" num="0008"><img file="EP0903376A2_D0008.tif" /></chemistry> where RC_1-10-Alkyl, preferably methyl and n denotes either 1 or 2. The polyarylene ether sulfides can be both random copolymers and block copolymers. Very particularly preferred polyphenylene sulfides contain 100 mol% of units of the general formula (IV).

0029Suitable end groups are, for example, halogen, thiol or hydroxyl, preferably halogen.

0030The polyarylene sulfides can be branched or unbranched. The preferred polyarylene sulfides have molecular weights of 1000 to 1000,000 g / mol.

0031Polyarylene sulfides are known per se or can be obtained by known methods. For example, as described in US Pat. No. 2,513,188, they can be prepared by reacting halogen aromatics with sulfur or metal sulfides. It is also possible to heat metal salts of halogen-substituted thiophenols (see GB-B 962 941). The preferred syntheses of polyarylene sulfides include the reaction of alkali metal sulfides with halogen aromatics in solution, such as, for example can be seen from US 3,354,129. Further methods are described in US 3,699,087, US 4,645,826 and JP Critchley et al., "Heat Resistant Polymers", pages 151 to 160 (1983), Plenum Press, New York.

Component C

0032The proportion of component C, the carboxy group-containing polyarylene ethers, in the thermoplastic molding compositions according to the invention is 1 to 20, preferably 1.5 to 15, in particular 2.5 to 12% by weight.

0033Component C is at least one modified, carboxyl group-containing polyaryl ether with recurring structural elements of the formula (V) and (VI).<chemistry id="chem0009" num="0009"><img file="EP0903376A2_D0009.tif" /></chemistry>    wherein<ul id="ul0003" list-style="none" compact="compact"><li>x represents 0.5 or 1,</li><li>t and q independently of one another represent 0, 1, 2 or 3,</li><li>n stands for an integer from 0 to 6,<dl id="dl0001" compact="compact"><dt>Q, T, Y</dt><dd>and E independently of one another are each a chemical bond or a group selected from -O-, -S-, -SO₂-, S = O, C = O, -N = N-, -R^dC = CR^e- and -CR^fR^G-,</dd></dl> mean where</li><li>R^d and R^e independently of one another each for a hydrogen atom or C_1-12-Alkyl stand and R^f and R^G independently of one another each for a hydrogen atom or C_1-12-Alkyl, C_1-12-Alkoxy or C_6-18-Aryl, where R^f and R^G optionally substituted independently of one another by fluorine and / or chlorine atoms or optionally together with the carbon atom to which they are attached, a carbon atom_3-12-Cycloalkyl group, optionally with one or more C_1-6Alkyl groups is substituted,</li><li>with the proviso that at least one of the groups T, Q and E for -SO₂- or C = O and, if t and q stand for 0, E for -SO₂- or C = O,<dl id="dl0002" compact="compact"><dt>Ar,</dt><dd>Ar¹, Ar² and Ar³ independently for C_6-18Aryls, these optionally with C_1-12-Alkyl, C_6-18-Aryl, C_1-12Alkoxy or halogen atoms are substituted,</dd><dt>R¹</dt><dd>for H, C_1-6-Alkyl, or - (CH₂)_n-COOH; and</dd></dl> wherein the molar ratio of units of the formula (V) to units of the formula (VI) is in the range from 0.05: 99.95 to 99.95: 0.05.</li></ul>

0034According to the invention, preference is given to those modified polyarylene ethers (component C) which have a proportion of units of the formula (VI) containing free acid groups of from about 0.05 to about 25 mol%, determined by ¹H-NMR.

0035Modified polyarylene ethers (component C) which comprise structural elements of the formula VI in which Ar² and Ar³ are each 1,4-phenylene, Y is SO₂, R¹ for C_1-6-Alkyl and n represents an integer from 1 to 6.

0036Alkyl radicals which can be used according to the invention comprise straight-chain or branched, saturated carbon chains having up to 12 carbon atoms. For example, the following radicals can be mentioned: C_1-6Alkyl radicals, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec. -Butyl, 2- or 3-methylpentyl; and longer chain residues such as unbranched heptyl, octyl, nonyl, decyl, undecyl, lauryl and the one or more branched analogues thereof.

0037The alkyl part of alkoxy groups which can be used according to the invention is defined as indicated above.

0038Cycloalkyl radicals which can be used according to the invention include in particular C_3-12-Cycloalkyl radicals, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylethyl, propyl, butyl, pentyl, hexyl, cyclohexylmethyl, cyclohexylmethyl.

0039Examples of C_6-18Arylene groups are phenylene groups such as 1,2-, 1,3- and 1,4-phenylene, naphthylene groups such as 1,6-, 1,7-, 2,6- and 2,7-naphthylene, and those of anthracene , Phenanthrene and naphthacene derived bridge groups.

0040The laterally carboxylated polyarylene ethers (component C), which comprise the structural elements of the formulas (V) and (VI), are used as compatibilizers in the molding compositions according to the invention, and compounds which are known per se or can be prepared by known processes.

0041For example, the polyarylene ethers modified according to the invention are accessible on the basis of EP-A-0 185 237 and according to those of IW Parsons et al., In Polymer, 34, 2836 (1993) and T. Koch, H. Ritter, in Macromol. Phys. 195, 1709 (1994).

0042Accordingly, the polyarylene ethers can be obtained, for example, by polycondensation of compounds of the general formula (VII)<chemistry id="chem0010" num="0010"><img file="EP0903376A2_D0010.tif" /></chemistry> where R² and n have the meanings given above, with at least one further, for example chlorine-functionalized, aromatic compound, such as bis- (4-chlorophenyl) sulfone, and optionally further hydroxy-functionalized compounds, such as bisphenol A and / or bisphenol S. Suitable reaction partners are known to the person skilled in the art.

0043Examples of suitable structural elements of the general formula (VI) are:<chemistry id="chem0011" num="0011"><img file="EP0903376A2_D0011.tif" /></chemistry> where n is an integer from 0 to 6.

0044The polyarylene ethers C containing acid groups used according to the invention have viscosity numbers of about 15 to 80 ml / g (determined in 1% strength NMP solution at 25 ° C.). The proportion of free acid groups in component C is 0.05 to 25, preferably 0.1 to 20 and in particular 0.1 to 15 mol%, the determination of the proportion of acid groups, as in IW Parsons et al., Polymer, 34, 2836 (1993)¹H-NMR takes place.

0045Different units of the formula (V) can be present randomly or in blocks in the polyarylene ether.

0046Polyaryl ether C which can be used according to the invention can be prepared, for example, in accordance with GB-A-1 152 035 and US Pat. No. 4,870,153. Suitable process conditions for the synthesis of polyarylene ethers are described, for example, in EP-A-0 113 112 and EP-A-0 135 130. As in the production of component A, 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. However, the introduction of terminal anhydride groups described therein is not absolutely necessary for the present invention. Examples of suitable polyarylene ethers C are those with at least one of the following recurring structural units I.₂₇ or I₂₈<chemistry id="chem0012" num="0012"><img file="EP0903376A2_D0012.tif" /></chemistry> or the structural units of the formulas I₁ to I_-26 II and III, which are described in component A.

0047Particularly preferred units of the formula I are units of the formulas II and III which can be present individually or in a mixture.

Component D

0048The proportion of component D impact-modifying rubber which has functional groups which are reactive towards carboxyl groups is 1 to 20, preferably 1.5 to 15, in particular 2.5 to 7,% by weight of the molding compositions according to the invention.

0049The rubber preferably has epoxy and / or oxazoline groups.

0050Preferred functionalized polyolefin rubbers are made up of the following components:<ul id="ul0004" list-style="none"><li>d1) 40 to 99% by weight of at least one α-olefin having 2 to 8 C atoms;</li><li>d2) 0 to 50% by weight of a diene;</li><li>d3) 0 to 45% by weight of a C_1-12Alkyl esters of acrylic acid or methacrylic acid or mixtures of such esters;</li><li>d4) 0 to 40% by weight of an ethylenically unsaturated C._2-20Mono- or dicarboxylic acid or a functional derivative of such an acid;</li><li>d5) 1 to 40% by weight of a monomer containing epoxy groups;</li><li>d6) 0 to 5% by weight of other radically polymerizable monomers.</li></ul>

0051Examples of suitable α-olefins d1) 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.

0052Suitable diene monomers d2) 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-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, like 3-methyltricyclo- (5.2.1.0.^2.6) -3,8-decadiene, 5-ethylidene-norbornene and dicyclopentadiene. The diene content is 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.

0053Examples of suitable esters d3) are methyl, ethyl and 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.

0054Instead of the esters d3) 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 d4).

0055Examples of monomers d4) are acrylic acid, methacrylic acid, tertiary alkyl esters of these acids, in particular tert-butyl acrylate and dicarboxylic acids, such as maleic acid and fumaric acid, or derivatives of these acids and their monoesters.

0056Latent 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 this are anhydrides of dicarboxylic acids having 2 to 20 carbon atoms, in particular maleic anhydride and tertiary carbon_1-12Alkyl esters of the abovementioned acids, in particular tert-butyl acrylate and tert-butyl methacrylate.

0057Ethylenically unsaturated dicarboxylic acids and anhydrides d4) can be represented by the following general formulas (VIII) and (IX):         R¹⁰C (COOR³) = C (COOR⁴) R⁵     (VIII)<chemistry id="chem0013" num="0013"><img file="EP0903376A2_D0013.tif" /></chemistry> where R¹⁰, R³, R⁴ and R⁵ independently of one another for H or C._1-6-Alkyl stand.

0058Monomers d5) bearing epoxy groups can be represented by the following general formulas (X) and (XI).<chemistry id="chem0014" num="0014"><img file="EP0903376A2_D0014.tif" /></chemistry> where R⁶, R⁷, R⁸, R⁹ and independently of one another for H or C._1-6-Alkyl stand, m is an integer from 0 to 20 and p is an integer from 0 to 10.

0059R are preferably³ to R¹⁰ for hydrogen, m for the value 0 or 1 and p for the value 1.

0060Preferred compounds d4) and d5) are maleic acid, fumaric acid and maleic anhydride or alkenyl glycidyl ether and vinyl glycidyl ether.

0061Particularly preferred compounds of the formulas (VIII) and (IX) or (X) and XI 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.

0062Olefin polymers of are particularly preferred<dl id="dl0003" compact="compact"><dt>50 up to 98.9.</dt><dd>in particular 60 to 94.85% by weight of ethylene,</dd><dt>1 up to 50.0,</dt><dd>in particular 5 to 40% by weight of an ester of acrylic or methacrylic acid, and</dd><dt>0.1 to 20.0,</dt><dd>in particular 0.15 to 15 wt .-% glycidyl acrylate and / or glycidyl methacrylate, acrylic acid and / or maleic anhydride.</dd></dl>

0063Functionalized rubbers D are particularly suitable<ul id="ul0005" list-style="none" compact="compact"><li>Ethylene methyl methacrylate glycidyl methacrylate,</li><li>Ethylene methyl acrylate glycidyl methacrylate</li><li>Ethylene methyl acrylate glycidyl acrylate and</li><li>Ethylene methyl methacrylate glycidyl acrylate polymers.</li></ul>

0064Other monomers d6) that can be used are, for example, vinyl esters and vinyl ethers.

0065The polymers described above can be prepared by processes known per se, preferably by random copolymerization under high pressure and elevated temperature.

0066The preparation of a rubber containing oxazine groups can be found by reacting a polymer (T) containing nitrile groups with a monoamino alcohol in the presence of a catalyst, the polymer T being melt-reacted with the monoamino alcohol in the presence of a catalyst in the absence of a solvent.

0067In principle, suitable polymers T containing nitrile groups are all polymers containing nitrile groups which are meltable.

0068Preferred polymers T generally contain from 0.5 to 80, preferably from 0.7 to 70,% by weight, based on the total weight of all units, of units derived from acrylonitrile or alkylacrylonitrile, including acrylonitrile or C_1-10-Alkylacrylonitrile, especially C_1-3-Alkylacrylonitrile are preferred. The polymers very particularly preferably contain T units which are derived from acrylonitrile or methacrylonitrile.

0069In addition to these units, the preferred polymers T contain from 20 to 99.5, preferably from 30 to 99.3,% by weight, based on the total weight of all units, of units which are derived from vinylaromatic compounds, vinyl esters, acrylic esters or other copolymerizable monomers .

0070A corresponding process is described in DE-A-196 06 198 with the title "Process for the preparation of polymers containing oxazine groups".

0071The melt index of the epoxy-modified rubbers is generally in the range from 1 to 80 g / 10 min (measured at 190 ° C. and 2.16 kg load).

Component E

0072As component E, the molding compositions according to the invention can contain up to 50% by weight, preferably up to 40% by weight, based on the total weight of components A to E, of further additives.

0073The molding compositions according to the invention preferably contain up to 50% by weight, particularly preferably 0.05 to 45% by weight, of fibrous or particulate fillers or mixtures thereof. These are preferably commercially available products. Processing aids and stabilizers such as UV stabilizers, lubricants, phosphorus stabilizers and antistatic agents are usually used in amounts of 0.01 to 5% by weight, reinforcing agents such as carbon fibers and glass fibers in contrast in amounts of 5 to 40% by weight. Carbon fibers and in particular glass fibers are particularly preferred as component G. The glass fibers used can be E, A or C glass and are preferably equipped with a size and an adhesion promoter. Their diameter is generally between 6 and 20 microns. Both continuous fibers (rovings) and chopped glass fibers with a length of 1 to 10 mm, preferably 3 to 6 mm, can be used. Fillers or reinforcing materials such as glass balls, mineral fibers, whiskers, aluminum oxide fibers, mica, quartz powder and wollastonite can also be added. Metal flakes (for example aluminum flakes from Transmet Corp.), metal powder, metal fibers, metal-coated fillers (for example nickel-coated glass fibers) and other additives which shield electromagnetic waves may also be mentioned. Al flakes (K 102 from Transmet) are particularly suitable for EMI purposes (electro-magnetic interference); further mixing of this mass with additional carbon fibers, carbon black or nickel-coated carbon fibers. The molding compositions according to the invention may also contain additives which are typical and customary for polyarylene ethers, polyarylene sulfide and rubbers. Examples of such additives are: dyes, pigments, antistatic agents and antioxidants.

Production of molding compounds

0074The molding compositions according to the invention are produced by mixing components A to D and, if appropriate, E.

0075The order in which components A to E are mixed is arbitrary.

0076The molding compositions according to the invention can be produced by processes known per se, for example extrusion. The molding compositions according to the invention can be produced, for example, by mixing the starting components in conventional mixing devices such as screw extruders, preferably twin-screw extruders, Brabender mixers or Banburry mixers and kneaders, and then extruding them. After the extrusion, the extrudate is cooled and crushed. 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.

0077In order to obtain the most homogeneous possible mixing, intensive mixing is advantageous. This generally requires average mixing times of 0.2 to 30 minutes at temperatures of 280 to 400 ° C, preferably 290 to 390 ° C. After the extrusion, the extrudate is usually cooled and crushed.

0078The thermoplastic molding compositions according to the invention can be processed by the known methods of thermoplastic processing, for example by extrusion, injection molding, calendering, blow molding, pressing or sintering.

0079The molding compositions and moldings, fibers and films made of them are distinguished by very good chemical resistance, very good notched impact strength and increased tracking resistance. The molding compounds also have good flow properties.

0080The invention is illustrated by the examples below.

Examples

0081The viscosity number of the products is determined in 1% solution of N-methylpyrrolidone (NMP) at 25 ° C. The proportion of units with acid groups in the copolyaryl ethers C) was as described in IW Parsons et al., Polymer 34, 2836 (1993)¹H-NMR spectroscopy determined.

Component A1

0082Ultrason® S 2010 (commercial product from BASF AG) was used as polyaryl ether A1. This product is characterized by a viscosity number of 56 ml / g, measured in 1% NMP solution at 25 ° C.

Component A2

0083Ultrason® E 1010 (commercial product from BASF AG) was used as polyaryl ether A2. This product is characterized by a viscosity number of 49 ml / g, measured in 1% NMP solution at 25 ° C.

Component B

0084Polyphenyl sulfide, modulus of elasticity = 3200 N / mm²; eg commercial product Fortron® 0214 from Hoechst.

Component C1

00855.742 kg of dichlorodiphenyl sulfone, 4.374 kg of bisphenol A and 112 g of 4,4'-di-hydroxyvaleric acid were dissolved in 29 kg of N-methylpyrrolidone under a nitrogen atmosphere, and 2.820 kg of anhydrous potassium carbonate were added.

0086The reaction mixture was first heated to 180 ° C. at a pressure of 300 mbar while continuously distilling off the water of reaction and N-methylpyrrolidone and then reacted further at 190 ° C. for 6 hours.

0087After adding 40 kg of N-methylpyrrolidone, the inorganic constituents were filtered off. Basic groups were neutralized by adding 50 ml of glacial acetic acid, and the polymer was then isolated by precipitation in water. After extraction three times with water, the product was dried at 240 ° C. under reduced pressure. A white powder was obtained.

0088The proportion of units with acid groups was determined by H-NMR to be 1.2 mol%, the viscosity number of the product was 38.1 ml / g.

Component C2

0089Under a nitrogen atmosphere, 5.742 kg of dichlorodiphenyl sulfone, 4.240 kg of bisphenol A and 280 kg of 4,4'-di-hydroxyvaleric acid were dissolved in 29 kg of N-methylpyrrolidone, and 2.820 kg of anhydrous potassium carbonate were added.

0090The reaction mixture was first heated to 180 ° C. at a pressure of 300 mbar while continuously distilling off the water of reaction and N-methylpyrrolidone and then reacted further at 190 ° C. for 6 hours.

0091After adding 40 kg of N-methylpyrrolidone, the inorganic constituents were filtered off. Basic groups were neutralized by adding 150 ml of glacial acetic acid, and the polymer was then isolated by precipitation in water. After extraction three times with water, the product was dried at 140 ° C. under reduced pressure. A white powder was obtained.

0092The proportion of units with acid groups was determined by H-NMR to be 3.1 mol%, the viscosity number of the product was 37.1 ml / g.

Component C3

00935.742 kg of dichlorodiphenyl sulfone, 5.076 kg of dihydroxydiphenyl sulfone and 305.8 g of 4,4'-dihydroxyvaleric acid were dissolved in 29 kg of N-methylpyrrolidone under a nitrogen atmosphere, and 2.820 kg of anhydrous potassium carbonate were added.

0094The reaction mixture was first heated to 180 ° C. at a pressure of 300 mbar while continuously distilling off the water of reaction and N-methylpyrrolidone and then reacted further at 190 ° C. for 6 hours.

0095After adding 40 kg of N-methylpyrrolidone, the inorganic constituents were filtered off. Basic groups were neutralized by adding 300 ml of glacial acetic acid, and the polymer was then isolated by precipitation in water. After extraction three times with water, the product was dried at 140 ° C. under reduced pressure. A white powder was obtained.

0096The proportion of units with acid groups was determined to be 3.0 mol% by means of H-HMR, the viscosity number of the product was 40.2 ml / g.

Component D

0097Ethylene-methyl methacrylate-glycidyl methacrylate polymer with 25% by weight MMA and 8% by weight GMA, characterized by a melt index (190 ° C, 2.16 kg) of 6 g / 10 min, for example Lotader AX 8900 from Elf- Atochem.

Production and testing of molding compounds

0098The components were mixed in a twin-screw extruder at a melt temperature of 300 to 350 ° C. The melt was passed through a water bath and granulated.

0099The molding compositions containing polysulfone were processed at a melt temperature of 310 ° C., while the molding compositions containing polyethersulfone were processed at 350 ° C. The mold temperature was 100 ° C in each case.

0100The heat resistance of the samples was determined using the Vicat softening temperature. The Vicat softening temperature was determined according to DIN 53 460 with a force of 49.05 N and a temperature increase of 50 K per hour on standard small bars.

0101The impact strength of the products was determined on ISO bars according to ISO 179 leA. To characterize the flowability of the products, the MVI values ​​were determined in accordance with DIN 53 735 at 300 or 320 ° C and 21.6 kg load.

0102The damage work was determined for unreinforced samples on round disks in accordance with DIN 53 443.

0103The chemical resistance of the products was characterized by storing molded articles in N-methylpyrrolidone for one hour. The weight loss of the molded body was determined as a measure of the chemical resistance. The tracking resistance was determined according to IEC 112.

0104The compositions of the molding compositions and comparative molding compositions V1 to V4 and the results of the tests are listed in Table 1. <tables id="tabl0001" num="0001"><table frame="all"><title>Table 1</title><tgroup cols="8" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="19.68mm" /><colspec colnum="2" colname="col2" colwidth="19.68mm" /><colspec colnum="3" colname="col3" colwidth="19.68mm" /><colspec colnum="4" colname="col4" colwidth="19.68mm" /><colspec colnum="5" colname="col5" colwidth="19.68mm" /><colspec colnum="6" colname="col6" colwidth="19.68mm" /><colspec colnum="7" colname="col7" colwidth="19.68mm" /><colspec colnum="8" colname="col8" colwidth="19.68mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left"><b>example</b></entry><entry namest="col2" nameend="col2" rowsep="0" align="left"><b>V1</b></entry><entry namest="col3" nameend="col3" rowsep="0" align="left"><b>V2</b></entry><entry namest="col4" nameend="col4" rowsep="0" align="left"><b>1</b></entry><entry namest="col5" nameend="col5" rowsep="0" align="left"><b>V3</b></entry><entry namest="col6" nameend="col6" rowsep="0" align="left"><b>2</b></entry><entry namest="col7" nameend="col7" rowsep="0" align="left"><b>V4</b></entry><entry namest="col8" nameend="col8" rowsep="0" align="left"><b>3</b></entry></row><row><entry namest="col1" nameend="col1" align="center">Component [% by weight]</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" /><entry namest="col6" nameend="col6" /><entry namest="col7" nameend="col7" /><entry namest="col8" nameend="col8" /></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">A1</entry><entry namest="col2" nameend="col2" align="char" char=",">80</entry><entry namest="col3" nameend="col3" align="char" char=",">70</entry><entry namest="col4" nameend="col4" align="char" char=",">66</entry><entry namest="col5" nameend="col5" align="char" char=",">76</entry><entry namest="col6" nameend="col6" align="char" char=",">71</entry><entry namest="col7" nameend="col7" align="char" char=",">-</entry><entry namest="col8" nameend="col8" align="char" char=",">-</entry></row><row><entry namest="col1" nameend="col1" align="left">A2</entry><entry namest="col2" nameend="col2" align="char" char=",">-</entry><entry namest="col3" nameend="col3" align="char" char=",">-</entry><entry namest="col4" nameend="col4" align="char" char=",">-</entry><entry namest="col5" nameend="col5" align="char" char=",">-</entry><entry namest="col6" nameend="col6" align="char" char=",">-</entry><entry namest="col7" nameend="col7" align="char" char=",">76</entry><entry namest="col8" nameend="col8" align="char" char=",">71</entry></row><row><entry namest="col1" nameend="col1" align="left">B</entry><entry namest="col2" nameend="col2" align="char" char=",">20</entry><entry namest="col3" nameend="col3" align="char" char=",">20</entry><entry namest="col4" nameend="col4" align="char" char=",">19</entry><entry namest="col5" nameend="col5" align="char" char=",">19</entry><entry namest="col6" nameend="col6" align="char" char=",">19</entry><entry namest="col7" nameend="col7" align="char" char=",">19</entry><entry namest="col8" nameend="col8" align="char" char=",">19</entry></row><row><entry namest="col1" nameend="col1" align="left">C1</entry><entry namest="col2" nameend="col2" align="char" char=",">-</entry><entry namest="col3" nameend="col3" align="char" char=",">10</entry><entry namest="col4" nameend="col4" align="char" char=",">10</entry><entry namest="col5" nameend="col5" align="char" char=",">-</entry><entry namest="col6" nameend="col6" align="char" char=",">-</entry><entry namest="col7" nameend="col7" align="char" char=",">-</entry><entry namest="col8" nameend="col8" /></row><row><entry namest="col1" nameend="col1" align="left">C2</entry><entry namest="col2" nameend="col2" align="char" char=",">-</entry><entry namest="col3" nameend="col3" align="char" char=",">-</entry><entry namest="col4" nameend="col4" align="char" char=",">-</entry><entry namest="col5" nameend="col5" align="char" char=",">-</entry><entry namest="col6" nameend="col6" align="char" char=",">5</entry><entry namest="col7" nameend="col7" align="char" char=",">_</entry><entry namest="col8" nameend="col8" align="char" char=",">-</entry></row><row><entry namest="col1" nameend="col1" align="left">C3</entry><entry namest="col2" nameend="col2" align="char" char=",">-</entry><entry namest="col3" nameend="col3" align="char" char=",">-</entry><entry namest="col4" nameend="col4" align="char" char=",">-</entry><entry namest="col5" nameend="col5" align="char" char=",">-</entry><entry namest="col6" nameend="col6" align="char" char=",">-</entry><entry namest="col7" nameend="col7" align="char" char=",">-</entry><entry namest="col8" nameend="col8" align="char" char=",">5</entry></row><row><entry namest="col1" nameend="col1" align="left">D</entry><entry namest="col2" nameend="col2" align="char" char=",">-</entry><entry namest="col3" nameend="col3" align="char" char=",">-</entry><entry namest="col4" nameend="col4" align="char" char=",">5</entry><entry namest="col5" nameend="col5" align="char" char=",">5</entry><entry namest="col6" nameend="col6" align="char" char=",">5</entry><entry namest="col7" nameend="col7" align="char" char=",">5</entry><entry namest="col8" nameend="col8" align="char" char=",">5</entry></row><row><entry namest="col1" nameend="col1" align="left">Vicat B [° C]</entry><entry namest="col2" nameend="col2" align="char" char=",">184</entry><entry namest="col3" nameend="col3" align="char" char=",">184</entry><entry namest="col4" nameend="col4" align="char" char=",">182</entry><entry namest="col5" nameend="col5" align="char" char=",">182</entry><entry namest="col6" nameend="col6" align="char" char=",">182</entry><entry namest="col7" nameend="col7" align="char" char=",">219</entry><entry namest="col8" nameend="col8" align="char" char=",">218</entry></row><row><entry namest="col1" nameend="col1" align="left">a_k[kJ / m²]</entry><entry namest="col2" nameend="col2" align="char" char=",">3,5</entry><entry namest="col3" nameend="col3" align="char" char=",">3,4</entry><entry namest="col4" nameend="col4" align="char" char=",">29,0</entry><entry namest="col5" nameend="col5" align="char" char=",">4,3</entry><entry namest="col6" nameend="col6" align="char" char=",">43</entry><entry namest="col7" nameend="col7" align="char" char=",">2,7</entry><entry namest="col8" nameend="col8" align="char" char=",">31</entry></row><row><entry namest="col1" nameend="col1" align="left">W_S [Nm]</entry><entry namest="col2" nameend="col2" align="char" char=",">12</entry><entry namest="col3" nameend="col3" align="char" char=",">43</entry><entry namest="col4" nameend="col4" align="char" char=",">53</entry><entry namest="col5" nameend="col5" align="char" char=",">12</entry><entry namest="col6" nameend="col6" align="char" char=",">51</entry><entry namest="col7" nameend="col7" align="char" char=",">4</entry><entry namest="col8" nameend="col8" align="char" char=",">52</entry></row><row><entry namest="col1" nameend="col1" align="left">MVI [rnl / 10 ']</entry><entry namest="col2" nameend="col2" align="char" char=",">100</entry><entry namest="col3" nameend="col3" align="char" char=",">109</entry><entry namest="col4" nameend="col4" align="char" char=",">98</entry><entry namest="col5" nameend="col5" align="char" char=",">90</entry><entry namest="col6" nameend="col6" align="char" char=",">89</entry><entry namest="col7" nameend="col7" align="char" char=",">95</entry><entry namest="col8" nameend="col8" align="char" char=",">99</entry></row><row><entry namest="col1" nameend="col1" align="left">Mass loss in NMP [%]</entry><entry namest="col2" nameend="col2" align="char" char=",">10,2</entry><entry namest="col3" nameend="col3" align="char" char=",">4,5</entry><entry namest="col4" nameend="col4" align="char" char=",">4,0</entry><entry namest="col5" nameend="col5" align="char" char=",">7,6</entry><entry namest="col6" nameend="col6" align="char" char=",">3,1</entry><entry namest="col7" nameend="col7" align="char" char=",">6,8</entry><entry namest="col8" nameend="col8" align="char" char=",">4,8</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">CTI</entry><entry namest="col2" nameend="col2" align="char" char=",">175</entry><entry namest="col3" nameend="col3" align="char" char=",">175</entry><entry namest="col4" nameend="col4" align="char" char=",">225</entry><entry namest="col5" nameend="col5" align="char" char=",">200</entry><entry namest="col6" nameend="col6" align="char" char=",">225</entry><entry namest="col7" nameend="col7" align="char" char=",">175</entry><entry namest="col8" nameend="col8" align="char" char=",">200</entry></row><row rowsep="1"><entry namest="col1" nameend="col8" align="justify">MVI: V4, 3: measuring temperature 320 ° C, otherwise 300 ° C VI to V4: comparative experiments</entry></row></tbody></tgroup></table></tables>