Method for producing low-halogen polybiphenylsulfone polymers

0001The present invention relates to a process for the preparation of halogen-poor Polybiphenylsulfon-polymers thus obtainable Polybiphenylsulfon-polymers with a content of polymer-bound Halogen of less than 400 ppm, thermoplastic molding compositions containing the above-mentioned Polybiphenylsulfon-polymers and their use for the production of moldings, fibers, films, membranes, or foams

0002Polybiphenylsulfon-polymers belong to the group of polyarylene ether, and thus to the class of high-performance thermoplastics. In addition to high heat resistance, the Polybiphenylsulfon-polymers have superior impact strength and excellent fire behaviour.

0003The production of Polybiphenylsulfon-polymers is, for example, from the <patcit id="pcit0001" dnum="DE1957091"><text>DE 1957091</text></patcit>the <patcit id="pcit0002" dnum="EP000361A"><text>EP 000361</text></patcit> and the <patcit id="pcit0003" dnum="EP0347669A"><text>EP 0 347 669</text></patcit> known. The <patcit id="pcit0004" dnum="WO2000018824A"><text>WHERE 2000/018824</text></patcit> a process for the preparation of Polybiphenylsulfon-revealed-cyclic Oligomers, polymers with a low proportion. The <patcit id="pcit0005" dnum="EP1272547A"><text>EP 1272547</text></patcit> describes Polybiphenylsulfon-polymers with very low intrinsic color, obtained by Condensation of the monomers 4,4'-Dihydroxybiphenyl and 4,4'-dichloro diphenyl sulfone in the presence of finely divided potash. In the prior art, the reactants are usually used in equimolar amounts.

0004From the known method, the resulting content of polymer bound Halogen, in particular chlorine in the Polybiphenylsulfon polymers, however, is too high for many applications and brand often doesn't suffice the protection needs. For applications in the field of electronics, such as for example, switches, casings, foils, often very low chlorine required levels. In addition, the intrinsic color of the according to the prior art available Polybiphenylsulfon polymers is often not satisfactory. Polybiphenylsulfon-polymers with a particularly low inherent colour would be thus desirable. From the prior art known Polybiphenylsulfon-polymers have, in addition, in many cases, insufficient elongation at break.

0005From <nplcit id="ncit0001" npl-type="s"><text>J. E. McGrath et. al., Polymer 25 (1984), 1827 </text></nplcit>is known in the art, such as, the molecular weight can be controlled in the Condensation of polyarylene sulfones based on Bisphenol-A. Commercial polyarylene ethers, e.g. Sumika Excel®, have predominantly chlorine end groups. A process for the preparation of Polybiphenylsulfon-polymers, using an Excess of the aromatic dihydroxy compound and in the presence of water and/or a metal hydroxide is not yet known.

0006<patcit id="pcit0006" dnum="US4794155A"><text>US 4 794 155 A</text></patcit> Polybiphenylsulfon describes Polymer, which contain activating groups, and the use of chlorine-containing Monomers are based.

0007<patcit id="pcit0007" dnum="EP0106023A"><text>EP 0 106 023 A</text></patcit> Polybiphenyl describes polymers which have mandatory unsaturated end-cap.

0008<patcit id="pcit0008" dnum="DE27109305A1"><text>DE 27 109 305 A1</text></patcit> Polybiphenyl describes polymers, the silane are end-capped.

0009The obtainable by the process Polybiphenylsulfon-polymers of the present invention is not or to a lesser extent, should have the aforementioned disadvantages. It was in particular an object of the present invention to provide a process for the preparation of Polybiphenylsulfon-polymers, which enables their manufacture with good control of the molecular weight. The Polybiphenylsulfon polymers should exhibit in addition, low shear rate, low viscosity and, in particular, in the form of tool flow.

0010The object of the present invention, in particular, Polybiphenylsulfon-polymers to provide superior mechanical properties, a low content of polymer bound Halogen, in particular chlorine-containing, and also a comparison with the prior art reduced Residual solvent content to have. The Polybiphenylsulfon polymers should also have a low intrinsic color.

0011The present object is achieved by a method for the production of Polybiphenylsulfon-polymers comprising<ol id="ol0001" compact="compact" ol-style=""><li>(a) providing the components (a1) composed of at least one aromatic dihydroxy compound and (a2) consisting of at least one aromatic sulfonic substituents compound having two Halogen, wherein the component (a1) of 4,4'-dihydroxy biphenyl, includes, and then</li><li>(b) the implementation of the component (a2) with a molar Excess of component (a1) in a solvent, using alkali metal carbonates as Base, wherein, during or after the reaction, water and/or a metal hydroxide is added.</li></ol>

0012Polybiphenylsulfon-polymers with a content of polymer bound Halogen, in particular chlorine of less than 400 ppm and at least 10 ppm, obtainable by this method are of the prior art so far not known.

0013Preferred embodiments are disclosed in the claims and the following description. Combinations of preferred embodiments are within the scope of the present invention, in particular with regard to combinations of preferred embodiments of the following steps (a) and (b).

Step (a)

0014In accordance with step (a) of the method according to the invention is the provision of components (a1) is composed of at least one aromatic dihydroxy compound and (a2) consisting of at least one aromatic sulfone compound having two halogen substituents, wherein the component (a1) of 4,4'-dihydroxy biphenyl includes.

0015Under Polybiphenylsulfon-Polymer, polyarylene ether sulfones are to be understood, which is 4,4'-dihydroxy biphenyl include, as a monomer unit. Consequently, the term Polybiphenylsulfon-Polymer includes, among other things, Polybiphenylsulfon-Homo - and copolymers. Under polyarylene ether sulfones are polymers which, arylenes units on oxygen, and sulfone bridges are present linked to. A Polybiphenylsulfon-Polymer, which is composed exclusively of the monomer units 4,4'-dihalo diphenyl sulfone and 4,4'-dihydroxy biphenyl, referred to as the Polybiphenylsulfon (PPSU).

0016In the context of the present invention is taken for the characterization of the structure of the Polybiphenylsulfon-polymers used monomer units. It is obvious to the skilled person that the monomer units in the Polymer are present in unreacted Form, and that the implementation of the Monomer by nucleophilic aromatic Halogen-tables polycondensation with theoretical elimination of one unit of hydrogen as a cleavage group. Consequently, the structure of the resulting polymer is independent of the precise nature of the spin-off group.

0017According to the invention, component (a1) consists of at least one aromatic dihydroxy compound, and comprises 4,4'-dihydroxy biphenyl. In addition, the component (a1) may include in particular the following Compounds:<ul id="ul0001" list-style="dash" compact="compact"><li>Dihydroxybenzenes, in particular hydroquinone and resorcinol;</li><li>Dihydroxynaphthalenes, in particular 1,5-Dihydroxynaphthalene, 1,6 - Dihydroxynaphthalene, 1,7 - dihydroxy naphthalene, and 2,7 - dihydroxy naphthalene;</li><li>Other dihydroxy biphenyls as 4,4'- Dihydroxybiphenyl, in particular 2,2'-Dihydroxybiphenyl;</li><li>Bisphenylmethylene ethers, in particular Bis(4-hydroxyphenyl)ether and Bis(2-hydroxyphenyl)ether;</li><li>Bisphenylmethylene propane, in particular, 2,2-Bis(4-hydroxyphenyl)propane, 2,2-Bis(3-methyl-4-hydroxyphenyl)propane, and 2,2-Bis(3,5-dimethyl-4-hydroxyphenyl)propane;</li><li>Bisphenylmethylene methane, in particular Bis(4-hydroxyphenyl)methane</li><li>Bisphenylmethylene cyclohexane, in particular Bis(4-hydroxyphenyl)-2,2,4-trimethyl cyclohexane;</li><li>Bisphenylmethylene sulfones, in particular Bis(4-hydroxyphenyl)sulfone;</li><li>Bisphenylmethylene sulfides, in particular Bis(4-hydroxyphenyl)sulfide;</li><li>Bisphenylmethylene ketones, in particular Bis(4-hydroxyphenyl)ketone;</li><li>Bisphenylmethylene HEXAFLUOROPROPANE, in particular 2,2-Bis(3,5-dimethyl-4-hydroxyphenyl)hexafluoro-propane; and</li><li>Bisphenylmethylene fluorene, in particular 9,9-Bis(4-hydroxyphenyl)fluorene.</li></ul>

0018Preferably, the component (a1) contains at least 50, especially at least 60, particularly preferably at least 80 Wt.-% 4,4'-dihydroxy biphenyl. Very particularly preferably, the component (a1) of 4,4'-dihydroxy biphenyl.

0019In the context of component (a2) suitable aromatic sulfonic compounds having two halogen substituents are generally known in the art. Preferred Compounds (a2) are, in particular, dihalo diphenyl sulfones such as 4,4'-dichloro diphenyl sulfone, 4,4'-difluoro diphenyl sulfone, 4,4'-dibromo diphenyl sulfone, Bis(2-chlorophenyl)sulfones, 2,2'-dichloro diphenyl sulfone, and 2,2'-difluoro diphenyl sulfone. 4,4'-dichloro diphenyl sulfone and 4,4'-difluoro diphenyl sulfone are particularly preferred. Very particularly preferably, 4,4'-dichloro diphenyl sulfone.

0020The reaction of 4,4'-Dihydroxybiphenyl as component (a1) and 4,4'-dihalo diphenyl sulfone results as the component (a2), from the Polybiphenylsulfon (PPSU) as a product, is particularly preferred.

Step (b)

0021According to the present invention, the method for the production of Polybiphenylsulfon-includes the implementation of the component (a2) polymers with a molar Excess of component (a1) in a solvent, wherein, after the reaction of components (a1) and (a2) water and/or a metal hydroxide is added.

0022In the Following it is referred to is called a water and/or metal hydroxide is generally considered to be "hydroxide source" reference.

0023The use of an Excess of component (a1), in combination with the use of the hydroxide source, associated with the addition of the hydroxide source in the case of high turnovers, the content of polymer-bonded Halogen, to reduce, in particular, chlorine.

0024The reaction of components (a1) and (a2) to a Polybiphenylsulfon-Polymer, the skilled person in relation to the temperature, the solvent and the length of time known. The reaction of the starting compounds (a1) and (a2) is carried out at a temperature of 80 to 250°C, preferably 100 to 220°C, wherein the upper limit of the temperature through the boiling point of the solution is by means of limited. The reaction is preferably carried out in a time interval of 2 to 12 h, in particular from 3 to 8 h.

0025The molar ratio of the components (a1) to (a2) is preferably from 1,005 to 1.2, in particular from 1,005 to 1.1. In a particularly preferred embodiment, the molar ratio of the components (a1) to (a2) from 1,005 up to 1.08, in particular from 1.01 to 1.05, very particularly preferably from 1,015 to 1.04. As a result, the molecular weight can be particularly effectively control and monitor at the same time an advantageous effect on the resulting content of polymer bound Halogen, in particular chlorine.

0026The hydroxide source, i.e. water, metal hydroxide, or a mixture of water and metal hydroxide is preferably used in an amount of 0.1 to 10 Wt.-parts, in particular in an amount of 0.5 to 6 Wt.-parts, particularly preferably in an amount of 1 to 5 Wt.-parts based on 100 parts by weight of the components (a1) and (a2) are added.

0027As a hydroxide source, especially water, alkali metal hydroxides and alkaline earth metal hydroxides, and mixtures thereof, and/or aqueous solutions should be considered. Preferred hydroxide sources of water and alkali metal hydroxides. Preferred alkali metal hydroxides LiOH, NaOH and KOH. Aqueous solutions of the above-mentioned metal hydroxides, in particular aqueous solutions of the aforementioned alkali metal hydroxides are particularly preferred. Thus, it is of particular advantage, if the hydroxide source are alkali metal hydroxides, in particular LiOH, NaOH and/or KOH, includes.

0028The addition of the hydroxide source can be done by various methods. Preferably, the addition is carried out in diluted Form, wherein the amount to be added of the hydroxide source, preferably in the same solvent is pre-solves, in which the reaction is carried out.

0029The time of addition of the hydroxide source may also vary. According to the invention, the reaction is started first, without the presence of the hydroxide source. Thus, it is carried out in accordance with step (b) initially the reaction in the solvent, and then the hydroxide source is added, so that after the reaction of components (a1) and (a2), the hydroxide source is present.

0030In the process according to the invention, the reaction is completed, while the runs out the polycondensation at the time of addition of the hydroxide source in the Material. In this case, the addition of water and/or metal hydroxides in connection to the implementation of the components (a1) and (a2), i.e. after the polycondensation. Due to this implementation variant, a reduction of the molecular is avoided weight effectively.

0031Under the implementation of the components (a1) and (a2), the polycondensation with the formation of a Polybiphenylsulfon-polymer.

0032The addition of the hydroxide source is preferably carried out at a turnover of at least 90%, particularly at least 95%, very especially preferably at least 98%. The turnover is in the context of the present invention, in principle, the molar proportion of the unreacted halogen groups of component (a2) in relation to the total amount of reacted and unreacted halogen groups of component (a2). In the case of the above-mentioned sales, the polycondensation is Essentially complete. The temperature during the further implementation (Post-implementation) is preferably from 100 to 200°C., in particular from 130°C to 180°C. The exact temperature of the After-implementation chooses the skilled artisan depending on the selected solvent.

0033It is for the present invention is advantageous to select the reaction conditions so that the turnover is at the end of step (b) at least 95 %, particularly preferably at least 98 %, particularly at least 99%. The final product has a more or less broad molecular weight distribution, if necessary including Oligomers wherein the end Groups either Halogen or hydroxy groups, or, in the case of further reaction, Alkyl - or aryloxy groups, and computers correspond to the 100% different sales.

0034In a preferred embodiment, immediately before it is reduced, at the same time or directly subsequently to the addition of the hydroxide source, the temperature, particularly preferably 15 to 80°C, especially 20 to 45°C compared to the temperature in the reaction of components (a1) and (a2), i.e., the temperature during the polycondensation. The temperature of the reaction mixture can effectively be reduced by the hydroxide source is diluted with a suitable amount of solvent is added, in particular room temperature, which has a low temperature.

0035The time duration may vary According to implementation, after the addition of the hydroxide source over a wide range. Usually, the time period of After-reaction with the hydroxide source from 15 minutes to 8 hours, especially 30 minutes to 4 hours, particularly preferably from 1 to 3 hours.

0036Without wishing to be limited, there is the notion that the inventive addition of the hydroxide source causes a Substitution of the Halogen end Groups with a reduction of the polymer-bound proportion of Halogen, in particular chlorine.

0037According to the present invention, the reaction of components (a1) and (a2) is carried out in a solvent. Preferred solvents are polar aprotic solvents. Suitable solvents have a boiling point in the range of 80 to 320°C, in particular 100 to 280°C, preferably from 150 to 250°C. Suitable polar aprotic solvents are, in particular, high-boiling ethers, esters, Ketones, asymmetrically halogenated hydrocarbons, Anisole, dimethylformamide, dimethyl sulfoxide, Sulfolane, N-Ethyl-2-pyrrolidone and N-Methyl-2-pyrrolidone (N-methyl pyrrolidone, NMP), and mixtures of the aforementioned solvents.

0038It has surprisingly been found that a particularly low content of polymer bound Halogen, in particular chlorine is obtained, if as a solvent used, the N-methyl pyrrolidone includes. N-methylpyrrolidone is preferred as a solvent is particularly. N-methyl pyrrolidone contributes to a high turnover of components (a1) and (a2), since the reaction of the invention proceeds according to the monomers very efficiently.

0039The reaction of components (a1) and (a2) is preferably carried out in the presence of a Base (B), in order to increase reactivity to the halogen substituents of the starting compounds (a2). It is preferred, on the basis of the above-mentioned aromatic dihydroxy compounds (a1) by adding a Base (B) their Dipotassium or disodium salts and the component (a2) to the reaction. Suitable bases (B) are known in the art.

0040Bases (B) are alkali metal carbonates. The combination of the use of alkali metal carbonates as Base (B) and the demanding proper implementation of the method leads to particularly favorable properties in terms of colour, mechanical properties and content of polymer bound Halogen, in particular chlorine.

0041Preferably, the bases are water-free. Suitable bases are, in particular, anhydrous alkali metal carbonate, preferably sodium, potassium, calcium carbonate or mixtures thereof, wherein potassium carbonate is particularly preferred, in particular potassium carbonate with volume-weighted mean particle size of less than 150 microns, determined using a particle size measuring instrument in a Suspension in a mixture of chlorobenzene/Sulfolane (60/40 by weight). A particularly preferred combination is N-Methyl-2-pyrrolidone as solvent and anhydrous potassium carbonate as Base (B).

0042It has also been found to be advantageous in the context of step (b) the amount of the Polybiphenylsulfon polymer based on the total weight of the mixture of Polybiphenylsulfon-Polymer, and solvent of 10 to 70 Wt.-%, preferably from 15 to 50 Wt.-% set.

0043In a preferred embodiment, is added during or after the reaction according to step (b) at least one aromatic organic monochloro compound as the component (a3).

0044Without wishing to be limited, there is the idea that the aromatic organic monochloro acts compound as a chain regulator. Preferably, the aromatic organic monochloro compound has a similar reactivity in the context of the reaction in step (b) as the component (a2).

0045Preferably, the component (a3) is an aromatic monochloro sulfone, in particular, 4-mono chloro diphenyl sulfone. In a preferred embodiment, the Excess of the component (a1) is compensated by the organic monochloro compound (a3), which contains a under the conditions of the reaction of components (a1) and (a2) reactive chloro group.

0046The molar quantity of component (a3) is preferably selected so that the Double of the Excess of the molar amount of the component (a1) is compared to the molar quantity of component (a2) in a ratio to the molar amount of the component (a3) from 0.98 to 1.02, in particular from 0.99 to 1.01. Accordingly, 2*((a1) is (a2)) / (a3) is preferably from 0.98 to 1.02, in particular from 0.99 to 1.01, where (a1), (a2) and (a3), the used molar amounts of the respective component reflect. The Duplicate of the ratio ((a1) - (a2) / (a3)) is preferably 1.

0047In a further preferred embodiment, which can be associated with the above-mentioned embodiments is advantageous, is in connection to step (b) according to step (c) is a reaction with at least one aliphatic organic halogen compound. As a result, reactive hydroxyl end Groups are further reacted, the Polymer stabilized, and Including a further build-up of the polymer chain in the framework of the further processing is prevented.

0048Preferred aliphatic organic halogen compounds are alkyl halides, particularly alkyl chlorides, with the linear or branched alkyl groups having from 1 to 10 carbon atoms, particularly primary alkyl chlorides, particularly preferably methyl halide, especially methyl chloride.

0049The reaction according to step (c) is preferably carried out at a temperature of 90° to 160°C., in particular from 100°C to 150°C. The time duration can vary over a wide period of time and is usually at least 5 minutes, in particular at least 15 minutes. Preferably, the time duration of the reaction according to step (c) from 15 minutes to 8 hours, especially 30 minutes to 4 hours.

0050The addition of the aliphatic organic halogen compound can be carried out via different methods. In addition, the addition of the aliphatic organic halogen compound can be carried out stoichiometrically or in Excess, wherein the Excess of, for example, up to 5-can be specialized. In a preferred embodiment, the addition of the aliphatic organic halogen compound takes place continuously, in particular by continuous feeding as the gas stream.

0051It has proven advantageous, following step (b) or step (c) is a Filtration of the polymer solution. As a result, the in the polycondensation formed of salt and any formed gel body is removed.

Polybiphenylsulfon-Polymers

0052A further object of the present invention Polybiphenylsulfon-polymers, which are in accordance with the method of the invention obtainable with a content of polymer bound Halogen, in particular chlorine of less than 400 ppm, in particular less than 300 ppm, particularly preferably less than 200 ppm.

0053The invention obtainable according to Polybiphenylsulfon-polymers have a content of polymer bound Halogen, in particular chlorine of less than 400 ppm, in particular less than 300 ppm, particularly preferably less than 200 ppm. The lower limit of the content of polymer bound Halogen, in particular chlorine is due to the process is usually at least 10 ppm, in particular at least 20 ppm.

0054The halogen content of the optional polymer corresponds to the content of the halogen end groups and is determined in the context of the present invention, by means of atomic spectroscopy. The content of polymer bound Halogen, in particular chlorine refers to in the context of the present invention, in principle the proportion by weight and can alternatively be in mg per kg of initial weight of the polymer indicated.

0055Polymer compositions which are obtainable by the novel process, more preferably have a content of polymer bound Halogen, in particular chlorine of less than 400 ppm, and at the same time a proportion of Residual solvent of less than 300 ppm.

0056The invention obtainable according to Polybiphenylsulfon-polymers are also characterized by a breaking elongation in the tensile test of more than 50%.

0057A further object of the present invention relates to thermoplastic molding compositions comprising a according to the invention, optional Polybiphenylsulfon-Polymer.

0058The thermoplastic molding compositions of the present invention may contain, in addition to the invention according to available Polybiphenylsulfon-Polymer is also at least one Polymer selected from polyarylene ether sulfones (other than the invention obtainable according to Polybiphenylsulfon-polymers), in particular polyether sulfone (PES), and/or polysulfone (PSU), as well as Polyetherimides, Polyphenylene sulfides, polyether ether ketone, Polyimide or Poly-p-phenylene.

0059Molding compositions of the invention can fillers in addition to this, in particular fibers, particularly preferably glass fibers contained. Appropriate fillers are known in the art.

0060If fillers are used, then these are preferably in an amount of 5 to 150 Weight based on 100 parts by weight of Polymer is added.

0061In the inventive thermoplastic molding compositions may, in particular, are known in the art for use in thermoplastic molding compositions suitable glass fibers. These glass fibers can be prepared by methods known in the art and optionally surface-treated. The glass fibers can be equipped to improve compatibility with the matrix material with a size, such as in <patcit id="pcit0009" dnum="DE10117715"><text>DE 10117715</text></patcit>described.

0062In a preferred embodiment, glass fibers with a diameter of 5 to 15 µm, preferably 7 to 13 microns, more preferably 9 to 11 microns.

0063The incorporation of the glass fibers can be in the Form of chopped glass fibers in the Form of continuous strands (Rovings). The length of the glass fibers is generally prior to incorporation as a section of glass fibers in the thermoplastic molding compositions typically 4 to 5 mm. After the processing of the glass fibers, for example by Co-Extrusion with the other components of the glass fibers are usually used in an average length of 100 to 400 microns, preferably 200 to 350 µm.

0064Molding compositions of the invention can be used as further component K materials, in particular processing AIDS, pigments, stabilizers, flame retardants or mixtures of different additives are auxiliary included. Usual additives are oxidation retarders, agents against thermal decomposition and decomposition by ultraviolet light, lubricants and mold release agents, dyes and plasticizers are, for example.

0065The proportion of the further components K in the molding compositions is in particular from 0 to 30, preferably from 0 to 20 Wt.-%, in particular, 0 to 15 Wt.-%, based on the total weight of the thermoplastic molding mass.

0066In the case that it is in the component K to the stabilizers, the proportion of these stabilizers is usually up to 2 Wt.-%, preferably 0.01 to 1 Wt.-%, in particular, 0.01 to 0.5 Wt.-%, based on the total weight of the thermoplastic molding mass.

0067Pigments and dyes are generally present in amounts of from 0 to 10, preferably from 0.05 to 7, and in particular from 0.1 to 5 Wt.-%, based on the total weight of the thermoplastic molding mass.

0068The pigments for coloring thermoplastics are generally known, see, for example, <nplcit id="ncit0002" npl-type="b"><text>R. Gächter and H. Müller, Handbook of plastics additives, Carl Hanser Verlag, 1983, pages 494 to 510</text></nplcit>. A first preferred group of pigments, white pigments, such as zinc oxide, zinc sulfide, lead white [2 PbCO₃·Pb(OH)₂], Lithopone, antimony white and titanium dioxide. Of the two most commonly used crystal modifications (rutile and anatase type) of titanium dioxide, especially the rutile form is used for white coloration of the inventive molding compositions. Black color pigments, the invention can be used according to are iron oxide black (Fe₃O₄), Spinel black [Cu(Cr, Fe)2O₄], Manganese black (mixture of manganese dioxide, silica and iron oxide), cobalt black and antimony black and particularly preferably carbon black, which is usually used in the Form of Furnace or gas black. See <nplcit id="ncit0003" npl-type="b"><text>G. Benzing, pigments for paints, Expert-Verlag (1988), pages 78 ff</text></nplcit>.

0069The particular shades inorganic can be pigments are Colorful, such as chromium oxide green or organic colored pigments, such as Azo pigments or phthalocyanines are used. Such pigments are generally commercially available.

0070Oxidation retarders and heat stabilizers which can be added to the thermoplastic molding compositions according to the invention are for example halides of metals of group I of the periodic system, for example, sodium, potassium, Lithium, halides, for example Chlorides, Bromides or iodides. Furthermore, zinc fluoride and zinc chloride may be used. Furthermore, hindered phenols, Hydroquinones, substituted representatives of this group, secondary aromatic amines, optionally in conjunction with phosphorus-containing acids or their salts, and mixtures of these Compounds are sterically, preferably in concentrations up to 1 Wt.-%, based on the total weight of the thermoplastic molding composition, can be used.

0071Examples of UV stabilizers are various substituted Resorcinols, salicylates, Benzotriazoles and benzophenones, which in General in amounts up to 2 Wt.-% be used.

0072Lubricants and mold release agents, usually in amounts up to 1 Wt.-% based on the total weight of the thermoplastic molding mass are added, are stearyl alcohol, stearic acid alkyl esters, and amides as well as esters of Pentaerythritol with long-chain fatty acids. It also dialkyl ketones can be used, for example, DISTEARYL ketone.

0073As a preferred component of the inventive molding compositions is from 0.1 to 2, preferably 0.1 to 1.75, particularly preferably 0.1 to 1.5 Wt.-% and, in particular, from 0.1 to 0.9 Wt.-% (based on the total weight of the thermoplastic molding composition) of stearic acid and/or Stearates. In principle other stearic acid derivatives such as esters of stearic acid are used.

0074Stearic acid is preferably produced by hydrolysis of fats. The products obtained are usually mixtures of stearic acid and palmitic acid. Therefore, such products have a broad softening range, for example from 50 to 70°C, depending on the composition of the product. Preference is given to products with a proportion of stearic acid of more than 20, particularly preferably more than 25 Wt.-% used. It is also pure stearic acid (> 98 Wt.-%) be used.

0075Furthermore, the inventive molding compositions may also contain stearates. Stearate can CaCl either by reaction of corresponding sodium salts with metal salt solutions (for example, ₂, MgCl₂, Aluminum salts) or by direct reaction of the fatty acid with metal hydroxide can be produced (see, for example, <nplcit id="ncit0004" npl-type="s"><text>Baerlocher Additives, 2005</text></nplcit>). Preferably, aluminum tristearate is used.

0076The order in which the components of the inventive thermoplastic molding composition are mixed is arbitrary.

0077Molding compositions of the invention can be prepared according to known methods, such as Extrusion. Molding compositions of the invention can be prepared, for example, by reacting the starting components in conventional mixing devices such as Screw extruders, preferably twin-screw extruders, Brabender mixers or Banbury mixers and kneading, mixing and then extruded. After Extrusion, the Extrudate is cooled and crushed. The order of mixing of the components can be varied, so two or possibly three components can be premixed, but it can also be mixed all the components together.

0078In order to obtain a homogeneous mixture, thorough mixing is advantageous. To do this, times of from 0.2 to 30 minutes at temperatures of from 280°to 380°C, preferably from 290 to 370 ° C are in General medium-sized mixing required. After Extrusion, the Extrudate is cooled and crushed in the rule.

0079Molding compositions of the invention are characterized in addition to the aforementioned advantages, it also has good flowability, high toughness, and a low intrinsic color. The inventive molding compositions are therefore suitable for the production of moldings for household items, electrical or electronic components, as well as for moldings for the vehicle sector.

0080The inventive thermoplastic molding compositions can be advantageously used for the production of moldings, fibers, films, membranes or foams used. A further object of the present invention, molded bodies, fibers, films, membranes, or foams comprising the inventive thermoplastic molding compositions are.

0081The following examples illustrate the invention without limiting it.

Examples

0082The viscosity number of the Polybiphenylsulfon-polymers was determined in 1% strength solution of N-Methyl-pyrrolidone at 25°C.

0083The obtained Polybiphenylsulfon-polymers were pelletized at a melt temperature of 370°C in a twin-screw extruder (ZSK 18). The processing of the Specimens was carried out at 375°C melt temperature and 160°C tool temperature.

0084The intrinsic color of the products was determined by measuring the Yellowness Index (YI) according to ASTM D 1925 on injection-molded plates (375°C melt temperature, 160°C tool temperature) to a thickness of 2 mm.

0085The monomers used (4,4'-dichloro diphenyl sulfone, 4,4'-dihydroxy biphenyl) had a purity of more than 99.5%.

0086There are various qualities of anhydrous K were ₂CO₃ (Potash) are used. The average particle size is understood as a volume-weighted average of the particle diameter and has a device with a Mastersizer 2000 particle measurement on a Suspension of the particles in a mixture of chlorobenzene/Sulfolane (60/40 by weight) is determined. Potash A: average particle size of 61 µm Potash B: average particle size of 120 microns.

Comparative experiment 1

0087It is a polyarylene ether by nucleophilic aromatic polycondensation of 574,16 g (2,000 mol) of dichloro diphenyl sulfone, 379,87 g (2,040 mol) of dihydroxy-biphenyl was produced under the influence of 286,09 g (2.07 mol) of potassium carbonate (potash A) in 2100 ml of NMP. This mixture was kept for 6 hours at 190°C. Thereafter, the mixture was diluted by addition of 1000 ml of NMP. The Suspension was then reacted at 130°C for 1 hour with methylene chloride (15 l/h). After Cooling to 80°C, the Suspension was drained, the solid constituents are separated off by Filtration and the polymer by precipitation in NMP/water 1/9 isolated. After thorough Washing with water the product was dried in vacuum at 120°C for 12 h. The viscosity number of the product was of 71.2 ml/g, the glass transition temperature at 225°C.

Comparative experiment 2

0088It is a polyarylene ether by nucleophilic aromatic polycondensation of 574,16 g (2,000 mol) of dichloro diphenyl sulfone, 379,87 g (2,040 mol) of dihydroxy-biphenyl was produced under the influence of 286,09 g (2.07 mol) of potassium carbonate (potash A) in 2100 ml of NMP. This mixture was kept for 6 hours at 190°C. Thereafter, the mixture was diluted by addition of 1000 ml of NMP. The Suspension was then reacted at 130°C for 1 hour with methylene chloride (15 l/h). After Cooling to 80°C, the Suspension was drained, the solid constituents were separated by Filtration and the polymer by precipitation in NMP/water 1/9 isolated. After thorough Washing with water the product was dried in vacuum at 120°C for 12 h. The viscosity number of the product was in 72,0 ml/g, the glass transition temperature at 225°C.

Comparative experiment 3

0089It is a polyarylene ether by nucleophilic aromatic polycondensation of 574,16 g (2,000 mol) of dichloro diphenyl sulfone, 379,87 g (2,040 mol) of dihydroxy-biphenyl was produced under the influence of 286,09 g (2.07 mol) of potassium carbonate (potash A) in 2100 ml of NMP. This mixture was kept for 8 hours at 190°C. Thereafter, the mixture was diluted by addition of 1000 ml of NMP. The Suspension was then reacted at 130°C for 1 hour with methylene chloride (15 l/h). After Cooling to 80°C, the Suspension was drained, the solid constituents were separated by Filtration and the polymer by precipitation in NMP/water 1/9 isolated. After thorough Washing with water the product was dried in vacuum at 120°C for 12 h. The viscosity number of the product was at 69,6 ml/g, the glass transition temperature at 225°C.

Comparative experiment 4

0090It is a polyarylene ether by nucleophilic aromatic polycondensation of 574,16 g (2,000 mol) of dichloro diphenyl sulfone, 379,87 g (2,040 mol) of dihydroxy-biphenyl was produced under the influence of 286,09 g (2.07 mol) of potassium carbonate (potash A) in 2100 ml of NMP. This mixture is kept for 10 hours at 190°C. Thereafter, the mixture is diluted by addition of 1000 ml of NMP. The Suspension was then reacted at 130°C for 1 hour with methylene chloride (15 l/h). After Cooling to 80°C the Suspension is drained, the solid constituents are separated off by Filtration and the polymer by precipitation in NMP/water 1/9 isolated. After thorough Washing with water the product is dried in vacuum at 120°C for 12 h. The viscosity number of the product was 64.6 ml/g, the glass transition temperature at 223°C.

Attempt 5

0091It is an object of the invention Polybiphenylsulfon-Polymer by nucleophilic aromatic polycondensation of 574,16 g (2,000 mol) of dichloro diphenyl sulfone, 379,87 g (2,040 mol) of dihydroxy-biphenyl was produced under the influence of 286,09 g (2.07 mol) of potassium carbonate (potash B) in 2100 ml of NMP. This mixture was kept for 4 hours at 190°C. Thereafter, the mixture was diluted by addition of 500 ml of NMP/30 ml of DEIONIZED water and a further 2 h at 160°C and stirred. Subsequently, a further 500 ml of NMP were added. The Suspension was then reacted at 130°C for 1 hour with methylene chloride (15 l/h). After Cooling to 80°C, the Suspension was drained, the solid constituents were separated by Filtration and the polymer by precipitation in NMP/water 1/9 isolated. After thorough Washing with water the product was dried in vacuum at 120°C for 12 h. The viscosity number of the product was 71.5 ml/g, the glass transition temperature at 225°C.

Attempt 6

0092It is an object of the invention Polybiphenylsulfon-Polymer by nucleophilic aromatic polycondensation of 574,16 g (2,000 mol) of dichloro diphenyl sulfone, 379,87 g (2,040 mol) of dihydroxy-biphenyl was produced under the influence of 286,09 g (2.07 mol) of potassium carbonate (potash B) in 2100 ml of NMP. This mixture was kept for 4 hours at 190°C. Thereafter, the mixture was diluted by addition of 500 ml of NMP/30 ml of DEIONIZED water and an additional hour at 160°C and stirred. Thereafter, a further 500 ml of NMP were added. The Suspension was then reacted at 130°C for 1 hour with methylene chloride (15 l/h). After Cooling to 80°C, the Suspension was drained, the solid constituents are separated off by Filtration and the polymer by precipitation in NMP/water 1/9 isolated. After thorough Washing with water the product was dried in vacuum at 120°C for 12 h. The viscosity number of the product was 71.5 ml/g, the glass transition temperature at 225°C.

Test 7

0093It is an object of the invention Polybiphenylsulfon-Polymer by nucleophilic aromatic polycondensation of 574,16 g (2,000 mol) of dichloro diphenyl sulfone, 379,87 g (2,040 mol) of dihydroxy-biphenyl was produced under the influence of 286,09 g (2.07 mol) of potassium carbonate (potash B) in 2100 ml of NMP. This mixture was kept for 4 hours at 190°C. After that, the approach by adding a mixture of 500 ml NMP and 0.78 g of NaOH was dissolved in 0.78 ml of DEIONIZED water and diluted a further hour at 160°C and stirred. Thereafter, a further 500 ml of NMP were added. The Suspension was then reacted at 130°C for 1 hour with methylene chloride (15 l/h). After Cooling to 80°C, the Suspension was drained, the solid constituents are separated off by Filtration and the polymer by precipitation in NMP/water 1/9 isolated. After thorough Washing with water the product was dried in vacuum at 120°C for 12 h. The viscosity number of the product was 69.4 ml/g, the glass transition temperature at 224°C.

Attempt 8

0094It is an object of the invention Polybiphenylsulfon-Polymer by nucleophilic aromatic polycondensation of 574,16 g (2,000 mol) of dichloro diphenyl sulfone, 379,87 g (2,040 mol) of dihydroxy-biphenyl was produced under the influence of 286,09 g (2.07 mol) of potassium carbonate (potash B) in 2100 ml of NMP. This mixture was kept for 4 hours at 190°C. Then, the mixture by addition of a mixture of 500 ml NMP and 1.56 g of NaOH was dissolved in 1.56 ml of DEIONIZED water and diluted a further hour at 160°C and stirred. Thereafter, a further 500 ml of NMP were added. The Suspension was then reacted at 130°C for 1 hour with methylene chloride (15 l/h). After Cooling to 80°C, the Suspension was drained, the solid constituents were separated by Filtration and the polymer by precipitation in NMP/water 1/9 isolated. After thorough Washing with water the product was dried in vacuum at 120°C for 12 h. The viscosity number of the product was compared to 68.5 ml/g, the glass transition temperature at 224°C.

0095The properties of the Polybiphenylsulfon-Polymereaus the experiments V1 to V4 and 5 to 8 and subsequent Extrusion as described above are summarized in table 1.<tables id="tabl0001" num="0001"><table frame="all"><title>Table 1:</title><tgroup cols="9"><colspec colnum="1" colname="col1" colwidth="80mm" /><colspec colnum="2" colname="col2" colwidth="11mm" /><colspec colnum="3" colname="col3" colwidth="11mm" /><colspec colnum="4" colname="col4" colwidth="11mm" /><colspec colnum="5" colname="col5" colwidth="11mm" /><colspec colnum="6" colname="col6" colwidth="11mm" /><colspec colnum="7" colname="col7" colwidth="11mm" /><colspec colnum="8" colname="col8" colwidth="11mm" /><colspec colnum="9" colname="col9" colwidth="11mm" /><thead><row><entry valign="top">Example</entry><entry valign="top">V1</entry><entry valign="top">V2</entry><entry valign="top">V3</entry><entry valign="top">V4</entry><entry valign="top">5</entry><entry valign="top">6</entry><entry valign="top">7</entry><entry valign="top">8</entry></row></thead><tbody><row><entry>Content of polymer-bonded Halogen (chlorine) [ppm]</entry><entry>710</entry><entry>670</entry><entry>560</entry><entry>540</entry><entry>330</entry><entry>360</entry><entry>120</entry><entry>70</entry></row><row><entry>Solvent content [ppm]</entry><entry>100</entry><entry>60</entry><entry>80</entry><entry>100</entry><entry>110</entry><entry>100</entry><entry>120</entry><entry>100</entry></row><row><entry>Yellowness Index YI</entry><entry>56</entry><entry>57</entry><entry>68</entry><entry>88</entry><entry>39</entry><entry>38</entry><entry>36</entry><entry>37</entry></row></tbody></tgroup></table></tables>

0096The comparison values for Radel ® 5000, a Polybiphenylsulfon with a viscosity of 73.2 ml/g (1 Wt.-% in NMP at RT) are: Cl content: 2900 ppm; solvent content: 2000 ppm, and YI: 67.

0097The inventive molding compositions are therefore in particular by a combination of very low content of polymer bound Halogen, in particular chlorine, low residual solvent content and good color.