Siloxane-containing block copolycarbonates with small domain sizes

Abstract

The present invention relates to a method for producing polysiloxane-polycarbonate block cocondensates using a siloxane component containing both aliphatic and aromatic groups as a medium. The present invention also relates to the use of specific siloxane components to reduce the particle size distribution of siloxane domains in polycarbonate compositions and also in polysiloxane-polycarbonate block cocondensates.

Description

[Technical Field]

[0001] The present invention relates to polysiloxane-polycarbonate block cocondensates (hereinafter also referred to as SiCoPC) having small siloxane domain sizes. The block cocondensates are preferably produced from specific polycarbonates and hydroxyaryl-terminated polysiloxanes by a melt transesterification process. The present invention particularly relates to polysiloxane-polycarbonate block cocondensates containing specific compatibilizers. Furthermore, the present invention relates to the production of such block cocondensates by reactive extrusion. The polysiloxane block cocondensates according to the present invention exhibit a fine polysiloxane domain distribution and are characterized by good mechanical properties and good melt stability. [Background technology]

[0002] Polysiloxane-polycarbonate block cocondensates are known to exhibit good properties in terms of low-temperature impact strength / low-temperature notched impact strength, chemical resistance, outdoor weathering resistance, aging characteristics, and fire resistance, and in some instances, polysiloxane-polycarbonate block cocondensates are superior to conventional polycarbonates (e.g., bisphenol A-based homopolycarbonates) in terms of these properties.

[0003] These cocondensates are usually industrially produced from monomers by an interfacial process using phosgene. The production of these polysiloxane-polycarbonate block cocondensates by a melt transesterification process using diphenyl carbonate is also known. These processes have the disadvantage that the industrial plants used for them are large in size, since they are used for the production of standard polycarbonates. The production of certain block cocondensates is often not economically viable in these plants due to the smaller volume of these products. Furthermore, the input materials required to produce the cocondensates, such as polydimethylsiloxane, can cause plant or solvent circuit contamination and therefore damage the plant. Furthermore, production requires input materials such as phosgene or involves high energy requirements, as in the melt transesterification process.

[0004] The preparation of polysiloxane-polycarbonate block cocondensates by the interfacial method is known from the literature and is described, for example, in US Pat. No. 5,629,299, ... and US Pat. No. 5,629,299.

[0005] The preparation of polysiloxane-polycarbonate block co-condensates from bisphenols, diaryl carbonates, silanol-terminated polysiloxanes, and catalysts by a melt transesterification process is described in Patent Document 5. The siloxane compounds used are polydiphenyl / polydimethylsiloxane telomers with silanol end groups. However, in contrast to diphenylsiloxanes with silanol end groups, it is known that such dimethylsiloxanes with silanol end groups exhibit an increasing tendency to self-condense in acidic or basic media as the chain length decreases, preventing their incorporation into the resulting copolymer. The cyclic siloxanes thus formed remain in the polymer, causing major problems in electrical / electronic applications.

[0006] Patent Document 6 describes the preparation of polysiloxane-polycarbonate block co-condensates by melt transesterification of carbonate-terminated silicones with bisphenols and diaryl carbonates. The high incompatibility of the siloxanes with bisphenols and diaryl carbonates results in the uniform incorporation of the siloxane into the polycarbonate matrix via the melt transesterification method being very difficult, if at all.

[0007] The disadvantages of all these methods include the use of organic solvents in at least one step of the synthesis of polysiloxane-polycarbonate block cocondensates, or the use of phosgene as an input material, or the poor quality of the cocondensates.In particular, the synthesis of cocondensates from monomers is very expensive and complicated, both in the interfacial method and especially in the melt transesterification method.For example, the melt method must use a slight vacuum and low temperature to prevent the removal of monomers by evaporation.Only in the subsequent reaction stage, when oligomers with higher molar masses are formed, can lower pressures and higher temperatures be used.This means that the reaction must be carried out as a multi-stage process, which results in a correspondingly long reaction time.

[0008] To avoid the above disadvantages, reactive extrusion methods for producing siloxane-based block copolycarbonates have also been described. These methods are disclosed, for example, in U.S. Patent No. 5,627,999 and U.S. Patent No. 5,627,999. This method involves reacting conventional polycarbonates with specific polydimethylsiloxanes in a reactive extrusion process. However, a disadvantage of this method is the use of expensive specific silicone components. Furthermore, this method uses highly active transesterification catalysts, which allow the production of cocondensates with short residence times in the extruder. However, these transesterification catalysts remain in the product and can only be inadequately deactivated at best. Therefore, injection-molded articles made from the cocondensates produced in this way exhibit poor aging properties, especially poor thermal aging properties. Therefore, the resulting block copolycarbonates are not suitable for high-quality applications. Compared to block copolycarbonates produced by the interfacial process, these products lack adequate properties, such as aging properties and mechanical properties.

[0009] Another problem in the production of siloxane-containing block cocondensates by melt transesterification starting from polycarbonate and polydimethylsiloxane is the high concentration of reactants in the reaction mixture. In comparison, the low concentration of reactants in the interfacial process is because this process is carried out in solution and proceeds from a monomer, i.e., bisphenol. Therefore, the bisphenol is condensed with the siloxane block in a dilute solution. This results in a significantly larger domain size in the melt transesterification process compared to the process carried out in a dilute solution and proceeds from a monomer, as long as oligocarbonate or polycarbonate is used as the starting material. Therefore, the corresponding materials produced by the melt transesterification process often suffer from surface defects. These surface defects are a direct result of the large domain size.

[0010] In the interfacial method, the domain size is typically less than 100 nm, which makes it possible to obtain semi-transparent or even transparent materials, since the small domain size causes little light scattering.

[0011] The production of siloxane-containing block cocondensates with low haze is known in principle. Patent Document 9 involves the preparation of a precondensate from an oligocarbonate and a siloxane in an interfacial process, followed by further condensation of this precondensate with a bisphenol in a second interfacial process.

[0012] It is known that additives can be used in principle to reduce the domain size of siloxane domain in block cocondensate.However, the addition of surfactants, such as those described in Patent Document 10, cannot be used in the method according to the present invention, because these substances are not compatible with the high temperature and relatively long residence time associated with melt transesterification process.Due to the high temperature, other compatibilizers also usually cannot be used.This is because they are decomposed or cause the product to have poor melt stability.

[0013] Patent Document 11 describes haze-free siloxane block cocondensates which proceed from siloxane blocks with particularly low molecular weights. These block cocondensates are also produced by the interfacial method.

[0014] The melt transesterification process has the disadvantage that it is essentially impossible to operate the process at high dilution, and the reactants are always highly concentrated. Experience has shown that this leads to the formation of siloxane domains with sizes between 0.1 μm and 10 μm.

[0015] Large domain sizes have a negative impact on processing characteristics. Large domains can lead to demixing, which can manifest as an inhomogeneous surface structure, leading in some cases to streamlines and streaks. Because large domains are shear-sensitive, such materials are also difficult to process by injection molding, and therefore only a very narrow processing window is possible. Therefore, it is sometimes necessary to use very low injection speeds, which is often undesirable because it reduces cycle time.

[0016] The melt transesterification process and especially the so-called reactive extrusion process, in principle, entails the risk that the catalyst will remain in the final product, which may result in a decrease in molecular weight in subsequent processing, for example, in injection molding. This may manifest itself in surface defects and generally poor processing properties.

[0017] Patent Documents 12 and 13 disclose specific siloxanes used in polycarbonate compositions to improve flame retardancy. These documents are silent about polysiloxane-polycarbonate block cocondensates and their preparation, and therefore do not provide any teaching about the behavior of the disclosed siloxanes in the preparation of polysiloxane-polycarbonate block cocondensates. [Prior art documents] [Patent documents]

[0018] [Patent Document 1] U.S. Patent No. 3,189,662 [Patent Document 2] U.S. Patent No. 3,419,634 [Patent Document 3] German Patent No. 334782 [Patent Document 4] European Patent No. 0122535 [Patent Document 5] U.S. Patent No. 5,227,449 [Patent Document 6] U.S. Patent No. 5,504,177 [Patent Document 7] U.S. Patent No. 5,414,054 [Patent Document 8] U.S. Patent No. 5,821,321 [Patent Document 9] International Publication No. 2004 / 016674 [Patent Document 10] German patent no. 19523000 [Patent Document 11] U.S. Patent Application Publication No. 2007 / 0238846 [Patent Document 12] U.S. Patent No. 6,284,824 [Patent Document 13] International Publication No. 2017 / 042272 Summary of the Invention [Problem to be solved by the invention]

[0019] Therefore, starting from the above-mentioned prior art, the object of the present invention is to overcome at least one of the disadvantages of the prior art. A specific object of the present invention is to develop polysiloxane-polycarbonate block cocondensates that have small siloxane domain sizes and at the same time exhibit good mechanical properties. The block cocondensates are preferably produced by the melt transesterification process.

[0020] The domain size should reach a D90 of less than 120 nm, preferably less than 110 nm, particularly preferably less than 100 nm. The proportion of particles with a diameter smaller than 100 nm, based on the total number of siloxane domains, should preferably be more than 70%, particularly preferably more than 80%, very particularly preferably more than 90%. [Means for solving the problem]

[0021] These problems are solved by the polycarbonate composition according to the invention, the method according to the invention and the use according to the invention.

[0022] Surprisingly, it has been found that the addition of a siloxane-based additive containing both aromatic and aliphatic groups makes it possible to obtain a block cocondensate with a small siloxane domain size. At the same time, a SiCoPC with high melt stability is obtained. Without wishing to be bound by a particular theory, it appears that the simultaneous presence of aromatic and aliphatic groups in the siloxane-based additive provides a compatibilizing effect between the different phases of polycarbonate and siloxane blocks. This leads to an improved distribution of reduced-size siloxane domains, especially in the melt transesterification process. This effect is superior to that of a siloxane-based additive containing only aromatic groups.

[0023] The improvement in siloxane domain size results in improved processing characteristics of SiCoPC: the tendency to demixing is reduced and the processing window for injection molding of polycarbonate compositions according to the invention is widened.

[0024] The present invention therefore provides, inter alia, A) at least one polycarbonate in the melt, B) at least one hydroxyaryl-terminated (poly)siloxane; C) General chemical formula (I), general chemical formula (Ia): [ka] (In the formula, Z1, Z2, and Z3 are each independently methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C5 to C6 18 alkyl, methacryloxypropyl, monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl, hydroxy, hydrogen, chlorine, fluorine, or CN; R8 and R9 each independently represent an aliphatic group or an aromatic group, provided that in formula (I) or formula (Ia), at least one R8 represents an aliphatic group and at least one R9 represents an aromatic group; and and s, s1, s2, s3, and s4 are natural numbers between 1 and 250), or any desired mixture thereof, characterized in that the method comprises the step of adding component C) to component A), component B), and / or a mixture of components A) and B).

[0025] The present invention also provides (i) at least one polysiloxane-polycarbonate block cocondensate; (ii) General chemical formula (I), general chemical formula (Ia): [ka] (In the formula, Z1, Z2, and Z3 are each independently methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C5 to C6 18 alkyl, methacryloxypropyl, 2,3-epoxypropyloxy, monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl, hydroxy, hydrogen, chlorine, fluorine, or CN; R8 and R9 each independently represent an aliphatic group or an aromatic group, provided that in formula (I) or formula (Ia), at least one R8 represents an aliphatic group and at least one R9 represents an aromatic group; and s, s1, s2, s3, and s4 are natural numbers between 1 and 250), or any desired mixture thereof; (iii) optionally at least one further polymer different from component (i); (iv) optionally at least one further additive; The present invention provides a polycarbonate composition comprising:

[0026] Such compositions are preferably obtained using the process according to the invention. The process according to the invention results in a polysiloxane-polycarbonate block cocondensate, which therefore preferably constitutes component (i) of the composition according to the invention. If the process according to the invention is carried out in the presence of component C), this component remains in the product in at least trace amounts, so that the direct product of the process can be a polycarbonate composition according to the invention.

[0027] The process according to the invention will first be described in more detail below, however, it will be understood that these descriptions also describe the polycarbonate composition according to the invention, for the reasons stated above.

[0028] The method according to the present invention preferably comprises or is particularly preferably a polycondensation method.Furthermore, it is preferred that the method according to the present invention is carried out by a melt transesterification method.Polycarbonate A) is preferably reacted with hydroxyaryl-terminated (poly)siloxane B) and component C) in the melt in an extruder or a high-viscosity reactor.This method is also known as a reactive extrusion method.

[0029] The melt transesterification and reactive extrusion processes are well known (see, for example, US Pat. Nos. 5,629,999, 5,629,999, and the references cited above).

[0030] The extruder or melt reactor may be a single-screw reactor, a twin-screw reactor, or a multi-screw reactor, such as a planetary roller extruder or a ring extruder. Large-volume kneader reactors may also be involved.

[0031] The process can be carried out in a single apparatus, such as a twin-screw extruder, or in two stages, i.e., in a reactor combination, preferably consisting of a pre-reactor, such as a twin-screw extruder, and a high-viscosity reactor.

[0032] The process is preferably carried out at temperatures of 280°C to 370°C, preferably 290°C to 360°C, more preferably 300°C to 350°C, and at pressures of 0.001 mbar to 5 mbar, preferably 0.005 mbar to 4 mbar, particularly preferably 0.02 mbar to 3 mbar, and very particularly preferably 0.03 mbar to 1 mbar, preferably in the presence of a catalyst. The reactor used is preferably a single-screw or twin-screw extruder, particularly preferably a co-rotating twin-screw extruder. Twin-screw extruders are characterized by comprising two or more vacuum zones. When using a twin-screw extruder, the processing temperature (melt temperature) is preferably 280°C to 400°C, preferably 290°C to 380°C, the pressure in the first stage is 500 mbar to 0.01 mbar, preferably 200 mbar to 0.1 mbar, and the pressure in the subsequent vacuum stage is 0.001 mbar to 50 mbar.

[0033] The reactive extrusion process can be carried out in a two-stage process. The reactor combination preferably consists of a twin-screw or single-screw extruder and a high-viscosity reactor, and the resulting low-molecular-weight decomposition products are removed by evaporation under vacuum. The twin-screw or single-screw extruder is used to melt the polycarbonate and mix it with additional materials, such as a silicone component and, optionally, a catalyst, optionally in the form of a masterbatch. The components are mixed and pre-reacted therein. The pre-product is then fed to the high-viscosity reactor, where thermal energy and mechanical energy are simultaneously supplied under vacuum to completely react the components to obtain a polycondensation product. Volatile low-molecular-weight decomposition products and other low-molecular-weight components can be removed either in the pre-reactor (single-screw or twin-screw extruder), downstream of the pre-reactor, and / or in the high-viscosity reactor. In a preferred embodiment, the low-molecular-weight components are already removed under vacuum in the pre-reactor. This is particularly preferably carried out in two vacuum stages, with the first stage preferably operating at an absolute pressure of 10 mbar to 800 mbar, particularly preferably at an absolute pressure of 10 mbar to 100 mbar, and the second vacuum stage preferably operating at an absolute pressure of 0.1 mbar to 100 mbar, particularly preferably at an absolute pressure of 0.2 mbar to 5 mbar. The reaction in the high-viscosity reactor is also carried out under vacuum. The vacuum is 0.001 mbar to 50 mbar, preferably 0.005 mbar to 40 mbar, particularly preferably 0.02 mbar to 30 mbar, and very particularly preferably 0.03 mbar to 5 mbar.

[0034] The apparatus used as the high-viscosity reactor according to the present invention includes apparatus suitable for processing high-viscosity melts, which provide sufficient residence time with good mixing and expose the melt to the vacuum required by the present invention. The patent literature describes many apparatuses that in principle meet these requirements and can be used according to the present invention. For example, reactors according to EP 460466, EP 528210, EP 638354, EP 715881, EP 715882, EP 798093, or reactors according to EP 329092, EP 517068, EP 1436073, or WO 20021114, or reactors according to EP 222599 can be used.

[0035] It is preferred to use a kinematically self-cleaning reactor according to EP 460466, which consists of two or more parallel shafts rotating in the same or opposite directions, preferably in the opposite directions, and a surrounding housing, on which axially staggered, though not necessarily circular, discs are arranged, with wipers distributed over the entire circumference of the discs. This reactor / mixer is characterized in that all surfaces of the wipers are kinematically cleaned, in particular in that, when the shafts rotate at the same speed in any radial cross section through the mixer, all outward-facing surfaces of the wipers of a shaft are concentric with the center of rotation insofar as they are cleaned by the housing, but otherwise have an axial distance approximately the same as the radius of curvature, are convex, and are cleaned by the wiper of an adjacent shaft or its wiper, in particular in that, when the shafts rotate at the same speed in any radial cross section through the mixer, all inward-facing surfaces of the wipers of a shaft are concave, have an axial distance approximately the same as the radius of curvature, and are cleaned by the wiper of another adjacent shaft. For better mixing, the melt can be passed through additional mixing elements, for example, a static mixer can be used between the pre-reactor and the high viscosity reactor.

[0036] A single-screw, twin-screw, or gear pump is used to discharge the fully reacted co-condensate from the high-viscosity reactor. Additives and / or additives can optionally be fed and mixed in. Addition of additives can be carried out in the discharge device or a downstream static mixer. The melt is shaped through one or more nozzles and fragmented in a conventional pelletizer.

[0037] The method according to the present invention makes it possible to obtain the corresponding block cocondensate in a short reaction time.In this context, a short reaction time should be understood to mean the reaction time required to mix siloxane components and produce a starting polycarbonate melted to the target viscosity.The reaction time is preferably less than 1 / 2 hour, particularly preferably less than 15 minutes, and very particularly preferably less than 7.5 minutes.In a particularly preferred embodiment, the reaction time is less than 30 minutes, particularly preferably less than 20 minutes.

[0038] The polycarbonates used according to the present invention and the (poly)siloxanes used according to the present invention can be reacted using a catalyst. In principle, a reaction without a catalyst is possible, but as a result, higher temperatures and longer residence times may have to be accepted.

[0039] Suitable catalysts for the process according to the invention are, for example, ammonium catalysts such as tetramethylammonium hydroxide, tetramethylammonium acetate, tetramethylammonium fluoride, tetramethylammonium tetraphenylborate, dimethyldiphenylammonium hydroxide, tetraethylammonium hydroxide, cetyltrimethylammonium tetraphenylborate, and cetyltrimethylammonium phenoxide, of formula (K): [ka] (In the formula, R a , R b , R c and R d are the same or different C1 to C 10-Alkyl, C6-C 14 -Aryl, C7-C 15 -arylalkyl or C5-C6-cycloalkyl, preferably methyl or C6-C 14 -aryl, particularly preferably methyl or phenyl, and X - may be an anion such as hydroxide, sulfate, hydrogen sulfate, bicarbonate, carbonate, or a halide, preferably chloride, or an alkylate or arylate of formula -OR, where R is a C-C 14 -Aryl, C7-C 15 -arylalkyl, or C5-C6-cycloalkyl, preferably phenyl) phosphonium catalysts are particularly suitable.

[0040] Particularly preferred catalysts are tetraphenylphosphonium chloride, tetraphenylphosphonium hydroxide, and tetraphenylphosphonium phenoxide, with tetraphenylphosphonium phenoxide being very particularly preferred. It is particularly preferred to use the alkali metal or alkaline earth metal salts of these ammonium and / or phosphonium catalysts.

[0041] The catalyst is preferably used in an amount of 0.0001% to 1.0% by weight, preferably 0.001% to 0.5% by weight, particularly preferably 0.005% to 0.3% by weight, very particularly preferably 0.01% to 0.15% by weight, based on the total composition.

[0042] The catalysts can be used alone or as a catalyst mixture and can be added in pure form or as a solution, for example as an aqueous solution or a phenolic solution (for example as a solid solution with phenol).

[0043] Similarly, polycarbonate and (poly)siloxane are mixed together at a pK in the range of 3 to 7. AIt is preferred to carry out the reaction in the presence of an organic or inorganic salt of a weak acid having a carboxylic acid content of 25°C. This salt may also be referred to as a cocatalyst. Suitable weak acids include carboxylic acids, preferably C2-C6. 22 -carboxylic acids such as acetic acid, propanoic acid, oleic acid, stearic acid, lauric acid, benzoic acid, 4-methoxybenzoic acid, 3-methylbenzoic acid, 4-tert-butylbenzoic acid, p-tolueneacetic acid, 4-hydroxybenzoic acid, and salicylic acid, partial esters of polycarboxylic acids such as monoesters of succinic acid, partial esters of phosphoric acid such as mono- or di-organophosphate esters, branched aliphatic carboxylic acids such as 2,2-dimethylpropionic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid, and 2-ethylhexanoic acid.

[0044] Suitable organic or inorganic salts are selected from or derived from bicarbonate, potassium bicarbonate, lithium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium oleate, potassium oleate, lithium oleate, sodium benzoate, potassium benzoate, lithium benzoate, disodium, dipotassium, and dilithium salts of bisphenol A. The salts may further include calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, and the corresponding oleates. The salts may be used alone or in any desired mixture.

[0045] The salts are particularly preferably selected from the group consisting of alkali metal and phosphonium salts of carboxylic acids. In a further preferred embodiment, the organic or inorganic salt is derived from a carboxylic acid.

[0046] The organic or inorganic salt is preferably used in an amount of 0.5 ppm to 1000 ppm, particularly preferably 1 ppm to 100 ppm, and very particularly preferably 1 ppm to 10 ppm, based on the total weight of the siloxane and the organic or inorganic salt. The organic or inorganic salt is preferably used in an amount of 0.0005 mmol / kg to 5 mmol / kg, particularly preferably 0.001 mmol / kg to 1 mmol / kg, and very particularly preferably 0.001 mmol / kg to 0.5 mmol / kg, based on the total weight of the siloxane, polycarbonate, and the organic or inorganic salt.

[0047] In a preferred embodiment, the organic or inorganic salt is a sodium salt, preferably a sodium salt of a carboxylic acid. The salt is preferably used in an amount such that the sodium content in the resulting polysiloxane-polycarbonate block cocondensate is in the range of 0.1 ppm to 1000 ppm, preferably 0.2 ppm to 100 ppm, particularly preferably 0.3 ppm to 10 ppm, and particularly preferably 0.4 ppm to 5 ppm, based on the total weight of the polysiloxane-polycarbonate block cocondensate formed. The sodium content of the cocondensate can be determined, for example, by atomic absorption spectroscopy.

[0048] The organic or inorganic salts can be used alone or in any desired mixture. The salts can be added as solids or in solution. In a preferred embodiment, the organic or inorganic salts are added in the form of a mixture comprising the siloxane and the organic or inorganic salt.

[0049] Suitable catalysts for the process according to the invention are the above-mentioned catalysts which are introduced into the reaction by means of a masterbatch with a suitable polycarbonate, in particular the polycarbonate according to the invention described above, or which can be introduced separately or additionally thereto.

[0050] The catalysts can be used alone or in mixtures and can be added in pure form or as a solution, for example as an aqueous or phenolic solution.

[0051] It is preferred if the catalyst is added in pure form, as a mixture or in a masterbatch to the prereactor, preferably to a twin-screw extruder.

[0052] Ingredient A) In the context of the present invention, the term polycarbonate includes both homopolycarbonates and copolycarbonates, as well as mixtures of polycarbonates. The polycarbonates may be linear or branched, as is known. The production of polycarbonates may be carried out, as is known, by the melt transesterification process or the interfacial process.

[0053] To prepare the polysiloxane-polycarbonate block cocondensates of the present invention, it is preferable to use polycarbonates having a molecular weight of 8,000 g / mol to 28,000 g / mol, particularly preferably 10,000 g / mol to 27,000 g / mol, and especially preferably 12,000 g / mol to 26,500 g / mol. These polycarbonates preferably have a phenolic OH group content of 250 ppm to 2,500 ppm, preferably 500 ppm to 2,000 ppm, and particularly preferably 1,000 ppm to 1,800 ppm. The phenolic OH group content is preferably determined by IR spectroscopy.

[0054] The method used to determine the molar masses reported in the context of this invention for the polycarbonate, siloxane component, or polysiloxane-polycarbonate block cocondensates is Currenta GmbH & Co. OHG, Method No. 2301-0257502-09D, which is available from Currenta on request.

[0055] It is more preferable to use a polycarbonate having a relative solution viscosity of 1.10 to 1.285 for producing the polysiloxane-polycarbonate block cocondensate according to the present invention. rel ; also called relative solution viscosity) is preferably determined at 25° C. in dichloromethane at a concentration of 5 g / l using an Ubbelohde viscometer.

[0056] Preferred diphenols for preparing polycarbonates are 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)-1-phenylpropane, 1,1-bis(4-hydroxyphenyl)phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (bisphenol M), ... bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,3-bis[2-(3,5-dimethyl-4-hydroxyphenyl)-2-propyl]benzene, 1,1-bis(4-hydroxyphenyl)cyclohexane, and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

[0057] Particularly preferred diphenols are 2,2-bis(4-hydroxyphenyl)propane (BPA), hydroquinone, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and 2,2-bis(3-methyl-4-hydroxyphenyl)propane.

[0058] In particular, polycarbonates based on bisphenol A are used. It is very particularly preferred if these polycarbonates contain phenol as a terminal group. In particular, polycarbonates prepared by the melt transesterification process are suitable for preparing the block cocondensates according to the invention.

[0059] When reactive extrusion is used to prepare the block co-condensate, a preferred embodiment involves using polycarbonates containing specific rearrangement structures. The polycarbonates used in this embodiment have the following structures (4) to (7): [ka] (wherein the phenyl rings may be mono- or di-substituted, independently of one another, with C1-C8 alkyl, halogen, preferably C1-C4 alkyl, particularly preferably methyl; and X represents a single bond, C1-C6 alkylene, C2-C5 alkylidene, or C5-C6 cycloalkylidene, preferably a single bond or C1-C4 alkylene, particularly preferably isopropylidene), and the total amount of structural units (4) to (7) (determined after hydrolysis) is generally within the range of 50 ppm to 1000 ppm, preferably within the range of 80 ppm to 850 ppm.

[0060] Furthermore, polycarbonates having phenol as a terminal group (phenyl-terminated polycarbonates) are preferred. Tert-butylphenol and cumylphenol are further possible terminal groups.

[0061] To determine the amount of rearrangement structures, each polycarbonate is subjected to total hydrolysis to form the corresponding degradation products of formula (4a) to formula (7a), the amount of which is determined by HPLC (this can be achieved, for example, as follows: a polycarbonate sample is hydrolyzed with sodium methoxide under reflux. The corresponding solution is acidified and concentrated to dryness. The dry residue is dissolved in acetonitrile and the corresponding degradation products of formula (1a) to formula (4a): [ka] of phenolic compounds is determined by HPLC with UV detection).

[0062] The amount of the compound of formula (4a) thus liberated is preferably 20 ppm to 800 ppm, particularly preferably 25 ppm to 700 ppm, and particularly preferably 30 ppm to 500 ppm.

[0063] The amount of the compound of formula (5a) thus liberated is preferably 0 ppm (ie, below the detection limit of 10 ppm) to 100 ppm, particularly preferably 0 ppm to 80 ppm, and particularly preferably 0 ppm to 50 ppm.

[0064] The amount of the compound of formula (6a) thus liberated is preferably 0 ppm (i.e. below the detection limit of 10 ppm) to 800 ppm, more preferably 10 ppm to 700 ppm, particularly preferably 20 ppm to 600 ppm, and very particularly preferably 30 ppm to 350 ppm.

[0065] The amount of the compound of formula (7a) thus liberated is preferably 0 ppm (ie, below the detection limit of 10 ppm) to 300 ppm, preferably 5 ppm to 250 ppm, particularly preferably 10 ppm to 200 ppm.

[0066] The preparation of such polycarbonates containing the above-mentioned rearrangement structures is described, for example, in DE 102008019503 A1.

[0067] Component B) Component B preferably has the formula (1): [ka] is a hydroxyaryl-terminated (poly)siloxane.

[0068] In general formula (1), R 5 represents hydrogen, C1-C4-alkyl, C1-C4-alkoxy, preferably hydrogen, methyl, methyloxy, particularly preferably hydrogen.

[0069] R 6 and R 7 are each independently aryl, preferably phenyl, C1-C4 alkyl, preferably methyl, in particular methyl.

[0070] Y represents a single bond, -CO-, -O-, C1-C5-alkylene, C2-C5-alkylidene or a C5-C6-cycloalkylidene group optionally mono- or polysubstituted with C1-C4-alkyl, preferably a single bond, -O-, isopropylidene or a C5-C6-cycloalkylidene group optionally mono- or polysubstituted with C1-C4-alkyl, in particular isopropylidene.

[0071] V represents oxygen, C2-C6 alkylene, or C3-C6 alkylidene, preferably oxygen or C3-alkylene.

[0072] When q=0, W represents a single bond.

[0073] When q=1, W represents oxygen, C2-C6-alkylene or C3-C6-alkylidene, preferably oxygen or C3-alkylene.

[0074] p and q each independently represent 0 or 1.

[0075] o represents an average number of repeating units of 10 to 400, preferably 10 to 100, and particularly preferably 15 to 50.

[0076] m represents the average number of repeating units of 1 to 10, preferably 1 to 6, and particularly preferably 1.5 to 5.

[0077] Particularly preferred are compounds of formula (2) and formula (3): [ka] (In the formula, R1 represents hydrogen, C1-C4-alkyl, preferably hydrogen or methyl, particularly preferably hydrogen, R2 independently in each occurrence represents aryl or alkyl, preferably methyl; X is a single bond, -SO2-, -CO-, -O-, -S-, C1-C6-alkylene, C2-C5-alkylidene, or a C6-C6 alkylene optionally fused to a further aromatic ring containing a heteroatom.12 -arylene, X is preferably a single bond, C1-C5-alkylene, C2-C5-alkylidene, C5-C 12 -Cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO2-, particularly preferably a single bond, isopropylidene, C5 to C 12 represents cycloalkylidene or oxygen, very particularly preferably isopropylidene, n represents an average number of 10 to 400, preferably 10 to 100, particularly preferably 15 to 50, and m represents an average number of 1 to 10, preferably 1 to 6, and particularly preferably 1.5 to 5).

[0078] The siloxane block also preferably has the following structure: [ka] (In formula (VII), formula (VIII) and formula (IX), a represents an average number of 10 to 400, preferably 10 to 100, particularly preferably 15 to 50).

[0079] The molecular weight of the siloxane component is preferably 1500 g / mol to 20000 g / mol, particularly preferably 3500 g / mol to 15000 g / mol. The molecular weight is preferably determined as described for component A) above.

[0080] The preparation of siloxanes of formula (1) to formula (3) is described, for example, in DE-A-3334782, DE-A-19710081 and WO-A-2015 / 05229.

[0081] The siloxane components of the formula (1), (2) or (3), or also of the formula (VII), (VIII) or (IX), are used in an amount of 0.5% by weight to 50% by weight, preferably 1% by weight to 40% by weight, particularly preferably 2% by weight to 20% by weight, and very particularly preferably 2.5% by weight to 10% by weight, based in each case on component A) and component B).

[0082] The preparation of siloxane blocks is known in principle; they can be prepared, for example, by the method described in US Patent Application Publication No. 20130267665.

[0083] Component C) As component C) according to the present invention, compounds of the general chemical formula (I), the general chemical formula (Ia): [ka] (In the formula, Z1, Z2, and Z3 are each independently methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C5 to C6 18 alkyl, methacryloxypropyl, monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl, hydroxy, hydrogen, chlorine, fluorine, or CN; R8 and R9 each independently represent an aliphatic group or an aromatic group, provided that in formula (I) or formula (Ia), at least one R8 represents an aliphatic group and at least one R9 represents an aromatic group; and At least one siloxane of formula (s, s1, s2, s3 and s4 each independently represent a natural number between 1 and 250, preferably between 1 and 100, particularly preferably between 1 and 75), or any desired mixture thereof, is used.

[0084] This component C) according to the invention corresponds to component (i) according to the invention in the polycarbonate composition according to the invention, and the following description therefore relates to both components according to the invention independently of each other.

[0085] It has surprisingly been found that the presence of at least one aliphatic group and at least one aromatic group in component C) in the process for preparing polysiloxane-polycarbonate block cocondensates leads to a significant reduction in the siloxane domain distribution and a significantly higher percentage of particles having a particle size of less than 100 nm. According to the invention, this is due to better compatibilization of components A) and B) by component C).

[0086] Component C) or component (ii) according to the invention is linear and / or has a comb and / or graft structure.

[0087] R8 in the general chemical formula (I) or the general chemical formula (Ia) is independently in each occurrence methyl, ethyl, propyl, butyl, isopropyl, vinyl, isobutyl, C5-C 18 -alkyl, or optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl, and R9 in the general chemical formula (I) or the general chemical formula (Ia) is independently in each occurrence methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, C5-C 18 -alkyl, or optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl, However, at least one R8 is methyl, ethyl, propyl, butyl, isopropyl, vinyl, isobutyl, or C5 to C 18Preference is given to the case where R represents -alkyl and at least one R represents an optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl. According to the invention, preference is given to the case where any alkyl or alkoxy substitutions are independently associated with each specific phenyl (i.e., phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl). According to the invention, it is particularly preferred if any optional substitutions of phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl are C1-C9 alkyl, methoxy, or ethoxy. In all embodiments of the invention, it is very particularly preferred if the optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl is -CH2CH2CH2(CR6R5), -CH2CH2(CR6R5), -CH2CH(CH3)-(CR6R5), or -CR6R5, where each R may, independently of one another, be H, alkyl, or alkoxy, preferably C1-C9 alkyl, methoxy, or ethoxy. Very particular preference is given to -CH2CH2CH2(C6H5), -CH2CH2(C6H5), -CH2CH(CH3)-(C6H5) or -C6H5.

[0088] Z1, Z2 and Z3 have the above definitions. It is preferred if Z1, Z2 and Z3 each independently represent methyl, vinyl, phenyl or hydroxy.

[0089] It is particularly preferred that R8 in general chemical formula (I) or general chemical formula (Ia) independently in each occurrence is methyl, ethyl, trimethylphenyl, -CH2-CH2-phenyl, -CH2-CH2-CH2-phenyl, -CH2-CH(CH3)-phenyl, -CH2-CH2-CH2-(2-methoxy)phenyl, or phenyl, and R9 in general chemical formula (I) independently in each occurrence is methyl, ethyl, trimethylphenyl, -CH2-CH2-phenyl, -CH2-CH2-CH2-phenyl, -CH2-CH(CH3)-phenyl, -CH2-CH2-CH2-(2-methoxy)phenyl, or phenyl, with the proviso that at least one R8 is methyl or ethyl and at least one R9 is trimethylphenyl or phenyl. Z1, Z2, and Z3 have the above definitions. It is preferred if Z1, Z2 and Z3 each independently represent methyl, vinyl, phenyl or hydroxy.

[0090] The groups R8 and R9 together with the Si—O group form a “D” unit known to those skilled in the art. A particularly preferred D unit has the following structure: [ka] (In the formula, Ph represents, independently at each occurrence, -CH-CH-phenyl, -CH-CH-CH-phenyl, -CH-CH(CH)-phenyl, or phenyl; and B is, independently in each case, C2 to C 18 The numbers of repeating units s, s1, s2, s3, and s4 are selected from the following, which are defined according to the present invention depending on whether the D units belong to structural formula (I) or structural formula (Ia). Those skilled in the art will be able to read these D units into structural formula (I) or structural formula (Ia).

[0091] Similarly, it is known to those skilled in the art that the last siloxane unit together with the terminal group Z1, Z2, or Z3 forms an "M" unit. Preferred M units according to the present invention are: [ka] wherein Ph, at each occurrence, independently represents -CH-CH-phenyl, -CH-CH-CH-phenyl, -CH-CH(CH)-phenyl, or phenyl. Those skilled in the art can read these M units into structural formula (I) or structural formula (Ia).

[0092] Those skilled in the art will also recognize that the structure of formula (Ia) within the brackets with index s4, together with the two oxygen atoms, forms a "T" unit. According to the present invention, the group R9 in this T unit is selected from the group consisting of a methyl group and a Ph group, where Ph represents, independently in each occurrence, -CH-CH-phenyl, -CH-CH-CH-phenyl, -CH-CH(CH)-phenyl, or phenyl. Those skilled in the art will be able to read these T units into structural formula (Ia).

[0093] In all of these preferences, it is preferred if s, s1, s2, s3, and s4 each independently represent a natural number between 3 and 50, preferably between 4 and 25, particularly preferably between 5 and 15, in the general formula (I). Pure substances or oligomeric mixtures may be involved. In the case of oligomeric mixtures, s, s1, s2, s3, and s4 are therefore the mean values ​​of the distribution and therefore represent average numbers. In this case, s, s1, s2, s3, and s4 may also be decimal numbers.

[0094] It is particularly preferred if component C) is a mixture of at least one siloxane of formula (I) and at least one siloxane of formula (Ia). It is preferred if the at least one siloxane of formula (Ia) is present in the mixture in an amount of up to 10% by weight, preferably 1% to 5% by weight, and very particularly preferably 2% to 4% by weight, based on the total weight of all siloxanes of formula (I) and formula (Ia) in the mixture.

[0095] At least one siloxane of component (ii) / component C) is represented by general chemical formula (II), general chemical formula (IIa), general chemical formula (III), and / or general chemical formula (IV): [ka] (In the formula, Z1, Z2, and Z3 are each independently methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C5 to C6 18 alkyl, methacryloxypropyl, monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl, hydroxy, hydrogen, chlorine, fluorine, or CN, preferably methyl, methoxy, ethoxy, hydrogen, or hydroxy, R 10 represents, independently in each occurrence, hydrogen, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, isooctyl, isononyl, or isodecyl; R 11 is, independently in each occurrence, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C5-C 18 alkyl, methacryloxypropyl, monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl, hydroxy, hydrogen, chlorine, fluorine, or CN; r is a natural number between 0 and 3, s and t are each independently a natural number between 1 and 250, preferably between 1 and 100, particularly preferably between 1 and 75, very particularly preferably between 1 and 50, likewise preferably between 4 and 25, particularly preferably between 5 and 15, w and v are each independently a natural number between 1 and 250, preferably between 1 and 100, particularly preferably between 5 and 75, and The groups having the indices s, w, v, t, and u can be randomly distributed in the siloxane of component (ii) / component C), and are preferably randomly distributed in the siloxane of component (ii) / component C).

[0096] It is particularly preferred if component (ii) / component C) is a mixture of at least one siloxane selected from the group consisting of general chemical formula (II), general chemical formula (IIa) and general chemical formula (III) with up to 5% by weight of a siloxane of formula (Ia), preferably formula (IV).

[0097] In the general chemical formula (II), the general chemical formula (IIa), the general chemical formula (III), and the general chemical formula (IV), Z1, Z2 and Z3 each independently represent methyl, vinyl, methoxy, ethoxy, hydrogen or hydroxy, preferably methyl, hydroxy or a mixture of methoxy and ethoxy, R 10 represents hydrogen or methyl; R 11 represents independently in each occurrence methyl, phenyl, vinyl, methoxy, ethoxy, hydrogen, or hydroxy, preferably methyl or phenyl; r is a natural number between 0 and 3, particularly preferably 0; s is a natural number between 1 and 100, preferably between 5 and 75, particularly preferably between 5 and 15, t is a natural number between 1 and 75, w is a natural number between 5 and 75, v is a natural number between 1 and 75, and It is particularly preferred if u is a natural number between 1 and 10. According to the present invention, it is preferred if the expression "a natural number between" includes a range of numbers and explicitly disclosed thresholds of the range.

[0098] In the general chemical formula (II), the general chemical formula (IIa), the general chemical formula (III), and the general chemical formula (IV), Z1, Z2, and Z3 are each independently hydroxy; R 10 is hydrogen, R 11 represents, independently in each occurrence, methyl or phenyl; r is 0, s is a natural number between 1 and 100, preferably between 5 and 75, particularly preferably between 5 and 15, t is a natural number between 1 and 75, w is a natural number between 5 and 75, v is a natural number between 1 and 75, and It is very particularly preferred if u is a natural number between 1 and 10. It is very particularly preferred if component (ii) / component C) is a mixture of at least one siloxane selected from the group consisting of general chemical formula (II), general chemical formula (IIa) and general chemical formula (III) with ≧0% to 5% by weight, preferably ≧0% to 3% by weight, of a siloxane of formula (Ia), preferably formula (IV).

[0099] The process according to the invention is particularly characterized in that the reaction melt is mixed with component C) in an amount of preferably 0.01% to 20% by weight, particularly preferably 0.01% to 10% by weight, particularly preferably 0.05% to 2.5% by weight, more particularly preferably 0.1% to 2.0% by weight, and very particularly preferably 0.20% to 1.0% by weight, based on the total composition (components A to C). The addition can be carried out at any desired point in the process and at any desired time. Component C) is preferably added to the reaction mixture at an early stage. It is preferred to dissolve component C in component B, preferably using a stirring device and heat, and then add the mixture to the polycarbonate melt. Component C) can also be added before the addition of components B) and / or A). For example, component C) can also be melted together with the polycarbonate at the start of the reaction or plasticized together with the polycarbonate in a reactive extrusion.

[0100] Component C) can be introduced directly or in the form of a masterbatch. Component C) can be mixed with other components, such as catalysts, for example catalysts according to structure (K). Suitable substrate materials for masterbatches are, for example, polycarbonates, in particular polycarbonates according to component A).

[0101] Component (C) is 0.5 parts by weight to 99.9 parts by weight of component C); 0.1 parts by weight to 99.5 parts by weight of a polycarbonate as component C3; 0 to 1 part by weight of a phosphonium catalyst as component C4; It is preferred that the copolymer is used as a masterbatch containing the following:

[0102] Likewise, it is preferred if 50.0% to 0.5% by weight of polycarbonate of component A) and 0.5% to 50.0% by weight of hydroxyaryl-terminated polysiloxane of component B) are used in the process according to the invention, based on the amounts of A) and B). It is particularly preferred if 98.0% to 80.0% by weight of polycarbonate of component A) and 2.0% to 20.0% by weight of hydroxyaryl-terminated polysiloxane of component B) are used, based on the amounts of A) and B).

[0103] In another aspect, the present invention provides a method for producing a pharmaceutical composition comprising: (i) at least one polysiloxane-polycarbonate block cocondensate; (ii) General chemical formula (I), general chemical formula (Ia): [ka] (In the formula, Z1, Z2, and Z3 are each independently methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C5 to C6 18alkyl, methacryloxypropyl, monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, phenyl, hydroxy, hydrogen, chlorine, fluorine, or CN; R8 and R9 each independently represent an aliphatic group or an aromatic group, provided that in formula (I) or formula (Ia), at least one R8 represents an aliphatic group and at least one R9 represents an aromatic group; and s, s1, s2, s3 and s4 each independently represent a natural number between 1 and 250, or any desired mixture thereof, (iii) optionally at least one further polymer different from component (i); (iv) optionally at least one further additive; The present invention provides a polycarbonate composition comprising:

[0104] Component (i) The polysiloxane-polycarbonate block cocondensate preferably comprises the following structural unit (X1): [ka] (In the formula, R X is a divalent substituted or unsubstituted aromatic group, a divalent linear or cyclic aliphatic group, or the structural unit (X1) is R X is a divalent substituted or unsubstituted aromatic group or R X is a mixture of structural units in which and structural unit (X2): [ka] (In the formula, R Y is, independently in each occurrence, a linear or branched aliphatic group, preferably a C1-C 12 - alkyl, particularly preferably C1-C4 alkyl, in particular methyl, or a substituted or unsubstituted aromatic group, preferably phenyl), It consists of:

[0105] The aromatic R in formula (X1) is X The proportion of alkyl groups is 60% to 100% by weight, and the proportion of aliphatic groups is 0% to 40% by weight. SiCoPc can preferably be constructed from siloxane blocks derivable from the above formula (1).

[0106] According to the present invention, the term "derivable" in this context is preferably understood to mean that the corresponding building block is esterified via a hydroxy group in the resulting polymer. 5 represents hydrogen or C1-C4 alkyl, preferably hydrogen or methyl, particularly preferably hydrogen. 6 and R 7 are each independently a C1-C4 alkyl, preferably methyl.

[0107] Y represents a single bond, -CO-, -O-, C1-C5-alkylene, C2-C5-alkylidene or a C5-C6-cycloalkylidene group optionally mono- or polysubstituted with C1-C4-alkyl, preferably a single bond, -O-, isopropylidene or a C5-C6-cycloalkylidene group optionally mono- or polysubstituted with C1-C4-alkyl, in particular isopropylidene.

[0108] V represents oxygen, C2-C6 alkylene, or C3-C6 alkylidene, preferably oxygen or C3-alkylene.

[0109] When q=0, W represents a single bond, and When q=1, W represents oxygen, C2-C6-alkylene or C3-C6-alkylidene, preferably oxygen or C3-alkylene.

[0110] p and q each independently represent 0 or 1;

[0111] o represents an average number of repeating units of 10 to 400, preferably 10 to 100, and particularly preferably 15 to 50.

[0112] m represents the average number of repeating units of 1 to 10, preferably 1 to 6, and particularly preferably 1.5 to 5.

[0113] The siloxane blocks of component (i) SiCoPC are particularly preferably obtained from the siloxanes of formula (2) and formula (3) above, During the ceremony, R1 represents hydrogen, C1-C4-alkyl, preferably hydrogen or methyl, particularly preferably hydrogen, R2 independently in each occurrence represents aryl or alkyl, preferably methyl; X is a single bond, -SO2-, -CO-, -O-, -S-, C1-C6-alkylene, C2-C5-alkylidene, or a C6-C6 alkylene optionally fused to a further aromatic ring containing a heteroatom. 12 -arylene, X is preferably a single bond, C1-C5-alkylene, C2-C5-alkylidene, C5-C 12 -Cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO2-, particularly preferably a single bond, isopropylidene, C5 to C 12 represents cycloalkylidene or oxygen, very particularly preferably isopropylidene, n represents an average number of 10 to 400, preferably 10 to 100, particularly preferably 10 to 50, and m represents an average number of 1 to 10, preferably 1 to 6, and particularly preferably 1.5 to 5.

[0114] As mentioned above, component (i) is preferably a polysiloxane-polycarbonate block cocondensate prepared by the process according to the present invention.

[0115] It is preferred if the polysiloxane-polycarbonate block cocondensate has a siloxane domain size D90 of less than 120 nm, preferably less than 110 nm, particularly preferably less than 100 nm. Likewise, it is preferred if the proportion of particles with a diameter of less than 100 nm is greater than 70%, particularly preferably greater than 80%, and very particularly preferably greater than 90% of the total number of siloxane domains. The D90 value and / or the proportion of particles with a diameter of less than 100 nm is determined by AFM. This is preferably carried out using the parameters and methods described in the Examples section. In a further embodiment, the siloxane blocks of the polysiloxane-polycarbonate block cocondensate have the following structure (IVa): [ka] (In the formula, R2 is as defined above, n is an average number of 10 to 400, preferably 10 to 100, particularly preferably 15 to 50, k may have a value of 0 or 1.

[0116] R3, independently in each occurrence, is the following structural element (V): [ka] (In the formula, R4, independently in each occurrence, is hydrogen, halogen, and / or C1-C 10 , preferably a C1-C4 linear or branched, unsubstituted or mono- or tetra-substituted alkyl or alkoxy group, wherein these alkyl and alkoxy groups are preferably unsubstituted, and R4 is particularly preferably hydrogen; e is 0 or a natural number from 2 to 12, preferably from 2 to 6, where k is 1 when e is 0), or a compound represented by formula (VI): [ka] (In the formula, R6 and R7 are each independently H, C1 to C18 -Alkyl, C1-C 18 -alkoxy, halogen such as Cl or Br, or in each case optionally substituted aryl or aralkyl, preferably independently of one another H or C1-C 12 -alkyl, particularly preferably H or C1-C8-alkyl, very particularly preferably independently of one another H or methyl, and X1 is -CO-, -O-, -S-, C1-C6-alkylene, C2-C5-alkylidene, C6-C 10 -C6-C optionally fused to a cycloalkylidene or further aromatic ring containing a heteroatom 12 -arylene) structural element.

[0117] Preference is given when X1 represents C1-C5-alkylene, C2-C5-alkylidene, C6-C9-cyclohexylidene, -O-, -SO-, -CO-, -S-, -SO2-, particularly preferably isopropylidene, 3,3,5-trimethylcyclohexylidene, or oxygen, in particular isopropylidene.

[0118] By way of example and preferably, the siloxane block may have the following structure: [ka] (In formula (VII), formula (VIII), or formula (IX), a represents an average number of 10 to 400, preferably 10 to 100, and particularly preferably 15 to 50).

[0119] In further embodiments, the above-described siloxane blocks are linked one or more times via terephthalic acid or isophthalic acid to form the following exemplary structural elements: [ka] (In the formula, p represents 0 or 1; R2, R3, n, and k are as defined for structural element (IVa) above).

[0120] The corresponding siloxane blocks for reaction with polycarbonates or with phosgene or diaryl carbonates together with diphenols derived from formula (III) or formula (IIIa), respectively, have terminal phenolic OH groups, i.e. [ka] (wherein R2, R3, n, k, and p are as defined for structural element (IXb) above).

[0121] Component (ii) Component (ii) according to the present invention has already been more particularly described above in component C).

[0122] Ingredient (iii) Component (iii) is at least one additional polymer different from component (i).Component (iii) is preferably polycarbonate, polyester carbonate, polystyrene, styrene copolymer, aromatic polyester, such as polyethylene terephthalate (PET), PET-cyclohexanedimethanol copolymer (PETG), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), cyclic polyolefin, polyacrylate or copolyacrylate and polymethacrylate or copolymethacrylate, such as polymethyl methacrylate or copolymethyl methacrylate (PMMA, etc.), and also copolymers with styrene, such as transparent polystyrene-acrylonitrile (PSAN), thermoplastic polyurethane, polymers based on cyclic olefin (such as TOPAS (trademark), Ticona's commercial products).Component (iii) is particularly preferably polycarbonate. Polycarbonates in the context of the present invention include not only homopolycarbonates but also copolycarbonates and / or polyestercarbonates, which may be linear or branched, as is known, and mixtures of polycarbonates can also be used according to the invention.

[0123] The polycarbonates, including thermoplastic aromatic polyester carbonates, preferably have an average molecular weight M of 20,000 g / mol to 32,000 g / mol, preferably 23,000 g / mol to 31,000 g / mol, in particular 24,000 g / mol to 31,000 g / mol. w (determined by measuring the relative viscosity in CH2Cl2 at 25°C at a concentration of 0.5g per 100ml of CH2Cl2).

[0124] Up to 80 mol %, preferably 20 mol % to 50 mol %, of the carbonate groups in the polycarbonates used according to the invention can be replaced by aromatic dicarboxylic acid ester groups. Polycarbonates of this type, which contain acid groups derived from aromatic dicarboxylic acids as well as from carbonic acid in the molecular chain, are called aromatic polyester carbonates. In the context of the present invention, these polycarbonates are encompassed by the general term "thermoplastic aromatic polycarbonates."

[0125] The polycarbonates are known to be prepared from diphenols, carbonic acid derivatives, optionally chain terminators, and optionally branching agents, and polyester carbonates are prepared by replacing part of the carbonic acid derivatives with aromatic dicarboxylic acids or derivatives of dicarboxylic acids to a degree that corresponds to the degree to which carbonate structural units in the aromatic polycarbonate should be replaced by aromatic dicarboxylic acid ester structural units.

[0126] Examples of dihydroxyaryl compounds (diphenols) are dihydroxybenzene, dihydroxydiphenyl, bis(hydroxyphenyl)alkanes, bis(hydroxyphenyl)cycloalkanes, bis(hydroxyphenyl)aryls, bis(hydroxyphenyl)ethers, bis(hydroxyphenyl)ketones, bis(hydroxyphenyl)sulfides, bis(hydroxyphenyl)sulfones, bis(hydroxyphenyl)sulfoxides, 1,1′-bis(hydroxyphenyl)diisopropylbenzene, and ring-alkylated and ring-halogenated compounds thereof.

[0127] Diphenols suitable for preparing polycarbonates for use according to the invention are, for example, hydroquinone, resorcinol, dihydroxydiphenyl, bis(hydroxyphenyl)alkanes, bis(hydroxyphenyl)cycloalkanes, bis(hydroxyphenyl)sulfides, bis(hydroxyphenyl)ethers, bis(hydroxyphenyl)ketones, bis(hydroxyphenyl)sulfones, bis(hydroxyphenyl)sulfoxides, α,α'-bis(hydroxyphenyl)diisopropylbenzene, and alkylated, ring-alkylated, and ring-halogenated compounds thereof.

[0128] Preferred diphenols are 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)-1-phenylpropane, 1,1-bis(4-hydroxyphenyl)phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (bisphenol M), 2,2-bis(3-methyl-4-hydroxyphenyl)propane, bis(3,5 bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,3-bis[2-(3,5-dimethyl-4-hydroxyphenyl)-2-propyl]benzene, and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC).

[0129] Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, 1,1-bis(4-hydroxyphenyl)phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC).

[0130] These and other suitable diphenols are described, for example, in U.S. Pat. Nos. 2,999,835, 3,148,172, 2,991,273, 3,271,367, 4,982,014, and 2,999,846, DE-A-1,570,703, DE-A-2,063,050, DE-A-2,036,052, DE-A-2,211,956, and DE-A-3,832,396, FR-A-1,561,518, the monographs "H. Schnell, Chemistry and Physics of Polycarbonates," Interscience Publishers, New York 1964, pp. 28ff and 102ff" and "D. G. Legrand, J. T. Bendler, Handbook of Polycarbonate Science and Technology," Marcel Dekker, New York, 1964, pp. 28ff and 102ff." 2000, p. 72ff.

[0131] In the case of homopolycarbonates, only one diphenol is used, and in the case of copolycarbonates, two or more diphenols are used. The diphenols used may be contaminated with contaminants from their own synthesis, handling, and storage, as well as any other chemicals and auxiliaries added to the synthesis. However, it is desirable to use raw materials with the highest possible purity.

[0132] Monofunctional chain terminators required for molecular weight control, such as phenol or alkylphenols, especially phenol, p-tert-butylphenol, isooctylphenol, cumylphenol, their chlorocarbonates or acyl chlorides of monocarboxylic acids, or mixtures of these chain terminators, are fed to the reaction together with the bisphenoxide(s), or are added at any desired point in the synthesis, as long as phosgene or chlorocarbonate end groups are still present in the reaction mixture, or, in the case of acyl chlorides and chlorocarbonates, sufficient phenol end groups are available for the polymer being formed. However, it is preferred if the chain terminator(s) are added after phosgenation at a position or time when phosgene is no longer present but the catalyst has not yet been added, or before, together with, or in parallel with the catalyst.

[0133] Any branching agent or mixture of branching agents used is added to the synthesis in the same way, but typically before the chain terminator.Typically used compounds are trisphenols, quaterphenols, or acyl chlorides of tricarboxylic or tetracarboxylic acids, or even mixtures of polyphenols or mixtures of acyl chlorides.

[0134] Some examples of compounds that can be used as branching agents and that have three or more phenolic hydroxyl groups include phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)hept-2-ene, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tri(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4-bis(4-hydroxyphenylisopropyl)phenol, and tetra(4-hydroxyphenyl)methane.

[0135] Some of the other trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride, and 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole.

[0136] Preferred branching agents are 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole and 1,1,1-tri(4-hydroxyphenyl)ethane.

[0137] The amount of branching agent which can optionally be used is likewise between 0.05 mol % and 2 mol %, relative to the number of moles of diphenol used in each case.

[0138] The branching agent may be initially charged in the alkaline aqueous phase together with the diphenol and chain terminator, or may be added dissolved in an organic solvent prior to phosgenation.

[0139] All of these procedures for producing polycarbonate are well known to those skilled in the art.

[0140] Suitable aromatic dicarboxylic acids for the preparation of polyester carbonates are, for example, orthophthalic acid, terephthalic acid, isophthalic acid, tert-butylisophthalic acid, 3,3'-diphenyldicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4-benzophenonedicarboxylic acid, 3,4'-benzophenonedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 2,2-bis(4-carboxyphenyl)propane, trimethyl-3-phenylindane-4,5'-dicarboxylic acid.

[0141] Among the aromatic dicarboxylic acids, it is particularly preferable to use terephthalic acid and / or isophthalic acid.

[0142] Derivatives of dicarboxylic acids are dicarbonyl dihalides and dialkyl dicarboxylates, especially dicarbonyl dichloride and dimethyl dicarboxylate.

[0143] The replacement of carbonate groups by aromatic dicarboxylic acid ester groups is essentially stoichiometric and quantitative, so that the molar ratio of reactants is maintained in the final polyester carbonate. The aromatic dicarboxylic acid ester groups can be incorporated randomly or in blocks.

[0144] Preferred modes of production of polycarbonates, including polyestercarbonates, used according to the present invention are the known interfacial process and the known melt transesterification process (see, for example, WO 2004 / 063249, WO 2001 / 05866, WO 2000 / 105867, U.S. Pat. No. 5,340,905, U.S. Pat. No. 5,097,002, U.S. Pat. No. 5,717,057).

[0145] In the former case, the acid derivatives used are preferably phosgene and optionally a dicarbonyl dichloride, and in the latter case, preferably diphenyl carbonate and optionally a dicarboxylic acid diester. Catalysts, solvents, workup, reaction conditions, etc. for the production of polycarbonates or polyester carbonates are well described and known in both cases.

[0146] Component (iv) The polymer composition according to the present invention may optionally contain at least one further additive as component (iv). This at least one additive may be selected from additives and / or fillers and reinforcing agents. These additives and / or fillers and reinforcing agents may be mixed in an amount of 0.0% to 5.0% by weight, preferably 0.01% to 1.00% by weight, based on the total of components (i) to (iv). Possible additives may be selected from at least one of the following groups: flame retardants, UV protection agents, gamma stabilizers, antistatic agents, optical brighteners, flow improvers, heat stabilizers, inorganic pigments, mold release agents, and processing aids.

[0147] The additives are conventional polymer additives, for example those described in EP-A-0 839 623, WO 96 / 15102, EP-A-0 500 496 or in "Plastics Additives Handbook", Hans Zweifel, 5th edition (2000), Hanser Verlag Publishing House, Munich.

[0148] These additives can be added to the polymer melt individually or in any desired mixture or mixtures of several separate additives. The additives can be added to the polycarbonate directly during the isolation of the polymer (for example, via a side unit such as a side extruder) as a pure substance or in the form of a masterbatch, or after the melting of the polycarbonate granules in a so-called compounding step. The additives or their mixtures can be added to the polymer melt as a solid, i.e., as a powder, or as a melt. Another way of metering is to use a masterbatch or a mixture of masterbatches of the additive or additive mixture.

[0149] In a preferred embodiment, the polymer composition comprises a heat or processing stabilizer. Advantageously, phosphites and phosphonites are suitable, as are phosphines.Examples include triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite), tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, 6-isooctyloxy-2 ,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenzo[d,g]-1,3,2-dioxaphosphocin, 2,2',2''-nitrilo[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2 ,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, triphenylphosphine (TPP), trialkylphenylphosphine, bisdiphenylphosphinoethane, or trinaphthylphosphine.Particularly preferably, triphenylphosphine (TPP), Irgafos™ 168 (tris(2,4-di-tert-butylphenyl)phosphite), and tris(nonylphenyl)phosphite, or mixtures thereof, are used.

[0150] Phenolic antioxidants such as alkylated monophenols, alkylated thioalkylphenols, hydroquinones, and alkylated hydroquinones can also be used. Particularly preferred are Irganox® 1010 (pentaerythritol-3-(4-hydroxy-3,5-di-tert-butylphenyl)propionate; CAS: 6683-19-8) and Irganox® 1076 (2,6-di-tert-butyl-4-(octadecaneoxycarbonylethyl)phenol).

[0151] Suitable UV absorbers are described, for example, in EP-A-1 308 084, DE-A-102007011069 and DE-A-10311063.

[0152] Particularly suitable UV absorbers are hydroxybenzotriazoles, such as 2-(3',5'-bis(1,1-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole (Tinuvin® 234, Ciba Spezialitaetenchemie, Basel), 2-(2'-hydroxy-5'-(tert-octyl)phenyl)benzotriazole (Tinuvin® 329, Ciba Spezialitaetenchemie, Basel), 2-(2'-hydroxy-3'-(2-butyl)-5'-(tert-butyl)phenyl)benzotriazole (Tinuvin® 350, Ciba Spezialitaetenchemie, Basel), bis(3-(2H-benzotriazolyl)-2-hydroxy-5-tert-octyl)methane (Tinuvin® 360, Ciba Spezialitaetenchemie, Basel), Spezialitaetenchemie, Basel), (2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol (Tinuvin® 1577, Ciba Spezialitaetenchemie, Basel), and the benzophenones 2,4-dihydroxybenzophenone (Chimasorb® 22, Ciba Spezialitaetenchemie, Basel) and 2-hydroxy-4-(octyloxy)benzophenone (Chimassorb® 81, Ciba, Basel), 2-propenoic acid, 2-cyano-3,3-diphenyl-2,2-bis[[(2-cyano-1-oxo-3,3-diphenyl-2-propenyl)oxy]methyl]-1,3-propanediyl ester (9CI) (Uvinul® 3030, BASF AG, Ludwigshafen), 2-[2-hydroxy-4-(2-ethylhexyl)oxy]phenyl-4,6-di(4-phenyl)phenyl-1,3,5-triazine (CGX UVA 006, Ciba Spezialitaetenchemie, Basel), or tetraethyl 2,2'-(1,4-phenylenedimethylidene)bismalonate (Hostavin™ B-Cap, Clariant AG).

[0153] It is also possible to use a mixture of these UV absorbers.

[0154] The polymer composition according to the invention may optionally comprise a release agent. Particularly suitable release agents for the composition according to the invention are pentaerythritol tetrastearate (PETS) or glycerol monostearate (GMS).

[0155] The polycarbonate composition according to the present invention preferably comprises: 10% to 99.95% by weight, preferably 50% to 99.5% by weight, particularly preferably 80% to 99.5% by weight of component (i), and in certain embodiments 98.0% to 99.5% by weight of component (i); 0.05% to 2.5% by weight, preferably 0.1% to 2.0% by weight, particularly preferably 0.20% to 1.0% by weight of component (ii); 0% to 90% by weight, preferably 0% to 50% by weight, particularly preferably 0% to 20% by weight of component (iii); 0% to 15% by weight of component (iv); Includes:

[0156] The weight percentages are based on the total of components (i) to (iv). It is particularly preferred if the polycarbonate composition consists solely of components (i) to (iv). The weight percentages add up to 100 weight percent. According to the present invention, the term "polycarbonate composition" is to be understood as meaning that the composition preferably comprises at least 85 weight percent of polycarbonate, including the polycarbonate present in component (i). Additional polycarbonates, which may be different from component (i), may be present in the composition through component (iii).

[0157] The block cocondensates obtainable by the process according to the invention and the polycarbonate compositions according to the invention can be processed into any desired moldings, as is known for thermoplastic polycarbonates.

[0158] In this context, the composition according to the present invention can be converted into products, moldings or molded articles, for example, by hot pressing, spinning, blow molding, thermoforming, extrusion or injection molding.The use in multilayer systems is also of interest.The application of the composition obtainable according to the present invention can be, for example, in multi-component injection molding or as a substrate for a coex layer.However, it can also be applied to preformed bodies, for example, by laminating with a film or coating with a solution.

[0159] Sheets or molded articles consisting of a base layer and any one outer layer / any number of outer layers (multilayer systems) can be produced by (co)extrusion, direct skinning, direct coating, insert molding, in-mold coating, or any other suitable method known to those skilled in the art.

[0160] The polysiloxane-polycarbonate block cocondensates obtainable by the process according to the invention and the polycarbonate compositions according to the invention can be used wherever known aromatic polycarbonates have been used and where good flowability, together with improved demolding properties, high toughness at low temperatures and better chemical resistance, are additionally required, such as for the production of exterior parts and exterior control boxes for heavy automobiles, seats, twin-wall seats, parts for electrical and electronic equipment, and optical storage media. Thus, the block cocondensates can be used in the IT sector for computer housings, multimedia housings and mobile phone housings, in the home appliance sector, for example in washing machines or dishwashers, and in the sports sector, for example as materials for helmets.

[0161] A further aspect of the present invention is a method for producing a polysiloxane-polycarbonate block cocondensate, comprising the step of: [ka] (In the formula, Z1, Z2, and Z3 are each independently methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C5 to C6 18 alkyl, methacryloxypropyl, monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, phenyl, hydroxy, hydrogen, chlorine, fluorine, or CN; R8 and R9 each independently represent an aliphatic group or an aromatic group, provided that in formula (I) or formula (Ia), at least one R8 represents an aliphatic group and at least one R9 represents an aromatic group; The present invention provides the use of siloxanes of the general formula (I) or (Ia), or any desired mixtures thereof, wherein s, s1, s2, s3, and s4 each independently represent a natural number between 1 and 250. As mentioned above, it has surprisingly been found that compounds of the general formula (I) or (Ia) are particularly suitable for compatibilizing different phases in the preparation of polysiloxane-polycarbonate block cocondensates, thus resulting in a smaller particle size distribution of the siloxane domains. The method for preparing the polysiloxane-polycarbonate block cocondensates preferably comprises at least one reactive extrusion or at least one melt transesterification. It is very particularly preferred if the method comprises reactive extrusion.

[0162] The siloxanes of general formula (I) or general formula (Ia) are more particularly described above under component C) (and also under component (ii)). These preferences also apply to the use according to the invention. DETAILED DESCRIPTION OF THE INVENTION [Example]

[0163] The present invention will be described in detail below with reference to examples, and unless otherwise stated, the determination methods described herein for all corresponding parameters in the present invention will be used.

[0164] MVR Unless otherwise specified, melt volume flow rate (MVR) is determined according to ISO 1133 (2011) (at 300°C; 1.2 kg) unless any other conditions are specified.

[0165] solution viscosity Determination of solution viscosity: Solution viscosity (η rel ; also called relative solution viscosity) was determined at 25°C at a concentration of 5 g / l in dichloromethane using an Ubbelohde viscometer.

[0166] Evaluation of siloxane domain size using atomic force microscopy (AFM) The size and distribution of siloxane domains were determined using atomic force microscopy. For this purpose, the corresponding samples (in the form of melt cake for laboratory batches or in the form of granules for extrusion batches) were cut using an ultramicrotome at low temperature (nitrogen cooling). A Bruker D3100 AFM microscope was used. AFM images were recorded at room temperature (25°C, 30% relative humidity). The measurements were performed using "Soft Intermittent Contact Mode" or "Tapping Mode". The force was approximately 2.8 Nm. -1 The sample was scanned using a "tapping mode cantilever" (Nanoworld point probe) with a spring constant of 0.01 and a resonant frequency of approximately 75 kHz. The tapping force was controlled by the ratio between the target amplitude and the free vibration amplitude (the amplitude of the probe tip due to free vibration in air). The sampling rate was set to 1 Hz. To record the surface morphology, phase contrast and topography images were recorded over a 2.5 μm × 2.5 μm area. Particle / siloxane domains were automatically evaluated via light-dark contrast (from the phase contrast images) using Olympus SIS image processing software (Olympus Soft Imaging Solutions GmbH, 48149, Münster, Germany). Particle diameters were determined from the diameter of a circle of equal area corresponding to the longest dimension of the particle.

[0167] Multiple phase contrast images (numbering over 200 particles) are evaluated as described above. Image processing software is used to classify individual diameters and capture a diameter distribution, which is used to assign individual D values. The D value indicates the percentage of particles smaller than a specified value. A D90 value of x indicates that 90% of the particles are smaller than x. The percentage of particles smaller than 100 nm is also determined from the distribution.

[0168] Effect of adding component C) Starting materials: Component A: Polycarbonate PC 1: The starting material used for reactive extrusion is a linear bisphenol A polycarbonate with phenolic end groups and a solution viscosity of 1.17 (see above for explanation). This polycarbonate does not contain additives such as UV stabilizers, mold release agents, or heat stabilizers. This polycarbonate was produced by the melt transesterification method described in DE 102008019503 A1. This polycarbonate has a phenolic end group content of 0.16%.

[0169] Component B: Siloxane A bisphenol A-terminated polydimethylsiloxane of Formula 3 (R1 = H, R2 = methyl, X = isopropylidene), where n is approximately 30 and m is in the range of 3-4, having a hydroxy content of 18 mg KOH / g and a viscosity of 400 mPa·s (23°C); this siloxane is blended with sodium octanoate to give a sodium content of 2.5 ppm.

[0170] Component C / (ii): Linear oligomeric siloxanes of formula (I) where Z1 and Z2 = OH, R8 = methyl, R9 = phenyl, and s is an average of about 4 (a mixture of oligomers having s = 2 to about 10 chains).

[0171] method: The scheme of the experimental setup is evident from FIG.

[0172] Figure 1 shows a scheme for producing siloxane-containing block cocondensates. Polycarbonate (component A) is metered into twin-screw extruder 1 via gravimetric feed 2. The extruder (ZSE 27 MAXX from Leistritz Extrusionstechnik GmbH, Nuremberg) is a co-rotating twin-screw extruder equipped with a vacuum zone for vapor removal. The extruder consists of 11 barrel sections (a-k) (see Figure 1). Polycarbonate is added in barrel section a via differential weighing balance 2, and the polycarbonate is melted in barrels b and c. The liquid siloxane component (component B) is added in barrel section d. Barrel sections d and e are also used for mixing in the liquid siloxane component (component B). Barrel sections e, g, i, and j are equipped with degassing openings for removing condensation products. Barrel section e is assigned to the first vacuum stage, and barrel sections g, i, and j are assigned to the second vacuum stage. The vacuum in the first vacuum stage is 45 mbar to 65 mbar absolute. The vacuum in the second vacuum stage is less than 1 mbar. The siloxane (component B) is initially charged into tank 3 and introduced into the extruder via metering pump 4. Vacuum is generated via vacuum pumps 5 and 6. Steam is entrained from the extruder and collected in two condensers 9. The molten strand is passed through a water bath 10 and fragmented by a granulator 11.

[0173] Example 1: For the preparation, polycarbonate (component A) was mixed with 0.5% of component C in a solids mixer.

[0174] 1.9 kg / h of polycarbonate (component A) were metered into twin-screw extruder 1 via gravimetric metering means 2. The extruder speed was set to 120 rpm. 0.09 kg / h of component B were introduced into barrel d of the extruder via pump 4. A vacuum of 55 mbar was applied to barrel e, and a vacuum of 0.5 mbar was applied to each of barrels g, i, and j. Barrels g to k were brought to a temperature of 350°C.

[0175] The resulting polycondensate was light-colored and had an MVR of 2.1. The AFM image, measuring 10 x 10 μm, contained 880 identified objects that could be assigned to the soft phase, and therefore the siloxane phase. The size distribution of the objects had a D90 diameter of 115 nm. The largest identified object corresponded to a circular equivalent diameter of 156 nm.

[0176] Comparative Example 2: 1.9 kg / h of polycarbonate (component A) were metered into twin-screw extruder 1 via gravimetric metering means 2. The extruder speed was set to 120 rpm. 0.09 kg / h of component B were introduced into barrel d of the extruder via pump 4. A vacuum of 63 mbar was applied to barrel e, and a vacuum of 0.5 mbar was applied to each of barrels g, i, and j. Barrels g to k were brought to a temperature of 325°C.

[0177] The resulting polycondensate was light-colored and had an MVR of 4.4. The AFM image, measuring 10 x 10 μm, contained 624 identified objects that could be assigned to the soft phase, and therefore the siloxane phase. The size distribution of the objects had a D90 diameter of 185 nm. The largest identified object corresponded to a circular equivalent diameter of 516 nm.

[0178] The following examples were carried out in the manner of Example 1 / Comparative Example 2, varying the reported parameters:

[0179] TIFF0007739178000023.tif86170

[0180] As can be seen from this table, Comparative Example 3 and Example 4 are essentially equivalent to each other. Despite the use of slightly different extruder speeds and barrel temperatures, polymers with equivalent MVRs are obtained. Thus, these examples differ in the addition of component C) in Example 4 and its absence in Comparative Example 3.

[0181] Similar conclusions can be drawn for the equivalence of Comparative Example 5 with Example 6, and Comparative Example 7 with Examples 8 and 9. These comparisons are suitable for assessing the effect of the addition of component C) (and also its amount).

[0182] TIFF0007739178000024.tif89170

[0183] Inventive Example 4 demonstrates the positive effect of the low molecular weight siloxane of the present invention when the throughput is 2.0 kg / h and the material has an MVR in the range of about 7 to 9 (Comparative Example 3 and Example 4). Compared to Comparative Example 3, Inventive Example 4 has a significantly lower D90 value, thus resulting in a polymer morphology with smaller siloxane domain size. Increasing the reaction temperature makes it possible to achieve lower viscosities (Comparative Example 5 and Example 6). Inventive Example 6, which includes the addition of a low molecular weight siloxane of the present invention, component C), exhibits a significantly lower D90 value than Comparative Example 5.

[0184] The favorable effect of adding specific siloxane components is also evident at relatively low throughputs (up to 1.4 kg / h compared to 2.0 kg / h). Comparative Example 7 shows a D90 value similar to that of Inventive Example 9, but the proportion of particles with a volume less than 200 nm is significantly greater than that of Inventive Example 9. Particles with large volumes are particularly important in terms of processing defects, for example, in injection molding. By increasing the proportion of the inventive siloxane components (Example 8), further advantages are achieved, as evidenced by the lower D90 value and better volume distribution (particles with a volume greater than 200 nm are no longer present).

[0185] Effect of the chemical structure of component C) Starting materials: Component A: Polycarbonate PC A: The starting material used for reactive extrusion had a viscosity of 59 cm3 measured at 300°C and a load of 1.2 kg (according to ISO 1033). 3 / 10 minutes~62cm 3The polycarbonate is a linear bisphenol A polycarbonate with phenolic end groups from Covestro Deutschland AG, with a melt volume index of 1 / 10 min. This polycarbonate does not contain additives such as UV stabilizers, mold release agents, or heat stabilizers. This polycarbonate was produced by the melt transesterification method described in DE 102008019503 A1. This polycarbonate has a phenolic end group content of approximately 600 ppm.

[0186] PC B: The starting material used for reactive extrusion is a linear bisphenol A polycarbonate with phenolic end groups and a solution viscosity of about 1.17. This polycarbonate does not contain additives such as UV stabilizers, mold release agents, or heat stabilizers. This polycarbonate was produced by the melt transesterification method described in DE 102008019503 A1. This polycarbonate has a phenolic end group content of about 1600 ppm.

[0187] Component B: Siloxane 1 A bisphenol A-terminated polydimethylsiloxane of Formula 3, where n is approximately 15 and m is within the range of 3-4 (R1 = H, R2 = methyl, X = isopropylidene), has a hydroxy content of 27.8 mg KOH / g and a viscosity of 165 mPa·s (23°C); the sodium content is approximately 4 ppm.

[0188] Siloxane 2: A hydroquinone-terminated polydimethylsiloxane of Formula 2, where n is about 20 and m is in the range of 3-4 (R1 = H, R2 = methyl), having a hydroxy content of 22.2 mg KOH / g and a viscosity of 177 mPa·s (23°C); the sodium content is about 3 ppm.

[0189] Siloxane 3: A bisphenol A-terminated polydimethylsiloxane of Formula 3, where n is approximately 30 and m is within the range of 3-4 (R1 = H, R2 = methyl, X = isopropylidene), has a hydroxy content of 17.9 mg KOH / g and a viscosity of 402 mPa·s (23°C); the sodium content is approximately 3 ppm.

[0190] Component C / (ii): Linear oligomeric siloxanes of formula (I) where Z1 and Z2 = OH, R8 = methyl, R9 = phenyl, and s is an average of about 4 (a mixture of oligomers having s = 2 to about 10 chains).

[0191] Comparison ingredients: 95% octaphenylcyclotetrasiloxane (CAS: 546-56-5) from ABCR GmbH & Co. KG (Karlsruhe, Germany).

[0192] Catalyst Masterbatch (without additional siloxane-based ingredients): The catalyst used is tetraphenylphosphonium phenoxide in the form of a masterbatch from Rhein Chemie Rheinau GmbH (Mannheim, Germany). The tetraphenylphosphonium phenoxide is used in the form of a solid solution with phenol and contains approximately 70% tetraphenylphosphonium phenoxide. The amounts below are based on the material obtained from Rhein Chemie (as a solid solution with phenol).

[0193] A masterbatch was prepared as a 0.25% mixture. For this purpose, 4982 g of polycarbonate PC A was mixed with 18 g of tetraphenylphosphonium phenoxide in a drum hoop mixer for 30 minutes. The masterbatch was metered in at a ratio of 1:10, so that the catalyst was present in a proportion of 0.025% by weight of the total amount of polycarbonate.

[0194] Comparative Example 10: In a 250 ml glass flask equipped with a stirrer and a short-path separator, 42.5 g of polycarbonate granules (PC A; 85% by weight), 2.5 g of Siloxane 1 (5% by weight), as well as 5 g (10% by weight) of the catalyst masterbatch and 0.1 g (0.2% by weight) of octaphenylcyclotetrasiloxane were weighed out. The apparatus was evacuated and inerted with nitrogen (three times in each case). The mixture was melted under vacuum for 10 minutes using a metal bath preheated to 350°C. The pressure in the apparatus was approximately 1.5 mbar. The reaction mixture was maintained under this vacuum with stirring for 30 minutes. The mixture was then inerted with nitrogen and the polymer melt was removed. An opaque white polymer was obtained. The product had a solution viscosity of η rel =1.345.

[0195] Comparative Example 11: In a 250 ml glass flask equipped with a stirrer and a short-path separator, 42.5 g of polycarbonate granules (PC A; 85% by weight), 2.5 g of Siloxane 2 (5% by weight), and 5 g (10% by weight) of catalyst masterbatch (which, unlike the previous one, additionally contained 1.66% by weight of octaphenylcyclotetrasiloxane) were weighed out. The apparatus was evacuated and inerted with nitrogen (three times in each case). The mixture was melted under vacuum for 10 minutes using a metal bath preheated to 350°C. The pressure in the apparatus was approximately 1.5 mbar. The reaction mixture was maintained under this vacuum with stirring for 30 minutes. The mixture was then inerted with nitrogen, and the polymer melt was removed. An opaque white polymer was obtained. The product had a solution viscosity of η rel = 1.46.

[0196] Example 12: 47.4 g of polycarbonate granules (PC B; 94.8% by weight) were weighed into a 250 ml glass flask equipped with a stirrer and a short-path separator. The apparatus was evacuated and inerted with nitrogen (three times in each case). The mixture was melted under atmospheric pressure for 10 minutes using a metal bath preheated to 350°C. A siloxane mixture consisting of 2.5 g of Siloxane 3 (5% by weight) and 0.13 g (0.2% by weight) of component C (dissolved in Siloxane 3) was added at 10 mbar. The pressure in the apparatus was then reduced to approximately 1.5 mbar. The reaction mixture was maintained under this vacuum with stirring for approximately 5 minutes. The mixture was then inerted with nitrogen and the polymer melt was removed. An opaque white polymer was obtained. The product had a solution viscosity of η rel = 1.38.

[0197] TIFF0007739178000025.tif36170

[0198] Comparative Examples 10 and 11 clearly showed a coarse particle distribution in the AFM, so accurate evaluation was avoided and only estimation was performed.

[0199] TIFF0007739178000026.tif41170

[0200] Comparison of Example 12 with Comparative Examples 10 and 11 shows that the addition of a compound containing both aliphatic and aromatic groups results in a reduction in siloxane domain distribution in the preparation of polysiloxane-polycarbonate block cocondensates, compared to a compound containing only aromatic groups.

Claims

1. (i) at least one polysiloxane-polycarbonate block cocondensate; (ii) General chemical formula (I), general chemical formula (Ia): 【Chemical 1】 (In the formula, Z １ , Z ２ , and Z ３ are each independently methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C ５ ~C １８ alkyl, methacryloxypropyl, monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl, hydroxy, hydrogen, chlorine, fluorine, or CN; R ８ and R ９ each independently represents an aliphatic group or an aromatic group, provided that in the formula (I) or formula (Ia), at least one R ８ represents an aliphatic group, and at least one R ９ represents an aromatic group, and s, s １ , s ２ , s ３ , and s ４ each independently represents a natural number between 1 and 250), or any desired mixture thereof, (iii) optionally at least one further polymer different from component (i); (iv) optionally at least one further additive; A polycarbonate composition comprising: A polycarbonate composition obtained by the following method: A) at least one polycarbonate in the melt, B) at least one hydroxyaryl-terminated (poly)siloxane; C) General chemical formula (I), general chemical formula (Ia): 【Chemistry 2】 (In the formula, Z １ , Z ２ , and Z ３ are each independently methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C ５ ~C １８ alkyl, methacryloxypropyl, monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl, hydroxy, hydrogen, chlorine, fluorine, or CN; R ８ and R ９ each independently represents an aliphatic group or an aromatic group, provided that in the formula (I) or formula (Ia), at least one R ８ represents an aliphatic group, and at least one R ９ represents an aromatic group, and s, s １ , s ２ , s ３ , and s ４ and B) are each independently a natural number between 1 and 250, or any desired mixture thereof, characterized in that the method comprises the step of adding component C) to component A), component B), and / or a mixture of components A) and B).

2. R in general chemical formula (I) or general chemical formula (Ia) ８ is independently in each occurrence methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, C ５ ~C １８ -alkyl, or optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl, R in general chemical formula (I) or general chemical formula (Ia) ９ is independently in each occurrence methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, C ５ ~C １８ -alkyl, or optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl, However, at least one R ８ is methyl, ethyl, propyl, butyl, isopropyl, vinyl, isobutyl, or C ５ ~C １８ - alkyl, and at least one R ９ represents optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl, and Z in general chemical formula (I) or general chemical formula (Ia) １ , Z ２ , and Z ３ 2. The polycarbonate composition according to claim 1, characterized in that each independently of the other has the definition set out in claim 1.

3. The at least one siloxane of component (ii) is represented by general chemical formula (II), general chemical formula (IIa), general chemical formula (III), and / or general chemical formula (IV): 【Chemistry 3】 (In the formula, Z １ , Z ２ , and Z ３ are each independently methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C ５ ~C １８ alkyl, methacryloxypropyl, monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl, hydroxy, hydrogen, chlorine, fluorine, or CN; R １０ represents, independently in each occurrence, hydrogen, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, isooctyl, isononyl, or isodecyl; R １１ is independently in each occurrence methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C ５ ~C １８ alkyl, methacryloxypropyl, monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl, hydroxy, hydrogen, chlorine, fluorine, or CN; r is a natural number between 0 and 3, s and t are each independently a natural number between 1 and 250, and w and v are each independently a natural number between 1 and 250, and 3. The polycarbonate composition according to claim 1 or 2, characterized in that the group having the indices s, w, v, t, and u is represented by the formula (2), which may have a random distribution in the siloxane of component (ii).

4. In the general chemical formula (II), the general chemical formula (IIa), the general chemical formula (III), and the general chemical formula (IV), Z １ , Z ２ , and Z ３ each independently represent methyl, vinyl, methoxy, ethoxy, hydrogen, or hydroxy; R １０ represents hydrogen or methyl, R １１ is independently in each occurrence methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C ５ ~C １８ alkyl, methacryloxypropyl, monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl, hydroxy, hydrogen, chlorine, fluorine, or CN; r is a natural number between 0 and 3, s is a natural number between 5 and 75, t is a natural number between 1 and 75, w is a natural number between 5 and 75, v is a natural number between 1 and 75, and 4. The polycarbonate composition of claim 3, wherein u is a natural number between 1 and 10.

5. A) at least one polycarbonate in the melt, B) at least one hydroxyaryl-terminated (poly)siloxane; C) General chemical formula (I), general chemical formula (Ia): 【Chemistry 4】 (In the formula, Z １ , Z ２ , and Z ３ are each independently methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C ５ ~C １８ alkyl, methacryloxypropyl, monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl, hydroxy, hydrogen, chlorine, fluorine, or CN; R ８ and R ９ each independently represents an aliphatic group or an aromatic group, provided that in the formula (I) or formula (Ia), at least one R ８ represents an aliphatic group, and at least one R ９ represents an aromatic group, and s, s １ , s ２ , s ３ , and s ４ and B) are each independently a natural number between 1 and 250, or any desired mixture thereof, characterized in that the method comprises the step of adding component C) to component A), component B), and / or a mixture of components A) and B).

6. Component B) is a compound represented by formula (1): 【Chemistry 5】 (In the formula, R ５ is hydrogen or C １ ~C ４ represents alkyl, R ６ and R ７ are, independently of each other, C １ ~C ４ represents alkyl, Y is a single bond, —CO—, —O—, C １ ~C ５ - alkylene, C ２ ~C ５ - alkylidene, or C １ ~C ４ -C optionally mono- or polysubstituted by alkyl ５ ~C ６ represents a cycloalkylidene group, V is oxygen, C ２ ~C ６ Alkylene, or C ３ ~C ６ represents alkylidene, When q=0, W represents a single bond; When q=1, W is oxygen, C ２ ~C ６ - alkylene, or C ３ ~C ６ represents alkylidene, p and q are each independently 0 or 1; o represents the average number of repeat units from 10 to 400, and 6. The method for producing a polysiloxane-polycarbonate block cocondensate according to claim 5, wherein m represents the average number of repeating units from 1 to 10.

7. R in general chemical formula (I) or general chemical formula (Ia) ８ is independently in each occurrence methyl, ethyl, trimethylphenyl, —CH ２ -CH ２ -phenyl, -CH ２ -CH ２ -CH ２ -phenyl, -CH ２ -CH(CH ３ )-phenyl, —CH ２ -CH ２ -CH ２ -(2-methoxy)phenyl or phenyl, and R in general chemical formula (I) or general chemical formula (Ia) ９ is independently in each occurrence methyl, ethyl, trimethylphenyl, —CH ２ -CH ２ -phenyl, -CH ２ -CH ２ -CH ２ -phenyl, -CH ２ -CH(CH ３ )-phenyl, —CH ２ -CH ２ -CH ２ -(2-methoxy)phenyl or phenyl, However, at least one R ８ represents methyl or ethyl, and at least one R ９ 7. The method for producing a polysiloxane-polycarbonate block cocondensate according to claim 5 or 6, wherein represents trimethylphenyl or phenyl.

8. The at least one siloxane of component C) is represented by general chemical formula (II), general chemical formula (IIa), general chemical formula (III), and / or general chemical formula (IV): 【Chemistry 6】 (In the formula, Z １ , Z ２ , and Z ３ are each independently methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C ５ ~C １８ alkyl, methacryloxypropyl, monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl, hydroxy, hydrogen, chlorine, fluorine, or CN; R １０ represents, independently in each occurrence, hydrogen, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, isooctyl, isononyl, or isodecyl; R １１ is independently in each occurrence methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C ５ ~C １８ alkyl, methacryloxypropyl, monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl, hydroxy, hydrogen, chlorine, fluorine, or CN; r is a natural number between 0 and 3, s and t are each independently a natural number between 1 and 250; w and v are each independently a natural number between 1 and 250, and The group having the indices s, w, v, t, and u may have a random distribution in the siloxane of component C).

9. A method for producing a polysiloxane-polycarbonate block cocondensate, comprising reducing the particle size distribution of siloxane domains in the polysiloxane-polycarbonate block cocondensate, the method comprising: 【Chemistry 7】 (In the formula, Z １ , Z ２ , and Z ３ are each independently methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C ５ ~C １８ alkyl, methacryloxypropyl, monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, optionally alkyl- or alkoxy-substituted phenylethyl, phenylisopropyl, 3-phenylpropyl, or phenyl, hydroxy, hydrogen, chlorine, fluorine, or CN; R ８ and R ９ each independently represents an aliphatic group or an aromatic group, provided that in the formula (I) or formula (Ia), at least one R ８ represents an aliphatic group, and at least one R ９ represents an aromatic group, and s, s １ , s ２ , s ３ , and s ４ each independently represent a natural number between 1 and 250), or any desired mixture thereof.

10. 10. Use according to claim 9, characterized in that the process for preparing the polysiloxane-polycarbonate block cocondensate comprises at least one reactive extrusion or at least one melt transesterification.

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