Polysiloxane-polycarbonate-block cocondensates made from specially terminated siloxane blocks

Abstract

The invention relates to a method for producing polysiloxane-polycarbonate-block co-condensates by using specially terminated polysiloxanes, to polysiloxane-polycarbonate-block co-condensates having at least one Si-O-C bond and a fine siloxane domain, to molding compounds comprising the polysiloxane-polycarbonate-block co-condensates according to the invention, to molding compounds comprising the polysiloxane-polycarbonate-block co-condensates according to the invention, and to molding compounds comprising the polysiloxane-polycarbonate-block co-condensates according to the invention. The invention relates to molded bodies comprising the polysiloxane-polycarbonate-block co-condensate according to the invention, to the use of a special bisphenol as a blocking group for polysiloxanes in order to increase the reactivity of polysiloxanes, and to a molded body comprising the polysiloxane-polycarbonate-block co-condensate according to the invention. The invention also relates to the use of special terminated polysiloxanes for increasing the ratio of covalent bonds between siloxane blocks and polycarbonate blocks in the production of polysiloxane-polycarbonate-block cocondensates.

Description

[0001] The present invention relates to a method for producing polysiloxane-polycarbonate block cocondensates (hereinafter also referred to as SiCoPC) by using special end-capped polysiloxanes, polysiloxane-polycarbonate block cocondensates having at least one Si-OC bond and fine siloxane domains, molding materials comprising the polysiloxane-polycarbonate block cocondensates according to the invention, moldings comprising the polysiloxane-polycarbonate block cocondensates according to the invention, the use of special bisphenols as end-capping groups for polysiloxanes for increasing the reactivity of polysiloxanes, and the use of special end-capped polysiloxanes for increasing the ratio of covalent bonds between siloxane blocks and polycarbonate blocks when producing polysiloxane-polycarbonate block cocondensates.

[0002] It is well known that polysiloxane-polycarbonate-block cocondensates exhibit good properties in low-temperature impact toughness or low-temperature notched impact toughness, chemical resistance and outdoor weathering resistance, as well as aging properties and fire resistance. In some cases, they are superior to conventional polycarbonates (e.g. homopolycarbonates based on bisphenol A) in these properties.

[0003] These co-condensates are usually produced industrially by the phase interface method with phosgene from monomers. It is also known to use diphenyl carbonate to produce these polysiloxane-polycarbonate-block co-condensates by the melt transesterification method. The disadvantage of these methods is that the industrial equipment used for this purpose is used to produce standard polycarbonates, and therefore has a large equipment scale. Since the volume of these products is relatively small, it is usually economically unfeasible to produce special block co-condensates in these equipment. In addition, the raw materials required for the production of co-condensates, such as polydimethylsiloxane, may damage the equipment because they may cause pollution of the equipment or solvent circuit. In addition, the production requires difficult raw materials, such as phosgene, or, for example, requires high energy requirements in the melt transesterification method.

[0004] The production of polysiloxane-polycarbonate block cocondensates by the interfacial process is known in the literature and is described, for example, in US Pat. Nos. 3,189,662, 3,419,634, DE-OS 334,782, US 2008 / 0081893 A1 and EP 0,122,535.

[0005] The production of polysiloxane-polycarbonate-block cocondensates by melt transesterification from bisphenols, diaryl carbonates, silanol-terminated polysiloxanes and catalysts is described in US 5227449. The siloxane compounds used are polydiphenyl or polydimethylsiloxane telomers with silanol end groups. However, it is known that such dimethylsiloxanes with silanol end groups have an increased tendency to self-condense in acidic or alkaline media as the chain length decreases compared to diphenylsiloxanes with silanol end groups, thus hindering their incorporation into the resulting copolymers. The cyclic siloxanes thus formed remain in the polymer and are extremely disruptive in applications in the electrical / electronics sector.

[0006] US 5504177 describes the production of polysiloxane-polycarbonate block cocondensates from carbonate-terminated silicones with bisphenols and diaryl carbonates by melt transesterification. Due to the extreme incompatibility of siloxanes with bisphenols and diaryl carbonates, homogeneous incorporation of siloxanes into the polycarbonate matrix by the melt transesterification process is not possible or can be achieved only with great difficulty.

[0007] The disadvantage of all these methods is the use of organic solvents or the use of phosgene as raw material or insufficient quality of the cocondensate in at least one step of the synthesis of the polysiloxane-polycarbonate-block cocondensate. In particular, the synthesis of cocondensates from monomers is very complicated in the phase interface method and especially in the melt transesterification method. Therefore, for example, a small amount of vacuum and low temperature must be used in the melt method to prevent evaporation and thus remove the monomers. Only in the later reaction phase of the formation of oligomers with higher molar masses can lower pressures and higher temperatures be used. This means that the reaction must be carried out through multiple stages, so the reaction time is correspondingly long.

[0008] In order to avoid the above-mentioned shortcomings, a reactive extrusion method for producing block copolycarbonates based on siloxanes has also been described. For example, this has been disclosed in US 5414054 and US 5821321. This includes reacting conventional polycarbonate with a special polydimethylsiloxane in a reactive extrusion method. However, the disadvantage of this method is the use of expensive special silicone components. In addition, a highly active transesterification catalyst is used in this method, which can produce cocondensates in an extruder within a short residence time. However, these transesterification catalysts remain in the product and cannot be deactivated or can only be inadequately deactivated. Therefore, the injection molded article made of the cocondensate produced in this way shows insufficient aging characteristics, especially insufficient heat aging characteristics. Therefore, the resulting block copolycarbonate is not suitable for high-quality applications. Compared with the block copolycarbonate from the interfacial method, the product does not show corresponding properties, such as aging characteristics and mechanical properties.

[0009] The siloxane blocks in the prior art usually have Si-C bonds. In the context of the present invention, the term "Si-C bond" and / or "Si-O-C bond" preferably refers to polysiloxanes with end caps. The end caps are preferably organic groups with phenolic OH groups. The organic groups with phenolic OH groups are preferably bonded via Si-C bonds or Si-O-C bonds. It is also possible that the Si-C bond and / or Si-O-C bond is present at another position in the polysiloxane. However, it is preferred that this at least refers to the bonding of the end groups (end capping groups) to the siloxane groups.

[0010] The hydrolytic stability of Si-C bonds is significantly higher than that of Si-OC bonds. However, polysiloxane blocks containing Si-C bonds need to be produced in a complicated manner by hydrosilylation catalyzed by Pd or Pt. Such catalysts are expensive. Typical polydimethylsiloxanes containing Si-C bonds are shown in formulas (I) to (III):

[0011]

[0012] Wherein n and m in formulae (I) to (III) represent the average number of repeating units.

[0013] In contrast, polysiloxanes with Si-OC bonds are significantly easier to obtain, without the need to use expensive Pd or Pt catalysts. For example, hydroquinone or BPA-terminated siloxanes with Si-OC bonds are known (see, for example, WO2013155046A1).

[0014] However, it has been found that the polysiloxanes terminated with BPA or hydroquinone are not completely uniformly incorporated into the block cocondensate. According to the present invention, the term "non-uniform incorporation" is preferably understood as the siloxane ratio of the acetone-soluble polymer portion containing only a low polycarbonate or low polycarbonate ratio. This highly polysiloxane-rich phase may impair the morphology of the polymer, i.e., form a large phase of polysiloxane-rich regions. Without wishing to be bound by theory, it can be considered that the formation of such large siloxane domains can sometimes also be promoted by polysiloxanes having Si-OC bonds and / or Si-C bonds being very inclined to self-condensation. According to the present invention, the term "self-condensation" is preferably understood as the reaction of a polysiloxane block with another polysiloxane block. However, compared with polysiloxanes having Si-C bonds, polysiloxanes having Si-OC bonds also seem to show a tendency to self-condensation, even if there is no carbonate donor (e.g., phosgene) or diaryl carbonate (e.g., diphenyl carbonate) participating in the reaction. Therefore, avoiding self-condensation seems to be a great challenge, especially for polysiloxanes with Si-OC bonds.

[0015] Large siloxane domain sizes can have a negative impact on the processing properties of SiCoPC. Due to the large domains, demixing can occur, which can manifest as an inhomogeneous surface structure and in some cases can also lead to flow line and streak formation. This material is also difficult to process in injection molding due to the shear sensitivity of the large domains, and therefore has only a very narrow processing window. This sometimes requires operating with very low injection speeds, which is generally undesirable because it reduces cycle time.

[0016] In particular when producing block cocondensates in the melt, large siloxane domains are formed in the prior art.

[0017] In the phase interface method, when using Si-C bonded siloxane blocks, the siloxane domain size of SiCoPC is typically below 100 nm. This allows for semi-transparent or even transparent materials to be obtained, since the small domain size hardly produces any light scattering.

[0018] In principle, it is known to produce siloxane-containing block cocondensates having low haze from Si—C-bonded polydimethylsiloxane blocks. In WO 2004016674 A1, precondensates are produced from oligocarbonates and siloxanes in the interfacial process and then further condensed with bisphenols in a second step in the interfacial process.

[0019] The disadvantage of the melt transesterification process is that it is in principle not possible to operate at high dilutions and that the reactants are always present in highly concentrated form. According to experience, this leads to the formation of siloxane domains with a size of 0.1 to 10 μm.

[0020] SiCoPC based on dihydroxydiphenylcycloalkanes of formula (1) are known in principle. Such structures are described, for example, in DE 3926850. However, these are block cocondensates formed from dihydroxydiphenylcycloalkanes, i.e. the polymers contain special bisphenols in the polymer chain. However, this can affect the properties (especially the glass transition temperature) of the resulting SiCoPC. This is not always desirable for various reasons.

[0021] EP 3036279 A1 likewise describes polysiloxanes which can be terminated in various ways. Termination with dihydroxydiphenylcycloalkanes is described here, but this is not preferred. The application provides no information on the incorporation behavior of such siloxane blocks in polycarbonates.

[0022] WO2016162301A1 describes a method for producing block cocondensates containing dihydroxydiphenylcycloalkanes and siloxanes. The corresponding block cocondensates are produced in a melt transesterification process. However, here, the dihydroxydiphenylcycloalkanes are also contained in the polycarbonate substructure and the siloxane substructure.

[0023] Therefore, starting from the prior art, the object of the present invention is to overcome at least one disadvantage of the prior art, preferably all disadvantages. The object of the present invention is in particular to minimize the self-condensation of polysiloxanes containing at least one Si-OC bond in the production of SiCoPC. On the contrary, the reaction of polysiloxanes with bisphenols or oligocarbonates or polycarbonates should preferably occur. Polysiloxanes containing at least one Si-OC bond should be used to avoid complex and expensive hydrosilylation catalyzed by Pd or Pt. The object of the present invention is in particular to provide polysiloxane-polycarbonate-block co-condensates, which do not contain a significant polysiloxane-rich proportion (only have a low PC proportion) and are characterized by a particularly fine siloxane domain distribution. If SiCoPC has a significant polysiloxane-rich proportion, the above-mentioned effect will occur. Polysiloxane-polycarbonate-block co-condensates should also preferably be produced in a melt transesterification process. A particular object of the present invention is to provide polysiloxane-polycarbonate block cocondensates in which at least 50% by volume, particularly preferably at least 75% by volume, very particularly preferably at least 90% by volume of all siloxane domains in the siloxane domain distribution of the polysiloxane-polycarbonate block cocondensates are between greater than 0 and 50 nm.

[0024] At least one of the above objects, preferably all of them, is achieved by the present invention.

[0025] Surprisingly, it can be found that polysiloxane blocks containing Si-OC bonds and terminated by alicyclic substituted or alicyclic containing bisphenols show significantly more uniform incorporation into SiCoPC. They also have a finer phase morphology. This indicates that the self-condensation of polysiloxanes can be slowed down or inhibited or minimized by special end-capping. Therefore, the reactivity of the special end-capped polysiloxane to compounds containing the structure of formula (2) appears to be greater than that of other special end-capped polysiloxanes. This is surprising because alicyclic bisphenols differ only slightly from alkyl-containing bisphenols (such as isopropylidene bisphenol (BPA)). Improved SiCoPC processing properties are obtained by improved siloxane domain size. The demixing tendency is reduced, and the injection molding processing window of the polycarbonate composition according to the present invention is widened.

[0026] Without being bound by theory, the particular end-capped polysiloxane blocks of the present invention may exhibit steric hindrance and / or electronic stabilization by virtue of the alicyclic structure, which makes the Si-OC bonds more stable and minimizes the tendency for self-condensation.

[0027] According to the invention, the expression "more uniformly incorporated into SiCoPC" is preferably understood to mean that a higher proportion of siloxane blocks are covalently bonded to the polycarbonate blocks than is the case with BPA-terminated (bisphenol A-terminated) siloxane blocks under the same conditions. The BPA-terminated siloxane blocks preferably have the same structure as the polysiloxanes used according to the invention, except that the BPA structure has been replaced according to the invention by specific cycloaliphatic bisphenols.

[0028] Likewise, according to the invention, the expressions "finer siloxane domains" or "finer phase morphology" are preferably understood to mean that the siloxane domains and / or the phase morphology are smaller than when using BPA-terminated siloxane blocks under otherwise identical conditions.

[0029] The present invention therefore provides a process for producing polysiloxane-polycarbonate block cocondensates by reacting at least one polysiloxane of the formula (1)

[0030] (i) reacting with at least one compound of the formula (2) and / or (2I) in the presence of at least one base and phosgene in a phase interface process,

[0031] (ii) reacting with at least one compound of formula (2) and at least one diaryl carbonate in a melt transesterification process, or

[0032] (iii) reaction in a melt transesterification process with at least one compound of the formula (2II) and optionally at least one diaryl carbonate,

[0033]

[0034] wherein each R1 and R2 independently represent hydrogen, halogen, C1-C8 alkyl, C5-C6 cycloalkyl, phenyl or C7-C 12 Aralkyl,

[0035] R3 and R4 can be selected individually for each X and independently of one another represent hydrogen or C1-C6-alkyl, p is an integer from 4 to 7 and X represents carbon,

[0036] each R5 and R6 independently of one another represent an aliphatic or aromatic group, preferably methyl, ethyl, trimethylphenyl, -CH2-CH2-phenyl, -CH2-CH2-CH2-phenyl, -CH2-CH(CH3)-phenyl, -CH2-CH2-CH2-(2-methoxy)phenyl or phenyl,

[0037] n is an average number of repeating units of 10 to 400, preferably 10 to 100, particularly preferably 15 to 50, and

[0038] m is the average number of repeating units of 1 to 10, preferably 1 to 6, particularly preferably 1.5 to 5,

[0039] in

[0040]

[0041] wherein each Z in formula (2), (2I) or (2II) is independently a single bond, -S(=O)2-, -C(=O)-, -O-, -S-, -S(=O)-, -CH(CN)-, a straight-chain or branched C1-C6-alkylene group which may optionally contain at least one carbonyl group, may optionally contain at least one halogen atom and / or may be optionally interrupted by at least one heteroatom, a C2-C6-alkylene group which may optionally contain at least one carbon-carbon double bond, may optionally contain at least one carbonyl group and / or may optionally contain at least one halogen atom, 10 - alkylidene group,

[0042] Each of R7 and R8 in formula (2), (2I) or (2II) independently represents hydrogen, halogen, C1-C8 alkyl, C5-C6 cycloalkyl, C1-C4 alkoxy, phenyl or C7-C 12 Aralkyl,

[0043] o in formula (2I) or (2II) represents the average number of repeating units, which may be 2 to 40, preferably 7 to 31.

[0044] Y in formula (2II) represents hydrogen or -(C=O)-O-Ph, wherein Ph represents an optionally substituted phenyl group, and

[0045] Y1 in formula (2II) represents an optionally substituted phenyl group or a compound of formula (2IIa) wherein

[0046]

[0047] wherein each Z, R7 and R8 are as defined above for formula (2II) and "*" indicates the structure of formula (2IIa) as the position at which Y1 is attached to formula (2II).

[0048] According to the present invention, preference is given to using polysiloxanes of formula (1) in which each R1 and R2 each independently represents hydrogen or C1-C8 alkyl, particularly preferably hydrogen, R3 and R4 can be selected individually for each X and independently represent hydrogen or C1-C3-alkyl, particularly preferably represent hydrogen or methyl, p represents an integer from 4 to 7, preferably from 4 to 6, particularly preferably from 4 to 5, and X represents carbon, each R5 and R6 each independently represents methyl, ethyl, trimethylphenyl, -CH2-CH2-phenyl, -CH2-CH2-CH2-phenyl, -CH2-CH(CH3)-phenyl, -CH2-CH2-CH2-(2-methoxy)phenyl or phenyl, preferably methyl or phenyl, n is an average number of repeating units of 10 to 400, preferably 10 to 100, particularly preferably 15 to 50, and m is an average number of repeating units of 1 to 10, preferably 1 to 6, particularly preferably 1.5 to 5.

[0049] It is obvious to those skilled in the art that the above formula (1) can also be expressed as formula (100):

[0050]

[0051] wherein each R1 and R2 independently represent hydrogen, halogen, C1-C8 alkyl, C5-C6 cycloalkyl, phenyl or C7-C 12 Aralkyl,

[0052] R3 and R4 may be selected individually for each X and independently of one another represent hydrogen or C1-C6-alkyl, n is an integer from 4 to 7, and

[0053] X represents carbon,

[0054] each R5 and R6 independently of one another represent an aliphatic or aromatic group, preferably methyl, ethyl, trimethylphenyl, -CH2-CH2-phenyl, -CH2-CH2-CH2-phenyl, -CH2-CH(CH3)-phenyl, -CH2-CH2-CH2-(2-methoxy)phenyl or phenyl,

[0055] n is an average number of repeating units ranging from 10 to 400, and

[0056] m is an average number of 1 to 10 repeating units.

[0057] According to the present invention, it is particularly preferred to use polysiloxanes of formula (1) in which each R1 and R2 each represents hydrogen, R3 and R4 can be selected individually for each X and independently of one another represent hydrogen or methyl, p is an integer of 4 or 5 and X represents carbon, each R5 and R6 each independently of one another represents methyl or phenyl, n is an average number of repeating units of 10 to 400, preferably 10 to 100, particularly preferably 15 to 50, and m is an average number of repeating units of 1 to 10, preferably 1 to 6, particularly preferably 1.5 to 5.

[0058] Very particular preference is given to using polysiloxanes of the formula (1A) in which

[0059]

[0060] Each R I Each independently represents hydrogen or methyl, n is an average number of repeating units of 10 to 400, preferably 10 to 100, particularly preferably 15 to 50, and m is an average number of repeating units of 1 to 10, preferably 1 to 6, particularly preferably 1.5 to 5. Particularly preferably, each R in formula (1A) I Represents methyl.

[0061] In the context of the present invention, reference is often made to the "endcapping" of the polysiloxanes of the formula (1). Endcapping is preferably understood to mean that all ends (usually 2) of the polysiloxane have a particular organic group (in this respect see, for example, formula (1)).

[0062] The special blocked polysiloxane of formula (1) can be produced by various methods. The special blocked polysiloxane can be obtained, for example, by reacting a diacetoxyacyloxy-blocked siloxane block with the corresponding dihydroxydiphenylcycloalkane. The production of acyloxy-blocked siloxanes is described, for example, in EP0003285 and US4584360. The special blocked polysiloxane can also be produced via α,ω-dichloropolydimethylsiloxane. This is described, for example, in US3821325. For example, a dichlorosiloxane compound is reacted with the corresponding alicyclic bisphenol in an inert solvent at a temperature of 0°C to 100°C in the presence of an acid acceptor.

[0063] The molecular weight (Mw) of the polysiloxane is preferably from 2000 to 20000 g / mol, particularly preferably from 2500 to 15000 g / mol. The molecular weight is preferably determined as described below.

[0064] The polysiloxane of formula (1) is preferably used in a proportion of 0.5 to 50% by weight, preferably 1 to 40% by weight, particularly preferably 2 to 20% by weight, very particularly preferably 2.5 to 10% by weight, based on the sum of the weights of the polysiloxane of formula (1) and the compound containing the structure of formula (2), (2I) and / or (2II), depending on which of these compounds is used.

[0065] According to the present invention, the polysiloxane of formula (1)

[0066] (i) reacting with at least one compound of the formula (2) and / or (2I) in the presence of at least one base and phosgene in a phase interface process,

[0067] (ii) reacting with at least one compound of formula (2) and at least one diaryl carbonate in a melt transesterification process, or

[0068] (iii) in a melt transesterification process with at least one compound of the formula (2II) and optionally at least one diaryl carbonate.

[0069] Preferably, each Z in formula (2), (2I) or (2II) is independently a single bond, -S(=O)2-, -C(=O)-, -O-, -S-, -S(=O)-, -CH(CN)-, a straight-chain or branched C1-C6-alkylene or a C2-C 10 -alkylidene, and

[0070] Each of R7 and R8 in formula (2), (2I) or (2II) each independently represents hydrogen, C1-C8 alkyl or C1-C4 alkoxy.

[0071] Particularly preferably, each Z in formula (2), (2I) or (2II) independently of one another represents a single bond or a C2-C6-alkylidene group, and

[0072] Each of R7 and R8 in the formula (2), (2I) or (2II) represents, independently of one another, hydrogen, C1-C3-alkyl or C1-C2-alkoxy.

[0073] Very particularly preferably, the individual Zs in formula (2), (2I) or (2II) each independently of one another represent a single bond or an isopropylidene group, and

[0074] Each of R7 and R8 in formula (2), (2I) or (2II) each independently represents hydrogen or methoxy, preferably hydrogen.

[0075] According to the invention, a polysiloxane of formula (1) is reacted with at least one compound of formula (2), (2I) or (2II). It is also conceivable to react at least two compounds of formula (2), (2I) or (2II) with a polysiloxane of formula (1). It is particularly preferred that, in the first compound of formula (2), (2I) or (2II), Z in each case represents an isopropylidene group and R7 and R8 each represent hydrogen. It is also preferred that, in the second compound of formula (2), (2I) or (2II), Z in each case represents a single bond and R7 and R8 each represent hydrogen.

[0076] Particularly preferably, Z in formula (2), (2I) or (2II) is isopropylidene. Therefore, formula (2), (2I) or (2II) is derived from bisphenol A.

[0077] The indicated o values ​​represent the average number of repeating units. The term "average number of repeating units" is known to the person skilled in the art. The person skilled in the art knows how to determine this parameter. This parameter can be determined in particular by GPC. It is preferably determined by the GPC method described in the context of the present invention.

[0078] In the context of the present invention, unless otherwise indicated, the term "alkyl" or "alkyl group" preferably refers to an alkane structure from which one hydrogen atom has been removed. The alkyl group according to the invention may be straight-chain or branched. It is saturated and therefore contains only single bonds between adjacent carbon atoms. Preferably, the alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, 1-ethyl-2-methylpropyl, and the like. If the number of carbon atoms were defined differently in the context of the present invention, the choice of these structures might be restricted.

[0079] In the context of the present invention, unless otherwise indicated, the term "alkylene" or "alkylene group" preferably refers to a bridged alkane structure with two hydrogen atoms removed from different carbon atoms. In this context, the two hydrogen atoms removed from the two carbon atoms can be removed from any carbon atom in the alkane structure. This means that the two carbon atoms can be adjacent, but do not necessarily have to be adjacent. The alkylene group can be straight-chain or branched. It is saturated. If the alkylene group contains only one carbon atom, it refers to a methylene group (-CH2-) connected to the rest of the molecule by two single bonds. Preferably, the alkylene group comprises methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, tert-butylene, n-pentylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, neopentylene, 1-ethylpropylene, n-hexylene, 1,1-dimethylpropylene, 1,2-dimethylpropylene, 1,2-dimethylpropylene, 1-methylpentylene, 2-methylpentylene, 3-methylpentylene, 4-methyl The alkylene radicals of the present invention are alkylene radicals, ... Examples of such alkylene groups include -C(=O)-(CH2)4-C(=O)-, -C(=O)-(CH2)3-C(=O)-, -C(=O)-(CH2)2-C(=O)-, -C(CF3)2, -O-(CH2)4-O-, -O-(CH2)3-O-, -O-(CH2)2-O-, and the like.

[0080] In the context of the present invention, unless otherwise indicated, the term "alkylidene" or "alkylidene group" preferably refers to a bridged alkane structure with two hydrogen atoms removed from the same carbon atom. The alkylidene group optionally contains at least one carbon-carbon double bond, optionally at least one carbonyl group and / or optionally at least one halogen atom. The alkylidene group preferably includes isopropylidene, n-propylidene, isoheptylidene, etc.

[0081] In the context of the present invention, unless stated otherwise, the term "aralkyl" preferably means in each case independently of one another a straight-chain, cyclic or branched alkyl radical which is mono-, di- or polysubstituted by aryl.

[0082] In the context of the present invention, unless otherwise indicated, the term "alkoxy" or "alkoxy group" preferably refers to a straight-chain, cyclic or branched alkyl group (-OR) which is bonded to an oxygen atom via a single bond. The alkoxy group according to the invention preferably has 1 to 6 carbon atoms. Particularly preferably, the alkoxy group includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, neopentoxy, 1-ethylpropoxy, cyclohexyloxy, cyclopentyloxy, n-hexyloxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1,2-dimethylpropoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy. The present invention also provides the following structures: 1,4-dimethylbutyloxy, 1,1-dimethylbutyloxy, 1,2-dimethylbutyloxy, 1,3-dimethylbutyloxy, 2,2-dimethylbutyloxy, 2,3-dimethylbutyloxy, 3,3-dimethylbutyloxy, 1-ethylbutyloxy, 2-ethylbutyloxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy, 1-ethyl-2-methylpropoxy or 1-ethyl-2-methylpropoxy. If the definition of the number of carbon atoms is different in the context of the present invention, the selection of these structures may be limited.

[0083] Based on the above definitions, those skilled in the art will be able to understand further definitions not explicitly mentioned above.

[0084] The reaction of the polysiloxane according to (i) with at least one compound of the formula (2) and / or (2I) is carried out according to the invention in an interfacial process. These processes and their specific process modes are known to those skilled in the art. The process is carried out in an interfacial process using phosgene and in the presence of a base. It is also known to those skilled in the art to use at least one base in an interfacial process. This is in particular an aqueous solution of an alkali metal hydroxide or an alkaline earth metal hydroxide. The at least one base is very particularly preferably an aqueous sodium hydroxide solution.

[0085] The interfacial process is described, for example, in H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964, p. 33 et seq. and in Polymer Reviews, Vol. 10, "Condensation Polymers by Interfacial and Solution Methods", Paul W. Morgan, Interscience Publishers, New York 1965, Chapter VIII, p. 325, and the reaction conditions employed are known to those skilled in the art. In addition, the interfacial process for the production of polycarbonates is also described, for example, in EP-A 0517044.

[0086] In the phase interface process, the disodium salts of diols / bisphenols or of mixtures of different diols / bisphenols, which are usually pre-charged in the form of an alkaline aqueous solution or suspension, are phosgenated in the presence of an organic solvent or solvent mixture. The latter is usually inert and forms a second organic phase in addition to the aqueous phase. The resulting oligocarbonates, which are predominantly present in the organic phase, are condensed with the aid of suitable catalysts to give high molecular weight polycarbonates dissolved in the organic phase, the molecular weight being controllable by suitable chain terminators (for example monofunctional phenols). The organic phase is finally separated off and the polycarbonate is isolated therefrom by various processing steps.

[0087] The condensation is generally carried out interfacially in an inert solvent in the presence of a base and a catalyst.

[0088] It is particularly known to those skilled in the art that the OH end groups of compounds of formula (1), (2) and / or (2I) do not usually react directly with each other. The reaction is carried out in the presence of a base. Salts can therefore be formed. The reaction can also be influenced by the addition time of the different reactants, as known to those skilled in the art. In particular, compounds of formula (2) and / or (2I) can be phosgenated together with polysiloxanes of formula (1), individual phosgenations of the components can be carried out, or only one of the components can be reacted with phosgene. Different dilutions can also be used for the operation. Similarly, it is obvious to those skilled in the art that compounds of formula (2) can be converted into compounds of formula (2I) according to the reaction mode. US20040039145A describes an advantageous method mode of the phase interface method which takes into account the avoidance of self-condensation of polysiloxanes (having Si-C bonds).

[0089] Alternatively, the polysiloxane of formula (1) is carried out in a melt transesterification process according to the reaction of (ii) or (iii). The method and the mode of operation are also known to those skilled in the art. The reaction is carried out by condensation in the melt by a compound of formula (2) and at least one diaryl carbonate, or by a compound of formula (2II) and optionally at least one diaryl carbonate and a special end-capped polysiloxane in the absence of a solvent. The method of the present invention is preferably carried out according to (ii) or (iii). The method of the present invention is very particularly preferably carried out according to (iii). It is obvious to those skilled in the art that there is a certain overlap between (ii) and (iii). In particular, by reacting according to (ii), a compound of formula (2II) can be formed, so that (ii) can also transition to (iii). According to the present invention, a clear boundary between (ii) and (iii) does not seem to be necessary.

[0090] The melt transesterification process is described, for example, in Encyclopedia of Polymer Science, Vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964) and DE-C 1031512. In the melt transesterification process, it is also known to those skilled in the art that the compounds of formula (2) and / or (2II) do not need to react directly, but can optionally have other end groups by further reaction. The method according to the invention is particularly preferably characterized in that the polysiloxane (iii) of formula (1) reacts with at least one compound of formula (2II) in the melt transesterification process.

[0091] The diaryl carbonate is preferably a compound of formula (III)

[0092]

[0093] in

[0094] R4 and R5 are independently H, C1-C 34 -alkyl, C7-C 34 -Arylalkyl, C6-C 34 -aryl or -COO-R', where R' corresponds to C1-C 34 -alkyl, C7-C 34 -Arylalkyl, C6-C 34 -aryl, and

[0095] m and m1 are independently of one another integers from 1 to 5, and if m is a value from 2 to 5, the individual radicals R4 may be identical or different, and if m1 is a value from 2 to 5, the individual radicals R5 may be identical or different.

[0096] Particularly preferably, the diaryl carbonate is diphenyl carbonate, 4-tert-butylphenyl phenyl carbonate, di(4-tert-butylphenyl) carbonate, biphenyl-4-ylphenyl carbonate, di(biphenyl-4-yl) carbonate, 4-(1-methyl-1-phenylethyl)phenyl phenyl carbonate and di[4-(1-methyl-1-phenylethyl)phenyl] carbonate, very particularly preferably diphenyl carbonate.

[0097] If the process according to the invention is carried out in a melt transesterification process, it is further preferred that the process according to the invention is carried out in an extruder, a high-viscosity reactor or a thin-film evaporator.

[0098] The extruder or melt reactor can be a single screw reactor, a twin screw reactor or a multi-screw reactor, such as a planetary roller extruder or a ring extruder. It can also be related to a high capacity kneader reactor. The method can be carried out in a single device (e.g. a twin screw extruder) or in two stages (i.e. a reactor combination). The reactor combination preferably consists of a pre-reactor (e.g. a twin screw extruder) and a high viscosity reactor. Advantageous method modes are particularly described in EP21187927 and EP21187920.

[0099] In addition, preferably, the compound comprising the structure of formula (2I) has a relative solution viscosity ηrel of 1.08 to 1.22, preferably 1.11 to 1.22, particularly preferably 1.13 to 1.20. The relative solution viscosity (ηrel; also referred to as eta rel) is preferably determined in dichloromethane at a concentration of 5 g / l using an Ubbelohde viscometer at 25°C. It is known to those skilled in the art to use an Ubbelohde viscometer to determine the relative solution viscosity. According to the present invention, this is preferably carried out according to DIN 51562-3; 1985-05. Here, the passage time of the compound under investigation is measured by an Ubbelohde viscometer in order to then determine the viscosity difference between the polymer solution and its solvent. To this end, the Ubbelohde viscometer is first calibrated by measuring the pure solvents dichloromethane, trichloroethylene and tetrachloroethylene (always at least 3 measurements and a maximum of 9 measurements). The actual calibration is then performed using the solvent dichloromethane. The sample is then weighed, dissolved in dichloromethane, and the flow time is then measured three times for the solution. The average value of the flow time is corrected by the Hagenbach correction method, and the relative solution viscosity is calculated.

[0100] The compound comprising the structure of formula (2I) is preferably a polycarbonate. In the context of the present invention, the term polycarbonate includes homopolycarbonates and copolycarbonates and mixtures of polycarbonates. Polycarbonates can be linear or branched in a known manner. The production of polycarbonates can be carried out in a known manner by melt transesterification or interfacial processes.

[0101] The molecular weight (Mw) of such polycarbonates is preferably 8000 to 19000 g / mol, particularly preferably 10000 to 18000 g / mol, especially preferably 12000 to 18000 g / mol. The phenolic OH group content of these polycarbonates is preferably 250 ppm to 2500 ppm, preferably 500 to 2000 ppm, especially preferably 1000 to 1800 ppm. The phenolic OH groups are preferably determined by infrared spectroscopy.

[0102] The method for determining the molar masses indicated for the polycarbonates, polysiloxanes or polysiloxane-polycarbonate block cocondensates in the present invention is the method number 2301-0257502-09D (2009 edition) of Currenta GmbH & Co. OHG, which can be obtained from Currenta at any time. Calibration is performed using a linear polycarbonate (composed of bisphenol A and phosgene) of known molar mass distribution from PSS Polymer Standards Service GmbH, Germany. The eluent is dichloromethane. Column combination of crosslinked styrene-divinylbenzene resin. Analytical column diameter: 7.5 mm; length: 300 mm. Particle size of the column material: 3 μm to 20 μm. Solution concentration: 0.2 wt.%. Flow rate: 1.0 ml / min, solution temperature: 30° C. Detection is performed using a refractive index (RI) detector, a UV detector or an IR detector, preferably a refractive index detector. Particularly preferably, detection is performed using an RI detector or a UV detector (in each case with an IR detector). RI detectors and UV detectors are particularly sensitive to polycarbonate-containing polymer chains, especially BPA-containing polycarbonate-containing polymer chains. In order to also be able to detect polysiloxane-containing polymer chains, especially polydimethylsiloxane-containing polymer chains, the IR detector is preferably adjusted to the Si-O vibration band. This is at about 1050 cm -1 Preferably, UV, RI and IR detectors are used simultaneously.

[0103] When the SiCoPC is produced by the melt transesterification method, a polycarbonate containing a specific rearranged structure is used in a preferred embodiment. The polycarbonate used in this embodiment contains at least one of the following structures (4) to (7), preferably multiple:

[0104]

[0105]

[0106] The benzene rings may be independently mono- or di-substituted by C1-C8 alkyl, halogen, preferably C1 to C4 alkyl, particularly preferably methyl, and X represents a single bond, C1 to C6 alkylene, C2 to C5 alkylidene or C5 to C6 cycloalkylidene, preferably a single bond or C1 to C4 alkylene, particularly preferably isopropylidene, wherein the total amount of structural units (4) to (7) (measured after saponification) is generally 50 to 1000 ppm, preferably 80 to 850 ppm.

[0107] To determine the amount of rearranged structures, the respective polycarbonate is completely saponified to form the corresponding decomposition products of the formulae (4a) to (7a), the amount of which is determined by HPLC. The structures (4a) to (7a) are shown, for example, for polycarbonates containing bisphenol A. (This can be achieved, for example, as follows: a polycarbonate sample is saponified under reflux with sodium methoxide. The corresponding solution is acidified and concentrated to dryness. The dry residue is dissolved in acetonitrile and the phenolic compounds of the formulae (1a) to (4a) are determined by HPLC with UV detection):

[0108]

[0109]

[0110] The amount of the compound of the formula (4a) thus released is preferably from 20 to 800 ppm, particularly preferably from 25 to 700 ppm, especially preferably from 30 to 500 ppm.

[0111] The amount of the compound of the formula (5a) thus released is preferably from 0 (ie below the detection limit of 10 ppm) to 100 ppm, particularly preferably from 0 to 80 ppm, especially preferably from 0 to 50 ppm.

[0112] The amount of the compound of the formula (6a) thus released is preferably from 0 (ie below the detection limit of 10 ppm) to 800 ppm, more preferably from 10 to 700 ppm, particularly preferably from 20 to 600 ppm and very particularly preferably from 30 to 350 ppm.

[0113] The amount of the compound of the formula (7a) thus released is preferably from 0 (ie below the detection limit of 10 ppm) to 300 ppm, preferably from 5 to 250 ppm, particularly preferably from 10 to 200 ppm.

[0114] The production of such polycarbonates containing the above-mentioned rearranged structure is described, for example, in DE 102008019503.

[0115] The process is preferably carried out in a melt transesterification process at a temperature of 280° C. to 400° C., preferably 290° C. to 380° C., more preferably 300° C. to 350° C. and a pressure of 0.001 mbar to 50 mbar, preferably 0.005 mbar to 40 mbar, particularly preferably 0.02 to 30 mbar, very particularly preferably 0.03 to 5 mbar, preferably in the presence of a catalyst.

[0116] In the process of the invention, the reactions according to (i) to (iii) are preferably carried out in the presence of at least one catalyst. Although in principle a reaction mode without the use of a catalyst is possible, optionally higher temperatures or longer residence times must be accepted. Catalysts for the interfacial process according to (i) are known to those skilled in the art.

[0117] If the process of the present invention is carried out by the melt transesterification process (see (ii) and (iii)), suitable catalysts include, for example:

[0118] Ammonium catalysts, such as tetramethylammonium hydroxide, tetramethylammonium acetate, tetramethylammonium fluoride, tetramethylammonium tetraphenylborate, dimethyldiphenylammonium hydroxide, tetraethylammonium hydroxide, hexadecyltrimethylammonium tetraphenylborate and hexadecyltrimethylammonium phenolate. Particularly suitable catalysts also include phosphonium catalysts of formula (K):

[0119]

[0120] Where R a , R b , R c and R d can be the same or different C1-C10 alkyl, C6-C14 aryl, C7-C15 aralkyl or C5-C6 cycloalkyl, preferably methyl or C6-C14 aryl, particularly preferably methyl or phenyl, and A - It can be an anion such as hydroxide, sulfate, bisulfate, bicarbonate, carbonate or halide, preferably chloride or an alkoxide or aryloxide of formula -OR, wherein R can be C6-C14 aryl, C7-C15 aralkyl or C5-C6 cycloalkyl, preferably phenyl.

[0121] Particularly preferred catalysts are tetraphenylphosphonium chloride, tetraphenylphosphonium hydroxide or tetraphenylphosphonium phenolate; very particular preference is given to tetraphenylphosphonium phenolate. Particular preference is given to using alkali metal or alkaline earth metal salts of these ammonium and / or phosphonium catalysts.

[0122] The amount of catalyst used is preferably 0.0001% to 1.0% by weight, based on the weight of the formula (2) or (2II), depending on which is used, 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.

[0123] The catalyst can be used alone or as a catalyst mixture, can be added in pure form or as a solution, for example in water or in phenol, for example as a mixed crystal with phenol. It can be introduced into the reaction, for example via a masterbatch, preferably together with the compound of formula (2II), or separately or additionally therefrom.

[0124] It is also preferred that the compound of formula (2II) and the polysiloxane of formula (1) have a pK A The reaction is carried out in the presence of an organic or inorganic salt of a weak acid with a molar mass of 3 to 7 (25° C.). Such salts may also be referred to as promoters. Suitable weak acids include carboxylic acids, preferably C2-C22 carboxylic acids, such as acetic acid, propionic 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-organophosphates, branched aliphatic carboxylic acids, such as 2,2-dimethylpropionic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid and 2-ethylhexanoic acid.

[0125] 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 or dilithium salts of bisphenol A. Salts may also 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. All of these salts may be used alone or in any mixture.

[0126] The salt is particularly preferably selected from the group consisting of alkali metal salts, alkaline earth metal salts and phosphonium salts of carboxylic acids. In a further preferred embodiment, the organic or inorganic salt is derived from a carboxylic acid.

[0127] The organic or inorganic salt is preferably used in an amount of 0.08 to 10 ppm, very particularly preferably 0.1 to 5 ppm, based on the total weight of polysiloxane and organic or inorganic salt.

[0128] In a preferred embodiment, the organic or inorganic salt is a sodium salt, preferably a sodium salt of a carboxylic acid. It is preferably used in such an amount that the sodium content in the resulting polysiloxane-polycarbonate-block cocondensate is within the range of 0.003ppm to 0.5ppm based on the gross weight of the polysiloxane-polycarbonate-block cocondensate to be formed. It is preferred that the cocatalyst is dissolved in the polysiloxane of formula (1) with a suitable solvent. The sodium content of the polysiloxane-polycarbonate-block cocondensate can be determined by, for example, atomic absorption spectroscopy.

[0129] The organic salt or inorganic salt can be used alone or in any mixture. It can be added in the form of a solid or a solution. In a preferred embodiment, the organic salt or inorganic salt is added in the form of a mixture comprising the polysiloxane of formula (1) and the organic salt or inorganic salt.

[0130] The catalysts can be used individually or in mixtures and can be added in pure form or as a solution, for example in water or phenol.

[0131] It is particularly preferred to admix the at least one catalyst to the compound of the formula (2II) and to admix the cocatalyst to the polysiloxane of the formula (1).

[0132] The amount of catalyst used is preferably 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 sum of polysiloxane and compound (2) or (2II), depending on which is used.

[0133] The method of the present invention is preferably characterized in that at least 50% by volume of all siloxane domains in the siloxane domain distribution of the polysiloxane-polycarbonate-block cocondensate, particularly preferably at least 60% by volume, also preferably at least 70% by volume, also preferably at least 75% by volume, also preferably at least 80% by volume, very particularly preferably at least 90% by volume are greater than 0 to 50nm, wherein the siloxane domain distribution is measured by atomic force microscopy. The siloxane domain distribution is the diameter of the siloxane domain. It is obvious to those skilled in the art that a siloxane domain equal to 0nm cannot exist. However, there is an evaluation procedure for calculating the siloxane domain distribution of 0 (and not more than 0nm) to 50nm. According to the present invention, it is preferred that the range of 0 to 50nm is also included in the defined range "greater than 0 to 50nm". The evaluation procedure also has a range of 50 to 100nm and 100 to 200nm. In each case, it can be seen that the ranges of 50nm and 100nm overlap. However, it is obvious to those skilled in the art (similar to "0nm") that the lower limit is preferably understood to be greater than 50nm or greater than 100nm. This means that the three ranges are preferably understood to be ">0 nm to 50 nm", ">50 nm to 100 nm" and ">100 nm to 200 nm". According to the invention it was found that a very fine siloxane domain distribution is obtained. By using special polysiloxanes, the self-condensation of the polysiloxanes is minimized, whereby the size of the siloxane domains is also kept small.

[0134] To determine the size of the polysiloxane domains, polymer samples are cut at low temperatures and examined by scanning electron microscopy, as described in more detail below. For this purpose, the parameters described in the Examples section and the methods described therein are preferably used. In the context of the present invention, the diameter of a polysiloxane domain is to be understood as the diameter of the corresponding circle of equal area of ​​the cross section of the polysiloxane domain visible in the cut.

[0135] Another aspect of the invention provides polysiloxane-polycarbonate block cocondensates containing at least one Si-OC bond, characterized in that at least 50% by volume, particularly preferably at least 60% by volume, also preferably at least 70% by volume, also preferably at least 75% by volume, also preferably at least 80% by volume, very particularly preferably at least 90% by volume of all siloxane domains of the siloxane domain distribution of the polysiloxane-polycarbonate block cocondensate are in the range of greater than 0 to 50 nm, wherein the siloxane domain distribution is measured by atomic force microscopy. Surprisingly, it has been found that very fine siloxane domain distributions can be obtained by minimizing the tendency of polysiloxanes themselves to self-condense with polysiloxanes containing at least one Si-OC bond. Thus, SiCoPCs obtainable from polysiloxanes are provided which do not require complex hydrosilylation using Pd or Pt catalysts, but at the same time exhibit a very fine siloxane domain distribution.

[0136] In one aspect, according to the process of the invention, in all configurations and preferred combinations, polysiloxane-polycarbonate block cocondensates according to the invention are obtained.

[0137] The polysiloxane-polycarbonate block cocondensate of the present invention is preferably characterized in that the polysiloxane-polycarbonate block cocondensate comprises a structure of formula (1a):

[0138]

[0139] wherein each R1 and R2 independently represent hydrogen, halogen, C1-C8 alkyl, C5-C6 cycloalkyl, phenyl or C7-C 12 Aralkyl,

[0140] R3 and R4 may be selected individually for each X and independently of each other represent hydrogen or C1-C6 alkyl, p is an integer from 4 to 7, and

[0141] X represents carbon,

[0142] each R5 and R6 independently of one another represent an aliphatic or aromatic group, preferably methyl, ethyl, trimethylphenyl, -CH2-CH2-phenyl, -CH2-CH2-CH2-phenyl, -CH2-CH(CH3)-phenyl, -CH2-CH2-CH2-(2-methoxy)phenyl or phenyl,

[0143] n is an average number of repeating units of 10 to 400, preferably 10 to 100, particularly preferably 15 to 50,

[0144] m is an average number of repeating units of 1 to 10, preferably 1 to 6, particularly preferably 1.5 to 5, and

[0145] "..." indicates the position at which the structure of the formula (1a) is incorporated into the polysiloxane-polycarbonate block cocondensate.

[0146] All preferences related to formula (1) also apply to formula (1a) in any combination. A person skilled in the art is able to establish the relationship between the polysiloxane of formula (1) and the SiCoPC containing the structure of formula (1a). This is especially because the structure of formula (1a) is derived from formula (1).

[0147] Further preferably, the polysiloxane-polycarbonate block cocondensate according to the invention comprises the structure of formula (2a)

[0148]

[0149] Each R X are independently a divalent substituted or unsubstituted aromatic group.

[0150] Preferably, formula (2a) is represented by formula (2A), wherein

[0151]

[0152] wherein each Z in formula (2A) is independently a single bond, -S(=O)2-, -C(=O)-, -O-, -S-, -S(=O)-, -CH(CN)-, a straight-chain or branched C1-C6-alkylene group which may optionally contain at least one carbonyl group, may optionally contain at least one halogen atom and / or may be optionally interrupted by at least one heteroatom, a C2-C6-alkylene group which may optionally contain at least one carbon-carbon double bond, may optionally contain at least one carbonyl group and / or may optionally contain at least one halogen atom, 10 - alkylidene group,

[0153] Each of R7 and R8 independently represents hydrogen, halogen, C1-C8 alkyl, C5-C6 cycloalkyl, C1-C4 alkoxy, phenyl or C7-C 12 Aralkyl,

[0154] o1 is the average number of repeating units, which may be preferably 2 to 31, more preferably 7 to 31, and

[0155] "..." indicates the position at which the structure of the formula (2A) is incorporated into the polysiloxane-polycarbonate block cocondensate.

[0156] The preferences for Z, R7 and R8 described for formulae (2), (2I) and (2II), respectively, also apply to formula (2A).

[0157] The polysiloxane-polycarbonate block cocondensates according to the invention are particularly preferably characterized in that the structure of formula (2a) is represented by the structure of formula (2b)

[0158]

[0159] Here m2 represents the average number of repeating units. In this case, the polycarbonate blocks of SiCoPC are derived from bisphenol A. o in formula (2b) is preferably 7 to 31, particularly preferably 10 to 29, likewise particularly preferably 15 to 28 and very particularly preferably 19 to 27.

[0160] According to the present invention, it is found that the ratio of covalent bonds between siloxane blocks and polycarbonate blocks is high. The ratio of covalent bonds between siloxane blocks and polycarbonate blocks is preferably higher than that when BPA-terminated polysiloxane of the same chemical structure is used under the same conditions.

[0161] The polysiloxane content of the SiCoPC according to the invention is preferably 2% to 15% by weight, particularly preferably 3% to 11% by weight, very particularly preferably 4% to 10% by weight, the polysiloxane content being based on the total weight of the polysiloxane-polycarbonate block copolymer.

[0162] The polysiloxane-polycarbonate-block cocondensates of the invention are also preferably characterized in that the weight-average molecular weight of the polysiloxane-polycarbonate-block cocondensates is from 24,000 to 40,000 g / mol, preferably from 25,000 to 36,000 g / mol, particularly preferably from 26,000 to 34,000 g / mol. The molecular weight is particularly preferably determined by GPC using polycarbonate standards and by RI detection. The above-described GPC method is preferably used.

[0163] The SiCoPC of the invention or the SiCoPC obtained by the process of the invention can be processed as such to provide all types of moldings. It can also be processed with other thermoplastics and / or polymer additives to provide thermoplastic molding compounds. Molding compounds and moldings are further subjects of the invention.

[0164] The polymer additives are preferably selected from flame retardants, anti-drip agents, flame retardant synergists, smoke suppressants, lubricants and release agents, nucleating agents, antistatic agents, conductive additives, stabilizers (such as hydrolysis, heat aging and UV stabilizers and transesterification inhibitors), flow promoters, phase compatibilizers, dyes and pigments, impact modifiers, and fillers and reinforcing agents.

[0165] The molding materials of the invention are thermoplastic. They can be produced, for example, by mixing SiCoPC with other ingredients in a known manner and melt compounding and melt extruding in conventional equipment (e.g. internal kneaders, extruders and twin-screw extruders) at temperatures preferably from 200° C. to 320° C. In the context of the present application, this process is generally referred to as compounding.

[0166] The term "molding compound" is therefore to be understood as a product obtained by melt compounding and melt extruding the ingredients of such a composition.

[0167] Moldings composed of the SiCoPC of the invention, SiCoPC obtained by the process of the invention or thermoplastic molding compounds containing SiCoPC can be produced, for example, by injection molding, extrusion and blow molding. Another form of processing is to produce moldings from previously produced sheets or films by deep drawing.

[0168] The polysiloxane-polycarbonate-block cocondensates obtainable by the process of the invention and the polycarbonate compositions of the invention can be used in any field in which known aromatic polycarbonates have been used to date and in which good flowability and improved demoulding properties and high toughness at low temperatures and improved chemical resistance are also required, for example for the production of large motor vehicle exterior parts and control boxes for exterior applications, panels, hollow chamber panels, electrical and electronic components and optical storage media. Thus, the block cocondensates can be used in computer housings, multimedia housings, mobile phone housings in the IT field, washing machines or dishwashers in the household field, and in the sports field, for example, helmet materials.

[0169] Another aspect of the present invention provides the use of a bisphenol of formula (3) for end-capping polysiloxanes to improve the reactivity of the end-capped polysiloxanes having Si-OC bonds when reacting with bisphenols, oligocarbonates and / or polycarbonates, wherein the polysiloxanes have at least one Si-OC bond after reacting with the bisphenol of formula (3).

[0170]

[0171] wherein R1 and R2 each independently represent hydrogen, halogen, C1-C8 alkyl, C5-C6 cycloalkyl, phenyl or C7-C 12 Aralkyl,

[0172] R3 and R4 may be selected individually for each X and independently of one another represent hydrogen or C1-C6-alkyl, p is an integer from 4 to 7, and

[0173] X represents carbon.

[0174] It is obvious to a person skilled in the art that all the above-mentioned preferences for R1-R4, X and p in formula (1) are also applicable to formula (3). It is very particularly preferred that formula (3) is formula (3a)

[0175]

[0176] Each R I Each independently represents hydrogen or methyl. Particularly preferably, each R in formula (3a) I In this case, it is bisphenol TMC.

[0177] It is also obvious to those skilled in the art that formula (3) can also be expressed by formula (300):

[0178]

[0179] wherein R1 and R2 each independently represent hydrogen, halogen, C1-C8 alkyl, C5-C6 cycloalkyl, phenyl or C7-C 12 Aralkyl,

[0180] R3 and R4 may be selected individually for each X and independently of one another represent hydrogen or C1-C6-alkyl, n is an integer from 4 to 7, and

[0181] X represents carbon.

[0182] According to the invention, it has been found that bisphenols of formula (3) increase the reactivity of the corresponding end-capped polysiloxanes relative to BPA, thereby minimizing the self-condensation of the resulting polysiloxanes. This makes it possible to obtain SiCoPCs having a fine siloxane domain distribution and an increased ratio of covalent bonds between siloxane blocks and polycarbonate blocks.

[0183] A further aspect of the invention is therefore the use of polysiloxanes of the formula (1) for increasing the proportion of covalent bonds between siloxane blocks and polycarbonate blocks in the production of polysiloxane-polycarbonate block cocondensates, wherein the polysiloxane has at least one Si-OC bond,

[0184]

[0185] wherein each R1 and R2 independently represent hydrogen, halogen, C1-C8 alkyl, C5-C6 cycloalkyl, phenyl or C7-C 12 Aralkyl,

[0186] R3 and R4 may be selected individually for each X and independently of one another represent hydrogen or C1-C6-alkyl, p is an integer from 4 to 7 and

[0187] X represents carbon,

[0188] each R5 and R6 independently of one another represent an aliphatic or aromatic group, preferably methyl, ethyl, trimethylphenyl, -CH2-CH2-phenyl, -CH2-CH2-CH2-phenyl, -CH2-CH(CH3)-phenyl, -CH2-CH2-CH2-(2-methoxy)phenyl or phenyl,

[0189] n is an average number of repeating units of 10 to 400, preferably 10 to 100, particularly preferably 15 to 50, and

[0190] m is an average number of repeating units of 1 to 10, preferably 1 to 6, particularly preferably 1.5 to 5.

[0191] Formula (1) has been described above in the further preferences, which can also be used for the use according to the invention. The SiCoPC according to the invention has also been described in more detail above. Surprisingly, it was found that the specially terminated polysiloxane blocks increase the proportion of covalent bonds between the siloxane blocks and the polycarbonate blocks. The increased proportion of covalent bonds between these blocks enables a finer siloxane domain distribution to be achieved. Description of the drawings:

[0192] Figure 1 : GPC curves of Example 3 using triple detection. The black curve represents the curve using UV detection. The light grey curve represents the curve using IR detection. The medium grey curve is the curve using refractive index (RI) detection.

[0193] Figure 2 : GPC curves of Example 4 using triple detection. The black curve represents the curve using UV detection. The light grey curve represents the curve using IR detection. The medium grey curve is the curve using refractive index (RI) detection. Example:

[0194] The present invention is described in more detail below in conjunction with the examples, wherein unless otherwise specified, all corresponding parameters in the present invention are determined by the measurement methods described herein.

[0195] MVR

[0196] Unless otherwise stated, melt volume flow rate (MVR) is determined according to ISO 1133 (2011) (at 300°C; 1.2 kg), unless other conditions are stated otherwise.

[0197] Solution viscosity

[0198] Determination of solution viscosity: The relative solution viscosity (η rel; also referred to as eta rel) was measured in dichloromethane at a concentration of 5 g / l at 25°C using an Ubbelohde viscometer.

[0199] Material:

[0200] Bisphenol A:

[0201] Dichlorosiloxane: poly(dimethylsiloxane), chlorine-terminated, viscosity 20-50 cSt.; molecular weight about 2000–4000 g / mol; CAS 67923-13-7; abcrGmbH; 76187Karlsruhe, Germany

[0202] Pyridine: anhydrous, 99%, CAS 110-86-1; Sigma-Aldrich, München, Germany

[0203] TMC bisphenol: 4,4'-(3,3,5-trimethylcyclohexylene) bisphenol, produced by Covestro Deutschland AG

[0204] PC-1: Linear bisphenol A polycarbonate with phenol-based end groups and a solution viscosity of 1.17. The polycarbonate does not contain any additives such as UV stabilizers, mold release agents or heat stabilizers. The polycarbonate was produced by the melt transesterification process described in DE102008019503. The polycarbonate has a phenol end group content of 0.16%.

[0205] Evaluation of siloxane domain size using atomic force microscopy (AFM)

[0206] The siloxane domain size and distribution were determined using atomic force microscopy. For this purpose, the corresponding samples (melt cake form) were cut using an ultrathin slicer 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 the "soft intermittent contact mode" or the "tapping mode". A spring constant of about 2.8 Nm was used. -1 The sample was scanned with a "tapping mode cantilever" (Nanoworld point probe) with a resonant frequency of about 75kHz. The tapping force was controlled by the ratio of the target amplitude and the free oscillation amplitude (the amplitude of the probe tip oscillating freely in the air). The sampling rate was set to 1Hz. In order to record the surface morphology, phase contrast and topographic images were recorded on a 2.5μm x 2.5μm area. Particles or siloxane domains were automatically evaluated by light and dark contrast (from phase contrast images) using OlympusSIS image processing software (Olympus Soft Imaging Solutions GmbH, 48149, Münster, Germany). The diameter of the particle is determined by the diameter of the corresponding equal area circle of the longest dimension of the particle.

[0207] As described above, multiple phase contrast images (particle count greater than 200) were evaluated. Image processing software was used to classify the individual diameters and capture the distribution of diameters. Each D value or corresponding volume fraction was thereby assigned. The D value represents the proportion of particles less than the indicated value. When the D90 value is x, 90% of the particles are less than x. The proportions of particles with diameters of 0-50nm, 50-100nm, and 100-200nm were also determined from the distribution.

[0208] GPC :

[0209] The molecular weight is determined by gel permeation chromatography with dichloromethane as eluent. The standard used is BPA polycarbonate. The signal from the refractive index detector is used. The corresponding method is defined under the number 2301-0257502-09D of Currenta GmbH & Co. OHG, which is available from Currenta on request at any time. In addition, for the interpretation of the GPC results, the polymer samples are detected using multiple detectors in order to be able to evaluate the distribution of UV-active components (bisphenols) and non-UV-active components. The UV detector is set to 254 nm and is therefore sensitive to BPA polycarbonate; other detectors used are the RI (refractive index) detector and the IR detector. The IR detector is set to 1050 cm -1 , and is therefore sensitive to Si-O-Si stretching vibrations. Therefore, it is possible to simultaneously identify the polymer component containing polycarbonate and the polymer component containing siloxane. This detection is also referred to as "triple detection" hereinafter.

[0210] Example 1 (Comparative Example) Production of BPA-terminated siloxane blocks

[0211] A 250 ml glass flask equipped with a stirrer and a dropping funnel was heated, evacuated and filled with dry argon. Under an argon atmosphere, 12.18 g (0.053 mol) of bisphenol A and 8.38 g (0.106 mol) of pyridine were pre-loaded in 100 ml of anhydrous dichloromethane and stirred to dissolve. 20 g (viscosity 20-50 cSt) of dichlorosiloxane was pre-loaded in the dropping funnel and added dropwise to the bisphenol A solution under vigorous stirring at room temperature within 50 minutes. Once all the siloxane derivatives were added, stir for another hour.

[0212] The solution was neutralized by dropwise addition of 1 M hydrochloric acid and adjusted to slightly acidic (pH <4); the solution was then transferred to a separatory funnel and washed at least three times with deionized water. If the solution was still clearly acidic, washing was continued until the pH value indicated a near neutral solution. The solvent was removed on a rotary evaporator, leaving a suspension. The crude product was dissolved in n-hexane, leaving excess BPA solids, then dried over molecular sieves (4A) and filtered. The solution was concentrated to the maximum extent at <1 mbar and 50° C. for at least 0.5 h and filtered through a 5 μm Teflon filter. This gave a colorless oil.

[0213] NMR: 1 H NMR (Bruker AVIII HD 600 MHz NMR spectrometer; CDCl3): 7.06-7.10 ppm (m, 4H), 6.78-6.81 (m, 2.18H), 6.70-6.73 (m, 1.81H), 1.60 ppm (s, 6.32H), 0-0.2 ppm (m, 108.39H).

[0214] This corresponds to an aryl-terminated siloxane of formula (10)

[0215]

[0216] Wherein n is about n=30, and m is about m=1.2.

[0217] Example 2 (Example of the Invention) Production of TMC BP-Terminated Siloxane Blocks

[0218] A 250 ml glass flask equipped with a stirrer and a dropping funnel was heated, evacuated and filled with dry argon. Under an argon atmosphere, 16.56 g (0.053 mol) of TMC bisphenol and 8.38 g (0.106 mol) of pyridine were pre-loaded in 100 ml of anhydrous dichloromethane and stirred to dissolve. 20 g (viscosity 20–50 cSt) of dichlorosiloxane was pre-loaded in a dropping funnel and added dropwise to the bisphenol TMC solution at room temperature under vigorous stirring within 50 minutes. Once all the siloxane derivatives were added, the mixture was stirred for another hour.

[0219] The solution was neutralized by dropwise addition of 1M hydrochloric acid and adjusted to slightly acidic (pH <4); the solution was then transferred to a separatory funnel and washed at least three times with deionized water. If the solution was still clearly acidic, it was washed until the pH value showed a near neutral solution. The solvent was removed on a rotary evaporator, leaving a suspension. The crude product was dissolved in n-hexane, leaving excess BP-TMC solid, then dried over molecular sieves (4A) and filtered. The solution was concentrated to the maximum extent for at least 0.5 hours at <1 mbar and 50°C and filtered through a 5 μm Teflon filter. This gave a colorless oil.

[0220] NMR: 1 HNMR(BrukerAVIII HD 600MHz NMR spectrometer; CDCl3): 7.19 (m, 2.0H), 7.0 (m, 2.09H), 6.80 (m, 1.1H), 6.73 (m, 2.1H), 6.65 (m, 0.9H), 2.61 (m, 1.0H), 2.37 (m, 1.0H), 2.0- 1.88(m, 2.0H), 1.36(m, 1.0H), 1.14(m, 1.0H), 0.97(m, 6.0H), 0.86(m, 1.0H), 0.36ppm(m, 3.0H), 0.25-0.20(m, 7.2H), 0.1-0.0(m, 98.7H).

[0221] This provides polysiloxanes of formula (1A) in which all R I = methyl, n is about 30 and m is about 1.2.

[0222] Example 3 (Comparative Example: Production of Si-block-containing cocondensate using BPA-terminated siloxane according to Example 1)

[0223] 47.5 grams of PC-1 are pre-loaded in a 250 ml glass flask equipped with a stirrer, a dropping funnel and a short-range separator. 2.5 grams of polydimethylsiloxane (5 wt %) containing about 2ppm of sodium (in the form of 0.036 mg of sodium 2-ethylhexanoate) from Example 1 are pre-loaded in a dropping funnel. The equipment is evacuated and purged with nitrogen (3 times in each case). PC-1 is melted for 5 minutes under atmospheric pressure (nitrogen) using a metal bath preheated to 350°C. Vacuum is then applied. Siloxane-catalyst mixture is quickly added dropwise at 100 mbar. The pressure is then reduced to the minimum value technically possible, which should be <1 mbar, and stirred at this pressure for 15 minutes. Subsequently, nitrogen is purged and the polymer melt is taken out. This obtains a very turbid to opaque polymer. The solution viscosity is 1.470.

[0224] Example 4 (Example of the present invention; production of Si-block-containing cocondensate using TMC-terminated siloxane according to Example 2)

[0225] 47.5 grams of PC-1 are pre-loaded in a 250 ml glass flask equipped with a stirrer, a dropping funnel and a short-range separator. 2.5 grams of polydimethylsiloxane (5 wt %) containing about 2ppm sodium (in the form of 0.036 mg of sodium 2-ethylhexanoate) from Example 2 are pre-loaded in a dropping funnel. The equipment is evacuated and purged with nitrogen (3 times in each case). PC-1 is melted for 5 minutes under atmospheric pressure (nitrogen) using a metal bath preheated to 350°C. Vacuum is then applied. Siloxane-catalyst mixture is quickly added dropwise at 100 mbar. The pressure is then reduced to the minimum value technically possible, which should be <1 mbar, reduced to about 1 mbar, and stirred at this pressure for 15 minutes. The mixture is subsequently purged with nitrogen and the polymer melt is taken out. This obtains a slightly turbid polymer. The solution viscosity is 1.436.

[0226] AFM analysis with evaluation of volume fraction of siloxane domains

[0227] Table 1:

[0228]

[0229] Obviously, the distribution in the embodiment of the present invention is finer.

[0230] Elution profile (GPC analysis; acetone extract)

[0231] To determine the binding behavior, the respective polymer was dissolved in dichloromethane and precipitated in acetone with stirring (ratio 1 part dichloromethane solution to 10 parts acetone). The precipitated polymer was filtered off and the mother liquor was concentrated to dryness.

[0232] GPC with triple detection was recorded from the acetone extract (soluble fraction, mother liquor); in addition to the UV signal (black curve), the IR detector detected a signal around 1050 cm -1 Siloxane signal of the Si-O band at (light grey curve).

[0233] The results of Example 3 are as follows Figure 1 The results of Example 4 are shown in Figure 2 As shown. Figure 1 and 2 It can be seen that essentially two curves are detected in the elution diagram. Here, the black or medium grey curve corresponds to the polycarbonate fraction soluble in acetone. This is especially the polycarbonate oligomers with a molecular weight of 0 to 10000 g / mol. This fraction consists almost exclusively of polycarbonate.

[0234] The light grey curve describes the part containing especially polydimethylsiloxane. Figure 1 ), the proportion of polycarbonate in the chain is very low (see black curve); in contrast, in the block cocondensate according to Example 4 ( Figure 2 ), the proportion of polycarbonate in the chain mainly based on polydimethylsiloxane is significantly greater. It is believed that this improves the compatibility between polydimethylsiloxane and polycarbonate.

Claims

1. by at least one polysiloxane of formula (1) (i) reacting with at least one compound of the formula (2) and / or (2I) in the presence of at least one base and phosgene in a phase interface process, (ii) reacting with at least one compound of formula (2) and at least one diaryl carbonate in a melt transesterification process, or (iii) a process for producing polysiloxane-polycarbonate block cocondensates by reaction with at least one compound of the formula (2II) and optionally at least one diaryl carbonate in a melt transesterification process, wherein each R1 and R2 independently represent hydrogen, halogen, C1-C8 alkyl, C5-C6 cycloalkyl, phenyl or C7-C 12 Aralkyl, R3 and R4 can be selected individually for each X and independently of one another represent hydrogen or C1-C6-alkyl, p is an integer from 4 to 7 and X represents carbon, each R5 and R6 independently of one another represent an aliphatic or aromatic group, preferably methyl, ethyl, trimethylphenyl, -CH2-CH2-phenyl, -CH2-CH2-CH2-phenyl, -CH2-CH(CH3)-phenyl, -CH2-CH2-CH2-(2-methoxy)phenyl or phenyl, n is an average number of repeating units of 10 to 400, preferably 10 to 100, particularly preferably 15 to 50, and m is the average number of repeating units of 1 to 10, preferably 1 to 6, particularly preferably 1.5 to 5, in wherein each Z in formula (2), (2I) or (2II) is independently a single bond, -S(=O)2-, -C(=O)-, -O-, -S-, -S(=O)-, -CH(CN)-, a straight-chain or branched C1-C6-alkylene group which may optionally contain at least one carbonyl group, may optionally contain at least one halogen atom and / or may be optionally interrupted by at least one heteroatom, a C2-C6-alkylene group which may optionally contain at least one carbon-carbon double bond, may optionally contain at least one carbonyl group and / or may optionally contain at least one halogen atom, 10 - alkylidene group, Each of R7 and R8 in formula (2), (2I) or (2II) independently represents hydrogen, halogen, C1-C8 alkyl, C5-C6 cycloalkyl, C1-C4 alkoxy, phenyl or C7-C 12 Aralkyl, o in formula (2I) or (2II) represents the average number of repeating units, which may be 2 to 40, preferably 7 to 31. Y in formula (2II) represents hydrogen or -(C=O)-O-Ph, wherein Ph represents an optionally substituted phenyl group, and Y1 in formula (2II) represents an optionally substituted phenyl group or a compound of formula (2IIa) wherein wherein each Z, R7 and R8 are as defined above for formula (2II) and "*" indicates the structure of formula (2IIa) as the position at which Y1 is attached to formula (2II).

2. The method according to claim 1, characterized in that Each Z in formula (2), (2I) or (2II) is independently a single bond or an isopropylidene group, and Each of R7 and R8 in formula (2), (2I) or (2II) each independently represents hydrogen or methoxy, preferably hydrogen.

3. The method according to claim 1 or 2, characterized in that: The polysiloxanes (iii) of the formula (1) are reacted with at least one compound of the formula (2II) in a melt transesterification process.

4. The method according to any one of claims 1 to 3, characterized in that The compound of formula (2II) has a relative solution viscosity ηrel of 1.08 to 1.

22.

5. The method according to any one of claims 1 to 4, characterized in that The reactions according to (i) to (iii) are carried out in the presence of at least one catalyst.

6. The method according to any one of claims 1 to 5, characterized in that At least 50% by volume of all siloxane domains in the siloxane domain distribution of the polysiloxane-polycarbonate block cocondensate are between greater than 0 and 50 nm, wherein the siloxane domain distribution is measured by atomic force microscopy.

7. Polysiloxane-polycarbonate block cocondensates containing at least one Si-OC bond, characterized in that At least 50% by volume of all siloxane domains in the siloxane domain distribution of the polysiloxane-polycarbonate block cocondensate are between greater than 0 and 50 nm, wherein the siloxane domain distribution is measured by atomic force microscopy.

8. The polysiloxane-polycarbonate block cocondensate according to claim 7, characterized in that The polysiloxane-polycarbonate block cocondensate comprises the structure of formula (1a): wherein each R1 and R2 independently represent hydrogen, halogen, C1-C8 alkyl, C5-C6 cycloalkyl, phenyl or C7-C 12 Aralkyl, R3 and R4 may be selected individually for each X and independently of each other represent hydrogen or C1-C6 alkyl, p is an integer from 4 to 7, and X represents carbon, each R5 and R6 independently of one another represent an aliphatic or aromatic group, preferably methyl, ethyl, trimethylphenyl, -CH2-CH2-phenyl, -CH2-CH2-CH2-phenyl, -CH2-CH(CH3)-phenyl, -CH2-CH2-CH2-(2-methoxy)phenyl or phenyl, n is an average number of repeating units of 10 to 400, preferably 10 to 100, particularly preferably 15 to 50, m is an average number of repeating units of 1 to 10, preferably 1 to 6, particularly preferably 1.5 to 5, and "..." indicates the position at which the structure of the formula (1a) is incorporated into the polysiloxane-polycarbonate block cocondensate.

9. The polysiloxane-polycarbonate block cocondensate according to any one of claims 7 or 8, characterized in that The polysiloxane-polycarbonate block cocondensate comprises the structure of formula (2a): Each R X are independently a divalent substituted or unsubstituted aromatic group.

10. The polysiloxane-polycarbonate block cocondensate according to claim 9, characterized in that The structure of formula (2a) is represented by the structure of formula (2b) Where m2 represents the average number of repeating units.

11. The polysiloxane-polycarbonate block cocondensate according to any one of claims 7 to 10, characterized in that The weight-average molecular weight of the polysiloxane-polycarbonate block cocondensate is 24,000 to 40,000 g / mol. 12 . Moulding material comprising the polysiloxane-polycarbonate block cocondensate according to claim 7 .

13. Mouldings containing the polysiloxane-polycarbonate block cocondensate according to any one of claims 7 to 11.

14. Use of a bisphenol of formula (3) for end-capping polysiloxanes to increase the reactivity of the end-capped polysiloxanes having Si-O-C bonds when reacting with bisphenols, oligocarbonates and / or polycarbonates, wherein the polysiloxanes have at least one Si-O-C bond after reaction with the bisphenol of formula (3), wherein R1 and R2 each independently represent hydrogen, halogen, C1-C8 alkyl, C5-C6 cycloalkyl, phenyl or C7-C 12 Aralkyl, R3 and R4 may be selected individually for each X and independently of one another represent hydrogen or C1-C6-alkyl, p is an integer from 4 to 7, and X represents carbon.

15. Use of a polysiloxane of the formula (1) for increasing the proportion of covalent bonds between siloxane blocks and polycarbonate blocks in the production of polysiloxane-polycarbonate block cocondensates, wherein the polysiloxane has at least one Si-OC bond, wherein each R1 and R2 independently represent hydrogen, halogen, C1-C8 alkyl, C5-C6 cycloalkyl, phenyl or C7-C 12 Aralkyl, R3 and R4 may be selected individually for each X and independently of one another represent hydrogen or C1-C6-alkyl, p is an integer from 4 to 7 and X represents carbon, each R5 and R6 independently of one another represent an aliphatic or aromatic group, preferably methyl, ethyl, trimethylphenyl, -CH2-CH2-phenyl, -CH2-CH2-CH2-phenyl, -CH2-CH(CH3)-phenyl, -CH2-CH2-CH2-(2-methoxy)phenyl or phenyl, n is an average number of repeating units of 10 to 400, preferably 10 to 100, particularly preferably 15 to 50, and m is an average number of repeating units of 1 to 10, preferably 1 to 6, particularly preferably 1.5 to 5.

Images