Polycarbonate co-condensates having phenolic structural units

Abstract

The present invention relates to a polycarbonate co-condensate comprising a specific phenolic structural unit and another phenolic structural unit different from the first phenolic structural unit, a molding compound comprising the polycarbonate co-condensate, a molded article comprising the polycarbonate co-condensate, and a molded article comprising the polycarbonate co-condensate. The invention relates to a method for producing a polycarbonate co-condensate comprising a specific phenolic structural unit and another phenolic structural unit different from the first phenolic structural unit, and to the use of a specific homopolycarbonate for producing a polycarbonate co-condensate comprising a specific phenolic structural unit.

Description

[0001] The present invention relates to a polycarbonate co-condensate comprising a specific phenolic structural unit and another phenolic structural unit different from the first phenolic structural unit, a molding compound comprising the polycarbonate co-condensate, a molded article comprising the polycarbonate condensate, a method for preparing a polycarbonate co-condensate comprising a specific phenolic structural unit and another phenolic structural unit different from the first phenolic structural unit, and use of a specific homopolycarbonate for preparing a polycarbonate co-condensate comprising a specific phenolic structural unit.

[0002] Polycarbonates, in particular aromatic polycarbonates, are known to exhibit a good profile of properties in terms of mechanical and optical properties, heat resistance and weathering resistance. Due to this profile of properties, they are used in a variety of indoor and outdoor applications. Typically, polycarbonates are prepared by an interphase phosgenation process or a melt transesterification process.

[0003] Lignocellulosic biomass has been recognized as having potential use in the production of chemicals and biomaterials. It contains cellulose, hemicellulose and lignin. Lignin is a highly cross-linked macromolecule consisting of different types of substituted phenols. The corresponding processing of lignin can provide various bisphenols, so lignin is expected to become a potential substitute for compounds used in petrochemicals, but based on natural and renewable sources at an affordable cost.

[0004] Some studies have been conducted focusing on the provision of bisphenols from lignin. For example, WO2019 / 002503A1 describes a method for producing o-alkoxybisphenols, which can be used as starting products for the preparation of biopolymers. The document mentions the reaction of these bisphenol compounds with phosgene or diaryl carbonates to form polycarbonates. However, no such reaction was performed in the experimental section.

[0005] WO2018 / 134427 A1 relates to the production of high-purity meta, meta-coupled bis(4-alkylphenol) derivatives from lignin-derived sources. The resulting bisphenols are said to be useful monomers for the production of polycarbonates, in particular using phosgene or diphenyl carbonate. However, polycarbonates are not prepared in this document either.

[0006] Polycarbonates were synthesized via a standard laboratory scale procedure using m,m'-bis(4-alkylguaiacol) and triphosgene in Green Chem., 2017, 19, 2561-2570. The resulting molecular weights given in the paper suggest that the reaction was not complete.

[0007] CN 105461912 A also describes the reaction of certain bisphenols with triphosgene.

[0008] WO 2015 / 183892 A1 describes the synthesis of novel reactive functionalized phenolic building blocks. The synthesis of bisguaiacol polycarbonate is described in Example 46. Bisguaiacol F is reacted with nitrochloroformate in acetonitrile.

[0009] WO2015 / 168225A2 describes the reaction of alkoxy bisphenols to polycarbonates by interphase phosgenation. In Example 5 of this document, a polycarbonate based on 4,4'-(2,2'-isopropylidene-bis(o-methoxy)phenol (PBMP) is prepared using interphase phosgenation and p-cumylphenol as a capping agent. This document mentions that alkoxy bisphenols exhibit a half-maximal inhibitory concentration (IC ) of less than 0.00025 M for α or β in vitro estradiol receptors. 50 ) of the additional monomers.

[0010] As can be seen from the prior art described above, the skilled person knows how to prepare specific bisphenols from lignin. In the examples of these documents, clear indications of the fact of how these bisphenols are prepared can be found. For the provision of bisphenols from lignin, these examples are incorporated herein by reference. Green Chem., 2018, 20, 1050-1058, in particular, shows how to prepare 5,5'-methylenebis(4-n-propylguaiacol).

[0011] Polycarbonate cocondensates are complex systems: by using different comonomers the resulting properties of the cocondensates can be fine-tuned, especially with regard to mechanical properties, glass transition temperature, optical properties, flame retardancy, etc. However, copolymerization is not always easy, for example due to the compatibility and / or reactivity of different comonomers.

[0012] Based on this prior art, it is necessary to provide and prepare polycarbonate co-condensates based at least in part on natural and renewable resources. In addition, it is necessary to provide polycarbonate co-condensates that can be prepared on an industrial scale. Due to the fact that it is a co-condensate of at least two different structural units, this polycarbonate co-condensate should have adjustable properties. In addition, this polycarbonate should show properties comparable to standard bisphenol A based polycarbonate co-condensates on the market (e.g., about processing properties, mechanical properties and optical properties, especially xanthochromia). Finally, it is necessary to have a method for preparing such polycarbonate condensates that is efficient, economical and ecologically favorable.

[0013] The present invention has solved at least one of the above-mentioned objects, preferably all of them. It has been found that the copolymerization of bisphenols from lignin with, for example, the monomer bisphenol A does not provide the freedom to fine-tune all the properties of the resulting cocondensates, because the higher the content of bisphenols from lignin (hereinafter also referred to as BPL) in such polycarbonate cocondensates, the lower the molecular weight. However, the molecular weight of the polycarbonate cocondensates is an important criterion for certain applications, the resulting mechanical properties, etc. At the same time, a large amount of BPL in the polycondensate is beneficial because this comonomer is based on natural and renewable resources. A large amount of renewable raw materials is very desirable. Renewable raw materials are also known to have a lower carbon footprint than fossil based raw materials.

[0014] Surprisingly, the inventors have found that when homopolycarbonates are used instead of monomers with bisphenols from lignin, high molecular weights of the resulting cocondensates can only be obtained when at least 20 mol % of lignin bisphenols are used. Such molecular weights are reasonable in the sense that the molecular weights of the cocondensates of the present invention are high enough to ensure good mechanical properties, preferably mechanical properties comparable to polycarbonates based on bisphenol A with comparable molecular weights. In addition, preferably, the cocondensates of the present invention exhibit properties comparable to standard bisphenol A-based polycarbonate cocondensates on the market (e.g., regarding processing properties, mechanical properties and / or optical properties). In addition, polycarbonate cocondensates having such reasonable molecular weights and simultaneously containing a large amount of bisphenols from lignin can be obtained. This means that the polycarbonate cocondensates of the present invention can be based at least in part, preferably in high amounts, on natural and renewable bisphenols. Finally, polycarbonate cocondensates with high glass transition temperatures can be obtained. This glass transition temperature ensures that the polycarbonate cocondensates of the present invention can be used for all applications that also use BPA-based polycarbonates. Preferably, the glass transition temperature may be determined by differential scanning calorimetry ISO 11357-2:2013-05 at a heating rate of 10° C. / min.

[0015] Therefore, the present invention provides a polycarbonate cocondensate comprising at least one structural unit (A) and at least one structural unit (B)

[0016]

[0017] in

[0018] Each X in the structural unit (A) independently represents a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or an organic group having 1 to 18 carbon atoms, wherein the organic group having 1 to 18 carbon atoms may be linear, branched or cyclic, aromatic or non-aromatic, and may further contain heteroatoms such as halogen, oxygen, nitrogen, sulfur, silicon or phosphorus,

[0019] R 1 and R 3 Each independently represents a monovalent hydrocarbon group, preferably C1-C 26 -alkyl, C7-C 26 Alkyl aryl or C7-C 26 -aralkyl,

[0020] R 2 and R 4 each independently represents a hydrogen atom, an alkoxy group or a monovalent hydrocarbon group, preferably a hydrogen atom, a C1-C6-alkoxy group or a C1-C6-alkyl group, and

[0021] p and q are each independently 1 or 2, preferably 1, and

[0022] n represents the average number of repeating units, wherein n is 1 to 10, preferably 1 to 6, more preferably 1 to 4,

[0023] wherein each Z in the structural unit (B) independently represents a single bond, -S(=O)2-, -C(=O)-, -O-, -S-, -S(=O)-, -CH(CN)-, a straight-chain or branched C1-C6-alkylene group optionally containing at least one carbonyl group, optionally containing at least one halogen atom and / or optionally interrupted by at least one heteroatom, a C2-C6-alkylene group optionally containing at least one carbon-carbon double bond, optionally containing at least one carbonyl group and / or optionally containing at least one halogen atom 10 -alkylidene, C5-C6-alkylene ... 12 -cycloalkylene, C5-C6-cycloalkylene, wherein the alicyclic group is optionally fused to at least one alicyclic and / or at least one aromatic ring 15 -cycloalkylidene, C7-C 20 -Arylalkylidene, C8-C 20 -aralkylene, a C6-C6-alkylene ring optionally fused to a further aromatic ring which may optionally contain at least one heteroatom 12 -arylene group, formula (B1-A), formula (B1-B), formula (B1-C) or formula (B1-D)

[0024]

[0025] wherein in formulae (B1-A), (B1-B) and (B1-C), each R' independently represents a linear C1-C4-alkyl group, a branched C3-C4-alkyl group, an aralkyl group or an aryl group, and "C*" represents a quaternary carbon atom at the position indicated as "Z" in formula (B), and

[0026] wherein in formula (B1-D), each R' independently represents a straight-chain C1-C4-alkyl group, a branched C3-C4-alkyl group, each R" independently represents a straight-chain C1-C4-alkylene group, a branched C3-C4-alkylene group, each R"' independently represents H or a straight-chain C1-C3-alkyl group, s is 0 to 2, and each s1 is independently 0 or 1, and "*" represents a bond connecting "Z" to the aromatic ring in formula (B),

[0027] R 5 and R 6 Each independently represents H, C1-C 18 -alkyl, C5-C6-cycloalkyl, C1-C5-alkenyl-, C1-C 18 -alkoxy, phenoxy, halogen atom, C6-C 18 -Aryl or C7-C 18 -aralkyl,

[0028] p1 and q1 are each 1 to 4, and

[0029] m2 represents the average number of repeating units, and m2 is 7 to 31,

[0030] The molar ratio of structural unit (A) to structural unit (B) is 20:80 to 95:5,

[0031] And the polycarbonate cocondensate has a weight average molecular weight of 15000 to 50000 g / mol, preferably 17000 to 40000 g / mol, more preferably 20000 to 35000 g / mol as determined by GPC in dichloromethane calibrated with BPA-based polycarbonate.

[0032] The skilled person will appreciate that there may be overlap between the structures of formulae (A) and (B). However, according to the present invention, the term "polycarbonate co-condensate" is preferably understood to mean that the structure of formula (A) must be different from the structure of formula (B). Only in this way can a polycarbonate co-condensate containing two different structural units be obtained. Therefore, the structure of formula (A) is preferably different from the structure of chemical unit (B).

[0033] Preferably, the polycarbonate cocondensates of the present invention are polycarbonate block cocondensates. Preferably, this means that at least the structural unit represented by formula (B) is a block in the sense that m2 is 7 to 31, preferably 10 to 29, more preferably 15 to 28, most preferably 19 to 27. These numbers should be understood as the average number of repeating units of a block of formula (B). The polycarbonate cocondensates may contain polymer chains having one or more blocks of formula (B).

[0034] In the same way, the polycarbonate cocondensates of the present invention comprise structural units (A), wherein n represents the average number of repeating units, wherein n is 1 to 10, preferably 1 to 6, more preferably 1 to 4. This number should be understood as one structural unit (A) comprising such an average number of repeating units. The polycarbonate cocondensates can and probably have more than one structural unit (A). Each structural unit (A) in a polycarbonate cocondensate chain has its own average number of repeating units n, wherein n is 1 to 10, preferably 1 to 6, more preferably 1 to 4.

[0035] The polycarbonate cocondensates of the present invention may be linear or branched, depending on the type of monomers used in the process of the present invention.

[0036] Preferably, the polycarbonate cocondensates of the present invention are obtained by melt transesterification. More preferably, the polycarbonates of the present invention are obtained by using the process of the present invention (as described below).

[0037] Preferably, the polycarbonate cocondensates according to the invention are at least partially bio-based. For the purposes of the present invention, the expression "bio-based" is understood to mean that the relevant compounds can be provided and / or obtained via renewable and / or sustainable raw materials on the application date. Renewable and / or sustainable raw materials are preferably understood to mean raw materials that are regenerated by natural processes at a rate comparable to their consumption rate (see CEN / TS16295:2012). This expression is particularly used to distinguish it from raw materials produced from fossil raw materials (also referred to as fossil-based according to the present invention). As an example, most bisphenol A-based polycarbonates represent commonly known fossil-based polycarbonates. Whether a raw material is bio-based or fossil-based can be determined by measuring the carbon isotopes in the raw materials, because the carbon isotopes C in fossil raw materials are 14 The relative amount of is low. This can be done, for example, according to ASTM D6866-18 (2018) or ISO 16620-1 to -5 (2015) or DIN SPEC 91236 2011-07. An exemplary bio-based material is bisphenol obtained from lignin.

[0038] "Alkyl" in the context of the present invention, for example and if not mentioned otherwise, refers to an alkane structure from which one hydrogen atom has been removed. An "alkyl" according to the present invention, which may be linear or branched, is saturated and therefore contains only single bonds between adjacent carbon atoms. Preferably, the alkyl group according to the present invention comprises 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. In the case where the carbon atoms of the alkyl group are defined in various ways in the present invention, these structures may be limited in selection.

[0039] "Alkylene" in the context of the present invention, for example and if not mentioned otherwise, refers to a bridged alkane structure in which two hydrogen atoms are removed from different carbon atoms. In this article, the two carbon atoms from which the two hydrogen atoms are removed can be any carbon atoms present in the alkane structure. This means that the two carbon atoms can but do not necessarily have to be adjacent to each other. The alkylene structure can be straight or branched and is saturated. In the case where the alkylene comprises only one carbon atom, the alkylene is a methylene group (-CH2-) connected to the rest of the molecule by two single bonds. Preferably, the alkylene according to the present invention 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 ... -methylpentylene, 1,1-dimethylbutylene, 1,2-dimethylbutylene, 1,3-dimethylbutylene, 2,2-dimethylbutylene, 2,3-dimethylbutylene, 3,3-dimethylbutylene, 1-ethylbutylene, 2-ethylbutylene, 1,1,2-trimethylpropylene, 1,2,2-trimethylpropylene, 1-ethyl-1-methylpropylene, 1-ethyl-2-methylpropylene, 1-ethyl-2-methylpropylene, etc. In the case where the present invention defines the carbon atoms of the alkylene in different ways, these structures may be limited in selection. In addition, the alkylene according to the present invention optionally contains at least one carbonyl group, optionally contains at least one halogen atom and / or is optionally interrupted by at least one heteroatom. Examples of such alkylene groups are -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.

[0040] "Alkylidene" in the context of the present invention, for example and if not mentioned otherwise, refers to a bridged alkane structure in which two hydrogen atoms are removed from the same carbon atom. Alkylidene optionally comprises at least one carbon-carbon double bond, optionally comprises at least one carbonyl group and / or optionally comprises at least one halogen atom. Preferably, the alkylidene according to the present invention and / or in formula (B) comprises CH2=C*, C(CH3)2=C*, isopropylidene, n-propylidene, isoheptylidene, C*(CH3)(C(=O)CH3), C(Cl2)=C*, C(Br2)=C*, etc., wherein "C*" represents the carbon atom at the position indicated as "Z" in formula (B).

[0041] "Cycloalkylene" in the context of the present invention, for example and if not mentioned otherwise, refers to a bridged cycloalkane structure in which two hydrogen atoms are removed from different carbon atoms in the ring. In this context, the two carbon atoms from which the two hydrogen atoms are removed can be any carbon atoms present in the cycloalkane structure. This means that the two carbon atoms can, but do not necessarily have to, be adjacent to each other. According to the present invention, the alicyclic radical of the cycloalkylene is fused to at least one further alicyclic ring. An example of such a cycloalkylene is adamantylene (tricyclo[3.3.1.13,7]decanediyl).

[0042] "Cycloalkylidene" in the context of the present invention, for example and if not mentioned otherwise, refers to a bridged cycloalkane structure in which two hydrogen atoms are removed from the same carbon atom in the ring. The alicyclic radical of the cycloalkylidene is optionally fused with at least alicyclic and / or at least one aromatic ring. Examples of such cycloalkylidene are cyclopentylidene, cyclohexylidene, 3,3,5-trimethylcyclohexylidene, cyclodecylidene, cyclododecylidene, tetrahydrodicyclopentylidene, 9-fluorenylidene, etc.

[0043] "Aralkylidene" in the context of the present invention, for example and if not mentioned otherwise, refers independently in each case to a bridged straight-chain, cyclic, branched or unbranched alkyl structure that has two hydrogen atoms removed from the same carbon atom and is monosubstituted, multiply or polysubstituted by an aryl group. At the same time, "aralkylene" refers independently in each case to a bridged straight-chain, cyclic, branched or unbranched alkyl structure that has two hydrogen atoms removed from different carbon atoms and is monosubstituted, multiply or polysubstituted by an aryl group. "Aryl" in the present invention, for example and if not mentioned otherwise, is a carbocyclic aromatic group. Examples of "aryl" are phenyl, o-, p-, m-tolyl, naphthyl, phenanthrenyl or anthracenyl. In particular, in formula (B), examples of such aralkylidene groups are phenyl-CH*, phenyl-C*(CH3), naphthyl-CH*, phenyl-C*-phenyl, etc., wherein "C*" represents the carbon atom at the position indicated as "Z" in formula (B). Examples of such aralkylene groups are m-diisopropylidenephenylene, p-diisopropylidenephenylene.

[0044] "Arylalkyl" in the context of the present invention, for example and if not mentioned otherwise, may be an aryl group as defined above having an alkyl, alkynyl or alkenyl group attached to an aromatic group.

[0045] "Alkoxy" in the context of the present invention, for example and if not mentioned otherwise, refers to a straight-chain, cyclic or branched alkyl group (-OR) which is singly bonded to oxygen. Preferably, the alkoxy group according to the invention has 1 to 6 carbon atoms and thus 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-methylpentyloxy, 2-methylpentyloxy. In the case where the present invention defines the carbon atom of the alkoxy group in different ways, these structures may be limited in selection.

[0046] "Halogen atom" in the context of the present invention, if not mentioned otherwise, refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I). Preferably, the halogen atom is F, Cl, Br or I, more preferably Cl or Br.

[0047] Based on the definitions given above, the skilled person knows how to understand further definitions not explicitly provided in the above paragraphs.The above enumeration should be understood as illustrative rather than limiting.

[0048] The term "average number of repeating units" is known to the skilled person. The skilled person knows how to determine this parameter. Typically, it is determined by using a GPC method. Preferably, it is determined using a GPC method as outlined in the present invention.

[0049] Preferably, in structural unit (A),

[0050] Each X independently represents a substituted or unsubstituted C3-C 18 -cycloalkylidene; formula—C(R c )(R d )—C1-C 18 -alkylidene, where R c and Rd are independently hydrogen, C1-C 12 -alkyl, C1-C 12 -Cycloalkyl, C7-C 12 -Arylalkyl, C1-C 12 -heteroalkyl or cyclic C7-C 12 -heteroarylalkyl; or a group of formula -C(=R c )—, wherein R c It is a two-valent C1-C 12 - a hydrocarbon group,

[0051] R 1 and R 3 Each independently represents C1-C 26 -alkyl, C7-C 26 Alkyl aryl or C7-C 26 -aralkyl,

[0052] R 2 and R 4 each independently represents a hydrogen atom, a C1-C6-alkoxy group or a C1-C6-alkyl group, and

[0053] p and q are each independently 1 and n represents the average number of repeating units.

[0054] Preferably, the polycarbonate cocondensate is characterized in that the structural unit (A) is represented by the following structural unit (Aa):

[0055]

[0056] Among them, X, R 1 , R 2 , R 3 , R 4 , p, q and n have the meanings given for the structural unit (A).

[0057] Preferably, X in the structural unit (A) or (Aa) may be a substituted or unsubstituted C3-C 18 -cycloalkylidene; formula—C(R c )(R d )—C1-C 18 -alkylidene, where R c and R d are independently hydrogen, C1-C 12 -alkyl, C1-C 12 -Cycloalkyl, C7-C 12 -Arylalkyl, C1-C 12 -heteroalkyl or cyclic C7-C 12 -heteroarylalkyl; or a group of formula -C(=R c )—, wherein Rc It is a two-valent C1-C 12 -hydrocarbon group. More preferably, R 1 and R 3 Each independently represents C1-C 26 -alkyl, C7-C 26 Alkyl aryl or C7-C 26 -aralkyl. Even more preferably, R 1 and R 3 Each independently represents a methyl group, an ethyl group, a propyl group, an octyl group, an isooctyl group, a benzyl group, an ethylphenyl group, a butylphenyl group, a propyldiphenyl group or a cyclohexylphenyl group. 1 and R 3 Each is a methyl group.

[0058] Preferably, X in the structural unit (A) or (Aa) represents methylene, cyclohexyl-methylene, 2-[2.2.1]-bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene or adamantylidene. More preferably, X represents the formula—C(R c )(R d )—C1-C 18 -alkylidene, where R c and R d are independently hydrogen, C1-C 12 -alkyl, C1-C 12 -Cycloalkyl, C7-C 12 -Arylalkyl, C1-C 12 -heteroalkyl or cyclic C7-C 12 -heteroarylalkyl, preferably hydrogen or C1-C 12 -alkyl. Even more preferably, R c and R d are each independently hydrogen or C1-C6 alkyl. Most preferably, R c is hydrogen and R d is methyl, ethyl, propyl or butyl. At the same time, most preferably, R 1 and R 3 Each is a methyl group.

[0059] Preferably, R in structural unit (A) or (Aa) 2 and R 4Each independently represents a hydrogen atom, an alkoxy group or a monovalent hydrocarbon group, preferably a hydrogen atom, a C1-C6-alkoxy group or a C1-C6-alkyl group, and even more preferably a hydrogen atom or a C1-C4-alkyl group.

[0060] Preferably, p and q in the structural unit (A) or (Aa) are each 1. In this case, it is most preferred that R 2 and R 4 All are C1-C4-alkyl.

[0061] Preferably, each X in the structural unit (A) or (Aa) independently represents the formula—C(R c )(R d )—C1-C6-alkylidene, wherein R c and R d Each is independently hydrogen or C1-C5-alkyl.

[0062] More preferably, in structural unit (A) or (Aa), each X independently represents the formula—C(R c )(R d )—C1-C4-alkylidene, wherein R c and R d are each independently hydrogen or C1-C3-alkyl, preferably hydrogen,

[0063] R 1 and R 3 each independently represents a methyl group or an ethyl group,

[0064] R 2 and R 4 Each independently represents a hydrogen atom, a methyl group, an ethyl group or a propyl group.

[0065] Preferably, Z in the structural unit (B) independently represents a single bond, -S(=O)2-, -C(=O)-, -O-, -S-, -S(=O)-, a straight-chain or branched C1-C6-alkylene group, a C2-C6-alkylene group optionally containing at least one carbon-carbon double bond, 10 -alkylidene, C5-C6-alkylidene, wherein the alicyclic group is optionally fused to at least one alicyclic and / or at least one aromatic ring 15 -cycloalkylidene, C7-C 15 -aralkylidene group, C8-C 15 -Arylene

[0066]

[0067] wherein in formula (B1-E), each R' independently represents a linear C1-C4-alkyl group, a branched C3-C4 alkyl group, each R" independently represents a linear C1-C4-alkylene group, a branched C3-C4 alkyl group, s is 0 to 2, and each s1 is independently 0 or 1, and "*" represents a bond connecting "Z" to the aromatic ring in formula (3),

[0068] Formula (B1-A), Formula (B1-B), Formula (B1-C),

[0069] R 5 and R 6 Each independently represents H, C1-C 18 -alkyl, C5-C6-cycloalkyl, C1-C 18 -alkoxy, phenoxy, C6-C 18 -Aryl or C7-C 18 -aralkyl,

[0070] p1 and q1 are each 1 to 4, and m2 represents the average number of repeating units.

[0071] independently represent a single bond, a C2-C5-alkylidene group or a C5-C 12 - cycloalkylidene, preferably single bond, isopropylidene or 3,3,5-trimethylcyclohexylidene.

[0072] More preferably, Z in formula (B) independently represents a single bond, a C2-C6-alkylidene group, a C5-C6-alkylidene group in which the alicyclic group is optionally fused to at least one aromatic ring. 12 -cycloalkylidene, formula (B1-A), formula (B1-B), formula (B1-C), R 5 and R 6 Each independently represents H, C1-C3-alkyl, C1-C 18 -alkoxy, p1 and q1 are each 1 to 4, and m2 represents the average number of repeating units.

[0073] More preferably, structural unit (B) is represented by a structural unit selected from the structural units of formulae (3a) to (3k)

[0074]

[0075] In formulae (3h), (3i) and (3j), R' represents a methyl group or a phenyl group.

[0076] Most preferably, the polycarbonate cocondensate of the present invention is characterized in that the structural unit (B) is represented by the following structural unit (Ba)

[0077]

[0078] wherein m2 represents the average number of repeating units and is 7 to 31.

[0079] Preferably, when the structural unit (B) is represented by the structural unit (Ba), the structural unit (A) is represented by the structural unit (Aa).

[0080] Structural units (A) and (B) or (Aa) and (Ba) list "n" and "m2" as the number of repeating units. Preferably, the average sum of all n and all m2 in one polymer chain of the polycarbonate co-condensate of the present invention is 30 to 80, more preferably 35 to 75, even more preferably 40 to 70, even more preferably 45 to 65, and most preferably 50 to 60. This does not mean that such polycarbonate co-condensates cannot contain any end groups or any other structures caused by impurities, etc. However, such polycarbonate co-condensates are essentially composed of the structures of formulas (A) and (B), and are composed of repeating units of only one type of structural units (A) and (B). The technician is able to convert this average sum of n1 and m2 into a number average molecular weight. Therefore, the technician is also able to calculate n and m2 based on the molecular weight and the ratio of structural units (A) and (B).

[0081] Preferably, the polycarbonate cocondensate of the present invention does not contain structural units of formula (100)

[0082]

[0083] wherein t represents the number of repeating units and is preferably 1 to 80, more preferably 2 to 75, even more preferably 40 to 70, even more preferably 45 to 65, and most preferably 50 to 60. However, this preferably does not exclude that structural units of formula (100) may be present in trace amounts in the polycarbonate co-condensates of the present invention. Preferably, the amount of structural units of formula (100) in the polycarbonate co-condensates of the present invention is less than 30% by weight, more preferably less than 20% by weight, and most preferably less than 10% by weight, wherein the % by weight is based on the total weight of the polycarbonate co-condensates.

[0084] According to the present invention, the polycarbonate cocondensate has a weight average molecular weight of 15000 g / mol to 50000 g / mol, preferably 17000 g / mol to 40000 g / mol, more preferably 20000 g / mol to 35000 g / mol, as determined by gel permeation chromatography using bisphenol A-polycarbonate calibration in dichloromethane. Preferably, the gel permeation chromatography is calibrated using bisphenol A polycarbonate and dichloromethane as eluents. Typically, linear polycarbonates (obtained from bisphenol A and phosgene) with known molecular weight distribution from PSS Polymer Standards Service GmbH, Deutschland can be used for calibration. Most preferably, calibration is performed according to method 2301-0257502-09D (2009 German version) from Currenta GmbH & Co. OHG, Leverkusen. The eluent is dichloromethane. Preferably, a combination of columns based on crosslinked styrene divinylbenzene resins is used. More preferably, the analytical column has a diameter of 7.5 mm and a length of 300 mm. The particle size of the column material is preferably 3 μm to 20 μm. The concentration of the solution is preferably 0.2 wt %. The flow rate is preferably 1.0 ml / min. The temperature of the solution is preferably 30° C. Preferably, UV- and / or RI- detection is used.

[0085] The weight average molecular weight as defined according to the invention ensures that the resulting polycarbonate cocondensates exhibit good mechanical properties in terms of tensile strength and processing parameters. It has surprisingly been found that the resulting tensile strength is comparable to that of bisphenol A based polycarbonates of comparable number average molecular weight.

[0086] In particular, the glass transition temperature of the polycarbonate condensate of the present invention is above 100° C., preferably above 110° C., more preferably above 116° C., even more preferably above 125° C., and most preferably above 130° C. Such a glass transition temperature ensures that the polycarbonate cocondensate of the present invention can be used in all applications in which BPA-based polycarbonates are also used. Preferably, the glass transition temperature can be determined by differential scanning calorimetry ISO 11357-2:2013-05 at a heating rate of 10° C. / min.

[0087] The polycarbonate co-condensate has a molar ratio of structural units (A) to structural units (B) of 20:80 to 95:5, preferably 25:75 to 93:7, more preferably 30:70 to 92:8, even more preferably 35:65 to 91:9, most preferably 39:61 to 90:10. Preferably, the molar ratio of structural units (A) and (B) can be determined by complete hydrolysis. Preferably, the respective polycarbonate co-condensate is subjected to complete hydrolysis to form the corresponding degradation products, which are the corresponding monomer structural units (A) and (B). The ratio of these degradation products can be determined by1 H-NMR or HPLC determination, the latter can be achieved, for example, as follows: a polycarbonate cocondensate sample is hydrolyzed under reflux with the aid of sodium methoxide. The corresponding solution is acidified and concentrated to dryness. The dry residue is dissolved in acetonitrile and the phenolic compounds are determined with the aid of HPLC with UV detection. Such polycarbonate cocondensates with a high content of structural units (A) are not provided in the prior art. In addition, if a high molecular weight is obtained with a monomer structure (B) (m2 about 1) in the prior art, these polycarbonates exhibit unfavorable optical properties. This is mainly due to a high terminal chlorine content.

[0088] According to the invention, the resulting properties can be fine-tuned by selecting the molar ratio of structural units (A) and (B). However, in order for the polycarbonate cocondensate to have a high content of bio-based structural units, it is preferred to have a high content of structural units (A).

[0089] Preferably, the polycarbonate cocondensate of the present invention comprises at least 30% by weight, more preferably at least 60% by weight, even more preferably at least 80% by weight, most preferably at least 90% by weight of the sum of the structural units (A) and (B), wherein the weight % is based on the total weight of the polycarbonate cocondensate. Most preferably, the polycarbonate cocondensate basic structural units (A) and (B) consist of or consist of the structural units (A) and (B). Obviously, the term "consisting of" in this case does not include the terminal groups that are additionally present.

[0090] Preferably, the polycarbonate cocondensate of the present invention contains at least one, preferably more than one, of the following structures (4x) to (7x):

[0091]

[0092] The phenyl rings may be independently mono- or disubstituted by C1-C8 alkyl, halogen, preferably C1 to C4 alkyl, particularly preferably methyl, 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 (4x) to (7x) (determined after hydrolysis) is generally 50 to 1000 ppm, preferably 80 to 850 ppm. The presence of these structures can have a positive influence on the properties of the resulting polycarbonate cocondensates.

[0093] To determine the amount of at least one of the structures (4x) to (7x), the respective polycarbonate cocondensate is subjected to complete hydrolysis to form the corresponding degradation products of the formulae (4y) to (7y), the amount of which is determined by HPLC (this can be achieved, for example, as follows: a sample of the polycarbonate cocondensate is hydrolyzed under reflux with the aid of 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 (ly) to (4y) are determined by means of HPLC with UV detection):

[0094]

[0095] The amount of the compound of the formula (4y) thus released is preferably from 20 to 800 ppm, particularly preferably from 25 to 700 ppm, especially preferably from 30 to 500 ppm.

[0096] The amount of the compound of the formula (5y) 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.

[0097] The amount of the compound of the formula (6y) 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.

[0098] The amount of the compound of the formula (7y) 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.

[0099] Most preferably, structures (4x) to (7x) are introduced into the polycarbonate cocondensates of the present invention by using a homopolycarbonate comprising structural units (B) and at least one of structures (4x) to (7x).

[0100] In a further aspect of the present invention, a molding compound is provided, which comprises the polycarbonate co-condensate of the present invention as in each of the definitions given above. Such a molding compound can be obtained by adding additional thermoplastic polymers and / or additives. In addition, another aspect of the present invention provides a molded article, which comprises the polycarbonate co-condensate of the present invention as in each of the definitions given above. Such a molded article can be obtained by methods known to the technician, such as extrusion, injection molding, blow molding or thermoforming of sheets or plates. In another aspect of the present invention, a method for producing a polycarbonate co-condensate having a high molecular weight and which may contain a high amount of structural units (A) as defined above is provided. Preferably, the method of the present invention produces the polycarbonate co-condensate of the present invention as in each of the definitions given above. This means that the molecular weight of the polycarbonate co-condensate as defined above can be obtained in particular by the method of the present invention.

[0101] Thus, a process for preparing polycarbonate cocondensates, preferably polycarbonate block cocondensates, is characterized in that at least one diol of the formula (1) is reacted with at least one homopolycarbonate and at least one diaryl carbonate of the formula (2),

[0102]

[0103] in

[0104] Each X in the structural unit (A) independently represents a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or an organic group having 1 to 18 carbon atoms, wherein the organic group having 1 to 18 carbon atoms may be linear, branched or cyclic, aromatic or non-aromatic, and may further contain heteroatoms such as halogen, oxygen, nitrogen, sulfur, silicon or phosphorus,

[0105] R 1 and R 3 Each independently represents a monovalent hydrocarbon group, preferably C1-C 26 -alkyl, C7-C 26 Alkyl aryl or C7-C 26 -aralkyl,

[0106] R 2 and R 4 each independently represents a hydrogen atom, an alkoxy group or a monovalent hydrocarbon group, preferably a hydrogen atom, a C1-C6-alkoxy group or a C1-C6-alkyl group, and

[0107] p and q are each independently 1 or 2, preferably 1,

[0108]

[0109] Where R5 and R 6 Each independently represents H, C1-C 34 -alkyl, C7-C 34 -Arylalkyl, C6-C 34 -aryl or -COO-R', where R' represents C1-C 34 -alkyl, C7-C 34 -aralkyl or C6-C 34 -aryl, and

[0110] r and s each represent 1 to 5,

[0111] The molar ratio of the at least one diol of formula (1) to the homopolycarbonate is 20:80 to 95:5.

[0112] Preferably, with respect to the diol of formula (1),

[0113] Each X independently represents a substituted or unsubstituted C3-C 18 -cycloalkylidene; formula—C(R c )(R d )—C1-C 18 -alkylidene, where R c and R d are independently hydrogen, C1-C 12 -alkyl, C1-C 12 -Cycloalkyl, C7-C 12 -Arylalkyl, C1-C 12 -heteroalkyl or cyclic C7-C 12 -heteroarylalkyl; or a group of formula -C(=R c )—, wherein R c It is a two-valent C1-C 12 - a hydrocarbon group,

[0114] R 1 and R 3 Each independently represents C1-C 26 -alkyl, C7-C 26 Alkyl aryl or C7-C 26 -aralkyl,

[0115] R 2 and R 4 each independently represents a hydrogen atom, a C1-C6-alkoxy group or a C1-C6-alkyl group, and

[0116] p and q are each independently 1.

[0117] Preferably, the process of the present invention is characterized in that the diol of formula (1) is represented by the following formula (1a):

[0118]

[0119] Among them, X, R 1 , R 2 , R 3 , R 4 , p, q and n have the meanings given with respect to formula (1).

[0120] Preferably, X in formula (1) or (1a) can be a substituted or unsubstituted C3-C 18 -cycloalkylidene; formula—C(R c )(R d )—C1-C 18 -alkylidene, where R c and R d are independently hydrogen, C1-C 12 -alkyl, C1-C 12 -Cycloalkyl, C7-C 12 -Arylalkyl, C1-C 12 -heteroalkyl or cyclic C7-C 12 -heteroarylalkyl; or a group of formula -C(=R c )—, wherein R c It is a two-valent C1-C 12 -hydrocarbon group. More preferably, R 1 and R 3 Each independently represents C1-C 26 -alkyl, C7-C 26 Alkyl aryl or C7-C 26 -aralkyl. Even more preferably, R 1 and R 3 Each independently represents a methyl group, an ethyl group, a propyl group, an octyl group, an isooctyl group, a benzyl group, an ethylphenyl group, a butylphenyl group, a propyldiphenyl group or a cyclohexylphenyl group. 1 and R 3 Each is a methyl group.

[0121] Preferably, X in formula (1) or (1a) represents methylene, cyclohexyl-methylene, 2-[2.2.1]-bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene or adamantylidene. More preferably, X represents a group of formula—C(Rc )(R d )—C1-C 18 -alkylidene, where R c and R d are independently hydrogen, C1-C 12 -alkyl, C1-C 12 -Cycloalkyl, C7-C 12 -Arylalkyl, C1-C 12 -heteroalkyl or cyclic C7-C 12 -heteroarylalkyl, preferably hydrogen or C1-C 12 -alkyl. Even more preferably, R c and R d are each independently hydrogen or C1-C6 alkyl. Most preferably, R c is hydrogen and R d is methyl, ethyl, propyl or butyl. At the same time, most preferably, R 1 and R 3 Each is a methyl group.

[0122] Preferably, R in formula (1) or (1a) 2 and R 4 Each independently represents a hydrogen atom, an alkoxy group or a monovalent hydrocarbon group, preferably a hydrogen atom, a C1-C6-alkoxy group or a C1-C6-alkyl group, and even more preferably a hydrogen atom or a C1-C4-alkyl group.

[0123] Preferably, p and q in formula (1) or (1a) are each 1. In this case, it is most preferred that R 2 and R 4 All are C1-C4-alkyl.

[0124] Preferably, each X in formula (1) or (1a) independently represents the formula—C(R c )(R d )—C1-C6-alkylidene, wherein R c and R d Each is independently hydrogen or C1-C5-alkyl.

[0125] More preferably, in formula (1) or (1a), each X independently represents the formula—C(R c )(R d )—C1-C4-alkylidene, wherein R c and R d are each independently hydrogen or C1-C3-alkyl, preferably hydrogen,

[0126] R 1 and R 3 each independently represents a methyl group or an ethyl group,

[0127] R2 and R 4 Each independently represents a hydrogen atom, a methyl group, an ethyl group or a propyl group.

[0128] Preferably, in the process of the present invention, no diol of formula (101) is used.

[0129]

[0130] This preferably does not exclude that structural units of the formula (101) may be present in trace amounts in the diols used. Preferably, the amount of diols of the formula (101) in the at least one diol of the formula (1) used according to the invention is less than 30% by weight, more preferably less than 20% by weight, most preferably less than 10% by weight, wherein the weight % is based on the total weight of all diols used.

[0131] Preferably, the homopolycarbonate has a relative solution viscosity etarel of 1.08 to 1.22, more preferably 1.11 to 1.22, most preferably 1.13 to 1.20. According to the invention, the relative solution viscosity (rel; also referred to as eta rel) is preferably determined using an Ubbelohde viscometer in dichloromethane at a concentration of 5 g / l at 25°C. The determination of the relative solution viscosity by means of an Ubbelohde viscometer is known to the skilled person. According to the invention, this is preferably carried out according to DIN 51562-3; 1985-05. In this method, the flow time of the respective polymer to be measured is measured by an Ubbelohde viscometer in order to subsequently determine the viscosity difference between the polymer solution and its solvent. For this purpose, the Ubbelohde viscometer is first calibrated by measuring the pure solvent dichloromethane (always at least 3 measurements, up to 9 measurements). Thereafter, the actual calibration is carried out with the solvent dichloromethane. The polymer sample is then weighed, dissolved in dichloromethane, and the flow time of the solution is determined three times. The mean values ​​of the flow times were corrected by Hagenbach correction and the relative solution viscosity was calculated.

[0132] Preferably, the homopolycarbonate used in the process of the present invention comprises the structural unit (B) as per the definitions and preferences given above. This preferably means that the homopolycarbonate used in the process of the present invention comprises the structural unit (B)

[0133]

[0134] wherein each Z in the structural unit (B) independently represents a single bond, -S(=O)2-, -C(=O)-, -O-, -S-, -S(=O)-, -CH(CN)-, a straight-chain or branched C1-C6-alkylene group optionally containing at least one carbonyl group, optionally containing at least one halogen atom and / or optionally interrupted by at least one heteroatom, a C2-C6-alkylene group optionally containing at least one carbon-carbon double bond, optionally containing at least one carbonyl group and / or optionally containing at least one halogen atom 10 -alkylidene, C5-C6-alkylene ... 12 -cycloalkylene, C5-C6-cycloalkylene, wherein the alicyclic group is optionally fused to at least one alicyclic and / or at least one aromatic ring 15 -cycloalkylidene, C7-C 20 -Arylalkylidene, C8-C 20 -aralkylene, a C6-C6-alkylene ring optionally fused to a further aromatic ring which may optionally contain at least one heteroatom 12 -arylene group, formula (B1-A), formula (B1-B), formula (B1-C) or formula (B1-D)

[0135]

[0136] wherein in formulae (B1-A), (B1-B) and (B1-C), each R' independently represents a linear C1-C4-alkyl group, a branched C3-C4-alkyl group, an aralkyl group or an aryl group, and "C*" represents a quaternary carbon atom at the position indicated as "Z" in formula (B), and

[0137] wherein in formula (B1-D), each R' independently represents a straight-chain C1-C4-alkyl group, a branched C3-C4-alkyl group, each R" independently represents a straight-chain C1-C4-alkylene group, a branched C3-C4-alkylene group, each R"' independently represents H or a straight-chain C1-C3-alkyl group, s is 0 to 2, and each s1 is independently 0 or 1, and "*" represents a bond connecting "Z" to the aromatic ring in formula (B),

[0138] R 5 and R 6 Each independently represents H, C1-C 18 -alkyl, C5-C6-cycloalkyl, C1-C5-alkenyl-, C1-C 18 -alkoxy, phenoxy, halogen atom, C6-C 18 -Aryl or C7-C 18 -aralkyl,

[0139] p1 and q1 are each 1 to 4, and

[0140] m2 represents the average number of repeating units, and m2 is 7 to 31.

[0141] All further preferences as given above for formula (B) also apply to the process of the invention.

[0142] Most preferably, the process according to the invention is characterized in that the homopolycarbonate comprises structural units of formula (Ba)

[0143]

[0144] wherein m2 represents the average number of repeating units and is 7 to 31.

[0145] More preferably, the homopolycarbonate used in the process of the present invention has a terminal OH group content of 250 ppm to 2500 ppm, more preferably 500 ppm to 2400 ppm, most preferably 1000 to 2300 ppm. This content of terminal OH groups is preferably determined by infrared spectroscopy. It can also be determined by 1 H-NMR determination. If determined by infrared spectroscopy, the homopolycarbonate is preferably dissolved in dichloromethane (2 g / 50 ml) and the concentration at 3583 cm -1 The spectral bands at the wavenumbers of . The required calibration of the infrared instrument is known to the skilled person.

[0146] The homopolycarbonate can be obtained as described in WO2019238419A1, DE10119851A1, W002077066A1, W002077067A2 or WO02085967A1.

[0147] In the method of the present invention, a diaryl carbonate of formula (2) is used. Preferably, in formula (2), R 5 and R 6 Each independently represents H, C1-C 10 -alkyl, C7-C 15 -Arylalkyl, C6-C 12 -aryl or -COO-R', wherein R' represents C1-C5-alkyl, C7-C 12 -aralkyl or C6-C 12 -aryl, and r and s each represent 1 to 3. More preferably, the diaryl carbonate of formula (2) is selected from diphenyl carbonate, 4-tert-butylphenyl-phenyl carbonate, di-(4-tert-butylphenyl) carbonate, biphenyl-4-yl-phenyl carbonate, di-(biphenyl-4-yl) carbonate, 4-(1-methyl-1-phenylethyl)-phenyl-phenyl carbonate and di-[4-(1-methyl-1-phenylethyl)-phenyl] carbonate.

[0148] Preferably, in the process of the present invention, the molar ratio of the diaryl carbonate of formula (2) to the sum of the diol of formula (1) and the homopolycarbonate is from 1.01 to 1.09, preferably from 1.03 to 1.07.

[0149] The method according to the invention can be carried out using techniques known to the technician. In principle, the method can be carried out in an interphase phosgenation or a melt process. Preferably, the method of the invention is characterized in that the reaction is carried out in a melt. This preferably means that the method is carried out at a temperature higher than the melting / glass transition temperature of all educts and products. The technician knows how to carry out the method (so-called melt transesterification) in the melt. Due to the less amount of these special matters (specialties), it is usually more economical and advantageous to prepare specific co-condensates by melt transesterification than by interphase phosgenation. In addition, reactants that require special treatment, such as phosgene, can be avoided. Finally, polymerization via melt transesterification does not require the use of solvents, and therefore requires less purification of the resulting product.

[0150] In the melt transesterification, the reactants are preferably melted under reduced pressure. Depending on the device configuration, atmospheric pressure, preferably mild vacuum, i.e., less than 200 mbar, particularly preferably 100-200 mbar, most preferably less than 100 mbar absolute pressure can be applied during the melting stage. However, the reactants can also be melted under standard pressure, preferably in a protective gas atmosphere, such as nitrogen. Melting is preferably carried out in the range of 175 to 400° C., more preferably in the range of 180 to 350° C., most preferably in the range of 185 to 320° C. For the reaction or condensation stage, the above-mentioned temperature and pressure are applicable. Preferably, the values ​​given above are applicable to BPA-based homopolycarbonates. However, the technician can adjust the respective parameters according to the melting temperature of the homopolycarbonate used.

[0151] According to the present invention, method steps (i) and (ii) or (ii') are preferably carried out in the absence of additional organic solvents. Therefore, the method according to the present invention can preferably be carried out without solvent. According to the present invention, this does not exclude the possibility that the used diaryl carbonate and the condensation product formed in the reaction may be present as solvent in these reaction steps (if possible). This is particularly true if the carbonate is used in a stoichiometric excess relative to diols and homopolycarbonate. This preferred method variant is particularly gentle. However, according to the present invention, preferably no additional organic solvent is added to the method. Due to the absence of additional organic solvents, the method can be carried out advantageously and in an environmentally friendly manner.

[0152] The diols of the formula (1) and the homopolycarbonates can be reacted according to the process of the invention using catalysts. A catalyst-free reaction mode is in principle possible, but higher temperatures and longer residence times may have to be accepted as a result.

[0153] 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, hexadecyltrimethylammonium tetraphenylborate and hexadecyltrimethylammonium phenol. Particularly suitable are phosphonium catalysts of formula (K):

[0154]

[0155] Where R a , R b , R c and R d It can be the same or different C1-C10-alkyl, C6-C14-aryl, C7-C15-arylalkyl or C5-C6-cycloalkyl, preferably methyl or C6-C14-aryl, particularly preferably methyl or phenyl, and X- can be an anion such as hydroxide, sulfate, hydrogensulfate, bicarbonate, carbonate or a halide, preferably chloride or an alkylate or arylate of the formula -OR, wherein R can be C6-C14-aryl, C7-C15-arylalkyl or C5-C6-cycloalkyl, preferably phenyl.

[0156] Particularly preferred catalysts are tetraphenylphosphonium hydroxide and tetraphenylphosphonium phenolate, with tetraphenylphosphonium phenolate being very particularly preferred. Particular preference is given to using alkali metal or alkaline earth metal salts of these ammonium and / or phosphonium catalysts.

[0157] The catalyst is preferably present in an amount of 1 to 10 moles based on 1 mole of the total amount of the diol of the formula (1) and the homopolycarbonate. -8 mol, preferably 10 -8 Up to 10 -3 mol, particularly preferably 10 -7 Up to 10 -4 Amount used.

[0158] Suitable catalysts for the process according to the invention are those listed above, which are introduced into the reaction together with a suitable homopolycarbonate, in particular the homopolycarbonate according to the invention described above, by means of a masterbatch, or can be introduced separately or additionally therewith. The catalyst can be used alone or in mixtures and added in pure form or as a solution (e.g. in water or in phenol).

[0159] Homopolycarbonates can be modified in a controlled manner using small amounts of chain terminators and / or branching agents. Suitable chain terminators and branching agents are known in the literature. Some are described, for example, in DE A 3833953. Preferred chain terminators used are phenols or alkylphenols, in particular phenol, p-tert-butylphenol, isooctylphenol, cumylphenol, their chlorocarbonates or the acid chlorides of monocarboxylic acids or mixtures of these chain terminators. Preferred chain terminators are phenol, cumylphenol, isooctylphenol, p-tert-butylphenol, in particular phenol. Examples of compounds suitable as branching agents are aromatic or aliphatic compounds having at least three, preferably three or four hydroxyl groups. Particularly suitable examples of compounds having three or more than three phenolic hydroxyl groups are 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-tri(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, tetrakis(4-hydroxyphenyl)methane. Examples of other trifunctional compounds suitable as branching agents are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole. Particularly preferred branching agents are 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole and 1,1,1-tris(4-hydroxyphenyl)ethane.

[0160] The reaction of the method of the present invention is carried out at the temperature and pressure specified above. Preferably, the reaction mixture is sheared. This can be carried out by rapid stirring in a tank or by means of suitable mixing elements such as static mixers, mixing elements on extruder screws, etc. Higher mixing is preferred over lower mixing.

[0161] In the process of the invention, the molar ratio of at least one diol of formula (1) to the homopolycarbonate is from 20:80 to 95:5, preferably from 25:75 to 93:7, more preferably from 30:70 to 92:8, even more preferably from 35:65 to 91:9, most preferably from 39:61 to 90:10. The skilled person knows how to determine this molar ratio. In particular, to calculate this ratio, the number average molecular weight of the homopolycarbonate is used.

[0162] In another aspect of the present invention, there is provided a use of a homopolycarbonate comprising structural unit (B) for preparing a polycarbonate cocondensate comprising structural unit (A)

[0163]

[0164] in

[0165] Each X in the structural unit (A) independently represents a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or an organic group having 1 to 18 carbon atoms, wherein the organic group having 1 to 18 carbon atoms may be linear, branched or cyclic, aromatic or non-aromatic, and may further contain heteroatoms such as halogen, oxygen, nitrogen, sulfur, silicon or phosphorus,

[0166] R 1 and R 3 Each independently represents a monovalent hydrocarbon group, preferably C1-C 26 -alkyl, C7-C 26 Alkyl aryl or C7-C 26 -aralkyl,

[0167] R 2 and R 4 each independently represents a hydrogen atom, an alkoxy group or a monovalent hydrocarbon group, preferably a hydrogen atom, a C1-C6-alkoxy group or a C1-C6-alkyl group, and

[0168] p and q are each independently 1 or 2, preferably 1, and

[0169] n represents the average number of repeating units, wherein n is 1 to 10, preferably 1 to 6, more preferably 1 to 4,

[0170] wherein each Z in the structural unit (B) independently represents a single bond, -S(=O)2-, -C(=O)-, -O-, -S-, -S(=O)-, -CH(CN)-, a straight-chain or branched C1-C6-alkylene group optionally containing at least one carbonyl group, optionally containing at least one halogen atom and / or optionally interrupted by at least one heteroatom, a C2-C6-alkylene group optionally containing at least one carbon-carbon double bond, optionally containing at least one carbonyl group and / or optionally containing at least one halogen atom 10 -alkylidene, C5-C6-alkylene ... 12 -cycloalkylene, C5-C6-cycloalkylene, wherein the alicyclic group is optionally fused to at least one alicyclic and / or at least one aromatic ring 15 -cycloalkylidene, C7-C 20 -Arylalkylidene, C8-C 20 -aralkylene, a C6-C6-alkylene ring optionally fused to a further aromatic ring which may optionally contain at least one heteroatom 12 -arylene group, formula (B1-A), formula (B1-B), formula (B1-C) or formula (B1-D)

[0171]

[0172] wherein in formulae (B1-A), (B1-B) and (B1-C), each R' independently represents a linear C1-C4-alkyl group, a branched C3-C4-alkyl group, an aralkyl group or an aryl group, and "C*" represents a quaternary carbon atom at the position indicated as "Z" in formula (B), and

[0173] wherein in formula (B1-D), each R' independently represents a straight-chain C1-C4-alkyl group, a branched C3-C4-alkyl group, each R" independently represents a straight-chain C1-C4-alkylene group, a branched C3-C4-alkylene group, each R"' independently represents H or a straight-chain C1-C3-alkyl group, s is 0 to 2, and each s1 is independently 0 or 1, and "*" represents a bond connecting "Z" to the aromatic ring in formula (B),

[0174] R 5 and R 6 Each independently represents H, C1-C 18 -alkyl, C5-C6-cycloalkyl, C1-C5-alkenyl-, C1-C 18 -alkoxy, phenoxy, halogen atom, C6-C 18 -Aryl or C7-C 18 -aralkyl,

[0175] p1 and q1 are each 1 to 4, and

[0176] m2 represents the average number of repeating units, and m2 is 7 to 31,

[0177] The molar ratio of structural unit (A) to structural unit (B) in the polycarbonate cocondensate is from 20:80 to 95:5. It is to be understood that this use preferably produces the polycarbonate cocondensate of the invention as described in detail and preferably above. Example

[0178] Size exclusion chromatography was performed using a PSS SECurity System; polycarbonate calibration (according to method 2301-0257502-09D of Currenta GmbH & Co. OHG, Leverkusen), dichloromethane as eluent, column 1 (PL-PC5), concentration 2 g / l, flow rate 1.0 ml / min, at a temperature of 30°C, using UV and / or RI detection.

[0179] The glass transition temperature (Tg) was determined by DSC using ISO 11357-2:2013-05 at a heating rate of 10°C / min. Tg is the onset temperature of the second heating at 10°C / min measured on a Mettler Toledo DSC.

[0180] The relative solution viscosity (also called etarel) is determined using an Ubbelohde viscometer in dichloromethane at a concentration of 5 g / l at 25° C. The determination is carried out in accordance with DIN 51562-3; 1985-05. In this method, the flow time of the polycarbonate to be measured is measured by an Ubbelohde viscometer in order to subsequently determine the viscosity difference between the polymer solution and its solvent. To this end, the Ubbelohde viscometer is first calibrated by measuring the pure solvent dichloromethane (at least 3 measurements, at most 9 measurements). Thereafter, the actual calibration is carried out with the solvent dichloromethane. The polymer sample is then weighed, dissolved in dichloromethane, and the flow time is then determined three times. The mean value of the flow time is corrected using the Hagenbach correction, and the relative solution viscosity is calculated.

[0181] To determine the OH groups, polycarbonate was dissolved in dichloromethane (2 g / 50 mL; 1 mm quartz cuvette) and analyzed using a Thermo Fisher Scientific FT infrared spectrometer Nicolet iS20. -1 The content of phenolic OH groups can be determined by observing the band at

[0182] Comparative Example - Copolymerization of BPL and BPA

[0183] Copolycarbonates are prepared by transesterification of diphenyl carbonate.

[0184] Comparative Example 3: 0.5623 g of diphenyl carbonate, 0.34 g of BPA and 0.3164 g of BPL1 (4,4'-propylenebis(2-methoxyphenol)) were melted together with 2.8 μl of tetraphenylphosphonium phenol solution (5 wt% TPPP, 5 wt% demineralized water and 90 wt% phenol) in an alkali-free glass test tube and subjected to batch transesterification under mechanical stirring (stirrer: homemade drill bit form). The temperature was increased using a heating block and the vacuum was gradually improved as follows:

[0185] 1. Step (45 minutes): 210°C, atmospheric pressure

[0186] 2. Step (15 minutes): 240°C, 100 mbar absolute pressure

[0187] 3. Step (10 minutes): 270°C, 50 mbar absolute pressure

[0188] 4. Step (10 minutes): 280° C., 25 mbar absolute pressure.

[0189] 5. Step (20 minutes): 300°C, 4 mbar absolute pressure

[0190] 6. Step (30 minutes): 300°C, <1 mbar absolute pressure

[0191] The results of this polymerization are summarized in Table 1. Comparative Examples 1, 2 and 4 were carried out in the same manner except that the ratio of BPA and BPL1 was varied as shown in Table 1.

[0192] Table 1:

[0193] BPA / BPL1 molar ratio <![CDATA[M w (g / mol)]]> Tg(℃) Comparative Example 1 100 / 0 31,087 - Comparative Example 2 90 / 10 33,720 141.1 Comparative Example 3 60 / 40 17,980 125.9 Comparative Example 4 30 / 70 11,230 113.9

[0194] *) Due to the catalyst added to the phenolic solution, a small amount of phenol is always present.

[0195] As can be seen from the results in Table 1, the reaction of monomeric BPL and monomeric BPA produces copolymers. However, as the amount of BPL increases, the total molecular weight of the resulting copolymer becomes smaller. This means that not all BPL / BPA ratios can be freely selected in order to fine-tune the properties of the copolymer and obtain a reasonable molecular weight for all applications. In particular, when using monomeric BPA, it is not easy to obtain a co-condensate with a large amount of BPL and a high molecular weight.

[0196] Example of the Invention - Copolymerization of BPL2 and BPA-Based Homopolycarbonate

[0197] Example 2 of the present invention: 0.0487 g of diphenyl carbonate, 0.86 g of homopolycarbonate (homoPC) and 0.0298 g of BPL2 (5,5'-methylenebis(4-n-propylguaiacol)) were melted together with 3.3 microliters of phenol tetraphenylphosphonium solution (5 wt% TPPP, 5 wt% demineralized water and 90 wt% phenol) in an alkali-free glass flask and transesterified in batches under mechanical stirring. The homopolycarbonate (homoPC) is a linear bisphenol A-based polycarbonate containing terminal OH groups and phenyl groups and having a relative solution viscosity of 1.16 (corresponding to a number average molecular weight of 6629 g / mol). The preparation of this homoPC is described in WO02085967A1. The content of terminal OH groups is 0.16%.

[0198] Increase the temperature and gradually improve the vacuum as follows:

[0199] 1. Step (45 minutes): 210°C, atmospheric pressure

[0200] 2. Step (5 minutes): 240°C, 100 mbar absolute pressure

[0201] 3. Step (5 minutes): 270°C, 50 mbar absolute pressure

[0202] 4. Step (5 minutes): 280° C., 25 mbar absolute pressure.

[0203] 5. Step (20 minutes): 300°C, 4 mbar absolute pressure

[0204] 6. Step (30 minutes): 300°C, <1 mbar absolute pressure

[0205] The reaction time was reduced to obtain a molecular weight comparable to that theoretically achievable with BPA homopolycarbonate (see Comparative Example 1).

[0206] The results of this polymerization are summarized in Table 2. Inventive Examples 1 and 3 were carried out in the same manner except that the ratio of homoPC and BPL2 was varied as shown in Table 2.

[0207] Table 2:

[0208] homoPC / BPL2 molar ratio <![CDATA[M w (g / mol)]]> Tg(℃) Embodiment 1 of the present invention 90 / 10 9,178 132.8 Embodiment 2 of the present invention 60 / 40 18,560 140.8 Embodiment 3 of the present invention 30 / 70 24,010 138.5

[0209] *) Due to the catalyst added to the phenolic solution, a small amount of phenol is always present.

[0210] Table 2 shows that when BPA-based polycarbonate is used instead of monomeric BPA to copolymerize with BPL, reasonable molecular weights can be obtained when at least 20 mol% of BPL monomer is used (80 mol% of "BPA" in the form of BPA-based polycarbonate is used). It can be concluded from the experiments that high molecular weights can be obtained even at high levels of BPL in the cocondensate.

Claims

1. A polycarbonate cocondensate comprising at least one structural unit (A) and at least one structural unit (B) in Each X in the structural unit (A) independently represents a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or an organic group having 1 to 18 carbon atoms, wherein the organic group having 1 to 18 carbon atoms may be linear, branched or cyclic, aromatic or non-aromatic, and may further contain heteroatoms such as halogen, oxygen, nitrogen, sulfur, silicon or phosphorus, R 1 and R 3 Each independently represents a monovalent hydrocarbon group, preferably C1-C 26 -alkyl, C7-C 26 Alkyl aryl or C7-C 26 -aralkyl, R 2 and R 4 each independently represents a hydrogen atom, an alkoxy group or a monovalent hydrocarbon group, preferably a hydrogen atom, a C1-C6-alkoxy group or a C1-C6-alkyl group, and p and q are each independently 1 or 2, preferably 1, and n represents the average number of repeating units, wherein n is 1 to 10, preferably 1 to 6, more preferably 1 to 4, wherein each Z in the structural unit (B) independently represents a single bond, -S(=O)2-, -C(=O)-, -O-, -S-, -S(=O)-, -CH(CN)-, a straight-chain or branched C1-C6-alkylene group optionally containing at least one carbonyl group, optionally containing at least one halogen atom and / or optionally interrupted by at least one heteroatom, a C2-C6-alkylene group optionally containing at least one carbon-carbon double bond, optionally containing at least one carbonyl group and / or optionally containing at least one halogen atom 10 -alkylidene, C5-C6-alkylene ... 12 -cycloalkylene, C5-C6-cycloalkylene, wherein the alicyclic group is optionally fused to at least one alicyclic and / or at least one aromatic ring 15 -Cycloalkylidene, C7-C 20 -Arylalkylidene, C8-C 20 -aralkylene, a C6-C6-alkylene ring optionally fused to a further aromatic ring which may optionally contain at least one heteroatom 12 -arylene group, formula (B1-A), formula (B1-B), formula (B1-C) or formula (B1-D) wherein in formulae (B1-A), (B1-B) and (B1-C), each R' independently represents a linear C1-C4-alkyl group, a branched C3-C4-alkyl group, an aralkyl group or an aryl group, and "C*" represents a quaternary carbon atom at the position indicated as "Z" in formula (B), and wherein in formula (B1-D), each R' independently represents a straight-chain C1-C4-alkyl group, a branched C3-C4-alkyl group, each R" independently represents a straight-chain C1-C4-alkylene group, a branched C3-C4-alkylene group, each R"' independently represents H or a straight-chain C1-C3-alkyl group, s is 0 to 2, and each s1 is independently 0 or 1, and "*" represents a bond connecting "Z" to the aromatic ring in formula (B), R 5 and R 6 Each independently represents H, C1-C 18 -alkyl, C5-C6-cycloalkyl, C1-C5-alkenyl-, C1-C 18 -alkoxy, phenoxy, halogen atom, C6-C 18 -Aryl or C7-C 18 -aralkyl, p1 and q1 are each 1 to 4, and m2 represents the average number of repeating units, and m2 is 7 to 31, The molar ratio of structural unit (A) to structural unit (B) is 20:80 to 95:5, And the polycarbonate co-condensate has a weight average molecular weight of 15000 g / mol to 50000 g / mol as determined by GPC in dichloromethane calibrated with BPA-based polycarbonate.

2. The polycarbonate cocondensate according to claim 1, characterized in that Each X in the structural unit (A) independently represents a substituted or unsubstituted C3-C 18 -cycloalkylidene; formula—C(R c )(R d )—C1-C 18 -alkylidene, where R c and R d are independently hydrogen, C1-C 12 -alkyl, C1-C 12 -Cycloalkyl, C7-C 12 -Arylalkyl, C1-C 12 -heteroalkyl or cyclic C7-C 12 -heteroarylalkyl; or a group of formula -C(=R c )—, wherein R c It is a two-valent C1-C 12 - a hydrocarbon group, R 1 and R 3 Each independently represents C1-C 26 -alkyl, C7-C 26 Alkyl aryl or C7-C 26 -aralkyl, R 2 and R 4 each independently represents a hydrogen atom, a C1-C6-alkoxy group or a C1-C6-alkyl group, and p and q are each independently 1, and n represents the average number of repeating units.

3. The polycarbonate cocondensate according to claim 1, characterized in that The structural unit (A) is represented by the following structural unit (Aa): Among them, X, R 1 , R 2 , R 3 , R 4 , p, q and n have the meanings given in claim 1 or 2 for the structural unit (A).

4. The polycarbonate cocondensate according to any one of claims 1 to 3, characterized in that In the structural unit (A) in claim 1 or the structural unit (Aa) in claim 3, Each X independently represents the formula -C(R c )(R d )—C1-C6-alkylidene, wherein R c and R d Each is independently hydrogen or C1-C5-alkyl.

5. The polycarbonate cocondensate according to any one of claims 1 to 4, characterized in that In the structural unit (A) in claim 1 or the structural unit (Aa) in claim 3, Each X independently represents the formula -C(R c )(R d )—C1-C4-alkylidene, wherein R c and R d are each independently hydrogen or C1-C3-alkyl, preferably hydrogen, R 1 and R 3 each independently represents a methyl group or an ethyl group, R 2 and R 4 Each independently represents a hydrogen atom, a methyl group, an ethyl group or a propyl group.

6. The polycarbonate cocondensate according to any one of claims 1 to 5, characterized in that The structural unit (B) is represented by the following structural unit (Ba) wherein m2 represents the average number of repeating units and is 7 to 31.

7. A molding compound comprising the polycarbonate cocondensate according to any one of claims 1 to 6.

8. A molded article comprising the polycarbonate cocondensate according to any one of claims 1 to 6.

9. A method for preparing a polycarbonate cocondensate, characterized in that reacting at least one diol of formula (1) with at least one homopolycarbonate and at least one diaryl carbonate of formula (2), in Each X in the structural unit (A) independently represents a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or an organic group having 1 to 18 carbon atoms, wherein the organic group having 1 to 18 carbon atoms may be linear, branched or cyclic, aromatic or non-aromatic, and may further contain heteroatoms such as halogen, oxygen, nitrogen, sulfur, silicon or phosphorus, R 1 and R 3 Each independently represents a monovalent hydrocarbon group, preferably C1-C 26 -alkyl, C7-C 26 Alkyl aryl or C7-C 26 -aralkyl, R 2 and R 4 each independently represents a hydrogen atom, an alkoxy group or a monovalent hydrocarbon group, preferably a hydrogen atom, a C1-C6-alkoxy group or a C1-C6-alkyl group, and p and q are each independently 1 or 2, preferably 1, Where R 5 and R 6 Each independently represents H, C1-C 34 -alkyl, C7-C 34 -Arylalkyl, C6-C 34 -aryl or -COO-R', where R' represents C1-C 34 -alkyl, C7-C 34 -aralkyl or C6-C 34 -aryl, and r and s each represent 1 to 5, The molar ratio of the at least one diol of formula (1) to the homopolycarbonate is 20:80 to 95:

5.

10. The method according to claim 9, characterized in that The homopolycarbonate has a relative solution viscosity eta rel of 1.08 to 1.

22.

11. The method according to claim 9 or 10, characterized in that The reaction is carried out in the melt.

12. The method according to any one of claims 9 to 11, characterized in that The homopolycarbonate comprises structural units (B) wherein each Z in the structural unit (B) independently represents a single bond, -S(=O)2-, -C(=O)-, -O-, -S-, -S(=O)-, -CH(CN)-, a straight-chain or branched C1-C6-alkylene group optionally containing at least one carbonyl group, optionally containing at least one halogen atom and / or optionally interrupted by at least one heteroatom, a C2-C6-alkylene group optionally containing at least one carbon-carbon double bond, optionally containing at least one carbonyl group and / or optionally containing at least one halogen atom 10 -alkylidene, C5-C6-alkylene ... 12 -cycloalkylene, C5-C6-cycloalkylene, wherein the alicyclic group is optionally fused to at least one alicyclic and / or at least one aromatic ring 15 -Cycloalkylidene, C7-C 20 -Arylalkylidene, C8-C 20 -aralkylene, a C6-C6-alkylene ring optionally fused to a further aromatic ring which may optionally contain at least one heteroatom 12 -arylene group, formula (B1-A), formula (B1-B), formula (B1-C) or formula (B1-D) wherein in formulae (B1-A), (B1-B) and (B1-C), each R' independently represents a linear C1-C4-alkyl group, a branched C3-C4-alkyl group, an aralkyl group or an aryl group, and "C*" represents a quaternary carbon atom at the position indicated as "Z" in formula (B), and wherein in formula (B1-D), each R' independently represents a straight-chain C1-C4-alkyl group, a branched C3-C4-alkyl group, each R" independently represents a straight-chain C1-C4-alkylene group, a branched C3-C4-alkylene group, each R"' independently represents H or a straight-chain C1-C3-alkyl group, s is 0 to 2, and each s1 is independently 0 or 1, and "*" represents a bond connecting "Z" to the aromatic ring in formula (B), R 5 and R 6 Each independently represents H, C1-C 18 -alkyl, C5-C6-cycloalkyl, C1-C5-alkenyl-, C1-C 18 -alkoxy, phenoxy, halogen atom, C6-C 18 -Aryl or C7-C 18 -aralkyl, p1 and q1 are each 1 to 4, and m2 represents the average number of repeating units, and m2 is 7 to 31.

13. The method according to any one of claims 9 to 12, characterized in that The homopolycarbonate has a terminal OH group content of 250 ppm to 2500 ppm.

14. The method according to any one of claims 9 to 13, characterized in that The homopolycarbonate comprises structural units of formula (Ba) wherein m2 represents the average number of repeating units and is 7 to 31.

15. Use of homopolycarbonate comprising structural unit (B) for preparing polycarbonate cocondensate comprising structural unit (A) in Each X in the structural unit (A) independently represents a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or an organic group having 1 to 18 carbon atoms, wherein the organic group having 1 to 18 carbon atoms may be linear, branched or cyclic, aromatic or non-aromatic, and may further contain heteroatoms such as halogen, oxygen, nitrogen, sulfur, silicon or phosphorus, R 1 and R 3 Each independently represents a monovalent hydrocarbon group, preferably C1-C 26 -alkyl, C7-C 26 Alkyl aryl or C7-C 26 -aralkyl, R 2 and R 4 each independently represents a hydrogen atom, an alkoxy group or a monovalent hydrocarbon group, preferably a hydrogen atom, a C1-C6-alkoxy group or a C1-C6-alkyl group, and p and q are each independently 1 or 2, preferably 1, and n represents the average number of repeating units, wherein n is 1 to 10, preferably 1 to 6, more preferably 1 to 4, wherein each Z in the structural unit (B) independently represents a single bond, -S(=O)2-, -C(=O)-, -O-, -S-, -S(=O)-, -CH(CN)-, a straight-chain or branched C1-C6-alkylene group optionally containing at least one carbonyl group, optionally containing at least one halogen atom and / or optionally interrupted by at least one heteroatom, a C2-C6-alkylene group optionally containing at least one carbon-carbon double bond, optionally containing at least one carbonyl group and / or optionally containing at least one halogen atom 10 -alkylidene, C5-C6-alkylene ... 12 -cycloalkylene, C5-C6-cycloalkylene, wherein the alicyclic group is optionally fused to at least one alicyclic and / or at least one aromatic ring 15 -Cycloalkylidene, C7-C 20 -Arylalkylidene, C8-C 20 -aralkylene, a C6-C6-alkylene ring optionally fused to a further aromatic ring which may optionally contain at least one heteroatom 12 -arylene group, formula (B1-A), formula (B1-B), formula (B1-C) or formula (B1-D) wherein in formulae (B1-A), (B1-B) and (B1-C), each R' independently represents a linear C1-C4-alkyl group, a branched C3-C4-alkyl group, an aralkyl group or an aryl group, and "C*" represents a quaternary carbon atom at the position indicated as "Z" in formula (B), and wherein in formula (B1-D), each R' independently represents a straight-chain C1-C4-alkyl group, a branched C3-C4-alkyl group, each R" independently represents a straight-chain C1-C4-alkylene group, a branched C3-C4-alkylene group, each R"' independently represents H or a straight-chain C1-C3-alkyl group, s is 0 to 2, and each s1 is independently 0 or 1, and "*" represents a bond connecting "Z" to the aromatic ring in formula (B), R 5 and R 6 Each independently represents H, C1-C 18 -alkyl, C5-C6-cycloalkyl, C1-C5-alkenyl-, C1-C 18 -alkoxy, phenoxy, halogen atom, C6-C 18 -Aryl or C7-C 18 -aralkyl, p1 and q1 are each 1 to 4, and m2 represents the average number of repeating units, and m2 is 7 to 31, The molar ratio of the structural unit (A) to the structural unit (B) in the polycarbonate co-condensate is 20:80 to 95:5.

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