Co (ester) carbonates stable to aqueous media and other chemicals and having good processability

Abstract

The present invention relates to co-(ester) carbonates made from specific units (A), (B) and (C) in specific amount proportions, wherein the structure and amount proportions render the co-(ester) carbonates excellent stability in aqueous media as well as to other chemicals such as rapeseed oil, lipid solutions or organic solvents. The invention also relates to a composition comprising a co-(ester) carbonate according to the invention, to molded parts comprising a co-(ester) carbonate according to the invention and to a method for producing a co-(ester) carbonate according to the invention.

Description

[0001] This invention relates to copoly(ester) carbonates made from specific units (A), (B), and (C) in specific proportions, wherein the structure and proportions result in excellent stability of the copoly(ester) carbonate in aqueous media and to other chemicals (e.g., rapeseed oil, lipid solutions, or organic solvents). The invention also relates to compositions comprising the copoly(ester) carbonate of this invention, molded parts comprising the copoly(ester) carbonate of this invention, and methods for producing the copoly(ester) carbonate of this invention.

[0002] Polyesters, polycarbonates, and polyester carbonates are known to possess good properties regarding mechanical properties, heat distortion resistance, and weather resistance. Depending on the monomers used, each polymer class exhibits some key characteristics specific to that material. For example, polycarbonates particularly exhibit good mechanical properties, while polyesters generally demonstrate better chemical resistance. Depending on the monomers selected, polyester carbonates possess the properties of both of these polymer classes. Depending on the reactants selected, (co)polycarbonates, (co)polyesters, or copoly(ester)carbonates can be formed.

[0003] While aromatic polycarbonates or polyesters generally exhibit good performance characteristics, they are deficient in terms of aging and weather resistance. For example, absorption of ultraviolet light can cause these thermoplastics to yellow, and optionally become brittle. Aliphatic polycarbonates and polyester carbonates have better performance in these aspects, particularly better aging and / or weather resistance and better optical properties (e.g., transmittance). A disadvantage of aliphatic polycarbonates or polyester carbonates is generally their low glass transition temperature. Therefore, it is advantageous to use alicyclic alcohols as (comonomers) because they can typically slightly increase the glass transition temperature.

[0004] Oh et al. described polyesters prepared by reacting cyclohexanedicarboxylate and isosorbide in Macromolecules 2013, 46, 2930-2940. However, a drawback of these polymers is their interaction with hot water. These polymers absorb moisture and swell, significantly altering their polymer morphology. For example, transparency is completely lost. This greatly limits the potential applications of such polyesters. Im et al. found that the polyesters prepared by cyclohexanedicarboxylate and isosorbide described above undergo structural deformation upon contact with hot water (Im et al., RSC Adv. 2017, 7, 6315, Structural deformation phenomenon of synthesized poly(isosorbide-1,4-cyclohexanedicarboxylate) in hot water). It can be shown (see the comparative examples of the present invention) that copolymers (esters) carbonates based on isosorbide and cyclohexanedicarboxylate (e.g., described in EP3026074) also interact with water in principle. The change in polymer morphology in hot water is equally significant. Therefore, such polymers can only be used in limited ways in humid and hot climates.

[0005] Terephthalic acid-based polyesters are known to have high water resistance or hydrolysis resistance. However, Duchateau et al., in Biomacromolecules, 2008, 9, 3090-3097 (Incorporation of Isosorbide into Poly(butylene terephthalate via solid state polymerization), pointed out that polyesters made from isosorbide, terephthalic acid, and other diols have insufficient thermal stability. For example, these polyesters have shown significant weight loss in TGA measurements below 300°C. However, thermal stability is crucial for traditional polycarbonate applications. Furthermore, systems containing aromatic monomers also exhibit poor resistance to ultraviolet radiation.

[0006] EP2033981 describes polycarbonates made from isosorbide and cyclic diols. These polycarbonates have good mechanical properties, but their stability to aqueous media is limited in certain cases (see comparative examples of the present invention). Their glass transition temperatures are also above 100°C. However, to obtain good mechanical properties, a certain proportion of cyclic diols derived from fossil fuels is required. This proportion is typically greater than 20%, which reduces the proportion of bio-based monomers in the polymer backbone. Furthermore, these aliphatic polycarbonates cannot be processed at high temperatures without decomposition. This makes these particular aromatic polycarbonates unsuitable for processing and use like conventional polycarbonates. Conventional aromatic polycarbonates are typically processed at injection molding temperatures approximately 150°C higher than their glass transition temperatures. For polycarbonates prepared from approximately 70% isosorbide and 30% cyclohexanediol, the glass transition temperature is approximately 120°C, thus the processing temperature is relatively close to the decomposition range. This indicates that these polymers are limited in processing, in addition to their poor tolerance to solvents and optional other chemicals.

[0007] EP2478031 describes polyesters made from isosorbide, terephthalic acid, and other monomers (e.g., cyclohexanediol). These materials are extremely stable in aqueous media. However, these polyesters contain aromatic dicarboxylic acids, particularly terephthalic acid. Similarly, the use of aromatic structural units makes such materials unsuitable for external applications without appropriate protection (e.g., coatings).

[0008] Copolycarbonates and copolyester carbonates made from isosorbide and long-chain aliphatic diols or acids are known. For example, Kamps et al. described them in Macromolecules, 2019, 52, 3187, and US8273849 and EP2203501. However, a common drawback of these materials is their limited transparency. They are generally cloudy or opaque. Furthermore, these polymers exhibit high melt viscosity (see comparative examples of the present invention). High melt viscosity is detrimental to processability. In particular, high melt viscosity is unfavorable because the processing temperatures of aliphatic polycarbonates or polyester carbonates are not as high as those of their corresponding aromatic polycarbonates and polyester carbonates. Opaque or severely cloudy materials can only be used, or not at all, in limited or unsuitable applications such as lighting, or in pharmaceutical applications such as Luer connectors, stopcock valves, and other intravenous infusion connectors. Therefore, such aliphatic polymers cannot simply meet the requirements of traditional applications of aromatic polycarbonates. In addition, such polymers have low surface hardness (see comparative examples of the present invention). This makes them easily scratched and unsuitable for uncoated external applications.

[0009] EP2840102 describes polymers with low water absorption, good heat distortion resistance, and low-temperature toughness. These polycarbonates or copoly(ester)carbonates contain certain oligomeric carbonate blocks derived from diols or certain blocks derived from low-polyesters. Polyester carbonates containing long-chain diols or diacids with more than 12 carbon atoms are not specifically described. Furthermore, properties such as hot water storage behavior are not discussed. Example 19 of EP2840102 describes a copoly(ester)carbonate containing isosorbide, which contains ester blocks derived from terephthalic acid and cyclohexanediethanol. However, this polymer contains only a low proportion (<50 mol%) of the bio-based monomer (isosorbide) and has a low glass transition temperature (approximately 100°C).

[0010] Existing technologies offer solutions for improving the specific properties of polycarbonates or copoly(ester)carbonates. However, there is currently a lack of guidance on how to simultaneously and positively influence multiple properties. In particular, there is a lack of guidance on how to provide polymer structures that can overcome at least one of the aforementioned drawbacks and simultaneously replace existing aromatic polycarbonates in terms of processing performance.

[0011] Based on existing technology, the object of the present invention is to overcome at least one, and preferably several, of the aforementioned disadvantages. In particular, the object of the present invention is to provide a polymer structure with high stability to water, especially hot water. Simultaneously, this polymer structure should possess inherent weather resistance, particularly inherent UV resistance, thus making it suitable for external applications. Furthermore, a polymer structure with high scratch resistance should also be provided. Preferably, this polymer structure should also possess high chemical resistance, such as resistance to solvents and / or lipid solutions, and particularly preferably, high resistance to fats, especially rapeseed oil. Therefore, the provided polymer structure preferably simultaneously possesses high hot water resistance, good fat resistance, and good processability, particularly preferably with processability comparable to conventional aromatic polycarbonates (e.g., based on bisphenol A), as well as high scratch resistance. This polymer structure preferably also possesses inherent weather resistance.

[0012] Another preferred object of the present invention is to provide a polymer structure with good thermal stability. In particular, the object is to have thermal stability comparable to that of conventional aromatic polycarbonates. Furthermore, it is also preferable to provide a polymer structure capable of meeting the same application requirements as conventional polycarbonates. Therefore, this polymer structure should preferably also have a high glass transition temperature, particularly above 110°C, preferably above 120°C. This preferably requires the polymer structure to have a sufficiently high molecular weight to provide suitable mechanical properties, particularly good ductility when subjected to unnotched impact testing at room temperature. "A polymer with a sufficiently high molecular weight" is preferably understood here to mean a polymer with a relative solution viscosity greater than 1.20, preferably 1.21 to 1.65, more preferably 1.22 to 1.63, particularly preferably 1.23 to 1.62, and very particularly preferably 1.26 to 1.55, which in each case is measured using an Ubbelohde viscometer at 25°C in dichloromethane at a concentration of 5 g / L.

[0013] The present invention achieves at least one, preferably all, of the above objectives. Surprisingly, it has been found that polyester carbonates or polycarbonates obtained from 1,4:3,6-disodehydrated hexitol, specific alicyclic diols, particularly TCD-diethanol, and long-chain diols or long-chain dicarboxylic acids achieve at least one, preferably all, of the above objectives.

[0014] According to the present invention, a copoly(ester) carbonate is provided, comprising units (A), (B), (C), optionally (D), and optionally units other than (A), (B), (C), and (D), wherein (A) (B) Where each r and each s are independent numbers from 0 to 4, and each R 1 Each of the following structures is independent of the other: (R1A), (R1B), (R1C), or (R1D). (R1A) Where a is 0 or 1, (R1B) Where b is 0 or 1, (R1C) (R1D) In equations (R1A) to (R1D), the positions marked with "~" represent (CH2) as shown in equation (B). r Group or (CH2) s The location of the group, and (C) Among them, two t and R 2 Independently both 0 and both 1, and each R 2 Each group is an aliphatic group having 16 to 44 carbon atoms, and optionally contains one or more double bonds. (D) In at least some cases, there are direct connections between units (A), (B), (C), and optional (D), as well as optional units other than (A), (B), (C), and (D). When there is a direct connection between at least two units selected from (A), (B), (C), and optional (D), the position marked with "*" in units (A), (B), (C), and (D) is connected to the position marked with "#" in the unit, except in the following cases: When t in equation (C) is 0, the two units (C) are not directly connected to each other. When t in equation (C) is 0, there is no direct connection between element (C) and element (D), and The two units (D) are not directly connected to each other. The copoly(ester) carbonate contains 4 to 25 mol% of unit (B), 2 to 14 mol% of unit (C), 0 to 5 mol% of unit (D) and at least 55 mol% of unit (A), wherein the mol% data is based on the total molar amount of units (A), (B), (C), optional (D) and optional units other than (A), (B), (C) and (D).

[0015] Surprisingly, the polymer structure of the present invention achieves excellent performance even with predominantly aliphatic structural units. As described in the prior art, almost all amorphous aliphatic polyesters or copoly(ester) carbonates exhibit insufficient water resistance. Conversely, polyesters composed of aromatic structural units such as terephthalic acid in terms of the acid component generally possess water resistance. However, these polyesters are inadequate in terms of UV resistance and weather resistance. The polymer structure of the present invention surprisingly provides a copoly(ester) carbonate that combines good water resistance (preferably hot water resistance), good resistance to aliphatic solutions and organic solvents, good processability, and good UV or weather resistance. Similarly, the surface hardness of the copoly(ester) carbonate of the present invention is superior to that of bisphenol A-based polycarbonates and prior art structures. A particular advantage provided by this is that the polymer of the present invention is suitable for external applications. In particular, no additional coating is required due to its high scratch resistance. This is especially surprising because copoly(ester) carbonates containing the same monomer structural units but with different proportions of these units do not possess these properties. Similarly, copoly(ester) carbonates that have one less unit than the specific units (A), (B), and (C) do not possess this property condition.

[0016] However, the aforementioned properties of the copoly(ester) carbonates of the present invention make them suitable for applications such as in the pharmaceutical industry (contact with corrosive drugs). Furthermore, although they are essentially composed of aliphatic structural units, they possess a high glass transition temperature of at least 110°C, preferably 120°C. In addition, they also exhibit good processability. Their melt viscosity allows them to be processed well, for example, during injection molding, without decomposition (due to good thermal stability). This means their processability is almost comparable to that of conventional aromatic polycarbonates, thus meeting at least the needs of conventional applications of aromatic polycarbonates. Simultaneously, the copoly(ester) carbonates of the present invention can also have a high proportion of bio-based monomers, since at least units (A) and (C) are obtainable from bio-based monomers. Similarly, the copoly(ester) carbonates of the present invention have sufficiently high molecular weights to ensure adequate mechanical properties, such as ductility when subjected to unnotched impact testing at room temperature. In particular, the copoly(ester) carbonates of the present invention can also be manufactured in a manner that does not require treatment of harmful raw materials, particularly phosgene. This makes the copoly(ester) carbonates of the present invention and their preparation methods both ecologically and economically advantageous.

[0017] This invention relates to "copoly(ester) carbonates". The brackets here are preferably understood to mean that the invention covers "copolycarbonates or copolyester carbonates". Those skilled in the art can identify whether the polymers of this invention contain ester groups. This depends particularly on whether the two "t"s in unit (C) are 1 (in which case polycarbonate is formed) or 0 (in which case copolyester carbonate is formed).

[0018] The copoly(ester) carbonate of the present invention comprises unit (A), wherein (A), The positions marked with # and * indicate the location of unit (A) incorporated into the copoly(ester) carbonate. Preferably, formula (A) is represented by formula (A*). (A*), Where n is the average number of repeating units, and the positions marked with # and * are the same as those for (A). More preferably, n is greater than 1. Particularly preferably, n is greater than 1 to 200, and more preferably, n is greater than 1 to 100. This means that unit (A) can also exist in the form of blocks of multiple directly interconnected units (A). Particularly preferably, the copoly(ester) carbonate of the present invention has at least two units (A) directly connected to each other.

[0019] In this invention, the term "average number of repeating units" is known to those skilled in the art. Those skilled in the art know how to determine this parameter. In particular, this parameter can be determined using Maldi-TOF, GPC, and / or... 1 H NMR and / or13 CNMR measurements. Specifically, in 1 H NMR and / or 13 In C NMR, the "end groups" of possible blocks (i.e., when blocks containing direct connections between identical units are present, the block preferably has end groups at its starting and ending points that are directly connected to units different from the related units) can provide information about the average number of repeating units. Clearly, the number of repeating units (i.e., blocks preferably containing identical units) in a polymer molecule is also variable. This number also varies depending on the polymer chain. This results in an "average" number of repeating units. Furthermore, those skilled in the art know that the average number of repeating units is affected by the molar ratio between the various structures. For example, in the copoly(ester) carbonate of the present invention, structures present in a high molar percentage are more likely to connect with other structures of the same type than structures present only in a low molar percentage. Those skilled in the art know that the upper limit of the average number of repeating units is so high that all structures of the same type condense to form a single block.

[0020] Preferably, (A) or (A*) is selected from at least one of structures (A1), (A2), and (A3), wherein (A1) (A2) (A3) The positions marked with # and * are the same as those defined for formula (A), and corresponding parentheses are present for formula (A*). Very particularly preferably, (A) or (A*) is represented by formula (A1) (optionally with corresponding parentheses for formula (A*)). Those skilled in the art will understand that these units are derived from / formulated from 1,4:3,6-didehydrohexitol. 1,4:3,6-didehydrohexitol is typically selected from isomannitol, isosorbide, and isosorbide. It can be a bio-based structural unit, thereby possessing all the advantages of bio-based monomers and polymers derived therefrom (e.g., better sustainability, due to availability from renewable raw materials). Particularly preferably, unit (A) or (A*) consists of unit (A1). Very particularly preferably, unit (A) or (A*) is bio-based.

[0021] Furthermore, the copoly(ester) carbonate of the present invention comprises unit (B), wherein (B), Where each r and each s is independently a number from 0 to 4, preferably 0 to 3, particularly preferably 0 to 2, very particularly preferably 0 or 1, and each R 1 Each of the following structures is independent of the other: (R1A), (R1B), (R1C), or (R1D). (R1A) Where a is 0 or 1, preferably 0. (R1B) Where b is 0 or 1, preferably 0. (R1C) (R1D) In equations (R1A) to (R1D), the positions marked with "~" represent (CH2) as shown in equation (B). r Group or (CH2) s The positions of the groups, and those marked with # and * are the positions where unit (B) is incorporated into the copoly(ester) carbonate.

[0022] Obviously, there can be more than one type of unit (R1A), (R1B), (R1C) or (R1D) in unit (B).

[0023] Preferably, unit (B) is represented by equation (B*). (B*), Where m is the average of the repeating units, and the positions marked with # and * are the same as those for (B). Particularly preferred is that unit (A) is also unit (A*). Particularly preferred is that m is greater than 1. Very particularly preferred is that m is greater than 1 to 80, particularly preferred is that m is greater than 1 to 50, and very particularly preferred is that m is greater than 1 to 10.

[0024] Preferably, in unit (B) or (B*), each r and each s is a number from 0 to 2 independently of each other, very particularly preferably 0 or 1, and each R 1 The structures are independent of each other and belong to equation (R1A). Particularly preferably, r and s in equations (B) and (B*) are 1, and R in equations (B) and (B*) is... 1 It is the structure of formula (R1A). Very particularly preferably, unit (B) or (B*) is represented by unit (B1), wherein... (B1), The positions marked with # and * are the same as those defined for (B). Very particularly preferably, unit (B) consists of unit (B1). Those skilled in the art will understand that unit (B1) is derived from TCD-diethanol (also known as TCD alcohol, tricyclodecanediethanol, or [8-(hydroxymethyl)-3-tricyclo[5.2.1.02,6]decyl]ethanol). TCD-diethanol typically exists as a mixture of isomers. Up to 32 isomers can be present. Depending on the polymerization conditions, the initial number and / or type of isomers in the monomer may also vary in the final polymer. Particularly preferably, unit (B1) is obtained from a mass-balanced TCD-diethanol. This is particularly advantageous as it reduces the CO2 footprint of the copoly(ester) carbonate of the present invention.

[0025] The copoly(ester) carbonate of the present invention further comprises unit (C), wherein (C) Among them, two t and R 2 Independently both 0 and both 1, and each R 2 Each R is an aliphatic group having 16 to 44 carbon atoms, optionally containing one or more double bonds, and wherein the positions marked with # and * are the positions where the unit (C) is incorporated into the copoly(ester) carbonate. Particularly preferably, each R 2 Each group is an aliphatic group having 17 to 44 carbon atoms, particularly preferably 18 to 44 carbon atoms, particularly preferably 19 to 44 carbon atoms, particularly preferably 20 to 44 carbon atoms, particularly preferably 21 to 44 carbon atoms, particularly preferably 22 to 43 carbon atoms, particularly preferably 23 to 42 carbon atoms, particularly preferably 24 to 41 carbon atoms, particularly preferably 25 to 40 carbon atoms, particularly preferably 26 to 39 carbon atoms, particularly preferably 27 to 38 carbon atoms, particularly preferably 28 to 37 carbon atoms, particularly preferably 29 to 37 carbon atoms, particularly preferably 30 to 37 carbon atoms, particularly preferably 31 to 37 carbon atoms, particularly preferably 32 to 37 carbon atoms, and very particularly preferably 33 to 37 carbon atoms.

[0026] In this invention, unless otherwise defined, the term "aliphatic" or "aliphatic group" refers to a hydrocarbon group that does not contain an aromatic unit. However, the group may have one or more double bonds. Furthermore, the group may have one or more rings. These rings may be fused together (i.e., one or more carbon atoms may belong to two rings), or interconnected by, for example, alkylene or alkylidene groups. The one or more rings may have one or more double bonds. However, it should be noted that, according to this invention, aromatic rings are not included within the definition of "aliphatic." Furthermore, the one or more rings or the aliphatic group itself may be interrupted by one or more heteroatoms. However, this is less preferred.

[0027] In this invention, unless otherwise stated, the term "alkyl" or "alkyl group" preferably refers to an alkane structure with one hydrogen atom removed. The alkyl group according to the invention can be straight-chain or branched. It is saturated, therefore there are 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, etc. The choice of these structures may be limited if the definition of the number of carbon atoms differs within the context of this invention.

[0028] In this invention, unless otherwise stated, the term "alkylene" or "alkylene group" preferably refers to a bridged alkane structure in which two hydrogen atoms are 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 not necessarily adjacent. The alkylene can be straight-chain or branched. It is saturated. If the alkylene has only one carbon atom, it is a methylene (-CH2-) bonded to the rest of the molecule by two single bonds. Preferably, the alkylene group includes 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 Examples of alkylene compounds include pentylene, 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, and 1-ethyl-2-methylpropylene. The choice of these structures may be limited if the definition of the number of carbon atoms differs in this invention. Furthermore, according to this invention, the alkylene group may optionally have at least one carbonyl group, optionally at least one halogen atom, and / or optionally be interrupted by at least one heteroatom. 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-, etc. However, according to the invention, the above structures are less preferred. Furthermore, the invention also refers to "cycloalkylene". In this case, the above description applies, and the group may also have one or more rings. These rings may be fused together (i.e., one or more carbon atoms may belong to two rings), or interconnected by, for example, alkylene groups. The one or more rings may have one or more double bonds. Furthermore, the one or more rings or aliphatic groups themselves may be interrupted by one or more heteroatoms. However, this is less preferred.

[0029] In this invention, unless otherwise stated, the term "alkylidene" or "alkylidene group" preferably refers to a bridged alkane structure in which two hydrogen atoms have been removed from the same carbon atom. The alkylidene group may optionally have at least one carbon-carbon double bond, optionally at least one carbonyl group, and / or optionally at least one halogen atom. Preferably, the alkylidene group includes isopropylidene, n-propylidene, isoheptidene, etc.

[0030] In this invention, unless otherwise stated, the term "aryl group" preferably refers, in each case independently, to a linear, cyclic, or branched alkyl group that is mono-, di-, or poly-substituted with an aryl group. In this invention, unless otherwise stated, the term "aryl" preferably refers to an aromatic hydrocarbon group. Examples of "aryl" include phenyl, o-tolyl, p-tolyl, m-tolyl, naphthyl, phenanthryl, or anthracene.

[0031] In this invention, unless otherwise stated, the term "alkoxy group" preferably refers to a linear, cyclic, or branched alkyl group connected to an oxygen atom by a single bond (-OR). Alkoxy groups according to the invention preferably have 1 to 6 carbon atoms. Particularly preferred, 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, cyclopentoxy, n-hexyloxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1,2-dimethylpropoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy, 1-ethyl-2-methylpropoxy, or 1-ethyl-2-methylpropoxy. The choice of these structures may be limited if the definition of the number of carbon atoms is different in this invention.

[0032] Based on the above definitions, those skilled in the art will understand other definitions not explicitly mentioned above.

[0033] According to a preferred embodiment of the present invention, R in formula (C) 2 It is represented by the following formula (R2A): (R2A) Wherein Y is a bridging structure selected from alkylene groups having 1 to 4 carbon atoms, alkylidene groups having 1 to 4 carbon atoms, and cycloalkylene groups having 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms, wherein the cycloalkylene group optionally comprises one or more double bonds and / or optionally is fused to one or more other cycloalkylene groups, wherein the one or more other cycloalkylene groups optionally each have one or more double bonds. R, which is adjacent to the bridging structure 11 The groups can be attached to any position in the bridging structure, and Each R 11 Each of the above can be an alkylene group having 1 to 12 carbon atoms or an alkylidene group having 1 to 12 carbon atoms, provided that the structure of formula (R2A) contains 16 to 44 carbon atoms, and that the position marked with "~" in formula (R2A) is (O) as shown in formula (C). t The position of each group.

[0034] Particularly preferably, formula (R2A) is represented by one of formulas (R2Aa), (R2Ab), (R2Ac), or (R2Ad), wherein (R2Aa), (R2Ab), (R2Ac) and (R2Ad), Each R 11 The definition of each "~" is the same as in (R2A). The rings in formula (R2Ac) optionally contain one or two double bonds, and each ring in formula (R2Ad) optionally contains one or two double bonds independently of each other. Furthermore, it is particularly preferred that R in formula (C) 2 It is represented by a mixture of at least two different formulas (R2Aa), (R2Ab), (R2Ac), and (R2Ad). This also includes mixtures of different groups belonging to the same formula (e.g., two groups belonging to formula (R2Aa)).

[0035] As mentioned above, the rings in formulas (R2Ac) and / or (R2Ad) can each contain one or two double bonds. This typically does not include the formation of aromatic rings. As explained further below, when R in formula (C) 2 When a mixture contains at least two different formulas (R2Aa), (R2Ab), (R2Ac), and (R2Ad), it may also contain a low proportion of an aromatic bridging structure Y of formula (R2A). However, this is less preferred.

[0036] Particularly preferred, each R in formula (R2A) and / or formula (R2Aa), (R2Ab), (R2Ac) or (R2Ad) 11Each is an alkylene group having 1 to 10 carbon atoms, provided that the structure in formula (R2A) and / or formula (R2Aa), (R2Ab), (R2Ac) or (R2Ad) contains 16 to 44 carbon atoms.

[0037] Similarly, preferably, unit (C) consists of R 2 The groups described by (R2A), (R2Aa), (R2Ab), (R2Ac), and / or (R2Ad) have 21 to 44 carbon atoms. Similarly, the preferred unit (C) is composed of R... 2 The groups described by (R2A), (R2Aa), (R2Ab), (R2Ac), and / or (R2Ad) have 17 to 44 carbon atoms, more preferably 18 to 44 carbon atoms, more preferably 19 to 44 carbon atoms, more preferably 20 to 44 carbon atoms, more preferably 21 to 44 carbon atoms, more preferably 22 to 43 carbon atoms, more preferably 23 to 42 carbon atoms, more preferably 24 to 41 carbon atoms, more preferably 25 to 40 carbon atoms, more preferably 26 to 39 carbon atoms, more preferably 27 to 38 carbon atoms, more preferably 28 to 37 carbon atoms, more preferably 29 to 37 carbon atoms, more preferably 30 to 37 carbon atoms, more preferably 31 to 37 carbon atoms, more preferably 32 to 37 carbon atoms, and very particularly preferably 33 to 37 carbon atoms. Those skilled in the art can apply this limited number of carbon atoms to the above-mentioned provisions regarding the number of carbon atoms.

[0038] Especially preferred are the different R values ​​in formulas (R2A) and / or (R2Aa), (R2Ab), (R2Ac), or (R2Ad). 11 They have different numbers of carbon atoms.

[0039] Very particularly preferably, the unit (C) according to the invention is obtained by the condensation of a dimer fatty acid and / or a dimer glycol obtained by the reduction of a dimer fatty acid.

[0040] As is known to those skilled in the art, dimer fatty acids are mixtures of different acids. Their main structures are as follows: Fully hydrogenated compounds are preferred here. Dimeric fatty acids are typically mixtures. They are formed by the condensation of various unsaturated fatty acids. For this purpose, fatty acids containing conjugated double bonds (conjugated acids) react with (one or more) other unsaturated fatty acids. Conjugated linoleic acid is particularly preferred for this purpose. This reaction is usually carried out via a Diels-Alder addition reaction, thereby generating a partially unsaturated C6 ring. Thus, the dimer fatty acid initially contains at least partially one or more double bonds. In addition to the dimer, the mixture of dimer fatty acids may also contain trimers and monomers of fatty acids. Oleic acid and linoleic acid are particularly preferred to react. The double bonds contained in the dimer fatty acid are usually hydrogenated.

[0041] To obtain a dimerized glycol from the reduction of a dimerized fatty acid, the acid group is reduced to the corresponding alcohol group. This is a method known to those skilled in the art. It should be noted that for the unit of formula (C), the R in the dimerized fatty acid and the dimerized glycol obtained from the reduction of the dimerized fatty acid... 2 The total number of carbon atoms in the functional groups differs, even when using the same dimer fatty acid in both cases. If the dimer fatty acid contains 36 carbon atoms, then R... 2 It contains 34 carbon atoms because the carbon atoms of the two acid groups appear once in formula (C) as (C=O) groups, while the (C=O) groups present, for example, in one of units (A) or (B) appear once (at the ends of the units marked with *). If a dimer fatty acid containing 36 carbon atoms is reduced to a dimer glycol, then the R of unit (C) 2 It contains 36 carbon atoms. The diol reacts with a carbonyl source, and the carbon atom of the (C=O) group shown in unit (C) originates from this carbonyl source. It is obvious how this can be applied to all units contained in unit (C).

[0042] The unit (C) according to the invention is particularly preferably obtained by condensation of a dimer fatty acid having 36 carbon atoms and / or a dimer glycol having 36 carbon atoms obtained by reduction of a dimer fatty acid.

[0043] Dimeric fatty acids are commercially available, for example, under the trade names Pripol 1009, Pripol 1006, Pripol 1025, Radicacid 0960, Radicacid 0975, Radicacid 0976, Radicacid 0977, Radicacid 0978, and Unidyme 18. Corresponding dimer glycols are known, for example, under the trade names Pripol 2030 and 2033. As described above, Pripol and Pripol derivatives are obtained via oligomerization of unsaturated fatty acids (preferably C18 acids). The dimerization reaction yields a mixture of monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids. The monofunctional compounds are typically separated by distillation. This usually yields a mixture of 80% difunctional compounds and 20% trifunctional compounds, which is further purified by distillation to enrich the difunctional compounds. Saturated compounds are obtained by hydrogenation. Pripol, as a dimer fatty acid or dimer glycol, is a purified mixture mainly containing a diacid or glycol having 36 carbon atoms.

[0044] The unit (C) can be a bio-based unit, thereby possessing all the advantages of bio-based monomers and polymers derived therefrom (e.g., better sustainability, as they can be made from renewable raw materials). Very particularly preferred is that the unit (C) is bio-based.

[0045] Furthermore, the copoly(ester) carbonate of the present invention may contain units of formula (D). (D) The positions marked with # and * indicate the position of unit (D) incorporated into the copoly(ester) carbonate. The content of unit (D) in the copoly(ester) carbonate of the present invention is at most 5 mol% (wherein the mol% data is based on the total molar amount of units (A), (B), (C), optional (D), and optional units other than (A), (B), (C), and (D)). Particularly preferably, the content of unit (D) in the copoly(ester) carbonate of the present invention is 0 to 5 mol%, more preferably 0 to 3 mol%, more preferably 0.01 to 2 mol%, and most preferably 0 mol%.

[0046] Unit (D) can be formed by condensation of cyclohexanedicarboxylic acid into the copoly(ester) carbonate of the present invention. However, it has been found that an excessively high molar proportion of unit (D) in the copoly(ester) carbonate of the present invention leads to a decrease in its hot water resistance. Therefore, it is preferable to keep the proportion of unit (D) in the copoly(ester) carbonate of the present invention as low as possible.

[0047] The copoly(ester) carbonate of the present invention has at least a partial direct link between units (A), (B), (C), optionally (D), and optionally units other than (A), (B), (C), and (D). Therefore, those skilled in the art will understand that this forms a polymer having carbonate groups and optionally also ester groups. According to the invention, the term "direct link" is preferably understood to mean that the units are directly linked to each other. This is preferably achieved by the absence of other units between the units. For example, unit (A) can be directly linked to unit (B) by directly linking the position marked with * in unit (A) to the position marked with # in unit (B) to form a carbonate group.

[0048] According to the provisions of the present invention, when there is a direct connection between at least two units selected from (A), (B), (C) and optional (D), the position marked with "*" in units (A), (B), (C), and (D) is connected to the position marked with "#" in the unit, except in the following cases: When t in equation (C) is 0, the two units (C) are not directly connected to each other. When t in equation (C) is 0, there is no direct connection between element (C) and element (D), and The two units (D) are not directly connected to each other.

[0049] The phrase "at least two units" here should be understood to also include direct connections between more units, such as direct connections (A)-(B)-(C), (A)-(A)-(B)-(C), (A)-(C)-(B)-(B), etc. These direct connections achieve the performance characteristics described above according to the present invention.

[0050] The exceptions, namely why there is no direct connection between the two units (C) when t in formula (C) is 0, no direct connection between unit (C) and unit (D) when t in formula (C) is 0, and no direct connection between the two units (D), are obvious to those skilled in the art. The unit (C) or unit (D) when t in formula (C) is 0 is obtained by incorporating a dicarboxylic acid into a copoly(ester) carbonate. This necessarily forms an ester group. According to the invention, other corresponding connections between these units are not possible.

[0051] In principle, positions marked with # or * indicate the location where the respective unit or structure is incorporated into the copoly(ester) carbonate of the present invention. Obviously, these positions do not represent "groups" but are merely for simplification. For clarity: for example, when unit (A) is directly connected to unit (B), the position marked with * in unit (A) is the oxygen atom next to the position marked with # in unit (B), thus forming a carbonate group. Those skilled in the art will understand that this applies to all other units. Since the present invention relates to copoly(ester) carbonate, units (A), (B), (C), and optionally (D) form carbonate groups in direct connection with each other (and optionally form ester groups when unit (C) is incorporated into the direct connection and t is 0 in each case, or when unit (D) is present).

[0052] However, in the copoly(ester) carbonate of the present invention, it is specified that only the positions marked with # and the positions marked with * are directly connected. Furthermore, in the copoly(ester) carbonate of the present invention, when t in formula (C) is 0, there is no direct connection between the two units (C). Similarly, when t in formula (C) is 0, there is no direct connection between unit (C) and unit (D). Furthermore, there is no direct connection between the two units (D). When there is a direct connection between two units (A) or two units (B), it can also be represented by unit (A*) or (B*), where the integers n and m represent the number of direct connections.

[0053] Particularly preferably, the copoly(ester) carbonate of the present invention has a direct link between units (A) and (C), while both t values ​​in unit (C) are simultaneously 0. This means that it is preferable to have a group in which a diehydrohexitol group is directly linked via an ester group to a group, for example, derived from a dimer fatty acid.

[0054] Preferably, the copoly(ester) carbonate of the present invention comprises a structure of unit (ABC). (ABC) Where n is 1, the average of the repeating units, or the preferred scheme described above; R 1 r and s have the definition of (B*) among all preferred solutions and combinations; m is 1, the average of the repeating units, or the preferred solution mentioned above; t and R 2The definition of unit (C) is provided, encompassing all preferred embodiments and combinations of possibilities. Those skilled in the art will understand that this unit (ABC) can be included in the polymer, and other structures may optionally be present in the copoly(ester) carbonate of the present invention. Furthermore, the sequence of monomers is preferably not fixed. In the present invention, this is preferably a copoly(ester) carbonate with random incorporation of monomers. In this case, only a low proportion of structures (ABC) may be present in the copoly(ester) carbonate of the present invention, as these reflect the specific sequence of the individual structural units. Through specific method variations, differences in reactivity, or the use of specific catalysts, monomers may not be randomly incorporated; this is also preferably included in the universal unit (ABC). Preferably, the copoly(ester) carbonate of the present invention comprises the following structures, wherein there is a direct connection of formulas (A)-(B), (A)-(C), (C)-(B), (A)-(B)-(C), (A)-(C)-(B), (A*)-(B), (A*)-(C), (A*)-(B)-(C), (A*)-(C)-(B), (A*)-(B*), (B*)-(C), (A*)-(B*)-(C), (A*)-(C)-(B*), or any mixture of two or more of these structures.

[0055] The copolycarbonate of the present invention preferably contains units (ABC*). (ABC*) Where n is 1, the average of the repeating units, or the preferred scheme described above; R 1 r and s have the definition of (B*) among all preferred solutions and combinations; m is 1, the average of the repeating units, or the above preferred solutions; R 2 The definition of unit (C) is given in all preferred schemes and combinations possible; o represents 1, the average of repeating units, or a number from 1 to 5. Those skilled in the art will understand that the above structure (ABC*) can be derived from units (A), (B), and (C), where t in equation (C) is 1.

[0056] Particularly preferred is the copoly(ester) carbonate comprising unit (AC) of the present invention. (AC), Where n is 1 or the average of repeated units, R 2 The definition of unit (C) is given in all preferred schemes and combinations possible.

[0057] Particularly preferably, the copoly(ester) carbonate of the present invention comprises units (ABC) and (AC).

[0058] Particularly preferably, the copoly(ester) carbonate of the present invention is characterized in that it comprises at least 80% by weight, more preferably at least 85% by weight, and even more preferably at least 90% by weight, units (A), (B), (C), and optionally (D). Therefore, the copoly(ester) carbonate of the present invention preferably contains only small amounts of structures other than units (A), (B), and (C). However, it should be noted here that end groups of the copoly(ester) carbonate of the present invention are preferably excluded. The copoly(ester) carbonate of the present invention may also contain functional units other than carbonate groups and optionally ester groups. However, more preferably, the copoly(ester) carbonate of the present invention does not contain functional units other than carbonate groups and / or optionally ester groups. Here, end groups are also excluded. This means that up to 20% by weight, preferably up to 15% by weight, especially preferably up to 10% by weight (which consists of units different from units (A), (B), (C) and optionally (D)) are preferably derived from other diols or dicarboxylic acids, which in turn produce carbonate or ester groups by incorporation into the copoly(ester) carbonate.

[0059] According to the present invention, the copoly(ester) carbonate comprises 4 to 25 mol% of unit (B), 2 to 14 mol% of unit (C), 0 to 5 mol% of unit (D), and at least 55 mol% of unit (A), wherein the mol% data is based on the total molar amount of units (A), (B), (C), optional (D), and optional units other than (A), (B), (C), and (D). Those skilled in the art will understand that these amounts may also refer to all preferred embodiments and combinations thereof associated with each unit (A), (B), and (C).

[0060] Particularly preferred, the copoly(ester) carbonate of the present invention comprises - 4 to 25 mol%, particularly preferred 5 to 20 mol%, also preferred 7 to 18 mol%, especially preferred 10 to 15 mol%, or very especially preferred 8 to 12 mol% of unit (B), - 2 to 14 mol%, particularly preferably 3 to 12 mol%, more preferably 3.5 to 7.0 mol% of unit (C), and - At least 55 mol%, particularly preferably at least 65 mol%, also preferably at least 75 mol%, and very particularly preferably at least 80 mol% of unit (A). The mole % data is based on the total mole quantity of units (A), (B), (C), optional (D), and optional units different from (A), (B), (C), and (D).

[0061] These molar ratios ensure that the copoly(ester) carbonate of the present invention has one or more, preferably all of the following properties: high glass transition temperature, good optical properties (e.g., transparency), good mechanical properties (e.g., ductility at room temperature), high thermal stability, good resistance to water media, good resistance to hot water, good resistance to grease, good resistance to lipid solutions, and good resistance to solvents.

[0062] Those skilled in the art can determine the molar amounts of the different units in the copoly(ester) carbonate of the present invention. Preferably, these can be determined by... 1 ¹H-NMR spectroscopy determination. Based on the preparation method of the copoly(ester) carbonate, it can be assumed that almost all monomers used react to form the polymer. In particular, embodiments of the present invention show that the molar ratio of monomers is also present in the resulting polymer. This means that those skilled in the art can influence the molar ratio of the resulting units in the polymer by adjusting the molar ratio of the monomers used. Also preferably, a specific molar percentage in the copoly(ester) carbonate of the present invention is determined by… 1 ¹H-NMR spectroscopy determination. This method is known to those skilled in the art. For example, the copoly(ester) carbonate can be dissolved in CDCl₃, and the corresponding peaks of the structural units can be identified. Depending on the compound used, those skilled in the art can assign these peaks to the corresponding structural units. The ratio and proportion can be determined by integration. On the other hand, the molar percentage according to the invention can also be determined by the molar amount and ratio of the monomers used. In this case, it must be assumed that all monomers are completely incorporated into the copoly(ester) carbonate at the same ratio. Therefore, those skilled in the art can also pre-set this ratio.

[0063] The molar ratio of the resulting units in the polymer can also be determined retrospectively through complete hydrolysis. For example, the polymer can be hydrolyzed with sodium methoxide under reflux conditions. The resulting solution can then be acidified and concentrated to dryness. The residue is soluble in a suitable organic solvent, and the contained compounds can be analyzed by HPLC. Appropriate calibration and measurement methods using HPLC are known to those skilled in the art.

[0064] In addition to units (A), (B), (C), and optional (D), the copoly(ester) carbonate of the present invention may also contain other units different from (A), (B), (C), and optional (D). Preferably, the copoly(ester) carbonate of the present invention comprises unit (E), wherein... (E) In this formula, both z and x are independently and simultaneously 0 or simultaneously 1, and each x is independently a linear or branched alkylene group having 4 to 20, preferably 5 to 15 carbon atoms (which may optionally be interrupted by at least one heteroatom), a cycloalkylene group having 4 to 20, preferably 5 to 15 carbon atoms (which may optionally be interrupted by at least one heteroatom, and wherein the cycloalkylene group may optionally contain multiple rings), or an aromatic group, and the positions marked with # and * are the positions where unit (E) is incorporated into the copoly(ester) carbonate, except where the two units (E) are not directly connected to each other when z in formula (E) is 0. Those skilled in the art will understand that the unit (E) must be different from unit (D). Particularly preferably, x in unit (E) is an aromatic group, particularly preferably an aromatic group containing up to 20 carbon atoms, which may optionally be interrupted by at least one heteroatom. Particularly preferably, x in unit (E) has the structure of formula (x1), (x2), or (x3). (x1), (x2), (x3), In equations (x1), (x2), and (x3), the positions marked with "~" correspond to (O) shown in equation (E). z The positions of the respective groups. Particularly preferably, x in formula (E) is a structure of formula (x1), (x2) or (x3), where both z are simultaneously 0.

[0065] The copoly(ester) carbonate of the present invention can also be branched. This can be achieved by using polyfunctional alcohols, such as glycerol, trimethylolpropane or tris(4-hydroxyphenyl)ethane (THPE), or polyfunctional carboxylic acids such as citric acid, trimellitic acid, etc., in the synthesis of the copoly(ester) carbonate of the present invention.

[0066] The copoly(ester) carbonate of the present invention preferably contains up to 25 mol%, more preferably up to 20 mol%, even more preferably up to 10 mol%, and very particularly preferably up to 5 mol% of aromatic groups. However, optional end groups are preferably excluded. Preferably, the content of unit (E) in the copoly(ester) carbonate of the present invention is up to 20 mol%, more preferably up to 10 mol%, and very particularly preferably up to 5 mol%. Particularly preferably, x in unit (E) has the structure of formula (x1), (x2) or (x3), wherein both z are simultaneously 0.

[0067] The copoly(ester) carbonate of the present invention preferably comprises end groups. These end groups are preferably generated by using a chain terminator during the synthesis process. Monofunctional acids or alcohols, especially phenols, can be used as chain terminators. Particularly preferably, the copoly(ester) carbonate of the present invention comprises end groups of formula (Z). (Z), Each R 7 Each q is independently hydrogen, an alkyl group having 1 to 34 carbon atoms, an aralkyl group having 7 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms, or a -COO-R' group, wherein R' is an alkyl group having 1 to 34 carbon atoms, an aralkyl group having 7 to 34 carbon atoms, or an aryl group having 6 to 34 carbon atoms, and each q is independently 1 to 5. The position marked with # indicates the position where unit (Z) is incorporated into the copoly(ester) carbonate. Obviously, the position marked with # is connected to the position marked with * in other units. Therefore, the copoly(ester) carbonate of the present invention can have aromatic units as end groups. They do not adversely affect the inherent weather resistance of the polymer because their concentration is very low. Particularly preferably, q in unit (Z) is 1. Also preferably, R 7 The end group is hydrogen or -COOCH3, with hydrogen being particularly preferred. Particularly preferably, the copoly(ester) carbonate of the present invention comprises end groups selected from formula (Z), -OH, -COOH, and any mixtures of these groups. Those skilled in the art will understand that formula (Z) particularly comprises phenyl ester end groups and / or phenyl carbonate end groups. Free acid end groups or OH end groups can be reduced, for example, by using epoxy groups or urethane derivatives. Such reactions are known to those skilled in the art.

[0068] Preferably, at least 50 mol% of the copoly(ester) carbonate of the present invention, more preferably at least 70 mol%, and very particularly preferably at least 75 mol%, is bio-based. For the purposes of this invention, the term "bio-based" means that the relevant chemical compound was available and / or obtained from renewable and / or sustainable raw materials at the date of application, and / or preferably from such renewable and / or sustainable raw materials. Renewable and / or sustainable raw materials are preferably understood as raw materials that are regenerated through natural processes at a rate commensurate with their degradation rate (see CEN / TS 16295:2012). This term is used in particular to distinguish raw materials produced from fossil raw materials (also known as petroleum-based raw materials). Whether a raw material is bio-based or petroleum-based can be determined by measuring the carbon isotope in the raw material, since the carbon isotope C in fossil raw materials is... 14 The relative amount is low. For example, this can be measured according to ASTM D6866-18 (2018), ISO 16620-1 to -5 (2015), or DIN SPEC 91236 2011-07. According to the invention, the term "bio-based" is preferably used for those with a concentration greater than 0.1 × 10⁻⁶. -12 More preferably greater than 0.2×10 -12 A very special preference is given to values ​​greater than 0.3 × 10⁻⁶. -12 C 14 Compounds with high isotopic content. In particular, isosorbide and dimer fatty acids or dimerized glycols obtained from the reduction of dimer fatty acids are bio-based.

[0069] The relative solution viscosity of the copoly(ester) carbonate of the present invention is preferably greater than 1.20, more preferably 1.21 to 1.65, more preferably 1.22 to 1.63, more preferably 1.23 to 1.62, also preferably 1.26 to 1.55, and most preferably 1.26 to 1.40. According to the present invention, the relative solution viscosity (ηrel; also called eta rel) is preferably determined at 25°C using an Ubbelohde viscometer in dichloromethane at a concentration of 5 g / L. Those skilled in the art are familiar with methods for determining relative solution viscosity using an Ubbelohde viscometer. According to the present invention, this is preferably performed according to DIN 51562-3; 1985-05. Here, the flow time of the copoly(ester) carbonate to be tested is measured using an Ubbelohde viscometer to subsequently determine the viscosity difference between the polymer solution and its solvent. For this purpose, the Ubbelohde viscometer is first calibrated using measurements of pure solvents dichloromethane, trichloroethylene, and tetrachloroethylene (always at least 3 measurements, up to 9 measurements are performed). A formal calibration is then performed using dichloromethane. The polymer sample was then weighed and dissolved in dichloromethane, and the flow time of this solution was measured three times. The average flow time was corrected using the Hagenbach correction method, and the relative solution viscosity was calculated.

[0070] This preferred relative solution viscosity ensures that the copoly(ester) carbonate of the present invention possesses sufficient mechanical properties. "Sufficient" here refers to its mechanical properties, particularly its ductility in an unnotched impact test at room temperature, which is comparable to that of conventional aromatic polycarbonates.

[0071] The invention also provides compositions comprising all of the above-described configurations, preferred embodiments, and combinations thereof of copoly(ester) carbonate and one or more additives. Preferably, the compositions of the invention are thermoplastic. The invention also provides molded articles comprising all of the above-described configurations, preferred embodiments, and combinations thereof of copoly(ester) carbonate or the compositions of the invention.

[0072] 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 (e.g., hydrolysis stabilizers, heat aging stabilizers, UV stabilizers and transesterification inhibitors), flow promoters, phase compatibilizers, dyes and pigments, impact modifiers, and fillers and reinforcing agents. Similarly, the compositions of the present invention may also contain other thermoplastics besides the copoly(ester) carbonates of the present invention. Other thermoplastics are preferably materials based on polystyrene, styrene copolymers, aromatic polyesters (e.g., polyethylene terephthalate (PET), PET-cyclohexanediol copolymer (PETG), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), cyclic polyolefins, polybutylene succinate (PBS), polyacrylates or copolyacrylates and polymethacrylates or copolymethacrylates, such as polymethyl methacrylate or copolymethyl methacrylate (e.g. PMMA), polyamides (preferably polyamide 6 (PA6) and polyamide 6.6 (PA 6.6)) and copolymers with styrene (e.g., transparent polystyrene-acrylonitrile (PSAN)), thermoplastic polyurethanes, cyclic olefin-based polymers (e.g., TOPAS®, a commercially available product of Ticona), and mixtures of said polymers.

[0073] The compositions of the present invention can be prepared, for example, by mixing copoly(ester) carbonate with other components in a known manner, and then performing melt compounding and melt extrusion in commonly used equipment such as an internal kneader, extruder, and twin-screw extruder at a temperature preferably between 220°C and 300°C. In this application, this process is generally referred to as compounding.

[0074] The molded parts of this invention can be produced by, for example, injection molding, extrusion, and blow molding. Another processing method is to produce molded parts by deep drawing using pre-produced sheet or film.

[0075] A compound of formula (I) is known, wherein (I), Where R 2 As defined in equation (C), including all preferred options and combinations of preferred options, each R 6 Each x is independently hydrogen, an alkyl group having 1 to 34 carbon atoms, an aralkyl group having 7 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms, or a -COO-R' group, wherein R' is an alkyl group having 1 to 34 carbon atoms, an aralkyl group having 7 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms, and each x is independently 1 to 5.

[0076] More preferably, R in equation (I) 2This refers to the formula (R2A) described in detail above, or the formulas (R2Aa), (R2Ab), (R2Ac), or (R2Ad) mentioned above. Preferably, x = 1, and R... 6 It is hydrogen or -COOCH3. Very particularly preferred is that formula (I) represents a diphenyl ester of a dimer fatty acid.

[0077] This intermediate has been found to be particularly suitable for the production of copoly(ester) carbonates according to the invention. Particularly preferred is the use of compounds of formula (I) to produce the copoly(ester) carbonates of the invention. Also preferred is the use of compounds of formula (I) via a melt transesterification reaction to produce the copoly(ester) carbonates, preferably the copoly(ester) carbonates of the invention. Melt transesterification reactions are known to those skilled in the art. For example, see Schnell, “Chemistry and Physics of Polycarbonates”, Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964. In the melt transesterification method, the starting materials undergo transesterification in a melt using a suitable catalyst and optionally other additives.

[0078] In particular, the process can be carried out without solvents and / or phosgene. The compounds of formula (I) can be generated in situ during the melt transesterification process, and / or can be generated in advance and added directly as reactants to the melt transesterification process.

[0079] Preferably, the compound of formula (I) can be derived from a mixture of diacids and HOOC-R. 2 -COOH is obtained by reacting it with a diaryl carbonate of formula (Ia): (Ia), Where x and R 6 The definition is the same as that in equation (I).

[0080] On the other hand, the present invention relates to a method for producing the copoly(ester) carbonate of the present invention, comprising at least a reaction of 1,4:3,6-disodehydrated hexitol, a diol of formula (B2), a diol selected from formula (C2), a compound of formula (C3), or any mixture thereof, and a carbonyl source, wherein... (B2) Where each r and each s are independent numbers from 0 to 4, and each R 1 The structures (R1A), (R1B), (R1C), and (R1D) are independent of each other. (R1A) Where a is 0 or 1, (R1B) Where b is 0 or 1, (R1C) (R1D) In equations (R1A) to (R1D), the positions marked with "~" represent (CH2) as shown in equation (B2). r Group or (CH2) s The location of the group, and (C2), (C3) Where each R in equations (C2) and (C3) 2 Each of the above is an aliphatic group having 16 to 44 carbon atoms, which optionally contains one or more double bonds; each R in formula (C3) 3 Each can be hydrogen, chlorine, or -OR'', where R'' is an aliphatic or aromatic group.

[0081] Preferably, the copoly(ester) carbonate of the present invention can be produced by the method of the present invention in all preferred embodiments and combinations thereof. Also preferably, the copoly(ester) carbonate of the present invention is produced by the method of the present invention.

[0082] Those skilled in the art can assign the structures of units (B2), (C2), and (C3) to units (B) and (C), respectively, and understand the corresponding configurations, preferred embodiments, and combinations of preferred embodiments. Formula (C3) is particularly preferred to include compounds of formula (I), wherein R... 3 For -OR''. This covers all preferred options and combinations of preferred options.

[0083] The method of the present invention preferably includes the reaction of the following components: - Up to 25 mol%, particularly preferred 5 to 20 mol%, also preferred 7 to 18 mol%, especially preferred 10 to 15 mol%, or very especially preferred 8 to 12 mol% of compound (B2), - 2 to 14 mol%, particularly preferred 3 to 12 mol%, very particularly preferred 3.5 to 8.0 mol% of the compound (C2) and / or (C3), and - At least 55 mol%, particularly preferably at least 65 mol%, also preferably at least 75 mol%, and very particularly preferably at least 80 mol% of 1,4:3,6-didehydrohexyl alcohol. The molar percentage data are based on the total molar amounts of 1,4:3,6-disodehydrated hexitol, compound (B2), and compounds (C2) and / or (C3).

[0084] According to the present invention, up to 5 mol%, preferably up to 3 mol%, and more preferably 0.01 to 2 mol% of cyclohexanedicarboxylic acid can also be used as a reactant. This will generate unit (D). However, this method is less preferred for the reasons described above.

[0085] The carbonyl source used in the method of the present invention can preferably be selected from phosgene and diaryl carbonates of formula (Ia). (Ia) Each R 6 Each x is independently hydrogen, an alkyl group having 1 to 34 carbon atoms, an aralkyl group having 7 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms, or a -COO-R' group, wherein R' is an alkyl group having 1 to 34 carbon atoms, an aralkyl group having 7 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms, and each x is independently 1 to 5.

[0086] As is known to those skilled in the art, copoly(ester) carbonates can generally be prepared by melt transesterification (see above) or by interfacial methods. Interfacial methods are also known in principle from, for example, H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964, p. 33 and thereafter, and Polymer Reviews, Vol. 10, “Condensation Polymers by Interfacial and Solution Methods”, Paul W. Morgan, Interscience Publishers, New York 1965, Chapter VIII, p. 325; therefore, the basic conditions are familiar to those skilled in the art.

[0087] The methods of this invention encompass both approaches. This should be indicated, in particular, by the statement "includes at least a reaction." Depending on the chosen method, it is preferable to react a diol, optionally an ester, preferably a compound of formula (I), with a diaryl carbonate of formula (Ia) (molten transesterification reaction). Alternatively, phosgene reacts with a diol and an acid at the interface of one or more organic solvents and water.

[0088] Therefore, those skilled in the art should also understand that, depending on the method used, the compound of formula (C3) exists in the form of an ester, a free acid, or an acyl chloride.

[0089] Catalysts used in such methods are familiar to those skilled in the art. Attached Figure Description

[0090] Figure 1 The copolycarbonate of Example 17 of the present invention in CDCl3 1 H-NMR spectrum Figure 2 The copolycarbonate of Example 16 of the present invention in CDCl3 1 H-NMR spectrum.

[0091] The following implementation schemes describe specific combinations of preferred implementation schemes. These contents have been covered in the overview text above.

[0092] Implementation Scheme 1: A copoly(ester) carbonate containing units (A), (B), (C), optional (D), and optional units different from (A), (B), (C), and (D), wherein (A) (B) Where each r and each s are independent numbers from 0 to 4, and each R 1 Each of the following structures is independent of the other: (R1A), (R1B), (R1C), or (R1D). (R1A) Where a is 0 or 1, (R1B) Where b is 0 or 1, (R1C) (R1D) In equations (R1A) to (R1D), the positions marked with "~" represent (CH2) as shown in equation (B). r Group or (CH2) s The location of the group, and (C) Among them, two t and R 2 Independently both 0 and both 1, and each R 2 Each group is an aliphatic group having 16 to 44 carbon atoms, and optionally contains one or more double bonds. (D) In at least some cases, there are direct connections between units (A), (B), (C), optional (D), and optional units other than (A), (B), (C), and (D). When there is a direct connection between at least two units selected from (A), (B), (C), and optional (D), the position marked with "*" in units (A), (B), (C), and (D) is connected to the position marked with "#" in the unit, except in the following cases: When t in equation (C) is 0, the two units (C) are not directly connected to each other. When t in equation (C) is 0, there is no direct connection between element (C) and element (D), and The two units (D) are not directly connected to each other. The copoly(ester) carbonate contains 4 to 25 mol% of unit (B), 2 to 14 mol% of unit (C), 0 to 5 mol% of unit (D) and at least 55 mol% of unit (A), wherein the mol% data is based on the total molar amount of units (A), (B), (C), optional (D) and optional units other than (A), (B), (C) and (D).

[0093] Implementation Scheme 2: The copoly(ester) carbonate according to Implementation Scheme 1, characterized in that it contains any one of claims 2 to 10.

[0094] Implementation Scheme 3: The copoly(ester) carbonate according to Implementation Scheme 1 or 2, characterized in that the copoly(ester) carbonate has direct connections between at least two units (A).

[0095] Implementation Scheme 4: The copoly(ester) carbonate according to any one of Implementation Schemes 1 to 3, characterized in that unit (A) or (A*) is composed of unit (A1).

[0096] Implementation Scheme 5: The copoly(ester) carbonate according to any one of Implementation Schemes 1 to 4, characterized in that unit (A) or (A*) is bio-based.

[0097] Implementation Scheme 6: The copoly(ester) carbonate according to any one of Implementation Schemes 1 to 5, characterized in that each r and each s in unit (B) is independently 0 to 4, preferably 0 to 3, particularly preferably 0 to 2, and very particularly preferably 0 or 1.

[0098] Implementation Scheme 7: A copoly(ester) carbonate according to any one of Implementation Schemes 1 to 6, characterized in that each r and each s in unit (B) is independently a number from 0 to 2, particularly preferably 0 or 1, and each R 1 Each is an independent structure of the formula (R1A).

[0099] Implementation Scheme 8: The copoly(ester) carbonate according to any one of Implementation Schemes 1 to 7, characterized in that unit (B) or (B*) is composed of unit (B1).

[0100] Implementation Scheme 9: The copoly(ester) carbonate according to any one of Implementation Schemes 1 to 8, characterized in that each R in formula (C) 2 The aliphatic groups are independently of each other and have 17 to 44 carbon atoms, more preferably 18 to 44 carbon atoms, more preferably 19 to 44 carbon atoms, more preferably 20 to 44 carbon atoms, more preferably 21 to 44 carbon atoms, more preferably 22 to 43 carbon atoms, more preferably 23 to 42 carbon atoms, more preferably 24 to 41 carbon atoms, more preferably 25 to 40 carbon atoms, more preferably 26 to 39 carbon atoms, more preferably 27 to 38 carbon atoms, more preferably 28 to 37 carbon atoms, more preferably 29 to 37 carbon atoms, more preferably 30 to 37 carbon atoms, more preferably 31 to 37 carbon atoms, more preferably 32 to 37 carbon atoms, and especially preferably 33 to 37 carbon atoms.

[0101] Implementation Scheme 10: A copoly(ester) carbonate according to any one of Implementation Schemes 1 to 9, characterized in that unit (C) is present at least twice in the copoly(ester) carbonate, and in this case, R in unit (C) 2 It represents at least two different expressions: (R2Aa), (R2Ab), (R2Ac), and (R2Ad).

[0102] Implementation Scheme 11: The copoly(ester) carbonate according to any one of Implementation Schemes 1 to 10, characterized in that unit (C) is obtained by condensation of dimer fatty acids and / or dimer glycols obtained by reduction of dimer fatty acids.

[0103] Implementation Scheme 12: The copoly(ester) carbonate according to any one of Implementation Schemes 1 to 11, characterized in that the unit (C) is obtained by condensation of a dimer fatty acid having 36 carbon atoms and / or a dimer glycol having 36 carbon atoms obtained by reduction of a dimer fatty acid.

[0104] Implementation Scheme 13: The copoly(ester) carbonate according to any one of Implementation Schemes 1 to 12, characterized in that unit (C) is bio-based.

[0105] Implementation Scheme 14: The copoly(ester) carbonate according to any one of Implementation Schemes 1 to 13, characterized in that the content of unit (D) in the copoly(ester) carbonate of the present invention is 0 to 5 mol%, particularly preferably 0 to 3 mol%, more preferably 0.01 to 2 mol%, and very particularly preferably 0 mol.

[0106] Implementation Scheme 15: The copoly(ester) carbonate according to any one of Implementation Schemes 1 to 14, characterized in that the copoly(ester) carbonate comprises units (ABC).

[0107] Implementation Scheme 16: The copoly(ester) carbonate according to any one of Implementation Schemes 1 to 15, characterized in that the copoly(ester) carbonate comprises unit (AC).

[0108] Implementation Scheme 17: The copoly(ester) carbonate according to any one of Implementation Schemes 1 to 16, characterized in that at least 80% by weight, more preferably at least 85% by weight, and even more preferably at least 90% by weight, of the copoly(ester) carbonate is composed of units (A), (B), (C) and optional (D).

[0109] Implementation Scheme 18: The copoly(ester) carbonate according to any one of Implementation Schemes 1 to 17, characterized in that the copoly(ester) carbonate does not contain any functional units other than carbonate groups and / or optional ester groups.

[0110] Implementation Scheme 19: The copoly(ester) carbonate according to any one of Implementation Schemes 1 to 18, characterized in that the copoly(ester) carbonate comprises - 4 to 25 mol%, particularly preferred 5 to 20 mol%, also preferred 7 to 18 mol%, especially preferred 10 to 15 mol%, or very especially preferred 8 to 12 mol% of unit (B), - 2 to 14 mol%, particularly preferred 3 to 12 mol%, very especially preferred 3.5 to 8.0 mol% of unit (C), and - At least 55 mol%, particularly preferably at least 65 mol%, also preferably at least 75 mol%, and very particularly preferably at least 80 mol% of unit (A). The mole % data is based on the total mole quantity of units (A), (B), (C), optional (D), and optional units different from (A), (B), (C), and (D).

[0111] Implementation Scheme 20: The copoly(ester) carbonate according to any one of Implementation Schemes 1 to 19, characterized in that the copoly(ester) carbonate has end groups of formula (Z).

[0112] Implementation Scheme 21: The copoly(ester) carbonate according to any one of Implementation Schemes 1 to 20, characterized in that, in formula (Z), q = 1 and R 7 It is hydrogen or -COOCH3.

[0113] Implementation Scheme 2: The copoly(ester) carbonate according to any one of Implementation Schemes 1 to 21, characterized in that x in unit (E) is a structure of formula (x1), (x2) or (x3), wherein both z are simultaneously 0. Example

[0114] Materials used: Cyclohexanedicarboxylic acid: Cyclohexane-1,4-dicarboxylic acid; CAS 1076-97-7, 99%; Tokyo Chemical Industries, Japan, abbreviated as CHDA.

[0115] Diphenyl carbonate: Diphenyl carbonate, 99.5%, CAS 102-09-0; Acros Organics (DPC), Belgium. 4-Dimethylaminopyridine: 4-Dimethylaminopyridine; ≥ 98.0%; pure; CAS 1122-58-3; Sigma-Aldrich, Munich, Germany, abbreviated as DMAP Isosorbide: Isosorbide (CAS: 652-67-5), 99.8%, Polysorb PS A; Roquette Frères (62136, Leytrem, France); abbreviated as ISB Lithium hydroxide monohydrate (CAS: 1310-66-3); >99.0%; Sigma-Aldrich Terephthalic acid (CAS: 100-21-0); 99%+%, Acros Organics, Belgium Tricyclodecanediethanol (CAS: 26896-48-0); mixture of isomers; OQ Chemicals, 40789 Monheim, Germany Dimer fatty acid: Pripol 1009 (CAS: 68783-41-5); Mn approx. 570 g / mol; hydrogenated, Croda, 41334 Nettal, Germany Sodium 2-ethylhexanoate (CAS: 19766-89-3); 97%; Sigma-Aldrich Munich, Germany Dimer glycol: Pripol 2030 (CAS: 147853-32-5); Croda, Nettal, 41334, Germany Methyl tert-butyl ether (CAS: 1634-04-4); Azelis Deutschland GmbH, 53757 Saint-Augustin, Germany, abbreviated as MTBE Methyl ethyl ketone (CAS: 78-93-3); Azelis Deutschland GmbH, 53757 St. Augustine, Germany, abbreviated as MEK Isopropyl alcohol (CAS: 67-63-0); Azelis Deutschland GmbH, 53757 St. Augustine, Germany Zeolite 4A: Sodium aluminum silicate (CAS: 1318-02-1) Polycarbonate based on isosorbide and cyclohexanediol (30:70) (CAS: 25037-45-0): can be produced according to EP2033981 A1; abbreviated as PC1 2-Butyl-2-ethylpropane-1,3-diol (CAS: 115-84-4); 99.0%; Sigma-Aldrich, Munich, Germany, abbreviated as BEPD Toluene (CAS: 108-88-3); 99%; Sigma-Aldrich, Munich, Germany 2,2,4-Trimethylpentane, or isooctane (CAS: 540-84-1); 99.5%; Sigma-Aldrich, Munich, Germany Lipid solution: SmofKabiven central infusion emulsion; Qualitative and quantitative composition: 1000 mL contains: 508 mL of electrolyte-containing amino acid solution, 302 mL of 42% glucose solution, and 190 mL of lipid emulsion. This corresponds to the following total composition: alanine 7.1 g, arginine 6.1 g, glycine 5.6 g, histidine 1.5 g, isoleucine 2.5 g, leucine 3.8 g, lysine acetate 3.4 g, methionine 2.2 g, phenylalanine 2.6 g, proline 5.7 g, serine 3.3 g, taurine 0.5 g, threonine 2.2 g, tryptophan 1.0 g, tyrosine 0.20 g, valine 3.1 g, calcium chloride (calculated as calcium chloride dihydrate) 0.2 g. 8g, sodium glycerophosphate (hydrate) 2.1g, magnesium sulfate (calculated as magnesium sulfate heptahydrate) 0.61g, potassium chloride 2.3g, sodium acetate (calculated as sodium acetate trihydrate) 1.7g, zinc sulfate (calculated as zinc sulfate heptahydrate) 0.0066g, glucose (calculated as glucose monohydrate in the European Pharmacopoeia) 127g, refined soybean oil (European Pharmacopoeia) 11.4g, medium-chain triglycerides 11.4g, refined olive oil 9.5g, and fish oil rich in omega-3 fatty acids 5.7g.

[0116] Analysis method: Solution viscosity: The relative solution viscosity (ηrel; also known as etarel) was determined at 25°C using an Ubbelohde viscometer in dichloromethane at a concentration of 5 g / L. The determination was performed according to DIN 51562-3; 1985-05. The flow time of the polyester carbonate under test was measured using the Ubbelohde viscometer to subsequently determine the viscosity difference between the polymer solution and its solvent. For this purpose, the Ubbelohde viscometer was first calibrated using measurements with pure solvents dichloromethane, trichloroethylene, and tetrachloroethylene (always at least 3 measurements, up to 9 measurements). Formal calibration was then performed using dichloromethane. The polymer sample was then weighed, dissolved in dichloromethane, and the flow time of this solution was measured three times. The average flow time was corrected using the Hagenbach correction method, and the relative solution viscosity was calculated.

[0117] Determination of glass transition temperature: The glass transition temperature was determined by dynamic differential scanning calorimetry (DSC) under a nitrogen atmosphere at a heating rate of 10 K / min, in accordance with DIN EN ISO 11357-1:2009-10 and ISO 11357-2:2013-05 standards. The glass transition temperature (Tg) was measured at the inflection point during the second heating process.

[0118] Hot water resistance test: The polymer sample was refluxed and boiled in deionized water for 4 hours, followed by visual inspection. If the sample was not completely deformed, it was boiled again under the same conditions for 4 hours, and the results were visually evaluated again.

[0119] Deformation and fracture behavior under unnotched impact stress (Charpy impact test): At room temperature, impact bending tests were conducted using a Polymerphysik-built drop hammer impact testing machine to test cases with or without a 2 mm V-notch. The drop hammer weighed 1.86 kg, the mandrel diameter was 20 mm, and the contact surface diameter was 62 mm.

[0120] Chemical resistance test (lipid solution, isooctane:toluene 1:1): At least two flat rods, each 80 mm long, 4 mm high, and 10 mm wide, are clamped in a circular template with a radius of 99 cm. This corresponds to 2% external fiber strain. The rod surfaces are contaminated through continuous immersion in the test medium or complete immersion. The time until fracture is measured. Measurements are stopped after 5–14 days.

[0121] Shear rheology measurement: The measurements were performed on a TA Instruments ARES-G2 rheometer. An isothermal oscillation frequency sweep test was conducted at 200°C within the range of 0.001 Hz to 10000 Hz to derive the complex viscosity.

[0122] Scratch resistance test: To determine scratch resistance, flat bars of 80 x 10 x 4 mm or sheets of 60 x 60 x 2 mm were injection molded at 245°C to 260°C. Measurements were performed using an Erichsen 318 test pen equipped with a No. 1 test tip (tungsten carbide ball) and a spring with a measuring range of 0-10 N. The test pen was clamped to a travel bracket so that a set force was applied to the test tip. The bracket, including the test pen, was set to 1 N and rolled 10 mm over the surface to be tested. If no scratches were found during visual inspection by two inspectors, the force was increased by 0.5 N and the test was repeated. This process was repeated until visible scratches appeared on the polymer. The maximum force applied was recorded.

[0123] 1 H NMR spectrum: Measurements were performed on a Bruker Avance NEO 600 MHz NMR spectrometer. Measurements were conducted in CDCl3. The analyte contained isosorbide, tricyclodecanediethanol, and dimerized glycol or dimerized fatty acid. The following steps were used to assess the molar ratios between these components: The individual characteristic signals of each monomer are integrated, and the number of protons in each case is "normalized".

[0124] The following examples illustrate the evaluation of polymers according to Examples 17 (containing dimer glycol) and 16 (containing dimer fatty acids) of the present invention. Reference should be made here. Figure 1 and 2 .

[0125] For polymers based on monomer compositions consisting of isosorbide, TCD-dimethylethanol, and dimerized glycol (in this example based on Pripol 2030; see Example 17 of the invention, see Example 17 of the invention), Figure 1 The molar ratio is calculated as follows: For isosorbide content, a signal of 5.3 ppm to 4.5 ppm was used.

[0126] The integral value is set to "40", corresponding to the 4 protons of isosorbide.

[0127] The contents of TCD-diethanol and dimerized glycol were determined by signals ranging from 4.2 to 3.8. This region contains four protons of isosorbide and two -CH2- groups (-O-CH2-) of TCD-diethanol and two CH2- groups (-O-CH2-) of dimerized glycol. Therefore, this region also contains four protons of both TCD-diethanol and dimerized glycol.

[0128] The relative proportion of TCD-diethanol can be determined in the region of 2.3 to 1.9 ppm. There are no dimerized glycol protons in this region. This region corresponds to approximately 4 protons in TCD-diethanol. Therefore, 1 proton corresponds to 5.281 / 4 = 1.32. In the signal range of 1.0 to 0.65 ppm, there are 8.3 H atoms in the dimerized glycol and 1 H atom in TCD-diethanol. For the dimerized glycol component, this corresponds to 6.527 – 1.32 = 5.207, therefore 5.207 / 8.3 = 0.627. The relative proportion of TCD-diethanol to dimerized glycol is therefore 1.32:0.627. These proportions are used to weight the integral in the region of 4.2 to 3.8 ppm. After deducting the isosorbide protons, the adjusted integral for the dimerized glycol and TCD-diethanol protons is as follows: 47.086 – 40 = 7.086. The integrals are weighted at a ratio of 1.32:0.627. This yields an adjusted integral of 4.80 for TCD-diethanol and 2.28 for dimerized glycol. 1H NMR spectroscopy can also be used to calculate the composition of Example 16 of the present invention, which is based on a polymer obtained from isosorbide, tricyclodecanediethanol and dimer fatty acids.

[0129] Isosorbide content was determined using a signal ranging from 5.3 to 4.5 ppm. The integral value was set to "40", corresponding to 4 protons of isosorbide.

[0130] The content of tricyclic decanediethanol was determined by a signal ranging from 4.2 to 3.8 ppm. This region contains four protons of isosorbide and two -CH2- groups (-O-CH2-) of tricyclic decanediethanol. Therefore, this region also contains four protons of tricyclic decanediethanol.

[0131] The content of dimer fatty acids was calculated by integrating the signal of 0.95-0.6 ppm.

[0132] This region contains two CH3 groups of the dimer fatty acid and one proton of tricyclodecanediethanol. The four protons of tricyclodecanediethanol correspond to 4.931 (the integral value from 4.2 to 3.8 ppm is 44.931 – 40 (four protons of isosorbide) = 4.931). 4.931 / 4 = 1.23, which corresponds to the intensity of one proton of tricyclodecanediethanol. Subtracting this signal intensity from the integral value from 0.95 to 0.6 ppm yields the intensity of the CH3 groups of the dimer fatty acid: 4.058 – 1.23 = 2.828. Preparation of reactants: Preparation of diphenyl fatty acid dimer 107.32 g (0.501 mol) of diphenyl carbonate, 142.5 g (0.250 mol) of dimer fatty acid, and 0.0025 g (100 ppm) of 4-dimethylaminopyridine were pre-loaded into a multi-necked flask. The mixture was inertized by evacuation and purging four times with nitrogen. The mixture was heated to 160 °C via a metal bath. Carbon dioxide was released from above approximately 140 °C. Once the volumetric flow rate decreased, the temperature was increased to a maximum of 240 °C. During this process, phenol was separated by distillation. Once gas release ceased, a vacuum was applied, and the pressure was gradually reduced to approximately 1 mbar. The reaction was continued in this manner until no more phenol was released.

[0133] Preparation of tetrabutylphosphonium acetate 483.38 g of tetrabutylphosphonium hydroxide aqueous solution (40% by mass) was pre-loaded into an Erlenmeyer flask. Approximately 40 mL (0.7 mol) of pure acetic acid was then added dropwise until the pH reached approximately 6. Water was removed by distillation at 80 °C and <0.2 mbar. 200 mL of isopropanol, zeolite (4A) for drying, and 0.5 g of activated carbon for purification were added, and the mixture was allowed to stand in a sealed container for at least 12 hours. The product was then filtered and concentrated to a minimum volume at 80 °C and <0.2 mbar. Upon cooling, the product crystallized at approximately 40 °C in an airtight container. Color: Light brown.

[0134] Preparation of diphenyl cyclohexane-1,4-dicarboxylate 200 g (1.1616 mol) CHDA, 500 g (2.334 mol) DPC and 0.14 g (200 ppm) DMAP were pre-loaded into a 1-liter three-necked flask equipped with a distillation bridge. The flask was evacuated and inertized with N2 four times to minimize the oxygen content.

[0135] After melting at 180°C, CO2 is released. Once the volumetric flow rate decreases, the temperature is raised to a maximum of 240°C (phenol distills out above approximately 220°C). After gas release stops (color changes), the pressure is reduced to approximately 50 mbar while continuing distillation. The container is purged with N2 and the receiving flask is replaced. The pressure is now further reduced. The middle fraction is DPC, which can also be removed. The third fraction (<5 mbar, 240°C) is the major product. It is distilled until the bottom product is concentrated to approximately 50 mL, and the white product is collected after cooling. A faint phenolic odor is detectable.

[0136] Recrystallization was performed using a hexane / ethyl acetate mixture (approximately 2:1), with activated carbon (2-5% of the total mass) used. The product obtained after vacuum filtration was a fine, bright white crystal.

[0137] Preparation of diphenyl terephthalate 428.44 g (2.00 mol) of DPC, 162.81 g (0.98 mol) of terephthalic acid, and 0.15 g (250 ppm) of DMAP were pre-loaded into a 1-liter three-necked flask equipped with a distillation bridge. The flask was evacuated and inertized with N2 four times to minimize the oxygen content.

[0138] Heating the suspension at 180°C releases CO2. Once the volumetric flow rate decreases, raise the temperature to a maximum of 260°C (to distill phenol above approximately 220°C). After gas release ceases (the clear solution now turns orange), reduce the pressure to approximately 50 mbar while distillation continues. Purge with N2 and replace the receiving flask. Now further reduce the pressure. The middle fraction, DPC, can be removed in the same manner. Once no more distillate is produced, discard the bottom product.

[0139] After cooling, the crude product was mechanically pulverized as finely as possible and boiled in acetone under reflux (the time depends on the amount of acetone used and the degree of pulverization). The acetone / diphenyl terephthalate mixture was then cooled to 10°C and filtered. The deep yellow mother liquor was discarded, and the pure, fine-crystalline product was further dried. The product has a pearly luster and is white with a slight yellow tinge.

[0140] Example (Comparative; PC1) Example 2: Polyester carbonate made from 67% isosorbide and 33% CHDA (comparison) 51.60 g (0.300 mol) of cyclohexane-1,4-dicarboxylic acid, 89.49 g (0.612 mol) of isosorbide, 192.90 g (0.900 mol) of diphenyl carbonate, 300 ppm DMAP (based on the total mass of all reactants), and 0.365 g (1.15 mmol) of tetrabutylphosphonium acetate were pre-loaded into a flask equipped with a short-path separator. Oxygen in the apparatus containing the reactants was removed by evacuation and purging four times with nitrogen. The mixture was then heated to 160 °C. Upon reaching this temperature, carbon dioxide was produced. Based on the observed reactivity, the temperature was gradually increased to 220 °C over approximately 90 minutes. During this process, phenol began to separate. The pressure was then gradually reduced. The pressure was lowered to 0.5 mbar over approximately 30 minutes. Stirring was continued at this pressure for 10 minutes.

[0141] A transparent, slightly orange polymer was obtained with an etarel of 1.293.

[0142] Example 3: Polyester carbonates made from cyclohexanedicarboxylic acid, terephthalic acid, dimer fatty acids, and isosorbide (comparison) 8.31 g (0.05 mol) terephthalic acid, 8.60 g (0.05 mol) CHDA, 4.275 g (0.0075 mol) dimer fatty acid, and 29.83 g (0.204 mol) isosorbide were pre-loaded into a flask equipped with a short-path separator. Simultaneously, 13.5 ppm sodium (in the form of MTBE solution of sodium 2-ethylhexanoate, concentration 0.5 g / L) and 0.0226 g (200 ppm) DMAP were added. The mixture was evacuated and purged four times with nitrogen to remove oxygen from the flask contents. The mixture was then melted and heated to 160 °C. Carbon dioxide release was observed during this process. The temperature was gradually increased to 225 °C over 60 minutes. Subsequently, the pressure was carefully reduced to 0.5 mbar in several steps over 60 minutes. The temperature was then increased to 235 °C. Stirring was continued for 10 minutes at 235 °C and 0.5 mbar. A yellow polymer was obtained with an etarel of 1.335.

[0143] Example 4: Preparation of TCD-free, dimerized glycol-containing copolycarbonates (comparative) 64.91 g (0.303 mol) of diphenyl carbonate, 8.1 g (0.015 mol) of Pripol 2030, and 41.65 g (0.285 mol) of isosorbide were pre-loaded into a flask equipped with a short-path separator. 0.0001 g of sodium ethylhexanoate (in 200 µL MTBE solution, 0.5 g / L) and 0.00389 g (38.9 µL) of tetrabutylphosphonium acetate (in MEK solution, 100 g / L) were also added to the mixture. The mixture was evacuated and inertized four times with nitrogen to remove oxygen, then heated to 160 °C under stirring at standard pressure and melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C with rapid stirring (approximately 500 rpm). During this operation, phenol distilled off above approximately 220 °C. The pressure was then carefully and gradually reduced to approximately 0.5 mbar. During this process, phenol was continuously removed. Stirring was continued at a low speed for 10 minutes under a pressure of approximately 0.5 mbar. The final product was a transparent, slightly yellow polymer with an etarel of 1.389.

[0144] Example 5: Preparation of TCD-free, dimerized glycol-containing copolycarbonates (comparative) This example was performed according to the method of Example 4, except that 64.91 g (0.303 mol) of diphenyl carbonate, 10 g (0.0185 mol) of Pripol 2030, and 41.14 g (0.281 mol) of isosorbide were used. A transparent, pale yellow polymer with an etarel of 1.329 was obtained.

[0145] Example 6: Preparation of TCD-free, dimerized glycol-containing copolycarbonates (comparative) This example was performed according to the method of Example 4, except that 64.91 g (0.303 mol) of diphenyl carbonate, 11.79 g (0.022 mol) of Pripol 2030, and 40.65 g (0.278 mol) of isosorbide were used. A transparent, pale yellow polymer with an etarel of 1.382 was obtained.

[0146] Example 7: Polycarbonate made from isosorbide and BEPD (comparison) 29.83 g (0.204 mol) of isosorbide, 64.3 g (0.3 mol) of diphenyl carbonate, and 20 ppm of lithium (in the form of 75 µL LiOH solution (100 g LiOH / L)) were pre-loaded into a flask equipped with a short-path separator. The mixture was evacuated and purged four times with nitrogen to remove oxygen from the contents. The mixture was heated to 180 °C. After 15 minutes, 16.35 g (0.102 mol) of 2-butyl-2-ethylpropane-1,3-diol was added. The temperature was gradually increased to 225 °C over 30 minutes. During this process, phenol began to separate. The pressure was carefully reduced to 0.5 mbar over 45 minutes. The temperature was then increased to 235 °C. Stirring was continued at this temperature and pressure for 10 minutes. A clear polymer with an etarel of 1.202 was obtained.

[0147] Example 8: Polyester carbonates with low CHDA content (comparison) 4.42 g (0.0225 mol) of tricyclodecanediethanol, 2.673 g (0.0083 mol) of diphenyl cyclohexane-1,4-dicarboxylate, and 4.87 g (0.0068 mol) of diphenyl dimeric acid diphenyl ester were pre-loaded into a flask equipped with a short-path separator and a dropping funnel. 0.0015 g (15 µl) of an aqueous lithium hydroxide solution (100 g / L) was also added. The mixture was evacuated and inertized four times with nitrogen to remove oxygen, melted, and heated to 160 °C under stirring at standard pressure. Based on the observed reactivity, the temperature was gradually increased to a maximum of 210 °C. The pressure was then reduced to approximately 50 mbar and maintained for 15 minutes to remove phenol. The mixture was then purged to atmospheric pressure with nitrogen, and 16.66 g (0.1140 mol) of isosorbide and 25.71 g (0.1200 mol) of diphenyl carbonate were added to the reaction mixture at 225 °C with rapid stirring. After complete addition, phenol was distilled off. The temperature was raised to a maximum of 235 °C, and the pressure was carefully and gradually reduced to <1 mbar; phenol was continuously removed during this process. Stirring was continued at a low speed for 10 minutes at approximately 0.5 mbar. A transparent, pale yellow polymer with a solution viscosity of 1.27 was obtained.

[0148] Example 9 (Comparison: Polyester carbonates containing CHDA and TCD) 7.86 g (0.04 mol) of tricyclodecanediethanol and 11.66 g (0.036 mol) of diphenyl cyclohexane-1,4-dicarboxylate were pre-loaded into a flask equipped with a short-path separator and a dropping funnel. 0.0015 g (15 µl) of an aqueous lithium hydroxide solution (100 g / L) was also added. The mixture was evacuated and inertized four times with nitrogen to remove oxygen, melted, and heated to 160 °C with stirring at standard pressure. Based on the observed reactivity, the temperature was gradually increased to a maximum of 210 °C. The pressure was then reduced to approximately 50 mbar and maintained for 15 minutes to remove phenol. The mixture was then purged to atmospheric pressure with nitrogen, and 16.66 g (0.1140 mol) of isosorbide and 25.71 g (0.1200 mol) of diphenyl carbonate were metered into the reaction mixture at 225 °C with rapid stirring. After complete addition, the phenol was distilled off. The temperature was raised to a maximum of 235°C, and the pressure was carefully and gradually reduced to <1 mbar; during this process, phenol was continuously removed. Stirring was continued at a low speed for 10 minutes at a pressure of approximately 0.5 mbar. A transparent, pale yellow polymer was obtained, with a solution viscosity of 1.27.

[0149] Example 10 (contrast) 64.91 g (0.303 mol) of diphenyl carbonate, 17.67 g (0.09 mol) of tricyclodecanediethanol and 30.69 g (0.210 mol) of isosorbide were pre-loaded into a flask equipped with a short-path separator. 0.0001 g of sodium ethylhexanoate (in 200 µL of MTBE solution, 0.5 g / L) and 0.00389 g (38.9 µL) of tetrabutylphosphonium acetate (MEK) solution (100 g / L) were also added to the mixture. The mixture was evacuated and inertized four times with nitrogen to remove oxygen, then heated to 160 °C under stirring at standard pressure and melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C with rapid stirring (approximately 500 rpm). During this operation, phenol was distilled off above approximately 220 °C. The pressure is now carefully and gradually reduced to approximately 0.5 mbar while the temperature is raised to a maximum of 255°C. Phenol is continuously removed during this process. Stirring continues at a low speed for 10 minutes at approximately 0.5 mbar. A slightly turbid yellow polymer with an etarel of 1.294 is obtained.

[0150] Example 11 (contrast) 70.32 g (0.3283 mol) of diphenyl carbonate, 5.90 g (0.03 mol) of tricyclodecanediethanol, 8.10 g (0.04 mol) of dodecane-1,12-diol, and 37.27 g (0.255 mol) of isosorbide were pre-loaded into a flask equipped with a short-path separator. 0.0001 g of sodium ethylhexanoate (in 200 µL of MTBE solution, concentration 0.5 g / L) and 0.00389 g (38.9 µL) of tetrabutylphosphonium acetate (MEK solution, concentration 100 g / L) were also added to the mixture. The mixture was evacuated and inertized four times with nitrogen to remove oxygen, then heated to 160 °C under stirring at standard pressure and melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C with rapid stirring (approximately 500 rpm). During this process, phenol is distilled off at approximately 220°C or higher. The pressure is then carefully gradually reduced to approximately 0.5 mbar while the temperature is raised to a maximum of 255°C. Phenol is continuously removed during this process. Stirring is continued at a low speed for 10 minutes at approximately 0.5 mbar. A clear yellow polymer with an etarel of 1.191 is finally obtained.

[0151] Example 12 (contrast) 73.65 g (0.344 mol) of diphenyl carbonate, 5.90 g (0.03 mol) of tricyclodecanediethanol, 8.10 g (0.0554 mol) of octanediol, and 37.27 g (0.255 mol) of isosorbide were pre-loaded into a flask equipped with a short-path separator. 0.0001 g of sodium ethylhexanoate (in 200 µL of MTBE solution, concentration 0.5 g / L) and 0.00389 g (38.9 µL) of tetrabutylphosphonium acetate (MEK solution, concentration 100 g / L) were also added to the mixture. The mixture was evacuated and inertized four times with nitrogen to remove oxygen, then heated to 160 °C under stirring at standard pressure and melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C with rapid stirring (approximately 500 rpm). During this process, phenol is distilled off at approximately 220°C or higher. The pressure is then carefully gradually reduced to approximately 0.5 mbar while the temperature is increased to a maximum of 255°C. Phenol is continuously removed during this process. Stirring is continued at a low speed for 10 minutes at approximately 0.5 mbar. The final product is a cloudy brown polymer with an etarel of 1.076.

[0152] Example 13 (contrast) 70.32 g (0.3283 mol) of diphenyl carbonate, 5.90 g (0.03 mol) of tricyclodecanediethanol, 8.10 g (0.040 mol) of sebacic acid, and 37.27 g (0.255 mol) of isosorbide were pre-loaded into a flask equipped with a short-path separator. 0.0001 g of sodium ethylhexanoate (in 200 µL of MTBE solution, concentration 0.5 g / L), 0.00389 g (38.9 µL) of tetrabutylphosphonium acetate (MEK solution, concentration 100 g / L), and 0.0243 g (200 ppm) of DMAP were also added to the mixture. The mixture was evacuated and inertized four times with nitrogen to remove oxygen, then heated to 160 °C under stirring at standard pressure and melted. Once a homogeneous, low-viscosity liquid is obtained, the temperature is slowly increased to 245°C under rapid stirring (approximately 500 rpm). Carbon dioxide release is observed, and phenol distills off above approximately 220°C. After gas release ceases, the pressure is carefully and gradually reduced to approximately 0.5 mbar while the temperature is increased to a maximum of 255°C. During this process, phenol is continuously removed. Stirring continues at a low speed for 10 minutes at approximately 0.5 mbar. A slightly turbid, light brown polymer with an etarel of 1.338 is obtained.

[0153] Example 14 (contrast) 64.91 g (0.303 mol) of diphenyl carbonate, 5.90 g (0.03 mol) of tricyclodecanediethanol, 26.5 g (0.045 mol) of Pripol 2030, and 32.88 g (0.225 mol) of isosorbide were pre-loaded into a flask equipped with a short-path separator. 0.0001 g of sodium ethylhexanoate (in 200 µL of MTBE solution, concentration 0.5 g / L) and 0.00389 g (38.9 µL) of tetrabutylphosphonium acetate (MEK solution, concentration 100 g / L) were also added to the mixture. The mixture was evacuated and inertized four times with nitrogen to remove oxygen, then heated to 160 °C under stirring at standard pressure and melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C with rapid stirring (approximately 500 rpm). During this process, phenol is distilled off at approximately 220°C or higher. The pressure is then carefully gradually reduced to approximately 0.5 mbar while the temperature is increased to 255°C. Phenol is continuously removed during this process. The mixture is then stirred at a low speed for 10 minutes at approximately 0.5 mbar. The final product is a transparent, pale yellow polymer with an etarel of 1.423.

[0154] Example 15 (contrast) 64.91 g (0.303 mol) of diphenyl carbonate, 26.50 g (0.135 mol) of tricyclodecanediethanol, 8.1 g (0.015 mol) of Pripol 2030, and 21.92 g (0.150 mol) of isosorbide were pre-loaded into a flask equipped with a short-path separator. 0.0001 g of sodium ethylhexanoate (in 200 µL of MTBE solution, concentration 0.5 g / L) and 0.00389 g (38.9 µL) of tetrabutylphosphonium acetate (MEK solution, concentration 100 g / L) were also added to the mixture. The mixture was evacuated and inertized four times with nitrogen to remove oxygen, then heated to 160 °C under stirring at standard pressure and melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C with rapid stirring (approximately 500 rpm). During this process, phenol is distilled off at approximately 220°C. The pressure is then carefully gradually reduced to approximately 0.5 mbar while the temperature is increased to 255°C. Phenol is continuously removed during this process. The mixture is then stirred at a low speed for 10 minutes at approximately 0.5 mbar. The final product is a slightly turbid, pale yellow polymer with an etarel of 1.339.

[0155] Example 16: Preparation of polyester carbonates containing dimer fatty acids (according to the present invention) 29.22 g (0.0405 mol) of diphenyl fatty acid dimer, 17.7 g (0.09 mol) of tricyclodecanediethanol, 0.0003 g (943.5 ppb) of sodium 2-ethylhexanoate (MTBE solution, concentration 5 g / L), and 0.0115 g (36 ppm) of tetrabutylphosphonium acetate (MEK solution, concentration 100 g / L) were pre-loaded into a flask equipped with a short-path separator and a dropping funnel. The mixture was evacuated and inertized four times with nitrogen to remove oxygen, melted, and heated to 160 °C under stirring at standard pressure. Based on the observed reactivity, the temperature was gradually increased to a maximum of 210 °C. The pressure was then reduced to approximately 50 mbar and maintained for 15 minutes to remove phenol. The reaction mixture was then purged to atmospheric pressure with nitrogen, and 177.21 g (0.8272 mol) of diphenyl carbonate and 112.45 g (0.7695 mol) of isosorbide were metered into the reaction mixture at 225 °C with rapid stirring. After complete addition, phenol was distilled off. The temperature was raised to a maximum of 235 °C, and the pressure was carefully and gradually reduced to <1 mbar; phenol was continuously removed during this process. Stirring was continued at a low speed for 10 minutes at a pressure of approximately 0.5 mbar. A pale yellow polymer with an etarel of 1.240 was obtained.

[0156] Example 17Preparation of copolycarbonates containing dimerized glycols (according to the present invention) 194.73 g (0.909 mol) of diphenyl carbonate, 24.3 g (0.045 mol) of Pripol 2030, 17.7 g (0.090 mol) of tricyclodecanediethanol and 111.8 g (0.765 mol) of isosorbide were pre-loaded into a flask equipped with a short-path separator. 0.001 g of sodium ethylhexanoate (in 600 µL of MTBE solution, concentration 0.5 g / L) and 116.5 µL of tetrabutylphosphonium acetate (MEK solution, concentration 100 g / L) were also added to the mixture. The mixture was evacuated and purged four times with nitrogen to remove oxygen, melted, and heated to 160 °C under stirring at standard pressure until melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C with rapid stirring (approximately 500 rpm). During this process, phenol was distilled off above approximately 220 °C. Now, carefully reduce the pressure gradually to approximately 0.5 mbar. During this process, phenol is continuously removed. Continue stirring at a low speed for 10 minutes at a pressure of approximately 0.5 mbar. A light-colored, transparent polymer with an etarel of 1.356 is obtained.

[0157] Example 18: Preparation of copolycarbonates containing dimerized diols (according to the present invention) This example was performed according to the method described in Example 17, except that 194.73 g (0.909 mol) of diphenyl carbonate, 30.0 g (0.055 mol) of Pripol 2030, 14.75 g (0.075 mol) of tricyclodecanediethanol, and 112.45 g (0.7695 mol) of isosorbide were used. A pale yellow polymer with an etarel of 1.320 was obtained.

[0158] Example 19: Preparation of copolycarbonates containing dimerized diols (according to the present invention) This example was performed according to Example 17, except that 194.73 g (0.909 mol) of diphenyl carbonate, 27.0 g (0.05 mol) of Pripol 2030, 17.7 g (0.09 mol) of tricyclodecanediethanol, and 111.07 g (0.760 mol) of isosorbide were used. A pale yellow polymer with an etarel of 1.325 was obtained.

[0159] Example 20: Preparation of copolycarbonates containing dimerized diols (according to the present invention) This example was performed according to Example 17, except that 32.46 g (0.1515 mol) of diphenyl carbonate, 4.05 g (0.0075 mol) of Pripol 2030, 4.43 g (0.0335 mol) of tricyclodecanediethanol, and 17.54 g (0.120 mol) of isosorbide were used. A pale yellow polymer with an etarel of 1.352 was obtained.

[0160] Example 21: Preparation of copolycarbonates containing dimerized diols (according to the present invention) This example was performed according to Example 17, except that 64.91 g (0.303 mol) of diphenyl carbonate, 8.10 g (0.015 mol) of Pripol 2030, 5.02 g (0.0255 mol) of tricyclodecanediethanol and 37.92 g (0.2595 mol) of isosorbide were used. A pale yellow polymer with an etarel of 1.331 was obtained.

[0161] Example 22: Preparation of a copolymer (ester) carbonate containing dimer fatty acids and terephthalic acid (according to the present invention) 64.23 g (0.300 mol) of diphenyl carbonate, 4.95 g (0.0253 mol) of tricyclodecanediethanol, 11.21 g (0.0625 mol) of terephthalic acid, 4.28 g (0.0075 mol) of dimer fatty acid, and 29.52 g (0.202 mol) of isosorbide were pre-loaded into a flask equipped with a short-path separator. 0.00571 g of tetrabutylphosphonium acetate and 0.0114 g of DMAP were also added to the mixture. The mixture was evacuated and inertized four times with nitrogen to remove oxygen, then heated to 160 °C under stirring at standard pressure and melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C with rapid stirring (approximately 500 rpm). Carbon dioxide release was observed, and phenol distilled off above approximately 220 °C. After the gas release ceased, the pressure was carefully and gradually reduced to approximately 0.5 mbar while the temperature was increased to a maximum of 255°C. During this process, phenol was continuously removed. Stirring was continued at a low speed for 10 minutes at a pressure of approximately 0.5 mbar. A transparent, pale red polymer with an etarel of 1.206 was obtained.

[0162] Table 1: Hot Water Resistance

[0163] Table 2: Further Tolerance Testing Example number Example rapeseed oil lipid solutions Isooctane / Toluene (1:1) 1 PC1; Comparison Break; 9 minutes Breakage; <10 seconds Breakage; <10 seconds 10 <![CDATA[Comparative Example (P(I 70 BDO2TCD 28 )]]> Fracture; 4 hours 42 minutes Fracture; 1 day >7 days; edge cracks 17 According to the present invention >5 days >5 days 7 days 16 According to the present invention >5 days 7 days 7 days

[0164] Table 3: Shear Rheology Example Complex viscosity at 0.01 Hz [Pa·s] Complex viscosity at 1 Hz [Pa·s] 4 contrast <![CDATA[1.2 x 10 6 ]]> <![CDATA[1.0 x 10 5 ]]> 5 contrast <![CDATA[5.0 x 10 5 ]]> <![CDATA[6.6 x 10 4 ]]> 6 contrast <![CDATA[7.6 x 10 5 ]]> <![CDATA[7.1 x 10 4 ]]> 16 According to the present invention <![CDATA[3.4 x 10 4 ]]> <![CDATA[1.6 x 10 4 ]]> 18 According to the present invention <![CDATA[5.1 x 10 4 ]]> <![CDATA[1.9 x 10 4 ]]> 19 According to the present invention <![CDATA[5.1 x 10 4 ]]> <![CDATA[2.4 x 10 4 ]]>

[0165] Clearly, the copoly(ester) carbonate of the present invention exhibits high hot water stability. Surprisingly, polymers made from common diols such as cyclohexanediol and isosorbide (Example 1) – as described in EP 2033981 – are very unstable under hot water loads. Other diols, such as combinations of sterically hindered diols like isosorbide and 2-butyl-2-ethylpropane-1,3-diol, also do not exhibit good stability (Example 7). This is surprising because these sterically hindered diols, such as BEPD or neopentyl glycol, generally improve hydrolytic stability. Example 2 shows that polyester carbonates of cyclohexane-1,4-dicarboxylic acid and isosorbide also do not exhibit good stability in hot water tests. This is surprising because polyesters, for example, made from cyclohexanediol and cyclohexane-1,4-dicarboxylic acid, have high stability in aqueous media.

[0166] Example 11 shows that the combination of isosorbide with long-chain diols (such as dodecanediol in this example, see EP2840102) does not necessarily yield better results. This polymer also exhibits significant defects in hot water testing. These polymers may also have other shortcomings, such as their typically low glass transition temperatures.

[0167] Aromatic polyesters are generally known to be stable under hot water loads. For example, polyesters such as polyethylene terephthalate and their derivatives are stable to hot water. However, as shown in Example 3, introducing such aromatic dicarboxylic acids, such as terephthalic acid or isophthalic acid, into polycarbonates or polyester carbonates that were originally composed of aliphatic structural units unexpectedly failed to yield stable products. Introducing dimer fatty acids into such structures also did not help. It was originally expected that the nonpolarity or hydrophobicity of aromatic acids or dimer fatty acids would improve their stability to water. Surprisingly, the same problem exists to some extent for polymers containing TCD alcohols. For example, polymers made of isosorbide, cyclohexanedicarboxylic acid, dimer fatty acids, and TCD-dimethylethanol are unexpectedly unstable (Example 8). This is likely due to the presence of cyclohexanedicarboxylic acid.

[0168] Surprisingly, the polymer, which is mainly composed of isosorbide and long-chain nonpolar fatty acids (such as sebacic acid), is also unstable in hot water (Example 13).

[0169] Dimeric glycols or combinations of dimer fatty acids with isosorbide exhibit high tolerance to aqueous media. However, the melt viscosity of these polymers is unexpectedly high (Examples 4 to 6). Rheological studies show a significant increase in viscosity compared to the polymers described in this invention. High melt viscosity is a key drawback as it significantly increases the processing difficulty of these materials. For aliphatic materials, it is not feasible to drastically increase the processing temperature to improve flowability because their stability is not as good as, for example, aromatic polycarbonates, and they are prone to decomposition and loss of molecular weight at higher processing temperatures. Surprisingly, the polymers according to the invention exhibit better surface hardness than bisphenol A-based polycarbonates and polymers based on ISB and dimer glycols (see Table 4 below). Polymers with a high proportion of TCD alcohols did not show good performance in hot water tests (Example 15). Therefore, it is quite surprising that only the copoly(ester) carbonates of the invention with the proportions of units (A), (B), and (C) according to the invention exhibit high hot water stability and good stability to solvents such as fuel mixtures (isooctane-toluene mixtures), while also exhibiting high surface hardness and sufficiently good mechanical properties.

[0170] Furthermore, it can be seen that the polymer according to the present invention has a glass transition temperature exceeding 110°C.

[0171] Table 4: Scratch Resistance Example composition Scratch resistance (N) Tg (°C) Eta rel 4 (Comparative Example) <![CDATA[P(I 95 Pripol20305)]]> 4.5-5 137 1.389 5 (Comparative Example) <![CDATA[P(I 94 Pripol20306)]]> 3.5 132 1.329 6 (Comparative Example) <![CDATA[P(I 92.7 Pripol2030 7.3 )]]> 2-2.5 135 1.382 17 (According to the present invention) <![CDATA[P(I 85 Pripol20305TCD 10 )]]> 9-10 123 1.356 20 (according to the present invention) <![CDATA[P(I 80 Pripol20305TCD 15 )]]> 7.5-8 113 1.352

[0172] The results in Table 4 show that scratch resistance decreases with increasing Pripol content and in the absence of TCD-dimethyl alcohol (although Tg and molecular weight do not vary significantly between different tests). In contrast, the copolymers of this invention with lower Tg but using TCD-dimethyl alcohol as a comonomer exhibit better scratch resistance.

[0173] Table 5: Charpy Impact Test Example Charpy impact test; unnotched 18 10x No breakage 16 10x No breakage 17 10x No breakage

[0174] Table 6: 1 H NMR spectroscopy ISB (moles%) TCD-DM (molar percentage) Dimeric fatty acids / dimeric glycols (molar percentage) Embodiment 16 of the present invention 85.4 10.5 4.0 Embodiment 17 of the present invention 85.0 10.2 4.8 Embodiment 18 of the present invention 85.3 8.9 5.8 Embodiment 19 of the present invention 84.6 10.1 5.3 Embodiment 21 of the present invention 86.8 8.4 4.8 Embodiment 20 of the present invention 80.1 14.8 5.1

[0175] As shown in Table 6, the monomers used are almost entirely incorporated into the copoly(ester) carbonate. Therefore, the molar ratio of the monomers used is also almost entirely present in the copoly(ester) carbonate. This means that the ratio and amount of structural units present in the resulting polymer can be controlled by the ratio and amount of raw materials.

Claims

1. A copoly(ester) carbonate containing units (A), (B), (C), optionally (D), and optionally units other than (A), (B), (C), and (D), wherein (A) (B) Where each r and each s are independent numbers from 0 to 4, and each R 1 Each of the following structures is independent of the other: (R1A), (R1B), (R1C), or (R1D). (R1A) Where a is 0 or 1, (R1B) Where b is 0 or 1, (R1C) (R1D) In equations (R1A) to (R1D), the positions marked with "~" represent (CH2) as shown in equation (B). r Group or (CH2) s The location of the group, (C) Among them, two t and R 2 Independently both 0 and both 1, and each R 2 Each group is an aliphatic group having 16 to 44 carbon atoms, and optionally contains one or more double bonds. (D) In at least some cases, there are direct connections between units (A), (B), (C), optional (D), and optional units other than (A), (B), (C), and (D). When there is a direct connection between at least two units selected from (A), (B), (C), and optional (D), the position marked with "*" in units (A), (B), (C), and (D) is connected to the position marked with "#" in the unit, except in the following cases: When t in equation (C) is 0, the two units (C) are not directly connected to each other. When t in equation (C) is 0, there is no direct connection between element (C) and element (D), and The two units (D) are not directly connected to each other. The copoly(ester) carbonate contains 4 to 25 mol% of unit (B), 2 to 14 mol% of unit (C), 0 to 5 mol% of unit (D) and at least 55 mol% of unit (A), wherein the mol% data is based on the total molar amount of units (A), (B), (C), optional (D) and optional units other than (A), (B), (C) and (D).

2. The copoly(ester) carbonate as described in claim 1, characterized in that, Unit (A) is represented by equation (A*). (A*)， Where n is the average of the repeating units. And / or unit (B) is represented by equation (B*), (B*)， Where m is the average number of repeating units.

3. The copoly(ester) carbonate as described in any one of claims 1 or 2, characterized in that, In equations (B) and (B*), r and s are both 1, and R in equations (B) and (B*) is 1. 1 It is the structure of formula (R1A).

4. The copoly(ester) carbonate according to any one of claims 1 to 3, characterized in that, R in equation (C) 2 It can be represented by the following formula (R2A): (R2A) Wherein Y is a bridging structure selected from alkylene groups having 1 to 4 carbon atoms, alkylidene groups having 1 to 4 carbon atoms, and cycloalkylene groups having 4 to 12 carbon atoms, wherein the cycloalkylene group optionally contains one or more double bonds and / or optionally is fused to one or more other cycloalkylene groups, wherein each of the one or more other cycloalkylene groups optionally has one or more double bonds. R, which is adjacent to the bridging structure 11 The group is attached to any position in the bridging structure, and Each R 11 Each of the above can be an alkylene group having 1 to 12 carbon atoms or an alkylidene group having 1 to 12 carbon atoms, provided that the structure of formula (R2A) contains 16 to 44 carbon atoms, and that the position marked with "~" in formula (R2A) is (O) as shown in formula (C). t The position of each group.

5. The copoly(ester) carbonate as described in claim 4, characterized in that, Equation (R2A) is represented by one of equations (R2Aa), (R2Ab), (R2Ac), or (R2Ad). (R2Aa), (R2Ab), (R2Ac) and (R2Ad), Each R 11 Each "~" is as defined in claim 4, and the rings of formula (R2Ac) optionally have one or two double bonds, and each ring of formula (R2Ad) optionally contains one or two double bonds independently of each other.

6. The copoly(ester) carbonate as described in claim 4 or 5, characterized in that, Each R 11 Each is an alkylene group having 1 to 10 carbon atoms, provided that the structure of formula (R2A) contains 16 to 44 carbon atoms.

7. The copoly(ester) carbonate according to any one of claims 1 to 6, characterized in that, Unit (C) consists of R 2 The groups described by (R2A), (R2Aa), (R2Ab), (R2Ac) and / or (R2Ad) have 21 to 44 carbon atoms.

8. The copoly(ester) carbonate according to any one of claims 1 to 7, characterized in that, The copoly(ester) carbonate comprises at least 80% by weight of units (A), (B), (C) and optional (D).

9. The copoly(ester) carbonate according to any one of claims 1 to 8, characterized in that, The copoly(ester) carbonate has a direct connection between units (A) and (C), and both t in unit (C) are simultaneously 0.

10. The copoly(ester) carbonate according to any one of claims 1 to 9, characterized in that, At least 50 mol% of the copolymer (ester) carbonate is bio-based.

11. The copoly(ester) carbonate according to any one of claims 1 to 10, characterized in that, The copoly(ester) carbonate contains - 5 to 20 mol% of units (B), - 3 to 12 mol% of units (C), and - At least 65 mol% of units (A), The mole % data is based on the total mole amount of units (A), (B), (C), optional (D), and optional units different from (A), (B), (C), and (D).

12. The copoly(ester) carbonate as described in claim 12, characterized in that, The copoly(ester) carbonate contains - 8 to 12 mol% of units (B), - 3.5 to 8.0 mol% of units (C), and - At least 80 mol% of units (A), The mole % data is based on the total mole amount of units (A), (B), (C), optional (D), and optional units different from (A), (B), (C), and (D).

13. A composition comprising a copoly(ester) carbonate as described in any one of claims 1 to 12 and one or more additives.

14. A molded part comprising any one of claims 1 to 12, or comprising the composition of claim 13.

15. A method for producing a copoly(ester) carbonate as described in any one of claims 1 to 12, comprising at least a reaction of 1,4:3,6-disodehydrated hexitol, a diol of formula (B2), a diol selected from formula (C2), a compound of formula (C3), or any mixture thereof, and a carbonyl source, wherein (B2) Where each r and each s are independent numbers from 0 to 4, and each R 1 The structures (R1A), (R1B), (R1C), and (R1D) are independent of each other. (R1A) Where a is 0 or 1, (R1B) Where b is 0 or 1, (R1C) (R1D) In equations (R1A) to (R1D), the positions marked with "~" represent (CH2) as shown in equation (B2). r Group or (CH2) s The location of the group, (C2)， (C3) Where each R in equations (C2) and (C3) 2 Each of the above is an aliphatic group having 16 to 44 carbon atoms, which optionally contains one or more double bonds; and each R in formula (C3) is an aliphatic group. 3 Each can be hydrogen, chlorine, or -OR'', where R'' is an aliphatic or aromatic group.

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