Polyester carbonate composed of various diols in specified ratios

Abstract

The present invention relates to a process for preparing polyestercarbonates based on cycloaliphatic diacids and at least one 1,4:3,6-dianhydrohexitol and at least one further aliphatic dihydroxy compound, to the polyestercarbonates, and to molding compounds and molded articles containing the polyestercarbonates. The polyestercarbonates according to the invention are characterized by good mechanical properties and molecular weight.

Description

[Technical Field]

[0001] The present invention relates to a copolyester carbonate of structural formula (1) having various structural units obtained from a specified ratio of diol, a molded compound, a molded article, and a method for preparing the corresponding polyester carbonate. [Background technology]

[0002] Polyesters, polycarbonates, and polyester carbonates are known to possess excellent properties in terms of mechanical properties, thermal deformation stability, and weather resistance. Depending on the monomer used, each polymer group has certain key characteristics that characterize such materials. For example, polycarbonates, in particular, have excellent mechanical properties, while polyesters often exhibit superior chemical stability. Depending on the selected monomer, polyester carbonates exhibit property profiles from both of the aforementioned groups.

[0003] While aromatic polycarbonates or polyesters often exhibit excellent property profiles, they have disadvantages in terms of aging resistance and weather resistance. For example, they yellow due to ultraviolet light absorption, and in some cases, these thermoplastic materials become brittle. In this respect, aliphatic polycarbonates and polyester carbonates have superior properties, particularly superior aging resistance and / or weather resistance, as well as superior optical properties (e.g., transmittance).

[0004] A disadvantage of aliphatic polycarbonates or polyester carbonates is often their low glass transition temperature. Therefore, it is advantageous to use alicyclic alcohols as (co)monomers. Examples of such alicyclic alcohols include TCD alcohol (tricyclodecanedimethanol; 8-(hydroxymethyl)-3-tricyclo[5.2.1.0 2,6Examples of bio-based diols based on 1,4:3,6-dianhydrohexitol include 1,4:3,6-dianhydrohexitol (decanyl)methanol, cyclohexanediol, cyclohexanedimethanol, and isosorbide and its isomers isomannide and isoidide. To further increase the glass transition temperature, alicyclic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, or 1,4-cyclohexanedicarboxylic acid, or corresponding naphthalene derivatives can be used as (co)monomers. In this case, a polyester or polyester carbonate can be obtained depending on the selection of reactants. This application relates to copolyester carbonates with improved properties based on 1,4:3,6-dianhydrohexitol such as isosorbide and its isomers, and further, alicyclic diacitors containing a specific amount of additional diols. The present invention further relates to a method for preparing these copolyester carbonates characterized by the direct reaction of the raw materials and without requiring any difficult-to-handle raw materials such as phosgene.

[0005] Polyesters of cyclohexanedicarboxylic acid and isosorbide are described in Non-Patent Document 1. However, the present invention preferably relates to polyester carbonates.

[0006] Polyesters are prepared on an industrial scale, for example, by transesterification of corresponding ester-containing monomers with diols. For example, starting with dimethyl esters of diacides, polyesters of 1,4-cyclohexanedimethanol and 1,4-cyclohexanedicarboxylic acid are produced (a blend of this polyester with polycarbonate: DuPont's Xyrex®).

[0007] However, with respect to transesterification reactions, phenyl esters are far more reactive than their aliphatic analogs. Patent documents 1 and 2 describe methods for preparing polyester carbonates having phenyl esters as an intermediate step.

[0008] Example 1 of Patent Document 1 describes obtaining the corresponding ester by the direct reaction of a diacid with phenol. In Example 2 of Patent Document 1, a dimethyl ester is reacted with phenol. However, both modifications for the preparation of phenyl esters still have room for improvement in terms of yield. Next, a polyester carbonate is prepared. This polyester carbonate is prepared from only one diol.

[0009] Patent Document 2 describes the preparation of diphenyl esters in a solvent using phosgene. Since the subsequent reaction to obtain aliphatic polyester carbonate does not require phosgene, combining the phosgene process and the transesterification process in a single plant unit is highly disadvantageous. Therefore, the method described in Patent Document 2 is also not optimal, as only one diol is used to prepare the polymer. In Patent Document 3, the polyester carbonate is prepared from isosorbide, cyclohexanedicarboxylic acid, and a further diol, which may be, for example, cyclohexanedimethanol. However, a very large amount of cyclohexanedimethanol is used here, and excess cyclohexanedimethanol often adversely affects the thermal properties of the polymer, particularly the glass transition temperature, which drops significantly.

[0010] Patent document 4 discloses a two-step method in which an additional acid such as terephthalic acid is used. Patent document 5 describes an isosorbide unit and an aliphatic C 14 ~C 44 diacid, aliphatic C 14 ~C 44Disclosed is an isosorbide-based polycarbonate comprising aliphatic units derived from diols or combinations thereof, and optionally isosorbide units and additional units different from the aliphatic units, wherein the isosorbide units, aliphatic units, and additional units are, respectively, carbonates or combinations of carbonate units and ester units. The common disadvantages of aliphatic polycarbonates or polyester carbonates have already been discussed above. In the examples, polymers derived from combinations of isosorbide, alicyclic diacids, and additionally aliphatic diols are not prepared. Furthermore, activated carbonates are used for transesterification.

[0011] For example, Patent Document 6 describes a simple preparation of aromatic polyester carbonates. This document reveals a direct synthesis or one-pot synthesis, i.e., a synthesis in which all structural elements forming the subsequent polyester carbonate are already present as monomers at the start of the synthesis. The monomers used here are aromatic dihydroxy compounds such as bisphenol A, carboxylic acid diesters, and aromatic diacides or linear aliphatic diacides. As a result of the fact that only aromatic polyester carbonates are prepared in this document, a temperature of 300°C can be used in the condensation reaction while removing the phenol that is formed. In the preparation of aliphatic polyester carbonates, the use of such a temperature is not possible, because under such thermal stress, aliphatic diols tend to undergo elimination and / or thermal decomposition. However, at the same time, high temperatures are necessary to reach the desired high molecular weight. Here, the difference in reactivity between aliphatic diols and aromatic diols becomes particularly apparent. For example, it is known from the literature that isosorbide is rarely completely incorporated into the polymer, and rather, up to 25% of isosorbide is lost during the polymerization reaction depending on the selected reaction conditions. Therefore, it is not immediately possible to apply the reaction conditions for aromatic diols to aliphatic diols. This is particularly evident from the fact that the reaction time for polycondensation (corresponding to step (ii)) in Patent Document 6 is significantly longer at higher temperatures than the reaction time observed according to the present invention.

[0012] Similarly, Patent Documents 7 and 8 use aromatic units and correspondingly high temperatures. For the reasons stated above, the teachings in the above documents cannot be carried over to aliphatic units.

[0013] Patent document 9, which is an unpublished application, discloses a one-pot synthesis of polyester carbonates comprising an alicyclic dicarboxylic acid, a diaryl carbonate, and an aliphatic dihydroxy compound.

[0014] The polyester carbonates described in Patent Documents 1 and 2 have high glass transition temperatures. However, the structure of these polyester carbonates is very rigid. This is a result of the isosorbide structure being incorporated into the polymer chain by condensation. Due to its rigid nature, the bicyclic substructure increases the glass transition temperature, but the polymer chain becomes less flexible, which can, in principle, lead to disadvantages. Park et al. state that the higher the amount of isosorbide in the polymer, the lower the molecular weight (Non-Patent Document 2). The authors state that the increase in molecular weight is hindered by the high melt viscosity. Failure to reach the critical molecular weight can result in insufficient mechanical properties. This is particularly important for inflexible polymer chains. Rigid chains require a relatively high molecular weight to be able to entangle. Failure to achieve this results in brittle behavior (critical entanglement molecular weight).

[0015] While cyclohexanedicarboxylic acid increases flexibility somewhat, the overall structure of the polymer chain remains very rigid. This can be a disadvantage during polymer preparation. Due to its inflexible nature, reaction partners (chain ends) become less likely to find each other as the molecular weight increases. As mentioned above, this limits the molecular weight. Furthermore, the rigid nature causes a rapid increase in viscosity during polymer synthesis. To compensate for this, the temperature is often increased in the final stage of polycondensation during polymer preparation to achieve better fluidity. However, this is only possible to a limited extent in the case of aliphatic polymers, because their thermal stability is significantly lower compared to, for example, aromatic polyesters or polycarbonates. Since the increase in viscosity cannot be compensated for by increasing the temperature, poor mixing and poor surface renewal result. Consequently, condensation products (e.g., phenol) can no longer be removed, and the polycondensation is interrupted.

[0016] To achieve better surface renewal, Patent Document 4 describes the use of horizontal polymer reactors such as polymer kneaders. These exert a high shear force on the polymer, enhancing surface renewal and allowing polycondensation to continue. However, the high shear force places a significant load on non-flexible polymers.

[0017] High shear stress can cause damage, which may manifest as deterioration of optical and mechanical properties.

Prior Art Documents

Patent Documents

[0018]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

Non-Patent Documents

[0019]

Non-Patent Document 1

Non-Patent Document 2

[0020] Therefore, starting from this prior art, the object of the present invention was to provide a polyester carbonate comprising at least one 1,4:3,6-dianhydrohexitol and at least one specific alicyclic dicarboxylic acid, characterized by a sufficiently high molecular weight. The term "sufficiently high molecular weight" is understood to mean a polymer having a relative solution viscosity of more than 1.20, preferably 1.20 to 1.70, more preferably 1.22 to 1.65, and particularly preferably 1.30 to 1.62, as measured in each case using an Ubbelohde viscometer at a concentration of 5 g / l in dichloromethane at 25°C. Furthermore, the polyester carbonate according to the present invention should have better processing properties and good mechanical properties. These should be due in particular to a sufficiently high molar mass. The high molecular weight can be obtained, for example, from better surface renewal in the preparation method. A further object was to provide the simplest possible method for preparing polyester carbonates by melt transesterification. In this context, "simple" is understood to mean a method that requires fewer equipment, involves fewer steps, especially fewer purification steps, and / or is therefore economically and environmentally advantageous. In particular, the method according to the present invention should not require difficult-to-handle starting materials, especially phosgene. [Means for solving the problem]

[0021] At least one, preferably all, of the above-mentioned problems have been solved by the present invention. Surprisingly, it has been found that in direct synthesis or one-pot synthesis, where all the structural elements forming the subsequent polyester carbonate are already present as monomers at the start of the synthesis, it is possible to synthesize polyester carbonates from at least one alicyclic diacid, at least one diaryl carbonate, at least one 1,4:3,6-dianhydrohexitol, and at least one further aliphatic dihydroxy compound by melt transesterification. However, it has been found that a polymer with the appropriate molar mass and therefore appropriate mechanical properties can only be obtained when a specific amount of at least one further diol HO-x-OH is used. Furthermore, this at least one further diol preferably has at least one branch. Firstly, despite the preconceptions described in the prior art, it was surprising that direct synthesis also works for the reaction of a diaryl carbonate with an alicyclic dicarboxylic acid, 1,4:3,6-dianhydrohexitol, at least one further aliphatic dihydroxy compound HO-x-OH (also called an "aliphatic diol" according to the present invention). It was also quite surprising that the amount of at least one further aliphatic dihydroxy compound HO-x-OH was important for obtaining a good increase in molecular weight. This made it possible to find a method that allows for the acquisition of polyester carbonates from an alicyclic dicarboxylic acid, 1,4:3,6-dianhydrohexitol, and at least one further aliphatic dihydroxy compound HO-x-OH, which is particularly simple, i.e., requires less equipment, involves fewer steps, especially fewer purification steps, and is therefore economically and environmentally advantageous.

[0022] Furthermore, it was found that the incorporation of small amounts of additional aliphatic dihydroxy compounds HO-x-OH, particularly branched aliphatic dihydroxy compounds, enhanced surface renewal during synthesis. It was particularly surprising that even small amounts of specific diols yielded favorable properties, while larger amounts were surprisingly detrimental. It was also surprising that even the incorporation of small amounts of additional diols significantly increased surface renewal, and therefore increased molecular weight. It was particularly surprising that branched diols were readily incorporated into the polymer chain by condensation despite steric hindrance. Those skilled in the art would have predicted that steric hindrance would hinder the increase in molecular weight. Therefore, overall, it was possible to provide polyester carbonates in which the constituent structural elements contribute to a good balance between the rigidity and flexibility of the polymer chain, while also exhibiting a sufficiently high molecular weight that yields correspondingly good mechanical properties.

[0023] Similarly, and perhaps surprisingly, the incorporation of additional branched aliphatic dihydroxy compounds HO-X-OH was found to result in polymers with lower shear viscosity. This is preferably true even when relatively high solution viscosity is observed. This is also preferably true even when comparable Tg is observed.

[0024] A method for preparing polyester carbonates according to the present invention can be schematically described as follows, for example, by the reaction of cyclohexanedicarboxylic acid, isosorbide, an additional diol HO-R-OH, and diphenyl carbonate: [ka] (These three specific starting materials are listed solely for illustrative purposes and should not be understood as limiting.)

[0025] In the direct synthesis according to the present invention, gas generation (leakage of carbon dioxide) was initially observed. After the gas generation essentially subsided, a sample of the mixture was taken, and analysis demonstrated that oligomers had already been formed. These oligomers were condensed in a further step to obtain the polyester carbonate according to the present invention. Therefore, the present invention relates to structural formula (1) [ka] A polyester carbonate containing, in the formula, A independently represents at least one of either structural unit (A) or structural unit (B) for each repeating unit, where, (A) is chemical formula (2) [ka] It represents, and, (B) is chemical formula (3) [ka] (wherein x represents a branched alkylene group having 4 to 20 carbon atoms, preferably 5 to 15, which can be optionally interrupted by at least one heteroatom, or a cycloalkylene group containing at least one branch, where the cycloalkylene group has 4 to 20 carbon atoms, preferably 5 to 15, which can be optionally interrupted by at least one heteroatom, and the cycloalkylene group may optionally contain multiple rings) y is independently either chemical formula (IIIa) or chemical formula (IIIb). [ka] (In the formula, Each B independently represents a CH2 group or a heteroatom selected from the group consisting of O and S, preferably a CH2 group or an oxygen atom. Each R1 independently represents an alkylene group having a single bond or 1 to 10 carbon atoms, preferably a single bond or an alkylene group having 1 to 5 carbon atoms, particularly preferably a single bond. n represents a number between 0 and 3, preferably 0 or 1, and, 0 <x<1であり、 In each case * This indicates the position where the chemical formula is incorporated into the polyester carbonate. Polyester carbonate, in each case, is calculated based on the sum of structural units (A) and structural units (B). 98 mol% to 75 mol%, preferably 97 mol% to 80 mol%, and particularly preferably 96 mol% to 82 mol%, of structural units (A), 2 mol% to 25 mol%, preferably 3 mol% to 20 mol%, and particularly preferably 4 mol% to 18 mol%, structural unit (B), Including, The polyester carbonate has a relative solution viscosity of 1.20 to 1.70, preferably 1.23 to 1.67, and particularly preferably 1.25 to 1.65, as measured at 25°C in dichloromethane at a concentration of 5 g / l using an Ubbelohde viscometer. We provide a polyester carbonate characterized by the following.

[0026] In structural formula (1), the component "A" is defined in more detail. A can represent at least either (A) or (B). This can be freely selected independently for each repeating unit. According to the present invention, the term "repeating unit" is preferably "[...] 1-x " or "[...] xrefers to a structure surrounded by any of the following. Therefore, the structural formula (1) already contains two different repeating units having either a carbonate structure or an ester structure in addition to A. A independently represents at least either structural unit (A) or structural unit (B) for each repeating unit of the structural formula (1). In this case, the use of the term "at least" means that A can also represent a further structural unit (C). However, the polyester carbonate according to the present invention always necessarily contains structural unit (A) and structural unit (B) in a defined molar ratio with respect to each other. Preferably, A consists only of structural unit (A) and structural unit (B) and does not contain any further structural unit (C). In this case, A independently represents either structural unit (A) or structural unit (B) for each repeating unit of the structural formula (1). Furthermore, it is obvious to those skilled in the art that (A) can contain two or more different structures of formula (2). Similarly, (B) can contain two or more different structures of formula (3). However, (A) preferably contains only one structure of formula (2). However, similarly preferably, (B) contains only one structure of formula (3). Particularly preferably, (A) and (B) each contain only one structure of formula (2) and formula (3).

[0027] Surprisingly, it has been found that when the amount of component (B) is within the range defined in the claims, an increase in molecular weight functions particularly well, so that a polyester carbonate having a relative solution viscosity of 1.20 to 1.70 can be obtained. Surprisingly, the higher the amount of (B), the only slight increase in molecular weight is observed. In this case, it was advantageous for (B) to have 2 to 11, preferably 3 to 10 carbon atoms. A polyester carbonate having good mechanical properties, particularly good elongation at break and good modulus of elasticity, was obtained. Furthermore, the polyester carbonate according to the present invention exhibits good impact strength.

[0028] According to the present invention, no distinction is made between repeating units, structural units, and structural motifs. Preferably, as already described above, the repeating unit is in formula (1) within brackets […] 1-x [[ID=]]or within brackets […]x It is understood to mean a structure enclosed by . Thus, structural formula (1) already contains two repeating units. As a result of A, it also further has at least structural unit (A) and structural unit (B). Structural unit (A) and structural unit (B) (and possibly (C) as well) each exist once in the repeating unit. These may differ from one repeating unit to another. According to the present invention, the term structural unit is preferably used for structures that do not have a carbonate structure or an ester structure and are therefore not repeating units in themselves. Furthermore, this is not a structural motif. Thus, the term is used for structures smaller than repeating units and structural motifs. According to the present invention, structural motif is preferably understood to mean a structure that can be derived from monomers used in a polymer-forming reaction. Thus, according to the present invention, a structural motif is at least the following structure: [ka] This is understood to mean the following. The first structural motif is derived from a diol that is incorporated into the polymer of structural formula (1) by reaction. Thus, oxygen is either a carbonate unit or an ester unit in structural formula (1). The second structural motif is derived from a dicarboxylic acid in a similar manner. The third structural motif is derived from 1,4:3,6-dianehydrohexitol in a similar manner.

[0029] Therefore, in contrast, the structural unit according to the present invention does not contain oxygen and cannot be directly assigned to a monomer. Thus, structural unit (A) is a structural motif excluding the oxygen atom. [ka] This corresponds to the structural unit (B), which is a structural motif excluding the oxygen atom. [ka] It corresponds to.

[0030] In particular, the polyester carbonate according to the present invention is a polyester carbonate with the following repeating units (i) to (iv) [ka] It is preferable that the formula contains (wherein a, b, c, and d each independently represent a natural number indicating the average number of repeating units in each case) in any order. Here again, the repeating units are enclosed in parentheses. The exponents of a, b, c, and d are preferably set to yield the solution viscosity according to the present invention. According to the present invention, it was surprising that a sufficiently high molecular weight was obtained because the numbers of a, b, c, and d were very high.

[0031] According to the present invention, it is preferable that the polyester carbonate consists of at least 80% by weight, preferably 85% by weight, and particularly preferably 90% by weight of structural formula (1), based on the total weight of the polyester carbonate. Therefore, the polyester carbonate according to the present invention preferably has only small amounts of structures other than the structure defined in structural formula (1). Furthermore, it is preferable that the polyester carbonate according to the present invention does not contain any functional structures other than the carbonate structure and / or ester structure. This means that 20% by weight or less, preferably 15% by weight or less, and particularly preferably 10% by weight or less, which do not consist of structural formula (1), may be derived from other diols or dicarboxylic acids, which further result in a carbonate structure or ester structure as a result of their incorporation into the polyester carbonate.

[0032] The polyester carbonate according to the present invention has the following structural motifs [ka] With respect to the total sum, 1 mol% to 20 mol%, preferably 2 mol% to 18 mol%, and particularly preferably 3 mol% to 15 mol%, of polyester carbonate constitutes the structural motif. [ka] It is preferable that the following are the characteristics.

[0033] According to the present invention, the ratio of monomers having hydroxyl functional value to dicarboxylic acid used can be freely adjusted in the polyester carbonate. The more dihydroxy compounds used, the more carbonate structures are obtained. The more dicarboxylic acid there is, the more ester structures are obtained. Therefore, as a result, the ratio of carbonate structures to ester structures can be freely selected. This has been found to settle particularly well in the method according to the present invention, in which all monomers forming the polyester carbonate are already present at the start of the synthesis. Thus, this results in a polyester carbonate having properties that can be adjusted in a controlled manner. However, for this to happen, the ratio of the two dihydroxy compounds that give rise to structural unit (A) and structural unit (B) must be kept within the range according to the present invention. Structural motifs that constitute structural unit (B) without containing oxygen atoms [ka] It was found that it is advantageous when the amount is not too high. If it is too low, the overall increase in molecular weight is inferior. If it is too high, the glass transition temperature of the polyester carbonate becomes suboptimal. In this case, the total carbonate structure is always obtained from the sum of the dihydroxy compound and dicarboxylic acid used.

[0034] Preferably, (A) is structure [ka] (A) is very preferably selected from at least one of the following: (A) is very preferably selected from [ka] That is the case.

[0035] Preferably, x represents a branched alkylene group having 4 to 20, preferably 5 to 15, particularly preferably 5 to 11, and very particularly preferably 5 to 10 carbon atoms, which can be optionally interrupted by at least one heteroatom. The heteroatom that can optionally interrupt the branched alkylene group is preferably oxygen or sulfur, particularly preferably oxygen. Particularly preferably, the branched alkylene group contains only one heteroatom or contains no heteroatoms. Particularly preferably, the branched alkylene group contains no heteroatoms at all. When there is at least one heteroatom present in the alkylene group, the indicated number of carbon atoms refers to the total number of carbon atoms in the alkylene group. For example, the group -CH2-CH2-O-CH2-CH2- contains 4 carbon atoms. The term "branched" is understood to refer to branching in an aliphatic carbon chain, as known to those skilled in the art. This means that the branched alkylene group preferably contains at least one tertiary carbon atom and / or at least one quaternary carbon atom. A branched alkylene group may have two or more branches. Each branch has a chain length of preferably 1 to 5 carbon atoms, particularly preferably 1 to 4 carbon atoms, and very particularly preferably 1 to 3 carbon atoms. These carbon atoms in the branch are taken into account in the total number of carbon atoms of the branched alkylene group. This means, for example, that the branched alkylene group -CH2-C(CH3)2-CH2- has 5 carbon atoms.

[0036] According to the present invention, the above description applies to heteroatoms when x is a cycloalkylene group having at least one branch, the cycloalkylene group has 4 to 20, preferably 5 to 15 carbon atoms, which can be optionally interrupted by at least one heteroatom, and the cycloalkylene group can optionally contain multiple rings. The heteroatom that can optionally interrupt the cycloalkylene group is preferably oxygen or sulfur, particularly preferably oxygen. Particularly preferably, the cycloalkylene group contains only one heteroatom or contains no heteroatoms. Particularly preferably, the cycloalkylene group has no heteroatoms at all. Preferably, the cycloalkylene group has at least one, preferably one ring, having 4 to 6 carbon atoms. Particularly preferably, the cycloalkylene group has a total of 4 to 20, preferably 5 to 15 carbon atoms, and a ring having 4 to 5 carbon atoms. In this case, the carbon atoms of the ring are considered in the total number of carbon atoms in the cycloalkylene group. This means that the tetramethylcyclobutenyl group has a total of eight carbon atoms and includes a ring having four carbon atoms. Furthermore, the cycloalkylene group has at least one branch. These branches may be present in the alicyclic chain and / or ring. Preferably, the branch is present in the ring. The term “branch” in relation to the cycloalkylene group is understood to refer to a branch known to those skilled in the art. This means that the branched cycloalkylene group preferably includes at least one tertiary carbon atom and / or at least one quaternary carbon atom. In this case, it is understood that the two tertiary carbon atoms connecting the ring and the polymer chain are not considered branches according to the present invention. This preferably means that when the cycloalkylene group has at least one branch on the ring, this ring has at least one tertiary carbon atom and / or quaternary carbon atom in addition to the two tertiary carbon atoms connecting the ring and the polymer chain (in formula (3) *(See also ). Similarly, branching can also be present in alkyl groups present on the ring (for example, when x is 2,2-bis(4-cyclohexylene)propane). Particularly preferably, “branched” with respect to a cycloalkylene group is understood to mean that the group has at least one quaternary carbon atom. Preferably, x is a cycloalkylene group having 5 to 15 carbon atoms including a ring, which optionally has at least one branch, preferably at least one branch, and has at least one ring, preferably a ring having 4 to 6 carbon atoms, particularly preferably 4 to 5 carbon atoms.

[0037] Overall, according to the present invention, it is preferable that x has 2 to 10 carbon atoms.

[0038] Particularly preferred, [ka] , 2,2-bis(4-cyclohexylene)propane, 2-butyl-2-ethyl-1,3-propylene, 2,2,4,4-tetramethyl-1,3-cyclobutylene, 2,2,4-trimethyl-1,3-pentylene, 2,2-dimethylpropane-1,3-ylene, 8-(methylene)-3-tricyclo[5.2.1.0 2,6 Selected from the group consisting of ]decanyl]methylene and any desired mixture thereof. In particular, [ka] In this, x is preferably selected from the group consisting of 2-butyl-2-ethyl-1,3-propylene, 2,2,4,4-tetramethyl-1,3-cyclobutylene, 2,2,4-trimethyl-1,3-pentylene, 2,2-dimethylpropane-1,3-ylene, and any desired mixture thereof. Similarly, [ka] In this, x is preferably selected from the group consisting of 2-butyl-2-ethyl-1,3-propylene, 2,2,4,4-tetramethyl-1,3-cyclobutylene, 2,2,4-trimethyl-1,3-pentylene, 2,2-dimethylpropane-1,3-ilene, and any desired mixture thereof. In particular, [ka] In this equation, x is preferably selected from the group consisting of 2-butyl-2-ethyl-1,3-propylene, 2,2,4,4-tetramethyl-1,3-cyclobutylene, 2,2,4-trimethyl-1,3-pentylene, 2,2-dimethylpropane-1,3-ilene, and any desired mixture thereof. As already described above, x may be a mixture of the above structures. However, x preferably represents only one structure.

[0039] According to the present invention, y is independently of chemical formula (IIIa) or chemical formula (IIIb) [ka] (In the formula, Each B independently represents a carbon atom or a heteroatom selected from the group consisting of O and S, preferably a carbon atom or an oxygen atom. Each R1 independently represents an alkylene group having a single bond or 1 to 10 carbon atoms, preferably a single bond or an alkylene group having 1 to 5 carbon atoms, particularly preferably a single bond. n represents a number between 0 and 3, preferably 0 or 1.

[0040] When R1 represents a single bond, it will be understood that R1 does not contain a carbon atom.

[0041] In particular, y is 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1,2-cyclohexanedimethylene, 1,3-cyclohexanedimethylene, 1,4-cyclohexanedimethylene, 2,2-bis(4-cyclohexylene)propane, tetrahydro-2,5-frangimethylene, 2-butyl-2-ethyl-1,3-propylene, 2-(2-ethyloxy)ethylene, 2,2,4,4-tetramethyl-1,3-cyclobutylene, 2,2,4-trimethyl-1,3-pentylene, 2,2-dimethylpropane-1,3-ylene, cyclobutane-1,1-diyldimethylene, 8-(methylene)-3-tricyclo[5.2.1.0 2,6 It is preferable that y is selected from the group consisting of decanyl methylene, 1,2-propylene, 1,3-propanylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,8-octylene, and any desired mixture thereof. Particularly preferable, y is selected from the group consisting of 1,2-cyclohexylene, 1,3-cyclohexylene, and 1,4-cyclohexylene.

[0042] Furthermore, a small amount of additional acid may be used with y in conjunction with the structure described above. Therefore, particularly preferably, y further comprises up to 20 mol%, more preferably up to 10 mol%, and very particularly preferably up to 5 mol%, of structural formula y1 and / or structural formula y2. Preferably, y1 does not contain a ring. Particularly preferably, y1 is selected from the group consisting of 2,2,4-trimethylbutylene, 2,4,4-trimethylbutylene, 2,2,5-trimethylbutylene, and 3,3-dimethylpropylene. Similarly, it is preferable to select y2 from the group consisting of structures derived from the following dicarboxylic acids: isophthalic acid, terephthalic acid, 2,5-franzicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. In this case, it can be seen that the formed ester group does not belong to structural unit y2. In these cases, according to the present invention, aliphatic polyester carbonates are still preferred. However, particularly preferably, the polyester carbonates according to the present invention do not contain any aromatic structures derived from aromatic dicarboxylic acids.

[0043] The polyester carbonate according to the present invention has a structural motif [ka] Total and structural motifs [ka] It is preferable that the molar ratio of is 6:4 to 9:1, more preferably 7:3 to 8:2. As already explained above, this ratio can be freely selected in the polyester carbonate according to the present invention. This achieves a good balance between the rigidity and flexibility of the polymer chain, and consequently results in good mechanical properties.

[0044] Similarly, the polyester carbonate according to the present invention has the following structural motifs [ka] With respect to the total sum, at least 45 mol%, preferably at least 50 mol%, of polyester carbonate is used as the structural motif. [ka] It is preferable that the composition consists of the following. This amount is particularly advantageous for achieving a high glass transition temperature.

[0045] Furthermore, according to the present invention, A may also represent a structural unit (C), which includes an aromatic structure. However, these are preferably present in small proportions. Preferably, (C) is present additionally in amounts of up to 20 mol%, more preferably up to 10 mol%, and very preferably up to 5 mol%, relative to the total sum of structural units (A), (B), and (C). In this case, the ratio of (A) to (B) as defined in the claims remains the same. In these cases, according to the present invention, aliphatic polyester carbonates are still preferably referred to. However, the polyester carbonate according to the present invention is particularly preferably free of structural unit (C). Similarly, the polyester carbonate according to the present invention preferably contains neither structural unit (C) nor aromatic structural unit y2. In general, aromatic compounds in polyester carbonates reduce the UV stability and weather resistance of the polyester carbonate. This is particularly disadvantageous for outdoor applications. Furthermore, aromatic components in polyester carbonate may reduce the surface hardness of molded articles produced therefrom, potentially necessitating coating. Additionally, diphenyl esters of aromatic acids that may form as intermediates are stable intermediates that can, for example, slow down polycondensation. Consequently, the use of further specific catalysts may be required in some cases. Therefore, it is preferable that A consists of (A) and (B).

[0046] These additional structural units (C) are preferably selected from the group of structural units derived from the following diols: bisphenol A, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl (DOD), 4,4'-dihydroxydiphenyl ether (DOD ether), bisphenol B, bisphenol M, bisphenol (I) to (III). [ka] (In these formulas (I) to (III), R' represents a C1-C4 alkyl, aralkyl, or aryl group, preferably methyl or phenyl, and very preferably methyl, in each case.) According to the present invention, the expression "derived from" preferably means that the corresponding monomer is introduced into the polyester carbonate formed either by the formation of an ester group or a carbonate group, via a hydroxyl group or even an acid group.

[0047] According to the present invention, it is preferable that the above-specified mol% and ratio are maintained for structural formula (1) or when further units exist in structural formula (1). In this case, the molar amounts of each newly defined unit are included therein.

[0048] Similarly, the specified mol% in the polyester carbonate according to the present invention 1 It is preferable to determine this by 1H NMR. This method is known to those skilled in the art. The polyester carbonate may be dissolved in, for example, CDCl3, and the corresponding peaks of the structural units may be identified. The ratios and proportions can be determined by integration. On the other hand, the mol% according to the present invention can also be determined by the molar amounts and ratios of monomers used. In this case, it is necessary to assume that all monomers are completely incorporated into the polyester carbonate in the same proportions. Thus, those skilled in the art can also pre-determine the ratios.

[0049] The polyester carbonate according to the present invention has a relative solution viscosity of 1.20 to 1.70, preferably 1.23 to 1.67, and particularly preferably 1.25 to 1.65. relThe relative viscosity (also called relative η) was determined at 25°C in dichloromethane at a concentration of 5 g / l using an Ubbelohde viscometer. Those skilled in the art are familiar with determining relative solution viscosity using an Ubbelohde viscometer. According to the present invention, this determination is preferably carried out according to DIN 51562-3; 1985-05. This method involves measuring the flow time of the polyester carbonate to be measured using an Ubbelohde viscometer, and then determining the difference in viscosity between the polymer solution and its solvent. For this purpose, the Ubbelohde viscometer is initially calibrated by measuring pure solvents, dichloromethane, trichloroethylene, and tetrachloroethylene (always at least 3 times, but at most 9 times). Subsequently, the actual calibration is performed using the solvent dichloromethane. Next, the polymer sample is weighed and dissolved in dichloromethane, and the flow time of this solution is determined 3 times. The relative solution viscosity is calculated by correcting the average value of the flow times via the Hagenbach correction.

[0050] Here's how to determine relative η.

[0051] In a further embodiment of the present invention, a method for preparing a polyester carbonate according to the present invention by melt transesterification, (i) at least chemical formula (IIa) or chemical formula (IIb) [ka] (In the formula, Each B independently represents a CH2 group or a heteroatom selected from the group consisting of O and S, preferably a CH2 group or an oxygen atom. Each R1 independently represents a single bond or an alkylene group having 1 to 10 carbon atoms, preferably a single bond or an alkylene group having 1 to 5 carbon atoms, particularly preferably a single bond, and n is a number between 0 and 3, preferably 0 or 1) and at least one dicarboxylic acid, Using at least one catalyst, a diaryl carbonate is combined with at least one component (A) at least one 1,4:3,6-dianehydrohexitol and component (B) chemical formula (I) HO-X-OH (I) The process involves reacting a mixture of dihydroxy compounds containing at least one further aliphatic dihydroxy compound of the formula (wherein X represents a branched alkylene group having 4 to 20, preferably 5 to 15 carbon atoms, which can be optionally interrupted by at least one heteroatom, where the cycloalkylene group has 4 to 20, preferably 5 to 15 carbon atoms, which can be optionally interrupted by at least one heteroatom, and the cycloalkylene group may optionally contain multiple rings), in the presence of the mixture of dihydroxy compounds. (ii) A step of further condensing the mixture obtained from step (i) while removing at least the chemical compounds that were removed during condensation, Includes, In each case, a mixture of dihydroxy compounds is calculated based on the sum of components (A) and (B). Component (A) in an amount of 98 mol% to 75 mol%, preferably 97 mol% to 80 mol%, and particularly preferably 96 mol% to 82 mol%, Component (B) in an amount of 2 mol% to 25 mol%, preferably 3 mol% to 20 mol%, and particularly preferably 4 mol% to 18 mol%, A method is provided characterized by comprising the following. According to the present invention, step (i) of the method involves a reaction between at least one alicyclic dicarboxylic acid and at least one diaryl carbonate. However, according to the present invention, further reactions cannot be ruled out as a result of the presence of at least one 1,4:3,6-dianhydrohexitol (hereinafter also referred to as component (A)) and at least one further aliphatic dihydroxy compound (hereinafter also referred to as component (B)) (it should be noted that components (A) and (B) subsequently lead to structural units (A) and (B) in the polyester carbonate according to the present invention). In fact, examples have demonstrated that as early as step (i) of the method, oligomers with a mass interval in a MALDI-ToF mass spectrometer corresponding to units formed from component (A) and / or component (B) and the carbonate (with two hydroxyl groups lost) are formed. This means that further reactions other than the formation of diesters may occur in step (i) of the method. However, according to the present invention, this also means that the reaction between all present alicyclic dicarboxylic acids and a stoichiometric equivalent amount of diaryl carbonate does not need to have occurred and been completed before the start of step (ii). However, according to the present invention, it is preferable to start step (ii) only after carrying out step (i) until a substantial reduction in gas formation can be observed, for example by applying a vacuum to remove chemical compounds desorbed during condensation. However, as already stated above, optionally, step (i) and step (ii) cannot be clearly distinguished from each other according to the present invention.

[0052] Method step (i) The method according to the present invention is called direct synthesis or even one-pot synthesis. This is because, in step (i) of the method, all structural elements that will form the subsequent polyester carbonate are already present as monomers. Preferably, according to the present invention, all aliphatic dihydroxy compounds (components (A) and (B) in each case), all alicyclic dicarboxylic acids, and all diaryl carbonates are present in this step, even if there are more than just the dihydroxy compounds, alicyclic dicarboxylic acids, and / or diaryl carbonates of components (A) and (B). Therefore, according to the present invention, it is preferable that all monomers that will be condensed to form a polyester carbonate in step (ii) are already present during step (i). The present invention may also include embodiments in which a small proportion of at least one diaryl carbonate is additionally added in step (ii). This can be used selectively to reduce the OH-terminated group content of the resulting polyester carbonate. Such an approach is described, for example, in Japanese Patent Application Publication No. 2010-077398. However, in this case, if all the structural elements that form the subsequent polyester carbonate are still present as monomers in step (i) and no further structural elements are added, then the at least one diaryl carbonate added in small amounts in step (ii) must correspond to the at least one diaryl carbonate present in step (i). Therefore, in this sense, this method can still be called direct synthesis or one-pot synthesis.

[0053] Furthermore, according to the present invention, the presence of aromatic dihydroxy compounds and / or aromatic dicarboxylic acids in step (i) is not excluded. However, these are preferably present only in small amounts. In step (i), it is particularly preferable that there be an additional up to 20 mol%, more preferably up to 10 mol%, and very particularly preferably up to 5 mol% of aromatic dihydroxy compounds (component (C)) relative to the total molar amount of dihydroxy compounds used. Here, the ratio of component (A) to component (B) as defined in the claims remains the same. In step (i), it is also particularly preferable that, optionally in addition to aromatic dihydroxy compounds, there be an additional up to 20 mol%, more preferably up to 10 mol%, and very particularly preferably up to 5 mol% of aromatic dicarboxylic acids relative to the total molar amount of dicarboxylic acids used. In these cases, according to the present invention, aliphatic polyester carbonates are still preferably mentioned. However, it is particularly preferable not to use aromatic dihydroxy compounds in step (i). Similarly, it is also preferable not to use aromatic dicarboxylic acids in step (i). Similarly, it is preferable not to use either aromatic dihydroxy compounds or aromatic dicarboxylic acids in step (i). Generally, aromatic compounds in polyester carbonates reduce their UV stability and weather resistance. This is particularly disadvantageous for outdoor applications. Furthermore, aromatic components in polyester carbonates can reduce the surface hardness of molded articles produced from them, sometimes necessitating coating. In addition, diphenyl esters of aromatic acids that may form as intermediates are stable intermediates that can, for example, slow down polycondensation. As a result, the use of additional specific catalysts may be required in some cases.

[0054] These additional aromatic dihydroxy compounds (component (C)) are preferably bisphenol A, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl (DOD), 4,4'-dihydroxydiphenyl ether (DOD ether), bisphenol B, bisphenol M, bisphenol (I) to bisphenol (III). [ka] (In these formulas (I) to (III), R' is selected from the group consisting of C1-C4 alkyl, aralkyl, or aryl, preferably methyl or phenyl, and very preferably methyl, in each case.)

[0055] These additional aromatic dicarboxylic acids are preferably selected from the group consisting of isophthalic acid, terephthalic acid, 2,5-franzicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. It is known that even small amounts of these aromatic diacides can reduce the water absorption of aliphatic polyester carbonates.

[0056] According to the present invention, in step (i) of the method, at least one 1,4:3,6-dianhydrohexitol is used as component (A). As is known to those skilled in the art, 1,4:3,6-dianhydrohexitol is generally selected from the group consisting of isomannides, isoidides, and isosorbides. This may include bio-based structural elements that have all the advantages of bio-based monomers and the resulting polymers (for example, they can be obtained from renewable raw materials and are therefore more sustainable). The method according to the present invention is particularly characterized in that at least one 1,4:3,6-dianhydrohexitol is isosorbide. It is preferable that component (A) consists of isosorbide.

[0057] According to the present invention, in step (i) of the method, at least one further aliphatic dihydroxy compound (component (B)) is used. Preferably, component (B) consists of two further aliphatic dihydroxy compounds. Similarly, preferably, component (B) consists of one further aliphatic dihydroxy compound. Therefore, it is particularly preferable that component (A) consists of isosorbide and component (B) consists of further aliphatic dihydroxy compounds. Optionally, component (C) containing an aromatic dihydroxy compound (see above) may be present in the mixture of dihydroxy compounds.

[0058] Here, at least one further aliphatic dihydroxy compound is given chemical formula (I): HO-X-OH (I) It is preferable that the formula has (wherein X represents a linear alkylene group having 2 to 22 carbon atoms, preferably 2 to 15, particularly preferably 2 to 10 carbon atoms, which can be optionally interrupted by at least one heteroatom, a branched alkylene group having 4 to 20, preferably 5 to 15 carbon atoms, which can be optionally interrupted by at least one heteroatom, or a cycloalkylene group having 4 to 20, preferably 5 to 15 carbon atoms, which can be optionally interrupted by at least one heteroatom, where the cycloalkylene group may optionally contain multiple rings and may optionally be branched in each case).

[0059] In formula (I), X represents a branched alkylene group having 4 to 20 carbon atoms, preferably 5 to 15 carbon atoms, or a cycloalkylene group containing at least one branch, which can be optionally interrupted by at least one heteroatom, wherein the cycloalkylene group has 4 to 20 carbon atoms, preferably 5 to 15 carbon atoms, can be optionally interrupted by at least one heteroatom, and the cycloalkylene group may optionally contain multiple rings.

[0060] According to the present invention, when X is a linear alkylene group that can be optionally interrupted by at least one heteroatom, it preferably has 2 to 15 carbon atoms, particularly preferably 2 to 12, very particularly preferably 2 to 11, particularly preferably 2 to 10, more preferably 2 to 6, and more preferably 3 to 4 carbon atoms. The heteroatom that can optionally interrupt the alkylene group is preferably oxygen or sulfur, particularly preferably oxygen. Particularly preferably, the alkylene group contains only one heteroatom or does not contain a heteroatom. When there is at least one heteroatom present in the alkylene group, the indicated number of carbon atoms refers to the total number of carbon atoms in the alkylene group. For example, the group -CH2-CH2-O-CH2-CH2- contains 4 carbon atoms. According to the present invention, a linear alkylene group that can be optionally interrupted by at least one heteroatom preferably has fewer than 12 carbon atoms, particularly preferably fewer than 10. Particularly preferably, the alkylene group does not contain any heteroatoms.

[0061] Preferably, X represents a branched alkylene group having 4 to 20, preferably 5 to 15, particularly preferably 5 to 11, and very particularly preferably 5 to 10 carbon atoms, which can be optionally interrupted by at least one heteroatom. The heteroatom that can optionally interrupt the branched alkylene group is preferably oxygen or sulfur, particularly preferably oxygen. Particularly preferably, the branched alkylene group contains only one heteroatom or contains no heteroatoms. Particularly preferably, the branched alkylene group contains no heteroatoms at all. When there is at least one heteroatom present in the alkylene group, the indicated number of carbon atoms refers to the total number of carbon atoms in the alkylene group. For example, the group -CH2-CH2-O-CH2-CH2- contains 4 carbon atoms. The term "branched" is understood to refer to branching in an aliphatic carbon chain, as known to those skilled in the art. This means that the branched alkylene group preferably contains at least one tertiary carbon atom and / or at least one quaternary carbon atom. A branched alkylene group may have two or more branches. Each branch has a chain length of preferably 1 to 5 carbon atoms, particularly preferably 1 to 4 carbon atoms, and very particularly preferably 1 to 3 carbon atoms. These carbon atoms in the branch are taken into account in the total number of carbon atoms of the branched alkylene group. This means, for example, that the branched alkylene group -CH2-C(CH3)2-CH2- has 5 carbon atoms.

[0062] According to the present invention, the above description applies to the heteroatom when X is a cycloalkylene group having 4 to 20, preferably 5 to 15 carbon atoms, which can be optionally interrupted by at least one heteroatom, and the cycloalkylene group may optionally contain multiple rings, each of which may optionally be branched. The heteroatom that can optionally interrupt the cycloalkylene group is preferably oxygen or sulfur, particularly preferably oxygen. Particularly preferably, the cycloalkylene group contains only one heteroatom or does not contain a heteroatom. Particularly preferably, the cycloalkylene group has no heteroatoms at all. Preferably, the cycloalkylene group has at least one, preferably one ring, having 4 to 6 carbon atoms. Particularly preferably, the cycloalkylene group has a total of 4 to 20, preferably 5 to 15 carbon atoms, and a ring having 4 to 5 carbon atoms. In this case, the carbon atoms of the ring are considered in the total number of carbon atoms in the cycloalkylene group. This means that the tetramethylcyclobutenyl group has a total of eight carbon atoms and includes a ring having four carbon atoms. The cycloalkylene group may further have at least one branch, which is particularly preferred. If branching is present, it may be present in the alicyclic chain and / or ring, if any. Preferably, the branching is present in the ring. Preferably, X is a cycloalkylene group having 5 to 15 carbon atoms including a ring, which optionally has at least one branch, preferably at least one branch, and has at least one ring, preferably a ring having 4 to 6 carbon atoms, particularly preferably a ring having 4 to 5 carbon atoms.

[0063] According to the present invention, the above description applies to heteroatoms when X is a branched cycloalkylene group having 4 to 20, preferably 5 to 15 carbon atoms, which can be optionally interrupted by at least one heteroatom, and the cycloalkylene group can optionally contain multiple rings. The heteroatom that can optionally interrupt the cycloalkylene group is preferably oxygen or sulfur, particularly preferably oxygen. Particularly preferably, the cycloalkylene group contains only one heteroatom or contains no heteroatoms. Particularly preferably, the cycloalkylene group has no heteroatoms at all. Preferably, the cycloalkylene group has at least one, preferably one ring, having 4 to 6 carbon atoms. Particularly preferably, the cycloalkylene group has a total of 4 to 20, preferably 5 to 15 carbon atoms, and a ring having 4 to 5 carbon atoms. In this case, the carbon atoms of the ring are considered in the total number of carbon atoms in the cycloalkylene group. This means that the tetramethylcyclobutenyl group has a total of 8 carbon atoms and contains a ring having 4 carbon atoms. Furthermore, the cycloalkylene group has at least one branch. These branches may be present in the alicyclic chain and / or within the ring. Preferably, the branch is within the ring. The term “branch” in relation to the cycloalkylene group is understood to refer to a branch known to those skilled in the art. This means that a branched cycloalkylene group preferably contains at least one tertiary carbon atom and / or at least one quaternary carbon atom. In this case, it is understood that the two tertiary carbon atoms connecting the ring and the polymer chain are not considered branches according to the present invention. This preferably means that when the cycloalkylene group has at least one branch on at least the ring, the ring has at least one tertiary carbon atom and / or quaternary carbon atom in addition to the two tertiary carbon atoms connecting the ring and the polymer chain (in formula (3) *(See also ). Similarly, branching can also be present in alkyl groups present on the ring (for example, when x is 2,2-bis(4-cyclohexylene)propane). Particularly preferably, “branched” with respect to a cycloalkylene group is understood to mean that the group has at least one quaternary carbon atom. Preferably, X is a cycloalkylene group having 5 to 15 carbon atoms including a ring, which optionally has at least one branch, preferably at least one branch, and has at least one ring, preferably a ring having 4 to 6 carbon atoms, particularly preferably a ring having 4 to 5 carbon atoms.

[0064] Overall, according to the present invention, it is preferable that at least one further aliphatic dihydroxy compound has 2 to 10 carbon atoms.

[0065] Particularly preferred is the method according to the present invention, in which at least one further aliphatic dihydroxy compound is 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2-bis(4-hydroxycyclohexyl)propane, tetrahydro-2,5-frangimethanol, 2-butyl-2-ethyl-1,3-propanediol, 2-(2-hydroxyethoxy)ethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethylpropane-1,3-diol, cyclobutane-1,1-diyldimethanol, 8-(hydroxymethyl)-3-tricyclo[5.2.1.0 2,6The present invention is characterized by being selected from the group consisting of ]decanyl]methanol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, and any desired mixture thereof. In particular, it is preferable that at least one further aliphatic dihydroxy compound is selected from the group consisting of 2-butyl-2-ethyl-1,3-propanediol, 2-(2-hydroxyethoxy)ethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethylpropane-1,3-diol, cyclobutane-1,1-diyldimethanol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, and any desired mixture thereof. Similarly, it is preferable that at least one further aliphatic dihydroxy compound is selected from the group consisting of 2-butyl-2-ethyl-1,3-propanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethylpropane-1,3-diol, cyclobutane-1,1-diyldimethanol, 1,4-butanediol, and any desired mixtures thereof. Most particularly preferred, at least one further aliphatic dihydroxy compound is selected from the group consisting of 2-butyl-2-ethyl-1,3-propanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethylpropane-1,3-diol, cyclobutane-1,1-diyldimethanol, and any desired mixtures thereof.

[0066] Similarly, the method according to the present invention provides for at least one further aliphatic dihydroxy compound, such as 2,2-bis(4-hydroxycyclohexyl)propane, 2-butyl-2-ethyl-1,3-propanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethylpropane-1,3-diol, 8-(hydroxymethyl)-3-tricyclo[5.2.1.0 2,6 It is preferable that the compound is selected from the group consisting of ]decanyl]methanol and any desired mixture thereof. In particular, it is preferable that at least one further aliphatic dihydroxy compound is selected from the group consisting of 2-butyl-2-ethyl-1,3-propanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethylpropane-1,3-diol and any desired mixture thereof. Similarly, it is preferable that at least one further aliphatic dihydroxy compound is selected from the group consisting of 2-butyl-2-ethyl-1,3-propanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethylpropane-1,3-diol and any desired mixture thereof. More preferably, at least one further aliphatic dihydroxy compound is selected from the group consisting of 2-butyl-2-ethyl-1,3-propanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethylpropane-1,3-diol, and any desired mixture thereof.

[0067] Similarly, according to the present invention, at least one alicyclic dicarboxylic acid is used in step (i) of the method. Here, at least one alicyclic dicarboxylic acid is of chemical formula (IIa), (IIb) [ka] (In the formula, Each B independently represents a CH2 group or a heteroatom selected from the group consisting of O and S, preferably a CH2 group or an oxygen atom. Each R1 independently represents a single bond or an alkylene group having 1 to 10 carbon atoms, preferably a single bond or an alkylene group having 1 to 5 carbon atoms, particularly preferably a single bond, and n is preferably selected from compounds or mixtures thereof (where n is a number between 0 and 3, preferably 0 or 1).

[0068] When R1 represents a single bond, it will be understood that R1 does not contain a carbon atom.

[0069] At least one alicyclic dicarboxylic acid is particularly preferably selected from the group consisting of 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, tetradihydro-2,5-franglicarboxylic acid, tetradihydro-2,5-dimethylfranglicarboxylic acid, decahydro-2,4-naphthalenedicarboxylic acid, decahydro-2,5-naphthalenedicarboxylic acid, decahydro-2,6-naphthalenedicarboxylic acid, and decahydro-2,7-naphthalenedicarboxylic acid. Any desired mixture can also be used. 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, or 1,2-cyclohexanedicarboxylic acid are particularly preferred.

[0070] In addition to alicyclic acids, small amounts of further aliphatic acids may also be used. In step (i) of the method, up to 20 mol%, more preferably up to 10 mol%, and very preferably up to 5 mol%, of further aliphatic acids may be present, where it is particularly preferable that these acids are not alicyclic acids. The further aliphatic acids are preferably selected from the group consisting of 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, 2,2,5-trimethyladipic acid, and 3,3-dimethylglutaric acid.

[0071] Similarly, according to the present invention, in step (i) of the method, at least one diaryl carbonate is used. Here, the at least one diaryl carbonate is a compound of formula (2) [ka] (In the formula, R, R', and R'' may be independent, identical or different, and each may be hydrogen, or an arbitrarily branched C1-C) 34 Alkyl, C7~C 34 Alkylaryl, C6~C 34 It is preferable to select from the group consisting of compounds (representing aryl, nitro, carbonyl-containing, carboxyl-containing, or halogen groups). Preferably, R, R', and R'' may be the same or different, each independently, and may include hydrogen, or optionally branched C1-C 34 Alkyl, C7~C 34 Alkylaryl, C6~C 34The term represents an aryl, nitro, carbonyl-containing, or halogen group. At least one diaryl carbonate is preferably diphenyl carbonate, 4-tert-butylphenyl carbonate, di(4-tert-butylphenyl) carbonate, biphenyl-4-ylphenyl carbonate, di(biphenyl-4-yl) carbonate, 4-(1-methyl-1-phenylethyl)phenylphenyl carbonate, di[4-(1-methyl-1-phenylethyl)phenyl] carbonate, bis(methylsalicyl) carbonate, bis(ethylsalicyl) carbonate, bis(propylsalicyl) carbonate, bis(2-benzoylphenyl) carbonate, bis(phenylsalicyl) carbonate, and / or bis(benzylsalicyl) carbonate. At least one diaryl carbonate is preferably diphenyl carbonate, 4-tert-butylphenyl carbonate, di(4-tert-butylphenyl) carbonate, biphenyl-4-ylphenyl carbonate, di(biphenyl-4-yl) carbonate, 4-(1-methyl-1-phenylethyl)phenylphenyl carbonate, di[4-(1-methyl-1-phenylethyl)phenyl] carbonate, bis(2-benzoylphenyl) carbonate, bis(phenylsalicylic) carbonate, and / or bis(benzylsalicylic) carbonate. At least one diaryl carbonate is particularly preferably diphenyl carbonate, 4-tert-butylphenylphenyl carbonate, di(4-tert-butylphenyl) carbonate, biphenyl-4-ylphenyl carbonate, di(biphenyl-4-yl) carbonate, 4-(1-methyl-1-phenylethyl)phenylphenyl carbonate, and / or di[4-(1-methyl-1-phenylethyl)phenyl] carbonate. At least one diaryl carbonate is particularly preferably diphenyl carbonate.

[0072] Furthermore, according to the present invention, at least one catalyst is present in step (i) of the method. This is preferably an inorganic base and / or an organic catalyst. The at least one catalyst is particularly preferably pK of 5 or less.b It is an inorganic or organic base that has [a certain characteristic].

[0073] At least one inorganic base or at least one organic catalyst is lithium, sodium, potassium, cesium, calcium, barium, and magnesium hydroxides, carbonates, halides, phenoxides, diphenoxides, fluorides, acetates, phosphates, hydrogen phosphates, and borates, tetramethylammonium hydroxide, tetramethylammonium acetate, tetramethylammonium fluoride, tetramethylammonium tetraphenylborate, tetraphenylphosphonium fluoride, tetraphenylphosphonium tetraphenylborate, dimethyldiphenylammonium hydroxide, tetraethylammonium hydroxide, cetyltrimethylammonium tetraphenylborate, cetyltrimethylammonium phenoxide, diazabicycloundecene (DBU), diazabicyclononene (DBN), 1,5,7-triazabicyclo[4.4.0] Deca-5-ene, 7-phenyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7,7'-hexylidenedi-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7,7'-decylidenedi-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7,7'-dodecylidenedi-1,5,7-triazabicyclo[4.4 It is also preferable to select from the group consisting of [0]deca-5-ene, phosphazene base P1-t-oct(tert-octyliminotris(dimethylamino)phosphoran), phosphazene base P1-t-butyl(tert-butyliminotris(dimethylamino)phosphoran), and 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diaza-2-phosphoran (BEMP). Any desired mixture can also be used.

[0074] At least one catalyst is particularly preferably an organic base, preferably the above organic bases, very particularly preferably an alkylamine, imidazole (derivative), a guanidine base such as triazabicyclodecene, DMAP and its corresponding derivative, DBN, and DBU, most preferably DMAP. These catalysts offer a particular advantage in step (ii) of the method according to the present invention, that they can be separated and removed along with the chemical compounds desorbed during condensation, for example by reduced pressure. This means that the resulting polyester carbonate contains only a small amount of catalyst, or even none at all. This offers a particular advantage that the polymer does not contain inorganic salts, for example, phosgene, which are always formed in pathways where phosgene is used. Such salts are known to adversely affect the stability of polyester carbonates, because ions can act as catalysts with respect to the corresponding decomposition.

[0075] It is preferable to use at least one catalyst in an amount of 1 ppm to 5000 ppm, preferably 5 ppm to 1000 ppm, and particularly preferably 20 ppm to 200 ppm, per 1 mole of alicyclic dicarboxylic acid.

[0076] In another embodiment, the method according to the present invention is characterized in that the reaction in step (i) is carried out in the presence of at least one first catalyst and / or a second catalyst, and the condensation in step (ii) is carried out in the presence of at least the first catalyst and the second catalyst, wherein the first catalyst is at least one tertiary nitrogen base, the second catalyst is at least one basic compound, preferably a basic alkali metal salt, and the proportion of alkali metal cations in step (ii) is 0.0008% to 0.0050% by weight with respect to all components used in step (i).

[0077] Therefore, in this embodiment, the first catalyst and / or the second catalyst are present in step (i) of the method.

[0078] The first catalyst is a tertiary nitrogen base. This first catalyst is preferably selected from bases derived from guanidine, 4-dimethylaminopyridine (DMAP), 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5-diazabicyclo[4.3.0]nona-5-ene, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, hexamethylphosphorimide triamide, 1,2-dimethyl-1,4,5,6-tetrahydropyridine, 7-methyl-1,5,7-triazabicyclodeca-5-ene, 1,8-diazabicyclo[5.4.0]undeca-7-ene (DBU), DBN, ethylimidazole, N,N-diisopropylethylamine (Hünig base), pyridine, TMG, and mixtures of these substances. More preferably, the first catalyst is selected from a base derived from guanidine, 4-dimethylaminopyridine (DMAP), 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5-diazabicyclo[4.3.0]nona-5-ene, and 1,5,7-triazabicyclo[4.4.0]deca-5-ene. The use of 4-dimethylaminopyridine is particularly preferred.

[0079] The first catalyst is preferably used in an amount of 0.002% to 0.10% by weight, more preferably 0.005% to 0.050% by weight, and particularly preferably 0.008% to 0.030% by weight, relative to all components used in step (i) of the method in each case.

[0080] The second catalyst is preferably selected from the group consisting of inorganic or organic alkali metal salts and inorganic or organic alkaline earth metal salts. More preferably, the alkali metal cations present in step (ii) are lithium cations, potassium cations, sodium cations, cesium cations, and mixtures thereof.

[0081] The second catalyst used is preferably an organic or inorganic alkali metal salt or alkaline earth metal salt of a weak acid (pKa between 3 and 7 at 25°C). Suitable weak acids include, for example, carboxylic acids, preferably C2-C2. 22 These include carboxylic acids, such as acetic acid, propionic acid, oleic acid, stearic acid, lauric acid, benzoic acid, 4-methoxybenzoic acid, 3-methylbenzoic acid, 4-tert-butylbenzoic acid, p-tolueneacetic acid, 4-hydroxybenzoic acid, salicylic acid, partial esters of polycarboxylic acids, such as monoesters of succinic acid, and branched aliphatic carboxylic acids, such as 2,2-dimethylpropanoic acid, 2,2-dimethylpropanoic acid, 2,2-dimethylbutanoic acid, and 2-ethylhexanoic acid. However, it is also possible to use organic or inorganic alkali metal salts or alkaline earth metal salts of strong acids, such as hydrochloric acid.

[0082] Suitable organic and inorganic salts include, or are derived from, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, sodium carbonate, lithium carbonate, potassium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium oleate, lithium oleate, potassium oleate, sodium benzoate, potassium benzoate, lithium benzoate, and disodium, dipotassium, and dilithium salts of BPA. Calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and their corresponding oleates can also be used. Phenols, particularly their corresponding salts, can also be used. These salts can be used individually or in mixtures.

[0083] The second catalyst is preferably selected from the group consisting of sodium hydroxide, lithium hydroxide, sodium phenoxide, lithium phenoxide, sodium benzoate, lithium benzoate, lithium chloride, lithium acetylacetonate, and cesium carbonate, and mixtures thereof. Sodium phenoxide, lithium phenoxide, sodium hydroxide, lithium hydroxide, sodium benzoate, lithium benzoate, lithium chloride, and / or lithium acetylacetonate are particularly preferred. Lithium chloride is preferably used as an aqueous solution, for example, in the form of a 15% solution.

[0084] It was found that the molar ratio of all aliphatic dihydroxy compounds present in step (i) to all alicyclic dicarboxylic acids present in step (i) before the reaction in step (i) is preferably 1:0.6 to 1:0.05, more preferably 1:0.5 to 1:0.15, and very preferably 1:0.4 to 1:0.2.

[0085] To achieve particularly advantageous mechanical properties, good chemical resistance, and good processability, it is preferable that the ratio of aliphatic dihydroxy compounds to alicyclic dicarboxylic acids in the subsequent polyester carbonate is not too high (i.e., the content of incorporated alicyclic dicarboxylic acids is not too low). Polymers with a high content of units derived from dihydroxy compounds such as isosorbide are usually very rigid and therefore have insufficient mechanical properties. If the content of units derived from alicyclic dicarboxylic acids is too low, the processability of the resulting polymer will also be more insufficient. Furthermore, since polyester units generally provide good chemical resistance to polyester carbonates, the content of units derived from alicyclic dicarboxylic acids should not be too low either.

[0086] According to the present invention, the molar ratio of all aliphatic dihydroxy compounds present in step (i) to all alicyclic dicarboxylic acids present in step (i) before the reaction in step (i) is preferably 1:0.6 to 1:0.05, more preferably 1:0.55 to 1:0.1, and particularly preferably 1:0.5 to 1:0.15. According to the present invention, it has been found that the increase in molecular weight, and therefore surface renewal, is particularly good, especially within this range.

[0087] According to the present invention, in the method according to the present invention, 60 to 90 parts of isosorbide, preferably 65 to 85 parts of isosorbide or isosorbide isomer, 40 to 10 parts of alicyclic dicarboxylic acid, preferably 35 to 15 parts of alicyclic dicarboxylic acid, preferably 1,4-cyclohexanedicarboxylic acid, This is particularly advantageous in that case.

[0088] 2 mol% to 25 mol%, preferably 3 mol% to 20 mol%, and particularly preferably 4 mol% to 18 mol% of isosorbide is replaced by at least one further aliphatic diol, particularly a linear, very preferably branched diol having 2 to 10 carbon atoms. Here, the total amount of at least one aliphatic diol in the whole composition is preferably less than 20 mol%, and particularly less than 15 mol%.

[0089] The method according to the present invention is characterized by the release of carbon dioxide during the process. According to the present invention, carbon dioxide is preferably desorbed in step (i) of the method (see the reaction scheme above). This procedure enables a rapid reaction with low thermal stress.

[0090] Furthermore, step (i) of the present invention preferably includes at least one, and particularly preferably all, of the following steps (ia) to (ic):

[0091] (ia) A step of melting all components present in step (i), namely at least one alicyclic dicarboxylic acid, at least one diaryl carbonate, and at least components (A) and (B) in the presence of at least one catalyst. This is preferably carried out under a protective gas atmosphere, preferably under nitrogen and / or argon. Step (ia) is preferably carried out in the absence of a solvent. The term “solvent” is known to those skilled in the art in this context. According to the present invention, the term “solvent” is preferably understood to mean a compound that does not undergo a chemical reaction in either step (i) or step (ii). Compounds formed by the reaction (e.g., phenol when diphenyl carbonate is used as at least one diaryl carbonate) are excluded. Naturally, the presence of trace amounts of solvent in the starting compounds cannot be excluded. In this case, it is preferable to include them according to the present invention. However, according to the present invention, it is preferable to avoid an active step of adding such a solvent.

[0092] (ib) A step of heating the mixture, preferably the molten material obtained from step (ia). Steps (ia) and (ib) may overlap, since heating may be required in step (ia) to produce the molten material. The heating is preferably carried out initially at a temperature of 150°C to 180°C.

[0093] (ic) A step in which the mixture, preferably the mixture obtained from step (ib), is reacted, preferably by stirring, while introducing mixing energy. In this case, step (ic) may overlap with step (ib), because the reaction of the mixture may have already started due to heating. In this case, the molten material is preferably already heated to a temperature between 150°C and 180°C as a result of step (ib) under standard pressure. Depending on the catalyst selected, the temperature can be kept in the range of 160°C to 200°C. On the other hand, the temperature in step (ic) can be gradually increased to 200°C to 300°C, preferably 210°C to 260°C, and particularly preferably 215°C to 240°C, depending on the reactivity observed. The reactivity can be estimated from the generation of gas, as is known to those skilled in the art. In this step, higher temperatures are possible in principle, but higher temperatures may cause secondary reactions (e.g., discoloration). Therefore, higher temperatures are not very preferable. The mixture is stirred under standard pressure until the generation of gas has almost stopped. According to the present invention, under these conditions, it is also possible to partially remove the aryl alcohol (for example, phenol when using diphenyl carbonate) formed by the reaction of at least one carboxylic acid with at least one diaryl carbonate.

[0094] According to the present invention, it was also observed that at least one of the dihydroxy compounds (A) and / or (B) had similarly begun to react by this point. For example, oligomers containing carbonate units from the reaction of at least one of the dihydroxy compounds (A) and / or (B) with at least one diaryl carbonate and / or ester units from the reaction of at least one of the dihydroxy compounds (A) and / or (B) with at least one dicarboxylic acid could be detected.

[0095] Therefore, according to the present invention, it is preferable that, before carrying out step (ii), the mixture obtained from step (i) contains an oligomer comprising a carbonate unit from the reaction of at least one dihydroxy compound (component (A) and / or component (B)) with at least one diaryl carbonate and / or an ester unit from the reaction of at least one dihydroxy compound (component (A) and / or component (B)).

[0096] The reaction time in step (ic) depends on the amount of starting material. Preferably, the reaction time in step (ic) is between 0.5 hours and 24 hours, more preferably between 0.75 hours and 5 hours, and particularly preferably between 1 hour and 3 hours. In this case, it is preferable to select a reaction time such that gas generation almost subsides (see the reaction scheme above).

[0097] According to the present invention, the molar ratio of the total amount of all dihydroxy compounds and all alicyclic dicarboxylic acids present in method step (i) before the reaction in method step (i) to all diaryl carbonates present in method step (i) is preferably 1:0.4 to 1:1.6, more preferably 1:0.5 to 1:1.5, more preferably 1:0.6 to 1:1.4, particularly preferably 1:0.7 to 1:1.3, especially preferably 1:0.8 to 1:1.2, and very particularly preferably 1:0.9 to 1:1.1. Those skilled in the art can select the corresponding optimal ratio according to the purity of the starting materials.

[0098] Method step (ii) In step (ii), the mixture obtained from step (i) is subjected to further condensation while removing at least the chemical compounds eliminated during condensation. According to the present invention, the expression "further" condensation should be understood to mean that at least some condensation has already occurred in step (i). This is preferably a reaction between at least one alicyclic dicarboxylic acid and at least one diaryl carbonate, with the elimination of an aryl alcohol. However, it is also preferable that further condensation has already occurred to form an oligomer (see step (i) for this).

[0099] If only the first catalyst or only the second catalyst is used in step (i), the catalyst not used in step (i) is added in step (ii).

[0100] The proportion of alkali metal cations in step (ii) is preferably 0.0009% to 0.0005% by weight, and particularly preferably 0.0010% to 0.0045% by weight, relative to all components used in step (i) in each case.

[0101] In a preferred embodiment, the first catalyst and the second catalyst are present in step (i) of the method.

[0102] It is also possible to use a portion of the first catalyst and / or a portion of the second catalyst in step (i), and then use the remainder of each in step (ii).

[0103] However, it is preferable to use the total amount of the first catalyst and / or the second catalyst in method step (i). It is most preferable to use the total amount of both catalysts in method step (i).

[0104] The term "condensation" is known to those skilled in the art. This is understood to mean a reaction in which two molecules (of the same or different substances) combine to form a larger molecule, and a molecule of a chemically simpler substance is eliminated. This compound eliminated during condensation is removed in step (ii) of the method. Here, it is preferable to remove the chemical compound eliminated during condensation by reduced pressure in step (ii). Therefore, it is preferable that the method according to the present invention is characterized by optionally removing volatile components having a boiling point lower than the alicyclic diester formed in step (i), lower than the mixture of dihydroxy compounds, and lower than at least one diaryl carbonate, by stepwise reduced pressure during the reaction in step (i). When removing various volatile components, it is preferable to choose stepwise removal. It is also preferable to choose stepwise removal in order to remove the volatile components (there may be multiple) as completely as possible. The volatile components are the chemical compounds (there may be multiple) eliminated during condensation.

[0105] Stepwise depressurization can be performed, for example, by immediately reducing the pressure as the overhead temperature drops, thus ensuring the continuous removal of chemical compounds desorbed during condensation. Once a pressure of 1 mbar, preferably less than 1 mbar, is reached, condensation is continued until the desired viscosity is reached. This can be done, for example, by monitoring the torque; that is, stopping the polycondensation when the desired agitator torque is reached.

[0106] The condensation product is preferably removed in step (ii) at a temperature of 200°C to 280°C, particularly preferably 210°C to 260°C, and especially preferably 220°C to 250°C. The vacuum during removal is more preferably 500 mbar to 0.01 mbar. It is particularly preferable to remove the product in stages by lowering the vacuum. The vacuum in the final stage is very preferably 10 mbar to 0.01 mbar.

[0107] The polyester carbonate according to the present invention can be directly processed into all types of molded articles. It can also be processed together with other thermoplastics and / or polymer additives to obtain thermoplastic molding compounds. Molding compounds and molded articles are further subjects of the present invention.

[0108] The polymer additive is preferably selected from the group consisting of flame retardants, drip inhibitors, flame retardant aids, smoke suppressants, lubricants and mold release agents, nucleating agents, antistatic agents, conductive additives, stabilizers (e.g., hydrolysis stabilizers, heat aging stabilizers and UV stabilizers, and further anti-transesterification agents), flow promoters, compatibilizers, dyes and pigments, impact resistance modifiers, and further fillers and reinforcing agents.

[0109] Thermoplastic molding compounds can be prepared by known methods, for example, by mixing polyester carbonate and further components and performing melt compounding and melt extrusion in conventional units, such as internal kneaders, extruders, and twin-screw systems, preferably at a temperature of 200°C to 320°C. In the context of the present invention, this method is generally referred to as compounding.

[0110] Therefore, the term “molded compound” is understood to mean the product obtained when the components of a composition are melt-compounded and then melt-extruded.

[0111] Molded articles formed from polyester carbonate or a thermoplastic molding compound containing polyester carbonate according to the present invention can be manufactured, for example, by injection molding, extrusion, and blow molding. Another form of processing is the manufacture of molded articles by thermoforming from a pre-made sheet or film. [Modes for carrying out the invention] [Examples]

[0112] Materials used: Cyclohexanedicarboxylic acid: 1,4-cyclohexanedicarboxylic acid; CAS 1076-97-7 99%; Tokyo Chemical Industry Co., Ltd. (Japan), abbreviated as CHDA. Elemental analysis revealed that CHDA contained less than 1 ppm of sodium. Diphenyl carbonate: Diphenyl carbonate, 99.5%, CAS 102-09-0; Acros Organics (Hale, Belgium), abbreviated as DPC. 4-Dimethylaminopyridine: 4-Dimethylaminopyridine; 98.0% or more; purum; CAS 1122-58-3; Sigma-Aldrich (Munich, Germany), abbreviated as DMAP. Isosorbide: Isosorbide (CAS: 652-67-5), 99.8%, Polysorb PS A; Roquette Freres (France, Restrom 62136); abbreviated as ISB. Lithium hydroxide monohydrate (CAS: 1310-66-3); over 99.0%; Sigma-Aldrich. 2-Butyl-2-ethyl-1,3-propanediol: CAS number 115-84-4; Aldrich (abbreviated as BEPD). 2,2,4,4-Tetramethyl-1,3-cyclobutanediol:98% (CAS:3010-96-6); ABCR (abbreviated as TMCBD). 2,2,4-trimethyl-1,3-pentanediol; CAS number: 144-19-4; Aldrich (abbreviated as TMPD). Neopentyl glycol (2,2-dimethylpropane-1,3-diol); CAS: 126-30-7; Aldrich (abbreviated as NPG). 1,4-Butanediol: CAS: 110-63-4; Merck 99%; (abbreviated as BDO). 1,4-Cyclohexanedimethanol: CAS: 105-08-8, Aldrich 99% (abbreviated as CHDM). 1,12-Dodecanediol: CAS: 5675-51-4, Aldrich 99% (abbreviated as DDD).

[0113] Analysis method: solution viscosity Relative solution viscosity (η rel The relative viscosity (also known as relative η) was determined at 25°C in dichloromethane at a concentration of 5 g / l using an Ubbelohde viscometer. This determination was carried out according to DIN 51562-3; 1985-05. This method involves measuring the flow time of the polyester carbonate to be measured using an Ubbelohde viscometer, and then determining the difference in viscosity between the polymer solution and its solvent. To this end, the Ubbelohde viscometer is initially calibrated by measuring pure solvents, dichloromethane, trichloroethylene, and tetrachloroethylene (always at least 3 times, but no more than 9 measurements). Subsequently, the actual calibration is performed using the solvent dichloromethane. Next, the polymer sample is weighed and dissolved in dichloromethane, and the flow time of this solution is determined 3 times. The relative solution viscosity is calculated by correcting the average of the flow times via the Hagenbach correction.

[0114] Determination of glass transition temperature The glass transition temperature was determined by differential scanning calorimetry (DSC) under nitrogen at a heating rate of 10 K / min, in accordance with standards DIN EN ISO 11357-1:2009-10 and ISO 11357-2:2013-05. Here, the glass transition temperature (Tg) was determined as the inflection point during the second heating process.

[0115] Tensile test The product was dissolved in dichloromethane and neutralized with approximately 50 mg of phosphonic acid (in water). After homogenization, the dichloromethane was evaporated under ambient air, and the remainder was removed in a vacuum drying cabinet under the highest possible vacuum at approximately 60°C. Mechanical grinding was then performed using a hand lever machine and a Retsch mill with a sieve size of 1.5 mm. Pre-drying was carried out in a vacuum drying cabinet at 70°C and less than 50 mbar for approximately 16 hours. The temperature was then increased to 110°C, and drying was continued for 5 hours.

[0116] For tensile testing, films manufactured in a melt press were cut into 5mm wide strips with a length of at least 50mm. Tensile testing was performed according to ASTM D 638 standard. The strips were stretched at room temperature of approximately 25°C and relative humidity of approximately 20%. The tensile modulus was confirmed by pre-tensile testing at 0.01 MPa at a test speed of 100 mm / min. The test speed for continuous measurements was 50 mm / min. The switching of the elongation speed from 100 mm / min to 50 mm / min was controlled by crosshead displacement. The clamp length was 20 mm. No clamp breakage was observed. The tensile test results were summarized as the average value from five individual measurements in each case.

[0117] The flow behavior is confirmed by measuring the melt viscosity using a plate-plate viscometer in accordance with ISO 6721-10 from 1999. In this case, viscosity values ​​at 1 Hz and 10 Hz are used.

[0118] The melt viscosity was determined using an Ares G-2 rotary rheometer manufactured by TA Instruments (Newcastle, Delaware, USA, 19720). A plate-to-plate configuration was used (25 mm diameter). The plate diameter was 25 mm (PP25). The sample containing evaporation residue was first dried in a vacuum drying cabinet at approximately 80°C, and then pressed into a thin film at 240°C using a hot press. The sample was measured at various temperatures above the glass transition temperature. The deformation during measurement was selected so that the measurements were performed within the linear elastic range. Subsequently, the measurement results at various temperatures were shifted to a master curve at a reference temperature of 200°C using time-temperature superposition.

[0119] Comparative Example 1 (Experiment without using additional diols) First, 17.20 g (0.10 mol) of 1,4-cyclohexanedicarboxylic acid, 29.83 g (0.204 mol) of isosorbide, 64.30 g (0.3 mol) of diphenyl carbonate, 0.0111 g of DMAP (4-dimethylaminopyridine; 100 ppm relative to the starting materials CHDA, DPC, and ISB), and 115 μl of an aqueous solution of lithium hydroxide (100 g / l), equivalent to approximately 30 ppm of Li, were placed in a flask equipped with a short-pass separator. Oxygen was removed from the mixture by degassing and aeration with nitrogen four times. The mixture was melted and heated to 160°C at standard pressure with stirring. The mixture was stirred at 160°C for 40 minutes, 175°C for 60 minutes, 190°C for 30 minutes, and 205°C for 10 minutes. Carbon dioxide was continuously generated during this operation. Once CO2 generation ceased, the bath temperature was adjusted to 220°C. After another 20 minutes, a vacuum was applied. The pressure was reduced to 10 mbar over 30 minutes. During this process, phenol was continuously removed. The mixture was stirred at 10 mbar for approximately 10 minutes. Next, the pressure was reduced to less than 1 mbar (approximately 0.7 mbar), and condensation was continued for another 10 minutes. After that, the processing of the mixture was stopped.

[0120] A pale yellow polymer with a solution viscosity of 1.33 relative η was obtained.

[0121] Other examples (Ex.) and comparative examples (Comp.) were carried out as described for Comparative Example 1. First, unlike in Example 1, the aliphatic diols specified in Table 1 were placed together with all other monomers and catalysts that form the polymer in a flask equipped with a short-stroke separator.

[0122] [Table 1]

[0123] Examples 1 to 9 of the present invention demonstrate that, as long as the amount of additional diol according to the present invention is observed, the desired polyester carbonate can be obtained with high viscosity by the method of the present invention. Here, it can be seen that the addition of further aliphatic, branched diols leads to a significant increase in molecular weight compared to the case without further aliphatic diols (see Comparative Example 1). The observation of better miscibility at higher temperatures suggests that a further increase in molecular weight may have occurred. When an excess amount of additional diol is used (see Comparative Examples 5 to 7), the increase in molecular weight is clearly lower. Furthermore, it can be seen that the presence of structural unit (B) in the polyester carbonate initially reduces mechanical properties such as elastic modulus and elongation at break, but a higher molecular weight can be achieved overall. The higher the proportion of structural unit (B), the better the mechanical properties such as elastic modulus and elongation at break. However, if the proportion of structural unit (B) is excessive, a lower molecular weight is obtained, and the mechanical properties deteriorate again. Therefore, a good balance between mechanical properties and molecular weight is achieved within the range of structural unit (B) amounts according to the present invention. Furthermore, a higher molecular weight leads to a lower end group content. Since the decrease in molecular weight usually originates from the chain ends, this is advantageous in principle.

[0124] It should be noted that the error values ​​for elastic modulus and elongation at fracture are relatively high. This is due to the fact that relatively small sample sizes were used and, in some cases, bubble formation occurred. However, those skilled in the art will understand that the values ​​obtained are significant despite these errors.

[0125] Similarly, it can be seen that the use of additional diols containing branching (both branched alkylene groups and branched cycloalkylene groups) results in lower shear viscosity at equivalent Tg values, despite higher solution viscosity.

Claims

1. Structural formula (1) 【Chemistry 1】 A polyester carbonate containing, in the formula, A independently represents at least one of either structural unit (A) or structural unit (B) for each repeating unit, where, (A) is chemical formula (2) 【Chemistry 2】 It represents, and, (B) is chemical formula (3) 【Transformation 3】 (wherein x represents a branched alkylene group having 4 to 20 carbon atoms, or a cycloalkylene group containing at least one branch, which can be optionally interrupted by at least one heteroatom, wherein the cycloalkylene group has 4 to 20 carbon atoms, can be optionally interrupted by at least one heteroatom, and the cycloalkylene group may optionally contain multiple rings.) y is independently either chemical formula (IIIa) or chemical formula (IIIb) 【Chemistry 4】 (In the formula, B is independent of CH ２ Represents a group, or a heteroatom selected from the group consisting of O and S. R １ Each of these independently represents an alkylene group having a single bond or 1 to 10 carbon atoms. n represents a number between 0 and 3, and, 0 < x < 1, In each case ＊ This indicates the position in which the chemical formula is incorporated into the polyester carbonate. In each case, the polyester carbonate is calculated as follows: Structural units (A) of 98 mol% to 75 mol%, Structural units (B) in amounts of 2 mol% to 25 mol%, Including, The polyester carbonate has a relative solution viscosity of 1.20 to 1.70, as measured at 25°C in dichloromethane at a concentration of 5 g / l using an Ubbelohde viscometer. Polyester carbonate, characterized by the following features.

2. The polyester carbonate according to claim 1, characterized in that at least 80% by weight of the polyester carbonate consists of structural formula (1) based on the total weight of the polyester carbonate.

3. The aforementioned polyester carbonate has the following repeating units (i) to (iv): 【Transformation 5】 The polyester carbonate according to claim 1 or 2, characterized by comprising in any order a, b, c, and d (wherein a, b, c, and d each independently represent natural numbers indicating the average number of repeating units in each case). 【Request Item 4】 【Chemistry 6】 2,2-bis(4-cyclohexylene)propane, 2-butyl-2-ethyl-1,3-propylene, 2,2,4,4-tetramethyl-1,3-cyclobutylene, 2,2,4-trimethyl-1,3-pentylene, 2,2-dimethylpropane-1,3-ylene, 8-(methylene)-3-tricyclo[5.2.1.0 ２，６ A polyester carbonate according to any one of claims 1 to 3, characterized by being selected from the group consisting of decanyl methylene and any desired mixture thereof.

5. The following structural motifs 【Transformation 7】 With respect to the total sum, at least 45 mol% of the polyester carbonate is the structural motif 【Transformation 8】 A polyester carbonate according to any one of claims 1 to 4, characterized by comprising the above.

6. A molded compound comprising the polyester carbonate according to any one of claims 1 to 5.

7. A molded article comprising the polyester carbonate described in any one of claims 1 to 5.

8. A method for preparing a polyester carbonate according to any one of claims 1 to 5 by melt transesterification, (i) at least chemical formula (IIa) or chemical formula (IIb) 【Chemistry 9】 (In the formula, B is independent of CH ２ Represents a group, or a heteroatom selected from the group consisting of O and S. R １ Each of these independently represents an alkylene group having a single bond or 1 to 10 carbon atoms, and n is a number between 0 and 3) and at least one dicarboxylic acid, Using at least one catalyst, (A) at least one 1,4:3,6-dianehydrohexitol and (B) chemical formula (I) HO-X-OH (I) The steps include reacting in the presence of a mixture of dihydroxy compounds including at least one further aliphatic dihydroxy compound of the formula (wherein X represents a branched alkylene group having 4 to 20 carbon atoms, which can be optionally interrupted by at least one heteroatom, or a cycloalkylene group containing at least one branch, where the cycloalkylene group has 4 to 20 carbon atoms, can be optionally interrupted by at least one heteroatom, and the cycloalkylene group can optionally contain multiple rings), (ii) A step of further condensing the mixture obtained from step (i) while removing at least the chemical compounds that were removed during condensation, Includes, The mixture of the dihydroxy compounds is, in each case, relative to the sum of component (A) and component (B), Component (A) in a concentration of 98 mol% to 75 mol%, Component (B) in a concentration of 2 mol% to 25 mol%, A method characterized by including

9. The method according to claim 8, characterized in that the molar ratio of all aliphatic dihydroxy compounds present in method step (i) to all alicyclic dicarboxylic acids present in method step (i) prior to the reaction in method step (i) is 1:0.6 to 1:0.

05.

10. At least one further aliphatic dihydroxy compound of the aforementioned chemical formula (I) is 2,2-bis(4-hydroxycyclohexyl)propane, 2-butyl-2-ethyl-1,3-propanediol, 2-(2-hydroxyethoxy)ethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethylpropane-1,3-diol, 8-(hydroxymethyl)-3-tricyclo[5.2.1.0 ２，６ The method according to claim 8 or 9, characterized in that it is selected from the group consisting of decanyl methanol and any desired mixture thereof.

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