Polyester carbonates based on alicyclic diacitors, 1,4:3,6-dianhydrohexitol, and specific amounts of additional aliphatic dihydroxy compounds.

Abstract

The present invention relates to a method for preparing polyestercarbonates based on cycloaliphatic diacids, at least one 1,4:3,6-dianhydrohexitol, and at least one additional aliphatic dihydroxy compound, the polyestercarbonates prepared according to the method, and molding compounds and molded bodies containing the polyestercarbonates. The method according to the invention is a direct synthesis in which all structural elements forming the subsequent polyestercarbonate are already present as monomers in the first process step. It is characterized by a specific ratio of 1,4:3,6-dianhydrohexitol to at least one additional aliphatic dihydroxy compound being advantageous.

Description

[Technical Field]

[0001] The present invention relates to a method for producing copolyester carbonates from an alicyclic diacid and 1,4:3,6-dianhydrohexitol containing a specific amount of additional aliphatic diol, and the corresponding polyester carbonates. [Background technology]

[0002] Polyesters, polycarbonates, and polyester carbonates are known to possess good mechanical properties as well as good stability against thermal deformation and weathering. Depending on the monomer used, each polymer group has certain important characteristics that characterize this type of material. For example, polycarbonates have particularly good mechanical properties, while polyesters often have better chemical stability. Polyester carbonates exhibit property profiles from both of the above groups, depending on the selected monomer.

[0003] Aromatic polycarbonates or polyesters often possess good property profiles, but they exhibit shortcomings in stability against aging or weathering. For example, the absorption of ultraviolet light leads to yellowing, and sometimes embrittlement, of these thermoplastic materials. Aliphatic polycarbonates and polyester carbonates have better properties in this regard, particularly better stability against aging and / or weathering, and better 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 alcohols (tricyclodecanedimethanol; 8-(hydroxymethyl)-3-tricyclo[5.2.1.02,6-decanyl]methanol), cyclohexanediols, cyclohexanedimethanol, and bio-based diols based on 1,4:3,6-dianhydrohexitol, such as isosorbide and its isomers isomannides and isoidides. To further increase the glass transition temperature, alicyclic acids, such as cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, or cyclohexane-1,4-dicarboxylic acid, or their corresponding naphthalene derivatives, can also be used as (co)monomers. Depending on the selection of reactants, polyesters or polyester carbonates are then obtained. This application relates to a copolyester carbonate having improved properties based on 1,4:3,6-dianhydrohexitol, such as isosorbide or its isomer, and an alicyclic diacid containing a specific amount of further diols. The present invention further relates to a method for producing the above-mentioned copolyester carbonate, characterized by the direct reaction of the raw materials and requiring no difficult-to-handle raw materials such as phosgene.

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

[0006] Polyesters are produced 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 cyclohexane-1,4-dimethanol and cyclohexane-1,4-dicarboxylic acid are produced (a blend of this polyester with polycarbonate: DuPont's Xyrex®).

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

[0008] Example 1 of Patent Document 1 describes the direct reaction of a diacid with phenol to form the corresponding ester. In Example 2 of Patent Document 1, a dimethyl ester is reacted with phenol. However, the yields for both variations of phenyl ester production can be further improved. Subsequently, a polyester carbonate is produced. Thus, this document describes a two-step method with corresponding disadvantages of multiple steps, such as complexity, increased cost, and the need for multiple purification steps.

[0009] Patent Document 2 describes the production of diphenyl esters using phosgene in a solvent. Since the subsequent reaction to form aliphatic polyester carbonate does not involve the use of phosgene, combining the phosgene method and the transesterification method in the same part of the plant is highly disadvantageous. Therefore, the method described in Patent Document 2 is also not optimal. Here too, a two-step method is described.

[0010] The two-step method is similarly described in Patent Documents 3, 4 (5), and 6. This means that all of these documents consistently describe obtaining the ester by the reaction of diacids. Subsequently, the initially isolated ester is converted to a polyester carbonate.

[0011] Patent Document 7 discloses an isosorbide-based polycarbonate comprising isosorbide units, aliphatic units derived from aliphatic C14-C44 diacides, aliphatic C14-C44 diols, or combinations thereof, and optionally additional units different from the isosorbide units and aliphatic units, wherein the isosorbide units, aliphatic units, and additional units are each a carbonate or a combination of a carbonate unit and an ester unit. The common disadvantages of aliphatic polycarbonates or polyester carbonates have already been discussed above. In the examples, polymers derived from combinations of isosorbide, alicyclic diacides, and additionally aliphatic diols are not produced. Furthermore, activated carbonates are used in transesterification.

[0012] Non-patent document 2 states that polyesters based on cyclohexanedicarboxylic acid and isosorbide cannot be obtained from cyclohexanedioic acid or cyclohexanedimethyl ester (or only very low molecular weights can be obtained), and can only be produced from acid chlorides of cyclohexanedicarboxylic acid.

[0013] Simple preparations of aromatic polyester carbonates are described, for example, in Patent Document 8. This describes direct synthesis or one-pot synthesis, i.e., synthesis in which all structural elements that form the subsequent polyester carbonate are already present as monomers at the start of the synthesis. In this case, aromatic dihydroxy compounds such as bisphenol A, carboxylic acid diesters, and aromatic diacides or linear aliphatic diacides are used as monomers. Since this document is limited to the preparation of aromatic polyester carbonates, it is possible to use a temperature of 300°C in the condensation reaction while removing the phenol formed. When preparing aliphatic polyester carbonates, it is not possible to use such a temperature, because aliphatic diols tend to undergo desorption and / or thermal decomposition when exposed to such thermal stress. However, at the same time, high temperatures are required to grow to the desired high molecular weight. Particularly evident in this case is the difference in reactivity between aliphatic diols and aromatic diols. 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 8 is considerably longer at higher temperatures than the reaction time observed according to the present invention.

[0014] Similarly, Patent Documents 9 and 10 use aromatic structural units and correspondingly high temperatures. For the reasons mentioned above, the teachings there cannot be applied to aliphatic structural units.

[0015] Patent document 11 describes a method for producing polyester containing isosorbide units. In this method, isosorbide is dissolved in water, as it should be added to an existing reactor in the simplest possible manner. Therefore, this document primarily relates to the production of polyester and further requires the presence of a solvent.

[0016] Patent document 12, 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.

[0017] 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 condensation of isosorbide structures within the polymer chains. While the rigid nature of the bicyclic substructure increases the glass transition temperature, the polymer chains become less flexible, which can, in principle, lead to disadvantages. Park et al. reported that the molecular weight decreases as the amount of isosorbide in the polymer increases (Non-Patent Document 3). The authors reported 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 need to have a relatively high molecular weight so that they can entangle. Failure to do so results in brittle behavior (critical entanglement molecular weight).

[0018] Cyclohexanedicarboxylic acid increases flexibility somewhat, but the overall structure of the polymer chain remains very rigid. This can lead to disadvantages during the production of the polymer. Due to the non-flexible nature, as the molecular weight increases, it becomes more difficult for the reaction partners (chain ends) to find each other. As described above, this limits the molecular weight. Furthermore, due to the rigid nature, a sharp increase in viscosity is caused during polymer synthesis. To compensate for this, the temperature is often increased at the final stage of polycondensation during polymer production to achieve better fluidity. However, this is only possible to a limited extent in the case of aliphatic polymers. This is because, for example, the thermal stability is significantly lower compared to aromatic polyesters or polycarbonates. Since the increase in viscosity cannot be compensated by increasing the temperature, poor mixing and poor surface renewal are brought about. At that time, the removal of the condensation product (such as phenol) becomes impossible, and the polycondensation may stop.

[0019] As a means to bring about better surface renewal, Patent Document 6 describes the use of a horizontal polymer reactor such as a polymer kneader. These exert a high shear force on the polymer, enhance surface renewal, and continue the polycondensation. However, the high shear force places a great load on the non-flexible polymer.

[0020] Thus, the high shear stress can cause damage, which may appear as a significant deterioration of the optical and mechanical properties.

Prior Art Documents

Patent Documents

[0021]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

[0022] [Non-Patent Document 1] Oh et al., in Macromolecules 2013, 46, 2930 - 2940 [Non-Patent Document 2] Kricheldorf et al., (Macromol. Chem. Phys 2010, 211, 1206 - 1214) [Non-Patent Document 3] S.A. Park et al. Polymer 2017, 116, 153 - 159; pp. 155 - 156 [Summary of the Invention] [Problems to be Solved by the Invention][[ID=�6]]

[0023] Therefore, starting from this prior art, the object of the present invention is to provide a method for producing a polyester carbonate comprising at least one 1,4:3,6-dianhydrohexitol and at least one alicyclic dicarboxylic acid, characterized by good surface renewal during production. Better surface renewal is supported, for example, by a higher molecular weight that can be achieved. This should make it possible to achieve a sufficiently high molecular weight in the polyester carbonate in particular. "Sufficiently high molecular weight" is understood to mean a polymer having a relative solution viscosity of preferably 1.25 to 1.65, more preferably 1.28 to 1.63, and particularly preferably 1.30 to 1.62, which is preferably above 1.22 as measured in each case using an Ubbelohde viscometer at a concentration of 5 g / l in dichloromethane at 25°C. Therefore, the polyester carbonate of the present invention should further have better processing properties and good mechanical properties. A further object was to provide the simplest possible method for producing polyester carbonate by melt transesterification. In this context, "simple" is understood to mean a method that requires little expenditure on equipment, involves few steps, especially fewer purification steps, and / or is therefore economically and environmentally advantageous. In particular, the method of the present invention should be free from the use of difficult-to-handle starting materials, especially phosgene. [Means for solving the problem]

[0024] At least one, preferably all, of the above-mentioned problems have been solved by the present invention. Surprisingly, it has been found that polyester carbonates can be synthesized by melt transesterification 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 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. However, it has been found that polymers with appropriate molar mass and therefore appropriate mechanical properties can only be obtained when a specific amount of at least one further diol is used. On the other hand, despite the preconceptions described in the prior art, it was surprising that direct synthesis also works for the reaction of alicyclic dicarboxylic acids, 1,4:3,6-dianhydrohexitol, at least one further aliphatic dihydroxy compound (also called "aliphatic diol" according to the present invention), and diaryl carbonates. It was also quite surprising that the amount of at least one additional aliphatic dihydroxy compound was important for obtaining a good increase in molecular weight. This led to the discovery of a method that makes it possible to obtain polyester carbonates from alicyclic diacids, 1,4:3,6-dianhydrohexitol, and at least one additional aliphatic dihydroxy compound, which is particularly simple, i.e., requires little expenditure on equipment, involves few steps, especially few purification steps, and is therefore economically and environmentally advantageous.

[0025] Furthermore, it was found that the incorporation of small amounts of additional aliphatic dihydroxy compounds, particularly branched aliphatic dihydroxy compounds, enhanced surface renewal during synthesis. Surprisingly, even the incorporation of small amounts of additional diols significantly increased surface renewal, and therefore molecular weight. Particularly surprising was the readily observed condensation of branched diols into the polymer chain despite steric hindrance. Those skilled in the art would have predicted that steric hindrance would prevent the increase in molecular weight.

[0026] Furthermore, a novel polyester carbonate was obtained that has a different structure from the polyester carbonates previously described in the prior art, namely, a different statistical distribution of structural elements.

[0027] A method for producing the polyester carbonate of the present invention can be schematically described below by, for example, the reaction of cyclohexanedicarboxylic acid, isosorbide, an additional diol HO-R-OH, and diphenyl carbonate: [ka] catalyst (These three specific starting materials are listed purely for illustrative purposes and should not be understood as limiting.)

[0028] In the direct synthesis according to the present invention, gas generation (emission of carbon dioxide) was initially observed. After the gas generation had almost subsided, a sample was taken from the mixture, and analysis demonstrated that oligomers had already been formed. These oligomers are condensed in a further step to form the polyester carbonate of the present invention. Examples of the present invention demonstrate that, as in the prior art, when only one derivative of cyclohexanedicarboxylic acid reacts with diphenyl carbonate, isosorbide, and further diols (for example), the statistical distribution of carbonate blocks and ester blocks in these oligomers (see scheme above) is already different from the pure statistical distribution of the blocks. Furthermore, the reactivity of such oligomers differs from the reactivity of pure cyclohexanediphenyl ester, isosorbide, further diols, and pure diphenyl carbonate. Therefore, the final result of the method of the present invention is to obtain polymers in which the statistical distribution of various blocks differs from the statistical distribution of polymers obtained from cyclohexanediphenyl ester, isosorbide, further diols, and diphenyl carbonate.

[0029] Therefore, the present invention relates to a method for producing polyester carbonate by molten transesterification, (i) A step of reacting at least one alicyclic dicarboxylic acid and at least one diaryl carbonate with at least one catalyst in the presence of a mixture of dihydroxy compounds comprising (A) at least one 1,4:3,6-dianhydrohexitol and (B) at least one further aliphatic dihydroxy compound, (ii) A step of subjecting the mixture obtained from step (i) to further condensation 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%, The present invention provides a method characterized by including the following:

[0030] Surprisingly, it was found that the increase in molecular weight occurred particularly easily when the amount of at least one further aliphatic dihydroxy compound was within the range defined in the claims. Surprisingly, the greater the amount of at least one further aliphatic dihydroxy compound, the smaller the increase in molecular weight. Furthermore, it was advantageous when at least one further dihydroxy compound had 2 to 11, preferably 3 to 10, carbon atoms.

[0031] According to the present invention, step (i) of the method comprises at least the reaction of at least one alicyclic dicarboxylic acid with at least one diaryl carbonate. However, according to the present invention, 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)) means that the possibility of further reactions cannot be ruled out. In fact, it has been demonstrated in examples that in step (i), oligomers with a mass difference in a MALDI-TOF mass spectrometer corresponding to units consisting of component (A) and / or component (B) and a carbonate (both hydroxyl groups are lost) are already formed. This means that in step (i), further reactions other than the formation of a diester may occur. However, according to the present invention, this also means that the reaction of all present alicyclic dicarboxylic acids with stoichiometric equivalents of diaryl carbonates does not need to proceed to completion before the start of step (ii). However, according to the present invention, it is preferable to start method step (ii) only after method step (i) has been carried out for a period of time necessary for the observed gas generation to almost cease, for example, by applying negative pressure to remove the chemical compounds desorbed during condensation. However, as already stated above, according to the present invention, it is not always possible to achieve a clear separation between method step (i) and method step (ii).

[0032] Method step (i) The method of the present invention is called direct synthesis or 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 one dihydroxy compound, one alicyclic dicarboxylic acid, and / or one diaryl carbonate in components (A) and (B). Therefore, according to the present invention, it is preferable that all monomers to be condensed into the polyester carbonate in step (ii) are already present during step (i). Similarly, the present invention includes 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 terminal OH group content of the resulting polyester carbonate. Such an approach is described, for example, in Japanese Patent Application Publication No. 2010-077398. However, in order to ensure that all structural elements forming the subsequent polyester carbonate are already present as monomers in step (i) and no further structural elements are added, it is necessary that the at least one diaryl carbonate added in small amounts in step (ii) is the same as 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.

[0033] Furthermore, the present invention does not exclude the presence of aromatic dihydroxy compounds and / or aromatic dicarboxylic acids in step (i) of the method. However, these are preferably present only in small amounts. In step (i) of the method, it is particularly preferable that aromatic dihydroxy compounds (component (C)) are further present in a content of up to 20 mol%, more preferably up to 10 mol%, and very particularly preferably up to 5 mol%, relative to the total molar amount of dihydroxy compounds used. The ratio of components (A) and (B) as defined in the claims remains the same. In step (i) of the method, it is equally particularly preferable that aromatic dicarboxylic acids are further present, optionally and in addition to aromatic dihydroxy compounds, in a content of up to 20 mol%, more preferably up to 10 mol%, and very particularly preferably up to 5 mol%, relative to the total molar amount of dicarboxylic acids used. In these cases, according to the present invention, it is still preferable to refer to the product as an aliphatic polyester carbonate. However, it is particularly preferable not to use aromatic dihydroxy compounds in step (i). It is also preferable not to use aromatic dicarboxylic acids in step (i). Similarly, it is preferable not to use aromatic dihydroxy compounds or aromatic dicarboxylic acids in step (i) of the method. Generally, aromatic compounds, when present in polyester carbonates, reduce UV stability and weather resistance. This is particularly disadvantageous for outdoor use. Furthermore, aromatic components in polyester carbonates may reduce the surface hardness of molded articles produced therefrom, potentially necessitating coating. In addition, diphenyl esters of aromatic acids that may form as intermediates are stable intermediates that can, for example, slow down polycondensation. This means that the use of further specific catalysts may be required.

[0034] These additional aromatic dihydroxy compounds (component (C)) are preferably bisphenol A, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxybiphenyl (DOD), 4,4'-dihydroxydiphenyl ether (DOD ether), bisphenol B, bisphenol M, and 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.)

[0035] These additional aromatic dicarboxylic acids are preferably selected from the group consisting of isophthalic acid, terephthalic acid, furan-2,5-dicarboxylic acid, and naphthalene-2,6-dicarboxylic acid. It is known that even small amounts of these aromatic diacids can reduce water absorption by aliphatic polyester carbonates.

[0036] 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 can be a bio-based structural element with all the associated advantages of bio-based monomers and polymers obtained therefrom (for example, being more sustainable because it is obtained from renewable raw materials). The method of 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.

[0037] 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.

[0038] At least one further aliphatic dihydroxy compound, with chemical formula (I): HO-X-OH (I) (wherein X is preferably a linear alkylene group having 2 to 22, preferably 2 to 15, more 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 two or more rings and may optionally be branched in each case).

[0039] 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, even more preferably 2 to 6, and even more preferably 3 to 4 carbon atoms. The heteroatom that can optionally interrupt the alkylene group is preferably oxygen or sulfur, more preferably oxygen. Particularly preferably, the alkylene group contains only one heteroatom or does not contain a heteroatom. When at least one heteroatom is present in the alkylene group, the indicated number of carbon atoms relates 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 interrupted by at least one heteroatom preferably has fewer than 12, more preferably fewer than 10 carbon atoms. Particularly preferably, the alkylene group does not contain a heteroatom.

[0040] According to the present invention, the above description applies to heteroatoms when X is 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, more preferably oxygen. Particularly preferably, the branched alkylene group contains only one heteroatom or does not contain a heteroatom. Particularly preferably, the branched alkylene group does not contain a heteroatom. The term “branched” is understood to refer to branching in an aliphatic carbon chain 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. It is possible for two or more branches to be present in the branched alkylene group. The branch has a chain length of preferably 1 to 5 carbon atoms, particularly preferably 1 to 4, and very particularly preferably 1 to 3 carbon atoms. These carbon atoms in the branching are taken into account in the total number of carbon atoms in the branched alkylene group. This means, for example, that the branched alkylene group -CH2-C(CH3)2-CH2- contains 5 carbon atoms.

[0041] According to the present invention, the above description applies to heteroatoms 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 two or more rings, each of which may optionally be branched. The heteroatom that can optionally interrupt the cycloalkylene group is preferably oxygen or sulfur, more preferably oxygen. Particularly preferably, the cycloalkylene group contains only one heteroatom or does not contain a heteroatom. Particularly preferably, the cycloalkylene group does not contain a heteroatom. Preferably, the cycloalkylene group contains at least one, preferably one ring, having 4 to 6 carbon atoms. Particularly preferably, the cycloalkylene group contains a total of 4 to 20, preferably 5 to 15 carbon atoms, and includes a ring having 4 to 5 carbon atoms. The carbon atoms of the ring are included 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 includes a ring having 4 carbon atoms. The cycloalkylene group may further include at least one branch, which is particularly preferred. If branching is present, it may be present in an optionally present alicyclic chain and / or ring. Preferably, the branching is present in a ring. Preferably, X is a cycloalkylene group having 5 to 15 carbon atoms and one ring, where the group 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, more preferably 4 to 5 carbon atoms.

[0042] Overall, according to the present invention, it is preferable that at least one further aliphatic dihydroxy compound has 2 to 10 carbon atoms.

[0043] The method of the present invention provides that at least one further aliphatic dihydroxy compound is cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclohexane-1,2-dimethanol, cyclohexane-1,3-dimethanol, cyclohexane-1,4-dimethanol, 2,2-bis(4-hydroxycyclohexyl)propane, tetrahydrofuran-2,5-dimethanol, 2-butyl-2-ethylpropane-1,3-diol, 2-(2-hydroxyethoxy)ethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, 2,2,4-trimethylpentane-1,3-diol, 2,2-dimethylpropane-1,3-diol, cyclobutane-1,1-diyldimethanol, 8-(hydroxymethyl)-3-tricyclo[5.2.1.0 2,6It is particularly preferable that the material be selected from the group consisting of decanyl methanol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, octane-1,8-diol, 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-ethylpropane-1,3-diol, 2-(2-hydroxyethoxy)ethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, 2,2,4-trimethylpentane-1,3-diol, 2,2-dimethylpropane-1,3-diol, cyclobutane-1,1-diyldimethanol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, octane-1,8-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-ethylpropane-1,3-diol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, 2,2,4-trimethylpentane-1,3-diol, 2,2-dimethylpropane-1,3-diol, cyclobutane-1,1-diyldimethanol, butane-1,4-diol, and any desired mixtures thereof. It is especially preferable that at least one further aliphatic dihydroxy compound is selected from the group consisting of 2-butyl-2-ethylpropane-1,3-diol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, 2,2,4-trimethylpentane-1,3-diol, 2,2-dimethylpropane-1,3-diol, cyclobutane-1,1-diyldimethanol, and any desired mixtures thereof.

[0044] According to the present invention, it has been found that an additional at least one further aliphatic dihydroxy compound can react with the also present at least one diaryl carbonate under the reaction conditions of step (i) of the method of the present invention. This is observed particularly in dihydroxy compounds where the two hydroxyl groups are in close proximity to each other (e.g., separated by only two or three carbon atoms). While not bound by any particular theory, it appears that an intramolecular carbonate that is no longer reactive is formed. This means that this intramolecular carbonate no longer participates in the reaction that forms the polyester carbonate. As a result, the amount of at least one further aliphatic dihydroxy compound added at the start of step (i) of the method does not necessarily always correspond to the amount of structural elements in the polyester carbonate derived from the above dihydroxy compound. This amount is generally less, especially in the case of compounds having two hydroxyl groups in close proximity to each other. This is particularly not true for cyclic dihydroxy compounds such as cyclohexanedimethanol. Methods for determining the proportion of structural units in the resulting polyester carbonate are known to those skilled in the art. These proportions are preferably 1 This can be determined by 1H NMR. This method is known to those skilled in the art. The polyester may be dissolved in, for example, CDCl3, and the corresponding peaks in the structural units can be identified. The ratios and proportions can be determined by integration.

[0045] According to the present invention, in step (i) of the method, at least one alicyclic dicarboxylic acid is used similarly. The at least one alicyclic dicarboxylic acid is of chemical formula (IIa), (IIb): [ka] (In the formula, In each case, 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. In each case, 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, more 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).

[0046] When R1 represents a single bond, it will be understood that R1 does not contain a carbon atom.

[0047] At least one alicyclic dicarboxylic acid is particularly preferably selected from the group consisting of cyclohexane-1,4-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, tetrahydrofuran-2,5-dicarboxylic acid, tetrahydrodimethylfuran-2,5-dicarboxylic acid, decahydronaphthalene-2,4-dicarboxylic acid, decahydronaphthalene-2,5-dicarboxylic acid, decahydronaphthalene-2,6-dicarboxylic acid, and decahydronaphthalene-2,7-dicarboxylic acid. Any desired mixture can also be used. Very preferably, this is cyclohexane-1,4-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, or cyclohexane-1,2-dicarboxylic acid.

[0048] In addition to alicyclic acids, small amounts of further aliphatic acids may also be used. In step (i) of the method, it is particularly preferable that further aliphatic acids that are not alicyclic acids be present in an amount of up to 20 mol%, more preferably up to 10 mol%, and very preferably up to 5 mol%. 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.

[0049] According to the present invention, in step (i) of the method, at least one diaryl carbonate is also used. The at least one diaryl carbonate is preferably 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 Selected 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. In particular, 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, and / or di[4-(1-methyl-1-phenylethyl)phenyl] carbonate. At least one diaryl carbonate is particularly preferably diphenyl carbonate.

[0050] 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 base or an organic base having

[0051] It is also preferred that at least one inorganic base or at least one organic catalyst is selected from the group consisting of hydroxides, carbonates, halides, phenoxides, diphenoxides, fluorides, acetates, phosphates, hydrogen phosphates, and borates of lithium, sodium, potassium, cesium, calcium, barium, and magnesium, 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]dec-5-ene, 7-phenyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7,7'-hexylidenedi-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7,7'-decylidenedi-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7,7'-dodecylidenedi-1,5,7-triazabicyclo[4.4.0]dec-5-ene, phosphazene base P1-t-oct (tert-octyliminotris(dimethylamino)phosphorane), phosphazene base P1-t-butyl (tert-butyl-iminotris(dimethylamino)phosphorane), and 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorane (BEMP). It is also possible to use any desired mixture.

[0052] 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 have the particular advantage in step (ii) of the method of the present invention that they can be removed, for example under reduced pressure, along with the chemical compounds eliminated during condensation. This means that the resulting polyester carbonate contains little to no residual catalyst. This has the particular advantage that inorganic salts, which are always formed in any route in which phosgene is used, are not present in the polymer. Such salts are known to adversely affect the stability of polyester carbonates because their ions can act catalytically with respect to the corresponding decomposition.

[0053] 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 more preferably 20 ppm to 200 ppm, per 1 mole of alicyclic dicarboxylic acid.

[0054] In another embodiment, the method of 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).

[0055] Therefore, in this embodiment, the first catalyst and / or the second catalyst are present in step (i) of the method.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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. The use of phenols, particularly their corresponding salts, is further possible. These salts can be used individually or in mixtures.

[0061] 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.

[0062] 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.

[0063] 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 having 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 stability to polyester carbonates, the content of units derived from alicyclic dicarboxylic acids should not be too low either.

[0064] According to the present invention, the polyester carbonate produced preferably has a relative solution viscosity η greater than 1.22, similarly preferably 1.25 to 1.65, particularly preferably 1.28 to 1.63, and very particularly preferably 1.30 to 1.62. Here, the relative solution viscosity is preferably measured 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 the 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. In this determination, the viscosity difference between the polymer solution and its solvent is determined after measuring the passage time of the polyester carbonate under investigation using an Ubbelohde viscometer. For this purpose, the Ubbelohde viscometer is initially calibrated through measurements of pure solvents, dichloromethane, trichloroethylene, and tetrachloroethylene (always at least 3 times and 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 for this solution is determined in triplicate. The relative solution viscosity is calculated by correcting the average flow time via the Hagenbach correction.

[0065] According to the present invention, these molar masses are preferably referred to as "sufficient" molar masses. According to the present invention, it is particularly preferable that the molar ratio of all aliphatic dihydroxy compounds present in method step (i) to all alicyclic dicarboxylic acids present in method step (i) before the reaction in method step (i) is 1:0.6 to 1:0.05, preferably 1:0.55 to 1:0.1, and more 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.

[0066] According to the present invention, in the method of 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 cyclohexane-1,4-dicarboxylic acid, This is particularly advantageous in that case.

[0067] 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%.

[0068] The method of 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.

[0069] Furthermore, step (i) of the present invention preferably includes at least one, more preferably all, of the following steps (ia) to (ic):

[0070] (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 an inert 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). An exception is a compound formed by the reaction (e.g., phenol when diphenyl carbonate is used as at least one diaryl carbonate). Naturally, the presence of trace amounts of solvent in the starting compounds cannot be ruled out. This possible situation should preferably be included in the scope of the present invention. However, according to the present invention, it is preferable to avoid an active step of adding such a solvent.

[0071] (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 initially to a temperature of 150°C to 180°C.

[0072] (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 has preferably already been heated to a temperature between 150°C and 180°C by step (ib) under standard pressure. Depending on the catalyst selected, the temperature can remain 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 more 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, 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 is already partially removed.

[0073] According to the present invention, it was also observed that at least one dihydroxy compound (A) and / or (B) had similarly already begun to react by this point. This was demonstrated by the detection of oligomers containing carbonate units from the reaction of at least one dihydroxy compound (A) and / or (B) with at least one diaryl carbonate and / or ester units from the reaction of at least one dihydroxy compound (A) and / or (B) with at least one dicarboxylic acid.

[0074] 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)).

[0075] 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. Preferably, a reaction time should be selected that ensures that gas generation is almost completely contained (see reaction scheme above).

[0076] 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, more preferably 1:0.7 to 1:1.3, particularly 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 an appropriate optimal ratio according to the purity of the starting materials.

[0077] Method step (ii) In step (ii) of the method, the mixture obtained from step (i) is subjected to further condensation while removing at least the chemical compounds eliminated during condensation. In the context of 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 to an oligomer has already occurred (see step (i) of the method).

[0078] 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).

[0079] The proportion of alkali metal cations in step (ii) is preferably 0.0009% to 0.0005% by weight, and more preferably 0.0010% to 0.0045% by weight, relative to all components used in step (i) in each case.

[0080] In a preferred embodiment, the first catalyst and the second catalyst are present in step (i) of the method.

[0081] 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 in step (ii).

[0082] 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).

[0083] 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. It is preferable to remove the chemical compound eliminated during condensation by reduced pressure in step (ii). Therefore, it is preferable that the method of the present invention is characterized by optionally removing volatile substances having a boiling point below that of the alicyclic diester formed in step (i), below that of the mixture of dihydroxy compounds, and below that of at least one diaryl carbonate, by stepwise reduced pressure during the reaction in step (i). In this case, stepwise removal is a preferred option when removing various volatile substances. It is also preferable to choose stepwise removal in order to remove the volatile substances as completely as possible. The volatile substances are the chemical compounds (which may be multiple) eliminated during condensation.

[0084] 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.

[0085] The removal of the condensation product in step (ii) is preferably carried out at a temperature of 200°C to 280°C, more preferably 210°C to 260°C, and most preferably 220°C to 250°C. The pressure during removal is even more preferably 500 mbar to 0.01 mbar. It is particularly preferable to perform stepwise removal by reducing the pressure. Very preferably, the vacuum in the final stage is 10 mbar to 0.01 mbar.

[0086] In further embodiments of the present invention, polyester carbonates obtained by the above-described methods of the present invention are provided in all disclosed combinations and preferred aspects. The polyester carbonates of the present invention can be processed as is into all kinds of molded articles. They can also be processed into thermoplastic molding compounds together with other thermoplastics and / or polymer additives. The present invention further provides molding compounds and molded articles.

[0087] 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.

[0088] The thermoplastic molding material of the present invention may be manufactured, for example, by mixing polyester carbonate and other components, and then melt-compounding and melt-extruding the resulting mixture using known methods and conventional equipment, such as an internal kneader, extruder, and twin-screw system, preferably at a temperature of 200°C to 320°C. This method is generally referred to as compounding in the context of this application.

[0089] 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.

[0090] Molded articles obtained from the polyester carbonate of the present invention, or from a thermoplastic molding compound containing the polyester carbonate, 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]

[0091] Materials used: Cyclohexanedicarboxylic acid: Cyclohexane-1,4-dicarboxylic 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 (Belgium, Hale), 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-ethylpropane-1,3-diol: CAS number 115-84-4; Aldrich (abbreviated as BEPD) 2,2,4,4-Tetramethylcyclobutane-1,3-diol:98% (CAS:3010-96-6); ABCR (abbreviated as TMCBD) 2,2,4-Trimethylpentane-1,3-diol; 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) Butane-1,4-diol: CAS: 110-63-4; Merck 99%; (abbreviated as BDO) Cyclohexane-1,4-dimethanol CAS:105-08-8, Aldrich 99% (abbreviated as CHDM) Dodecane-1,12-diol: CAS: 5675-51-4, Aldrich 99% (abbreviated as DDD).

[0092] 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. In this determination, the viscosity difference between the polymer solution and its solvent is determined after measuring the passage time of the polyester carbonate under investigation using an Ubbelohde viscometer. For this purpose, the Ubbelohde viscometer is initially calibrated through measurements of pure solvents, dichloromethane, trichloroethylene, and tetrachloroethylene (always at least 3 times and 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 in triplicate. The relative solution viscosity is calculated by correcting the average value of the flow time via the Hagenbach correction.

[0093] 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.

[0094] MALDI-TOF-MS The sample was dissolved in chloroform. The matrix used was ditranol containing LiCl. The sample was analyzed in positive reflector mode and linear mode.

[0095] Comparative Example 1 (Experiment without using additional diols) 17.20 g (0.10 mol) of cyclohexane-1,4-dicarboxylic 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-path separator. Oxygen was removed from the mixture by degassing and releasing the vacuum 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, negative pressure 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.

[0096] A pale yellow polymer with a solution viscosity of 1.33 relative η was obtained.

[0097] Other examples (Ex.) and comparative examples (Comp.) were carried out as described for Comparative Example 1. Unlike Example 1, the aliphatic diols specified in Table 1 were also placed in a flask equipped with a short-path separator, along with all other monomers and catalysts that form the polymer.

[0098] [Table 1]

[0099] Examples 1 to 12 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 diols, particularly branched diols, causes 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 2 to 4), the increase in molecular weight is clearly lower.

[0100] Example 13 of the present invention: Reaction in step (i) of the method 0.10 mol of cyclohexane-1,4-dicarboxylic acid, 0.02 mol of BEPD (10%), 0.18 mol of isosorbide, 0.3 mol of diphenyl carbonate, 100 ppm of DMAP (4-dimethylaminopyridine; relative to the starting materials CHDA, BEPD, DPC, and ISB), and 0.0763 ml of aqueous lithium hydroxide solution (100 g / l), equivalent to approximately 20 ppm of Li, were placed in a flask equipped with a short-pass separator. Oxygen was removed from the mixture by four degassing and release of the vacuum with nitrogen. The mixture was heated stepwise to 190°C. Carbon dioxide was continuously generated during this operation. Next, a 3 mL sample was taken and analyzed by MALDI-TOF-MS. To ensure that the batch continued to polymerize, the reactants were heated to 220°C, and then the pressure was gradually reduced to less than 1 mbar. An increase in viscosity was observed.

[0101] The results of the analysis are summarized in Table 2. The mass of each is Li adduct M + Li *This corresponds to the following. Various peaks were identified that may have been reacted not only by ISB but also by BEPD. This clearly indicates that isosorbide and BEPD have already reacted under the method conditions of method step (i). In Table 2, ISB represents the isosorbide unit with two terminal OH groups removed (these are listed separately), CHDA represents cyclohexane (cyclohexanedicarboxylic acid with two carboxylic acid groups removed), and BEPD represents 2-butyl-2-ethylpropane-1,3-diol with two OH groups removed.

[0102] [Table 2]

[0103] These results suggest that the method of the present invention yields polyester carbonates different from those produced by a two-step process (i.e., the initial reaction of an alicyclic dicarboxylic acid with a diaryl carbonate to produce a diaryl dicarboxylate and the subsequent purification of the diaryl dicarboxylate, followed by the condensation of the diaryl dicarboxylate with a diaryl carbonate and an aliphatic dihydroxy compound). It is highly probable that various statistical distributions of carbonate units and / or ester units exist in various polyester carbonates.

Claims

1. A method for producing polyester carbonate by molten transesterification, (i) A step of reacting at least one alicyclic dicarboxylic acid and at least one diaryl carbonate with at least one catalyst in the presence of a mixture of dihydroxy compounds comprising (A) at least one 1,4:3,6-dianhydrohexitol and (B) at least one further aliphatic dihydroxy compound, (ii) A step of subjecting the mixture obtained from step (i) to further condensation 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

2. The method according to claim 1, 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.

3. The method according to claim 1 or 2, 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, and the proportion of alkali metal cations in step (ii) is 0.0008% by weight to 0.0030% by weight with respect to all components used in step (i).

4. The aforementioned at least one further aliphatic dihydroxy compound has chemical formula (I): HO-X-OH (I) The method according to any one of claims 1 to 3, characterized by having (wherein X is a linear alkylene group having 2 to 22 carbon atoms that can be optionally interrupted by at least one heteroatom, a branched alkylene group having 4 to 20 carbon atoms that can be optionally interrupted by at least one heteroatom, or a cycloalkylene group having 4 to 20 carbon atoms that can be optionally interrupted by at least one heteroatom, wherein the cycloalkylene group may optionally contain two or more rings and may optionally be branched in each case).

5. The at least one further aliphatic dihydroxy compound is cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclohexane-1,2-dimethanol, cyclohexane-1,3-dimethanol, cyclohexane-1,4-dimethanol, 2,2-bis(4-hydroxycyclohexyl)propane, tetrahydrofuran-2,5-dimethanol, 2-butyl-2-ethylpropane-1,3-diol, 2-(2-hydroxyethoxy)ethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, 2,2,4-trimethylpentane-1,3-diol, 2,2-dimethylpropane-1,3-diol, cyclobutane-1,1-diyldimethanol, 8-(hydroxymethyl)-3-tricyclo[5.2.1.0 ２，６ The method according to claim 4, characterized in that it is selected from the group consisting of decanyl methanol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, octane-1,8-diol, and any desired mixture thereof.

6. The at least one alicyclic dicarboxylic acid is of chemical formula (IIa), (IIb): 【Chemistry 1】 (In the formula, B is independent in each case, CH ２ Represents a group, or a heteroatom selected from the group consisting of O and S. R １ In each case, independently, represents a single bond or a linear alkylene group having 1 to 10 carbon atoms, and The method according to any one of claims 1 to 5, characterized in that n is selected from compounds or mixtures thereof (where n is a number between 0 and 3).

7. The method according to claim 3, characterized in that the first catalyst is selected from the group consisting of a base derived from guanidine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undeca-7-ene (DBU), 1,5-diazabicyclo[4.3.0]nona-5-ene (DBN), 1,5,7-triazabicyclo[4.4.0]deca-5-ene, and mixtures thereof.

8. A polyester carbonate obtained by the method described in any one of claims 1 to 7.

9. A molded compound comprising the polyester carbonate described in claim 8.

10. A molded article comprising the polyester carbonate described in claim 8.

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