Polyester carbonates from cycloaliphatic diacids and aliphatic diols, and methods for producing same

Abstract

The present invention relates to a method for producing polyestercarbonates starting from cycloaliphatic diacids and aliphatic diols, as well as to the polyestercarbonates produced by said method. The method according to the invention is a direct synthesis, in which all components that form the subsequent polyestercarbonate are already present as monomers in the first process step.

Description

[Technical field]

[0001] The present invention relates to a process for the preparation of polyestercarbonates starting from cycloaliphatic diacids and aliphatic diols, and to the polyestercarbonates prepared by said process. [Background technology]

[0002] Polyesters, polycarbonates and polyestercarbonates are known to have good mechanical properties and good stability against heat deformation and weathering.Depending on the monomers used, each polymer group has certain important features that characterize this type of material.For example, polycarbonates have particularly good mechanical properties, while polyesters often show better chemical stability.Polyestercarbonates show property profiles from both of the above groups, depending on the monomers selected.

[0003] Aromatic polycarbonates or polyesters often have a good property profile, but show shortcomings in their stability against aging and weathering. For example, absorption of UV light leads to yellowing and sometimes embrittlement of these thermoplastic materials. Aliphatic polycarbonates and polyester carbonates have better properties in this respect, in particular better stability against aging and / or weathering, as well as better optical properties (e.g. transmittance). A further advantage of aliphatic polymers is that the raw materials are more readily available from biological sources. Aliphatic monomers, such as sugar derivatives or isosorbide, are available today from bio-based raw materials, whereas aromatic monomers are available from bio-based raw materials, but only to a limited extent. In the context of the present invention, the expression "bio-based" is understood to mean that the relevant chemical compounds are available and / or accessible via renewable and / or sustainable raw materials at the filing date, and / or are preferably such renewable and / or sustainable raw materials. This expression is used as a means of distinguishing, in particular, from raw materials derived from fossil resources. Whether a feedstock is biobased or fossil-based can be determined by measuring the carbon isotopes in the feedstock, since the relative amount of the carbon isotope C14 is lower in fossil feedstocks. This can be done, for example, according to ASTM D6866-18 (2018) or ISO 16620-1 to ISO 16620-5 (2015).

[0004] A disadvantage of aliphatic polycarbonates or polyestercarbonates is often their low glass transition temperature. It is therefore advantageous to use cycloaliphatic alcohols as (co)monomers. These have a particularly favorable effect on the mechanical properties. In order to further increase the glass transition temperature, cycloaliphatic acids, such as cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid or cyclohexane-1,4-dicarboxylic acid or the corresponding naphthalene derivatives, can also be used as (co)monomers. Depending on the choice of reactants, polyesters or polyestercarbonates are then obtained. The present application relates to the direct conversion of raw materials, i.e., for example, isosorbide and cycloaliphatic diacids, into the corresponding polyestercarbonates. Polyesters of cyclohexanedicarboxylic acid and isosorbide have been described in J. Appl. Chem. Soc. 1999, 143, 1999, 1999, 1999, 1999, 1999, 2000, 1999, 2001, 1999, 2002, 1999, 2003, 1999, 2004, 1999, 2005, 1999, 2006 ...

[0005] Large-scale industrial production of polyestercarbonates from free acids is generally only possible to a limited extent. They are often produced by transesterification of the corresponding ester-containing monomers with diols. For example, polyesters from cyclohexane-1,4-dimethanol and cyclohexane-1,4-dicarboxylic acid are produced starting from the dimethyl esters of the diacids (Patent Document 1, Patent Document 2 or Non-Patent Document 2). However, according to the present invention, it has surprisingly been found that cycloaliphatic diacids esterified with aliphatic alcohols show only low reactivity in the transesterification reaction to polyestercarbonates, which means that the molecular weight of the corresponding polyestercarbonates after the transesterification reaction is rather low (see Example 6). Such polymers therefore show poor properties.

[0006] In WO 02 / 063639, reactions starting from the corresponding diphenyl esters of cycloaliphatic acids are described. However, the preparation of the diesters required for this is complicated. The processes described in WO 02 / 063639 and WO 02 / 063639 for preparing diphenyl esters and the resulting polymers are not optimal, since they either result in low yields of precursors (Example 1; WO 02 / 063639) or require the use of hazardous substances such as phosgene (Examples 1 and 2 of WO 02 / 063639). The use of solvents is also necessary, which requires costly processing steps. The processes described are therefore relatively complicated, in particular requiring additional purification steps.

[0007] Patent Document 4 discloses an isosorbide-based polycarbonate polymer, which is composed of isosorbide units, aliphatic units derived from an aliphatic C14-C44 diacid, an aliphatic C14-C44 diol, or a combination thereof, and optionally additional units different from the isosorbide units and the aliphatic units, wherein the isosorbide units, the aliphatic units, and the additional units are each carbonate, or a combination of carbonate units and ester units. The main drawbacks of aliphatic polycarbonates or polyester polycarbonates have already been described above.

[0008] Kricheldorf et al. (Non-Patent Document 3) report that polyesters based on cyclohexanedicarboxylic acid and isosorbide cannot be obtained (or only at very low molecular weights) from cyclohexanedioic acid or from cyclohexanedimethyl ester, but can only be prepared from the acid chloride of cyclohexanedicarboxylic acid.

[0009] The easy preparation of aromatic polyester carbonates is described, for example, in US Pat. No. 5,399,633. This describes a direct or one-pot synthesis, i.e. a synthesis in which all the building blocks that will later form the polyester carbonate are already present as monomers at the start of the synthesis. Here, aromatic dihydroxy compounds such as bisphenol A, carboxylic acid diesters and aromatic or linear aliphatic diacids are used as monomers. Since this document is limited to the preparation of aromatic polyester carbonates, it is possible to employ temperatures of 300° C. in the condensation reaction in which the phenol formed is removed. It is not possible to use such temperatures when preparing aliphatic polyester carbonates, since the aliphatic diols tend to undergo elimination and / or thermal decomposition when exposed to such thermal stress. But at the same time, this high temperature is necessary to grow to the desired high molecular weight. Particularly evident here is the difference in reactivity between aliphatic and aromatic diols. For example, it is known in the literature that isosorbide is rarely fully incorporated into the polymer, and depending on the reaction conditions selected, up to 25% of isosorbide is instead lost during the polymerization reaction. Therefore, the reaction conditions for aromatic diols are not easily transferable to aliphatic diols, which is especially evident from the fact that the reaction times for the polycondensation (corresponding to process step (ii)) in WO 2005 / 023991 are significantly longer at higher temperatures than those observed according to the present invention.

[0010] US Pat. Nos. 5,993,333 and 5,993,523 similarly use aromatic building blocks and corresponding high temperatures, but for the reasons stated above, their teachings cannot be transferred to aliphatic building blocks.

[0011] In the unpublished patent application US Pat. No. 5,399,436, it is described that the reaction of diphenyl carbonate with cyclohexanedicarboxylic acid to obtain cyclohexanediphenyl esters results in a browned mixture, and that distillative purification of the cyclohexanediphenyl esters is necessary to obtain polyester carbonates with good optical properties. Furthermore, it was observed that without distillation, impurities that cause discoloration are incorporated into the polymer and therefore cannot be removed by precipitation. This means that without distillation, polyester carbonates with good optical properties cannot be obtained. Based on this observation, a person skilled in the art would not think to consider a one-pot synthesis in the presence of all the monomers, since he would consider purification of the cyclohexanediphenyl esters formed as intermediates to be essential for the optical quality of the polymer. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] European Patent Application Publication No. 3248999 [Patent Document 2] U.S. Patent No. 5,986,040 [Patent Document 3] European Patent Application Publication No. 3026074 [Patent Document 4] US Patent Application Publication No. 2009 / 105393 [Patent Document 5] WO 01 / 32742 [Patent Document 6] JP 1992-345616 A [Patent Document 7] DE 2438053 [Patent Document 8] European Patent Application No. 18189636.6 [Non-patent literature]

[0013] [Non-Patent Document 1] Macromolecules 2013, 46, 2930-2940 [Non-Patent Document 2] J. Polym Sci, Part A, Polym Chem, 2004, vol. 42, 3996 [Non-Patent Document 3] Macromol. Chem. Phys 2010, 211, 1206-1214 Summary of the Invention [Problem to be solved by the invention]

[0014] Based on this prior art, therefore, the basic object of the present invention is to provide a particularly simple method for producing polyestercarbonates from cycloaliphatic diacids and aliphatic diols by melt transesterification. In this context, "simple" should be understood to mean, in particular, a method that requires little equipment expenditure, involves few steps, in particular few purification steps, and / or is therefore economically and environmentally advantageous. This method should in particular be simpler than the described prior art methods for producing polyestercarbonates from cycloaliphatic diacids and aliphatic diols. In particular, the basic object of the present invention was to provide a method for producing polyestercarbonates from cycloaliphatic diacids and aliphatic diols, which additionally provides the corresponding polyestercarbonates, preferably with a sufficiently high molar mass. "Sufficiently high molar mass" is preferably understood herein to mean a polymer with a relative solution viscosity of at least 1.12 (preferably measured with an Ubbelohde viscometer in dichloromethane at a concentration of 5 g / l at 25° C.) and / or a weight-average molar mass of at least 40 000 g / mol (preferably determined by gel permeation chromatography in dichloromethane with polystyrene calibration). [Means for solving the problem]

[0015] At least one, and preferably all, of the above-mentioned objects have been achieved by the present invention. Surprisingly, it has been found that the synthesis of polyestercarbonates from cycloaliphatic diacids and aliphatic diols by melt transesterification is possible in a direct or one-pot synthesis, where all the building blocks that will later form the polyestercarbonate are already present as monomers at the start of the synthesis. However, it has become clear that only certain molar ratios of cycloaliphatic diacids and aliphatic diols give rise to polymers with suitable molar masses and therefore also suitable mechanical properties. Firstly, surprisingly, and in spite of the preconceptions of the prior art described, the direct synthesis also works for the reaction of cycloaliphatic dicarboxylic acids, aliphatic dihydroxy compounds (also referred to as aliphatic diols according to the present invention) and diaryl carbonates. Moreover, the total surprise was that the molar ratio of all aliphatic dihydroxy compounds to all cycloaliphatic dicarboxylic acids is important in order to obtain the corresponding polymers in particular. This has led to the discovery of a method that provides access to polyestercarbonates from cycloaliphatic diacids and aliphatic diols. The process is particularly simple, i.e. it requires low installation expenditures and involves only few steps, in particular only few purification steps, and is therefore both economically and environmentally advantageous.

[0016] Furthermore, new polyestercarbonates have been obtained which have a different structure, i.e. a different statistical distribution of the constituent elements, than the polyestercarbonates of the prior art mentioned above. The process for producing polyestercarbonates according to the invention can be illustrated diagrammatically, for example, by the reaction of cyclohexanedicarboxylic acid, isosorbide and diphenyl carbonate, as shown below: [ka] (The description of these three particular starting materials is merely to clarify the invention and should not be construed as limiting).

[0017] In the direct synthesis according to the invention, gas evolution was observed at first (evolution of carbon dioxide). By taking a sample from the mixture when the gas evolution has almost ceased, it is possible to analytically demonstrate that oligomers have already formed. These oligomers condense in a further step to form the polyester carbonates according to the invention. The examples according to the invention show that the statistical distribution of carbonate and ester blocks (see scheme above) in these oligomers is already different from the pure statistical distribution of blocks when, as in the prior art, only derivatives of cyclohexanedicarboxylic acid react with diphenyl carbonate and isosorbide (one example). Moreover, the reactivity of such oligomers is different from that of pure cyclohexanediphenyl esters, isosorbide and pure diphenyl carbonate. The net result of the process according to the invention is therefore to obtain polymers in which the statistical distribution of the various blocks is different from that of the polymers obtained from cyclohexanediphenyl esters, isosorbide and diphenyl carbonate.

[0018] Furthermore, the polyester carbonate according to the present invention has 1 It was observed in H NMR that the polyester carbonates exhibited more terminal phenyl groups than the polyester carbonates described in US Pat. No. 5,399,433, which were prepared by a two-step process. In the examples according to the invention, terminal phenyl groups were still formed, even though a slight excess of isosorbide was used. This is advantageous, since terminal OH groups are hydrolytically unstable, especially at the high processing temperatures of the polymer, and can lead to transesterification reactions and can reduce thermal stability.

[0019] The present invention therefore provides a process for producing polyestercarbonates by melt transesterification, comprising the steps of: (i) reacting at least one cycloaliphatic dicarboxylic acid with at least one diaryl carbonate in the presence of at least one aliphatic dihydroxy compound using at least one catalyst; (ii) subjecting the mixture resulting from process step (i) to a further condensation, while removing at least the chemical compounds released during the condensation; Including, The method is characterized in that the molar ratio of all aliphatic dihydroxy compounds present in process step (i) to all alicyclic dicarboxylic acids present in process step (i) prior to the reaction in process step (i) is from 1:0.6 to 1:0.05.

[0020] According to the invention, process step (i) at least comprises the reaction of at least one cycloaliphatic dicarboxylic acid with at least one diaryl carbonate. However, the presence of at least one aliphatic dihydroxy compound means that further reactions cannot be excluded according to the invention. Indeed, in the examples according to the invention, it was demonstrated that in process step (i), oligomers are already formed with a mass difference in the MALDI-ToF mass spectrometer corresponding to one unit (missing two hydroxy groups) from the aliphatic dihydroxy compound with carbonate. This means that in process step (i), further reactions can occur besides the formation of diesters. However, according to the invention, this also means that the reaction of all the cycloaliphatic dicarboxylic acids present with a stoichiometric equivalent of diaryl carbonate does not have to have proceeded to completion before process step (ii) is started. However, according to the invention, process step (i) is preferably proceeded until it is observed that the evolution of gas has almost stopped, and only when this point is reached is process step (ii) started, for example by applying a vacuum to remove chemical compounds that have been eliminated during the condensation. However, as already mentioned above, according to the invention it may not always be possible to clearly separate the method steps (i) and (ii).

[0021] Method step (i) The process according to the invention is a direct synthesis or one-pot synthesis, since in process step (i) all the building blocks that will subsequently form the polyestercarbonate are already present as monomers. This means that preferably, according to the invention, all the aliphatic dihydroxy compounds, all the cycloaliphatic dicarboxylic acids and also all the diarylcarbonates are present in this step, even if there are several dihydroxy compounds, several cycloaliphatic dicarboxylic acids and / or several diarylcarbonates. Thus, according to the invention, it is preferred that all the monomers that are subjected to condensation to the polyestercarbonate in process step (ii) are already present during process step (i). The invention likewise includes an embodiment in which a small proportion of at least one diarylcarbonate is additionally added in process step (ii). This can be used selectively to lower the terminal OH group content of the polyestercarbonate formed. Such an approach is described, for example, in JP2010077398A. However, in order that all the components that will form the subsequent polyester carbonate are already present as monomers in process step (i) and no further components are added, it is necessary here that the at least one diaryl carbonate added in small amounts in process step (ii) is the same as the at least one diaryl carbonate present in process step (i).The process can therefore still be referred to in this sense as a direct synthesis or one-pot synthesis.

[0022] Furthermore, the present invention does not exclude the presence of aromatic dihydroxy compounds and / or aromatic dicarboxylic acids in process step (i). However, these are preferably only present in small proportions. It is particularly preferred that aromatic dihydroxy compounds are additionally present in process step (i) in a content of up to 20 mol%, more preferably up to 10 mol%, most preferably up to 5 mol%, respectively, based on the total molar amount of dihydroxy compounds used. Likewise, it is particularly preferred that aromatic dicarboxylic acids are additionally present in process step (i), optionally in addition to aromatic dihydroxy compounds, in a content of up to 20 mol%, more preferably up to 10 mol%, most preferably up to 5 mol%, respectively, based on the total molar amount of dicarboxylic acids used. In these cases, it is still preferred according to the present invention to refer to the product as an aliphatic polyester carbonate. However, it is particularly preferred not to use aromatic dihydroxy compounds in process step (i). Similarly, it is also preferred not to use aromatic dicarboxylic acids in process step (i). Similarly, it is preferred not to use aromatic dihydroxy compounds or aromatic dicarboxylic acids in process step (i).

[0023] These additional aromatic dihydroxy compounds are preferably bisphenol A, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxybiphenyl (DOD), 4,4'-dihydroxybiphenyl ether (DOD ether), bisphenol B, bisphenol M and bisphenols (I) to (III): [ka] (In these formulas (I) to (III), R' represents, respectively, C1 to C4 alkyl, aralkyl or aryl, preferably methyl or phenyl, most preferably methyl).

[0024] These additional aromatic dicarboxylic acids are preferably selected from the group consisting of isophthalic acid, terephthalic acid, furandicarboxylic acid and naphthalene-2,6-dicarboxylic acid. It is known that small proportions of these aromatic diacids can reduce the absorption of water by aliphatic polyestercarbonates.

[0025] According to the present invention, at least one aliphatic dihydroxy compound is used in the process step (i). This at least one aliphatic dihydroxy compound is preferably selected from the group consisting of cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclohexane-1,2-dimethanol, cyclohexane-1,3-dimethanol, cyclohexane-1,4-dimethanol, tricyclodecane dimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2-bis(4-hydroxycyclohexyl)propane, tetrahydro-2,5-furandiethanol, and 1,4:3,6-dianhydrohexitol, such as isomannide, isoidide, and isosorbide. Any desired mixtures may also be used. The at least one aliphatic dihydroxy compound is most preferably isosorbide.

[0026] According to the invention, at least one cycloaliphatic dicarboxylic acid is also used in process step (i). The at least one cycloaliphatic dicarboxylic acid is preferably of the formula (IIa), (IIb): [ka] (wherein, each B independently represents a carbon atom or a heteroatom selected from the group consisting of O, S and N, and n is a number from 0 to 3) or a mixture thereof. More preferably, B represents a carbon atom or O, and n is a number from 0 to 3, preferably 0 or 1.

[0027] In particular, it is preferred that the at least one alicyclic dicarboxylic acid is selected from the group consisting of cyclohexane-1,4-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, tetradihydro-2,5-furandicarboxylic acid, tetradihydro-2,5-dimethylfurandicarboxylic acid, decahydronaphthalene-2,4-dicarboxylic acid, decahydronaphthalene-2,5-dicarboxylic acid, decahydronaphthalene-2,6-dicarboxylic acid, and decahydronaphthalene-2,7-dicarboxylic acid. Any desired mixtures may also be used. Most preferred are cyclohexane-1,4-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, or cyclohexane-1,2-dicarboxylic acid.

[0028] According to the invention, at least one diaryl carbonate is also used in process step (i). The at least one diaryl carbonate preferably has the formula (2): [ka] (wherein R, R', and R'' are each independently the same or different and represent hydrogen, an optionally branched C1-C34 alkyl, a C7-C34 alkylaryl, a C6-C34 aryl, a nitro group, a carbonyl-containing group, a carboxyl-containing group, or a halogen moiety). The at least one diaryl carbonate is preferably diphenyl carbonate, 4-tert-butylphenyl phenyl carbonate, di(4-tert-butylphenyl)carbonate, biphenyl-4-ylphenyl carbonate, di(biphenyl-4-yl)carbonate, 4-(1-methyl-1-phenylethyl)phenyl phenyl carbonate, di[4-(1-methyl-1-phenylethyl)phenyl]carbonate, bis(methyl salicyl)carbonate, bis(ethyl salicyl)carbonate, bis(propyl salicyl)carbonate, bis(2-benzoylphenyl)carbonate, bis(phenyl salicyl)carbonate and / or bis(benzyl salicyl)carbonate. In particular, the 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)phenyl phenyl carbonate and / or di[4-(1-methyl-1-phenylethyl)phenyl]carbonate. The at least one diaryl carbonate is particularly preferably diphenyl carbonate.

[0029] Furthermore, according to the invention, in process step (i) at least one catalyst is present. This is preferably an inorganic base and / or an organic catalyst. The at least one catalyst particularly preferably has a pK b is an inorganic or organic base having the formula:

[0030] The at least one inorganic base or the at least one organic catalyst may be selected from the group consisting of hydroxides, carbonates, halides, phenols, diphenols, 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'-hexylidene-di-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7,7'-decylidene-di-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7,7'-dodecylidene-di-1,5,7-triazabicyclo[4.4.0]dec-5-ene, [4.4.0] It is also preferred to select from the group consisting of dec-5-ene, phosphazene base P1-t-octo (tert-octylimino tris (dimethylamino) phosphorane), phosphazene base P1-t-butyl (tert-butyl-iminotris (dimethylamino) phosphorane), and 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diaza-2-phosphorane (BEMP). Any desired mixtures may also be used.

[0031] At least one catalyst is very preferably an organic base, preferably those mentioned above, particularly preferably alkylamines, imidazole (derivatives), guanidine bases, such as triazabicyclodecene, DMAP and corresponding derivatives, DBN and DBU, most preferably DMAP. These catalysts have the special advantage that they can be removed in the process step (ii) according to the invention, for example under reduced pressure, together with the chemical compounds that are eliminated during condensation. This means that the polyester carbonate obtained contains minimal or no residual catalyst. This has the advantage, in particular, that inorganic salts, which are necessarily formed in all routes, for example, in which phosgene is used, are not present in the polymer. It is known that such salts can have a negative effect on the stability of polyester carbonates, since the ions can catalyze the corresponding decomposition.

[0032] Preferably, the at least one catalyst is used in an amount of 1 ppm to 5000 ppm, preferably 5 ppm to 1000 ppm, more preferably 20 ppm to 200 ppm, based on 1 mol of alicyclic dicarboxylic acid.

[0033] According to the invention, it has been found that in order to obtain polyestercarbonates of sufficient molar mass, the molar ratio of all aliphatic dihydroxy compounds present in process step (i) to all cycloaliphatic dicarboxylic acids present in process step (i) must be between 1:0.6 and 1:0.05, prior to the reaction in process step (i). Preferably, this ratio is between 1:0.55 and 1:0.1, likewise preferably between 1:0.5 and 1:0.15, most preferably between 1:0.4 and 1:0.2. It should be noted here that the ratio of aliphatic dihydroxy compounds to cycloaliphatic dicarboxylic acids in the subsequent polyestercarbonate should not be too high (i.e. the incorporation of cycloaliphatic dicarboxylic acids should not be too low), since otherwise polymers with undesirable properties are obtained. Polymers with a high content of units derived from dihydroxy compounds such as isosorbide are usually very hard and, as a consequence, have poor mechanical properties. If the content of units derived from cycloaliphatic dicarboxylic acids is too low, the processability of the resulting polymer will likewise be poor. Furthermore, the polyester units generally give the polyestercarbonates good chemical stability, which is why the content of units deriving from cycloaliphatic dicarboxylic acids must likewise not be too low.

[0034] According to the present invention, the polyester carbonate produced preferably has a relative solution viscosity eta rel of 1.12 to 1.60, more preferably 1.18 to 1.50, and most preferably 1.20 to 1.40, wherein the relative solution viscosity is preferably measured in dichloromethane at a concentration of 5 g / l at 25° C. using an Ubbelohde viscometer.

[0035] Likewise, the polyester carbonates produced preferably have a weight average molar mass of 40000 g / mol to 150000 g / mol, more preferably 45000 g / mol to 90000 g / mol, preferably determined by gel permeation chromatography in dichloromethane using polystyrene calibration. This weight average is most preferably determined by the gel permeation chromatography method described in the Examples section.

[0036] According to the invention, these molar masses are preferably referred to as "sufficient" molar masses.

[0037] Furthermore, step (i) of the method according to the present invention preferably comprises at least one, more preferably all, of the following steps (ia) to (ic):

[0038] (ia) at least melting all components present in process step (i), i.e. at least one cycloaliphatic dicarboxylic acid, at least one diaryl carbonate and at least one aliphatic dihydroxy compound, 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 the skilled person 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 process step (i) or (ii). Exceptions are compounds formed by reaction (e.g. phenol, when diphenyl carbonate is used as at least one diaryl carbonate). Of course, the presence of traces of solvent in the starting compounds cannot be excluded. This is preferably included in the present invention. However, according to the present invention, active steps of adding such solvents are preferably avoided.

[0039] (ib) heating the mixture, preferably the melt obtained from step (ia). Steps (ia) and (ib) may overlap, since heating may also be required to produce a melt in step (ia). Heating is preferably initially to a temperature of 150°C to 180°C.

[0040] (ic) reacting the mixture, preferably the mixture obtained from step (ib), while introducing mixing energy, preferably by stirring. Here too, step (ic) may overlap with step (ib), since the reaction of the mixture can already be started by heating. The melt here has preferably already been heated by step (ib) to a temperature of 150°C to 180°C under standard pressure. The temperature in step (ic) is increased stepwise to 210°C to 300°C, preferably to 220°C to 260°C, depending on the reactivity observed. The reactivity can be estimated from the evolved gases in a manner known to the skilled person. Higher temperatures are basically possible in this step, but side reactions (for example discoloration) can occur at higher temperatures. Higher temperatures are therefore less preferred. The mixture is stirred under standard pressure until the evolution of gases has almost stopped. According to the invention, under these conditions, the aryl alcohol (for example phenol when diphenyl carbonate is used) resulting from the reaction of at least one carboxylic acid with at least one diaryl carbonate is already partially removed.

[0041] It was also observed according to the invention that the at least one dihydroxy compound had already started to react by this time as well, as evidenced by the detection of oligomers containing carbonate units from the reaction of the at least one dihydroxy compound with the at least one diaryl carbonate and / or ester units from the reaction of the at least one dihydroxy compound with the at least one dicarboxylic acid.

[0042] Therefore, according to the invention, it is preferred that, prior to carrying out process step (ii), the mixture resulting from process step (i) comprises oligomers comprising carbonate units from the reaction of at least one dihydroxy compound with at least one diaryl carbonate and / or ester units from the reaction of at least one dihydroxy compound.

[0043] The reaction time in step (ic) depends on the amount of raw materials. Preferably, the reaction time in step (ic) is 0.5 hours to 24 hours, preferably 0.75 hours to 5 hours, more preferably 1 hour to 3 hours. The reaction time should preferably be selected to ensure that gas evolution has almost stopped (see reaction scheme above).

[0044] According to the present invention, the molar ratio of the sum of all aliphatic dihydroxy compounds present in process step (i) and all alicyclic dicarboxylic acids present in process step (i) to all diaryl carbonates present in process step (i) before the reaction in process step (i) is 1:0.4-1:1.6, preferably 1:0.5-1:1.5, more preferably 1:0.6-1:1.4, more preferably 1:0.7-1:1.3, particularly preferably 1:0.8-1:1.2, most preferably 1:0.9-1:1.1. Those skilled in the art can select an appropriate optimal ratio according to the purity of the raw materials.

[0045] Method step (ii) In process step (ii), the mixture obtained from process step (i) is subjected to further condensation, which at least involves the removal of chemical compounds that are 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 process step (i). This is preferably the reaction of at least one cycloaliphatic dicarboxylic acid with at least one diaryl carbonate, with the elimination of aryl alcohol. However, it is preferred that further condensation to oligomers has also already occurred (see process step (i)).

[0046] The term "condensation" is known to the skilled person. It is preferably understood to mean a reaction in which two molecules (of the same or different substances) combine to form a larger molecule, with the elimination of a molecule of a chemically simple substance. This compound eliminated during the condensation is removed in process step (ii). The chemical compound eliminated during the condensation is preferably removed in process step (ii) by reduced pressure. Thus, the process according to the invention is preferably characterized in that volatile substances having a boiling point less than the cycloaliphatic diester formed in process step (i), less than the at least one aliphatic dihydroxy compound and less than the at least one diaryl carbonate are removed during the reaction in process step (i), optionally under stepwise reduced pressure. If different volatile substances are removed, it is preferred here to choose a stepwise removal. Likewise, it is preferred to choose a stepwise removal in order to ensure that the volatile substances are removed as completely as possible. The volatile substances are the chemical compound(s) eliminated during the condensation.

[0047] To ensure the continuous removal of chemical compounds released during condensation, a stepwise depressurization can be performed, for example, by depressurization as soon as the overhead temperature drops. When a pressure of 1 mbar, preferably less than 1 mbar, is reached, the condensation is continued until the desired viscosity is reached. This can be done, for example, by monitoring the torque, i.e., the polycondensation is stopped when the desired stirrer torque is reached.

[0048] The removal of the condensation product in process step (ii) is preferably carried out at temperatures between 210° C. and 280° C., more preferably between 215° C. and 260° C., particularly preferably between 220° C. and 250° C. The pressure during removal is further preferably between 500 mbar and 0.01 mbar. It is particularly preferred that the removal is carried out stepwise by reducing the pressure. The pressure in the final stage is most preferably between 10 mbar and 0.01 mbar.

[0049] In one embodiment, at least one catalyst can be added in process step (ii). Such addition is also included in the present invention, since all the components that form the subsequent polyester carbonate are nevertheless present as monomers in process step (i). This additional at least one catalyst can be the same as or different from the catalyst present in process step (i). The at least one catalyst is preferably selected from the catalysts mentioned in process step (i). Such a procedure can be advantageous when the catalyst shows different reactivity with respect to the reactions that mainly occur in process step (i) and process step (ii).

[0050] In a further aspect of the present invention, polyestercarbonates are provided which are obtainable by the process according to the invention as described above, in all the disclosed combinations and preferred features. As already explained above, the polyestercarbonates according to the invention are different from polyestercarbonates prepared via a two-step process (i.e. initial preparation of diaryldicarboxylates by reaction of cycloaliphatic dicarboxylic acids with diarylcarbonates and purification of said diaryldicarboxylates, followed by condensation of the diaryldicarboxylates with diarylcarbonates and aliphatic dihydroxy compounds) insofar as the carbonate and / or ester units have a different statistical distribution. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS EXAMPLES

[0051] Materials used: Cyclohexanedicarboxylic acid: Cyclohexane-1,4-dicarboxylic acid; CAS 1076-97-7, 99%; Sigma-Aldrich, Munich, Germany, abbreviated as CHDA Hydrogenated dimer acid CAS 68783-41-5, 98% or higher, Sigma-Aldrich (Munich, Germany), as a comparison material Diphenyl carbonate: Diphenyl carbonate, 99.5%, CAS 102-09-0; Acros Organics, Geel, Belgium; abbreviated as DPC 4-Dimethylaminopyridine: 4-(Dimethylamino)pyridine; 98.0% or higher; purum; CAS 1122-58-3; Sigma-Aldrich (Munich, Germany) Isosorbide: Isosorbide (CAS: 652-67-5), 99.8%, Polysorb PS A; Roquette Freres (Restron, France 62136); abbreviated as ISB Dimethylcyclohexane-1,4-dicarboxylate: CAS 94-60-0 Sigma Aldrich (97%); cis / trans mixture

[0052] Analysis method: Determination of Glass Transition Temperature: The glass transition temperature is determined by differential scanning calorimetry (DSC) in accordance with the DIN EN ISO 11357-1:2009-10 and ISO 11357-2:2013-05 standards at a heating rate of 10 K / min under nitrogen, and the glass transition temperature (Tg) is measured as the inflection point on the second heating.

[0053] Chemical characterization: 1 H NMR: 600MHz; Bruker AV III HD 600 spectrometer; Solvent: CDCl3

[0054] solution viscosity Determination of solution viscosity: The relative solution viscosity (η rel; also called eta rel) was determined at 25° C. in dichloromethane at a concentration of 5 g / l using an Ubbelohde viscometer.

[0055] Gel Permeation Chromatography Mass average molar mass M w , number average molar mass M nand dispersity (D) values ​​were determined by gel permeation chromatography using dichloromethane as eluent, calibrated with polystyrene standards, measured by Currenta GmbH & Co. OHG (Leverkusen). The eluent for calibration was also dichloromethane. Column combination of crosslinked styrene-divinylbenzene resin. Analytical column diameter: 7.5 mm; length: 300 mm. Column material particle size: 3 μm-20 μm. Solution concentration: 1.0 g / l. Flow rate: 1.0 ml / min, solution temperature: 21°C. Detection using a refractive index (RI) detector.

[0056] MALDI-ToF-MS The samples were dissolved in chloroform. The matrix used was dithranol containing LiCl. The samples were analyzed in positive reflector mode and linear mode.

[0057] Example 1: Present invention; ISB:CHDA 1:0.5 A flask equipped with a short-path separator was charged with 17.22 g (0.10 mol) of cyclohexane-1,4-dicarboxylic acid, 29.815 g (0.204 mol) of isosorbide, 64.26 g (0.3 mol) of diphenyl carbonate, and 0.01113 g (100 ppm) (corresponding to 0.010% by weight) of DMAP (4-dimethylaminopyridine). The mixture was evacuated four times with nitrogen to remove oxygen. The mixture was melted and heated to 160°C under stirring at standard pressure. According to the observed reactivity, the temperature was increased in stages to 240°C. Stirring was continued until the evolution of CO2 ceased, which took about 1 h (from the melt at 160°C). During this operation, the phenol was distilled off.

[0058] After the evolution of CO2 had ceased, the pressure was carefully reduced stepwise to 100 mbar over about 20 minutes. Phenol was continuously distilled off during this operation. Evacuation was continued until the pressure was less than 1 mbar. Stirring was continued at this pressure for about another 30 minutes, after which mixing was stopped.

[0059] The crude product was a brown resin (5.9 g); NMR (1H NMR) confirmed that the target compound was obtained.

[0060] A light brown polymer was obtained with a solution viscosity eta rel of 1.335.

[0061] Further data are shown in Table 1.

[0062] Example 2: Present invention; ISB:CHDA 1:0.4 The test was carried out essentially as described in Example 1, except that 17.22 g (0.10 mol) of cyclohexane-1,4-dicarboxylic acid, 37.26 g (0.255 mol) of isosorbide, and 74.97 g (0.35 mol) of diphenyl carbonate were used. The same amount of catalyst as in Example 1 was used.

[0063] A light brown polymer was obtained with a solution viscosity eta rel of 1.288.

[0064] Example 3: Present invention; ISB:CHDA 1:0.3 The test was carried out essentially as described in Example 1, except that 17.22 g (0.10 mol) of cyclohexane-1,4-dicarboxylic acid, 49.25 g (0.337 mol) of isosorbide, and 92.75 g (0.433 mol) of diphenyl carbonate were used. The same amount of catalyst as in Example 1 was used.

[0065] A light brown polymer was obtained with a solution viscosity eta rel of 1.278.

[0066] Example 4: Comparative Example 1: ISB:CHDA=1:1 The test was carried out essentially as described in Example 1, except that 17.20 g (0.10 mol) of cyclohexane-1,4-dicarboxylic acid, 14.90 g (0.102 mol) of isosorbide, and 42.80 g (0.20 mol) of diphenyl carbonate were used. The same amount of catalyst as in Example 1 was used.

[0067] A brittle brown melt was obtained with a solution viscosity eta rel of 1.025.

[0068] Example 5: Comparative Example 1: ISB:CHDA=0.8:1 The test was carried out essentially as described in Example 1, except that 17.20 g (0.10 mol) of cyclohexane-1,4-dicarboxylic acid, 18.70 g (0.128 mol) of isosorbide, and 48.20 g (0.225 mol) of diphenyl carbonate were used. The same amount of catalyst as in Example 1 was used.

[0069] A brittle brown melt was obtained with a solution viscosity eta rel of 1.053.

[0070] Example 6: Comparative Example Using Dimethyl Ester of CHDA Instead of CHDA The test was carried out essentially as described in Example 1, except that 20.20 g (0.10 mol) of dimethylcyclohexane-1,4-dicarboxylate, 37.26 g (0.255 mol) of isosorbide, and 32.13 g (0.15 mol) of diphenyl carbonate were used. The same catalyst as in Example 1 was used, but in an amount of 1000 ppm.

[0071] A brittle brown melt was obtained with a solution viscosity eta rel of 1.054.

[0072] Example 7: Comparative Example Using an Acid Not of the Invention The test was carried out essentially as described in Example 1, except that 27.70 g (0.05 mol) of hydrogenated dimer acid (CAS 68783-41-5), 24.64 g (0.169 mol) of isosorbide, and 46.40 g (0.217 mol) of diphenyl carbonate were used. The same amount of catalyst as in Example 1 was used.

[0073] A liquid product was obtained, and a solution viscosity determination was omitted since it was apparent that sufficient polymer growth had not occurred.

[0074] [Table 1]

[0075] Examples 1 to 3 show that the process of the present invention can produce the desired polyester carbonates with high viscosity as long as the ratio of isosorbide to CHDA according to the present invention is met.

[0076] This was surprising, since transesterification starting from free acids does not work (see Non-Patent Document 2). Transesterification starting from aliphatic esters (see Comparative Example 6) surprisingly shows only very little molecular weight growth, even when the ratio according to the invention is met.

[0077] Similarly, a comparison of Example 7 with Example 3 shows that the choice of acid component is important for sufficient polymer growth: when acids such as those described in US Pat. No. 5,999,231 are used, only liquid products are obtained.

[0078] Moreover, surprisingly, polymers with specific ISB:CHDA ratios cannot be synthesized. That is, Comparative Examples 4 and 5 show that at ratios with a higher proportion of cyclohexanedicarboxylic acid, the desired polymers are not obtained and the molecular weights obtained are very low. This was also not known / could not be inferred from this document.

[0079] Example 8: Reaction in process step (i) A flask equipped with a short-path separator was charged with 17.22 g (0.10 mol) cyclohexane-1,4-dicarboxylic acid, 29.228 g (0.20 mol) isosorbide, 42.84 g (0.2 mol) diphenyl carbonate, and 0.0089 g (100 ppm) DMAP (4-dimethylaminopyridine). The mixture was evacuated with nitrogen four times to remove oxygen. The mixture was melted at 160°C, then the temperature was increased to 190°C. Over a period of about 30 minutes, the temperature was increased to 240°C. The mixture was stirred at 240°C for about 30 minutes. Then, a slight vacuum was applied for 20 minutes, with the pressure gradually reduced. After 20 minutes, the pressure was reduced to 200 mbar to stop the reaction. The slight vacuum was applied to remove phenol, which would otherwise interfere with the analysis.

[0080] To remove residual phenol and polar substances such as CHDA, the mixture was dissolved in dichloromethane and extracted three times with water. The products were analyzed by MALDI-ToF-MS.

[0081] Peaks separated by 172 Da were observed, providing clear evidence of the formation of ISB carbonate units (mass corresponds to the Li adduct: M+Li*).

[0082] Additionally, a peak at 555 Da was identified, which may correspond to HO-ISB-carbonate-ISB-ester-CHDA-phenyl, where ISB refers to the isosorbide unit minus the two terminal OH groups (described separately) and CHDA stands for cyclohexane (cyclohexanedicarboxylic acid minus the two carboxylic acid groups).

[0083] The peak observed at 607 Da likely corresponds to the HO-ISB-carbonate-ISB-ester-CHDA-ester-ISB-OH oligomer.

[0084] Similarly, the peak observed at 717 Da would correspond to the HO-ISB-carbonate-ISB-carbonate-ISB-OH oligomer, an additional peak at 665 Da would correspond to the presence of HO-ISB-ester-CHDA-ester-ISB-ester-CHDA-ester-phenyl, and the peak at 837 Da would correspond to an additional ISB unit.

[0085] Example 9: Invention; ISB:CHDA 1:0.5; Different catalyst) The test was conducted essentially as described in Example 1, except that 17.22 g (0.10 mol) of cyclohexane-1,4-dicarboxylic acid, 29.815 g (0.204 mol) of isosorbide, 64.26 g (0.3 mol) of diphenyl carbonate, and 0.0555 g (500 ppm) (equivalent to 0.010 wt %) of DBN (1,5-diazabicyclo[4.3.0]non-5-ene) were charged to a flask equipped with a short-path separator.

[0086] A light brown polymer was obtained with a solution viscosity eta rel of 1.14.

Claims

1. 1. A process for producing a polyester carbonate by melt transesterification, comprising the steps of: (i) reacting at least one alicyclic dicarboxylic acid with at least one diaryl carbonate in the presence of isosorbide using at least one catalyst; (ii) subjecting the mixture resulting from process step (i) to a further condensation, while removing at least the chemical compounds released during the condensation; Including, 1. Process according to claim 1 , characterized in that the molar ratio of isosorbide present in process step (i) to all cycloaliphatic dicarboxylic acids present in process step (i) prior to the reaction in process step (i) is from 1:0.6 to 1:0.

05.

2. The method according to claim 1, characterized in that the method step (i) is carried out until gas evolution is observed to have ceased.

3. The at least one alicyclic dicarboxylic acid is represented by the formula (IIa), (IIb): 【Chemistry 1】 (In the formula, 3. The method according to claim 1 or 2, characterized in that each B independently represents a carbon atom or a heteroatom selected from the group consisting of O, S and N, and n is a number from 0 to 3) or a mixture thereof.

4. 4. The method of claim 3, wherein the at least one alicyclic dicarboxylic acid is selected from the group consisting of cyclohexane-1,4-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, tetradihydro-2,5-furandicarboxylic acid, tetradihydro-2,5-dimethylfurandicarboxylic acid, decahydronaphthalene-2,4-dicarboxylic acid, decahydronaphthalene-2,5-dicarboxylic acid, decahydronaphthalene-2,6-dicarboxylic acid, and decahydronaphthalene-2,7-dicarboxylic acid.

5. The at least one diaryl carbonate has the formula (2): 【Chemistry 2】 (In the formula, R, R', and R'' may each independently be the same or different and represent hydrogen, an optionally branched C1-C34 alkyl, a C7-C34 alkylaryl, a C6-C34 aryl, a nitro group, a carbonyl-containing group, a carboxyl-containing group, or a halogen moiety. The method according to any one of claims 1 to 4, characterized in that the compound is selected from the group consisting of

6. 6. The process according to claim 1, characterized in that, before the reaction in process step (i), the molar ratio of the isosorbide present in process step (i) and the sum of all cycloaliphatic dicarboxylic acids present in process step (i) to all diaryl carbonates present in process step (i) is from 1:0.4 to 1:1.

6.

7. 7. The process according to claim 1, characterized in that at least one inorganic base and / or at least one organic catalyst is used in process step (i).

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

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