Oligoesters containing resorcinol and isophthalic acid and / or terephthalic acid, corresponding polyester carbonates and their preparations

Abstract

The present invention relates to mixtures containing oligoesters, polyestercarbonates containing ester blocks, and a method for preparing polyestercarbonates having ester blocks by melt transesterification.

Description

[Technical Field]

[0001] The present invention relates to a mixture containing oligoesters, a polyester carbonate containing ester blocks, and a method for preparing a polyester carbonate having ester blocks. [Background technology]

[0002] Aromatic polyester carbonates are known to have good properties with respect to mechanical properties and heat deformation resistance. Certain polyester carbonates are also known to have high weather resistance, especially when they contain ester blocks formed from aromatic diacides and resorcinols.

[0003] In particular, polyester carbonates containing ester blocks formed from isophthalic acid and / or terephthalic acid and resorcinol are known to have good weather resistance. These materials are particularly interesting because they do not require any coating to protect them from the effects of harmful weathering and especially from UV light. The ester structure formed from resorcinol and isophthalic acid and / or terephthalic acid can initiate a so-called photofleece rearrangement upon contact with UV light. This forms a hydroxybenzophenone structure incorporated into the polymer chain. Hydroxybenzophenone is known to have UV-absorbing properties, which explains the good weather resistance. This subject is described, for example, in Patent Document 1. In contrast, the alternative use of UV absorbers is extremely ineffective because most of the UV absorber accumulates in bulk. In particular, the concentration of the UV absorber on the surface to be protected from UV light is relatively low. If those skilled in the art wish to use higher concentrations of UV absorbers, they face further drawbacks. For example, low molecular weight compounds degrade mechanical properties, especially at relatively high concentrations. This is undesirable. To fix relatively high concentrations of UV absorbers to a surface, it is customary to protect UV-sensitive materials such as polycarbonate with a coating layer containing a high concentration of UV absorbers. However, painting is an additional process that is costly and not always a desirable solution for sustainability reasons. In particular, in the field of automotive applications, it is advantageous when materials inherently possess weather resistance and the laborious painting process can be omitted.

[0004] The polyester carbonates described are conventionally produced by interfacial processes. In this process, aromatic diols and OH-terminated ester blocks are incorporated by condensation with phosgene. Similarly, OH-terminated ester blocks can be prepared in solution by condensation with phosgene, starting from aromatic diacides and aromatic diols. Such methods for preparing oligoesters and corresponding polyester carbonates are described in Patent Document 2. This document describes, as a preferred polymer, a polyester carbonate formed from a bisphenol A-containing ester block formed from terephthalic acid / isophthalic acid. Here, the ester block is prepared in a dichloromethane / water mixture using an aqueous NaOH solution, starting from an acid chloride of an aromatic diacide and resorcinol. The polyester solution containing the hydroxy-terminated ester block is transferred to a phosgenation reactor. Preferably, an alkaline bisphenol A solution is added, and the reactants react with phosgene.

[0005] A known process based on molten transesterification is used for polycarbonates, offering the advantage of avoiding difficult-to-handle feedstocks such as phosgene. Furthermore, it has the significant advantage of not requiring solvent consumption. Therefore, preparing polyester carbonates by molten transesterification would be industrially advantageous. However, this process also has its challenges. For example, replacing highly reactive acid chlorides with other feedstocks is always difficult. Transesterification processes often involve long residence times in the corresponding reactors. High temperatures frequently generate decomposition products that negatively impact product quality. Because molten transesterification typically does not require complex post-treatment steps, impurities, including catalyst residues, remain in the product. These can degrade product quality.

[0006] Furthermore, polycarbonates prepared by the melt transesterification process will have a significantly higher content of hydroxy-terminated groups (phenolic OH group content) compared to the corresponding products from the interfacial process. These phenolic OH groups can be damaged by the oxidation process, which degrades the quality of the product. This particularly affects the optical properties. However, obtaining good optical properties is important, especially for products characterized by high inherent weather resistance. Therefore, a low phenolic OH group content is advantageous. However, in this regard, the prior art only concerns the preparation of polyester carbonates by interfacial reactions, and therefore there is no teaching in the prior art regarding the polyester carbonates mentioned. Consequently, those skilled in the art do not know how such polyester carbonates with a low OH group content should be prepared by the melt transesterification process.

[0007] For the reasons stated above, the reactivity of the reactants is lower compared to the feedstocks in the interfacial process, and therefore, it is not known how to prepare the above polyester carbonates with high viscosity or molecular weight.

[0008] Patent Document 3 describes the preparation of hydroxy-terminated oligoester blocks in a molten material. The question here is how to achieve an oligoester with an OH-terminated group content equivalent to that obtained by solvent-based processes. For this purpose, the effects of different catalysts and operating methods (e.g., different temperatures and reduced pressure) were also tested. The resulting oligoesters have relatively low molecular weights. While the oligoesters described here have phenoxy-terminated groups, Patent Document 3 does not describe the molecular weight distribution of the oligoester oligomers. Furthermore, the oligoesters are subsequently incorporated by condensation via an interfacial process to obtain polyester carbonates. Therefore, this document cannot contain any teachings on how the end group and / or oligomer distribution affects the preparation of polyester carbonates by melt transesterification.

[0009] Patent Document 4 describes an oligoester prepared by a melt transesterification process, characterized by having a high proportion of carboxyl-terminated groups. These carboxyl-terminated groups are then used to incorporate the oligoester into a coating system. However, free acids are relatively unreactive in the melt transesterification process for preparing polyester carbonates, and therefore these precursors are not suitable for the melt-based polyester carbonates described above. Consequently, there is no description of their use in the melt transesterification process.

[0010] Patent Document 1 describes the preparation of oligomers from aromatic diacides and resorcinols. The problem solved by Patent Document 1 is to provide OH-terminated units that can subsequently be converted to polyester carbonates by an interfacial process. Similar to Patent Document 3, the oligomer distribution, end group ratio, or their influence on melt transesterification of the oligoester are not addressed here. [Prior art documents] [Patent Documents]

[0011] [Patent Document 1] U.S. Patent Application Publication No. 20030050400 [Patent Document 2] International Publication No. 0026275 [Patent Document 3] International Publication No. 2005021616 [Patent Document 4] International Publication No. 2006057810 [Overview of the project] [Problems that the invention aims to solve]

[0012] Starting from this prior art, the problem addressed by the present invention was to overcome at least one disadvantage of the prior art. More specifically, the problem addressed by the present invention was to provide a polyester carbonate containing ester blocks based on isophthalic acid and / or terephthalic acid and resorcinol, which can be obtained by a melt transesterification process. What is desirably to be obtained here is a polyester carbonate having good processability and at the same time a minimum content of phenolic OH end groups. Accordingly, the polyester carbonate is preferably weathering-stable and / or otherwise substantially stable to yellowing, and / or should substantially not have a tendency toward polymer degradation, for example by oxidative decomposition. It is likewise preferable that raw materials which pose handling problems, for example phosgene, are not used in the preparation of the polyester carbonate. [Means for Solving the Problems]

[0013] At least one, and preferably all of the above problems have been solved by the present invention. It has surprisingly been found that processable polyester carbonates can only be provided via a melt transesterification process when the oligoester has a defined end group content and a defined proportion of small oligomers. If a mixture comprising an oligoester having not more than 0.5% by weight of OH end groups, such as phenolic OH end groups, is used, wherein the groups in the end groups are substantially a specific aromatic group, preferably phenyl, and only when the proportion of oligomers having a molecular weight of less than 1000 g / mol is low, polyester carbonates having a sufficiently low content of phenolic OH end groups at the same time as a high (but not excessively high) molecular weight, whereby the polyester carbonate has, for example, high stability against degradation, can be obtained by melt transesterification. The effect of using specific polyester carbonates is that novel polyester carbonates are obtained in which isophthalic acid and / or terephthalic acid groups are highly directly bonded to carbonate blocks. In the prior art, oligoesters are used with a maximum OH end group content. As a result of this effect, automatically, the diol used (for example resorcinol) forms the end groups of these oligoesters. These then bond to the carbonate blocks, resulting in, for example, carbonate-resorcinol linkages. In contrast, the oligoesters according to the invention are terminated substantially by specific aromatic esters of isophthalic acid and / or terephthalic acid. The effect of this is that the polyester carbonate has novel linkages via isophthalic acid and / or terephthalic acid. By providing specific oligoesters, it has been possible to obtain polyester carbonates from oligocarbonate and oligoester blocks by melt transesterification, which has good properties with respect to the above-described desired objectives.

[0014] Accordingly, the present invention is a mixture comprising an oligoester of formula (1), wherein

Chemical Formula

[0015] According to the present invention, the expression "a mixture containing the oligoester of formula (1)" should be understood to mean that the mixture substantially consists of the oligoester of formula (1). This means that preferably, at least 80% by weight, more preferably at least 90% by weight, and most preferably at least 95% by weight of the mixture consists of the oligoester of formula (1). However, as a result of preparation, it cannot be ruled out that the mixture also contains a certain proportion of oligoesters having formula (1), but in which at least one q is 0, and in this case, Z at the end of this chain of the oligoester q=0 is hydrogen. In this case, R1 and p have the above definitions. This means that the oligoester is terminated by isophthalic acid / terephthalic acid on at least one side (-COOH as the terminal group).

[0016] When an oligoester of formula (1), wherein at least one q is 0, and in this case Z at the end of the chain of the oligoester where q=0 is hydrogen, is present in the mixture according to the present invention, these OH-terminal groups (-COOH-terminal groups) are not included in the defined weight percentage of OH-terminal groups (via Z in formula (1)) in the mixture according to the present invention. Preferably, the proportion of -COOH-terminal groups in the mixture according to the present invention (via the case where at least one q is 0, and Z at the end of the chain of the oligoester where q=0 is hydrogen) is 10% by weight or less, more preferably 8% by weight or less, even more preferably 5% by weight or less, and most preferably 2% by weight or less, based on the total weight of the mixture. Those skilled in the art know how these -COOH-terminal groups can be determined. In particular, C 13 NMR measurement can determine the carbon atoms that are part of the acid terminal group. For this purpose, deuterated DMSO is a particularly suitable solvent. The carbon atoms that are part of the acid terminal group should normally be in the range of 160 ppm to 170 ppm, and especially 163 ppm to 169 ppm. According to the present invention, it is preferable that the content of formula (1), in which at least one q is 0 and Z at the chain end of the oligoester where q=0 is hydrogen, is low in the mixture according to the present invention.

[0017] According to the present invention, the mixture contains OH-terminated groups in a total amount of 0.5% by weight or less, preferably 0.45% by weight or less, more preferably 0.4% by weight or less, and most preferably 0.35% by weight or less, relative to the total weight of the mixture (preferably 1 (Detected by 1H NMR is preferable.)

[0018] Preferably, R1 in formula (1) is hydrogen. This means that the ring substituted by R1 is preferably derived from resorcinol.

[0019] Preferably, R2 in formula (2) is hydrogen. This, in combination with formula (1), means that the group in formula (2) where R2 is present is preferably isophthalic acid and / or phenyl terephthalate.

[0020] Similarly, preferably, R2' in formula (2a) is hydrogen. This, in combination with formula (1), means that the group in formula (2a) where R2' exists is preferably resorcinolphenyl carbonate.

[0021] Particularly preferred is that R1 in formula (1) is hydrogen, R2 in formula (2) is hydrogen, and R2' in formula (2a) is hydrogen.

[0022] In formula (1), p represents the number of repeating units of the oligoester. p preferably has an average value of at least 4. More preferably, p in formula (1) has an average value of at least 4 and at most 30, more preferably at least 5 and at most 27, and most preferably at least 5 and at most 24. The oligoester mixture is particularly preferably having a number-average molar mass in the range of 1300 g / mol to 6000 g / mol, more preferably 1400 g / mol to 5500 g / mol, and most preferably 1500 g / mol to 5000 g / mol. This M nThe molecular weight is preferably determined by gel permeation chromatography in dichloromethane using bisphenol A polycarbonate as a standard. The molecular weights Mw (weight average) and Mn (number average) of the oligoesters or polyester carbonates used according to the present invention were determined by size exclusion chromatography (gel permeation chromatography, GPC; according to DIN 55672-1:2007-08 using BPA polycarbonate calibration) unless otherwise specified. Calibration was performed using linear polycarbonates with known molar mass distributions (e.g., from PSS Polymer Standards Service GmbH, Germany). This was done using method 2301-0257502-09D (from 2009 in German) from Currenta GmbH & Co. OHG, Leverkusen. Dichloromethane was used as the eluent. The column combination consisted of cross-linked styrene-divinylbenzene resin. GPC is used for polymers, particularly those with a weight-average molar mass of 2000 g / mol to 100000 g / mol. w This may include one or more commercially available GPC columns connected in series for size exclusion chromatography, selected to adequately separate the molar mass of aromatic polycarbonates having [specific properties]. The analytical columns typically have a diameter of 7.5 mm and a length of 300 mm. The particle size of the column material ranges from 3 μm to 20 μm.

[0023] The mixture according to the present invention is preferably characterized in that R1 in formula (1) is hydrogen, 0.4% by weight or less of the Z groups in the mixture are hydrogen, and the percentage of oligomers having a molecular weight of less than 1000 g / mol is less than 10%.

[0024] The mixture according to the present invention has 0.5% by weight or less, preferably 0.45% by weight or less, more preferably 0.4% by weight or less, and most preferably 0.35% by weight or less of OH-terminated groups (meaning that Z in formula (1) is hydrogen) relative to the whole mixture. This OH-terminated group content can be determined by methods known to those skilled in the art. The OH-terminated group content is preferably 1This is determined by 1H NMR. This can be done, for example, using tetramethylsiloxane as an internal standard in dichloromethane. For this purpose, the area under the signal of the OH group (which is usually in the range of 5.3 ppm to 5.6 ppm) can be expressed relative to the area of ​​other signals in the oligomer.

[0025] Surprisingly, it has been found that when the OH-terminated group content of the mixture according to the present invention exceeds 0.5% of the total mixture, this oligoester mixture exhibits high reactivity, thereby yielding a polyester carbonate with a relative solution viscosity (i.e., typically above 1.35 eta-rel) that is no longer processable by melt transesterification. In other words, the result is a polyester carbonate that is always difficult to process, for example, to obtain molded articles by injection molding. At the same time, many of these polyester carbonates obtained in this way also have a phenolic OH content. This usually leads to unstable polymers that are susceptible to degradation by temperature and / or light. In contrast, when the OH-terminated group content of the mixture according to the present invention is 0.5% by weight or less of the total mixture, considering its molecular weight (measured as eta-rel) and the resulting phenolic OH-terminated group content, it is possible to obtain a polyester carbonate that not only has good processability (e.g., by injection molding) but is also very stable against decomposition.

[0026] According to the present invention, the ratio of terminal groups in formula (1) where Z corresponds to formula (2a) and / or formula (2) to terminal groups where Z is hydrogen (and in these terminal groups q=1) is preferably 10:1 to 2:1, more preferably 9:1 to 3:1, and most preferably 8:1 to 4:1. This ratio of terminal groups can be determined by methods known to those skilled in the art. In particular, this ratio is 1This can be determined by 1H NMR, preferably at least 700 MHz. This can be done, for example, using tetramethylsiloxane as an internal standard in dichloromethane. For this purpose, the area under the signal of the OH group (which is usually at 5.3 ppm to 5.6 ppm) can be expressed relative to the area of ​​other signals of the oligomer. Depending on the peak overlap and the selection of monomers forming the oligoester according to the present invention, it is also possible, for example, to express the area of ​​the peak at about 7.4 ppm corresponding to the phenyl terminal group (2 protons) relative to the area of ​​the peak at 6.6 ppm to 6.8 ppm corresponding to the resorcinol terminal group (3 protons).

[0027] Similarly, and surprisingly, it has been found that in order to sufficiently increase the molecular weight of the polyester carbonate by melt transesterification, the proportion of oligomers having a molecular weight of less than 1000 g / mol in the mixture according to the present invention must be less than 12%, preferably less than 11%, and more preferably less than 10%. If the proportion is greater than 12%, the oligoester mixture will not be sufficiently reactive to obtain a sufficient increase in molecular weight. This means that the resulting polyester carbonate will not have the desired properties with respect to processability, mechanical properties, and optical properties. According to the present invention, the proportion of oligomers having a molecular weight of less than 1000 g / mol is determined by the ratio of the area under the molecular weight distribution curve of the mixture to the refractive index signal (from gel permeation chromatography) in the range of less than 1000 g / mol to the total area under that molecular weight distribution curve. Here, gel permeation chromatography is carried out in dichloromethane using a bisphenol A polycarbonate standard (see also the precise description of gel permeation chromatography above). The refractive index signal curve versus molecular weight can be integrated by methods known to those skilled in the art, in particular by GPC software. The area under the curve for less than 1000 g / mol is expressed here relative to the total area. It will be clear that the Mn of the oligoester mixture affects the amount of oligomers having a molecular weight of less than 1000 g / mol. This means, firstly, that if the Mn value of the oligoester is low, there will be a relatively narrow molecular weight distribution where the proportion of oligomers having a molecular weight of less than 1000 g / mol is less than 12%. Secondly, however, this may also preferably mean that the oligoester has a relatively high Mn, and therefore the proportion of oligomers having a molecular weight of less than 1000 g / mol is less than 12%.

[0028] The mixture according to the present invention, comprising oligoester of formula (1) in all of the above preferred and preferred combinations, (i) At least isophthalic acid and / or terephthalic acid are mixed with a diol of formula (3) and at least one diaryl carbonate of formula (4), [ka] In the formula, R1 is a hydrogen atom, a halogen, or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen. [ka] In the formula, R2 is independently in each case either hydrogen or -COOCH3, preferably hydrogen. (ii) The mixture from step (i) is heated in the presence of at least one catalyst, (iii) To obtain a mixture containing oligoesters, the mixture from step (ii) is subjected to reduced pressure. It is preferable that it be manufactured through a process.

[0029] Optionally, this process according to the present invention may be supplemented by step (iv) in which the oligoester-containing mixture obtained from step (iii) is precipitated. For this purpose, the mixture is preferably dissolved in dichloromethane. Equally preferably, it can then be precipitated in a non-solvent, such as methanol. Subsequently, the precipitated mixture containing the oligoester is separated from the non-solvent and optionally dried to obtain the mixture according to the present invention containing the oligoester. Step (iv) can be used when the proportion of oligomers having a molecular weight of less than 1000 g / mol in the mixture is greater than 12%. The effect of precipitation is that oligomers with low molecular weight remain in the solution. Thus, the proportion of oligomers having a molecular weight of less than 1000 g / mol in the mixture can be reduced.

[0030] Similarly, optionally, the process according to the present invention may optionally include, in addition to step (iv), a further step (v) in which a mixture containing an oligoester obtained from or from step (iv) is reacted with a diphenyl dioxide ester, preferably diphenyl isophthalate and / or diphenyl terephthalate. Process step (v) is particularly useful when the OH-terminated group content of the mixture containing the oligoester obtained from step (iii) or step (iv) is greater than 0.5% by weight. Additional reaction with the diphenyl dioxide ester can convert at least some of the OH-terminated groups to phenoxy-terminated groups (i.e., Z in formula (1) is phenyl). In this way, the OH-terminated group content of the mixture containing the oligoester can be reduced. Those skilled in the art will also recognize alternative steps (v) for reducing the OH-terminated group content. However, the described step (v) is particularly preferred because the introduction of the described end groups leads to reactivity in the subsequent melt transesterification process that yields the polyester carbonate.

[0031] However, according to the present invention, even after step (iii), by selecting appropriate parameters and, more particularly, an appropriate catalyst in step (ii), it is also possible to obtain a mixture containing oligoesters that directly satisfy the characteristics required by the present invention regarding the OH-terminated group content and the proportion of oligomers having a molecular weight of less than 1000 g / mol. In this case, neither step (iv) nor step (v) is necessary.

[0032] For example, in step (i), the ratio of isophthalic acid and / or terephthalic acid to the diol of formula (3) can directly affect the ratio of terminal groups obtained in the mixture containing the oligoester. The ratio of isophthalic acid and / or terephthalic acid to the diol of formula (3) is preferably 1.00 to 1.15, more preferably 1.03 to 1.13, and most preferably 1.04 to 1.12. It has been found that when the ratio is less than 1.00, a high proportion of oligomers with a molecular weight of less than 1000 g / mol are formed. As already described, these can be removed from the mixture by step (iv). However, it is therefore preferable that this ratio is above 1.00. Conversely, an excessively high ratio leads to the termination of very high OH terminal groups. Here again, it has already been described that this can be reduced by step (v). Nevertheless, it is therefore preferable that this ratio is 1.15 or less.

[0033] Preferably, both isophthalic acid and terephthalic acid are used in process step (i). When both diacides are used, it is even more preferable that the ratio of isophthalic acid to terephthalic acid is 0.25 to 4.0:1, more preferably 0.4 to 2.5:1, and most preferably 0.67 to 1.5:1. It is equally preferable that the diol of formula (3) is resorcinol. It is equally and preferably simultaneously preferable that the diaryl carbonate of formula (4) is diphenyl carbonate.

[0034] It is particularly preferable to use a ratio of isophthalic acid and / or terephthalic acid to the diaryl carbonate of formula (4) of 1:2 to 2.5, more preferably 1.0:2.01 to 2.25, and most preferably 1.0:2.05.

[0035] In process step (ii), the mixture from process step (i) is heated in the presence of at least one catalyst. Preferably, in this process step (ii), the individual components from process step (i) are melted. However, terephthalic acid in particular does not dissolve under given conditions, at least initially. However, this can be changed during process step (ii). Carbon dioxide is usually released in process step (ii). This procedure allows for a rapid reaction with low thermal stress. Process step (ii) is preferably carried out under a protective gas atmosphere, preferably under nitrogen and / or argon. Step (ii) is preferably carried out in the absence of a solvent. The term “solvent” in this context is known to those skilled in the art. According to the present invention, the term “solvent” is preferably understood to mean a compound that does not initiate a chemical reaction in any of process steps (i), (ii), and / or (iii). This excludes compounds that are formed by the reaction (e.g., phenol when the diaryl carbonate used is diphenyl carbonate). Of course, the presence of trace amounts of solvent in the starting compound cannot be ruled out. This possible situation is preferably covered by the present invention. However, according to the present invention, it is preferable to avoid the active step of adding such solvent.

[0036] The heating in process step (ii) is preferably carried out at a temperature of 180°C to 300°C, preferably 190°C to 270°C, and particularly preferably 195°C to 250°C. Under these temperature conditions, the corresponding aryl alcohol, preferably phenol, of the diaryl carbonate can be distilled off. Process step (ii) is preferably carried out under standard pressure. Here, it is preferable to stir under standard pressure until gas generation substantially ceases. Alternatively, depending on the observed reactivity, the temperature may be increased stepwise to 200°C to 300°C, preferably 210°C to 260°C, and particularly preferably 215°C to 240°C. The reactivity can be estimated from the gas generation in a manner known to those skilled in the art. Higher temperatures are possible in principle in this step, but higher temperatures may cause side reactions (such as discoloration). Therefore, higher temperatures are less preferable.

[0037] It has been found that at least one catalyst used in process step (ii) can affect the oligomer distribution of the mixture according to the present invention, which contains an oligoester. In process step (ii), it is also possible to use a catalyst containing alkali metal ions, preferably sodium ions. However, alkali metal ions remain in the mixture according to the present invention, which are then condensed by molten transesterification. However, since alkali metal ions, especially sodium ions, can catalyze molten transesterification, the amount of sodium remaining in the mixture should be precisely known and, if necessary, determined. Therefore, it is advantageous not to use a catalyst containing alkali metal ions in process step (ii).

[0038] At least one catalyst is more preferably an organic base, preferably an alkylamine, imidazole (derivative), a guanidine base such as triazabicyclodecene, DMAP and its corresponding derivatives, 1,5-diazabicyclo[4.3.0]nona-5-ene (DBN) and diazabicycloundecene (DBU), most preferably DMAP. These catalysts offer the particular advantage that they can be removed by the reduced pressure applied in process step (iii) according to the present invention. This means that the resulting mixture containing oligoesters may contain only a small amount of catalyst, or even none at all. This offers the particular advantage that the mixture of oligoesters does not contain inorganic salts, which are always obtained by routes using, for example, phosgene, and therefore the same applies to the subsequent polyester carbonate. Such salts are known to have adverse effects on the stability of polyester carbonates because their ions can act catalytically in the case of the corresponding decomposition.

[0039] It is preferable to use a mixture of at least one organic base, such as an alkylamine, imidazole (derivative), guanidine base such as triazabicyclodecene, DMAP and its corresponding derivative, DBN, or DBU, together with a phosphonium catalyst of formula (VIII) (see further below). The catalyst used in process step (ii) is most preferably a mixture of 4-(dimethylamino)pyridine (DMAP) and tetrabutylphosphonium acetate.

[0040] At least one catalyst is preferably used in an amount of 1 ppm to 5000 ppm, preferably 5 ppm to 1000 ppm, more preferably 20 ppm to 500 ppm, relative to the total mass of isophthalic acid and / or terephthalic acid, the diol of formula (3), and the diaryl carbonate of formula (4). If two or more catalysts are used in the reaction, these catalysts are preferably used in an amount of 1 ppm to 5000 ppm, preferably 5 ppm to 1000 ppm, more preferably 300 ppm to 700 ppm.

[0041] In process step (iii), reduced pressure is applied to the mixture obtained from process step (ii). As a result, the corresponding aryl alcohol, preferably phenol, of the diaryl carbonate used is distilled off, and the equilibrium of the reaction shifts towards the oligoester. The aryl alcohol is a chemical compound eliminated by the condensation reaction.

[0042] The term "condensation" is known to those skilled in the art. It is preferably understood to mean a reaction in which two molecules (of the same or different substances) combine to form one larger molecule, involving the elimination of one molecule of a chemically simple substance. This compound eliminated during condensation is removed by reduced pressure in process step (iii). Therefore, the process according to the present invention is preferably characterized in that, in process step (iii), volatile components having a boiling point below the boiling point of the oligoester mixture formed in process step (ii) are removed by optionally stepwise reduction of pressure. Stepwise removal is preferably selected when different volatile components are to be removed. Stepwise removal is also preferably selected to ensure that the volatile components (which may be more than one) are removed as completely as possible. The volatile components are chemical compounds (which may be more than one) eliminated during condensation, preferably phenols.

[0043] To ensure the continuous removal of chemical compounds released during condensation, the pressure can be gradually reduced, for example, by lowering the pressure as soon as the overhead temperature decreases.

[0044] The condensation product is removed in process step (iii) at a temperature of preferably 200°C to 280°C, more preferably 210°C to 270°C, and particularly preferably 220°C to 265°C. Furthermore, the reduced pressure during the removal process is preferably 500 mbar to 0.01 mbar. It is particularly preferable that the removal is carried out in stages by reduced pressure. The vacuum level in the final stage is most preferably 10 mbar to 0.01 mbar.

[0045] In the first aspect of the present invention, (A) an ester group of formula (I)

Chemical Formula

Chemical Formula

Chemical Formula

Chemical Formula

[0046] The existence of the structure of formula (VII) can be determined by NMR. This is indicated, for example, by the direct bonding of a bisphenol unit to isophthalic acid and / or terephthalic acid units. This bond is an ester bond. The existence of this bond can be determined by determining the chemical shift of the carbonyl carbon atom identified by the arrow in formula (VIIa). 13 This can be determined by 13C NMR spectroscopy. [ka]

[0047] In the experimental section, 13To discover / calibrate the position of the carbon atom identified by the arrow in formula (VIIa) in 1C NMR, we will explain the synthesis of a model compound formed from bisphenol A and isophthalic acid / terephthalic acid as an example.

[0048] Polyester carbonates produced by interfacial processes containing ester groups (A) and (B) do not have structural formula (VII) (see Figure 1). In such reactions, the OH-terminated oligoester reacts with the corresponding oligocarbonate that yields a carbonate upon reaction with bisphenol (usually bisphenol A) or phosgene. This means, for example, that resorcinol units directly bonded to the BPA unit via the carbonate group are always present.

[0049] It will be apparent to those skilled in the art that ester groups (A) and carbonate groups (B) can repeatedly form in polyester carbonates. Similarly, it will be apparent that n and m, and the number of ester groups (A) and / or carbonate groups (B), must be selected so as to yield the corresponding solution viscosity of the polyester carbonate. Here, the polyester carbonate according to the present invention preferably has a ratio of ester groups (A) of 5% to 90% by weight, more preferably 8% to 30% by weight, and most preferably 9% to 25% by weight, to the total weight of ester groups (A) and carbonate groups (B). The polyester carbonate according to the present invention is equally preferably composed of units of formulas (I) and (II) in an amount of at least 80% by weight, more preferably at least 90% by weight, and most preferably at least 95% by weight.

[0050] The polyester carbonate according to the present invention is preferably characterized by having a relative solution viscosity of at least 1.26 to a maximum of 1.34. As already described above, this relative solution viscosity ensures good processability of the polyester carbonate, for example, by injection molding. This relative solution viscosity also allows it to exhibit good mechanical properties for areas of interest such as automobile exteriors. The polyester carbonate has high stability and is inherently stable against weathering.

[0051] According to the present invention, the relative solution viscosity (ηrel; also called etarel) is preferably determined using an Ubbelohde viscometer at a concentration of 5 g / l in dichloromethane at 25°C. Those skilled in the art are familiar with the determination of relative solution viscosity using an Ubbelohde viscometer. According to the present invention, this is preferably carried out in accordance with DIN 51562-3; 1985-05. This involves measuring the flow time of the polyester carbonate to be analyzed through the Ubbelohde viscometer in order to determine the difference in viscosity between the polymer solution and its solvent. For this purpose, the Ubbelohde viscometer is first calibrated by analyzing the pure solvents dichloromethane, trichloroethylene, and tetrachloroethylene (always performing at least 3 and at most 9 measurements). This is followed by a proper calibration using the solvent dichloromethane. Next, the polymer sample is weighed and dissolved in dichloromethane, and then the flow time for this solution is determined 3 times. The average value of the flow time is corrected by the Hagenbach correction to calculate the relative solution viscosity.

[0052] The polyester carbonate according to the present invention preferably has a phenolic OH group content in the range of 50 ppm to 400 ppm, more preferably 80 ppm to 350 ppm. This phenolic OH group content is preferably determined by infrared spectroscopy. As described above with respect to the OH terminal groups of the mixture according to the present invention, 1It can also be determined by 1H NMR. However, there is a possibility of signal overlap. Therefore, it is preferable to determine the phenolic OH group content by infrared spectroscopy. For this purpose, the polyester carbonate is preferably dissolved in dichloromethane (2 g / 50 ml) and heated to 3583 cm⁻¹. -1 This is determined by evaluating the band at the wavenumber. Calibration of infrared equipment required for this purpose is known to those skilled in the art.

[0053] According to the present invention, it is preferable that R1 in formula (I) is hydrogen. Similarly, it is preferable that Y in formula (II) has the structure of formula (III).

[0054] Furthermore, R6 and R7 in formula (III) are each independently hydrogen or C1~C 12 Alkyl, more preferably hydrogen or C1-C8 alkyl, most preferably hydrogen or methyl is preferred.

[0055] It is very, very preferable that Y is introduced to the carbonate group (B) via a diphenol selected from the group consisting of 4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, dimethylbisphenol A, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene, and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, more preferably via bisphenol A.

[0056] The polyester carbonate according to the present invention can be processed as is to obtain all kinds of molded articles. It can also be processed together with other thermoplastics and / or polymer additives to obtain thermoplastic molding compounds. The present invention further provides molding compounds and molded articles. The polymer additive is preferably selected from the group consisting of flame retardants, anti-drip agents, flame retardant synergies, smoke inhibitors, lubricants and release agents, nucleating agents, antistatic agents, conductive additives, stabilizers (e.g., hydrolysis, heat aging and UV stabilizers, and transesterification inhibitors), flow promoters, phase compatibilizers, dyes and pigments, impact modifiers, and fillers and reinforcing agents.

[0057] Thermoplastic molding compounds can be produced by known methods, for example, by mixing polyester carbonate with further components, and then melt-compounding and melt-extruding these components at a temperature of preferably 200°C to 320°C in conventional equipment such as an internal kneader, extruder, or twin-screw system. In the context of this application, this process is commonly referred to as compounding. Therefore, the term “molding compound” is understood to mean the product obtained when the components of a composition are melt-compounded and melt-extruded.

[0058] Molded articles formed from the polyester carbonate according to 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 processes. A further form of processing is the manufacture of molded articles by thermoforming from a previously manufactured sheet or film.

[0059] In a further embodiment of the present invention, a method for producing a polyester carbonate according to the present invention is provided, characterized in that a mixture according to the present invention containing an oligoester is reacted with a mixture of oligocarbonates by melt transesterification.

[0060] The process of melt transesterification is known to those skilled in the art. For example, one can refer to Schnell, "Chemistry and Physics of Polycarbonates," Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964. In particular, this is a process that can be carried out without solvent and / or phosgene. For this purpose, it is necessary to melt a mixture containing oligoesters and further a mixture of oligocarbonates. Suitable temperatures for this purpose are typically 280°C to 400°C, preferably 300°C to 390°C, more preferably 305°C to 350°C, and even more preferably 310°C to 340°C. However, according to the present invention, temperatures below 320°C, preferably above 280°C to 315°C, have been found to be advantageous with respect to the incorporation of oligoester blocks into polyester carbonates. This is especially true when a mixture containing oligoesters having a high OH-terminated group content within the range defined by the present invention is used.

[0061] Simultaneously, a reduced pressure is applied to shift the reaction equilibrium towards the polyester carbonate side. The pressure used for this purpose is preferably 0.001 mbar to 50 mbar, more preferably 0.005 mbar to 40 mbar, even more preferably 0.02 mbar to 30 mbar, and even more preferably 0.03 mbar to 5 mbar.

[0062] Here, the oligocarbonate mixture preferably has a phenolic OH group content of 250 ppm to 2500 ppm, more preferably 500 ppm to 2400 ppm, and particularly preferably 1000 ppm to 2300 ppm. The determination of the phenolic OH group content has already been described above.

[0063] The oligocarbonate mixture is equally preferable to have a relative solution viscosity of 1.08 to 1.22, preferably 1.11 to 1.22, and preferably 1.13 to 1.20. The determination of the relative solution viscosity has already been described above.

[0064] Those skilled in the art can select the chemical properties of the oligocarbonate so that the carbonate group (B) of the polyester carbonate according to the present invention is obtained. Bisphenol A-based oligocarbonates are particularly preferred.

[0065] The method according to the present invention is preferably carried out in the absence of a catalyst. This has the advantage that the catalyst does not need to be removed from the resulting polyester carbonate and does not remain therein. Depending on the catalyst, this may affect the stability of the polyester carbonate. The method according to the present invention can also be carried out in the presence of a catalyst, particularly preferably a basic catalyst.

[0066] Suitable catalysts include all inorganic or organic basic compounds, such as hydroxides, carbonates, halides, phenoxides, diphenoxides, fluorides, acetates, phosphates, hydrogen phosphates and borates of lithium, sodium, potassium, cesium, calcium, barium and magnesium, nitrogen bases and phosphite bases, such as tetramethylammonium hydroxide, tetramethylammonium acetate, tetramethylammonium fluoride, tetramethylammonium tetraphenylborate, tetraphenylphosphonium fluoride, tetraphenylphosphonium tetraphenylborate, dimethyldiphenylammonium hydroxide, tetraethylammonium hydroxide, cetyltrimethylammonium tetraphenylborate, cetyltrimethylammonium phenoxide, 1,8-diazabicyclo[5.4.0]undeca-7-ene (DBU), 1,5-diazabicyclo[4.3.0]nona-5-ene ( DBN) or guanidine derivatives, e.g., 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-phenyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7,7'-hexylidenedi-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7,7'-decylidenedi-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7,7'-dodecyl Examples include redendi-1,5,7-triazabicyclo[4.4.0]deca-5-ene, or phosphazenes, such as the phosphazene base P1-t-oct=tert-octyliminotris(dimethylamino)phosphorane, the phosphazene base P1-t-butyl=tert-butyliminotris(dimethylamino)phosphorane, and BEMP=2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diaza-2-phosphorane.

[0067] Phosphonium catalysts of formula (VIII) are particularly suitable: [ka] In the formula, Ra, Rb, Rc, and Rd are the same or different C1-C10 Alkyl, C6~C 14 Aryl, C7~C 15 Arylalkyl or C5-C6 cycloalkyl, preferably methyl or C6-C 14 The aryl, particularly preferably methyl or phenyl, may be X - This may be an anion such as a hydroxide, sulfate, bisulfate, bicarbonate, carbonate, or halide, preferably a chloride, or an alkoxide or alloxide of formula -OR, where R is C6-C6. 14 Aryl, C7~C 15 The material may be an arylalkyl or C5-C6 cycloalkyl, preferably a phenyl compound.

[0068] Particularly preferred catalysts are tetraphenylphosphonium chloride, tetraphenylphosphonium hydroxide, and tetraphenylphosphonium phenoxide, with tetraphenylphosphonium phenoxide being especially preferred. Tetrabutylphosphonium acetate is similarly preferred.

[0069] These catalysts are 10 per 1 mole of oligoester mixture -2 mol~10 -8 It is preferably used in moles. The amount of alkali salt used as a co-catalyst can be in the range of 1 ppb to 500 ppb, preferably 5 ppb to 300 ppb, and particularly preferably 5 ppb to 200 ppb.

[0070] Further embodiments of the present invention provide polyester carbonates obtained by the above-described method according to the present invention in all disclosed combinations and preferred forms. [Brief explanation of the drawing]

[0071] [Figure 1] This figure shows details from the 13C NMR spectra of a commercially available product containing isophthalic acid / terephthalic acid-resorcinol ester block and BPA, prepared by an interfacial process. [Modes for carrying out the invention] [Examples]

[0072] Materials used: Terephthalic acid: for synthesis, CAS 100-21-0, Bernd Kraft, Duisburg Isophthalic acid: 99%, CAS 121-91-5, Sigma-Aldrich Resorcinol: 99%, CAS108-46-3, ABCR Diphenyl carbonate: Diphenyl carbonate, 99.5%, CAS 102-09-0; Acros Organics, Hale, Belgium, abbreviated as DPC. 4-Dimethylaminopyridine: 4-Dimethylaminopyridine; ≥98.0%; Pure; CAS 1122-58-3; Sigma-Aldrich, Munich, Germany, abbreviated as DMAP Prepared according to Tetrabutylphosphonium Acetate:CAS-34430-94-9, Angewandte Chemie, International Edition, Vol. 48, Issue: 40, 7398-7401; 2009. Sodium benzoate: ≥99%, CAS 532-32-1, Sigma-Aldrich Oligocarbonate: The starting material used for the preparation of the polyester carbonate was a linear bisphenol A oligocarbonate containing phenyl and phenolic OH-terminated groups and having a relative solution viscosity of 1.17. This oligocarbonate contained no additives such as UV stabilizers, release agents, or heat stabilizers. The oligocarbonate was prepared by a molten transesterification method as described in International Publication No. 02085967 and immediately removed at the outlet of the first horizontal reactor. The oligocarbonate had a phenolic end-group content of 0.16% by weight.

[0073] Analysis method: Solution viscosity: Determination of solution viscosity: The relative solution viscosity (ηrel; also called etarel) was determined using an Ubbelohde viscometer in dichloromethane at a concentration of 5 g / l at 25°C.

[0074] GPC: The molecular weight was determined by gel permeation chromatography using dichloromethane as the eluent. BPA polycarbonate was used as the standard. The signal from the refractive index detector was used. The corresponding method is defined in Currenta GmbH & Co. OHG No. 2301-0257502-09D and can be obtained from Currenta at any time.

[0075] The oligomer content was similarly determined by GPC, using refractive index signals (RID). The oligomer range was defined as the molecular weight distribution range of less than 1000 g / mol. The range of less than 1000 g / mol was evaluated as an area percentage by integration compared with the total area of ​​the distribution curve.

[0076] Determination of phenolic OH-terminal group content: Infrared Spectroscopy: Polyester carbonate dissolved in dichloromethane (2g / 50ml; 1mm quartz cuvette) was analyzed using a Nicolet iS10 FT infrared spectrometer from Thermo Fisher Scientific. The phenolic OH-terminated group content was measured at wavenumber 3583 cm⁻¹. -1 The decision was made by evaluating the bands in that context. 1 Measurements by 1H NMR spectroscopy were performed in dichloromethane using tetramethylsiloxane as an internal standard. OH group content is reported as weight % relative to the oligomer. For evaluation, the OH group signal was integrated and expressed relative to the signal from the oligomer. Typically, the resonance of the OH group in the oligomer is between 5.3 ppm and 5.6 ppm. (However, those skilled in the art will recognize that the OH signal in NMR may vary depending on conditions such as the water content in the solvent).

[0077] The ratio of phenyl terminal groups to OH terminal groups is 1 The results were determined by 1H NMR spectroscopy (Bruker, 700 MHz). Measurements were performed in dichloromethane using tetramethylsiloxane as an internal standard. Here, the area of ​​the peak at approximately 7.4 ppm (2 protons) is expressed relative to the area of ​​the peak between 6.6 ppm and 6.8 ppm (3 protons).

[0078] The bond between isophthalic acid and / or terephthalic acid units and bisphenol A (see chemical formula (VII)) 13 It was detected by 13C NMR spectroscopy.

[0079] The carbonyl carbon atom shows a shift at 164 ppm to 165 ppm, while isophthalic acid and / or terephthalic acid resorcinol esters show a signal at approximately 163 ppm to 164 ppm.

[0080] Measurements were performed using a Bruker Avance III HD 600 MHz NMR spectrometer. The measurements were performed in CDCl3 with tetramethylsilane as the standard.

[0081] Preparation of model ester compounds from BPA and terephthalic acid / isophthalic acid 21.9 mmol of BPA and a total of 21.9 mmol of diphenyl esters formed from terephthalic acid and isophthalic acid formed the initial input in a multi-necked round-bottom flask. 2.4 mg of tetrabutylphosphonium acetate was added, representing 0.02% of the total mass. Oxygen was removed from the flask contents by four evacuations and deactivation with nitrogen. The mixture was heated to 200°C with constant stirring. Continuous condensation occurred. As phenol formation increased, the initially cloudy liquid mixture gradually became clearer. An orange color was established, and its intensity increased as the temperature rose to 230°C. Approximately 80 minutes after the start of the reaction, the pressure was reduced to 10 mbar to 100 mbar to remove the phenol. A homogeneous, orange-brownish product was removed.

[0082] 13 ¹³C NMR (600 MHz): 164.2 ppm~164.5 ppm (m, 1C); IPS / TPS-BPA ester C atom (bonding of isophthalic acid and / or terephthalic acid units to resorcinol) [ka]

[0083] This substance was prepared to clearly identify the signal from the ester carbon atom that characterizes esters formed from BPA and terephthalic acid or isophthalic acid. The corresponding signal was shown to be at 164.2 ppm–164.5 ppm.

[0084] Preparation of oligoesters for comparative examples Example 1 In a flask equipped with a single-path separator, 24.93 g (0.15 mol) terephthalic acid, 24.93 g (0.15 mol) isophthalic acid, 42.94 g (0.39 mol) resorcinol, and further 130.46 g (0.609 mol) diphenyl carbonate, and 0.0447 g DMAP (4-dimethylaminopyridine; 200 ppm relative to the starting material), and 9.9 μl aqueous solution of sodium benzoate (131.37 g / l) (corresponding to approximately 1 ppm sodium) were added. Oxygen was removed from the mixture by four evacuations and nitrogen fillings. The mixture was melted and heated to 200°C at standard pressure with stirring. Since terephthalic acid did not initially dissolve in the molten material, the result was a suspension. The reaction mixture was stirred at that temperature for approximately 3 hours. This released carbon dioxide. The mixture was gradually heated to 240°C. Phenol was removed by distillation. The mixture was stirred at 240°C for approximately 1 hour. Finally, the mixture was stirred at 260°C for a further half hour. After gas generation ceased, the reaction mixture was cooled to 210°C and the pressure was reduced. The pressure was gradually reduced to 60 mbar within 45 minutes. The temperature was raised to 230°C and the mixture was stirred at that temperature for half an hour. Next, the temperature was raised to 245°C. The reaction mixture was stirred for a further 0.5 hours, and then the pressure was reduced to the minimum technically feasible value (approximately 1 mbar). This yielded a light brown molten material. The analytical data is summarized in Table 1.

[0085] Example 2 The examples were basically carried out in the same manner as in Example 1.

[0086] Unlike in Example 1, 26.18 g (0.1575 mol) of terephthalic acid, 26.18 g (0.1575 mol) of isophthalic acid, 33.03 g (0.30 mol) of resorcinol, and an additional 141.69 g (0.6615 mol) of diphenyl carbonate, 0.0441 g of DMAP (4-dimethylaminopyridine; 200 ppm relative to the starting material), and 9.9 μl of an aqueous solution of sodium benzoate (131.37 g / l) (equivalent to approximately 1 ppm of sodium) were added to a flask equipped with a single-path separator.

[0087] Unlike Example 1, a greenish oligoester was obtained.

[0088] Example 3 The examples were basically carried out in the same manner as in Example 1.

[0089] Unlike in Example 1, 8.31 g (0.0500 mol) of terephthalic acid, 8.31 g (0.0500 mol) of isophthalic acid, 11.56 g (0.105 mol) of resorcinol, and further 43.91 g (0.205 mol) of diphenyl carbonate, 0.0144 g of DMAP (4-dimethylaminopyridine; 200 ppm relative to the starting material), and 3.2 μl of an aqueous solution of sodium benzoate (131.37 g / l) (equivalent to approximately 1 ppm of sodium) were added to a flask equipped with a single-path separator.

[0090] The mixture was melted at 160°C and heated to 260°C as quickly as possible, as long as gas generation allowed. A 0.5-hour holding period was followed when no more gas was released and the suspension had turned into a solution. The reduced pressure step was carried out in the same manner as in Example 1.

[0091] Example 4 The examples were basically carried out in the same manner as in Example 1.

[0092] Unlike in Example 1, 24.93 g (0.1500 mol) of terephthalic acid, 24.93 g (0.1500 mol) of isophthalic acid, 42.94 g (0.39 mol) of resorcinol, 130.46 g (0.609 mol) of diphenyl carbonate, and 0.04465 g of DMAP (4-dimethylaminopyridine; 200 ppm relative to the feedstock) were added to a flask equipped with a single-path separator.

[0093] The oligoesters prepared using these modified preparation parameters had similar characteristics to their sodium counterparts, except for the OH concentration.

[0094] Example 5 The product from Example 4 was dissolved in dichloromethane and then precipitated in methanol.

[0095] Example 6 The example was basically carried out in the same manner as in Example 2.

[0096] Unlike in Example 2, 25.35 g (0.1525 mol) of terephthalic acid, 25.35 g (0.1525 mol) of isophthalic acid, 33.03 g (0.30 mol) of resorcinol, 131.73 g (0.609 mol) of diphenyl carbonate, and 0.0858 g of DMAP (4-dimethylaminopyridine; 400 ppm relative to the feedstock) were placed in a flask equipped with a single-path separator.

[0097] The oligoesters prepared using these modified preparation parameters exhibited similar characteristics to their sodium-based counterparts.

[0098] Preparation of oligoesters for embodiments of the present invention Example 7 The oligoesters from Example 6 were dissolved in dichloromethane and then precipitated in methanol.

[0099] Example 8 The examples were basically carried out in the same manner as in Example 1.

[0100] Unlike in Example 1, 20.77 g (0.125 mol) of terephthalic acid, 20.77 g (0.125 mol) of isophthalic acid, 28.90 g (0.2625 mol) of resorcinol, 109.79 g (0.5125 mol) of diphenyl carbonate, 0.036 g of DMAP (4-dimethylaminopyridine; 200 ppm relative to the feedstock), and 0.054 g of tetrabutylphosphonium acetate (300 ppm) were added to a flask equipped with a single-path separator.

[0101] The experimental procedure was the same as in Example 1. Unlike Examples 2-7, the product had a significantly increased melt viscosity during removal.

[0102] Example 9 The examples were basically carried out in the same manner as in Example 1.

[0103] Unlike in Example 1, 20.77 g (0.125 mol) of terephthalic acid, 20.77 g (0.125 mol) of isophthalic acid, 30.28 g (0.275 mol) of resorcinol, 109.79 g (0.5125 mol) of diphenyl carbonate, 0.036 g of DMAP (4-dimethylaminopyridine; 200 ppm relative to the feedstock), and 0.054 g of tetrabutylphosphonium acetate (300 ppm) were added to a flask equipped with a single-path separator.

[0104] The experimental procedure was the same as in Example 1.

[0105] [Table 1]

[0106] Examples of polyester carbonate synthesis from oligocarbonates and oligoester blocks from Examples 1-9 Example 10 (Comparative Example) 32.0 g (80 wt%) of oligocarbonate and 8.0 g (20 wt%) of oligocarbonate from Example 1 were placed in a flask equipped with a single-path separator. Oxygen was removed from the mixture by four evacuations and nitrogen fillings. The mixture was melted at 160°C under standard pressure. The temperature was then increased to 320°C. The pressure was reduced to the minimum technically possible value (approximately 1.5 mbar). The temperature was gradually increased to approximately 335°C within 30 minutes; phenol was continuously removed. A clear molten material was obtained. The analytical data are shown in Table 2.

[0107] Example 11 (Comparative Example) The experiment was carried out as described in Example 10. The difference was that 36.0 g of oligocarbonate (90% by weight) and 4.0 g of oligoester (10% by weight) from Example 1 were used.

[0108] Example 12 The experiment was conducted as described in Example 10. The only difference was that the oligocarbonate from Example 2 was used.

[0109] Example 13 The experiment was carried out as described in Example 10. The difference was that 36.0 g of oligocarbonate (90% by weight) and 4.0 g of oligoester (10% by weight) from Example 2 were used.

[0110] Example 14 The experiment was conducted as described in Example 10. The only difference was that the oligocarbonate from Example 3 was used.

[0111] Example 15 The experiment was conducted as described in Example 10. The difference was that 36.0 g of oligocarbonate (90% by weight) and 4.0 g of oligoester (10% by weight) from Example 3 were used.

[0112] Example 16 The experiment was carried out as described in Example 10. The difference was that 36.0 g of oligocarbonate (90% by weight) and 4.0 g of oligoester (10% by weight) from Example 4 were used.

[0113] Example 17 The experiment was conducted as described in Example 10. The only difference was that the oligocarbonate from Example 4 was used.

[0114] Example 18 The experiment was conducted as described in Example 10. The difference was that 36.0 g of oligocarbonate (90% by weight) and 4.0 g of oligoester (10% by weight) from Example 5 were used.

[0115] Example 19 The experiment was conducted as described in Example 10. The only difference was that the oligocarbonate from Example 5 was used.

[0116] Example 20 The experiment was conducted as described in Example 10. The difference was the use of 36.0 g of oligocarbonate (90% by weight) and 4.0 g of oligoester (10% by weight) from Example 6. The increase in viscosity was smaller compared to the previous examples.

[0117] Example 21 The experiment was conducted as described in Example 10. The difference was that the oligocarbonate from Example 5 was used. The increase in viscosity was smaller compared to the previous examples.

[0118] Example 22 The experiment was carried out as described in Example 10. The difference was that 36.0 g of oligocarbonate (90% by weight) and 4.0 g of oligoester (10% by weight) from Example 7 were used.

[0119] Example 23 The experiment was conducted as described in Example 10. The only difference was the use of the oligocarbonate from Example 7.

[0120] Example 24 The experiment was carried out as described in Example 10. The difference was that 36.0 g of oligocarbonate (90% by weight) and 4.0 g of oligoester (10% by weight) from Example 8 were used.

[0121] Example 25 The experiment was conducted as described in Example 10. The difference was that the oligocarbonate from Example 8 was used.

[0122] Example 26 The experiment was conducted as described in Example 10. The difference was that 36.0 g of oligocarbonate (90% by weight) and 4.0 g of oligoester (10% by weight) from Example 9 were used.

[0123] Example 27 The experiment was conducted as described in Example 10. The only difference was the use of the oligocarbonate from Example 9.

[0124] [Table 2]

[0125] Experiments using Na catalysts In Example 1, a predominantly OH-terminated oligoester is obtained (0.6 wt% OH). The GPC of the oligoester shows only low levels of oligomers in the range of less than 1000 g / mol. This oligoester was used in Examples 1 and 2. Each final product exhibits a relatively high phenolic OH value. In Example 1, it exceeds 500 ppm. Since no product with an OH value below 500 ppm was obtained in any case, this indicates that the ester block is not very suitable. Also, although Example 2 has an OH value of less than 500 ppm, its viscosity, and therefore molecular weight, is very high. Therefore, it is very likely that the 500 ppm limit will be exceeded in the case of correspondingly lower molecular weights.

[0126] In Example 2, an oligoester with a low OH content was prepared (0.2 wt%). This block was mostly phenyl-terminated. However, this block contained a distinct amount of oligomers in the range of less than 1000 g / mol. Similar to Example 13, which used the oligoester block from Example 2, the increase in molecular weight was small compared to the other examples. Therefore, it was found that the activity was lower in the case of phenyl-terminated blocks with a relatively high oligomer content. Surprisingly, the desired molecular weight could not be achieved despite the use of the catalyst.

[0127] In Example 3, an oligoester with a relatively high OH content (0.85 wt%) was prepared. Furthermore, this product has a relatively high oligomer content in the range of less than 1000 g / mol. Example 15 shows that the corresponding polyester carbonate has a phenolic OH value greater than 500 ppm. Therefore, it is not possible to produce the entire range of polyester carbonates with different ester content.

[0128] Example 4 shows a predominantly OH-terminated (0.80 wt% OH) oligoester. Examples 16 and 17 have relatively high molecular weights (no catalyst required), thus demonstrating that the OH-terminated block has high reactivity. However, the corresponding final products have a high content of phenolic OH-terminated groups (over 500 ppm) in both the 10% and 20% ester block content cases.

[0129] In Example 5, the ester block obtained from Example 4 is precipitated. Consequently, the content of phenolic OH-terminated groups decreases from 0.8% by weight to 0.7% by weight. However, even with this block, it is not possible to produce a product with an acceptable OH content (see Examples 18 and 19).

[0130] In Example 6, an oligoester block with an acceptable OH content was used. However, the oligomer content in the range of less than 1000 g / mol was relatively high. Similar to Example 13, the reactivity was low here as well (Examples 20 and 21), and the target molecular weight range could not be achieved.

[0131] In Examples 22 and 23 of the present invention, polyester carbonates having a low proportion of phenolic OH groups are prepared starting from an oligoester block (from Example 7). Therefore, it is found that when using oligoesters with a moderate OH content, polyester carbonates according to the objective can be prepared. Surprisingly, despite the relatively low OH content of the oligoester block, it was possible to achieve a relatively high molecular weight in the polyester carbonate.

[0132] Surprisingly, even with a very low OH content (oligoester block from Example 8), it was possible to achieve a high molecular weight in the polyester carbonate (Examples 24 and 25). Furthermore, the resulting material has a low OH content.

[0133] Examples 26 and 27 of the present invention similarly have a low OH content. Here, an oligoester block having 0.2% by weight of phenolic OH groups was used.

Claims

1. A mixture containing the oligoester of formula (1), 【Chemistry 1】 During the ceremony, Each R １ These are independently a hydrogen atom, a halogen, or an alkyl group having 1 to 4 carbon atoms. Each q is independently either 0 or 1. When q=1: Each Z is independently -H or an aromatic group of formula (2a), 【Chemistry 2】 In the formula, R ２ ' is hydrogen or -COOCH ３ The asterisk (*) indicates the position where formula (2a) bonds with the oxygen atom in formula (1). When q = 0: Each Z is independently an aromatic group of formula (2), 【Transformation 3】 In the formula, R ２ is hydrogen or -COOCH ３ The asterisk (*) indicates the position where formula (2) bonds with the oxygen atom in formula (1). p indicates the number of repeating units. In a mixture, The Z group in the mixture is hydrogen at a concentration of 0.5% by weight or less, and the percentage of oligomers having a molecular weight of less than 1000 g / mol in the mixture is less than 12%, where the percentage of oligomers is determined by the ratio of the area under the molecular weight distribution curve of the mixture to the total area under the molecular weight distribution curve for refractive index signals (from gel permeation chromatography) in the range of less than 1000 g / mol, where the gel permeation chromatography is performed in dichloromethane using a bisphenol A polycarbonate standard. A mixture characterized by the following:

2. R in equation (1) １ It is hydrogen, The Z group in the mixture is 0.4% by weight or less and is hydrogen. The percentage of oligomers having a molecular weight of less than 1000 g / mol is less than 10%. The mixture according to claim 1, characterized in that...

3. (A) Ester group of formula (I) 【Chemistry 4】 (In the formula, R １ In each case, independently, is a hydrogen atom, a halogen, or an alkyl group having 1 to 4 carbon atoms, n is at least 4, and "*" indicates the position where the ester group is incorporated into the polyester carbonate. (B) Carbonate group of formula (II) 【Transformation 5】 (In each case, Y independently has the structure of formula (III), (IV), (V), or (VI), 【Transformation 6】 During the ceremony, R6 and R7 are each independently hydrogen, C １ -C １８ alkyl, C １ -C １８ alkoxy, halogen, or in each case aryl, aralkyl, substituted aryl or substituted aralkyl, X is a single bond, -CO-, -O-, -S-, C １ ~C ６ Alkylene, C ２ ~C ５ Alkyridene, C ６ ~C １０ Cycloalkylidene, C ６ ~C １２ C condensed with a further aromatic ring containing arylene or heteroatoms ６ ~C １２ It is arrine, 【Transformation 7】 In these equations (IV) to (VI), R ３ In each case, C １ ~C ４ Alkyl, aralkyl or aryl, preferably methyl or phenyl, most preferably methyl, The asterisk (*) indicates the position in each case where formula (III), (IV), (V), or (VI) is bonded to the carbonate group of formula (II). m is at least 5, and "*" indicates the position in which the carbonate group is incorporated into the polyester carbonate in each case. In a polyester carbonate containing, At least a portion of the ester group (A) is directly bonded to at least a portion of the carbonate group (B) via formula (VII), 【Transformation 8】 In the formula, Y has the above definition with respect to (B), (A) represents a bond to the ester group (A), and (B) represents a bond to the carbonate group (B). The polyester carbonate has a phenolic OH group content in the range of more than 0 ppm to 500 ppm or less. The polyester carbonate has a relative solution viscosity of at least 1.255 to a maximum of 1.

35. A polyester carbonate characterized by the following features.

4. The polyester carbonate according to claim 3, characterized in that Y in formula (II) has the structure of formula (III).

5. The polyester carbonate according to claim 3 or 4, characterized in that the polyester carbonate has a phenolic OH group content in the range of more than 50 ppm and 400 ppm or less.

6. A molded compound comprising the polyester carbonate according to claim 3 or 4.

7. A molded article comprising the polyester carbonate described in claim 3 or 4.

8. A method for preparing a polyester carbonate according to claim 3 or 4, characterized by reacting a mixture containing the oligoester according to claim 1 or 2 with a mixture of oligocarbonates by melt transesterification.

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