WO2023208897A1 - Mélange de carbonate de polyester et sa production par l'intermédiaire d'un prépolymère de carbonate de polyester - Google Patents

Mélange de carbonate de polyester et sa production par l'intermédiaire d'un prépolymère de carbonate de polyester Download PDF

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Publication number
WO2023208897A1
WO2023208897A1 PCT/EP2023/060755 EP2023060755W WO2023208897A1 WO 2023208897 A1 WO2023208897 A1 WO 2023208897A1 EP 2023060755 W EP2023060755 W EP 2023060755W WO 2023208897 A1 WO2023208897 A1 WO 2023208897A1
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Prior art keywords
polyestercarbonate
formula
blend
polycarbonate
prepolymer
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PCT/EP2023/060755
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German (de)
English (en)
Inventor
Alexander Meyer
Ulrich Liesenfelder
Lukas Fabian SCHULZ
Paul Buijsen
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Covestro Deutschland Ag
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Publication of WO2023208897A1 publication Critical patent/WO2023208897A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/19—Hydroxy compounds containing aromatic rings
    • C08G63/191—Hydroquinones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/42—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to a process for producing a polyestercarbonate prepolymer, a polyestercarbonate prepolymer, a process for producing a polyestercarbonate blend using the polyestercarbonate prepolymer, a polyestercarbonate blend and a use of the polyestercarbonate prepolymer.
  • Polyester carbonates which contain ester blocks of iso- and/or terephthalic acid and resorcinol, have good weather resistance. These materials are particularly interesting because they do not require painting to protect them from harmful weather conditions and especially from UV light.
  • the ester structures made from resorcinol and iso- and/or terephthalic acid can undergo so-called photo-Fries rearrangements when they come into contact with UV light. This creates, among other things, hydroxybenzophenone structures that are built into the polymer chain. Hydroxybenzophenones are known to have UV absorption properties. This explains the good weather resistance. This situation is described, for example, in US20030050400 Al.
  • UV absorbers on the other hand, is far less effective because most of the UV absorber accumulates in the mass of the molded part.
  • UV-sensitive materials such as polycarbonate with layers of lacquer that have high concentrations of UV absorbers.
  • painting is an additional step that incurs costs and is not always the preferred solution for sustainability reasons. Particularly in the area of automotive exterior applications, it is advantageous if materials are intrinsically weather-stable and complex painting is not necessary.
  • the polyester carbonates described are produced using a phase interface process.
  • aromatic diols and OH-terminated ester blocks are condensed using phosgene.
  • the OH-terminated ester blocks can also be prepared by condensation with phosgene starting from aromatic diacids and aromatic diols in solution.
  • Such a process for producing the oligoesters and the corresponding polyester carbonates is described in WO0026275 Al.
  • the preferred polymers described in this document are polyester carbonates made from bisphenol A containing ester blocks made from resorcinol and terephthal/isophthalic acid.
  • the ester blocks are produced in a dichloromethane/water mixture using aqueous NaOH solution starting from the Acid chlorides of aromatic diacid and resorcinol.
  • the polyester solution containing hydroxy-terminated ester blocks is transferred to a phosgenation reactor.
  • alkaline bisphenol A solution is introduced and the reactants are reacted with phosgene.
  • the polyester carbonates described are obtained by means of solid-state polymerization.
  • the process described is relatively complex because a step must always be carried out in which the polycarbonate used is at least partially crystallized.
  • the document shows that in particular the use of activated carbonate sources (such as methyl salicylate-capped polycarbonate) achieves sufficient molecular weights of the polyester carbonate and that randomization of the groups can be at least partially suppressed.
  • activated carbonate sources such as methyl salicylate-capped polycarbonate
  • This document only uses OH-terminated oligoester blocks (i.e. the terminal groups of the oligoester are usually resorcinol). This results in the same connections between the oligoester and the polycarbonate as described above for the phase interface process (see also Figure 2).
  • melt transesterification processes based on the melt transesterification process known for polycarbonate are known and have the advantage that starting materials that are difficult to handle, such as phosgene, can be dispensed with. They also have the great advantage that no solvents are necessary. Therefore, it would be industrially advantageous to produce polyester carbonates using the melt transesterification process.
  • this process also involves challenges.
  • the highly reactive acid chlorides are difficult to replace with other input materials.
  • Transesterification processes often have long residence times in corresponding reactors. Due to the high temperatures, by-products often arise, which have a negative impact on product quality. Since melt transesterification processes usually do not require complex processing steps, impurities as well as catalyst residues remain in the product. These can worsen the product quality.
  • polycarbonates that are produced in the melt transesterification process have significantly higher contents of hydroxy-terminated end groups (content of phenolic OH groups) in comparison with corresponding products from the phase interface process.
  • phenolic OH groups can be damaged by oxidative processes, which deteriorates product quality.
  • the optical properties in particular suffer. It is However, it is important to maintain good optical properties, especially for a product that is supposed to be characterized by high intrinsic weather stability. It is therefore advantageous if the content of phenolic OH end groups in the resulting polymer is low.
  • the polyester carbonates mentioned since the prior art relates exclusively to the production of the polyester carbonates by means of a phase interface reaction.
  • oligoester blocks from aromatic diacids such as isophthalic acid and/or terephthalic acid and aromatic diols such as resorcinol is known. This is described, for example, in the not yet disclosed application EP21179513.3.
  • aromatic diacids and the aromatic diols are reacted using DPC. Using this process it is possible to produce oligoesters with different end groups, for example OH end groups or phenyl ester or phenyl carbonate end groups.
  • WO2005021616 Al describes the production of hydroxy-terminated oligoester blocks in the melt.
  • a content of OH end groups in the oligoesters can be achieved, which is comparable to oligoesters that can be achieved in a process with a solvent.
  • Different catalysts and the influence of driving style e.g. different temperatures and vacuum
  • the oligoesters are then condensed into a polyester carbonate using a phase interface process. Therefore, this document cannot contain any teaching as to how the ester structures formed from isophthalic acid and/or terephthalic acid and resorcinol are retained in the production of a polyester carbonate by means of melt transesterification.
  • oligoesters are described using the melt transesterification process, which are characterized in that they have a high proportion of carboxyl end groups. These carboxyl end groups are then used to incorporate the oligoesters into paint systems. Accordingly, the use of oligoesters in a melt transesterification process is not described here.
  • US20030050400 Al describes the production of oligomers from aromatic diacids and resorcinol.
  • the US20030050400 Al is based on the task of providing OH-terminated building blocks, which can then be converted into polyester carbonates using phase interface processes. Similar to WO2005021616 Al, only the phase interface process is reported here and conclusions about the preservation of the desired ester structures in a melt process are therefore not possible.
  • the present invention was based on the object of overcoming at least one disadvantage of the prior art.
  • the present invention was based on the object of providing a polyester carbonate blend comprising ester blocks based on isophthalic acid and/or terephthalic acid and an aromatic diol, preferably resorcinol, which are accessible by a melt transesterification process.
  • the corresponding polyester carbonate blends should contain the highest possible concentrations of ester structures made from aromatic acid and aromatic diol (not bisphenol). It was therefore an aspect of this invention that the resulting polyester carbonate blends have good intrinsic weather resistance.
  • polyester carbonate blends should preferably also have good processability. Very particularly preferably, the blends should at the same time have the lowest possible phenolic OH end group content.
  • the polyester carbonate blends should therefore preferably be weather-stable and/or essentially yellowing-stable and/or essentially not prone to polymer degradation, for example through oxidative degradation.
  • polyester carbonate blends are used in the production of the polyester carbonate blend.
  • a process for producing polyester carbonate blends should be provided which is as simple as possible, that is to say, for example, comprising as few and/or inexpensive and/or energy-intensive steps as possible. At least one, preferably all, of the above-mentioned tasks have been solved by the present invention.
  • a polyester carbonate blend with a high proportion on ester structures from aromatic diol and aromatic acid can be obtained.
  • the process according to the invention using the special polyester carbonate prepolymers results in a polyester carbonate blend being obtained in which a high proportion of the isophthalic acid and/or terephthalic acid groups are directly linked to the aromatic diol such as resorcinol.
  • ester linkages from aromatic bisphenol such as bisphenol A and aromatic diacid are also included.
  • the first process step in which the oligoester is converted in a large excess to the oligo- and/or polycarbonate, appears to lead to a polyestercarbonate prepolymer in which the few carbonate units are bound to the oligoester, to lead to good compatibility with the polycarbonate to be used in the second process step.
  • This homogeneous mixture has both good optical and mechanical properties.
  • a large part of the isophthalic acid and/or terephthalic acid ester to the aromatic diol, which differs from bisphenol A remains, so that the resulting blend is also intrinsically weather-stable.
  • the polyester carbonate blend can be produced in a solvent-free process.
  • the use of substances that are difficult to handle, such as phosgene, can be dispensed with.
  • the method according to the invention only has a few steps (in particular no complex step of crystallization, for example of the polycarbonate). Additionally, these steps do not require the presence of a solvent (such as crystallization).
  • the polyester carbonate blend is therefore accessible using a simple and ecologically and/or economically advantageous process.
  • the method according to the invention is also capable of scale-up. This preferably means that the method according to the invention also can be carried out on an industrial scale. This shows in particular that the method according to the invention can be controlled and thus the scale can be increased predictably.
  • a prepolymer and/or a blend can be provided without the use of an activated carbonate source (such as an oligocarbonate or a polycarbonate with 2-methoxycarbonylphenoxy end groups, see also DE60212172T2).
  • activated carbonate sources are usually more expensive than classic “unactivated” groups (e.g. an oligocarbonate or a polycarbonate with phenoxy end groups) and, above all, have to be produced separately in an additional step.
  • step (c) reacting 65 to 95% by weight of the oligoester from step (a) with 35 to 5% by weight of the oligocarbonate and / or polycarbonate from step (b), the% by weight being the sum of Weight of oligoester from step (a) and of oligocarbonate and / or polycarbonate from step (b), by means of condensation reaction in the melt to obtain a polyestercarbonate prepolymer.
  • oligoester from process step (a) is known in the prior art.
  • a corresponding process is disclosed in WO2005/021616 A1 for producing, in particular, OH-terminated oligoesters (see, for example, Example 1 of WO2005/021616A1).
  • a process for producing an oligoester is described in the not yet disclosed application EP21179513.3. It is preferred that the oligoester of step (a) is prepared in the absence of a solvent. This means that no further purification steps are necessary to implement the oligoester in step (c) according to the invention.
  • the oligoester of step (a) is particularly preferably prepared by a process in which
  • At least isophthalic acid and / or terephthalic acid are mixed with a diol of the formula (3) and at least one diaryl carbonate of the formula (4), whereby in which Ri represents a hydrogen atom, a halogen or an alkyl group with 1 to 4 carbon atoms, preferably hydrogen and where in which R2 each independently represents hydrogen or -COOCH3, preferably hydrogen,
  • this mixture from step [I] is heated in the presence of at least one catalyst and
  • the workup of the oligoester - if necessary and/or desired - can be carried out in a manner known to those skilled in the art, for example by precipitation. However, it is preferred that no solvents are used during the workup.
  • R 1 for example in formula (I), formula (3), formula (300), formula (la) and/or formula (7), is chosen from the position in such a way that the photo- Frieze rearrangements are possible. For example, not all ortho positions may be blocked by R 1 .
  • the possible substitution pattern is obvious to the person skilled in the art based on his or her specialist knowledge.
  • an “aromatic diol” is sometimes spoken of. This term is used in particular to distinguish it from a “bisphenol” (it is also often pointed out that an aromatic diol does not mean a bisphenol). It is known to those skilled in the art that a bisphenol in the broadest sense is also an aromatic diol. However, in the context of the present invention, he can make a corresponding distinction based on his Expertise (particularly when it comes to which structures have intrinsic UV activity and which do not).
  • An aromatic diol is preferably understood to mean a structure of the formula (3).
  • An aromatic diol is particularly preferably understood to mean resorcinol or a compound derived from resorcinol.
  • a “bisphenol” in the sense of the present invention is preferably a compound which is represented by formula (III) (see also “Y” in formula (II), where in formula (III) an OH group is present on each (
  • the structure of formula (III) is therefore a bisphenol structure, which was created by the reaction of the OH groups; this connection is known to the person skilled in the art).
  • a particularly preferred bisphenol is bisphenol A.
  • the process described can have a further step in which the oligoester is reacted with a diacid diphenyl ester, preferably isophthalic acid diphenyl ester and/or terephthalic acid diphenyl ester.
  • a diacid diphenyl ester preferably isophthalic acid diphenyl ester and/or terephthalic acid diphenyl ester.
  • the oligoester of process step (a) can be OH-terminated, phenyl ester-terminated, acid-terminated or phenylcarbonate-terminated, or contain mixtures of the end groups mentioned.
  • the oligoester is preferably OH-, phenylester-, phenylcarbonate-terminated or any mixture of the aforementioned terminations is present.
  • the person skilled in the art can adapt the process according to the invention to the end group(s) contained.
  • the termination can be influenced by the composition/ratio of the monomers used, the reaction temperature, the catalyst used, the application and also the strength of vacuum. This can also influence the viscosity and the resulting glass transition temperature of the oligoester.
  • the oligoester of process step (a) according to the invention at least partially has no OH terminations.
  • the resulting polyestercarbonate prepolymer or the resulting polyestercarbonate blend thus preferably has essentially no, particularly preferably no, links from, for example, resorcinol to, for example, BPA via a carbonate bridge.
  • the polyestercarbonate prepolymer according to the invention and/or the polyestercarbonate blend according to the invention have essentially no, particularly preferably no, structures of the formula (300), where in the structure of the formula (300) Ri independently represents a hydrogen atom, a halogen or an alkyl group with 1 to 4 carbon atoms, preferably represents the meanings given for Ri of the formula (la), Y independently represents a structure of the formulas (III), (IV), (V) or (VI), preferably stands for the meanings given for formula (II) and the “*” each indicate the positions with which the structure of the formula (300) is inserted into the Polymer chain of the polyester carbonate attaches/would attach.
  • the oligoester of process step (a) according to the invention has at least partially no OH terminations and that the polyestercarbonate prepolymer according to the invention is particularly preferably obtained via this process.
  • the resulting end group ratio in the oligoester can preferably be influenced by the molar ratio of isophthalic acid and/or terephthalic acid to the diol of the formula (3).
  • the molar ratio of isophthalic acid and/or terephthalic acid to the diol of the formula (3) is preferably 0.50 to 1.20, particularly preferably 0.70 to 1.15, very particularly preferably 0.75 to 1.12.
  • the diol of the formula (3) is preferably also referred to as “resorcinol or a compound derived from resorcinol”. This preferably means that if a substituent Ri is present, a compound derived from resorcinol is present which has the substituent Ri with the meanings given.
  • Both isophthalic acid and terephthalic acid are preferably used in process step (I). If both diacids are used, then it is additionally preferred that the molar ratio of isophthalic acid to terephthalic acid is 0.25-4.0 to 1, particularly preferably 0.4-2.5 to 1 and very particularly preferably 0.67-1 .5 to 1. It is also preferred that the diol of formula (3) is resorcinol. Likewise and preferably at the same time, it is preferred that the diaryl carbonate of the formula (4) is diphenyl carbonate.
  • a molar ratio of isophthalic acid and/or terephthalic acid to the diaryl carbonate of formula (4) of 1 to 2 - 2.5 is particularly preferred, more preferably 1.0 to 2.01 - 2.25 and most preferably 1.0 used at 2.05.
  • process step (II) the mixture from process step (I) is heated in the presence of at least one catalyst.
  • the individual components from process step (I) are preferably melted.
  • terephthalic acid in particular is among the not soluble under the given conditions, at least initially. However, this can change in the course of process step (II).
  • Carbon dioxide is generally released in process step (II). This procedure allows a quick reaction under low temperature stress.
  • Process step (II) is preferably carried out under a protective gas atmosphere, preferably under nitrogen and/or argon.
  • Step (II) preferably takes place in the absence of a solvent.
  • solvent is known to those skilled in the art in this context.
  • the term “solvent” is preferably understood to mean a compound that does not enter into a chemical reaction in any of the process steps (I), (II) and/or (III). Excluded are those compounds that are formed by the reaction (for example phenol when diphenyl carbonate is used as diaryl carbonate). Of course, it cannot be ruled out that the starting compounds contain traces of solvents. This case should preferably be included according to the invention. However, according to the invention, an active step of adding such a solvent is preferably avoided.
  • the heating in process step (II) is preferably carried out at temperatures of 180 ° C to 320 ° C, preferably 190 ° C to 310 ° C and particularly preferably from 230 ° C to 300 ° C. Under these temperature conditions it may be that the corresponding aryl alcohol of the diaryl carbonate, preferably phenol, is already distilled off.
  • Process step (II) is preferably carried out under normal pressure. Stirring is preferably carried out under normal pressure until the evolution of gas essentially stops.
  • the temperature can also be increased gradually - depending on the reactivity observed - to 200 ° C - 320 ° C, preferably 210 - 310 ° C, particularly preferably 215 - 300 ° C.
  • the reactivity can be estimated via gas evolution in a manner known to those skilled in the art. In principle, higher temperatures are also possible in this step, but side reactions can occur at higher temperatures (e.g. discoloration). Therefore, higher temperatures are less preferred.
  • the at least one catalyst is particularly preferably an organic base or a Lewis acidic transition metal compound.
  • the organic base is preferably alkylamines, imidazole (derivatives), guanidine bases such as triazabicyclodecene, DMAP and corresponding derivatives, l,5-diazabicyclo[4.3.0]non-5-ene (DBN) and diazabicycloundecene (DBU), am most preferred DMAP.
  • DBN diazabicycloundecene
  • DBU diazabicycloundecene
  • a mixture of at least one organic base such as alkylamines, imidazole (derivatives), guanidine bases such as triazabicyclodecene, DMAP and corresponding derivatives, DBN or DBU, is preferably used together with a phosphonium catalyst of the formula (VIII) (see below).
  • a mixture of 4-(dimethylamino)pyridine (DMAP) and tetrabutylphosphonium acetate is particularly preferably used as the catalyst in process step (II).
  • the catalyst is a Lewis acidic transition metal compound
  • alkoxides of metals from Group IVB or of tin or derivatives of metals, metal oxides or metal carboxylates from Group IVA of the periodic table are used.
  • the Lewis acidic transition metal compound is particularly preferably selected from the group consisting of titanium butoxide (Ti(OBu)4), titanium isopropoxide (Ti(OiPr)4), titanium phenoxide (TiOPhü), antimony trioxide, zirconium butoxide (Zr(OBu)4), dialkyltin dialkoxides, dibutyltin oxide , dibutyltin diester, tin phenoxide, monobutyltin oxide and any mixture of the aforementioned. Titanium butoxide is particularly preferred.
  • the at least one catalyst is preferably in amounts of 1 to 5000 ppm, preferably 5 to 1000 ppm and particularly preferably 20 to 500 ppm, based on the sum of the masses of isophthalic acid and / or terephthalic acid, the diol of formula (3) and the diaryl carbonate the formula (4) is used. If more than one catalyst is used in the reaction, these catalysts are preferably used in total in amounts of 1 to 5000 ppm, preferably 5 to 1000 ppm and particularly preferably 300 to 700 ppm.
  • process step (III) vacuum is applied to the mixture obtained from process step (II).
  • the corresponding aryl alcohol of the diaryl carbonate used preferably phenol
  • the equilibrium of the reaction is shifted towards oligoesters.
  • Aryl alcohol is the chemical compound split off by the condensation reaction.
  • condensation or “condensation reaction” is known to those skilled in the art. This is preferably understood to mean a reaction in which two molecules (of the same substance or different substances) combine to form a larger molecule, with one molecule of a chemically simple substance being split off. This compound split off during the condensation is removed in process step (III) using vacuum. Accordingly, it is preferred that the process according to the invention is characterized in that during process step (III), the volatile components which have a boiling point below the mixture of oligoestems formed in process step (II) are separated off, if necessary by gradually reducing the pressure. A stepwise separation is preferably chosen if different volatile components are separated off. A gradual separation is also preferably chosen in order to achieve the most complete separation possible of the volatile component(s).
  • the volatile components are the chemical compound or compounds split off during the condensation, preferably phenol.
  • the condensation product is separated off in process step (III) preferably at temperatures of 200 ° C to 280 ° C, particularly preferably 210 ° C to 270 ° C and particularly preferably 220 ° C to 265 ° C.
  • the vacuum during separation is preferably 500 mbar to 0.01 mbar.
  • the vacuum in the last stage is very particularly preferably 10 mbar to 0.01 mbar.
  • the oligoester obtained in this way can, if necessary, be used in process step (a) after further purification. It is preferred that the oligoester of step (a) has a number-average molecular weight Mn of 500 g/mol to 8000 g/mol, preferably 600 g/mol to 5000 g/mol and particularly preferably 700 g/mol to 3000 g/mol having. Unless otherwise stated, this M n and/or all other molecular weights of the invention are preferably determined via gel permeation chromatography in dichloromethane with a bisphenol A polycarbonate as a standard.
  • the molecular weights according to the invention Mw (weight average) and Mn (number average) of the oligesters, oligocarbonates, polycarbonates or polyester carbonates used were - unless otherwise stated - using size exclusion chromatography (gel permeation chromatography GPC; based on DIN 55672-1:2007-08 using a BPA Polycarbonate calibration).
  • the calibration was carried out with linear polycarbonates of known molecular weight distribution (e.g. from PSS Polymer Standards Service GmbH, Germany).
  • the column combination consisted of cross-linked styrene-divinylbenzene resins.
  • the GPC can comprise one or more commercially available GPC columns for size exclusion chromatography connected in series, which are selected so that an adequate separation of the molar masses of polymers, in particular of aromatic polycarbonates with weight-average molar masses M w of 2,000 to 100,000 g/mol, is possible .
  • the analytical columns have a diameter of 7.5 mm and a length of 300 mm.
  • the particle sizes of the column material are in the range from 3 pm to 20 pm.
  • the oligoester prefferably has a number average molecular mass in the range from 1000 g/mol to 16000 g/mol, particularly preferably 1200 g/mol to 10000 g/mol and very particularly preferably 2000 g/mol to 8000 g/mol having.
  • the M n is preferably measured via GPC with polystyrene calibration in THF.
  • the calibration is preferably carried out with polystyrenes in a molecular weight range of 500 to 7,000,000 g/mol.
  • the GPC is preferably carried out in tetrahydrofuran (preferably THF stabilized with 0.007-0.015% by weight of butylhydroxytoluene), which has been modified with 0.8% acetic acid.
  • the flow rate is preferably 1 mL/min at 40 °C.
  • the oligoester of step (a) preferably has as end groups at least one type of end group, which is selected from the group consisting of -OH end groups (e.g.
  • terminal resorcinol from terminal resorcinol
  • -COOH end groups isophthalic acid / terephthalic acid - Ester-phenol end groups or resorcinol carbonate-phenol end groups.
  • end groups can also be present in any mixtures. They can also be present in any quantities or ratios to one another.
  • an oligocarbonate and/or a polycarbonate is provided.
  • the term “oligo” carbonate or “oligo” ester is used in particular to distinguish it from the term “poly” carbonate.
  • the definition of “oligo” and “poly” is known to those skilled in the art. In particular, this means that, for example, a polycarbonate has a higher number of repeating units and therefore a higher molecular weight than an oligocarbonate.
  • the term “oligo”mer is preferably used when the substance concerned does not have sufficient mechanics on its own. However, a corresponding “polymer” does. According to the invention, a sharp separation of the two terms does not seem to be decisive.
  • the oligocarbonate of step (b) has a relative solution viscosity of 1.08 to 1.22, preferably 1.11 to 1.22, particularly preferably 1.13 to 1.20. It is also preferred that the polycarbonate of step (b), but also of step (iii) of the process according to the invention for producing a polyestercarbonate blend, has a weight-average molecular weight Mw of 24,000 g/mol to 40,000 g/mol, particularly preferably of 24,500 g /mol to 34,000 g/mol, very particularly preferably from 25,000 g/mol to 32,000 g/mol determined by gel permeation chromatography, calibrated against bisphenol A polycarbonate standards using dichloromethane as eluent.
  • the polycarbonate of step (b) and/or step (iii) has a relative solution viscosity of greater than 1.20 to 1.36, particularly preferably greater than 1.22 to 1.35 and most preferably greater than 1 .27 to 1.34.
  • the relative solution viscosity (r
  • Ubbelohde viscometer The person skilled in the art is familiar with the determination of the relative solution viscosity using a Ubbelohde viscometer. According to the invention, this is preferred according to DIN 51562-3; Carried out 1985-05.
  • the throughput times of the polyester carbonate to be measured are measured using the Ubbelohde viscometer in order to then determine the difference in viscosity between the polymer solution and its solvent.
  • the Ubbelohde viscometer is first calibrated by measuring the pure solvents dichloromethane, trichlorethylene and tetrachlorethylene (always at least 3 measurements and a maximum of 9 measurements). The actual calibration then takes place with the solvent dichloromethane. The polymer sample is then weighed, dissolved in dichloromethane and the flow time for this solution is then determined three times. The average of the flow times is corrected using the Hagenbach correction and the relative solution viscosity is calculated.
  • the oligocarbonate has a phenolic OH group content of 250 ppm to 2500 ppm, preferably 500 to 2400 ppm, and particularly preferably 1000 to 2300 ppm.
  • the determination of the phenolic OH group content is described below in relation to the polyester carbonate blend.
  • the oligocarbonate and/or polycarbonate used in process step (b) do not have any end groups of the formula (301). where in formula (301) the “*” stands for the connection of the structure of formula (301) to the oligocarbonate and/or polycarbonate. This means that no activated carbonate source is preferably used. According to the invention, this is preferably not necessary since the reaction in process step (c) proceeds well under the defined conditions.
  • step (c) the oligoester from step (a) is reacted with the oligocarbonate and/or the polycarbonate, the oligoester always being used in excess of the oligocarbonate and/or polycarbonate.
  • 65 to 95% by weight of the oligoester from step (a) is reacted with 35 to 5% by weight of the oligocarbonate and/or polycarbonate from step (b).
  • step (c) a condensation reaction takes place.
  • condensation reaction has already been defined above. The person skilled in the art knows how to influence such equilibrium reactions to produce the desired product.
  • step (c) is carried out at a pressure that is reduced in relation to the ambient pressure. This allows the compound formed during condensation to be removed using a vacuum. Accordingly, it is preferred that the process according to the invention is characterized in that during process step (c) the volatile components which have a boiling point below the polyester carbonate prepolymer formed in process step (c) are separated off, if necessary with a gradual reduction of the pressure. A stepwise separation is preferably chosen if different volatile components are separated off.
  • a stepwise separation is also preferably chosen in order to ensure the most complete separation possible of the volatile component(s).
  • the volatile components are preferably the chemical compound or compounds split off during the condensation, preferably phenol.
  • the volatile components can also be the not yet fully reacted diol of the formula (3) and/or the not yet fully reacted diaryl carbonate of the formula (4) and/or low molecular weight oligomers (such as dimers or trimers) with correspondingly low boiling points.
  • the person skilled in the art also knows that appropriate temperatures may be necessary in process step (c) in order to obtain appropriate yields of polyester carbonate prepolymer.
  • oligoester used in process step (a) and/or the oligocarbonate and/or polycarbonate used in process step (b) are amorphous.
  • a polyestercarbonate prepolymer is provided, which is obtained by the process according to the invention for producing a polyestercarbonate prepolymer in preferably all of the embodiments described above, in particular also in a combination of preferences. Also provided is a polyester carbonate prepolymer comprising
  • R6 and R7 each independently represent hydrogen, Ci-Cis-alkyl, Ci-Cis-alkoxy, halogen or optionally substituted aryl or aralkyl, and
  • Cio-cycloalkylidene or for C - to Ci2-arylene which may optionally be fused with aromatic rings containing further heteroatoms,
  • R 3 each represents Ci-C4-alkyl, aralkyl or aryl, preferably methyl or phenyl, very particularly preferably methyl
  • the “*” each indicate the positions with which the formulas (III), (IV), (V) or (VI) attach to the carbonate group in formula (II)
  • m indicates the average number of repeating units and each indicates the positions with which the carbonate groups are incorporated into the polyester carbonate blend are, wherein at least some of the ester groups (A) are directly linked to one another with at least some of the carbonate groups (B) via the formula (VII), where
  • polyestercarbonate prepolymer contains more mol% of carbon atoms, as marked with an arrow in formula (la), than mol% of carbon atoms, as marked with an arrow in formula (VII), have.
  • This polyestercarbonate prepolymer is preferably obtained by the process according to the invention for producing a polyestercarbonate prepolymer in preferably all of the configurations described above, in particular also in a combination of preferences.
  • the polyestercarbonate prepolymer according to the invention has a higher molecular weight than the starting oligoester of step (a), but its molecular weight depends largely on the oligocarbonate and/or polycarbonate used.
  • the reaction also causes the polyester carbonate prepolymer to have structures of the formula (7):
  • Y has the meanings given below (Y is derived from the bisphenols that were used to produce the oligocarbonate and/or polycarbonate) and the “.. .” represent a logical continuation of the chain (in particular further esters from the oligoester of step (a) or further carbonates from the oligocarbonate and / or polycarbonate from step (b)).
  • Formula (7) shows an ester linkage between an isophthalic acid/terephthalic acid and the bisphenol of the oligocarbonate and/or polycarbonate.
  • the polyestercarbonate prepolymer according to the invention is produced by reacting an oligoester as described above with the oligocarbonate and/or the polycarbonate, the oligoester always being used in excess of the oligocarbonate and/or polycarbonate.
  • the oligoester Preferably 65 to 95% by weight of the oligoester (for example from step (a), as described above) with 35 to 5% by weight of the oligocarbonate and / or polycarbonate (for example from step (b), as described above) implemented.
  • the polyestercarbonate prepolymer according to the invention preferably has corresponding weight ratios of the different structures with ester groups and structures with carbonate groups.
  • the polyester carbonate prepolymer according to the invention preferably does not contain any methyl 2-hydroxybenzoate. Traces of such a compound can be detected in the prepolymer, for example by NMR spectroscopy. You can use it in polyester carbonate Prepolymer remain when activated carbonate sources (e.g. oligocarbonates and / or polycarbonates with end groups of formula (301)) are used to produce the polyestercarbonate prepolymer. Likewise, the polyester carbonate prepolymer according to the invention preferably does not have any end group of the formula (301).
  • polyestercarbonate prepolymer was essentially transparent.
  • transparent is here preferably understood as described for the polyester carbonate blend.
  • the resulting polyestercarbonate prepolymer is suitable for providing a polyestercarbonate blend by mixing and/or reacting with another polycarbonate, which on the one hand meets the high mechanical and optical requirements of a standard polycarbonate, but at the same time intrinsically Has weather resistance.
  • the polyestercarbonate prepolymer appears to act as a compatibilizer allowing a homogeneous mixture to be achieved between the ester groups and the polycarbonate.
  • the polyestercarbonate prepolymer according to the invention is suitable for use in the process according to the invention for producing a polyestercarbonate blend.
  • process step (iii) converting the polyestercarbonate prepolymer from step (i) and the polycarbonate from step (ii) into a molten state and mixing in the molten state 5 to 25% by weight of the polyestercarbonate prepolymer with 95 to 75% by weight of polycarbonate, where the weight percent refers to the sum of the weight of polyestercarbonate prepolymer from step (i) and polycarbonate from step (ii) to obtain a polyestercarbonate blend.
  • process step (i) preferably comprises process steps (a) to (c) described above.
  • the polycarbonate used in process step (ii) can be the same as or different from the polycarbonate optionally used in step (b).
  • the process for producing the polyestercarbonate blend according to the invention differs from that for producing the polyestercarbonate prepolymer according to the invention in that in the production of the polyestercarbonate blend according to the invention, on the one hand, a polycarbonate is necessarily used (and not an oligocarbonate) and, on the other hand, this polycarbonate is used Excess to the polyester carbonate prepolymer is used.
  • polycarbonate in contrast to an oligocarbonate
  • This polycarbonate is preferably an aromatic polycarbonate.
  • the polycarbonate is very particularly preferably a polycarbonate with repeating units of the formula (II) in which Y independently represents a structure of the formulas (III), (IV), (V) or (VI), where in the
  • R6 and R7 each independently represent hydrogen, Ci-Cis-alkyl, Ci-Cis-alkoxy, halogen or optionally substituted aryl or aralkyl, and
  • R 3 each represents Ci-C4-alkyl, aralkyl or aryl, preferably methyl or phenyl, very particularly preferably methyl, and the “*” indicates the positions with which the formulas (III), (IV), (V) or (VI) attach to the carbonate group in formula (II), and m indicates the number of repeating units (m can be replaced by the defined molecular weight of the polycarbonate used can be calculated).
  • the polycarbonate of process step (b) is particularly preferably based on bisphenol A.
  • the polyestercarbonate prepolymer from step (i) and the polycarbonate from step (ii) are first converted into a molten state. This can be done in a manner known to those skilled in the art by supplying energy.
  • a temperature should be chosen at which both components are in a molten state. In particular, a temperature must therefore be selected which is above the glass transition temperature and/or the melting point, preferably above the glass transition temperature of the polyestercarbonate prepolymer and the polycarbonate. During process step (iii), at least this temperature must be maintained in order to mix the components in the molten state.
  • the polyestercarbonate prepolymer is used in excess of the polycarbonate. Preference is given to 8 to 35% by weight, particularly preferably 10 to 30% by weight, very particularly preferably 15 to 25% by weight of the polyester carbonate prepolymer with 92 to 65% by weight, particularly preferably 90 to 70% by weight. -%, very particularly preferably mixed with 85 to 75% by weight of the polycarbonate in the molten state, the weight% being the sum of the weight of polyestercarbonate prepolymer from step (i) and of polycarbonate from step (ii) relate.
  • a reaction can take place between the polyestercarbonate prepolymer and the polycarbonate. This is in particular a condensation reaction, as described in more detail above. In another embodiment, no reaction occurs between the two components. This gives you a physical one Mixture.
  • the polyester carbonate blend according to the invention is in any case a single-phase, homogeneous mixture.
  • the term “homogeneous mixture” means that with regard to the phase morphology there are no two discrete phases that can be distinguished from one another, but only one homogeneous phase. This can be demonstrated in particular by the transparency of the polyester carbonate blends according to the invention.
  • “transparent” is preferably understood to mean blends that have a light transmission in the VIS range of the spectrum (380 to 780 nm) of more than 20% (transmittance TVIS), determined according to DIN ISO 13468-2:2006 (D65 , 10°, layer thickness of the sample plate: 4 mm). They also preferably have a haze of less than 10%, determined according to ASTM D1003:2013. In particular, this refers to blends that show visual transparency, ie depict the background and can therefore be used as a transparent cover, for example.
  • the term “blend” includes both physical mixtures and mixtures in which at least part of the polyestercarbonate prepolymer has reacted with the polycarbonate.
  • process step (iii) is carried out at a pressure that is reduced in relation to the ambient pressure. This allows the compound formed during condensation to be removed using a vacuum. Accordingly, it is preferred that the process according to the invention is characterized in that during process step (iii) the volatile components which have a boiling point below the polyester carbonate blend formed in process step (ii) are separated off, if necessary with a gradual reduction of the pressure.
  • a stepwise separation is preferably chosen if different volatile components are separated off.
  • a stepwise separation is also preferably chosen in order to ensure the most complete separation possible of the volatile component(s).
  • the volatile components are the chemical compound or compounds split off during condensation.
  • a catalyst that is common to those skilled in the art can be used in process step (iii).
  • the process according to the invention is preferably carried out in the absence of a catalyst. This has the advantage that the catalyst does not have to be separated from the resulting polyester carbonate blend or does not remain in it. Depending on the catalyst, this can have an impact on the stability of the polyester carbonate blend.
  • the method according to the invention can also be carried out in the presence of a catalyst, particularly preferably in the presence of a basic catalyst.
  • Catalysts include all inorganic or organic basic compounds, for example lithium, sodium, potassium, cesium, calcium, barium, magnesium, hydroxides, carbonates, halides, phenolates, diphenolates, fluorides, -acetates, -phosphates, hydrogenphosphates, -boranates, nitrogen and phosphorus bases such as, for example
  • Tetramethyl ammonium hydroxide tetramethyl ammonium acetate, tetramethyl ammonium fluoride, tetramethyl ammonium tetraphenyl boranate, tetraphenyl phosphonium fluoride, tetraphenyl phosphonium tetraphenyl boranate, dimethyl diphenyl ammonium hydroxide, tetraethyl ammonium hydroxide, cethyl trimethyl ammonium tetraphenyl boranate, cethyl trimethyl ammonium phenolate, l,8-diazabi cyclo[5.4.0]undec-7- en (DBU), 1,5-diazabicyclo [4.3.0]non-5-ene (DBN) or guanidine systems such as l,5,7-triazabicyclo-[4,4,0]-dec-5-ene, 7-Phenyl-l,5,7-triazabicyclo-[4,
  • Phosphonium catalysts of the formula (VIII) are particularly suitable: where Ra, Rb, Rc and Rd are the same or different Cl-C10 alkyls, C6-C14 aryls, C7-C15 arylalkyls or C5-C6 cycloalkyls, preferably methyl or C6-C14 aryls, particularly preferably methyl or phenyl can, and Arylalkyl or C5-C6-cycloalkyl, preferably phenyl.
  • catalysts are tetraphenylphosphonium chloride, tetraphenylphosphonium hydroxide and tetraphenylphosphonium phenolate; Tetraphenylphosphonium phenolate is very particularly preferred. Tetrabutylphosphonium acetate is also preferred.
  • These catalysts are preferably used in amounts of 10' 2 to 10' 8 mol, based on 1 mol of the polyester carbonate prepolymer.
  • the amounts of alkaline salts used as co-catalyst can be in the range from 1 to 500 ppb, preferably 5 to 300 ppb and particularly preferably 5 to 200 ppb.
  • Process step (iii) is preferably carried out at temperatures of 280°C to 400°C, preferably 300°C to 390°C, particularly preferably 305°C to 350°C and further preferably 310°C to 340°C. carried out. It is also preferred that process step (iii) is carried out at a pressure of 0.001 mbar to 50 mbar, particularly preferably 0.005 to 40 mbar, very particularly preferably 0.02 to 30 mbar and further preferably 0.03 to 5 mbar becomes. It is also preferred that no vacuum is applied in process step (iii). It is particularly preferred that process step (iii) is carried out at the above-mentioned temperatures in combination with the above-mentioned pressures.
  • process steps (i) and (ii) are initially present as a solid.
  • they are preferably transferred into the melt via an increasing temperature profile.
  • the temperatures mentioned above are preferably the final temperatures.
  • the mixing in process step (iii) preferably takes place at this temperature.
  • the mixing of the components in the molten state in process step (iii) can be achieved in a manner known to those skilled in the art. A distinction must be made as to whether a reaction of the components is explicitly desired or whether a mixing should take place. However, according to the invention, it cannot be ruled out that even in the latter case a reaction can occur between the components.
  • the mixing is preferably achieved by laminar mixing of the components present in the molten state.
  • reactors which are suitable for the processing of highly viscous masses, which provide sufficient residence time with good mixing and which expose the polyester carbonate prepolymers and the polycarbonates to the desired vacuum, if necessary.
  • extruders in particular twin-screw extruders or thin-film evaporators, are preferably used for process step (iii).
  • Thin-film evaporators that are fundamentally suitable for carrying out the method according to the invention are, for example, in EP3318311A1, EP1792643A1, DE19535817A1, DE102012103749A1, DE2011493A1 or DD-226778B1 or in publication [1] “Platzer (ed.): Polymerization Kinetics and Technology, Advances in Chemistry; American Chemical Society: Washington, DC, 1973, pages 51 to 67: Fritz Widmer: Behavior of Viscous Polymers during Solvent Stripping or Reaction in an Agitated Thin Film; Swiss Federal Institute of Technology, Zurich, Switzerland”, whereby the one in DE19535817A1, the DD-226778B1 or the one in the EP3318311A1 or the one in [1], Fig.
  • reactors according to EP460466A1, EP528210A1, EP638354A1, EP715881A2, EP715882A2, EP798093A2 can also be used or those according to EP329092A1, according to EP517068A1, or EP1436073A1 as well as those according to EP222599A2 can be used.
  • time for which the components are mixed in process step (iii) depends, in a manner known to those skilled in the art, on the reactor(s) used. In principle, short times are preferred.
  • Process step (iii) can be carried out without the presence of at least one stabilizer. However, it has proven to be advantageous if at least one stabilizer is present in process step (iii). Likewise, process step c) can also be carried out in the presence of at least one stabilizer. If at least one stabilizer is used in both process step c) and process step (iii), it can be the same or different in both process steps.
  • Such a stabilizer is also often referred to as a stabilizing additive.
  • These stabilizing additives which can be used in the present invention, primarily serve to suppress the transesterification reactions between the individual oligomers or polymers. However, this may also lead to a suppression of the actual reaction of the oligomers or polymers with one another.
  • the suitability of a particular compound for use as a stabilizer in the sense of the present invention and the determination of the suitable amount of such a stabilizer in the sense of the invention can be determined by preparing a mixture of the polyester carbonate blend and the additive and determining the effect on melt viscosity, relative solution viscosity and/or transesterification activity.
  • a compound is particularly suitable as a stabilizer in the sense of the present invention, the lower the increase in molecular weight (for example measured via the relative solution viscosity). If no vacuum is applied in process step (iii), a compound is particularly suitable as a stabilizer in the sense of the present invention, the lower the molecular weight reduction is (for example measured via the relative solution viscosity).
  • the transesterification activity of a compound can be determined by measuring a 13 C NMR spectrum and comparing the different ester bands (see also the process description in the example section).
  • Brönstedt acids are used here.
  • useful Brönsted acid compounds include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, boric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, adipic acid, azelaic acid, dodecanoic acid, L-ascorbic acid, aspartic acid, benzoic acid, formic acid, acetic acid , citric acid, glutamic acid, salicylic acid, nicotic acid, fumaric acid, maleic acid, oxalic acid, benzenesulfmic acid, toluenesulfmic acid and sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, trifluorome
  • phosphoric acid particularly preferred are phosphoric acid, phosphorous acid, their salts and esters.
  • preferred salts are hydrogen phosphates such as zinc or calcium hydrogen phosphates. These are preferably used in amounts of 0.0001 to 0.1, in particular 0.0001 to 0.05% by weight, based on the total composition. These acid compounds can be used either individually or in combination. It is also possible for the acids, esters and salts to be used in the form of a masterbatch based on polycarbonate or polyester or polyester carbonate.
  • Epoxy compounds which have at least one epoxy group in the molecule can also be used as stabilizers. These can be used in amounts of 0.001% by weight to 0.5% by weight, preferably 0.005 to 0.2% by weight, based on the total weight of all components used.
  • Specific examples of useful epoxy compounds as mentioned above include epoxidized soybean oil, epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4- Epoxy-6-methylcyclohexanecarboxylate, 2,3-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4-(3,4-epoxy-5-methylcyclohexyl)
  • alkyl phosphates e.g. B. mono-, di- and trihexyl phosphate, triisoctyl phosphate and trinonyl phosphate can be used as a stabilizer.
  • the preferred alkyl phosphate used is triisooctyl phosphate (tris-2-ethyl-hexyl phosphate).
  • Mixtures of different mono-, di- and trialkyl phosphates can also be used. These can be used in amounts of 0.001 to 0.1% by weight, preferably 0.005 to 0.05% by weight, based on the total weight of all components used.
  • At least one further additive can also be present during process step (iii) and/or process step c) (which differs from the stabilizer described above, which may be present).
  • additives as are usually added to polycarbonates, are in particular thermal or processing stabilizers, antioxidants, in particular phenolic antioxidants, mold release agents, flame retardants, anti-dripping agents, UV absorbers, IR absorbers, antistatic agents, optical brighteners, fillers, light scattering agents, hydrolysis stabilizers and / or additives for laser marking, especially in the usual amounts for polycarbonate-based compositions.
  • additives are described, for example, in EP 0 839 623 Al, WO 96/15102 Al, EP 0 500 496 Al or in the “Plastics Additives Handbook”, Hans Doubt, 5th Edition 2000, Hanser Verlag, Kunststoff. These additives can be added individually or in a mixture.
  • phosphites and phosphonites as well as phosphines can be used as thermal or processing stabilizers.
  • examples are triphenyl phosphite, diphenyl alkyl phosphite, phenyldialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,
  • TPP triphenylphosphine
  • Irgafos® 168 tris(2,4-di-tert-butyl-phenyl) phosphite) and tris(nonylphenyl) phosphite or mixtures thereof.
  • Preferred phenolic antioxidants include alkylated monophenols, alkylated thioalkylphenols, hydroquinones and alkylated hydroquinones. Particularly preferred are Irganox® 1010 (pentaerythritol 3-(4-hydroxy-3,5-di-tert-butylphenyl) propionate; CAS: 6683-19-8) and Irganox 1076® (2,6-di-tert-butyl -4-(octadecanoxycarbonylethyl) ⁇ phenol) is used.
  • Irganox® 1010 penentaerythritol 3-(4-hydroxy-3,5-di-tert-butylphenyl) propionate
  • Irganox 1076® 2,6-di-tert-butyl -4-(octadecanoxycarbonylethyl) ⁇ phenol
  • thermal or processing stabilizers and/or phenolic antioxidants can be used in amounts of 0.5 to 0.001% by weight, based on the total weight of all components present. These can be used individually or as mixtures with the above-mentioned additives. They can be added directly or as a masterbatch.
  • the method according to the invention for producing a polyestercarbonate blend thus delivers a polyestercarbonate blend, which is either a physical mixture and/or a reaction product from the polyestercarbonate prepolymer and the polycarbonate. Therefore, according to the invention, a polyestercarbonate blend is also provided, which was obtained by the method according to the invention for producing a polyestercarbonate blend, preferably in the above-mentioned embodiments or all combinations of preferences.
  • R6 and R7 each independently represent hydrogen, Ci-Cis-alkyl, Ci-Cis-alkoxy, halogen or each optionally substituted aryl or aralkyl, preferably hydrogen, and
  • the polyester carbonate blend according to the invention is also characterized by the fact that the isophthalic acid/terephthalic acid is linked to the repeating unit of the polycarbonate (possibly also oligocarbonate, for example from unreacted residues of process step (c) or by reaction in process step (c)) is present via an ester (see formula (VII).
  • Formula (VII) is explained in more detail above by formula (7).
  • a structure of formula (VII) can be determined via NMR.
  • NMR NMR-NMR spectroscopy
  • the existence of this connection can be determined via 13 C-NMR spectroscopy can be determined by determining the chemical shift of the carbonyl carbon atom marked with an arrow in formula (Vila).
  • Polyester carbonates produced using the phase interface process which include the ester groups (A) and (B), do not have the structural formula (VII) (see Figure 2).
  • an OH-terminated oligoester reacts with a bisphenol (usually bisphenol A) or a corresponding oligocarbonate by reacting with phosgene to form a carbonate.
  • a bisphenol usually bisphenol A
  • a corresponding oligocarbonate by reacting with phosgene to form a carbonate.
  • a resorcinol unit is always linked directly to a BPA unit via a carbonate group.
  • the carbon atom which is marked with an arrow in formula (VII) above, can be formed either by reaction of the chain end of the oligoester with an oligocarbonate and/or polycarbonate in process step (c) and/or (iii). However, it can also be formed by transesterification reactions in process step (c) and/or (iii). Such a transesterification reaction is essentially undesirable because it reduces the intrinsic UV absorbency of the polymer. There must be a certain block length of these esters so that the resulting product has intrinsic weather stability. Nevertheless, the polyester carbonate blend according to the invention always has certain detectable proportions of these carbon atoms.
  • formula (VII) was shown above once with and once without an arrow.
  • formula (VII) with arrow can also be referred to as formula (VIIx). Therefore, according to the invention, it is essential that there are more mol% of carbon atoms, as marked with an arrow in formula (la), in the polyester carbonate blend than mol% of carbon atoms, as marked with an arrow in formula (VII).
  • formula (la) was shown above once with and once without an arrow.
  • the formula (la) with an arrow can also be referred to as the formula (lax).
  • the ratio of the different ester compounds to one another can ensure that the resulting polyester carbonate blend has both good mechanical properties and intrinsic weather stability.
  • the ratio of the mol% of the carbon atoms marked in the formulas (lax) and (VIIx) can preferably be determined via 13 C NMR spectroscopy. This is preferred Polyester carbonate blend dissolved in CDCI. Tetramethylsilane is more preferably used as a standard. It has been shown that a 600 MHz NMR spectrometer is sufficient to distinguish the individual carbon signals of the formula (lax) and (VIIx).
  • the chemical shift of the carbon signal of formula (VIIx) depends on the repeating unit of the oligo- and/or polycarbonate. If a bisphenol A based oligocarbonate and/or polycarbonate is used, the corresponding signal can be found at approx. 164-165 ppm (see also experimental section).
  • the carbon atom marked in formula (lax) is typically found at a chemical shift of 163-164 ppm when the diol of formula (3) is resorcinol.
  • the area under the signals is integrated and related to each other. This is a process known to those skilled in the art.
  • ester groups (A) and the carbonate groups (B) can each occur multiple times in a polyester carbonate blend. It can also be seen that n and m as well as the number of ester groups (A) and/or carbonate groups (B) must be chosen so that the corresponding solution viscosity of the polyester carbonate blend results. Conversely, the person skilled in the art is able to go from a solution viscosity to a number-average molecular weight. It is also obvious to the person skilled in the art to conclude that n or m is based on such a number-average molecular weight and the proportion of ester groups (A) and/or carbonate groups (B).
  • the person skilled in the art can also estimate the magnitude of the average number of repetition units n and/or m based on the starting substances.
  • the person skilled in the art is able to assess possible effects on n and/or m through reactions in process step (iii).
  • the m in formula (II) is preferably at least 5, preferably 8 to 300, particularly preferably 10 to 250 and very particularly preferably 25 to 200.
  • the polyester carbonate blend according to the invention has a ratio of 5 to 25% by weight. , particularly preferably 8 to 23% by weight and very particularly preferably 10 to 20% by weight of ester groups (A) in relation to the total weight of the ester groups (A) and the carbonate groups (B).
  • the polyester carbonate according to the invention consists of at least 80% by weight, particularly preferably at least 90% by weight and very particularly preferably at least 95% by weight of the units of the formula (la) and (II). .
  • the term “blend” is preferably to be understood at this point to mean that the polyester carbonate according to the invention comprises a mixture of different polymers. These can be polyester carbonates, but also pure polycarbonates. This becomes particularly evident when the polyestercarbonate blend according to the invention is produced by the process according to the invention for producing a polyestercarbonate blend.
  • the polyestercarbonate blend according to the invention preferably additionally comprises a component (X), which is a is polycarbonate. This is particularly preferably a polycarbonate with repeating units of the formula (II), as explained in more detail above.
  • X is a is polycarbonate.
  • This is particularly preferably a polycarbonate with repeating units of the formula (II), as explained in more detail above.
  • the person skilled in the art is in particular able to transfer the statements regarding the method according to the invention for producing a polyestercarbonate blend to the polyestercarbonate blend according to the invention.
  • the polyester carbonate blend according to the invention preferably does not contain any methyl 2-hydroxybenzoate. Traces of such a compound can be detected in the blend, for example by NMR spectroscopy. They can remain in the polyestercarbonate blend if activated carbonate sources (e.g. polycarbonates with end groups of formula (301)) are used to prepare the polyestercarbonate blend. Likewise, the polyester carbonate blend according to the invention preferably does not have any end group of the formula (301).
  • the polyestercarbonate blend according to the invention is characterized in that the polyestercarbonate blend has a relative solution viscosity of at least 1.19 to at most 1.40, preferably 1.20 to 1.38, particularly preferably 1.21 to 1. 35 and most preferably 1.22 to 1.33.
  • This relative solution viscosity ensures that the polyester carbonate blend can be easily processed, for example by injection molding. This relative solution viscosity also makes it possible to demonstrate good mechanical properties for interesting areas of application such as automotive exteriors.
  • the polyester carbonate blend has high stability and is intrinsically weather-stable.
  • the polyester carbonate blend according to the invention has a content of phenolic OH groups in the range from 100 ppm to 1200 ppm, preferably 150 ppm to 1000 ppm, particularly preferably 200 ppm to 800 ppm.
  • the polyester carbonate blend according to the invention has a content of phenolic OH groups in the range from 0 ppm to 500 ppm, preferably greater than 50 ppm to 350 ppm, particularly preferably greater than 80 ppm to 800 ppm.
  • This content of phenolic OH groups is preferably determined using infrared spectroscopy. It can also be determined using 1 H-NMR. However, the signals can overlap here.
  • the content of phenolic OH groups is determined using infrared spectroscopy.
  • the polyester carbonate blend is preferably dissolved in dichloromethane (2g/50 ml) and determined by evaluating the band at a wave number of 3583 cm' 1 .
  • the required calibration of the infrared device is known to those skilled in the art.
  • Both the polyestercarbonate prepolymer according to the invention and the polyestercarbonate blend according to the invention can contain rearrangement structures (for example the Fries rearrangement structures known to those skilled in the art). On the one hand, this can result from the fact that in the Process reactions according to the invention are carried out in the melt. As those skilled in the art know, corresponding structures can form under melt transesterification conditions.
  • the oligocarbonates and/or polycarbonates used according to the invention can also already have such frieze structures. According to the invention, it has been found that these Fries rearrangement structures do not have a particularly adverse effect on the properties of the polyestercarbonate prepolymer and/or blend according to the invention.
  • the polyestercarbonate prepolymer according to the invention and/or the polyestercarbonate blend according to the invention and/or the oligocarbonate and/or polycarbonate to be used can contain at least one, preferably several, of the following structures (4y) to (7y): in which the phenyl rings can be independently substituted once or twice with Cl - C8 alkyl, halogen, preferably CI to C4 alkyl, particularly preferably with methyl and X represents a single bond, C 1 to C6 alkylene, C2 to C5 alkylidene or C5 bis C6 cycloalkylidene, preferably a single bond or C1 to C4 alkylene and particularly preferably isopropylidene.
  • the amount of structural units (4y) to (7y) is in total (determined after saponification) generally in the range from 10 ppm to 1000 ppm, preferably greater than 10 ppm to 900 ppm, particularly preferably in the range from 50 to 850 ppm, preferably in the range from 80 to 800 ppm.
  • the respective polymer is subjected to total saponification and the corresponding degradation products of the formulas (4ya) to (7ya) are formed, the amount of which is determined using HPUC.
  • the structures (4ya) to (7ya) are given as examples for the use of a polycarbonate comprising bisphenol A. (This can be done, for example, as follows: The polycarbonate sample is saponified using sodium methylate under reflux. The corresponding solution is acidified and evaporated to dryness.
  • the drying residue is dissolved in acetonitrile and the phenolic compounds of the formula (4ya) to (7ya) using HPUC with UV -detection determined):
  • the amount of the compound of the formula (4ya) released is preferably 20 to 800 ppm, particularly preferably 25 to 700 ppm and particularly preferably 30 to 500 ppm.
  • the amount of the compound of formula (5ya) released is preferably 0 (ie below the detection limit of 10 ppm) to 100 ppm, particularly preferably 0 to 80 ppm and particularly preferably 0 to 50 ppm.
  • the amount of the compound of formula (6ya) released is preferably 0 (ie below the detection limit of 10 ppm) to 800 ppm, more preferably 10 to 700 ppm and particularly preferably 20 to 600 ppm and very particularly preferably 30 to 350 ppm.
  • the amount of compound of formula (7ya) released is preferably 0 (i.e. below the detection limit of 10 ppm) to 300 ppm, preferably 5 to 250 ppm and particularly preferably 10 to 200 ppm.
  • the polyestercarbonate prepolymer according to the invention is used, preferably in all previously described embodiments and/or combinations of preferences, for compatibilizing an oligoester comprising structures of the formula (I), in which Ri independently represents a hydrogen atom, a halogen or an alkyl group with 1 to 4 carbon atoms and n is at least 4, with a polycarbonate.
  • the polyestercarbonate prepolymer improves the incorporation of the oligoester groups into a polycarbonate.
  • the result is the single-phase system described above.
  • the polyestercarbonate prepolymer can also be bonded to the polycarbonate by a chemical reaction.
  • Preferred definitions in the chemical structures are given below. These preferences apply to the process according to the invention for producing a polyestercarbonate prepolymer, the polyestercarbonate prepolymer according to the invention, the process according to the invention for producing a polyestercarbonate blend, the polyestercarbonate blend and / or the use of the polyestercarbonate prepolymer according to the invention, each independently of one another or simultaneously . It will be apparent to the person skilled in the art that some chemical formulas are related (e.g. formula (I) and formula (la)) or that they can be derived from one another.
  • Ri in formula (I) and/or (la) represents hydrogen. It is also preferred that Y in formula (II) represents a structure of formula (III). It is further preferred that Ri in formula (I) and/or (la) stands for hydrogen and Y in formula (II) stands for a structure of the formula (III). It is also preferred that R6 and R7 in formula (III) each independently represent hydrogen or Ci-Ci2-alkyl, particularly preferably hydrogen or C'i-Cx-alkyl and very particularly preferably hydrogen or methyl. This applies in particular to the case that Ri in formula (I) and/or (la) represents hydrogen and Y in formula (II) represents a structure of the formula (III).
  • X in formula (III) represents isopropylidene.
  • Ri in formula (I) and/or (la) stands for hydrogen
  • Y in formula (II) stands for a structure of the formula (III) and R6 and R7 in formula (III) are each independent each other represent hydrogen or Ci-Ci2-alkyl, particularly preferably hydrogen or C'i-Cx-alkyl and very particularly preferably hydrogen or methyl.
  • Y is introduced into the carbonate group (B) via diphenols which are selected from the group consisting of 4'-dihydroxydiphenyl, 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A) , 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, l,l-bis-(4-hydroxyphenyl)-p-diisopropylbenzene, 2, 2-bis-(3-methyl-4-hydroxyphenyl)-propane , Dimethyl - Bisphenol 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, l,l-bis-(3,5-dimethyl-4-hydroxyphenyl)-sul
  • the polyester carbonate blend according to the invention can be processed as such into all kinds of molded articles. It can also be processed with other thermoplastics and/or polymer additives to form thermoplastic molding compounds, which are then formed into moldings.
  • the shaped bodies are further objects of the present invention.
  • the polymer additives are preferably from the group consisting of flame retardants, anti-dripping agents, flame retardant synergists, smoke inhibitors, lubricants and mold release agents, nucleating agents, antistatic agents, conductivity additives, stabilizers (e.g. hydrolysis and heat aging stabilizers and transesterification inhibitors), flowability promoters, phase compatibilizers, dyes and pigments, impact strength modifiers as well as fillers and reinforcing materials.
  • the shaped bodies containing the polyestercarbonate blend according to the invention can be produced, for example, by injection molding, extrusion and blow molding processes. Another form of processing is the production of molded parts by deep drawing from previously manufactured panels or foils. Short description of the characters:
  • FIG. 4 schematic representation of the experimental setup of Example 5 according to the invention
  • FIG. 5 Schematic representation of the experimental setup of Examples 6 and 7 according to the invention. Explanation of the reference numbers:
  • Terephthalic acid for synthesis, CAS 100-21-0, Bernd Kraft Duisburg
  • Isophthalic acid 99%, CAS 121-91-5, Sigma-Aldrich
  • Resorcinol 99%, CAS 108-46-3, ABCR
  • Diphenyl carbonate 99.5%, CAS 102-09-0; Acres Organics, Geel, Belgium, abbreviated as DPC
  • Tetrabutylphosphonium acetate (TBPAc): CAS-34430-94-9, prepared according to Angewandte Chemie, International Edition, Vol. 48, Issue: 40, 7398-7401; 2009
  • ADK Rod PEP 36 3,9-Bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane; CAS 80693-00-1; ADEKA Europe GmbH 40212 Düsseldorf Germany
  • Tetrabutylphosphonium acetate 300 ppm
  • Tetrabutylphosphonium acetate 300 ppm
  • the mixture was freed of oxygen by evacuation four times and aerating with nitrogen.
  • the mixture was melted and heated to 200 ° C under normal pressure with stirring. A suspension was created because the terephthalic acid did not initially dissolve in the melt.
  • the mixture was stirred at this temperature for approximately 3 hours. Carbon dioxide was released. It was slowly heated to 240 °C. Phenol distilled off. The mixture was stirred at 240 °C for about 1 hour. Finally, the mixture was stirred at 260 °C for half an hour. After the evolution of gas had ended, 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 stirred at this temperature for half an hour.
  • the synthesis of the oligoester was carried out in principle like that of the oligoester 1.
  • the maximum temperature was 245°C bath temperature and replaced the 260°C stage with the holding time remaining the same.
  • oligoester 3 was carried out in principle like that of oligoester 1.
  • the maximum temperature was 245°C bath temperature and replaced the 260°C stage with the holding time remaining the same.
  • Oligocarbonate Linear bisphenol A oligocarbonate containing phenyl end groups and phenolic OH end groups with a relative solution viscosity of 1.17 was used as the starting material for the production of the polyester carbonate. This oligocarbonate did not contain any additives such as UV stabilizers, mold release agents or thermal stabilizers. The oligocarbonate was produced using a melt transesterification process as described in WO02085967A1 and was removed directly at the outlet of the first horizontal reactor. The oligocarbonate has a phenolic end group content of 0.16% by weight.
  • Polycarbonate linear bisphenol A polycarbonate with phenyl end groups with an MVR of 13 g/20 min according to ISO 1133.
  • the relative solution viscosity (prel; also referred to as eta rel) was determined in dichloromethane at a concentration of 5 g/1 at 25 °C using an Ubbeloh deviscometer.
  • the molecular weights were determined using gel permeation chromatography with dichloromethane as eluent. BPA polycarbonate was used as a standard. The signal from the refractive index detector (RID) was used. The corresponding method is defined under No. 2301-0257502-09D of Currenta GmbH & Co. OHG, which can be requested from Currenta at any time.
  • the linkage of isophthalic acid and/or terephthalic acid units and bisphenol A was demonstrated via 13 C-NMR spectroscopy. It is also referred to below as IPS/TPS-BPA ester.
  • the linkage of the isophthalic acid and/or terephthalic acid units and resorcinol was also demonstrated (see chemical formula (lax)). It is also referred to below as IPS-TPS resorcinol ester.
  • the carbonyl carbon atom of the isophthalic acid and/or terephthalic acid linkage with bisphenol A showed a shift at 164-165 ppm whereas the isophthalic and/or terephthalic acid resorcinol ester showed a signal at approximately 163-164 ppm.
  • the measurement was carried out on a Bruker Avance III HD 600 MHz NMR spectrometer. The measurement was carried out in CDCI, with tetramethylsilane as a standard. The ratio of the different groups was determined by integrating the corresponding signals (ratio of the areas to each other).
  • the glass transition temperature (Tg) was determined using dynamic differential calorimetry (DSC) according to the standard DIN EN ISO 11357-1:2009-10 and ISO 11357-2:2013-05 at a heating rate of 10 K/min under nitrogen with determination of the glass transition temperature (Tg ) measured as the turning point in the second heating process.
  • DSC dynamic differential calorimetry
  • This substance was prepared to clearly identify the signal of the ester carbon atom, which characterizes the ester of BPA and terephthalic acid or isophthalic acid. It was shown that the corresponding signal is at 164.2 to 164.5 ppm.
  • the contents of the flask were freed of oxygen by four times evacuation and inerting with nitrogen.
  • the mixture was immersed in a metal bath at a temperature of 300°C.
  • the melt was homogenized using a stirrer within 15 minutes.
  • the stirring speed was then set to 280-400rpm and the pressure was quickly reduced to the technically possible minimum, which must reach at least ⁇ 3mbar.
  • Comparative Example 1 shows that, under the selected reaction conditions, surprisingly an almost complete transesterification towards the IPS/TPS-BPA ester occurs. The high intensity of the corresponding signal in the 13 C NMR spectrum proves this. There is only a small amount of IPS/TPS resorcinol ester left. Comparative example 2
  • Educt weight 4g of the oligoester 1 and 36g of the polycarbonate were placed in a multi-necked flask.
  • the driving style was identical to comparative example 1
  • Comparative Example 1 an oligocarbonate with a relatively high OH end group content was used. This product therefore has a higher reactivity than the high molecular weight polycarbonate (with a lower content of phenolic OH groups) in Comparative Example 2. That's why it was all the more surprising that in this case too it was practically complete Transesterification occurs.
  • the production of a uniform copolymer at low temperatures does not seem possible, since both polymer phases are present next to each other without a reaction occurring. At higher temperatures, however, complete transesterification occurs without any significant amount of IPS-TPS resorcinol ester being present.
  • Educt weight 4g of the oligoester 1 and 36g of the oligocarbonate were placed in a multi-necked flask.
  • the contents of the flask were freed of oxygen by four times evacuation and inerting with nitrogen.
  • the mixture was immersed in a metal bath at a temperature of 300°C.
  • the melt was homogenized using a stirrer within 15 minutes.
  • the stirring speed was then set to 280-400rpm and the pressure was quickly reduced to the technically possible minimum, which must reach at least ⁇ 3mbar.
  • Educt weight 8g of the oligoester 2 and 2g of the oligocarbonate were placed in a multi-necked flask.
  • the contents of the flask were freed of oxygen by four times evacuation and inerting with nitrogen.
  • the mixture was immersed in a metal bath at a temperature of 310°C.
  • the melt was homogenized using a stirrer within 15 minutes.
  • the stirring speed was then set to 280-400rpm and the pressure was quickly reduced to the technically possible minimum, which must reach at least ⁇ 3mbar. As the process progressed, a significantly increasing melt viscosity and slight condensate separation were observed.
  • Educt weight 8g of the oligoester 3 and 2g of the oligocarbonate were in one
  • Educt weight 1.875 g from the product of the experiment described in Example 1 according to the invention and 13.125 g of the polycarbonate were placed in a multi-necked flask so that a mass fraction of the oligoester of 10% was achieved.
  • PEP-36 added.
  • the contents of the flask were freed of oxygen by blanketing with nitrogen for 10 minutes.
  • the mixture was immersed in a metal bath at a temperature of 300°C. As soon as possible, the melt was homogenized using a stirrer within 15 minutes. A sample (0 min.) was then taken. Now the stirring speed was set to 280-400rpm and the pressure was quickly reduced to the technically possible minimum, which must reach at least ⁇ 3mbar. As the process progressed, a significantly increasing melt viscosity and slight condensate separation were
  • Educt weight 1.875 g from the product of the experiment described in Example 2 according to the invention and 13.125 g of the polycarbonate were placed in a multi-necked flask so that a mass fraction of the oligoester of 10% was achieved. There were 7.5 mg of 3', 4'-epoxycyclohexane)methyl 3,4-epoxycyclohexylcarboxylate and 15 mg of ADK rod. PEP-36 added. The driving style was identical to “Inventive Example 3”.
  • the reactor (2) was cooled and 600.6 g of oligocarbonate were added to the reaction mixture.
  • the mixture was melted at 250 °C and the pressure was gradually reduced to ⁇ 1 mbar.
  • the melt was stirred with a reversible stirrer at 17.5 rpm and conveyed with the gear pump (3.1) through the circuit line with the static mixer (4).
  • the melt was conveyed in a circle in this way for 75 minutes.
  • the polymer melt was then continuously conveyed to the twin-screw extruder (1) (type ZSE 27 MAXX with 11 housings) by a second gear pump (3.2) at a throughput of 1.2 kg/h Leistritz Extrusionstechnik GmbH, Nuremberg).
  • the extruder housings are designated in Figure 4 with the letters “a” to “k”.
  • the extruder was operated at 100 rpm at a housing temperature of 310 ° C.
  • the melt was fed into the fourth housing (d) of the extruder.
  • Reverse degassing with 25 mbar absolute pressure took place via the first housing (a) of the extruder (a).
  • a vacuum of 25 mbara was applied to the housing of the extruder (e) and a vacuum of 3-5 mbara was applied to the housings (g), (i) and (j).
  • the polymer melt was extruded at a melt temperature of 311 ° C, passed into a water bath (9) and granulated using a strand granulator (10).
  • the polymer sample had an Mn of 3750 g/mol and an Mw of 8300 g/mol (RID).
  • the mixture was continuously fed into the feed housing (a) of the twin-screw extruder (1) via the differential metering scale (2) at a throughput of 2 kg/h (type ZSE 27 MAXX with 11 housings from Leistritz Extrusionstechnik GmbH, Nuremberg) and at 150 rpm extruded.
  • the extruder housings are designated in Figure 5 with the letters “a” to “k”.
  • the mixture was at a housing temperature of 160°C for housing (b), 240°C for housing (c), 300°C for housing (d) and 320°C for housings (f) to (k) with a Melt temperature of 329 ° C, passed into the water bath (9) and granulated with the strand granulator (10).
  • the extruder has degassing zones on the housings (e), (g), (i) and (j). These were operated under normal pressure.
  • the product has the following analytical data: transparent granules, Eta rel: 1.225, Tg: 143 °C, the 13 C spectrum predominantly shows IPS-TPS resorcinol ester (ratio approx. 1:2.6).
  • the mixture from example 6 according to the invention was continuously fed into the feed housing (a) of the twin-screw extruder (1) via the differential metering scale (2) at a throughput of 1.4 kg/h (type ZSE 27 MAXX with 11 housings from Leistritz Extrusionstechnik). GmbH, Nuremberg) and extruded at 100 rpm.
  • the extruder housings are designated in Figure 5 with the letters “a” to “k”.
  • the mixture was at a housing temperature of 160°C for housing (b), 240°C for housing (c), 300°C for housing (d) and 320°C for housings (f) to (k) with a Melt temperature of 328 ° C is extruded, passed into the water bath (9) and granulated with the strand granulator (10).
  • a vacuum of 32 mbar was applied to housing (e) of the extruder and a vacuum of ⁇ 1 mbar was applied to housing (g), (i) and (j).
  • the product has the following analytical data: transparent granules, eta rel: 1.230, Tg: 145 °C, the 13 C spectrum predominantly shows IPS-TPS resorcinol ester (ratio approx. 1:2.6).

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne un procédé de production d'un prépolymère de carbonate de polyester, un prépolymère de carbonate de polyester, un procédé de production d'un mélange de carbonate de polyester à l'aide du prépolymère de carbonate de polyester, un mélange de carbonate de polyester et une utilisation du prépolymère de carbonate de polyester.
PCT/EP2023/060755 2022-04-29 2023-04-25 Mélange de carbonate de polyester et sa production par l'intermédiaire d'un prépolymère de carbonate de polyester WO2023208897A1 (fr)

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