EP4055080A1 - Procédé de préparation de carbonates de polyester - Google Patents

Procédé de préparation de carbonates de polyester

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Publication number
EP4055080A1
EP4055080A1 EP20797519.4A EP20797519A EP4055080A1 EP 4055080 A1 EP4055080 A1 EP 4055080A1 EP 20797519 A EP20797519 A EP 20797519A EP 4055080 A1 EP4055080 A1 EP 4055080A1
Authority
EP
European Patent Office
Prior art keywords
acid
carbonate
bis
hydroxyphenyl
melt transesterification
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20797519.4A
Other languages
German (de)
English (en)
Inventor
Alexander Meyer
Ulrich Liesenfelder
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Covestro Intellectual Property GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of EP4055080A1 publication Critical patent/EP4055080A1/fr
Pending legal-status Critical Current

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Classifications

    • 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
    • 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
    • C08G63/78—Preparation processes
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • 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
    • C08L69/005—Polyester-carbonates

Definitions

  • the present invention relates to a method for producing polyester carbonates in the melt transesterification process starting from polycarbonates or polycarbonate oligomers.
  • the process relates to the production of polyester carbonates in one
  • polyester carbonates produced have a balanced set of properties with regard to molecular weight, glass transition temperature and residual phenolic OH content.
  • the present use also relates to the use of the polyester carbonates produced according to the invention. It is known that polyesters, polycarbonates and polyester carbonates have good mechanical properties, heat resistance and weathering resistance. Depending on the monomers used, each polymer group has certain key characteristics that distinguish such materials. Polycarbonates have particularly good mechanical properties, whereas polyesters often show better chemical resistance. Polyester carbonates show depending on the chosen
  • Polyester carbonates made from aromatic diols and linear diacids often have improved flowability compared to aromatic polycarbonates. Furthermore, they show a better level of mechanical properties at lower temperatures. Polyester carbonates from aromatic diols and aliphatic diacids are now manufactured using the phase interface process. Although there are publications relating to the melt transesterification process, this process has not caught on. A disadvantage of the interfacial process is often the need for discontinuous operation of these special products. Since the phase boundary systems, which are designed, for example, for the production of aromatic polycarbonate, usually have large capacities, such special products can only be produced with great effort and often with little economic efficiency.
  • the task was therefore to develop a method that is flexible and can be implemented cost-effectively on small systems. Furthermore, the task was to start from available raw materials. Furthermore, the task was to achieve the shortest possible dwell times on the corresponding production units. Surprisingly, the object could be achieved by a melt transesterification process, preferably carried out in an extruder, polymer kneader or other reactor. For this purpose, starting from an aromatic polycarbonate or a corresponding oligomer, the corresponding polyester carbonate is produced by adding an aliphatic and / or an aromatic dicarboxylic acid and a diaryl carbonate.
  • EP1230288 describes a transesterification process starting from aromatic carbonate oligomers and linear fatty acids. However, the process times there are very long, so that this is not a promising process for a reactive extrusion process. The longer the residence times in a continuously operating extruder or polymer kneader, the less economical the process. A residence time of 30 minutes or less is aimed for in a reactive extrusion process. In contrast, the process times described in EP1230288 are several hours.
  • EP1307421 describes a process for the preparation of diphenyl esters of dicarboxylic acids. These can be reacted with aromatic diols or with oligomers. However, this two-stage process cannot be implemented or can only be implemented with great difficulty in a continuous reactive extrusion process. Similarly, EP1242498 describes a multistage process for the production of polyester carbonates, which is unsuitable for a reactive extrusion process.
  • EP1307421 and EP1230288 describe ratios between dicarboxylic acid and diaryl carbonate, which surprisingly have proven extremely negative for reactive extrusion processes.
  • the present invention was therefore based on the object of developing a process for producing a polyester carbonate from aromatic carbonate oligomers and aliphatic and / or aromatic diacids, which method improves the above-described disadvantage of the prior art.
  • the present invention was based on the object of providing a process in which no use of phosgene is necessary.
  • a method is to be provided which can be carried out without solvents.
  • the process should in principle also be suitable for reactive extrusion processes or melt transesterification processes, i.e. the new process should be characterized by short process times, i.e. less than 1 hour.
  • the polymer should have high molecular weights (significantly increased compared to the starting material) and relatively low OH end group contents.
  • At least one, preferably all of the above-mentioned objects have been achieved by the present invention.
  • the direct reaction of an aromatic oligocarbonate or polycarbonate with at least one aliphatic and / or aromatic diacid and at least one aromatic carbonate in the presence of a basic Catalyst leads to the desired product.
  • only certain ratios of oligomer, diacid and carbonate diester lead to the desired product properties. This is neither described nor suggested in the prior art. In this way, it was possible to find a method for producing a polyester carbonate containing aliphatic and / or aromatic diacids which does not require the use of phosgene and is therefore not associated with appropriate safety precautions.
  • the process can be carried out without solvents. This makes the method according to the invention environmentally friendly. Furthermore, the procedure can be carried out within short process times. This means that the desired properties, such as the molecular weight and the OH end group content, can be set within short process times.
  • Ci2-arylene Z for a single bond, -SO2-, -CO-, -O-, -S-, Ci- to C ö -alkylene, C2- to C5- alkylidene or C5- to Ci2-cycloalkylidene, also for CV to Ci2-arylene , which may optionally be condensed with further aromatic rings containing heteroatoms,
  • Rl and R2 independently of one another for H, Ci to Cis-alkyl, Ci to Cis-alkoxy, halogen such as Cl or Br or for C f , to Cis-aryl or C7 to Cis-aralkyl, preferably for H or Ci- to C 12 alkyl, particularly preferably for H or
  • R3 for optionally heteroatoms, such as oxygen or sulfur, containing Ci- to C44-alkylene, C5- to C44-cycloalkylene, C7- to C44-
  • Aralkylene or CV to C24 arylene, di- or polyarylene, preferably C f to C 16 alkylene, and
  • R4 and R5 independently of one another represent H, C1-C34-alkyl, C 7 -C 34 aralkyl, C 6 -C 34 aryl or -COO-R ', where R' is a C 1 -C 34 alkyl, C 7 -C 4 -aralkyl, C 6 -C 4 -aryl, are, m and ml are independently of one another an integer from 1 to 5, and if m is a number from 2 to 5, each radical R4 can be identical or different can, and if ml is a number from 2 to 5, each radical R5 can be the same or different, be reacted, wherein the molar ratio of dicarboxylic acid of the formula P to diaryl carbonate of the formula III is 1: 1.01 to 1: 1.9.
  • melt transesterification “melt transesterification process” or also “melt transesterification process”, which are used synonymously according to the invention, are known to the person skilled in the art. Melt transesterification processes are described in WO 2001/05866 A1, WO 2000/105867, US Pat. No. 5,340,905 A, US Pat. No. 5,097,002 A or US Pat. No. 5,717,057 A, for example.
  • the components required for the reaction in particular components (A), (B) and (C) according to the invention and possibly other components, are reacted with one another in the melt.
  • melt transesterification In the case of a melt transesterification, the entire reaction mixture is kept in the melt during the entire reaction time.
  • the oligomeric structures that are initially formed typically have a lower melting or softening point than the final target products of the copolyester carbonates.
  • the temperatures in the melt transesterification are chosen so that the copolyester carbonates to be achieved are also present in the melt. Only when the target product has been reached, in particular the desired molecular weight or the desired viscosity, are the temperatures adjusted so that the target product is then obtained as a solid during work-up.
  • a melt transesterification to be a process in which the entire reaction, in particular the reaction of components (A), (B) and (C) and also possibly other components, takes place in the melt.
  • this pressure does not have to be present for the entire reaction time.
  • This pressure is preferably used in process step ii or ii 'which is preferred according to the invention (described later).
  • higher pressures are used at early reaction times in order to prevent low molecular weight reaction products / starting materials from being removed in vacuo.
  • lower pressures are usually used in order, as described above, to enable sufficient removal of the condensation products;
  • the viscosity increases with the progress of the reaction and that the removal of the low molecular weight condensation product (s) becomes more difficult. For this reason, the above-described thorough mixing and the low pressures are usually necessary.
  • the resulting copolyester carbonate contains structural units of the following formulas IV and V
  • RI, R2, R3, Z, n and nl correspond to the description above for formulas I and II, and z and y are natural numbers> 1.
  • Z preferably represents a single bond, C j to C 5 alkylene, C 2 to C 5 alkylidene, C 5 to C 6 cycloalkylidene, -O-, -SO-, -CO-, -S-, -S0 2 - or for a radical of the formula (VI)
  • oligocarbonate / s is to be understood as meaning polymers or polymer mixtures that have a solution viscosity of ⁇ 1.210 eta rel and the term “polycarbonate / s” or “polyester carbonate / s” those that have a solution viscosity> 1.210 eta rel to 1.38, preferably 1.23 to 1.36, each determined in dichloromethane at a concentration of 5 g / 1 at 25 ° C. with an Ubbeloh viscometer.
  • the Lachmann knows how to determine the relative solution viscosity using an Ubbeloh viscometer. According to the invention, this is preferred in accordance with DIN 51562-3; Conducted 1985-05.
  • the throughput times of the polyester carbonate to be measured are measured by the Ubbelohde viscometer in order to then determine the viscosity difference between the polymer solution and its solvent.
  • the Ubbelohde viscometer is first calibrated by measuring the pure solvents dichloromethane, trichlorethylene and tetrachlorethylene (at least 3 measurements, 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 mean value of the flow times is corrected using the Hagenbach correction and the relative solution viscosity is calculated.
  • diphenols from which the poly- and oligocarbonates to be used according to the invention are derived are: dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) aryls, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, l, l'-bis (hydroxyphenyl) diisopropylbenzenes and their nucleus alkylated and nuclear halogenated compounds.
  • the divalent radicals -Ar (Rl) n-Z-Ar (R2) nl- in Lormel I can be obtained by removing 2 hydroxyl groups from these diphenols.
  • Particularly preferred diphenols on which the poly- and oligocarbonates to be used in the process according to the invention are based, are 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -l-phenylpropane, l, l-bis (4- hydroxyphenyl) phenylethane, 2,2-bis- (4-hydroxyphenyl) propane, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,3-bis- [2- (4-hydroxyphenyl) -2 propyl] benzene (bisphenol M), 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 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-methylbutan
  • diphenols are 4,4'-dihydroxydiphenyl, l, l-bis- (4-hydroxyphenyl) -phenyl-ethane, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (Bisphenol TMC).
  • the monofunctional chain terminators required to regulate the molecular weight such as phenols or alkylphenols, in particular phenol, p-tert. Butylphenol, iso-octylphenol, cumylphenol, their chlorocarbonic acid esters or acid chlorides of monocarboxylic acids or mixtures of these chain terminators are either added to the reaction with the bisphenolate or bisphenolates or added at any point in the synthesis as long as phosgene or chlorocarbonic acid end groups are still in the reaction mixture are present, or in the case of the acid chlorides and chlorocarbonic acid esters as chain terminators, as long as sufficient phenolic end groups of the polymer being formed are available.
  • the chain terminator or terminators are added after the phosgenation at one point or at a time when no more phosgene is present but the catalyst has not yet been metered in, or they are metered in before the catalyst, together with the catalyst or in parallel.
  • Any branching agents or branching mixtures to be used are added to the synthesis in the same way, but usually before the chain terminators.
  • trisphenols, quarter phenols or acid chlorides of tri- or tetracarboxylic acids or mixtures of the polyphenols or the acid chlorides are used.
  • Some of the compounds with three or more than three phenolic hydroxyl groups that can be used as branching agents are, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) hepten-2, 4,6-dimethyl-2, 4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tris- (4-hydroxyphenyl) -benzene, l, l, l-tri- (4-hydroxyphenyl) -ethane, tris- (4 -hydroxyphenyl) -phenylmethane, 2,2-bis- [4,4-bis- (4-hydroxyphenyl) -cyclohexyl] -propane, 2,4-bis- (4-hydroxyphenyl-isopropyl) -phenol, tetra- (4 - hydroxyphenyl) methane.
  • trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride, and 3,3-bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.
  • Preferred branching agents are 3,3-bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 1,1,1-tri (4-hydroxyphenyl) ethane.
  • the amount of branching agents to be used is 0.05 mol% to 2 mol%, again based on the moles of diphenols used in each case.
  • the branching agents can either be initially introduced with the diphenols and the chain terminators in the aqueous alkaline phase or dissolved in an organic solvent and added before the phosgenation.
  • a polycarbonate with an OH end group content of ⁇ 0.1% by weight, preferably ⁇ 0.08% by weight, determined by means of IR spectroscopy is used in the process according to the invention.
  • the determination can be carried out as follows: The polycarbonate, dissolved in dichloromethane (2 g / 50 ml; 1 mm quartz cuvette), is analyzed in the FT infrared spectrometer Nicolet iS 10 from Thermo Fisher Scientific. The content of phenolic OH end groups is determined by evaluating the band at wave number 3583 cm-1.
  • Aliphatic and / or aromatic dicarboxylic acids can be used as dicarboxylic acids of the formula II.
  • the aliphatic dicarboxylic acids are linear aliphatic and cycloaliphatic dicarboxylic acids.
  • Examples include: orthophthalic acid, terephthalic acid, isophthalic acid, tert-butyl isophthalic acid, 3,3'-diphenyldicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 3,4'-benzophenonedicarboxylic acid, 4,4'- Diphenyletherdicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 2,2-bis- (4-carboxyphenyl) propane, trimethyl-3-phenylindane-4,5'-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1, 2-cyclohexanedicarboxylic acid, tetradihydro-2,5-furandicarboxylic acid, tetradihydro-2,5-dimethyl-furanedicarboxylic
  • Dimer fatty acids are mixtures that are produced by the oligomerization of unsaturated fatty acids.
  • Unsaturated C12 to C22 fatty acids such as, for example, Ci « fatty acids such as linolenic, linoleic and / or oleic acid, can be used as starting materials.
  • the carboxyl groups of the dimer fatty acids are linked to one another by hydrocarbon radicals which predominantly have 24 to 44 carbon atoms.
  • hydrocarbon radicals are usually branched and can have double bonds, C6-cycloaliphatic hydrocarbon radicals or C6-aromatic hydrocarbon radicals; the cycloaliphatic radicals and / or the aromatic radicals can also be present in condensed form.
  • the radicals which connect the carboxyl groups of the dimer fatty acids preferably have no aromatic hydrocarbon radicals, very particularly preferably no unsaturated bonds and no aromatic hydrocarbon radicals.
  • Preferred diacids of the formula II are terephthalic acid, isophthalic acid, 3,3'-diphenyldicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, tetradihydro-2,5-furanedicarboxylic acid, dodecanedioic acid, adipic acid, octadecanedioic acid and sebacic acid.
  • Particularly preferred diacids are dodecanedioic acid, adipic acid, octadecanedioic acid and sebacic acid.
  • Diaryl carbonates corresponding to formula III are described in EP-A 1 609 818, for example.
  • Diphenyl carbonate, 4-tert-butylphenyl-phenyl-carbonate, di- (4-tert-butylphenyl) - are preferred carbonate, biphenyl-4-yl-phenyl-carbonate, di- (biphenyl-4-yl) -carbonate, 4- (1-methyl-1-phenylethyl) -phenyl-phenyl-carbonate and di- [4- (1 -methyl -1-phenylethyl) phenyl] carbonate.
  • Substituted or unsubstituted, preferably unsubstituted, diphenyl carbonate is very particularly preferably used as the carbonate in the process according to the invention.
  • the carbonates can also be used with residual amounts of the monohydroxyaryl compounds from which they were produced.
  • the residual contents of the monohydroxyaryl compounds can be up to 20%, preferably 10%, particularly preferably up to 5% and very particularly preferably up to 2%. This means that in the process according to the invention it is also possible to use carbonates which do not have to be subjected to expensive purification after their production process.
  • the monohydroxyaryl compound from which the carbonate was obtained is obtained again as a condensation product Ar — OH and is preferably separated off, these impurities do not interfere with the reaction.
  • the process according to the invention can be made even more economically advantageous overall by means of such a cheaply produced carbonate.
  • the at least one carbonate can also be produced in a phosgene-free manner.
  • the process according to the invention for the production of polyester carbonates by melt transesterification comprises the following process steps: i) conversion of the dicarboxylic acid component B and the diaryl carbonate component C to a diaryl ester D, ii) further condensation of the diaryl ester D obtained from process step i with the poly / oligocarbonate component A.
  • Step i It is clear to the person skilled in the art that the reaction schemes of process step (i) and (ii) shown above are only to be understood as examples and not restrictive. In particular, it cannot be ruled out according to the invention that further reactions also take place, in particular in process step (i). For example, it is very likely that macromolecules (molecules in which the individual monomers are already partially condensed) are already forming in process step (i). However, further side reactions and / or intermediate stages can also arise. Likewise, the reaction in process step (i) does not have to be complete, but can in some cases only take place in process step (ii). However, in process step (i) it has already essentially been completed.
  • process step (i) is preferably carried out until a substantial decrease in gas formation can be observed, and only then process step (ii) is initiated, for example by applying a vacuum to remove the chemical compound split off during the condensation.
  • process steps (i) and (ii) may not be sharply separated from one another according to the invention.
  • the process can also be carried out in such a way that only part of the total amount of diaryl carbonate component C to be used in the process is used in the first process step i, and the remaining part of the diaryl carbonate component C is added to the reaction mixture obtained from process step i before or during the second process step ii , so that further diaryl esters are formed in the second process step, while the above-described condensation takes place in parallel (process step ii ').
  • process steps i) and ii) or ii ‘) follow one another directly. This means that, for example, there is no recrystallization, precipitation, addition of a solvent or the like step.
  • process step ii the further condensation of the reaction mixture obtained from process step i takes place.
  • the expression “further” condensation is to be understood as meaning that condensation has already taken place in process step i. This is preferably the reaction of the dicarboxylic acid B with the diaryl carbonate C with elimination of an aryl alcohol.
  • process step i preferably further comprises one of the following two steps ia): melting a mixture of components A, B and C or placing the melted component A in the first place and adding components B and C separately in liquid form.
  • process step i only part of component C is melted with components A and B, or added to the initially charged, melted component A in liquid form, and the remaining part of component C is then before or during process step ii 'added in liquid form.
  • an extruder for example a twin-screw extruder, in which the polycarbonate and the other reactants are mixed and plasticized.
  • the oligo or polycarbonate is initially charged in melted form and the diacid and the diaryl carbonate are metered in as a liquid via an extruder dome.
  • the mixing can, however, also take place via dynamic or static mixers.
  • the reaction in process step i is preferably carried out at a temperature of 280 to 320 ° C., a pressure of 20 to 800 mbar, preferably 100 to 600 mbar and for a duration of up to 20 minutes, preferably 1 to 15 minutes.
  • Process step i can be carried out, for example, on a twin-screw extruder; Furthermore, kneaders, basket or disk reactors and falling film evaporators are also possible.
  • Process step ii or ii ‘ is particularly preferably carried out at a pressure of 0.1 to 100 mbar, preferably 0.2 to 1 mbar and a temperature of 300 to 350.degree. These conditions ensure that a good balance between energy input, reaction time and yield is obtained. Short reaction times are possible according to the invention. These do not expose the copolyester carbonate to be achieved to thermal stress for too long, so that the resulting product qualities are excellent. A reaction time of 10 to 60 minutes, particularly preferably 15 to 45 minutes, is therefore preferably used in process step ii or ii ‘. These reaction times also allow, among other things, that the entire process according to the invention can also be carried out continuously.
  • the process according to the invention can be carried out continuously or batchwise. However, it is preferably carried out continuously.
  • the molar ratio of dicarboxylic acid of the formula II to diaryl carbonate of the formula III is 1: 1.01 to 1: 1.9, preferably 1: 1.05 to 1: 1.5, particularly preferably 1: 1.35.
  • the dicarboxylic acid component B is used in an amount of 2 to 20% by weight, preferably 3 to 15% by weight and particularly preferably 4 to 10% by weight, based on the total weight of the polycarbonate / oligocarbonate component A.
  • the ratio of the starting materials is decisive for the later quality of the polyester carbonate.
  • only part of the diaryl carbonate component C is initially used in process step i.
  • the remaining portion can be added to the melt mixture at a late stage of the reaction (process step ii ‘) - the above-mentioned ratios must not be changed.
  • the process is preferably carried out in the presence of a catalyst, particularly preferably in the presence of a basic catalyst.
  • the catalyst can be used in step i and / or ii or ii ‘.
  • Catalysts are all inorganic or organic basic compounds, for example fithium, sodium, potassium, cesium, calcium, barium, magnesium, hydroxides, carbonates, halides, phenolates, diphenolates, fluorides, acetates, phosphates, - hydrogen phosphate, -boranate, nitrogen and phosphorus bases such as tetramethylammonium hydroxide, tetramethyl ammonium acetate, tetramethyl ammonium fluoride, boronate phenylphosphoniumtetraphenyl-Tetramethylammoniumtetraphenylboranat, Tetraphenylphosphoniumfluorid, tetra-, dimethyl diphenylammoniumhydoxid, ammonium hydroxide, tetraethyl, Cethyltrimethylammonium tetraphenylborate, Cethyltrimethylammonium phenolate, 1,8-diazabicyclo [5.4.0]
  • Phosphonium catalysts of the formula (VII) are particularly suitable: where Ra, Rb, Rc and Rd are the same or different CI -CIO-alkyls, C6-C14-aryls, C7-C15-aryl-alkyls or C5-C6-cycloalkyls, preferably methyl or C6-C14-aryls, particularly preferably methyl or phenyl can be, and X- can be an anion such as hydroxide, sulfate, hydrogen sulfate, hydrogen carbonate, carbonate or a halide, preferably chloride or an alkylate or arylate of the formula -OR, where R is a C6-C14-aryl, C7-Cl 5 - Arylalkyl or C5-C6-cycloalkyl, preferably phenyl.
  • catalysts are tetraphenylphosphonium chloride, tetraphenylphosphonium hydroxide and tetraphenylphosphonium phenolate; Tetraphenylphosphonium phenate is very particularly preferred.
  • These catalysts are preferably used in amounts of from 10 2 to 10 8 mol, based on 1 mol of the dicarboxylic acid component B.
  • the amounts of the alkaline salts as cocatalyst can be used in the range from 1 to 500 ppb, preferably from 5 to 300 ppb and particularly preferably from 5 to 200 ppb.
  • one or more stabilizers can be added to the melt.
  • antioxidants such as phosphorus-based antioxidants or phenolic antioxidants.
  • These stabilizers are preferably selected from the group consisting of P-containing stabilizers and / or phenolic radical scavengers.
  • Phosphites and phosphonites and phosphines are particularly suitable. Examples are triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite,
  • Diisodecylpentaerythritol diphosphite bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4- dicumylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) - pentaerythritol diphosphite, bis ( 2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'
  • Triphenylphosphine (TPP), Irgafos® 168 (tris (2,4-di-tert-butyl-phenyl) phosphite) and tris (nonylphenyl) phosphite or mixtures thereof are particularly preferably used.
  • phenolic radical scavengers such as alkylated monophenols, alkylated
  • Irganox® 1010 penentaerythritol 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.
  • both process steps (i) and (ii) or (ii ') are preferably carried out in the absence of an additional organic solvent.
  • the method according to the invention can thus preferably be carried out without a solvent. According to the invention, this does not rule out that both the diaryl carbonate used and the condensation product formed in the reactions may be present as solvents in these reaction steps (as far as possible). This is the case in particular when the carbonate is used in a stoichiometric excess to the dicarboxylic acid. This preferred variant of the method is particularly gentle. However, it is preferred according to the invention that no additional organic solvent is added to the process. The absence of an additional organic solvent means that the process can be carried out inexpensively and in an environmentally friendly manner.
  • the method according to the invention ensures that the proportion of OH end groups and acid end groups is very low.
  • the OH groups remaining in low concentration and here in particular free acid end groups can be further reduced at the end of the reaction by epoxy-containing additives and / or by carbodiimide-containing additives.
  • All known carbodiimides of the formula are used as oligomeric and / or polymeric carbodiimides
  • R aromatic, aliphatic, cycloaliphatic and / or araliphatic radical
  • RI and R2 are identical or different and are C1-C20-alkyl, C3-C20-cycloalkyl, -aryl, C7-C18 Aralkyl, oligo / polyethylene and / or propylene glycols and R3 has one of the meanings of RI or a polyester or polyamide radical, and m is an integer from 1 to 5,000 corresponds, and in the case of oligomeric carbodiimides m corresponds to an integer from 1 to 5, and in the case of polymeric carbodiimides m corresponds to an integer> 5, and / or the formula (IX)
  • NH-R ', -S-CO-NH- R' R Cl-C18-alkyl, C5-C18-cycloalkyl, aryl, C7-C18-aralkyl, - R '"- NH-COS-Rl, R"" -COORl, -R , -ORl -R "'- N (R1) 2, - R"' - SR1, -R '"- OH, -R'" - NH2, -R "'- NHR1, -R"'-Epoxy, - R'"- NCO, -R '" - NHCONHRl, -R'"- NHCONRlR2 or - R '" - NHCOOR3, where RI and R2 are the same or different and are a C1-C20 -alkyl, C3-C20- cycloalkyl, aryl, C7-C18-arylkyl radical,
  • Z Y, polyester, polyether, polyamides and R ’" describes an aromatic and / or araliphatic radical. Particularly preferred are aromatic oligomeric and / or polymeric carbodiimides of the aforementioned formula (VIII) with m> 2.
  • the polymeric and / or oligomeric carbodiimide are compounds of the formula (IX) in which R '"1,3-substituted-2,4,6-triisopropylphenyl and / or 1,3-bis - (l-methyl-l-isocyanato-ethyl) -benzene and / or tetramethylxylylene derivatives and / or 2,4-substituted tolylene and / or 2,6-substituted tolylene and / or mixtures of 2,4- or 2,6- substituted tolylene corresponds.
  • the aforementioned carbodiimides are commercially available compounds that are available from Rhein Chemie Rheinau GmbH under the trade names Stabaxol® P (NCN content: 12.5-13.5%), Stabaxol® P 100 (NCN content: 12 , 5 - 13.5%) and Stabaxol® P 400 (NCN content: 12.5 - 13.5%) are commercially available.
  • As epoxy-containing additives that can be used to cap carboxylic acid functions for example, compounds of bisphenol A and epichlorohydrin according to the following formula X, in which n is about 0 (ie only one BPA unit is present), such as. B. the compounds sold under the trade names "Epikote 828" and "Araldite GY-260";
  • n is about 1, such as e.g. B. the compounds sold under the trade names "Epikote 834" and "Araldite GY-280"; Compounds in which n is about 2, e.g. B. the compounds sold under the trade names "Epikote 1001" and “Araldite 6071”; Compounds in which n is about 3, such as e.g. B. the compounds sold under the trade names "Epikote 1002" and “Araldite 7072"; and compounds where n is about 4, e.g. B.
  • Epikote 1004" and “Araldite 6084” are trademarks of Hexion and Huntsman Advanced Materials, respectively .; n stands for the mean value of the polymerization, which is why it can be said, for example, that " n is about 0 ").
  • an alicyclic Epoxy compound may be mentioned as a useful additive such as e.g. B. 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate.
  • the epichlorohydrin bisphenol A epoxy compounds can be used in amounts of up to 0.01 to 5% by weight, preferably 0.1 to 1% by weight, based on the weight of the polyester carbonate to be produced.
  • the present invention also relates to polyester carbonates which can be obtained by the process according to the invention described above. These have phenolic OH end group contents of preferably less than 0.13% by weight, particularly preferably less than 0.12% by weight and very particularly preferably less than 0.11% by weight, determined by means of IR spectroscopy. The determination can be carried out as follows: The polyester carbonate, dissolved in dichloromethane (2 g / 50 ml; 1 mm quartz cuvette), is analyzed in the FT infrared spectrometer Nicolet iS 10 from Thermo Fisher Scientific. The content of phenolic OH end groups is determined by evaluating the band at wave number 3583 cm-1.
  • Diphenyl carbonate Diphenyl carbonate, 99.5%, CAS 102-09-0; Acros Organics, Geel, Belgium
  • Tetraphenylphosphonium phenol at: tetraphenylphosphonium phenolate, 66.5%, CAS 15464-47-8; Rheinchemie
  • Irganox B900 (manufacturer: BASF)
  • Polycarbonate 1 linear bisphenol A polycarbonate with end groups based on phenol having a melt volume index 59-62 cm 3/10 min measured at 300 ° C and 1.2 kg load (ISO 1033) and a solution viscosity of about 1, 21 used.
  • This polycarbonate does not contain any additives such as UV stabilizers, mold release agents or thermal stabilizers with a proportion greater than 10 ppm.
  • the polycarbonate has a phenol content of 108 ppm, a bisphenol A content of 29 ppm, a diphenyl carbonate content of 500 ppm (each determined by means of reverse phase chromatography, as described below), a content of phenolic end groups of approx. 700 ppm (determined by means of IR spectroscopy, as described below).
  • This oligocarbonate does not contain any additives such as UV stabilizers, mold release agents or thermal stabilizers with a proportion greater than 10 ppm.
  • the oligocarbonate has a phenol content of 275 ppm, a bisphenol A content of 124 ppm and a diphenyl carbonate content of 533 ppm (determined by means of reverse phase chromatography, as described below).
  • the content of phenolic OH end groups is approx. 0.16% by weight (determined by means of IR spectroscopy, as described below).
  • the sample was dissolved in dichloromethane and then precipitated with acetone / methanol. After separating the precipitated polymer, the filtrate was concentrated. The residual monomers were quantified by reverse phase chromatography in acetonitrile. Detection was carried out using UV detectors.
  • the polycarbonate or oligocarbonate or polyester carbonate dissolved in dichloromethane (2g / 50 ml; 1mm quartz cuvette), was analyzed in the FT infrared spectrometer Nicolet iS 10 from Thermo Fisher Scientific. The content of phenolic OH end groups was determined by evaluating the band at wave number 3583 cm-1.
  • the glass transition temperature was measured by means of 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) as Turning point determined in the second heating process.
  • DSC dynamic differential calorimetry
  • the relative solution viscosity fh rc I was determined in dichloromethane at a concentration of 5 g / 1 at 25 ° C with an Ubbeloh viscometer. The determination was carried out according to DIN 51562-3; 1985-05. The throughput times of the polyester carbonate to be measured are measured by the Ubbelohde viscometer in order to then determine the viscosity difference between the polymer solution and its solvent.
  • the Ubbelohde viscometer is first calibrated by measuring the pure solvents dichloromethane, trichlorethylene and tetrachlorethylene (this takes place always at least 3 measurements, at most 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 mean value of the flow times is corrected using the Hagenbach correction and the relative solution viscosity is calculated. Determination of the glass transition temperature.
  • Example 2 comparative example; ratio of diacid to DPC 1: 1)
  • Step 1 47.0 g of oligocarbonate 1, 3 g (6% by weight) of sebacic acid (0.015 mol) and 3.18 g of diphenyl carbonate (0.015 mol) were placed in a flask with a short path separator together with 12.5 mg of TPP-P. The mixture was deoxygenated by evacuating and venting with nitrogen four times. The mixture was melted and heated to 280 ° C. with stirring. The pressure was reduced to 500 mbar; the temperature was increased to 300 ° C within 20 minutes. (Step 1)
  • Example 3 comparative example; ratio of diacid to DPC 1: 1.5
  • Example 4 comparative example; ratio of diacid to DPC 1: 2;
  • Example 5 (according to the invention; ratio of diacid to DPC 1: 1.25;)
  • Example 6 comparative example; ratio of diacid to DPC 1: 0;
  • Example 7 comparative example; ratio of diacid to DPC 1: 1;
  • Example 9 (according to the invention; ratio of diacid to DPC 1: 1.2;)
  • Example 10 (according to the invention; ratio of diacid to DPC 1: 1.25)
  • Example 11 (comparative example, analogous to example 1 of W001 / 48050A1)
  • Example 1 The low eta rel value in Example 1 shows that diacids cannot be incorporated into oligocarbonate oligomers, or only to a very inadequate extent, if no diaryl carbonate is added to the reaction. Despite the high reactivity of the oligocarbonate oligomer and despite the high OH end group content, no increase in molecular weight can be achieved. The experiment with polycarbonate (Example 6) shows the same result.
  • Examples 2 and 7 surprisingly show that a molar deficiency of diaryl carbonate to acid group equivalents leads to an oligo- or polyester carbonate with a high molecular weight. This is surprising since, in the light of EP1230288 (Examples 3 and 4), an at least equimolar ratio of diaryl carbonate to carboxylic acid equivalents is required in order to form the corresponding diaryl ester.
  • the oligo- or polyester carbonate of Examples 2 and 7 shows, however, that the content of phenolic OH groups is above 1300 ppm.
  • a high content of OH end groups can have a negative effect on the performance of poly (ester) carbonate. This can discolour through oxidation processes, e.g. during processing.
  • the presence of acid-OH groups can increase the susceptibility of the polymer to hydrolysis. It is therefore preferred that the polyester carbonate has the lowest possible OH end group contents; the OH end group content is preferably ⁇ 0.13% by weight.
  • Comparative example 11 shows that if no conditions are selected which are known to the person skilled in the art for melt transesterification (such as sufficient removal of the condensation product to shift the equilibrium, e.g. by applying a low pressure), there is insufficient molecular weight build-up - actually even a molecular weight degradation - to be observed.

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

Abstract

La présente invention concerne un procédé de préparation de carbonates de polyester par un procédé de transestérification à l'état fondu à partir de polycarbonates ou d'oligomères de polycarbonate. Le procédé concerne en particulier la préparation de carbonates de polyester dans un procédé d'extrusion réactive. Le procédé est caractérisé en ce que les carbonates de polyester préparés ont un profil de propriétés équilibré en termes de poids moléculaire, de température de transition vitreuse et de quantités résiduelles d'OH phénolique. L'invention concerne en outre l'utilisation des carbonates de polyester préparés selon l'invention.
EP20797519.4A 2019-11-07 2020-11-03 Procédé de préparation de carbonates de polyester Pending EP4055080A1 (fr)

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