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
  • 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
  • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
• • 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
  • C08G63/78—Preparation processes
  • C08G63/82—Preparation processes characterised by the catalyst used
  • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
• • 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
  • C08G64/04—Aromatic polycarbonates
• • 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
  • C08G64/307—General preparatory processes using carbonates and phenols

Definitions

• the present invention relates to a process for producing a polyester carbonate starting from aliphatic, preferably cycloaliphatic, diacids and aliphatic diols, the polyester carbonate itself produced by the process, a molding composition containing the polyester carbonate and molded articles containing the polyester carbonate.
• polyesters, polycarbonates and polyester carbonates have good mechanical properties, heat resistance and weathering resistance.
• the polymer group has certain key features that distinguish such materials.
• polycarbonates have good mechanical properties
• polyesters often have better properties
• polyester carbonates exhibit profiles of properties from both of the groups mentioned.
• Aromatic polycarbonates or polyesters often have a good profile of properties, but show weaknesses in terms of resistance to aging and weathering. For example, the absorption of UV light leads to yellowing and possibly embrittlement of these thermoplastic materials.
• aliphatic polycarbonates and polyester carbonates have better properties, in particular better aging and / or weathering resistance and better optical properties (for example transmission).
• cycloaliphatic alcohols are, for example, TCD alcohol (tricyclodecanedimethanol), cyclohexanediol, cyclohexanedimethanol and bio-based diols based on 1,4: 3,6-dianhydrohexitols such as isosorbide and the isomers isomannide and iosidide.
• cycloaliphatic acids such as 1,2, 1,3 or 1,4 cyclohexanedicarboxylic acids or corresponding naphthalene derivatives can also be used as (co) monomers.
• polyesters or polyester carbonates are then obtained. This application relates to the direct conversion of the raw materials, i.e., for example, of isosorbide and aliphatic, preferably cycloaliphatic, diacids to give the corresponding polyester carbonates.
• polyesters of cyclohexanedicarboxylic acid and isosorbide are described by Oh et al. in Macromolecules 2013, 46, 2930-2940.
• the present invention is preferably directed to polyester carbonates.
• Polyester carbonates are produced on an industrial scale, for example, by transesterification of corresponding ester-containing monomers with diols.
• the polyester is produced from 1,4-cyclohexanedimethanol and 1,4-cyclohecxanedicarboxylic acid starting from the dimethyl ester of the diacid (blend of this polyester and polycarbonate: Xyrex ® from DuPont).
• Example 1 of EP 3026074 A1 describes the direct reaction of the diacid with phenol to give the corresponding ester.
• example 2 of EP 3026074 A1 a dimethyl ester is reacted with phenol.
• the yield for both variants of the phenyl ester production can, however, still be improved.
• the polyester carbonate is then produced.
• EP 3248999 A1 describes the production of a diphenyl ester in a solvent and using phosgene. Since the subsequent reaction to form the aliphatic polyester carbonate does not require phosgene, the combination of a phosgene process with a transesterification process in one part of the plant is very disadvantageous. The method described in EP 3248999 A1 is therefore not optimal either.
• aromatic polyester carbonates are described, for example, in WO 01/32742 A1.
• a direct synthesis or also a one-pot synthesis is shown there, that is to say a synthesis in which all the structural elements which later make up the polyester carbonate are already present as monomers at the beginning of the synthesis.
• aromatic dihydroxy compounds such as bisphenol A, carboxylic acid diesters and aromatic or linear aliphatic diacids are used as monomers.
• temperatures of 300 ° C. can be used in the condensation reaction with removal of the phenol formed. The use of such temperatures is not possible in the production of aliphatic polyester carbonates, since aliphatic diols eliminate at this temperature load and / or tend to thermal decomposition.
• the present invention was therefore based on the object of providing a process for producing a polyester carbonate from aliphatic, preferably cycloaliphatic, diacids and aliphatic diols by means of melt transesterification, which is particularly simple and at the same time provides a polyester carbonate with a suitable molecular weight.
• “simple” is to be understood in particular as a process which is inexpensive in terms of apparatus, comprises a few stages, in particular purification stages, and / or is therefore economically and also ecologically advantageous.
• a suitable molar mass is understood to mean a polymer which has a relative solution viscosity of 1.17 to 1.35, preferably 1.18 to 1.32 and particularly preferably 1.20 to 1.31, each measured in dichloromethane at a concentration of 5 g / 1 at 25 ° C with an Ubbeloh viscometer.
• the person skilled in the art is familiar with the determination of 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 three times certainly. The mean value of the flow times is corrected using the Hagenbach correction and the relative solution viscosity is calculated.
• thermoplastic processability is only possible with difficulty. Too low a solution viscosity leads to inadequate mechanical and thermal properties.
• At least one, preferably all of the above-mentioned objects have been achieved by the present invention.
• the synthesis of a polyester carbonate from aliphatic, preferably cycloaliphatic, diacids and aliphatic diols by means of melt transesterification in a direct synthesis or one-pot synthesis, in which all structural elements making up the subsequent polyester carbonate are already present as monomers at the beginning of the synthesis, is possible .
• polyester carbonate The process for producing a polyester carbonate according to the invention can be described schematically, for example, by the reaction of cyclohexanedicarboxylic acid, isosorbide and diphenyl carbonate, as follows:
• step (ii) further condensation of the mixture obtained from process step (i) in the presence of the first and the second catalyst at least with removal of the chemical compound split off during the condensation, the first catalyst being at least one tertiary nitrogen base, wherein the second catalyst is at least one alkaline metal salt and wherein the proportion of alkali metal cations in process step (ii) is 0.0008 to 0.0030% by weight, based on all components used in process step (i).
• a method for producing a polyester carbonate by means of melt transesterification is likewise provided according to the invention, comprising the steps
• the proportion of alkali metal cations in process step (ii) according to the invention is preferably from 0.0009 to 0.0025% by weight and particularly preferably from 0.0010 to 0.0020% by weight, based in each case on all components used in process step (i).
• the first catalyst and the second catalyst are present in process step (i).
• the total amount of the first and / or the second catalyst is preferably used in process step (i). Most preferably, the total amount of both catalysts is used in process step (i).
• process step (i) at least one reaction of at least one linear aliphatic dicarboxylic acid and / or at least one cycloaliphatic dicarboxylic acid with at least one diaryl carbonate takes place.
• 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) cannot, however, according to the invention, be sharply separated from one another.
• the process according to the invention is referred to as direct synthesis or also one-pot synthesis, since in process step (i) all structural elements which later make up the polyester carbonate are already present as monomers.
• This preferably means that, according to the invention, all aliphatic dihydroxy compounds, all linear aliphatic and / or cycloaliphatic dicarboxylic acids and also all diaryl carbonates are present in this step, even if there is more than just one dihydroxy compound, linear aliphatic and / or cycloaliphatic Dicarboxylic acid and / or a diaryl carbonate is. It is therefore preferred according to the invention that all monomers which are condensed to the polyester carbonate in process step (ii) are already present during process step (i).
• the embodiment in which a small proportion of the at least one diaryl carbonate is additionally added in process step (ii) can also be included according to the invention. This can be used specifically to reduce the OH end group content of the resulting polyester carbonate. Such a procedure is described in JP2010077398 A, for example. In this case, however, it is necessary that the at least one diaryl carbonate added in small amounts in process step (ii) corresponds to the at least one diaryl carbonate present in process step (i) so that all structural elements which later make up the polyester carbonate are still present as monomers in process step (i) and no further structural elements are added. In this sense, one can still speak of a direct synthesis or one-pot synthesis.
• aromatic dihydroxy compounds and / or aromatic dicarboxylic acids are present in process step (i). However, these are preferably only present in small proportions. Particularly preferred in process step (i) are additionally up to 20 mol%, further preferably up to 10 mol% and very particularly preferably up to 5 mol% of an aromatic dihydroxy compound based on the total amount of substance of the dihydroxy compound used available. It is also particularly preferred that in process step (i) in addition, if appropriate in addition to the aromatic dihydroxy compound, up to 20 mol%, further preferably up to 10 mol% and very particularly preferably up to 5 mol% of an aromatic dicarboxylic acid is present in relation to the total amount of substance of the dicarboxylic acid used.
• aromatic dihydroxy compounds are preferably selected from the group consisting of bisphenol A, l, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxybiphenyl (DOD), 4, 4'-dihydroxybiphenyl ether (DOD ether), bisphenol B, bisphenol M, the bisphenols (I) to (III) where in these formulas (I) to (III) R 'each represents C1-C4-alkyl, aralkyl or aryl, preferably methyl or phenyl, very particularly preferably methyl.
• aromatic dicarboxylic acids are preferably selected from the group consisting of isophthalic acid, terephthalic acid, furandicarboxylic acid and 2,6-naphthalene dicarboxylic acid. It is known that small proportions of these aromatic diacids can reduce the water absorption of an aliphatic polyester carbonate.
• At least one aliphatic dihydroxy compound is used in process step (i).
• This at least one aliphatic dihydroxy compound is preferably selected from the group consisting of 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4- Cyclohexanedimethanol,
• the at least one aliphatic dihydroxy compound is very particularly preferably isosorbide.
• At least one linear aliphatic and / or at least one cycloaliphatic dicarboxylic acid is used in process step (i). At least one cycloaliphatic dicarboxylic acid is preferably used. At least one linear is also preferred aliphatic dicarboxylic acid used. A mixture of a linear aliphatic dicarboxylic acid and a cycloaliphatic dicarboxylic acid is also preferably used.
• the at least one linear aliphatic dicarboxylic acid and / or the at least one cycloaliphatic dicarboxylic acid is represented by the general formula (1): in which A stands for R3 or one of the formulas (Ia) or (Ib), where R 3 is furthermore preferred for a linear alkylene group having 3 to 16 carbon atoms, preferably 3 to 8 carbon atoms, particularly preferably 3 to 6 carbon atoms 3 or 4 carbon atoms and this alkylene group can optionally be mono- or polysubstituted or wherein
• Ri each independently represents a single bond or an alkylene group with 1 to
• R2 is in each case, independently of one another, an alkylene group having 1 to 10 carbon atoms, preferably 1 to 9 carbon atoms, particularly preferably 1 to 8 carbon atoms, also preferably a single bond or an alkylene group with 1 to 5 carbon atoms, particularly preferred is a single bond
• R2 is in each case, independently of one another, an alkylene group having 1 to 10 carbon atoms, preferably 1 to 9 carbon atoms, particularly preferably 1 to 8 carbon atoms
• n is a number between 0 and 3, preferably between 0 and 2, particularly preferably is between 0 and 1, very particularly preferably 1
• m is a number between 0 and 6, preferably between 0 and 3, particularly preferably between 0 and 2, very particularly preferably 0, and the “*” indicate the positions at which the carboxylic acid groups of the formula (1) are present.
• Ri represents a single bond
• Ri thus comprises zero carbon atoms.
• linear alkylene group or “linear (aliphatic) dicarboxylic acid” is used to distinguish it from a “cycloaliphatic alkylene group” or “cycloaliphatic dicarboxylic acid”.
• the linear variant does not contain any cycle.
• R 3 which represents a linear alkylene group, may optionally be substituted.
• the linear alkylene group can also be referred to in the broadest sense as “branched”.
• the term “linear alkylene group” preferably also includes “branched alkylene groups”. In no case do they contain cycles.
• R3 stands for a linear alkylene group with 3 to 16 carbon atoms, preferably 3 to 8 carbon atoms, particularly preferably 3 to 6 carbon atoms, furthermore preferably 3 or 4 carbon atoms, and this alkylene group can optionally be substituted one or more times.
• This alkylene group can preferably be substituted with at least one alkylene group, which preferably has 1 to 5 carbon atoms.
• the linear alkylene group is particularly preferably unsubstituted or substituted by at least one alkylene group which has 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms, particularly preferably 1 to 3 carbon atoms.
• the linear alkylene group R3 is particularly preferably unsubstituted or substituted by one to three alkylene groups. If there is more than one substitution, this can be present on one carbon atom (a quaternary carbon atom results) or also on several carbon atoms (two tertiary carbon atoms result) of the linear alkylene group R3.
• the linear alkylene group R3 is also preferably unsubstituted or substituted by one to three methyl groups.
• R 3 is very particularly preferably selected from -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 - CH 2 -
• R 3 is also preferred selected from -CH2-CH2-CH2-CH2-, -CH2-C (CH 3 ) 2-CH 2 -, -CH2-CH (CH 3 ) -CH2-C (CH 3 ) 2-, -CH 2 -C (CH 3 ) 2 -CH 2 -CH (CH 3 ) - and -CH (CH 3 ) -CH 2 -CH 2 -C (CH 3 ) 2 -.
• R 3 very particularly preferably represents -CH2-C (CH 3 ) 2-CH2- (3,3-dimethylglutaric acid).
• B each independently represents a Cfb group, O or S, preferably represents a Cfh group
• Ri in each case, independently of one another, represents a single bond or a linear alkylene group having 1 to 10 carbon atoms, particularly preferably a single bond, and
• R2 in each case, independently of one another, represents a linear alkylene group having 1 to 10 carbon atoms, preferably 1 to 9 carbon atoms, particularly preferably 1 to 8 carbon atoms, n is a number between 0 and 3, preferably between 0 and 2, particularly preferably between 0 and 1 , very particularly preferably 1, m is a number between 0 and 6, preferably between 0 and 3, particularly preferably between 0 and 2, very particularly preferably 0 and the “*” indicate the positions at which the carboxylic acid groups of the formula (1 ) available.
• the cycloaliphatic dicarboxylic acid is hydrogenated dimer fatty acid or a compound of the formula (Ha), (IIb) or mixtures thereof.
• Hydrogenated dimer fatty acids are known to those skilled in the art. In particular, it is known that it can be a mixture of different compounds. This mixture can also contain cycloaliphatic and linear compounds. According to the invention, these are encompassed by the use of at least one linear aliphatic dicarboxylic acid and at least one cycloaliphatic dicarboxylic acid.
• Hydrogenated dimer fatty acid is thus preferably used as the linear aliphatic and / or cycloaliphatic dicarboxylic acid according to the invention. It is preferred that the at least one cycloaliphatic dicarboxylic acid is selected from a compound of the chemical formula (Ha), (IIb) or mixtures thereof
• B each independently represents a carbon atom or a heteroatom selected from the group consisting of O and S, preferably a CH2 group or a heteroatom selected from the group consisting of O and S and n is a number between 0 and 3. It is further preferred that B stands for a carbon atom or O, preferably stands for a CH2 group or O and n is a number between 0 and 3, preferably 0 or 1.
• the at least one linear aliphatic dicarboxylic acid is selected from the group consisting of 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, 2,2,5-trimethyladipic acid and 3,3-dimethylglutaric acid. It is very particularly preferably 3,3-dimethylglutaric acid.
• the at least one cycloaliphatic dicarboxylic acid is selected from the group consisting of 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, tetradihydro-2,5-furandicarboxylic acid, tetradihydro-2,5 dimethyl furandicarboxylic acid, decahydro-2,4-naphthalenedicarboxylic acid, decahydro-2,5-naphthalenedicarboxylic acid, decahydro-2,6-naphthalenedicarboxylic acid, decahydro-2,7-naphthalenedicarboxylic acid and hydrogenated dimer fatty acid.
• the at least one cycloaliphatic dicarboxylic acid is selected from the group consisting of 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid,
• Tetradihydro-2,5-furandicarboxylic acid Tetradihydro-2,5-furandicarboxylic acid, tetradihydro-2,5-dimethyl-furandicarboxylic acid, decahydro-2,4-naphthalenedicarboxylic acid, decahydro-2,5-naphthalenedicarboxylic acid, decahydro-2,6-naphthalenedicarboxylic acid and decahydro-2,7-naphthalenedicarboxylic acid. Any mixtures can also be used. It is very particularly preferably 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid or 1,2-cyclohexanedicarboxylic acid.
• a mixture of a linear aliphatic dicarboxylic acid and a cycloaliphatic dicarboxylic acid is used.
• the at least one linear aliphatic dicarboxylic acid is selected from the group consisting of 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, 2,2,5-trimethyladipic acid and 3,3-dimethylglutaric acid and that the at least one cycloaliphatic dicarboxylic acid is selected from the group consisting of 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, tetradihydro-2,5-furandicarboxylic acid, tetradihydro-2,5-dimethyl-furandicarboxylic acid, decahydro-2,4-naphthalenedicarboxylic acid,
• Decahydro-2,5-naphthalene dicarboxylic acid decahydro-2,6-naphthalene dicarboxylic acid, decahydro-2,7-naphthalene dicarboxylic acid and hydrogenated dimer fatty acid.
• a mixture of 3,3-dimethylglutaric acid and 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid or 1,2-cyclohexanedicarboxylic acid is preferred.
• At least one diaryl carbonate is also used in process step (i) according to the invention.
• the at least one diaryl carbonate is selected from the group consisting of a compound of the formula (2) wherein R, R 'and R "can each independently be the same or different and represent hydrogen, optionally branched C1-C34 alkyl, C7-C34-alkylaryl, C6-C34-aryl, a nitro group, a carbonyl-containing group, a carboxyl -containing group or a halogen group.
• the at least one diaryl carbonate is preferably diphenyl carbonate, 4-tert-butylphenylphenyl carbonate, di- (4-tert-butylphenyl) carbonate, biphenyl-4-yl-phenyl- carbonate, di- (biphenyl-4-yl) carbonate, 4- (l -methyl- 1 -phenylethyl) -phenyl-phenyl-carbonate, di- [4- (1 -methyl-1-phenylethyl) -phenyl] - carbonate, bis (methylsalicyl) carbonate, bis (ethylsalicyl) carbonate, bis (propylsalicyl) carbonate, bis (2-benzoylphenyl carbonate),
• the at least one diaryl carbonate is particularly preferably diphenyl carbonate, 4-tert-butylphenyl phenyl carbonate, di- (4-tert-butylphenyl) carbonate, biphenyl-4-yl-phenyl carbonate, di- (biphenyl- 4-yl) carbonate, 4- (1-methyl-1-phenylethyl) -phenyl-phenyl-carbonate and / or di- [4- (1-methyl-1-phenylethyl) -phenyl] -carbonate.
• the at least one diaryl carbonate diphenyl carbonate is particularly preferred.
• a first catalyst and / or a second catalyst is present in process step (i).
• the first catalyst is a tertiary nitrogen base.
• This first catalyst is preferably selected from bases derived from guanidine, 4-dimethylaminopyridine (DMAP), 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene , 1,5,7-
• the first catalyst is more preferably selected from bases derived from guanidine, 4-dimethylaminopyridine (DMAP), 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene , l, 5,7-triazabicyclo [4.4.0] dec-5-ene.
• DMAP 4-dimethylaminopyridine
• 1,8-diazabicyclo [5.4.0] undec-7-ene 1,5-diazabicyclo [4.3.0] non-5-ene
• l 1,5-diazabicyclo [4.3.0] non-5-ene
• l 5,7-triazabicyclo [4.4.0] dec-5-ene.
• 4-Dimethylaminopyridine is particularly preferably used.
• the first catalyst is preferably used in an amount of 0.002 to 0.10% by weight, more preferably in an amount of 0.005 to 0.050% by weight, particularly preferably in an amount of 0.008 to 0.030% by weight, based in each case on all in process step (i) components used.
• the alkali metal cations contained in process step (ii) are preferably lithium cations, potassium cations, sodium cations, cesium cations and mixtures thereof.
• the second catalyst used is the organic or inorganic alkali or alkaline earth salt of a weak acid (pKa between 3 and 7 at 25 ° C).
• Suitable weak acids are, for example, carboxylic acids, preferably C2-C22 carboxylic acids, such as acetic acid, propionic acid, oleic acid, stearic acid, lauric acid, benzoic acid, 4-methoxybenzoic acid, 3-methylbenzoic acid, 4-tert.-butylbenzoic acid, p-toluene acetic acid, 4-hydroxybenzoic acid, salicylic acid Partial esters of polycarboxylic acids, such as monoesters of succinic acid, branched aliphatic carboxylic acids, such as 2,2-dimethylpropanoic acid, 2,2-dimethylpropanoic acid, 2,2-dimethylbutanoic acid, 2-ethylhexanoic acid.
• Suitable organic and inorganic salts are or are derived from sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, lithium carbonate, potassium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium oleate, lithium oleate, potassium oleate, sodium benzoate, potassium benzoate, lithium -, and dilithium salts of BPA.
• Learner can use calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate and corresponding oleates.
• Corresponding salts of phenols, in particular of phenol, can also be used. These salts can be used individually or in a mixture.
• the second catalyst is preferably selected from the group consisting of sodium hydroxide, lithium hydroxide, sodium phenolate, lithium phenolate, sodium benzoate, lithium benzoate, lithium chloride, lithium acetylacetonate and cesium carbonate and mixtures of these substances.
• Sodium phenolate, lithium phenolate, sodium hydroxide, lithium hydroxide, sodium benzoate, lithium benzoate, lithium chloride and / or lithium acetyl cetonate are particularly preferably used.
• Lithium chloride is preferably used as an aqueous solution, for example in the form of a 15% solution.
• the second catalyst is also preferably selected from the group consisting of sodium hydroxide, sodium phenolate, sodium benzoate and cesium carbonate and mixtures of these substances.
• Sodium phenolate, sodium hydroxide and / or sodium benzoate are particularly preferably used.
• Sodium benzoate is preferably used as an aqueous solution, for example in the form of a 15% solution.
• the molar ratio of all aliphatic dihydroxy compounds present in process step (i) to all cycloaliphatic dicarboxylic acids present in process step (i) before the reaction in process step (i) is preferably 1: 0.6 to 1: 0.05, more preferably 1: 0.5 to 1: 0.15 and very particularly preferably 1: 0.4 to 1: 0.2.
• the ratio of aliphatic dihydroxy compounds and cycloaliphatic dicarboxylic acids in the subsequent polyester carbonate should preferably not be too high (i.e. not too few cycloaliphatic dicarboxylic acids incorporated) in order to achieve particularly favorable mechanical properties, good chemical resistance and good processing properties.
• process step (i) preferably comprises at least one, particularly preferably all of the following steps (ia) to (ic):
• Step (ia) Melting of all components present in process step (i), i.e. at least the at least one linear aliphatic and / or at least one cycloaliphatic dicarboxylic acid, the at least one diaryl carbonate and the at least one aliphatic dihydroxy compound in the presence of the at least one catalyst. This is preferably done under a protective gas atmosphere, preferably under nitrogen and / or argon. Step (ia) is preferably carried out in the absence of a solvent.
• solvent is known to the person skilled in the art in this context. According to the invention, the term “solvent” is preferably understood to mean a compound which does not enter into a chemical reaction in any of process steps (i) and (ii).
• step (ib) heating the mixture, preferably the melt obtained from step (ia).
• Step (ia) and step (ib) can also overlap, since heating may also be necessary to generate a melt in step (ia).
• the heating is preferably carried out initially to 150.degree. C. to 180.degree.
• step (ic) Reaction of the mixture, preferably the mixture obtained from step (ib), with the introduction of mixing energy, preferably by stirring.
• step (ic) can overlap with step (ib), since the reaction of the mixture can already be initiated by heating.
• the melt is preferably already heated to temperatures between 150 and 180 ° C. by step (ib) under normal pressure. Depending on the selected catalyst, the temperature can be left in the range 160 - 200 ° C.
• the temperature in step (ic) is gradually increased - depending on the observed reactivity - to 200 ° C.-300 ° C., preferably 210-260 ° C., particularly preferably 215-240 ° C.
• the reactivity can be estimated from the gas evolution in a manner known to the person skilled in the art. In principle, higher temperatures are also possible in this step, but secondary reactions (e.g. discoloration) can occur at higher temperatures. Therefore, higher temperatures are less preferred.
• the mixture is stirred under normal pressure until the evolution of gas essentially stops. According to the invention, it is possible that under these conditions the aryl alcohol formed by the reaction of the at least one carboxylic acid with the at least one diaryl carbonate (for example phenol when using diphenyl carbonate) is also partially removed.
• the at least one dihydroxy compound had already entered into reactions at this point in time. It was thus possible to detect oligomers comprising carbonate units from the reaction of the at least one dihydroxy compound with the at least one diaryl carbonate and / or ester units from the reaction of the at least one dihydroxy compound with the at least one dicarboxylic acid.
• the reaction time in step (ic) depends on the amount of the starting materials.
• the reaction time of step (ic) is preferably between 0.5 h and 24 h, preferably between 0.75 h and 5 h and particularly preferably between 1 h and 3 h. It is preferred to choose the reaction time so that the evolution of gas has essentially subsided (see reaction scheme above).
• the molar ratio of the sum of all aliphatic dihydroxy compounds present in process step (i) and all linear aliphatic and / or cycloaliphatic dicarboxylic acids present in process step (i) to all diaryl carbonates present in process step (i) before the reaction in Process step (i) 1: 0.4 to 1: 1.6, preferably 1: 0.5 to 1: 1.5, furthermore preferably 1: 0.6 to 1: 1.4, particularly preferably 1: 0, 7 to 1: 1.3, particularly preferably 1: 0.8, to 1: 1.2 and very particularly preferably 1: 0.9 to 1: 1.1.
• the person skilled in the art is able to select appropriate optimally suitable ratios depending on the purity of the starting substances.
• process step (ii) the further condensation of the mixture obtained from process step (i) takes place at least with removal of the chemical compound split off during the condensation.
• the expression “further” condensation is to be understood as meaning that condensation has already taken place at least partially in process step (i). This is preferably the reaction of the at least one linear aliphatic and / or at least one cycloaliphatic dicarboxylic acid with the at least one diaryl carbonate with elimination of an aryl alcohol.
• a further condensation to give oligomers has preferably already taken place (see process step (i)).
• condensation is known to the person 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, one molecule of a chemically simple substance being split off. This compound split off during the condensation is removed in process step (ii). It is preferred here that the chemical compound split off during the condensation is removed in process step (ii) by means of a vacuum.
• the process according to the invention is characterized in that during the reaction in process step (i) the volatile constituents which have a boiling point below the cycloaliphatic diester formed in process step (i), the at least one aliphatic dihydroxy compound and below the have at least one diaryl carbonate, optionally separated off with gradual reduction of the pressure.
• a step-by-step separation is preferred if different volatile constituents are separated off.
• a step-by-step separation is also preferably chosen in order to ensure that the volatile constituent or constituents are separated off as completely as possible. With the fleeting ones Components are the chemical compound or compounds split off during condensation.
• a step-by-step lowering of the pressure can take place, for example, in such a way that as soon as the head temperature falls, the pressure is lowered in order to ensure continuous removal of the chemical compound split off during condensation.
• a pressure of 1 mbar, preferably ⁇ Imbar is reached, condensation continues until the desired viscosity is reached. This can be done, for example, by checking the torque, i.e. the polycondensation is stopped when the desired torque of the stirrer is reached.
• the condensation product is separated off in process step (ii) preferably at temperatures of 200.degree. C. to 280.degree. C., particularly preferably 210.degree. C. to 260.degree. C. and particularly preferably 220.degree. C. to 250.degree.
• the vacuum during the separation is preferably from 500 mbar to 0.01 mbar.
• the separation take place step-by-step by reducing the vacuum.
• the vacuum in the last stage is very particularly preferably 10 mbar to 0.01 mbar.
• a polyester carbonate is provided which is obtained by the above-described process according to the invention in all of the disclosed combinations and preferences.
• the polyester carbonate according to the invention can be processed as such into molded articles of all kinds. It can also be processed with other thermoplastics and / or polymer additives to form thermoplastic molding compounds.
• the molding compositions and moldings are further objects of the present invention.
• the polymer additives are preferably selected from the group consisting of flame retardants, antidripping agents, flame retardant synergists, smoke inhibitors, lubricants and mold release agents, nucleating agents, antistatic agents, conductivity additives, stabilizers (e.g. hydrolysis, heat aging and UV stabilizers, as well as transesterification inhibitors and phase inhibitors), flowability promoters Pigments, impact strength modifiers as well as fillers and reinforcing materials.
• flame retardants e.g. hydrolysis, heat aging and UV stabilizers, as well as transesterification inhibitors and phase inhibitors
• flowability promoters Pigments e.g. hydrolysis, heat aging and UV stabilizers, as well as transesterification inhibitors and phase inhibitors
• impact strength modifiers as well as fillers and reinforcing materials.
• thermoplastic molding compositions can be prepared, for example, by mixing the polyester carbonate and the other constituents in a known manner and melt-compounding and melt-extruding them at temperatures of preferably 200 ° C. to 320 ° C. in conventional units such as internal kneaders, extruders and twin-screw screws. This process is generally referred to as compounding in the context of this application.
• Molding compound is understood to mean the product that is obtained when the constituents of the composition are melt-compounded and melt-extruded.
• the moldings from the polyester carbonate according to the invention or the thermoplastic molding compositions containing the polyester carbonate can be produced, for example, by injection molding, extrusion and blow molding processes. Another form of processing is the production of moldings by deep drawing from previously produced sheets or foils.
• a method for producing a polyester carbonate by means of melt transesterification comprising the steps
• step (ii) further condensation of the mixture obtained from process step (i) in the presence of the first catalyst and the second catalyst at least with removal of the chemical compound split off during the condensation, the first catalyst being at least one tertiary nitrogen base, the second catalyst being at least one basic active alkali metal salt and wherein the proportion of alkali metal cations in process step (ii) is 0.0008 to 0.0030% by weight, based on all components used in process step (i).
• a process for producing a polyester carbonate by means of melt transesterification comprising the steps
• the at least one aliphatic dihydroxy compound is selected from the group consisting of 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2- Cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8, 10-tetraoxaspiro [5.5] undecane, 2.2 -to 4-
• this alkylene group can optionally be mono- or polysubstituted or wherein
• B each independently represents a CH2 group, O or S,
• Ri each independently represents a single bond or an alkylene group with 1 to 10 carbon atoms, preferably a single bond or an alkylene group with 1 to 9 carbon atoms, particularly preferably a single bond or an alkylene group with 1 to 8 carbon atoms, also preferred a single bond or an alkylene group having 1 to 5 carbon atoms, particularly preferably a single bond, and
• R2 is in each case, independently of one another, an alkylene group having 1 to 10 carbon atoms, preferably 1 to 9 carbon atoms, particularly preferably 1 to 8 carbon atoms, n is a number between 0 and 3, preferably between 0 and 2, particularly preferably between 0 and
• m is a number between 0 and 6, preferably between 0 and 3, particularly preferably between 0 and 2, very particularly preferably 0 and the “*” indicate the positions at which the carboxylic acid groups of the formula ( 1) are available. 4.
• R3 is selected from -CH2-
• B in each case, independently of one another, represents a carbon atom or a heteroatom which is selected from the group consisting of O and S, preferably a CH2 group or a heteroatom which is selected from the group consisting of O and S and n is a number between 0 and 3.
• the at least one cycloaliphatic dicarboxylic acid is selected from the group consisting of 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid,
• Decahydro-2,4-naphthalene dicarboxylic acid decahydro-2,5-naphthalene dicarboxylic acid, decahydro-2,6-naphthalene dicarboxylic acid, decahydro-2,7-naphthalene dicarboxylic acid and hydrogenated
• Dimer fatty acid 7.
• the at least one cycloaliphatic dicarboxylic acid is selected from the group consisting of 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,2-cyclohexanedicarboxylic acid and mixtures of these aliphatic dicarboxylic acids.
• R, R 'and R can each independently be the same or different and represent hydrogen, optionally branched C1-C34-alkyl, C7-C34-alkylaryl, C6-C34-aryl, a nitro group, a carbonyl-containing group, a carboxyl-containing group Group or a halogen group.
• the at least one diaryl carbonate is diphenyl carbonate.
• the first catalyst is selected from the group consisting of is selected from the group consisting of bases derived from guanidine, 4-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec -7-en (DBU), 1,5-diazabicyclo [4.3.0] non-5-en (DBN), 1,5,7-triazabicyclo [4.4.0] dec-5-en and mixtures of these substances.
• alkali metal cations in method step (ii) are selected from lithium cations, potassium cations, sodium cations, cesium cations and mixtures thereof.
• the second catalyst is selected from the group consisting of sodium phenolate, lithium phenolate, sodium hydroxide, lithium hydroxide, sodium benzoate, lithium benzoate and mixtures thereof, is preferably selected from the group consisting of sodium phenolate, sodium hydroxide, sodium benzoate and Mixtures of these.
• method step (ii) is carried out at temperatures in the range from 210 ° C to 280 ° C.
• Polyester carbonate obtainable by the process according to one of embodiments 0 to 22.
• Molding composition containing a polyester carbonate according to embodiment 23.
• Shaped body containing a polyester carbonate according to embodiment 23 Shaped body containing a polyester carbonate according to embodiment 23.
• Cyclohexanedicarboxylic acid 1,4-cyclohexanedicarboxylic acid; CAS 1076-97-799%; Tokyo Chemical Industries, Japan, abbreviated as CHDA.
• the CHDA contained less than 1 ppm sodium by elemental analysis
• Diphenyl carbonate Diphenyl carbonate, 99.5%, CAS 102-09-0; Acros Organics, Geel, Belgium, abbreviated as DPC
• Isosorbide Isosorbide (CAS: 652-67-5), 99.8%, Polysorb PS A; Roquette Freres (62136 Lestrem, France); abbreviated as ISB
• 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 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 difference in viscosity between the polymer solution and its solvent. To do this, the Ubbelohde viscometer is first calibrated by measuring the pure solvents dichloromethane, trichlorethylene and tetrachlorethylene (at least 3 measurements, at most 9 measurements, are always carried out).
• 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.
• Example 1 10 ppm Na 17.20 g (0.10 mol) 1,4-cyclohexanedicarboxylic acid and 29.83 g (0.204 mol) isosorbide and 64.30 g (0.3 mol) diphenyl carbonate, 0.0111 g DMAP (4-dimethylaminopyridine; 100 ppm based on the starting materials CHDA, DPC and ISB) and 50.2 ⁇ l of an aqueous solution of sodium benzoate (141.4 g / l), corresponding to approx. 10 ppm Na, were placed in a flask with a short path separator. The mixture was freed of oxygen by evacuating and venting 4 times with nitrogen.
• the mixture was melted and heated to 160 ° C. under normal pressure with stirring. The mixture was stirred at 160 ° C. for 50 minutes, at 175 ° C. for 50 minutes, at 190 ° C. for 30 minutes and at 205 ° C. for 50 minutes. In the process, carbon dioxide develops continuously. After the evolution of CO2 has ceased, the bath temperature is set to 220 ° C. After a further 20 minutes, a vacuum is applied. The pressure is reduced to 10 mbar within 30 minutes.
• Phenol is continuously removed in the process.
• the mixture is stirred at 10 mbar for about 10 minutes.
• the pressure is lowered to ⁇ Imbar (approx. 0.7 mbar) and condensation is continued for a further 10 minutes. The approach was then stopped.
• Examples 1 to 4 show that the inventive process provides the desired polyester carbonates in the desired viscosity window. If the content of alkali ions is too low - as shown in Comparative Examples 1 and 2 - only an insufficient increase in molecular weight can be achieved. If the alkali content is too high - as shown in Comparative Example 3 - viscosities result which can practically no longer be processed. If only one catalyst is used (comparative example 4), the viscosity obtained is again too low.
• Example 4 103.2 g (0.60 moles) 1,4-cyclohexanedicarboxylic acid and 176.35 g (1.206 moles) isosorbide and 385.8 g
• phase 2 the condensation phase (phase 2) is initiated (if at this point in time a development of CO2 can still be observed, it is waited until it ceases; at this point in time 100 ppm DMAP can be added again - this is necessary, should this catalyst must have been completely removed in the first stage - this can be noticed by a slow polycondensation phase).
• the pressure is set to 140 mbar and the bath temperature to 105 ° C.
• the pressure is reduced to 70 mbar within 15 minutes.
• the pressure is reduced to imbar within 50 minutes and the bath temperature is raised to 240.degree.
• the mixture is stirred at 1 mbar and 240 ° C. for a further 20 minutes. If the melt pulls up on the stirrer, it is removed from the stirrer and returned to the melt. To do this, the approach must be ventilated for a short time. A light brown polycondensate with an eta rel of 1.32 is obtained.
• Example 4 shows that the reaction time in phase 1 can be significantly reduced by means of the process according to the invention by means of vacuum. Despite the higher quantities used, phase 1 could be shortened significantly.
• Example 5 3,3-dimethylglutaric acid
• the temperature was then gradually increased to 225 ° C over 1.5 hours. elevated.
• the pressure was reduced to 500 mbar within 30 minutes. Phenol was continuously removed.
• the temperature was increased to 235 ° C. and the pressure was slowly reduced to 0.1 mbar over the course of 2 hours. After stirring for 10 minutes at 235 ° C. and 0.1 mbar, the reaction was terminated and the melt was removed.
• a light-colored polymer melt with a solution viscosity of 1.256 and a glass transition temperature of 121 ° C. was obtained.
• the temperature was increased to 175 ° C. and stirring was carried out for 75 minutes at this temperature. Then another 100 ppm (0.0111 g) DMAP were added and the mixture was stirred at 175 ° C. for a further 30 minutes. After the evolution of gas had ceased, the temperature was gradually increased to 220 ° C. over the course of 1.5 hours. Phenol was continuously removed. The temperature was then increased to 230 ° C. and the pressure was gradually reduced to 1 mbar over the course of 1 hour. The mixture was stirred for a further 10 minutes at 1 mbar and the melt was then removed.
• a light-colored polymer melt with a solution viscosity of approximately 1.24 was obtained.
• Examples 5 and 6 show that linear aliphatic dicarboxylic acids and also mixtures of linear aliphatic dicarboxylic acids with cycloaliphatic dicarboxylic acids give a polyester carbonate with the desired and processable viscosities.

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