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WO2025068165A1 - Copoly(ester) carbonate stable contre des milieux aqueux et d'autres produits chimiques et ayant une bonne aptitude au traitement - Google Patents

Copoly(ester) carbonate stable contre des milieux aqueux et d'autres produits chimiques et ayant une bonne aptitude au traitement Download PDF

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Publication number
WO2025068165A1
WO2025068165A1 PCT/EP2024/076755 EP2024076755W WO2025068165A1 WO 2025068165 A1 WO2025068165 A1 WO 2025068165A1 EP 2024076755 W EP2024076755 W EP 2024076755W WO 2025068165 A1 WO2025068165 A1 WO 2025068165A1
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Prior art keywords
ester
copoly
mol
units
carbonate
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German (de)
English (en)
Inventor
Alexander Meyer
Lukas Fabian KOLAROV
Ulrich Liesenfelder
Anton DE VYLDER
Annabelle Bertin
Paulus Franciscus Anna Buijsen
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Covestro Deutschland AG
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Covestro Deutschland AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G64/305—General preparatory processes using carbonates and alcohols

Definitions

  • the present invention relates to a copoly(ester)carbonate composed of defined units (A), (B), and (C) in defined proportions. This structure and proportions result in the copoly(ester)carbonate exhibiting excellent stability in aqueous media and also against other chemicals such as rapeseed oil, lipid solutions, or organic solvents.
  • the present invention also relates to a composition comprising the copoly(ester)carbonate according to the invention, a molded part comprising the copoly(ester)carbonate according to the invention, and a process for producing the copoly(ester)carbonate according to the invention.
  • Polyesters, polycarbonates, and polyestercarbonates are known to exhibit good mechanical properties, heat resistance, and weathering resistance. Each polymer group exhibits certain key characteristics, depending on the monomers used, that distinguish such materials. Polycarbonates, in particular, exhibit good mechanical properties, whereas polyesters often exhibit better chemical resistance. Depending on the monomers selected, polyestercarbonates exhibit property profiles from both of these groups. Depending on the reactants, (co)polycarbonates, (co)polyesters, or copoly(ester)carbonates can be formed.
  • aromatic polycarbonates or polyesters While aromatic polycarbonates or polyesters often exhibit a good property profile, they exhibit weaknesses in terms of aging and weathering resistance. For example, UV light absorption leads to yellowing and possibly embrittlement of these thermoplastic materials. Aliphatic polycarbonates and polyestercarbonates exhibit better properties in this regard, particularly better aging and/or weathering resistance, as well as better optical properties (e.g., transmission).
  • the disadvantage of aliphatic polycarbonates or polyestercarbonates is often their low glass transition temperature. Therefore, it is advantageous to use cycloaliphatic alcohols as (co)monomers, as these can generally slightly increase the glass transition temperatures.
  • polyesters obtained by the reaction of cyclohexanedicarboxylic acid and isosorbide are described by Oh et al. in Macromolecules 2013, 46, 2930-2940.
  • these polymers have the disadvantage of interacting with hot water.
  • Such polymers absorb water and swell. This drastically changes the polymer morphology. For example, transparency is completely lost. This drastically limits the potential uses of such polyesters.
  • Im et al. showed that the aforementioned polyesters made from cyclohexanedicarboxylic acid and isosorbide exhibit structural deformations upon contact with hot water (Im et al, RSC Adv.
  • Terephthalic acid-based polyesters are known to exhibit high stability against water and hydrolysis.
  • Duchateau et al. in Biomacromolecules, 2008, 9, 3090-3097 Incorporation of Isosorbide into Poly(butylene terephthalate via solid state polymerization)
  • polyesters made from isosorbide, terephthalic acid, and other diols lack thermal stability.
  • Such polyesters exhibit significant weight loss in TGA measurements below 300 °C.
  • thermal stability is of great importance for conventional polycarbonate applications.
  • systems containing aromatic monomers are not sufficiently resistant to UV radiation.
  • Polycarbonates made from isosorbide and cyclic diols are described in EP2033981. These polycarbonates exhibit good mechanical properties, but sometimes limited stability against aqueous media (see comparative examples of the present invention). Furthermore, they exhibit glass transition temperatures above 100°C. However, to achieve good mechanical properties, a certain proportion of cyclic diol from fossil raw materials is necessary. This proportion is usually greater than 20%, which reduces the proportion of bio-based monomers in the polymer backbone. Furthermore, these aliphatic polycarbonates cannot be processed at high temperatures without decomposition. Thus, these special aromatic polycarbonates cannot be processed and used like conventional polycarbonates. Typically, processing temperatures for conventional aromatic polycarbonates in injection molding are approximately 150°C above the glass transition temperature.
  • the glass transition temperature is approximately 120 °C, meaning the processing temperature is relatively close to the decomposition range. This illustrates that this Polymers are limited in terms of processing in addition to their lack of resistance to solvents and other chemicals.
  • Polyesters made from isosorbide, terephthalic acid, and other monomers such as cyclohexanedimethanol are described in EP2478031. These materials are extremely stable in aqueous media. However, these polyesters contain aromatic dicarboxylic acids—particularly terephthalic acid. Here, too, the use of aromatic structural units makes such materials unsuitable for outdoor use without appropriate protection, such as a coating.
  • Copolycarbonates and copolyestercarbonates made from isosorbide and long-chain aliphatic diols or acids are known. These are described, for example, by Kamps et al. in Macromolecules, 2019, 52, 3187, as well as in US8273849 and EP2203501. However, these often have the disadvantage of only limited transparency. They are usually cloudy or opaque. Furthermore, it has been shown that these polymers have a high melt viscosity (see comparative examples of the present invention). However, a high melt viscosity is disadvantageous with regard to processability.
  • a high melt viscosity is disadvantageous because aliphatic polycarbonates or polyestercarbonates do not have the high processing temperatures of the corresponding aromatic polycarbonates and polyestercarbonates.
  • Non-transparent or highly opaque materials have limited or no use for optical applications such as lighting or pharmaceutical applications, such as in Luer lock fittings, stopcocks, and other IV connectors. This makes it impossible to simply serve traditional applications of aromatic polycarbonates with such aliphatic polymers.
  • such polymers exhibit lower surface hardness (see comparative examples of the present invention). This makes them prone to scratching and cannot be used in unpainted outdoor applications.
  • EP2840102 describes polymers with low water absorption, good heat resistance, and low-temperature toughness. These polycarbonates or copoly(ester)carbonates contain blocks of certain oligocarbonates made from diols or certain blocks made from oligoesters. Polyestercarbonates with long-chain diols or diacids with more than 12 carbon atoms are not specifically described. Properties such as behavior during storage in hot water are not discussed.
  • Example 19 of EP2840102 describes an isosorbide-containing copoly(ester)carbonate containing an ester block made from terephthalic acid and cyclohexanedimethanol. However, the polymer only has a low proportion ( ⁇ 50 mol%) of bio-based monomers (isosorbide) and a low glass transition temperature (approx. 100 °C).
  • the present invention was therefore based on the object of remedying at least one, preferably several, of the disadvantages described above.
  • the invention was based on the object of providing a polymer structure that exhibits high stability against water, in particular hot water.
  • the polymer structures should be intrinsically weather-stable, in particular intrinsically UV-resistant, and thus suitable for outdoor applications.
  • a polymer structure should be provided that exhibits high scratch resistance.
  • the polymer structure should preferably simultaneously exhibit high resistance to chemicals such as solvents and/or lipid solutions and particularly preferably simultaneously exhibit high grease resistance, in particular rapeseed oil resistance.
  • the provided polymer structure should preferably simultaneously exhibit high hot water resistance, good grease resistance, and good processability, particularly preferably processability comparable to classic aromatic polycarbonates (e.g., based on bisphenol A), and high scratch resistance.
  • the polymer structure should simultaneously be intrinsically weather-stable.
  • a preferred object of the present invention was to provide a polymer structure that has good thermal stability.
  • it was an object to achieve thermal stability comparable to that of conventional aromatic polycarbonates.
  • it was an aim to provide polymer structures that can serve the same range of applications as conventional polycarbonates.
  • the polymer structure should preferably simultaneously have high glass transition temperatures, in particular of over 110 °C, preferably of over 120 °C.
  • the polymer structures have a sufficiently high molecular weight in order to exhibit corresponding mechanical properties, in particular ductility in an unnotched impact test at room temperature.
  • a polymer with a sufficiently high molecular weight is understood to mean a polymer which has a relative solution viscosity above 1.20, preferably 1.21 to 1.65, more preferably 1.22 to 1.63, particularly preferably from 1.23 to 1.62 and very particularly preferably from 1.26 to 1.55, each measured in dichloromethane at a concentration of 5 g/l at 25 °C using an Ubbelohde viscometer.
  • polyester carbonates or polycarbonates obtained from 1,4:3,6-dianhydrohexitol, specific cycloaliphatic diols, especially TCD-dimethanol, and long-chain diols or long-chain dicarboxylic acids fulfill at least one, preferably all, of the above-mentioned objects.
  • a copoly(ester)carbonate containing the units (A), (B), (C), optionally (D) and optionally units other than (A), (B), (C) and (D), where each r and each s independently represents a number between 0 and 4, and each R 1 independently represents a structure of the formulas (RIA), (RIB), (R1C) or (R1D) where a is 0 or 1, marked positions in formulas (RIA) to (RID) are the positions at which the (CH2) r group or (CH2)s group shown in formula (B) is located, and
  • the polymer structure according to the invention can achieve good property profiles even with predominantly aliphatic building blocks.
  • aliphatic polyesters or copoly(ester)carbonates which are amorphous, lack stability against water.
  • polyesters consisting of aromatic building blocks, such as terephthalic acid, with regard to the acid component are usually stable against water.
  • the polymer structure according to the invention surprisingly provides copoly(ester)carbonates which exhibit both good stability against water, preferably hot water stability, and good grease resistance, as well as good resistance to lipid solutions and organic solvents, with good processability and good UV and weathering stability.
  • the copoly(ester)carbonates according to the invention exhibit improved surface hardness compared to polycarbonates based on bisphenol A and also compared to prior art structures. This offers the particular advantage that the polymers according to the invention are suitable for outdoor applications. This is especially true without the need for additional coating, since their scratch resistance is high. This is particularly surprising since copoly(ester)carbonates with the same monomer units but different proportions of these monomer units do not exhibit these properties. Likewise, copoly(ester)carbonates containing one less unit of the defined units (A), (B), and (C) also do not exhibit this property profile.
  • the above-mentioned property profile of the copoly(ester)carbonates according to the invention means that they can be used, for example, in the pharmaceutical sector (contact with aggressive pharmaceuticals).
  • they are essentially composed of aliphatic building blocks, they have high glass transition temperatures of at least 110 °C, preferably 120 °C.
  • they also have good processability. They have a melt viscosity such that they can be easily processed, for example by injection molding, without decomposition (due to their good thermal stability). This makes them almost as processable as classic aromatic polycarbonates and thus at least the classic areas of application for classic aromatic polycarbonates can be served.
  • the copoly(ester)carbonates according to the invention can also have a high proportion of bio-based monomers, since at least units (A) and (C) can be obtained from bio-based monomers.
  • the copoly(ester)carbonates of the invention have such a high molecular weight that the resulting mechanical properties are sufficient, e.g., they exhibit ductility in an unnotched impact test at room temperature.
  • the copoly(ester)carbonates of the invention can also be produced using processes that do not require the handling of challenging feedstocks, particularly phosgene. This also makes the copoly(ester)carbonates of the invention and their production process advantageous from both an ecological and economic perspective.
  • the invention relates to "copoly(ester)carbonates.”
  • the brackets are preferably to be understood as meaning that the invention encompasses “copolycarbonates or copolyestercarbonates.”
  • the skilled person is able to recognize when the polymer of the invention contains ester groups or not. This depends in particular on whether both "t"s in unit (C) are 1 (in which case a polycarbonate is formed) or 0 (in which case a copolyestercarbonate is formed).
  • the copoly(ester)carbonate according to the invention comprises the unit (A), with where the positions marked with # and * are the positions with which the unit (A) is incorporated into the copoly(ester)carbonate.
  • formula (A) is represented by formula (A*) with where n represents the average number of repeat units, and the positions marked with # and * have the meanings given for (A).
  • n is greater than 1.
  • n is greater than 1 to 200, and especially preferably, n is greater than 1 to 100.
  • unit (A) can also be present as a block of several directly linked units (A).
  • the copoly(ester)carbonate according to the invention particularly preferably has direct links between at least two units (A).
  • the term "average number of repeating units" is known to those skilled in the art. The skilled person knows how to determine this parameter.
  • this parameter can be determined using Maldi-TOF, GPC and/or 'FI-NMR and/or 13 C-NMR.
  • the "end groups" of possible blocks i.e., preferably, if a block is present with direct links of the same units, this block has end groups at the beginning and end which have direct links to units that are different from the units under consideration) can provide information about the average number of repeating units.
  • repeating units i.e., preferably of a block of identical units
  • This number also differs from polymer chain to polymer chain. This results in an "average" number of repeating units.
  • the skilled person is aware that the average number of repeating units can be influenced by the molar ratios of the individual structures to one another. Thus, a structure present at a high molar percentage in the copoly(ester)carbonate of the invention is more likely to be bonded to another structure of the same type than a structure present only at a low molar percentage.
  • (A) or (A*) is selected from at least one of the structures (A1), (A2) and (A3), where , where the positions marked with # and * have the meanings given for (A) and corresponding brackets are present for formula (A*).
  • Very particular preference is given to (A) or (A*) being represented by formula (A1) (if appropriate with corresponding brackets for formula (A*)). It will be apparent to the person skilled in the art that these units are derived from/formed from 1,4:3,6-dianhydrohexitols.
  • 1,4:3,6-dianhydrohexitols are generally selected from the group consisting of isomannide, isoidide, and isosorbide.
  • This can be a bio-based structural element, which entails all the advantages of a bio-based monomer and the resulting polymer (e.g., better sustainability, as it is obtainable from renewable raw materials).
  • Unit (A) or (A*) particularly preferably consists of unit (A1). Very particular preference is given to unit (A) or (A*) being bio-based.
  • the copoly(ester)carbonate according to the invention comprises the unit (B), wherein where each r and each s independently represents a number between 0 and 4, preferably between 0 and 3, more preferably between 0 and 2, most preferably 0 or 1, and each R 1 independently represents a structure of the formulas (RIA), (R1B), (R1C) or (R1D) where a is 0 or 1, preferably 0, where b is 0 or 1, preferably 0, , w
  • the positions marked in the formulas (RIA) to (RID) are the positions at which the (CH2) r group or (CH2) S group shown in formula (B) is located, and the positions marked with # and * are the positions at which the unit (B) is incorporated into the copoly(ester)carbonate.
  • unit (B) more than one of the units (RIA), (RIB), (R1C) or (R1D) can be present.
  • unit (B) is represented by formula (B*) with
  • unit (B*) where m represents the average number of repeating units, and the positions marked with # and * have the meanings given for (B). This is particularly preferred if unit (A) also represents unit (A*).
  • m is greater than 1. Very particularly preferably, m is greater than 1 to 80, especially preferably, m is greater than 1 to 50, and very particularly preferably, m is greater than 1 to 10.
  • each r and each s independently represents a number between 0 and 2, most preferably 0 or 1, and each R 1 independently represents a structure of the formula (RIA).
  • r and s in the formulas (B) and (B*) are 1 and R 1 in the formulas (B) and (B*) represents the structure of the formula (RIA).
  • unit (B) or (B*) is represented by the unit (B1), where (Bl), where the ones marked with # and *
  • unit (B) consists of unit (B1).
  • this unit (B1) is a unit derived from TCD-dimethanol (also referred to as TCD-alcohol, tricyclodecanedimethanol, or [8-(hydroxymethyl)-3-tricyclo[5.2.1.02,6]decanyl]methanol).
  • TCD-dimethanol is generally present as an isomer mixture. Up to 32 isomers are possible. Depending on the reaction conditions of the polymerization, the initial number and/or types of isomers in the monomer can also change in the resulting polymer.
  • unit (B1) is obtained from a mass-balanced TCD-dimethanol. This has the particular advantage that the CCE footprint of the copoly(ester)carbonate according to the invention can thus be reduced.
  • the copoly(ester)carbonate according to the invention further comprises the unit (C), wherein where both t are independently of R 2 simultaneously either 0 or 1 and each R 2 independently represents an aliphatic group having 16 to 44 carbon atoms, which optionally contains one or more double bonds and where the radicals denoted by # and the positions marked with * are the positions with which the unit (C) is incorporated into the copoly(ester)carbonate.
  • each R 2 independently represents an aliphatic group having 17 to 44 carbon atoms, particularly preferably having 18 to 44 carbon atoms, particularly preferably having 19 to 44 carbon atoms, particularly preferably having 20 to 44 carbon atoms, particularly preferably having 21 to 44 carbon atoms, particularly preferably having 22 to 43 carbon atoms, particularly preferably having 23 to 42 carbon atoms, particularly preferably having 24 to 41 carbon atoms, particularly preferably having 25 to 40 carbon atoms, particularly preferably having 26 to 39 carbon atoms, particularly preferably having 27 to 38 carbon atoms, particularly preferably having 28 to 37 carbon atoms, particularly preferably having 29 to 37 carbon atoms, particularly preferably having 30 to 37 carbon atoms, particularly preferably having 31 to 37 carbon atoms, particularly preferably having 32 to 37 carbon atoms and very particularly preferably having 33 to 37 carbon atoms.
  • aliphatic refers to a hydrocarbon group which does not contain any aromatic units. However, this group may contain one or more double bonds. In addition, this group may contain one or more rings. These rings may be condensed with one another (i.e., for example, one or more carbon atoms may belong to two rings) or be linked to one another by, for example, alkylene groups or alkylidene groups. This one or more rings may contain one or more double bonds.
  • aromatic rings are not encompassed by the definition of "aliphatic”.
  • the one or more rings or the aliphatic group itself may be interrupted by one or more heteroatoms. However, this is less preferred.
  • alkyl or “alkyl group” preferably refers, unless otherwise stated, to an alkane structure from which a hydrogen atom has been removed.
  • the alkyl group according to the present invention can be linear or branched. It is saturated and therefore comprises only single bonds between the adjacent carbon atoms.
  • the alkyl group preferably comprises methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1- Dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-eth
  • alkylene or “alkylene group” preferably refers, unless otherwise stated, to a bridging alkane structure from which two hydrogen atoms have been removed from different carbon atoms.
  • the two hydrogen atoms removed from the two carbon atoms can be removed from any carbon atoms in the alkane structure. This means that the two carbon atoms can be adjacent, but do not necessarily have to be adjacent.
  • An alkylene group can be linear or branched. It is saturated. If the alkylene group comprises only one carbon atom, it is a methylene group (-CH2-), which is linked to the rest of the molecule via two single bonds.
  • the alkylene group preferably comprises methylene, ethylene, n-propylene, iso-propylene, n-butylene, sec-butylene, tert-butylene, n-pentylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, neopentylene, 1-ethylpropylene, n-hexylene, 1,1-dimethylpropylene, 1,2-dimethylpropylene, 1,2-dimethylpropylene, 1-methylpentylene, 2-methylpentylene, 3-methylpentylene, 4-methylpentylene, 1,1-dimethylbutylene, 1,2-dimethylbutylene, 1,3-dimethylbutylene, 2,2-dimethylbutylene, 2,3-dimethylbutylene, 3,3-dimethylbutylene, 1-ethylbutylene, 2-ethylbutylene, 1,1,2-trimethylpropylene, 1,2,2-trimethylpropylene, 1-eth
  • alkylene group according to the present invention may optionally contain at least one carbonyl group, optionally contain at least one halogen atom, and/or optionally be interrupted by at least one heteroatom.
  • the aforementioned structures are less preferred according to the invention.
  • the term "cycloalkylene group" is also used according to the invention. The above statements apply here with the addition that the group can additionally have one or more cycles.
  • cycles can be condensed with one another (i.e., for example, one or more carbon atoms can belong to two cycles) or by
  • alkylene groups can be linked together.
  • This one or more rings can have one or more double bonds.
  • the one or more rings or the aliphatic group itself can be interrupted by one or more heteroatoms. However, this is less preferred.
  • alkylidene or “alkylidene group” preferably refers, unless otherwise stated, to a bridging alkane structure in which two hydrogen atoms have been removed from the same carbon atom.
  • the alkylidene group optionally comprises at least one carbon-carbon double bond, optionally at least one carbonyl group, and/or optionally at least one halogen atom.
  • the alkylidene group comprises isopropylidene, n-propylidene, isoheptylidene, and the like.
  • aralkyl preferably refers, unless otherwise stated, in each case independently of one another, to a linear, cyclic, or branched alkyl group which is mono-, di-, or polysubstituted by aryl radicals.
  • aryl preferably refers, unless otherwise stated, to an aromatic hydrocarbon radical. Examples of “aryl” are phenyl, o-, p-, and m-toluyl, naphthalene, phenanthryl, or anthranyl.
  • alkoxy or “alkoxy group” preferably refers, unless otherwise stated, to a linear, cyclic, or branched alkyl group that is singly bonded to an oxygen atom (-OR).
  • Alkoxy groups according to the present invention preferably have 1 to 6 carbon atoms.
  • Alkoxy groups particularly preferably include methoxy, ethoxy, ⁇ -propoxy, iso-propoxy, n-butoxy, and sec-butoxy.
  • R 2 in the formula (C) is represented by the following formula (R2A) with
  • R 11 CH ' 3 R2A
  • Y represents a bridging structure selected from the group consisting of an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms, and a cycloalkylene group having 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms, where the cycloalkylene group optionally contains one or more double bonds and/or is optionally condensed to one or more further cycloalkylene groups, where the one or more further cycloalkylene groups optionally each have one or more double bonds, where the R 11 groups adjacent to the bridging structure are bonded to any position of the bridging structure, and where each R 11 independently represents an alkylene group having 1 to 12 carbon atoms or an alkylidene group having 1 to 12 carbon atoms, with the proviso that the structure of formula (R2A) 16 to 44 carbon atoms and wherein the positions marked with , in the formula (R2A) are the positions at which
  • the formula (R2A) is represented by one of the formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad), with where each R 11 and each has the meanings given for (R2A), the cycle of formula (R2Ac) optionally has one or two double bonds, and each cycle of formula (R2Ad) independently of one another optionally contains one or two double bonds.
  • R2 in formula (C) is represented by a mixture of at least two different formulas (R2Aa), (R2Ab), (R2Ac), and (R2Ad). This also includes mixtures of different groups which, however, fall under the same formula (i.e., for example, two groups which fall under the formula (R2Aa)).
  • the cycles of the formulas (R2Ac) and/or (R2Ad) can each have one or two double bonds. This generally does not involve the formation of an aromatic ring.
  • R2 in formula (C) comprises a mixture of at least two different formulas (R2Aa), (R2Ab), (R2Ac), and (R2Ad), it may also contain small amounts of aromatic bridging structures Y according to formula (R2A). However, this is less preferred.
  • each R 11 in the formula (R2A) and/or in the formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad) independently of one another represents an alkylene group having 1 to 10 carbon atoms, with the proviso that the structure of the formula (R2A) and/or in the formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad) comprises 16 to 44 carbon atoms.
  • the group described by R 2 , (R2A), (R2Aa), (R2Ab), (R2Ac) and/or (R2Ad) in the unit (C) has 21 to 44 carbon atoms. It is preferred that the group described by R 2 , (R2A), (R2Aa), (R2Ab), (R2Ac) and/or (R2Ad) in the unit (C) has 17 to 44 carbon atoms, particularly preferably 18 to 44 carbon atoms, particularly preferably 19 to 44 carbon atoms, particularly preferably 20 to 44 carbon atoms, particularly preferably 21 to 44 carbon atoms, particularly preferably 22 to 43 carbon atoms, particularly preferably 23 to 42 carbon atoms, particularly preferably 24 to 41 carbon atoms, particularly preferably 25 to 40 carbon atoms, particularly preferably 26 to 39 carbon atoms, particularly preferably 27 to 38 carbon atoms, particularly preferably 28 to 37 carbon atoms, particularly preferably 29 to 37 carbon atoms, particularly preferably 30 to 37
  • R 11 in the formula (R2A) and/or in the formulas (R2Aa), (R2Ab), (R2Ac) or (R2Ad) comprise a different number of carbon atoms.
  • the unit (C) according to the invention is very particularly preferably obtained by condensing dimer fatty acid and/or a dimer diol obtained by reducing dimer fatty acid.
  • dimer fatty acid is a mixture of different acids.
  • Dimer fatty acids are generally a mixture. They are produced by condensing various unsaturated fatty acids. A fatty acid with conjugated double bonds (conjuenic acid) is reacted with other unsaturated fatty acids. Conjugated linoleic acids are particularly preferred for this purpose. The reaction usually takes place via Diels-Alder addition, forming a partially unsaturated C6 ring. Thus, dimer fatty acids initially comprise at least some of one or more double bonds. In addition to the dimer, the mixture of dimer fatty acids can also comprise trimers and monomers of the fatty acids. Oleic acid and linoleic acid are particularly preferred for the reaction. The double bonds contained in the dimer fatty acid are usually hydrogenated.
  • the acid groups are reduced to the corresponding alcohol groups. This is a process known to those skilled in the art.
  • the unit of formula (C) it should be noted that the total number of carbon atoms in the R 2 group differs for dimer fatty acid and for a dimer diol obtained by reducing dimer fatty acid, even if the same dimer fatty acid is used in both cases.
  • the unit (C) according to the invention is very particularly preferably obtained by condensing dimer fatty acid having 36 carbon atoms and/or a dimer diol having 36 carbon atoms obtained by reducing dimer fatty acid.
  • Dimer fatty acids are commercially available and are known, for example, under the trade names Pripol 1009, Pripol 1006, Pripol 1025, Radiacid 0960, Radiacid 0975, Radiacid 0976, Radiacid 0977, Radiacid 0978, and Unidyme 18.
  • the corresponding dimer diols are known, for example, under the trade names Pripol 2030 and 2033.
  • Pripol and Pripol derivatives are produced, as described above, by oligomerization of unsaturated fatty acids—preferably C18 acids. Dimerization yields a mixture of mono-, di-, and tricarboxylic acids. The monofunctional compounds are usually separated by distillation.
  • Pripol as a dimer fatty acid or dimer diol, is a purified mixture consisting predominantly of a diacid or diol with 36 carbon atoms.
  • Unit (C) can be a bio-based unit, which provides all the advantages of a bio-based monomer and the resulting polymer (e.g. better Sustainability, as it is made from renewable raw materials. Unit (C) is particularly preferred to be bio-based.
  • a unit of formula (D) may be present in the copoly(ester)carbonate according to the invention, with where the positions marked with # and * are the positions at which the unit (D) is incorporated into the copoly(ester)carbonate.
  • the unit (D) is only present to a maximum of 5 mol% in the copoly(ester)carbonate according to the invention (where mol% data relate to the total amount of the units (A), (B), (C), optionally (D) and optionally units other than (A), (B), (C) and (D)).
  • the unit (D) is particularly preferably present in the copoly(ester)carbonate according to the invention in an amount of 0 to 5 mol%, particularly preferably 0 to 3 mol%, further preferably 0.01 to 2 mol% and very particularly preferably 0 mol%.
  • Unit (D) can be formed by condensing cyclohexanedicarboxylic acid into the copoly(ester)carbonate of the invention.
  • unit (D) can be formed by condensing cyclohexanedicarboxylic acid into the copoly(ester)carbonate of the invention.
  • an excessively high molar proportion of unit (D) in the copoly(ester)carbonate of the invention leads to a deterioration in hot water resistance. Therefore, it is preferable to keep the proportion of unit (D) in the copoly(ester)carbonate of the invention as low as possible.
  • the copoly(ester)carbonate according to the invention has at least some direct links between the units (A), (B), (C), optionally (D) and optionally units other than (A), (B), (C) and (D).
  • direct linkage is preferably understood to mean that the stated units are directly linked to one another. This is preferably achieved by there being no further unit between the stated units.
  • a unit (A) can have a direct linkage to a unit (B) in that the position marked with * of unit (A) is directly attached to the position marked with # of unit (B) to form a carbonate group.
  • the position of the units (A), (B), (C), (D) marked with "*" is then linked to the position of these units marked with "#", with the exception that if t in formula (C) is 0, there is no direct link between two units (C) with one another, if t in formula (C) is 0, there is no direct link between the unit (C) and the unit (D) and there is no direct link between two units (D) with one another.
  • Unit (C), when t in formula (C) is 0, or unit (D) are obtained by incorporating dicarboxylic acids into the copoly(ester)carbonate. This must result in the formation of ester groups. Corresponding other linkages of these units are preferably not possible according to the invention.
  • the positions marked with # or * indicate the positions at which the respective unit or structure is incorporated into the copoly(ester)carbonate according to the invention. It is clear that these positions do not represent a "group" but merely serve to simplify the representation. To clarify: if, for example, a unit (A) has a direct link to a unit (B), the position marked with * in unit (A) is the oxygen atom next to the position marked with # in unit (B), so that a carbonate group is formed. This is transferable to all other units by a person skilled in the art.
  • the units (A), (B), (C) and optionally (D) form carbonate groups in the direct linkage with one another (and optionally ester groups if unit (C) is included in the direct linkage and t is 0 in each case, or if unit (D) is present).
  • the copoly(ester)carbonate according to the invention provides that only positions marked with # are directly linked to positions marked with *.
  • the copoly(ester)carbonate according to the invention has direct linkages between units (A) and (C) and, at the same time, both t in unit (C) are simultaneously 0.
  • a group is preferably present in which a dianhydrohexitol group is directly linked via an ester group to, for example, a group derived from dimer fatty acid.
  • copoly(ester)carbonate according to the invention preferably comprises structures of the unit (ABC)
  • ABSC in which n is 1, the average number of repeating units or the preferences described above, R 1 , r and s have the meanings given for (B*) in all preferences and possible combinations, and m is 1, the average number of repeating units or the preferences described above, and t and R 2 have the meanings given for unit (C) in all preferences and possible combinations.
  • this unit (ABC) can be encompassed by the polymer and that further structures can optionally be present in the copoly(ester)carbonate according to the invention.
  • the sequence of the monomers is preferably not fixed. According to the invention, it is preferably a Copoly(ester)carbonate with random incorporation of the monomers.
  • the structure (ABC) can be present only in a small proportion in the copoly(ester)carbonate of the invention because it reflects the specific sequence of individual structural elements. Due to certain process variants, differences in reactivity, or the use of certain catalysts, the monomers may not be incorporated randomly; this is also preferably encompassed by the generic unit (ABC).
  • the copoly(ester)carbonate according to the invention preferably comprises structures in which direct linkages of the formulas (A)-(B), (A)-(C), (C)-(B), (A)-(B)-(C), (A)-(C)-(B), (A*)-(B), (A*)-(C), (A*)-(B)-(C), (A*)-(C)-(B), (A*)-(B*), (B*)-(C), (A*)-(B*)-(C), (A*)-(B*)-(C), (A*)-(C)-(B*) or any mixtures of two or more of these structures are present.
  • the copolycarbonate according to the invention comprises unit (ABC*), in which n stands for 1, the average number of repeating units or the preferences described above, R 1 , r and s have the meanings given for (B*) in all preferences and combinations, and m stands for 1, the average number of repeating units or the preferences described above, R 2 has the meanings given for unit (C) in all preferences and combinations, and o stands for 1, the average number of repeating units or a number between 1 and 5.
  • unit (ABC*) shown above can be derived from the units (A), (B) and (C), where t in formula (C) is 1.
  • copoly(ester)carbonate according to the invention comprises unit (AC),
  • the copoly(ester)carbonate according to the invention particularly preferably comprises the unit (ABC) and (AC).
  • the copoly(ester)carbonate according to the invention is particularly preferably characterized in that it consists of at least 80% by weight, particularly preferably at least 85% by weight, and likewise preferably at least 90% by weight, of the units (A), (B), (C) and optionally (D).
  • the copoly(ester)carbonate according to the invention therefore preferably has only small amounts of structures other than those of the units (A), (B) and (C).
  • the end groups of the copoly(ester)carbonate according to the invention are preferably excluded. It is possible for the copoly(ester)carbonate according to the invention to also have functional units other than carbonate groups and optionally ester groups.
  • the copoly(ester)carbonate according to the invention it is further preferred for the copoly(ester)carbonate according to the invention to have no functional units other than carbonate and/or optionally ester groups.
  • the end groups can be excluded.
  • the maximum 20 wt.%, preferably maximum 15 wt.%, particularly preferably maximum 10 wt.%, which consist of units other than units (A), (B), (C) and optionally (D) can preferably be derived from other diols or dicarboxylic acids, which in turn lead to carbonate or ester groups when incorporated into the copoly(ester)carbonate.
  • the copoly(ester)carbonate contains 4 to 25 mol% of unit (B), 2 to 14 mol% of unit (C), 0 to 5 mol% of unit (D) and at least 55 mol% of unit (A), where the mol% data relate to the total amount of units (A), (B), (C), optionally (D) and optionally units different from (A), (B), (C) and (D). It will be apparent to the person skilled in the art that these amounts also apply to all Preferences and combinations of preferences can relate to the individual units (A), (B) and (C).
  • the copoly(ester)carbonate according to the invention comprises
  • the copoly(ester)carbonate according to the invention has one or more, preferably all, of the following properties: a high glass transition temperature, good optical properties such as transparency, good mechanical properties such as ductility at room temperature, high thermal stability, good stability against aqueous media, good hot water stability, good grease resistance, good resistance to lipid solutions and good solvent resistance.
  • the skilled person can determine the molar amounts of the various units in the copoly(ester)carbonate according to the invention. These can preferably be determined by means of 'H NMR spectroscopy. Depending on the process for preparing the copoly(ester)carbonate, it can be assumed that almost all of the monomers used react to form the polymer. In particular, the examples according to the invention showed that the molar ratios of the monomers are also reflected in the resulting polymer. This means that the skilled person can influence the molar ratios of the resulting units in the polymer by changing the molar ratios of the monomers used.
  • the defined mol % in the copoly(ester)carbonate according to the invention be determined by means of 'H NMR spectroscopy. This method is known to the skilled person.
  • the copoly(ester)carbonate can, for example, be dissolved in CDCF and the corresponding peaks of the structural units are identified. Depending on the compounds used, the skilled person is able to assign these peaks to the structural units.
  • the ratios and proportions can be determined using the integrals.
  • the mol % according to the invention can also be determined using the amounts and ratios of the monomers used. It must be assumed that all monomers are fully incorporated into the copoly(ester)carbonate in the same ratio. This also allows the skilled person to adjust the ratio in advance.
  • the polymer can be hydrolyzed, for example, under reflux with sodium methoxide.
  • the resulting solution can then be acidified and evaporated to dryness.
  • the residue can be dissolved in suitable organic solvents, and the compounds present can be analyzed by HPLC.
  • HPLC The appropriate calibration and measurement using HPLC are known to those skilled in the art.
  • the copoly(ester)carbonate according to the invention can also have further units different from (A), (B), (C) and optionally (D).
  • the copoly(ester)carbonate according to the invention preferably has unit (E), where
  • each x independently of one another, represents a linear or branched alkylene group having 4 to 20, preferably 5 to 15 carbon atoms, which may optionally be interrupted by at least one heteroatom, a cycloalkylene group having 4 to 20, preferably 5 to 15 carbon atoms, which may optionally be interrupted by at least one heteroatom and where the cycloalkylene group may optionally contain several rings, or an aromatic group, and where the positions marked with # and * are the positions with which the unit (E) is incorporated into the copoly(ester)carbonate, with the exception that when z in formula (E) is 0, there is no direct linkage between two units (E) with one another.
  • this unit (E) must be different from the unit (D). It is particularly preferably x in unit (E) is an aromatic group, particularly preferably an aromatic group having up to 20 carbon atoms, which may optionally be interrupted by at least one heteroatom. x in unit (E) is particularly preferably a structure of the formula (x1), (x2) or (x3), with
  • x in unit (E) is a structure of formula (xl), (x2) or (x3), where both z's are simultaneously 0.
  • the copoly(ester)carbonate according to the invention can be branched. This can be influenced by the use of polyfunctional alcohols such as glycerol, trimethylolpropane, or tris(4-hydroxyphenyl)ethane (THPE), etc., or polyfunctional carboxylic acids such as citric acid, trimellitic acid, etc., in the synthesis of the copoly(ester)carbonate according to the invention.
  • polyfunctional alcohols such as glycerol, trimethylolpropane, or tris(4-hydroxyphenyl)ethane (THPE), etc.
  • THPE tris(4-hydroxyphenyl)ethane
  • carboxylic acids such as citric acid, trimellitic acid, etc.
  • the copoly(ester)carbonate according to the invention preferably comprises at most 25 mol%, particularly preferably at most 20 mol%, furthermore preferably at most 10 mol%, and very particularly preferably at most 5 mol% of aromatic groups. However, any end groups present are preferably excluded. It is preferred that unit (E) is present in the copoly(ester)carbonate according to the invention in an amount of at most 20 mol%, furthermore preferably at most 10 mol%, and very particularly preferably at most 5 mol%. It is particularly preferred that x in unit (E) is a structure of the formula (x1), (x2), or (x3), where both z's are simultaneously 0.
  • the copoly(ester)carbonate according to the invention preferably comprises end groups. These are preferably formed by the use of chain terminators during the synthesis. Monofunctional acids or alcohols, including phenols, can be used as chain terminators.
  • the copoly(ester)carbonate according to the invention particularly preferably comprises end groups of the formula (Z)
  • each R 7 independently represents hydrogen, an alkyl group having 1 to 34 carbon atoms, an aralkyl group having 7 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms, or a -COO-R' group, where R' represents an alkyl group having 1 to 34 carbon atoms, an aralkyl group having 7 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms, and each q independently represents 1 to 5, and the position marked with # is the position at which the unit (Z) is attached to the copoly(ester)carbonate. It can be seen that the position marked with # is attached to the position of the other units marked with *.
  • the copoly(ester)carbonate of the invention can have aromatic units as end groups. These do not adversely affect the intrinsic weathering stability of the polymer because their concentration is very low.
  • q in unit (Z) is 1.
  • R 7 is likewise preferably hydrogen or -COOCH s, very particularly preferably hydrogen.
  • the copoly(ester)carbonate according to the invention particularly preferably comprises end groups selected from the group consisting of the formula (Z), -OH, -COOH and any mixtures of these groups. It is apparent to the person skilled in the art that formula (Z) particularly encompasses phenyl ester end groups and/or phenyl carbonate end groups. Free acid or OH end groups can be reduced, for example, by the use of epoxy groups or carbamate derivatives. Such reactions are known to the person skilled in the art.
  • the copoly(ester)carbonate according to the invention is at least 50 mol%, particularly preferably at least 70 mol%, and most preferably at least 75 mol% bio-based.
  • bio-based is understood to mean that the chemical compound in question is accessible, obtainable, and/or preferably is such a renewable and/or renewable raw material at the time of application.
  • a renewable and/or renewable raw material is preferably understood to mean a raw material that is regenerated by natural processes at a rate comparable to its degradation rate (see CEN/TS 16295:2012).
  • the term serves in particular, the distinction from raw materials made from fossil fuels, also referred to as petro-based.
  • Whether a raw material is bio-based or petro-based can be determined by measuring carbon isotopes in the raw material, since the relative amounts of the carbon isotope C 14 are lower in fossil fuels. This can be done, for example, according to ASTM D6866-18 (2016) or ISO16620-1 to -5 (2015) or DIN SPEC 91236 2011-07.
  • the term "bio-based” is preferably used for compounds that have a C 14 isotope content of more than 0.1 x 10' 12 , particularly preferably of more than 0.2 x 10' 12 , and most preferably of more than 0.3 x 10 12 .
  • isosorbide and also dimer fatty acid or the dimer diol obtained by reduction of dimer fatty acid are bio-based.
  • the copoly(ester)carbonate according to the invention preferably has a relative solution viscosity above 1.20, particularly preferably from 1.21 to 1.65, further preferably from 1.22 to 1.63, especially preferably from 1.23 to 1.62, equally preferably from 1.26 to 1.55, and most preferably from 1.26 to 1.40.
  • the relative solution viscosity (prel; also referred to as eta rel) is preferably determined in dichloromethane at a concentration of 5 g/l at 25°C using an Ubbelohde viscometer. The determination of the relative solution viscosity using an Ubbelohde viscometer is known to those skilled in the art.
  • this is preferably carried out according to DIN 51562-3; 1985-05.
  • the flow times of the copoly(ester)carbonate to be measured through the Ubbelohde viscometer are measured to subsequently determine the viscosity difference between the polymer solution and its solvent.
  • the Ubbelohde viscometer is first calibrated by measuring the pure solvents dichloromethane, trichloroethylene, and tetrachloroethylene (at least three measurements are always taken, and no more than nine). This is followed by the actual calibration with the solvent dichloromethane.
  • the polymer sample is then weighed, dissolved in dichloromethane, and the flow time for this solution is determined three times. The mean of the flow times is corrected using the Hagenbach correction, and the relative solution viscosity is calculated.
  • compositions are further provided comprising the copoly(ester)carbonate in all of the above-described embodiments, preferred forms, and combinations of preferred forms, and one or more additives.
  • the composition according to the invention is preferably thermoplastic.
  • the invention provides a molded part comprising the copoly(ester)carbonate in all of the above-described embodiments, preferred forms, and combinations of preferred forms, or the composition according to the invention.
  • the polymer additives are preferably selected from the group consisting of flame retardants, anti-drip 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), flow promoters, phase compatibilizers, dyes and pigments, impact modifiers, and fillers and reinforcing agents.
  • the composition according to the invention may also contain other thermoplastics that differ from the copoly(ester)carbonate according to the invention.
  • the other thermoplastics are preferably materials based on polystyrene, styrene copolymers, aromatic polyesters such as polyethylene terephthalate (PET), PET-cyclohexanedimethanol copolymer (PETG), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), cyclic polyolefin, polybutylene succinate (PBS), poly- or copolyacrylates and poly- or copolymethacrylates, e.g. poly- or copolymethyl methacrylates (such as PMMA), polyamides (preferably polyamide 6 (PA6) and polyamide 6,6 (PA6,6)) as well as copolymers with styrene, e.g.
  • aromatic polyesters such as polyethylene terephthalate (PET), PET-cyclohexanedimethanol copolymer (PETG), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), cyclic poly
  • PSAN transparent polystyrene-acrylonitrile
  • thermoplastic polyurethanes polymers based on cyclic olefins (e.g. TOPAS,® a commercially available product from Ticona) and mixtures of the polymers mentioned.
  • TOPAS,® a commercially available product from Ticona
  • compositions according to the invention can be prepared, for example, by mixing the copoly(ester)carbonate and the other components in a known manner and melt compounding and melt extruding them at temperatures of preferably 220°C to 300°C in conventional units such as internal kneaders, extruders, and twin-screw extruders. This process is generally referred to as compounding in the context of this application.
  • the molded articles according to the invention can be produced, for example, by injection molding, extrusion, and blow molding. Another processing method is the production of molded articles by deep drawing from previously produced sheets or films.
  • R 2 has the meanings given for formula (C) also in all preferences and combinations of preferences and each R 6 independently represents hydrogen, an alkyl group having 1 to 34 carbon atoms, an aralkyl group having 7 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms or a -COO-R'- group, where R' represents an alkyl group having 1 to 34 carbon atoms, an aralkyl group having 7 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms and each x independently represents 1 to 5.
  • this intermediate is particularly suitable for preparing copoly(ester)carbonates according to the present invention.
  • Particular preference is given to using the compound of formula (I) to prepare the copoly(ester)carbonate according to the invention.
  • the compound of formula (I) be used to prepare a copoly(ester)carbonate, preferably the copoly(ester)carbonate according to the invention, by melt transesterification.
  • the melt transesterification process is known per se to the person skilled in the art. Reference can be made, for example, to Schnell, "Chemistry and Physics of Polycarbonates," Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964.
  • the starting materials are transesterified in the melt with the aid of suitable catalysts and, if appropriate, other additives.
  • this is a process that can be carried out without solvents and/or phosgene.
  • the compound of formula (I) can be formed either in situ during the melt transesterification process and/or formed beforehand and added as such as a reactant to the melt transesterification process.
  • the compound of formula (I) can be obtained by a process comprising the reaction between a diacid HOOC-R 2 -COOH with a diaryl carbonate of formula (Ia):
  • the present invention relates to a process for preparing the copoly(ester)carbonate according to the invention, comprising at least the reaction of a 1,4:3,6-dianhydrohexitol, a diol of the formula (B2), at least one further compound selected from the group consisting of a diol of the formula (C2), a compound of the formula (C3) or any mixtures thereof and a carbonyl source, wherein where each r and each s independently represents a number between 0 and 4 and each R 1 independently represents a structure of the formulas (RIA), (RIB), (R1C) and (R1D) where a is 0 or 1, where the marked positions in formulas (RIA) to (RID) are the positions at which the (CH2) r group or (CH2)s group shown in formula (B2) is located, and wherein each R 2 in formulas (C2) and (C3) independently of one another represents an aliphatic group having 16 to 44 carbon atoms, which optionally
  • the person skilled in the art is able to assign the structures of the units (B2), (C2) and (C3) to the units (B) and (C) described above and to design the corresponding configurations, Preferences and combinations of preferences can be read into it.
  • the formula (C3) particularly preferably comprises the compound of the formula (I) when R 3 is -OR. This also includes all preferences and combinations of preferences.
  • the process according to the invention preferably comprises the reaction of up to 25 mol%, particularly preferably 5 to 20 mol%, equally preferably 7 to 18 mol% and very particularly preferably 10 to 15 mol% or very particularly preferably 8 to 12 mol% of the compound (B2),
  • up to 5 mol%, preferably up to 3 mol%, particularly preferably 0.01 to 2 mol% of cyclohexanedicarboxylic acid can also be used as a reactant.
  • the carbonyl source used in the process according to the invention can preferably be selected from phosgene and a diaryl carbonate of the formula (Ia),
  • each R 6 independently represents hydrogen, an alkyl group having 1 to 34 carbon atoms, an aralkyl group having 7 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms or a -COO-R' group, wherein R' represents an alkyl group having 1 to 34 carbon atoms, an aralkyl group having 7 to 34 carbon atoms, an aryl group having 6 to 34 carbon atoms and each x independently represents 1 to 5.
  • copoly(ester)carbonate can generally be produced by melt transesterification (see above) or by the interfacial process.
  • the interfacial process is also fundamentally known, for example, from H.
  • Embodiment 1 Copoly(ester)carbonate containing the units (A), (B), (C), optionally (D) and optionally units different from (A), (B), (C) and (D), with where each r and each s independently represents a number between 0 and 4, and each R 1 independently represents a structure of the formulas (RIA), (RIB), (R1C) or (R1D)
  • g marked positions in formulas (RIA) to (RID) are the positions at which the (CFfijr group or (CFFf group) shown in formula (B) is located, and
  • Embodiment 2 Copoly(ester)carbonate according to embodiment 1, characterized in that the copoly(ester)carbonate is according to one of claims 2 to 10.
  • Embodiment 3 Copoly(ester)carbonate according to embodiment 1 or 2, characterized in that the copoly(ester)carbonate has direct links between at least two units (A).
  • Embodiment 4 Copoly(ester)carbonate according to one of embodiments 1 to 3, characterized in that unit (A) or (A*) consists of the unit (Al).
  • Embodiment 5 Copoly(ester)carbonate according to one of embodiments 1 to 4, characterized in that unit (A) or (A*) is bio-based.
  • Embodiment 6 Copoly(ester)carbonate according to one of embodiments 1 to 5, characterized in that each r and each s in unit (B) independently of one another represents a number between 0 and 4, preferably between 0 and 3, particularly preferably between 0 and 2, most particularly preferably 0 or 1.
  • Embodiment 7 Copoly(ester)carbonate according to one of embodiments 1 to 6, characterized in that in unit (B) each r and each s independently of one another represents a number between 0 and 2, very particularly preferably 0 or 1, and each R 1 independently of one another represents a structure of the formula (RIA).
  • Embodiment 8 Copoly(ester)carbonate according to one of embodiments 1 to 7, characterized in that the unit (B) or (B*) consists of unit (B1).
  • Embodiment 9 Copoly(ester)carbonate according to one of embodiments 1 to 8, characterized in that each R 2 in the unit (C) independently of one another represents an aliphatic group having 17 to 44 carbon atoms, particularly preferably having 18 to 44 carbon atoms, particularly preferably having 19 to 44 carbon atoms, particularly preferably having 20 to 44 carbon atoms, particularly preferably having 21 to 44 carbon atoms, particularly preferably having 22 to 43 carbon atoms, particularly preferably having 23 to 42 carbon atoms, particularly preferably having 24 to 41 carbon atoms, particularly preferably having 25 to 40 carbon atoms, particularly preferably having 26 to 39 carbon atoms, particularly preferably having 27 to 38 carbon atoms, particularly preferably having 28 to 37 carbon atoms, particularly preferably having 29 to 37 carbon atoms, particularly preferably having 30 to 37 carbon atoms, particularly preferably having 31 to 37 carbon atoms, particularly preferably 32 to 37 carbon atoms and most preferably 33 to 37 carbon atoms.
  • Embodiment 10 Copoly(ester)carbonate according to one of embodiments 1 to 9, characterized in that (C) is present at least twice in the copoly(ester)carbonate and R 2 in the unit (C) represents at least two different formulas (R2Aa), (R2Ab), (R2Ac) and (R2Ad).
  • Embodiment 11 Copoly(ester)carbonate according to any one of embodiments 1 to 10, characterized in that the unit (C) is obtained by condensing dimer fatty acid and/or a dimer diol obtained by reducing dimer fatty acid.
  • Embodiment 12 Copoly(ester)carbonate according to one of embodiments 1 to 11, characterized in that the unit (C) is obtained by condensing dimer fatty acid with 36 carbon atoms and/or a dimer diol having 36 carbon atoms obtained by reduction of dimer fatty acid.
  • Embodiment 13 Copoly(ester)carbonate according to one of embodiments 1 to 12, characterized in that unit (C) is bio-based.
  • Embodiment 14 Copoly(ester)carbonate according to one of embodiments 1 to 13, characterized in that the unit (D) is present in the copoly(ester)carbonate according to the invention in an amount of 0 to 5 mol%, particularly preferably 0 to 3 mol%, further preferably 0.01 to 2 mol% and very particularly preferably 0 mol%.
  • Embodiment 15 Copoly(ester)carbonate according to one of embodiments 1 to 14, characterized in that the copoly(ester)carbonate comprises the unit (ABC).
  • Embodiment 16 Copoly(ester)carbonate according to one of embodiments 1 to 15, characterized in that the copoly(ester)carbonate comprises the unit (AC).
  • Embodiment 17 Copoly(ester)carbonate according to one of embodiments 1 to 16, characterized in that the copoly(ester)carbonate consists of at least 80% by weight, particularly preferably at least 85% by weight, likewise preferably at least 90% by weight of the units (A), (B), (C) and optionally (D).
  • Embodiment 18 Copoly(ester)carbonate according to one of embodiments 1 to 17, characterized in that the copoly(ester)carbonate has no functional units other than carbonate and/or optionally ester groups.
  • Embodiment 19 Copoly(ester)carbonate according to one of embodiments 1 to 18, characterized in that the copoly(ester)carbonate
  • (A) includes, where the mol% information refers to the total amount of the units (A), (B), (C), optionally (D) and optionally units different from (A), (B), (C) and (D).
  • Embodiment 20 Copoly(ester)carbonate according to one of embodiments 1 to 19, characterized in that the copoly(ester)carbonate has end groups of the formula (Z).
  • Embodiment 22 Copoly(ester)carbonate according to one of embodiments 1 to 21, characterized in that x in unit (E) is a structure of the formula (x1), (x2) or (x3), where both z are simultaneously 0.
  • Cyclohexanedicarboxylic acid 1,4-Cyclohexanedicarboxylic acid; CAS 1076-97-7 99%; Tokyo Chemical Industries, Japan, abbreviated as CHDA.
  • 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
  • Lithium hydroxide monohydrate (CAS: 1310-66-3); >99.0%; Sigma-Aldrich
  • Terephthalic acid (CAS: 100-21-0), 99+%, Acros Organics, Geel, Belgium
  • Tricyclodecanedimethanol (CAS: 26896-48-0) ; mixture of isomers ; OQ Chemicals, 40789 Monheim, Germany
  • Dimer fatty acid Pripol 1009 (CAS: 68783-41-5); Mn approx. 570 g/mol; hydrogenated, Croda, 41334 Nettetal, Germany
  • Methyl tert-butyl ether (CAS: 1634-04-4); Azelis Germany GmbH, 53757 Sankt Augustin, Germany, abbreviated as MTBE
  • Methyl ethyl ketone (CAS: 78-93-3); Azelis Germany GmbH, 53757 Sankt Augustin, Germany, abbreviated as MEK
  • Zeolite 4A Sodium aluminum silicate (CAS: 1318-02-1)
  • Polycarbonate based on isosorbide and cyclohexanedimethanol 30:70 (CAS: 25037-45-0): producible according to EP2033981 Al; abbreviated as PCI 2-Butyl-2-ethyl-1,3-propanediol (CAS: 115-84-4); 99.0%; Sigma-Aldrich, Kunststoff
  • Lipid solution SmofKabiven central emulsion for infusion; qualitative and quantitative composition: 1000 ml contains: 508 ml amino acid solution with electrolytes, 302 ml glucose solution 42%, 190 ml lipid emulsion.
  • the relative solution viscosity (qrck, also referred to as eta rel) was determined in dichloromethane at a concentration of 5 g/l at 25 °C using an Ubbelohde viscometer. The determination was carried out according to DIN 51562-3; 1985-05. The flow times of the polyester carbonate to be measured through the Ubbelohde viscometer are measured to subsequently determine the viscosity difference between the polymer solution and its solvent. For this purpose, the Ubbelohde viscometer is first calibrated by measuring the pure solvents dichloromethane, trichloroethylene, and tetrachloroethylene (at least three measurements are always taken, but no more than nine).
  • the glass transition temperature was determined by differential scanning calorimetry (DSC) according to DIN EN ISO 11357-1:2009-10 and ISO 11357-2:2013-05 at a heating rate of 10 K/min under nitrogen with determination of the glass transition temperature (Tg) measured as the inflection point in the second heating process.
  • DSC differential scanning calorimetry
  • the polymer samples were boiled under reflux in deionized water for 4 hours and then visually inspected. If they were not completely deformed, they were boiled for another 4 hours under the same conditions, and the results were visually evaluated.
  • At least two flat bars measuring 80 mm in length, 4 mm in height, and 10 mm in width were clamped in a circular template with a radius of 99 cm. This corresponded to an edge fiber strain of 2%.
  • the surface of the bars was contaminated by continuous wetting with or complete immersion in the test medium. The time to fracture was measured. The measurement was stopped after 5–14 days.
  • the measurement was performed on an ARES-G2 rheometer from TA.
  • the oscillatory frequency sweep test in the range 0.001 Hz to 10,000 Hz was performed isothermally at 200°C, and the complex viscosity was derived from this.
  • 80x10x4mm flat bars or 60x60x2mm plates were injection molded at 245 °C to 260 °C.
  • the measurement was carried out with a Erichsen test rod 318, equipped with test tip 1 (hard metal ball) and a spring with a measuring range of 0-1 N, was clamped into a chassis so that the set force acted on the test tip.
  • the chassis, including the test rod, was set to N and rolled 10 mm over the surface to be tested. If no scratch marks were visually visible to two testers, the force was increased by 0.5 N and the test was repeated. This was repeated until a visible scratch mark remained in the polymer. The highest force exerted is reported.
  • the measurements were performed on a Bruker Avance NEO 600 MHz NMR spectrometer. The measurements were carried out in CDCl3. The samples contained isosorbide, tricyclodecane dimethanol, and dimer diol or dimer fatty acid. The molar ratios of these components were evaluated as follows:
  • the signals between 5.3 and 4.5 ppm were used.
  • the integral was set to “40” and corresponds to 4 protons of isosorbide.
  • TCD-dimethanol and dimerdiol The content of TCD-dimethanol and dimerdiol was determined from the signals between 4.2 and 3.8. This region contains 4 protons of isosorbide, as well as 2 -CH2- groups of TCD-dimethanol (-O-CH2-), and 2 -CH2- groups of dimerdiol (-O-CH2-). Thus, 4 protons of TCD-dimethanol and 4 protons of dimerdiol are also located in this range.
  • Example 16 based on a polymer of isosorbide, tricyclodecanedimethanol and dimer fatty acid can also be calculated from the H-NMR spectrum.
  • the signals between 5.3 and 4.5 ppm were used.
  • the integral was set to "40" and corresponds to 4 protons of isosorbide.
  • the tricyclodecanedimethanol content was determined from the signals between 4.2 and 3.8 ppm. This range contains four protons of isosorbide and two -CH2- groups of tricyclodecanedimethanol (-O-CH2-). Thus, four protons of tricyclodecanedimethanol are also present in this range.
  • the dimer fatty acid content was calculated by integrating the signals at 0.95 - 0.6 ppm.
  • Recrystallization was performed using a hexane/ethyl acetate mixture (approximately 2:1 ratio) and 2-5% of the total mass of activated carbon.
  • the vacuum-filtered product was finely crystalline and bright white.
  • the mixture was mechanically ground as finely as possible and boiled with acetone under reflux (the time depended on the amount of acetone used and the degree of comminution of the crude product).
  • the acetone/diphenyl terephthalate mixture was then cooled to 10 °C and filtered with suction.
  • the intensely yellow mother liquor was discarded, and the pure, finely crystalline product was dried.
  • the product had a pearly sheen and a whitish, slightly yellowish color.
  • Example 2 Polyester carbonate made from 67% isosorbide and 33% CHDA (comparison)
  • the temperature was gradually increased to 220 °C over a period of approximately 90 minutes, depending on the observed reactivity. Phenol began to separate.
  • the pressure was then gradually reduced to 0.5 mbar over a period of approximately 30 minutes. Stirring was continued for 10 minutes at this pressure.
  • Example 3 Polyester carbonate from cyclohexanedicarboxylic acid, terephthalic acid, dimer fatty acid and isosorbide (comparison)
  • Example 4 The example was carried out as in Example 4, except that 64.91 g (0.303 mol) of diphenyl carbonate, 10 g (0.0185 mol) of Pripol 2030, and 41.14 g (0.281 mol) of isosorbide were used. A transparent, yellowish polymer with an eta rel of 1.329 was obtained.
  • Example 4 The example was carried out as in Example 4, except that 64.91 g (0.303 mol) of diphenyl carbonate, 11.79 g (0.022 mol) of Pripol 2030, and 40.65 g (0.278 mol) of isosorbide were used. A transparent, yellowish polymer with an eta rel of 1.382 was obtained.
  • Example 7 Polycarbonate from isosorbide and BEPD (comparison)
  • Example 8 Polyester carbonate with a low CHDA content (comparison)
  • the temperature was gradually increased to a maximum of 210 °C.
  • the pressure was then reduced to approximately 50 mbar and held for 15 minutes to remove phenol.
  • the reaction mixture was then vented to ambient pressure with nitrogen, and 16.66 g (0.1140 mol) of isosorbide and 25.71 g (0.1200 mol) of diphenyl carbonate were added to the reaction mixture at 225 °C with rapid stirring. After the addition was complete, phenol distilled off.
  • the temperature was increased to 235 °C and the pressure was carefully reduced stepwise to ⁇ 1 mbar, with phenol continuously removed. Stirring was continued at approximately 0.5 mbar for a further 10 minutes at low speed. A transparent, yellowish polymer with a solution viscosity of 1.27 was obtained.
  • the mixture was freed of oxygen by four evacuations and inerting with nitrogen, and then heated to 160 °C at atmospheric pressure with stirring and melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C while stirring rapidly (approx. 500 rpm). Phenol distilled off at approximately 220 °C. The pressure was then carefully reduced stepwise to approximately 0.5 mbar, while the temperature was simultaneously increased to 255 °C. Phenol was continuously removed. Stirring was continued at approximately 0.5 mbar for a further 10 minutes at low speed. A transparent, yellow-colored polymer with an eta rel. of 1.191 was obtained.
  • the mixture was freed of oxygen by evacuating four times and inerting with nitrogen.
  • the mixture was heated to 160 °C at atmospheric pressure with stirring and melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C with rapid stirring (approx. 500 rpm). Phenol distilled off at approximately 220 °C. The pressure was then carefully and gradually reduced to approximately 0.5 mbar, and the temperature was increased in parallel to 255 °C. Phenol was continuously removed. Stirring was continued at low speed at approximately 0.5 mbar for a further 10 minutes. A cloudy, brown-colored polymer with an eta rel. of 1.076 was obtained.
  • the mixture was freed of oxygen by four evacuations and inerting with nitrogen, and then heated to 160 °C at atmospheric pressure with stirring and melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C while stirring rapidly (approx. 500 rpm). Carbon dioxide evolution was observed, and phenol distilled off at approximately 220 °C. Once gas evolution had ceased, the pressure was carefully reduced step by step to approximately 0.5 mbar, while the temperature was simultaneously increased to 255 °C. Phenol was continuously removed. Stirring was continued at approximately 0.5 mbar for a further 10 minutes at low speed. A slightly cloudy, light-brown polymer with an eta rel. of 1.338 was obtained.
  • the mixture was freed of oxygen by evacuating four times and inerting with nitrogen.
  • the mixture was heated to 160 °C at atmospheric pressure with stirring and melted.
  • the temperature was slowly increased to 245 °C with rapid stirring (approx. 500 rpm).
  • Phenol distilled off at approx. 220 °C.
  • the pressure was then carefully and gradually reduced to approx. 0.5 mbar and, in parallel, the temperature was increased to 255 °C. Phenol was continuously removed. Stirring was continued at low speed at approx. 0.5 mbar for a further 10 minutes.
  • a transparent, light yellow polymer with an eta rel. of 1.423 was obtained.
  • the mixture was freed of oxygen by evacuating four times and purging with nitrogen.
  • the mixture was heated to 160 °C at atmospheric pressure with stirring and melted. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C while stirring rapidly (approx. 500 rpm). Phenol distilled off at approximately 220 °C. The pressure was then carefully reduced step by step to approximately 0.5 mbar, while the temperature was simultaneously increased to 255 °C. Phenol was continuously removed. Stirring was continued at approximately 0.5 mbar at low speed for a further 10 minutes. A slightly cloudy, light yellow polymer with an eta rel. of 1.339 was obtained.
  • Example 16 Preparation of a polyester carbonate containing dimer fatty acid
  • the temperature was gradually increased to a maximum of 210 °C.
  • the pressure was then reduced to approximately 50 mbar and held for 15 minutes. to remove phenol.
  • the reaction mixture was then vented to ambient pressure with nitrogen, and 177.21 g (0.8272 mol) of diphenyl carbonate and 112.45 g (0.7695 mol) of isosorbide were added to the reaction mixture at 225 °C with rapid stirring. After the addition was complete, phenol distilled off.
  • the temperature was increased to 235 °C, and the pressure was carefully and gradually reduced to ⁇ 1 mbar, with phenol continuously removed. Stirring was continued at approximately 0.5 mbar for a further 10 minutes at low speed. A light yellow polymer with an eta rel of 1.240 was obtained.
  • Example 17 Preparation of a copolycarbonate with dimerdiol (according to the invention)
  • the mixture was freed of oxygen by four-fold evacuation and purging with nitrogen, melted, and heated to 160 °C at atmospheric pressure with stirring. Once a homogeneous, low-viscosity liquid was obtained, the temperature was slowly increased to 245 °C while stirring rapidly (approx. 500 rpm). Phenol distilled off at approximately 220 °C. The pressure was then carefully reduced step by step to approximately 0.5 mbar, with phenol continuously removed. Stirring was continued at approximately 0.5 mbar for a further 10 minutes at low speed. A light-colored, transparent polymer with an eta rel. of 1.356 was obtained.
  • Example 17 The example was carried out as in Example 17, except that 194.73 g (0.909 mol) of diphenyl carbonate, 30.0 g (0.055 mol) of Pripol 2030, 14.75 g (0.075 mol) of tricyclodecanedimethanol, and 112.45 g (0.7695 mol) of isosorbide were used. A light yellow polymer with an eta rel of 1.320 was obtained.
  • Example 20 Preparation of a copolycarbonate with dimerdiol (according to the invention)
  • Example 17 The example was carried out as in Example 17, except that 32.46 g (0.1515 mol) of diphenyl carbonate, 4.05 g (0.0075 mol) of Pripol 2030, 4.43 g (0.0335 mol) of tricyclodecanedimethanol, and 17.54 g (0.120 mol) of isosorbide were used. A light yellow polymer with an eta rel of 1.352 was obtained.
  • Example 17 The example was carried out as in Example 17; however, 64.91 g (0.303 mol) of diphenyl carbonate, 8.10 g (0.015 mol) of Pripol 2030, 5.02 g (0.0255 mol) of tricyclodecanedimethanol, and 37.92 g (0.2595 mol) of isosorbide were used. A light yellow polymer with an eta rel of 1.331 was obtained.
  • Example 22 Preparation of a copolyestercarbonate containing dimer fatty acid and terephthalic acid (according to the invention)
  • Table 3 Shear rheology hot water.
  • polymers made from frequently used diols such as cyclohexanedimethanol and isosorbide (Example 1) - as described, for example, in EP 2033981 - are not very stable against hot water exposure.
  • Other diols such as the combination of sterically hindered diols such as isosorbide and 2-butyl-2-ethyl-1,3-propanediol, also do not exhibit good stability (Example 7). This is surprising because these sterically hindered diols Such as BEPD or neopentyl glycol, typically improve hydrolysis stability.
  • Example 2 shows that polyester carbonates made from 1,4-cyclohexanedicarboxylic acid and isosorbide also do not exhibit good stability in the hot water test. This was surprising, since polyesters made from cyclohexanedimethanol and 1,4-cyclohexanedicarboxylic acid, for example, exhibit high stability in aqueous media.
  • Example 11 shows that the combination of isosorbide and long-chain diols—in this case, dodecanediol (cf. EP2840102)—does not necessarily lead to better results.
  • This polymer also exhibited significant weaknesses in the hot water test. These polymers can also be disadvantageous in other respects; for example, they often exhibit low glass transition temperatures.
  • polyesters are often stable against hot water exposure. Polyesters such as polyethylene terephthalate and corresponding derivatives are stable against hot water.
  • aromatic diacids such as terephthalic acid or isophthalic acid
  • a polycarbonate or polyester carbonate otherwise consisting of aliphatic building blocks surprisingly does not lead to stable products, as shown in Example 3.
  • dimer fatty acids into such structures does not help either. It would have been expected that the nonpolar or hydrophobic properties of the aromatic acids or dimer fatty acids would improve stability against water. Surprisingly, this also applies in part to polymers containing TCD alcohol.
  • a polymer composed of isosorbide, cyclohexanedicarboxylic acid, dimer fatty acid, and TCD dimethanol is surprisingly unstable (Example 8). This can be attributed to the presence of cyclohexanedicarboxylic acid.
  • polymers that essentially consist only of isosorbide and long-chain non-polar fatty acids such as sebacic acid are also not stable against hot water (Example 13).
  • dimer diol or dimer fatty acid and isosorbide demonstrates high resistance to aqueous media.
  • these polymers exhibit a high melt viscosity (Examples 4 to 6)
  • Rheological studies demonstrate that the viscosity is significantly higher than that of the polymers according to the invention.
  • the high melt viscosity is a crucial disadvantage because it significantly complicates the processing of these materials. A significant increase in process temperatures to increase flowability is not possible with aliphatic materials, as they are not as stable as, for example, aromatic polycarbonates and therefore tend to decompose and lose molecular weight at higher process temperatures.
  • the polymers according to the invention exhibit better surface hardness than polycarbonates based on bisphenol A and also than polymers based on ISB and dimerdiol (see Table 4 below).
  • Polymers with a high proportion of TCD alcohol do not exhibit good properties in the hot water test (Example 15). It was therefore very surprising that only the copoly(ester)carbonates according to the invention with the proportions of units (A), (B) and (C) according to the invention exhibit both high hot water stability and good stability against solvents such as fuel mixtures (isooctane-toluene mixture) and at the same time exhibit high surface hardness with sufficiently good mechanical properties.
  • the polymers according to the invention have glass transition temperatures of more than 110 °C.
  • the monomers used are almost completely incorporated into the copoly(ester)carbonate.
  • the molar ratios of the monomers used remain almost completely present in the copoly(ester)carbonate. This means that the ratio and amount of the starting materials can be used to control the ratio and amount of the structural units present in the resulting polymer.

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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)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne un copoly(ester) carbonate d'unités définies (A), (B) et (C) ayant des proportions de quantité définies, ladite structure et lesdits rapports de quantité amenant le copoly(ester) carbonate à avoir une excellente stabilité dans des milieux aqueux et également contre d'autres produits chimiques tels que de l'huile de colza, une solution lipidique ou des solvants organiques. La présente invention concerne également une composition contenant le carbonate de copoly(ester) selon l'invention, un moulage contenant le copoly(ester) carbonate selon l'invention, et un procédé de production du copoly(ester) carbonate selon l'invention.
PCT/EP2024/076755 2023-09-25 2024-09-24 Copoly(ester) carbonate stable contre des milieux aqueux et d'autres produits chimiques et ayant une bonne aptitude au traitement Pending WO2025068165A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002010111A1 (fr) * 2000-07-28 2002-02-07 General Electric Company Processus destine a la synthese de diarylesters d'acides dicarboxyliques
EP2033981A1 (fr) 2006-06-19 2009-03-11 Mitsubishi Chemical Corporation Copolymère de polycarbonate et son procédé de production
EP2203501A1 (fr) 2007-10-18 2010-07-07 Sabic Innovative Plastics IP B.V. Polycarbonates à base d'isosorbide, procédé de fabrication et objets formés à partir de ceux-ci
EP2478031A2 (fr) 2009-09-14 2012-07-25 SK Chemicals Co., Ltd. Résine de polyester et procédé de préparation
US8273849B2 (en) 2009-12-30 2012-09-25 Sabic Innovative Plastics Ip B.V. Isosorbide-based polycarbonates, method of making, and articles formed therefrom
EP2840102A1 (fr) 2012-04-18 2015-02-25 Teijin Limited Copolycarbonate
EP3026074A1 (fr) 2013-07-24 2016-06-01 SK Chemicals Co., Ltd. Poly(ester de carbonate) hautement résistant à la chaleur et hautement transparent et son procédé de préparation

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002010111A1 (fr) * 2000-07-28 2002-02-07 General Electric Company Processus destine a la synthese de diarylesters d'acides dicarboxyliques
EP2033981A1 (fr) 2006-06-19 2009-03-11 Mitsubishi Chemical Corporation Copolymère de polycarbonate et son procédé de production
EP2203501A1 (fr) 2007-10-18 2010-07-07 Sabic Innovative Plastics IP B.V. Polycarbonates à base d'isosorbide, procédé de fabrication et objets formés à partir de ceux-ci
EP2203501B1 (fr) * 2007-10-18 2012-08-15 SABIC Innovative Plastics IP B.V. Polycarbonates à base d'isosorbide, procédé de fabrication et objets formés à partir de ceux-ci
EP2478031A2 (fr) 2009-09-14 2012-07-25 SK Chemicals Co., Ltd. Résine de polyester et procédé de préparation
US8273849B2 (en) 2009-12-30 2012-09-25 Sabic Innovative Plastics Ip B.V. Isosorbide-based polycarbonates, method of making, and articles formed therefrom
EP2840102A1 (fr) 2012-04-18 2015-02-25 Teijin Limited Copolycarbonate
EP3026074A1 (fr) 2013-07-24 2016-06-01 SK Chemicals Co., Ltd. Poly(ester de carbonate) hautement résistant à la chaleur et hautement transparent et son procédé de préparation

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Title
ACROS ORGANICS, no. 1076-97-7 99
DUCHATEAU ET AL., BIOMACROMOLECULES, vol. 9, 2008, pages 3090 - 3097
IM ET AL., RSC ADV., vol. 7, 2017, pages 6315
KAMPS ET AL., MACROMOLECULES, vol. 52, 2019, pages 3187
no. 1122-58-3
OH ET AL., MACROMOLECULES, vol. 46, 2013, pages 2930 - 2940
PAUL W. MORGAN: "Polymer Reviews", vol. 10, 1965, INTERSCIENCE PUBLISHERS, article "Condensation Polymers by Interfacial and Solution Methods", pages: 325

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